Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010100960X/gd1157sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010100960X/gd1157Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010100960X/gd1157IIsup3.hkl |
CCDC references: 173358; 173359
[PtCl2(SPh2)2] was prepared according to Tayim & Bailar (1967). To prepare the cis compound, [PtCl2(SPh2)2] (0.2 g, 3.13 mmol) was dissolved in 10 ml of benzene to give a clear solution. Ph3SnH (0.109 g, 3.195 mmol) dissolved in 2 ml benzene was added and the reaction mixture was left stirring overnight and then filtered. Benzene was removed to give a brown solid which was dissolved in CH2Cl2/benzene and MeOH. A dirty white solid was removed by filtration and yellow crystals were obtained from the filtrate. The trans compound was prepared by adding SnCl2 (0.04 g, 2.35 mmol) to a 10 ml acetone solution of [PtCl2(SPh2)2] (0.15 g, 2.35 mmol). The clear solution became dark and was left over night. The solution was filtered and dark orange crystals were obtained by slow evaporation.
For both compounds, data collection: SMART (Bruker, 1995); cell refinement: SAINT (Bruker, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Diamond (Brandenburg, 2000); software used to prepare material for publication: SHELXL97.
[PtCl2(C12H10S)2] | Dx = 1.814 Mg m−3 |
Mr = 638.51 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 5997 reflections |
a = 10.281 (2) Å | θ = 2–29° |
b = 17.244 (3) Å | µ = 6.42 mm−1 |
c = 26.382 (5) Å | T = 293 K |
V = 4676.9 (16) Å3 | Plate, yellow |
Z = 8 | 0.15 × 0.13 × 0.03 mm |
F(000) = 2464 |
Bruker SMART CCD diffractometer | 5802 independent reflections |
Radiation source: rotating anode | 4144 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
Detector resolution: 512 pixels mm-1 | θmax = 28.3°, θmin = 1.5° |
ω scans | h = −12→13 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −22→22 |
Tmin = 0.446, Tmax = 0.831 | l = −33→35 |
32399 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0309P)2 + 15.350P] where P = (Fo2 + 2Fc2)/3 |
5802 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 1.71 e Å−3 |
0 restraints | Δρmin = −1.08 e Å−3 |
[PtCl2(C12H10S)2] | V = 4676.9 (16) Å3 |
Mr = 638.51 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.281 (2) Å | µ = 6.42 mm−1 |
b = 17.244 (3) Å | T = 293 K |
c = 26.382 (5) Å | 0.15 × 0.13 × 0.03 mm |
Bruker SMART CCD diffractometer | 5802 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 4144 reflections with I > 2σ(I) |
Tmin = 0.446, Tmax = 0.831 | Rint = 0.064 |
32399 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0309P)2 + 15.350P] where P = (Fo2 + 2Fc2)/3 |
5802 reflections | Δρmax = 1.71 e Å−3 |
262 parameters | Δρmin = −1.08 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Pt1 | 0.54809 (2) | 0.041713 (16) | 0.109699 (10) | 0.04797 (10) | |
Cl1 | 0.5181 (2) | 0.17423 (12) | 0.11908 (9) | 0.0739 (6) | |
Cl2 | 0.32932 (18) | 0.02004 (14) | 0.11951 (9) | 0.0756 (6) | |
S1 | 0.59436 (17) | −0.08727 (10) | 0.10366 (7) | 0.0534 (4) | |
S2 | 0.75958 (17) | 0.07588 (10) | 0.09557 (6) | 0.0485 (4) | |
C111 | 0.4601 (6) | −0.1448 (4) | 0.0828 (3) | 0.0495 (15) | |
C112 | 0.3836 (7) | −0.1871 (5) | 0.1149 (3) | 0.068 (2) | |
