Di-μ-chlorido-bis­[chlorido(dimethoxy­phenyl­phosphine)palladium(II)]

Slawin, A.M.Z.; Waddell, P.G.; Woollins, J.D.

doi:10.1107/S1600536810012055

metal-organic compounds

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Volume 66| Part 5| May 2010| Page m499

https://doi.org/10.1107/S1600536810012055

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Di-μ-chlorido-bis[chlorido(dimethoxyphenylphosphine)palladium(II)]

Alexandra M. Z. Slawin,^a ^* Paul G. Waddell ^a and J. Derek Woollins ^a

^aDepartment of Chemistry, University of St Andrews, St Andrews KY16 9ST, Scotland
^*Correspondence e-mail: amzs@st-and.ac.uk

(Received 19 March 2010; accepted 30 March 2010; online 10 April 2010)

The title compound, [Pd₂Cl₄(C₈H₁₁O₂P)₂], is binuclear and disposed about a crystallographic centre of symmetry with a Pd⋯Pd distance of 3.4662 (17) Å. It has a similar geometry to that observed in the triphenylphosphite and triphenylphosphine analogues. The Pd—P bond length is ca 0.04 Å shorter than those in mononuclear PdCl₂(P(OMe)₂Ph)₂, possibly due to the lower trans-influence of the bridging Cl⁻ compared to a single-bonded Cl⁻ atom.

Related literature

For binuclear analogues, see: Grigsby & Nicholson (1992 ); Sui-Seng et al. (2003 ). For the related mononuclear palladium compound, see: Slawin et al. (2010 ).

Experimental

Crystal data

[Pd₂Cl₄(C₈H₁₁O₂P)₂]
M_r = 694.91
Triclinic, $[P \overline 1]$
a = 7.078 (3) Å
b = 8.938 (3) Å
c = 9.838 (5) Å
α = 87.54 (3)°
β = 89.55 (3)°
γ = 69.46 (2)°
V = 582.3 (4) Å³
Z = 1
Mo Kα radiation
μ = 2.16 mm⁻¹
T = 125 K
0.21 × 0.12 × 0.09 mm

Data collection

Rigaku Mercury70 CCD diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.591, T_max = 0.823
6130 measured reflections
2087 independent reflections
1993 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.075
S = 1.10
2087 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Pd1—P1	2.1940 (14)
Pd1—Cl2	2.2820 (15)
Pd1—Cl1ⁱ	2.3163 (15)
Pd1—Cl1	2.4170 (14)

P1—Pd1—Cl2	86.39 (5)
P1—Pd1—Cl1ⁱ	95.34 (5)
Cl2—Pd1—Cl1ⁱ	176.98 (4)
P1—Pd1—Cl1	178.39 (4)
Cl2—Pd1—Cl1	92.45 (5)
Cl1ⁱ—Pd1—Cl1	85.86 (5)
Pd1ⁱ—Cl1—Pd1	94.14 (5)
Symmetry code: (i) -x, -y+1, -z.

Data collection: SCXMini (Rigaku, 2006 ); cell refinement: SCXMini; data reduction: SCXMini; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2009 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810012055/br2142sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012055/br2142Isup2.hkl

checkCIF report

Comment top

In the structure of the title compound the palladium atoms are in distorted square planar environments. The Pd-Cl bondlengths vary with the shortest being the terminal Pd-Cl, the longest being the bridging Pd-Cl trans to P and the intermediate length being for bridging Pd-Cl trans to Cl. This pattern is also observed in the known analogues: the triphenylphosphine analogue (Sei-Sung et al., 2003) has Pd-P 2.2278 (6) Å, Pd-Cl(terminal) 2.2722 (7) Å, Pd-Cl (bridging trans to P) 2.4128 (6) Å and Pd-Cl (bridging trans to Cl) 2.3228 (6) Å whilst in the P(OPh)₃ analogue (Grigsby & Nicholson, 1992) the values are Pd-P 2.2187 (3), Pd-Cl(terminal) 2.269 (3) Pd-Cl (bridging trans to P) 2.413 (2) Pd-Cl (bridging trans to Cl) 2.309 (2) Å. The Pd-P distance in the title compound (2.1940 (14) Å) is shorter than either of the above previously published structures.

Related literature top

For binuclear analogues, see: Grigsby & Nicholson (1992); Sui-Seng et al. (2003). For the related monuclear palladium compound, see: Slawin et al. (2010).

