trans-Dibromidobis[tris­(4-chloro­phen­yl)phosphine]palladium(II)

Kirsten, L.; Steyl, G.

doi:10.1107/S1600536809045413

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1565

doi:10.1107/S1600536809045413

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trans-Dibromidobis[tris(4-chlorophenyl)phosphine]palladium(II)

Leo Kirsten ^a ^* and Gideon Steyl ^a

^aDepartment of Chemistry, University of the Free State, Bloemfontein 9300, South Africa
^*Correspondence e-mail: leokirsten@gmail.com

(Received 21 October 2009; accepted 29 October 2009; online 14 November 2009)

In the title compound, [PdBr₂(C₁₈H₁₂Cl₃P)₂], the Pd^II ion is situated on a centre of symmetry and is coordinated by two Br anions [Pd—Br = 2.4252 (2) Å] and two P-donor ligands [Pd—P = 2.3317 (6) Å] in a slightly distorted square-planar geometry [P—Pd—Br = 86.589 (15)°].

Related literature

The title compound is isostructural with the corresponding dichlorido complex, trans-[PdCl₂{P(p-ClPh)₃}₂], see: Kolosova et al. (1986 ).

Experimental

Crystal data

[PdBr₂(C₁₈H₁₂Cl₃P)₂]
M_r = 997.41
Monoclinic, P 2₁ /n
a = 10.3453 (3) Å
b = 17.4489 (6) Å
c = 10.6180 (4) Å
β = 103.385 (2)°
V = 1864.63 (11) Å³
Z = 2
Mo Kα radiation
μ = 3.18 mm⁻¹
T = 100 K
0.33 × 0.30 × 0.25 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.378, T_max = 0.453
20106 measured reflections
4487 independent reflections
3916 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.060
S = 1.04
4487 reflections
214 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2004 ); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809045413/cv2637sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045413/cv2637Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is one of a few literature structures containing a Pd centre coordinated by to Br atoms and two P donor ligands in a trans configuration. Our research is aimed at expanding the number of known structures of the aforementioned type and to finally generalize on the crystallization mode, if any, of these complexes.

The molecule of (I) (Fig. 1), is centrosymmetric with pairs of equivalent P donor ligands trans to one another in a slightly distorted square-planar geometry [P—Pd—Br 86.589 (15)°].

The corresponding chloro complex (Kolosova et al., 1986) is iso-structural to (I) when comparing the geometrical parameters. The RMS error of 0.097 Å also indicate the iso-structurality of the two complexes (the title complex superimposed with the corresponding dichloro-palladium complex (Kolosova et al., 1986) including all the atoms except the hydrogen atoms).

Related literature top

The title compound is isostructural with the corresponding dichloro complex, trans-[PdCl₂{P(p-ClPh)₃}₂], see: Kolosova et al. (1986).

Experimental top

The title complex was synthesized by the addition of 2.2 equivalents of tris(4-Cl-phenyl)-phosphine (21 mg, 0.059 mmol) to [Pd(COD)Br₂] (10 mg, 0.026 mmol) in 10 ml of dichloromethane while stirring for 5 minutes. Slow evaporation of the solvent resulted in orange crystals suitable for X-Ray diffraction (yield 74%, 19 mg).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Representation of the title compound, showing the numbering scheme and displacement ellipsoids (50% probability). For the carbon rings, the first digit refers to ring number, second digit to atom in the ring. Hydrogen atoms omitted for clarity [symmetry code: (i) 1 - x,1 - y,1 - z].

trans-Dibromidobis[tris(4-chlorophenyl)phosphine]palladium(II) top

Crystal data top

[PdBr₂(C₁₈H₁₂Cl₃P)₂]	F(000) = 976
M_r = 997.41	D_x = 1.776 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7624 reflections
a = 10.3453 (3) Å	θ = 2.3–28.4°
b = 17.4489 (6) Å	µ = 3.18 mm⁻¹
c = 10.6180 (4) Å	T = 100 K
β = 103.385 (2)°	Cuboid, orange
V = 1864.63 (11) Å³	0.33 × 0.30 × 0.25 mm
Z = 2

