2,4,6,8-Tetra­kis(4-bromo­phen­yl)-3,7-diaza­bicyclo­[3.3.1]nonan-9-one

Wan-Sin Loh; Hoong-Kun Fun; S Sarveswari; V Vijayakumar; B Palakshi Reddy

doi:10.1107/S1600536809055226

. 2010 Jan 9;66(Pt 2):o265–o266. doi: 10.1107/S1600536809055226

2,4,6,8-Tetrakis(4-bromophenyl)-3,7-diazabicyclo[3.3.1]nonan-9-one

Wan-Sin Loh ^a,^‡, Hoong-Kun Fun ^a,^*,^§, S Sarveswari ^b, V Vijayakumar ^b, B Palakshi Reddy ^b

PMCID: PMC2979866 PMID: 21579706

Abstract

In the title compound, C₃₁H₂₄Br₄N₂O, one of the bromophenyl rings is disordered over two orientations with occupancies of 0.69 (2) and 0.31 (2). The bicyclo[3.3.1]nonane ring system adopts a chair–boat conformation. In the crystal structure, molecules are linked into chains along the c axis by intermolecular C—H⋯O and N—H⋯O hydrogen bonds. Further stabilization is provided by C—H⋯π interactions.

Related literature

For applications of bicyclo[3.3.1]nonane derivatives, see: Arias-Perez et al. (1997 ▶). For applications of N,N-diphenyl derivatives, see: Srikrishna & Vijayakumar (1998 ▶); Chinar Pathak et al. (2007 ▶). For bicyclic systems with aryl groups, see: Vijayakumar et al. (2000 ▶). For a related structure: see: Fun et al. (2009 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₃₁H₂₄Br₄N₂O
M _r = 760.16
Monoclinic,
a = 14.7409 (5) Å
b = 27.7762 (10) Å
c = 7.1538 (2) Å
β = 101.067 (2)°
V = 2874.62 (16) Å³
Z = 4
Mo Kα radiation
μ = 5.63 mm⁻¹
T = 296 K
0.89 × 0.19 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.082, T _max = 0.614
37831 measured reflections
8336 independent reflections
4019 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.141
S = 1.01
8336 reflections
409 parameters
180 restraints
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809055226/ci2986sup1.cif

e-66-0o265-sup1.cif^{(29.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055226/ci2986Isup2.hkl

e-66-0o265-Isup2.hkl^{(407.8KB, hkl)}

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

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

Cg1, Cg2 and Cg3 are the centroids of the C12A–C17A, C19–C24 and C26–C31 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1ⁱ	0.86	2.58	3.319 (4)	145
C18—H18A⋯O1ⁱⁱ	0.98	2.50	3.294 (5)	138
C5—H5A⋯Cg2	0.93	2.77	3.614 (5)	151
C28—H28A⋯Cg1ⁱ	0.93	2.67	3.433 (9)	140
C31—H31A⋯Cg3ⁱⁱⁱ	0.93	2.80	3.640 (5)	151
C13B—H13B⋯Cg3	0.93	2.76	3.53 (5)	141

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

Acknowledgments

HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). WSL thanks the Malaysian Government and USM for the award of the post of Assistant Research Officer under the Research University Golden Goose Grant (1001/PFIZIK/811012). VV is grateful to the DST-India for funding through the Young Scientist Scheme (Fast Track Proposal).

supplementary crystallographic information

Comment

Bicyclo[3.3.1]nonane moieties are present in many biologically active molecules like alkaloids and drugs (Arias-Perez et al., 1997). Functionalized 3-azabicyclo[3.3.1]nonanes have been studied intensively because of their pharmaceutical use and these compounds find applications as an important class of organic compounds in the field of molecular recognition. The 1,5-diphenyl-3,7-diazabicyclo[3.3.1]nonan-9-ones are local anesthetics. Some of them possess hypotensive activity. N,N-diphenyl derivatives are found to be antichloristic and anti-thrombic (Srikrishna & Vijayakumar, 1998; Chinar Pathak et al., 2007). The synthesis and stereochemistry of 3,7-diazabicyclo[3.3.1]nonan-9-ones and their derivatives are of much interest due to their diverse biological activities, such as antibacterial, antifungal, anti-arrhythmic, antiphologistic, antithrombic, calcium antagonistic, hypotensive and neuroleptic and also because of their presence in naturally occurring lupin alkaloids. The conformational analysis of 3,7-diazabicyclo[3.3.1]nonanes (bispidines) is of considerable interest both from the theoretical view point and due to their biological activity. In recent years the 2,4,6,8-tetraaryl-3,7-diazabicyclo[3.3.1]nonanes constitutes an interesting case for the study because of the presence of four aryl groups. If all the aryls are in equatorial orientations, molecular models indicate close proximity of the aryls in both rings in the bicyclic systems (Vijayakumar et al., 2000).

The bicyclo[3.3.1]nonane ring system (O1/N1/N2/C7–C11/C18/C25) adopts a chair-boat conformation with puckering parameter Q = 0.770 (4) Å, Θ = 91.8 (3)° and φ = 2.2 (3)° for one of the piperidine rings (N1/C7–C11) and Q = 0.640 (4) Å, Θ = 0.0 (4)° and φ = 139 (12)° for the other piperidine ring (N2/C8–C10/C18/C25) (Cremer & Pople, 1975). The N atoms adopt a pyramidal configuration. The phenyl rings substituted at C7 (C1–C6) and C11 [C12A–C17A (major component) and C12B–C17B (minor component)] positions are oriented with one another with an angle of 40.0 (7)° [41.2 (18)° in the minor component]. The phenyl rings substituted at C18 (C19–C24) and C25 (C26–C31) form a dihedral angle of 31.3 (2)°. Two bromophenyl groups substituted at C7 and C11 are in equatorial orientations with torsion angles C6—C7—C8—C9 = 123.3 (3)°, C9—C10—C11—C12A = -112.7 (7)° for major component and C9—C10—C11—C12B = -125.5 (19)° for minor component. The other two bromophenyl groups substituted at C18 and C25 have torsion angles of C9—C8—C18—C19 = -175.2 (3)° and C9—C10—C25—C26 = 176.6 (3)°. Bond lengths (Allen et al., 1987) and angles are within the normal range and are comparable to a closely related structure (Fun et al., 2009).

In the crystal structure (Fig. 2), intermolecular C18—H18A···O1 and N2—H1N2···O1 hydrogen bonds link the molecules into chains along c axis. The structure is further stabilized by C—H···π interactions (Table 1).

Experimental

0.4 ml of acetone, 3.70 g of 4-bromobenzaldehyde and 0.7708 g of dry ammonium acetate were taken in a 1:4:2 molar ratio in ethanol and the mixture was heated on a water bath till it changes to red orange colour. The mixture was allowed to stand until a solid appears. The solid product was washed with ether and ethanol (1:1) until the disappearance of yellow colour. The separated solid was filtered off and recrystallized from chloroform-benzene mixture. The purity of the compound was checked by TLC and melting point recorded (yield: 57%, m. p. 511 K).