2,8-Dichloro-6H,12H-5,11-ethano­dibenzo[b,f][1,5]diazo­cine

Masoud Faroughi; Andrew C Try; Peter Turner

doi:10.1107/S1600536807062642

. 2007 Dec 6;64(Pt 1):o39. doi: 10.1107/S1600536807062642

2,8-Dichloro-6H,12H-5,11-ethanodibenzo[b,f][1,5]diazocine

Masoud Faroughi ^a, Andrew C Try ^a,^*, Peter Turner ^b

PMCID: PMC2914998 PMID: 21200913

Abstract

In the molecule of the title compound, C₁₆H₁₄Cl₂N₂, the ethano-strapped 2,8-dichloro analogue of Tröger’s base, the dihedral angle between the two benzene rings is 87.01 (3)°.

Related literature

For related literature, see: Tröger (1887 ▶); Hamada & Mukai (1996 ▶); Ishida et al. (2005 ▶). For related structures, see: Spielman (1935 ▶); Larson & Wilcox (1986 ▶); Solano et al. (2005 ▶); Faroughi et al. (2006a ▶,b ▶); Faroughi, Try, Klepetko & Turner (2007 ▶); Faroughi, Try & Turner (2007 ▶).

Experimental

Crystal data

C₁₆H₁₄Cl₂N₂
M _r = 305.19
Triclinic,
a = 6.8801 (11) Å
b = 10.1951 (17) Å
c = 10.2466 (16) Å
α = 85.320 (3)°
β = 84.956 (2)°
γ = 76.470 (3)°
V = 694.70 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 150 (2) K
0.63 × 0.44 × 0.41 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: Gaussian (XPREP; Coppens et al., 1965 ▶; Siemens, 1995 ▶) T _min = 0.773, T _max = 0.869
6876 measured reflections
3188 independent reflections
2992 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.089
S = 1.06
3188 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Siemens, 1995 ▶); cell refinement: SAINT (Siemens, 1995 ▶); data reduction: SAINT and XPREP (Siemens, 1995 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: Xtal3.6 (Hall et al., 1999 ▶), ORTEPII (Johnson, 1976 ▶) and WinGX (Farrugia, 1999 ▶); software used to prepare material for publication: WinGX.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062642/hk2402sup1.cif

e-64-00o39-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062642/hk2402Isup2.hkl

e-64-00o39-Isup2.hkl^{(156.4KB, hkl)}

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

Acknowledgments

The authors thank the Australian Research Council for a Discovery Project grant to ACT (grant No. DP0345180) and Macquarie University for the award of a Macquarie University Research Development grant.

supplementary crystallographic information

Comment

Tröger's base was first prepared in 1887 (Tröger, 1887) and its structure was elucidated until over 30 years latter (Spielman, 1935). The strucural assignment was confirmed by X-ray crystallography (Larson & Wilcox, 1986). Since then large number of related compounds have been reported and the dihedral angle, between the least-squares planes through the aromatic rings, has been measured across a range of simple dibenzo Tröger's base analogues and found to lie between 82° (Solano et al., 2005) and 108° (Faroughi et al., 2006b). A common structural feature in all of these compounds is the methano-strapped diazocine bridge. The conversion of methano-strapped compounds to ethano-strapped analogues of Tröger's base have been reported for 2,8-dimethyl- and 2,8-dimethoxy- (Hamada & Mukai, 1996) as well as 2,8-dibromo- (Ishida et al., 2005; Faroughi, Try, Klepetko & Turner, 2007) substitution patterns. We have previously reported that the dihedral angle in methano-strapped 2,8-dibromo Tröger's base is 94.5° (Faroughi et al., 2006a) whilst the corresponding angle in the ethano-strapped 2,8-dibromo analogue is 86.1° (Faroughi, Try, Klepetko & Turner, 2007). In the present case, the dihedral angle of ethano-strapped 2,8-dichloro Tröger's base (I), whose molecular structure is shown in Fig. 1, was also found to be reduced [87.01 (3)°] in comparison with the methano-strapped analogue, which has a dihedral angle of 95.6° (Faroughi, Try & Turner et al., 2007).

Experimental

The title compound was prepared according to the literature procedure (Hamada & Mukai, 1996) in 72% yield. Single crystals of (I) were produced from slow evaporation of a dichloromethane solution.