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The title compound, cis-[Pt(CH3COO)2(C2H6S)2], crystallizes in the P21/c space group with a pseudo-square-planar coordination geometry. The complex forms centrosymmetric dimeric packing units, with C-H...O-Pt inter­actions and a short Pt...Pt distance [3.5868 (2) Å]. The coordination mode of the acetate ligands is monodentate and they are oriented almost perpendicular to the coordination plane. Cambridge Structural Database [Allen (2002). Acta Cryst. B58, 380-388] data show a preferred staggered conformation with respect to the coordination plane for Me2S in complexes with PtII.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107061902/sq3114sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107061902/sq3114Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108270107061902/sq3114sup3.pdf
Supplementary material

CCDC reference: 677204

Comment top

No diacetatoplatinum(II) complex with sulfur donor ligands has previously been reported to the Cambridge Structural Database (CSD; Version 5.28 of November 2006; Allen, 2002). Out of 13 acetatoplatinum(II) complexes found in the CSD, eight contain acetate ligands that bridge two platinum(II) ions (in one case one acetate ligand coordinates to three platinum ions), two are cis- and two trans-complexes, and one complex contains a single acetate ligand. Only one diacetatoplatinum(II) complex with nonbridging acetate ligands and identical nonchelating neutral ligands is reported, trans-[Pt(CH3COO)2(PPh3)2] (Basato et al., 2003). Acetate and nitrate ions are topologically related, and the structure of cis-[Pt(Me2S)2(NO3)2] has recently been reported (Hansson & Oskarsson, 2007). We report here the crystal structure of the title compound with emphasis on (i) the coordination mode of the acetate ion compared with the nitrate ion; (ii) the packing of the title compound in relation to other PtX2L2 compounds, X being a ligand with charge -1 and L being a neutral ligand; and (iii) the coordination mode of dimethyl sulfide (dms) in relation to other PtIIA4-n(Me2S)n (where A is any ligand and n = 1–4) complexes.

cis-[Pt(CH3COO)2(Me2S)2], (I), has a pseudo-square-planar coordination geometry (Fig. 1). The Pt—O and Pt—S bonds (Table 1) illustrate the different trans influence of the O and S atoms, which was previously observed in cis-[Pt(Me2S)2(NO3)2] (Hansson & Oskarsson, 2007). The Pt—O distances are elongated by ~0.04 Å compared with those in [Pt(NO3)4]2- (Elding & Oskarsson, 1985) and the Pt—S distances are shortened ~0.06 Å compared with [Pt(Me2S)4]2+ (Bugarcic et al., 1991)

The two acetate ligands coordinate in a monodentate fashion via one of the O atoms, as shown by the differences in the Pt1—O1/Pt1—O2 and Pt1—O3/Pt1—O4 distances being more than 1 Å and thus fulfilling the criterion of a difference of more than 0.6 Å suggested by Kleywegt et al. (1985) for monodentate nitrate ligands. This is further supported by the differences in the C5—O1/ C5—O2 and C7—O3/C7—O4 distances, which are approximately 0.1 Å (Table 1). Both acetate ligands are oriented almost perpendicular to the coordination plane, as shown by the torsion angles S2—Pt1—O1—C5 [-81.8 (3)°] and S1—Pt1—O3—C7 [79.9 (3)°], and both the noncoordinated O2 and O4 atoms are on the same side of the coordination plane. In the corresponding cis-[PtL2(NO3)2] complexes, seven have nitrate ions on opposite sides, five on the same side and two in the plane (Hansson & Oskarsson, 2007). The most striking difference in behavior between acetate and nitrate in these systems is the greater tendency of the acetate ion to form bridging polynuclear complexes compared with the nitrate ion.

The dms ligands are oriented similarly and coordinate to the platinum in a semi-staggered conformation, with C—S1—Pt1—S2 and C—S2—Pt1—O1 torsion angles of ~79 and ~-27°.