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	4487 independent reflections
Radiation source: fine-focus sealed tube	3916 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 512 pixels mm^-1	θ_max = 28.0°, θ_min = 2.3°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −20→23
T_min = 0.378, T_max = 0.453	l = −10→14
20106 measured reflections

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)] = 0.026	Hydrogen site location: riding model
wR(F²) = 0.060	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0187P)² + 1.3608P] where P = (F_o² + 2F_c²)/3
4487 reflections	(Δ/σ)_max = 0.002
214 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

[PdBr₂(C₁₈H₁₂Cl₃P)₂]	V = 1864.63 (11) Å³
M_r = 997.41	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.3453 (3) Å	µ = 3.18 mm⁻¹
b = 17.4489 (6) Å	T = 100 K
c = 10.6180 (4) Å	0.33 × 0.30 × 0.25 mm
β = 103.385 (2)°

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	4487 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	3916 reflections with I > 2σ(I)
T_min = 0.378, T_max = 0.453	R_int = 0.046
20106 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.04	Δρ_max = 0.67 e Å⁻³
4487 reflections	Δρ_min = −0.74 e Å⁻³
214 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Pd	0.5000	0.5000	0.5000	0.01113 (6)
Br	0.66195 (2)	0.551557 (14)	0.68290 (2)	0.01764 (7)
P	0.54624 (5)	0.60598 (3)	0.38405 (5)	0.01106 (12)
C11	0.7244 (2)	0.61782 (12)	0.4023 (2)	0.0121 (4)
C12	0.7977 (2)	0.55569 (14)	0.3742 (2)	0.0181 (5)
H12	0.7539	0.5087	0.3466	0.022*
C13	0.9335 (2)	0.56171 (14)	0.3862 (2)	0.0202 (5)
H13	0.9827	0.5200	0.3637	0.024*
C14	0.9961 (2)	0.62964 (14)	0.4314 (2)	0.0167 (5)
C15	0.9267 (2)	0.69103 (14)	0.4626 (2)	0.0180 (5)
H15	0.9716	0.7371	0.4943	0.022*
C16	0.7899 (2)	0.68506 (13)	0.4474 (2)	0.0166 (5)
H16	0.7410	0.7274	0.4682	0.020*
Cl1	1.16679 (6)	0.63849 (4)	0.44886 (6)	0.02709 (15)
C21	0.4895 (2)	0.69919 (13)	0.4282 (2)	0.0127 (4)
C22	0.4671 (2)	0.71256 (14)	0.5508 (2)	0.0165 (5)
H22	0.4778	0.6720	0.6121	0.020*
C23	0.4291 (2)	0.78460 (14)	0.5841 (2)	0.0193 (5)
H23	0.4141	0.7936	0.6678	0.023*
C24	0.4134 (2)	0.84297 (13)	0.4944 (2)	0.0158 (5)
C25	0.4340 (2)	0.83135 (14)	0.3719 (2)	0.0169 (5)
H25	0.4222	0.8721	0.3109	0.020*
C26	0.4722 (2)	0.75940 (13)	0.3396 (2)	0.0160 (5)
H26	0.4869	0.7509	0.2557	0.019*
Cl2	0.36890 (6)	0.93429 (3)	0.53545 (6)	0.02335 (14)
