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The title compound, cis-[PtCl2(C4H10S)2], crystallizes in the space group P21/n with pseudo-square-planar coordination geometry. The orientation of the ethyl groups on the S atoms is staggered with respect to the coordination plane, giving the complex approximate C2v symmetry. The complex does not form dimeric packing units with short Pt...S intra­dimeric distances as seen in some related complexes, but instead displays C-H...Cl inter­actions in three dimensions. These C-H...Cl-Pt contacts are compared with those of related compounds reported in the Cambridge Structural Database, which show a frequency maximum in the range 120-170° for the C-H...Cl angle.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107030417/sq3085sup1.cif
Contains datablocks I_295K, I_150K, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107030417/sq3085I_295Ksup2.hkl
Contains datablock I_295K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107030417/sq3085I_150Ksup3.hkl
Contains datablock I_150K

doc

Microsoft Word (DOC) file https://doi.org/10.1107/S0108270107030417/sq3085sup4.doc
Supplementary material

CCDC references: 659111; 659112

Comment top

In the solid state, the complex cis-PtCl2(Me2S)2 (Horn et al., 1990) has one dimethyl sulfide (dms) ligand in staggered and one in eclipsed orientation with respect to the PtCl2S2 coordination plane. A similar situation has been observed in cis-PtCl2(tx)2 (tx = 1,4-thioxane, SC4H8O; Bugarcic et al., 1993). Both structures form centrosymmetric dimeric units with Pt···S distances of 3.58 and 3.59 Å for the dimers [cis-PtCl2(tx)2]2 and [cis-PtCl2(Me2S)2]2, respectively. On the other hand, the complex cis-PtCl2(Ph2S)2 (Johansson et al., 2001) does not form a centrosymmetric unit with a short Pt···S distance but is stabilized by C—H···Cl interactions. In order to gain more information on the formation of dimeric packing units with a short Pt···S distance, the title complex cis-PtCl2(Et2S)2, (I), has been examined.

The title complex possesses a pseudo-square-planar coordination geometry, with angles around Pt in the range 87.40 (4)–91.43 (5)° at 295 K and 87.90 (3)–90.75 (4)° at 150 K. Selected bond distances and bond angles for the 150 K structure are shown in Table 1. Both diethyl sulfide ligands are orientated in a staggered manner with one ethyl group above and one beneath the coordination plane. The organic groups of the two sulfide ligands are directed away from each other and the complex adopts approximately C2v symmetry (Fig. 1).

The packing arrangement of the complex may be described as consisting of layers of complexes in the (1 0 1) plane formed by C—H···Cl interactions with H···Cl distances in the range 2.78–2.90 Å and C—H···Cl angles of 135–157° at 150 K (Table 1, Fig. 2). However, if the interval is extended to 3.20 Å, it is seen that the layers are connected by four additional Cl···H contacts to form a three-dimensional network. Two of these interactions between the layers have C—H···Cl angles in the range 108–110°, whereas the other two are in the same range as the interactions within the layers.

With the exception of the molecules that straddle 0 0 1/2, which have a short H7A···H7Aii contact of 2.31 Å, the symmetry centres create voids of different sizes (symmetry codes are given in Table 1). Four molecules form a ring around 0 0 0 with H1A···Cl2iii and H2B···Cl2iv contacts of 2.90 and 3.12 Å, respectively. Dimers are formed around 0 1/2 0 with a H4B···Cl2v distance of 3.10 Å. A ring of four molecules is formed around 1/2 0 0 with contacts H1A···Cl1iii and H5A···Cl2vi with a H···Cl distance of 2.80 and 2.78 Å, respectively. The Pt···S2i distance across the ring is 5.3822 (10) Å.

There are no significant differences between the Pt—Cl or Pt—S bond lengths of cis-PtCl2(Me2S)2 and the title compound. The S—Pt—S angle at 150 K is 87.90 (3)° in the diethyl sulfide complex and 94.75° in the complex with dms ligands, probably reflecting the different ways in which the two ligands orientate around the PtII ion. Since one of the dms ligands has one methyl group placed in the coordination plane, the ligand demands more space and thus the S—Pt—S angle becomes larger, mostly at the expense of the neighbouring S—Pt—Cl angle. The sulfide ligands in the trans-isomer of PtCl2(Et2S)2 (Skvortsov et al., 1994) are staggered with respect to the coordination plane and the complex posseses Ci symmetry.