H112 | 0.3948 | −0.1835 | 0.1498 | 0.082* | |
C113 | 0.2889 (8) | −0.2354 (5) | 0.0947 (3) | 0.074 (2) | |
H113 | 0.2388 | −0.2659 | 0.1162 | 0.088* | |
C114 | 0.2685 (8) | −0.2389 (5) | 0.0444 (4) | 0.072 (2) | |
H114 | 0.2027 | −0.2702 | 0.0314 | 0.086* | |
C115 | 0.3445 (10) | −0.1966 (5) | 0.0125 (3) | 0.078 (3) | |
H115 | 0.3312 | −0.2000 | −0.0222 | 0.093* | |
C116 | 0.4414 (9) | −0.1484 (5) | 0.0310 (3) | 0.069 (2) | |
H116 | 0.4926 | −0.1192 | 0.0091 | 0.083* | |
C121 | 0.6213 (7) | −0.1204 (4) | 0.1669 (3) | 0.062 (2) | |
C122 | 0.7171 (8) | −0.1764 (5) | 0.1723 (4) | 0.086 (3) | |
H122 | 0.7636 | −0.1946 | 0.1445 | 0.103* | |
C123 | 0.7407 (13) | −0.2040 (8) | 0.2200 (7) | 0.134 (6) | |
H123 | 0.8041 | −0.2418 | 0.2245 | 0.161* | |
C124 | 0.6734 (17) | −0.1776 (9) | 0.2614 (5) | 0.140 (6) | |
H124 | 0.6917 | −0.1967 | 0.2936 | 0.168* | |
C125 | 0.5794 (14) | −0.1227 (8) | 0.2546 (5) | 0.118 (4) | |
H125 | 0.5339 | −0.1044 | 0.2826 | 0.142* | |
C126 | 0.5498 (10) | −0.0935 (6) | 0.2068 (3) | 0.082 (3) | |
H126 | 0.4841 | −0.0571 | 0.2022 | 0.098* | |
C211 | 0.8472 (6) | −0.0029 (4) | 0.0681 (3) | 0.0445 (14) | |
C212 | 0.8198 (7) | −0.0183 (4) | 0.0183 (3) | 0.0559 (17) | |
H212 | 0.7604 | 0.0123 | 0.0007 | 0.067* | |
C213 | 0.8803 (8) | −0.0789 (5) | −0.0056 (3) | 0.070 (2) | |
H213 | 0.8608 | −0.0901 | −0.0392 | 0.083* | |
C214 | 0.9695 (8) | −0.1232 (5) | 0.0199 (4) | 0.077 (3) | |
H214 | 1.0117 | −0.1636 | 0.0034 | 0.093* | |
C215 | 0.9961 (8) | −0.1077 (5) | 0.0694 (4) | 0.076 (2) | |
H215 | 1.0563 | −0.1382 | 0.0866 | 0.091* | |
C216 | 0.9350 (7) | −0.0472 (4) | 0.0948 (3) | 0.064 (2) | |
H216 | 0.9528 | −0.0369 | 0.1287 | 0.077* | |
C221 | 0.8409 (6) | 0.0916 (4) | 0.1540 (2) | 0.0492 (15) | |
C222 | 0.9590 (8) | 0.1300 (5) | 0.1523 (3) | 0.074 (2) | |
H222 | 0.9930 | 0.1462 | 0.1214 | 0.089* | |
C223 | 1.0253 (9) | 0.1439 (6) | 0.1962 (4) | 0.090 (3) | |
H223 | 1.1062 | 0.1680 | 0.1953 | 0.108* | |
C224 | 0.9724 (10) | 0.1222 (5) | 0.2416 (4) | 0.084 (3) | |
H224 | 1.0167 | 0.1331 | 0.2715 | 0.100* | |
C225 | 0.8560 (9) | 0.0851 (6) | 0.2436 (3) | 0.079 (2) | |
H225 | 0.8209 | 0.0709 | 0.2747 | 0.094* | |
C226 | 0.7896 (7) | 0.0684 (5) | 0.1992 (3) | 0.0626 (19) | |
H226 | 0.7110 | 0.0418 | 0.2003 | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.04323 (14) | 0.05905 (16) | 0.04163 (15) | 0.01396 (11) | −0.00095 (11) | 0.00426 (12) |
Cl1 | 0.0760 (13) | 0.0656 (12) | 0.0800 (14) | 0.0296 (10) | 0.0047 (10) | 0.0033 (10) |
Cl2 | 0.0427 (9) | 0.1050 (16) | 0.0791 (14) | 0.0149 (10) | −0.0016 (9) | −0.0104 (12) |
S1 | 0.0427 (8) | 0.0555 (10) | 0.0621 (11) | 0.0029 (7) | 0.0060 (8) | 0.0043 (9) |
S2 | 0.0501 (9) | 0.0500 (9) | 0.0453 (9) | 0.0078 (7) | 0.0011 (7) | 0.0056 (7) |
C111 | 0.050 (4) | 0.053 (4) | 0.046 (4) | 0.010 (3) | 0.000 (3) | −0.002 (3) |
C112 | 0.053 (4) | 0.096 (6) | 0.056 (5) | −0.005 (4) | 0.008 (4) | −0.002 (4) |
C113 | 0.056 (5) | 0.092 (6) | 0.073 (6) | −0.014 (4) | 0.000 (4) | 0.000 (5) |
C114 | 0.061 (5) | 0.068 (5) | 0.086 (6) | 0.011 (4) | −0.021 (5) | −0.011 (5) |
C115 | 0.101 (7) | 0.075 (5) | 0.058 (5) | 0.017 (5) | −0.027 (5) | −0.008 (4) |
C116 | 0.089 (6) | 0.060 (5) | 0.058 (5) | 0.010 (4) | −0.002 (4) | 0.007 (4) |
