Cis/trans isomers of PtX₂L₂ (X = halogen, L = neutral ligand); the crystal structure of trans-di­chlorobis(di­methyl sulfide)platinum(II) and the pressure dependence of its unit-cell dimensions

trans-PtCl₂(dms)₂ (dms is dimethyl sulfide) crystallizes in the space group P2₁/n and adopts the molecular point group C_i, which is the most frequently occurring point group for trans-PtX₂L₂ complexes (78%), as observed in the Cambridge Structural Database (CSD; 2005 release), followed by C₁ (16%). Density functional theory calculations show that the observed geometry for trans-PtCl₂(dms)₂ has slightly higher energy than the most favorable geometry in the point group C_2h, but this geometry would require a space group that hampers close packing, thus showing that intermolecular forces determine the point group for the title compound. High-pressure powder diffraction studies of trans-PtCl₂(dms)₂ show no phase transformation up to 8.0 GPa. The bulk modulus is 8.1 (6) GPa and the pressure derivative 8.1 (4). In the CSD, the number of cis- and trans-PtX₂L₂ compounds are almost equal, viz. 156 cis and 160 trans compounds, showing no preference for either isomer in the solid state.

1. Introduction

A synthetic procedure resulting in a mixture of cis- and trans-PtCl₂(dms)₂ was published as early as 1934 (Cox et al., 1934) and a tentative structure for the trans isomer, based on rotation X-ray photographs, was given. Horn et al. (1990) have determined the structure of the cis isomer but, besides a preliminary report (Johansson, 2001), no detailed structural model for the trans complex has been published previously.

Studies of the effects of high pressure on molecular crystals are at the initial stage but some characteristics have been reported, i.e. conformational changes and compression of weak intermolecular bonds (Boldyreva, 2003). As a result one can observe either a structural reconstruction, i.e. a phase transition, or a continuous distortion within the limits of stability of the same phase. No high-pressure investigation on trans-PtCl₂(dms)₂ has yet been published, and we present here a powder diffraction study up to 8.0 GPa.

Whether the formation of the cis and/or trans isomer of a complex is guided by thermodynamic and/or kinetic effects is an interesting and important question since the cis and trans isomers will have different properties. In many cases it is important to synthesize an isomerically clean product. In, for example, the Heck reaction it is the cis complex that goes into the catalytic cycle (Nilsson, 2005). Beck et al. (2002) have performed DFT (density functional theory) calculations on the structure and stability of some chelate complexes [X(H₃P)Pt(N,O-chelate)], X = Cl or CH₃, which exist in either cis or trans form (N donor with respect to the PH₃ ligand). They concluded that for X = CH₃ the cis isomer has slightly lower total energy than the trans isomer (1 kJ mol⁻¹), while the order is reversed for X = Cl (27 kJ mol⁻¹) in the gas phase and at 0 K. These findings stimulated us to search the Cambridge Structural Database (CSD; 2005 release; Allen, 2002) for one class of compounds, PtX₂L₂ (X is one and the same halogen and L is one and the same neutral ligand), to investigate the distribution of the cis and trans isomers. However, one must be cautious when attempting to derive regularities from such data, since they represent the existing set of crystal structures, and any observed trend may change in the future. In order to investigate the relative stabilities of the isomers we have performed DFT calculations in the gas phase optimizing the geometry of those complexes observed as both cis and trans isomers in the solid state in the CSD.

We have applied the question put forward by Brock & Dunitz (1994) – `Exactly what molecular symmetries are retained in the crystal?' – to trans-PtX₂L₂, with potential C_i symmetry. Most of these complexes have potential C_2h symmetry, but some compounds may also contain stereoisomers not adopting C_i symmetry. We have screened the CSD for the crystal class distribution (Belsky et al., 1995), which contains information about molecular point-group symmetry.

2. Experimental

2.1. Synthesis

trans-PtCl₂(dms)₂ was synthesized by the method of Cox et al. (1934). K₂[PtCl₄] (1.0005 g, 2.4103 mmol) was dissolved in water (20 ml) in an ice-bath. Dimethyl sulfide (0.40 ml, 5.47 mmol) was added and the reaction mixture was stirred for 16 h. The light-yellow precipitate was filtered off and washed with water (3 × 5 ml). The precipitate was dried and then treated with ice-cold chloroform in order to extract PtCl₂(dms)₂. The insoluble part of the precipitate {i.e. [Pt(dms)₄][PtCl₄]} was filtered off and the chloroform was then allowed to evaporate.

The product was recrystallized from acetone. From the mixture of crystals of both cis- and trans-PtCl₂(dms)₂ a yellow monoclinic plate of trans-PtCl₂(dms)₂ was selected.

2.2. X-ray measurements and structure determination

Intensity data were collected on a Siemens Bruker SMART CCD diffractometer equipped with a rotating anode (Mo Kα radiation, wavelength 0.71073 Å) at 295 K using exposure times of 20 s per frame. A total of 2300 frames were collected with ω scans and a frame width of 0.2°. The SMART software (Siemens, 1995) was used for the data collection. Completeness of 99.8% was accomplished out to θ = 30.1°. The first 50 frames were recollected at the end of the data collection to check for decay. No decay was observed.

The intensities were merged and integrated with SAINT-Plus (Siemens, 1998), and the effects of absorption were corrected using SADABS (Sheldrick, 1996). Structure determination was performed with Patterson and difference Fourier methods and refinement by full-matrix least-squares calculations using SHELXL97 (Sheldrick, 1997b). H-atom positions were calculated as riding on the adjacent C atom (methyl group C—H distance 0.96 Å), while non-H atoms were refined anisotropically. Figures of the complex and its packing arrangement were prepared using DIAMOND (Brandenburg, 2000).