The title compound does not form dimeric packing units of the type seen in cis-PtCl2(Me2S)2 and cis-PtCl2(tx)2. A dimerization with short Pt···S interactions requires a reorientation of one of the thioether ligands. The cost in energy for this must be compensated by the combined effect of the dimerization and the energy of packing the dimers. There seems to be a delicate balance between these factors since cis-PtCl2(Me2S)2 and cis-PtCl2(tx)2 form dimers with short Pt···S interactions while cis-PtCl2(Et2S)2 and cis-PtCl2(Ph2S)2 do not. It may be possible for cis-PtCl2(Et2S)2 to form more C—H···Cl contacts in three dimensions than cis-PtCl2(Me2S)2, since more H atoms are present, and the formation of C—H···Cl interactions probably stabilizes the packing of the title compound. This is supported by data in the Cambridge Structural Database (CSD, Version 5.28 Release ?; Allen, 2002) which has been searched using CONQUEST software (Bruno et al., 2002). Most PtII—Cl complexes in the CSD have C—H···Cl angles in the range 120–170°. CH(methyl)···Cl and CH(methylene)···Cl angles have a mean of 141 and 139°, respectively, for a H···Cl cut-off distance of 3.2 Å. A cut-off distance of 3.0 Å increases the mean values to 150 and 145° for CH(methyl)···Cl and CH(methylene)···Cl, respectively (deposited material).

The complexes [PtCl3(Me2S)]- (Kukushkin et al., 1994), cis/trans-PtCl2(Me2S)2 (Horn et al., 1990; Hansson et al., 2006) and [PtCl(Me2S)3]+ (Hansson et al., 2003) make up a series of complexes with dms and chloro ligands in different ratios. Dimeric units with a short Pt···S interaction have been found in cis-PtCl2(Me2S)2 (as discussed above) and [PtCl(Me2S)3]+ but not in the other complexes in the series.

Most of the 13 PtII complexes with one or more diethyl sulfide ligands in the CSD (Allen, 2002) contain diethyl sulfide molecules in which the orientation of the ethyl groups is similar to that seen in the title compound, but exceptions do occur. The complex (8-methoxynaphthyl)platinum chloride bis(diethyl sulfide) (Wehman et al., 1988) contains one diethyl sulfide ligand with ethyl groups in staggered orientation, and one which is turned so that one methylene carbon is approximately in the coordination plane i.e. a similar orientation to that seen in cis-PtCl2(Me2S)2. However, this orientation is probably governed by the steric demand of the 8-methoxynaphthyl ligand.

The so-called Kitaigorodsky packing index (KPI), i.e. the ratio between occupied volume and the total unit-cell volume, has been calculated using the VOID option in the PLATON software (Spek, 2003) for the title compound at 295 and 150 K, and for the related complexes cis-PtCl2(Me2S)2, cis-PtCl2(Ph2S)2, cis-PtCl2(tx)2 and their trans-counterparts (Table 2). No H-atom positions were reported for trans-PtCl2(Et2S)2 and cis/trans-PtCl2(Me2S)2 so H atoms had to be added to the structures before the KPI could be calculated. The observed range of KPI, 0.65–0.73, is within the interval proposed for organic molecules, 0.65–0.77 (Kitaigorodsky, 1973). The KPI of cis-PtCl2(Me2S)2 is larger than the KPI of the title compound, indicating that the former complex is able to pack more efficiently.

When comparing cis- and trans-isomers of compounds with the general formula PtCl2(S-donor)2, it is observed that the trans-isomer often seems to be more densely packed than the corresponding cis-isomer (Table 2). However, the differences are small, <3%. The difference in density for the title compound at 295 and 150 K is 3.5%, and the volume expansion coefficient (1/V dV/dT) is 2.3 × 10 -4 K-1, indicating that thermal expansion properties are very important for these types of compounds, and no general conclusion about packing efficiency between cis- and trans-complexes can be drawn.

Related literature top

For related literature, see: Allen (2002); Bruno et al. (2002); Bugarcic et al. (1993); Hansson et al. (2003, 2006); Horn et al. (1990); Johansson et al. (2001); Kitaigorodsky (1973); Kukushkin et al. (1994); Skvortsov et al. (1994); Spek (2003); Wehman et al. (1988).

