Triethyl­ammonium [2-eth­oxy­carbonyl-2-(2-methyl­benz­yl)-6,9-dinitro-3-oxo­bicyclo­[3.3.1]non-6-en-8-yl­idene]azinate

Vaduganathan Manickkam; Doraisamyraja Kalaivani; S Rajeswari

doi:10.1107/S1600536811018095

. 2011 May 20;67(Pt 6):o1469. doi: 10.1107/S1600536811018095

Triethylammonium [2-ethoxycarbonyl-2-(2-methylbenzyl)-6,9-dinitro-3-oxobicyclo[3.3.1]non-6-en-8-ylidene]azinate

Vaduganathan Manickkam ^a, Doraisamyraja Kalaivani ^a,^*, S Rajeswari ^b

PMCID: PMC3120539 PMID: 21754840

Abstract

In the title salt, C₆H₁₆N⁺·C₂₀H₂₀N₃O₉ ⁻, the cations and anions are connected by N—H⋯O hydrogen bonds. The structure is consolidated by weak C—H⋯O interactions.

Related literature

For general background to adducts containing a bicyclic [3.3.1]nonane skeleton and the synthesis of closely related compounds, see: Gnanadoss & Kalaivani (1985 ▶). For related structures, see: Balasubramani et al. (2011 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₆H₁₆N⁺·C₂₀H₂₀N₃O₉ ⁻
M _r = 548.59
Triclinic,
a = 8.2820 (3) Å
b = 10.9776 (4) Å
c = 15.9881 (6) Å
α = 97.103 (2)°
β = 100.991 (5)°
γ = 93.283 (2)°
V = 1411.08 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.971, T _max = 0.981
25290 measured reflections
4754 independent reflections
3459 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.197
S = 1.07
4754 reflections
361 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SIR92 (Altomare et al., 1993) ▶; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811018095/pv2406sup1.cif

e-67-o1469-sup1.cif^{(26.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018095/pv2406Isup2.hkl

e-67-o1469-Isup2.hkl^{(232.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811018095/pv2406Isup3.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
N4—H1A⋯O4ⁱ	0.97 (4)	1.78 (4)	2.740 (3)	168 (3)
C17—H17A⋯O7ⁱⁱ	0.96	2.55	3.434 (5)	154

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

Acknowledgments

The authors thank the SAIF, IIT Madras, for the data collection.

supplementary crystallographic information

Comment

A series of adducts containing bicycle [3.3.1]nonane skeleton, closely related to the title molecule, has been synthesized in our laboratory (Gnanadoss & Kalaivani, 1985). We have recently reported the structures of two such bicyclic molecules derived from 1,3,5-trinitrobenzene, ethyl 2-benzyl-3-oxobutanoate / ethyl 2(4-nitrophenylmethyl)-3-oxobutanoate and triethylamine (Balasubramani et al., 2011). In this article we report the crystal structure of the title compound (Fig. 1) which is a bicyclic adduct derived from 1,3,5-trinitrobenzene, ethyl 2(2-methylphenylmethyl)-3-oxobutanoate and triethylamine. The values of puckering parameters (Cremer & Pople, 1975) of the six membered ring (C1/C2/C3/C4/C5/C9) atoms: Q = 0.501 (3) Å, θ = 52.6 (3)° and φ = 304.1 (4)°, imply that this ring has slightly distorted chair conformation. The puckering parameters of another six membered ring (C1/C8/C7/C6/C5/C9) with values, Q = 0.604 (3) Å, θ = 170.5 (3)° and φ = 119.4 (16)°, indicated that it has slightly distorted envelope conformation. The hydrogen bonding observed between the N–H group of triethylammonium cation and oxygen atom of the nitronate ion (Tab. 1 & Fig. 2) may probably be the driving force for the extraordinary stability of the adduct.

Experimental

A saturated ethanolic solution of 1,3,5-trinitrobenzene (2.1 g, 0.01 mol) was mixed with a saturated ethanolic solution of ethyl 2(2-methylphenylmethyl)-3-oxobutanoate (2.3 g, 0.01 mol). To this mixture triethylamine (6 ml) was added and shaken well for about two hours. The resulting maroon red coloured solution was kept as such for twenty four hours till the colour changed from maroon red to orange red. The orange solution was distilled under reduced pressure to get a viscous mass which was washed repeatedly with 100 ml of dry ether and redissolved in absolute alcohol (20 ml). To the alcoholic solution, 200 ml of dry ether was added and refrigerated between 273 - 283 K for 6 h to get the red orange crystals of the title compound (yield 60%). Single crystals were obtained from ethanol at room temperature by slow evaporation (m.p. 409 (2) K).