Di-μ-chlorido-bis-{[2-(di-tert-butyl-phosphan-yl)biphenyl-3-yl-κ(2)C(3),P]palladium(II)} dichloro-methane disolvate.

The asymmetric unit of the title compound, [Pd(2)Cl(2)(C(20)H(26)P)(2)]·2CH(2)Cl(2), contains one half-mol-ecule of the palladium complex and a dichloro-methane solvent mol-ecule. In the complex, two Pd(II) atoms are bridged by two Cl atoms, with the other two coordination sites occupied by a C atom of the biphenyl system and a P atom, resulting in a distorted square-planar coordination geometry of the Pd(II) atom and a cyclo-metallated four-membered ring. The Pd(2)Cl(2) unit is located about an inversion center. The planes of the rings of the biphenyl system make a dihedral angle of 66.36 (11)°.

Related literature

For background to palladacycles, see: Beletskaya & Cheprakov (2004 ▶); Orlye & Jutland (2005 ▶); Herrmann et al. (2003 ▶). For their applications as catalysts for meth­oxy­carbonylation, see: Omondi et al. (2011 ▶); Williams et al. (2008 ▶). For related structures with PdII in ortho-position, see: Sole et al. (2004 ▶); Mohr et al. (2006 ▶); Bennett et al. (2010 ▶); Christmann et al. (2006 ▶); Garrou et al. (1981 ▶).

Experimental

Crystal data

[Pd2Cl2(C20H26P)2]·2CH2Cl2

M = 1048.31

Triclinic,

a = 9.4741 (15) Å

b = 10.1805 (15) Å

c = 12.0677 (18) Å

α = 103.250 (4)°

β = 95.443 (3)°

γ = 97.080 (3)°

V = 1115.2 (3) Å3

Z = 1

Mo Kα radiation

μ = 1.27 mm−1

T = 100 K

0.08 × 0.07 × 0.02 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.905, T max = 0.975

15104 measured reflections

5515 independent reflections

4344 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.094

S = 1.01

5515 reflections

241 parameters

1 restraint

H-atom parameters constrained

Δρmax = 1.16 e Å−3

Δρmin = −1.09 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812051136/kj2217sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051136/kj2217Isup2.hkl

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

[Pd2Cl2(C20H26P)2]·2CH2Cl2	Z = 1
Mr = 1048.31	F(000) = 532
Triclinic, P1	Dx = 1.561 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4741 (15) Å	Cell parameters from 15104 reflections
b = 10.1805 (15) Å	θ = 1.8–28.3°
c = 12.0677 (18) Å	µ = 1.27 mm−1
α = 103.250 (4)°	T = 100 K
β = 95.443 (3)°	Block, yellow
γ = 97.080 (3)°	0.08 × 0.07 × 0.02 mm
V = 1115.2 (3) Å3

Bruker X8 APEXII 4K KappaCCD diffractometer	4344 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
φ and ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→12
Tmin = 0.905, Tmax = 0.975	k = −13→13
15104 measured reflections	l = −15→16
5515 independent reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0476P)2] where P = (Fo2 + 2Fc2)/3
5515 reflections	(Δ/σ)max = 0.001
241 parameters	Δρmax = 1.16 e Å−3
1 restraint	Δρmin = −1.09 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. >>> The Following ALERTS were generated <<< Format: alert-number_ALERT_alert-type_alert-level text 232_ALERT_2_C Hirshfeld Test Diff (M—X) Pd1 – Cl1.. 5.30 su Apllying DELU restraints does not remove this alert. 250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ···. 2.23 Visual inspections of ellipsoids show no abnormalities. R = 3.8%. 911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 3 912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 62 Noted, no measures taken

