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The effective ionic radii of Shannon & Prewitt [Acta Cryst. (1969), B25, 925-945] are revised to include
more unusual oxidation states and coordinations. Revisions are based on new structural data, empirical
bond strength-bond length relationships, and plots of (1) radii vs volume, (2) radii vs coordination
number, and (3) radii vs oxidation state. Factors which affect radii additivity are polyhedral distortion,
partial occupancy of cation sites, covalence, and metallic character. Mean NbS+-O and Mo6+-O
octahedral distances are linearly dependent on distortion. A decrease in cation occupancy increases
mean Li+-O, Na+-O, and Ag+-O distances in a predictable manner. Covalence strongly shortens
Fe2+-X, Co2+-X, Ni2+-X, Mn2+-X, Cu+-X, Ag+-X, and M - H - bonds as the electronegativity of X
or M decreases. Smaller effects are seen for Zn2+-X, Cd2+-X, In3+-X, pb2+-X, and TI+-X. Bonds with
delocalized electrons and therefore metallic character, e.g. Sm-S, V-S, and Re-O, are significantly
shorter than similar bonds with localized electrons.
Introduction Procedure
A thorough and systematic knowledge of the relative The same basic methods used in SP 69 were employed
sizes of ions in halides and chalcogenides is rapidly in preparing the revised list of effective ionic radii
being developed by crystal chemists as a result of (1) (Table 1). Some of the same assumptions were made:
extensive synthesis within certain structure types, e.g. (1) Additivity of both cation and anion radii to re-
rocksalt, spinel, perovskite and pyrochlore; (2) prepar- produce interatomic distances is valid if one considers
ation of new compounds with unusual oxidation states coordination number (CN), electronic spin, covalency,
and coordination numbers; and (3) the abundance of repulsive forces, and polyhedral distortion.*
accurate crystal structure refinements of halides, chal- (2) With these limitations, radii are independent of
cogenides, and molecular inorganic compounds. A set structure type.
of effective ionic radii which showed a number of (3) Both cation and anion radii vary with coordina-
systematic trends with valence, electronic spin state, tion number.
and coordination was recently developed (Shannon & (4) With a constant anion, unit-cell volumes of iso-
Prewitt, 1969, hereafter referred to as SP 69). This work structural series are proportional (but not necessarily
has since been supplemented and improved by studies linearly) to the cation volumes.
of certain groups of ions: rare earth and actinide ions Other assumptions made in SP 69 have been modi-
(Peterson & Cunningham, 1967, 1968); tetrahedral fied:
oxyanions (K~ilm~in, 1971); tetravalent ions in perov- (1) The effects of covalency on the shortening of
skites (Fukunaga & Fujita, 1973); rare earth ions M - F and M - O bonds are not comparable.
(Greis & Petzel, 1974); and tetravalent cations (Knop (2) Average interatomic distances in similar poly-
& Carlow, 1974). hedra in one structure are not constant but vary in a
Further, the relative sizes of certain ions or ion pairs predictable way with the degree of polyhedral distor-
were studied by Khan & Baur (1972)" N H + ; Ribbe & tion (and anion CN). Both of these modified assump-
Gibbs (1971): O H - ; Wolfe & Newnham (1969): tions will be discussed in detail later.
Bi3+-La 3+; McCarthy (1971): Eu2+-Sr2+; Silva, The anion radii used in SP 69 were subtracted from
McDowell, Keller & Tarrant (1974): No 2+. These available average distances. Approximately 900 dis-
authors' results have been incorporated here into a tances from oxide and fluoride structures were used,
comprehensive modification of the Shannon-Prewitt and Table 2 lists their references according to CN and
radii. spin. These references generally cover from 1969 to
In this paper the revised list of effective ionic radii, 1975. The cation radii were derived to a first approxim-
along with the relations between radii, coordination ation from these distances, and then adjusted to be
number, and valence is presented. The factors respon- consistent with both the experimental interatomic dis-
sible for the deviation of radii sums from additivity tances and radii-unit cell volume (r 3 vs V) plots, as in
such as polyhedral distortion, partial occupancy of
cation sites, covalence, and metallic behavior (electron
delocalization) will be discussed. * Polyhedral distortion was not considered in SP 69.
A C 32A - 1
752 REVISED EFFECTIVE IONIC RADII IN HALIDES AND CHALCOGENIDES
SP 69. Although such r a v s V plots are not always VI"RE3+ radii) for consistency with experimental inter-
linear (Shannon, 1975), their regular curvilinear nature atomic distances and radii-CN plots.
still allows prediction of radii. This system is partic- Where structural data were not available or not ac-
ularly accurate for radii in the middle of a series, and curate, plots of (1) radii v s unit cell volumes, (2) radii
least reliable for large polarizable cations like Cs +, v s CN and (3) radii v s oxidation state, or combinations
Ba z +, and T13 +. Radii-volume plots were used by Knop of these were used to obtain estimated values. Fig. 1
& Carlow (1974) and Fukunaga & Fujita (1973) to shows examples of radii-valence plots used to provide
derive radii of tetravalent cations. These radii were consistency between experimental radii and those anti-
used along with experimental interatomic distances in cipated from the regular nature of these plots. Cations
deriving the final radii. Greis & Petzel (1974) derived whose final radii values were derived from both
rare earth radii in eight- and nine-coordination using estimated values and experimental interatomic dis-
accurate cell dimensions for rare earth trifluorides and tances a r e : V l O s S + , VIOs6+, VIOs 7+, VlRe4+, VIRES+,
distances calculated using the structural parameters VlRe6+, VIReT+, VIRh4+, vI1U4+, VIIUS+, and VIIU6+.
of YF3 and LaF3. These radii were used in Table 1 Fig. 2(a)-(e) shows plots of radii v s C N . Generally,
after applying small corrections ( + 0.030 ,~ to lXLa3+, it was assumed that radii-CN plots for two different
IXCe3+, 'Xpr3+, and ~XNd3+; +0.025 A to all other ions do not cross. Radii for 'VCu+, V'Cu+, IXRb+,
Greis & Petzel ~XRE3+ radii, and 0.015 A to all VNi2+, VIIEr3+' vIIyb3+ ' WITb3+ ' X.Nd3+ ' IVCr4+'
Ble3 65 2
~ l .59
1.10
. 6 5 'C
.96 C
vI I
Vl I
1.27
1.33
1.13
1.19
vllI
X
1.300
1.356
l.lbO R
1.216 R
Vl
Vlll
1.17
1.31
1.03
1.17
Re
R
UYe3 6F 9 Vl
VII
1.052
1.11
.g12
.97
R
xli
I 1.41
1.50
1.27
1.36 G
815 5 0 1 0 V l .go .76 E Vlll 1.167 1.027 R Lll IS 2 IV .730 .590
8K+3 5F 8 Vl 1.1o .96 R IX 1,223 1.083 g Vl .90 .7&
b K 6 5F 7 V l .97 .83 R E&e3 4 F 1 1 V l 1.030 .ago R VIII 1.06 .92 C
VlIl 1.07 .93 R Vl 1 1.085 .9~5 LU*3 4F14 Vl 1.ooi .8bl R
8 R - I 6P 6 V l 1.82 l.Vb p Vl I 1.144 1.004 R Vlll 1.117 .977 R
8 R e 3 6P 2 IVSO .73 .59 IX 1.202 1.062 R 1X 1.172 1.032 R
8R+5 45 2 I I I P Y .65 .31 EU2 4F 7 V l 1.31 1.17 MG+2 2P 6 IV .71 .57
8R7 3010 IV .39 .25 Vll 1.34 1.20
Vl .53 .39 A VIII 1.39 1.25 860 .720 *
c e 4 15 2 l l I .06 -.08 IX 1.44 1.30 il ll ......
1.03 .89 G
IV .29 .15 P x 1.49 1.35 HN2 30 5 I V HS .80 .66
VI .30 .16 A EUe3 4F 6 V i 1,087 .g6~ R V H5 .89 .75 C
CA+2 3P 6 Vl 1.14 1.oo Vll 1.15 1.01 Vl LS .81 .67 E
Vll 1.20 1.06 * Vlll 1.206 1.066 R H$ .970 .830 Re
Vlli 1.26 1.12 IX 1.260 1.120 R Vll HS 1.04 .90 C
~ x 1.32
1.37
1.18
1.23
F - 1 2P 6 i l
Ill
1.145
1 .16
1.285
1.30 MN3 30 6
~lll 1.10
.72
.9b
.58
R
C F * 3 bD I VI
II 1.28
l.og
1.16
.95 R
GAe3 3010
IV
V
.61
.69
.47
.55
* "
N
:l 2,
2S
) iv
Vl
1.32
.30
....
.16 A
C F * 6 5F 8 V l .961 .821R Vl .TbO .620 R* N 5 I S 2 I l l .044 -.106
GD3 ~F ? V l 1.078 .938 R Vl .27 .13 A
R. D. S H A N N O N 753
Table 1 (cont.)
