Mat. Res. Bull., Vol. 20, pp. 1181-1189, 1985. Printed in the USA.

0025-5408/85 $3.00 + .00 Copyright (c) 1985 Pergamon Press Ltd.

STRUCTURAL DETERMINATION OF SOME MPS_ LAYERED

PHASES (M = Mn, F e , Co, N i and ~ d )

G. Ouvrard, R. Brec and J. Rouxel

L a b o r a t o i r e de Chimie des S o l i d e s , L.A. 279
2, rue de la Houssini~re - 44072 Nantes Cedex, (France)

(Received June 27, 1985; Communicated by P. Hagenmuller)

ABSTRACT
The s t r u c t u r e s o f m o s t o£ the MPS phases (M = Mn, Fe, Co, Ni, Cd)
were determined from s i n g l e crysta~ a n a l y s i s . They show the expected
CdCI2 s t r u c t u r a l type, some weak d i s o r d e r on the c a t i o n i c s i t e s being
detected on NIPS_ and CoPS3. F a i r s t o i c h i o m e t r y is i n f e r r e d f o r the
phases since no l n t e r s l a b c a t i o n could be seen zn the Van der Waals
gap o f the s t r u c t u r e s . Polytypism may occur in the case o f NiPS3.

I. INTRODUCTION

The e x i s t e n c e o f MPS3 l a y e r e d t h i o p h o s p h a t e s was f i r s t shown by F r i e d e l

( 1 ) , who h e a t e d t o g e t h e r t h e e l e m e n t s M ( t r a n s i t i o n e l e m e n t ) , P" and S in t h e
1/1/3 stoichiometric proportions. An e x t e n s i v e s t u d y o f t h e s e phases was done
more r e c e n t l y by K l i n g e n and Hahn ( 2 - 5 ) , w h e re a s A. Wold p r e p a r e d I n 2 / 3 P S 3
~1). A l t h o u g h a l l t h e u n i t c e l l p a r a m e t e r s were d e t e r m i n e d f r o m s i n g l e c r y s -
t a l X-Ray a n a l y s i s , o n l y FePS 3 was s u b j e c t t o f u l l structural determinations
( 4 ) . From the c e l l constants, ~he CdCl2 s t r u c t u r a l type of the iron d e r i v a t i -
ve has been assumed f o r a l l the other MPS3 compounds (M = V, Mn, Fe, Co, Ni,
Zn, Cd), but t h i s has never been ascertained by any complete s t r u c t u r a l c a l -
cuLations. We showed r e c e n t l y (6) t h a t the c e l l parameters p r e v i o u s l y a t t r i -
buted to VPS3, a c t u a l l y correspond to a non s t o i c h i o m e t r i c mixed valence
phase to be w r i t t e n V l l 4 V I I ~ 4 [ ] 2 PS (V PS ). I t was f e l t necessary to
0.3 . O. O. 8
check the s t o i c h i o m e t r y oP the who~e ~PS3 ~ami~y through s t r u c t u r e c a l c u -
l a t i o n s and, in the process, to determine possible defects and/or c a t i o n i c
occupancy o f the Van der Waals'gap. Also, accurate s t r u c t u r a l data (ato-
mic c o o r d i n a t e s , interatomic a n g l e s and d i s t a n c e s ) were s t i l l m i s s i n g and
needed in order to conduct proper physical c a l c u l a t i o n s such as f o r example

1181
1182 G. OUVRARD, et al. Vol. 20, No. I0

b a n d s t r u c t u r e a n d f o r c e constants. We give in t h i s a r t i c l e the r e s u l t s of

the s t r u c t u r e refinements performed on MnPS3, FePS3, COPS3, NiPS3 and CdPS3.
Results concerning non s t o i c h i o m e t r i c VO.78PS3 have been published elsewhere
(6).
II. EXPERIMENTAL

