6H,12H-5,11-Ethano­dibenzo[b,f][1,5]diazo­cine

Masoud Faroughi; Andrew C Try; Peter Turner

doi:10.1107/S1600536808000883

. 2008 Jan 16;64(Pt 2):o458. doi: 10.1107/S1600536808000883

6H,12H-5,11-Ethanodibenzo[b,f][1,5]diazocine

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

PMCID: PMC2960262 PMID: 21201485

Abstract

In the molecule of the title compound, C₁₆H₁₆N₂, the ethano-strapped analogue of unsubstituted Tröger’s base, the dihedral angle between the two benzene rings is 75.85 (4)°, the smallest angle measured for an ethano-strapped analogue.

Related literature

For related literature, see: Hamada & Mukai (1996 ▶); Ishida et al. (2005 ▶); Solano et al. (2005 ▶); Faroughi et al. (2006a ▶,b ▶); Faroughi, Try & Turner (2007 ▶); Faroughi, Jensen & Try (2007 ▶). For related structures, see: Faroughi, Try, Klepetko et al. (2007 ▶); Faroughi et al. (2008 ▶).

Experimental

Crystal data

C₁₆H₁₆N₂
M _r = 236.31
Orthorhombic,
a = 11.717 (2) Å
b = 8.907 (2) Å
c = 22.829 (4) Å
V = 2382.5 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 150 (2) K
0.43 × 0.42 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: Gaussian (Coppens et al., 1965 ▶) and XPREP (Siemens, 1995 ▶) T _min = 0.968, T _max = 0.990
21723 measured reflections
2913 independent reflections
2398 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.099
S = 1.03
2913 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.20 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, 2008 ▶); molecular graphics: TEXSAN (Molecular Structure Corporation, 1998 ▶), 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/S1600536808000883/tk2243sup1.cif

e-64-0o458-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000883/tk2243Isup2.hkl

e-64-0o458-Isup2.hkl^{(143.1KB, 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 compounds related to the title compound, (I), Fig. 1, are formed from an acid catalysed condensation of anilines, or a range of other amino aromatics, with either formaldehyde or formaldehyde equivalents. The compounds are characterized by the presence of a methano-strapped diazocine ring that is fused to two aromatic rings and this strapped ring system imparts a V-shaped structure on the compounds. The dihedral angle between the aromatic rings has been measured for over 20 simple dibenzo Tröger's base analogues and has been found to lie between 82° (Solano et al., 2005) and 108° (Faroughi et al., 2006b). It has been shown that reaction of 1,2-dibromoethane with several Tröger's base compounds affords ethano-straped analogues (Hamada & Mukai, 1996; Ishida et al., 2005; Faroughi et al., 2007a; Faroughi et al., 2008), as outlined in Fig. 2. The structure of (I) is the third reported structure of an ethano-strapped analogue of Tröger's base. All three structures support the results of molecular modelling studies, which predict that the ethano-strapped analogues should have smaller dihedral angles in comparison with their methano-strapped precursors. The size of the angle for the methano-strapped structures (2,8-dibromo, 2,8-dichloro and unsubstituted, respectively) are as follows: 95° (Faroughi et al., 2006a), 96° (Faroughi et al., 2007b) and 95° (Faroughi, Jensen & Try, 2007), whilst the corresponding values for the ethano-strapped structures are 86° (Faroughi et al., 2007a), 87° (Faroughi et al., 2008) and, for the subject of this report, (I) 76°.

Experimental

The title compound was prepared according to the literature procedure (Hamada & Mukai, 1996) in 37% yield. Single crystals were produced from slow evaporation of a dichloromethane solution of (I).