ION EC CN SP CR eIRt ION EC CN SP CR fiR*
ND+Z 6F 6 VIII
VIII. .88
1.63
.76
1.29
~o.05~vi
RA*2 6P VIII
.85
1,62
.71
1.48
1 X
XI
1,27
1,32
1,13
1.18
E
C
IX 1.49 1.35 XlI 1.86 1.70 R Xll 1,35 1.21 C
N O + ~ 6F 3 V l 1.123 .983 R RB+L4P 6 VI 1.66 1.52 TI+2 30 2 Vl 1.00 .86 E
VIII 1.249 1.109 R* vll 1o70 1.56 T 1 + 3 30 1 VI .810 .670 R
IX 1.303 1.163 R VIll 1.75 1.61 r l + ~ 3P 6 I V .$6 .42 G
XlI 1.61 1.27 E IX 1.77 1.63 E v .65 .51 C
N I 2 3 0 8 IV .69 .55 X 1.80 1.66 Vl .745 .605 R
IVSQ .63 .69 Xl 1.83 1.69 VIII .88 .74 C
v .77 .63 E xlI 1.86 1.72 1 L * 1 6S 2 v l 1.64 1.50 a
VI .830 .690 R XlV 1.97 1.83 VIII 1.73 1.59 R
N I * J 3 0 7 Vl LS .70 .56 R RE*~ 50 3 Vl .77 .63 RM Xll 1.84 1,70 RE
HS .74 .60 E RE+5 50 2 VI .72 .58 E T L + 3 5D10 I V .89 ,75
NI4 30 6 Vl LS .62 .68 R RE+O 50 I Vl .69 .55 E Vl 1.025 ,885 R
RE*/ 5P b IV .52 .38 VIII 1,12 .98
NO+2 5F16 VI 1.26 1.I E
NP2 5F 5 VI 1.26 1.10 Vl .67 .53 TM+2 4 F 1 3 V I 1.17 1,03
NP*3 5F 6 VI 1.13 1.01 R RH+3 40 b Vl .805 .665 R VII 1.23 l.Oq
NP+6 5F 3 V[ 1.oi .87 R RH+4 4D 5 VI .74 .60 RM TM+) k F l 2 V I 1.020 .880 R
Viil 1.12 .98 R AHe~ 40 6 V[ .69 .55 viii 1.13~ ,994 R
NP+5 5F 2 VI .89 .75 RU*3 40 5 VI ,82 .68 IX 1.192 1.052 R
NPeb 5F 1 V I .86 .72 R RU*4 40 6 VI .760 .620 RM 0 + J 5F 3 V I 1,165 1,025 R
NP+7 6P 6 V I .85 .71 A RU*5 40 3 VI .705 .565 ER O 4 5F 2 V I 1.03 .89
o -2 2P b I f 1.21 1.35 RO*/ 40 1 IV .52 .38 VII 1.09 .95 E
Ill 1.22 1.36 RU*8 4P 6 IV .50 .36 viii 1.14 1.00 Re
IV 1.26 1.38 IX 1.19 1.05
VI 1.26 1.40 +6 3 5 Vl .51 .37 A Xll 1,31 1,17 E
VIII 1.28 1.62 5 .6 2P 6 IV .26 .12 u +5 5F 1 V l .90 .76
OH-I 11 1.18 1.32 vl .43 .29 c vii .98 .84
Ill 1.20 1.36 58+3 5 5 . 2 IVPY .90 .76 U +b 6P 6 I 1 .59 .45
IV 1.21 1.35 E v .96 .80 IV .66 .52
Vl 1.23 1.37 E vl .90 .76 A Vl .87 .73 *
0S+6 5D 6 VI .770 .630 RM $85 4010 Vl .76 .60 * Vll .95 ;81 E
0S+5 5 0 3 Vl .715 .575 E 5 C 3 3P 0 v I .885 .765 R Vlll 1.00 .86
0S.0 50 2 V .63 .49 VIII 1.OLO .870 Re v * 2 30 J V l .93 .79
Vl .685 .545 E S E - 2 6P 6 VI 1.84 1.98 P v . 3 3 0 2 Vl .780, .640 Re
05"7 50 1Vl .665 .525 E S E * 6 6S 2 v I .64 .so A v +4 3 0 I v .67 .53
0S,8 5P 6 I V .53 .39 S E * 6 3D10 IV .62 .28 Vl .72 .58 R*
p .3 3S 2 vl .58 .46 A Vl .56 .62 c VIII .85 .72 E
p *5 2P 6 I V .31 .17 * SI.6 2P 6 IV .40 .26 * V +5 3P 6 I V .495 .355 R*
v .43 .29 vl .540 .~oo R* v .6o .46 *
Vl .52 .38 C $H+2 6F 6 VIl 1.36 1.22 Vl .68 .54
PA+3 5F 2 Vl 1.18 1.0 e Vl I I 1.41 1.27 w +~ 50 2 V I .80 .66 RH
PAt4 6D 1 V l 1.06 .90 g IX 1.46 1.32 w +5 50 1Vl .76 .62 R
viii 1.15 1.01 SN*3 4F 5 v I 1.098 .958 R w +6 5P 6 IV .56 .42 *
PA~5 bP 6 Vl .92 .70 Vll 1~16 1.o2 E v .65 .51
VIII 1.05 .91 VIII 1.219 1.079 R vl .7~ .bO *
IX 1.09 .95 IX 1.272 1.132 R XE+8 4D10 IV .54 .40
P8+Z 6 5 2 IVPY 1.12 .98 c Ill 1.38 1.24 C vl .62 .~8
VI 1.33 1.19 SN*4 4010 IV .69 .55 R Y +J 4P 6 v I 1.040 .900 Re
VII 1.37 1.23 C VII 1.10 .96
VIII 1.63 1.29 C 830 .690 Vill 1.159 1.019 R*
IX 1.69 1.35 c VII .09 .75 IX 1.215 1.075 R
x 1.54 1.40 C VIII .95 .81 c YB+2 4 F 1 4 VI 1.16 1.02
XI 1.59 1.45 C SR*2 4P 6 V l 1.32 1.18 Vll 1.22 1.08 E
XIl 1.63 1.49 VII 1.35 1.21 VIII 1.28 1.14
PB*6 5 0 1 0 IV .79 .65 E VIII 1.40 1.26 Y8+3 4F13 Vl 1.008 .868 R*
V .87 .73 E IX 1.65 1.31 Vll 1.065 .925 E
Vf .915 .775 R Vlll 1.125 .985 R
~lI 1.50 1.36
VIII 1.08 .96 R 1.58 1.46 IX 1.182 1.042 R
p0l 6 0 9 II .73 .59 TA*J 5 0 2 VI .86 .72 E I N * 2 3 0 1 0 IV .7~ .0o
PD2 4 0 0 IVSO .70 .66 TA*4 50 1 Vl ,82 .68 E v .82 .68 *
Vl 1.oo .86 TA*5 5P 6 V l .78 .04 vI .880 .740 R*
POJ 60 7 VI .90 .76 VII .83 .69 VIII 1.04 .90 C
POe6 40 6 Vl .755 .615 R VIII .88 ,76 Z R + ~ 6P 6 I V .73 .59 R
P~*3 6F 4 V l 1.11 .97 R T 8 + 3 4F 8 VI 1.063 .923 R V .80 .66 C
Viii 1.233 1.093 k VII 1.12 .98 Vl .86 .72 R
IX 1.286 1.146 g VIII 1.180 1.040 Vll .92 .78 *
PO4 65 2 VI 1.08 .96 R IX 1.235 1.095 R VIII .98 .8~ *,
rill 1.22 1.08 R T 0 . 6 4F 7 Vl .90 .76 R IX 1.03 .89
POeb 5010 VI .81 .07 A Vill 1.02 .88
vIIIV4+, IVpb4+, and XTh4+ obtained from these plots majority of radii were derived from oxides and fluor-
were used to help determine the values in Table 1. The ides,* some were taken from chlorides, bromides,
first estimate of vIHV4+ was made from distances in iodides, and sulfides. For large electropositive cations
C32H28SsV (Bonamico, Dessy, Fares & Scaramuzza, with highly ionic bonds, very little covalent shortening
19741. is believed to occur and radii derived from these other
Another method used to estimate radii was based on compounds should differ only slightly from those
the empirical relationship between interatomic dis- derived from fluorides and Oxides. Examples are dival-
tances and bond strengths. Brown & Shannon (1973) ent rare earths such as Yb 2+ , Tm 2+, Dy 2+ , Sm 2+, Nd 2+
derived these relationships for the cations in the first and the ions Am 2+, Ac 3, Np a+, and U 4.
three rows of the periodic table from a large number of Another useful scheme for estimation of radii is the
experimental interatomic distances. These curves can comparison of unit-cell volumes of compounds con-
be used to calculate hypothetical distances for cations taining cations of similar size. McCarthy (1971) pre-
in any coordination (Brown & Shannon, 19731 Shan- pared a number 6f isotypic Sr 2 and Eu 2 ternary
non, 19751 Brown, 1975). Examples of cations whose oxides and generally found the unit cells of the Sr 2
radii were calculated in this way are: lVMn2+, V[Be2+,
VtB3+ ' wps+, v l S 6 + ' V m M g 2 + ' and VmFe 2+. These are
* Because of covalency differences in M - O and M - F bonds,
marked with a C in Table l. In certain cases, these oxide distances were emphasized. Therefore the radii in Table 1
values were combined with known structural data (see are m o r e applicable to oxides than fluorides. This subject is
Table 2) to obtain the radii in Table 1. Although the treated further in the discussion Effects of covalence.
A C 32A - I*
754 REVISED EFFECTIVE IONIC RADII IN HALIDES AND CHALCOGENIDES
Table 2 (cont.)
74 2AACA 403 I R3 VS V |OY F 3 ) 73 ACBCA 29 8 6 9 HG NO 0 4 74
AGSCA JO 2 4 9 1 M G 2 V2 0 1
ER*3 Vl H0*J VIII T|
ANM|A 86 | 5 8 3 NG 1 8 6 O f I 0 H I 6 1 * Z H | U
7~ ACbCA 26 484 ER2 S12 OT T~ ACBCA 30 2049 K HO BE F6 73
ANMIA $8 1 0 Z 9 MG C OS
ER*3 VII TO SSCOA 8 1745 H 0 3 FE5 0 1 2 74
CJCNR $2 11S5 CA L l ~G2 HZ I P 0 4 1 1 6
TO SPHCA 13 36 ER2 GE2 0 7 72 8UFCA 9S 437 H0 Pb 0 1 4 10 INOCA q I S I ~G I O N P ~ 1 3 (CA 0 4 1 2
