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Acta Cryst. (2007). E63, m2583    [ doi:10.1107/S1600536807045540 ]

cis-Dichloridobis(diethylphenylphosphine-[kappa]P)platinum(II)

W. Domanska-Babul, J. Pikies and J. Chojnacki

Abstract top

In the title compound, [PtCl2(C10H15P)2], the Pt atom adopts a slightly distorted square-planar geometry. The phenyl rings form dihedral angles of 82.21 (11) and 79.98 (11)° with the PtCl2P2 mean plane. The crystal structure is stabilized by weak intra- and intermolecular C-H...Cl hydrogen bonds.

Comment top

We have a standing interest in the reactivity of [(R3P)2PtCl2] compounds towards diphosphanes (Domanska-Babul, Chojnacki, Matern & Pikies, 2007). The title compound, [(Et2PhP)2PtCl2], was obtained according to the published procedure (Matern et al., 2000) and recovered from the reaction mixture during the studies.

An ORTEP plot of the title compound is shown in Fig. 1. The geometry of the Pt atom is slightly distorted square planar with the metal displaced by only 0.0007 (2) Å from the PtCl2P2 mean plane. The Cl and P atoms display a substantial tetrahedral distortion, being displaced by 0.1647 (13), −0.1394 (13), −0.1349 (13) and 0.1267 (12) Å for Cl1, Cl2, P1 and P2 respectively. For comparison, the displacements found for the same atoms in the related complex [(EtPh2P)2PtCl2] (Domanska-Babul, Chojnacki & Pikies 2007) are −0.0238 (5), −0.0008 (5), −0.0251 (5) and −0.0060 (5) Å respectively. Even more significant departures from planarity are observed in the case of sterically demanding phosphanes ligands, viz. in [cis-(tBu2PhP)2PtCl2] (Porzio et al., 1980). The bond angle P1–Pt–P2 of 94.43 (4)° indicates steric repulsion of the PhEt2P groups smaller than those observed for the EtPh2P groups in [(EtPh2P)2PtCl2] (100.23 °) and for the MePh2P groups in [(MePh2P)2PtCl2] (98.11 °; Ho et al., 1982). The average Pt–P and Pt–Cl distances of 2.253 (13) Å and 2.356 (12) Å respectively are typical for [cis-(R3P)2PtCl2] complexes. The dihedral angles formed by the C1—C6 and C11—C16 phenyl rings with the PtCl2P2 mean plane are 82.21 (11) and 79.98 (11) ° respectively. The crystal structure is reinforced by weak intra- and intermolecular C—H···Cl hydrogen interactions (Table 1).

Related literature top

For the structure of the related cis-dichloridobis(ethyldiphenylphosphine-κP)platinum(II) compound, see: Domanska-Babul, Chojnacki & Pikies (2007). For related literature, see: Chojnacki et al. (2007); Domanska-Babul, Chojnacki, Matern & Pikies (2007); Ho et al. (1982); Matern et al. (2000); Porzio et al. (1980).

Experimental top

The title compound compound [cis-{C6H5(C2H5)2P}2PtCl2] has been obtained as yellow powder in the reaction of a solution of phenyl(diethyl)phosphane in ethanol with a solution of potassium tetrachloroplatinate(II) in water (Matern et al., 2000). Slow crystallization from THF at ambient temperature yielded crystals suitable for X-ray analysis.

Refinement top

All C–H hydrogen atoms were refined as riding on carbon atoms with methyl C–H = 0.98 Å, methylen C–H = 0.99 Å, aromatic C–H = 0.95 Å and Uiso(H) = 1.2 Ueq(C) for aromatic CH, 1.3 for CH2 groups and 1.5 for methyl groups.