Experimental details and crystal data are shown in Table 1.¹

Table 1
Experimental details

Crystal data
Chemical formula	C4H12Cl2PtS2
Mr	390.25
Cell setting, space group	Monoclinic, P21/n
Temperature (K)	295 (2)
a, b, c (Å)	8.4637 (13), 6.0176 (10), 10.1812 (16)
α, β, γ (°)	90.00, 105.747 (3), 90.00
V (Å^3)	499.08 (14)
Z	2
Dx (Mg m^–3)	2.597
Radiation type	Mo Kα
No. of reflections for cell parameters	2881
θ range (°)	2.8–31.8
μ (mm^–1)	14.94
Specimen form, colour	Plate, yellow
Specimen size (mm)	0.28 × 0.12 × 0.06
Data collection
Diffractometer	Bruker SMART CCD
Data collection method	ω scans
Absorption correction	Empirical
Tmin	0.111
Tmax	0.321
No. of measured, independent and observed reflections	5797, 1553, 1018
Criterion for observed reflections	I > 2σ(I)
Rint	0.081
θmax (°)	31.8
Range of h, k, l	−12 → h → 12
	−8 → k → 8
	−14 → l → 14
Refinement
Refinement on	F^2
R[F^2> 2σ(F^2)], wR(F^2), S	0.046, 0.109, 0.96
Reflection/profile data	1553
No. of parameters	43
H-atom treatment	Constrained to parent site
Weighting scheme	w = 1/[σ^2(Fo^2) + (0.060P)^2], where P = (Fo^2 + 2Fc^2)/3
(Δ/σ)max	<0.0001
Δρmax, Δρmin (e Å^–3)	1.78, −2.62
Computer programs used: SMART (Bruker, 1995), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997b), DIAMOND (Brandenburg, 2000).

2.3. High-pressure experiments

High-pressure powder diffraction data were collected at Beamline I711, MAX-lab synchrotron source, Lund, Sweden (Cerenius et al., 2000), using diamond–anvil cell (DAC) techniques [see e.g. Eremets (1996) for a full review]. The beam was monochromated and focused, and finally the spot size on the sample was reduced by the MAR Desktop slit system to 0.1 × 0.1 mm². Calibration of the wavelength (λ = 0.9264 Å) and sample–detector distance (d = 120 mm) was performed using powder diffraction data from LaB₆ powder in a capillary. The software FIT2D (Hammersley, 1997) was used in all data integration and calibration procedures. A Marresearch 165 mm 2000 × 2000 pixels CCD (Marresearch, 2002) was used to collect complete powder diffraction rings from samples, contained in a membrane-driven DAC (DXR-6, Diacel Products).

A well grounded powder sample of trans-PtCl₂(dms)₂ was loaded into the gasket hole (0.15 mm diameter and 0.1 mm deep), together with a small ruby crystal for pressure measurement and the methanol/ethanol (4:1) pressure transmitting medium. Pressure was calibrated by laser-induced fluorescence in the ruby crystal (Piermarini et al., 1975). The pressure dependence of the R1 peak shift, calibrated by Mao et al. (1986), was used to estimate the pressure inside the DAC. The experiments were performed with the DAC mounted on a special stage fitted between the slit system and the CCD of the MAR Desktop. The sample-to-CCD distance was checked by a motorized rotation of the DAC to face a microscope perpendicular to the X-ray beam; this apparatus was used simultaneously for optical inspection and pressure determination by laser-induced ruby fluorescence. Thus, the DAC did not have to be removed from the experimental setup when increasing the pressure, which ensures a good reproducibility in the sample-to-detector distance.

Data were collected at 12 increasing pressures up to 8 GPa and two pressures when decreasing to ambient conditions. No phase transitions were observed, and the unit-cell dimensions appeared to be fully recovered when decreasing from 8 GPa to ambient pressure. Unit-cell dimensions were obtained from the powder diffraction data by using a combination of WinPlotr (Roisnel & Rodriguez-Carvajal, 2001) and TREOR (Werner et al., 1985). Finally, a Le Bail-type peak-fitting procedure (Le Bail et al., 1988) was performed in GSAS (Larson & Von Dreele, 1994) before refining the unit-cell dimensions. Powder diffraction data have been deposited in CIF format. Unit-cell parameters are given in Table 2 and in Figs. 1 and 2.

Table 2
Cell parameters of the title compound at different pressures

Pressure (GPa)	a (Å)	b (Å)	c (Å)	β (°)	Volume (Å^3)
0.0001	8.4860 (6)	6.0353 (6)	10.2175 (8)	105.716 (6)	503.73 (5)
0.1370	8.4061 (5)	6.0034 (5)	10.1606 (6)	105.829 (6)	493.31 (4)
0.4110	8.3155 (9)	5.9607 (8)	10.112 (1)	106.02 (1)	481.8 (1)
0.8490	8.1889 (8)	5.9050 (6)	10.010 (1)	106.349 (8)	464.47 (8)
2.2190	7.963 (1)	5.7915 (8)	9.820 (1)	106.93 (1)	433.3 (1)
3.0410	7.867 (1)	5.7418 (7)	9.735 (1)	107.300 (9)	419.83 (9)
3.5890	7.8065 (7)	5.7061 (4)	9.6871 (7)	107.409 (6)	411.74 (6)
4.2740	7.7447 (7)	5.6735 (5)	9.6219 (7)	107.559 (7)	403.08 (6)
5.3980	7.6626 (7)	5.6223 (4)	9.5448 (7)	107.815 (7)	391.48 (6)
5.8090	7.6343 (8)	5.6073 (4)	9.5122 (7)	107.911 (7)	387.46 (6)
6.3020	7.5999 (7)	5.5911 (4)	9.4814 (7)	107.995 (7)	383.18 (5)
7.1790	7.5511 (7)	5.5626 (4)	9.4311 (7)	108.221 (8)	376.28 (6)
7.4800	7.5316 (7)	5.5530 (4)	9.4148 (8)	108.253 (8)	373.94 (6)
8.0010	7.5335 (8)	5.5545 (4)	9.4126 (9)	108.256 (9)	374.04 (6)

