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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2591–o2592.
Published online 2009 September 30. doi:  10.1107/S1600536809036757
PMCID: PMC2970425

1,6-Bis(diphenyl­arsino)hexa­ne

Abstract

The title diphenyl­arsino compound, C30H32As2 or Ph2As(CH2)6AsPh2, lies about a crystallographic inversion centre located at the mid-point of the central Csp 3—Csp 3 bond of the methyl­ene chain. The two benzene rings bonded to As are inclined to one another at a dihedral angle of 75.98 (8)°. In the crystal structure, weak inter­molecular C—H(...)π inter­actions stack the mol­ecules down the b axis.

Related literature

For general background to and applications of diphenyl­arsino derivatives, see: Hill et al. (1983 [triangle]); Song et al. (2005 [triangle]). For the preparation of the title compound, see: Aguiar & Archibald (1967 [triangle]); Burfield et al. (1977 [triangle], 1978 [triangle]); Tzschach & Lange (1962 [triangle]). For closely related structures, see: Hill et al. (2001 [triangle]); Shawkataly et al. (2005 [triangle]). For information on the Cambridge Structural Database, see: Allen (2002 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 [triangle]).

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Object name is e-65-o2591-scheme1.jpg

Experimental

Crystal data

  • C30H32As2
  • M r = 542.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2591-efi1.jpg
  • a = 12.3774 (2) Å
  • b = 5.7145 (1) Å
  • c = 18.1263 (3) Å
  • β = 101.076 (1)°
  • V = 1258.20 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.67 mm−1
  • T = 100 K
  • 0.44 × 0.29 × 0.03 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.384, T max = 0.919
  • 24043 measured reflections
  • 5572 independent reflections
  • 4144 reflections with I > 2σ(I)
  • R int = 0.052

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.084
  • S = 1.03
  • 5572 reflections
  • 209 parameters
  • All H-atom parameters refined
  • Δρmax = 0.58 e Å−3
  • Δρmin = −0.47 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809036757/sj2648sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036757/sj2648Isup2.hkl

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

Acknowledgments

The authors would like to thank the Malaysian Government and Universiti Sains Malaysia (USM) for the Research Grant (No. 1001/PJJAUH/811115). HKF and JHG thank USM for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). IAK is grateful to USM for a Postdoctoral Fellowship and Gokhale Centenary College, Ankola, India, for study leave. JHG also thanks USM for the award of a USM fellowship.

supplementary crystallographic information

Comment

1,6-Bis(diphenylarsino)hexane has been used for trans chelation in transition metal complexes (Hill et al., 1983). A search of the November 2008 release of the Cambridge Structural Database (Allen, 2002) revealed no structures of complexes containing the above ligand. Among bis(diphenylarsino)alkanes, only the structure of 1,2-bis(diphenylarsino)ethane (Hill et al., 2001) and complexes of the ligand 1,3-bis(diphenylarsino)propane (Song et al., 2005) are known.

The title compound (Fig. 1), contains a crystallographic inversion centre at the mid-point of the central Csp3—Csp3 (C15—C15A) bond [symmetry code of atoms labellel with suffix A: -x+1, -y+1, -z+1]. The C1-C6 and C7-C12 benzene rings are inclined to one another, with a dihedral angle of 75.98 (8)°. The bond lengths (Allen et al., 1987) are comparable to those found in closely related structures (Hill et al., 2001; Shawkataly et al., 2005). In the crystal structure (Fig. 2), the molecules are stacked down the b axis. The crystal structure is consolidated by intermolecular C15—H15B···Cg1, C4—H4···Cg2 and C9—H9···Cg2 interactions (Table 1).

Experimental

Solvents were dried by recommended literature routes (Burfield et al., 1977, 1978) and the title compound was prepared by the reaction of diphenylarsino lithium with 1,6-dibromohexane in dry THF at 273 K under nitrogen atmosphere (Aguiar et al., 1967; Tzschach & Lange, 1962). Colourless plates of suitable quality for single crystal X-ray diffraction studies were obtained by slow evaporation from ethanol solution.

Refinement

All the H atoms were located from difference Fourier map and allowed to refine freely [range of C—H = 0.89 (2) – 0.99 (3) Å].

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme. The suffix A corresponds to the symmetry code [-x+1, -y+1, -z+1].
Fig. 2.
The crystal structure of the title compound viewed along the b axis, showing stacking of molecules along the b axis.

