supplementary materials


sj5279 scheme

Acta Cryst. (2012). E68, m1552    [ doi:10.1107/S160053681204809X ]

trans-Tris(4-bromophenyl)dichloridoantimony(V)

Y. Qiao, J. Jiang and J. Cui

Abstract top

The SbV atom in the title compound, [SbCl2(C6H4Br)3], has an almost regular trigonal-bipyramidal geometry with the equatorial plane made up of three C atoms of the bromophenyl groups and the axial positions occupied by two Cl- ions in a trans configuration. In the crystal, C-H...Br hydrogen bonds link the molecules into zigzag chains along the b-axis direction. Pairs of C-H...Cl hydrogen bonds further link molecules into cyclic dimers with R22(10) ring motifs, generating a three-dimensional network.

Comment top

The molecular structure of the compound is depicted in Fig.1. The Sb atom has an almost regular trigonal bipyramid geometry with the equatorial plane made up of three C atoms, C1, C7 and C13 of the bromophenyl ligands and the axial positions occupied by two Cl- ions. C17—H17···Br1 hydrogen bonds link the molecules into zig-zag chains along b. Pairs of C2—H2···Cl2 hydrogen bonds further link molecules into cyclic dimers with R222(10) ring motifs (Bernstein et al., 1995) generating a three-dimensional network.

Related literature top

For related structures, see: Mahalakshmi et al. (2001); Sharutin et al. (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995)

Experimental top

All operations were carried out under a protective nitrogen atmosphere. 1,4-dibromobenzene (0.5 mol), dissolved in dry ether was added dropwise to Mg turnings (0.5 mol) at 0 °C. The resulting Grignard solution was cooled to -12 °C and antimony(III)chloride (0.1 mol) dissolved in dry ether was added. This mixture was stirred for an additional hour at room temperature and after completion of the reaction was treated with a saturated NH4Cl solution. The ether layer was separated and dried over Na2SO4. The solvent was then evaporated from the solution in vacuo and the residue recrystallized from ethanol. The resulting solid, tris(4-bromophenyl)antimony, was dissolved in petroleum ether at 6 °C and then chlorine was passed slowly into the solution to yield the title compound as a white powder which was recrystallised from dichloromethane (Yield 43%). Anal. Calcd (%) for C18H12Cl2Br3Sb (Mr = 660.67): C, 32.72; H, 1.83; Cl, 10.73; Br, 36.28. Found (%): C, 32.66; H, 1.78; Cl, 10.81; Br, 36.23.

