CdS formation upon decomposition of Cd(n-BuOCS2)2 in EtOH and DMF and the crystal structure of Cd(Ph3P)(n-BuOCS 2)2 · Ph3P

Article abstract of DOI:10.1134/S0036023612030163

The thermal decomposition of the chelate Cd(n-BuOCS₂) ₂ (I) in EtOH and DMF, either in the absence or in the presence of Ph₃P, yields finely disperse CdS particles. Mixed-ligand complex Cd(Ph₃P)(n-BuOCS₂)₂ (II) has been synthesized. Cd(Ph₃P)(n-BuOCS₂)₂ · Ph₃P (III) single crystals have been grown. By X-ray crystallography, the crystal structure of III is built of [Cd(Ph₃P)(n-BuOCS₂) ₂] mononuclear complex molecules and uncoordinated Ph₃P molecules, which reside inside channels formed by complex II molecules. The coordination polyhedron around a Cd atom is a tetragonal pyramid where the base is formed by the four S atoms of the two bidentate chelating ligands n-BuOCS₂^- and the P atom of the Ph₃P ligand is at the axial vertex. In the structure of III, there are supramolecular assemblies of two complex II molecules.

Full text of DOI:10.1134/S0036023612030163

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2012, Vol. 57, No. 3, pp. 378–385. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © S.V. Larionov, T.G. Leonova, L.A. Glinskaya, R.F. Klevtsova, N.I. Batrachenko, I.V. Korol’kov, V.S. Danilovich, 2012, published in Zhurnal Neorganꢀ
icheskoi Khimii, 2012, Vol. 57, No. 3, pp. 431–438.
COORDINATION COMPOUNDS
CdS Formation upon Decomposition of Cd(
n
ꢀBuOCS2)2 in EtOH
ꢀBuOCS2)2 · Ph3P
and DMF and the Crystal Structure of Cd(Ph3P)(
n
S. V. Larionov, T. G. Leonova, L. A. Glinskaya, R. F. Klevtsova†,
N. I. Batrachenko, I. V. Korol’kov, and V. S. Danilovich
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 3, Novosibirsk, Russia
eꢀmail: lar@niic.nsc.ru
Received December 22, 2010
Abstract—The thermal decomposition of the chelate Cd(
absence or in the presence of Ph3P, yields finely disperse CdS particles. Mixedꢀligand complex Cd(Ph3P)(
BuOCS2)2 (II) has been synthesized. Cd(Ph3P)( ꢀBuOCS2)2 · Ph3P (III) single crystals have been grown. By
Xꢀray crystallography, the crystal structure of III is built of [Cd(Ph3P)( ꢀBuOCS2)2] mononuclear complex
nꢀBuOCS2)2 (I) in EtOH and DMF, either in the
n
ꢀ
n
n
molecules and uncoordinated Ph3P molecules, which reside inside channels formed by complex II moleꢀ
cules. The coordination polyhedron around a Cd atom is a tetragonal pyramid where the base is formed by
the four S atoms of the two bidentate chelating ligands nꢀBuOCS–2 and the P atom of the Ph3P ligand is at
the axial vertex. In the structure of III, there are supramolecular assemblies of two complex II molecules.
DOI: 10.1134/S0036023612030163
†
Syntheses of metal sulfides by means of solidꢀphase atmosphere [17]. As a result, particles of hexagonal
or vaporꢀphase decomposition of molecular precurꢀ
sors (which are diverse metal complexes with sulfurꢀ
containing ligands) have been described [1–11]. Great
attention is paid to complexes of bidentate sulfurꢀconꢀ
taining ligands that have CS2− and PS2− functionalities.
