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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): m295.
Published online 2010 February 13. doi:  10.1107/S1600536810005520
PMCID: PMC2983664

trans-Chlorido(dimethyl sulfoxide-κS)(pyridine-2-carboxyl­ato-κ2 N,O)platinum(II)

Abstract

In the title complex, [Pt(C6H4NO2)Cl(C2H6OS)], the PtII ion is in a distorted square-planar environment defined by the N and O atoms from the chelating pyridine-2-carboxyl­ate (pic) anionic ligand, one S atom of the dimethyl sulfoxide mol­ecule and one Cl ion. The complex is disposed about a crystallographic mirror plane parallel to the ac plane passing through all the atoms of the complex except the methyl atoms of the dimethyl sulfoxide. The mol­ecules are stacked in columns along the b axis with a Pt(...)Pt distance of 4.9508 (5) Å. Within the column, inter­molecular C—H(...)O hydrogen bonds and weak π–π inter­actions between adjacent pyridine rings are present, the shortest centroid–centroid distance being 5.153 (4) Å.

Related literature

For the crystal structure of the title complex with the monoclinic space group P21/n, see: Annibale et al. (1986 [triangle]). For details of Pt(IV)–pic complexes, see: Griffith et al. (2005 [triangle]); Kim et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m295-scheme1.jpg

Experimental

Crystal data

  • [Pt(C6H4NO2)Cl(C2H6OS)]
  • M r = 430.77
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m295-efi1.jpg
  • a = 19.5900 (15) Å
  • b = 6.9450 (6) Å
  • c = 8.1266 (6) Å
  • V = 1105.64 (15) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 13.11 mm−1
  • T = 200 K
  • 0.21 × 0.17 × 0.09 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.631, T max = 1.000
  • 6423 measured reflections
  • 1169 independent reflections
  • 1085 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.027
  • wR(F 2) = 0.065
  • S = 1.10
  • 1169 reflections
  • 89 parameters
  • H-atom parameters constrained
  • Δρmax = 2.60 e Å−3
  • Δρmin = −0.79 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536810005520/si2243sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005520/si2243Isup2.hkl

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

Acknowledgments

This work was supported by Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2009–0094056).

supplementary crystallographic information

Comment

The title complex, [Pt(C6H4NO2)Cl(C2H6OS)], crystallized in the orthorhombic space group Pnma, whereas, in the previously reported X-ray structure analysis, the complex crystallized in the monoclinic space group P21/n (Annibale et al., 1986). The PtII ion lies in a distorted square-planar environment defined by the N and O atoms from the chelating pyridine-2-carboxylate (pic) anionic ligand, one S atom of the dimethyl sulfoxide molecule and one Cl ion (Fig. 1). The tight O1—Pt1—N1 chelate angle [81.0 (2)°] results in non-linear trans axes [<O1—Pt1—S1 = 177.70 (16)° and <N1—Pt1—Cl1 = 169.97 (19)°] (Table 1). The complex is disposed about a crystallographic mirror plane parallel to the ac plane passing through all the atoms of the complex at the special positions (x,1/4,z), except the methyl atoms of the dimethyl sulfoxide (Fig. 2). The molecules are stacked in columns along the b axis with a Pt···Pt distance of 4.9508 (5) Å. In the column, intermolecular C—H···O hydrogen bond (Table 2) and weak π-π interactions between adjacent pyridine rings are present, the shortest centroid-centroid distance being 5.153 (4) Å, and the ring planes are parallel and shifted for 3.807 Å. The intramolecular C—H···O and C—H···Cl hydrogen bonds are also observed (Table 2).

Experimental

Single crystals of the title complex were unexpectedly obtained by reacting K2PtCl4 (0.2000 g, 0.482 mmol) and pyridine-2-carboxylic acid (0.1192 g, 0.968 mmol) in H2O (10 ml) under reflux for 5 h. Crystals suitable for X-ray analysis were obtained by slow evaporation from a dimethyl sulfoxide solution of the pale yellow reaction product at 80 °C.

Refinement

H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.95 (aromatic) or 0.98 Å (CH3) and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C)]. The highest peak (2.60 e Å-3) and the deepest hole (-0.79 e Å-3) in the difference Fourier map are located 0.87 and 1.04 Å, respectively, from the atom Pt1.

