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

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536809027408

metal-organic compounds

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Volume 65| Part 8| August 2009| Page m940

doi:10.1107/S1600536809027408

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

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 1 July 2009; accepted 12 July 2009; online 18 July 2009)

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, C 2/c
a = 12.2314 (2) Å
b = 14.4754 (2) Å
c = 20.1653 (3) Å
β = 92.477 (1)°
V = 3567.02 (9) Å³
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[F² > 2σ(F²)] = 0.023
wR(F²) = 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

Table 1
Selected bond lengths (Å)

Pd1—P1	2.3360 (5)
Pd1—Br1	2.4277 (2)

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809027408/hy2209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027408/hy2209Isup2.hkl

checkCIF report

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 70% probability level.

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

Crystal data top

[PdBr₂(C₁₈H₁₅P)₂]·CHCl₃	F(000) = 1800
M_r = 910.13	D_x = 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 top

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

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0263P)² + 6.7144P] where P = (F_o² + 2F_c²)/3
4110 reflections	(Δ/σ)_max = 0.001
222 parameters	Δρ_max = 0.47 e Å⁻³
24 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[PdBr₂(C₁₈H₁₅P)₂]·CHCl₃	V = 3567.02 (9) Å³
M_r = 910.13	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.2314 (2) Å	µ = 3.10 mm⁻¹
b = 14.4754 (2) Å	T = 153 K
c = 20.1653 (3) Å	0.30 × 0.25 × 0.20 mm
β = 92.477 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	4110 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3266 reflections with I > 2σ(I)
T_min = 0.456, T_max = 0.576	R_int = 0.018
16862 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	24 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.02	Δρ_max = 0.47 e Å⁻³
4110 reflections	Δρ_min = −0.36 e Å⁻³
222 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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, º) top

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 code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[PdBr₂(C₁₈H₁₅P)₂]·CHCl₃
M_r	910.13
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	153
a, b, c (Å)	12.2314 (2), 14.4754 (2), 20.1653 (3)
β (°)	92.477 (1)
V (Å³)	3567.02 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.10
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.456, 0.576
No. of measured, independent and observed [I > 2σ(I)] reflections	16862, 4110, 3266
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.02
No. of reflections	4110
No. of parameters	222
No. of restraints	24
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.36

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Selected bond lengths (Å) top

Pd1—P1

2.3360 (5)

Pd1—Br1

2.4277 (2)

Acknowledgements

We thank the University of Malaya (RG020/09AFR) for supporting this study.

References

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