Figure 1 The relative change in unit-cell parameters versus pressure. Open squares, circles and triangles represent the a, b and c axes, respectively. Filled circles represent the β angle. The parameters at ambient pressure which were used for the normalization were a0 = 8.4860 (7), b0 = 6.0353 (6), c0 = 10.2175 (1) Å and β0 = 105.716 (6)°.

Figure 2 The pressure dependence of the unit-cell volume. The solid line represents a fit of the Vinet equation-of-state. The refined parameters V0, K0 and are 503 (2) Å^3, 8.1 (6) GPa and 8.1 (4), respectively.

2.4. DFT calculations

Quantum chemical geometry optimizations were performed with the density functional method at the s-VWN level, as implemented in the Turbomole5.5 software (Alrichs et al., 1989). Two models were used: one with a combination of larger basis sets (6-31g* for the lighter atoms hydrogen, carbon, nitrogen and oxygen, def-TZVPP for platinum, and TZVPP for all other atoms) and another with a combination of smaller basis sets [default in Turbomole 5.5; SV(P) for all atoms but hydrogen and ECP for platinum].

Results are given in Tables 3 and 4.

Table 3
Calculated energy differences for compounds existing as both cis and trans isomers found in the CSD

The first column is based on the larger basis set combination and the second on the smaller basis set combination (see §2).

Compound	Etrans − Ecis (kJ mol^−1)	Etrans − Ecis (kJ mol^−1)
PtCl2(dms)2	−18.1	−19.7
PtCl2(py)2	−41.9	−41.9
PtCl2(MeCN)2	−19.5	−13.2
PtCl2(EtCN)2	−18.0	−10.3
PtCl2(PhCN)2	−16.2	2.4
PtCl2(NH2-cBu)2	−47.3	−46.3
PtCl2(tx)2	−17.2	−11.9
PtCl2(Ph2S)2	−1.3	13.5
PtCl2[S=C(OEt)(NMe2)]2	1.0	3.0
PtCl2(Pr2SO)2	15.8	15.8
PtCl2(PPh3)2	16.5	15.8
PtCl2(AsPh3)2	11.1	11.8

Table 4
Selected bond distances (Å), angles (°) and torsion angles (°) for trans-PtCl₂(dms)₂

`Crystal' is the observed geometry in the solid state, C_2h is the structure optimized by DFT calculations with the larger basis set combination (see §2) using the crystal data as starting parameters and C_i is similar to C_2h but the torsion angles were fixed to those observed in the solid state. No symmetry constraints were used in the calculations.

	Crystal	C2h	Ci
Pt1—Cl1	2.289 (2)	2.300	2.300
Pt1—S1	2.3024 (19)	2.288	2.286
S1—C1	1.799 (10)	1.794	1.792
S1—C2	1.778 (9)	1.794	1.793
Cl1—Pt1—S1	87.54 (8)	88.7	88.2
C2—S1—C1	98.8 (5)	98.7	100.3
C2—S1—Pt1	108.6 (3)	104.3	106.7
C1—S1—Pt1	105.2 (4)	104.8	103.2
Cl1—Pt1—S1—C1	−59.3 (5)	−51.7	−59.3
Cl1—Pt1—S1—C2	45.7 (4)	51.5	45.7

3. Results and discussion

The CSD was searched using the ConQuest software (Bruno et al., 2002) for compounds belonging to the class of mononuclear complexes PtX₂L₂, where X is a halogen and L is a ligand with a donor atom belonging to groups 14, 15 or 16. Simple solvates are included but no chelates are included, and eight structures with no coordinates, obscure connectivity or disorder have been excluded. There are 156 cis complexes and 160 trans complexes (deposited material), which may be regarded as a fairly large data set, indicating that there is no preference for either of the two isomers in the solid state.

The next step in the analysis was to choose compounds in the CSD that are reported as both cis and trans isomers, optimize the geometries with DFT calculations, using the crystallographically observed geometry as the starting geometry, and compare the total energy of the optimized structures in the gas phase. We have found 12 compounds reported as both cis and trans complexes, and their energy differences are given in Table 3. There is no clear-cut cis/trans division; of the 12 complexes the larger basis set combination has eight trans complexes as the favoured complex in the gas phase at 0 K, while the smaller basis set combination favours six trans complexes. The densities for trans- and cis-PtCl₂(MeCN)₂ are equal, while for all the others the trans compound has a larger density, which may indicate that the crystallization process may favour the trans compounds.

