trans-Dibromidobis(triphenyl­phosphine-κP)palladium(II) chloro­form monosolvate

Abstract

The Pd^II atom in the title compound, [PdBr₂{P(C₆H₅)₃}₂]·CHCl₃, lies on a twofold rotation axis and is coordinated in a distorted square-planar geometry by two P atoms from two triphenyl­phosphine ligands and by two Br atoms in a trans arrangement. The chloro­form solvent mol­ecule is equally disordered about another twofold rotation axis.

Related literature

For isostructural PdI₂(PPh₃)₂·CHCl₃, see: Kubota et al. (1991 ▶). For the other solvates of PdBr₂(PPh₃)₂, see: Crawforth et al. (2005 ▶); Rodríguez et al. (2007 ▶); Stark & Whitmire (1997 ▶).

Experimental

Crystal data

• [PdBr₂(C₁₈H₁₅P)₂]·CHCl₃

• M _r = 910.13

• Monoclinic,

• a = 12.2314 (2) Å

• b = 14.4754 (2) Å

• c = 20.1653 (3) Å

• β = 92.477 (1)°

• V = 3567.02 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 3.10 mm⁻¹

• T = 153 K

• 0.30 × 0.25 × 0.20 mm

Data collection

• Bruker SMART APEX CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.456, T _max = 0.576 (expected range = 0.426–0.538)

• 16862 measured reflections

• 4110 independent reflections

• 3266 reflections with I > 2σ(I)

• R _int = 0.018

Refinement

• R[F ² > 2σ(F ²)] = 0.023

• wR(F ²) = 0.061

• S = 1.02

• 4110 reflections

• 222 parameters

• 24 restraints

• H-atom parameters constrained

• Δρ_max = 0.47 e Å⁻³

• Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Pd1—P1	2.3360 (5)
Pd1—Br1	2.4277 (2)

supplementary crystallographic information

Experimental

Commercially available dark-brown bis(triphenylphosphine)palladium dichloride (0.70 g, 1 mmol) and 4-dimethylaminopyridinium hydrobromide perbromide (0.36 g, 1 mmol) were heated in an ethanol/chloroform mixture (1:1 v/v, 100 ml) for an hour. The solution was filtered and a small amount of deep yellow crystals were isolated along with some dark brown material.

Refinement

H atoms were placed at calculated positions (C–H = 0.95 and 1.00 Å) and treated as riding on their parent atoms, with U_iso(H) = 1.2U_eq(C). The chloroform molecule is disordered about a twofold rotation axis, and was allowed to refine off the symmetry element as a whole molecule of 0.5 site occupancy. The three C—Cl distances were restrained to within 0.01 Å of each other, as were the Cl···Cl distances. The anisotropic displacements of the Cl atoms were restrained to be nearly isotropic.

Figures

Fig. 1.

Molecular structure of the title compound. Displacement ellipsoids are drawn at the 70% probability level.

Crystal data

[PdBr2(C18H15P)2]·CHCl3	F(000) = 1800
Mr = 910.13	Dx = 1.695 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6987 reflections
a = 12.2314 (2) Å	θ = 2.4–28.3°
b = 14.4754 (2) Å	µ = 3.10 mm−1
c = 20.1653 (3) Å	T = 153 K
β = 92.477 (1)°	Prism, brown
V = 3567.02 (9) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	4110 independent reflections
Radiation source: fine-focus sealed tube	3266 reflections with I > 2σ(I)
graphite	Rint = 0.018
φ and ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.456, Tmax = 0.576	k = −18→18
16862 measured reflections	l = −26→26