C121 | 0.049 (4) | 0.061 (4) | 0.077 (5) | −0.011 (3) | −0.019 (4) | 0.017 (4) |
C122 | 0.062 (5) | 0.071 (5) | 0.124 (8) | 0.003 (4) | −0.025 (5) | 0.019 (6) |
C123 | 0.106 (9) | 0.121 (10) | 0.176 (14) | −0.013 (8) | −0.077 (10) | 0.073 (11) |
C124 | 0.164 (15) | 0.151 (13) | 0.104 (10) | −0.042 (11) | −0.079 (10) | 0.064 (10) |
C125 | 0.147 (11) | 0.132 (10) | 0.076 (7) | −0.033 (9) | −0.026 (7) | 0.025 (7) |
C126 | 0.093 (6) | 0.093 (6) | 0.060 (5) | −0.009 (5) | −0.008 (5) | 0.016 (5) |
C211 | 0.041 (3) | 0.043 (3) | 0.050 (4) | 0.001 (3) | 0.006 (3) | 0.004 (3) |
C212 | 0.048 (4) | 0.064 (4) | 0.055 (4) | −0.008 (3) | 0.001 (3) | −0.003 (3) |
C213 | 0.064 (5) | 0.077 (5) | 0.068 (5) | −0.011 (4) | 0.015 (4) | −0.018 (4) |
C214 | 0.068 (5) | 0.058 (5) | 0.106 (8) | −0.004 (4) | 0.018 (5) | −0.025 (5) |
C215 | 0.062 (5) | 0.068 (5) | 0.098 (7) | 0.018 (4) | −0.003 (5) | 0.002 (5) |
C216 | 0.062 (5) | 0.063 (4) | 0.067 (5) | 0.014 (4) | 0.002 (4) | 0.009 (4) |
C221 | 0.050 (4) | 0.055 (4) | 0.043 (4) | 0.010 (3) | −0.003 (3) | 0.001 (3) |
C222 | 0.078 (5) | 0.091 (6) | 0.053 (5) | −0.012 (5) | −0.004 (4) | −0.002 (4) |
C223 | 0.076 (6) | 0.114 (8) | 0.081 (7) | −0.026 (6) | −0.011 (5) | −0.005 (6) |
C224 | 0.091 (7) | 0.091 (6) | 0.069 (6) | 0.014 (6) | −0.025 (5) | −0.015 (5) |
C225 | 0.084 (6) | 0.105 (7) | 0.047 (5) | 0.024 (6) | 0.000 (4) | 0.006 (5) |
C226 | 0.055 (4) | 0.082 (5) | 0.051 (4) | 0.004 (4) | −0.001 (3) | 0.003 (4) |
Pt1—S1 | 2.2801 (19) | C221—C226 | 1.364 (10) |
Pt1—S2 | 2.2832 (18) | C221—C222 | 1.383 (10) |
Pt1—Cl1 | 2.319 (2) | C222—C223 | 1.367 (12) |
Pt1—Cl2 | 2.295 (2) | C223—C224 | 1.366 (13) |
S1—C111 | 1.787 (7) | C224—C225 | 1.358 (13) |
S1—C121 | 1.785 (8) | C225—C226 | 1.385 (11) |
S2—C211 | 1.785 (6) | C112—H112 | 0.93 |
S2—C221 | 1.776 (7) | C113—H113 | 0.93 |
C111—C112 | 1.368 (10) | C114—H114 | 0.93 |
C111—C116 | 1.379 (10) | C115—H115 | 0.93 |
C112—C113 | 1.389 (11) | C116—H116 | 0.93 |
C113—C114 | 1.345 (12) | C122—H122 | 0.93 |
C114—C115 | 1.360 (12) | C123—H123 | 0.93 |
C115—C116 | 1.385 (12) | C124—H124 | 0.93 |
C121—C126 | 1.364 (12) | C125—H125 | 0.93 |
C121—C122 | 1.387 (11) | C126—H126 | 0.93 |
C122—C123 | 1.366 (16) | C212—H212 | 0.93 |
C123—C124 | 1.37 (2) | C213—H213 | 0.93 |
C124—C125 | 1.364 (19) | C214—H214 | 0.93 |
C125—C126 | 1.393 (14) | C215—H215 | 0.93 |
C211—C212 | 1.370 (9) | C216—H216 | 0.93 |
C211—C216 | 1.376 (10) | C222—H222 | 0.93 |
C212—C213 | 1.370 (10) | C223—H223 | 0.93 |
C213—C214 | 1.370 (12) | C224—H224 | 0.93 |
C214—C215 | 1.360 (13) | C225—H225 | 0.93 |
C215—C216 | 1.391 (11) | C226—H226 | 0.93 |
S1—Pt1—S2 | 92.39 (6) | C224—C225—C226 | 119.9 (8) |
S1—Pt1—Cl1 | 175.16 (7) | C221—C226—C225 | 119.1 (8) |
S1—Pt1—Cl2 | 93.06 (7) | C111—C112—H112 | 120.51 |
S2—Pt1—Cl1 | 83.68 (7) | C113—C112—H112 | 120.51 |
S2—Pt1—Cl2 | 173.62 (7) | C112—C113—H113 | 119.47 |
Cl1—Pt1—Cl2 | 91.03 (8) | C114—C113—H113 | 119.47 |
Pt1—S1—C111 | 113.7 (2) | C113—C114—H114 | 120.15 |
Pt1—S1—C121 | 106.2 (3) | C115—C114—H114 | 120.15 |
Pt1—S2—C211 | 110.5 (2) | C114—C115—H115 | 119.41 |
Pt1—S2—C221 | 110.3 (2) | C116—C115—H115 | 119.41 |
C111—S1—C121 | 103.3 (3) | C115—C116—H116 | 120.81 |
C211—S2—C221 | 103.4 (3) | C111—C116—H116 | 120.81 |