The title complex has a pseudo-square-planar geometry, SP-4–1 (Fig. 3), with Pt^II on an inversion centre, thus conforming to the molecular point group C_i, which is the highest allowed for the complex in the space group observed (P2₁/n). Other possible point groups, C_2h, C_2v, C₂ and C_s, do not conform to this space group. Relevant geometrical parameters from the crystal structure determination as well as two geometries in the gas phase optimized by DFT calculations are given in Table 4. There is a very good agreement between observed and calculated (in the gas phase) bond distances and angles (maybe with the exception of the C—S—Pt angles). The Cl—Pt—S—C angles show the largest discrepancies, which is not surprising since packing effects should have a large influence on these angles. The calculated geometry is not only close to C_i but also very close to the highest symmetry possible for the complex, C_2h. There are many energy minima in the conformational space, with energies fairly close to the minimum for the C_2h conformation shown in Table 4. A systematic study of the conformational space with starting parameters obeying C_i was performed changing the Cl—Pt—S—C torsion angles by 10° between each subsequent calculation. One minimum, with Cl—Pt—S—C angles of 10 and 115° for one-half of the molecule, is observed with an energy of only 2.3 kJ  mol⁻¹ above the lowest C_2h minimum. All calculations converged to either the lowest C_2h or to this minimum. In conclusion the observed conformation in the solid state is not at either the anticipated global (C_2h) or the local minimum, but slightly (5–7° for relevant torsion angles) off the global minimum. The energy difference between the lowest C_2h minimum and the observed geometry in the solid state is probably very small; a DFT optimization calculation starting from the crystal structure parameters and keeping the Cl—Pt—S—C torsion angles fixed at the observed value resulted in an energy only 1.7 kJ mol⁻¹ larger than the lowest C_2h minimum (the larger basis set combination was used). It is evidently more advantageous to crystallize in P2₁/n, which allows close packing (Kitaigorodsky, 1973), than in P2/m, which is required for the C_2h point group.

Figure 3 The atomic numbering scheme for trans-PtCl2(dms)2. Displacement ellipsoids are shown at the 30% probability level.

A comparison of the Pt—Cl and Pt—S distances in the two isomers as observed in the crystal structures shows that the Pt—Cl distances are 0.028 (3) Å longer and the Pt—S distances are 0.031 (3) Å shorter in the cis complex (Horn et al., 1990). The differences are probably significant even when taking packing effects into account and show that sulfur has a larger trans influence than chlorine, which has been shown previously by Lövqvist (1996).

The packing of trans-PtCl₂(dms)₂ is shown in Fig. 4. The Pt^II centre forms an I-centred monoclinic unit cell, but the other atoms break the I-centring, thus giving a primitive unit cell. The complexes are stacked along the b axis, with agostic interactions Pt⋯H of 3.08 and 3.31 Å. These rows may be regarded as forming layers in the bc plane, which feature a ring of six methyl groups with soft H⋯H interactions of 2.68 and 2.97 Å. The Pt—Cl bond in the two adjacent layers points slightly off the inversion centre of the ring, with a Cl⋯Cl distance of 4.037 (3) Å. The five close Cl⋯H interactions on each side of a layer are in the range 2.96–3.28 Å. Mulliken analysis of the crystallographically observed geometry and the larger basis set combination resulted in Pt = −0.6, S = 0.4, Cl = −0.2 and CH₃ = 0.04 (the smaller basis-set combination gives Pt = −0.3, S = 0.2, Cl = −0.2 and CH₃ = 0.12). It is thus reasonable to assume that electrostatic interactions contribute to stabilizing the packing arrangement as manifested in the synthon –Cl⋯(CH₃)_n⋯Cl–. Most Pt^II–Cl complexes in the CSD have Cl⋯Cl distances in the interval 3.8–3.9 Å (deposited material), and it is assumed that there are no Cl⋯Cl contacts at ambient pressure.

Figure 4 A stereoview of the packing arrangement of trans-PtCl2(dms)2.

The result of the high-pressure experiments is shown in Table 2 and in Figs. 1 and 2. There is a decrease of cell volume by 26% with no phase transformation when the compound is exposed to pressures of up to 8.0 GPa. One way of describing the compression of a material is to estimate its bulk modulus by fitting an equation-of-state (EOS) to the unit-cell volume data. After first testing the Murnaghan (1937) and Birch–Murnaghan (Birch, 1947) EOS, we found that the EOS of Vinet et al. (1986), derived from cohesive energies in condensed systems, best describes the p–V data. It can be expressed as

where y = V/V₀, and K₀, and V₀ are the bulk modulus, its pressure derivative and the unit-cell volume at ambient pressure, respectively. The parameters K₀, and V₀ were fitted to the unit-cell volume data using the software EOSFIT5.2 (Angel, 2001). The fitted bulk modulus, K₀ = 8.1 (6) GPa, is consistent with highly compressible materials such as mol­ecular crystals. Comparable values are found for other mol­ecular crystalline materials, e.g. lithium- and potassium­cyclo­pentadienide (Dinnebier et al., 2005), for which K₀ was fitted to 8 and 5 GPa, respectively ( = 7 and 11, respectively). The fitted pressure derivative for trans-PtCl₂(dms)₂ is = 8.1 (4) and describes a large curvature in the p–V data. For minerals a value of around 4 is frequently found, but for `softer' materials, such as the cyclopentadienides mentioned above, higher values are common. Other examples are 4-(5-methyl-1,3,4-oxadiazole-2-yl)-N,N′-dimethylphenyl­amine (6.3 GPa and 6.8 for the bulk modulus and its pressure dependence, respectively) and 2,5-diphenyl-1,3,4-oxadiazole (7.3 GPa and 6.8; Franco et al., 2002). The volume decrease in the title compound shows the largest effect on the a axis, i.e. perpendicular to the layers, and about the same for the b and c parameters, i.e. within the layers. This result would be explained if the Cl atoms move towards the ring formed by the methyl groups, thus successively filling the void in the ring. Now the Cl atoms must slide beside each other resulting in the β angle increasing with pressure, which is also observed (Table 2).

