(OC-6-35)-(2,2'-Bipyridine-κN,N')dimeth-yl(3-sulfido-propionato-κS,O)platinum(IV).

The title complex, [Pt(CH(3))(2)(SCH(2)CH(2)CO(2))(C(10)H(8)N(2))], is formed by the unusual oxidative addition of the disulfide, R(2)S(2) (R = CH(2)CH(2)CO(2)H), to (2,2'-bipyridine)-dimethyl-platin-um(II) with elimination of RSH. The product contains an unusual six-membered thiol-ate-carboxyl-ate chelate ring. This slightly distorted octa-hedral complex exhibits cis angles ranging from 77.55 (11) to 97.30 (8)° due to the presence of the thiol-ate-carboxyl-ate chelate ring and the constrained bipyridine group. The crystal packing appears to be controlled by a combination of π-stacking [centroid-centroid distance = 3.611 (2) Å] and C-H⋯O inter-actions.

Related literature

For general background to metal complexes with thiol­ate–carboxyl­ate chelates, see: Henderson et al. (2000 ▶); McCready & Puddephatt (2011 ▶); Phillips & Burford (2008 ▶). For the utility and application of disulfides and their reactivity towards transition metals, see: Aye et al. (1993 ▶); Bonnington et al. (2008 ▶); Wei et al. (2005 ▶). For normal ranges of bond angles at platinum(IV) between cis ligands, see: Achar et al. (1993 ▶); Aye et al. (1988 ▶). For inter­planar spacing between bipyridine rings in platinum(IV) complexes of 2,2′-bipyridine, see: Au et al. (2009 ▶). For the preparation of dimeth­yl(2,2′-bipyridine)­plat­inum(II), see: Monaghan & Puddephatt (1984 ▶).

Experimental

Crystal data

[Pt(CH3)2(C3H4O2S)(C10H8N2)]

M = 485.46

Monoclinic,

a = 14.0759 (6) Å

b = 7.7487 (3) Å

c = 14.2306 (5) Å

β = 98.978 (2)°

V = 1533.11 (10) Å3

Z = 4

Mo Kα radiation

μ = 9.29 mm−1

T = 150 K

0.04 × 0.04 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.708, T max = 0.858

52534 measured reflections

4672 independent reflections

3735 reflections with I > 2σ(I)

R int = 0.074

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.049

S = 1.04

4672 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.92 e Å−3

Δρmin = −1.42 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013626/tk2735sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013626/tk2735Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Pt(CH3)2(C3H4O2S)(C10H8N2)]	F(000) = 928
Mr = 485.46	Dx = 2.103 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7767 reflections
a = 14.0759 (6) Å	θ = 2.2–23.9°
b = 7.7487 (3) Å	µ = 9.29 mm−1
c = 14.2306 (5) Å	T = 150 K
β = 98.978 (2)°	Block, orange
V = 1533.11 (10) Å3	0.04 × 0.04 × 0.02 mm
Z = 4

Bruker APEXII CCD diffractometer	4672 independent reflections
Radiation source: fine-focus sealed tube	3735 reflections with I > 2σ(I)
graphite	Rint = 0.074
φ and ω scans	θmax = 30.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −20→20
Tmin = 0.708, Tmax = 0.858	k = −11→11
52534 measured reflections	l = −20→20