Refinement top

The C–H H atoms were positioned with idealized geometry and were refined isotropically with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the compound, showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. Packing diagram.
trans-Tris(4-bromophenyl)dichloridoantimony(V) top
Crystal data top
[SbCl2(C6H4Br)3]F(000) = 2480
Mr = 660.66Dx = 2.151 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2728 reflections
a = 15.1050 (13) Åθ = 2.9–26.1°
b = 20.124 (2) ŵ = 7.49 mm1
c = 15.1701 (14) ÅT = 298 K
β = 117.748 (1)°Block, colourless
V = 4081.0 (7) Å30.26 × 0.22 × 0.12 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer
3582 independent reflections
Radiation source: fine-focus sealed tube2159 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.060
φ and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1716
Tmin = 0.246, Tmax = 0.467k = 2315
10608 measured reflectionsl = 1817
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 0.91 w = 1/[σ2(Fo2) + (0.0456P)2]
where P = (Fo2 + 2Fc2)/3
3582 reflections(Δ/σ)max < 0.001
217 parametersΔρmax = 0.90 e Å3
0 restraintsΔρmin = 0.61 e Å3
Crystal data top
[SbCl2(C6H4Br)3]V = 4081.0 (7) Å3
Mr = 660.66Z = 8
Monoclinic, C2/cMo Kα radiation
a = 15.1050 (13) ŵ = 7.49 mm1
b = 20.124 (2) ÅT = 298 K
c = 15.1701 (14) Å0.26 × 0.22 × 0.12 mm
β = 117.748 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3582 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2159 reflections with I > 2σ(I)
Tmin = 0.246, Tmax = 0.467Rint = 0.060
10608 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.097Δρmax = 0.90 e Å3
S = 0.91Δρmin = 0.61 e Å3
3582 reflectionsAbsolute structure: ?
217 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sb10.47083 (3)0.31132 (2)0.45721 (3)0.05088 (16)
C10.3297 (5)0.3457 (3)0.3455 (5)0.0502 (16)
C20.3204 (5)0.3658 (4)0.2544 (5)0.065 (2)
H20.37510.36320.24200.078*
C30.2300 (5)0.3899 (4)0.1816 (5)0.069 (2)
H30.22250.40270.11960.083*
C40.1522 (5)0.3943 (3)0.2032 (5)0.0574 (18)
C50.1589 (5)0.3734 (4)0.2912 (6)0.0641 (19)
H50.10390.37640.30300.077*
C60.2484 (5)0.3475 (3)0.3632 (5)0.0580 (18)
H60.25350.33160.42290.070*
C70.5462 (5)0.3531 (3)0.6018 (5)0.0496 (16)
C80.6001 (5)0.3122 (3)0.6817 (5)0.0620 (18)
H80.60030.26660.67190.074*
C90.6535 (5)0.3378 (4)0.7757 (5)0.066 (2)
H90.69090.31010.82930.079*
C100.6509 (5)0.4053 (4)0.7895 (5)0.0617 (19)
C110.5935 (5)0.4463 (4)0.7094 (5)0.070 (2)
H110.59000.49160.71940.084*
C120.5421 (5)0.4199 (4)0.6156 (5)0.0609 (19)
H120.50460.44730.56160.073*
C130.5404 (5)0.2323 (3)0.4187 (4)0.0532 (17)
C140.6240 (6)0.2423 (4)0.4084 (6)0.079 (2)
H140.65180.28450.41690.095*
C150.6669 (6)0.1895 (5)0.3854 (7)0.096 (3)
H150.72430.19630.37860.115*
C160.6274 (6)0.1278 (4)0.3725 (5)0.067 (2)
C170.5454 (6)0.1176 (4)0.3810 (6)0.080 (2)
H170.51890.07500.37260.096*
C180.4980 (6)0.1699 (4)0.4024 (6)0.072 (2)
H180.43880.16280.40560.087*
Cl10.38762 (13)0.23427 (9)0.52062 (13)0.0672 (5)
Cl20.55520 (13)0.39558 (9)0.40399 (13)0.0642 (5)
Br10.03004 (6)0.43361 (5)0.10847 (6)0.0882 (3)
Br20.72426 (7)0.44321 (5)0.91767 (6)0.0951 (3)
Br30.68965 (7)0.05538 (5)0.34275 (8)0.1048 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.0547 (3)0.0527 (3)0.0488 (3)0.0014 (3)0.0270 (2)0.0039 (2)
C10.052 (4)0.049 (4)0.051 (4)0.001 (3)0.025 (3)0.003 (3)
C20.064 (5)0.081 (5)0.052 (4)0.000 (4)0.029 (4)0.009 (4)
C30.073 (5)0.082 (6)0.051 (4)0.007 (5)0.029 (4)0.011 (4)
C40.056 (4)0.042 (4)0.065 (5)0.004 (4)0.021 (4)0.009 (4)
C50.057 (5)0.067 (5)0.073 (5)0.007 (4)0.034 (4)0.003 (4)
C60.067 (5)0.066 (5)0.054 (4)0.007 (4)0.039 (4)0.007 (4)
C70.055 (4)0.053 (4)0.046 (4)0.002 (4)0.028 (3)0.008 (3)
C80.072 (5)0.045 (4)0.063 (5)0.001 (4)0.027 (4)0.003 (4)