trans-PtCl₂(dms)₂ retains the molecular point group C_i rather than the other possibilities, C₁, C_s, C₂, C_2v and C_2h, in the solid state. In order to investigate if the retention of C_i in the solid state is a general feature for trans-PtX₂L₂ complexes, we have investigated the 160 compounds found in the CSD. The structural class (Belsky et al., 1995; Belsky & Zorkii, 1977) distribution for these compounds (deposited material) shows that the molecular symmetry C_i is retained in 78% of the structures (compared with 99% for structures in general in the CSD; Pidcock et al., 2003), followed by C₁ (16%), C₂ (4%) and C_2h (2%). More than 60% of the complexes have potential C_2h molecular symmetry, but this symmetry is retained in only 2% of cases. Molecular symmetry C_2h requires platinum in crystallographic point symmetry 2/m, which is found in space groups that hamper close packing (Kitaigorodsky, 1973). Inversion centres thus seem to be especially favourable for crystal packing, as is also proposed by Brock & Dunitz (1994).

In conclusion, there is no preference in frequency of either cis or trans isomers of PtX₂L₂ compounds in the CSD (2005 release). The molecular point group C_i is retained in the crystal for 78% of reported trans-PtX₂L₂ complexes, followed by C₁ with 16%. The high-pressure investigation shows that the unit-cell volume is decreased by 26% up to 8.0 GPa without any phase transition.

Supporting information

Computing details

Data collection: SMART (Bruker, 1995) for trans-PtCl2dms2; MAR CCD for tptcl2dms2_0.000GPa_publ, tptcl2dms2_0.137GPa_publ, tptcl2dms2_0.411GPa_publ, tptcl2dms2_0.849GPa_publ, tptcl2dms2_2.219GPa_publ, tptcl2dms2_3.041GPa_publ, tptcl2dms2_3.589GPa_publ, tptcl2dms2_4.274GPa_publ, tptcl2dms2_5.398GPa_publ, tptcl2dms2_5.809GPa_publ, tptcl2dms2_6.302GPa_publ, tptcl2dms2_7.179GPa_publ, tptcl2dms2_7.480GPa_publ, tptcl2dms2_8.001GPa_publ. Cell refinement: SAINT-Plus (Bruker, 1998) for trans-PtCl2dms2. Data reduction: SAINT-Plus (Bruker, 1998) for trans-PtCl2dms2; Fit2D for tptcl2dms2_0.000GPa_publ, tptcl2dms2_0.137GPa_publ, tptcl2dms2_0.411GPa_publ, tptcl2dms2_0.849GPa_publ, tptcl2dms2_2.219GPa_publ, tptcl2dms2_3.041GPa_publ, tptcl2dms2_3.589GPa_publ, tptcl2dms2_4.274GPa_publ, tptcl2dms2_5.398GPa_publ, tptcl2dms2_5.809GPa_publ, tptcl2dms2_6.302GPa_publ, tptcl2dms2_7.179GPa_publ, tptcl2dms2_7.480GPa_publ, tptcl2dms2_8.001GPa_publ. Program(s) used to solve structure: SHELXS ver 5.10 (Sheldrick, 1997) for trans-PtCl2dms2. Program(s) used to refine structure: SHELXL ver 5.10 (Sheldrick, 1997) for trans-PtCl2dms2; GSAS for tptcl2dms2_0.000GPa_publ, tptcl2dms2_0.137GPa_publ, tptcl2dms2_0.411GPa_publ, tptcl2dms2_0.849GPa_publ, tptcl2dms2_2.219GPa_publ, tptcl2dms2_3.041GPa_publ, tptcl2dms2_3.589GPa_publ, tptcl2dms2_4.274GPa_publ, tptcl2dms2_5.398GPa_publ, tptcl2dms2_5.809GPa_publ, tptcl2dms2_6.302GPa_publ, tptcl2dms2_7.179GPa_publ, tptcl2dms2_7.480GPa_publ, tptcl2dms2_8.001GPa_publ. Molecular graphics: DIAMOND (Brandenburg, 2000) for trans-PtCl2dms2.

Figures

(trans-PtCl2dms2) trans-dichlorodi(dimethylsulfide)platinum(II)

Crystal data

C4H12Cl2PtS2	F(000) = 360
Mr = 390.25	Dx = 2.597 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.4637 (13) Å	Cell parameters from 2881 reflections
b = 6.0176 (10) Å	θ = 2.8–31.8°
c = 10.1812 (16) Å	µ = 14.94 mm^−1
β = 105.747 (3)°	T = 295 K
V = 499.08 (14) Å^3	Plate, yellow
Z = 2	0.28 × 0.12 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer	1553 independent reflections
Radiation source: Rotating anode	1018 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
ω–scans	θmax = 31.8°, θmin = 2.8°
Absorption correction: empirical SADABS (Sheldrick, 1996)	h = −12→12
Tmin = 0.111, Tmax = 0.321	k = −8→8
5797 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.060P)^2] where P = (Fo^2 + 2Fc^2)/3
1553 reflections	(Δ/σ)max < 0.001
43 parameters	Δρmax = 1.78 e Å^−3
0 restraints	Δρmin = −2.62 e Å^−3

Special details

Experimental. DFT calculations were performed using the SVWN method and the basis sets def-TZVPP; ecp: def-ecp for platinum atoms, TZVPP for chlorine-, phosphorus- and sulfur atoms, and 6–31g* for carbon-, hydrogen- and nitrogen atoms.

