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Acta Cryst. (2009). E65, m667    [ doi:10.1107/S1600536809017966 ]

Dichloridobis(pyridine-2-carboxylato-[kappa]2N,O)platinum(IV) acetonitrile solvate

N.-H. Kim, I.-C. Hwang and K. Ha

Abstract top

The asymmetric unit of the title compound, [PtCl2(C6H4NO2)2]·CH3CN, contains a neutral PtIV complex and an acetonitrile solvent molecule. In the complex, the Pt4+ atom is six-coordinated in a distorted octahedral environment by two N atoms and two O atoms from two pyridinecarboxylate (pic) ligands and two Cl atoms. The Cl atoms are cis with respect to each other. The compound displays inter- and intramolecular C-H...O and C-H...Cl hydrogen bonding.

Comment top

The asymmetric unit of the title compound, [PtCl2(C6H4NO2)2].CH3CN, contains a neutral PtIV complex and a CH3CN solvent molecule (Fig. 1). In the complex, the Pt4+ ion is six-coordinated in a distorted octahedral environment by two N atoms and two O atoms from two pyridinecarboxylate (pic) anion ligands and two Cl atoms. The Cl atoms are disposed in the cis position. The main contributions to the distortion are the tight O—Pt—N chelate angles (82.32 (14)° and 82.16 (13)°), which result in non-linear trans axes (<Cl1—Pt1—N1 = 175.68 (10)°, <Cl2—Pt1—O3 = 178.67 (10)° and <O1—Pt1—N2 = 173.39 (14)°). The different trans effects of the Cl, O and N atoms are not distinct, because the Pt1—Cl, Pt1—O and Pt1—N bond lengths are almost equal (Pt1—Cl: 2.3003 (13) and 2.2910 (14) Å; Pt1—O 1.999 (3) and 2.022 (3) Å; Pt1—N 2.025 (4) and 2.013 (3) Å), respectively (Table 1). The compound displays inter- and intramolecular C—H···O and C—H···Cl hydrogen bonding (Table 2 and Fig. 2). There may also be weak intermolecular π-π interactions between adjacent pyridine rings, with a shortest centroid-centroid distance of 5.223 (4) Å.

Related literature top

For the synthesis and structure of the Pt(IV)-pic complex, [PtCl4(pic)]-, see: Griffith et al. (2005). For a related Pt(II)-dipicolinate complex, see: Goodgame et al. (1995).

Experimental top

A suspension of K2PtCl6 (0.2148 g, 0.442 mmol) and pyridine-2-carboxylic acid (0.2000 g, 1.459 mmol) in H2O (10 ml) was refluxed for 5 h. The formed precipitate was separated by filtration and washed with water (20 ml) and dried under vacuum, to give a pale green powder (0.2304 g). Colorless crystals suitable for X-ray analysis were obtained by slow evaporation from a CH3CN solution.

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.93 (aromatic) or 0.96 Å (CH3) and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C)].

Computing details top

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

Figures top
[Figure 1] Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 30% probability level for non-H atoms.
[Figure 2] Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.
Dichloridobis(pyridine-2-carboxylato-κ2N,O)platinum(IV) acetonitrile solvate top
Crystal data top
[PtCl2(C6H4NO2)2]·C2H3NF000 = 1040
Mr = 551.25Dx = 2.182 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 979 reflections
a = 6.103 (3) Åθ = 2.5–25.9º
b = 27.988 (12) ŵ = 8.71 mm−1
c = 9.823 (4) ÅT = 293 K
β = 91.076 (7)ºStick, colorless
V = 1677.7 (12) Å30.20 × 0.15 × 0.15 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		3437 independent reflections
Radiation source: fine-focus sealed tube3051 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 293 Kθmax = 26.4º
φ and ω scansθmin = 1.5º
Absorption correction: Multi-scan
(SADABS; Bruker, 2000)		h = −6→7
Tmin = 0.203, Tmax = 0.271k = −35→33
9732 measured reflectionsl = −12→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.052  w = 1/[σ2(Fo2) + (0.0126P)2 + 3.1343P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
3437 reflectionsΔρmax = 1.04 e Å−3
218 parametersΔρmin = −0.58 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[PtCl2(C6H4NO2)2]·C2H3NV = 1677.7 (12) Å3
Mr = 551.25Z = 4
Monoclinic, P21/cMo Kα
a = 6.103 (3) ŵ = 8.71 mm−1
b = 27.988 (12) ÅT = 293 K
c = 9.823 (4) Å0.20 × 0.15 × 0.15 mm
β = 91.076 (7)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		3437 independent reflections
Absorption correction: Multi-scan
(SADABS; Bruker, 2000)		3051 reflections with I > 2σ(I)
Tmin = 0.203, Tmax = 0.271Rint = 0.025
9732 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023218 parameters
wR(F2) = 0.052H-atom parameters constrained
S = 1.11Δρmax = 1.04 e Å−3
3437 reflectionsΔρmin = −0.58 e Å−3
Special details top