C31	0.4774 (2)	0.60521 (12)	0.2097 (2)	0.0123 (4)
C32	0.3402 (2)	0.61279 (13)	0.1658 (2)	0.0151 (5)
H32	0.2860	0.6153	0.2267	0.018*
C33	0.2820 (2)	0.61675 (13)	0.0353 (2)	0.0154 (5)
H33	0.1885	0.6221	0.0059	0.018*
C34	0.3626 (2)	0.61276 (12)	−0.0525 (2)	0.0150 (5)
C35	0.4977 (2)	0.60225 (13)	−0.0127 (2)	0.0170 (5)
H35	0.5508	0.5975	−0.0743	0.020*
C36	0.5555 (2)	0.59876 (13)	0.1195 (2)	0.0151 (5)
H36	0.6488	0.5919	0.1483	0.018*
Cl3	0.28975 (6)	0.62480 (3)	−0.21644 (5)	0.02222 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd	0.01157 (11)	0.01282 (13)	0.00824 (12)	−0.00270 (9)	0.00075 (8)	0.00108 (9)
Br	0.01929 (12)	0.01956 (13)	0.01117 (12)	−0.00653 (9)	−0.00241 (9)	0.00144 (9)
P	0.0110 (3)	0.0124 (3)	0.0096 (3)	−0.0017 (2)	0.0020 (2)	0.0013 (2)
C11	0.0124 (10)	0.0127 (11)	0.0109 (10)	−0.0004 (8)	0.0019 (8)	0.0035 (8)
C12	0.0186 (11)	0.0145 (12)	0.0192 (12)	0.0000 (9)	0.0002 (9)	−0.0033 (9)
C13	0.0218 (12)	0.0213 (13)	0.0168 (12)	0.0098 (10)	0.0033 (10)	−0.0025 (10)
C14	0.0118 (10)	0.0272 (13)	0.0112 (11)	0.0012 (10)	0.0027 (8)	0.0019 (9)
C15	0.0157 (11)	0.0157 (12)	0.0229 (13)	−0.0039 (9)	0.0051 (9)	−0.0008 (9)
C16	0.0153 (11)	0.0121 (11)	0.0237 (13)	0.0013 (9)	0.0069 (9)	0.0000 (9)
Cl1	0.0114 (3)	0.0469 (4)	0.0236 (3)	0.0021 (3)	0.0054 (2)	0.0013 (3)
C21	0.0094 (10)	0.0157 (12)	0.0126 (11)	−0.0022 (8)	0.0020 (8)	−0.0005 (9)
C22	0.0165 (11)	0.0195 (12)	0.0149 (11)	−0.0026 (9)	0.0062 (9)	0.0029 (9)
C23	0.0200 (12)	0.0221 (13)	0.0184 (12)	−0.0005 (10)	0.0099 (10)	−0.0033 (10)
C24	0.0105 (10)	0.0146 (12)	0.0235 (12)	−0.0017 (9)	0.0065 (9)	−0.0043 (9)
C25	0.0155 (11)	0.0181 (12)	0.0168 (11)	0.0004 (9)	0.0030 (9)	0.0033 (9)
C26	0.0176 (11)	0.0189 (12)	0.0124 (11)	0.0009 (9)	0.0054 (9)	0.0009 (9)
Cl2	0.0251 (3)	0.0184 (3)	0.0303 (3)	0.0016 (2)	0.0141 (3)	−0.0046 (2)
C31	0.0165 (11)	0.0090 (11)	0.0110 (10)	−0.0012 (8)	0.0022 (8)	0.0011 (8)
C32	0.0166 (11)	0.0169 (12)	0.0125 (11)	−0.0008 (9)	0.0050 (9)	0.0017 (9)
C33	0.0152 (11)	0.0128 (12)	0.0164 (11)	−0.0010 (9)	0.0002 (9)	0.0021 (9)
C34	0.0247 (12)	0.0098 (11)	0.0082 (10)	−0.0006 (9)	−0.0006 (9)	−0.0015 (8)
C35	0.0237 (12)	0.0161 (12)	0.0131 (11)	0.0016 (9)	0.0079 (9)	−0.0009 (9)
C36	0.0156 (11)	0.0151 (12)	0.0158 (11)	0.0016 (9)	0.0058 (9)	0.0005 (9)
Cl3	0.0325 (3)	0.0227 (3)	0.0093 (3)	0.0015 (3)	0.0003 (2)	−0.0014 (2)