Experimental top

K2PtCl4 (0.506 g, 1.21 mmol) was dissolved in 20 ml water. Diethyl sulfide (3.7 ml, 34.3 mmol) was added, giving a dark yellow precipitate. The reaction mixture was left stirring for 24 h. The yellow precipitate was filtered off and dried. Recrystallization from acetone gave yellow greenish crystals suitable for X-ray diffraction experiments.

Refinement top

H-atom positions were calculated as riding on the adjacent C atom constrained to parent sites (methyl group C—H distance 0.96 Å, methylene group C—H distance 0.97 Å) with Uiso(H) = 1.5Ueq(C) (methyl) and Uiso(H) = 1.2Ueq(C) (methylene).

At 150 K, the highest peak in the final difference map, 3.61 e Å-3, is situated 1.94 Å from C8 and 3.01 Å from C2, while the lowest peak, -1.19 e Å-3, is 0.68 Å from Pt1.

Computing details top

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD or RED? (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003), enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. The numbering scheme for (I) at 150 K. The displacement ellipsoids are drawn at 30% probability.
[Figure 2] Fig. 2. The hydrogen-bonded layer (1 0 1). Dashed lines indicate C—H···Cl interactions. Symmetry code (viii) x + 1/2 - y + 1/2 z - 1/2. Other symmetry codes are as in Table 1.
(I_295K) cis-Dichloridobis(diethyl sulfide-κS)platinum(II) top
Crystal data top
[PtCl2(C4H10S)2]F(000) = 848
Mr = 446.35Dx = 1.999 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6329 reflections
a = 10.7928 (2) Åθ = 2.3–33.1°
b = 11.4223 (2) ŵ = 10.07 mm1
c = 12.2417 (2) ÅT = 295 K
β = 100.619 (1)°Prism, clear yellow
V = 1483.30 (5) Å30.24 × 0.11 × 0.06 mm
Z = 4
Data collection top
Oxford Diffraction XCALIBUR3
diffractometer
5157 independent reflections
Radiation source: Sealed tube3266 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω–scansθmax = 33.1°, θmin = 2.3°
Absorption correction: analytical
CrysAlis CCD or RED? (Oxford Diffraction, 2006)
h = 1416
Tmin = 0.257, Tmax = 0.618k = 1717
14809 measured reflectionsl = 1811
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0358P)2 + 0.0966P]
where P = (Fo2 + 2Fc2)/3
5157 reflections(Δ/σ)max = 0.001
122 parametersΔρmax = 1.72 e Å3
0 restraintsΔρmin = 1.09 e Å3
Crystal data top
[PtCl2(C4H10S)2]V = 1483.30 (5) Å3
Mr = 446.35Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.7928 (2) ŵ = 10.07 mm1
b = 11.4223 (2) ÅT = 295 K
c = 12.2417 (2) Å0.24 × 0.11 × 0.06 mm
β = 100.619 (1)°
Data collection top
Oxford Diffraction XCALIBUR3
diffractometer
5157 independent reflections
Absorption correction: analytical
CrysAlis CCD or RED? (Oxford Diffraction, 2006)
3266 reflections with I > 2σ(I)