	x	y	z	Uiso*/Ueq
C1	0.4506 (3)	0.2051 (4)	0.3645 (3)	0.0143 (7)
C2	0.5538 (3)	0.1684 (4)	0.2933 (3)	0.0144 (7)
C3	0.6977 (3)	0.1820 (4)	0.3385 (3)	0.0178 (7)
H3	0.7687	0.1578	0.2902	0.021*
C4	0.7336 (3)	0.2319 (4)	0.4564 (3)	0.0189 (7)
H4	0.831	0.2437	0.4889	0.023*
C5	0.6289 (3)	0.2652 (4)	0.5278 (3)	0.0178 (7)
H5	0.6566	0.2975	0.6082	0.021*
C6	0.4844 (3)	0.2521 (3)	0.4840 (3)	0.0133 (7)
C7	0.3771 (3)	0.2810 (4)	0.5662 (3)	0.0161 (7)
C8	0.3568 (4)	0.1982 (4)	0.6430 (3)	0.0198 (8)
H8	0.4105	0.1251	0.6417	0.024*
C9	0.2587 (4)	0.2219 (4)	0.7209 (3)	0.0245 (8)
H9	0.2457	0.1656	0.773	0.029*
C10	0.1794 (4)	0.3281 (4)	0.7226 (3)	0.0288 (9)
H10	0.1098	0.3426	0.7741	0.035*
C11	0.2018 (4)	0.4135 (4)	0.6489 (3)	0.0259 (9)
H11	0.1495	0.4878	0.6517	0.031*
C12	0.3009 (4)	0.3899 (4)	0.5708 (3)	0.0201 (8)
H12	0.3164	0.4484	0.5207	0.024*
C13	0.1586 (3)	0.0291 (4)	0.2698 (3)	0.0161 (7)
C14	0.2346 (4)	−0.0917 (4)	0.2839 (3)	0.0221 (8)
H14A	0.3069	−0.0628	0.3518	0.033*
H14B	0.2812	−0.1234	0.2156	0.033*
H14C	0.1642	−0.1661	0.2933	0.033*
C15	0.0822 (4)	0.0747 (4)	0.3750 (3)	0.0215 (8)
H15A	0.0348	0.1531	0.3674	0.032*
H15B	0.1524	0.1008	0.4443	0.032*
H15C	0.0104	−0.0006	0.3809	0.032*
C16	0.0503 (4)	−0.0164 (4)	0.1600 (3)	0.0210 (8)
H16A	−0.0155	−0.097	0.1637	0.032*
H16B	0.1018	−0.0389	0.0931	0.032*
H16C	−0.0043	0.0577	0.1532	0.032*
C17	0.2358 (4)	0.3161 (4)	0.2158 (3)	0.0178 (7)
C18	0.1118 (4)	0.3638 (4)	0.2795 (3)	0.0239 (8)
H18A	0.1377	0.3755	0.3622	0.036*
H18B	0.0258	0.2954	0.2527	0.036*
H18C	0.0927	0.451	0.2645	0.036*
C19	0.1888 (4)	0.2829 (4)	0.0851 (3)	0.0217 (8)
H19A	0.1082	0.208	0.0641	0.033*
H19B	0.2692	0.2557	0.0442	0.033*
H19C	0.1593	0.3638	0.0641	0.033*
C20	0.3659 (4)	0.4295 (4)	0.2461 (3)	0.0207 (8)
H20A	0.3418	0.5083	0.2185	0.031*
H20B	0.4469	0.3958	0.2095	0.031*
H20C	0.3922	0.4568	0.3295	0.031*
C21	0.3306 (4)	0.6222 (4)	−0.0511 (3)	0.0265 (9)
H21A	0.3451	0.6825	−0.1041	0.032*
H21B	0.3437	0.5292	−0.0916	0.032*
Cl1	0.32540 (8)	−0.02556 (9)	−0.05326 (7)	0.01603 (17)
Cl2	0.15439 (10)	0.61906 (11)	−0.01468 (10)	0.0332 (2)
Cl3	0.46013 (9)	0.68133 (10)	0.07196 (8)	0.0267 (2)
P7	0.30128 (8)	0.16081 (9)	0.24901 (7)	0.01217 (18)
Pd1	0.46067 (2)	0.08342 (3)	0.13497 (2)	0.01217 (8)