,/'; I I . 1 . Synthesis. The MPS3 phases

have been obtained from pure pow-
der elements taken in the s t o i -
I ".
I I ".. c h i o m e t r i c p r o p o r t i o n s M/P/S =
I/I/3 (M = Mn, Fe, Co, Ni, Cd)
CELL
.... hexagonal and heated under c o n d i t i o n s r e -
or t hohexagonal ¢ ported in ( 5 , 7 , 8 ) . In the case
- - monoclinlc o f the c o b a l t d e r i v a t i v e , i t is
necessary to maintain the tempe-
r a t u r e synthesis f o r a very long

Y time ( 8 ) , because CoS2 i s formed

first, and hence a t l e a s t two
months are necessary to obtain
a homogeneous CoPS3 product. For
FePS3, i t has already been r e p o r -
ted t h a t use of s t o i c h i o m e t r i c
ratios leaves unreacted sulfur
FIG. 1
(9). Some e x c e s s s u l f u r is hence
added to achieve better stoichio-
Axis relations between the hexagonal
metric reaction.
and the m o n o c l i n i c cell in the MPS 3
phases (from Klingen (1)).
II.2. C r y s t a l Choice. Using the
above p r e p a r a t i o n procedures, small f l a t hexagonal c r y s t a l s , having a s u i t a -
hie Size f o r X-Ray d i f f r a c t i o n data r e c o r d i n g , were gathered. Good q u a l i t y
X-Ray d i f f r a c t i o n f i l m diagrams f o r MnPS and CdPS w e r e r e a d i l y obtained,
3 3
whereas FePS3, CoPS and NiPS3 e x h i b i t e d poorer p a t t e r n s t h a t rendered more
3
difficult s e l e c t i n g o f s a t i s f a c t o r y samples. In a d d i t i o n to these d i f f e r e n -
ces, NiPS3 presented r a t h e r complex c r y s t a l h a b i t s . As compared to expected
regular p a t t e r n and c e l l parameters ( 5 ) , many c r y s t a l s studied showed, on
Weissenberg f i l m s , e i t h e r e x t r a spots corresponding to the m u l t i p l i c a t i o n
of the C parameter, Or d i f f u s e
Lines indicative of a strong
disorder in the stacking plane
sequences. Although in some
107.40~" cases this phenomenon could
be a t t r i b u t e d to crystal twin-
107,30 f ning, in some other instances

#
°T
'
: "/ ~
it seemed to invoive some kind
of polytypism. However, seve-

-:/ ' \ . f -
IOX~C
ral selected crystals of NiPS
107.10 showed the regular crysta~
stacking and it was d e c i d e d
10~0¢ to start the present study
with t h i s type o f s t r u c t u r e .
[ Z In any c a s e and considering
I i 1 clo ~ ,
V Mn Fe N Zn
t h a t the many samples synthe-
sized had always powder X-Ray
FIG. 2
spectra very w e l l indexed with
MPS 3 m o n o c l i n i c c e l l / 3 v~lue variation the r e g u l a r c e l l constants (9),
r e s p e c t i v e to the M + c a t i o n . it can be assumed t h a t the
Vol. 20, No. 10 MPS3 LAYERED PHASES 1183

TABLE I

Cell Parameters, Refinement Conditions and R e s u l t s .

I
Compound FePS3 MnPS CdPS3 CoPS3 NIPS3
3
o
a (in A) 5.947(1) 6.077(1) 6.218(1) 5.901(11 5.812(2)
0
b (in A) 10.300(I) 10.524(3) 10.763(2) 10.222(2) I0.070(3)
o
c (in A) 6.7222(8) 6.796(i) 6.867(I) 6.658(2) 6.632(I)

B (in o) I07.16(1) 107.35(2) 107.58(1) 107.17(2) 106.98(3)

V (in ~3) 393.3(2) 414.7(5) 438.1(2) 383.7(3) 371.2(4)

Number of recorded
1065 748 1149 1038 1948
reflexions

Utilized reflexions
573 684 883 467 568
with I > 3q(1)

Refined parameters 28 28 28 31 31

Extinction
coefficient
13.2(3).i0-6 1.8(1).10-6 5.21(4).10-6 0.6(i).i0-~ 0.7(2).i0-6

Difference Fourier
maximum peako_ 3 0.6(i) 0.6(2) 1.0(I) 0.9(I) 0.7(2)
intensity (in e.A )

R (in %) 4.0 3.6 2.5 3.8 4.7

R (in %) 5.0 4.2 2.9 4.# 5.5

w

Dulk of the NiPSL3P samples corresponds to the regular FePS structural stac-
king. Indeed, Nz S 3 polytypism needs Further study and {his will be done
later.

