A triclinic polymorph of bis­(μ-di-tert-butyl­phosphanido)bis­[(di-tert-butyl­phosphane)palladium(I)]

Breunig, J.; Lerner, H.-W.; Bolte, M.

doi:10.1107/S1600536812023574

metal-organic compounds

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Volume 68| Part 6| June 2012| Page m836

doi:10.1107/S1600536812023574

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A triclinic polymorph of bis(μ-di-tert-butylphosphanido)bis[(di-tert-butylphosphane)palladium(I)]

Jens Breunig,^a Hans-Wolfram Lerner ^a and Michael Bolte ^a ^*

^aInstitut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany
^*Correspondence e-mail: bolte@chemie.uni-frankfurt.de

(Received 23 May 2012; accepted 23 May 2012; online 31 May 2012)

A new polymorph of the title compound, [Pd₂(C₈H₁₈P)₂(C₈H₁₉P)₂], has been found. It belongs to the triclinic P-1 space group, whereas the known form [Leoni, Sommovigo, Pasquali, Sabatino & Braga (1992 ), J. Organomet. Chem. 423, 263–270] crystallizes in the monoclinic C2/c space group. The title compound features a dinuclear palladium complex with a planar central Pd₂(μ-P)₂ core (r.m.s. deviation = 0.003 Å). The Pd—Pd distance of 2.5988 (5) Å is within the range of a Pd^I—Pd^I bond. The molecules of both polymorphs are located on a crystallographic centre of inversion. The molecular conformations of the two polymorphs are essentially identical. The crystal packing patterns, on the other hand, are slightly different.

Related literature

For synthetic background, see: Dornhaus et al. (2006a ,b ); Kückmann et al. (2005 ); Lerner (2005 ); Sänger et al. (2012 ). For the monoclinic polymorph of the title compound, see: Leoni et al. (1992). For the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Pd₂(C₈H₁₈P)₂(C₈H₁₉P)₂]
M_r = 795.59
Triclinic, $[P \overline 1]$
a = 9.0721 (5) Å
b = 10.5156 (6) Å
c = 11.5351 (6) Å
α = 89.064 (5)°
β = 67.307 (4)°
γ = 75.330 (5)°
V = 978.06 (9) Å³
Z = 1
Mo Kα radiation
μ = 1.10 mm⁻¹
T = 173 K
0.23 × 0.14 × 0.04 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2009 ; Blessing, 1995 ) T_min = 0.786, T_max = 0.957
13922 measured reflections
4481 independent reflections
4083 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.111
S = 1.05
4481 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.31 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812023574/ng5274sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023574/ng5274Isup2.hkl

checkCIF report

Comment top

Recently, we have made a comparison of cyclopentadienyliron dicarbonyl complexes with two series of isoelectronic and largely isosteric ligands (Sänger et al., 2012), namely phosphanes PR₃, phosphanyl borohydrides [PR₂BH₃]^- (Dornhaus et al., 2006a), and silanides [SiR₃]^- (Lerner, 2005), and the corresponding chalcogene derivatives SPtBu₃, [SPtBu₂BH₃]^- (Dornhaus et al., 2006b) and [SSitBu₃]^- (Kückmann et al., 2005). We have concluded that, with respect to electron donor strength, phosphanyl borohydrides occupy an intermediate position between phosphanes (weakest donors) and silyl ligands (strongest donors). In addition we found that electron-rich tBu-substituted silanides tend to liberate isobutene. In this paper we report the structure of a new polymorph of [(tBu₂HP)PdPtBu₂]₂, (I). The title compound was obtained via photolysis of Pd(PtBu₃)₂ accompanied by liberation of isobutene and dihydrogen (Fig. 1).

A perspective view of the title compound is shown in Fig. 2. The molecules lie on a crystallographic centre of inversion. In the monoclinic form, the molecules also show C_i symmetry. A least-squares fit of the P and Pd atoms (r.m.s. deviation 0.004 Å) of the two polymorphs shows that the two structures are essentially identical (Fig. 3). The crystal packing patterns, on the other hand, are slightly different (Figs. 4 and 5). The value of the acyclic P—Pd bond [2.2860 (8) Å] agrees well with 2.29 (4) Å, which was found for comparable structures in the Cambridge Structural Database (Version 5.33 of November 2011, plus one update; Allen, 2002). The cyclic P—Pd bonds [2.3374 (9) Å, 2.3405 (8) Å] and the Pd···Pd [2.5988 (5) Å] distance, on the other hand, are slightly longer than the database values [P—Pd = 2.315 (16) Å and Pd···Pd = 2.31 (3) Å].

