trans-Di-μ-chloro-bis­[chloro­(tri­phenyl­phosphine)­palladium] benzene disolvate

The title complex, trans-[PdCl₂(PPh₃)]₂, in the crystal structure of its benzene disolvate, [Pd₂Cl₄(C₁₈H₁₅P)₂]·2C₆H₆,occupies a special position in the inversion centre. The Pd atom has a distorted square-planar coordination environment formed by a tri­phenyl­phosphine [Pd—P 2.2278 (6) Å], a terminal chloride [Pd–Cl 2.2722 (7) Å], and two bridging chloride ligands. The Pd—μ-Cl bond in the trans-position to the phosphine ligand [2.4128 (6) Å] is considerably longer than the Pd—μ-Cl bond in the trans-position to the terminal chloride [2.3228 (6) Å].

Key indicators

• Single-crystal X-ray study
• T = 220 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.034
• wR factor = 0.089
• Data-to-parameter ratio = 17.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97.

(I)

Crystal data

[Pd2Cl4(C18H15P)2]·2C6H6	F(000) = 1040
Mr = 1035.40	Dx = 1.542 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 7164 reflections
a = 9.6895 (2) Å	θ = 2.3–72.8°
b = 18.9619 (3) Å	µ = 9.64 mm^−1
c = 12.8905 (2) Å	T = 220 K
β = 109.743 (1)°	Block, dark orange–red
V = 2229.17 (7) Å^3	0.27 × 0.14 × 0.10 mm
Z = 2

Data collection

Bruker AXS SMART 2K/Platform diffractometer	4387 independent reflections
Radiation source: normal-focus X-ray tube	3992 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
Detector resolution: 5.5 pixels mm^-1	θmax = 72.8°, θmin = 4.3°
ω scans	h = −10→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −23→23
Tmin = 0.238, Tmax = 0.382	l = −15→15
26449 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0666P)^2] where P = (Fo^2 + 2Fc^2)/3
4387 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 1.41 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

Special details

Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a glass fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 2 K Charged-Coupled Device (CCD) Area Detector using the program SMART and normal focus sealed tube source graphite monochromated Cu—Kα radiation. The crystal-to-detector distance was 4.908 cm, and the data collection was carried out in 512 x 512 pixel mode, utilizing 4 x 4 pixel binning. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 9.0 degree scan in 30 frames over four different parts of the reciprocal space (120 frames total). One complete sphere of data was collected, to better than 0.8 Å resolution. Upon completion of the data collection, the first 101 frames were recollected in order to improve the decay correction analysis.

