CHALKOGENIDES OF THE TRANSITION ELEMENTS

111. MOLYBDENUM DITELLURIDE1.?

OSVALDKNOPAND RODERICIC
D. MACDONALD~

MoTe, prepared by dry synthesis from the elements a t 460' C and annealed a t 600° C has
r e the C 7 type with ao = 3.5182f 14 A and co = 13.9736f 40 A. T h e param-
a layer s t r ~ ~ c t uof
eter of the telluriun~atom has been determined fro111 closely reprocl~~cible X-ray diffractom-
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eter powder intensities as 0 . 8 2 1 f 1. The nearest-neighbor co-ordir~ation polyhedron of the

molybdenum atom is a trigonal prism with a Mo-Te distance of 2.71(j+12 A. T h e distance
of nearest approach of the tellurium atoms between layers is 3.945f 25 A and thus greater than
the similar distance between chains in metallic tellurium. I t is shown t h a t the observed intensi-
ties are not compatible with a stacking secluence of the CB7 type, which differs from the C7
arrangement in the geometry of the co-ordination polyhedra of the metal atoms.

INTRODUCTION
I t has beell recently reported that molybdenum disulphide does not always have a
crystal structure of tlie C7 type, whose prototype it is, but tliat it can exist as a t least
two, and possibly three, polymorphs ( 1 , 2 , 3 , 4 ) .The two structures of tlie sulphide which
are linown in detail, i.e., the hexagonal C7 structure and the rhoniboliedral form first
described by Bell and Herfert (3) and later structurally reinterpreted by Jellinek et al.
For personal use only.

(4), are both layer structures consisting of planar sheets of superposable hexagonal
networlis of molybdenum and sulphur atoms stacked parallel to the basal plane. They
differ in the sequence and period of displaceinent of the molybdenum - and
- sulphur net-
works xvith respect t o each other. T h e sequence is . . .AMABNBAMABNBAMA
-- .. .
for tlie C7 form and . . . APACMCBNBAPACMCBNBAPA . . . for the rhombohedra1
form (A, B, C refer to sulphur layers, M , N, P , to molybdenum layers), but in both cases
the stacking sequences result in trigonal-prismatic nearest-neighbor co-ordination of the
molybdenum atom. Other sequences are theoretically possible, in some of which the
environment of the nietal atom is trigonal antiprismatic (distorted octahedral). A structure
of this type mould be, for example, the C27-type structure ltnown from p-Cdl?, which
Hagg and Schonberg (1) proposed as a possible MoS? structure to account for the observed
X-ray intensities of some of their MoSz samples showing reportedly large disagreement
between I, and I,(C7).'3
Altliougli the crystal structure of tlie corresponding telluride, MoTez, has not been
determined before, it was usually assumed tliat i t belonged to tlie C7 group; in reference 5,
for instance, this follows by implication. When evidence for tlie polymorphism of MoSz
appeared, it became clear tliat the telluride need not necessarily have the stacking
arrangement of a C7 compound and even if i t does, the structure may be of lower
symmetry, as has been found to be probably the case with the corresponding wolfram
compound (6).
'illaizzrsoipf received J a i ~ z c a ~9,y 1061.
Contrzbzilioi~froin the Departilzent of CJzenzical Etzgiizeering, Nova Scotia Technical College, H a l i f e z , N.S.,
wilhjiizancial assislaizce fronz the National Research Couizcil of Canada.
2Part 11 of tizis series appeared iiz Can. J . Chei~z.39, 207 (1961).
3Prescnt address: Fzlels Developmeiat Branch, Atoi~zicEnergy of Canada, Ltd., Chalk River, Oictario.
+TJze 1~lalio)zslzipbetzt'eeiz the C 7 and the rl~ombokedralform of MoSa i s the same as that betweeiz the Cd7 and
the C1,9 ICdCly) strzicture, except that the ineta1 co-ordinatioi~i s trigoiaal prisi)zatic in thejirst pair and distorted
octahedral in the secoizd.
Can. J. Chem. Vol. 39 (1061)
 898 C.-\X;\DI.-\XJOUKN.\L O F CHEMISTRY. VOL. 39. 1961