Tmin = 0.257, Tmax = 0.618Rint = 0.029
14809 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.076H-atom parameters constrained
S = 1.00Δρmax = 1.72 e Å3
5157 reflectionsΔρmin = 1.09 e Å3
122 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt10.549331 (14)0.212870 (13)0.794965 (12)0.04585 (7)
S10.64828 (11)0.03671 (10)0.82103 (10)0.0592 (3)
S20.50166 (12)0.19129 (10)0.96671 (10)0.0573 (3)
Cl10.43979 (13)0.38752 (11)0.76964 (13)0.0786 (4)
Cl20.60710 (17)0.23480 (14)0.62392 (12)0.0870 (4)
C50.3325 (5)0.2013 (5)0.9528 (5)0.0820 (17)
H5A0.30960.19791.02580.098*
H5B0.30370.27570.91920.098*
C10.8138 (5)0.0593 (6)0.8136 (6)0.100 (2)
H1A0.85360.01610.80830.120*
H1B0.81930.10330.74690.120*
C70.5453 (7)0.3268 (6)1.0440 (4)0.091 (2)
H7A0.49670.39121.00620.109*
H7B0.52470.31991.11760.109*
C60.2695 (5)0.1034 (7)0.8824 (5)0.101 (2)
H6A0.29010.10830.80950.151*
H6B0.17980.10930.87680.151*
H6C0.29820.02980.91570.151*
C30.6007 (7)0.0509 (5)0.6964 (5)0.099 (2)
H3A0.61950.00830.63280.119*
H3B0.64910.12290.70330.119*
C20.8812 (6)0.1214 (7)0.9094 (7)0.121 (3)
H2A0.83570.19110.92120.182*
H2B0.96360.14240.89660.182*
H2C0.88930.07210.97380.182*
C40.4644 (8)0.0794 (8)0.6770 (7)0.141 (3)
H4A0.44550.12150.73980.212*
H4B0.44320.12680.61150.212*
H4C0.41610.00830.66730.212*
C80.6839 (7)0.3533 (7)1.0547 (6)0.127 (3)
H8A0.73230.28841.08940.191*
H8B0.70430.42231.09920.191*
H8C0.70340.36620.98220.191*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.04467 (10)0.04577 (10)0.05069 (10)0.00108 (7)0.01819 (7)0.00317 (7)
S10.0603 (7)0.0502 (6)0.0702 (7)0.0091 (5)0.0200 (6)0.0007 (5)
S20.0651 (7)0.0612 (6)0.0511 (6)0.0080 (6)0.0248 (5)0.0049 (5)
Cl10.0815 (8)0.0588 (7)0.1032 (10)0.0220 (6)0.0375 (8)0.0244 (7)
Cl20.1087 (12)0.0966 (10)0.0685 (8)0.0086 (9)0.0499 (8)0.0145 (7)
C50.067 (3)0.097 (4)0.094 (4)0.017 (3)0.046 (3)0.024 (3)
C10.064 (4)0.098 (4)0.146 (6)0.023 (4)0.041 (4)0.003 (4)
C70.138 (6)0.089 (4)0.050 (3)0.010 (4)0.028 (3)0.023 (3)
C60.067 (4)0.140 (6)0.098 (4)0.028 (4)0.022 (3)0.012 (4)
C30.118 (5)0.072 (4)0.112 (5)0.024 (4)0.033 (4)0.019 (3)
C20.069 (4)0.118 (6)0.169 (8)0.005 (4)0.004 (5)0.015 (6)
C40.130 (7)0.118 (6)0.158 (7)0.001 (5)0.018 (5)0.067 (6)
C80.119 (6)0.139 (7)0.117 (6)0.026 (6)0.005 (5)0.065 (5)
Geometric parameters (Å, º) top
Pt1—S22.2682 (11)C7—H7B0.9700
Pt1—S12.2728 (11)C6—H6A0.9600
Pt1—Cl22.3059 (12)C6—H6B0.9600
Pt1—Cl12.3105 (12)C6—H6C0.9600
S1—C31.818 (6)C3—C41.483 (9)
S1—C11.823 (6)C3—H3A0.9700
S2—C51.806 (6)C3—H3B0.9700
S2—C71.830 (6)C2—H2A0.9600
C5—C61.497 (8)C2—H2B0.9600
C5—H5A0.9700C2—H2C0.9600
C5—H5B0.9700C4—H4A0.9600
C1—C21.447 (9)C4—H4B0.9600
C1—H1A0.9700C4—H4C0.9600
C1—H1B0.9700C8—H8A0.9600