Experimental top

1 g (2.6 mmol) of bis(benzonitrile)palladium(II) dichloride was dissolved in 25 ml of dichloromethane to which 0.84 ml (5.3 mmol) of dimethyl phenylphosphonite was added. The solution was stirred at room temperature for 30 mins before being filtered and then precipitated by slow addition of hexane to give a pale yellow solid. Crystals were grown for X-ray crystallographyv ia slow diffusion of hexane into a solution of the product in dichloromethane.Yield: 0.321 g (0.46 mmol), 19 %.

Structure description top

For binuclear analogues, see: Grigsby & Nicholson (1992); Sui-Seng et al. (2003). For the related monuclear palladium compound, see: Slawin et al. (2010).

Computing details top

Data collection: SCXMini (Rigaku, 2006); cell refinement: SCXMini (Rigaku, 2006); data reduction: SCXMini (Rigaku, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2009); software used to prepare material for publication: CrystalStructure (Rigaku, 2009).

Figures top

Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level, hydrogen atoms omitted for clarity.

Di-µ-chlorido-bis[chlorido(dimethoxyphenylphosphine)palladium(II)] top

Crystal data top

[Pd₂Cl₄(C₈H₁₁O₂P)₂]	Z = 1
M_r = 694.91	F(000) = 340.00
Triclinic, P1	D_x = 1.982 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 7.078 (3) Å	Cell parameters from 2478 reflections
b = 8.938 (3) Å	θ = 2.1–26.4°
c = 9.838 (5) Å	µ = 2.16 mm⁻¹
α = 87.54 (3)°	T = 125 K
β = 89.55 (3)°	Prism, orange
γ = 69.46 (2)°	0.21 × 0.12 × 0.09 mm
V = 582.3 (4) Å³

Data collection top

Rigaku Mercury70 CCD diffractometer	1993 reflections with F² > 2σ(F²)
ω scans	R_int = 0.042
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	θ_max = 25.4°
T_min = 0.591, T_max = 0.823	h = −8→8
6130 measured reflections	k = −10→9
2087 independent reflections	l = −11→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0152P)² + 1.7632P] where P = (F_o² + 2F_c²)/3
2087 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

[Pd₂Cl₄(C₈H₁₁O₂P)₂]	γ = 69.46 (2)°
M_r = 694.91	V = 582.3 (4) Å³
Triclinic, P1	Z = 1
a = 7.078 (3) Å	Mo Kα radiation
b = 8.938 (3) Å	µ = 2.16 mm⁻¹
c = 9.838 (5) Å	T = 125 K
α = 87.54 (3)°	0.21 × 0.12 × 0.09 mm
β = 89.55 (3)°