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. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R-factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
Pd1	0.059522 (19)	0.077817 (9)	0.574033 (14)	0.02316 (9)
Cl1	0.10130 (7)	0.01308 (3)	0.42624 (5)	0.03129 (15)
Cl2	0.22125 (8)	0.16325 (4)	0.56831 (6)	0.04067 (18)
P1	0.02311 (7)	0.13824 (3)	0.71075 (5)	0.02407 (15)
C11	−0.1258 (3)	0.10080 (14)	0.7488 (2)	0.0286 (5)
C12	−0.0943 (4)	0.04479 (16)	0.8241 (3)	0.0383 (6)
H12	0.0035	0.0311	0.8603	0.046*
C13	−0.2066 (4)	0.00979 (17)	0.8451 (3)	0.0477 (8)
H13	−0.1853	−0.0274	0.8963	0.057*
C14	−0.3514 (4)	0.02930 (19)	0.7907 (3)	0.0522 (9)
H14	−0.4280	0.0048	0.8041	0.063*
C15	−0.3822 (4)	0.0841 (2)	0.7177 (4)	0.0529 (9)
H15	−0.4802	0.0977	0.6822	0.063*
C16	−0.2702 (3)	0.11998 (17)	0.6953 (3)	0.0397 (7)
H16	−0.2925	0.1571	0.6440	0.048*
C21	−0.0252 (3)	0.22907 (13)	0.6715 (2)	0.0266 (5)
C22	0.0329 (3)	0.28559 (15)	0.7409 (2)	0.0361 (6)
H22	0.1008	0.2776	0.8118	0.043*
C23	−0.0092 (4)	0.35396 (16)	0.7056 (3)	0.0456 (8)
H23	0.0308	0.3921	0.7526	0.055*
C24	−0.1091 (4)	0.36628 (17)	0.6020 (3)	0.0466 (8)
H24	−0.1376	0.4127	0.5788	0.056*
C25	−0.1673 (4)	0.31029 (17)	0.5323 (3)	0.0444 (7)
H25	−0.2359	0.3185	0.4618	0.053*
C26	−0.1248 (3)	0.24255 (15)	0.5664 (2)	0.0369 (6)
H26	−0.1634	0.2047	0.5181	0.044*
C31	0.1784 (3)	0.13582 (14)	0.8376 (2)	0.0283 (5)
C32	0.1653 (4)	0.16284 (15)	0.9344 (2)	0.0355 (6)
H32	0.0768	0.1838	0.9331	0.043*
C33	0.2819 (4)	0.15895 (17)	1.0323 (2)	0.0437 (7)
H33	0.2736	0.1782	1.0971	0.052*
C34	0.4099 (4)	0.12685 (19)	1.0346 (3)	0.0505 (8)
H34	0.4884	0.1238	1.1015	0.061*
C35	0.4249 (4)	0.0992 (2)	0.9406 (3)	0.0563 (9)
H35	0.5133	0.0775	0.9433	0.068*
C36	0.3087 (3)	0.10341 (19)	0.8411 (3)	0.0419 (7)
H36	0.3183	0.0844	0.7765	0.050*
C41	0.3147 (4)	0.8808 (3)	0.6636 (3)	0.0656 (12)
H41	0.2362	0.9074	0.6702	0.079*
C42	0.4027 (6)	0.9086 (3)	0.6116 (4)	0.0743 (13)
H42	0.3856	0.9546	0.5826	0.089*
C43	0.5179 (5)	0.8691 (3)	0.6013 (4)	0.0837 (15)
H43	0.5792	0.8877	0.5650	0.100*
C44	0.5408 (5)	0.8022 (3)	0.6453 (4)	0.0803 (15)
H44	0.6188	0.7749	0.6393	0.096*
C45	0.4524 (5)	0.7754 (2)	0.6969 (4)	0.0699 (12)
H45	0.4691	0.7296	0.7265	0.084*
C46	0.3404 (5)	0.8139 (3)	0.7064 (3)	0.0648 (11)
H46	0.2794	0.7949	0.7427	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.03141 (13)	0.01733 (13)	0.02153 (13)	−0.00016 (6)	0.00996 (8)	−0.00179 (6)
Cl1	0.0483 (4)	0.0214 (3)	0.0309 (3)	−0.0055 (2)	0.0222 (3)	−0.0057 (2)
Cl2	0.0472 (4)	0.0329 (4)	0.0486 (4)	−0.0126 (3)	0.0249 (3)	−0.0071 (3)
P1	0.0294 (3)	0.0203 (3)	0.0224 (3)	−0.0005 (2)	0.0087 (2)	−0.0041 (2)
C11	0.0357 (14)	0.0242 (13)	0.0291 (13)	−0.0032 (10)	0.0150 (11)	−0.0081 (10)
C12	0.0471 (17)	0.0303 (15)	0.0402 (16)	−0.0017 (12)	0.0182 (13)	0.0003 (12)
C13	0.068 (2)	0.0353 (17)	0.0481 (19)	−0.0081 (15)	0.0309 (17)	−0.0005 (14)
C14	0.056 (2)	0.047 (2)	0.065 (2)	−0.0154 (16)	0.0357 (18)	−0.0128 (17)
C15	0.0383 (18)	0.055 (2)	0.072 (3)	−0.0037 (14)	0.0270 (18)	−0.0054 (18)
C16	0.0374 (15)	0.0366 (16)	0.0464 (18)	0.0007 (12)	0.0160 (13)	−0.0009 (13)
C21	0.0327 (13)	0.0208 (12)	0.0272 (13)	−0.0017 (10)	0.0112 (10)	−0.0035 (10)
C22	0.0459 (16)	0.0271 (14)	0.0309 (15)	−0.0074 (12)	0.0073 (12)	−0.0054 (11)
C23	0.067 (2)	0.0234 (14)	0.0443 (18)	−0.0091 (14)	0.0164 (15)	−0.0090 (13)
C24	0.064 (2)	0.0225 (15)	0.053 (2)	0.0020 (13)	0.0187 (16)	0.0049 (13)
C25	0.0536 (19)	0.0338 (16)	0.0393 (17)	0.0019 (13)	0.0073 (14)	0.0055 (13)
C26	0.0482 (17)	0.0258 (14)	0.0299 (14)	−0.0012 (12)	0.0045 (12)	−0.0038 (11)
C31	0.0331 (13)	0.0248 (13)	0.0248 (13)	−0.0017 (10)	0.0067 (10)	−0.0025 (10)
C32	0.0468 (17)	0.0314 (15)	0.0286 (14)	0.0011 (12)	0.0132 (12)	−0.0028 (11)
C33	0.065 (2)	0.0340 (16)	0.0264 (15)	−0.0057 (14)	0.0079 (14)	−0.0037 (12)
C34	0.054 (2)	0.051 (2)	0.0330 (17)	−0.0033 (15)	−0.0041 (14)	0.0006 (14)
C35	0.0410 (19)	0.070 (3)	0.047 (2)	0.0113 (17)	0.0012 (15)	−0.0042 (18)
C36	0.0388 (16)	0.0519 (19)	0.0327 (16)	0.0052 (14)	0.0091 (13)	−0.0040 (14)
C41	0.052 (2)	0.079 (3)	0.050 (2)	0.009 (2)	−0.0028 (17)	−0.027 (2)
C42	0.074 (3)	0.063 (3)	0.065 (3)	−0.006 (2)	−0.004 (2)	0.005 (2)
C43	0.063 (3)	0.116 (5)	0.073 (3)	−0.022 (3)	0.023 (2)	−0.005 (3)
C44	0.052 (2)	0.090 (4)	0.086 (3)	0.015 (2)	0.006 (2)	−0.028 (3)
C45	0.065 (3)	0.060 (3)	0.064 (3)	−0.002 (2)	−0.005 (2)	−0.006 (2)
C46	0.060 (2)	0.080 (3)	0.045 (2)	−0.010 (2)	0.0051 (17)	−0.009 (2)