As far as we lanow, tlne occurrence of the C7 type of structure is restricted to chalko-

genides of niobium (4), molybdenum, tantalum (7), wolfram, rhenium (8), and possibly
hafnium.'These compounds and tlne rho~nnbohedralpolymorphs of the clisulphides of
molybdenum, niobium, and ta~ltalu~nl are, moreover, almost the only lcl~olvn instances
of structures in which the metal atom has trigonal-prismatic nearest-neighbor co-ordina-
tion,? which would seem to indicate a strong preference for this rather than for octahedral
co-ordination. T h e observed bullr diamagnetism of MoS2 (11) (and also of WTe2 (13))
is in agree~nentwith the assumption that tlne trigonal-prismatic co-ordination is tlne
result of d4sp bonding. Further support of this contention comes from the appreciable
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diamagnetic anisotropy of single crystals of molybdenite, the negative susceptibility

parallel to the hexagonal axis being almost twice as large as t h a t in the direction normal
t o the axis (12). Such magnetic behavior wit11 its strong temperature dependence and tlne
appreciable electrical conductivity of molybdenite along the basal plane both point to
the presence of a system of largely delocalized nob bile .rr electrons within the MoS? layers;
the existence of such a system can again be explained from tlne d"sp orbital configuration
on the molybdenum atom, or more particularly fro111 its ~ ( 9 % system ) of trigonal sym-
metry. T h e telluride, which, too, has been shown to be diamagnetic (13), can accordingly
be expected t o have a C7 structure or its rhombohedra1 modification. Furtlnermore,
unless I-Iagg and Schonberg's MoS2 preparations were paramagnetic, a n explanation of
the observed discrepancies in tlne diffraction intensities of these sa~nplescannot be
advanced on the basis of a C27-type structure with its sp3d"or d%p3) boilding and its
For personal use only.

associated magnetic n~oment.

On the other hand, ReS. (14) and WS2 (15) have been reported to be paramag~~etic.
'The effective inagnetic inonlent of l i e s ? is snlall and inclependent of temperature, but
natural WS2, tungstenite, has been stated to be strongly paramagnetic with a curious
temperature dependence and a pronounced anisotropy. T h e effective moment of tung-
stenite a t room temperature was found higher than would correspond t o the "spin-only"
value for two unpaired 5d-electrons. 'The ad hoc explanation for tlne paramagnetism of
tungstenite profered by Dutta ancl Clnolvdhury (15) and based on the assumption of a
C7 structure, fails to establish why molybdenite, for which the same qualitative arguments
apply, is diamagnetic. If the reported magnetic behavior of tungstenite is genuine and
not caused by ferromagnetic or strongly paramagnetic impurities in the natural material$
the orbital configuration on the tungsten at0111cannot be dbp. 'The paramagnetism could
be due to d3p3or d3sp2bonding, b u t then the stereochemistry of the WS6group mould not
be consistent with the 6 symmetry of the regular trigonal prism. 'The difference in co-
ordination could be brought to light by crystal-structure analysis, but a sufficiently
accurate detailed study of WS2 has not yet been made. If orbital configurations of
geometries different fro111 t h a t of d 5 p are, however, admitted t o explain tlne para-
magnetism of WS2, one should bear in mind t h a t this last configuration is not tlne only
one to account for the observed diamagnetism of iVIo'Te2, but t h a t this telluride might
conceivably exist with a d4p2configuration on the molybdenum atom. Since neither the
magnetic properties of WS2 nor its crystal structure has been established beyond doubt
* T h i s case i s now z~nderinvestigation i n this laboratory.
t I n the B8 (nickel arsenide) strzrctz~rethe atonzs with trigonal-prisn~aticco-ordinalion are the non-vzetal
atoms. A sinzilar sitzlation obtains, for itzstance, i n R q B , R L I ~ B ~ , olher borides (9), and also i n some carbides
and
and phosplzides. I n the borides R I I B - ~ , ~and PtB, Izo7ucver, 7uhich lzave been reported to have anti-NiAs strzictures,
the nearest-neighbor co-ordination of the nzetal atoms i s triyonal prisnzatic (10).
$The t ~ ~ n y s t e n i used
t e by Dzitta and Chowdlzziry was, to tlze azitlzors' own admission, inzpure, but chenzical
analyses of the nzineral are not sl~own.The inzpz~ritycontent varied with tlze source of tlze ~tzaterbal;tlze spread
of the experimental densities of the individz~alcrystals (nzetlzod not stated) was veTy appreciable, 7.00-8.2.
 to either eliminate 01- include the possibility of co-ordination other than trigonal prismatic
in the above group of clichalkogenides, prediction of the crystal structure of n40Tes is
not entirely straightfor~varcl.
As for the differences caused by the stacking secluences of M X ? layers ol a particular
type, either ti-igonal-pi-isinatic or octahedral, polymorphs of this liind woulcl not be
expected to have widely dissimilar lattice energies. This is borne out by the relative
readiness with which inixed sequences are formed in, for instance, caclniium or nicltel
bromides, although the ratio of the ;~tomicradii does to some extent cletermine the
stacl<ing arrangeinei~t(cf. a-Ccl12 ancl CdCI?).
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In view of the contraclicting statements in the literature coi~cerni~ig the i ~ ~ o l ~ ~ b d e n u n ~