72 JCMLB Z 1 9 7 ER8 U i T H D ) I O 10 H ) 1 2 74 ZAACA 4 0 3 1 R3 VS V IHO F 3 I 72 C J C H i SO 3 6 1 9 NG Y2 U6
ER+~ V I I I HO+3 I x 7~ ACBCA 29 2 6 1 1 M G 3 AS2 0 8
6 8 CHPL8 2 4 7 ER ~ 0 4 . ER V 0 4 14 ZAACA 4 0 3 | R3 V$ V I H U F J ) NG*Z V I I I
?0 [NOCA 9 2AO0 ER I C 2 0 4 ) I H C2 0 4 ) . 3 H 2 0 7 4 ACOCA 30 2 6 1 3 HOICZ H5 S 0 6 ) 3 . 9 H 2 0 73 AGRC8 29 266 CALGULAIIO
7O SSCOA 8 1 7 4 5 ER3 F E 5 0 L 2 H0+3 X MN*Z I V HS
7L ACSAA 28 372 E~ | H U C H2 G 0 O 8 3 . 2 H 2 0 T4 INOCA 13 2S35"HOIN2 014 IH C 0313.2H2 0 70 ANNIA 55 1 4 8 9 NN? S | AS U | 2
~4 ZAACA 4O3 I R3 VS V (eR F31 75 CJEHA S3 83L IN OIZIHOIN 03)51 6 9 ZAAA 369 306 Iq~ VZ 0 4
72 JGHL8 2 I97 ER8 0 I T H D ) I O I 0 N ) 1 2 1.5 Ill F I AGBCA 2T 1 0 4 6 NN CO CA 0 4
ER.3 IX 71JCPSA 54 2 3 5 0 N H~ I 03 6 9 PMSSA J2 Kql MN R2 0 4
5 9 ZKKKA 112 3 6 2 EK I C 2 H3 S 0 4 ) 3 . 9 H 2 0 6 6 ACCRA 20 750 L| | O] 13 ACACB 29 266 GALGULATEO
?4 ZAACA 4O3 I R3 V$ V IER F31 6 6 ACCRA 21 841LI 1 03 NN*~ V HS
EU+2 V l 58 ACGRA 9 1015 CEII 0314 6e ANNIA 53 1 8 6 1 M N 2 0 H AS 04
7O ZAACA 374 201 L! EU3 O4 58 ACCRA It 794 C i I I 0314.H2 0 74 MPMTA 21 2 6 6 NN2 AS OA OH
EU+2 V I I 4 3 RTCPB 6Z 7 2 9 N H4 I 03 ~N*Z VI LS
70 2AACA 3 7 4 201CI EU3 O4 I+5 Vl 0 9 ACBCA 28 9 2 8 R VS 0 LECTMONS
6 9 ACRCA 25 It04 EU 12 7 t JCPSA 54 2 5 5 6 N H4 I 03 MN*~ Vl HS
7 3 REF 3 L I 2 EUS 0 8 1+7 IV 6 9 SGIEA 168 SR6 ~ Z GE U6
EU*2 VIII ?0 RCBC~ 26 1782 NA I 0 4 6 q JCPSA 51 4 9 2 8 BA MN F 4
UNPUt EU F Z , EU 8RZ 2 6 ZEPYA 3g 308 A I 04 70 ZKK~A l~Z INNS tO N l z $ 1 2 0 8
EU+2 I x 71 J C S I A A971 1 8 5 7 II*TI-U 6 g ANMIA 5 4 | 3 6 2 NN eE2 | P 0 4 l Z I O H I 2 . S H 2 0
73 RVCMA |0 7~ EU CL2 I*7 VI 70 N J ~ I A 113 1MN? ~A|2 IS 0~)1$.18H2 0
UNPUl EU F2 6,,cc. 20 7o~.s. ,'/6 6 5 ACCRA 19 8 8 ~ MN S O~
EU+Z x 6 5 ACCRA 19 6 2 9 K4 2 0t0.8H2 0 72 A N N I A ST 6 2 1 M N 2 GE 04
? l NATMA S8 2 1 8 EU2 SI 04 37 JACSA 59 2 0 3 6 I N H 4 1 Z H ) [ 0 6 6 7 PRLAA 9~ i ~ 5 NN C 03
EU+3 V l IN.3 IV 67 HCACA )020)) MN) 0 8
68 REF 4 EU4 AL2 0 9 T4 ZAACA 409 97 ~82 IN4 07 MN*2 V I I
7 0 ZAACA 374 201 L | EU3 0 4 73 ZAACA 393 2 8 0 SR2 I N Z 0 3 72 AMNIA S? 621MN2 GE O~
73 REF 3 L I 2 EU5 08 IN*3 VI MN*Z V I A l
EU3 V I I 74 ZAACA 409 9 7 R82 I N 4 0 7 6 9 ZKKKA 229 427 ~ N ) FE2 GE$ 0 1 2
68 REF 4 EU4 AL2 o g ~ t ACSAA IS t437 IN O H S 04.lHZ 012 71AMM|A 56 791 GARNETS
13 REF 3 L 1 2 EU5 8 8 6 0 ACOCA 24 3 e 8 CUE I N Z OS 73 SSCOA 12 L09 NN3 AL2 GE3 0 1 2
EU+S V I I I 70 ACSAA 24 1662 IN 0 0 H 74 JCPS6 6~ 1899 MN U4 0 7
65 JCP$A 48 l o g 4 EU3 FE2 GA3 0 1 2
NN*J V! HS
~ ZAACA 4O3 I R3 VS V (EU ~38 AC6CA 30 1882 NA I N S l Z 0 6 0 7 ACSAA Z& ZO?| MNZ 0 3
3 ACSAA 27 2 5 2 7 EU2 I C 3 H2 0 4 1 3 . e H 2 0 74 SPHOA 18 7 6 t I N Z GE2 07 b 7 ZKKKA 124 428 NNZ 0 3
EU+3 [ X IR'4 Vl b8 ACSCA 24 1233 jl~ 0 0 H
74 ZAAC~ 4O3 A R3 VS V I E U F 3 | 7A J 5 $ C 8 3 1 7 4 SR ZR 0 3 6 9 JCPSA 50 1066 I N H 4 ) 2 RN F5
73 ACSAA 27 2 8 2 7 EU2 ( C 3 H2 0 4 ) 3 . 8 H 2 0 IR+S V I 6 3 PHSSA 3 K.46 f'~Z 03
71ACSAA 25 33~7 EU TRISGLYCOLATE 74 NROUA 9 1177 R3 VS V ICO2 I R 2 071 6 8 BUFCA 9~ 339 TO NN 0 8 , PR n N O ) , N u x N O )
F E * Z I V SQ H$ K*I IV 7A JS$C8 3 238 LA JCN 03, RN3 04,
74 AMHIA 59 llbE BA FE S14 0 1 0 68 ZAACA 3SR 2 4 1 K AG O L A . 9 S CA.o5 #N 0 3
FE*Z IV HS RE~ 2 K2 0 7J JSSC8 6 16 NA MN? 0 1 2
69 $C]EA L&6 139g ( N A , K ) 2 FE4 S [ A 2 030.H2 0 K*Z VI 7~ A N N I A 39 9as NGZ ~N e o s
6 9 ZAACA 3 6 9 3O6 FE V2 O4 SA ZAACA 2 6 4 144 K 58 F6 6 8 ACBCA 2 4 11A4 NA4 MN~ TLS OAR
TI JUPSA 31 452 FE2 TI 0 4
12 JUPSA 33 |29& FE2 MO 04
6 8 SPHOA
09 CCJDA
12 1095 K Y N02 0 8
II 6 0 6 K2 ZR2 O5 ~
* INOCA
4 INOCA
13 IRSA
13 1 8 6 4
~N I t 7 H5 0 Z 1 3 , 1 1 4 C6 HS CH$
~N IACACi3
FE*Z VI LS b 9 ACUGA 2 5 1919 ~ U2 F9 NN*~ IV
69 ACRCA 28 V25 R VS A I F E S21 K*L vii 7S JSSC8 L3 2 7 5 R3 V$ V IM4 NN O ~ l
FE+2 V I HS ~e CJCHA 46 9 3 5 ~2 R2 0 7 NN+~ V l
&9 NJMMA 1 9 6 9 4 3 0 FE AL~ IP O412 IO H J 2 l 0 H236 69 JCSIA 19~9 8 4 q KZ NO 0 4 73 JS$CB 8 23k 8 6 NN O3
.2H2 0 TA S~COA S 3 3 8 ~ FE F4 6 9 INOCA 8 33S NIL2 NN NBL2 0 3 8 . S O N 2 0
7O SUFCA 93 tgO ~E S O4 K*I Vlll 6 3 CZYPA 13 39e NAT H4 MN I I 0 6 I S * I T H 2 0
71SPHCA |5 g 9 9 FE3 BE S I 3 0 9 [ F I O H I 2 ~0 ZKKKA 74 3O6 K H2 P 0 4 6 7 HCACA SO 2 0 2 3 NN5 GO, c o 2 MN) 0 5
6 ? ACCRA 22 7 7 5 FE ( N H 4 ) 2 ( $ 0 4 ) 2 , 6 H 2 0 62 ZKKKA |AT 4A1K2 TI6 013 .N*6 IV
6 8 GIWYA 68 290 LIFE P O4 37 ZKKKA 98 2 6 6 K H2 I H 3 O) 85 0 1 0 12 ACOCA 2 8 2 8 4 S K2 MN O~
14 A ~ N [ A 59 4 8 & F~2 SA 0 4 7A INUCA 7 8 7 3 K H C2 0 4 M~*7 I v
FE*2 rill 6 8 CJCHA 46 9 3 5 K2 CR2 O7 6 8 ACOCA 2 ~ 1 0 5 3 AG NN 0 4
TA AMMIA $6 79A GARNE~$ 70 J C S I A 1 9 7 0 3 0 9 2 K AU I N 0 3 ) 4 MO+3 V I
71ZKK~A 134 333 FE3 A L 2 S I 3 0L2 6 5 ACCRA 19 6 2 9 K4 H2 12 0 1 0 . 8 H 2 0 6 9 ACBCA 25 4 0 0 KJ NO CL~
T3 ACAC8 29 2 6 6 CALCULATEO K*| IX 6 9 INOCA 8 2 6 9 4 K8 NO F6
FE+J AV H$ 70 ZKKKA 132 27 K A . 6 N A S . 5 CAO.3 A L T . 3 .0.~ vl
TO ACECA 26 1469 CA2 FE2 OS L18*5 032 7A MRUUA 6 5 5 5 L 1 2 MO F 6
70 SSCOA 8 1745 M3 FE5 0 1 2 6 9 ~CBCA 25 6 0 0 K CE F4 MO+~ IV
?1ACRCA 27 A263 BA FE2 0 4 6 9 ACSCA 25 1 9 1 9 K U2 F9 7 4 INOCA 13 2 7 1 5 R3 VS V AE N 0 0 * l
I I MREUA 6 T2S BA CA FE4 0 8 K*A X ~O.S Vl
71AESAA 2S 36A6 CA2 FE2 05 73 CJCHA $1 2 6 1 3 K AL P2 0 7 7 t INOCA t0 9 2 2 8A2 NO NO 0 6
73 ACBCA 29 832 6A FE2 0 4 K +I XII
FE+3 v 6 8 SPHCA 13 4 2 0 K Y ~2 08 68 JCPSA 48 2 6 t 9 CU N0 O~
TA JS$CB ~ I FE V 0 4 ? l INOCA 10 1264 K2 P8 CO I N 0 2 1 6 6 8 SPHDA 12 LOgS K Y N 0 2 0 8
FE*3 vI H$ 67 I~0CA 5 5 1 4 K2 BA CO I N U 2 8 6 69 JCS|A 1969 8 4 9 K2 1~3 0 4
TO ACSCA 26 Z469 CAZ FEZ O5 74 IACSA 9 6 6 6 0 6 K2 CA CO I N 0 2 ) 6 72 ACUCA 28 6 0 GU2 NO) OA2
70 SSCOA 6 1745 ~3 FE5 0 1 2 75 ACOEA 3A $ 9 6 K2 8A CU I N 0 2 1 6 6 9 JCPSA 50 8 6 N02 NO3 0 1 2
71SSCOA 9 335 K FE F4 57 PASAA 56 643 K CL 0 ~ 71 SPH~A 18 611LI3 FE NO3 0 1 2
?L JS$CB ~ I FE v 0 4 LA*3 Vl ?A SPHCA 15 8 2 9 K AL N02 0 8 . K FE ROE 0 8
TL JPCSA 32 6315 B I FE O3 6 9 ZKKKA 129 2 ~ 9 CU LA 02 71JCPSA 55 1093 CA N0 0 ~ , SR NO 0 *
11ACSAA 25 3616 CA2 F E 2 0 S T3 NRUUA 8 1 2 6 9 ~ 3 V$ V I ~ E 2 ~ 3 0 A 2 1 73 ACBCA 29 2 0 7 4 LA2 NO) O12
67 ACCRA 23 239 FE lOS H7 0213 LA+3 V I I ! 71JCSIA 1971 1 8 5 7 NO(*63 - O
6 9 CCJO~ 1 9 6 9 440 FE I C 7 H5 0 2 1 3 ?4 A N N I A 59 1277 LA4 ~G2 T I 3 S [ 4 0 2 2 NO*6 V
FE*) VIII 73 ACRCA 2 9 2 0 7 4 LA2 H03 U I 2 67 CCJOA 1967 3 7 4 ~2 NO3 0 1 0
