Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006754/ya6021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006754/ya6021Isup2.hkl |
CCDC reference: 165636
rac-1,3-Bis(phenylsulfinyl)propane (Bpsp) was prepared according to the reported procedure of Zhang et al. (1997). To an aqueous solution of K2PtCl4 (100 mg, 0.24 mmol) under heating was slowly added a chloroform solution of equimolar Bpsp (70.4 mg, 0.24 mmol) with vigorous stirring. The white complex soon precipitated. Colorless single crystals of the title compound suitable for X-ray diffraction were obtained from a dimethylformamide–methane solution by slow evaporation of the solvent. Yield: 87.4 mg (65%). FT—IR data (KBr pellet, cm-1): 1131 (s, S═O). Analysis calculated for the title complex: C 32.26, H 2.89%; found: C 32.18, H 2.88%.
The C-bound H atoms were placed in their geometrically calculated positions and included in the final refinement in the riding-model approximation with displacement parameters derived from the atoms to which they were bonded. The Uiso for the H atoms were set to be 1.2Ueq for the parent atom. The highest peak is 1.34 Å from Pt1 and the deepest hole is 0.81 Å from Pt1.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998).
Fig. 1. ORTEPII (Johnson, 1976) view of the title complex with 30% probability displacement ellipsoids. |
[PtCl2(C15H16O2S2)] | F(000) = 1064 |
Mr = 558.39 | Dx = 2.105 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5755 (4) Å | Cell parameters from 7023 reflections |
b = 21.6570 (12) Å | θ = 2.7–25.0° |
c = 11.0354 (6) Å | µ = 8.51 mm−1 |
β = 103.300 (1)° | T = 298 K |
V = 1761.94 (17) Å3 | Prism, colorless |
Z = 4 | 0.30 × 0.25 × 0.25 mm |
Bruker SMART 1000 diffractometer | 2798 reflections with I > 2σ(I) |
ω scans | Rint = 0.084 |
Absorption correction: multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] | θmax = 25.0° |
Tmin = 0.185, Tmax = 0.225 | h = −8→9 |
7105 measured reflections | k = −24→25 |
3062 independent reflections | l = −9→13 |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0646P)2 + 3.6575P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.114 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 1.51 e Å−3 |
3062 reflections | Δρmin = −1.94 e Å−3 |
199 parameters |
[PtCl2(C15H16O2S2)] | V = 1761.94 (17) Å3 |
Mr = 558.39 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.5755 (4) Å | µ = 8.51 mm−1 |
b = 21.6570 (12) Å | T = 298 K |
c = 11.0354 (6) Å | 0.30 × 0.25 × 0.25 mm |
β = 103.300 (1)° |
Bruker SMART 1000 diffractometer | 3062 independent reflections |
Absorption correction: multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] | 2798 reflections with I > 2σ(I) |
Tmin = 0.185, Tmax = 0.225 | Rint = 0.084 |
7105 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 199 parameters |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.51 e Å−3 |
3062 reflections | Δρmin = −1.94 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. Full-MATRIX |
x | y | z | Uiso*/Ueq | ||
Pt1 | 0.66712 (4) | 0.164140 (11) | 0.70368 (2) | 0.03829 (15) | |