	U11	U22	U33	U12	U13	U23
C1	0.0082 (14)	0.0204 (18)	0.0149 (16)	0.0042 (13)	−0.0005 (12)	0.0051 (14)
C2	0.0097 (15)	0.0189 (17)	0.0145 (16)	0.0039 (13)	−0.0009 (12)	0.0040 (14)
C3	0.0091 (15)	0.0250 (19)	0.0186 (18)	0.0056 (14)	0.0036 (13)	0.0016 (15)
C4	0.0058 (14)	0.029 (2)	0.0196 (18)	0.0048 (14)	−0.0031 (13)	0.0029 (16)
C5	0.0126 (16)	0.0218 (18)	0.0170 (17)	0.0037 (14)	−0.0014 (13)	0.0018 (15)
C6	0.0103 (15)	0.0157 (17)	0.0134 (16)	0.0029 (13)	0.0014 (12)	0.0022 (13)
C7	0.0079 (14)	0.0224 (18)	0.0123 (16)	−0.0026 (13)	0.0005 (12)	−0.0042 (14)
C8	0.0131 (16)	0.027 (2)	0.0156 (17)	−0.0011 (14)	−0.0021 (13)	0.0022 (15)
C9	0.0169 (17)	0.037 (2)	0.0172 (18)	−0.0062 (16)	0.0018 (14)	0.0069 (17)
C10	0.0174 (18)	0.040 (2)	0.021 (2)	−0.0046 (17)	0.0088 (15)	−0.0054 (18)
C11	0.0153 (17)	0.027 (2)	0.032 (2)	0.0062 (15)	0.0051 (15)	−0.0019 (18)
C12	0.0136 (16)	0.025 (2)	0.0191 (18)	0.0023 (14)	0.0015 (14)	0.0012 (15)
C13	0.0090 (15)	0.0232 (19)	0.0148 (16)	0.0007 (13)	−0.0006 (12)	0.0036 (14)
C14	0.0157 (17)	0.0221 (19)	0.029 (2)	−0.0014 (15)	0.0012 (15)	0.0091 (16)
C15	0.0147 (16)	0.032 (2)	0.0166 (18)	−0.0025 (15)	0.0038 (13)	0.0055 (16)
C16	0.0121 (16)	0.031 (2)	0.0161 (17)	−0.0043 (15)	0.0001 (13)	0.0023 (16)
C17	0.0142 (16)	0.0217 (18)	0.0171 (17)	0.0050 (14)	0.0038 (13)	0.0017 (15)
C18	0.0174 (17)	0.029 (2)	0.026 (2)	0.0107 (16)	0.0057 (15)	0.0034 (17)
C19	0.0218 (18)	0.028 (2)	0.0159 (18)	0.0101 (16)	−0.0006 (14)	0.0053 (16)
C20	0.0211 (18)	0.0208 (19)	0.0203 (18)	0.0043 (15)	0.0045 (14)	0.0039 (15)
C21	0.0205 (18)	0.031 (2)	0.027 (2)	0.0032 (16)	0.0027 (15)	0.0062 (18)
Cl1	0.0066 (3)	0.0255 (5)	0.0139 (4)	0.0042 (3)	0.0010 (3)	−0.0001 (3)
Cl2	0.0144 (4)	0.0346 (6)	0.0501 (7)	0.0044 (4)	0.0032 (4)	0.0093 (5)
Cl3	0.0176 (4)	0.0300 (5)	0.0311 (5)	0.0015 (4)	−0.0002 (4)	0.0073 (4)
P7	0.0049 (3)	0.0191 (4)	0.0116 (4)	0.0028 (3)	0.0008 (3)	0.0014 (3)
Pd1	0.00434 (11)	0.01965 (14)	0.01151 (13)	0.00282 (9)	0.00054 (8)	0.00138 (10)

