Acta Cryst. (2008). E64, m425 [ doi:10.1107/S1600536808002006 ]
In the crystal structure of the title complex, [Pt(C5H4NOS)2], the Pt atom is coordinated by two O atoms and two S atoms in a cis configuration, forming a distorted square-planar coordination geometry. The molecule exhibits pseudo-C2v symmetry and is essentially planar, with a maximum deviation from planarity of 0.0124 (2) Å. The dihedral angle between the two pyridine rings is 5.85 (2)°.
By heating a mixture of dichlorido(ethane1,2–diamine)platinum(II), Pt(en)Cl2 (0.326 g,1 mmol) and 1-hydroxypyridine-2- thione sodium salt (0.298 g, 2 mmol) in 20 ml of water at 338 K with magnetic stirring for 1 h, a red-orange compound was obtained. This was filtered and dried (0.32 g, 80% yield). The compound was dissolved in methanol and allowed to undergo slow evaporation. Fine red crystals were obtained after a week.
H atoms were placed in calculated positions [C—H = 0.95 Å] and refined in the riding model approximation; Uiso(H) = 1.2Ueq (C). The highest residual electron density peak is 1.724 Å from C13 and the deepest hole lies 1.688 Å from N1.
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP2 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./wn2232fig1thm.gif)
| Fig. 1. View of the title compound, with displacement ellipsoids drawn at the 50% probability level. |
| [Pt(C5H4NOS)2] | F000 = 832 |
| Mr = 447.39 | Dx = 2.545 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71069 Å |
| Hall symbol: -P 2yn | Cell parameters from 9973 reflections |
| a = 6.9832 (3) Å | θ = 2.8–28º |
| b = 22.3897 (11) Å | µ = 12.36 mm−1 |
| c = 8.1495 (4) Å | T = 193 (2) K |
| β = 113.572 (3)º | Block, orange |
| V = 1167.87 (10) Å3 | 0.27 × 0.22 × 0.08 mm |
| Z = 4 |
| Bruker APEXII Kappa-CCD diffractometer | Rint = 0.068 |
| CCD scan | θmax = 27.9º |
| Absorption correction: multi-scan (SADABS; Blessing, 1995, 1997) | θmin = 1.8º |
| Tmin = 0.051, Tmax = 0.372 | h = −9→9 |
| 25638 measured reflections | k = −29→29 |
| 2778 independent reflections | l = −10→10 |
| 2610 reflections with I > 2σ(I) |
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0153P)2 + 17.8973P] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.054 | (Δ/σ)max = 0.001 |
| wR(F2) = 0.114 | Δρmax = 1.73 e Å−3 |
| S = 1.32 | Δρmin = −3.86 e Å−3 |
| 2778 reflections | Extinction correction: none |
| 154 parameters |
| [Pt(C5H4NOS)2] | V = 1167.87 (10) Å3 |
| Mr = 447.39 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 6.9832 (3) Å | µ = 12.36 mm−1 |
| b = 22.3897 (11) Å | T = 193 (2) K |
| c = 8.1495 (4) Å | 0.27 × 0.22 × 0.08 mm |
| β = 113.572 (3)º |
| Bruker APEXII Kappa-CCD diffractometer | 2778 independent reflections |
| Absorption correction: multi-scan (SADABS; Blessing, 1995, 1997) | 2610 reflections with I > 2σ(I) |
| Tmin = 0.051, Tmax = 0.372 | Rint = 0.068 |
| 25638 measured reflections |
| R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
| wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0153P)2 + 17.8973P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.32 | Δρmax = 1.73 e Å−3 |
| 2778 reflections | Δρmin = −3.86 e Å−3 |
| 154 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. |
| x | y | z | Uiso*/Ueq | ||
| Pt1 | 0.75198 (6) | 0.117494 (18) | 0.60862 (6) | 0.03763 (14) | |
| N1 | 0.5870 (13) | 0.1570 (4) | 0.2386 (12) | 0.0373 (18) | |