Data collection top

Rigaku Mercury70 CCD diffractometer	2087 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1993 reflections with F² > 2σ(F²)
T_min = 0.591, T_max = 0.823	R_int = 0.042
6130 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.10	Δρ_max = 0.58 e Å⁻³
2087 reflections	Δρ_min = −0.67 e Å⁻³
127 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Pd1	0.09659 (5)	0.37691 (4)	0.14271 (3)	0.01955 (12)
Cl1	0.13513 (17)	0.60837 (13)	0.02692 (11)	0.0258 (3)
Cl2	0.33715 (18)	0.36169 (14)	0.30113 (11)	0.0293 (3)
P1	0.06174 (17)	0.16984 (13)	0.25330 (11)	0.0196 (2)
O1	−0.1234 (5)	0.1371 (3)	0.1902 (3)	0.0247 (7)
O2	0.0252 (5)	0.1858 (3)	0.4113 (3)	0.0251 (7)
C1	0.2737 (7)	−0.0122 (5)	0.2477 (4)	0.0213 (9)
C2	0.3205 (7)	−0.0794 (6)	0.1210 (5)	0.0278 (10)
H2	0.2425	−0.0274	0.0432	0.033*
C3	0.4803 (7)	−0.2215 (6)	0.1083 (5)	0.0337 (12)
H3	0.5114	−0.2680	0.0221	0.040*
C4	0.5941 (8)	−0.2954 (6)	0.2212 (5)	0.0340 (12)
H4	0.7038	−0.3932	0.2126	0.041*
C5	0.5504 (8)	−0.2288 (6)	0.3467 (5)	0.0352 (12)
H5	0.6306	−0.2802	0.4238	0.042*
C6	0.3898 (7)	−0.0872 (5)	0.3604 (5)	0.0275 (10)
H6	0.3592	−0.0415	0.4469	0.033*
C7	−0.1241 (8)	0.3299 (5)	0.4628 (5)	0.0323 (11)
H7A	−0.0918	0.4235	0.4313	0.039*
H7B	−0.1226	0.3227	0.5625	0.039*
H7C	−0.2584	0.3403	0.4293	0.039*
C8	−0.1806 (8)	0.0038 (6)	0.2437 (5)	0.0294 (11)
H8A	−0.1043	−0.0933	0.1967	0.035*
H8B	−0.3253	0.0287	0.2288	0.035*
H8C	−0.1504	−0.0132	0.3413	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0218 (2)	0.01731 (19)	0.01916 (19)	−0.00664 (14)	0.00007 (14)	0.00122 (13)
Cl1	0.0318 (6)	0.0231 (6)	0.0250 (6)	−0.0135 (5)	−0.0074 (5)	0.0059 (4)
Cl2	0.0299 (6)	0.0328 (6)	0.0272 (6)	−0.0140 (5)	−0.0073 (5)	0.0044 (5)
P1	0.0213 (6)	0.0180 (6)	0.0182 (5)	−0.0055 (5)	0.0010 (4)	0.0018 (4)
O1	0.0244 (17)	0.0238 (17)	0.0275 (17)	−0.0109 (13)	−0.0029 (13)	0.0053 (13)
O2	0.0333 (19)	0.0188 (16)	0.0196 (15)	−0.0050 (14)	0.0041 (13)	0.0022 (12)
C1	0.024 (2)	0.019 (2)	0.022 (2)	−0.0081 (18)	0.0047 (18)	0.0003 (17)
C2	0.025 (3)	0.032 (3)	0.023 (2)	−0.006 (2)	0.0001 (19)	−0.0027 (19)
C3	0.026 (3)	0.034 (3)	0.040 (3)	−0.009 (2)	0.005 (2)	−0.011 (2)
C4	0.027 (3)	0.023 (3)	0.047 (3)	−0.003 (2)	0.012 (2)	−0.001 (2)
C5	0.032 (3)	0.034 (3)	0.032 (3)	−0.002 (2)	0.000 (2)	0.014 (2)
C6	0.028 (3)	0.029 (3)	0.023 (2)	−0.007 (2)	0.005 (2)	0.0020 (19)
C7	0.034 (3)	0.026 (3)	0.033 (3)	−0.005 (2)	0.010 (2)	−0.007 (2)
C8	0.033 (3)	0.030 (3)	0.032 (3)	−0.021 (2)	0.004 (2)	0.000 (2)

Geometric parameters (Å, º) top

Pd1—P1	2.1940 (14)	C3—C4	1.379 (7)
Pd1—Cl2	2.2820 (15)	C3—H3	0.9500
Pd1—Cl1ⁱ	2.3163 (15)	C4—C5	1.379 (7)
Pd1—Cl1	2.4170 (14)	C4—H4	0.9500
Cl1—Pd1ⁱ	2.3163 (14)	C5—C6	1.384 (7)
P1—O1	1.577 (3)	C5—H5	0.9500
P1—O2	1.578 (3)	C6—H6	0.9500
P1—C1	1.788 (4)	C7—H7A	0.9800
O1—C8	1.463 (5)	C7—H7B	0.9800
O2—C7	1.458 (5)	C7—H7C	0.9800
C1—C6	1.384 (6)	C8—H8A	0.9800
C1—C2	1.394 (6)	C8—H8B	0.9800
C2—C3	1.383 (7)	C8—H8C	0.9800
C2—H2	0.9500

P1—Pd1—Cl2	86.39 (5)	C2—C3—H3	120.2
P1—Pd1—Cl1ⁱ	95.34 (5)	C5—C4—C3	120.6 (4)
Cl2—Pd1—Cl1ⁱ	176.98 (4)	C5—C4—H4	119.7
P1—Pd1—Cl1	178.39 (4)	C3—C4—H4	119.7
Cl2—Pd1—Cl1	92.45 (5)	C4—C5—C6	120.1 (5)
Cl1ⁱ—Pd1—Cl1	85.86 (5)	C4—C5—H5	120.0
Pd1ⁱ—Cl1—Pd1	94.14 (5)	C6—C5—H5	120.0
O1—P1—O2	107.39 (18)	C1—C6—C5	119.9 (4)
O1—P1—C1	107.02 (19)	C1—C6—H6	120.1
O2—P1—C1	101.72 (18)	C5—C6—H6	120.1
O1—P1—Pd1	108.39 (12)	O2—C7—H7A	109.5
O2—P1—Pd1	116.15 (12)	O2—C7—H7B	109.5
C1—P1—Pd1	115.53 (15)	H7A—C7—H7B	109.5
C8—O1—P1	120.3 (3)	O2—C7—H7C	109.5
C7—O2—P1	120.0 (3)	H7A—C7—H7C	109.5
C6—C1—C2	119.7 (4)	H7B—C7—H7C	109.5
C6—C1—P1	123.8 (3)	O1—C8—H8A	109.5
C2—C1—P1	116.5 (3)	O1—C8—H8B	109.5
C3—C2—C1	120.1 (4)	H8A—C8—H8B	109.5
C3—C2—H2	120.0	O1—C8—H8C	109.5
C1—C2—H2	120.0	H8A—C8—H8C	109.5
C4—C3—C2	119.7 (5)	H8B—C8—H8C	109.5
C4—C3—H3	120.2