etc. clichall~ogeniclesancl since the tellui-ides of the above elements have so far received
only scanty attention, we thought it of interest to ilivestigate ~vhethei-the trigoi~al-
prismatic co-orclinatioi~of molybdenum, ~vhichis apparently cllaracteristic for the typical
~uolybdenumclisulphicle ancl cliselei~icle,is preservecl in the clitelluricle; and if this is the
case, whether the structure correspo~iclsto t-he C7 type, n7ith 01-~ v i t h o i distal-tion,
~t or to
ai~otherstaclri~igarraiigement.
ISSI'ERIMESI'fII,
'The ditelluride was 111-epai-edby clry synthesis froin the elemelits in vncllo i l l 1 1 1 ~ 1 ~ 1the
1
same way as pi-eviously W e . ( 6 ) . Failsteel molyb(lei~un~ powclel- type 352 of avei-age
particle size of 4-5 n~icronsand of specified m i ~ ~ i ~ n purity
um ol 98.9% ancl specified
minimum impurity coiltent of 0.015y0 C , 0.125% 0, ancl 0.020jo Ni, was reclucecl before
For personal use only.

use \vith purified hydrogen a t 690-700" C. T h e telluriun~metal uras I;incll\. clonated by

Canaclial~Copper Refinel-s, Ltcl., and coiitainecl, accol-ding to the supplied analysis (in
p.p.m.), 0.4 Cu, 3.0 Al, and 0.5 AiIg. I-Ig (detection linlit 2 p.p.m.), I'b (0.5), Fe ( I ) ,
As ( l o ) , Sb (0.5), Sn (0.5), Bi (0.5), Xi ( I ) , Cr (0.5), Z n ( l o ) , .4g (0.1), Na (4), aitd
Si (1) \\.ere not detectecl.
X stoichiometric mixture ol molybdeiiun~and telluriun~powcle~-stotalli~lg15 g was
sealecl i l l a degassed, evacuated tube of clear quartz ancl Irept a t il(iOOC for 16 hoiil-s. 011
removal from the furllace the tube \\:as openecl aiicl the reactecl mixture crushecl lightly
to pass a 125-mesh screen. The thoroughly mixed powcler was the11resealecl ancl annealed
a t 600" C for 18 hours. 'I'he product was a loose clal-1;-gray polvcler of uniform appearance
consistil~gof very filie needles and platelets. T h e crystals were too sniall ancl often
intimately intergrown to be suitable for a single-crystal stucly. KO foreign pal-ticles \\;ere
detected uncler magnifications up to 30 diameters.
Specimens for X-ray po\vde~-diffractioli were prepared by mounting i\IoTe2 powder
that had beell crushecl to pass completely a 325-mesh screen, 011 very thin pyrex fibers
coatecl thinly ancl uniformly \vith vacuum grease. Powder photographs were talcell i l l
114.6-mm Straumanis-type cameras with filtel-ed Cu K , Fe K , ancl Cr R radiations.
I'owder specimens for the Norelco diffractornetel- miere preparecl by sifting the annealed
po~vclerthrough a 325-mesh screen on a cy-lilidrical aluminum specimen mount coated
evenly \\Tit11 a thin, flat layer of stiff silicon grease. T h e diffractometer patterns were
obtainecl \vith rotati~igspecimens using 1/2, I , and 4" slits and a pulse-lleight analyzer.
They were used for the integratecl intensities only. T h e same ~v:~velengths ~vcreilsecl as
are quoted in the seconcl paper of this series.