T3 JSSCB 8 33L ESTIMATED 6 8 INOCk 7 2 2 9 5 LA ( C 5 H7 0 2 ) 3 I H Z 0 4 2 08 J C S I A 1968 1 3 9 8 KZ X0$ O10
FE*4 Vl 74 ZAACA +03 A R3 VS V ( L A F31 NO+6 VI
73 JSSCB 8 3 3 1 R3 VS V I P E R O V S K I T E S I 7~ SPHCA L8 67S LA2 SR3 (B 0 3 1 4 68 JCSIA 19&8 13V8 K2 M03 0ZO
R3 VS V I S ~ Fe O3) LA*3 IX 70 JSSCB 1 kS& AG6 M010 0 3 3
FE+o I V 71NRBUA 6 2 3 LA FE 0 3 70 INOCA 9 2 2 2 8 NA3 ICR MO 0 6 0 2 ~ H b I * R H 2 0
z~ JSSCB 8 *3 K2 FE 0 4 ?~ Z ~ C A ~O~ A ~ ) VS V ( L ~ ~31 r o ACSAA 24 3711Cl ~ 0 0 2 AS O~
R3 VS v (K2 FE 0 4 ) 74 A~IA 59 12T7 LA~ NG2 T13 S I 4 0 2 2 6 6 ACSAA 20 2 6 9 8 NO F 6 IGASI
oA+~ I V LI+A IV TO CCJOA 1970 SO NO 0 3 ( H 2 0 ) 2
16 ACRC~ 2T 6t6 L | 5 GA 0 4 3V ZKKKA A02 119 L I O HoHZ O
T5 AC~CA 36 56O S~ OAZ S l Z 08 TO 2AACA 3 7 9 | 5 7 L I Z CU 02 6~ INOCA 1603 K I R 0 O2 C2 O4I H2 0 1 2 O
GA.) V l 70 INOCA 9 1 0 9 6 Y8 L [ F4 73 ACRCA 29 8 6 9 HG NO 0 4
14 A T R I A 3O 1364 ItS HAl Ob O& 71AMNIA 56 18 NA3 AL2 L l 3 F 1 2 74 ACECA 30 11V5 NO 03VHZ O
GD*3 V I I 71ACSCA 27 0 6 6 L 1 5 OA O4 N-J Iv
70 &CBCA 26 4 8 4 GDZ S I 2 0 7 T3 JSSCB 6 538 L I 3 V O4 REF 6 NG3 N 2 , S I 3 N~.8 NITI N
?2 ACSCA 28 6 0 GO2 NO3 O12 73 ACRCA 2 9 2&Z$ L I {N~ HSI 8E F4 N*5 Ill
T2 SPHC~ 16 7 9 0 G O 2 0 E Z 07 T ) ACBCA 2 9 ~ 6 2 8 L [ N H3 0 H $ 04 REF 6 NHk N O3t~L~ N 0 3 t K N OAt
O9 [VNM& 5 1823 G O g . 3 3 S I 6 0 2 6 6~ ACCRA 17 7 8 3 L I 2 C2 0 4 RAin 0312,TIIN O314
T2 JSSCB S 266 0 0 9 . 3 3 $ 1 b 0 2 6 14 ACSCA 30 2 4 h 6 L I Z 8E Sl 0 4 NA+I I V
GO*J V I I I LI+L V| 74 ZAACA 409 6 9 N A 6 ZN 0 4
IA SPHCA 1~ 9 2 6 NA GO S ] 0 4 &8 ACBCA 24 2 2 3 L | 3 AL F6 REF 2 NA2 O
l Z SPHCA 16 79O ~ 0 2 GE2 O? 6 9 2AACA )TA 3 0 6 L 1 2 ZR O3 NA+A V
74 ZAACA 4O3 A R3 V$ V IO0 F ) | 70 ZKKKA 132 I 1 8 L I 2 AL2 S [ 3 0 l O 68 ACeCA 2 4 1077 ~A2 S I 2 OS
~ 0 ~ 3 ZX TA ~RRUA 6 ~ U Z ~0 F6 6 8 SPHOA A2 9 8 7 NA2 ZNZ S l 2 07
72 SPHE& 16 7 9 0 GO2 GEZ QT 6~ AC~A 19 ~ 0 1 L I C6 07 H7 6~ ZAACA 329 110 NA2 HO O2
6 9 IVNNA 5 IR23 GD9.33 S]6 026 74 AIEA 66 819 LI N8 P 0204 NA+I Vl
7~ ZAACA 4O3 A R3 VS V IO0 F 3 ) 68 CZ~YA 66 29O Ll Fe 70 ACSAA 2 4 1287 N&~ SN2 GE4 0 1 2 I0 H)4
OE*4 I V ?l ASA6 2~ 3387 LI N ~ O8 6 5 ACCeA 19 5 6 1 N A C6 0 7 H7
68 ZKKKA t26 299 CO 0E 0 8 73 IJCHA ~Z 26~ LI V OJ 63 ,ccA, i~ 1233 NA o I O . I * . Z , 2 0
69 $ C I E A 165 586 AN2 GE 0 4 T3 ACBCA 29 2 2 9 4 L I 2 ZR F6 60 ZKKRA 115 6)0 NA2 AL2 S I S O [ O * 2 H Z 0
69 Z~KKA 129 427 ~N3 FEZ GE3 OAZ CU+3 V l 58 ZKKKA 111 Z4I NA CL 0 3
7O JS$CB Z 612 ~ 0 2 8 G E| O 0 4 8 7O ZAACA 3T7 70 C~ LU2 O4 ~6 ACCRA ~ 811 INAsAS RAIN
Zl sP-c* 18 ~a~ ~ sm GE o~ ?z J*CC* 4 2 ~ ~ u e o~
70 ACSAA 24 1287 NA4 $N2 GE4 0 1 2 I 0 H I 4 LU*~ VIA! s g ACCRA 1 5 2 6 NA U ACETATE
6 7 ACSAA 2A 12B! NAB SN4 GEIO 0 3 0 (O H I 4 74 ZAACA *03 | R3 VS V ( L U F31 74 ACRCA 30 1872 NA2 u O4
7~ NOCNe A02 964 NAZ 0 O3 LU+3 IX 78 ACBCA 31 8 9 0 NA2 C O 3 . H Z O
I1 " 0 C ~ 6 IOZ I245 K 2 0 E ~ O9 7~ ZAACA ~ 0 3 A R~ VS v ( L U F31 NA*I VII
72 SPHCA t7 244 CO GE O3 ~G*2 I v 71 SPHCA IS 9 2 6 NA GO S l 0 4
12 ROCk5 103 1560 GE5 0 ( P 0 4 1 6 72 ACC~ 28 2 6 7 KZ NGS $ I 1 2 0 3 0 ;0 NJNlA 113 I NN7 NAA2 I $ O 4 1 3 . 1 5 N 2 0
GE*4 v i T ) ACBCA 29 RqO NA2 OR2 07 ALPHA
10 SSCO~ 1 $ 5 7 CA2 GE O4 AC~CA 2 3583 , G 2 NAZ $ ] 6 OAR NA*A V I I I
I0 J$$C8 2 662 . G 2 8 GEtO O48 ~4 ACUC6 30 2667 K~ NG 84 6 8 AGBGA 24 1 7 0 3 NA 8 F4
TA ,OCM8 Ao2 I Z 4 S K 2 0 E 4 0 9 ~0+2 V 6 8 SPHOA A2 V8? NA~ Z . Z $12 0 7
TA AC~CA 2T 2 1 3 3 OE 02 6~ ~CSAA ZZ A966 ~G) P2 0 8 71ANMIA 56 18 NA3 AL2 L I 3 FAZ
12 ANN1& ~1 62 MN2 GE 0 4 OELT& &6 , J N N A 1966 A42 MG 84 0 7 NA+I Xll
12 2KKKA 186 38T Ge I O H I P 04 UNPU$ NG3 P2 O8 [ l J$SC8 3 89 NA|3 N833 094
TZ ~OCM8 103 AS60 GES 0 I P 0 4 ) 6 UNPU3 RG2 P2 07 32 ZKKRA 81 13S NA A~ S I 0 4
.,A I NO*2 V l Ne.3 vl
....... + ,3 7 65 CJCH& ~) A l S q . G 2 P2 07 7. ACIEA U6 RA9 L I NU OZ
6 JCPSA 2 ZT~ ~ 68 UAPCA 11 36A ~G2 A$2 OT ,8.~ Viii
~P.~ Iv TO ACeCA 26 1419 , G , H4 P O* 75 JACSA 9? 2713 NBIOPNI~
TS J 5 5 C 8 13 2 7 5 6 3 V5 V 1~4 . F o41 NR+~ v l
NF.~ Vll INOCA 8 A665 E$4 H03 FAO 6 8 JCPSA *a 5048 8 A 2 7 S R 7 . 5 NB2 0 5 . 7 8
............ ~ o2 ~9 ZKKKA IZ9 6~ NG S l U3 70 JS~C~ l .19 ~ - , 8 2 OS
~ ~C$AA ZJ 3341 I0 ,42 S 04*~Z 0 698P.C, lI 93,,.. 70 JSSC8 1 *S~ NA2 . 8 4 OAA
14 AC>AA 2T 3467 . P ~ ( O , 1 8 IC~ 0 4 1 4 . , Z 0 10 J 5 5 C 8 ~12 . G 2 e I0 O48 70 ~ l A ss 90 c a NSZ 0 6
.F*4 VIII 6 ~ .NL.O 196~ i v 6 . ~ AL 6 o , $5 PRVAA 98 go3 C~2 NEZ 07
TJ &CSAA 27 Z * 5 5 NF ( 0 H I 2 S 04 70 BSC++ 1970 + 2 4 3 "G $ 0 4 . . Z 0 71J5$CB J 09 N ~ l $ NeS~ O94
.0,1 vl 71 l c e c l z? 813 .~ =E o 6 71Z*~c~ 3co 119 ~ ~96 0 6
? l CCJO& | 9 1 | 4 6 6 NO2 F2 bB &CSAA 22 A466 MG$ P2 08 14 J I N C A 36 1965 CA2 NB2 U7
ro 6 k F A C~ MO Sl O4 It JCSI& lVll AZIO 8 l ~ NRA7 O * 7
756 REVISED EFFECTIVE IONIC RADII IN HALIDES AND CHALCOGENIDES
Table 2 (cont.)
Table 2 (cont.)
72 ACBCA 28 9 5 6 B& TO O ) It JINCA 33 2 8 6 7 CR2 U 0 6 b9 PHSSA 32 KQ| ZN FEZ 0 4
TC*~ VI 72 ACBCA 2 8 3 ~ 8 9 U O2 I 0 H I 2 73 ACSAA 27 1541ZN $ 03.2 1/2H2 0
67 STBGA 3 I R3 VS V I F L U O R I O E S ) 13 ACBCA 29 7 U E8 bA INOCA 3 2 6 5 . ZN 10PMI2
I C 7 IV U~6 VII ZN*Z V
6 g MILER 8 381 TO2 0 7 ?2 ACBCA 28 3609 U 03 70 JSSCB 1 1 2 0 ZN2 P2 0 7
71ZRACA 3B0 146 TCZ 0 7 U*6 VIIi 73 CJCHA 51 I 0 0 4 ZNZ V2 0 7
7E*4 IV 0 9 ACBCA 25 7 8 7 CA U 0 4 7 l AMNIA 56 1 1 4 7 ZN~ AS2 0 8 IO H ) 2 . 2 H 2 0
b 9 ACBCA 25 I S S L H3 FE2 TE4 0 1 2 CL 6 5 ACCRA 19 2 0 5 RB U 0 2 IN 03)3 ZN*Z Vl
7 l ACBGA 27 6 0 2 T l TE3 0 8 , SN TE3 O8~ TE 02~ V*Z Vl b5 CJEHA 43 1147 ZN2 PZ 0 7
HF TE3 0 B , ZR TE$ 0 6 UNPU3 V F2 6 8 SPNCA 13 127 ZN M 0 4
71ACBCA 27 60B U 7E~ O9 V*) VI 70 JSSCB 1 1 2 0 ZNZ P2 0 7
7 E 4 Vl 70 PRVBA 2 3771 V2 0 3 71CJCHA 49 3 0 S b Z N ) V2 OB
61ZKKKA ~18 34S 7E 0 2 7J JESTS 6 419 V4 O7 71AHMIA 56 1 1 k 7 ZN4 AS2 0 8 IO H I 2 . 2 H Z 0
71ACBCA 27 6 0 2 M TE3 o e 6 9 ACECA 2 5 1334 V I C 3 H7 0 2 ) J 73 ACUCA 29 2741Zfl S| Fb.6H2 O
71ACBCA Z? 60B U TE3 0 9 b 9 ZAACA 369 306 N VZ 0 4 73 ACSAA 27 1 5 4 l ZN S 0 3 . 2 I / Z M Z 0
TE,6 IV 74 MRBUA 9 1091 IV0.99 CRO.01IZ 03 ZR*4 IV
11JCSIA Iq71 | 8 S 7 T E ( 6 1 - O 7 0 JPCSA 31Z~69 V2 O3 75 JSSCB 13 ZTB R3 VS V IM~ ZR OAI
TE~6 V I V*4 V ZR*4 V
6 9 ZENBA 24 6 4 ? L I 6 TE 0 8 b5 ACGRA 19 4 3 2 L I V2 0 5 b 9 CCJOA 1 9 6 9 7 2 7 K2 ZR 0 3
7O MRBUA 5 19q RG3 TE O6 b l JCPSA SS 53 V O I t S H7 0 2 1 2 70 JSSCe 2 4 1 0 KZ ZR 0 3