C112—C111—C116 | 120.6 (7) | C121—C122—H122 | 121.22 |
S1—C111—C112 | 123.3 (6) | C123—C122—H122 | 121.22 |
S1—C111—C116 | 116.0 (6) | C122—C123—H123 | 119.04 |
C111—C112—C113 | 119.0 (8) | C124—C123—H123 | 119.04 |
C114—C113—C112 | 121.1 (8) | C123—C124—H124 | 120.56 |
C113—C114—C115 | 119.7 (8) | C125—C124—H124 | 120.56 |
C114—C115—C116 | 121.2 (8) | C124—C125—H125 | 119.17 |
C111—C116—C115 | 118.4 (8) | C126—C125—H125 | 119.17 |
C126—C121—C122 | 122.7 (9) | C125—C126—H126 | 121.39 |
S1—C121—C122 | 115.4 (8) | C121—C126—H126 | 121.39 |
S1—C121—C126 | 121.9 (6) | C211—C212—H212 | 120.18 |
C123—C122—C121 | 117.6 (12) | C213—C212—H212 | 120.18 |
C122—C123—C124 | 121.9 (13) | C212—C213—H213 | 119.87 |
C125—C124—C123 | 118.9 (12) | C214—C213—H213 | 119.87 |
C124—C125—C126 | 121.7 (13) | C213—C214—H214 | 120.09 |
C121—C126—C125 | 117.2 (11) | C215—C214—H214 | 120.09 |
C212—C211—C216 | 121.3 (7) | C214—C215—H215 | 119.41 |
S2—C211—C212 | 115.7 (5) | C216—C215—H215 | 119.41 |
S2—C211—C216 | 123.0 (6) | C215—C216—H216 | 121.09 |
C211—C212—C213 | 119.6 (7) | C211—C216—H216 | 121.09 |
C214—C213—C212 | 120.3 (8) | C221—C222—H222 | 120.23 |
C215—C214—C213 | 119.8 (8) | C223—C222—H222 | 120.23 |
C214—C215—C216 | 121.2 (8) | C222—C223—H223 | 120.11 |
C211—C216—C215 | 117.8 (8) | C224—C223—H223 | 120.11 |
C226—C221—C222 | 120.6 (7) | C223—C224—H224 | 119.53 |
S2—C221—C222 | 117.2 (6) | C225—C224—H224 | 119.53 |
S2—C221—C226 | 122.2 (6) | C224—C225—H225 | 120.03 |
C223—C222—C221 | 119.5 (8) | C226—C225—H225 | 120.03 |
C224—C223—C222 | 119.8 (9) | C225—C226—H226 | 120.44 |
C225—C224—C223 | 120.9 (8) | C221—C226—H226 | 120.44 |
S1—Pt1—S2—C211 | 17.8 (2) | Pt1—S2—C221—C222 | −165.1 (5) |
S1—Pt1—S2—C221 | −95.9 (3) | Pt1—S2—C221—C226 | 13.8 (7) |
S2—Pt1—S1—C111 | −152.6 (3) | Cl1—Pt1—S1—C111 | 171.8 (8) |
S2—Pt1—S1—C121 | 94.5 (3) | Cl1—Pt1—S1—C121 | 58.9 (9) |
Pt1—S1—C111—C112 | −100.3 (6) | Cl2—Pt1—S1—C111 | 24.2 (3) |
Pt1—S1—C111—C116 | 83.6 (6) | Cl2—Pt1—S1—C121 | −88.8 (3) |
Pt1—S1—C121—C122 | −143.9 (5) | Cl1—Pt1—S2—C211 | −165.1 (2) |
Pt1—S1—C121—C126 | 37.7 (7) | Cl1—Pt1—S2—C221 | 81.2 (2) |
Pt1—S2—C211—C212 | 73.4 (5) | Cl2—Pt1—S2—C211 | −130.9 (7) |
Pt1—S2—C211—C216 | −105.3 (6) | Cl2—Pt1—S2—C221 | 115.3 (7) |
[PtCl2(C12H10S)2] | F(000) = 616 |
Mr = 638.51 | Dx = 1.830 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.8742 (12) Å | Cell parameters from 5997 reflections |
b = 16.980 (3) Å | θ = 2–30° |
c = 11.733 (2) Å | µ = 6.47 mm−1 |
β = 97.99 (3)° | T = 293 K |
V = 1158.9 (4) Å3 | Plate, orange |
Z = 2 | 0.35 × 0.19 × 0.08 mm |
Bruker SMART CCD diffractometer | 3583 independent reflections |
Radiation source: rotating anode | 2811 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 512 pixels mm-1 | θmax = 31.8°, θmin = 2.1° |
ω scans | h = −6→8 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −24→21 |
Tmin = 0.177, Tmax = 0.383 | l = −17→17 |
9455 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0424P)2 + 2.6752P] where P = (Fo2 + 2Fc2)/3 |
3583 reflections | (Δ/σ)max < 0.001 |
133 parameters | Δρmax = 1.27 e Å−3 |
0 restraints | Δρmin = −2.07 e Å−3 |
[PtCl2(C12H10S)2] | V = 1158.9 (4) Å3 |
