A second polymorph of [1,2-bis­(di-tert-butyl­phosphino)ethane]dichlorido­platinum(II)

Gunay, A.; Brennessel, W.W.; Jones, W.D.

doi:10.1107/S1600536808000603

metal-organic compounds

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Volume 64| Part 3| March 2008| Page m454

doi:10.1107/S1600536808000603

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A second polymorph of [1,2-bis(di-tert-butylphosphino)ethane]dichloridoplatinum(II)

Ahmet Gunay,^a William W. Brennessel ^a and William D. Jones ^a ^*

^aDepartment of Chemistry, University of Rochester, Box 270216, Rochester, NY 14627-0216, USA
^*Correspondence e-mail: jones@chem.rochester.edu

(Received 18 December 2007; accepted 7 January 2008; online 6 February 2008)

The title complex, [PtCl₂(C₁₈H₄₀P₂)], contains a Pt^II center in an approximately square-planar geometry [cis angle range = 88.09 (3)–91.39 (3)°; twist angle = 1.19 (5)°]. The Pt—P bond lengths of 2.2536 (8) and 2.2513 (8) Å and the Pt—Cl bond lengths of 2.3750 (8) and 2.3588 (8) Å are normal. This crystal form is a polymorph of a structure reported previously [Harada, Kai, Yasuoka & Kasai (1976 ). Bull. Chem. Soc. Jpn, 49, 3472–3477].

Related literature

For related literature, see: Crascall & Spencer (1990 ); Green et al. (1977 ); McDermott et al. (1976 ); Ogoshi et al. (2004 ).

Experimental

Crystal data

[PtCl₂(C₁₈H₄₀P₂)]
M_r = 584.43
Monoclinic, P 2₁ /n
a = 11.0981 (10) Å
b = 15.3242 (13) Å
c = 14.5413 (13) Å
β = 109.287 (1)°
V = 2334.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 6.38 mm⁻¹
T = 100.0 (1) K
0.20 × 0.14 × 0.08 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.342, T_max = 0.600
20415 measured reflections
8022 independent reflections
6312 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.060
S = 1.01
8022 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 1.11 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Pt1—P2	2.2513 (8)
Pt1—P1	2.2536 (8)
Pt1—Cl2	2.3588 (8)
Pt1—Cl1	2.3750 (8)

P2—Pt1—P1	89.70 (3)
P2—Pt1—Cl2	90.82 (3)
P1—Pt1—Cl2	178.77 (3)
P2—Pt1—Cl1	178.84 (3)
P1—Pt1—Cl1	91.39 (3)
Cl2—Pt1—Cl1	88.09 (3)

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Bruker, 2000 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808000603/pv2062sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000603/pv2062Isup2.hkl

checkCIF report

Comment top

One of the most commonly used Pt(0) precursors, Pt(COD)₂, COD = 1,5-cyclooctadiene, is generally synthesized by the reduction of platinumdichlorides, like Pt(COD)Cl₂, with Li₂(COT), COT = cyclooctatetraene (Green et al., 1977; Crascall & Spencer, 1990), or with SmI₂ (Ogoshi et al., 2004). The latter reduction with 20 equivalents of SmI₂ afforded Pt(COD)₂ in moderate yields (45% average). After addition of chelating ligand 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) to the SmI₂ reduction product, it was observed that some Pt^II remained, based on the formation of the title compound, Pt(dtbpe)Cl₂ (I). An independent synthesis of (I) was performed to support these observations, in which dtbpe was added directly to Pt(COD)Cl₂ (see experimental section). The resulting pure product in 88% yield was characterized by ¹H, ¹³C, ³¹P NMR spectroscopies and by single-crystal X-ray diffraction.

Related literature top

For related literature, see: Crascall & Spencer (1990); Green et al. (1977); McDermott et al. (1976); Ogoshi et al. (2004).

Experimental top

Pt(COD)Cl₂, COD = 1,5-cyclooctadiene, was synthesized according to the published procedure (McDermott et al., 1976). Under an atmosphere of dinitrogen, bis(di-tert-butylphosphino)ethane (dtbpe) (212 mg, 0.67 mmol) was added to a light yellow suspension of Pt(COD)Cl₂ (250 mg, 0.67 mmol) in THF (25 ml). The reaction mixture was heated with stirring for 12 h at 373 K. After complete conversion to (I) was verified by ³¹P NMR spectroscopy, the volatiles (THF, COD) were removed in vacuo, leaving the white powdery product (343.4 mg, 0.59 mmol) in 88% yield. Crystals of (I) were grown by vapor diffusion of hexanes into THF.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

Fig. 1. Displacement ellipsoid (50% probability) drawing of (I) with H atoms omitted.

