A triclinic polymorph of bis-(μ-di-tert-butyl-phosphanido)bis-[(di-tert-butyl-phosphane)palladium(I)].

A new polymorph of the title compound, [Pd(2)(C(8)H(18)P)(2)(C(8)H(19)P)(2)], has been found. It belongs to the triclinic P-1 space group, whereas the known form [Leoni, Sommovigo, Pasquali, Sabatino & Braga (1992 ▶), J. Organo-met. Chem.423, 263-270] crystallizes in the monoclinic C2/c space group. The title compound features a dinuclear palladium complex with a planar central Pd(2)(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 mol-ecules of both polymorphs are located on a crystallographic centre of inversion. The mol-ecular 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 = 795.59

Triclinic,

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[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.111

S = 1.05

4481 reflections

176 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 2.31 e Å−3

Δρmin = −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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023574/ng5274sup1.cif

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

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

[Pd2(C8H18P)2(C8H19P)2]	Z = 1
Mr = 795.59	F(000) = 418
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0669P)2 + 1.1837P] where P = (Fo2 + 2Fc2)/3
4481 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 2.31 e Å−3
0 restraints	Δρmin = −1.34 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)