| C2 | 0.5399 (16) | 0.1976 (5) | 0.1045 (15) | 0.042 (2) | |
| H2 | 0.5774 | 0.2384 | 0.1308 | 0.05* | |
| C3 | 0.4376 (18) | 0.1791 (6) | −0.0694 (17) | 0.050 (3) | |
| H3 | 0.4097 | 0.2066 | −0.165 | 0.059* | |
| C4 | 0.3746 (18) | 0.1195 (6) | −0.1053 (16) | 0.048 (3) | |
| H4 | 0.3007 | 0.1064 | −0.2251 | 0.058* | |
| C5 | 0.4207 (16) | 0.0803 (5) | 0.0340 (15) | 0.042 (2) | |
| H5 | 0.3772 | 0.0399 | 0.0102 | 0.05* | |
| C6 | 0.5318 (17) | 0.0990 (5) | 0.2124 (15) | 0.039 (2) | |
| O7 | 0.6952 (11) | 0.1788 (3) | 0.4073 (10) | 0.0380 (15) | |
| S8 | 0.5946 (4) | 0.05080 (12) | 0.3916 (4) | 0.0413 (6) | |
| N9 | 0.9639 (13) | 0.1639 (4) | 0.9685 (12) | 0.0378 (19) | |
| C10 | 1.0646 (17) | 0.2052 (5) | 1.0962 (16) | 0.042 (2) | |
| H10 | 1.0885 | 0.2441 | 1.0617 | 0.051* | |
| C11 | 1.1311 (17) | 0.1915 (5) | 1.2724 (16) | 0.044 (2) | |
| H11 | 1.1986 | 0.2208 | 1.3612 | 0.053* | |
| C12 | 1.0994 (17) | 0.1342 (5) | 1.3215 (15) | 0.043 (2) | |
| H12 | 1.147 | 0.1239 | 1.4445 | 0.051* | |
| C13 | 0.9994 (17) | 0.0921 (5) | 1.1923 (15) | 0.042 (2) | |
| H13 | 0.9763 | 0.053 | 1.2263 | 0.051* | |
| C14 | 0.9315 (16) | 0.1069 (5) | 1.0105 (14) | 0.038 (2) | |
| O15 | 0.8948 (11) | 0.1822 (3) | 0.7947 (9) | 0.0381 (16) | |
| S16 | 0.8174 (4) | 0.05572 (12) | 0.8401 (4) | 0.0394 (6) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Pt1 | 0.0364 (2) | 0.0382 (2) | 0.0391 (2) | 0.00055 (17) | 0.01591 (17) | 0.00058 (17) |
| N1 | 0.032 (4) | 0.039 (5) | 0.042 (5) | −0.002 (3) | 0.017 (4) | −0.001 (4) |
| C2 | 0.033 (5) | 0.049 (6) | 0.039 (6) | 0.006 (4) | 0.009 (4) | 0.011 (5) |
| C3 | 0.043 (6) | 0.063 (7) | 0.046 (7) | 0.003 (5) | 0.021 (5) | 0.013 (6) |
| C4 | 0.040 (6) | 0.062 (7) | 0.041 (6) | 0.001 (5) | 0.014 (5) | 0.000 (5) |
| C5 | 0.031 (5) | 0.056 (7) | 0.041 (6) | −0.003 (5) | 0.016 (4) | −0.003 (5) |
| C6 | 0.037 (5) | 0.041 (5) | 0.045 (6) | 0.001 (4) | 0.023 (5) | 0.000 (4) |
| O7 | 0.035 (4) | 0.043 (4) | 0.036 (4) | −0.003 (3) | 0.016 (3) | −0.002 (3) |
| S8 | 0.0440 (14) | 0.0404 (13) | 0.0391 (14) | −0.0015 (11) | 0.0164 (12) | 0.0009 (11) |
| N9 | 0.032 (4) | 0.041 (5) | 0.044 (5) | 0.002 (3) | 0.020 (4) | 0.000 (4) |
| C10 | 0.039 (6) | 0.039 (5) | 0.050 (7) | −0.001 (4) | 0.019 (5) | −0.003 (5) |
| C11 | 0.037 (6) | 0.050 (6) | 0.044 (6) | 0.000 (5) | 0.016 (5) | −0.009 (5) |
| C12 | 0.039 (6) | 0.052 (6) | 0.038 (6) | 0.003 (5) | 0.016 (5) | −0.001 (5) |
| C13 | 0.042 (6) | 0.047 (6) | 0.043 (6) | 0.004 (5) | 0.024 (5) | 0.007 (5) |
| C14 | 0.032 (5) | 0.044 (6) | 0.040 (6) | 0.001 (4) | 0.017 (4) | −0.001 (4) |
| O15 | 0.038 (4) | 0.042 (4) | 0.034 (4) | 0.000 (3) | 0.014 (3) | 0.005 (3) |
| S16 | 0.0399 (14) | 0.0399 (13) | 0.0381 (14) | −0.0016 (10) | 0.0154 (11) | −0.0001 (10) |
| Pt1—O15 | 2.045 (7) | N9—C14 | 1.364 (13) |
| Pt1—O7 | 2.052 (7) | C10—C11 | 1.356 (16) |
| Pt1—S16 | 2.234 (3) | C11—C12 | 1.389 (16) |
| Pt1—S8 | 2.239 (3) | C12—C13 | 1.376 (16) |
| N1—C6 | 1.348 (13) | C13—C14 | 1.403 (15) |
| N1—C2 | 1.357 (13) | C14—S16 | 1.730 (11) |
| N1—O7 | 1.367 (11) | C2—H2 | 0.9500 |
| C2—C3 | 1.372 (16) | C3—H3 | 0.9500 |
| C3—C4 | 1.399 (17) | C4—H4 | 0.9500 |
| C4—C5 | 1.367 (16) | C5—H5 | 0.9500 |
| C5—C6 | 1.410 (15) | C10—H10 | 0.9500 |
| C6—S8 | 1.725 (11) | C11—H11 | 0.9500 |
| N9—C10 | 1.359 (14) | C12—H12 | 0.9500 |
| N9—O15 | 1.363 (11) | C13—H13 | 0.9500 |
| O15—Pt1—O7 | 90.0 (3) | C10—N9—C14 | 122.1 (10) |