[1,2-bis(di-tert-butylphosphino)ethane]dichloridoplatinum(II) top

Crystal data top

[PtCl₂(C₁₈H₄₀P₂)]	F(000) = 1160
M_r = 584.43	D_x = 1.663 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4040 reflections
a = 11.0981 (10) Å	θ = 3.0–32.9°
b = 15.3242 (13) Å	µ = 6.38 mm⁻¹
c = 14.5413 (13) Å	T = 100 K
β = 109.287 (1)°	Block, colorless
V = 2334.2 (4) Å³	0.20 × 0.14 × 0.08 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	8022 independent reflections
Radiation source: fine-focus sealed tube	6312 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
area detector, ω scans per ϕ	θ_max = 32.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −15→16
T_min = 0.342, T_max = 0.600	k = −22→22
20415 measured reflections	l = −19→21

Refinement top

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0232P)²] where P = (F_o² + 2F_c²)/3
8022 reflections	(Δ/σ)_max = 0.002
208 parameters	Δρ_max = 1.11 e Å⁻³
0 restraints	Δρ_min = −0.81 e Å⁻³

Crystal data top

[PtCl₂(C₁₈H₄₀P₂)]	V = 2334.2 (4) Å³
M_r = 584.43	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.0981 (10) Å	µ = 6.38 mm⁻¹
b = 15.3242 (13) Å	T = 100 K
c = 14.5413 (13) Å	0.20 × 0.14 × 0.08 mm
β = 109.287 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	8022 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	6312 reflections with I > 2σ(I)
T_min = 0.342, T_max = 0.600	R_int = 0.034
20415 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.02	Δρ_max = 1.11 e Å⁻³
8022 reflections	Δρ_min = −0.81 e Å⁻³
208 parameters

Special details top

Experimental. ¹H NMR (CDCl₃, 20 °C): δ 1.5 (d, ³J_HP = 14.1 Hz, 36 H, -(CH₃)₃), 1.9 (d, ²J_HP = 16 Hz, 4 H, -CH₂-); ¹³C NMR (CDCl₃, 20 °C): δ 24.5 (d, ¹J_CP = 33 Hz, -CH₂-), 30.4 (s, -(CH₃)₃), 37.6 (d, ¹J_CP = 30 Hz, -C-); ³¹P NMR (CDCl₃, 20 °C): δ 75.7 (s, with platinum satellites ¹J_PPt = 3643.2 Hz).