'The films were of surprisingly good quality, considering the frequently pool- tlefinition
of the cliffraction lilies obtained with tellurides of the transition elements. ,As coulcl be
 $w.l C.\S.4DI2\X JOURNAL O F CIIllhIISTRY. VOL. 30, 1961

expected, the photographs tal;en wit11 filtered Cu K mcliation had t h e best appearance
i o nlattice parameters. All lines could be indexed
and were used in t h e final d e t e r ~ l ~ i ~ l a tof
on a hexagonal u n i t cell (Table I). After sis cycles of refining a and c by least squares

TABLE I
for i\,IoTe? ( C L I Rol radiation)
Observed ant1 calculatctl sin20 \ d u e s ant1 X-ray powder inte~~sities
- -- -
--
..----.ppp -- - - . ..

10'. sin20 i1 lo4.S ~ I I ? O

likl* crlcd.
--
obs. Ict$$ I":$ 1, -

--
obs. Ictl§ 1015 -
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 14.232.214.253 on 07/01/20

- .. - - - -

003 0122 012zt 12.0 2 1 1 6 11s (i429 6427 5 0 5.1

004 0487 0493 12.7 13.0 / 10. 14 6605 6Gll 0.7 1.0
100 0040 0641 37.0 40.4 1 306 6858 6852 1.5 2.3
101 0670 0673 9.0 10.9 i20.13 6944 - 0.41 -
10" 0762 0764 3.7 3.3 j 219 6947 0.2<
103 0914 0918 100 100 10.15 748j] 74941 1.3
006 1096 1109 3.4 3.8 , 21.10(1) 7512 0.0' 2.1
104 1127 1141 (i.2 6.3 21.10(2) 7550 7533
105 1401 1403 :;6.8 36.9 ; 220 S(i82 7679 5.6
106 l73i 1753 2.4 2.8 20.13(1) 7690) 3.1
110 1921 1922 27.3) 11308(1) 7 ~ 9 ~ 17706 11.1
418
008
112
1948
2043
1967
2048
S.G(
3.0 3.4 / 320 08 (13(21
2) ) i73Y
107 2132 2147 3.2 3.8 1 00.16(1) 7777 - 1.7' 31.211
111 2108 2411 7.6 7.7 ii222(1) 7791
200 2561 2568 4.3 5.1 22?(2) 7829 7835
108 2588 7.6: 11.14(1) 7871
For personal use only.

20 1 2591) "08 11) S.8 ll.lI(?) 7913 i928

202 2683 - 0.3 S159 15.6
203 2885 2843 14.4 15.2 224(1) 8155 2.4, 19.3
116 3017) 3.8)
00.10 3030 0.0 5.9 224(2) 8196( S202

11
204 1.31 310(1) 8308 8307) :i,2\
109 3106 - 0.2 - :310(;?) 83501 3.8
205 3322 8336 8.2 8.8 311(1) 8338 834S 0.9'
206 3657'1 10.16(1) 8416 2.9
10.10
118
3li841
3869
3"4)
3887 16.2
0 8
18,4 3I2(l)
10. lG(;?)
8430
5450
0.41 4,
207 4053 4063 1.2 1.2 . :112(2) 84721 8480
10.11 4323 4351 20.14(1) 8510 8525 1.01
00.12 4383 - \ 14.9
210 4-181) 3.41
208 4505 3.31 7.8 226(1) 8763 8766
211 1. O J ; 30. io(1) 8790) 8802
212
213
11.10
4603
4755
-19fi5)
-
4768
497-L
0.4
13.0
0.1
0.4
13.3
314(1)
1 0 . 10(2)
/i j 3 1 4 ( 2 )
:::{
8839) 8855
l G 3.57

214 4968 1.21 2,0 , 2 1 12(1) M49J 1.3

10. 12
209
215(1)
5023/
50271
5231 5249)
0.5(
0.1) 1 315(1)
315(1)
20. 5 1
9068
9114
93921
) 13':
2.5
12'6