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.049	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0113P)2 + 3.0575P] where P = (Fo2 + 2Fc2)/3
4672 reflections	(Δ/σ)max = 0.001
192 parameters	Δρmax = 0.92 e Å−3
0 restraints	Δρmin = −1.42 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	0.032981 (10)	0.174968 (18)	0.254103 (9)	0.01904 (4)
S1	0.12815 (8)	0.07657 (14)	0.14873 (7)	0.0283 (2)
O1	−0.1206 (2)	−0.2968 (4)	0.2172 (2)	0.0406 (8)
N1	−0.0415 (2)	0.2693 (4)	0.3609 (2)	0.0195 (6)
C1	0.0013 (3)	0.2400 (5)	0.4520 (2)	0.0196 (7)
O2	−0.0384 (2)	−0.0655 (3)	0.26891 (18)	0.0277 (6)
N2	0.1270 (2)	0.1055 (4)	0.3823 (2)	0.0195 (6)
C2	−0.1257 (3)	0.3538 (5)	0.3450 (3)	0.0260 (8)
H2	−0.1548	0.3754	0.2813	0.031*
C3	−0.1716 (3)	0.4105 (5)	0.4185 (3)	0.0311 (9)
H3	−0.2312	0.4701	0.4054	0.037*
C4	−0.1293 (3)	0.3790 (5)	0.5112 (3)	0.0283 (9)
H4	−0.1599	0.4159	0.5627	0.034*
C5	−0.0424 (3)	0.2938 (5)	0.5284 (3)	0.0230 (8)
H5	−0.0126	0.2718	0.5919	0.028*
C6	0.0944 (2)	0.1480 (4)	0.4640 (2)	0.0182 (7)
C7	0.2101 (3)	0.0196 (5)	0.3870 (3)	0.0257 (8)
H7	0.2328	−0.0094	0.3295	0.031*
C8	0.2641 (3)	−0.0284 (5)	0.4728 (3)	0.0277 (8)
H8	0.3227	−0.0898	0.4742	0.033*
C9	0.2314 (3)	0.0143 (5)	0.5566 (3)	0.0256 (8)
H9	0.2668	−0.0188	0.6162	0.031*
C10	0.1464 (3)	0.1060 (5)	0.5524 (3)	0.0242 (8)
H10	0.1239	0.1397	0.6092	0.029*
C11	0.1008 (3)	−0.1529 (5)	0.1446 (3)	0.0308 (9)
H11B	0.1342	−0.2073	0.0959	0.037*
H11A	0.1273	−0.2044	0.2069	0.037*
C12	−0.0063 (3)	−0.1973 (5)	0.1222 (3)	0.0304 (9)
H12B	−0.0372	−0.1179	0.0720	0.036*
H12A	−0.0129	−0.3159	0.0961	0.036*
C13	−0.0603 (3)	−0.1864 (5)	0.2073 (3)	0.0260 (8)
C14	0.0972 (3)	0.4106 (5)	0.2463 (3)	0.0272 (8)
H14A	0.0999	0.4385	0.1796	0.041*
H14B	0.1625	0.4071	0.2821	0.041*
H14C	0.0597	0.4990	0.2735	0.041*
C15	−0.0667 (3)	0.2486 (6)	0.1408 (3)	0.0296 (9)
H15A	−0.0815	0.3714	0.1466	0.044*
H15B	−0.1255	0.1806	0.1400	0.044*
H15C	−0.0409	0.2291	0.0816	0.044*

	U11	U22	U33	U12	U13	U23
Pt1	0.02214 (7)	0.01977 (7)	0.01574 (6)	0.00002 (7)	0.00464 (4)	0.00076 (6)
S1	0.0343 (5)	0.0298 (6)	0.0236 (5)	0.0024 (4)	0.0135 (4)	0.0001 (4)
O1	0.0444 (19)	0.0335 (18)	0.0450 (18)	−0.0164 (15)	0.0105 (15)	−0.0097 (14)
N1	0.0218 (15)	0.0184 (15)	0.0189 (14)	−0.0009 (12)	0.0043 (12)	−0.0014 (12)
C1	0.0235 (18)	0.0144 (17)	0.0219 (17)	−0.0065 (14)	0.0071 (14)	−0.0009 (14)
O2	0.0382 (16)	0.0254 (15)	0.0205 (13)	−0.0109 (12)	0.0081 (12)	−0.0025 (11)
N2	0.0202 (15)	0.0218 (16)	0.0165 (14)	−0.0022 (13)	0.0029 (11)	0.0011 (12)
C2	0.0268 (19)	0.023 (2)	0.0285 (19)	−0.0001 (16)	0.0050 (16)	0.0001 (16)
C3	0.026 (2)	0.028 (2)	0.041 (2)	0.0060 (17)	0.0090 (18)	−0.0030 (18)
C4	0.034 (2)	0.023 (2)	0.032 (2)	−0.0028 (17)	0.0162 (17)	−0.0061 (16)
C5	0.031 (2)	0.019 (2)	0.0215 (17)	−0.0050 (15)	0.0107 (15)	−0.0021 (14)
C6	0.0217 (17)	0.0154 (18)	0.0183 (15)	−0.0055 (14)	0.0054 (13)	−0.0030 (13)
C7	0.0204 (18)	0.034 (2)	0.0231 (18)	0.0031 (16)	0.0038 (14)	0.0014 (16)
C8	0.0207 (18)	0.030 (2)	0.032 (2)	−0.0005 (17)	0.0007 (16)	0.0047 (17)
C9	0.0265 (19)	0.026 (2)	0.0220 (17)	−0.0073 (16)	−0.0028 (15)	0.0045 (15)
C10	0.027 (2)	0.024 (2)	0.0215 (18)	−0.0057 (16)	0.0031 (15)	−0.0022 (15)
C11	0.039 (2)	0.027 (2)	0.0275 (19)	0.0063 (18)	0.0086 (17)	−0.0018 (17)
C12	0.043 (2)	0.025 (2)	0.0225 (18)	0.0005 (19)	0.0037 (17)	−0.0041 (16)
C13	0.0288 (19)	0.024 (2)	0.0237 (17)	0.0000 (18)	−0.0001 (15)	0.0049 (16)
C14	0.032 (2)	0.023 (2)	0.029 (2)	−0.0021 (17)	0.0106 (17)	0.0023 (16)
C15	0.030 (2)	0.033 (2)	0.0233 (19)	0.0091 (18)	−0.0045 (16)	0.0001 (17)