S1 | 0.4718 (2) | 0.24269 (8) | 0.65150 (15) | 0.0412 (4) | |
S2 | 0.5251 (3) | 0.11308 (8) | 0.83136 (15) | 0.0424 (4) | |
Cl1 | 0.8204 (3) | 0.20609 (10) | 0.5647 (2) | 0.0655 (6) | |
Cl2 | 0.8760 (3) | 0.08485 (9) | 0.7383 (2) | 0.0553 (5) | |
O1 | 0.3489 (9) | 0.2361 (3) | 0.5300 (5) | 0.0668 (16) | |
O2 | 0.6379 (8) | 0.0847 (3) | 0.9427 (5) | 0.0617 (15) | |
C1 | 0.3355 (11) | 0.2567 (4) | 0.7623 (8) | 0.056 (2) | |
H1A | 0.4119 | 0.2730 | 0.8383 | 0.067* | |
H1B | 0.2445 | 0.2876 | 0.7290 | 0.067* | |
C2 | 0.2419 (12) | 0.1986 (4) | 0.7926 (9) | 0.060 (2) | |
H2A | 0.1366 | 0.2102 | 0.8235 | 0.072* | |
H2B | 0.1997 | 0.1749 | 0.7168 | 0.072* | |
C3 | 0.3627 (14) | 0.1589 (3) | 0.8870 (9) | 0.058 (2) | |
H3A | 0.2872 | 0.1313 | 0.9227 | 0.070* | |
H3B | 0.4279 | 0.1852 | 0.9535 | 0.070* | |
C4 | 0.5894 (11) | 0.3153 (4) | 0.6609 (6) | 0.0456 (16) | |
C5 | 0.5202 (12) | 0.3572 (4) | 0.5690 (8) | 0.057 (2) | |
H5A | 0.4241 | 0.3471 | 0.5029 | 0.068* | |
C6 | 0.5994 (17) | 0.4151 (4) | 0.5789 (12) | 0.077 (3) | |
H6A | 0.5550 | 0.4450 | 0.5190 | 0.093* | |
C7 | 0.7410 (19) | 0.4289 (4) | 0.6748 (13) | 0.086 (4) | |
H7A | 0.7906 | 0.4684 | 0.6811 | 0.103* | |
C8 | 0.8134 (16) | 0.3844 (6) | 0.7644 (11) | 0.090 (4) | |
H8A | 0.9151 | 0.3934 | 0.8270 | 0.108* | |
C9 | 0.7330 (18) | 0.3273 (4) | 0.7591 (9) | 0.071 (3) | |
H9A | 0.7746 | 0.2977 | 0.8202 | 0.085* | |
C10 | 0.3895 (9) | 0.0548 (3) | 0.7417 (6) | 0.0396 (14) | |
C11 | 0.3520 (12) | 0.0554 (4) | 0.6124 (7) | 0.057 (2) | |
H11A | 0.3900 | 0.0883 | 0.5704 | 0.068* | |
C12 | 0.2581 (14) | 0.0071 (5) | 0.5474 (9) | 0.071 (3) | |
H12A | 0.2351 | 0.0067 | 0.4610 | 0.086* | |
C13 | 0.1975 (12) | −0.0411 (4) | 0.6097 (10) | 0.068 (2) | |
H13A | 0.1328 | −0.0736 | 0.5654 | 0.081* | |
C14 | 0.2341 (14) | −0.0404 (4) | 0.7388 (11) | 0.070 (3) | |
H14A | 0.1930 | −0.0725 | 0.7811 | 0.084* | |
C15 | 0.3299 (10) | 0.0070 (4) | 0.8043 (8) | 0.055 (2) | |
H15A | 0.3549 | 0.0070 | 0.8908 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.0531 (2) | 0.0277 (2) | 0.0379 (2) | −0.00753 (9) | 0.01858 (14) | −0.00044 (9) |
S1 | 0.0533 (10) | 0.0337 (9) | 0.0365 (8) | −0.0047 (7) | 0.0103 (7) | −0.0031 (7) |
S2 | 0.0559 (10) | 0.0362 (9) | 0.0377 (8) | −0.0111 (8) | 0.0165 (7) | 0.0031 (7) |
Cl1 | 0.0877 (15) | 0.0543 (12) | 0.0693 (12) | 0.0009 (11) | 0.0488 (12) | 0.0168 (10) |
Cl2 | 0.0668 (12) | 0.0350 (9) | 0.0683 (12) | 0.0050 (8) | 0.0241 (10) | 0.0022 (8) |
O1 | 0.075 (4) | 0.073 (4) | 0.045 (3) | −0.010 (3) | −0.001 (3) | −0.011 (3) |
O2 | 0.065 (3) | 0.074 (4) | 0.041 (3) | −0.018 (3) | 0.001 (2) | 0.018 (3) |
C1 | 0.070 (5) | 0.042 (4) | 0.064 (4) | 0.002 (4) | 0.031 (4) | 0.001 (4) |
C2 | 0.050 (5) | 0.059 (5) | 0.079 (6) | −0.005 (4) | 0.028 (4) | −0.009 (4) |
C3 | 0.085 (6) | 0.040 (4) | 0.063 (5) | −0.011 (4) | 0.045 (5) | −0.004 (3) |
C4 | 0.068 (5) | 0.038 (4) | 0.033 (3) | −0.006 (4) | 0.016 (3) | −0.002 (3) |
C5 | 0.066 (5) | 0.049 (5) | 0.063 (5) | 0.024 (4) | 0.030 (4) | 0.016 (4) |
C6 | 0.095 (8) | 0.042 (5) | 0.115 (9) | 0.013 (5) | 0.065 (7) | 0.025 (5) |
