6-Phenyl-6,7-dihydro­dibenzo[c,f][1,5]aza­bis­mocin-12(5H)-yl perchlorate

Xiao-Wen Zhang; Ting Fan

doi:10.1107/S1600536811021039

. 2011 Jun 11;67(Pt 7):m875. doi: 10.1107/S1600536811021039

6-Phenyl-6,7-dihydrodibenzo[c,f][1,5]azabismocin-12(5H)-yl perchlorate

Xiao-Wen Zhang ^a,^*, Ting Fan ^b

PMCID: PMC3151844 PMID: 21836870

Abstract

In the title compound, [Bi(C₂₀H₁₇N)(ClO₄)] or C₂₀H₁₇BiClNO₄, the Bi^III ion assumes a distorted ψ trigonal–bipyramidal geometry, with two C atoms and the electron lone pair of the Bi atom at the equatorial positions and an amine N atom and a perchlorate O atom at the apical positions. Weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For the synthesis of 12-chloro-6-phenyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azabismocine, see: Zhang et al. (2009 ▶). For general background, see: Shimada et al. (2004 ▶); Yin et al. (2008 ▶); Zhang et al. (2010 ▶); Tan & Zhang (2011 ▶). For related structures, see: Ohkata et al. (1989 ▶); Minoura et al. (1999 ▶).

Experimental

Crystal data

[Bi(C₂₀H₁₇N)(ClO₄)]
M _r = 579.78
Monoclinic,
a = 12.0635 (10) Å
b = 14.0755 (12) Å
c = 11.5121 (10) Å
β = 107.590 (2)°
V = 1863.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 9.63 mm⁻¹
T = 293 K
0.32 × 0.21 × 0.20 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan(SADABS; Bruker, 2001 ▶) T _min = 0.100, T _max = 0.145
9267 measured reflections
3279 independent reflections
2585 reflections with I > 2σ(I)
R _int = 0.166

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.163
S = 1.02
3279 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 4.89 e Å⁻³
Δρ_min = −4.14 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811021039/xu5208sup1.cif

e-67-0m875-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021039/xu5208Isup2.hkl

e-67-0m875-Isup2.hkl^{(157.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811021039/xu5208Isup3.cml

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

Table 1. Selected bond lengths (Å).

Bi—N1	2.387 (10)
Bi—O1	2.546 (10)
Bi—C1	2.245 (13)
Bi—C8	2.204 (12)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O3ⁱ	0.93	2.46	3.137 (17)	130
C14—H14B⋯O2ⁱⁱ	0.97	2.55	3.398 (16)	146

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors acknowledge the National Science Foundation of China (grant No. 51074093) for supporting this work.

supplementary crystallographic information

Comment

Bismuth is a nontoxic and noncarcinogenic element and many of its compounds are low in toxicity and can be safely used in areas such as medicine, catalysis, and synthesis (Shimada et al., 2004; Yin et al., 2008; Zhang, Qiu, Tan et al., 2010). The 5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine framework is highly stable as a organobismuth Fragment because the weakly coordination exists between bismuth and nitrogen atoms on 1,5-azabismocine (Ohkata et al.,1989; Minoura et al.,1999), and therefore, is suitable for the study of organobismuth compounds bearing various groups on the bismuth and nitrogen atom for potential uses.

In the present paper, we report the crystal structure of the title compound (Fig. 1). The central bismuth–containing part of the complex exhibits a distorted pseudo trigonal–bipyramidal structure. The C (8), C (1) atoms and a lone electron pair of the Bi atom exist at the equatorial positions while the N (1) and O (1) atoms are located at the apical positions. The Bi–C (8) and Bi–C (1) distance is 2.250 (13) Å and 2.204 (12) Å, respectively. The C (8)–Bi–C (1) angle is 92.5 (5) ° while the N (1)–Bi–O (1) angle is 154.0 (3)°(rather than 180°). The Bi–N (1) distance (2.388 (10) Å) is shorter than 2.607 (5) Å of the precursor, C₆H₅N(CH₂C₆H₄)₂BiCl.The Bi–O (1) distance(2.546 (10) Å) is shorter than Bi–Cl(1) distance 2.597 (19) Å also(Zhang, Xia, Yan et al., 2009).

Experimental

The following procedures are recommended for synthesis of the title compound (I): 12-chloro-6-phenyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azabismocine (0.516 g, 1.0 mmol) was dissolved in 15 ml THF, then a solution of AgClO₄(0.207 g, 1.0 mmol) in 15.0 ml THF was added. After the mixture was stirred in the dark at room temperature for 2 h, it was filtered. The filtrate mixed with 1.0 ml hexane was refrigerated for 24 h, giving colorless crystals (0.539 g, 93.0%).