215(2) 5260 52671 S.8 316(l) 9402 9104 1.6

2 16 5577) 0.8'1 10.17(1) 04201 4.09
20.10 5605( 5592 0.0/ 20.15(2) 9441)
300 5762 5760 5.3) /16(2 5/41 9451
10.13(1) 5773 5789) L 10.17(2) 9408
10.13(9) 5803 .5815( 2.9~ 21.13(1) 9608 15.01
302 5884 - 0.6 228(1) 9613 27.3 Si,O
00.14
217
20.11 (1)
304(1)
20. I l(9)
5966
5973
6232
62381
G2641
I 5971
G247
0.5)
1.5(
6.4)
2.11
2'6

11.3
1
'
1 ' 21.13(2)
228((W
ll.lB(1I
l~.l(i(
31i(l)
965i
9DT,(i2
4
~9745
)
0797
9659
9706'
9754) 28'7 29's**
304(;?)
I E3t 6281
1.7)
317(11
I 0018,l) )
I *Re$ol~erln-rloublets are indicaterl b y ( I ) and ( 2 ) . ? F o r e = 0.621; ten?l~eraturefactor not included. TiYormalized to I(103).
$Intcnsitlcs of the a, and a 2components are taken together. 1) Overlap. -Extent of maxima uncertain. *:~DiRractometercutoff.
 CII..\LIiOGENIDES
IiNOP A N D ~ ~ A c D O N A L D : OF TRANSITION ELlSMBNTS. 111 '301

using Nelson-Riley extrapolation for reflections with 0 > 30° the final values of the
lattice para~neterswere a. = 3.51522~14 A, co = 13.9736f 40 A, and co/ao = 3.972.
The volume of the unit cell is 149.79f 17 A3.
T h e density of R/IoTez (125-) was detel-mined in the same way as described in Part I1
of this series. Average of three detel-minations gave d4?j = 7 . 6 8 1 f 1 8 g/cm3, which
corresponds to 1.974 MoTe, per unit cell. This density compares rather more favorably
with the density calculated from the lattice parameters, 7.7843~9g/cm3, than the value
quoted by Morette (13), del" 7.60Ofl g/cm3, and is only -1.28% lower than the
X-ray density. I t is difficult to say whether the discrepancy has a real significance as
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regards the existence of molybdenum and tellurium vacancies in the structure.'Unreacted

molybdenum and tellurium in amounts lower than the minimum amounts capable of
producing observable diffraction lines cannot be detected in a stoichiometric MoTez
sample by density measurement because of the almost identical densities of MoTe,
and a 1 :2 mixture of molybdenum and tellurium.
Reflections of the (Izkk) type with h-k = 3n, I = 212+1 were absent. This condition
is satisfied in eight space groups, viz., DG$-P &/rnmc, D31:-P &c, C6,-P Ci3mc,
D66-P G322, CGl,?-P 63/7n, CGG-P 63, DBd2-P SIC,and CjULp 3/c, but the symmetries
and equipoints of these space groups are compatible not only with the C7, but also with,
for instance, the C27 structure, which has been claimed as possible for solne MoSz samples
(cf. Introduction).
T h e first model tried was a C7 structure (space group DG1,"-P 63/mmc) with 2 A110 in
For personal use only.