Related literature top

For synthetic background, see: Dornhaus et al. (2006a, 2006b); Kückmann et al. (2005); Lerner (2005); Sänger et al. (2012). For the monoclinic polymorph of the title compound, see: Leoni et al. (1992). For the Cambridge Structural Database, see: Allen (2002).

Experimental top

All experiments were carried out under an atmosphere of dry nitrogen or argon using Schlenk techniques or in an argon filled glovebox. Solvents ([D₆]benzene, benzene) were freshly distilled from sodium/benzophenone prior to use. NMR spectra were recorded on a Bruker Avance 400 (¹H, ¹H³¹P-COSY) or a Bruker Avance 300 (³¹P, ³¹P{1H}) instrument. Chemical shift values (¹H) are reported in p.p.m. relative to SiMe₄ and were referenced to residual solvent signals. The ³¹P{¹H} and ³¹P NMR chemical shift values were referenced to external H₃PO₄ (85%). Abbreviations: d = doublet, t = triplet, m = multiplet, br = broad. Pd(PtBu₃)₂ (38 mg, 0.074 mmol) was dissolved in 0.5 ml C₆D₆ in a vial. The vial was sealed and stored at room temperature under daylight for six weeks. During this period red plate-shaped crystals formed. Those were collected atop a frit and washed with 2 ml of benzene. Drying in vacuo yielded the title compound (8 mg, 0.009 mmol, 24%).

¹H (400.13 MHz, [D₆]Benzene, 25°C): δ = 1.56 (m, PtBu₂), 1.39 (m, HPtBu₂); ³¹P{¹H} NMR (121.45 MHz, [D₆]Benzene, 25°C): δ = 284.3 (t, ²J_PP = 32.2 Hz, PtBu₂), 57.9 (t, ²J_PP = 32.2 Hz, HPtBu₂); ³¹P NMR (121.45 MHz, [D₆]Benzene, 25°C): δ = 284.3 (br, PtBu₂), 57.9 (d br, ¹J_HP = 280 Hz, HPtBu₂).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Reaction scheme for obtaining the title compound.
	Fig. 2. A perspective view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms bonded to C are omitted for clarity. Atoms with the suffix A were generated by the symmetry operator -x + 1, -y, -z + 1.
	Fig. 3. Least-squares fit of the two polymorphs of the title compound. The triclinic polymorph is drawn with full bonds, the monoclinic form with open bonds.
	Fig. 4. Packing diagram of the triclinic polymorph of the title compound.
	Fig. 5. Packing diagram of the monoclinic polymorph of the title compound.

bis(µ-di-tert-butylphosphanido)bis[(di-tert- butylphosphane)palladium(I)] top

Crystal data top

[Pd₂(C₈H₁₈P)₂(C₈H₁₉P)₂]	Z = 1
M_r = 795.59	F(000) = 418
Triclinic, P1	D_x = 1.351 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0721 (5) Å	Cell parameters from 11232 reflections
b = 10.5156 (6) Å	θ = 3.5–28.0°
c = 11.5351 (6) Å	µ = 1.10 mm⁻¹
α = 89.064 (5)°	T = 173 K
β = 67.307 (4)°	Plate, red
γ = 75.330 (5)°	0.23 × 0.14 × 0.04 mm
V = 978.06 (9) Å³

Data collection top

Stoe IPDS II two-circle diffractometer	4481 independent reflections
Radiation source: fine-focus sealed tube	4083 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ω scans	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −11→11
T_min = 0.786, T_max = 0.957	k = −13→13
13922 measured reflections	l = −14→14

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0669P)² + 1.1837P] where P = (F_o² + 2F_c²)/3
4481 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 2.31 e Å⁻³
0 restraints	Δρ_min = −1.34 e Å⁻³