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

	x	y	z	U_iso*/U_eq
Pt1	0.268368 (10)	0.706474 (7)	0.781256 (8)	0.01505 (3)
Cl1	0.17379 (7)	0.80168 (5)	0.86681 (6)	0.02422 (16)
Cl2	0.44219 (8)	0.80401 (5)	0.81687 (6)	0.02415 (16)
P1	0.09956 (7)	0.61552 (5)	0.74524 (5)	0.01603 (14)
P2	0.36188 (7)	0.61746 (5)	0.70173 (6)	0.01776 (15)
C1	0.0577 (3)	0.5718 (2)	0.8529 (2)	0.0227 (6)
C2	−0.0053 (4)	0.4814 (2)	0.8323 (3)	0.0323 (8)
H2A	−0.0253	0.4613	0.8896	0.048*
H2B	0.0533	0.4400	0.8177	0.048*
H2C	−0.0842	0.4851	0.7763	0.048*
C3	−0.0326 (3)	0.6333 (2)	0.8823 (3)	0.0287 (7)
H3A	−0.0520	0.6085	0.9380	0.043*
H3B	−0.1120	0.6402	0.8273	0.043*
H3C	0.0083	0.6903	0.9002	0.043*
C4	0.1821 (3)	0.5634 (2)	0.9392 (2)	0.0308 (8)
H4A	0.1632	0.5409	0.9960	0.046*
H4B	0.2227	0.6208	0.9547	0.046*
H4C	0.2400	0.5231	0.9221	0.046*
C5	−0.0478 (3)	0.6578 (2)	0.6491 (2)	0.0232 (7)
C6	−0.1592 (3)	0.5927 (2)	0.6247 (3)	0.0302 (8)
H6A	−0.2334	0.6177	0.5744	0.045*
H6B	−0.1812	0.5807	0.6834	0.045*
H6C	−0.1342	0.5383	0.6006	0.045*
C7	−0.0919 (3)	0.7459 (2)	0.6749 (3)	0.0316 (8)
H7A	−0.1686	0.7645	0.6224	0.047*
H7B	−0.0240	0.7891	0.6833	0.047*
H7C	−0.1113	0.7406	0.7357	0.047*
C8	−0.0127 (3)	0.6711 (3)	0.5569 (3)	0.0388 (9)
H8A	−0.0871	0.6932	0.5046	0.058*
H8B	0.0143	0.6154	0.5370	0.058*
H8C	0.0573	0.7133	0.5700	0.058*
C9	0.5007 (3)	0.5527 (2)	0.7849 (2)	0.0246 (7)
C10	0.5670 (4)	0.4957 (2)	0.7285 (3)	0.0349 (9)
H10A	0.6377	0.4637	0.7747	0.052*
H10B	0.5999	0.5329	0.6874	0.052*
H10C	0.5053	0.4541	0.6874	0.052*
C11	0.5985 (3)	0.6126 (2)	0.8564 (3)	0.0340 (8)
H11A	0.6690	0.5774	0.8984	0.051*
H11B	0.5573	0.6440	0.8967	0.051*
H11C	0.6317	0.6546	0.8199	0.051*
C12	0.4469 (3)	0.4907 (2)	0.8451 (3)	0.0298 (8)
H12A	0.5166	0.4561	0.8890	0.045*
H12B	0.3840	0.4516	0.8011	0.045*
H12C	0.4058	0.5249	0.8834	0.045*
C13	0.4076 (3)	0.6704 (2)	0.5996 (2)	0.0241 (7)
C14	0.5394 (3)	0.7143 (2)	0.6356 (3)	0.0292 (7)
H14A	0.5579	0.7404	0.5802	0.044*
H14B	0.6046	0.6707	0.6667	0.044*
H14C	0.5396	0.7600	0.6829	0.044*
C15	0.4083 (4)	0.6035 (2)	0.5199 (3)	0.0374 (9)
H15A	0.4322	0.6329	0.4687	0.056*
H15B	0.3230	0.5780	0.4919	0.056*
H15C	0.4702	0.5572	0.5489	0.056*
C16	0.3071 (3)	0.7402 (2)	0.5518 (3)	0.0286 (7)
H16A	0.3286	0.7684	0.4988	0.043*
H16B	0.3055	0.7839	0.6006	0.043*
H16C	0.2229	0.7126	0.5256	0.043*
C31	0.1465 (3)	0.5180 (2)	0.6924 (2)	0.0216 (6)
H31A	0.1853	0.4755	0.7452	0.026*
H31B	0.0690	0.4908	0.6465	0.026*
C32	0.2411 (3)	0.5363 (2)	0.6385 (2)	0.0211 (6)
H32A	0.1938	0.5577	0.5721	0.025*
H32B	0.2842	0.4813	0.6320	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.01739 (5)	0.01316 (5)	0.01369 (5)	0.00118 (5)	0.00389 (4)	−0.00008 (4)
Cl1	0.0232 (4)	0.0226 (4)	0.0254 (4)	0.0034 (3)	0.0061 (3)	−0.0079 (3)
Cl2	0.0275 (4)	0.0195 (4)	0.0271 (4)	−0.0052 (3)	0.0112 (3)	−0.0035 (3)
P1	0.0182 (4)	0.0177 (4)	0.0132 (3)	−0.0006 (3)	0.0066 (3)	−0.0002 (3)
P2	0.0202 (4)	0.0158 (4)	0.0199 (4)	−0.0004 (3)	0.0102 (3)	−0.0011 (3)
C1	0.0277 (16)	0.0264 (16)	0.0185 (15)	0.0043 (13)	0.0137 (13)	0.0043 (12)
C2	0.046 (2)	0.0275 (18)	0.0333 (19)	−0.0032 (16)	0.0261 (17)	0.0057 (15)
C3	0.0365 (19)	0.0297 (18)	0.0269 (17)	0.0024 (15)	0.0201 (15)	0.0022 (14)
C4	0.0348 (19)	0.041 (2)	0.0186 (16)	0.0045 (16)	0.0116 (14)	0.0099 (15)
C5	0.0185 (15)	0.0330 (18)	0.0165 (15)	−0.0029 (13)	0.0034 (12)	0.0040 (13)
C6	0.0208 (16)	0.037 (2)	0.0302 (19)	−0.0070 (14)	0.0053 (14)	−0.0058 (15)
C7	0.0222 (17)	0.0323 (19)	0.034 (2)	0.0028 (14)	0.0009 (15)	0.0085 (16)
C8	0.0208 (17)	0.071 (3)	0.0212 (18)	−0.0038 (17)	0.0018 (14)	0.0117 (18)
C9	0.0239 (16)	0.0186 (15)	0.0326 (18)	0.0045 (12)	0.0109 (14)	0.0015 (13)
C10	0.0326 (19)	0.0228 (17)	0.056 (2)	0.0042 (15)	0.0233 (18)	−0.0002 (16)
C11	0.0236 (17)	0.0309 (18)	0.041 (2)	0.0022 (15)	0.0021 (15)	0.0048 (16)
C12	0.0287 (18)	0.0263 (17)	0.036 (2)	0.0079 (14)	0.0126 (15)	0.0104 (15)
C13	0.0296 (17)	0.0250 (16)	0.0238 (17)	−0.0025 (14)	0.0172 (14)	−0.0011 (13)
C14	0.0272 (17)	0.0292 (18)	0.0363 (19)	0.0001 (14)	0.0173 (15)	0.0008 (15)
C15	0.050 (2)	0.042 (2)	0.0306 (19)	−0.0120 (19)	0.0282 (18)	−0.0071 (17)
C16	0.0315 (18)	0.0327 (18)	0.0255 (18)	−0.0035 (15)	0.0148 (15)	0.0084 (14)
C31	0.0270 (16)	0.0180 (15)	0.0243 (16)	−0.0022 (12)	0.0144 (13)	−0.0048 (12)
C32	0.0244 (15)	0.0202 (15)	0.0221 (15)	−0.0033 (12)	0.0125 (12)	−0.0046 (12)