Geometric parameters (Å, º) top

Pd—Pⁱ	2.3317 (6)	C22—C23	1.387 (3)
Pd—P	2.3317 (6)	C22—H22	0.9500
Pd—Br	2.4252 (2)	C23—C24	1.378 (3)
Pd—Brⁱ	2.4252 (2)	C23—H23	0.9500
P—C11	1.820 (2)	C24—C25	1.381 (3)
P—C31	1.823 (2)	C24—Cl2	1.742 (2)
P—C21	1.827 (2)	C25—C26	1.383 (3)
C11—C16	1.384 (3)	C25—H25	0.9500
C11—C12	1.394 (3)	C26—H26	0.9500
C12—C13	1.386 (3)	C31—C36	1.393 (3)
C12—H12	0.9500	C31—C32	1.394 (3)
C13—C14	1.382 (3)	C32—C33	1.379 (3)
C13—H13	0.9500	C32—H32	0.9500
C14—C15	1.372 (3)	C33—C34	1.389 (3)
C14—Cl1	1.739 (2)	C33—H33	0.9500
C15—C16	1.391 (3)	C34—C35	1.376 (3)
C15—H15	0.9500	C34—Cl3	1.742 (2)
C16—H16	0.9500	C35—C36	1.394 (3)
C21—C26	1.394 (3)	C35—H35	0.9500
C21—C22	1.395 (3)	C36—H36	0.9500

Pⁱ—Pd—P	180.000 (17)	C23—C22—C21	120.5 (2)
Pⁱ—Pd—Br	93.411 (15)	C23—C22—H22	119.7
P—Pd—Br	86.589 (15)	C21—C22—H22	119.7
Pⁱ—Pd—Brⁱ	86.589 (15)	C24—C23—C22	119.3 (2)
P—Pd—Brⁱ	93.411 (15)	C24—C23—H23	120.4
Br—Pd—Brⁱ	180.000 (10)	C22—C23—H23	120.4
C11—P—C31	104.88 (10)	C23—C24—C25	121.6 (2)
C11—P—C21	104.43 (10)	C23—C24—Cl2	119.94 (17)
C31—P—C21	101.18 (10)	C25—C24—Cl2	118.50 (18)
C11—P—Pd	111.12 (7)	C24—C25—C26	118.8 (2)
C31—P—Pd	116.79 (7)	C24—C25—H25	120.6
C21—P—Pd	116.95 (7)	C26—C25—H25	120.6
C16—C11—C12	119.1 (2)	C25—C26—C21	121.1 (2)
C16—C11—P	122.37 (17)	C25—C26—H26	119.5
C12—C11—P	118.44 (17)	C21—C26—H26	119.5
C13—C12—C11	120.8 (2)	C36—C31—C32	119.1 (2)
C13—C12—H12	119.6	C36—C31—P	123.10 (17)
C11—C12—H12	119.6	C32—C31—P	117.81 (16)
C14—C13—C12	118.7 (2)	C33—C32—C31	121.0 (2)
C14—C13—H13	120.6	C33—C32—H32	119.5
C12—C13—H13	120.6	C31—C32—H32	119.5
C15—C14—C13	121.6 (2)	C32—C33—C34	118.8 (2)
C15—C14—Cl1	118.69 (18)	C32—C33—H33	120.6
C13—C14—Cl1	119.69 (18)	C34—C33—H33	120.6
C14—C15—C16	119.3 (2)	C35—C34—C33	121.7 (2)
C14—C15—H15	120.4	C35—C34—Cl3	119.80 (17)
C16—C15—H15	120.4	C33—C34—Cl3	118.46 (18)
C11—C16—C15	120.5 (2)	C34—C35—C36	118.9 (2)
C11—C16—H16	119.8	C34—C35—H35	120.5
C15—C16—H16	119.8	C36—C35—H35	120.5
C26—C21—C22	118.8 (2)	C31—C36—C35	120.4 (2)
C26—C21—P	119.79 (16)	C31—C36—H36	119.8
C22—C21—P	121.43 (17)	C35—C36—H36	119.8