Geometric parameters (Å, º)

Pd1—P1	2.2278 (6)	C25—C26	1.375 (4)
Pd1—Cl2	2.2722 (7)	C25—H25	0.9400
Pd1—Cl1^i	2.3228 (6)	C26—H26	0.9400
Pd1—Cl1	2.4128 (6)	C31—C36	1.391 (4)
Cl1—Pd1^i	2.3228 (6)	C31—C32	1.393 (4)
P1—C31	1.810 (3)	C32—C33	1.383 (4)
P1—C21	1.811 (3)	C32—H32	0.9400
P1—C11	1.818 (3)	C33—C34	1.373 (5)
C11—C16	1.383 (4)	C33—H33	0.9400
C11—C12	1.401 (4)	C34—C35	1.372 (5)
C12—C13	1.377 (4)	C34—H34	0.9400
C12—H12	0.9400	C35—C36	1.394 (4)
C13—C14	1.390 (5)	C35—H35	0.9400
C13—H13	0.9400	C36—H36	0.9400
C14—C15	1.365 (5)	C41—C42	1.356 (7)
C14—H14	0.9400	C41—C46	1.372 (6)
C15—C16	1.392 (5)	C41—H41	0.9400
C15—H15	0.9400	C42—C43	1.388 (8)
C16—H16	0.9400	C42—H42	0.9400
C21—C22	1.387 (4)	C43—C44	1.376 (7)
C21—C26	1.397 (4)	C43—H43	0.9400
C22—C23	1.389 (4)	C44—C45	1.349 (7)
C22—H22	0.9400	C44—H44	0.9400
C23—C24	1.379 (5)	C45—C46	1.348 (6)
C23—H23	0.9400	C45—H45	0.9400
C24—C25	1.382 (5)	C46—H46	0.9400
C24—H24	0.9400
P1—Pd1—Cl2	87.38 (2)	C26—C25—C24	119.9 (3)
P1—Pd1—Cl1^i	95.59 (2)	C26—C25—H25	120.0
Cl2—Pd1—Cl1^i	176.98 (2)	C24—C25—H25	120.0
P1—Pd1—Cl1	179.39 (2)	C25—C26—C21	121.0 (3)
Cl2—Pd1—Cl1	92.04 (2)	C25—C26—H26	119.5
Cl1^i—Pd1—Cl1	84.99 (2)	C21—C26—H26	119.5
Pd1^i—Cl1—Pd1	95.01 (2)	C36—C31—C32	119.3 (3)
C31—P1—C21	109.49 (12)	C36—C31—P1	120.6 (2)
C31—P1—C11	103.85 (12)	C32—C31—P1	120.0 (2)
C21—P1—C11	107.04 (12)	C33—C32—C31	120.3 (3)
C31—P1—Pd1	113.34 (9)	C33—C32—H32	119.9
C21—P1—Pd1	111.30 (8)	C31—C32—H32	119.9
C11—P1—Pd1	111.40 (8)	C34—C33—C32	119.8 (3)
C16—C11—C12	119.4 (3)	C34—C33—H33	120.1
C16—C11—P1	121.6 (2)	C32—C33—H33	120.1
C12—C11—P1	118.4 (2)	C35—C34—C33	121.0 (3)
C13—C12—C11	120.0 (3)	C35—C34—H34	119.5
C13—C12—H12	120.0	C33—C34—H34	119.5
C11—C12—H12	120.0	C34—C35—C36	119.8 (3)
C12—C13—C14	120.2 (3)	C34—C35—H35	120.1
C12—C13—H13	119.9	C36—C35—H35	120.1
C14—C13—H13	119.9	C31—C36—C35	119.8 (3)
C15—C14—C13	119.9 (3)	C31—C36—H36	120.1
C15—C14—H14	120.0	C35—C36—H36	120.1
C13—C14—H14	120.0	C42—C41—C46	120.0 (4)
C14—C15—C16	120.7 (4)	C42—C41—H41	120.0
C14—C15—H15	119.6	C46—C41—H41	120.0