C7—C81.508 (9)C8—H8B0.9600
C7—H7A0.9700C8—H8C0.9600
Pt1···S2i5.5424 (12)H7A···H7Aii2.49
S2—Pt1—S187.40 (4)C5—C6—H6A109.5
S2—Pt1—Cl2177.47 (5)C5—C6—H6B109.5
S1—Pt1—Cl291.43 (5)H6A—C6—H6B109.5
S2—Pt1—Cl191.17 (5)C5—C6—H6C109.5
S1—Pt1—Cl1177.21 (4)H6A—C6—H6C109.5
Cl2—Pt1—Cl190.10 (5)H6B—C6—H6C109.5
C3—S1—C199.4 (3)C4—C3—S1111.9 (5)
C3—S1—Pt1108.5 (2)C4—C3—H3A109.2
C1—S1—Pt1107.9 (2)S1—C3—H3A109.2
C5—S2—C798.9 (3)C4—C3—H3B109.2
C5—S2—Pt1107.7 (2)S1—C3—H3B109.2
C7—S2—Pt1107.8 (2)H3A—C3—H3B107.9
C6—C5—S2110.5 (4)C1—C2—H2A109.5
C6—C5—H5A109.5C1—C2—H2B109.5
S2—C5—H5A109.5H2A—C2—H2B109.5
C6—C5—H5B109.5C1—C2—H2C109.5
S2—C5—H5B109.5H2A—C2—H2C109.5
H5A—C5—H5B108.1H2B—C2—H2C109.5
C2—C1—S1112.4 (5)C3—C4—H4A109.5
C2—C1—H1A109.1C3—C4—H4B109.5
S1—C1—H1A109.1H4A—C4—H4B109.5
C2—C1—H1B109.1C3—C4—H4C109.5
S1—C1—H1B109.1H4A—C4—H4C109.5
H1A—C1—H1B107.9H4B—C4—H4C109.5
C8—C7—S2111.8 (4)C7—C8—H8A109.5
C8—C7—H7A109.3C7—C8—H8B109.5
S2—C7—H7A109.3H8A—C8—H8B109.5
C8—C7—H7B109.3C7—C8—H8C109.5
S2—C7—H7B109.3H8A—C8—H8C109.5
H7A—C7—H7B107.9H8B—C8—H8C109.5
S2—Pt1—S1—C3133.8 (2)Cl2—Pt1—S2—C768.2 (11)
Cl2—Pt1—S1—C348.5 (2)Cl1—Pt1—S2—C751.6 (3)
Cl1—Pt1—S1—C374.8 (10)C7—S2—C5—C6175.2 (4)
S2—Pt1—S1—C1119.4 (3)Pt1—S2—C5—C663.2 (4)
Cl2—Pt1—S1—C158.3 (3)C3—S1—C1—C2175.8 (5)
Cl1—Pt1—S1—C1178 (18)Pt1—S1—C1—C271.2 (5)
S1—Pt1—S2—C5123.4 (2)C5—S2—C7—C8171.6 (5)
Cl2—Pt1—S2—C5174.1 (11)Pt1—S2—C7—C859.7 (5)
Cl1—Pt1—S2—C554.2 (2)C1—S1—C3—C4177.5 (6)
S1—Pt1—S2—C7130.7 (3)Pt1—S1—C3—C464.9 (6)
Symmetry codes: (i) x+1, y, z+2; (ii) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···Cl1iii0.972.813.600 (7)140
C1—H1A···Cl2iii0.972.973.849 (7)151
C2—H2B···Cl2iv0.963.243.630 (7)106
C4—H4B···Cl2v0.963.094.033 (9)168
C5—H5A···Cl2vi0.972.793.566 (7)138
C6—H6B···Cl1vii0.963.233.619 (7)106
C8—H8B···Cl1ii0.963.264.028 (8)138
Symmetry codes: (ii) x+1, y+1, z+2; (iii) x+3/2, y1/2, z+3/2; (iv) x+1/2, y+1/2, z+1/2; (v) x+1, y, z+1; (vi) x1/2, y+1/2, z+1/2; (vii) x+1/2, y1/2, z+3/2.
(I_150K) cis-Dichloridobis(diethyl sulfide-κS)platinum(II) top
Crystal data top
[PtCl2(C4H10S)2]F(000) = 848
Mr = 446.35Dx = 2.066 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 8446 reflections
a = 10.7598 (5) Åθ = 2.3–33.1°
b = 11.1976 (5) ŵ = 10.40 mm1
c = 12.1559 (5) ÅT = 150 K
β = 101.536 (4)°Prism, clear yellow
V = 1435.00 (11) Å30.24 × 0.11 × 0.06 mm
Z = 4
Data collection top
Oxford Diffraction XCALIBUR3
diffractometer
5054 independent reflections
Radiation source: Sealed tube4061 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ω–scansθmax = 33.1°, θmin = 2.3°
Absorption correction: analytical
CrysAlis CCD or RED? (Oxford Diffraction, 2006)
h = 1615
Tmin = 0.222, Tmax = 0.635k = 1616