11.3. C r y s t a l Data Collection. Because of the layered structure o£ the MPS 3

phases~ ~ ~ h ~ ~rystal-~E T r e v e r y f l a t and t h i n . I t was hence d e c i d e d t o d e -
termine the s a m p l e s f a c e s i n d i c e s and t o c o r r e c t t h e X-Ray d i f f r a c t i o n data
for absorption, All t h e MPS3 s t r u c t u r e s (see below) are built From a c l o s e
packed stacking of sulfur a n i o n s i n t h e ABC s e q u e n c e (CdC12 t y p e ) , The p h a s e s
c o u l d t h e n be e x p e c t e d t o r e t a i n the trigonal s y m m e t r y and h e x a g o n a l c e l l g e -
nerally e n c o u n t e r e d f o r such a t o m i c a r r a y . However l e a s t s q u a r e s r e f i n e m e n t
parameters were o b t a i n e d f r o m X-Ray powder s p e c t r a u s i n g FePS 3 m o n o c l i n i c
cell contants ( g ) . These p a r a m e t e r s show f o r a l l t h e m a t e r i a l s the b/a ratio
to r e m a i n p r e c i s e l y equal to /~. The ( 2 , ~ ) D l a n e i s p a r a l l e l to the layers
and t h i s r e s u l t indicates t h a t t h e r e i s no d i s t o r t i o n in the stacking planes
and t h a t a p o s s i b l e deviation from the trigonal s y m m e t r y must be l o o k e d a t
on t h e m o n o c l l n i c B a n g l e v a l u e . F i g u r e 1 shows how t h e m o n o c l i n i c cell is
1184 G, OUVRARD, et a l . V o l . 20, No. i0

r e l a t e d to the hexagonal
one. The value o f B f o r
an u n d i s t o r t e d c e l l can be
c a l c u l a t e d and i s equal
to 107.16° . On f i g u r e 2 i s
drawn the angles values,
determined from l e a s t squa-
res refinement~$ respecti-
ve to the M cations.
FePS and COPS_ exhibit
the ~ d e a l B angle 3 value
and indeed, both phases
OM
-( spectra can be p e r f e c t l y
indexed and the parameters
s a t i s f a c t o r i l y l e a s t squa-
res r e f i n e d from a hexago-
nal c e l l ( F , 8 ) .

In the case o f FePS3,

P r o j e c t i o n of the MPS
( S u b s t i t u t i n g M' a n ~ P ' atoms not represented.
refinement results
Klingen (4) r e f i n e d the
s t r u c t u r e in monoclinic
symmetry. From a h a l f spa-
ce r e c o r d i n g , we checked
FIG. 3 on FePS3 t h a t the symmetry
was indeed monoclinic and
~ s t r u c t u r e along the b a x i s . all the other phases (par-
ticularly CoPS ) were theq
See t e x t ) . considered to 3 belong to
the C2/m space group. From
(see b e l o w ) this assumption p r o v e d t o be c o r r e c t .

Single c r y s t a l X - R a y d i f f r a c t i o n data were recorded on an automatic

f o u r c i r c l e d i f f r a c t o m e t e r CAD 4 Nonius. The c e l l dimensions, r e f i n e d from
25 r e f l e x i o n s , w e r e found in good agreement with p r e v i o u s l y reported values
( 8 , 9 ) . These o n e s obtained from X-Ray powder d i f f r a c t i o n data are given in
T a b l e I . An i n d e p e n d a n t q u a r t e r space was
r e c o r d e d (a h a l f f o r NIPS_) and d i f f r a c -
t i o n data were processed, including absorp-
tion corrections, using programs belonging
to t h e SOP-PLUS p a cka g e (1982 version)
M M
distributed by E n r a f - N o n i u s and w r i t t e n
by F r e n z ( 1 0 ) . The r e f i n e m e n t conditions
and results, along with positional parame-
M M ters and their estimated standard devia-
tions (E.S.D.) are given in Tabies I and
II.