Of special interest is to synthesize metal sulfides at relꢀ
CdS were obtained with sizes of ~4 nm. Pradhan and
Efrima [18] used a cadmium(II) chelate with hexadeꢀ
cylxanthogenate ion as the CdS precursor [18] with
hexadecylamine as the solvent. They showed that CdS
particles with sizes of 3.5–5.2 nm can be obtained at
lower temperatures (70–90 C). Further, Pradhan and
°
ο
atively low temperatures (50–300 С). In this context,
Efrima [18] did not use an inert atmosphere in CdS
synthesis. Further studies into manufacturing finely
disperse CdS particles by decomposing cadmium(II)
xanthogenates in organic media are promising.
promising precursors are metal xanthogenates
M(ROCS2)n, for the reason that the onset thermolysis
temperatures of these complexes are lower than for
compounds of other bidentate sulfurꢀcontaining
anionic ligands [2, 12, 13]. As2S3 formation was noted
upon thermolysis of As(EtOCS2)3 [14]. Thermal
decomposition of Tl(EtOCS2), M(EtOCS2)2 (M =
Cd, Pb), and M(EtOCS2)3 (M = Sb, Bi) was found to
yield the corresponding metal sulfides [15]. Decomposiꢀ
tion of Sb(EtOCS2)3–Bi(EtOCS2)3 solid solutions has
been used to prepare Sb2S3–Bi2S3 solid solutions [16].
This study was targeted at studying whether it is
possible to prepare finely disperse CdS particles by
means of decomposing the chelate Cd(nꢀBuOCS2)2
upon heating in EtOH and dimethylformamide
(DMF). Earlier [19], we prepared CdS by decomposꢀ
ing the chelate Cd(Et2NCS2)2 in EtOH–ethylenediꢀ
amine mixtures at 50–80
BuOCS2)2 as the precursor, we were guided by the
availability of alkali metal ꢀbutylxanthogenates,
which are widely used flotation reagents [20, 21]. Furꢀ
ther, we found it pertinent to study how CdS synthesis
is affected by addition] of Ph3P (a stabilizer of disperse
metal sulfide particles) to EtOH and DMF. It was
interesting to prepare the mixedꢀligand complex
°
С [19]. In choosing Cd(nꢀ
Currently, attention is focused on the preparation
of finely disperse metal sulfides, specifically, CdS,
which is demanded by the synthesis of semiconductor
materials in nanoparticles [8]. Cadmium(II) xanthoꢀ
genates are among the precursors of CdS whose study
is underway. In particular, decomposition of precurꢀ
sors by heating in organic media is used for preparing
finely disperse CdS particles. For example, the syntheꢀ
sis of CdS nanoparticles is described by decomposing
n
Cd(Ph3P)
reaction of Cd(
(
n
ꢀ
BuOCS2)2, which can be produced by a
BuOCS2)2 ) and Ph3P in the course
Сd(EtOCS2)2 in the triꢀnꢀoctylphosphine–triꢀnꢀ
nꢀ
(I
octylphosphine oxide system at 160–280 C in an N2
°
of CdS synthesis in the presence of Ph3P, and to solve
its crystal structure.
†
Deceased.
378

CdS FORMATION UPON DECOMPOSITION
379
Table 1. Results of the decomposition of chelate
I
upon heating in EtOH (
T
= 80
°
C) and DMF (
T
= 110°C)
Product weight Percentage in the product
Solid product in percent of the
Run
no.
Chelate portion, g Organic phase
Time, h
(Ph3P portion, g)
volume, mL
weight, g
initial portion
weigh
Cd
C
H
N
1
2
3
4
5
6
0.6423
EtOH, 120
EtOH, 100
EtOH, 150
EtOH, 100
DMF, 120
DMF, 60
5
12
15
5
0.2394
0.1880
0.2773
0.1963
0.2125
0.1214
37.1
37.5
36.4
38.6
36.7
37.6
70.7
72.7
72.6
71.9
70.1
71.3
2.9
2.4
2.9
3.2
3.7
4.4
0.6
0.5
0.5
0.5
0.5
0.7
0.4
0.2
0.3
0.4
0.7
0.7
0.5004
0.7616
0.5086 (0.3379)
0.5718
5
0.3230 (0.2130)
5
Note: The calculated CdS amount in compound I is 35.1%. The calculated Cd amount in CdS is 77.8%.