Crystal data

C30H32As2F(000) = 556
Mr = 542.40Dx = 1.432 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5477 reflections
a = 12.3774 (2) Åθ = 3.1–32.2°
b = 5.7145 (1) ŵ = 2.67 mm1
c = 18.1263 (3) ÅT = 100 K
β = 101.076 (1)°Plate, colourless
V = 1258.20 (4) Å30.44 × 0.29 × 0.03 mm
Z = 2

Data collection

Bruker SMART APEXII CCD area-detector diffractometer5572 independent reflections
Radiation source: fine-focus sealed tube4144 reflections with I > 2σ(I)
graphiteRint = 0.052
[var phi] and ω scansθmax = 35.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −19→20
Tmin = 0.384, Tmax = 0.919k = −9→8
24043 measured reflectionsl = −29→26

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084All H-atom parameters refined
S = 1.03w = 1/[σ2(Fo2) + (0.0344P)2 + 0.3375P] where P = (Fo2 + 2Fc2)/3
5572 reflections(Δ/σ)max = 0.001
209 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = −0.47 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.
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 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 > 2sigma(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)

xyzUiso*/Ueq
As10.351354 (13)0.98218 (3)0.284872 (8)0.01668 (5)
C10.29473 (13)0.8690 (3)0.18275 (8)0.0183 (3)
C20.32226 (14)0.6566 (3)0.15347 (9)0.0226 (3)
C30.27896 (15)0.5965 (4)0.07878 (10)0.0264 (4)
C40.20763 (15)0.7469 (4)0.03339 (10)0.0299 (4)
C50.17979 (17)0.9578 (4)0.06212 (10)0.0313 (4)
C60.22374 (16)1.0190 (3)0.13583 (10)0.0257 (3)
C70.20975 (13)0.9750 (3)0.31860 (8)0.0165 (3)
C80.13587 (13)0.7891 (3)0.30118 (9)0.0192 (3)
C90.03431 (14)0.7930 (3)0.32299 (9)0.0224 (3)
C100.00492 (14)0.9838 (3)0.36256 (9)0.0225 (3)
C110.07749 (14)1.1692 (3)0.38019 (9)0.0235 (3)
C120.17944 (14)1.1653 (3)0.35879 (9)0.0208 (3)
C130.41464 (14)0.6910 (3)0.33284 (9)0.0195 (3)
C140.43828 (15)0.7124 (3)0.41818 (9)0.0218 (3)
C150.48951 (15)0.4927 (3)0.45720 (9)0.0234 (3)
H20.3700 (19)0.552 (4)0.1820 (12)0.026 (6)*
H30.303 (2)0.458 (4)0.0593 (13)0.031 (6)*
H40.1799 (19)0.704 (4)−0.0149 (13)0.040 (6)*
H50.128 (2)1.066 (5)0.0299 (15)0.048 (7)*
H60.2055 (18)1.172 (4)0.1569 (12)0.034 (6)*
H80.1550 (16)0.654 (4)0.2729 (11)0.026 (5)*
H9−0.0121 (17)0.669 (4)0.3102 (12)0.033 (6)*
H10−0.063 (2)0.989 (4)0.3763 (14)0.033 (7)*
H110.0573 (18)1.300 (4)0.4072 (12)0.036 (6)*
H120.2278 (16)1.291 (4)0.3710 (11)0.024 (5)*
H13A0.4768 (18)0.668 (4)0.3164 (12)0.033 (6)*
H13B0.364 (2)0.570 (4)0.3189 (13)0.032 (6)*
H14A0.370 (2)0.752 (5)0.4355 (13)0.043 (7)*
H14B0.4872 (17)0.844 (4)0.4344 (11)0.026 (5)*
H15A0.4390 (19)0.362 (5)0.4414 (13)0.037 (6)*
H15B0.556 (2)0.465 (4)0.4373 (14)0.032 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
As10.01574 (8)0.01865 (8)0.01533 (7)−0.00094 (6)0.00222 (5)0.00114 (6)
C10.0172 (6)0.0221 (7)0.0160 (6)−0.0017 (6)0.0044 (5)0.0026 (5)
C20.0218 (7)0.0269 (8)0.0194 (7)0.0002 (7)0.0050 (6)0.0007 (6)
C30.0285 (9)0.0296 (9)0.0225 (8)−0.0069 (7)0.0087 (7)−0.0053 (7)
C40.0283 (9)0.0462 (11)0.0147 (7)−0.0115 (8)0.0028 (6)−0.0013 (7)
C50.0299 (9)0.0430 (11)0.0185 (7)0.0012 (8)−0.0011 (7)0.0079 (7)
C60.0269 (8)0.0299 (9)0.0195 (7)0.0042 (7)0.0027 (6)0.0046 (6)
C70.0169 (6)0.0182 (7)0.0137 (6)0.0008 (5)0.0014 (5)0.0017 (5)
C80.0195 (7)0.0187 (7)0.0188 (7)0.0003 (6)0.0022 (5)−0.0016 (5)
C90.0204 (7)0.0243 (8)0.0217 (7)−0.0025 (6)0.0018 (6)−0.0010 (6)
C100.0173 (7)0.0303 (9)0.0198 (7)0.0033 (6)0.0035 (6)0.0008 (6)
C110.0258 (8)0.0243 (8)0.0200 (7)0.0046 (7)0.0034 (6)−0.0030 (6)
C120.0219 (7)0.0195 (7)0.0200 (7)−0.0005 (6)0.0013 (6)−0.0013 (6)
C130.0186 (7)0.0239 (8)0.0156 (6)0.0047 (6)0.0022 (5)0.0022 (6)
C140.0235 (8)0.0263 (8)0.0149 (6)0.0071 (7)0.0016 (6)0.0015 (6)
C150.0250 (8)0.0283 (9)0.0154 (6)0.0096 (7)0.0003 (6)0.0008 (6)

