Tris(biphenyl-4-yl)arsane

Omar bin Shawkataly; Imthyaz Ahmed Khan; Siti Syaida Sirat; Chin Sing Yeap; Hoong-Kun Fun

doi:10.1107/S160053681100211X

. 2011 Jan 22;67(Pt 2):o457–o458. doi: 10.1107/S160053681100211X

Tris(biphenyl-4-yl)arsane

Omar bin Shawkataly ^a,^*,^‡, Imthyaz Ahmed Khan ^a,^§, Siti Syaida Sirat ^a, Chin Sing Yeap ^b,^¶, Hoong-Kun Fun ^b,^‡‡

PMCID: PMC3051659 PMID: 21523119

Abstract

The asymmetric unit of title compound, C₃₆H₂₇As, contains two crystallographically independent molecules, A and B, with similar conformations. The two phenyl rings of each biphenyl unit are twisted slightly away from each other with dihedral angles of 6.0 (2), 27.7 (3) and 33.4 (2)° in molecule A and 5.7 (3), 27.5 (2) and 33.0 (2)° in molecule B. The As-bonded phenyl rings make dihedral angles of 54.9 (2), 76.0 (2) and 88.2 (2),° with each other in molecule A, and 60.3 (2), 78.1 (2) and 79.5 (2)° in molecule B. In the crystal, the molecules are stacked down the b axis. Weak intermolecular C—H⋯π interactions stabilize the crystal structure. The crystal studied was a racemic twin, the refined ratio of twin components being 0.461 (7):0.539 (7).

Related literature

For structures of related trisaryl arsane derivatives, see: Cullen et al. (1995 ▶); Shawkataly et al. (2010a ▶,b ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₃₆H₂₇As
M _r = 534.50
Monoclinic,
a = 17.3718 (19) Å
b = 5.9561 (8) Å
c = 27.727 (3) Å
β = 114.762 (5)°
V = 2605.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.33 mm⁻¹
T = 100 K
0.33 × 0.07 × 0.03 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.671, T _max = 0.961
23087 measured reflections
11576 independent reflections
8126 reflections with I > 2σ(I)’
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.093
S = 1.01
11576 reflections
668 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.75 e Å⁻³
Absolute structure: Flack (1983 ▶), 5634 Friedel pairs
Flack parameter: 0.461 (7)

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 datablocks global, I. DOI: 10.1107/S160053681100211X/ng5092sup1.cif

e-67-0o457-sup1.cif^{(41.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100211X/ng5092Isup2.hkl

e-67-0o457-Isup2.hkl^{(566KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1, Cg2, Cg3, Cg4, Cg5, Cg6 and Cg7 are the centroids of the C25B–C30B, C19B–C24B, C7B–C12B, C31A–C36A, C1A–C6A, C31B–C36B and C13B–C18B benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4B—H4BA⋯Cg1ⁱ	0.93	2.77	3.583 (6)	147
C9A—H9A⋯Cg2ⁱⁱ	0.93	2.99	3.872 (6)	160
C11A—H11A⋯Cg3ⁱⁱⁱ	0.93	2.88	3.723 (7)	153
C13B—H13B⋯Cg4	0.93	2.79	3.596 (5)	147
C14A—H14A⋯Cg5ⁱ	0.93	2.93	3.834 (5)	172
C24A—H24A⋯Cg6^iv	0.93	2.70	3.582 (6)	160
C28B—H28B⋯Cg7^v	0.93	2.56	3.313 (6)	139
C36A—H36A⋯Cg3^vi	0.93	2.96	3.651 (6)	133

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

The authors would like to thank the Malaysian Government and Universiti Sains Malaysia (USM) for the Research Grant 1001/PJJAUH/811115. IAK is grateful to USM for a Visiting Researcher position. SSS thanks USM for the G A position. HKF and CSY thank USM for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Trisaryl arsanes have been used in the synthesis of Osmium and Ruthenium cluster derivatives (Cullen et al., 1995; Shawkataly et al., 2010a, b). In continuation of our work on trisaryl arsanes, we report the synthesis and structure of title compound.

The asymmetric unit consists of two crystallographically independent molecules of trisaryl arsane, A and B, with similar conformation (Fig. 1). Both phenyl rings of biphenyl are slightly twisted from each other with the dihedral angles of 33.4 (2), 27.7 (3) and 6.0 (2)° in molecule A whereas these angles are 5.7 (3), 27.5 (2) and 33.0 (2)° in molecule B. The arsane-substituted phenyl rings make dihedral angles of 88.2 (2), 54.9 (2) and 76.0 (2)° with each other in molecule A whereas 79.5 (2), 78.1 (2) and 60.3 (2)° in molecule B. In the crystal packing, the molecules are stacked down the b axis (Fig 2). Weak intermolecular C—H···π interactions stabilize the crystal structure (Table 1).

Experimental

All manipulations were performed under a dry oxygen-free nitrogen atmosphere using standard Schlenk techniques. All solvents were dried over sodium and distilled from sodium benzophenone ketyl under dry oxygen free nitrogen. Tris(1-biphenyl)arsane was prepared from arsenic trichloride and biphenyl magnesiumbromide in tetrahydrofuran. Crystals suitable for X-ray diffraction were grown by slow solvent / solvent diffusion of CH₃OH into CHCl₃.