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: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. View of the title compound (50% probability displacement ellipsoids). H atoms are omitted for clarity.
cis-Dichloridobis(diethylphenylphosphine-κP)platinum(II) top
Crystal data top
[PtCl2(C10H15P)2]F000 = 1168
Mr = 598.37Dx = 1.811 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12825 reflections
a = 14.8957 (5) Åθ = 2.3–32.4º
b = 9.0402 (5) ŵ = 6.79 mm−1
c = 16.3565 (5) ÅT = 120 (2) K
β = 94.865 (3)ºPrism, colourless
V = 2194.63 (16) Å30.16 × 0.11 × 0.06 mm
Z = 4
Data collection top
Oxford Diffraction KM-4 CCD
diffractometer		4145 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.013
0.75° ω scansθmax = 26º
Absorption correction: analytical
[CrysAlis RED; Oxford Diffraction (2006), Clark & Reid (1995)]		θmin = 2.5º
Tmin = 0.278, Tmax = 0.398h = −17→18
9492 measured reflectionsk = −11→8
4301 independent reflectionsl = −20→19
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0454P)2 + 6.1376P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.025(Δ/σ)max = 0.003
wR(F2) = 0.089Δρmax = 1.33 e Å−3
S = 1.36Δρmin = −1.25 e Å−3
4301 reflectionsExtinction correction: none
230 parameters
Crystal data top
[PtCl2(C10H15P)2]V = 2194.63 (16) Å3
Mr = 598.37Z = 4
Monoclinic, P21/cMo Kα
a = 14.8957 (5) ŵ = 6.79 mm−1
b = 9.0402 (5) ÅT = 120 (2) K
c = 16.3565 (5) Å0.16 × 0.11 × 0.06 mm
β = 94.865 (3)º
Data collection top
Oxford Diffraction KM-4 CCD
diffractometer		4301 independent reflections
Absorption correction: analytical
[CrysAlis RED; Oxford Diffraction (2006), Clark & Reid (1995)]		4145 reflections with I > 2σ(I)
Tmin = 0.278, Tmax = 0.398Rint = 0.013
9492 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025230 parameters
wR(F2) = 0.089H-atom parameters constrained
S = 1.36Δρmax = 1.33 e Å−3
4301 reflectionsΔρmin = −1.25 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt10.251723 (11)0.969895 (18)0.300696 (10)0.01372 (9)
Cl10.23065 (9)0.71248 (14)0.29244 (8)0.0258 (3)
Cl20.27795 (9)0.93276 (16)0.44366 (7)0.0252 (3)
P10.20696 (9)0.99057 (15)0.16603 (8)0.0161 (2)
P20.29263 (8)1.20887 (13)0.31503 (7)0.0142 (2)
C10.1381 (3)1.1543 (6)0.1407 (3)0.0172 (9)
C20.1664 (3)1.2704 (6)0.0932 (3)0.0211 (10)
H20.22291.2640.07060.025*
C30.1137 (4)1.3946 (6)0.0786 (3)0.0255 (11)
H30.13441.47340.04670.031*
C40.0304 (4)1.4047 (7)0.1106 (3)0.0283 (12)
H4−0.00581.49030.10070.034*
C50.0006 (3)1.2896 (7)0.1570 (3)0.0277 (12)