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
Pt10.67421 (3)0.119200 (6)0.082756 (17)0.03061 (6)
Cl10.47415 (19)0.06563 (4)−0.04645 (12)0.0421 (3)
Cl20.9275 (2)0.12741 (4)−0.08481 (13)0.0454 (3)
O10.5138 (5)0.17577 (11)0.0066 (3)0.0444 (8)
O20.4983 (9)0.25418 (14)0.0228 (6)0.0971 (19)
O30.4557 (5)0.11261 (11)0.2338 (3)0.0389 (7)
O40.3574 (6)0.06264 (14)0.3949 (4)0.0533 (10)
N10.8376 (6)0.17036 (13)0.1894 (4)0.0336 (8)
N20.8101 (6)0.06220 (12)0.1765 (4)0.0297 (8)
C11.0064 (8)0.16447 (16)0.2751 (5)0.0410 (11)
H11.05350.13370.29610.049*
C21.1128 (9)0.20275 (18)0.3335 (5)0.0504 (14)
H21.23200.19800.39230.060*
C31.0415 (10)0.2478 (2)0.3040 (6)0.0610 (16)
H31.11080.27430.34280.073*
C40.8651 (11)0.25356 (19)0.2158 (7)0.0680 (19)
H40.81370.28410.19570.082*
C50.7654 (9)0.21476 (17)0.1578 (5)0.0452 (12)
C60.5793 (10)0.21694 (19)0.0564 (6)0.0550 (15)
C70.9907 (8)0.03922 (17)0.1407 (5)0.0380 (11)
H71.07350.05090.06950.046*
C81.0567 (9)−0.00183 (17)0.2081 (5)0.0451 (12)
H81.1841−0.01760.18320.054*
C90.9325 (10)−0.01915 (18)0.3122 (6)0.0520 (14)
H90.9745−0.04680.35810.062*
C100.7448 (9)0.00483 (18)0.3481 (5)0.0476 (13)
H100.6595−0.00640.41870.057*
C110.6848 (7)0.04566 (16)0.2781 (4)0.0341 (10)
C120.4840 (8)0.07409 (17)0.3081 (5)0.0386 (11)
N30.7810 (12)0.1214 (2)0.5485 (7)0.091 (2)
C130.4113 (12)0.1411 (2)0.6554 (7)0.0761 (19)
H13A0.37230.17340.63310.114*
H13B0.42260.13760.75250.114*
H13C0.30070.11980.62010.114*
C140.6175 (14)0.1297 (2)0.5963 (7)0.0677 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.02912 (10)0.02809 (10)0.03449 (10)0.00214 (7)−0.00261 (7)0.00113 (7)
Cl10.0381 (6)0.0414 (6)0.0465 (7)−0.0055 (5)−0.0040 (5)−0.0048 (5)
Cl20.0479 (7)0.0448 (7)0.0439 (7)−0.0037 (5)0.0083 (5)0.0066 (5)
O10.044 (2)0.0332 (18)0.055 (2)0.0085 (15)−0.0173 (17)0.0024 (15)
O20.122 (4)0.035 (2)0.131 (4)0.026 (2)−0.079 (4)−0.002 (2)
O30.0307 (17)0.0435 (18)0.0428 (19)0.0064 (14)0.0072 (14)−0.0001 (15)
O40.048 (2)0.063 (2)0.049 (2)−0.0049 (18)0.0169 (18)−0.0001 (18)
N10.033 (2)0.030 (2)0.037 (2)0.0027 (16)−0.0055 (17)−0.0021 (16)
N20.031 (2)0.0259 (18)0.0325 (19)0.0037 (15)−0.0014 (16)−0.0002 (15)
C10.040 (3)0.031 (2)0.052 (3)0.002 (2)−0.009 (2)0.001 (2)
C20.051 (3)0.044 (3)0.055 (3)−0.002 (2)−0.019 (3)−0.006 (2)
C30.069 (4)0.039 (3)0.074 (4)−0.005 (3)−0.023 (3)−0.010 (3)
C40.084 (5)0.027 (3)0.092 (5)0.009 (3)−0.031 (4)−0.009 (3)
C50.052 (3)0.030 (3)0.053 (3)0.010 (2)−0.013 (3)0.000 (2)