Mr = 638.51 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.8742 (12) Å | µ = 6.47 mm−1 |
b = 16.980 (3) Å | T = 293 K |
c = 11.733 (2) Å | 0.35 × 0.19 × 0.08 mm |
β = 97.99 (3)° |
Bruker SMART CCD diffractometer | 3583 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2811 reflections with I > 2σ(I) |
Tmin = 0.177, Tmax = 0.383 | Rint = 0.046 |
9455 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.27 e Å−3 |
3583 reflections | Δρmin = −2.07 e Å−3 |
133 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Pt1 | 0.0000 | 0.0000 | 0.0000 | 0.03365 (8) | |
Cl1 | −0.2106 (4) | 0.11045 (12) | −0.05019 (13) | 0.1001 (8) | |
S1 | −0.0252 (2) | 0.03810 (7) | 0.18596 (9) | 0.0380 (2) | |
C111 | 0.1725 (8) | 0.1171 (3) | 0.2199 (4) | 0.0392 (9) | |
C112 | 0.3608 (9) | 0.1281 (3) | 0.1619 (5) | 0.0471 (11) | |
H112 | 0.3874 | 0.0941 | 0.1031 | 0.056* | |
C113 | 0.5071 (10) | 0.1900 (3) | 0.1930 (6) | 0.0575 (14) | |
H113 | 0.6328 | 0.1981 | 0.1543 | 0.069* | |
C114 | 0.4695 (12) | 0.2400 (3) | 0.2808 (6) | 0.0632 (16) | |
H114 | 0.5702 | 0.2815 | 0.3012 | 0.076* | |
C115 | 0.2859 (13) | 0.2290 (4) | 0.3379 (5) | 0.0659 (18) | |
H115 | 0.2622 | 0.2631 | 0.3972 | 0.079* | |
C116 | 0.1337 (11) | 0.1676 (3) | 0.3086 (4) | 0.0515 (12) | |
H116 | 0.0078 | 0.1602 | 0.3475 | 0.062* | |
C121 | 0.0849 (8) | −0.0357 (3) | 0.2877 (4) | 0.0390 (9) | |
C122 | 0.3030 (9) | −0.0357 (4) | 0.3459 (5) | 0.0531 (12) | |
H122 | 0.4068 | 0.0033 | 0.3319 | 0.064* | |
C123 | 0.3689 (11) | −0.0947 (4) | 0.4266 (5) | 0.0602 (15) | |
H123 | 0.5159 | −0.0943 | 0.4680 | 0.072* | |
C124 | 0.2184 (12) | −0.1529 (4) | 0.4449 (5) | 0.0578 (14) | |
H124 | 0.2641 | −0.1922 | 0.4985 | 0.069* | |
C125 | 0.0005 (12) | −0.1542 (4) | 0.3853 (5) | 0.0620 (15) | |
H125 | −0.1004 | −0.1947 | 0.3971 | 0.074* | |
C126 | −0.0681 (10) | −0.0942 (4) | 0.3066 (5) | 0.0558 (13) | |
H126 | −0.2167 | −0.0937 | 0.2671 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.03983 (13) | 0.03065 (12) | 0.02844 (12) | 0.00357 (9) | −0.00241 (8) | 0.00124 (8) |
Cl1 | 0.166 (2) | 0.0916 (13) | 0.0416 (7) | 0.0891 (14) | 0.0106 (10) | 0.0139 (8) |
S1 | 0.0408 (5) | 0.0392 (5) | 0.0324 (5) | 0.0027 (4) | 0.0000 (4) | −0.0001 (4) |
C111 | 0.050 (2) | 0.031 (2) | 0.034 (2) | 0.0034 (18) | −0.0016 (18) | −0.0048 (16) |
C112 | 0.049 (3) | 0.041 (2) | 0.050 (3) | −0.001 (2) | 0.003 (2) | −0.007 (2) |
C113 | 0.056 (3) | 0.046 (3) | 0.068 (4) | −0.005 (2) | 0.000 (3) | 0.002 (3) |
C114 | 0.076 (4) | 0.040 (3) | 0.065 (3) | −0.008 (3) | −0.021 (3) | 0.000 (2) |
C115 | 0.100 (5) | 0.047 (3) | 0.045 (3) | 0.005 (3) | −0.010 (3) | −0.016 (2) |
C116 | 0.067 (3) | 0.048 (3) | 0.038 (2) | 0.008 (2) | 0.003 (2) | −0.008 (2) |
C121 | 0.047 (2) | 0.037 (2) | 0.031 (2) | 0.0009 (19) | −0.0009 (17) | 0.0020 (17) |
C122 | 0.048 (3) | 0.052 (3) | 0.057 (3) | −0.002 (2) | −0.004 (2) | 0.010 (3) |
C123 | 0.065 (4) | 0.060 (3) | 0.050 (3) | 0.007 (3) | −0.009 (3) | 0.009 (3) |
C124 | 0.082 (4) | 0.054 (3) | 0.037 (3) | 0.010 (3) | 0.003 (3) | 0.010 (2) |
C125 | 0.075 (4) | 0.062 (3) | 0.051 (3) | −0.011 (3) | 0.012 (3) | 0.015 (3) |
C126 | 0.058 (3) | 0.058 (3) | 0.048 (3) | −0.010 (3) | −0.004 (2) | 0.012 (2) |
Pt1—Cl1 | 2.2786 (15) | C122—C123 | 1.395 (8) |