Figures

Fig. 1.
The structure of the title complex, with displacement ellipsoids drawn at the 50% probability level for non-H atoms [Symmetry code: (a) x, 1/2 - y, z].
Fig. 2.
View of the unit-cell contents of the title complex. Hydrogen-bond interactions are drawn with dashed lines.

Crystal data

[Pt(C6H4NO2)Cl(C2H6OS)]F(000) = 800
Mr = 430.77Dx = 2.588 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 3961 reflections
a = 19.5900 (15) Åθ = 2.7–26.0°
b = 6.9450 (6) ŵ = 13.11 mm1
c = 8.1266 (6) ÅT = 200 K
V = 1105.64 (15) Å3Block, colorless
Z = 40.21 × 0.17 × 0.09 mm

Data collection

Bruker SMART 1000 CCD diffractometer1169 independent reflections
Radiation source: fine-focus sealed tube1085 reflections with I > 2σ(I)
graphiteRint = 0.042
[var phi] and ω scansθmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −24→23
Tmin = 0.631, Tmax = 1.000k = −8→8
6423 measured reflectionsl = −7→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.065H-atom parameters constrained
S = 1.10w = 1/[σ2(Fo2) + (0.0345P)2 + 1.8204P] where P = (Fo2 + 2Fc2)/3
1169 reflections(Δ/σ)max = 0.001
89 parametersΔρmax = 2.60 e Å3
0 restraintsΔρmin = −0.79 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
Pt10.087714 (15)0.25001.04929 (4)0.01771 (13)
Cl10.14026 (11)0.25001.3016 (2)0.0265 (5)
S10.18928 (11)0.25000.9332 (2)0.0209 (4)
O1−0.0036 (3)0.25001.1647 (7)0.0243 (13)
O2−0.1160 (3)0.25001.1182 (8)0.0311 (14)
O30.1947 (3)0.25000.7524 (8)0.0353 (15)
N10.0258 (3)0.25000.8489 (8)0.0204 (15)
C10.0441 (5)0.25000.6884 (10)0.029 (2)
H10.09110.25000.65960.035*
C2−0.0051 (5)0.25000.5652 (11)0.035 (2)
H20.00850.25000.45300.042*
C3−0.0726 (4)0.25000.6045 (12)0.0274 (19)
H3−0.10660.25000.52110.033*
C4−0.0903 (4)0.25000.7672 (12)0.028 (2)
H4−0.13720.25000.79680.034*
C5−0.0410 (4)0.25000.8904 (11)0.0205 (17)
C6−0.0570 (4)0.25001.0681 (10)0.0217 (18)
C70.2372 (3)0.0507 (9)1.0071 (8)0.0300 (14)
H7A0.2145−0.06940.97550.045*
H7B0.24050.05771.12730.045*
H7C0.28320.05390.95930.045*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pt10.0175 (2)0.02225 (19)0.0134 (2)0.0000.00107 (12)0.000
Cl10.0231 (11)0.0425 (12)0.0138 (10)0.000−0.0040 (8)0.000
S10.0195 (11)0.0258 (10)0.0174 (10)0.0000.0024 (8)0.000
O10.018 (3)0.044 (3)0.011 (3)0.0000.003 (2)0.000
O20.024 (3)0.047 (4)0.022 (3)0.0000.003 (3)0.000
O30.036 (4)0.055 (4)0.015 (3)0.0000.016 (3)0.000
N10.023 (4)0.019 (3)0.019 (4)0.0000.000 (3)0.000
C10.028 (5)0.049 (5)0.009 (4)0.0000.003 (3)0.000
C20.037 (6)0.047 (6)0.020 (5)0.000−0.001 (4)0.000
C30.021 (5)0.038 (5)0.023 (5)0.000−0.006 (4)0.000
C40.023 (5)0.033 (5)0.028 (5)0.0000.001 (4)0.000
C50.023 (4)0.013 (3)0.025 (4)0.000−0.002 (4)0.000
C60.019 (4)0.024 (4)0.022 (5)0.0000.002 (3)0.000
C70.023 (3)0.029 (3)0.038 (4)0.007 (3)0.005 (3)0.005 (3)

Geometric parameters (Å, °)