H5−0.05681.29550.17810.033*
C60.0542 (3)1.1656 (6)0.1728 (3)0.0216 (10)
H60.03381.08780.20560.026*
C70.1319 (3)0.8410 (6)0.1277 (3)0.0246 (11)
H7A0.16360.74550.13710.032*
H7B0.07840.83990.15970.032*
C80.1001 (4)0.8539 (7)0.0362 (3)0.0300 (12)
H8A0.07850.95470.02430.045*
H8B0.05110.78350.02270.045*
H8C0.15050.83180.00330.045*
C90.2961 (4)0.9903 (6)0.0959 (3)0.0201 (10)
H9A0.2690.99860.03870.026*
H9B0.33571.07710.10740.026*
C100.3520 (4)0.8496 (7)0.1050 (4)0.0295 (12)
H10A0.38080.84320.1610.044*
H10B0.39840.85140.06590.044*
H10C0.31280.76360.09380.044*
C110.3676 (3)1.2696 (5)0.2393 (3)0.0152 (9)
C120.3512 (3)1.3932 (6)0.1890 (3)0.0187 (9)
H120.29881.45150.19380.022*
C130.4116 (4)1.4313 (6)0.1317 (3)0.0235 (10)
H130.39871.51260.09590.028*
C140.4902 (3)1.3512 (6)0.1268 (3)0.0250 (11)
H140.53111.37760.08780.03*
C150.5094 (3)1.2316 (6)0.1794 (3)0.0233 (10)
H150.56461.17950.17790.028*
C160.4478 (3)1.1887 (6)0.2339 (3)0.0205 (10)
H160.45971.10440.26770.025*
C170.2020 (3)1.3438 (5)0.3135 (3)0.0175 (9)
H17A0.22771.44220.32820.023*
H17B0.17211.35030.25720.023*
C180.1314 (4)1.3038 (7)0.3732 (3)0.0274 (12)
H18A0.10151.21110.35570.041*
H18B0.08661.38310.37340.041*
H18C0.16121.29170.42860.041*
C190.3615 (3)1.2459 (6)0.4116 (3)0.0194 (10)
H19A0.3241.22950.45790.025*
H19B0.41171.17390.41710.025*
C200.4005 (4)1.4016 (6)0.4183 (3)0.0251 (11)
H20A0.44171.41650.37530.038*
H20B0.43351.41440.47230.038*
H20C0.35151.47410.41160.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01339 (12)0.01029 (13)0.01751 (13)0.00008 (6)0.00151 (8)0.00160 (6)
Cl10.0306 (6)0.0100 (5)0.0368 (7)−0.0006 (5)0.0024 (5)0.0022 (5)
Cl20.0323 (6)0.0244 (6)0.0186 (6)−0.0026 (5)−0.0003 (5)0.0078 (5)
P10.0162 (6)0.0141 (5)0.0176 (6)−0.0015 (5)−0.0002 (5)−0.0014 (5)
P20.0155 (5)0.0109 (5)0.0162 (5)−0.0012 (4)0.0015 (4)0.0004 (4)
C10.014 (2)0.020 (3)0.017 (2)0.0010 (18)−0.0018 (17)−0.0036 (19)
C20.023 (2)0.024 (3)0.016 (2)−0.001 (2)0.0022 (18)−0.001 (2)
C30.033 (3)0.023 (3)0.020 (2)0.004 (2)−0.002 (2)−0.001 (2)
C40.030 (3)0.029 (3)0.025 (3)0.014 (2)−0.006 (2)−0.004 (2)
C50.018 (2)0.038 (3)0.026 (3)0.008 (2)−0.002 (2)−0.007 (2)
C60.017 (2)0.027 (3)0.021 (2)−0.002 (2)0.0008 (18)−0.004 (2)
C70.019 (2)0.021 (3)0.032 (3)−0.004 (2)−0.001 (2)−0.005 (2)
C80.027 (3)0.031 (3)0.031 (3)−0.005 (2)−0.004 (2)−0.010 (2)
C90.019 (2)0.022 (2)0.019 (2)0.001 (2)0.0013 (19)−0.005 (2)
C100.027 (3)0.029 (3)0.033 (3)0.009 (2)0.007 (2)−0.006 (2)
C110.012 (2)0.016 (2)0.018 (2)−0.0026 (17)0.0007 (16)−0.0025 (18)