C1—C2	1.391 (5)	C14—H14C	0.98
C1—C6	1.403 (5)	C15—H15A	0.98
C1—P7	1.824 (3)	C15—H15B	0.98
C2—C3	1.398 (4)	C15—H15C	0.98
C2—Pd1	1.978 (3)	C16—H16A	0.98
C3—C4	1.389 (5)	C16—H16B	0.98
C3—H3	0.95	C16—H16C	0.98
C4—C5	1.397 (5)	C17—C18	1.532 (5)
C4—H4	0.95	C17—C20	1.535 (5)
C5—C6	1.399 (4)	C17—C19	1.544 (5)
C5—H5	0.95	C17—P7	1.879 (4)
C6—C7	1.495 (4)	C18—H18A	0.98
C7—C12	1.389 (5)	C18—H18B	0.98
C7—C8	1.400 (5)	C18—H18C	0.98
C8—C9	1.387 (5)	C19—H19A	0.98
C8—H8	0.95	C19—H19B	0.98
C9—C10	1.388 (6)	C19—H19C	0.98
C9—H9	0.95	C20—H20A	0.98
C10—C11	1.391 (6)	C20—H20B	0.98
C10—H10	0.95	C20—H20C	0.98
C11—C12	1.396 (5)	C21—Cl2	1.764 (4)
C11—H11	0.95	C21—Cl3	1.771 (4)
C12—H12	0.95	C21—H21A	0.99
C13—C15	1.529 (5)	C21—H21B	0.99
C13—C14	1.534 (5)	Cl1—Pd1i	2.4154 (8)
C13—C16	1.539 (4)	Cl1—Pd1	2.4444 (9)
C13—P7	1.860 (3)	P7—Pd1	2.2328 (9)
C14—H14A	0.98	Pd1—Cl1i	2.4154 (8)
C14—H14B	0.98
C2—C1—C6	122.1 (3)	H15A—C15—H15C	109.5
C2—C1—P7	95.0 (2)	H15B—C15—H15C	109.5
C6—C1—P7	142.8 (3)	C13—C16—H16A	109.5
C1—C2—C3	120.7 (3)	C13—C16—H16B	109.5
C1—C2—Pd1	109.9 (2)	H16A—C16—H16B	109.5
C3—C2—Pd1	129.1 (3)	C13—C16—H16C	109.5
C4—C3—C2	117.9 (3)	H16A—C16—H16C	109.5
C4—C3—H3	121	H16B—C16—H16C	109.5
C2—C3—H3	121	C18—C17—C20	110.1 (3)
C3—C4—C5	121.1 (3)	C18—C17—C19	109.4 (3)
C3—C4—H4	119.4	C20—C17—C19	108.6 (3)
C5—C4—H4	119.4	C18—C17—P7	115.1 (3)
C4—C5—C6	121.7 (3)	C20—C17—P7	106.2 (2)
C4—C5—H5	119.1	C19—C17—P7	107.3 (2)
C6—C5—H5	119.1	C17—C18—H18A	109.5
C5—C6—C1	116.4 (3)	C17—C18—H18B	109.5
C5—C6—C7	118.7 (3)	H18A—C18—H18B	109.5
C1—C6—C7	124.8 (3)	C17—C18—H18C	109.5
C12—C7—C8	119.3 (3)	H18A—C18—H18C	109.5
C12—C7—C6	121.9 (3)	H18B—C18—H18C	109.5
C8—C7—C6	118.7 (3)	C17—C19—H19A	109.5
C9—C8—C7	120.5 (4)	C17—C19—H19B	109.5
C9—C8—H8	119.8	H19A—C19—H19B	109.5
C7—C8—H8	119.8	C17—C19—H19C	109.5
C8—C9—C10	119.9 (4)	H19A—C19—H19C	109.5
C8—C9—H9	120.1	H19B—C19—H19C	109.5
C10—C9—H9	120.1	C17—C20—H20A	109.5
C9—C10—C11	120.1 (4)	C17—C20—H20B	109.5
C9—C10—H10	120	H20A—C20—H20B	109.5
C11—C10—H10	120	C17—C20—H20C	109.5
C10—C11—C12	120.0 (4)	H20A—C20—H20C	109.5
C10—C11—H11	120	H20B—C20—H20C	109.5
C12—C11—H11	120	Cl2—C21—Cl3	111.6 (2)
C7—C12—C11	120.2 (4)	Cl2—C21—H21A	109.3
C7—C12—H12	119.9	Cl3—C21—H21A	109.3