EXPERIMENTAL
amount of the solid remained on flask’s walls) and
centrifuged at ~8000 rpm for 10 min. The mother
solution was decanted from the precipitate and added
to the flask; then, the residual solid was removed from
the flask’s walls with a Teflon spatula. The resulting
mixture was transferred to the centrifugal tube with the
precipitate and again centrifuged; then, the mother
solution was decanted. For washing the precipitate, 25 mL
DMF was added to the tube; the mixture was stirred,
then left to stand for 10 min, again stirred, and centriꢀ
fuged; the washes were decanted. Washing was repeated
The chemicals used in syntheses were СdCl2
⋅
2.5H2O (pure for analysis grade), BuOCS2K and
n
ꢀ
Ph3P (both of pure grade), rectified EtOH, and aceꢀ
tone, hexane, and DMF (high purity, pure for analysis,
and chemically pure grade, respectively).
Synthesis of Cd(
late was prepared by means of an exchange decompoꢀ
sition reaction between СdCl2 and BuOCS2K in
nꢀBuOCS2)2 (I). This known cheꢀ
n
ꢀ
aqueous solution. For a white product obtained in this
way, the cadmium percentage was determined (calcd., %:
27.35; found, %: 27.0).
with the use of 25 mL DMF and then diethyl ether (
2
×
25 mL). The tube with the precipitate was dried and
then weighed.
Synthesis of bis(
nylphosphinecadmium Cd(Ph3P)(
a solution of chelate (0.41 g; 1 mmol) in DMF (80
n
ꢀbutylxanthogenato)tripheꢀ
n
ꢀBuOCS2)2 (II). To
The decomposition product of chelate
I in DMF
I
was prepared as described above excluding DMF
washing (Table 1). For washing, 25 mL of diethyl ether
was added to the tube, the mixture was stirred and cenꢀ
trifuged, and the washes were decanted. The precipitate
mL), was added a solution of Ph3P(0.26 g; 1 mmol) in
DMF (10 mL). The mixture was stirred for 1 h and filꢀ
tered through a dense paper filter; then, the solvent
was removed from the mother solution by evaporation
to achieve an oily consistency of the mother solution.
The oil was dissolved in 60 mL acetone, the solution
was filtered through a dence paper filter, and then the
excess solvent was evaporated off. The viscous yellowꢀ
green material obtained in this way was filtered on a
dense glass filter and then washed with hexane (5 mL).
Washing made the precipitate friable; it was dried in
vacuo. Yield: 0.32 g (48%).
was additionally washed with diethyl ether (
2 25 mL),
×
and further according to the aboveꢀdescribed proceꢀ
dure. Experiments on the decomposition of weighed
portions chelate I added to a solution of Ph3P in EtOH
or DMF were carried out in the same manner (Table
1). Products were analyzed for Cd and for C, H, and
N. Xꢀray diffraction patterns and IR spectra were
taken for the products.
Elemental analysis was performed on a Euro EA
3000 analyzer. Cadmium was determined complexoꢀ
metrically (Trilon B, Chromogen Black indicator)
after a weighed portion of the complex was digested by
For C28H33CdO2PS4 anal. calcd., %: C, 49.95; H,
4.95; Cd, 16.7.
Found, %: C, 49.7; H, 4.6; Cd, 16.7.
Synthesis of Cd(Ph3P)(nꢀBuOCS2)2 · PPh3 (III).
Air exposure of a solution of complex II in DMF for
several days at room temperature yielded single crystals,
which corresponded to a compound of the specified
composition as determined by Xꢀray crystallography.
Decomposition of chelate I. In studying the thermal
HNO3–H2O2
.
