cis-[1,2-Bis(diphenyl­arsan­yl)ethane-κ2 As,As’]tetra­carbonyl­chromium(0)

M N Norlidah; M Y Azhar; Omar Bin Shawkataly; Mohd Mustaqim Rosli; Hoong-Kun Fun

doi:10.1107/S1600536811032314

. 2011 Aug 27;67(Pt 9):m1267–m1268. doi: 10.1107/S1600536811032314

cis-[1,2-Bis(diphenylarsanyl)ethane-κ² As,As’]tetracarbonylchromium(0)

M N Norlidah ^a,^‡, M Y Azhar ^a, Omar Bin Shawkataly ^b,^§, Mohd Mustaqim Rosli ^c, Hoong-Kun Fun ^c,^*,^¶

PMCID: PMC3200751 PMID: 22065153

Abstract

In the title compound, [Cr(C₂₆H₂₄As₂)(CO)₄], the Cr atom is octahedrally coordinated by four carbonyl ligands and one bidentate 1,2-bis(diphenylarsanyl)ethane ligand, which chelates in a cis manner with an As—Cr—As bite angle of 82.513 (9)°. The dihedral angles between the pairs of benzene rings attached to each As atom are 84.63 (9) and 77.15 (8)°. In the crystal, molecules are linked by C—H⋯O interactions, forming infinite chains along the a axis. The crystal structure is further stabilized by C—H⋯π interactions.

Related literature

X-ray structure determinations of chromium carbonyls with arsine ligands are rare. A search of the Cambridge Crystallographic Structural Database (Allen, 2002 ▶) reveals only 12 complexes of chromium carbonyl disubtituted with tertiary arsines. For related structures, see: Bennett et al. (1971 ▶); Nowell et al. (1972 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Cr(C₂₆H₂₄As₂)(CO)₄]
M _r = 650.33
Orthorhombic,
a = 17.0231 (4) Å
b = 12.6200 (3) Å
c = 25.5527 (6) Å
V = 5489.5 (2) Å³
Z = 8
Mo Kα radiation
μ = 2.84 mm⁻¹
T = 100 K
0.53 × 0.25 × 0.05 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.313, T _max = 0.871
87112 measured reflections
9352 independent reflections
7454 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.065
S = 1.02
9352 reflections
334 parameters
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811032314/ng5210sup1.cif

e-67-m1267-sup1.cif^{(25.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032314/ng5210Isup2.hkl

e-67-m1267-Isup2.hkl^{(457.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

As1—Cr1	2.4461 (3)
As2—Cr1	2.4512 (3)
Cr1—C2	1.8457 (17)
Cr1—C1	1.8511 (17)
Cr1—C3	1.8894 (17)
Cr1—C4	1.8935 (18)

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Table 2. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O1ⁱ	0.93	2.57	3.345 (2)	141
C16—H16A⋯Cg1ⁱⁱ	0.93	2.60	3.519 (2)	169

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors would like to thank the Malaysian Government and Universiti Sains Malaysia for the Research Grant 1001/PJJauh/811115. HKF thanks USM for the Research University Grant No. 1001/PFIZIK/811160. MNN is grateful to Universiti Malaysia Pahang for a research position.

supplementary crystallographic information

Comment

Very few chromium carbonyls with bidentate arsine ligands have been reported (Allen, 2002). The C—C bond length and the As—Cr—As bite angle of the title complex are comparable to similar complexes of chromium carbonyls substituted with bidentate arsine with two carbon atom backbone (Nowell et al.,1972). The title compound is isostructural to Cr(CO)₄(Ph₂P(CH₂)₂PPh₂) and this gives further support that the formation of stable cis-M(CO)₄L₂ compounds is prefered when the L₂ groups are combined in a chelating bidentate ligand (Bennett et al. 1971).

The Cr—As bond lengths show an average value of 2.449 Å and the As—Cr—As bite angle has a value of 82.51 (1)° (Table 1) while in Cr(CO)₄(Ph₂P(CH₂)₂PPh₂), the average of Cr—P bond lengths is 2.360Å and the P—Cr—P bite angle has a value of 83.41 (8).

In the molecule, the dihedral angle between the two benzene ring attached to the As1 and As2 are 84.63 (9)° (C7—C12 & C13—C18 rings) and 77.15 (8)° (C19—C24 & C25—C30 rings), respectively. The molecules form infinite chains along the a axis (Fig. 2) throught C9—H9A···O1ⁱ (Table 2) intermolecular interactions. The crystal structure is further stabilized by C—H···π interaction involving Cg1, Cg1 is the centroid of C7—C12 (Table 2).

Experimental

All manipulations were performed under a dry, oxygen-free nitrogen atmosphere using standard Schlenk techniques. All solvents were dried over sodium under dry oxygen free nitrogen. Chromium hexacarbonyl (200 mg, 0.909 mmol) and ethylenebisdiphenyl-arsanylethane (441.9 mg, 0.9086 mmol) in 35 ml of pet ether (100–130°C) was refluxed for 12 h. Suitable single crystals were obtained by solvent-solvent diffusion in a mixture of dichloromethane/methanol.