C90.078 (5)0.060 (5)0.049 (5)0.005 (4)0.019 (4)0.013 (4)
C100.064 (5)0.065 (5)0.056 (4)0.002 (4)0.028 (4)0.005 (4)
C110.084 (5)0.062 (5)0.055 (5)0.008 (4)0.025 (4)0.001 (4)
C120.067 (5)0.056 (5)0.050 (4)0.012 (4)0.019 (4)0.013 (4)
C130.058 (4)0.059 (5)0.041 (4)0.006 (4)0.022 (3)0.001 (3)
C140.080 (6)0.067 (5)0.112 (7)0.016 (5)0.062 (5)0.017 (5)
C150.079 (6)0.094 (7)0.138 (8)0.013 (6)0.071 (6)0.018 (7)
C160.063 (5)0.077 (6)0.058 (5)0.010 (5)0.025 (4)0.006 (4)
C170.088 (6)0.068 (6)0.087 (6)0.011 (5)0.044 (5)0.016 (5)
C180.077 (5)0.067 (5)0.085 (6)0.007 (5)0.048 (5)0.008 (4)
Cl10.0733 (12)0.0662 (12)0.0739 (13)0.0075 (10)0.0442 (10)0.0113 (10)
Cl20.0704 (12)0.0661 (12)0.0652 (11)0.0121 (10)0.0390 (10)0.0037 (10)
Br10.0780 (6)0.0830 (6)0.0792 (6)0.0122 (5)0.0160 (5)0.0039 (5)
Br20.1167 (7)0.0916 (7)0.0552 (5)0.0110 (6)0.0218 (5)0.0049 (5)
Br30.1026 (7)0.0967 (7)0.1100 (8)0.0208 (6)0.0453 (6)0.0252 (6)
Geometric parameters (Å, º) top
Sb1—C12.129 (6)C8—H80.9300
Sb1—C72.119 (6)C9—C101.377 (10)
Sb1—C132.132 (7)C9—H90.9300
Sb1—Cl12.4566 (16)C10—C111.388 (9)
Sb1—Cl22.4716 (17)C10—Br21.893 (7)
C1—C61.373 (8)C11—C121.372 (9)
C1—C21.384 (8)C11—H110.9300
C2—C31.385 (9)C12—H120.9300
C2—H20.9300C13—C141.357 (8)
C3—C41.363 (9)C13—C181.380 (9)
C3—H30.9300C14—C151.371 (10)
C4—C51.357 (9)C14—H140.9300
C4—Br11.904 (7)C15—C161.351 (10)
C5—C61.384 (9)C15—H150.9300
C5—H50.9300C16—C171.320 (9)
C6—H60.9300C16—Br31.900 (7)
C7—C121.366 (9)C17—C181.392 (10)
C7—C81.375 (9)C17—H170.9300
C8—C91.370 (9)C18—H180.9300
C7—Sb1—C1123.5 (2)C9—C8—H8119.6
C7—Sb1—C13118.9 (2)C7—C8—H8119.6
C1—Sb1—C13117.6 (2)C8—C9—C10118.9 (7)
C7—Sb1—Cl188.37 (17)C8—C9—H9120.5
C1—Sb1—Cl190.64 (18)C10—C9—H9120.5
C13—Sb1—Cl192.52 (19)C9—C10—C11120.2 (7)
C7—Sb1—Cl287.45 (17)C9—C10—Br2120.6 (6)
C1—Sb1—Cl289.71 (17)C11—C10—Br2119.2 (6)
C13—Sb1—Cl291.56 (19)C12—C11—C10119.9 (7)
Cl1—Sb1—Cl2175.20 (6)C12—C11—H11120.0
C6—C1—C2120.3 (6)C10—C11—H11120.0
C6—C1—Sb1120.6 (5)C7—C12—C11119.7 (6)
C2—C1—Sb1119.2 (5)C7—C12—H12120.1
C1—C2—C3120.1 (6)C11—C12—H12120.1
C1—C2—H2119.9C14—C13—C18119.5 (7)
C3—C2—H2119.9C14—C13—Sb1121.7 (6)
C4—C3—C2118.2 (6)C18—C13—Sb1118.8 (5)
C4—C3—H3120.9C13—C14—C15119.3 (7)
C2—C3—H3120.9C13—C14—H14120.3
C5—C4—C3122.6 (6)C15—C14—H14120.3
C5—C4—Br1118.3 (5)C16—C15—C14121.3 (7)
C3—C4—Br1119.1 (6)C16—C15—H15119.4
C4—C5—C6119.4 (6)C14—C15—H15119.4
C4—C5—H5120.3C17—C16—C15120.0 (8)
C6—C5—H5120.3C17—C16—Br3119.7 (7)
C1—C6—C5119.3 (6)C15—C16—Br3120.4 (7)
C1—C6—H6120.4C16—C17—C18120.9 (8)
C5—C6—H6120.4C16—C17—H17119.6
C12—C7—C8120.3 (6)C18—C17—H17119.6
C12—C7—Sb1120.5 (5)C13—C18—C17118.9 (7)
C8—C7—Sb1119.2 (5)C13—C18—H18120.5
C9—C8—C7120.8 (7)C17—C18—H18120.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl2i0.932.933.723 (7)144
C17—H17···Br1ii0.932.993.900 (9)167
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+1/2, y1/2, z+1/2.
Selected bond lengths (Å) top
Sb1—C12.129 (6)Sb1—Cl12.4566 (16)
Sb1—C72.119 (6)Sb1—Cl22.4716 (17)
Sb1—C132.132 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl2i0.932.933.723 (7)143.5
C17—H17···Br1ii0.932.993.900 (9)167.3
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+1/2, y1/2, z+1/2.
Acknowledgements top

We acknowledge the National Natural Foundation of China (21105042), the National Basic Research Program (No. 2010CB234601) and the Natural Science Foundation of Shandong Province (ZR2011BM007, ZR2010BQ021) for financial support.

references
References top

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.

Mahalakshmi, H., Jain, V. K. & Tiekink, E. R. T. (2001). Main Group Met. Chem. pp. 391–392.

Sharutin, V. V., Senchurin, V. S., Sharutina, O. K. & Chagarova, O. V. (2010). Russ J. Gen. Chem. pp. 1789–1792.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.