DSpace at VNU: 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

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 disol

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,a* Truong Hong Hieu,bAnatoly T

Soldatenkov,bSvetlana A Soldatovaband Victor N

Khrustalevc

a

Department of Chemistry, Vietnam National University, 144 Xuan Thuy, Cau Giay,

Hanoi, Vietnam,bOrganic Chemistry Department, Russian Peoples Friendship

University, Miklukho-Maklaya St 6, Moscow 117198, Russian Federation, and

c

X-Ray Structural Centre, A N Nesmeyanov Institute of Organoelement

Compounds, Russian Academy of Sciences, 28 Vavilov St, B-334, Moscow 119991,

Russian Federation

Correspondence e-mail: vkh@xray.ineos.ac.ru

Received 27 January 2011; accepted 29 January 2011

Key indicators: single-crystal X-ray study; T = 100 K; mean (C–C) = 0.003 A ˚;

R factor = 0.044; wR factor = 0.107; data-to-parameter ratio = 16.0.

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

(piper-idine, 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

C 36 H 31 N 2 O 3+C 2 H 3 O 2



2C 2 H 6 O

M r = 690.81 Monoclinic, P21=c

a = 13.5464 (10) A˚

b = 20.1124 (15) A˚

c = 14.2535 (11) A˚

 = 105.118 (2) 

V = 3749.0 (5) A˚3

Z = 4

Mo K radiation

 = 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 > 2(I)

Rint= 0.062

Refinement R[F 2 > 2(F 2 )] = 0.044 wR(F 2 ) = 0.107

S = 1.01

7399 reflections

463 parameters H-atom parameters constrained

 max = 0.23 e A˚3

min= 0.24 e A˚3

Table 1

Hydrogen-bond geometry (A˚ ,)

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  O6 ii

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

Symmetry codes: (i) x þ 1; y þ 1; z; (ii) x þ 1; y þ 1; z þ 1.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; soft-ware used to prepare material for publication: SHELXTL

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2264)

Structure Reports

Online

ISSN 1600-5368

Baliah, V., Jeyaraman, R & Chandrasekaran, L (1983) Chem Rev 83, 379–

423.

Bruker (2001) SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2005) APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.

Le Tuan Anh, Soldatenkov, A T., Truong Hong Hieu, Soldatova, S A., Levov,

A N & Polyanskii, K B (2008) Chem Heterocycl Compd, 44, 1527–1531.

Sheldrick, G M (2003) SADABS Bruker AXS Inc., Madison, Wisconsin,

USA.

Soldatenkov, A T., Kuleshova, L N., Mandal, T K., Nesterov, V N., Mamyrbekova, Zh A & Struchkov, Yu T (1996) Chem Heterocycl Compd, 32, 233–237.

Soldatenkov, A T., Polyanskii, K B & Mamyrbekova, Zh A (2002) Russ J Org Chem 38, 480–481.

Soldatenkov, A T., Truong Hong Hieu, Le Tuan Anh, Kolyadina, N M & Soldatova, S A (2010) Chem Heterocycl Compd, 46, 1910–1912.

Acta Cryst (2011) E67, 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

L T Anh , T H Hieu , A T Soldatenkov , S A Soldatova and V N Khrustalev

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[3.3.11,5]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

config-uration 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, J7.8 = 9.0), 4.23 (d, 1H, H9, J5,9 = 1.5), 4.32 (d, 1H, H7, J7,8= 9.0), 4.41 (br, 4H, 2(Alk)OH, +NH2), 4.48 (d, 1H, H5, J5,9 = 1.5), 6.41–7.50 (br m, 22H, Harom), 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.

The hydrogen atoms of the hydroxy and amino groups were localized in the difference Fourier map and included in the

refinement with fixed positional and isotropic displacement parameters [Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N)] The other hydrogen atoms were placed in calculated positions with C—H = 0.95–1.00Å and refined in the riding model with fixed

isotropic displacement parameters [Uiso(H) = 1.5Ueq(C) for CH3-groups and Uiso(H) = 1.2Ueq(C) for the other groups].

Figures

Fig 1 Molecular structure of I with the atom numbering scheme Displacement ellipsoids are shown at the 50% probability level H atoms are presented as a small spheres of arbitrary

radi-us Dashed lines indicate hydrogen bonds.

Fig 2 Crystal packing of I Dashed lines indicate hydrogen bonds.

Fig 3 Domino condensation of dibenzyl ketone with salicylic aldehyde and ammonium acet-ate.

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

Crystal data

Hall symbol: -P 2ybc Mo Kα radiation, λ = 0.71073 Å

b = 20.1124 (15) Å θ = 2.5–23.7°

Data collection

Bruker APEXII CCD

Radiation source: fine-focus sealed tube 4951 reflections with I > 2σ(I)

Absorption correction: multi-scan

Tmin = 0.977, Tmax = 0.989 k = −24→24

Refinement

Refinement on F2 Primary atom site location: structure-invariant directmethods

Least-squares matrix: full Secondary atom site location: difference Fourier map

R[F2 > 2σ(F2)] = 0.044 Hydrogen site location: difference Fourier map

where P = (Fo + 2Fc)/3

Special details

Geometry All s.u.'s (except the s.u in the dihedral angle between two l.s planes) are estimated using the full covariance matrix The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s planes