Crystal data top

[Pd₂(C₈H₁₈P)₂(C₈H₁₉P)₂]	γ = 75.330 (5)°
M_r = 795.59	V = 978.06 (9) Å³
Triclinic, P1	Z = 1
a = 9.0721 (5) Å	Mo Kα radiation
b = 10.5156 (6) Å	µ = 1.10 mm⁻¹
c = 11.5351 (6) Å	T = 173 K
α = 89.064 (5)°	0.23 × 0.14 × 0.04 mm
β = 67.307 (4)°

Data collection top

Stoe IPDS II two-circle diffractometer	4481 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	4083 reflections with I > 2σ(I)
T_min = 0.786, T_max = 0.957	R_int = 0.066
13922 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 2.31 e Å⁻³
4481 reflections	Δρ_min = −1.34 e Å⁻³
176 parameters

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

	x	y	z	U_iso*/U_eq
Pd1	0.50058 (3)	0.07733 (2)	0.41089 (2)	0.01892 (10)
P1	0.46490 (10)	0.14997 (8)	0.61308 (7)	0.02064 (18)
P2	0.49486 (11)	0.23437 (8)	0.27214 (8)	0.02250 (18)
H2	0.479 (6)	0.345 (5)	0.312 (4)	0.033 (11)*
C1	0.2544 (4)	0.2667 (4)	0.7086 (3)	0.0275 (7)
C2	0.6381 (4)	0.2167 (3)	0.6181 (3)	0.0256 (7)
C3	0.3122 (5)	0.2678 (4)	0.2244 (3)	0.0305 (7)
C4	0.6950 (5)	0.2228 (4)	0.1328 (3)	0.0290 (7)
C11	0.2300 (6)	0.4002 (4)	0.6554 (5)	0.0476 (11)
H11A	0.3097	0.4445	0.6620	0.071*
H11B	0.1170	0.4546	0.7034	0.071*
H11C	0.2476	0.3874	0.5666	0.071*
C12	0.2212 (6)	0.2872 (5)	0.8483 (4)	0.0439 (10)
H12A	0.2370	0.2013	0.8827	0.066*
H12B	0.1070	0.3404	0.8943	0.066*
H12C	0.2983	0.3328	0.8574	0.066*
C13	0.1300 (5)	0.1985 (4)	0.6982 (4)	0.0379 (9)
H13A	0.1452	0.1125	0.7325	0.057*
H13B	0.1476	0.1859	0.6094	0.057*
H13C	0.0171	0.2533	0.7461	0.057*
C21	0.6472 (6)	0.3438 (4)	0.5533 (5)	0.0418 (10)
H21A	0.6534	0.3300	0.4676	0.063*
H21B	0.7460	0.3685	0.5496	0.063*
H21C	0.5480	0.4146	0.6013	0.063*
C22	0.6292 (6)	0.2379 (6)	0.7517 (4)	0.0456 (11)
H22A	0.6238	0.1561	0.7931	0.068*
H22B	0.5299	0.3085	0.8000	0.068*
H22C	0.7281	0.2626	0.7476	0.068*
C23	0.7975 (5)	0.1095 (4)	0.5433 (4)	0.0360 (8)
H23A	0.7947	0.0269	0.5837	0.054*
H23B	0.8935	0.1373	0.5416	0.054*
H23C	0.8063	0.0956	0.4568	0.054*
C31	0.1604 (5)	0.2900 (6)	0.3489 (4)	0.0508 (13)
H31A	0.1710	0.2125	0.3963	0.076*
H31B	0.0602	0.3038	0.3315	0.076*
H31C	0.1526	0.3679	0.3986	0.076*
C32	0.2917 (7)	0.3882 (6)	0.1519 (5)	0.0564 (14)
H32A	0.2869	0.4658	0.2005	0.085*
H32B	0.1889	0.4024	0.1382	0.085*
H32C	0.3862	0.3741	0.0703	0.085*
C33	0.3187 (7)	0.1459 (6)	0.1504 (6)	0.0576 (14)
H33A	0.3317	0.0689	0.1981	0.086*
H33B	0.4130	0.1307	0.0686	0.086*
H33C	0.2157	0.1599	0.1370	0.086*
C41	0.6962 (6)	0.3430 (5)	0.0581 (5)	0.0507 (12)
H41A	0.6656	0.4223	0.1148	0.076*
H41B	0.6163	0.3516	0.0186	0.076*
H41C	0.8074	0.3328	−0.0075	0.076*
C42	0.8260 (6)	0.2088 (6)	0.1887 (4)	0.0475 (11)
H42A	0.7977	0.2872	0.2458	0.071*
H42B	0.9349	0.1998	0.1204	0.071*
H42C	0.8292	0.1303	0.2356	0.071*
C43	0.7432 (7)	0.0998 (5)	0.0447 (4)	0.0513 (12)
H43A	0.7428	0.0222	0.0928	0.077*
H43B	0.8544	0.0899	−0.0208	0.077*
H43C	0.6635	0.1081	0.0051	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.02206 (14)	0.01645 (14)	0.01839 (13)	−0.00473 (9)	−0.00844 (9)	0.00263 (8)
P1	0.0242 (4)	0.0166 (4)	0.0205 (4)	−0.0051 (3)	−0.0085 (3)	0.0012 (3)
P2	0.0298 (4)	0.0190 (4)	0.0194 (4)	−0.0058 (3)	−0.0110 (3)	0.0036 (3)
C1	0.0252 (16)	0.0240 (17)	0.0274 (16)	−0.0013 (13)	−0.0072 (13)	−0.0011 (13)
C2	0.0277 (16)	0.0240 (17)	0.0263 (16)	−0.0077 (13)	−0.0115 (13)	−0.0001 (12)
C3	0.0291 (17)	0.0328 (19)	0.0302 (17)	−0.0051 (15)	−0.0144 (14)	0.0069 (14)
C4	0.0316 (18)	0.0306 (19)	0.0247 (16)	−0.0105 (15)	−0.0098 (14)	0.0054 (13)
C11	0.038 (2)	0.026 (2)	0.062 (3)	0.0038 (17)	−0.010 (2)	0.0070 (19)
C12	0.038 (2)	0.052 (3)	0.0302 (19)	−0.0041 (19)	−0.0060 (17)	−0.0134 (18)
C13	0.0273 (18)	0.040 (2)	0.042 (2)	−0.0073 (16)	−0.0103 (16)	−0.0037 (17)
C21	0.046 (2)	0.030 (2)	0.058 (3)	−0.0197 (18)	−0.025 (2)	0.0115 (18)
C22	0.040 (2)	0.069 (3)	0.035 (2)	−0.018 (2)	−0.0187 (18)	−0.005 (2)
C23	0.0261 (17)	0.034 (2)	0.043 (2)	−0.0082 (15)	−0.0092 (16)	−0.0012 (16)
C31	0.030 (2)	0.078 (4)	0.038 (2)	−0.006 (2)	−0.0127 (18)	0.017 (2)
C32	0.048 (3)	0.060 (3)	0.066 (3)	−0.011 (2)	−0.031 (2)	0.038 (3)
C33	0.061 (3)	0.059 (3)	0.070 (3)	−0.010 (3)	−0.047 (3)	−0.008 (3)
C41	0.043 (2)	0.052 (3)	0.050 (3)	−0.017 (2)	−0.009 (2)	0.027 (2)
C42	0.035 (2)	0.073 (3)	0.037 (2)	−0.019 (2)	−0.0144 (18)	0.009 (2)
C43	0.056 (3)	0.052 (3)	0.033 (2)	−0.013 (2)	−0.004 (2)	−0.0114 (19)