The packing of the title compound features centrosymmetric dimers (Fig. 2) across (1/2, 0, 0) and (1/2, 1/2, 1/2), which are held together by C—H···O—Pt interactions (H2B—O1i = 2.58 Å and H4B—O3i = 2.60 Å; all symmetry codes as in Table 2). The Pt1···Pt1i distance is 3.5868 (2) Å, which probably also represents an attractive interaction, since the stabilizing energy of the dimer is 57 kJ mol-1 monomer according to density functional theory (DFT) calculations. The centers of gravity of the dimers form an I-centered monoclinic unit cell (easily seen after a suitable unit-cell transformation), i.e. each dimer is surrounded by 14 others. It is interesting to note that such a packing is common for centrosymmetric trans-[PtX2L2] compounds (Hansson et al., 2006). The four carbonyl O atoms point towards neighbouring dimers and are directed along the c axis. These atoms take part in C—H···OC interactions with H2A—O4ii = 2.50 Å, H4C—O2iii = 2.62 Å and H3A—O2iii = 2.65 Å. Voids are formed at (0, 0, 0), (0, 0, 1/2) and (1/2, 0, 1/2). Six-membered rings are formed around the voids with C—H···O interactions.

A CONQUEST (Bruno et al., 2002) search of the CSD for PtII compounds with one or more dms molecules coordinated to the metal centre resulted in 44 complexes of the type [PtIIA4-n(Me2S)n] (where A is any ligand), containing in total 79 dm s ligands (deposited material). Complexes with bridging dms ligands and compounds without atomic coordinates reported in the database were excluded. The angle between the two Me—S bonds and the coordination plane was estimated using the C—S—Pt—A torsion angle (where A is cis to the Me2S ligand, and n = 1–4). Three different behaviours are observed. Four Me2S (5%) ligands have both methyl groups on the same side of the coordination plane, and 15 (19%) are close to eclipsed with one torsion angle in the range 2–12°. However, the staggered conformation with torsion angle 35–55° dominates strongly (69% of the 79 reported Me2S ligands).

Related literature top

For related literature, see: Allen (2002); Alrichs et al. (1989); Basato et al. (2003); Bruno et al. (2002); Bugarcic et al. (1991); Elding & Oskarsson (1985); Hansson & Oskarsson (2007); Hansson et al. (2006); Kleywegt et al. (1985).

Experimental top

Pt(Me2S)2I2 (0.317 g, 0.554 mmol) was dissolved in 15 ml of acetone. Ag(CH3COO) (0.192 g, 1.15 mmol) was added, and the reaction mixture was stirred for 90 min. Solid AgI was then removed by filtration. The pale-yellow acetone solution was left to evaporate slowly, which resulted in a yellow solid. Crystals suitable for X-ray diffraction experiments were obtained from recrystallization in a diethyl ether–ethanol mixture (2:1 in volume). DFT calculations were performed at the s-VWN level with the basis sets def-TZVPP for Pt, TZVPP for S and O, and 6–31G* for C and H atoms, using the software TURBOMOLE 5.5 (Alrichs et al., 1989).

Refinement top

H-atoms were positioned geometrically and treated as riding on the adjacent C atom [C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C)].