C60.064 (4)0.036 (3)0.064 (4)0.013 (3)−0.024 (3)0.001 (3)
C70.036 (3)0.038 (3)0.040 (3)0.003 (2)0.003 (2)−0.002 (2)
C80.044 (3)0.037 (3)0.055 (3)0.010 (2)−0.007 (2)−0.004 (2)
C90.065 (4)0.034 (3)0.057 (3)0.004 (3)−0.011 (3)0.006 (2)
C100.060 (4)0.042 (3)0.041 (3)−0.002 (3)0.002 (3)0.012 (2)
C110.036 (3)0.035 (2)0.032 (2)−0.005 (2)−0.001 (2)0.0020 (19)
C120.038 (3)0.043 (3)0.035 (3)−0.003 (2)0.002 (2)−0.009 (2)
N30.097 (5)0.099 (5)0.078 (4)0.003 (4)−0.014 (4)−0.009 (4)
C130.097 (6)0.065 (4)0.067 (4)−0.004 (4)0.001 (4)0.012 (3)
C140.092 (6)0.057 (4)0.053 (4)−0.002 (4)−0.017 (4)−0.002 (3)
Geometric parameters (Å, °) top
Pt1—O11.999 (3)C3—H30.9300
Pt1—N22.013 (3)C4—C51.364 (7)
Pt1—O32.022 (3)C4—H40.9300
Pt1—N12.025 (4)C5—C61.498 (7)
Pt1—Cl22.2910 (14)C7—C81.382 (6)
Pt1—Cl12.3003 (13)C7—H70.9300
O1—C61.311 (6)C8—C91.373 (7)
O2—C61.197 (6)C8—H80.9300
O3—C121.312 (6)C9—C101.379 (7)
O4—C121.205 (6)C9—H90.9300
N1—C11.328 (6)C10—C111.379 (6)
N1—C51.352 (6)C10—H100.9300
N2—C71.329 (6)C11—C121.495 (6)
N2—C111.350 (5)N3—C141.134 (10)
C1—C21.373 (6)C13—C141.432 (10)
C1—H10.9300C13—H13A0.9600
C2—C31.364 (7)C13—H13B0.9600
C2—H20.9300C13—H13C0.9600
C3—C41.379 (8)
O1—Pt1—N2173.39 (14)C5—C4—H4119.8
O1—Pt1—O391.24 (14)C3—C4—H4119.8
N2—Pt1—O382.16 (13)N1—C5—C4119.7 (5)
O1—Pt1—N182.32 (14)N1—C5—C6115.4 (4)
N2—Pt1—N197.41 (15)C4—C5—C6124.9 (5)
O3—Pt1—N190.57 (14)O2—C6—O1122.7 (5)
O1—Pt1—Cl289.09 (11)O2—C6—C5121.5 (5)
N2—Pt1—Cl297.51 (11)O1—C6—C5115.7 (4)
O3—Pt1—Cl2178.67 (10)N2—C7—C8120.7 (5)
N1—Pt1—Cl288.19 (11)N2—C7—H7119.6
O1—Pt1—Cl193.37 (10)C8—C7—H7119.6
N2—Pt1—Cl186.89 (11)C9—C8—C7119.4 (5)
O3—Pt1—Cl189.70 (10)C9—C8—H8120.3
N1—Pt1—Cl1175.68 (10)C7—C8—H8120.3
Cl2—Pt1—Cl191.57 (5)C8—C9—C10119.4 (5)
C6—O1—Pt1114.4 (3)C8—C9—H9120.3
C12—O3—Pt1113.7 (3)C10—C9—H9120.3
C1—N1—C5120.3 (4)C9—C10—C11119.3 (5)
C1—N1—Pt1127.5 (3)C9—C10—H10120.3
C5—N1—Pt1112.1 (3)C11—C10—H10120.3
C7—N2—C11120.9 (4)N2—C11—C10120.2 (4)
C7—N2—Pt1126.8 (3)N2—C11—C12116.2 (4)
C11—N2—Pt1112.1 (3)C10—C11—C12123.6 (4)
N1—C1—C2121.5 (4)O4—C12—O3122.2 (5)
N1—C1—H1119.2O4—C12—C11122.5 (5)
C2—C1—H1119.2O3—C12—C11115.3 (4)
C3—C2—C1119.2 (5)C14—C13—H13A109.5
C3—C2—H2120.4C14—C13—H13B109.5
C1—C2—H2120.4H13A—C13—H13B109.5
C2—C3—C4118.9 (5)C14—C13—H13C109.5
C2—C3—H3120.6H13A—C13—H13C109.5
C4—C3—H3120.6H13B—C13—H13C109.5
C5—C4—C3120.5 (5)N3—C14—C13178.8 (8)
O3—Pt1—O1—C689.9 (4)C1—N1—C5—C4−0.8 (8)
N1—Pt1—O1—C6−0.5 (4)Pt1—N1—C5—C4−176.9 (5)
Cl2—Pt1—O1—C6−88.8 (4)C1—N1—C5—C6177.9 (5)