Geometric parameters (Å, º) top

Pt1—P2	2.2513 (8)	C8—H8B	0.9800
Pt1—P1	2.2536 (8)	C8—H8C	0.9800
Pt1—Cl2	2.3588 (8)	C9—C11	1.535 (5)
Pt1—Cl1	2.3750 (8)	C9—C10	1.542 (5)
P1—C31	1.833 (3)	C9—C12	1.540 (5)
P1—C5	1.881 (3)	C10—H10A	0.9800
P1—C1	1.897 (3)	C10—H10B	0.9800
P2—C32	1.837 (3)	C10—H10C	0.9800
P2—C9	1.895 (3)	C11—H11A	0.9800
P2—C13	1.903 (3)	C11—H11B	0.9800
C1—C4	1.534 (5)	C11—H11C	0.9800
C1—C3	1.535 (4)	C12—H12A	0.9800
C1—C2	1.537 (5)	C12—H12B	0.9800
C2—H2A	0.9800	C12—H12C	0.9800
C2—H2B	0.9800	C13—C16	1.536 (5)
C2—H2C	0.9800	C13—C14	1.536 (5)
C3—H3A	0.9800	C13—C15	1.549 (5)
C3—H3B	0.9800	C14—H14A	0.9800
C3—H3C	0.9800	C14—H14B	0.9800
C4—H4A	0.9800	C14—H14C	0.9800
C4—H4B	0.9800	C15—H15A	0.9800
C4—H4C	0.9800	C15—H15B	0.9800
C5—C7	1.525 (5)	C15—H15C	0.9800
C5—C8	1.528 (5)	C16—H16A	0.9800
C5—C6	1.536 (4)	C16—H16B	0.9800
C6—H6A	0.9800	C16—H16C	0.9800
C6—H6B	0.9800	C31—C32	1.529 (4)
C6—H6C	0.9800	C31—H31A	0.9900
C7—H7A	0.9800	C31—H31B	0.9900
C7—H7B	0.9800	C32—H32A	0.9900
C7—H7C	0.9800	C32—H32B	0.9900
C8—H8A	0.9800

