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10 J. Chem. SOC.(A), 1971

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Single-crystal Raman and Far-infrared Spectra of Tetrakis(thiourea)-

nickel(ii) Dichloride
By D. M. Adams” and R. R. Smardzewski, Department of Chemistry, University of Leicester, Leicester LEI 7RH

Raman and far-i.r. spectra for single crystals of tetrakis(thiourea)nickel(ii) dichloride have been obtained at ca.
120 K and at ambient temperature. The results allow unambiguous assignment to A , 6, and E species (in C4
symmetry). Descriptions of many of the internal modes are also offered.

WE have previously reported the far-i.r. spectra of
several series of thiourea (tu) complexes and made
assignments which at the time appeared to be internally
consistent. In view of the complexity of the spectra,
and because part of our argument was based upon
recently discredited X-ray structural data: we have
studied the low-frequency vibrational spectrum of one
of the more important compounds by single-crystal
techniques, viz, trarts-[Ni(tu),Cl,].
Theory.-trarts-[Ni (tu),Cld cryst allises in the tetragonal
system, space group 14 = C4 (No. 79) with 2 = 2.4
This is an exceptionally favourable crystal for our
TABLE1
Factor-group analysis of [Ni(tu),Cl,]
C45 Total TA R N# Activity
A 9 1 1 +
7 I.r.(z); Raman (atzz a’vv,a’J
B 6 0 0 6 Raman (dm-
E 9 1 1 7 I.r.(%,y); Raman (aW,a’=)
TA= acoustic modes; R = rotatory lattice modes; N f =
internal modes, excluding v(C=S) but including torsions.
purposes since factor group, site symmetry, and molecular
symmetry are all C4, and there is only one formula unit
in the primitive cell. Hence, as shown by the factor-
group analysis (Table l),the only optical branch lattice
1 D. M. Adams and J. B. Cornell, J. Chem. SOC.( A ) , 1967, 884.
2 J. E. O’Connor and E. L. Amma, Chem. Comm., 1968, 892:
Inorg. Chem., 1969, 8, 2367.
modes are of the rotatory type. Since we are not
concerned with the internal modes of thiourea, we
consider the ligand only as C=S for purposes of factor-
group analysis; we then subtract the v(C=S) modes
+ +
( A B E ) which occur above 600 cm-l and add the
torsional modes ( A B + +E ) which are not included
when this approximation is used.
EXPERIMENTAL
Crystals of [Ni(tu),ClJ were obtained as golden-yellow
rods by slow evaporation of an aqueous solution of NiCl,,-
6H,O and thiourea. They showed well-developed { 100)
and { 001) faces.
Raman spectra were obtained with a Coderg PH 1
spectrometer with 632.8 nm excitation. A ‘ Cryocirc ’
cold cell was employed for work at liquid nitrogen tem-
perature. The crystal space group allows optical rotation,
in principle, although we found no evidence of rotatory
power under the polarising microscope. Nevertheless, we
restricted incident and outgoing beams to the x- and y-
axial directions in which optical rotation is much less
likely to occur. The excellent extinction between different
orientations confirms this.
Far-i.r. spectra were obtained as described e l s e ~ h e r e . ~ ~ ~
3 M. Nardelli, L. Cavalca, and A. Braibanti, Guzzetta, 1956,
86, 867.
4 A. Lopez-Castro and M. R. Truter, J. Chem. SOL, 1963,
1309.
5 D. M. Adams and R. R. Smardzewski, preceding paper.
D. M. Adams and R. R. Smardzewski, to be published.
 View Article Online

Inorg. Phys. Theor. 11

A specially designed cold-cell was used, based upon a
metal bellows, which permitted final adjustment of the
crystal in the beam whilst under vacuum. Thin crystal
sections ca. 7 x 2 mm2 face cut parallel to the (100) plane
were ground to a few tens of microns thickness and then
polished until they transmitted an adequate amount of
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radiation. .-c
0

VI
Y)
.-

RESULTS AND DISCUSSION

The crystals were of good optical quality and yielded
excellent spectra. Extinction between the various
allowed orientations was complete for both Raman and
i.r. spectra (Figures 1 and 2). Resolution was improved
on cooling the specimen to ca. 120 K ; our discussion
concerns the spectra at this temperature.

1.r. spectra of [Ni(tu),ClJ at ca. 120 K; full line,

electric vector parallel to crystal z-axis; dashed line, electric
vector parallel to crystal x-axis. P = Polythene absorption
/ u
’+- -J- . . -_-----
1’

. l h /. . TABLE3
250 ZOO 150 100 50 16 250 ZOO 150 100 50 16
Bands in the far4.r. spectrum of [Ni(tu),C1,]
Symmetry Polaris- Temp.
species ationa (K) v(cm-l)
a z 298’ 236sh, 204s, 169s, 126s, llOs, 84sh
77 232sh, 212s, 172s. 132s, 118s, 96s
e x 298 232s, 202sh,b 166sh,b 142s, 94s, 49s
L .
77 224s, 192sh,b l68sh,b 150s, 102s, 59s,
250 200 150 100 50 16250 200 150 fD0 50 16 48s
1 Raman spectra of [Ni(tu),Cl,] at ambient
FIGURE a C,-axis E crystal z-axis. b Estimated.
temperature
TABLE4
TABLE2 Correlation of internal modes of [Ni(tu),Cl,j between
Relative peak heights in the Raman spectrum of groups
[Ni(tu)&Id Symmetry Molecule
co- Molecule and Factor
slit- ordinates * (C*J Site (C,) Group (C,3
Symmetry Orient- Temp. width
species ation (K) (cm-l) Av(cm-l)
u x(zz)y 298’ 4 216(8)br,a128(43), 109(100),
87(31)
77 2 215(8)br,a131(43), 112(100), 7A b
-
, 7A
b x(yx)y 298 4
93(31)
181(2),a 131(12), 75(91),
(Tz
; a’, + a’w,a’z,)
50( 100)
77 2 188(2),a 137(8),= 76(64),
51(100)
e x(yz)y 27978 4 96(18), 61(69), 52(100)
2 216(3),a 205(3),0 164(8),=
146(8),a 96(22), 62(60), (a‘Z.2 - a’w)
50(100) t---------B
6- 6B
e x(zx)y 298
77
4
2
96(18), 61(67), 50(100)
215(2),a 205(2),“ 163(7),a
148(6),0 98(18), 61(67),
k}
SU
3B,
(a’*)
2 (a’= - a’,,&-)
50(100)
a = slit-width 8 cm-1.