2(c): f ( 1 / 3 , 2/3, 1/4) and 4 T e in 4Cf): f (1/3, 2/3, z); f (1/3, 2/3, 1/2-z), z,, = 0.625
( = 5,s'). A set of intensities was calculated for Cu I C a radiation using Thomas-Fermi
atonlic scattering factors tabulated in reference IS. T h e agreement between I, and I, was
good, but it was felt that the integrated powder intensities, which had been obtained by
careful planirnetering of several dirfracto~netercharts, would justify further refinement.
Six other values of z varying from 0.618 to 0.628 were then tried. Since out of the 70
observable reflections with I, >, 0.5 (normalized to 1,(1.03)) only 26 were fully resolved,
the extent of agreement could not be assessed from the reliability index, R = C F,I (1
I 1,
- 1 F, (/C( I;, customary in structure analysis from single-crystal data. Hoivever, the
sum C 1 I,-I, 1, though not a n unambiguous measure of the progress of refinement, ivas
found to be q ~ l i t esensitive to variations in z. T h e agreement of I, ancl I, for z = 0.621 f 1 ,
\vhich mas the value corresponding to the nlinimum of the difference sum located analytic-
ally for a parabolic least-squares fit, was indeed remarlably good (Table I). T h e C7
structure adopted in the first trial can thus be considered correct, the existence of 1101110-
metric structures conlpatible with the observed dinlensions and symmetry of the unit
cell being not very probable.
The close agreement of the intensities also demonstrates that the diffracto~neter
specimens were free fro111 orientation effects which are frequently present in specimens of
compounds with fully developed layer structures. Stacking disorder in our i\40Te2
preparation must have been negligible for the same reason. The increase of I,- I, ( with I
0 for individual reflections was so small that it did not justify inclusion of an isotropic
temperature factor. Jn particular, there ii7asno systeinatic weakening of I, for reflections
with h-k # 3.12 wit11 increasing I, nor was there selective line-broaclening affecting
particular orders.
As for the possibility that MoTe? has a C27-type structure (space group C,j,4- P G3mc),
" S i v ~ i l n r a, n d eocn greater, pycnonzetric a n d X - r a y reported for
disulplzide (16, 17).
 '302 CANADIAN JOURNAL 01' CIIEMISTRY. VOL. 39, 19Gl

it is readily seen that a iilodel structure with 2 Mo in 2(b): %(1/3, 2/3, 1/4), 2 T e in
2(b): (1/3, 2/3, z), (2/3, 1/3, 1/2+e), 2 T e in ',(a): (0, 0, -z), (0, 0, 1/2-z), and z,,
= 3/8.' is not isovectorial with C7' and cannot account satisfactorily for the observed
intcnsities. In particular, the calculated intensities of the reflections (100) and (2001,
\\~hosegeomctrical structure factors do not contain z, diffcr very considerably froin the
corresponcling I. values, the ratios F I O O ( C ~ ~ ' ) / F I O Oand
( C ~F' )~ o o ( C X ? ~ ) / F ~ Obeing
O(C~')
-0.072 ancl -0.081, respectively, and thus far from unity. A similar situation is obtained
\vitli another conceivable moclcl structure, viz. that based on the structure of the recently
described llcsagonal NbS? (4), even though the nearest-neighbor co-ordination of the
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metal atom is trigonal prismatic.

The interatomic distances and boltd angles in the iVIoTe. structure are as follows
(Fig. 1 ) :
For personal use only.

FIG. 1. Nearest-neighbor co-ordination of the mol>.bdcnum and t e l l u r i ~ ~ matoms i n il~olybdenum

ditelluride. 1~~111
circles, molybdenum; open circles, tellurium.

dl(i\40-'re) = 2.716% 12 A cr(Te--A'Io-Te) = cu(Mo-'re-Mo)

d?(i\dlo-Mo) = d:,(Te-Te) = no = 80.74&0.50°
= 3.5182% 14 A P(Te-i\iIo-Te) = 83.10%0.60"
di(Tc-Te) = 3.603f25 y(Te--140-Te) = 135.95%0.60"
ds(Te-Te) = 3.945% 25 A G(Te--Te-Te) = 52.96% 0.40"
d6(Mo-Mo, bctmeen layers) ~(i\/Io-Te-Te) = 100.59%0.60".
= 7.276k5 A

T h e Te-Te distance d5 is about 14% longer than the distance of nearest approach
bet\veen chains in inetallic tellurium, 3.468 A (10), and the similal- Te-Te clistance,
3.46% 8 A, in NiTe?(CG) (20), but it is fairly close to the Te-Te distaltce between
layers in y(V, Te)(CG), 3.82-8.85 A (21). The as-)m~netric TeI-TeIr-TeI angle betmeen
iteighboring chains I and I1 in tellurium which subteiicls the shortest Te-Te distance
in a chain, 2.864 A, is only 35.4" ailcl thus appreciably smaller than the corresponcling
angle 6 in MoTe2. A symmetric TeI-TeII-Te, angle in telluriullt is equal to 80.0°,
but i t subtends not the shortest Te-Te distance but the distance between ncxt-nearest
neighbors in the tellurium helix, 4.864 A. T h e bond angle 6 in i\/IoTe2is thus almost the
arithmetic average of these two boncl angles. T h e Te-Mo-Te angles are very nearly
the same as the corresponcling S-Mo-S angles in MoS.(C7').
"Origi~ashiflcd by (0, 0, I/.+) zuitl~rrspecl lo the orici?~alclesuiptio?~of the C27 t y p e ns represetrted b y P-Ctll:..
 I<KOP Ah'D M.\cDON.\LD: CII.ALI;OGENIDES O F Tl<:1hTSITION ELEMENTS. 111 903