14202 measured reflectionsl = 1018
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0504P)2 + 0.6066P]
where P = (Fo2 + 2Fc2)/3
5054 reflections(Δ/σ)max = 0.002
122 parametersΔρmax = 3.61 e Å3
0 restraintsΔρmin = 1.19 e Å3
Crystal data top
[PtCl2(C4H10S)2]V = 1435.00 (11) Å3
Mr = 446.35Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.7598 (5) ŵ = 10.40 mm1
b = 11.1976 (5) ÅT = 150 K
c = 12.1559 (5) Å0.24 × 0.11 × 0.06 mm
β = 101.536 (4)°
Data collection top
Oxford Diffraction XCALIBUR3
diffractometer
5054 independent reflections
Absorption correction: analytical
CrysAlis CCD or RED? (Oxford Diffraction, 2006)
4061 reflections with I > 2σ(I)
Tmin = 0.222, Tmax = 0.635Rint = 0.023
14202 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.080H-atom parameters constrained
S = 1.02Δρmax = 3.61 e Å3
5054 reflectionsΔρmin = 1.19 e Å3
122 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt10.551099 (12)0.207082 (11)0.797594 (11)0.01868 (5)
S10.65185 (9)0.02843 (8)0.83172 (8)0.02354 (17)
S20.49999 (10)0.19254 (8)0.96944 (8)0.02274 (18)
Cl10.43971 (10)0.38470 (9)0.76390 (9)0.0314 (2)
Cl20.61162 (12)0.22069 (9)0.62606 (9)0.0334 (2)
C50.3288 (4)0.2031 (4)0.9485 (4)0.0307 (9)
H5A0.30310.20001.02050.037*
H5B0.30080.27880.91320.037*
C10.8180 (4)0.0510 (4)0.8262 (4)0.0337 (9)
H1A0.85960.02590.82640.040*
H1B0.82400.09180.75710.040*
C70.5419 (5)0.3336 (4)1.0418 (4)0.0345 (9)
H7A0.49170.39721.00060.041*
H7B0.52140.32961.11590.041*
C60.2674 (4)0.1018 (5)0.8752 (4)0.0398 (10)
H6A0.28350.11120.80080.060*
H6B0.17760.10260.87230.060*
H6C0.30220.02720.90600.060*
C30.6052 (4)0.0655 (4)0.7087 (4)0.0351 (9)
H3A0.62650.02590.64400.042*
H3B0.65170.14010.72000.042*
C20.8838 (4)0.1232 (5)0.9243 (4)0.0396 (10)
H2A0.84290.19930.92410.059*
H2B0.97090.13470.91920.059*
H2C0.88000.08170.99270.059*
C40.4641 (5)0.0910 (5)0.6865 (4)0.0457 (12)
H4A0.44250.12740.75170.069*
H4B0.44250.14430.62370.069*
H4C0.41800.01770.67020.069*
C80.6798 (5)0.3627 (5)1.0534 (5)0.0463 (12)
H8A0.73000.29711.08860.069*
H8B0.69950.43311.09850.069*
H8C0.69840.37650.98040.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01871 (7)0.01765 (7)0.02097 (8)0.00046 (5)0.00707 (5)0.00078 (4)
S10.0240 (4)0.0196 (4)0.0279 (4)0.0034 (3)0.0071 (3)0.0006 (3)
S20.0257 (4)0.0230 (4)0.0213 (4)0.0022 (3)0.0090 (3)0.0002 (3)
Cl10.0345 (5)0.0236 (4)0.0388 (5)0.0087 (4)0.0140 (4)0.0097 (4)
Cl20.0404 (6)0.0389 (6)0.0256 (5)0.0047 (4)0.0177 (4)0.0050 (4)
C50.0257 (19)0.029 (2)0.042 (2)0.0005 (15)0.0182 (18)0.0025 (16)
C10.0187 (17)0.038 (2)0.046 (2)0.0054 (16)0.0097 (17)0.0029 (19)
C70.046 (3)0.030 (2)0.029 (2)0.0017 (19)0.0093 (18)0.0098 (17)
C60.029 (2)0.048 (3)0.043 (2)0.007 (2)0.0098 (19)0.001 (2)