Pt1—Cl1i | 2.2786 (15) | C123—C124 | 1.363 (9) |
Pt1—S1 | 2.3002 (12) | C124—C125 | 1.371 (9) |
Pt1—S1i | 2.3002 (12) | C125—C126 | 1.396 (8) |
S1—C111 | 1.783 (5) | C112—H112 | 0.93 |
S1—C121 | 1.789 (5) | C113—H113 | 0.93 |
C111—C112 | 1.389 (7) | C114—H114 | 0.93 |
C111—C116 | 1.391 (6) | C115—H115 | 0.93 |
C112—C113 | 1.374 (7) | C116—H116 | 0.93 |
C113—C114 | 1.376 (9) | C122—H122 | 0.93 |
C114—C115 | 1.359 (10) | C123—H123 | 0.93 |
C115—C116 | 1.385 (9) | C124—H124 | 0.93 |
C121—C122 | 1.365 (7) | C125—H125 | 0.93 |
C121—C126 | 1.379 (7) | C126—H126 | 0.93 |
Cl1—Pt1—Cl1i | 180.0 | C124—C125—C126 | 119.2 (6) |
Cl1—Pt1—S1 | 84.80 (5) | C121—C126—C125 | 119.9 (5) |
Cl1i—Pt1—S1 | 95.20 (5) | C111—C112—H112 | 120.51 |
Cl1—Pt1—S1i | 95.20 (5) | C113—C112—H112 | 120.51 |
Cl1i—Pt1—S1i | 84.80 (5) | C112—C113—H113 | 119.47 |
S1—Pt1—S1i | 180.00 (6) | C114—C113—H113 | 119.47 |
Pt1—S1—C111 | 107.32 (16) | C113—C114—H114 | 120.15 |
Pt1—S1—C121 | 111.79 (16) | C115—C114—H114 | 120.15 |
S1—C111—C112 | 122.0 (4) | C114—C115—H115 | 119.41 |
S1—C111—C116 | 117.5 (4) | C116—C115—H115 | 119.41 |
C111—S1—C121 | 102.4 (2) | C115—C116—H116 | 120.81 |
C112—C111—C116 | 120.6 (5) | C111—C116—H116 | 120.81 |
C113—C112—C111 | 118.9 (5) | C121—C122—H122 | 121.22 |
C112—C113—C114 | 120.7 (6) | C123—C122—H122 | 121.22 |
C115—C114—C113 | 120.4 (6) | C122—C123—H123 | 119.04 |
C114—C115—C116 | 120.6 (6) | C124—C123—H123 | 119.04 |
C115—C116—C111 | 118.8 (6) | C123—C124—H124 | 120.56 |
C122—C121—C126 | 120.4 (5) | C125—C124—H124 | 120.56 |
S1—C121—C122 | 124.2 (4) | C124—C125—H125 | 119.17 |
S1—C121—C126 | 115.4 (4) | C126—C125—H125 | 119.17 |
C121—C122—C123 | 119.5 (5) | C125—C126—H126 | 121.39 |
C124—C123—C122 | 120.2 (6) | C121—C126—H126 | 121.39 |
C123—C124—C125 | 120.8 (5) | ||
Cl1—Pt1—S1—C111 | −76.55 (18) | Pt1—S1—C111—C116 | 157.8 (4) |
Cl1—Pt1—S1—C121 | 171.97 (19) | Pt1—S1—C121—C122 | 96.5 (5) |
Pt1—S1—C111—C112 | −23.1 (4) | Pt1—S1—C121—C126 | −84.5 (4) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [PtCl2(C12H10S)2] | [PtCl2(C12H10S)2] |
Mr | 638.51 | 638.51 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.281 (2), 17.244 (3), 26.382 (5) | 5.8742 (12), 16.980 (3), 11.733 (2) |
α, β, γ (°) | 90, 90, 90 | 90, 97.99 (3), 90 |
V (Å3) | 4676.9 (16) | 1158.9 (4) |
Z | 8 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 6.42 | 6.47 |
Crystal size (mm) | 0.15 × 0.13 × 0.03 | 0.35 × 0.19 × 0.08 |
Data collection | ||
Diffractometer | Bruker SMART CCD diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.446, 0.831 | 0.177, 0.383 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32399, 5802, 4144 | 9455, 3583, 2811 |
Rint | 0.064 | 0.046 |
(sin θ/λ)max (Å−1) | 0.667 | 0.741 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.106, 1.16 | 0.036, 0.100, 1.09 |
No. of reflections | 5802 | 3583 |
No. of parameters | 262 | 133 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0309P)2 + 15.350P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0424P)2 + 2.6752P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.71, −1.08 | 1.27, −2.07 |
Computer programs: SMART (Bruker, 1995), SAINT (Bruker, 1995), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Diamond (Brandenburg, 2000), SHELXL97.