Xꢀray powder diffraction patterns of polycrystalline
decomposition products were measured on a DRONꢀ
3M diffractometer (Cu
K
radiation, Ni filter,
, exposure time per
α
2
θ
range:
5
°
–60
°
, steps: 0.03
°
decomposition of the chelate in EtOH, weighed porꢀ point: 2 s) at room temperature. The products were
tions of the chelate were added to EtOH in roundꢀbotꢀ triturated in the presence of heptane; then, the susꢀ
tomed flasks equipped with a refluxer (Table 1). Mixꢀ pension was spread over the polished side of a standard
tures were refluxed on a water bath for 5, 12, and 15 h. quartz cell. The resulting test samples were ~100ꢀ mꢀ
µ
After cooling a mixture to room temperature, it was thick layers. The external reference was a polycrystalꢀ
transferred to a weighed centrifugal tube (a small line silicon sample prepared in a similar way.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 3 2012

380
LARIONOV et al.
Table 2. Crystallographic data and details of the diffraction Table 3. Selected interatomic distances (
d
) and bond angles
, Å
experiment and structure refinement for compound III ) in the structure of compound III
(
ω
Bond , Å Bond
d
d
Empirical formula
Formula weight
System
C46H48CdO2P2S4
935.42
Cd(1)–S(2)
Cd(1)–S(4)
Cd(1)–S(3)
Cd(1)–S(1)
Cd(1)–P(1)
S(1)–C(1)
S(2)–C(1)
S(3)–C(6)
S(4)–C(6)
C(1)–O(1)
O(1)–C(2)
C(2)–C(3)
C(3)–C(4)
2.5406(7) C(4)–C(5)
2.6162(7) C(6)–O(2)
2.6596(7) O(2)–C(7)
2.7925(7) C(7)–C(8)
2.5939(6) C(8)–C(9)
1.679(3) C(9)–C(10)
1.714(2) P(1)–C(13f)
1.680(3) P(1)–C(7f)
1.698(3) P(1)–C(1f)
1.328(3) P(2)–C(25f)
1.458(3) P(2)–C(31f)
1.496(4) P(2)–C(19f)
1.513(5)
1.469(5)
1.339(3)
1.465(3)
1.518(4)
1.495(5)
1.532(5)
1.818(2)
1.820(2)
1.824(2)
1.835(3)
1.838(3)
1.839(3)
Triclinic
Space group
P
1
a
, Å
, Å
, Å
, deg
, deg
, deg
9.2630(3)
13.6216(5)
19.0848(7)
93.278(1)
b
c
α
β
99.414(1)
γ
106.503(1)
2264.05(14)
V
, Å3
Z
2
ρcalc, g/cm3
(Mo
), mm–1
1.372
0.773
Angle
ω
, deg
Angle
ω
, deg
μ
K
α
S(2)Cd(1)P(1) 116.23(2) O(1)C(1)S(1)
S(2)Cd(1)S(4) 131.59(2) O(1)C(1)S(2)
P(1)Cd(1)S(4) 109.59(2) S(1)C(1)S(2)
S(2)Cd(1)S(3) 105.14(2) C(1)O(1)C(2)
P(1)Cd(1)S(3) 112.98(2) O(1)C(2)C(3)
123.2 (2)
113.7(2)
123.1(1)
118.3(2)
106.7(2)
Crystal size, mm
scan range, deg
0.45
×
0.12 × 0.05
θ
2.18–25.00
Measured reflections
Unique reflections
14480
7671
S(4)Cd(1)S(3) 68.68(2) C(13f)P(1)C(7f) 106.7(1)
S(2)Cd(1)S(1) 67.83(2) C(13f)P(1)C(1f) 103.3(1)
[R
(int)]
[0.0210]
6090
Reflections with
I
> 2σ(I)
P(1)Cd(1)S(1) 93.43(2) C(7f)P(1)C(1f)
104.8(1)
Refined parameters
541
S(4)Cd(1)S(1) 95.39(2) C(13f)P(1)Cd(1) 115.36(8)
S(3)Cd(1)S(1) 152.29(2) C(7f)P(1)Cd(1) 115.29(8)
C(1)S(1)Cd(1) 80.79(9) C(1f)P(1)Cd(1) 110.23(8)
C(1)S(2)Cd(1) 88.17(9) C(25f)P(2)C(31f) 101.8(1)
C(6)S(3)Cd(1) 83.29(9) C(25f)P(2)C(19f) 102.8(1)
C(6)S(4)Cd(1) 84.34(9) C(31f)P(2)C(19f) 101.8(1)
C(6)O(2)C(7) 118.7(2)
GOOF over F2
1.035
R
for ,
I
>2σ(I)
R1
0.0289
0.0621
wR2
R
(for all Ihkl)
R1
0.0454
0.0663
Note: f denotes atoms of phenyl groups; C–C bond lengths in
phenyl groups of coordinated molecules fall in the range of
1.375–1.395 Å; C–C bond lengths in the phenyl groups of
phenyl groups of uncoordinated molecules are in the range
of 1.364–1.400 Å.