C30.037 (2)0.027 (2)0.041 (2)0.0069 (18)0.0069 (18)0.0078 (17)
C20.026 (2)0.041 (2)0.050 (3)0.0060 (19)0.0023 (19)0.002 (2)
C40.042 (3)0.044 (3)0.048 (3)0.002 (2)0.001 (2)0.017 (2)
C80.041 (3)0.047 (3)0.048 (3)0.007 (2)0.002 (2)0.018 (2)
Geometric parameters (Å, º) top
Pt1—S22.2699 (9)C7—H7B0.9700
Pt1—S12.2736 (9)C6—H6A0.9600
Pt1—Cl22.3105 (10)C6—H6B0.9600
Pt1—Cl12.3159 (9)C6—H6C0.9600
S1—C31.815 (4)C3—C41.515 (7)
S1—C11.820 (4)C3—H3A0.9700
S2—C51.812 (4)C3—H3B0.9700
S2—C71.820 (5)C2—H2A0.9600
C5—C61.509 (6)C2—H2B0.9600
C5—H5A0.9700C2—H2C0.9600
C5—H5B0.9700C4—H4A0.9600
C1—C21.497 (6)C4—H4B0.9600
C1—H1A0.9700C4—H4C0.9600
C1—H1B0.9700C8—H8A0.9600
C7—C81.498 (7)C8—H8B0.9600
C7—H7A0.9700C8—H8C0.9600
Pt1···S2i5.3822 (10)H7A···H7Aii2.31
S2—Pt1—S187.90 (3)C5—C6—H6A109.5
S2—Pt1—Cl2177.68 (4)C5—C6—H6B109.5
S1—Pt1—Cl290.72 (4)H6A—C6—H6B109.5
S2—Pt1—Cl190.71 (3)C5—C6—H6C109.5
S1—Pt1—Cl1177.30 (3)H6A—C6—H6C109.5
Cl2—Pt1—Cl190.75 (4)H6B—C6—H6C109.5
C3—S1—C199.3 (2)C4—C3—S1111.0 (3)
C3—S1—Pt1108.43 (15)C4—C3—H3A109.4
C1—S1—Pt1107.90 (16)S1—C3—H3A109.4
C5—S2—C799.1 (2)C4—C3—H3B109.4
C5—S2—Pt1107.00 (16)S1—C3—H3B109.4
C7—S2—Pt1107.47 (15)H3A—C3—H3B108.0
C6—C5—S2110.3 (3)C1—C2—H2A109.5
C6—C5—H5A109.6C1—C2—H2B109.5
S2—C5—H5A109.6H2A—C2—H2B109.5
C6—C5—H5B109.6C1—C2—H2C109.5
S2—C5—H5B109.6H2A—C2—H2C109.5
H5A—C5—H5B108.1H2B—C2—H2C109.5
C2—C1—S1110.9 (3)C3—C4—H4A109.5
C2—C1—H1A109.5C3—C4—H4B109.5
S1—C1—H1A109.5H4A—C4—H4B109.5
C2—C1—H1B109.5C3—C4—H4C109.5
S1—C1—H1B109.5H4A—C4—H4C109.5
H1A—C1—H1B108.0H4B—C4—H4C109.5
C8—C7—S2112.3 (3)C7—C8—H8A109.5
C8—C7—H7A109.2C7—C8—H8B109.5
S2—C7—H7A109.2H8A—C8—H8B109.5
C8—C7—H7B109.2C7—C8—H8C109.5
S2—C7—H7B109.2H8A—C8—H8C109.5
H7A—C7—H7B107.9H8B—C8—H8C109.5
S2—Pt1—S1—C3133.31 (16)Cl2—Pt1—S2—C777.3 (9)
Cl2—Pt1—S1—C348.56 (16)Cl1—Pt1—S2—C751.49 (17)
Cl1—Pt1—S1—C374.3 (8)C7—S2—C5—C6172.7 (3)
S2—Pt1—S1—C1120.01 (16)Pt1—S2—C5—C661.2 (3)
Cl2—Pt1—S1—C158.13 (16)C3—S1—C1—C2177.3 (3)
Cl1—Pt1—S1—C1179 (100)Pt1—S1—C1—C269.8 (3)
S1—Pt1—S2—C5123.52 (14)C5—S2—C7—C8169.7 (4)
Cl2—Pt1—S2—C5177 (17)Pt1—S2—C7—C858.5 (4)
Cl1—Pt1—S2—C554.16 (14)C1—S1—C3—C4175.4 (4)
S1—Pt1—S2—C7130.83 (17)Pt1—S1—C3—C462.9 (4)
Symmetry codes: (i) x+1, y, z+2; (ii) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···Cl1iii0.972.803.550 (5)135
C1—H1A···Cl2iii0.972.903.797 (5)154
C2—H2B···Cl2iv0.963.123.560 (5)110
C4—H4B···Cl2v0.963.103.996 (5)157
C5—H5A···Cl2vi0.972.783.587 (5)141
C6—H6B···Cl1vii0.963.073.497 (5)108
C8—H8B···Cl1ii0.963.203.966 (6)139
Symmetry codes: (ii) x+1, y+1, z+2; (iii) x+3/2, y1/2, z+3/2; (iv) x+1/2, y+1/2, z+1/2; (v) x+1, y, z+1; (vi) x1/2, y+1/2, z+1/2; (vii) x+1/2, y1/2, z+3/2.