b 9 ACSAA 2~ 3082 NA2 K4 TE2 0 8 IO H ) 2 [ H 2 0 ) 1 4 73 ACBCA 29 269 CA V3 0 T ZR*4 vl
6 4 INOCA b 3 ~ TE 0 I 0 H I S . H 2 0 73 ACBCA 2 g 1335 CA V4 0 9 6 9 ACBCA Z5 2658 ZR (M AS 0 4 I Z . M Z 0
6 4 NATMA $l 5SZ 7E O O H V*4 Vi b 9 ZAACA 371 306 L 1 2 ZR 0 3
6 6 ACSAA 2 0 2 1 3 8 K4 TEE O6 10 H ) 4 * H 2 0 72 JSSC8 5 4 4 6 CU V 0 3 70 JSSC8 L 478 2 ZRZ OS
I o H;MA ~7 ~ HG~ TE O6 T5 JSSC~ A 419 vk at eO A C S ~2 Ia2Z ~ ZR2 P 3 0 l Z
?0 ZAACA 3 7 8 129 SR2 NI TE Ob 72 PRVBA 5 2361V OZ CR ; 3 ACBCA Z9 2294 L I Z ZR F6
70 ACSAA 24 3 1 7 8 75 l 0 H I 6 74 ACBCA S0 2 6 ~ 4 V3 0 7 71ACBCA 2T 1944 RBS ZRA F Z I
66 ACSAA 2 0 153S TE F6 71ACSAA 2 5 2 6 7 5 Vb 0 1 3 14 CJCHA 52 2 1 7 5 R3 V S V
7L ACBCA Z7 8 1 5 ~G3 TE 0 6 7 0 ACSAA Z4 4 ~ 0 V02 Z R * 4 VII
6 5 ZAACA 3 3 4 2 2 3 TE 0 2 { 0 H I 3 74 PRVBA I0 4 9 o VO2 6 e ACBCA Z5 21e4 NAZ ZR F6
6 8 CHDBA 2 6 7 1433 CUE TE Ob V*5 IV 70 AGBCA 26 417 I N H 4 1 3 ZR F t
b 9 NOCMB 100 1809 AGE TE 0 2 l 0 H I 4 be RCBCA 24 292 Y V 04 70 JACTA 53 12b ZR OZ
71 B U F C 94 172 TE ( 0 H ) 6 6O CHPLB 2 47 ER V 0 4 73 ACSAA 27 177 ZR4 I 0 N l 6 (CR 0 4 I S . H E 0
73 ACBCA 29 &43 TEE 0 5 6 7 ACSAA 2L 590 MN2 VZ 0 7 73 ACSAA Z7 Z614 ZR ( 0 H I Z S O4,.MZ 0
13 ACBCA 29 9 5 6 HZ TEZ 0 6 70 Z K K 13l 161 5&3 I V O412 11ACBCA 27 1944 Re5 ZR4 F21
73 ACSAA 27 B TE IO N ) 6 71 JESTS 3 4~a NO V 0 4 ZR*4 viii
7 4 ACdCA 30 1813 HZ TE 0 4 71ACBCA 2~ 2 1 2 4 NA3 V 0 4 . 1 2 H 2 0 b 9 ACBCA E3 1558 ZRZ (S 0 4 1 4 I H 2 O I B . 6 H 2 0
14 ACBCA 3 0 2 0 7 S I N H 4 ) 6 ITE M0b 0 2 4 ) TE {OHI6 70 INOCA 2259 CA2 V O4 CL b 9 ACBCA 2S IB66 ZR2 i S 0 4 1 4 (HE O I B . E H Z O
7H2 0 1L CJCHA 4V 1 6 2 9 MG3 V2 0 8 b 9 ACBCA ZS IStZ ERE I S 0 4 1 4 . H E 0
THe4 V | 73 ACBCA 29 2304 C03 VZ 0 e , N i 3 vz 08 71ACBCA 2T 63B NZ H6 ZR F6
74 CJCHA 5 2 2 1 7 S R3 VS V 72 JSSCB 4 29 FE v 0 4 71AMMIA 56 Tee ZR S I Ok
TH*~ VIii 13 CJCHA 51 1 0 0 ZN2 VZ 07 b 3 INOCA 2 243 ZR ( A C A I 4
7 l ACBEA 2? e L ~ K5 TH F 9 71CJCHA A9 3 0 S 6 ZN3 V 2 0 B ?L ACBC& 27 1944 RE5 ZR4 F 2 1
1 l ACBGA 2 7 2 2 9 0 7 TH6 F31 73 JSSCB 6 $38 L 1 3 v O4 b J INOCA 2 250 NA4 ZR ICE 0 4 ) 6 * 3 H 2 0
7~ ICHAA B 2 7 ] K TM P3 0 1 0 12 CJCHA 50 3 9 6 4 CU3 v z 0 8
?H*4 IX 73 CJCHA $1 70 PB2 VZ O7 KEF | G. E. BR0~N, PH.0. THESIS, VIRGINIA
B8 CCJOA 1 9 6 8 9 9 0 ( N H 4 | 4 TH F8 73 ACBCA 29 14! Y V 04 POLYTECH.INST.,UNIV.MICROFILNS,TE-49B
6 9 ACBCA 2S 1958 I N H 4 ) 4 TH F8 73 ACBCA 29 133B CUB VZ O10 REF 2 R.M.G.MVC0FF,CRYSTAL STRUCTURES,WILEY,
bB CCACA 40 147 THZ P3 O12 . 73 CJCHA $1 265 Li V 03 N.Y.eI96B
l O ICHAA 4 STZ N TN2 { P 0 4 | 3 ~,,CRCA 3~ 16~BN, v 0 3 REF 3 H.BARNIGHAUSEN ET A L . , P R O C . 1 0 7 H R . E .
71ACBCA 2 7 1 8 2 3 R6 TH3 F 1 3 4 NJMMA ZI0 CAS I V 0 4 1 3 0 H RES.CONF.CAREEREE,AR|ZII973)P.490
73 ACBCA 2 9 2 9 7 6 NA3 BE 7 H I 0 F4S V*5 V REF 4 C.BRANOLEeH.STEiNFIN.PROC.7TH R.E.
70 ACBCA 2 6 1 1 8 5 K NA TH Fb SO ACSAA 4 1119 vz 05 RES.CONF.eCORONAOO,CAL.OCT 2 8 , 1 9 6
71ACBCA 27 2 2 T q I N H 4 1 3 TH FT 71RVCMA 8 ~O9 Li V2 0 5 REF S R.D.SHANNON,U.S.PAT.3&bSIBLtNAYIb.1972
7H'4 X 7 4 ACBCA 30 2 6 4 4 V3 0 7 REF b W.H.BAUR,NITROGEN,HANOBOOK OF GEUCHEM.
7 5 ACBCA 2 g Z 6 8 7 TH I N 0 3 ) 4 ( ( C A H 5 3 3 P 0 ) 2 74 ACBCA 30 2 4 9 1 H G Z V2 0 T SPRINGER-VERLAG,N.Y.1974
7H,4 Xl 7 3 ACECA 29 S&7 HG2 V2 0 7 REF 7 A.M.SLEIGHTtU.S.PAT.38&9544,NOV 19,1974
6 6 ACCRA 20 B42 TH I N O 3 ) 4 . 5 H 2 0 TO CMOCA 270 9SZ CA VZ 0 6 UNPUI H.BARNIGHAUSEN,PERSONAL COMMUNICATION
6 6 ACCRA 20 8 3 b TH I N 0 3 ) ~ . B H 2 0 V*5 Vi UNPU2 A.M.SLEIGMTePERSONAL COMMUNICATION
7He4 Xll 73 JSSCB 3 432 V P 05 UNPU3 C.CLVOePERSONAL COMMUNICATION
6S ACCRA 18 6 9 8 ~G TH I N 0 3 1 b . BH2 O 11ACSAA 25 2 6 7 5 V6 0 1 3 UNPU4 C . T . P R E M I T T , P E R S O N A L COMMUNICATION
ZZ CJCHA 50 3619 NG V2 06 UNPUS M . H . B A U R , P E R S O N A L COMMUNICATION
TI*~ Vl
73 JSSC8 6 213 T[4 07 73 CJCHA $1 2621V P O3 ALPHA
b 3 PHRVA 1 3 0 2 Z 3 0 7 1 2 0 3 T~ CJCMA 52 2 1 8 4 K3 V OZ C2 O 4 . 3 H Z 0 ACACB ACTA t R Y S T . SECT. A
74 J $ S C 8 9 2 3 5 712 0 3 73 ACBCA 29 1743 GU VZ 0 6 ACOCA ACTA CRYST. SECT. B
74 ACBCA 30 6 6 2 CS T I t S 04)2.12H20 M*3 Vl CCRA A C I A CRYST.
T14 IV bT STBGA 3 I R3 VS V { F L U O R I O E S I ACIEA ANGEM. CHEH. I N T . EO.
7 3 ACbCA 2 9 2 0 0 9 BA2 T [ 0 4 M+6 IV ACSAA ACTA CHEM. SCAND.
6L CCRA 14 8 7 5 8A2 T I 0 4 b 9 ACBCA 25 |704 K2 H 0 4 ADCSA AOV. CHEM. SER.
1 1 J C S I A 1971 1657 T [ I * 4 1 - 0 ~1SPHOA 13 b 5 6 N02 M 0 6 MMIA AM. M I N E R .
74 ZAACA 4 0 8 6 0 RB2 T I 0 3 T I SPHCA 13 92B PB M Ok ANCPA ANNLS C N I H .
TI*k V 72 ACBCA 28 3 1 7 4 SN w O4 AREA ARK. KEM]
6 8 ACBCA 2 4 132T YZ TI O5 71JCPSA 5 5 IO93 SR M O 4 , B A M Ok BAPCA B U L L . ACAO. POL. S C I . SER. S C I . C H I H .
71,4 VI BCSJA B U L L . CHEN. SOC. JAPAN
70 2KKKA 131 2 7 6 Y2 T I 2 0 7 ACBCA 30 1872 N Z "M 0 4 8SCFA B U L L . SOC. C . I M . F R .
71ACBCA 27 6 ) S NZ H6 T l P6 T~ ACBCA ~O l e t 8 L Z IM O~33 OUFCA B U L L . BOG. F R . H I N E R . CMISTALLOGR.
11JSSCB 3 340 TI~ 07 W*6 V CANIA CAN. MINERALOGIST
70 ACACB Z6 ~36 eA TI O)" T4 ACBCA 3O Z3e7 CA3 M O~ CLZ CCACA CROAT. CHEM. ACTA
M.6 Vl CCJDA CHEM. COMMUN.
~4 CCRA
71 ~cps,
72 CSCMC
B~32~ ,,
IT 2 4 0 CO T I 0 3
o2
8A T I b O13
6 9 SPHCA
b 9 SSCOA
13
7
933
1797
HG H 04
6 1 2 M O&
CHOBA
CHOIR
C . R . HEBD. SEAN. ACAO. S C I . SEA. B
C . R . HEBO. BEAN. ACAO. S C I . SERe C
72 ZKKKA 136 273 T[ 02 70 SPHCA 14 B18 K NO (M 0 4 ) 2 CHPLB CHEM. PHYS. L E T T .
7~ ZKKKA 139 103 K TIP 05 10 SPHCA 14 $15 L i 2 FE MZ OB CIMYA CRNEGIE iNST. MASH. YEARBOOK
72 INOCA 11 2989 ITi O(CB H7 0 2 1 2 1 2 7 0 SPHCA 15 28 PRZ MZ 0 9 CJCHA CAN. J . CHEN.
T4 ICHAA 11 243 (NHA)2 TI O(C20~elE.HZ O T0 ACBCA 26 1020 CU M O4 CSCMC CRYST. STRUCT. COMM.
74 ACBCA 30 2894 8A T I Z O5 7 0 JSSCB 2 Z/8 LIFE (H O4)2 CZYPA CZECH. J . PHYS.
T4 CJCHA 52 21TS R3 VS V 66 ACSAA Z0 269B H Fb IGAS) DANK 0 0 R L . AKAD. N A U , SSSR
TI*4 VIII 72 ZENSA 27 ZO3 SN M 0 4 HCACA H E L V . CMIM. ACTA
66 JC$1A 196B 1496 T[ {N 0314 T I SPHCA 13 991 N~4 M3 013 ICHAA INORG. C H I N . AGTA
7L'1Vl 74 JSSC8 10 3 FEE N 0 b INOC INORG. CHEM.
R3 VS V I N F ) 74 CBCA 30 2069 6A M 0 4 |NOMA RUSS. J . INORG. CHEM.
XE,~ IV INUC INORG. N U C L . CHEM. L E T T *
TL*t VIII
75 C B C 31 3 6 5 TL N 03 71JCPSA $2 8 | 2 XE 0~ iVNMA I Z V . A A D . NAUK SSSR, NEORD. CHEH.
71JCSIA lg71 1837 XE{+8)-O JCSA J . AH. CHEM. SOC.
7L3 IV
71ZAACA 381 IZ9 LI5 TL 0 4 xE*e Vl JACG J . A P P L . CRYSIALLOGR.
