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

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

doi:10.1107/S160053681100376X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Pages o560-o561

doi:10.1107/S160053681100376X

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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 and Victor N. Khrustalev ^c

^aDepartment 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 ^cX-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; online 5 February 2011)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.044
wR(F²) = 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

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

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100376X/rk2264sup1.cif

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

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

Figures top

	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 radius. 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 acetate.

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 top

Crystal data top

C₃₆H₃₁N₂O₃⁺·C₂H₃O₂⁻·2C₂H₆O	F(000) = 1472
M_r = 690.81	D_x = 1.224 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 451–453 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.5464 (10) Å	Cell parameters from 4349 reflections
b = 20.1124 (15) Å	θ = 2.5–23.7°
c = 14.2535 (11) Å	µ = 0.08 mm⁻¹
β = 105.118 (2)°	T = 100 K
V = 3749.0 (5) Å³	Prism, light-yellow
Z = 4	0.28 × 0.15 × 0.13 mm

Data collection top

Bruker APEXII CCD diffractometer	7399 independent reflections
Radiation source: fine-focus sealed tube	4951 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 26.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −16→16
T_min = 0.977, T_max = 0.989	k = −24→24
35569 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: difference Fourier map
wR(F²) = 0.107	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.044P)² + 0.8P] where P = (F_o² + 2F_c²)/3
7399 reflections	(Δ/σ)_max = 0.001
463 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₃₆H₃₁N₂O₃⁺·C₂H₃O₂⁻·2C₂H₆O	V = 3749.0 (5) Å³
M_r = 690.81	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.5464 (10) Å	µ = 0.08 mm⁻¹
b = 20.1124 (15) Å	T = 100 K
c = 14.2535 (11) Å	0.28 × 0.15 × 0.13 mm
β = 105.118 (2)°