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003) and enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. The numbering scheme for the title compound. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A stereoscopic view of the packing of the title compound. One centrosymmetric dimeric pair of complexes is visible at the center of the cell.
cis-Bis(acetato-κO)bis(dimethyl sulfide-κS)platinum(II) top
Crystal data top
[Pt(C2H3O2)2(C2H6S)2]F(000) = 832
Mr = 437.43Dx = 2.156 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6622 reflections
a = 8.7306 (5) Åθ = 2.4–32.5°
b = 10.3274 (5) ŵ = 10.71 mm1
c = 15.5205 (9) ÅT = 295 K
β = 105.623 (3)°Plate, yellow
V = 1347.69 (13) Å30.28 × 0.12 × 0.05 mm
Z = 4
Data collection top
Oxford Diffraction XCALIBUR3
diffractometer
4530 independent reflections
Radiation source: Sealed tube3389 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
ω–scansθmax = 32.5°, θmin = 2.4°
Absorption correction: numerical
(CrysAlis RED; Oxford Diffraction, 2006)
h = 1212
Tmin = 0.115, Tmax = 0.629k = 1510
12845 measured reflectionsl = 2223
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0352P)2]
where P = (Fo2 + 2Fc2)/3
4530 reflections(Δ/σ)max = 0.002
136 parametersΔρmax = 1.71 e Å3
0 restraintsΔρmin = 1.15 e Å3
Crystal data top
[Pt(C2H3O2)2(C2H6S)2]V = 1347.69 (13) Å3
Mr = 437.43Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.7306 (5) ŵ = 10.71 mm1
b = 10.3274 (5) ÅT = 295 K
c = 15.5205 (9) Å0.28 × 0.12 × 0.05 mm
β = 105.623 (3)°
Data collection top
Oxford Diffraction XCALIBUR3
diffractometer
4530 independent reflections
Absorption correction: numerical
(CrysAlis RED; Oxford Diffraction, 2006)
3389 reflections with I > 2σ(I)
Tmin = 0.115, Tmax = 0.629Rint = 0.059
12845 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.073H-atom parameters constrained
S = 0.97Δρmax = 1.71 e Å3
4530 reflectionsΔρmin = 1.15 e Å3
136 parameters
Special details top

Experimental. The intensity data was collected on an Oxford Diffraction Xcalibur3 diffractometer at 295 K. Exposure time was 20 s and frame width 0.75°. For each crystal, 552 frames were collected with one reference frame every 50t h frame. No decay was observed.

The structure was solved using Patterson and difference Fourier methods, and the structure was refined with full-matrix least-square calculations. All non-H atoms were refined anisotropically.