Br—Pd—P—C11	49.81 (8)	Pd—P—C21—C22	23.8 (2)
Brⁱ—Pd—P—C11	−130.19 (8)	C26—C21—C22—C23	−0.4 (3)
Br—Pd—P—C31	170.03 (8)	P—C21—C22—C23	177.41 (17)
Brⁱ—Pd—P—C31	−9.97 (8)	C21—C22—C23—C24	0.2 (3)
Br—Pd—P—C21	−69.94 (8)	C22—C23—C24—C25	0.3 (3)
Brⁱ—Pd—P—C21	110.06 (8)	C22—C23—C24—Cl2	−178.76 (17)
C31—P—C11—C16	109.0 (2)	C23—C24—C25—C26	−0.4 (3)
C21—P—C11—C16	3.0 (2)	Cl2—C24—C25—C26	178.59 (17)
Pd—P—C11—C16	−123.98 (18)	C24—C25—C26—C21	0.2 (3)
C31—P—C11—C12	−73.49 (19)	C22—C21—C26—C25	0.2 (3)
C21—P—C11—C12	−179.49 (17)	P—C21—C26—C25	−177.63 (17)
Pd—P—C11—C12	53.56 (19)	C11—P—C31—C36	11.9 (2)
C16—C11—C12—C13	−2.6 (3)	C21—P—C31—C36	120.28 (19)
P—C11—C12—C13	179.82 (18)	Pd—P—C31—C36	−111.59 (18)
C11—C12—C13—C14	2.5 (4)	C11—P—C31—C32	−166.98 (17)
C12—C13—C14—C15	−0.9 (4)	C21—P—C31—C32	−58.60 (19)
C12—C13—C14—Cl1	179.37 (18)	Pd—P—C31—C32	69.53 (18)
C13—C14—C15—C16	−0.6 (4)	C36—C31—C32—C33	−2.4 (3)
Cl1—C14—C15—C16	179.15 (18)	P—C31—C32—C33	176.56 (18)
C12—C11—C16—C15	1.0 (3)	C31—C32—C33—C34	0.2 (3)
P—C11—C16—C15	178.56 (17)	C32—C33—C34—C35	2.4 (3)
C14—C15—C16—C11	0.5 (3)	C32—C33—C34—Cl3	−175.38 (17)
C11—P—C21—C26	78.41 (19)	C33—C34—C35—C36	−2.7 (3)
C31—P—C21—C26	−30.3 (2)	Cl3—C34—C35—C36	175.00 (18)
Pd—P—C21—C26	−158.34 (15)	C32—C31—C36—C35	2.0 (3)
C11—P—C21—C22	−99.40 (19)	P—C31—C36—C35	−176.87 (17)
C31—P—C21—C22	151.87 (18)	C34—C35—C36—C31	0.5 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[PdBr₂(C₁₈H₁₂Cl₃P)₂]
M_r	997.41
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.3453 (3), 17.4489 (6), 10.6180 (4)
β (°)	103.385 (2)
V (Å³)	1864.63 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.18
Crystal size (mm)	0.33 × 0.30 × 0.25

Data collection
Diffractometer	Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.378, 0.453
No. of measured, independent and observed [I > 2σ(I)] reflections	20106, 4487, 3916
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.060, 1.04
No. of reflections	4487
No. of parameters	214
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.74

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006).

Acknowledgements

Financial assistance from the University of the Free State and Professor A. Roodt is gratefully acknowledged. Part of this material is based on work supported by the South African National Research Foundation (NRF) under grant No. GUN 2068915.

References

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