Data collection top

Bruker APEXII CCD diffractometer	7399 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	4951 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.989	R_int = 0.062
35569 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.01	Δρ_max = 0.23 e Å⁻³
7399 reflections	Δρ_min = −0.24 e Å⁻³
463 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.31447 (13)	0.45725 (9)	0.26034 (13)	0.0241 (4)
H1	0.3562	0.4309	0.3162	0.029*
C2	0.27020 (13)	0.41161 (8)	0.17702 (13)	0.0238 (4)
C3	0.31983 (14)	0.35414 (9)	0.15984 (14)	0.0286 (4)
H3	0.3835	0.3423	0.2031	0.034*
C4	0.27796 (14)	0.31398 (9)	0.08085 (15)	0.0332 (5)
H4	0.3128	0.2749	0.0698	0.040*
C5	0.18468 (14)	0.33100 (9)	0.01773 (14)	0.0308 (4)
H5	0.1562	0.3036	−0.0370	0.037*
C6	0.13298 (13)	0.38735 (8)	0.03375 (13)	0.0253 (4)
H6	0.0687	0.3985	−0.0089	0.030*
C7	0.17631 (13)	0.42725 (8)	0.11278 (12)	0.0224 (4)
O8	0.11919 (8)	0.48161 (5)	0.12638 (8)	0.0223 (3)
C9	0.16377 (13)	0.52919 (8)	0.20072 (12)	0.0218 (4)
C10	0.22947 (12)	0.58026 (8)	0.16205 (13)	0.0229 (4)
H10	0.2529	0.6143	0.2143	0.027*
C11	0.32643 (12)	0.54871 (8)	0.14383 (12)	0.0222 (4)
H11	0.3046	0.5182	0.0867	0.027*
N12	0.38139 (10)	0.50797 (7)	0.22941 (10)	0.0226 (3)
H12A	0.4342	0.4854	0.2119	0.027*
H12B	0.4088	0.5347	0.2840	0.027*
C13	0.23087 (12)	0.49527 (8)	0.29266 (12)	0.0235 (4)
H13	0.2660	0.5317	0.3365	0.028*
N1	0.08334 (10)	0.56563 (7)	0.22658 (10)	0.0232 (3)
C14	−0.00930 (13)	0.54651 (9)	0.20077 (13)	0.0256 (4)
H14	−0.0258	0.5075	0.1623	0.031*
C15	−0.09103 (13)	0.58249 (9)	0.22817 (13)	0.0260 (4)
C16	−0.07164 (14)	0.64102 (10)	0.28307 (14)	0.0335 (5)
O1	0.02500 (10)	0.66495 (7)	0.31689 (12)	0.0508 (4)
H1O	0.0648	0.6343	0.2931	0.076*
C17	−0.15130 (15)	0.67540 (10)	0.30517 (16)	0.0420 (5)
H17	−0.1381	0.7155	0.3416	0.050*
C18	−0.24953 (15)	0.65141 (11)	0.27434 (15)	0.0411 (5)
H18	−0.3037	0.6752	0.2899	0.049*
C19	−0.27084 (15)	0.59328 (10)	0.22123 (15)	0.0392 (5)
H19	−0.3388	0.5768	0.2012	0.047*
C20	−0.19200 (14)	0.55965 (10)	0.19783 (14)	0.0333 (5)
H20	−0.2064	0.5201	0.1603	0.040*
C21	0.16999 (12)	0.61709 (8)	0.07242 (13)	0.0239 (4)
C22	0.15273 (13)	0.58968 (9)	−0.01999 (13)	0.0264 (4)
H22	0.1762	0.5460	−0.0273	0.032*
C23	0.10186 (13)	0.62515 (9)	−0.10155 (14)	0.0301 (4)
H23	0.0917	0.6059	−0.1642	0.036*
C24	0.06575 (14)	0.68840 (10)	−0.09224 (15)	0.0347 (5)
H24	0.0309	0.7127	−0.1482	0.042*
C25	0.08082 (14)	0.71584 (9)	−0.00093 (16)	0.0366 (5)
H25	0.0554	0.7591	0.0060	0.044*
C26	0.13278 (13)	0.68080 (9)	0.08103 (15)	0.0298 (4)
H26	0.1431	0.7004	0.1435	0.036*
C27	0.39849 (12)	0.59989 (9)	0.12015 (13)	0.0241 (4)
C28	0.43138 (13)	0.59222 (9)	0.03550 (13)	0.0257 (4)
O2	0.39434 (9)	0.54015 (6)	−0.02342 (9)	0.0311 (3)
H2O	0.4183	0.5416	−0.0816	0.047*
C29	0.49980 (14)	0.63804 (10)	0.01430 (14)	0.0340 (5)
H29	0.5235	0.6326	−0.0423	0.041*
C30	0.53299 (15)	0.69114 (10)	0.07520 (16)	0.0394 (5)
H30	0.5798	0.7220	0.0603	0.047*
C31	0.49895 (15)	0.70016 (10)	0.15790 (15)	0.0361 (5)
H31	0.5206	0.7376	0.1988	0.043*
C32	0.43302 (13)	0.65386 (9)	0.18001 (14)	0.0293 (4)
H32	0.4109	0.6592	0.2376	0.035*
C33	0.17145 (13)	0.45525 (9)	0.35001 (13)	0.0268 (4)
C34	0.12157 (14)	0.39565 (10)	0.31830 (14)	0.0332 (5)