P2—Pt1—P1	89.70 (3)	C5—C8—H8C	109.5
P2—Pt1—Cl2	90.82 (3)	H8A—C8—H8C	109.5
P1—Pt1—Cl2	178.77 (3)	H8B—C8—H8C	109.5
P2—Pt1—Cl1	178.84 (3)	C11—C9—C10	110.2 (3)
P1—Pt1—Cl1	91.39 (3)	C11—C9—C12	107.7 (3)
Cl2—Pt1—Cl1	88.09 (3)	C10—C9—C12	107.1 (3)
C31—P1—C5	105.46 (15)	C11—C9—P2	111.3 (2)
C31—P1—C1	103.85 (14)	C10—C9—P2	112.8 (2)
C5—P1—C1	110.23 (14)	C12—C9—P2	107.4 (2)
C31—P1—Pt1	105.77 (10)	C9—C10—H10A	109.5
C5—P1—Pt1	114.31 (11)	C9—C10—H10B	109.5
C1—P1—Pt1	115.98 (11)	H10A—C10—H10B	109.5
C32—P2—C9	105.70 (15)	C9—C10—H10C	109.5
C32—P2—C13	103.69 (14)	H10A—C10—H10C	109.5
C9—P2—C13	110.56 (15)	H10B—C10—H10C	109.5
C32—P2—Pt1	106.44 (10)	C9—C11—H11A	109.5
C9—P2—Pt1	113.88 (11)	C9—C11—H11B	109.5
C13—P2—Pt1	115.45 (11)	H11A—C11—H11B	109.5
C4—C1—C3	108.6 (3)	C9—C11—H11C	109.5
C4—C1—C2	108.2 (3)	H11A—C11—H11C	109.5
C3—C1—C2	108.1 (3)	H11B—C11—H11C	109.5
C4—C1—P1	107.8 (2)	C9—C12—H12A	109.5
C3—C1—P1	111.9 (2)	C9—C12—H12B	109.5
C2—C1—P1	112.1 (2)	H12A—C12—H12B	109.5
C1—C2—H2A	109.5	C9—C12—H12C	109.5
C1—C2—H2B	109.5	H12A—C12—H12C	109.5
H2A—C2—H2B	109.5	H12B—C12—H12C	109.5
C1—C2—H2C	109.5	C16—C13—C14	108.5 (3)
H2A—C2—H2C	109.5	C16—C13—C15	107.8 (3)
H2B—C2—H2C	109.5	C14—C13—C15	107.8 (3)
C1—C3—H3A	109.5	C16—C13—P2	107.9 (2)
C1—C3—H3B	109.5	C14—C13—P2	113.0 (2)
H3A—C3—H3B	109.5	C15—C13—P2	111.7 (2)
C1—C3—H3C	109.5	C13—C14—H14A	109.5
H3A—C3—H3C	109.5	C13—C14—H14B	109.5
H3B—C3—H3C	109.5	H14A—C14—H14B	109.5
C1—C4—H4A	109.5	C13—C14—H14C	109.5
C1—C4—H4B	109.5	H14A—C14—H14C	109.5
H4A—C4—H4B	109.5	H14B—C14—H14C	109.5
C1—C4—H4C	109.5	C13—C15—H15A	109.5
H4A—C4—H4C	109.5	C13—C15—H15B	109.5
H4B—C4—H4C	109.5	H15A—C15—H15B	109.5
C7—C5—C8	107.0 (3)	C13—C15—H15C	109.5
C7—C5—C6	109.4 (3)	H15A—C15—H15C	109.5
C8—C5—C6	107.7 (3)	H15B—C15—H15C	109.5
C7—C5—P1	113.1 (2)	C13—C16—H16A	109.5
C8—C5—P1	106.7 (2)	C13—C16—H16B	109.5
C6—C5—P1	112.6 (2)	H16A—C16—H16B	109.5
C5—C6—H6A	109.5	C13—C16—H16C	109.5
C5—C6—H6B	109.5	H16A—C16—H16C	109.5
H6A—C6—H6B	109.5	H16B—C16—H16C	109.5
C5—C6—H6C	109.5	C32—C31—P1	113.8 (2)
H6A—C6—H6C	109.5	C32—C31—H31A	108.8
H6B—C6—H6C	109.5	P1—C31—H31A	108.8
C5—C7—H7A	109.5	C32—C31—H31B	108.8
C5—C7—H7B	109.5	P1—C31—H31B	108.8
H7A—C7—H7B	109.5	H31A—C31—H31B	107.7
C5—C7—H7C	109.5	C31—C32—P2	112.3 (2)
H7A—C7—H7C	109.5	C31—C32—H32A	109.2
H7B—C7—H7C	109.5	P2—C32—H32A	109.2
C5—C8—H8A	109.5	C31—C32—H32B	109.2
C5—C8—H8B	109.5	P2—C32—H32B	109.2
H8A—C8—H8B	109.5	H32A—C32—H32B	107.9