73 ZAACA 396 IT3 SR4 TL2 O7 6~ INOC, 3 1~12 NA4 XE 0 6 . B . 2 0 JACTA J . AM. CERAN. SOC.
7 4 ZAACA 403 19T BA2 7 L 2 0 S 6 h INOCA 3 1417 N 4 XE 0 6 . B H Z 0 JAPIA J . A P P L . PHYS.
K4 XE 0 6 . 0 H Z 0 JCNLB J* CRYST. MOLEC. STRUCT.
7L*~ Vl
6 8 ZKKKA 12& 143 TL2 0 3 V,3 Vl JCOMA J . L,'SS-OHMON METALS
74 ZAACA 409 l g 7 BA2 T L 2 0 S 6T ACCR~ ZZ 3Sk YZ BE O4 JCPSA J . CHEM. PHYS.
75 ZAACA AIZ S7 R8 71 F4 ............. ~R TZs~% JCSIA J . CMEM S a c . LON0. 10ALTOM)
67 SPHCA 11 ~83 A Y JCSPA J * CHEM. SOC. LONO* ( P C K I N I | !
TLeJ Vlll
72 ZAACA 393 2 2 3 TL F ) 6 9 ACBCA 2S 2 1 4 0 Y2 0 3 JESUA J . ELECTROCHEN. SOC.
71sp.c 1~ Bo6Yz Sl OB JIHCA J . INORG. N U C L . CHEM.
TH,Z Vl
UNPUl TH IZ ~k J C S l A 1 9 7 k 2 2 9 C6& H I 2 [ 3 N12 0 6 Y JMOSA J . MOLEC. SPECTROSC,
Y*3 V l i JNBAA J . RES. N A T . SUB. STAND. SECT. A
TM*Z V I I
UNPUI TM C L Z , T M BR2 6B INOCA T 17TT YIC6HSCOCHCOCH3J~.H20 J0P~A J . P~YS. I F R . |
Y*3 V l l i JPCHA J . PHYS. CHEM.
TM*J V l
a 3 PHSSA 3 K4Ab TM2 0 3 6~ AC~CA 24 Z92 ~ V O~ JPCS J . PHYS CHEM. SOLIOS
57 AECRA 10 Z39 Y3 FE5 0 1 2 JSbCS J . SOLID STATE CHEM.
TM*J r i l l
70 SSGO& 8 174S TN3 FES O12 o 8 EPHOR 12 1095 Y NOZ 0E JSTCA J . STRUCT. CHEM.
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758 REVISED EFFECTIVE I O N I C R A D I I IN H A L I D E S AND CHALCOGENIDES
compounds to be slightly larger than those of the E u 2 + A similar study of relative cell volumes of isotypic
compounds. This difference was assumed to exist for compounds involving the pairs Cu-Li +, Ag+-Na +,
all Sr z+ and Eu 2+ coordinations. Because compounds TI+-Rb , and pb2+-Sr 2 was used to obtain more
of Am 2+ and Sr 2+ have similar cell volumes, the radius reliable estimates of the radii of Cu +, Ag +, TI , and
of Am 2+ was made equal to that of Sr 2+ Pb 2 (Shannon & Gumerman, 1975).
Wolfe & Newnham (1969) studied Bi4_xRExTi3012 The nature of Sn 2, NH~-, and H - made it impos-
and concluded that Bi3 and La 3+ have nearly equal sible to define their ionic radii. The coordination of
radii. From a study of BiTaO4 Sleight & Jones (1975) Sn 2 by oxygen or fluorine is always extremely ir-
have concluded that although Bia + and La 3 have es- regular,* leading to average distances which depend
sentially equal radii, the size of Bi3 depends on the on the degree of distortion. Since this distortion varies
degree of the 6s 2 lone-pair character. When BiTaO4 widely from one compound to another, it is not mean-
transforms from a structure where the lone-pair char- ingful to define an ionic radius.
acter is dominant to the LaTaO4 structure, it undergoes Khan & Baur (1972) derived an apparent radius of
a volume reduction. Table 3 shows a comparison of the NH4+ ion by analyzing the N - O distances in a large
isotypic Bia+ and La a+ compounds where the lone-pair number of ammonium salts. They concluded that
character of Bi3+ is (1) constrained and (2) dominant. NH + has an octahedral radius of 1.61 A, between that
Bi pyrochlores such as Bi2Ru207, Bi2Ir207 and Bi2Pt207 of Rb (1.52 A) and Cs (1.67 A). Alternatively, cell
were omitted from the table because no corresponding volumes of NH~ and Rb fluorides, chlorides,
La pyrochlore exists, but they have unit-cell volumes bromides, iodides and oxides may be compared. This
close to those of the Sm or Nd pyrochlores and thus leads to the conclusion that N H ~ is not significantly
have smaller volumes than those of La. When Bi3 is different in size from Rb . No explanation is offered
forced into high symmetry, a Bi 3+ compound has a for this inconsistency and therefore the radius of NH~
smaller volume than that of La 3+, but when the lone- is not included.
pair character is dominant, the Bi a+ compound is dis- The radius of the hydride ion, H - , has been the
torted and Bi 3 and La a+ compounds have approx- subject of some controversy. A number of different
imately equal volumes. This behavior was also noted radii have been proposed: 2.08 (Pauling, 1960); 1.40
in the highly symmetric garnet structure where the (Gibb, 1962); and 1.53 A (Morris & Reed, 1965). Gibb
hypothetical BiaFesOlz was estimated to have cell studied interatomic distances in many hydrides and
dimensions between those of the hypothetical concluded that good agreement between observed and
NdaFesO12 and Pr3FesO12 (Geller, Williams, Espinosa, calculated distances could be obtained using r(V~H -) =
Sherwood & Gilleo, 1963). For practical purposes, 1.40 A if corrected for cation and anion coordination.
Bi a+ is listed as slightly smaller than La 3+ but this The value of r(IVH -) was taken to be 1.22 A.
dependence on lone-pair character must be kept in Morris & Reed (1965) concluded that differences in
mind when comparing the volumes of Bi a + and La a+ observed distances in hydrides were caused by the
compounds. Similar behavior may also exist for Pb 2+ large H - polarizability. Because of such wide varia-
and Sr 2+, but this relationship was not investigated. tions in the apparent H - radius, it was omitted. How-
ever, an explanation for the variations based on coval-
ence differences will be discussed later.
Table 3. Cell volumes of isotypic Bi 3+ and La 3+
* Although cell dimensions of Sn2M207 pyrochlores were
compounds used in SP 69 to derive r(VmSn2+), Stewart, Knop, Meads &
(a) Lone pair character of Bi a+ constrained Parker (1973) and Birchall & Sleight (1975) recently found that
the pyrochlore A site in Sn2Ta207 is not fully occupied. Thus,
Compound Cell volume Ratio even this example of apparently regular Sn 2 polyhedra is not
BiLi(MoO4)2 314.7 0.96 valid.
LaLi(MoOa)z 328.7
BiNa(MoO4)z 320-5 0"97
LaNa(MoO4)2 332.1 .90 I I I I I
BiOF 87.6 0.90
LaOF 97.7
BiOCI 110.7 0.95 .80 V
LaOC1 116.8
BiOBr 123.8 0.98
LaOBr 126.4 .70 ~---------"~ To "91'
BiPO4 293-0 0.96
LaPO4 304.7
(b) Lone pair character of Bi a + dominant
.50 -
BizMoO6 268.5 ( 8) 1-00
LazMoO6 267.3
BiFeO3 62.49 ( x 6) 1"03 ,40 I r I I I
+2 4"5 +4 +5 .+6 +7
LaFeO3 60.77 ( x 4)
OXIDATION STATE
Bi2Sn207 1219.9 ( x 8) 1"00
La2SnzO7 1225.3 Fig. 1. Effective ionic radius (,~) vs oxidation state.
R. D. SHANNON 759
Results and discussion other set is based on r(WO z-) = 1.26 and r(V~F-)= 1.19
A,, and corresponds to crystal radii as defined by Fumi
In Table 1 two sets of radii are included. The first is a & Tosi (1964). As pointed out in SP 69, crystal radii
set of traditional radii based on r(V'Oz-) = 1.40 A. The differ from traditional radii only by a constant factor
2.oo1---~--~ . . . . r - I I -- I I 1 I I
1.70 , , , . . . . .
1.901 1.60
Cs -
1.50
~iaoi Rbd 1.40
1.70
J
1.30
. 1.60
1.20
1.50
1.10
1.40 r
1.00
1.30
.90
1.20
.80
~
1.10
Y0 Ni2-~
1.00
.60
Li +
.90
.50
80
Be +
.4O
.70
.30
.60 .20
I I 1 I I I
. .
1.20
. . . . - ~Bi3+ ,
1.10
J I i I I la3F+~]
1.00
j . ~.~TL3
1.30
.90
.80
.70 p 3+
.50
A0
~ AI 3+
1.00
~Tm Er
~""~'~"Lu-'yb3
..
-.
.30 .90
_ B 3 +
.20
.10
0
CN
Zi
.7
=
6
I I
7 8
CN
I
9
1
10
.
!i
]
12
(c) (d)
F i g . 2. (a)-(e) Effective ionic radius ( ) vs C N for some common cations.
760 REVISED EFFECTIVE I O N I C R A D I I IN H A L I D E S AND CHALCOGENIDES
1.20
'1
Th 4
Ahrens (1952) ionic radius was used whereas P means
Pauling's (1960) crystal radius was used. The symbol
M means that the radius was derived from a com-
i.I0 p o u n d having metallic conductivity. Distances cal-
culated from these radii may be too small for use in
!.00 compounds having localized electrons. (See discussion
~ p.4+
Bk 4+ Effects of electron delocalization.)
.90
In addition, the sources of the radii are indicated
:Hf4 + in Table 2.
.80
Fig. 2(a)-(e) shows that r - C N plots are reasonably
Ti 4+
.70 ~/4+ regular. Notable exceptions are IVNa+, VNa+, and
~VK+. It is apparent that N a - O and K - O distances do
.60 not decrease as much as anticipated from the r - C N
curve* when the CN falls below six. Typical distances
.50 / Ge4+ and corresponding radii in Table 4 show that N a - O
distances in four-coordination are only slightly less
.40
.10
Rc.<c~_[ANacl Bc,c~_]~I('-~)
CN RNaCl L Acscl BNaCl
(e)
where R = i n t e r a t o m i c distance, A = M a d e l u n g con-
Fig. 2. (cont.) stant, B = t h e cation CN and n = Born repulsion coef-
ficient. It appears that this equation is not valid for
four-coordinated Na or K +.
of 0.14 ~ . Although their inclusion in Table 1 may seem There are a few small irregularities in r - C N plots
superfluous, it is felt that crystal radii correspond more probably caused by poor or insufficient data, e.g.
closely to the physical size of ions in a solid. They curves for TI 3+ vs y3+. The differences in slopes of
should be used, for example, in discussions of closest Ti 4+ VS C r 4+ and V s + vs As 5 are probably caused by
packing of spheres, structure field maps (Muller & Ti4+-O and V5+-O octahedra being generally more
Roy, 1974), and diffusion in solids (Flygare & Huggins, distorted, which leads to greater average interatomic
1973). Traditional radii have been retained because of distances.
their familiarity to crystal chemists and physicists. It is also interesting to compare distances in square
They will probably continue to be used for comparison planar coordination v e r s u s tetrahedral coordination.
of unit-cell volumes and interatomic distances. In the Radii of square planar Cu 2 and Ag are equal to or
table, the ion is followed by electron configuration slightly greater than corresponding tetrahedral radii,
(EC), coordination number (CN), spin state (SP), consistent with the trend anticipated from anion
crystal radius (CR), and effective ionic radius (IR),
and in the last column, a symbol indicating the deriva- * Extrapolation of the Na curve gives r(~VNa)=0-90 A.
tion of the radii and their reliability. Those with a
question mark are doubtful because of: uncertainty in
CN, or deviation from radii vs CN, or radii v s valence
plots. Where at least five structural determinations \
resulted in radii differing by no more than + 0.01 A, Ul S b . . . . . . -' .'!ll,
the values are marked with an asterisk. [ \ , %.