III. STRUCTURE R E F I N E M E N T

All the structure calculations were

FIG. 4
started in C2/m space g ro u p f r o m a t o m i c
MPS c a t i o n s o r d e r e d d i s t r i b u t i o n coordinates calculated f o r FePS 3. I n &11
zn & cases, the least squares refinement quick-
e ( a , b ) p l a n e . ( S 6) o c t a h e d r a l
g r o u p s a r e r e p r e s e n t e d by a c i r c l e ly converged to yield low reliability fac-
and s i x s u i t a b l e segments, tors indicating that all t h e MPS3 d e r i v a -
t i v e s b e l o n g t o t h e FePS 3 s t r u c t u r a l type
Vol. 20, No. i0 MPS 3 LAYERED PHASES 1185

TABLE I l a

Positional Parameters and T h e i r Estimated Standard Deviations.

02
Atom x y z B(A ) Multiplicity xT

Mn 0.0 0.33258(9) 0.0 1.22 (1)

0.0556(2) 0.000 0.1686(2) 0.77 (2)
S1 0.7593(2) 0.000 0.2497(?) 0.96 (2)
S2 0.2438(I) 0.16120(9) o.2516(i) 0.96 (1)

Fe 0.0 0.3326(1) 0.0 1.11 ( i )

P 0.0566(3) 0.000 0.1692(3) 0.65 (2)
St 0.7501(3) 0.000 0.2470(3) 0.88 (2)
S2 0.2488(2) 0.1655(i) 0.2485(2) 0.87 (i)

Co 0.0 0.3327(I) 0.0 1.o6 (2) 0.483(2)

P 0.0574(3) 0.000 0.1702(3) 0.67 (3) 0.472(3)
51 0.7469(3) 0.000 0.2451(3) 0.83 (3)
S2 0.2495(2) 0.1675(1) 0.2461(2) 0.85 (2)
Co ' 0.0 0,000 0.0 0.7 0.015(2)
P' 0.057 0,333 0,170 0.7 0.015

Ni 0.0 0°3330(2) 0.0 0.75 (2) 0.492(2)

P 0.0584(6) 0.000 0.1693(5) 0.67 (5) 0.481(4)
s1 o.7418(5) 0,000 0.2432(5) 0.71 (4)
S2 0.2514(3) 0.1698(2) 0.2434(3) 0.73 (3)
N~' 2.0 0.000 0.0 0.7 o.o15(2)
P' 0.059 0.333 0.170 0.7 0.015

Cd 0.0 0.33221(3) 0.0 1.741(5)

P 0.0551(2) 0.000 0.1697(2) o.85 (i)
S1 0.7689(2) 0,000 0.2542 1.19 (2)
s2 0.2400(i) 0.18659(7) 0.2584(1) 1.24 (I)
1186 G. OUVRARD, et al. Vol. 20, N o . I0

TABLE l l b

Temperature Factors ( B e t a ' s ) and TheLr Est±mated Standard Oev±at±ons.

Atom 8(1.1) 8(2.2) 8(3.3) B(1.2) 8(1.3) B(2.3)

Mn 0.0070(2 ) 0.00220(6 ) 0.0114(2) 0 o.oo96(2) o

P 0.0045(2 ) 0.00166(9) 0.0064(2 ) 0 o.oo57(4) o

sI 0.0056(2 ) 0.00244(9) 0.0072(2) 0 0.0082(3) o

s2 0.0061(2 ) 0.00188(6) o.oo76(i) -0.0014(2) 0.0058(2) -0.0010(2)