Pt1—C15	2.046 (4)	C5—H5	0.9500
Pt1—C14	2.048 (4)	C6—C10	1.393 (5)
Pt1—N1	2.107 (3)	C7—C8	1.385 (5)
Pt1—O2	2.143 (3)	C7—H7	0.9500
Pt1—N2	2.149 (3)	C8—C9	1.383 (5)
Pt1—S1	2.2916 (9)	C8—H8	0.9500
S1—C11	1.818 (4)	C9—C10	1.384 (5)
O1—C13	1.230 (5)	C9—H9	0.9500
N1—C2	1.342 (5)	C10—H10	0.9500
N1—C1	1.361 (4)	C11—C12	1.531 (6)
C1—C5	1.395 (5)	C11—H11B	0.9900
C1—C6	1.478 (5)	C11—H11A	0.9900
O2—C13	1.287 (5)	C12—C13	1.529 (5)
N2—C7	1.338 (5)	C12—H12B	0.9900
N2—C6	1.355 (4)	C12—H12A	0.9900
C2—C3	1.383 (5)	C14—H14A	0.9800
C2—H2	0.9500	C14—H14B	0.9800
C3—C4	1.382 (6)	C14—H14C	0.9800
C3—H3	0.9500	C15—H15A	0.9800
C4—C5	1.378 (5)	C15—H15B	0.9800
C4—H4	0.9500	C15—H15C	0.9800
C15—Pt1—C14	87.88 (17)	C10—C6—C1	123.3 (3)
C15—Pt1—N1	96.54 (14)	N2—C7—C8	122.1 (3)
C14—Pt1—N1	90.17 (13)	N2—C7—H7	118.9
C15—Pt1—O2	92.60 (15)	C8—C7—H7	118.9
C14—Pt1—O2	176.55 (12)	C9—C8—C7	119.0 (4)
N1—Pt1—O2	86.39 (11)	C9—C8—H8	120.5
C15—Pt1—N2	174.03 (14)	C7—C8—H8	120.5
C14—Pt1—N2	92.92 (14)	C8—C9—C10	119.2 (4)
N1—Pt1—N2	77.55 (11)	C8—C9—H9	120.4
O2—Pt1—N2	86.26 (11)	C10—C9—H9	120.4
C15—Pt1—S1	88.64 (12)	C9—C10—C6	119.2 (3)
C14—Pt1—S1	87.34 (11)	C9—C10—H10	120.4
N1—Pt1—S1	174.16 (9)	C6—C10—H10	120.4
O2—Pt1—S1	96.09 (7)	C12—C11—S1	115.0 (3)
N2—Pt1—S1	97.30 (8)	C12—C11—H11B	108.5
C11—S1—Pt1	101.78 (13)	S1—C11—H11B	108.5
C2—N1—C1	119.3 (3)	C12—C11—H11A	108.5
C2—N1—Pt1	125.0 (2)	S1—C11—H11A	108.5
C1—N1—Pt1	115.6 (2)	H11B—C11—H11A	107.5
N1—C1—C5	120.6 (3)	C13—C12—C11	114.7 (3)
N1—C1—C6	116.3 (3)	C13—C12—H12B	108.6
C5—C1—C6	123.0 (3)	C11—C12—H12B	108.6
C13—O2—Pt1	129.2 (2)	C13—C12—H12A	108.6
C7—N2—C6	119.3 (3)	C11—C12—H12A	108.6
C7—N2—Pt1	125.7 (2)	H12B—C12—H12A	107.6
C6—N2—Pt1	114.9 (2)	O1—C13—O2	121.6 (4)
N1—C2—C3	122.2 (4)	O1—C13—C12	119.4 (4)
N1—C2—H2	118.9	O2—C13—C12	119.0 (3)
C3—C2—H2	118.9	Pt1—C14—H14A	109.5
C4—C3—C2	118.9 (4)	Pt1—C14—H14B	109.5
C4—C3—H3	120.6	H14A—C14—H14B	109.5
C2—C3—H3	120.6	Pt1—C14—H14C	109.5
C5—C4—C3	119.5 (3)	H14A—C14—H14C	109.5
C5—C4—H4	120.2	H14B—C14—H14C	109.5
C3—C4—H4	120.2	Pt1—C15—H15A	109.5
C4—C5—C1	119.5 (4)	Pt1—C15—H15B	109.5
C4—C5—H5	120.3	H15A—C15—H15B	109.5