wR2
Residual electron density
(max/min), e Å–3
0.582/–0.374
IR spectra were recorded on a Specord 75 IR specꢀ
trophotometer. Particle sizes were estimated using
micrographs obtained with a Jeol JSMꢀ6700F scanꢀ
ning electron microscope.
Xꢀray crystallography. Unit cell parameters and
reflection intensities for selected acicular crystals of
compound III were measured on a Bruker X8 Apex
CCD automated diffractometer equipped with an area
detector using a standard procedure at room temperaꢀ
and structure refinement for compound III are listed
in Table 2. The structure was solved by a direct method
and refined by fullꢀmatrix least squares over F2 in the
anisotropic approximation for nonꢀhydrogen atoms
using the SHELXLꢀ97 program package [22]. During
the refinement in difference electronꢀdensity syntheꢀ
sis Δρ(xyz), some peaks were revealed in addition to
those assigned to atoms of complex II molecules; these
additional peaks were interpreted as arising from
atoms of a Ph3P molecule. The H atoms were geneꢀ
ture (Мо
К
radiation, = 0.71073 Å, graphite monoꢀ
λ
α
chromator, scans of narrow frames). Crystallographic rated geometrically and included into the refinement
parameters and details of the diffraction experiment in the isotropic approximation together with the nonꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 3 2012

CdS FORMATION UPON DECOMPOSITION
381
I
1
2
20
25
30
35
40
45
, deg
2
θ
Fig. 1. Measured diffraction patterns of the decomposition products of chelate
I: (1) in DMF in the presence of PPh (run 6) and
3
(2
) in DMF (run 5). CdS and CdSO line positions are marked by “*” and “^”, respectively.
4
hydrogen atoms. The final values of interatomic disꢀ CdS formation. Xꢀray powder diffraction data verify
tances and bond angles are found in Table 3. The comꢀ
plete tables of atomic coordinates, bond lengths, bond
angles, and anisotropic thermal parameters of basis
atoms have been deposited with the Cambridge Strucꢀ
tural Database (CCDC deposition No. 804658) and
are available from the authors.
CdS formation. Figure 1 is an Xꢀray diffraction pattern
for the product of decomposition of chelate in DMF
I
in the presence of Ph3P (run 6). By Xꢀray powder difꢀ
fraction, this sample contains the hexagonal CdS
phase; there are no peaks of other compounds. In the
other cases (runs 1–5), powder Xꢀray diffraction
shows a CdSO4 phase in the decomposition products
in addition to CdS (Fig. 1). The positive test of Ba2+
ions with the solution obtained from water treatment
of such the decomposition products verified the presꢀ
ence of sulfate ions. The weight of the solid decompoꢀ
sition products is 1.3–3.5% greater than the calculated
RESULTS AND DISCUSSION
When chelate
well as in a solution of Ph3P in EtOH and DMF, the
I is heated in EtOH and DMF, as
solid phase becomes orange, which is an indication of
100 nm
100 nm
30000
×
30000
×
Fig. 2. Micrograph of the decomposition product of cheꢀ
late in DMF.