" i\",
When the choice of a radius was influenced by any (.9 .~%
Z
of the various correlations described earlier, it is in- "'
n,, ~ ........ I- - -t~ --~,,
dicated by the following: R - from r 3 vs unit cell volume I ! ~ ',
plots; C - calculated from bond length-bond strength ci I i ~ ',
7 !I ii I",,:,
equations; E - estimated from one or more plots of r ....... "__'__i
"' s, Ti- - Ti ~ I i - ]l , ~
v s valence, r v s CN, and r vs cell volume. E implies poor I I I I
or nonexistent structural data. Radii in this category i I
_1 I
include VIFeZ+LS, WMn2+LS, vlcIa+LS, vIV2+, Rb R! R2 R,
VINo2+ ' VINia+HS, wit3+, WMo 3+, VITa3+, Wpaa+, AVERAGE INTERATOMIC DISTANCE , R
VlTa4+ ' IVpb4+ ' V~IrS+' WOsS+ ' WReS+, WpuS+, WBiS+, Fig. 3. Typical bond length vs bond strength plot.
R. D. S H A N N O N 761
repulsion effects. A similar comparison with Fe 2+ and Table 4. lnteratomic distances in some compounds
Ni 2+ cannot be made because of electron distribution containing tetrahedral and octahedral Na +
changes from tetrahedral to square planar coordina- Compound R (/~,) r (/~) Reference
tion. (a) lVNa+
Na20 2.40 1-02
NasP3010 2.37 0.99 60 A C C R A 13 263
i I , NaOH.H20 2.36 1.00 57 A C C R A 10 462
2.05 -v'r NbS+ Na6ZnO4 2.39 0.99 69 Z A A C A 4 0 9 69
Mean 2-38 1.00
(b) VlNa+
2.04 R= 1.976 + 6.45 A Na2WO4 2.38 1.00 74 A C B C A 30 1872
NaC6OTH7 2-37 1.01 65 A C C R A 19 561
2.03 Na4Sn2GeaO12(OH)a 2"39 1-02 70 A C S A A 24 1287
Na2P2OT. 10H20 2.48 1.10 64 A C C R A 17 672
2.02
NaHCO3 2.44 1.06 65 A C C R A 18 818
Na2B406(OH)2.3H20 2.41 1.04 67 S C I E A 154 1453
Na4P4OI2.4H20 2-415 1.05 61 A C C R A 14 555
2.01 NaAI(SO4)2.12H20 2.45 1.10 67 A C C R A 22 182
~~) NaB(OH)4.2H20 2-460 1-09 63 A C C R A 16 1233
2.00 N a U acetate 2.375 1.025 59 A C C R A 12 526
CloHI3NsNaO6P.6H20 2-406 1.046 75 A C B C A 31 19
1.99
Mean 2.42 1.05
The effects of distortion on m e a n bond lengths in date. In fact, the M o 6 + - O octahedra in Mo2(O2C6C14)6
numerous polyhedra have been determined. Although with a very small distortion have the short mean dis-
distortions in tetrahedra are not as important as in tance of 1.919 A.
octahedra, they can contribute to variations in m e a n Table 7 also lists the results of regression analyses
tetrahedral distances (Baur, 1974; Hawthorne, 1973). for TaS+-O and W 6 + - O octahedra but they are only
Strongly distorted octahedra like those containing V 5+, approximate because of the scarcity of accurate struc-
Cu 2+, and M n 3+ show a significant variation in m e a n tural data. Analysis of Ti4+-O octahedra was unsuc-
distance with distortion, A* (Brown & Shannon, 1973; cessful because of scatter in the data. Distances in
S h a n n o n & Calvo, 1973a; Shannon, G u m e r m a n & Ba6Ti17040 (Tillmanns & Baur, 1970) and BaTiO3
Chenavas, 1975). Octahedra containing Mg 2+, Zn z+, (Evans, 1951) deviated significantly from a linear
Co 2+, and Li + are generally less distorted than those relation.
of V 5+, Cu 2+, and M n 3+ and show a less pronounced Relations between m e a n distance and distortion
dependence on m e a n bond length (Brown & Shannon, should be particularly useful to help determine oxida-
1973). tion states in mixed valence compounds with such
The effects of distortion on m e a n bond lengths in combinations as MoS+-Mo 6+, W s + - W 6+, v a + - v 5+,
N b S + , O and M o 6 + - O octahedra are illustrated in Nb4+-Nb 5+ and Mn3+-Mn 4+. Such considerations
Figs. 4 and 5. Tables 5 and 6 list the data used to derive helped rationalize M n - O distances in NaMnvO12 and
the figures. the mineral pinakiolite (Shannon, G u m e r m a n &
Table 7 lists the results of linear regression analyses Chenavas, 1975).
of m e a n bond length on distortion for all octahedra The radii in Table 1 are generally derived for an
studied. It is clear from Fig. 4 that undistorted N b 5+ average degree of distortion. Thus, interatomic dis-
octahedra in pyrochlores have a distinctly smaller mean tances calculated from these radii m a y be inaccurate
value than in compounds like NbOPO4, CaNb206, and if the distortion in a particular c o m p o u n d is much less
NaaNbO4. Most of the accurately refined molybdates or greater than usual. This applies particularly to cat-
have relatively distorted octahedra. However, certain ions whose polyhedra frequently show a large distor-
ordered perovskites with no octahedral distortion such tion, e.g. MO 6+, N b s+, V 5+, Ba 2+, and the alkali ions.
as BazCaMoO6 would be expected to have much
smaller m e a n Mo6+-O distances than a typical molyb- 2. Effects of partial occupancy of cation sites on mean
cation-anion distances
In compounds with partially occupied sites, ab-
* Octahedral distortion is defined by A=~Y(R~-R/R) z
where R=average bond length and Rl=an individual bond normally large c a t i o n - a n i o n distances are usually
length. found, as expected if the anions surrounding unoc-
T a b l e 7. Variation o f mean M - O distance and effective ionic radius in octahedral environments as a function o f distortion
Maximum Correlation G o o d n e s s
Ion A x 104 N* Rot r0:l: m coefficient of fit ( x 103)
M o ~+ 212 38 1.920 3-73 0.74 67
0.572 3.01 0-63 70
W e+ 122 7 1-925 3-30 0.75 19
0"565 3.28 0.66 24
V 5+ 576 16 1.887 2.62 0.98 8
N b s 83 29 1.976 6.45 0.69 71
0.599 6.83 0.44 99
Ta 5+ 79 6 1.984 6.70 0.81 18
0.617 3.79 0-15 46
M n 3+ 71 15 1"994 7"08 0-82 30
0-624 6.15 0"54 50
Cu 2+ 316 26 2.085 3"99 0"82 77
Mg 2 156 28 2.094 8.31 0.72 21
' 0"728 8"86 0"77 18
Co 2+ 46 15 2"106 7"38 0"42 19
0"734 11 "70 0-70 16
Zn 2 + 71 16 2"099 7"70 0-64 21
0"736 8"20 0.74 16
Li 148 il 2"159 8"42 0"81 30
0"784 9.02 0-79 35
* N = n u m b e r of independent octahedra
t R=Ro+mA.
r = ro+ mzl.
764 R E V I S E D E F F E C T I V E I O N I C R A D I I IN H A L I D E S A N D C H A L C O G E N I D E S
cupied sites relax toward their bonded cation neigh- ides, bromides, sulfides, selenides, etc. and (2) tetra-
bors. Therefore average distances should increase as hedral oxyanions such as the VO]- and AsO ]- groups.
the occupancy factor decreases. In general, partial oc- The effects of covalence show up as a lack of additivity
cupancy seems to be more prevalent for cations which of the radii and are generally referred to as 'covalent
are weakly bonded to oxygen like Cu , Ag , alkali shortening'.
ions, and large alkaline earths. The most prominent (a) Halides and chalcogenides. Covalence effects can
examples are Li and Na compounds. Table 8 sum- be observed by comparing the relative contraction of
marizes the existent data on some structures with par- cation-anion distances in two different isotypic com-
tial cation occupancy. Fig. 6 shows the dependence of pounds as the anion becomes less electronegative, e.g.
mean Li-O bond length on the degree of occupancy. Fe 2+ in Fe2GeO4 and Fe2GeS4 vs Mg 2+ in Mg2GeO4
Although the data are not extensive, it is apparent that and Mg2GeS4. Covalence shortens both Fe-S and
mean distance increases as occupancy factor decreases. Mg-S bonds relative to Fe-O and Mg-O bonds, but
Extrapolation of the Li curve in Fig. 6 to zero occu- because of the greater electronegativity of Fe 2+ (1.8)
pancy, i.e. a tetrahedral Li vacancy, gives 2.10-2.15 A, compared to Mg 2+ (1.2), the Fe-S bonds are shortened
which is close to the 2.11 A found for c~-LisGaO4 by to a greater extent. Thus a 'covalency contraction'
Stewner & Hoppe (1971) and for fl eucryptite by parameter (Shannon & Vincent, 1974) can be defined:
Tscherry, Schulz & Laves (1972). d(Fe-X) a
Another example of the effects of partial occupancy Ra= d(Mg_X)3
can be found in the non-stoichiometric feldspar
Sr0.a4Na0.03vq0.13All.69Si2.2908 reported by Grundy & where d ( F e - X ) = m e a n Fe-X distance.
Ito (1974). The mean Sr-O distance in this compound A similar parameter
is 0.03 A greater than in the stoichiometric SrA1ESi2Oa V(Fer, Xn)
(Chiari, Calleri, Bruno & Ribbe, 1975). Rv=
V(MgmXn)
The relation between mean distance and occupancy
probably cannot be quantified precisely because the compares the volume of an Fe 2+ compound with that
relaxation of oxygen ions will depend on the nature of an isotypic Mg 2+ compound. To see the effects of
and number of other cation neighbors. covalence on the Fe-X distance relative to the Mg-X
distance, the ratio Rv or Rd may be plotted against the
3. Effects of covalence difference in electronegativity of the Fe-X bond,
Changes in interatomic distances due to covalence AZFe-x. Such schematic Rv-A Z plots are shown in
effects are anticipated in compounds with (1) anions Fig. 7. The reference ions for Cd 2 and In 3+ are Ca 2+
less electronegative than fluorine or oxygen, i.e. chlor- and Sc3+ respectively. Such plots usually show a strong
z.15 / , , , i IL~ i i
dependence of Rv on ZIZ. For Fe2+-Mg 2+ the Fe 2+
VACANCY fluoride volumes are ~ 1 1 0 % of the corresponding*
| IN ,, UsC.-aO
4
2'10I LiALSi206 T AND .8 EUCRYPTITE
e Mg 2+ fluoride volumes whereas the Fe 2 sulfide vol-
(~ SPODUMENE)l umes are ~ 9 6 % of the corresponding Mg z+ sulfide
2.05~- LiAISi04~ ,,~
(~ EUCRYPTITE)
~LiAISiz06]I[
= UzAIzSisO~o volumes. Plots for the cations with filled 'd' shells show
~UAtSi04 a markedly smaller dependence on zlg. This appears
2"00i (,8 EUCRYPTITE)
to be due to the difference in covalence of hybrid or-
e~TYPICAL bitals formed from metal 'd' orbitals vs metal 's-p' or-
i .95F-Li+-O DISTANCE bitals.
These relations show that effective ionic radii derived
I'S/~- i I t
primarily from oxides are not strictly applicable to
1.0 .9 .8 .7
I
5 ,
I
.2
I
,
I I
0
fluorides - note the change in Rv for Fe 2+, Co 2+, Ni 2+,
OCCUPANCY and Mn 2+ from fluorides to oxides. This effect is par-
Fig. 6. Mean Li-O bond length us partial occupancy. ticularly noticeable in R~-ZIX plots for the pairs
Cu+-Li and Ag+-Na (Shannon & Gumerman,
1975). The Cu+-Li + and Ag+-Na plots are very steep,
e.g. the volume of AgF is 120 % of the volume of NaF,
1.20 | I I I
whereas the volume of Ag2Se is only 72 % of the volume
of Na2Se. Although most of this change arises from
UNFILLED "d" SHELL
2+,Mn2+, C02+,N j2+ covalency, double repulsion effects present in the Li
1.10
and Na halides described by Pauling (1960) may also
play a role.