C16—C15—H15	119.6	C41—C42—C43	119.8 (5)
C11—C16—C15	119.8 (3)	C41—C42—H42	120.1
C11—C16—H16	120.1	C43—C42—H42	120.1
C15—C16—H16	120.1	C44—C43—C42	118.8 (5)
C22—C21—C26	118.8 (3)	C44—C43—H43	120.6
C22—C21—P1	123.0 (2)	C42—C43—H43	120.6
C26—C21—P1	118.3 (2)	C45—C44—C43	120.6 (5)
C21—C22—C23	119.9 (3)	C45—C44—H44	119.7
C21—C22—H22	120.0	C43—C44—H44	119.7
C23—C22—H22	120.0	C46—C45—C44	120.4 (5)
C24—C23—C22	120.5 (3)	C46—C45—H45	119.8
C24—C23—H23	119.7	C44—C45—H45	119.8
C22—C23—H23	119.7	C45—C46—C41	120.4 (4)
C23—C24—C25	119.9 (3)	C45—C46—H46	119.8
C23—C24—H24	120.0	C41—C46—H46	119.8
C25—C24—H24	120.0
Cl2—Pd1—Cl1—Pd1^i	179.43 (3)	C26—C21—C22—C23	0.5 (4)
Cl1^i—Pd1—Cl1—Pd1^i	0.0	P1—C21—C22—C23	−179.9 (2)
Cl2—Pd1—P1—C31	−70.50 (10)	C21—C22—C23—C24	0.3 (5)
Cl1^i—Pd1—P1—C31	108.92 (10)	C22—C23—C24—C25	−0.4 (6)
Cl2—Pd1—P1—C21	53.44 (9)	C23—C24—C25—C26	−0.3 (5)
Cl1^i—Pd1—P1—C21	−127.14 (9)	C24—C25—C26—C21	1.2 (5)
Cl2—Pd1—P1—C11	172.82 (10)	C22—C21—C26—C25	−1.2 (5)
Cl1^i—Pd1—P1—C11	−7.77 (10)	P1—C21—C26—C25	179.1 (3)
C31—P1—C11—C16	151.0 (2)	C21—P1—C31—C36	−120.0 (3)
C21—P1—C11—C16	35.2 (3)	C11—P1—C31—C36	126.0 (3)
Pd1—P1—C11—C16	−86.6 (2)	Pd1—P1—C31—C36	5.0 (3)
C31—P1—C11—C12	−37.3 (2)	C21—P1—C31—C32	63.9 (3)
C21—P1—C11—C12	−153.1 (2)	C11—P1—C31—C32	−50.2 (3)
Pd1—P1—C11—C12	85.0 (2)	Pd1—P1—C31—C32	−171.2 (2)
C16—C11—C12—C13	−0.6 (4)	C36—C31—C32—C33	1.5 (4)
P1—C11—C12—C13	−172.5 (2)	P1—C31—C32—C33	177.8 (2)
C11—C12—C13—C14	0.8 (5)	C31—C32—C33—C34	−1.5 (5)
C12—C13—C14—C15	−1.2 (5)	C32—C33—C34—C35	0.8 (5)
C13—C14—C15—C16	1.3 (6)	C33—C34—C35—C36	−0.2 (6)
C12—C11—C16—C15	0.8 (5)	C32—C31—C36—C35	−0.9 (5)
P1—C11—C16—C15	172.3 (3)	P1—C31—C36—C35	−177.1 (3)
C14—C15—C16—C11	−1.1 (5)	C34—C35—C36—C31	0.2 (6)
C31—P1—C21—C22	−10.9 (3)	C46—C41—C42—C43	0.4 (7)
C11—P1—C21—C22	101.1 (3)	C41—C42—C43—C44	−0.5 (7)
Pd1—P1—C21—C22	−137.0 (2)	C42—C43—C44—C45	0.3 (7)
C31—P1—C21—C26	168.8 (2)	C43—C44—C45—C46	−0.1 (7)
C11—P1—C21—C26	−79.3 (2)	C44—C45—C46—C41	0.1 (6)
Pd1—P1—C21—C26	42.7 (2)	C42—C41—C46—C45	−0.2 (6)

Symmetry code: (i) −x, −y, −z+1.