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

Qiao, Y.; Jiang, J.; Cui, J.

doi:10.1107/S160053681204809X

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page m1552

doi:10.1107/S160053681204809X

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

Yanling Qiao,^a Jin Jiang ^a and Jichun Cui ^a ^*

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: jchcui@163.com

(Received 2 November 2012; accepted 22 November 2012; online 28 November 2012)

The Sb^V 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.

Related literature

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

Experimental

Crystal data

[SbCl₂(C₆H₄Br)₃]
M_r = 660.66
Monoclinic, C 2/c
a = 15.1050 (13) Å
b = 20.124 (2) Å
c = 15.1701 (14) Å
β = 117.748 (1)°
V = 4081.0 (7) Å³
Z = 8
Mo Kα radiation
μ = 7.49 mm⁻¹
T = 298 K
0.26 × 0.22 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.246, T_max = 0.467
10608 measured reflections
3582 independent reflections
2159 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.097
S = 0.91
3582 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Selected bond lengths (Å)

Sb1—C1	2.129 (6)
Sb1—C7	2.119 (6)
Sb1—C13	2.132 (7)
Sb1—Cl1	2.4566 (16)
Sb1—Cl2	2.4716 (17)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cl2ⁱ	0.93	2.93	3.723 (7)	144
C17—H17⋯Br1ⁱⁱ	0.93	2.99	3.900 (9)	167
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681204809X/sj5279sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681204809X/sj5279Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of the compound, showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity.
	Fig. 2. Packing diagram.

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

Crystal data top

[SbCl₂(C₆H₄Br)₃]	F(000) = 2480
M_r = 660.66	D_x = 2.151 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2728 reflections
a = 15.1050 (13) Å	θ = 2.9–26.1°
b = 20.124 (2) Å	µ = 7.49 mm⁻¹
c = 15.1701 (14) Å	T = 298 K
β = 117.748 (1)°	Block, colourless
V = 4081.0 (7) Å³	0.26 × 0.22 × 0.12 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	3582 independent reflections
Radiation source: fine-focus sealed tube	2159 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→16
T_min = 0.246, T_max = 0.467	k = −23→15
10608 measured reflections	l = −18→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0456P)²] where P = (F_o² + 2F_c²)/3
3582 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.90 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

[SbCl₂(C₆H₄Br)₃]	V = 4081.0 (7) Å³
M_r = 660.66	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.1050 (13) Å	µ = 7.49 mm⁻¹
b = 20.124 (2) Å	T = 298 K
c = 15.1701 (14) Å	0.26 × 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)
T_min = 0.246, T_max = 0.467	R_int = 0.060
10608 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 0.91	Δρ_max = 0.90 e Å⁻³
3582 reflections	Δρ_min = −0.61 e Å⁻³
217 parameters