C120.017 (2)0.019 (2)0.020 (2)−0.0029 (18)0.0009 (18)−0.0012 (19)
C130.025 (3)0.022 (2)0.023 (2)−0.007 (2)0.002 (2)0.004 (2)
C140.023 (2)0.029 (3)0.025 (2)−0.008 (2)0.008 (2)−0.005 (2)
C150.015 (2)0.024 (3)0.031 (3)−0.001 (2)0.0034 (19)−0.006 (2)
C160.020 (2)0.017 (2)0.024 (2)0.0005 (19)0.0007 (19)−0.001 (2)
C170.019 (2)0.012 (2)0.021 (2)0.0048 (18)0.0011 (18)0.0007 (18)
C180.024 (3)0.034 (3)0.026 (3)0.006 (2)0.011 (2)0.003 (2)
C190.017 (2)0.022 (3)0.018 (2)−0.0030 (19)−0.0016 (17)−0.0003 (19)
C200.025 (3)0.027 (3)0.023 (2)−0.005 (2)0.000 (2)−0.005 (2)
Geometric parameters (Å, °) top
Pt1—P22.2515 (12)C9—H9A0.99
Pt1—P12.2544 (13)C9—H9B0.99
Pt1—Cl12.3505 (12)C10—H10A0.98
Pt1—Cl22.3619 (12)C10—H10B0.98
P1—C91.828 (5)C10—H10C0.98
P1—C11.828 (5)C11—C121.397 (7)
P1—C71.831 (5)C11—C161.409 (7)
P2—C171.818 (5)C12—C131.396 (7)
P2—C111.822 (5)C12—H120.95
P2—C191.840 (5)C13—C141.385 (8)
C1—C21.392 (7)C13—H130.95
C1—C61.400 (7)C14—C151.395 (8)
C2—C31.379 (8)C14—H140.95
C2—H20.95C15—C161.387 (7)
C3—C41.390 (8)C15—H150.95
C3—H30.95C16—H160.95
C4—C51.383 (9)C17—C181.537 (7)
C4—H40.95C17—H17A0.99
C5—C61.388 (8)C17—H17B0.99
C5—H50.95C18—H18A0.98
C6—H60.95C18—H18B0.98
C7—C81.535 (8)C18—H18C0.98
C7—H7A0.99C19—C201.523 (7)
C7—H7B0.99C19—H19A0.99
C8—H8A0.98C19—H19B0.99
C8—H8B0.98C20—H20A0.98
C8—H8C0.98C20—H20B0.98
C9—C101.520 (7)C20—H20C0.98
P2—Pt1—P194.43 (4)C10—C9—H9B109.4
P2—Pt1—Cl1171.72 (4)P1—C9—H9B109.4
P1—Pt1—Cl189.94 (5)H9A—C9—H9B108
P2—Pt1—Cl290.73 (5)C9—C10—H10A109.5
P1—Pt1—Cl2171.70 (5)C9—C10—H10B109.5
Cl1—Pt1—Cl285.77 (5)H10A—C10—H10B109.5
C9—P1—C1106.4 (2)C9—C10—H10C109.5
C9—P1—C7103.8 (2)H10A—C10—H10C109.5
C1—P1—C7101.9 (2)H10B—C10—H10C109.5
C9—P1—Pt1116.29 (18)C12—C11—C16119.0 (4)
C1—P1—Pt1113.72 (16)C12—C11—P2123.7 (4)
C7—P1—Pt1113.26 (19)C16—C11—P2117.3 (4)
C17—P2—C11106.6 (2)C13—C12—C11120.1 (5)
C17—P2—C19104.4 (2)C13—C12—H12120
C11—P2—C19101.5 (2)C11—C12—H12120
C17—P2—Pt1116.61 (16)C14—C13—C12120.4 (5)
C11—P2—Pt1113.22 (16)C14—C13—H13119.8
C19—P2—Pt1112.99 (17)C12—C13—H13119.8
C2—C1—C6118.4 (5)C13—C14—C15120.0 (5)
C2—C1—P1123.1 (4)C13—C14—H14120
C6—C1—P1118.4 (4)C15—C14—H14120
C3—C2—C1121.1 (5)C16—C15—C14120.0 (5)
C3—C2—H2119.5C16—C15—H15120
C1—C2—H2119.5C14—C15—H15120
C2—C3—C4120.1 (5)C15—C16—C11120.4 (5)
C2—C3—H3120C15—C16—H16119.8
C4—C3—H3120C11—C16—H16119.8
C5—C4—C3119.7 (5)C18—C17—P2112.3 (3)
C5—C4—H4120.1C18—C17—H17A109.1
C3—C4—H4120.1P2—C17—H17A109.1
C4—C5—C6120.2 (5)C18—C17—H17B109.1
