9-[(2-Hy­droxy­benzyl­idene)amino]-11-(2-hy­droxy­phen­yl)-10,13-diphenyl-8-oxa-12-azoniatricyclo­[7.3.1.02,7]trideca-2(7),3,5-triene acetate ethanol disolvate

Le Tuan Anh; Truong Hong Hieu; Anatoly T Soldatenkov; Svetlana A Soldatova; Victor N Khrustalev

doi:10.1107/S160053681100376X

. 2011 Feb 5;67(Pt 3):o560–o561. doi: 10.1107/S160053681100376X

9-[(2-Hydroxybenzylidene)amino]-11-(2-hydroxyphenyl)-10,13-diphenyl-8-oxa-12-azoniatricyclo[7.3.1.0^2,7]trideca-2(7),3,5-triene acetate ethanol disolvate

Le Tuan Anh ^a,^*, Truong Hong Hieu ^b, Anatoly T Soldatenkov ^b, Svetlana A Soldatova ^b, Victor N Khrustalev ^c

PMCID: PMC3052148 PMID: 21522325

Abstract

The title compound, C₃₆H₃₁N₂O₃ ⁺,C₂H₃O₂ ⁻·2C₂H₅OH, the product of a domino condensation of dibenzyl ketone with salicylic aldehyde and ammonium acetate, crystallized as the ethanol disolvate. The cation of the salt comprises a fused tricyclic system containing three six-membered rings (piperidine, dihydro-2H-pyran and benzene). The piperidine ring has the usual chair conformation, while the dihydropyran ring adopts a slightly distorted sofa conformation. In the crystal, there are six (one intra- and five intermolecular) independent hydrogen-bonding interactions: the intermolecular hydrogen bonds link the cations and anions and ethanol solvent molecules into ribbons along [001]. The ribbons are stacked along the a axis.

Related literature

For general background to the method proposed by our group for obtaining 2-oxa-6-azabenzobicyclononanes using commercially available dibenzyl ketone, salicylic aldehyde and ammonium acetate as starting materials, see: Baliah et al. (1983 ▶); Soldatenkov et al. (1996 ▶); Le Tuan Anh et al. (2008 ▶). For related compounds, see: Soldatenkov et al. (2002 ▶, 2010 ▶).

Experimental

Crystal data

C₃₆H₃₁N₂O₃ ⁺·C₂H₃O₂ ⁻·2C₂H₆O
M _r = 690.81
Monoclinic,
a = 13.5464 (10) Å
b = 20.1124 (15) Å
c = 14.2535 (11) Å
β = 105.118 (2)°
V = 3749.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.28 × 0.15 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.977, T _max = 0.989
35569 measured reflections
7399 independent reflections
4951 reflections with I > 2σ(I)
R _int = 0.062

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.107
S = 1.01
7399 reflections
463 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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 datablocks global, I. DOI: 10.1107/S160053681100376X/rk2264sup1.cif

e-67-0o560-sup1.cif^{(31.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100376X/rk2264Isup2.hkl

e-67-0o560-Isup2.hkl^{(362KB, hkl)}

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
O1—H1O⋯N1	0.94	1.73	2.608 (2)	154
O2—H2O⋯O3ⁱ	0.97	1.67	2.637 (2)	177
O5—H5O⋯O6ⁱⁱ	0.97	1.69	2.651 (2)	174
O6—H6O⋯O4	0.98	1.65	2.617 (2)	173
N12—H12A⋯O3	0.93	1.77	2.697 (2)	172
N12—H12B⋯O5	0.94	1.77	2.709 (2)	173

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

supplementary crystallographic information

Comment

Recently our group has found an efficient method of the one-step synthesis of potentially bioactive substances having oxazocine skeletal structure. These molecules are formed by domino condensation from commercially available dibenzyl ketone, salicylic aldehyde and ammonium acetate as starting materials (Soldatenkov et al., 2010). The key step of this condensation is Petrenko–Kritchenko reaction (Baliah et al., 1983) leading to the formation of the substituted γ-piperidone (Le Tuan Anh et al., 2008), which then reacts with the excess of ammonium acetate and aldehyde. This work reports the structural characterization of a product of such reaction - 2-oxa-6-aza-3,4-benzobicyclo[3.3.1^1,5]nonan-6-ium acetate (I).

Compound I crystallizes as diethanol solvate, i.e., C₃₈H₃₄N₂O₅^.2(C₂H₆O). The cation of the salt I comprises a fused tricyclic system containing three six-membered rings (piperidine, dihydro-2H-pyran and benzene) (Fig. 1). The piperidine ring has the usual chair conformation, while the dihydropyran ring adopts the slightly distorted sofa conformation (the C13 carbon atom deviates from the plane passed through the other atoms of the ring by 0.691 (2) Å). The phenyl substituents at the C10 and C11 carbon atoms occupy the sterically favorable equatorial positions, whereas the phenyl substituent at the C13 carbon atom is axially disposed.

The cation of I possesses four asymmetric centers at the C1, C10, C11, and C13 carbon atoms and can have potentially numerous diastereomers. The crystal of I is racemic and consists of enantiomeric pairs with the following relative configuration of the centers: rac-1S*,10R*,11S*, 13S*.

In the crystal, there are six (one intra- and five intermolecular) independent hydrogen bonding interactions (Table 1). The intermolecular hydrogen bonds link the cations and anions of I and ethanol solvate molecules into ribbons along the direction [0 0 1] (Fig. 2). The crystal packing of the ribbons is stacked along the a axis.

Experimental

Ammonium acetate (4.0 g, 52 mmol) was added to a solution of dibenzyl ketone (2.1 g, 10 mmol) and salicylic aldehyde (3.66 g, 30 mmol) in ethanol (50 ml) (Fig. 3). The reaction mixture was stirred for 96 h at 293 K (monitoring by TLC until disappearance of the starting ketone spot). At the end of the reaction, the formed precipitate was filtered off, one half of the mother liquid solvent removed under reduced pressure and the residue was cooled to give 1.45 g of light-yellow crystals of I. Yield is 21%. M.p. = 451–453 K. IR (KBr), ν/cm^-1: 1623, 1748, 3405, 3460. ¹H NMR (DMSO-d₆, 400 MHz, 300 K): δ = 1.08 (t, 6H, CH₃CH₂O, J = 6.8), 3.30 (s, 3H, CH₃CO), 3.47 (q, 4H, CH₃CH₂O, J = 6.8), 3.77 (d, 1H, H8, J_7.8 = 9.0), 4.23 (d, 1H, H9, J_5,9 = 1.5), 4.32 (d, 1H, H7, J_7,8= 9.0), 4.41 (br, 4H, 2(Alk)OH, ⁺NH₂), 4.48 (d, 1H, H5, J_5,9 = 1.5), 6.41–7.50 (br m, 22H, H_arom), 7.94 (s, 1H, N=CH), 10.63 (br, 1H, (Ar)OH), 12.48 (s, 1H, (Ar)OH). Anal. Calcd. for C₄₂H₄₆N₂O₇: C, 73.04; H, 6.67; N, 4.06. Found: C, 73.13; H, 6.79; N, 4.23.