Fe 0.0070(2 ) 0.00208(6 ) 0.0096(2) 0 o.oo6o(3) o

P 0.0039(3 ) 0.0012(1) 0.0060(3) 0 o.oo39(5) o

s1 o.oo54(3) o.oo18(1) o.oo8o(3) 0 0.0068(5) 0

s2 0.0054(2) o.oo143(6 ) 0.0079(2) -0.0010(3) 0.0039(3) -0.0008(2)

Co o.oo89(2) 0.00230(8) 0.0076(2) 0 o.oo31(3) 0

P 0.0046(5) o.oo15(2) 0.0044(4) 0 o.oo15(7) o

s1 o.oo51(4) 0.0022(1) 0.0059(3) 0 o.oo37(6) o

s2 o.oo57(3) 0.00187(9) 0.0058(2) -0.Q012(3) o.oo15(4) -0.0008(3)

0.0059(3) 0.0017(1) 0.0054(3) 0 o.oo41(5) o

P 0.0050(7) o.oo17(2) o.oo42(5) 0 o.oo2(1) o

s1 o.oo59(8) 0.0017(2) o.ooso(5) 0 o.oo55(8) o

s2 0.0062(4) o.oo14(1) 0.0052(3) -0.0007(5) o.oo34(6) -0.0006(4)

Cd 0.00911(6) 0.0o216(2) 0.01757(7) 0 o.oio2(i) o

P 0.0056(2) 0.00136(5) 0.0066(2) 0 o.oo4o(3) o

S1 0.0070(2) 0.00282(7) 0.0082(2) 0 o.oo73(3) 0

S2 o.oo89(1) 0.00191(4) 0.0088(I) -0.0023(1) o.oo43(2) -o.oo11(i)

Vol. 20, No. 10 MPS 3 LAYERED PHASES 1187

TABLE III
o
Main I n t e r a t o m L c D ± s t a n c e s ( i n A)
For c o m p a r i s o n s s a k e , VO.78PS 3 d a t a have been a d d e d .

Compound V0.78PS3 MnPS3 FePS3 CoPS3 NiPS3 CdPS3

M-S2(x2 ) 2,504(1) 2.534(1) 2.552(1) 2.510(1) 2.461(2) 2.740(1)

M-S2(x2) 2.500(2) 2.519(1) 2.544(1) 2.506(1) 2.463(1) 2.711(I)

M-SI(X2) 2.504(2) 2,622(1) 2.547(1) 2.511(1) 2.456(2) 2.709(1)

Average M-S 2.503 2.625 2.548 2.509 2.463 2.720

P-S2(x2) 2.030(2) 2.030(2) 2.032(I) 2.033(I) 2.025(2) 2.027(I)

P-SI(XI) 2.035(2) 2.034(i) 2.039(2) 2.036(2) 2.038(3) 2.032(2)

Average P-S 2.032 2.031 2.034 2.034 2.029 2.029

P-P 2.159(4) 2.187(3) 2.174(3) 2.165(3) 2.148(4) 2.222(2)

(CdC12). However, foP two phases, COPS3 and NiPS , i t was necessary, from
3
d i f f e r e n c e Fourier map r e s u l t s , to consider the occurrence of a s l i g h t (around
3 %) d i s o r d e r at the c a t i o n (M and P) octahedral s i t e s , whereas f o r FePS3,
MnPS~ and CdPS~ f u l l occupancy by metal and phosphorus of the ordered s i t e s
is t~e r u l e . ~hese f a c t s being taken i n t o account, the c l a s s i c a l f a c t o r o£
c o o f ± d e n c e <R = s l l F o I - I P c l l / Z l F o l ) ranged from 2.5 % to 4.7 % (Table I)o
Projections of the structure a l o n g ~he b a x i s and o£ t h e c a t i o n d i s t r i b u t i o n
within a slab are given in figure 3 and f i g u r e 4. T a b l e I I I g a t h e r s t h e main
interactomic d i s t a n c e s f o r t h e compounds.