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 (Å2) top
xyzUiso*/Ueq
Pt10.434083 (16)0.095433 (13)0.900324 (9)0.03304 (5)
S10.65690 (11)0.02181 (10)0.86853 (6)0.0391 (2)
S20.27365 (13)0.05173 (10)0.81290 (7)0.0431 (2)
O10.2535 (4)0.1649 (3)0.94666 (18)0.0479 (7)
O30.5713 (4)0.2267 (3)0.98561 (18)0.0485 (7)
O20.1427 (5)0.2960 (4)0.8336 (2)0.0688 (10)
O40.5971 (5)0.3568 (4)0.8767 (2)0.0695 (10)
C70.6168 (5)0.3325 (4)0.9550 (3)0.0412 (8)
C50.1497 (5)0.2469 (4)0.9055 (3)0.0427 (9)
C20.6406 (6)0.1478 (4)0.8385 (3)0.0516 (10)
H2A0.55950.15890.78330.077*
H2B0.61330.19660.88490.077*
H2C0.74050.17790.83140.077*
C10.6592 (7)0.0864 (5)0.7605 (4)0.0615 (14)
H1A0.74100.04440.74010.092*
H1B0.67980.17780.76570.092*
H1C0.55790.07140.71840.092*
C40.1166 (6)0.0896 (5)0.8629 (4)0.0623 (14)
H4A0.06270.01150.87110.093*
H4B0.16030.13030.91990.093*
H4C0.04250.14750.82460.093*
C80.6983 (7)0.4268 (5)1.0266 (4)0.0656 (15)
H8A0.73110.50150.99940.098*
H8B0.78990.38631.06570.098*
H8C0.62610.45271.06030.098*
C30.1627 (7)0.0336 (5)0.7156 (3)0.0614 (13)
H3A0.07230.01720.68510.092*
H3B0.22910.04880.67640.092*
H3C0.12720.11490.73320.092*
C60.0294 (6)0.2790 (5)0.9570 (4)0.0610 (12)
H6A0.05260.33310.92090.092*
H6B0.08160.32381.01110.092*
H6C0.01700.20050.97140.092*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.03463 (8)0.03450 (8)0.03047 (8)0.00007 (6)0.00960 (6)0.00010 (5)
S10.0342 (5)0.0454 (5)0.0381 (5)0.0001 (4)0.0102 (4)0.0028 (4)
S20.0391 (5)0.0388 (5)0.0502 (6)0.0039 (4)0.0101 (4)0.0053 (4)
O10.0521 (18)0.0533 (17)0.0442 (15)0.0164 (14)0.0233 (14)0.0079 (13)
O30.0639 (19)0.0463 (15)0.0335 (13)0.0093 (15)0.0099 (13)0.0051 (12)
O20.074 (2)0.087 (3)0.0485 (18)0.033 (2)0.0219 (17)0.0194 (17)
O40.093 (3)0.070 (2)0.0440 (18)0.028 (2)0.0160 (19)0.0047 (17)
C70.038 (2)0.044 (2)0.043 (2)0.0018 (16)0.0136 (17)0.0095 (17)
C50.038 (2)0.046 (2)0.043 (2)0.0012 (17)0.0095 (17)0.0055 (17)
C20.049 (3)0.043 (2)0.060 (3)0.007 (2)0.011 (2)0.006 (2)
C10.070 (4)0.069 (3)0.058 (3)0.011 (2)0.039 (3)0.016 (2)
C40.041 (2)0.083 (4)0.060 (3)0.020 (2)0.009 (2)0.008 (2)
C80.073 (4)0.065 (3)0.059 (3)0.018 (3)0.019 (3)0.027 (2)
C30.077 (4)0.065 (3)0.035 (2)0.008 (3)0.003 (2)0.003 (2)
C60.050 (3)0.068 (3)0.073 (3)0.014 (2)0.030 (2)0.005 (3)
Geometric parameters (Å, º) top
Pt1—O12.032 (3)C2—H2C0.9600
Pt1—O32.043 (3)C1—H1A0.9600
Pt1—S22.2559 (10)C1—H1B0.9600
Pt1—S12.2633 (10)C1—H1C0.9600
S1—C21.808 (4)C4—H4A0.9600
S1—C11.809 (5)C4—H4B0.9600
S2—C31.791 (5)C4—H4C0.9600
S2—C41.792 (5)C8—H8A0.9600
O1—C51.278 (5)C8—H8B0.9600
O3—C71.296 (5)C8—H8C0.9600
O2—C51.213 (5)C3—H3A0.9600
O4—C71.207 (5)C3—H3B0.9600
C7—C81.504 (6)C3—H3C0.9600
C5—C61.517 (6)C6—H6A0.9600
C2—H2A0.9600C6—H6B0.9600
C2—H2B0.9600C6—H6C0.9600
Pt1···Pt1i3.5868 (2)
O1—Pt1—O384.94 (13)H1A—C1—H1B109.5
O1—Pt1—S292.04 (10)S1—C1—H1C109.5
O3—Pt1—S2176.24 (9)H1A—C1—H1C109.5
O1—Pt1—S1171.97 (9)H1B—C1—H1C109.5
O3—Pt1—S188.61 (9)S2—C4—H4A109.5
S2—Pt1—S194.21 (4)S2—C4—H4B109.5
C2—S1—C197.9 (2)H4A—C4—H4B109.5
C2—S1—Pt1111.66 (16)S2—C4—H4C109.5
C1—S1—Pt1107.61 (18)H4A—C4—H4C109.5
C3—S2—C499.8 (3)H4B—C4—H4C109.5
C3—S2—Pt1106.43 (17)C7—C8—H8A109.5
C4—S2—Pt1108.07 (18)C7—C8—H8B109.5
C5—O1—Pt1124.8 (3)H8A—C8—H8B109.5
C7—O3—Pt1120.4 (3)C7—C8—H8C109.5
O4—C7—O3124.7 (4)H8A—C8—H8C109.5
O4—C7—C8121.3 (4)H8B—C8—H8C109.5
O3—C7—C8114.0 (4)S2—C3—H3A109.5
O2—C5—O1126.1 (4)S2—C3—H3B109.5
O2—C5—C6121.5 (4)H3A—C3—H3B109.5
O1—C5—C6112.4 (4)S2—C3—H3C109.5
S1—C2—H2A109.5H3A—C3—H3C109.5
S1—C2—H2B109.5H3B—C3—H3C109.5
H2A—C2—H2B109.5C5—C6—H6A109.5
S1—C2—H2C109.5C5—C6—H6B109.5
H2A—C2—H2C109.5H6A—C6—H6B109.5
H2B—C2—H2C109.5C5—C6—H6C109.5
S1—C1—H1A109.5H6A—C6—H6C109.5
S1—C1—H1B109.5H6B—C6—H6C109.5
O3—Pt1—S1—C2150.75 (19)O3—Pt1—O1—C5100.4 (3)
S2—Pt1—S1—C226.75 (17)S2—Pt1—O1—C581.8 (3)
O3—Pt1—S1—C1102.9 (2)O1—Pt1—O3—C7104.8 (3)
S2—Pt1—S1—C179.6 (2)S1—Pt1—O3—C779.9 (3)
O1—Pt1—S2—C379.1 (2)Pt1—O3—C7—O47.4 (6)
S1—Pt1—S2—C3105.9 (2)Pt1—O3—C7—C8172.3 (3)
O1—Pt1—S2—C427.3 (2)Pt1—O1—C5—O20.3 (6)
S1—Pt1—S2—C4147.70 (19)Pt1—O1—C5—C6179.6 (3)
Symmetry code: (i) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2B···O1i0.962.583.216 (5)124
C4—H4B···O3i0.962.603.392 (6)139
C2—H2A···O4ii0.962.503.425 (6)163
C4—H4C···O2iii0.962.623.479 (6)150
C3—H3A···O2iii0.962.653.552 (7)156
C1—H1B···S2iv0.963.123.996 (6)153
Symmetry codes: (i) x+1, y, z+2; (ii) x+1, y1/2, z+3/2; (iii) x, y1/2, z+3/2; (iv) x+1, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[Pt(C2H3O2)2(C2H6S)2]
Mr437.43
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)8.7306 (5), 10.3274 (5), 15.5205 (9)
β (°) 105.623 (3)
V3)1347.69 (13)
Z4
Radiation typeMo Kα
µ (mm1)10.71
Crystal size (mm)0.28 × 0.12 × 0.05
Data collection
DiffractometerOxford Diffraction XCALIBUR3
diffractometer
Absorption correctionNumerical
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.115, 0.629
No. of measured, independent and
observed [I > 2σ(I)] reflections
12845, 4530, 3389
Rint0.059
(sin θ/λ)max1)0.757
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.073, 0.97
No. of reflections4530
No. of parameters136
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.71, 1.15