P2—Pt1—P1—C31	8.74 (11)	C1—P1—C5—C6	−48.9 (3)
Cl1—Pt1—P1—C31	−170.88 (11)	Pt1—P1—C5—C6	178.4 (2)
P2—Pt1—P1—C5	−106.82 (12)	C32—P2—C9—C11	−169.3 (2)
Cl1—Pt1—P1—C5	73.55 (12)	C13—P2—C9—C11	79.1 (3)
P2—Pt1—P1—C1	123.22 (11)	Pt1—P2—C9—C11	−52.8 (3)
Cl1—Pt1—P1—C1	−56.40 (11)	C32—P2—C9—C10	66.3 (3)
P1—Pt1—P2—C32	9.20 (11)	C13—P2—C9—C10	−45.3 (3)
Cl2—Pt1—P2—C32	−169.68 (11)	Pt1—P2—C9—C10	−177.3 (2)
P1—Pt1—P2—C9	−106.85 (12)	C32—P2—C9—C12	−51.6 (2)
Cl2—Pt1—P2—C9	74.27 (12)	C13—P2—C9—C12	−163.2 (2)
P1—Pt1—P2—C13	123.65 (12)	Pt1—P2—C9—C12	64.9 (2)
Cl2—Pt1—P2—C13	−55.24 (12)	C32—P2—C13—C16	81.9 (2)
C31—P1—C1—C4	83.6 (2)	C9—P2—C13—C16	−165.2 (2)
C5—P1—C1—C4	−163.8 (2)	Pt1—P2—C13—C16	−34.1 (3)
Pt1—P1—C1—C4	−31.9 (3)	C32—P2—C13—C14	−158.1 (2)
C31—P1—C1—C3	−157.1 (2)	C9—P2—C13—C14	−45.2 (3)
C5—P1—C1—C3	−44.5 (3)	Pt1—P2—C13—C14	85.9 (2)
Pt1—P1—C1—C3	87.4 (2)	C32—P2—C13—C15	−36.4 (3)
C31—P1—C1—C2	−35.4 (3)	C9—P2—C13—C15	76.5 (3)
C5—P1—C1—C2	77.2 (3)	Pt1—P2—C13—C15	−152.4 (2)
Pt1—P1—C1—C2	−151.0 (2)	C5—P1—C31—C32	91.5 (2)
C31—P1—C5—C7	−172.7 (2)	C1—P1—C31—C32	−152.5 (2)
C1—P1—C5—C7	75.7 (3)	Pt1—P1—C31—C32	−30.0 (2)
Pt1—P1—C5—C7	−57.0 (3)	P1—C31—C32—P2	39.6 (3)
C31—P1—C5—C8	−55.3 (3)	C9—P2—C32—C31	91.6 (2)
C1—P1—C5—C8	−166.8 (2)	C13—P2—C32—C31	−152.0 (2)
Pt1—P1—C5—C8	60.4 (3)	Pt1—P2—C32—C31	−29.8 (2)
C31—P1—C5—C6	62.6 (3)

Experimental details

Crystal data
Chemical formula	[PtCl₂(C₁₈H₄₀P₂)]
M_r	584.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	11.0981 (10), 15.3242 (13), 14.5413 (13)
β (°)	109.287 (1)
V (Å³)	2334.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.38
Crystal size (mm)	0.20 × 0.14 × 0.08

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.342, 0.600
No. of measured, independent and observed [I > 2σ(I)] reflections	20415, 8022, 6312
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.060, 1.02
No. of reflections	8022
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.11, −0.81

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 2000).

Selected geometric parameters (Å, º) top

Pt1—P2	2.2513 (8)	Pt1—Cl2	2.3588 (8)
Pt1—P1	2.2536 (8)	Pt1—Cl1	2.3750 (8)

P2—Pt1—P1	89.70 (3)	P2—Pt1—Cl1	178.84 (3)
P2—Pt1—Cl2	90.82 (3)	P1—Pt1—Cl1	91.39 (3)
P1—Pt1—Cl2	178.77 (3)	Cl2—Pt1—Cl1	88.09 (3)

Acknowledgements

We thank the US Department of Energy for support (grant FG02–86ER13569).

References

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