Geometric parameters (Å, °)

As1—C11.9590 (15)C8—H80.98 (2)
As1—C71.9644 (16)C9—C101.391 (2)
As1—C131.9688 (16)C9—H90.91 (2)
C1—C21.393 (2)C10—C111.386 (3)
C1—C61.394 (2)C10—H100.93 (3)
C2—C31.400 (2)C11—C121.390 (2)
C2—H20.93 (2)C11—H110.95 (2)
C3—C41.384 (3)C12—H120.94 (2)
C3—H30.94 (2)C13—C141.523 (2)
C4—C51.383 (3)C13—H13A0.89 (2)
C4—H40.91 (2)C13—H13B0.93 (3)
C5—C61.387 (3)C14—C151.519 (2)
C5—H50.99 (3)C14—H14A0.98 (2)
C6—H60.99 (2)C14—H14B0.98 (2)
C7—C81.398 (2)C15—C15i1.525 (3)
C7—C121.399 (2)C15—H15A0.98 (3)
C8—C91.388 (2)C15—H15B0.97 (3)
C1—As1—C796.24 (6)C10—C9—H9121.6 (14)
C1—As1—C13100.26 (7)C11—C10—C9119.72 (16)
C7—As1—C1398.51 (7)C11—C10—H10119.9 (13)
C2—C1—C6118.37 (15)C9—C10—H10120.4 (14)
C2—C1—As1125.33 (12)C10—C11—C12120.41 (16)
C6—C1—As1116.28 (13)C10—C11—H11119.8 (14)
C1—C2—C3120.38 (17)C12—C11—H11119.8 (14)
C1—C2—H2121.8 (14)C11—C12—C7120.44 (16)
C3—C2—H2117.8 (14)C11—C12—H12119.7 (12)
C4—C3—C2120.32 (18)C7—C12—H12119.9 (13)
C4—C3—H3120.8 (14)C14—C13—As1111.29 (11)
C2—C3—H3118.7 (15)C14—C13—H13A110.1 (14)
C5—C4—C3119.60 (16)As1—C13—H13A105.9 (15)
C5—C4—H4121.5 (16)C14—C13—H13B108.8 (15)
C3—C4—H4118.9 (16)As1—C13—H13B108.4 (15)
C4—C5—C6120.16 (18)H13A—C13—H13B112 (2)
C4—C5—H5119.9 (16)C15—C14—C13112.84 (14)
C6—C5—H5119.9 (16)C15—C14—H14A110.5 (15)
C5—C6—C1121.15 (18)C13—C14—H14A109.6 (13)
C5—C6—H6121.0 (13)C15—C14—H14B108.6 (12)
C1—C6—H6117.9 (12)C13—C14—H14B110.8 (12)
C8—C7—C12118.61 (15)H14A—C14—H14B104.2 (19)
C8—C7—As1121.98 (12)C14—C15—C15i113.73 (18)
C12—C7—As1119.36 (12)C14—C15—H15A107.9 (14)
C9—C8—C7120.81 (15)C15i—C15—H15A108.3 (14)
C9—C8—H8119.0 (12)C14—C15—H15B105.7 (14)
C7—C8—H8120.2 (12)C15i—C15—H15B113.3 (15)
C8—C9—C10120.01 (16)H15A—C15—H15B107.6 (19)
C8—C9—H9118.4 (14)
C7—As1—C1—C2−114.45 (14)C1—As1—C7—C12−134.94 (13)
C13—As1—C1—C2−14.60 (15)C13—As1—C7—C12123.67 (13)
C7—As1—C1—C667.51 (14)C12—C7—C8—C90.2 (2)
C13—As1—C1—C6167.36 (13)As1—C7—C8—C9−177.24 (12)
C6—C1—C2—C3−0.2 (2)C7—C8—C9—C100.1 (2)
As1—C1—C2—C3−178.21 (13)C8—C9—C10—C11−0.1 (2)
C1—C2—C3—C4−0.5 (3)C9—C10—C11—C12−0.2 (3)
C2—C3—C4—C50.4 (3)C10—C11—C12—C70.6 (2)
C3—C4—C5—C60.5 (3)C8—C7—C12—C11−0.6 (2)
C4—C5—C6—C1−1.2 (3)As1—C7—C12—C11176.96 (12)
C2—C1—C6—C51.0 (3)C1—As1—C13—C14−165.02 (12)
As1—C1—C6—C5179.24 (15)C7—As1—C13—C14−67.05 (13)
C1—As1—C7—C842.50 (13)As1—C13—C14—C15−178.78 (13)
C13—As1—C7—C8−58.90 (13)C13—C14—C15—C15i−178.14 (19)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C15—H15B···Cg1ii0.97 (3)2.81 (3)3.776 (2)169.9 (18)
C4—H4···Cg2iii0.91 (2)2.80 (2)3.708 (2)173.2 (19)
C9—H9···Cg2iv0.91 (2)2.97 (2)3.617 (2)129.5 (16)

Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z−3/2; (iv) −x, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2648).

References

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