Pt1—O12.020 (5)C1—H10.9500
Pt1—N12.031 (7)C2—C31.361 (13)
Pt1—S12.202 (2)C2—H20.9500
Pt1—Cl12.2945 (19)C3—C41.367 (14)
S1—O31.473 (6)C3—H30.9500
S1—C7i1.778 (6)C4—C51.390 (13)
S1—C71.778 (6)C4—H40.9500
O1—C61.308 (10)C5—C61.477 (12)
O2—C61.225 (11)C7—H7A0.9800
N1—C51.352 (10)C7—H7B0.9800
N1—C11.352 (11)C7—H7C0.9800
C1—C21.390 (13)
O1—Pt1—N181.0 (2)C3—C2—H2119.8
O1—Pt1—S1177.70 (16)C1—C2—H2119.8
N1—Pt1—S1101.31 (19)C2—C3—C4118.2 (8)
O1—Pt1—Cl188.98 (16)C2—C3—H3120.9
N1—Pt1—Cl1169.97 (19)C4—C3—H3120.9
S1—Pt1—Cl188.72 (7)C3—C4—C5121.4 (8)
O3—S1—C7i107.4 (3)C3—C4—H4119.3
O3—S1—C7107.4 (3)C5—C4—H4119.3
C7i—S1—C7102.3 (5)N1—C5—C4119.5 (8)
O3—S1—Pt1119.5 (3)N1—C5—C6116.7 (7)
C7i—S1—Pt1109.4 (2)C4—C5—C6123.8 (8)
C7—S1—Pt1109.4 (2)O2—C6—O1123.7 (8)
C6—O1—Pt1115.4 (5)O2—C6—C5121.7 (8)
C5—N1—C1119.8 (7)O1—C6—C5114.7 (7)
C5—N1—Pt1112.2 (6)S1—C7—H7A109.5
C1—N1—Pt1127.9 (6)S1—C7—H7B109.5
N1—C1—C2120.7 (8)H7A—C7—H7B109.5
N1—C1—H1119.6S1—C7—H7C109.5
C2—C1—H1119.6H7A—C7—H7C109.5
C3—C2—C1120.3 (9)H7B—C7—H7C109.5
N1—Pt1—S1—O30.0N1—C1—C2—C30.000 (2)
Cl1—Pt1—S1—O3180.0C1—C2—C3—C40.000 (2)
N1—Pt1—S1—C7i124.3 (3)C2—C3—C4—C50.000 (2)
Cl1—Pt1—S1—C7i−55.7 (3)C1—N1—C5—C40.000 (2)
N1—Pt1—S1—C7−124.3 (3)Pt1—N1—C5—C4180.000 (2)
Cl1—Pt1—S1—C755.7 (3)C1—N1—C5—C6180.000 (2)
N1—Pt1—O1—C60.000 (2)Pt1—N1—C5—C60.000 (2)
Cl1—Pt1—O1—C6180.000 (2)C3—C4—C5—N10.000 (2)
O1—Pt1—N1—C50.000 (1)C3—C4—C5—C6180.000 (2)
S1—Pt1—N1—C5180.000 (1)Pt1—O1—C6—O2180.000 (2)
Cl1—Pt1—N1—C50.000 (4)Pt1—O1—C6—C50.000 (2)
O1—Pt1—N1—C1180.000 (1)N1—C5—C6—O2180.000 (2)
S1—Pt1—N1—C10.000 (1)C4—C5—C6—O20.000 (2)
Cl1—Pt1—N1—C1180.000 (3)N1—C5—C6—O10.000 (2)
C5—N1—C1—C20.000 (2)C4—C5—C6—O1180.000 (2)
Pt1—N1—C1—C2180.000 (1)

Symmetry codes: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1···O30.952.162.995 (11)145
C2—H2···O1ii0.952.353.255 (11)158
C7—H7A···O2iii0.982.423.323 (8)152
C7—H7B···Cl10.982.773.355 (7)119

Symmetry codes: (ii) x, y, z−1; (iii) −x, y−1/2, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2243).

References

  • Annibale, G., Cattalini, L., Canovese, L., Pitteri, B., Tiripicchio, A., Tiripicchio Camellini, M. & Tobe, M. L. (1986). J. Chem. Soc. Dalton Trans. pp. 1101–1105.
  • Bruker (2000). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Griffith, D., Lyssenko, K., Jensen, P., Kruger, P. E. & Marmion, C. J. (2005). Dalton Trans. pp. 956–961. [PubMed]
  • Kim, N.-H., Hwang, I.-C. & Ha, K. (2009). Acta Cryst. E65, m667. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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