Fig. 3. Micrograph of the decomposition product of cheꢀ
late in DMF in the presence of PPh .
I
I
3
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 3 2012

382
LARIONOV et al.
(а)
С(4f)
С(5f)
C(3f)
C(9f)
C(8f)
C(7f)
C(6f)
C(15f)
C(14f)
C(10f)
C(11f)
C(1f)
P(1)
C(2f)
C(16f)
C(18f)
C(13f)
S(1)
C(12f)
C(17f)
C(5)
S(4)
C(6)
C(1)
C(2)
Cd(1)
O(2)
C(9)
C(4)
S(3)
C(3)
C(10)
O(1)
C(7)
S(2)
C(8)
(b)
C(22f)
C(21f)
C(20f)
C(23f)
C(24f)
C(19f)
C(32f)
P(2)
C(25f)
C(26f)
C(33f)
C(31f)
C(30f)
C(34f)
C(36f)
C(27f)
C(29f)
C(35f)
C(28f)
Fig. 4. Geometry of (a) an acentric [Cd(Ph P)(nꢀBuOCS ) ] complex molecule with nonꢀhydrogen atom numbering and (b) a
2 2
3
Ph P molecule. Thermal ellipsoids are shown at the 50% probability level.
3
CdS percentage in chelate
EtOH for 15 h, the product weight is most close to the solid products. In the IR spectra of solid products in
calculated CdS percentage in complex
. The cadꢀ the range 900–1500 cm–1, there are no strong bands
mium percentage in decomposition products is that are observed in the spectrum of chelate . This
I (Table 1). Upon boiling in EtOH and where DMF was used only for washing
I
I
noticeably lower than the calculated cadmium perꢀ suggests the absence of noticeable amounts of the iniꢀ
centage in CdS (Table 1). The results of runs 1–3 tial chelate. In the spectra of products obtained by
(boiling in EtOH) prove that the cadmium percentage boiling in EtOH, there are mediumꢀintensity bands at
increases with boiling time. Heating in DMF lasted ~1650 and 1390 cm–1, which may be assigned to the
5 h; longer heating times deteriorated the results. Solid vibrations in DMF used for washing. In the spectra of
decomposition products contained small amounts of the products obtained by boiling in DMF, there are
C and H; some products also contained N, and in runs 2 stronger bands in this range. These data agree with the
and 3, N amounts were at the level of analysis error results of elemental analysis for nitrogen. Likely, washꢀ
(Table 1). For the samples obtained in runs 5 and 6 ing leaves some amount of DMF in solid phases, and
(heating in DMF), the N contents were far higher than this amount is greater when the decomposition is carꢀ
in the runs where decomposition was carried out in ried out in DMF.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 3 2012

CdS FORMATION UPON DECOMPOSITION
383
c
0
b
Fig. 5. Packing of [Cd(Ph P)(nꢀBu OCS ) ] complex molecules in insertion compound III as projected along axis a and arrangeꢀ
2 2 2
3
ment of Ph P molecules in the channels formed in this way. H atoms are omitted.
3
It is impossible to refine coherent scattering
domain sizes of decomposition product particles by
Xꢀray powder diffraction data, for the reason that indiꢀ
vidual peaks from a CdS phase cannot be recognized
in diffraction patterns. Line intensities are too low;
peaks are broad and overlapping. Electron microscopy
The crystal structure of III is built of [Cd(Ph3P)(nꢀ
BuOCS2)2] mononuclear complex molecules, where
all atoms are in general positions (Fig. 4a), and Ph3Р
molecules (Fig. 4b). The coordination polyhedron
around the Cd(1) atom is a distorted tetragonal pyraꢀ
mid where the apical position is occupied by the P
ligand of the Ph3P ligand and the base is formed by the
−
showed that the decomposition of complex I in EtOH
produces fine CdS particles with sizes of 100–200 nm,
a considerable portion being in conglomerates. Addiꢀ
tion of Ph3P decreases the degree of aggregation.