Pt1—S1 | 2.2801 (19) | S1—C111 | 1.787 (7) |
Pt1—S2 | 2.2832 (18) | S1—C121 | 1.785 (8) |
Pt1—Cl1 | 2.319 (2) | S2—C211 | 1.785 (6) |
Pt1—Cl2 | 2.295 (2) | S2—C221 | 1.776 (7) |
S1—Pt1—S2 | 92.39 (6) | C111—S1—C121 | 103.3 (3) |
S1—Pt1—Cl1 | 175.16 (7) | C211—S2—C221 | 103.4 (3) |
S1—Pt1—Cl2 | 93.06 (7) | S1—C111—C112 | 123.3 (6) |
S2—Pt1—Cl1 | 83.68 (7) | S1—C111—C116 | 116.0 (6) |
S2—Pt1—Cl2 | 173.62 (7) | S1—C121—C122 | 115.4 (8) |
Cl1—Pt1—Cl2 | 91.03 (8) | S1—C121—C126 | 121.9 (6) |
Pt1—S1—C111 | 113.7 (2) | S2—C211—C212 | 115.7 (5) |
Pt1—S1—C121 | 106.2 (3) | S2—C211—C216 | 123.0 (6) |
Pt1—S2—C211 | 110.5 (2) | S2—C221—C222 | 117.2 (6) |
Pt1—S2—C221 | 110.3 (2) | S2—C221—C226 | 122.2 (6) |
S1—Pt1—S2—C211 | 17.8 (2) | Pt1—S1—C111—C112 | −100.3 (6) |
S1—Pt1—S2—C221 | −95.9 (3) | Pt1—S1—C121—C122 | −143.9 (5) |
S2—Pt1—S1—C111 | −152.6 (3) | Pt1—S2—C211—C212 | 73.4 (5) |
S2—Pt1—S1—C121 | 94.5 (3) | Pt1—S2—C221—C222 | −165.1 (5) |
Pt1—Cl1 | 2.2786 (15) | S1—C111 | 1.783 (5) |
Pt1—S1 | 2.3002 (12) | S1—C121 | 1.789 (5) |
Cl1—Pt1—S1 | 84.80 (5) | S1—C111—C116 | 117.5 (4) |
Cl1i—Pt1—S1 | 95.20 (5) | C111—S1—C121 | 102.4 (2) |
Pt1—S1—C111 | 107.32 (16) | S1—C121—C122 | 124.2 (4) |
Pt1—S1—C121 | 111.79 (16) | S1—C121—C126 | 115.4 (4) |
S1—C111—C112 | 122.0 (4) | ||
Cl1—Pt1—S1—C111 | −76.55 (18) | Pt1—S1—C111—C112 | −23.1 (4) |
Cl1—Pt1—S1—C121 | 171.97 (19) | Pt1—S1—C121—C122 | 96.5 (5) |
Symmetry code: (i) −x, −y, −z. |
Compound | Pt-Cl(Å) | ROP | Pt-S(Å) | ROP |
cis-[PtCl2(S(C6H5)2)2]a | 2.295 (2) | 0.449 | 2.280 (2) | 0.539 |
2.319 (2) | 0.416 | 2.283 (2) | 0.518 | |
trans-[PtCl2(S(C6H5)2)2]a | 2.2786 (15) | 0.446 | 2.3002 (12) | 0.507 |
cis-[PtCl2(dms)2]b | 2.315 (1) | 0.440 | 2.269 (1) | 0.531 |
2.319 (1) | 0.434 | 2.272 (1) | 0.536 | |
trans-[PtCl2(dms)2]c | 2.288 (2) | 0.448 | 2.303 (2) | 0.517 |
cis-[PtCl2(tioxane)2]d | 2.321 (2) | 0.439 | 2.273 (2) | 0.512 |
2.327 (2) | 0.438 | 2.273 (2) | 0.520 | |
trans-[PtCl2(tioxane)2]d | 2.300 (2) | 0.441 | 2.298 (2) | 0.534 |
Notes: (a) This study; (b) Horn et al. (1990); (c) Johansson et al. (2001); (d) Bugarcic et al. (1993) |
In square-planar platinum(II) complexes the trans-influence is a well known phenomenon which has been widely studied for a large number of complexes; cis/trans-[PtCl2(dms)2] (Horn et al., 1990; Johansson et al., 2001), cis-[PtCl2(dmso)2] (Melanson & Rochon, 1975; Shibaeva, 1983) and cis/trans-[PtCl2(tioxane)2] (Bugarcic et al., 1993). The trans-influence is larger for thioether sulfur than for chloride, but the substituents on the sulfur atom are expected to modulate the influence. In the light of this, we have investigated the structures of cis- and trans-[dichlorobis(diphenylsulfide)platinum(II)], (I) and (II), respectively. \sch
In cis-[PtCl2(SPh2)2] (Fig. 1), the coordination around Pt is disordered square planar with angles ranging from 83.68 (7) to 93.06 (7)°. The RMS deviation from the Cl2PtS2 plane is 0.0550 Å, where S2 shows the largest deviation [-0.0652 (11) Å]. The closest non-bonding contact to Pt is intramolecular to H226, 2.92 Å, where H226 is approximately situated at an octahedral position of the coordination sphere of platinum. On the other side of the coordination plane the closest contact in the octahedral position is intermolecular to H116 at (2 - x, 1 - y, -z) with a distance of 3.43 Å, too long to be a Pt···H interaction. The two closest Cl1···H interactions are 2.84 and 2.97 Å to H113 at (1/2 - x, 1/2 + y, z) and H224 at (1/2 + x, y, 1/2 - z), respectively. The closest Cl2···H interaction is 2.93 Å to H225 (1/2 + x, y, 1/2 - z). The torsion angles S—Pt—S—C show that for each ligand one S—C bond is fairly close to the coordination plane while the other S—C bonds are close to perpendicular to this plane (Table 1).