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 (Ų)

	x	y	z	Uiso*/Ueq
Pt1	0.0000	0.0000	0.0000	0.03065 (15)
S1	0.0931 (3)	0.1946 (3)	0.20090 (19)	0.0383 (4)
Cl1	0.2561 (3)	0.0429 (4)	−0.0311 (3)	0.0474 (5)
C2	0.0294 (15)	0.0530 (14)	0.3311 (10)	0.049 (2)
H2A	0.0916	−0.0815	0.3547	0.074*
H2B	−0.0852	0.0176	0.2988	0.074*
H2C	0.0474	0.1465	0.4102	0.074*
C1	−0.0389 (17)	0.4335 (16)	0.1828 (10)	0.062 (3)
H1A	−0.0192	0.5302	0.1139	0.093*
H1B	−0.0164	0.5115	0.2681	0.093*
H1C	−0.1514	0.3862	0.1567	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.0341 (2)	0.0336 (2)	0.0264 (2)	0.00096 (18)	0.01192 (15)	0.00056 (17)
S1	0.0429 (11)	0.0435 (10)	0.0303 (9)	−0.0012 (9)	0.0132 (7)	−0.0040 (8)
Cl1	0.0384 (11)	0.0656 (14)	0.0431 (12)	−0.0050 (9)	0.0196 (9)	−0.0057 (9)
C2	0.075 (7)	0.046 (5)	0.030 (4)	0.004 (4)	0.021 (4)	0.009 (3)
C1	0.099 (10)	0.044 (4)	0.043 (6)	0.023 (6)	0.020 (6)	−0.003 (4)

Geometric parameters (Å, º)

Pt1—Cl1	2.289 (2)	C2—H2A	0.9600
Pt1—Cl1^i	2.289 (2)	C2—H2B	0.9600
Pt1—S1	2.3024 (19)	C2—H2C	0.9600
Pt1—S1^i	2.3024 (19)	C1—H1A	0.9600
S1—C2	1.778 (9)	C1—H1B	0.9600
S1—C1	1.799 (10)	C1—H1C	0.9600
Cl1—Pt1—Cl1^i	180.00 (11)	H2A—C2—H2B	109.5
Cl1—Pt1—S1	87.54 (8)	S1—C2—H2C	109.5
Cl1^i—Pt1—S1	92.46 (8)	H2A—C2—H2C	109.5
Cl1—Pt1—S1^i	92.46 (8)	H2B—C2—H2C	109.5
Cl1^i—Pt1—S1^i	87.54 (8)	S1—C1—H1A	109.5
S1—Pt1—S1^i	180.0	S1—C1—H1B	109.5
C2—S1—C1	98.8 (5)	H1A—C1—H1B	109.5
C2—S1—Pt1	108.6 (3)	S1—C1—H1C	109.5
C1—S1—Pt1	105.2 (4)	H1A—C1—H1C	109.5
S1—C2—H2A	109.5	H1B—C1—H1C	109.5
S1—C2—H2B	109.5

Symmetry code: (i) −x, −y, −z.