Experimental details

(I_295K)(I_150K)
Crystal data
Chemical formula[PtCl2(C4H10S)2][PtCl2(C4H10S)2]
Mr446.35446.35
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)295150
a, b, c (Å)10.7928 (2), 11.4223 (2), 12.2417 (2)10.7598 (5), 11.1976 (5), 12.1559 (5)
β (°) 100.619 (1) 101.536 (4)
V3)1483.30 (5)1435.00 (11)
Z44
Radiation typeMo KαMo Kα
µ (mm1)10.0710.40
Crystal size (mm)0.24 × 0.11 × 0.060.24 × 0.11 × 0.06
Data collection
DiffractometerOxford Diffraction XCALIBUR3
diffractometer
Oxford Diffraction XCALIBUR3
diffractometer
Absorption correctionAnalytical
CrysAlis CCD or RED? (Oxford Diffraction, 2006)
Analytical
CrysAlis CCD or RED? (Oxford Diffraction, 2006)
Tmin, Tmax0.257, 0.6180.222, 0.635
No. of measured, independent and
observed [I > 2σ(I)] reflections
14809, 5157, 3266 14202, 5054, 4061
Rint0.0290.023
(sin θ/λ)max1)0.7690.768
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.076, 1.00 0.027, 0.080, 1.02
No. of reflections51575054
No. of parameters122122
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.72, 1.093.61, 1.19

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis CCD or RED? (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXTL (Sheldrick, 1998), DIAMOND (Brandenburg, 2000), CRYSTALS (Betteridge et al., 2003), enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) for (I_150K) top
Pt1—S22.2699 (9)S1—C31.815 (4)
Pt1—S12.2736 (9)S1—C11.820 (4)
Pt1—Cl22.3105 (10)S2—C51.812 (4)
Pt1—Cl12.3159 (9)S2—C71.820 (5)
Pt1···S2i5.3822 (10)H7A···H7Aii2.31
S2—Pt1—Cl2177.68 (4)C1—S1—Pt1107.90 (16)
S1—Pt1—Cl1177.30 (3)C5—S2—Pt1107.00 (16)
C3—S1—Pt1108.43 (15)C7—S2—Pt1107.47 (15)
Symmetry codes: (i) x+1, y, z+2; (ii) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) for (I_150K) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···Cl1iii0.972.803.5504 (48)135.1
C1—H1A···Cl2iii0.972.903.7967 (46)154.1
C2—H2B···Cl2iv0.963.123.5602 (46)109.9
C4—H4B···Cl2v0.963.103.9963 (50)156.9
C5—H5A···Cl2vi0.972.783.5868 (52)140.9
C6—H6B···Cl1vii0.963.073.4968 (50)108.3
C8—H8B···Cl1ii0.963.203.9659 (61)138.6
Symmetry codes: (ii) x+1, y+1, z+2; (iii) x+3/2, y1/2, z+3/2; (iv) x+1/2, y+1/2, z+1/2; (v) x+1, y, z+1; (vi) x1/2, y+1/2, z+1/2; (vii) x+1/2, y1/2, z+3/2.
Table 2. Density and KPI for four thioether cis/trans-complexes top
Compound formulaDensity (g cm-3)KPI
cis-PtCl2(Me2S)2a2.520.698
cis-PtCl2(Et2S)2 (295 K)b2.000.654
cis-PtCl2(Et2S)2 (150 K)b2.070.676
cis-PtCl2(Ph2S)2c1.810.666
cis-PtCl2(tx)2d2.390.728
trans-PtCl2(Me2S)2e2.600.726
trans-PtCl2(Et2S)2f2.060.675
trans-PtCl2(Ph2S)2 c1.830.674
trans-PtCl2(tx)2d2.370.730
Notes: (a) Horn et al. (1990); (b) this paper; (c) Johansson et al. (2001); (d) Bugarcic et al. (1993); (e) Hansson et al. (2006); (f) Skvortsov et al. (1994).
 

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