Refinement

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0263P)2 + 6.7144P] where P = (Fo2 + 2Fc2)/3
4110 reflections	(Δ/σ)max = 0.001
222 parameters	Δρmax = 0.47 e Å−3
24 restraints	Δρmin = −0.36 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd1	0.5000	0.250839 (14)	0.2500	0.01811 (6)
Br1	0.322982 (17)	0.253392 (15)	0.299982 (11)	0.02692 (7)
P1	0.59326 (4)	0.25342 (3)	0.35355 (3)	0.01868 (11)
C1	0.70341 (17)	0.16892 (14)	0.35728 (10)	0.0226 (4)
C2	0.6778 (2)	0.08037 (16)	0.33385 (12)	0.0324 (5)
H2	0.6064	0.0675	0.3159	0.039*
C3	0.7560 (2)	0.01137 (17)	0.33665 (13)	0.0418 (6)
H3	0.7378	−0.0492	0.3217	0.050*
C4	0.8602 (2)	0.0307 (2)	0.36119 (13)	0.0465 (7)
H4	0.9142	−0.0165	0.3624	0.056*
C5	0.8869 (2)	0.1177 (2)	0.38400 (14)	0.0443 (7)
H5	0.9591	0.1303	0.4008	0.053*
C6	0.80823 (19)	0.18742 (17)	0.38251 (11)	0.0306 (5)
H6	0.8264	0.2473	0.3987	0.037*
C7	0.51852 (17)	0.22807 (14)	0.42793 (10)	0.0218 (4)
C8	0.4458 (2)	0.29338 (17)	0.45150 (12)	0.0339 (5)
H8	0.4357	0.3504	0.4287	0.041*
C9	0.3886 (2)	0.2759 (2)	0.50751 (13)	0.0405 (6)
H9	0.3397	0.3212	0.5231	0.049*
C10	0.4014 (2)	0.19368 (19)	0.54117 (12)	0.0369 (6)
H10	0.3613	0.1820	0.5796	0.044*
C11	0.4724 (2)	0.12875 (17)	0.51881 (12)	0.0356 (6)
H11	0.4821	0.0721	0.5421	0.043*
C12	0.53046 (19)	0.14535 (15)	0.46205 (11)	0.0292 (5)
H12	0.5787	0.0995	0.4466	0.035*
C13	0.65111 (17)	0.36690 (14)	0.37174 (10)	0.0219 (4)
C14	0.6954 (2)	0.38791 (16)	0.43498 (11)	0.0314 (5)
H14	0.6938	0.3432	0.4694	0.038*
C15	0.7417 (2)	0.47408 (16)	0.44744 (12)	0.0352 (6)
H15	0.7720	0.4881	0.4904	0.042*
C16	0.7439 (2)	0.53955 (15)	0.39760 (12)	0.0316 (5)
H16	0.7776	0.5978	0.4060	0.038*
C17	0.6973 (2)	0.52028 (15)	0.33583 (12)	0.0315 (5)
H17	0.6968	0.5660	0.3020	0.038*
C18	0.65112 (18)	0.43408 (14)	0.32274 (11)	0.0258 (5)
H18	0.6193	0.4211	0.2799	0.031*
Cl1	0.0544 (6)	0.4068 (4)	0.1875 (3)	0.083 (2)	0.50
Cl2	−0.0249 (2)	0.23500 (12)	0.23506 (13)	0.0769 (8)	0.50
Cl3	−0.0654 (5)	0.4028 (2)	0.3067 (2)	0.0454 (8)	0.50
C19	0.0330 (4)	0.3413 (3)	0.2596 (2)	0.0423 (13)	0.50
H19	0.1030	0.3321	0.2862	0.051*	0.50