| O15—Pt1—S16 | 86.4 (2) | O15—N9—C14 | 121.0 (9) |
| O7—Pt1—S16 | 176.3 (2) | C11—C10—N9 | 120.6 (10) |
| O15—Pt1—S8 | 176.4 (2) | C10—C11—C12 | 119.2 (11) |
| O7—Pt1—S8 | 86.4 (2) | C13—C12—C11 | 120.2 (11) |
| S16—Pt1—S8 | 97.13 (10) | C12—C13—C14 | 120.0 (10) |
| C6—N1—C2 | 123.8 (10) | N9—C14—C13 | 117.8 (10) |
| C6—N1—O7 | 120.7 (9) | N9—C14—S16 | 119.2 (8) |
| C2—N1—O7 | 115.4 (9) | C13—C14—S16 | 122.9 (9) |
| N1—C2—C3 | 119.2 (11) | N9—O15—Pt1 | 115.1 (6) |
| C2—C3—C4 | 119.6 (11) | C14—S16—Pt1 | 98.1 (4) |
| C5—C4—C3 | 119.3 (11) | N1—C2—H2 | 120.0 |
| C4—C5—C6 | 121.0 (11) | C3—C2—H2 | 120.0 |
| N1—C6—C5 | 117.0 (10) | C2—C3—H3 | 120.0 |
| N1—C6—S8 | 120.6 (8) | C4—C3—H3 | 120.0 |
| C5—C6—S8 | 122.4 (9) | C3—C4—H4 | 120.0 |
| N1—O7—Pt1 | 114.7 (6) | C5—C4—H4 | 120.0 |
| C6—S8—Pt1 | 97.5 (4) | C4—C5—H5 | 119.0 |
| C10—N9—O15 | 116.8 (9) | C6—C5—H5 | 120.0 |
| Pt1—O15 | 2.045 (7) | Pt1—S16 | 2.234 (3) |
| Pt1—O7 | 2.052 (7) | Pt1—S8 | 2.239 (3) |
| O15—Pt1—O7 | 90.0 (3) | O15—Pt1—S8 | 176.4 (2) |
| O15—Pt1—S16 | 86.4 (2) | O7—Pt1—S8 | 86.4 (2) |
| O7—Pt1—S16 | 176.3 (2) | S16—Pt1—S8 | 97.13 (10) |
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N-oxides and their derivatives show a broad spectrum of biological activity, such as antifungal, antibacterial, antimicrobial and antibiotic activities (Lobana & Bhatia, 1989; Symons et al., 1985). These compounds are also found to be involved in DNA strand scission under physiological conditions (Katsuyuki et al., 1991; Bovin et al.; 1992). Pyridine N-oxides bearing a sulfur group at the 2-position display significant antimicrobial activity (Leonard et al., 1955). The crystal structure of the title compound in the trans configuration has already been reported (Zhou et al., 2005). The crystal structures of cis-bis(2-mercaptopyridine N-oxide)palladium and cis-bis(2-mercaptopyridine N-oxide)nickel have already been reported (Shi et al., 1997; Chen et al., 1991).
In the title compound, the Pt is coordinated by two O atoms and two S atoms from two mercaptopyridine N-oxide ligands in a cis configuration. The coordination geometry is distorted square-planar. The whole molecule exhibits pseudo-C2v symmetry, with a pseudo-C2 axis passing through the platinum atom. The average Pt—O and Pt—S distances of 2.048 (7) and 2.236 (3) Å of the title compound are comparable with the values reported in the literature (Dyksterhouse et al., 2000). The mean Pt—S bond length (2.236 (3) Å,) is shorter while the mean Pt—O bond length (2.048 (7) Å) is longer than those reported for the trans isomer (Pt—S 2.270 Å; Pt—O 2.007 Å) (Zhou et al., 2005). The C—S bond distances [1.725 (11) and 1.730 (11) Å] are slightly longer than those reported for the uncoordinated thione molecule [1.692 (2)–1.698 (2) Å; Ohms et al., 1982]. The mean C—S bond length (1.727 Å) shows partial double bond character; it is shorter than the normal covalent bond distance of 1.81 (2) Å, for a C—S single bond (Lydon et al., 1982). This further results in the fact that complexes with mercaptopyridine oxide (mpo) ligands have little ability to bridge another metal ion through a sulfur atom to form polynuclear complexes (Shi et al., 1997). The entire molecule is essentially planar, with a maximum deviation from planarity of 0.0124 (2) Å for atom C3. The dihedral angle between the two pyridine rings is 5.85 (2)°.