Since the distances dg and d4 are not equal, the axial ratio of the trigoiial prism is not
exactly unity, as claimed by Pauling (22, 11.175) for molybdenite, but slightly different,
d4/de = 1.024.
T h e shortest 340-Te distance, dl, agrees quite \\re11 with the sum of the appropriate
atoinic radii, rnhicl~is bet\\~een2.64 and 2.74 A, depending on whether the value for T e
is ta1;en as the "single-bond" or the "double-bond" radius (22).
Allowing for the fact that WTe? is orthorho~llbicwith b -
a 4 3 (6) and taking the
unit-cell dinlensions for h/IoS2 ancl WS2 fro111 (23) and (24), respectively, the square roots
of the ratio of the basal areas ancl the cube roots of the unit-cell volu~nesare nearly the
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same for corresponding pairs:

(basal area)'/' (vol uine)
(IVS2) / (A11OS2) 0.998 1.008
(1/2 WTe2)/(i\/Iorre2) 1.014 1.009
(3:IoTe2)/(i\/IoS?) 1.113 1.121
(1 / 2 WTe?)/(WSr) 1.131 1.122.
Since the estimatecl radius of Mo in molybdenite is 1.37 and that of W in tungstenite
l g about 57;, it is clear that the dimensioi~sof
is 1.44 (2'3), the difference a i n o u ~ l t i ~ to
the unit cells of these compounds are determined essentially by the chalkogen atoms.
The stability of A,IoTc2on heating under orthobaric co~lditio~ls is greater than that of
WTe?. There is no isotllernlal transition between room temperature ancl 1200° C (cf. (G)).
For personal use only.

T h e failure to observe melting ill this temperature range is in full agreement with the
result of NIorette (13), ~ v h oheated a sanlple of NIoTe? \vith excess t e l l u r i ~ i ~inn uacuo
up to 1130' ~vitlioutfusion.
The trigonal-prismatic co-ordination of the molybtlenum at0111 in MoTet established
in this iuvestigation ancl the observed diamagnetisin of h/IoTe2ant1 WTen (13) as well as
of RloS? throw some doubt on the strong paramagnetism of WS? reported for natural
material in reference 15. Work is in progress in this laboratory to cletermine whether
3110S2 and IVS? fol-111mixed phases; and if so, IIOI\~ the magnetic properties of such phases
clepend on their compositio~l.I t is also i~ltendedto re-examine the CI-ystalstructure of WSZ
ill the light of the conceivable structural ambiguities clisc~isseclin the introduction and to
obtain a more accurate value for the sulphur parameter than the approximate value of
6/8 first 1,roposecl by van Arkel in 1926 (25) and quoted ever since.

.\CI<SO\VLEL)GMESTS
One of the authors (R. D. RII.) wisllcs to express his gratitude to the Eldorado Mining
and Refining Limited for the award of the Charles G. Williams l~ellowship,and to
Atomic Energy of Canada, Ltd., for leave of absence. T h e assistance of Dr. R. I-I. Tux-
worth of Atomic Energ\i of Canacla, Ltd., Chalk River, Ontario, ~ v h oprovided the
preliminary diffraction charts, and of Mr. Muntaz Ali, who carried out some of the
calculatio~~sand cletermined the density of molybdenum ditelluricle, is hereby gratefully
acl;no\\~ledgecl
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and F. D.
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18. INTERNATIONALE TABELLEN ZUR BESTII\II\IUNG VON KRISTALLSTRUKTUREN. Bd. 2. Gebr. Borntraeger,
Berlin. 1935.
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For personal use only.