Covalence effects are useful in explaining certain
differences between the effective ionic radii of Table 1
FI LLED "d" SHELL
1.00 ~ - ~ Zn2+ Cd2+ in3+
and the ionic radii of Pauling (1927) and Ahrens (1952).
Pauling's radii for Cu (0.96 A) and Ag (1.26/~) are
Rv
or considerably larger than those in Table 1 (0.77 and
Rd 1.15 A respectively). Since these radii were derived
0.90 from comparison of alkali halide distances, using an
equation relating effective nuclear charge and screening
constants (Pauling, 1927), they are valid in primarily
ionic crystals. The smaller radii in Table 1 are applic-
0.80 able in the more covalent oxides. Extrapolation of R vs
CHLORIDES SULFIDES/SELENIDES-
FLUORIDES OXIDES J BROMIDES | /IODIDES ZIX curves such as in Fig. 7 leads to values of 0.91 /~
and 1.23 A for fluorides, which are close to Pauling's
2.5 2.0 1.5 1.0 0.5 0.0 ionic values.
L~
A final example of covalence effects concerns
Fig. 7. Covalency contraction parameter, Ro or Ra, vs ,dZ for M + - H - distances. According to Gibb (1962), the ra-
filled and unfilled d shell cations.
dius of the hydride ion is slightly larger than the radius
of the fluoride ion. To rationalize the behavior of the
hydride ion, the M - H bond has been treated as coval-
1.30 t i i i i
ent. Therefore, it is useful to make R~ vs AZ plots similar
,2o-C'-.": ~_~"
eNa-H
to those just discussed for Fe 2+, Cu +, etc. In this case,
the reference ion is F - and volumes of certain hydrides
LIO
eLi-H are compared to those of isotypic fluorides. The results
1.00 eLiBaH3 of this analysis are shown in Fig. 8. The solid circles
Mg-H
0.90
represent volume ratios, R~ = V ( M = H , ) / V ( M m F , ) ; open
Rv aSi-H squares represent ratios of typical distances Rd=
f ~ 0.80
aAt-H d ( M - H ) 3 / d ( M - F ) 3. In the more ionic hydrides of Cs,
0.70 B-H
o
D P-H
a As-H
Rb, K, and Na, hydride volumes are considerably
larger than those of the fluorides. For the Li and Mg
0.60
aC-H compounds, hydride and fluoride volumes are approx-
O.5C imately equal, whereas the more covalent hydrides have
I N-Ho
increasingly smaller relative volumes than the corre-
0.,~ l~ ,Io & oo' -~.s -o9 sponding fluorides. Fig. 8 partly explains the differ-
z~x
ences in reported radii. The Morris & Reed (1965)
Fig. 8. Covalency contraction parameter, R, or Rd, vs AX for value of 1.53 A was derived essentially from the large
hydrides. Solid circles represent ratios of cell volumes of
isotypic compounds. Squares represent ratios of the cubed alkali halides, while Gibb's value of 1.40 A was derived
M-H distances to the cubed M-F distances. primarily from hydrides of the more electronegative
766 REVISED EFFECTIVE I O N I C R A D I I IN H A L I D E S A N D C H A L C O G E N I D E S
metals such as: Sc, Ti, Y, Zr, HI', Nb, Ta, and Th. measurements indicate Curie-Weiss behavior and
Because of this strong dependence of M - H distances therefore nearly localized electrons (van Bruggen,
on cation electronegativity, it does not seem very useful 1969). This is in contrast to the Pauli paramagnetic
to quote a unique radius for H - . behavior of the corresponding V sulfides (de Vries &
(b) Tetrahedral oxyanions. Lack of additivity also Haas, 1973) characteristic of delocalized electrons.
appears in most small tetrahedral groups and is par- Thus, in SmS and the sulfides of V metallic character
ticularly noticeable for the ions lVB3+, ~VFe3+, IVGe4+, accompanied by electron delocalization appears to be
tVA:+, IvVS+, IVS6+, XVSe6+, and IVflT+. The devia- associated with reduced bond distances.
tions in vanadates have been studied in detail (Shannon A further example of delocalization effects occurs in
& Calvo, 1973b). Assuming that the V-O bond is the compound NaVS2 (Weigers, van der Meer, van
strongly covalent, and that relatively electronegative Heinigen, Kloosterboer & Alberink, 1974). The mol-
cations such as Cu 2+, Ni 2+, and Co 2+ tend to remove ecular volume of Pauli paramagnetic NaVS2 1 (67.9 .&3)
electron density from the V-O bond, a V-O bond is significantly less than that of NaVS2 II (72.7 .&3).
length increase in Cu, Ni, and Co vanadates is anti- NaVS2 II is characterized by localized electrons (Jel-
cipated. Plots of mean radii (~) vs mean cation electro- linek, 1975) and its molecular volume is consistent with
negativity (:~) show a marked slope with a gradual in- that of isotypic NaCrS2 (71.1 N3).
crease in ~(~vvs+) from vanadates of the alkali and If electron delocalization in oxides results in reduced
alkaline earth ions to those of Cu, Ni, and Co. Similar metal-oxygen distances and thereby an effective in-
plots for other ions, ps+, AsS+ (Shannon & Calvo, crease in valence, radii derived for the ions Mo 4+,
1973b), B 3+, Si 4+, Se 6+ (Shannon, 1975), showed the TC4+, Ru 4+, Rh 4+, W 4+, Re 4+, Os 4+, and Ir s+ from
same behavior. The statistical data on the tetrahedra metallic oxides may not be reliable when applied to
of B3+, SIS+, Ge4+, p5+, ASS+, 56+, Se6+, Cr6+, M06+, insulating oxides. Thus, radii obtained from distances
W 6+, and C17+ have been summarized by Shannon in the metallic phases, e.g. RhOz, ReOz, and Cd2IrzO7,
(1975). The slopes of the i vs '2 plots were greatest for will be smaller than radii obtained from semiconduct-
V 5+, Se 6+, and C17+, and least for Si4+. Although the ing or insulating compounds.* When both types of
evidence for covalence as the origin of these effects in compounds have been studied, a significant difference
the above systems is only indirect, this behavior is in distances is generally found. The mean octahedral
consistent with accepted ideas of 'covalent shortening' Re4+-O distance in insulating K4[Re202(C204)4]. 3H20
of bonds. (Lis, 1975) of 2.021 (10)/~ (r=0.671 A) is greater than
The evidence for covalent shortening of lVFe3+-O the estimated mean distance in metallic ReO2 of 1-99/~
bonds is more direct. Jeitschko, Sleight, McClellan & (r=0.63/k). Knop & Carlow's (1974) value o f r = 0 . 6 6 2
Weiher (1976) have found a good correlation between A derived from cell volumes of the insulating Cs2ReF6
(1) the Fe M6ssbauer isomer shift and mean Fe-O phases is consistent with the radius of Re 4+ from
distance and (2) ~ and mean Fe-O distance (R). Thus, K4[Re202(CEO4)4].3H20. The ReS+-O distance in
in fl-NaFeO2/~= 1.86/~ and 3=0.18 mm s -1 relative Nd4Re2Olt (Wilhelmi, Lagervall & Muller, 1970) of
to ~ Fe whereas in Bia(FeO4) (MOO4)2/~ = 1.909 A and 1"987 (12) ,~ (r=0.607 A) is significantly greater than
= 0.282 mm s- 1. the distance in metallic Cd2Re207 (Sleight, 1975) of
1.93 (2)/k (r=0.55 A). The radii of 0"58 A derived from
4. Effects o f electron delocalization XeFsRuF6 and 0.60 A from XeFRuF6 (Bartlett, Gen-
At a pressure of 6.5 kbar SmS (NaCI structure) nis, Gibler, Morrell & Zalkin, 1973) are greater than
undergoes a semiconductor to metal transition and a the radius of 0.565 A derived from the r a - V plot for
reduction in cell edge from 5.97 to 5.70 A. (Jayaraman, metallic Cd2Ru207. In contrast, however, the Mo 4+
Narayanamurti, Bucher & Maines, 1970). The reduc- radius of 0.64 /~ derived from insulating Li2MoF6
tion in cell volume was attributed to a partial conver- (Brunton, 1971) is not greatly different from the radius
sion of Sm 2+ to Sm 3+ ; some of the electrons presumably of 0.65 A derived from metallic MoO2 (Brandt &
go into a conduction band. Skapski, 1967).
Electron delocalization effects can also be seen by Although there appears to be ample evidence to
comparing the volumes of the conducting V sulfides show that M - O bond distances in compounds with
VS, VTSs, V3S4 and VsSs with the corresponding Cr localized electrons are greater than M - O distances in
sulfides which have localized 'd' electrons (de Vries & compounds with delocalized electrons, the data are not
Jellinek, 1974). The V compounds have volumes ~ 5 % yet sufficient to derive a reliable set of radii for semi-
smaller than the corresponding chromium compounds. con2ucting compounds4containing+Mo4+, Tc 4+ , Ru 4+ ,
This does not agree with the relative sizes of V and Cr Rh , W , Re , Os , and Ir . This will become
in oxides and fluorides, e.g. r(WV3+)=0"64 and possible as additional accurate structure refinements of
r(WCr3+)=0.615 A. For the sulfides, this unit-cell vol- fluorides, molecular inorganic compounds, and semi-
ume anomaly is not simply attributable to metallic vs conducting oxides containing these ions become avail-
semiconducting behavior. While Cr3S4, Cr556, and able.
Cr7Sa show a positive temperature dependence of re- * This assumes that metallic character can be equated with
sistivity typical of a metal, magnetic susceptibility delocalized electron behavior in these compounds.
R. D. S H A N N O N 767
I would like to acknowledge the help of F. Jellinek JEITSCHKO, W., SLEIGHT, A. W., MCCLELLAN, W. R. &
for providing unpublished data on NaVS2, F. C. Haw- WEIHER, J. F. (1976). Acta Cryst. B32, 1163-1170.
thorne for pointing out numerous structures containing JELLINEK, F. (1975). Private communication.
partially occupied cation sites, O. Muller for several KA,LM~.N, A. (1971). Chem. Commun. pp. 1857-1859.
KHAN, A. A. BAUR, W. (1972). Acta Cryst. B28, 683-693.
sources of radii of unusual ions, M. Fouassier for un- KNOP, O. & CARLOW, J. S. (1974). Canad. J. Chem. 52,
published data on K4MO4 compounds, I. D. Brown for 2175-2183.
unpublished bond length-bond strength curves, and P. S. LIs, T. (1975). Acta Cryst. B31, 1594-1597.
Gumerman for assistance with data collection. Struc- MCCARTHY, G. J. (1971). Mater. Res. Bull. 6, 31-40.
ture data on rare earth halides and an analysis of the MORRIS, D. F. C. & REED, G. L. (1965). J. Inorg. Nucl.
radii of divalent rare earths provided by H. Bg.rnig- Chem. 27, 1715-1717.
hausen were especially valuable. I am particularly in- MULLER, O. & ROY, R. (1974). Crystal Chemistry of Non-
debted to Ruth Shannon for the tabulation of data and Metallic Materials. 4. The Major Ternary Structural
Families. New York: Springer-Verlag.
proof reading. Finally, I would like to thank R. J.
PAULING, L. (1927). J. Amer. Chem. Soc. 49, 765-794.
Bouchard, W. H. Baur, and H. B/irnighausen for PAULING, L. (1960). The Nature of the Chemical Bond.
critically reviewing the manuscript prior to publication. Ithaca: Cornell Univ. Press.
PETERSON, J. R. & CUNNINGHAM,B. B. (1967). Inorg. Nucl.
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