Refinement Refinement of F2 against ALL reflections The weighted R-factor wR and goodness of fit S are based on F2, conventional

R-factors R are based on F, with F set to zero for negative F2 The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc and is not relevant to the choice of reflections for refinement R-factors based on F2 are statistically about twice as large

as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

C2 0.27020 (13) 0.41161 (8) 0.17702 (13) 0.0238 (4)

O2 0.39434 (9) 0.54015 (6) −0.02342 (9) 0.0311 (3)

Atomic displacement parameters (Å2)

C4 0.0349 (11) 0.0221 (10) 0.0505 (13) −0.0001 (8) 0.0252 (10) −0.0016 (9) C5 0.0350 (11) 0.0241 (10) 0.0391 (11) −0.0062 (8) 0.0200 (9) −0.0069 (8) C6 0.0261 (10) 0.0251 (10) 0.0277 (10) −0.0021 (7) 0.0125 (8) −0.0005 (8)

C14 0.0298 (10) 0.0239 (9) 0.0257 (10) −0.0014 (8) 0.0117 (8) −0.0019 (8) C15 0.0266 (10) 0.0263 (10) 0.0271 (10) 0.0006 (7) 0.0103 (8) 0.0003 (8) C16 0.0303 (11) 0.0330 (11) 0.0398 (12) −0.0020 (8) 0.0138 (9) −0.0090 (9)

C17 0.0369 (12) 0.0369 (12) 0.0552 (14) 0.0023 (9) 0.0178 (10) −0.0153 (10) C18 0.0308 (11) 0.0492 (13) 0.0459 (13) 0.0067 (9) 0.0145 (10) −0.0095 (11) C19 0.0261 (11) 0.0481 (13) 0.0455 (13) −0.0007 (9) 0.0130 (9) −0.0105 (10) C20 0.0295 (11) 0.0368 (11) 0.0352 (11) −0.0037 (8) 0.0115 (9) −0.0082 (9)

C23 0.0260 (10) 0.0335 (11) 0.0321 (11) −0.0022 (8) 0.0098 (8) 0.0061 (9) C24 0.0261 (10) 0.0317 (11) 0.0447 (13) −0.0012 (8) 0.0066 (9) 0.0136 (9) C25 0.0313 (11) 0.0211 (10) 0.0584 (15) 0.0014 (8) 0.0134 (10) 0.0061 (9) C26 0.0266 (10) 0.0234 (10) 0.0414 (12) −0.0015 (8) 0.0125 (9) −0.0015 (8)

C29 0.0336 (11) 0.0381 (12) 0.0342 (11) −0.0049 (9) 0.0156 (9) 0.0045 (9) C30 0.0366 (12) 0.0350 (12) 0.0502 (13) −0.0092 (9) 0.0179 (10) 0.0060 (10) C31 0.0329 (11) 0.0288 (10) 0.0461 (13) −0.0074 (8) 0.0094 (9) −0.0046 (9) C32 0.0253 (10) 0.0318 (11) 0.0322 (11) −0.0015 (8) 0.0099 (8) −0.0021 (8) C33 0.0237 (9) 0.0326 (10) 0.0248 (10) −0.0006 (8) 0.0075 (8) 0.0018 (8) C34 0.0349 (11) 0.0405 (12) 0.0261 (10) −0.0098 (9) 0.0113 (8) −0.0003 (9) C35 0.0465 (13) 0.0471 (13) 0.0373 (12) −0.0188 (10) 0.0163 (10) −0.0013 (10) C36 0.0536 (14) 0.0591 (15) 0.0381 (13) −0.0189 (11) 0.0259 (11) 0.0012 (11) C37 0.0578 (14) 0.0557 (15) 0.0352 (12) −0.0153 (11) 0.0289 (11) −0.0087 (11) C38 0.0383 (11) 0.0382 (12) 0.0351 (11) −0.0071 (9) 0.0178 (9) −0.0051 (9)

C41 0.0284 (10) 0.0357 (11) 0.0389 (12) −0.0008 (8) 0.0045 (9) −0.0025 (9) C42 0.0394 (12) 0.0343 (12) 0.0590 (15) −0.0062 (9) 0.0067 (11) 0.0009 (11)

O6 0.0375 (8) 0.0375 (8) 0.0361 (8) 0.0077 (6) 0.0102 (6) −0.0005 (6) C43 0.0541 (14) 0.0419 (13) 0.0465 (14) 0.0159 (11) 0.0171 (11) 0.0013 (11) C44 0.0503 (14) 0.0439 (13) 0.0507 (14) 0.0129 (10) 0.0177 (11) 0.0050 (11) C39 0.0282 (10) 0.0365 (11) 0.0344 (11) 0.0031 (8) 0.0133 (9) 0.0011 (9) C40 0.0419 (13) 0.0696 (17) 0.0522 (15) 0.0227 (12) 0.0238 (11) 0.0142 (12)

Geometric parameters (Å, °)

C18—C19 1.382 (3) C43—H43A 0.9900

N12—C11—C10 110.66 (13) C34—C35—H35 119.7

C13—C1—C2—C7 28.1 (2) C14—C15—C16—C17 177.75 (18)

Hydrogen-bond geometry (Å, °)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1.

Fig 1

Fig 2

Fig 3

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