C7 | 0.127 (10) | 0.038 (5) | 0.112 (9) | −0.012 (6) | 0.066 (9) | −0.009 (6) |
C8 | 0.100 (8) | 0.088 (9) | 0.086 (7) | −0.045 (7) | 0.028 (6) | −0.035 (7) |
C9 | 0.109 (8) | 0.049 (5) | 0.051 (5) | −0.026 (5) | 0.013 (5) | −0.002 (4) |
C10 | 0.043 (4) | 0.029 (3) | 0.049 (4) | −0.003 (3) | 0.013 (3) | 0.001 (3) |
C11 | 0.072 (5) | 0.045 (4) | 0.052 (4) | −0.014 (4) | 0.011 (4) | −0.005 (4) |
C12 | 0.085 (6) | 0.064 (6) | 0.063 (5) | −0.024 (5) | 0.010 (5) | −0.017 (4) |
C13 | 0.064 (5) | 0.049 (5) | 0.089 (6) | −0.015 (4) | 0.015 (5) | −0.020 (5) |
C14 | 0.065 (5) | 0.043 (5) | 0.105 (7) | −0.015 (4) | 0.029 (5) | 0.010 (5) |
C15 | 0.060 (5) | 0.040 (5) | 0.068 (5) | −0.009 (3) | 0.020 (4) | 0.015 (3) |
Pt1—S1 | 2.2412 (18) | C5—C6 | 1.384 (14) |
Pt1—S2 | 2.2501 (15) | C5—H5A | 0.9300 |
Pt1—Cl1 | 2.3118 (17) | C6—C7 | 1.355 (16) |
Pt1—Cl2 | 2.3067 (19) | C6—H6A | 0.9300 |
S1—O1 | 1.453 (6) | C7—C8 | 1.399 (19) |
S1—C1 | 1.798 (8) | C7—H7A | 0.9300 |
S1—C4 | 1.798 (8) | C8—C9 | 1.374 (15) |
S2—O2 | 1.461 (6) | C8—H8A | 0.9300 |
S2—C3 | 1.795 (9) | C9—H9A | 0.9300 |
S2—C10 | 1.778 (7) | C10—C15 | 1.376 (10) |
C1—C2 | 1.519 (12) | C10—C11 | 1.390 (10) |
C1—H1A | 0.9700 | C11—C12 | 1.371 (11) |
C1—H1B | 0.9700 | C11—H11A | 0.9300 |
C2—C3 | 1.491 (14) | C12—C13 | 1.384 (14) |
C2—H2A | 0.9700 | C12—H12A | 0.9300 |
C2—H2B | 0.9700 | C13—C14 | 1.388 (14) |
C3—H3A | 0.9700 | C13—H13A | 0.9300 |
C3—H3B | 0.9700 | C14—C15 | 1.364 (13) |
C4—C5 | 1.373 (12) | C14—H14A | 0.9300 |
C4—C9 | 1.373 (15) | C15—H15A | 0.9300 |
S1—Pt1—S2 | 98.71 (7) | C5—C4—C9 | 123.8 (8) |
S1—Pt1—Cl2 | 174.19 (6) | C5—C4—S1 | 115.8 (7) |
S2—Pt1—Cl2 | 86.50 (7) | C9—C4—S1 | 120.3 (6) |
S1—Pt1—Cl1 | 86.21 (7) | C4—C5—C6 | 117.1 (10) |
S2—Pt1—Cl1 | 173.70 (7) | C4—C5—H5A | 121.4 |
Cl2—Pt1—Cl1 | 88.42 (7) | C6—C5—H5A | 121.4 |
O1—S1—C4 | 110.0 (4) | C7—C6—C5 | 120.8 (10) |
O1—S1—C1 | 107.3 (4) | C7—C6—H6A | 119.6 |
C4—S1—C1 | 99.7 (4) | C5—C6—H6A | 119.6 |
O1—S1—Pt1 | 114.1 (3) | C6—C7—C8 | 120.7 (10) |
C4—S1—Pt1 | 111.1 (3) | C6—C7—H7A | 119.6 |
C1—S1—Pt1 | 113.7 (3) | C8—C7—H7A | 119.6 |
O2—S2—C10 | 108.7 (4) | C9—C8—C7 | 119.5 (11) |
O2—S2—C3 | 105.0 (4) | C9—C8—H8A | 120.2 |
C10—S2—C3 | 103.2 (4) | C7—C8—H8A | 120.2 |
O2—S2—Pt1 | 117.5 (2) | C4—C9—C8 | 117.8 (10) |
C10—S2—Pt1 | 107.4 (2) | C4—C9—H9A | 121.1 |
C3—S2—Pt1 | 114.0 (3) | C8—C9—H9A | 121.1 |
C2—C1—S1 | 112.3 (6) | C15—C10—C11 | 120.6 (7) |
C2—C1—H1A | 109.1 | C15—C10—S2 | 118.0 (6) |
S1—C1—H1A | 109.1 | C11—C10—S2 | 121.3 (5) |
C2—C1—H1B | 109.1 | C12—C11—C10 | 119.2 (8) |
S1—C1—H1B | 109.1 | C12—C11—H11A | 120.4 |
H1A—C1—H1B | 107.9 | C10—C11—H11A | 120.4 |
C3—C2—C1 | 112.9 (8) | C11—C12—C13 | 120.5 (9) |
C3—C2—H2A | 109.0 | C11—C12—H12A | 119.8 |
C1—C2—H2A | 109.0 | C13—C12—H12A | 119.8 |
C3—C2—H2B | 109.0 | C12—C13—C14 | 119.4 (8) |
C1—C2—H2B | 109.0 | C12—C13—H13A | 120.3 |
H2A—C2—H2B | 107.8 | C14—C13—H13A | 120.3 |
C2—C3—S2 | 116.0 (6) | C15—C14—C13 | 120.5 (8) |
C2—C3—H3A | 108.3 | C15—C14—H14A | 119.7 |
S2—C3—H3A | 108.3 | C13—C14—H14A | 119.7 |