C4—C5—H5119.9P2—C17—H17B109.1
C6—C5—H5119.9H17A—C17—H17B107.9
C5—C6—C1120.5 (5)C17—C18—H18A109.5
C5—C6—H6119.8C17—C18—H18B109.5
C1—C6—H6119.8H18A—C18—H18B109.5
C8—C7—P1114.0 (4)C17—C18—H18C109.5
C8—C7—H7A108.8H18A—C18—H18C109.5
P1—C7—H7A108.8H18B—C18—H18C109.5
C8—C7—H7B108.8C20—C19—P2114.3 (4)
P1—C7—H7B108.8C20—C19—H19A108.7
H7A—C7—H7B107.6P2—C19—H19A108.7
C7—C8—H8A109.5C20—C19—H19B108.7
C7—C8—H8B109.5P2—C19—H19B108.7
H8A—C8—H8B109.5H19A—C19—H19B107.6
C7—C8—H8C109.5C19—C20—H20A109.5
H8A—C8—H8C109.5C19—C20—H20B109.5
H8B—C8—H8C109.5H20A—C20—H20B109.5
C10—C9—P1111.1 (4)C19—C20—H20C109.5
C10—C9—H9A109.4H20A—C20—H20C109.5
P1—C9—H9A109.4H20B—C20—H20C109.5
Cl1—Pt1—P1—C1141.79 (18)C17—P2—C11—C12−3.0 (5)
Cl1—Pt1—P1—C726.11 (18)C17—P2—C11—C16174.8 (4)
Cl1—Pt1—P1—C9−94.1 (2)C19—P2—C11—C12−112.1 (4)
P2—Pt1—P1—C1−45.25 (18)C19—P2—C11—C1665.8 (4)
P2—Pt1—P1—C7−160.93 (18)Pt1—P2—C17—C1850.7 (4)
P2—Pt1—P1—C978.9 (2)C11—P2—C17—C18178.3 (3)
Cl2—Pt1—P2—C11135.17 (17)C19—P2—C17—C18−74.8 (4)
Cl2—Pt1—P2—C17−100.55 (18)Pt1—P2—C19—C20172.4 (3)
Cl2—Pt1—P2—C1920.46 (17)C11—P2—C19—C2050.8 (4)
P1—Pt1—P2—C11−51.34 (17)C17—P2—C19—C20−59.9 (4)
P1—Pt1—P2—C1772.95 (18)P1—C1—C2—C3−177.3 (4)
P1—Pt1—P2—C19−166.05 (17)C6—C1—C2—C30.5 (7)
Pt1—P1—C1—C2113.7 (4)P1—C1—C6—C5178.3 (4)
Pt1—P1—C1—C6−64.1 (4)C2—C1—C6—C50.4 (7)
C7—P1—C1—C2−124.1 (4)C1—C2—C3—C4−0.7 (8)
C7—P1—C1—C658.2 (4)C2—C3—C4—C5−0.1 (8)
C9—P1—C1—C2−15.6 (5)C3—C4—C5—C61.1 (8)
C9—P1—C1—C6166.6 (4)C4—C5—C6—C1−1.2 (8)
Pt1—P1—C7—C8179.5 (3)P2—C11—C12—C13−179.2 (4)
C1—P1—C7—C857.0 (4)C16—C11—C12—C133.0 (7)
C9—P1—C7—C8−53.4 (4)P2—C11—C16—C15−178.0 (4)
Pt1—P1—C9—C1058.3 (4)C12—C11—C16—C150.0 (7)
C1—P1—C9—C10−173.8 (4)C11—C12—C13—C14−3.1 (8)
C7—P1—C9—C10−66.8 (4)C12—C13—C14—C150.1 (8)
Pt1—P2—C11—C12126.5 (4)C13—C14—C15—C162.9 (8)
Pt1—P2—C11—C16−55.6 (4)C14—C15—C16—C11−2.9 (8)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···Cl10.992.673.178 (5)112
C19—H19A···Cl20.992.773.155 (5)103
C5—H5···Cl1i0.952.783.677 (5)158
C17—H17A···Cl1ii0.992.513.382 (5)146
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···Cl10.992.673.178 (5)112
C19—H19A···Cl20.992.773.155 (5)103
C5—H5···Cl1i0.952.783.677 (5)158
C17—H17A···Cl1ii0.992.513.382 (5)146
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, y+1, z.
Acknowledgements top

WD—B and JP thank the Polish State Committee for Scientific Research (project No. 1 T09A 148 30) for financial support.

references
References top

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