Cl2—Pd1—Cl1—Pd1ⁱ	177.49 (4)	O1—P1—C1—C6	−125.2 (4)
Cl1ⁱ—Pd1—Cl1—Pd1ⁱ	0.0	O2—P1—C1—C6	−12.7 (4)
Cl2—Pd1—P1—O1	173.14 (13)	Pd1—P1—C1—C6	114.0 (4)
Cl1ⁱ—Pd1—P1—O1	−9.34 (14)	O1—P1—C1—C2	54.7 (4)
Cl2—Pd1—P1—O2	52.20 (15)	O2—P1—C1—C2	167.2 (3)
Cl1ⁱ—Pd1—P1—O2	−130.28 (15)	Pd1—P1—C1—C2	−66.1 (4)
Cl2—Pd1—P1—C1	−66.83 (17)	C6—C1—C2—C3	1.0 (7)
Cl1ⁱ—Pd1—P1—C1	110.69 (17)	P1—C1—C2—C3	−178.9 (4)
O2—P1—O1—C8	−54.4 (3)	C1—C2—C3—C4	−0.7 (7)
C1—P1—O1—C8	54.1 (4)	C2—C3—C4—C5	−0.1 (8)
Pd1—P1—O1—C8	179.4 (3)	C3—C4—C5—C6	0.6 (8)
O1—P1—O2—C7	−74.4 (4)	C2—C1—C6—C5	−0.5 (7)
C1—P1—O2—C7	173.4 (3)	P1—C1—C6—C5	179.5 (4)
Pd1—P1—O2—C7	47.1 (4)	C4—C5—C6—C1	−0.3 (8)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Pd₂Cl₄(C₈H₁₁O₂P)₂]
M_r	694.91
Crystal system, space group	Triclinic, P1
Temperature (K)	125
a, b, c (Å)	7.078 (3), 8.938 (3), 9.838 (5)
α, β, γ (°)	87.54 (3), 89.55 (3), 69.46 (2)
V (Å³)	582.3 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.16
Crystal size (mm)	0.21 × 0.12 × 0.09

Data collection
Diffractometer	Rigaku Mercury70 CCD
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.591, 0.823
No. of measured, independent and observed [F² > 2σ(F²)] reflections	6130, 2087, 1993
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.075, 1.10
No. of reflections	2087
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.67

Computer programs: SCXMini (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2009).

Selected geometric parameters (Å, º) top

Pd1—P1	2.1940 (14)	Pd1—Cl1ⁱ	2.3163 (15)
Pd1—Cl2	2.2820 (15)	Pd1—Cl1	2.4170 (14)

P1—Pd1—Cl2	86.39 (5)	Cl2—Pd1—Cl1	92.45 (5)
P1—Pd1—Cl1ⁱ	95.34 (5)	Cl1ⁱ—Pd1—Cl1	85.86 (5)
Cl2—Pd1—Cl1ⁱ	176.98 (4)	Pd1ⁱ—Cl1—Pd1	94.14 (5)
P1—Pd1—Cl1	178.39 (4)

Symmetry code: (i) −x, −y+1, −z.

References

Grigsby, W. J. & Nicholson, B. K. (1992). Acta Cryst. C48, 362–364. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2006). SCXmini Benchtop Crystallography System Software. Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Rigaku (2009). Crystal Structure. Rigaku/MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Slawin, A. M. Z., Waddell, P. G. & Woollins, J. D. (2010). Acta Cryst. E66, m321. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sui-Seng, C., Bélanger-Gariépy, F. & Zargarian, D. (2003). Acta Cryst. E59, m618–m619. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page m499

https://doi.org/10.1107/S1600536810012055

Open

access