C2—C3—H3B | 108.3 | C14—C15—C10 | 119.7 (8) |
S2—C3—H3B | 108.3 | C14—C15—H15A | 120.1 |
H3A—C3—H3B | 107.4 | C10—C15—H15A | 120.1 |
Experimental details
Crystal data | |
Chemical formula | [PtCl2(C15H16O2S2)] |
Mr | 558.39 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 7.5755 (4), 21.6570 (12), 11.0354 (6) |
β (°) | 103.300 (1) |
V (Å3) | 1761.94 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.51 |
Crystal size (mm) | 0.30 × 0.25 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] |
Tmin, Tmax | 0.185, 0.225 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7105, 3062, 2798 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.114, 1.04 |
No. of reflections | 3062 |
No. of parameters | 199 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.51, −1.94 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Bruker, 1998).
Pt1—S1 | 2.2412 (18) | S1—C1 | 1.798 (8) |
Pt1—S2 | 2.2501 (15) | S1—C4 | 1.798 (8) |
Pt1—Cl1 | 2.3118 (17) | S2—C3 | 1.795 (9) |
Pt1—Cl2 | 2.3067 (19) | S2—C10 | 1.778 (7) |
S1—O1 | 1.453 (6) | ||
S1—Pt1—S2 | 98.71 (7) | S1—Pt1—Cl1 | 86.21 (7) |
S1—Pt1—Cl2 | 174.19 (6) | S2—Pt1—Cl1 | 173.70 (7) |
S2—Pt1—Cl2 | 86.50 (7) | Cl2—Pt1—Cl1 | 88.42 (7) |
A number of Pt complexes with monosulfoxide have been isolated and fairly well characterized (Calligaris & Carugo, 1996). It was indicated that the sulfoxide group normally coordinates soft metals (Pt, Pd etc.) via its S atom (Kagan & Ronan 1992). PtII usually bonds to bis(sulfoxides) in a cis-chelate mode which may potentially produce complexes with antitumor activity. There are, however, just a few examples of the complexes of this type which were structurally characterized (Cattalini et al., 1979). In this paper, we report the crystal structure of a new PtII complex with the bis(sulfoxide) ligand, namely cis-[rac-1,3-bis(phenylsulfinyl)propane]dichloroplatinum(II), (I).
The crystal represents the racemate formed by the molecules with the (R,R) and (S,S) configurations of the sulfur chiral centres in the chelate ring. The central PtII atom in the title complex, (I), is four-coordinated with two S-donors of the chelate ligand and two terminal Cl ligands, in a slightly distorted square-planar geometry, as shown in Fig. 1. The chelate ring adopts a distorted chair conformation flattened at the platinum end; the displacements of the Pt1 and C2 atoms from the least-squares plane drawn through the S1/C1/S2/C3 atoms (which holds to within 0.04 Å) are equal to 0.4836 (4) and -0.771 (3) Å, respectively. The C4 and C10 atoms are displaced from this plane by 1.241 (3) and -1.631 (2) Å. The pseudo-torsion angle between two S═O groups (O1═S1···S2═O2) is 165.8 (2)° and the dihedral angle formed by the planes of two phenyl rings is 146.5 (2)°. A number of similar conformational features have been reported for the PtII complex of rac-1,2-bis(phenylsulphinyl)ethane with a five-membered chelate cycle (Cattalini et al., 1979); the bond distances and angles in the latter complex are also in good agreement with those found for (I).