C11—C12—H12	119.9	Cl2—C21—H21B	109.3
C15—C13—C14	109.0 (3)	Cl3—C21—H21B	109.3
C15—C13—C16	110.7 (3)	H21A—C21—H21B	108
C14—C13—C16	108.7 (3)	Pd1i—Cl1—Pd1	92.33 (3)
C15—C13—P7	114.4 (2)	C1—P7—C13	112.74 (15)
C14—C13—P7	105.4 (2)	C1—P7—C17	112.13 (16)
C16—C13—P7	108.4 (2)	C13—P7—C17	114.90 (15)
C13—C14—H14A	109.5	C1—P7—Pd1	85.84 (11)
C13—C14—H14B	109.5	C13—P7—Pd1	115.73 (12)
H14A—C14—H14B	109.5	C17—P7—Pd1	112.17 (11)
C13—C14—H14C	109.5	C2—Pd1—P7	68.84 (10)
H14A—C14—H14C	109.5	C2—Pd1—Cl1i	97.07 (10)
H14B—C14—H14C	109.5	P7—Pd1—Cl1i	165.87 (3)
C13—C15—H15A	109.5	C2—Pd1—Cl1	174.81 (10)
C13—C15—H15B	109.5	P7—Pd1—Cl1	106.44 (3)
H15A—C15—H15B	109.5	Cl1i—Pd1—Cl1	87.67 (3)
C13—C15—H15C	109.5
C6—C1—C2—C3	−2.4 (5)	C14—C13—P7—C1	−55.2 (3)
P7—C1—C2—C3	179.9 (3)	C16—C13—P7—C1	−171.4 (2)
C6—C1—C2—Pd1	172.0 (3)	C15—C13—P7—C17	−65.6 (3)
P7—C1—C2—Pd1	−5.8 (2)	C14—C13—P7—C17	174.7 (2)
C1—C2—C3—C4	0.5 (5)	C16—C13—P7—C17	58.4 (3)
Pd1—C2—C3—C4	−172.6 (3)	C15—C13—P7—Pd1	161.1 (2)
C2—C3—C4—C5	1.2 (6)	C14—C13—P7—Pd1	41.4 (3)
C3—C4—C5—C6	−1.2 (6)	C16—C13—P7—Pd1	−74.9 (2)
C4—C5—C6—C1	−0.6 (5)	C18—C17—P7—C1	−93.1 (3)
C4—C5—C6—C7	176.1 (3)	C20—C17—P7—C1	28.9 (3)
C2—C1—C6—C5	2.4 (5)	C19—C17—P7—C1	144.9 (2)
P7—C1—C6—C5	178.7 (3)	C18—C17—P7—C13	37.4 (3)
C2—C1—C6—C7	−174.1 (3)	C20—C17—P7—C13	159.4 (2)
P7—C1—C6—C7	2.2 (7)	C19—C17—P7—C13	−84.6 (3)
C5—C6—C7—C12	114.5 (4)	C18—C17—P7—Pd1	172.3 (2)
C1—C6—C7—C12	−69.1 (5)	C20—C17—P7—Pd1	−65.7 (2)
C5—C6—C7—C8	−63.4 (4)	C19—C17—P7—Pd1	50.3 (3)
C1—C6—C7—C8	113.0 (4)	C1—C2—Pd1—P7	5.1 (2)
C12—C7—C8—C9	1.8 (5)	C3—C2—Pd1—P7	178.8 (4)
C6—C7—C8—C9	179.8 (3)	C1—C2—Pd1—Cl1i	−176.0 (2)
C7—C8—C9—C10	0.3 (5)	C3—C2—Pd1—Cl1i	−2.3 (3)
C8—C9—C10—C11	−2.2 (6)	C1—P7—Pd1—C2	−3.63 (15)
C9—C10—C11—C12	1.9 (6)	C13—P7—Pd1—C2	−116.91 (16)
C8—C7—C12—C11	−2.0 (5)	C17—P7—Pd1—C2	108.59 (16)
C6—C7—C12—C11	−180.0 (3)	C1—P7—Pd1—Cl1i	−8.08 (19)
C10—C11—C12—C7	0.2 (5)	C13—P7—Pd1—Cl1i	−121.36 (17)
C2—C1—P7—C13	121.0 (2)	C17—P7—Pd1—Cl1i	104.15 (17)
C6—C1—P7—C13	−55.8 (5)	C1—P7—Pd1—Cl1	174.08 (11)
C2—C1—P7—C17	−107.4 (2)	C13—P7—Pd1—Cl1	60.80 (12)
C6—C1—P7—C17	75.7 (5)	C17—P7—Pd1—Cl1	−73.70 (12)
C2—C1—P7—Pd1	4.8 (2)	Pd1i—Cl1—Pd1—P7	179.47 (3)
C6—C1—P7—Pd1	−172.0 (4)	Pd1i—Cl1—Pd1—Cl1i	0
C15—C13—P7—C1	64.6 (3)