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Pd1	0.02113 (11)	0.01538 (10)	0.01773 (11)	0.000	−0.00004 (8)	0.000
Br1	0.02633 (11)	0.02758 (12)	0.02707 (12)	−0.00200 (9)	0.00362 (8)	0.00051 (9)
P1	0.0216 (2)	0.0161 (2)	0.0182 (2)	0.0013 (2)	−0.00033 (19)	0.00040 (19)
C1	0.0282 (11)	0.0208 (10)	0.0190 (10)	0.0061 (8)	0.0032 (8)	0.0033 (8)
C2	0.0430 (14)	0.0238 (11)	0.0302 (12)	0.0056 (10)	0.0000 (10)	−0.0027 (9)
C3	0.0663 (19)	0.0268 (12)	0.0327 (13)	0.0174 (12)	0.0091 (13)	0.0022 (10)
C4	0.0561 (18)	0.0461 (16)	0.0382 (15)	0.0334 (14)	0.0129 (13)	0.0146 (12)
C5	0.0313 (13)	0.0581 (18)	0.0434 (15)	0.0148 (12)	0.0005 (11)	0.0121 (13)
C6	0.0291 (12)	0.0335 (12)	0.0292 (12)	0.0037 (9)	0.0019 (10)	0.0050 (9)
C7	0.0223 (10)	0.0233 (10)	0.0194 (10)	−0.0015 (8)	−0.0020 (8)	0.0006 (8)
C8	0.0394 (13)	0.0319 (13)	0.0311 (13)	0.0094 (11)	0.0082 (11)	0.0063 (10)
C9	0.0385 (14)	0.0485 (15)	0.0353 (14)	0.0093 (12)	0.0113 (11)	−0.0042 (12)
C10	0.0363 (13)	0.0515 (16)	0.0234 (12)	−0.0087 (12)	0.0078 (10)	0.0012 (11)
C11	0.0462 (15)	0.0323 (13)	0.0286 (12)	−0.0070 (11)	0.0047 (11)	0.0071 (10)
C12	0.0361 (13)	0.0232 (11)	0.0284 (12)	0.0003 (9)	0.0031 (10)	0.0021 (9)
C13	0.0247 (10)	0.0178 (9)	0.0232 (10)	0.0005 (8)	0.0011 (8)	−0.0023 (8)
C14	0.0429 (14)	0.0257 (11)	0.0253 (11)	−0.0031 (10)	−0.0036 (10)	0.0004 (9)
C15	0.0459 (14)	0.0312 (12)	0.0279 (12)	−0.0034 (11)	−0.0060 (11)	−0.0074 (10)
C16	0.0375 (13)	0.0212 (11)	0.0366 (13)	−0.0056 (10)	0.0062 (10)	−0.0084 (9)
C17	0.0429 (14)	0.0206 (10)	0.0315 (12)	−0.0019 (10)	0.0077 (11)	0.0018 (9)
C18	0.0329 (12)	0.0210 (10)	0.0233 (11)	0.0002 (9)	0.0012 (9)	−0.0008 (8)
Cl1	0.087 (3)	0.103 (3)	0.059 (2)	0.013 (2)	0.0104 (18)	0.0265 (19)
Cl2	0.078 (2)	0.0667 (10)	0.089 (2)	−0.0211 (10)	0.0363 (14)	−0.0134 (10)
Cl3	0.0476 (13)	0.0525 (16)	0.0375 (14)	0.0017 (12)	0.0166 (12)	−0.0003 (12)
C19	0.030 (3)	0.056 (3)	0.041 (3)	0.004 (2)	−0.003 (2)	0.007 (3)

Geometric parameters (Å, °)