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXTL (Sheldrick, 1998), DIAMOND (Brandenburg, 2000), CRYSTALS (Betteridge et al., 2003) and enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) top
Pt1—O12.032 (3)O3—C71.296 (5)
Pt1—O32.043 (3)O2—C51.213 (5)
Pt1—S22.2559 (10)O4—C71.207 (5)
Pt1—S12.2633 (10)C7—C81.504 (6)
O1—C51.278 (5)C5—C61.517 (6)
Pt1···Pt1i3.5868 (2)
O1—Pt1—O384.94 (13)O3—Pt1—S188.61 (9)
O1—Pt1—S292.04 (10)S2—Pt1—S194.21 (4)
O3—Pt1—S2176.24 (9)C5—O1—Pt1124.8 (3)
O1—Pt1—S1171.97 (9)C7—O3—Pt1120.4 (3)
Symmetry code: (i) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2B···O1i0.962.583.216 (5)124
C4—H4B···O3i0.962.603.392 (6)139
C2—H2A···O4ii0.962.503.425 (6)163
C4—H4C···O2iii0.962.623.479 (6)150
C3—H3A···O2iii0.962.653.552 (7)156
C1—H1B···S2iv0.963.123.996 (6)153
Symmetry codes: (i) x+1, y, z+2; (ii) x+1, y1/2, z+3/2; (iii) x, y1/2, z+3/2; (iv) x+1, y+1/2, z+3/2.
 

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