C1—C5—H5	120.3	Pt1—C15—H15C	109.5
N2—C6—C10	121.1 (3)	H15A—C15—H15C	109.5
N2—C6—C1	115.5 (3)	H15B—C15—H15C	109.5
C15—Pt1—S1—C11	−98.02 (19)	N1—Pt1—N2—C6	1.7 (2)
C14—Pt1—S1—C11	174.04 (18)	O2—Pt1—N2—C6	−85.4 (2)
N1—Pt1—S1—C11	109.3 (8)	S1—Pt1—N2—C6	178.9 (2)
O2—Pt1—S1—C11	−5.56 (16)	C1—N1—C2—C3	−0.9 (6)
N2—Pt1—S1—C11	81.44 (16)	Pt1—N1—C2—C3	179.1 (3)
C15—Pt1—N1—C2	−2.1 (3)	N1—C2—C3—C4	0.0 (6)
C14—Pt1—N1—C2	85.8 (3)	C2—C3—C4—C5	0.6 (6)
O2—Pt1—N1—C2	−94.3 (3)	C3—C4—C5—C1	−0.2 (6)
N2—Pt1—N1—C2	178.7 (3)	N1—C1—C5—C4	−0.7 (5)
S1—Pt1—N1—C2	150.4 (7)	C6—C1—C5—C4	179.9 (3)
C15—Pt1—N1—C1	177.9 (3)	C7—N2—C6—C10	0.8 (5)
C14—Pt1—N1—C1	−94.2 (3)	Pt1—N2—C6—C10	178.0 (3)
O2—Pt1—N1—C1	85.7 (3)	C7—N2—C6—C1	−179.0 (3)
N2—Pt1—N1—C1	−1.2 (2)	Pt1—N2—C6—C1	−1.9 (4)
S1—Pt1—N1—C1	−29.5 (10)	N1—C1—C6—N2	0.8 (5)
C2—N1—C1—C5	1.3 (5)	C5—C1—C6—N2	−179.8 (3)
Pt1—N1—C1—C5	−178.8 (3)	N1—C1—C6—C10	−179.0 (3)
C2—N1—C1—C6	−179.3 (3)	C5—C1—C6—C10	0.4 (5)
Pt1—N1—C1—C6	0.7 (4)	C6—N2—C7—C8	0.3 (6)
C15—Pt1—O2—C13	56.8 (3)	Pt1—N2—C7—C8	−176.4 (3)
C14—Pt1—O2—C13	155 (2)	N2—C7—C8—C9	−0.3 (6)
N1—Pt1—O2—C13	153.2 (3)	C7—C8—C9—C10	−0.9 (6)
N2—Pt1—O2—C13	−129.1 (3)	C8—C9—C10—C6	2.0 (6)
S1—Pt1—O2—C13	−32.1 (3)	N2—C6—C10—C9	−2.0 (5)
C15—Pt1—N2—C7	170.6 (13)	C1—C6—C10—C9	177.8 (3)
C14—Pt1—N2—C7	−91.9 (3)	Pt1—S1—C11—C12	53.1 (3)
N1—Pt1—N2—C7	178.6 (3)	S1—C11—C12—C13	−81.1 (4)
O2—Pt1—N2—C7	91.5 (3)	Pt1—O2—C13—O1	−162.2 (3)
S1—Pt1—N2—C7	−4.2 (3)	Pt1—O2—C13—C12	20.8 (5)
C15—Pt1—N2—C6	−6.3 (15)	C11—C12—C13—O1	−139.6 (4)
C14—Pt1—N2—C6	91.2 (3)	C11—C12—C13—O2	37.5 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O2i	0.95	2.33	3.175 (5)	148

Pt1—C15	2.046 (4)
Pt1—C14	2.048 (4)
Pt1—N1	2.107 (3)
Pt1—O2	2.143 (3)
Pt1—N2	2.149 (3)
Pt1—S1	2.2916 (9)

C15—Pt1—C14	87.88 (17)
C15—Pt1—N1	96.54 (14)
C14—Pt1—N1	90.17 (13)
C15—Pt1—O2	92.60 (15)
N1—Pt1—O2	86.39 (11)
C14—Pt1—N2	92.92 (14)
N1—Pt1—N2	77.55 (11)
O2—Pt1—N2	86.26 (11)
C15—Pt1—S1	88.64 (12)
C14—Pt1—S1	87.34 (11)
N1—Pt1—S1	174.16 (9)
O2—Pt1—S1	96.09 (7)
N2—Pt1—S1	97.30 (8)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O2i	0.95	2.33	3.175 (5)	148

Symmetry code: (i) .