I V . RESULTS AND DISCUSSION

I V . 1 FePS 3 a n d MnPS_. B o t h s t r u c t u r e s were r e f i n e d straight-forwardly respec-

• 3
tively t o R = 4 . 0 % and R = 3 . 6 %. The d i f f e r e n c e F o u r i e r map p r o v e d f e a t u ~ e ~
l e s s a t t h e end o f t h e r e f i n e m e n t c y c l e s , w i t h a maximum v a l u e o f O . 6 ( 2 ) e . A - ,
the following intensities decreasing smoothly. T h i s shows a n d / o r c o n f i r m s
t h a t C2/m ±s t h e r i g h t space g r o u p and t h a t , within the diffraction method
accuracy, t h e Van d e r Waa1's gap i s e4npty. I t R u s t be p o l n t e d o u t t h a ~ t h e
equivalent thermal factors B o f Mn L+ a n ~ + F e L+, r e s p e c t i v e l y 1.22 ~ and
1 . 1 1 ~ , a r e h i g h ~s c o m p a r e ~ q t o t h a t o f N i ( 0 . 7 5 A ) and t h a t o f v a n a d i u m
in VO.78PS 3 ( 0 . 7 0 ~ ) .

I V o 2 . CdPS3. A g a i n , i n t h a t c a s e and w i t h FePS 3 c o o r d i n a t e s , refinement lead

directly tO t h e f i n a l v a l u e o f R = 2 . 5 %. H o w e v e r , t h e d i f f e r e n c e F o u r i e r map
reveals a first p e a k a t (O.O4, 0 . 3 3 , 0.08) with a higher electron density
t h a n i n t h e c a s e o£ i r o n and manganese d e r i v a t i v e s (D = 1 . O ( 1 ) e . J - ) , f o l i o -
wed b~ a s h a r p d r o p a t 0 . 4 6 e . ~ - ° , S i n c e t h e p o s i t i o n is very close to that
o f Cd + (O, 0 . 3 3 , O ) , t h i s o b v i o u s l y corresponds to a uncompletely corrected
1188 G. O U V R A R D , e t a l . Vol. 20, No. I0

a b s o r p t i o n . We f i n d again no occupancy o f the Van der Waal~'gap s i t e s , and

l i k e f ~ MnPS3 and FePS3, a high thermal f a c t o r (B = 1.74 ~ ) i s c a l c u l a t e d
f o r CdL+. The atomic motion i s very strong in t h ~ case again and the more
so as f o r h e a v i e r atoms one expects s m a l l e r Beq.

I V . 3 . CoPS3 and NiPS3. The refinement procedure e x p l a i n e d b e f o r e was a l s o

f o l l o w e d f o r these two phases and lead to a R value between 5 % and 6 %. A l -
though somewhat p o o r e r than f o r a l l the o t h e r Mrs , these r e s u l t s were accep-
2
t a b l e not o n l y in themselves, but because the d z f f r a c t i o n spots were not so
sharp f o r both compounds. However, the ~ f e r e n c e F o u r i e r map r e v e a l e d two
s i g n i f i c a n t , i f weak, peaks between 2 e.A and 4 e.~ -3 a t around (0, O, O)
and (0.05, 0.333, 0 . 1 7 ) . Normal weak background span the space below these
more i n t e n s e d i f f e r e n c e F o u r i e r peaks. These p o s i t i o n s correspond to o c t a h e -
d r a l s i t e ~ n o r m a l l y f u l l y occupied r e s p e c t i v e l y by the P phosphorus p a i r s
and the ML+ c a t i o n s (see t a b l e I I ) w i t h i n the s l a b s . Th~ i n t r o d u c t i o n o f
these new p o s i t i o n s e t s was to be c o r r e l a t i v e l y accompanied by a l o w e r i n g o f
the occupancy r a t i o o f the p r e v i o u s c a t i o n ~ s i t e s . A c t u a l l y , such change
corresponds to s u b s t i t u t e a few percents o f M + c a t i o n s by some P2 groups and
vice versa. Because o f the r a t h e r weak e x t r a p o s i t i o n c o n t r i b u t z o n s , atomic
p o s i t i o n a l parameters values were kept f i x e d and s e t i d e n t i c a l to t h a t found
on the d i f f e r e n c e F o u r i e r maiD, w h i l e o n l y the i s o t r o p i c thermal f a c t o r was
considered and f i x e d a t 0.7 A ~ .