Geometric parameters (Å, º) top

Pd1—P2	2.2860 (8)	C13—H13B	0.9800
Pd1—P1ⁱ	2.3374 (9)	C13—H13C	0.9800
Pd1—P1	2.3405 (8)	C21—H21A	0.9800
Pd1—Pd1ⁱ	2.5988 (5)	C21—H21B	0.9800
P1—C2	1.896 (4)	C21—H21C	0.9800
P1—C1	1.898 (4)	C22—H22A	0.9800
P1—Pd1ⁱ	2.3373 (9)	C22—H22B	0.9800
P2—C4	1.881 (4)	C22—H22C	0.9800
P2—C3	1.891 (4)	C23—H23A	0.9800
P2—H2	1.21 (5)	C23—H23B	0.9800
C1—C11	1.521 (6)	C23—H23C	0.9800
C1—C13	1.523 (5)	C31—H31A	0.9800
C1—C12	1.529 (5)	C31—H31B	0.9800
C2—C21	1.526 (5)	C31—H31C	0.9800
C2—C22	1.529 (5)	C32—H32A	0.9800
C2—C23	1.533 (5)	C32—H32B	0.9800
C3—C32	1.517 (6)	C32—H32C	0.9800
C3—C33	1.528 (6)	C33—H33A	0.9800
C3—C31	1.528 (6)	C33—H33B	0.9800
C4—C41	1.519 (6)	C33—H33C	0.9800
C4—C43	1.520 (6)	C41—H41A	0.9800
C4—C42	1.532 (6)	C41—H41B	0.9800
C11—H11A	0.9800	C41—H41C	0.9800
C11—H11B	0.9800	C42—H42A	0.9800
C11—H11C	0.9800	C42—H42B	0.9800
C12—H12A	0.9800	C42—H42C	0.9800
C12—H12B	0.9800	C43—H43A	0.9800
C12—H12C	0.9800	C43—H43B	0.9800
C13—H13A	0.9800	C43—H43C	0.9800