(tptcl2dms2_0.000GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 503.73 (5) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 10.2175 (8) Å	T = 295 K
b = 6.0353 (6) Å	Yellow
c = 8.4860 (7) Å	cylinder, 0.3 × 0.3 mm
β = 105.716 (6)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 24.053 #4(LX) = 0.487 #5(LY) = 56.657 #6(trns) = 0.000 #7(asym) = -0.0241 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.015	5 parameters
Rwp = 0.025	0 restraints
Rexp = 0.008	(Δ/σ)max = 0.04
χ^2 = 10.433	Background function: GSAS Background function number 1 with 12 terms. Shifted Chebyshev function of 1st kind 1: 14914.7 2: -4489.36 3: 1998.02 4: -1301.99 5: -184.871 6: 391.248 7: -476.595 8: 134.606 9: 101.756 10: -103.360 11: 243.570 12: -11.4511
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_0.137GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 493.40 (7) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 8.4070 (6) Å	T = 295 K
b = 6.0038 (5) Å	Yellow
c = 10.1607 (9) Å	cylinder, 0.3 × 0.3 mm
β = 105.829 (7)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 23.330 #4(LX) = 4.199 #5(LY) = 17.907 #6(trns) = 0.000 #7(asym) = 0.0558 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.014	9 parameters
Rwp = 0.023	0 restraints
Rexp = 0.007	(Δ/σ)max = 0.12
χ^2 = 9.986	Background function: GSAS Background function number 1 with 14 terms. Shifted Chebyshev function of 1st kind 1: 17544.3 2: -1723.37 3: 3594.87 4: -1070.73 5: -882.421 6: 72.8259 7: -815.020 8: 417.042 9: 266.055 10: -207.867 11: 290.725 12: -123.815 13: 146.183 14: 0.923252
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_0.411GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 481.76 (10) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 8.3155 (9) Å	T = 295 K
b = 5.9607 (8) Å	Yellow
c = 10.1123 (13) Å	cylinder, 0.3 × 0.3 mm
β = 106.021 (11)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 15.399 #4(LX) = 7.895 #5(LY) = 10.692 #6(trns) = 0.000 #7(asym) = 0.0880 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.019	9 parameters
Rwp = 0.033	0 restraints
Rexp = 0.007	(Δ/σ)max = 0.07
χ^2 = 21.437	Background function: GSAS Background function number 1 with 14 terms. Shifted Chebyshev function of 1st kind 1: 17544.3 2: -1723.37 3: 3594.87 4: -1070.73 5: -882.421 6: 72.8259 7: -815.020 8: 417.042 9: 266.055 10: -207.867 11: 290.725 12: -123.815 13: 146.183 14: 0.923252
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_0.849GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 464.47 (9) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	? radiation, λ = 0.9249 Å
a = 8.1889 (8) Å	T = 295 K
b = 5.9050 (6) Å	Yellow
c = 10.0100 (11) Å	cylinder, 0.3 × 0.3 mm
β = 106.349 (8)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 14.252 #4(LX) = 3.577 #5(LY) = 42.720 #6(trns) = 0.000 #7(asym) = -0.2305 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.020	9 parameters
Rwp = 0.029	0 restraints
Rexp = 0.008	(Δ/σ)max = 0.24
χ^2 = 14.213	Background function: GSAS Background function number 1 with 12 terms. Shifted Chebyshev function of 1st kind 1: 14702.2 2: -801.697 3: 3033.11 4: -769.432 5: -814.527 6: 65.9191 7: -760.341 8: 398.713 9: 232.968 10: -208.985 11: 365.053 12: -108.993
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_2.219GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 433.28 (10) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.9633 (13) Å	T = 295 K
b = 5.7915 (8) Å	Yellow
c = 9.8203 (12) Å	cylinder, 0.3 × 0.3 mm
β = 106.933 (10)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 22.272 #4(LX) = 1.268 #5(LY) = 54.449 #6(trns) = 0.000 #7(asym) = -0.0107 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.023	9 parameters
Rwp = 0.035	0 restraints
Rexp = 0.008	(Δ/σ)max = 0.07
χ^2 = 22.468	Background function: GSAS Background function number 1 with 14 terms. Shifted Chebyshev function of 1st kind 1: 16323.8 2: -1179.26 3: 3230.77 4: -835.427 5: -520.062 6: -239.890 7: -684.504 8: 433.192 9: 239.561 10: -183.214 11: 133.121 12: -298.543 13: 184.337 14: 74.8771
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_3.041GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 419.83 (9) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.8667 (12) Å	T = 295 K
b = 5.7418 (7) Å	Yellow
c = 9.7349 (11) Å	cylinder, 0.3 × 0.3 mm
β = 107.299 (9)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 21.987 #4(LX) = 2.301 #5(LY) = 49.132 #6(trns) = 0.000 #7(asym) = -0.1328 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.021	9 parameters
Rwp = 0.034	0 restraints
Rexp = 0.008	(Δ/σ)max = 0.06
χ^2 = 19.981	Background function: GSAS Background function number 1 with 10 terms. Shifted Chebyshev function of 1st kind 1: 15919.1 2: -813.040 3: 3165.85 4: -910.777 5: -552.463 6: -27.2954 7: -689.474 8: 166.274 9: 237.419 10: -160.846
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_3.589GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 411.74 (5) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.8065 (7) Å	T = 295 K
b = 5.7061 (4) Å	Yellow
c = 9.6871 (7) Å	cylinder, 0.3 × 0.3 mm
β = 107.409 (6)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 25.814 #4(LX) = 4.707 #5(LY) = 21.572 #6(trns) = 0.000 #7(asym) = 0.0246 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.013	9 parameters
Rwp = 0.021	0 restraints
Rexp = 0.007	(Δ/σ)max = 0.06
χ^2 = 9.610	Background function: GSAS Background function number 1 with 10 terms. Shifted Chebyshev function of 1st kind 1: 19104.8 2: -1183.62 3: 3807.35 4: -1198.99 5: -644.656 6: 35.5141 7: -756.546 8: 393.985 9: 348.089 10: -264.405
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_4.274GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 403.08 (6) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.7447 (7) Å	T = 295 K
b = 5.6735 (5) Å	Yellow
c = 9.6219 (7) Å	cylinder, 0.3 × 0.3 mm
β = 107.559 (7)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 25.503 #4(LX) = 5.080 #5(LY) = 20.012 #6(trns) = 0.000 #7(asym) = 0.0382 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.014	9 parameters
Rwp = 0.022	0 restraints
Rexp = 0.007	(Δ/σ)max = 0.06
χ^2 = 10.176	Background function: GSAS Background function number 1 with 10 terms. Shifted Chebyshev function of 1st kind 1: 18695.6 2: -936.709 3: 3634.68 4: -1186.61 5: -530.824 6: -2.11428 7: -737.818 8: 354.038 9: 317.528 10: -249.133
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_5.398GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 391.48 (5) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.6626 (7) Å	T = 295 K
b = 5.6223 (4) Å	Yellow
c = 9.5448 (7) Å	cylinder, 0.3 × 0.3 mm
β = 107.815 (7)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 24.891 #4(LX) = 4.098 #5(LY) = 34.644 #6(trns) = 0.000 #7(asym) = 0.0595 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.013	9 parameters
Rwp = 0.020	0 restraints
Rexp = 0.007	(Δ/σ)max = 0.05
χ^2 = 9.486	Background function: GSAS Background function number 1 with 10 terms. Shifted Chebyshev function of 1st kind 1: 21383.8 2: -846.217 3: 3860.94 4: -1378.03 5: -455.919 6: 175.649 7: -722.233 8: 591.181 9: 466.361 10: -394.047
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_5.809GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 387.46 (6) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.6343 (8) Å	T = 295 K
b = 5.6073 (4) Å	Yellow
c = 9.5122 (7) Å	cylinder, 0.3 × 0.3 mm
β = 107.911 (7)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 29.610 #4(LX) = 3.214 #5(LY) = 43.460 #6(trns) = 0.000 #7(asym) = -0.0803 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.012	9 parameters
Rwp = 0.019	0 restraints
Rexp = 0.006	(Δ/σ)max = 0.08
χ^2 = 9.120	Background function: GSAS Background function number 1 with 14 terms. Shifted Chebyshev function of 1st kind 1: 22761.4 2: -777.612 3: 4108.43 4: -1587.94 5: -695.207 6: 75.6433 7: -824.620 8: 536.946 9: 487.648 10: -266.760 11: 327.023 12: 39.5019 13: 374.400 14: 222.108
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_6.302GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 383.18 (5) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.5999 (7) Å	T = 295 K
b = 5.5911 (4) Å	Yellow
c = 9.4814 (7) Å	cylinder, 0.3 × 0.3 mm
β = 107.995 (7)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 26.913 #4(LX) = 3.275 #5(LY) = 52.810 #6(trns) = 0.000 #7(asym) = -0.2437 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.011	9 parameters
Rwp = 0.017	0 restraints
Rexp = 0.006	(Δ/σ)max = 0.06
χ^2 = 7.236	Background function: GSAS Background function number 1 with 10 terms. Shifted Chebyshev function of 1st kind 1: 23304.8 2: -907.157 3: 4089.03 4: -1772.91 5: -594.810 6: -22.0385 7: -882.801 8: 285.606 9: 403.010 10: -356.673
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_7.179GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 376.28 (5) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.5511 (7) Å	T = 295 K
b = 5.5626 (4) Å	Yellow
c = 9.4311 (7) Å	cylinder, 0.3 × 0.3 mm
β = 108.221 (8)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 33.250 #4(LX) = 4.192 #5(LY) = 59.953 #6(trns) = 0.000 #7(asym) = 0.1116 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.009	9 parameters
Rwp = 0.014	0 restraints
Rexp = 0.006	(Δ/σ)max = 0.08
χ^2 = 4.973	Background function: GSAS Background function number 1 with 10 terms. Shifted Chebyshev function of 1st kind 1: 22977.7 2: -820.928 3: 3784.06 4: -1768.46 5: -549.023 6: 7.12432 7: -703.674 8: 431.695 9: 479.986 10: -322.118
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_7.480GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 373.94 (6) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.5316 (7) Å	T = 295 K
b = 5.5530 (4) Å	Yellow
c = 9.4148 (8) Å	cylinder, 0.3 × 0.3 mm
β = 108.253 (8)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 39.954 #4(LX) = 1.913 #5(LY) = 80.740 #6(trns) = 0.000 #7(asym) = 0.2152 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.009	9 parameters
Rwp = 0.013	0 restraints
Rexp = 0.006	(Δ/σ)max = 0.08
χ^2 = 4.162	Background function: GSAS Background function number 1 with 10 terms. Shifted Chebyshev function of 1st kind 1: 22401.3 2: -720.024 3: 3582.51 4: -1760.75 5: -700.758 6: 102.978 7: -902.042 8: 299.650 9: 317.562 10: -317.216
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