In a d d i t i o n , o n l y the product o f the occupancy r a t i o by the m u l t i p l i c i -

t y f a c t o r o f the e x t r a metal p o s i t i o n was r e f i n e d , t h a t o f e x t r a phosphorus
p o s i t i o n s being s e t equal to t h a t p r o d u c t . The s u b s t i t u t i n g atoms are noted
C o ' , N i ' ~ P' in Table I I . Resuming the r e f i n e m e n t c a l c u l a t i o n ~ the R f a c t o r
improved by about 15 % the t o t a l amountofP and M remaining w i t h i n e r r o r equal
to I . A l a s t d i f f e r e n c e F o u r i e r map r e v e a l e d then normal background f o r both
CoPS3 and NIPS_,3 w i t h in p a r t i c u l a r a continuous i n t e n s i t y decrease. F i n a l
parameters and r e s u l t s are gathered in Tables I and I I .

The o c c u r r e n c e of the cationic substitution which has also been found

i n t h e c a s e o f V __PS_ ( 6 ) , may be s e e n as h a v i n g s e v e r a l possible origins
o.(~
I t may come f r o m a s m a l l d i s o r d e r between the metal and the phosphorus atoms
distribution i n t h e [SM2 3(P ) 3 . _ S ] l a y e r s , l e a d i n g to the f o r m u l a
[ S l M~,~ ( P~ I I ( p~ ) I . ^ / M~2 S] /.~ I t may a l s o a r i s e e i t h e r from a s l i g h t c r y s -
z~-E L L /J-E . . . . .
tal ~wznning o r f r o m some ~ a u l t s takzng place wzthzn the szngle crystal zn
the stacking sequences of the atomic planes. I t m u s t be r e c a l l e d here that
for both phases the greatest difficulties have been encountered to sort out
proper samples. Yet the crystals used finally were of rather poor quality and
may e x p l a i n the results obtained.

F i n a l l Y , 2 e x a m i n i n g the thermal f a c t o r s , we observe again a h i ~ value

f o r Co (1.05 ~ ), whereas an expected one i s c a l c u l a t e d f o r Ni (0.75 A ).

V. CONCLUSION

All t h e MPS 3 c o m p o u n d s w i t h M b e i n g a f i r s t row transition metal pre-

sent single crystals that crystallize in the monoclinic symmetry, space group
C 2 / m . From X - R a y a n a l y s i s , it appears that the phases exhibit t h e FePS 3 s t r u c -
tural type deriving f r o m a ABC s u l f u r close packing. The v a n a d i u m d e r z v a t i v e
differs from the others with the occurrence of cationic vacancies that lead
to a mixed valence phase. Within the accuracy of the X-Ray diffraction study,
no i n t e r s l a b cation could be d e t e c t e d i n t h e Van d e r W a a l s ' g a p of the strut-
Vol. 20, No. i0 MPS3 LAYERED PHASES 1189

Lures. This implies a fairly good s t o i c h i o m e t r y o f t h e p h a s e s , a t l e a s t as

single crystal, F o r two m a t e r i a l s , CoPS~ and NiPS 3 some s l i g h t metal-phospho-
r u s s u b s t i t u t i o n has been found on the otherwise o r d e r l y arrangement o f M and
P on the o c t a h e d r a l s i t e s of the s l a b s , w i t h o u t being i d e n t i f i e d . I t must be
p o i n t e d out t h a t although the NiPS3 c r y s t a l s t u d i e d has presented the expec-
ted FePS3 type p a t t e r n , some other samples showed occasional changes in X-Ray
s i n g l e c r y s t a l diagrams. Occurrence of p o l y t y p i s m may take place in t h i s ma-
terial. MPS s t r u c t u r a l f e a t u r e s are s t u d i e d in d e t a i l and compared to each
o t h e r and i~ r e l a t i o n s h i p w i t h t h e i r chemical behaviour in the f o l l o w i n g a r -
t i c l e o f this j o u r n a l .

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