P2—Pd1—P1ⁱ	130.80 (3)	C1—C13—H13C	109.5
P2—Pd1—P1	116.70 (3)	H13A—C13—H13C	109.5
P1ⁱ—Pd1—P1	112.50 (2)	H13B—C13—H13C	109.5
P2—Pd1—Pd1ⁱ	172.88 (3)	C2—C21—H21A	109.5
P1ⁱ—Pd1—Pd1ⁱ	56.31 (2)	C2—C21—H21B	109.5
P1—Pd1—Pd1ⁱ	56.19 (2)	H21A—C21—H21B	109.5
C2—P1—C1	110.95 (16)	C2—C21—H21C	109.5
C2—P1—Pd1ⁱ	120.70 (11)	H21A—C21—H21C	109.5
C1—P1—Pd1ⁱ	121.18 (12)	H21B—C21—H21C	109.5
C2—P1—Pd1	114.53 (11)	C2—C22—H22A	109.5
C1—P1—Pd1	114.77 (12)	C2—C22—H22B	109.5
Pd1ⁱ—P1—Pd1	67.50 (2)	H22A—C22—H22B	109.5
C4—P2—C3	111.79 (16)	C2—C22—H22C	109.5
C4—P2—Pd1	116.35 (12)	H22A—C22—H22C	109.5
C3—P2—Pd1	115.50 (12)	H22B—C22—H22C	109.5
C4—P2—H2	96 (2)	C2—C23—H23A	109.5
C3—P2—H2	99 (2)	C2—C23—H23B	109.5
Pd1—P2—H2	115 (2)	H23A—C23—H23B	109.5
C11—C1—C13	109.2 (3)	C2—C23—H23C	109.5
C11—C1—C12	109.4 (4)	H23A—C23—H23C	109.5
C13—C1—C12	108.0 (3)	H23B—C23—H23C	109.5
C11—C1—P1	112.3 (3)	C3—C31—H31A	109.5
C13—C1—P1	104.7 (3)	C3—C31—H31B	109.5
C12—C1—P1	113.1 (3)	H31A—C31—H31B	109.5
C21—C2—C22	109.5 (3)	C3—C31—H31C	109.5
C21—C2—C23	108.1 (3)	H31A—C31—H31C	109.5
C22—C2—C23	108.3 (3)	H31B—C31—H31C	109.5
C21—C2—P1	112.6 (3)	C3—C32—H32A	109.5
C22—C2—P1	113.2 (3)	C3—C32—H32B	109.5
C23—C2—P1	104.7 (2)	H32A—C32—H32B	109.5
C32—C3—C33	110.2 (4)	C3—C32—H32C	109.5
C32—C3—C31	108.5 (4)	H32A—C32—H32C	109.5
C33—C3—C31	107.5 (4)	H32B—C32—H32C	109.5
C32—C3—P2	115.2 (3)	C3—C33—H33A	109.5
C33—C3—P2	110.3 (3)	C3—C33—H33B	109.5
C31—C3—P2	104.7 (3)	H33A—C33—H33B	109.5
C41—C4—C43	109.4 (4)	C3—C33—H33C	109.5
C41—C4—C42	108.2 (4)	H33A—C33—H33C	109.5
C43—C4—C42	108.0 (4)	H33B—C33—H33C	109.5
C41—C4—P2	114.6 (3)	C4—C41—H41A	109.5
C43—C4—P2	111.1 (3)	C4—C41—H41B	109.5
C42—C4—P2	105.1 (3)	H41A—C41—H41B	109.5
C1—C11—H11A	109.5	C4—C41—H41C	109.5
C1—C11—H11B	109.5	H41A—C41—H41C	109.5
H11A—C11—H11B	109.5	H41B—C41—H41C	109.5
C1—C11—H11C	109.5	C4—C42—H42A	109.5
H11A—C11—H11C	109.5	C4—C42—H42B	109.5
H11B—C11—H11C	109.5	H42A—C42—H42B	109.5
C1—C12—H12A	109.5	C4—C42—H42C	109.5
C1—C12—H12B	109.5	H42A—C42—H42C	109.5
H12A—C12—H12B	109.5	H42B—C42—H42C	109.5
C1—C12—H12C	109.5	C4—C43—H43A	109.5
H12A—C12—H12C	109.5	C4—C43—H43B	109.5
H12B—C12—H12C	109.5	H43A—C43—H43B	109.5
C1—C13—H13A	109.5	C4—C43—H43C	109.5
C1—C13—H13B	109.5	H43A—C43—H43C	109.5
H13A—C13—H13B	109.5	H43B—C43—H43C	109.5