Decomposition in DMF produces smaller particle
sizes (20–50 nm), but the vast number of particles,
however, form conglomerates (Fig. 2). When decomꢀ
position is carried out in DMF in the presence of
Ph3P, particle sizes decrease to 10–30 nm, and the
degree of their aggregation is far lower (Fig. 3).
four S atoms of the two
bidentate chelatꢀ
nꢀBuOCS2
ing ligands. Cd(1)–S distances in the CdPS4 coordiꢀ
nation cores are significantly differentiated and range
within 2.5406(7)–2.7925(7) Å. The coordination of
nꢀBuOCS2−
ligands gives rise to two distorted fourꢀ
membered chelate rings CdS2C, which are practically
planar: the average departure of the atoms from the
meanꢀsquare planes of the CdS2C rings are 0.022(1) and
0.024(1) Å. Cd–S and Cd–P bond lengths and bond
It cannot be ruled out that, when the decomposiꢀ
tion of chelate I is carried out in the presence of Ph3P,
not only the chelate itself decomposes but also mixedꢀ
ligand complex II does; this complex can form by the
angles in the coordination cores of [Cd(Ph3P)(nꢀ
BuCS2)2] are close to those found in Cd(S2COPri)2PPh3
[23]. The symmetry of Ph3P molecules is pseudotrigoꢀ
nal: the P atom lying on the trigonal pseudoꢀaxis has
umbrella coordination with similar P–C distances,
which are 1.835(3)–1.839(3) Å for an uncoordinated
molecule and 1.818(2)–1.824(2) Å for a coordinated
Ph3P molecule.
reaction of I with Ph3P. We managed to obtain comꢀ
plex II by reacting chelate I with Ph3P in DMF. The
complex Cd(S2COPri)2PPh3 has been described [23].
We failed to grow single crystals of complex II, but
obtained single crystals of Cd(Ph3P)
(
nꢀ
BuOCS2)2
⋅
Ph3P III). Likely, this complex can partially dissociꢀ
(
When complex II molecules are packed in the
structure of compound III, channels are formed lying
along [100] (with sizes of ~12 × 11 Å), inside which
uncoordinated Ph3P molecules reside (Fig. 5). These
ate upon dissolution of complex II in DMF, and for
this reason single crystals of compound III are precipꢀ
itated upon DMF evaporation.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 3 2012

384
LARIONOV et al.
S(4')
S(1')
Cd(1')
C(6')
S(3')
C(1')
S(2')
S(2)
C(1)
S(3)
C(6)
Cd(1)
S(4)
S(1)
Fig. 6. Supramolecular dimeric assembly in the crystal structure of III
.
molecules are weakly bound with complex molecules:
the minimal distance O(2)···C(27f) = 3.608(4) Å.
Structural data allow us to classify compound III with
insertion compounds. The inspection of intermolecuꢀ
lar distances showed that, in a crystal of III, there are
short contacts between neighboring complex II moleꢀ
cules: Cd(1)···S(2) = 3.558(1) and S(2)···S(2)' =
3.320(1) Å. These distances are greater than the sums
of the covalent or ionic radii of Cd and S, but smaller
than the sums of the van der Waals radii, which equal
3.95 and 3.70 Å, respectively [24]. These contacts give
rise to centrosymmetric supramolecular assemblies of
two complex II molecules (Fig. 6).
ACKNOWLEDGMENTS
We are grateful to L.I. Myachina for carrying out
cadmium determination, O.S. Koshcheeva for providꢀ
ing elemental analysis data, and N.I. Alferova for meaꢀ
suring IR spectra.
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