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

	x	y	z	U_iso*/U_eq
Sb1	0.47083 (3)	0.31132 (2)	0.45721 (3)	0.05088 (16)
C1	0.3297 (5)	0.3457 (3)	0.3455 (5)	0.0502 (16)
C2	0.3204 (5)	0.3658 (4)	0.2544 (5)	0.065 (2)
H2	0.3751	0.3632	0.2420	0.078*
C3	0.2300 (5)	0.3899 (4)	0.1816 (5)	0.069 (2)
H3	0.2225	0.4027	0.1196	0.083*
C4	0.1522 (5)	0.3943 (3)	0.2032 (5)	0.0574 (18)
C5	0.1589 (5)	0.3734 (4)	0.2912 (6)	0.0641 (19)
H5	0.1039	0.3764	0.3030	0.077*
C6	0.2484 (5)	0.3475 (3)	0.3632 (5)	0.0580 (18)
H6	0.2535	0.3316	0.4229	0.070*
C7	0.5462 (5)	0.3531 (3)	0.6018 (5)	0.0496 (16)
C8	0.6001 (5)	0.3122 (3)	0.6817 (5)	0.0620 (18)
H8	0.6003	0.2666	0.6719	0.074*
C9	0.6535 (5)	0.3378 (4)	0.7757 (5)	0.066 (2)
H9	0.6909	0.3101	0.8293	0.079*
C10	0.6509 (5)	0.4053 (4)	0.7895 (5)	0.0617 (19)
C11	0.5935 (5)	0.4463 (4)	0.7094 (5)	0.070 (2)
H11	0.5900	0.4916	0.7194	0.084*
C12	0.5421 (5)	0.4199 (4)	0.6156 (5)	0.0609 (19)
H12	0.5046	0.4473	0.5616	0.073*
C13	0.5404 (5)	0.2323 (3)	0.4187 (4)	0.0532 (17)
C14	0.6240 (6)	0.2423 (4)	0.4084 (6)	0.079 (2)
H14	0.6518	0.2845	0.4169	0.095*
C15	0.6669 (6)	0.1895 (5)	0.3854 (7)	0.096 (3)
H15	0.7243	0.1963	0.3786	0.115*
C16	0.6274 (6)	0.1278 (4)	0.3725 (5)	0.067 (2)
C17	0.5454 (6)	0.1176 (4)	0.3810 (6)	0.080 (2)
H17	0.5189	0.0750	0.3726	0.096*
C18	0.4980 (6)	0.1699 (4)	0.4024 (6)	0.072 (2)
H18	0.4388	0.1628	0.4056	0.087*
Cl1	0.38762 (13)	0.23427 (9)	0.52062 (13)	0.0672 (5)
Cl2	0.55520 (13)	0.39558 (9)	0.40399 (13)	0.0642 (5)
Br1	0.03004 (6)	0.43361 (5)	0.10847 (6)	0.0882 (3)
Br2	0.72426 (7)	0.44321 (5)	0.91767 (6)	0.0951 (3)
Br3	0.68965 (7)	0.05538 (5)	0.34275 (8)	0.1048 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.0547 (3)	0.0527 (3)	0.0488 (3)	−0.0014 (3)	0.0270 (2)	0.0039 (2)
C1	0.052 (4)	0.049 (4)	0.051 (4)	0.001 (3)	0.025 (3)	0.003 (3)
C2	0.064 (5)	0.081 (5)	0.052 (4)	0.000 (4)	0.029 (4)	0.009 (4)
C3	0.073 (5)	0.082 (6)	0.051 (4)	−0.007 (5)	0.029 (4)	0.011 (4)
C4	0.056 (4)	0.042 (4)	0.065 (5)	−0.004 (4)	0.021 (4)	−0.009 (4)
C5	0.057 (5)	0.067 (5)	0.073 (5)	0.007 (4)	0.034 (4)	−0.003 (4)
C6	0.067 (5)	0.066 (5)	0.054 (4)	0.007 (4)	0.039 (4)	0.007 (4)
C7	0.055 (4)	0.053 (4)	0.046 (4)	0.002 (4)	0.028 (3)	0.008 (3)
C8	0.072 (5)	0.045 (4)	0.063 (5)	0.001 (4)	0.027 (4)	0.003 (4)
C9	0.078 (5)	0.060 (5)	0.049 (5)	0.005 (4)	0.019 (4)	0.013 (4)
C10	0.064 (5)	0.065 (5)	0.056 (4)	0.002 (4)	0.028 (4)	0.005 (4)
C11	0.084 (5)	0.062 (5)	0.055 (5)	0.008 (4)	0.025 (4)	−0.001 (4)
C12	0.067 (5)	0.056 (5)	0.050 (4)	0.012 (4)	0.019 (4)	0.013 (4)
C13	0.058 (4)	0.059 (5)	0.041 (4)	−0.006 (4)	0.022 (3)	0.001 (3)
C14	0.080 (6)	0.067 (5)	0.112 (7)	−0.016 (5)	0.062 (5)	−0.017 (5)
C15	0.079 (6)	0.094 (7)	0.138 (8)	−0.013 (6)	0.071 (6)	−0.018 (7)
C16	0.063 (5)	0.077 (6)	0.058 (5)	0.010 (5)	0.025 (4)	−0.006 (4)
C17	0.088 (6)	0.068 (6)	0.087 (6)	−0.011 (5)	0.044 (5)	−0.016 (5)
C18	0.077 (5)	0.067 (5)	0.085 (6)	−0.007 (5)	0.048 (5)	−0.008 (4)
Cl1	0.0733 (12)	0.0662 (12)	0.0739 (13)	−0.0075 (10)	0.0442 (10)	0.0113 (10)
Cl2	0.0704 (12)	0.0661 (12)	0.0652 (11)	−0.0121 (10)	0.0390 (10)	0.0037 (10)
Br1	0.0780 (6)	0.0830 (6)	0.0792 (6)	0.0122 (5)	0.0160 (5)	0.0039 (5)
Br2	0.1167 (7)	0.0916 (7)	0.0552 (5)	−0.0110 (6)	0.0218 (5)	−0.0049 (5)
Br3	0.1026 (7)	0.0967 (7)	0.1100 (8)	0.0208 (6)	0.0453 (6)	−0.0252 (6)