P2—Pd1—P1—C2	−65.64 (13)	C1—P1—C2—C21	−65.6 (3)
P1ⁱ—Pd1—P1—C2	114.74 (13)	Pd1ⁱ—P1—C2—C21	143.7 (3)
Pd1ⁱ—Pd1—P1—C2	114.74 (13)	Pd1—P1—C2—C21	66.4 (3)
P2—Pd1—P1—C1	64.42 (13)	C1—P1—C2—C22	59.4 (3)
P1ⁱ—Pd1—P1—C1	−115.21 (13)	Pd1ⁱ—P1—C2—C22	−91.3 (3)
Pd1ⁱ—Pd1—P1—C1	−115.21 (13)	Pd1—P1—C2—C22	−168.7 (3)
P2—Pd1—P1—Pd1ⁱ	179.63 (3)	C1—P1—C2—C23	177.2 (2)
P1ⁱ—Pd1—P1—Pd1ⁱ	0.0	Pd1ⁱ—P1—C2—C23	26.5 (3)
P1ⁱ—Pd1—P2—C4	−67.41 (14)	Pd1—P1—C2—C23	−50.9 (3)
P1—Pd1—P2—C4	113.05 (14)	C4—P2—C3—C32	−54.6 (4)
P1ⁱ—Pd1—P2—C3	66.64 (15)	Pd1—P2—C3—C32	169.3 (3)
P1—Pd1—P2—C3	−112.90 (14)	C4—P2—C3—C33	71.0 (4)
C2—P1—C1—C11	63.1 (3)	Pd1—P2—C3—C33	−65.1 (4)
Pd1ⁱ—P1—C1—C11	−146.4 (3)	C4—P2—C3—C31	−173.6 (3)
Pd1—P1—C1—C11	−68.7 (3)	Pd1—P2—C3—C31	50.3 (3)
C2—P1—C1—C13	−178.6 (2)	C3—P2—C4—C41	56.2 (4)
Pd1ⁱ—P1—C1—C13	−28.1 (3)	Pd1—P2—C4—C41	−168.2 (3)
Pd1—P1—C1—C13	49.6 (3)	C3—P2—C4—C43	−68.6 (4)
C2—P1—C1—C12	−61.3 (3)	Pd1—P2—C4—C43	67.1 (3)
Pd1ⁱ—P1—C1—C12	89.3 (3)	C3—P2—C4—C42	174.9 (3)
Pd1—P1—C1—C12	167.0 (3)	Pd1—P2—C4—C42	−49.5 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Pd₂(C₈H₁₈P)₂(C₈H₁₉P)₂]
M_r	795.59
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.0721 (5), 10.5156 (6), 11.5351 (6)
α, β, γ (°)	89.064 (5), 67.307 (4), 75.330 (5)
V (Å³)	978.06 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.10
Crystal size (mm)	0.23 × 0.14 × 0.04

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Spek, 2009; Blessing, 1995)
T_min, T_max	0.786, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	13922, 4481, 4083
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 1.05
No. of reflections	4481
No. of parameters	176
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.31, −1.34

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008).

References

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