1-[(Z)-1-Bromo-2-(butyl­dichloro-λ4-tellan­yl)ethen­yl]cyclo­hex-1-ene

Julio Zukerman-Schpector; Ignez Caracelli; Rafael Carlos Guadagnin; Hélio A Stefani; Edward R T Tiekink

doi:10.1107/S1600536811023142

. 2011 Jun 18;67(Pt 7):o1751–o1752. doi: 10.1107/S1600536811023142

1-[(Z)-1-Bromo-2-(butyldichloro-λ⁴-tellanyl)ethenyl]cyclohex-1-ene

Julio Zukerman-Schpector ^a,^*, Ignez Caracelli ^b, Rafael Carlos Guadagnin ^c, Hélio A Stefani ^d, Edward R T Tiekink ^e

PMCID: PMC3151772 PMID: 21837135

Abstract

The Te^IV atom in the title compound, [Te(C₄H₉)(C₈H₁₀Br)Cl₂] or C₁₂H₁₉BrCl₂Te, is in a distorted ψ-trigonal–bipyramidal geometry, with the lone pair of electrons projected to occupy a position in the equatorial plane, and with the Cl atoms being mutually trans [172.48 (4)°]. Close intramolecular [Te⋯Br = 3.3444 (18) Å] and intermolecular [Te⋯Cl = 3.675 (3) Å] interactions are observed. The latter lead to centrosymmetric dimers which assemble into layers in the bc plane. The primary connections between layers are of the type C—H⋯Cl.

Related literature

For background to the synthesis, see: Guadagnin et al. (2008 ▶). For related X-ray structures, see: Zukerman-Schpector et al. (1998 ▶, 2008 ▶). For coordination polyhedra around Te^IV atoms, see: Zukerman-Schpector & Haiduc (2002 ▶); Tiekink & Zukerman-Schpector (2010 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₂H₁₉BrCl₂Te
M _r = 441.67
Triclinic,
a = 6.311 (3) Å
b = 10.243 (6) Å
c = 12.334 (9) Å
α = 103.34 (2)°
β = 91.53 (2)°
γ = 91.411 (14)°
V = 775.1 (8) Å³
Z = 2
Mo Kα radiation
μ = 4.82 mm⁻¹
T = 98 K
0.22 × 0.20 × 0.15 mm

Data collection

Rigaku Saturn724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.360, T _max = 0.486
7151 measured reflections
3012 independent reflections
2898 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.086
S = 1.12
3012 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: MarvinSketch (Chemaxon, 2010 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811023142/hg5055sup1.cif

e-67-o1751-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023142/hg5055Isup2.hkl

e-67-o1751-Isup2.hkl^{(144.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811023142/hg5055Isup3.cml

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

Table 1. Selected geometric parameters (Å, °).

Te—Cl1	2.5381 (15)
Te—Cl2	2.4859 (15)
Te—C1	2.092 (4)
Te—C3	2.143 (4)

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Cl1—Te—Cl2

172.48 (4)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3a⋯Cl2ⁱ	0.97	2.80	3.576 (5)	138

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the Brazilian agencies FAPESP (07/59404–2 to HAS), CNPq (306532/2009–3 to JZ-S, 308116/2010–0 to IC) and CAPES (808/2009 to JZ-S and IC) for financial support.

supplementary crystallographic information

Comment

The title compound, (I), was synthesized using a palladium-catalyzed cross-coupling reaction of a potassium aryltrifluoroborate salt with various (Z)-2-chloro vinylic tellurides (Guadagnin et al., 2008). Complementing these studies are crystallographic studies (Zukerman-Schpector et al. 1998; Zukerman-Schpector et al., 2008) focused upon determining coordination polyhedra and supramolecular aggregation patterns (Zukerman-Schpector & Haiduc, 2002; Tiekink & Zukerman-Schpector, 2010) which lead to the crystallographic characterization of (I).

The immediate coordination geometry about the Te^IV atom in (I) is defined by two Cl atoms and two C atoms which, along with a stereochemically active lone pair of electrons, define a ψ-trigonal bi-pyramidal geometry, Table 1. In this description the lone pair is assumed to occupy a position in the equatorial plane, and the Cl atoms to be mutually trans. Additional Te···X interactions are evident and contribute to the distortion of the coordination geometry. Thus, an intramolecular Te···Br interaction [3.3444 (18) Å] is noted. In addition, there is an intermolecular Te···Cl contact [Te···Cl1ⁱ = 3.675 (3) Å, symmetry operation i: 1 - x, 1 - y, 1 - z]. The latter interaction explains the elongation of the Te—Cl1 bond compared to the Te—Cl2 bond, Table 1. Within the substituted ligand, the configuration about the C1═C2 bond [1.327 (6) Å] is Z. The cyclohexene ring adopts a half-chair conformation with puckering parameters: q₂ = 0.364 (5) Å and q₃ = -0.278 (5) Å, and amplitudes: Q = 0.458 (6) Å, θ = 127.4 (6) ° and φ₂ = 30.2 (8) ° (Cremer & Pople, 1975).

The most prominent feature of the crystal packing are the aforementioned Te···Cl1 interactions. These lead to centrosymmetric dimers that assemble into chains along the b axis. These partially inter-digitate along the c axis. The layers thus formed in the bc plane, Fig. 2, are connected via C—H···Cl interactions, Table 2, along the a axis, Fig. 3.

Experimental

The starting (Z)-(2-bromo-2-cyclohexenylvinyl)(butyl)tellane was prepared as described in previous work (Guadagnin et al., 2008) and a solution of it (1 mmol, 0.370 g) in hexane (5 ml) at 273 K was poured into a two-necked round-bottomed flask under a nitrogen atmosphere and then SO₂Cl₂ (1 mmol, 1.37 g) added drop wise. A white solid formed immediately. The mixture was warmed to room temperature. The resulting solid was filtered and dried. Crystals of (I) were obatined by slow evaporation from its CHCl₃ solution held at room temperature.