(tptcl2dms2_8.001GPa_publ) trans-bis(dimethyl sulfide)platinum dichloride.

Crystal data

C4H12Cl2PtS2	V = 374.05 (6) Å^3
Mr = 390.25	Z = 2
Monoclinic, P21/n	Synchrotron radiation, λ = 0.9249 Å
a = 7.5335 (8) Å	T = 295 K
b = 5.5545 (4) Å	Yellow
c = 9.4126 (9) Å	cylinder, 0.3 × 0.3 mm
β = 108.256 (9)°	Specimen preparation: Prepared at 295 K

Data collection

MAR Desktop Beamline diffractometer	Specimen mounting: diamond-anvil cell
Radiation source: Synchrotron, MAX-lab bemline I711	Data collection mode: transmission
Si 111 monochromator	Scan method: Stationary detector

Refinement

Least-squares matrix: full	Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 32.510 #4(LX) = 4.215 #5(LY) = 74.050 #6(trns) = 0.000 #7(asym) = 0.1757 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 0.00 #11(ptec)= 0.00 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0040 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.011	9 parameters
Rwp = 0.015	0 restraints
Rexp = 0.006	(Δ/σ)max = 0.08
χ^2 = 5.712	Background function: GSAS Background function number 1 with 10 terms. Shifted Chebyshev function of 1st kind 1: 22926.2 2: -573.762 3: 3936.17 4: -1756.64 5: -589.832 6: 17.5958 7: -634.628 8: 250.588 9: 507.526 10: -322.147
1453 data points

Special details

Experimental. High-pressure measurement at ambient pressure in diamond-anvil cell

Refinement. Profile refinement, Lebail type, was performed to obtain unit-cell dimensions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
PT1	0.1	0.2	0.3	0.025*

 

Footnotes

‡Current address: MAX-laboratory, Box 118, SE-221 00 Lund, Sweden.

§Current address: Solid State Analysis, AstraZeneca R&D Mölndal, SE-431 83 Mölndal, Sweden.

¶On leave from Zhongshan University, Guangzhou, People's Republic of China.

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: RY5001 ). Services for accessing these data are described at the back of the journal.