12-Chloro-6-cyclo­hexyl-5,6,7,12-tetra­hydro­dibenzo[c,f][1,5]aza­stibocine

Weiguo Yi; Nianyuan Tan

doi:10.1107/S1600536811021477

. 2011 Jun 11;67(Pt 7):m917. doi: 10.1107/S1600536811021477

12-Chloro-6-cyclohexyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine

Weiguo Yi ^a,^*, Nianyuan Tan ^b,^*

PMCID: PMC3151782 PMID: 21836902

Abstract

In the title organometallic complex, [Sb(C₂₀H₂₃N)Cl], the central antimony-containing part of the complex exhibits a pseudo-trigonal-bipyramidal geometry, where two C atoms and a lone electron pair of the Sb atom exist at the equatorial positions, while the N and Cl atoms are located at the apical positions, and a transannular interaction exists between the Sb and N atoms on 1,5-azastibocine. Intermolecular C—H⋯Cl hydrogen bonds are also observed.

Related literature

For general background, see: Yin et al. (2008 ▶); Chovancová et al. (2009 ▶); Opris et al. (2009 ▶); Svoboda et al. (2010 ▶); Tan & Zhang (2011 ▶). For related structures, see: Kakusawa et al. (2006 ▶); Xia et al. (2010 ▶).

Experimental

Crystal data

[Sb(C₂₀H₂₃N)Cl]
M _r = 434.59
Monoclinic,
a = 10.0771 (7) Å
b = 16.2881 (12) Å
c = 12.2040 (9) Å
β = 111.812 (1)°
V = 1859.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.63 mm⁻¹
T = 293 K
0.37 × 0.35 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1999 ▶) T _min = 0.653, T _max = 1.000
10058 measured reflections
3644 independent reflections
3107 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.092
S = 1.05
3644 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811021477/vm2099sup1.cif

e-67-0m917-sup1.cif^{(21KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021477/vm2099Isup2.hkl

e-67-0m917-Isup2.hkl^{(178.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811021477/vm2099Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯Cl1ⁱ	0.97	2.80	3.695 (4)	154

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the NSFC for financial support (grant No. 21003040).

supplementary crystallographic information

Comment

The chemistry of hypervalent compounds bearing heavier pnictogens (in particular Sb, Bi) has been studied intensively in recent years (Yin et al., 2008; Chovancová et al., 2009; Svoboda et al., 2010; Tan & Zhang, 2011). Intramolecular interactions between antimony and sp³-nitrogen atoms have been widely reported (Kakusawa et al., 2006; Opris et al., 2009; Xia et al., 2010). Here, we reported the crystal structure of the title organometallic complex (Fig. 1). The central antimony-containing part of the complex shows a distorted pseudo trigonal-bipyramidal structure. The C1, C8 atoms along with a lone electron pair of the Sb atom exist at the equatorial positions while the N1 and Cl1 atoms are located at the apical positions. The Sb–C1 and Sb–C8 distance is 2.144 (4) Å and 2.134 (3) Å, respectively. The C1–Sb–C8 angle is 98.17 (12)°, while the N1–Sb–Cl1 angle is 162.92 (7)° (rather than 180°). The Sb–N1 distance (2.397 (3) Å) is shorter than the sum of the van der Waals radii of nitrogen and antimony atoms (3.74 Å) (Kakusawa et al., 2006), indicating that coordination exists between the two atoms. The complex also displays intermolecular hydrogen-bonding interaction between the CH₂ groups and chlorine atom Cl1 (Table 1).

Experimental

N,N-bis(2-bromobenzyl)cyclohexanamine (2.186 g, 5.0 mmol) was allowed to react with n-BuLi (2.5 M, 4.0 ml, 10 mmol) at -50 ^oC, and the resulting solution was added to a mixture of SbCl₃ (1.141 g, 5.0 mmol) in Et₂O (80 ml) at -78 ^oC. The obtained mixture was gradually warmed to room temperature and stirred for 12 h. Then the solvent was removed under vacuum and the residue was extracted with toluene, and the insoluble material was removed by filtration. The organic layer was washed with de-ionized H₂O and dried over anhydrous Na₂SO₄. After the solvent was removed under reduced pressure, the residue was recrystallized from CH₂Cl₂/hexane to obtain the title compound in the form of colorless crystals.