A Species.-Both i.r. (z-polarisation) and Raman 7E- -E7 7E

spectra [a(zz) tensor component] are exceptionally clear (a’w,a‘,: L,#)
and in good agreement. The importance of having both
spectra even though the selection rules require complete * The symmetry co-ordinates (Table 5) have C4 symmetry;
coincidence is clear; the intense i.r. band at 172 cm-l the correlation to C ,, shows which co-ordinates would be
involved in each C,, species.
was not found in the Raman spectrum.
Six of the eight predicted bands were observed. A slightly by rotation about the M-S bonds makes the
possible reason for the absence of two predicted bands symmetry C4d. Two of the A-modes in C, come from
follows from Table 4. Distortion of the molecule a,(C,,) and are inactive in CdV.
 View Article Online

12 J. Chem. SOC. (A), 1971

Beyond this stage, group theory cannot help us. (equivalent to stretching the 2-52 A Ni-Cl bond). The
Although the various modes in each symmetry species bond is so long that it must be very largely ionic.
will interact to some extent, we can offer reasonable Movement of the chloride along the z-axis provides an
suggestions as to the dominant contribution for some of oscillating dipole which w ill interact strongly with
them by invoking other evidence. z-polarised radiation. By the same token, the associated
low polarisability change will lead to vanishingly weak
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TABLE6 Raman intensity.

Symmetry co-ordinates for [Ni(tu),Cl,] a 23-S$ecies.-These modes are only Raman-active,
A-block Four of the six predicted were found. The intense
4 51 cm-l line must be an internal mode since, for our
Sl = 4.x ri crystal, no lattice modes are allowed in the B-species.
t-1
s2 = t,; s3= t, We therefore consider it as either a torsional mode or
4
S,, S, S,, and S, are of the form 4 xdwhere xj is respectively as an out-of-plane mode of the (MS$ moiety. Its
i-1 intensity suggests the former because correlation from
h, St, At, and q. C4vshows the b, modes to be Raman-active by virtue of
B-block the (xy) tensor component.
S,--S13 are of the form &(xl - x, + x3 - x4) where xi is E-S$ecies.-Seven out of the eight predicted Raman
respectively vi, 61, pi, q, At, and E{.
lines were observed. Above ca. 160 cm-l i.r. absorption
E-block (x-polarised) is intense and we were unable to obtain
are of the form - (xl - xg) where xf is respectively crystal sections sufficiently thin to allow resolution of
1
S,4--S2,
4.2
yi,
%I crr, a, 7% Ail and Y. the three or four overlapping bands between 160 and
a See Figure 3 for numbering scheme. Q is a set of dihedral 230 cm-l. The Raman spectrum shows three very
angles describing torsional motion about the S=C bond. The weak bands in this region, which must have i.r. counter-
angles describe bending motion in the MSC planes, whilst
the set A1 describe motion perpendicular to these planes parts if, as we assume, they are the E fundamentals.
(equivalent to torsions about M-S bonds). We can be sure that the rotatory lattice mode, the
thiourea torsion and G(SNiS) will be below 150 cm-1.
A broad band centred near 144 cm-l in the i.r. spectrum
of the mull is known to be halogen-sensitive.1 It is
therefore very probable that the E mode at 160 cm-1
in the crystal is either 8(Ni-C1) of the ' short ' Ni-Cl
bond (most unlikely) or, more probably, the E trans-
latory mode of the chloride ion: this argument further
supports the description of the 172 cm-l band as a
' localised lattice mode.' By elimination the three
lines found above 160 cm-l must be the v(Ni-S), G(NiSC),
I and p(NiSC) modes. The width of, and probably some
14
I of the structure on, the broad and intense i.r. complex
CI above 160 cm-l is most probably due to the presence of
FIGURE 3 Labelling scheme for internal co-ordinates combination bands which have gained intensity by
Fermi resonance. We have evidence from a study of
v(M-S) is placed at 232 cm-l because it is the highest NMe,[MnClJ and many related compounds that this is a
halogen-insensitive band> The 213 cm-l mode is general effect.6
probably due to v(Ni-Cl) of the shorter N i x 1 bond The single-crystal results substantiate and clarify
(2.4 A) because a band at 202 cm-1 in the i.r. spectrum earlier generalised assignments.l The main error made
of a Nujol mull is known to be halogen-sensitive. previously was in assignment of the band at 172 cm-l.
The complete absence in the Raman spectrum of a We thank the S.R.C. for support.
band equivalent to the intense i.r. band at 172 cm-l,
follows if we assign it to a ' localised lattice mode' [0/1040 Received, Jzcne 19th, 1970)