Cl1—Pt1—O1—C6179.7 (4)Pt1—N1—C5—C61.8 (6)
O1—Pt1—O3—C12173.1 (3)C3—C4—C5—N11.3 (10)
N2—Pt1—O3—C12−7.2 (3)C3—C4—C5—C6−177.3 (6)
N1—Pt1—O3—C12−104.6 (3)Pt1—O1—C6—O2−179.1 (6)
Cl1—Pt1—O3—C1279.7 (3)Pt1—O1—C6—C51.6 (7)
O1—Pt1—N1—C1−176.5 (4)N1—C5—C6—O2178.3 (6)
N2—Pt1—N1—C110.1 (4)C4—C5—C6—O2−3.0 (11)
O3—Pt1—N1—C192.3 (4)N1—C5—C6—O1−2.4 (8)
Cl2—Pt1—N1—C1−87.2 (4)C4—C5—C6—O1176.3 (6)
O1—Pt1—N1—C5−0.8 (3)C11—N2—C7—C8−1.0 (7)
N2—Pt1—N1—C5−174.1 (3)Pt1—N2—C7—C8−174.9 (3)
O3—Pt1—N1—C5−92.0 (4)N2—C7—C8—C90.7 (7)
Cl2—Pt1—N1—C588.5 (3)C7—C8—C9—C10−0.3 (8)
O3—Pt1—N2—C7−179.5 (4)C8—C9—C10—C110.3 (8)
N1—Pt1—N2—C7−89.9 (4)C7—N2—C11—C101.0 (7)
Cl2—Pt1—N2—C7−0.8 (4)Pt1—N2—C11—C10175.7 (4)
Cl1—Pt1—N2—C790.4 (4)C7—N2—C11—C12−179.2 (4)
O3—Pt1—N2—C116.2 (3)Pt1—N2—C11—C12−4.5 (5)
N1—Pt1—N2—C1195.7 (3)C9—C10—C11—N2−0.7 (7)
Cl2—Pt1—N2—C11−175.1 (3)C9—C10—C11—C12179.6 (5)
Cl1—Pt1—N2—C11−84.0 (3)Pt1—O3—C12—O4−173.6 (4)
C5—N1—C1—C2−0.3 (8)Pt1—O3—C12—C116.7 (5)
Pt1—N1—C1—C2175.1 (4)N2—C11—C12—O4178.8 (4)
N1—C1—C2—C30.9 (8)C10—C11—C12—O4−1.4 (7)
C1—C2—C3—C4−0.3 (9)N2—C11—C12—O3−1.5 (6)
C2—C3—C4—C5−0.8 (10)C10—C11—C12—O3178.3 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2i0.932.453.207 (7)139
C7—H7···Cl1ii0.932.753.583 (5)150
C7—H7···Cl20.932.763.334 (5)121
C10—H10···O4iii0.932.423.223 (6)145
C13—H13A···O2iv0.962.433.256 (8)144
C13—H13B···Cl1v0.962.843.625 (7)140
Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) x+1, y, z; (iii) −x+1, −y, −z+1; (iv) x, −y+1/2, z+1/2; (v) x, y, z+1.
Table 1
Selected geometric parameters (Å) top
Pt1—O11.999 (3)Pt1—N12.025 (4)
Pt1—N22.013 (3)Pt1—Cl22.2910 (14)
Pt1—O32.022 (3)Pt1—Cl12.3003 (13)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2i0.932.453.207 (7)139
C7—H7···Cl1ii0.932.753.583 (5)150
C7—H7···Cl20.932.763.334 (5)121
C10—H10···O4iii0.932.423.223 (6)145
C13—H13A···O2iv0.962.433.256 (8)144
C13—H13B···Cl1v0.962.843.625 (7)140
Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) x+1, y, z; (iii) −x+1, −y, −z+1; (iv) x, −y+1/2, z+1/2; (v) x, y, z+1.
Acknowledgements top

This work was supported by a Korea Research Foundation grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).

references
References top

Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

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Griffith, D., Lyssenko, K., Jensen, P., Kruger, P. E. & Marmion, C. J. (2005). Dalton Trans. pp. 956–961.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.