In trans-[PtCl2(SPh2)2] (Fig. 2), the coordination is pseudo-square planar with Pt at a centre of inversion and bond angles 84.80 (5) and 95.20 (5)° around platinum. Atoms H112 are located in an approximate octahedral site on both sides of the platinum, 2.90 Å, which is the closest non-bonding contact (intramolecular) with platinum. The closest non-bonding interaction to chloride is intermolecular to H114 at (1 + x, 1/2 - y, 1/2 + z), 2.73 Å. The torsion angles Cl—Pt—S—C show that one S—C bond in the ligand is fairly close to the coordination plane while the other S—C bonds are close to perpendicular to this plane (Table 2).
The Cambridge Structural Database (CSD; Allen & Kennard, 1993) has been searched for compounds of the types [PtCl2R2], [PtS4]2+ and [PtCl4]2-, where R irepresents a ligand with a sulfur donor atom connected to two carbon atoms. 31 cis- and 7 trans-[PtCl2R2] examples were found. From the CSD search a mean value of 2.319 (12) Å was calculated for the distances in ten [PtS4]2+ complexes (no chelating ligands) and this value may be used as a reference value for a discussion of the cis/trans-influence. The cis-[PtCl2R2] compounds have a Pt—S mean distance of 2.24 (2) Å (62 distances), while the similar trans-compounds give a mean of 2.301 (9) Å (14 distances). The Pt—S distances in cis-[PtCl2(SPh2)2] are 2.280 (2) and 2.283 (2) Å, which are significantly longer than the mean value in other cis-compounds. It is similar to the distances found in cis-[PtCl2(S(C6H4Cl)2)2], 2.292 (6) and 2.278 (7) Å (Spofford et al., 1971) and shorter than distances in [PtS4]2+ complexes. Thus the combined cis(Cl/S)- and trans(Cl)-influence may shorten the Pt—S bond, by 0.04 Å compared to [PtS4]2+, but not as much as in other analogous compounds (Table 3). In trans-[PtCl2(SPh2)2] the Pt—S distances are 2.3002 (12) Å which is in a normal range for such bonds [mean 2.301 (9) Å]. The cis(Cl/Cl)-influence shortens it by 0.02 Å compared to [PtS4]2+ compounds. The mean Pt—Cl distance found in 33 [PtCl4]2- complexes, 160 distances, is 2.302 (16) Å. The Pt—Cl distances in cis-[PtCl2(SPh2)2], 2.295 (2) and 2.319 (2) Å, are in good agreement with distances found for related cis-compounds, mean of 2.312 (11) for 62 distances, while the Pt—Cl distances in trans-[PtCl2(SPh2)2], 2.2786 (15) Å, are shorter than in related trans-compounds, mean of 2.299 (5) for 14 distances. The cis(S/S)-influence of SPh2 shortens the Pt—Cl bond in trans-[PtCl2(SPh2)2] by 0.02 Å compared to [PtCl4]2-, but also compared to analogous trans-[PtCl2R2] compounds.
The reduced overlap population (ROP) may be used as a measure of the bond strength. We have calculated the ROP in the Pt-ligand bonds using the crystallographic observed geometries (Table 3) at Extended Hückel (EH) level using the program CACAO (Maelli & Prosperpio, 1990). The Pt—S bonds have higher ROP-values than the Pt—Cl bonds. This is true even in the trans-compounds where the Pt—S bonds are equal or slightly longer than the Pt—Cl bonds. All the cis-complexes, except one, cis-[PtCl2(tioxane)2], have larger ROP for the Pt—S bonds than the corresponding trans-compounds, thus following the trends in the Pt—S distances. However, in the tioxane compounds the ROP for the trans-compound is the larger one, in spite of the fact that the Pt—S distance is 2.298 (2) Å compared to 2.273 (2) Å in the cis-compound.
The total energy for trans-[PtCl2(SPh2)2] was also calculated at 20° intervals for a 360° rotation around the Pt—S bond keeping all other geometric parameters constant. It is interesting to note that the observed conformation of trans-[PtCl2(SPh2)2] is the one with the lowest energy. It is well known that EH-calculations are reasonably successful in calculating conformational energies (Jolly, 1991) and it is concluded that the packing has small effects, not only on bond distances and angles as normally observed (Johansson et al., 2000), but also on the conformation in this case.