Geometric parameters (Å, º) top

Sb1—C1	2.129 (6)	C8—H8	0.9300
Sb1—C7	2.119 (6)	C9—C10	1.377 (10)
Sb1—C13	2.132 (7)	C9—H9	0.9300
Sb1—Cl1	2.4566 (16)	C10—C11	1.388 (9)
Sb1—Cl2	2.4716 (17)	C10—Br2	1.893 (7)
C1—C6	1.373 (8)	C11—C12	1.372 (9)
C1—C2	1.384 (8)	C11—H11	0.9300
C2—C3	1.385 (9)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.357 (8)
C3—C4	1.363 (9)	C13—C18	1.380 (9)
C3—H3	0.9300	C14—C15	1.371 (10)
C4—C5	1.357 (9)	C14—H14	0.9300
C4—Br1	1.904 (7)	C15—C16	1.351 (10)
C5—C6	1.384 (9)	C15—H15	0.9300
C5—H5	0.9300	C16—C17	1.320 (9)
C6—H6	0.9300	C16—Br3	1.900 (7)
C7—C12	1.366 (9)	C17—C18	1.392 (10)
C7—C8	1.375 (9)	C17—H17	0.9300
C8—C9	1.370 (9)	C18—H18	0.9300

C7—Sb1—C1	123.5 (2)	C9—C8—H8	119.6
C7—Sb1—C13	118.9 (2)	C7—C8—H8	119.6
C1—Sb1—C13	117.6 (2)	C8—C9—C10	118.9 (7)
C7—Sb1—Cl1	88.37 (17)	C8—C9—H9	120.5
C1—Sb1—Cl1	90.64 (18)	C10—C9—H9	120.5
C13—Sb1—Cl1	92.52 (19)	C9—C10—C11	120.2 (7)
C7—Sb1—Cl2	87.45 (17)	C9—C10—Br2	120.6 (6)
C1—Sb1—Cl2	89.71 (17)	C11—C10—Br2	119.2 (6)
C13—Sb1—Cl2	91.56 (19)	C12—C11—C10	119.9 (7)
Cl1—Sb1—Cl2	175.20 (6)	C12—C11—H11	120.0
C6—C1—C2	120.3 (6)	C10—C11—H11	120.0
C6—C1—Sb1	120.6 (5)	C7—C12—C11	119.7 (6)
C2—C1—Sb1	119.2 (5)	C7—C12—H12	120.1
C1—C2—C3	120.1 (6)	C11—C12—H12	120.1
C1—C2—H2	119.9	C14—C13—C18	119.5 (7)
C3—C2—H2	119.9	C14—C13—Sb1	121.7 (6)
C4—C3—C2	118.2 (6)	C18—C13—Sb1	118.8 (5)
C4—C3—H3	120.9	C13—C14—C15	119.3 (7)
C2—C3—H3	120.9	C13—C14—H14	120.3
C5—C4—C3	122.6 (6)	C15—C14—H14	120.3
C5—C4—Br1	118.3 (5)	C16—C15—C14	121.3 (7)
C3—C4—Br1	119.1 (6)	C16—C15—H15	119.4
C4—C5—C6	119.4 (6)	C14—C15—H15	119.4
C4—C5—H5	120.3	C17—C16—C15	120.0 (8)
C6—C5—H5	120.3	C17—C16—Br3	119.7 (7)
C1—C6—C5	119.3 (6)	C15—C16—Br3	120.4 (7)
C1—C6—H6	120.4	C16—C17—C18	120.9 (8)
C5—C6—H6	120.4	C16—C17—H17	119.6
C12—C7—C8	120.3 (6)	C18—C17—H17	119.6
C12—C7—Sb1	120.5 (5)	C13—C18—C17	118.9 (7)
C8—C7—Sb1	119.2 (5)	C13—C18—H18	120.5
C9—C8—C7	120.8 (7)	C17—C18—H18	120.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl2ⁱ	0.93	2.93	3.723 (7)	144
C17—H17···Br1ⁱⁱ	0.93	2.99	3.900 (9)	167

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

Experimental details

Crystal data
Chemical formula	[SbCl₂(C₆H₄Br)₃]
M_r	660.66
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	15.1050 (13), 20.124 (2), 15.1701 (14)
β (°)	117.748 (1)
V (Å³)	4081.0 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	7.49
Crystal size (mm)	0.26 × 0.22 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.246, 0.467
No. of measured, independent and observed [I > 2σ(I)] reflections	10608, 3582, 2159
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.097, 0.91
No. of reflections	3582
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.90, −0.61

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Sb1—C1	2.129 (6)	Sb1—Cl1	2.4566 (16)
Sb1—C7	2.119 (6)	Sb1—Cl2	2.4716 (17)
Sb1—C13	2.132 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl2ⁱ	0.93	2.93	3.723 (7)	143.5
C17—H17···Br1ⁱⁱ	0.93	2.99	3.900 (9)	167.3

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

Acknowledgements

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

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