Pd1—P1	2.3360 (5)	C9—C10	1.376 (4)
Pd1—P1i	2.3360 (5)	C9—H9	0.9500
Pd1—Br1	2.4277 (2)	C10—C11	1.369 (4)
Pd1—Br1i	2.4277 (2)	C10—H10	0.9500
P1—C1	1.819 (2)	C11—C12	1.394 (3)
P1—C13	1.820 (2)	C11—H11	0.9500
P1—C7	1.827 (2)	C12—H12	0.9500
C1—C6	1.385 (3)	C13—C18	1.386 (3)
C1—C2	1.397 (3)	C13—C14	1.397 (3)
C2—C3	1.382 (3)	C14—C15	1.388 (3)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.377 (4)	C15—C16	1.383 (3)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.375 (4)	C16—C17	1.376 (3)
C4—H4	0.9500	C16—H16	0.9500
C5—C6	1.394 (3)	C17—C18	1.390 (3)
C5—H5	0.9500	C17—H17	0.9500
C6—H6	0.9500	C18—H18	0.9500
C7—C12	1.386 (3)	Cl1—C19	1.764 (5)
C7—C8	1.395 (3)	Cl2—C19	1.756 (4)
C8—C9	1.377 (3)	Cl3—C19	1.800 (5)
C8—H8	0.9500	C19—H19	1.0000
P1—Pd1—P1i	178.16 (3)	C10—C9—C8	120.8 (2)
P1—Pd1—Br1	92.204 (14)	C10—C9—H9	119.6
P1i—Pd1—Br1	87.768 (14)	C8—C9—H9	119.6
P1—Pd1—Br1i	87.768 (14)	C11—C10—C9	119.5 (2)
P1i—Pd1—Br1i	92.204 (14)	C11—C10—H10	120.3
Br1—Pd1—Br1i	178.256 (14)	C9—C10—H10	120.3
C1—P1—C13	108.54 (10)	C10—C11—C12	120.3 (2)
C1—P1—C7	103.12 (9)	C10—C11—H11	119.8
C13—P1—C7	102.70 (9)	C12—C11—H11	119.8
C1—P1—Pd1	111.00 (7)	C7—C12—C11	120.7 (2)
C13—P1—Pd1	111.42 (7)	C7—C12—H12	119.7
C7—P1—Pd1	119.22 (7)	C11—C12—H12	119.7
C6—C1—C2	119.5 (2)	C18—C13—C14	119.07 (19)
C6—C1—P1	123.88 (17)	C18—C13—P1	120.10 (16)
C2—C1—P1	116.65 (17)	C14—C13—P1	120.83 (16)
C3—C2—C1	120.4 (2)	C15—C14—C13	120.0 (2)
C3—C2—H2	119.8	C15—C14—H14	120.0
C1—C2—H2	119.8	C13—C14—H14	120.0
C4—C3—C2	119.7 (2)	C16—C15—C14	120.3 (2)
C4—C3—H3	120.1	C16—C15—H15	119.8
C2—C3—H3	120.1	C14—C15—H15	119.8
C5—C4—C3	120.6 (2)	C17—C16—C15	119.9 (2)
C5—C4—H4	119.7	C17—C16—H16	120.0
C3—C4—H4	119.7	C15—C16—H16	120.0
C4—C5—C6	120.2 (3)	C16—C17—C18	120.2 (2)
C4—C5—H5	119.9	C16—C17—H17	119.9
C6—C5—H5	119.9	C18—C17—H17	119.9
C1—C6—C5	119.7 (2)	C13—C18—C17	120.4 (2)
C1—C6—H6	120.2	C13—C18—H18	119.8
C5—C6—H6	120.2	C17—C18—H18	119.8
C12—C7—C8	118.1 (2)	Cl2—C19—Cl1	108.1 (3)
C12—C7—P1	122.38 (17)	Cl2—C19—Cl3	108.1 (3)
C8—C7—P1	119.50 (17)	Cl1—C19—Cl3	107.2 (3)
C9—C8—C7	120.6 (2)	Cl2—C19—H19	111.1
C9—C8—H8	119.7	Cl1—C19—H19	111.1
C7—C8—H8	119.7	Cl3—C19—H19	111.1
Br1—Pd1—P1—C1	134.30 (8)	C13—P1—C7—C8	50.5 (2)
Br1i—Pd1—P1—C1	−47.44 (8)	Pd1—P1—C7—C8	−73.26 (19)
Br1—Pd1—P1—C13	−104.60 (7)	C12—C7—C8—C9	0.6 (4)
Br1i—Pd1—P1—C13	73.65 (7)	P1—C7—C8—C9	−179.9 (2)
Br1—Pd1—P1—C7	14.74 (8)	C7—C8—C9—C10	−0.4 (4)
Br1i—Pd1—P1—C7	−167.00 (8)	C8—C9—C10—C11	0.4 (4)
C13—P1—C1—C6	11.4 (2)	C9—C10—C11—C12	−0.6 (4)
C7—P1—C1—C6	−97.0 (2)	C8—C7—C12—C11	−0.9 (3)
Pd1—P1—C1—C6	134.19 (17)	P1—C7—C12—C11	179.67 (18)
C13—P1—C1—C2	−169.57 (17)	C10—C11—C12—C7	0.9 (4)
C7—P1—C1—C2	82.00 (18)	C1—P1—C13—C18	112.87 (18)
Pd1—P1—C1—C2	−46.79 (18)	C7—P1—C13—C18	−138.41 (18)
C6—C1—C2—C3	0.9 (3)	Pd1—P1—C13—C18	−9.6 (2)
P1—C1—C2—C3	−178.16 (19)	C1—P1—C13—C14	−67.5 (2)
C1—C2—C3—C4	−1.6 (4)	C7—P1—C13—C14	41.2 (2)
C2—C3—C4—C5	1.1 (4)	Pd1—P1—C13—C14	169.98 (16)
C3—C4—C5—C6	0.0 (4)	C18—C13—C14—C15	−2.0 (3)
C2—C1—C6—C5	0.2 (3)	P1—C13—C14—C15	178.35 (19)
P1—C1—C6—C5	179.22 (18)	C13—C14—C15—C16	0.2 (4)
C4—C5—C6—C1	−0.7 (4)	C14—C15—C16—C17	1.8 (4)
C1—P1—C7—C12	−17.3 (2)	C15—C16—C17—C18	−2.1 (4)
C13—P1—C7—C12	−130.09 (19)	C14—C13—C18—C17	1.8 (3)
Pd1—P1—C7—C12	106.19 (18)	P1—C13—C18—C17	−178.57 (17)
C1—P1—C7—C8	163.24 (19)	C16—C17—C18—C13	0.2 (4)

Symmetry codes: (i) −x+1, y, −z+1/2.