H34	0.1256	0.3769	0.2582	0.040*
C35	0.06608 (16)	0.36341 (11)	0.37368 (15)	0.0427 (5)
H35	0.0325	0.3227	0.3513	0.051*
C36	0.05916 (17)	0.39003 (12)	0.46139 (16)	0.0477 (6)
H36	0.0200	0.3682	0.4987	0.057*
C37	0.10967 (17)	0.44863 (11)	0.49416 (16)	0.0464 (6)
H37	0.1066	0.4667	0.5549	0.056*
C38	0.16484 (15)	0.48112 (10)	0.43867 (14)	0.0357 (5)
H38	0.1986	0.5217	0.4615	0.043*
O5	0.46371 (10)	0.57558 (7)	0.39577 (9)	0.0374 (3)
H5O	0.4207	0.5946	0.4335	0.056*
C41	0.56962 (14)	0.57329 (10)	0.44520 (15)	0.0351 (5)
H41A	0.6090	0.5584	0.3995	0.042*
H41B	0.5804	0.5405	0.4987	0.042*
C42	0.60860 (16)	0.63970 (10)	0.48591 (17)	0.0454 (6)
H42A	0.6826	0.6371	0.5146	0.068*
H42B	0.5747	0.6526	0.5360	0.068*
H42C	0.5941	0.6729	0.4338	0.068*
O6	0.66244 (10)	0.37980 (6)	0.50427 (10)	0.0369 (3)
H6O	0.6265	0.3937	0.4387	0.055*
C43	0.70231 (18)	0.31419 (11)	0.50708 (16)	0.0468 (6)
H43A	0.7738	0.3162	0.5021	0.056*
H43B	0.6617	0.2886	0.4508	0.056*
C44	0.69941 (17)	0.27955 (11)	0.59883 (16)	0.0474 (6)
H44A	0.7292	0.2351	0.5997	0.071*
H44B	0.6284	0.2757	0.6024	0.071*
H44C	0.7388	0.3051	0.6546	0.071*
C39	0.59166 (14)	0.42003 (10)	0.25775 (14)	0.0321 (4)
C40	0.69533 (16)	0.39181 (13)	0.25958 (17)	0.0524 (6)
H40A	0.7006	0.3464	0.2854	0.079*
H40B	0.7487	0.4195	0.3010	0.079*
H40C	0.7040	0.3911	0.1934	0.079*
O3	0.54470 (9)	0.45292 (6)	0.18438 (9)	0.0316 (3)
O4	0.55567 (10)	0.41052 (8)	0.32869 (10)	0.0459 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0223 (9)	0.0253 (9)	0.0253 (10)	−0.0004 (7)	0.0072 (7)	0.0040 (8)
C2	0.0242 (9)	0.0216 (9)	0.0288 (10)	−0.0005 (7)	0.0125 (8)	0.0047 (7)
C3	0.0266 (10)	0.0247 (10)	0.0386 (11)	0.0017 (7)	0.0159 (8)	0.0058 (8)
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)
C7	0.0257 (9)	0.0186 (9)	0.0282 (10)	−0.0005 (7)	0.0161 (8)	0.0007 (7)
O8	0.0229 (6)	0.0206 (6)	0.0247 (7)	0.0012 (5)	0.0084 (5)	−0.0030 (5)
C9	0.0227 (9)	0.0214 (9)	0.0232 (9)	0.0003 (7)	0.0092 (7)	−0.0042 (7)
C10	0.0204 (9)	0.0220 (9)	0.0281 (10)	−0.0014 (7)	0.0095 (7)	−0.0032 (7)
C11	0.0217 (9)	0.0233 (9)	0.0223 (9)	0.0008 (7)	0.0070 (7)	0.0004 (7)
N12	0.0196 (7)	0.0264 (8)	0.0233 (8)	0.0020 (6)	0.0082 (6)	0.0002 (6)
C13	0.0232 (9)	0.0252 (9)	0.0231 (9)	−0.0017 (7)	0.0077 (7)	−0.0021 (7)
N1	0.0222 (8)	0.0225 (8)	0.0281 (8)	−0.0005 (6)	0.0122 (6)	−0.0022 (6)
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)
O1	0.0290 (8)	0.0438 (9)	0.0836 (12)	−0.0086 (6)	0.0216 (8)	−0.0343 (8)
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)
C21	0.0168 (9)	0.0237 (9)	0.0329 (10)	−0.0022 (7)	0.0095 (7)	0.0018 (8)
C22	0.0222 (9)	0.0248 (10)	0.0334 (11)	0.0013 (7)	0.0093 (8)	0.0024 (8)
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)
C27	0.0191 (9)	0.0246 (9)	0.0293 (10)	0.0007 (7)	0.0073 (7)	0.0024 (8)
C28	0.0211 (9)	0.0276 (10)	0.0281 (10)	0.0017 (7)	0.0062 (8)	0.0022 (8)
O2	0.0320 (7)	0.0357 (8)	0.0297 (7)	−0.0059 (6)	0.0151 (6)	−0.0045 (6)
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)
O5	0.0285 (7)	0.0497 (9)	0.0331 (8)	−0.0006 (6)	0.0064 (6)	−0.0104 (7)
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)
O3	0.0268 (7)	0.0401 (8)	0.0302 (7)	0.0057 (6)	0.0117 (6)	0.0035 (6)
O4	0.0382 (8)	0.0664 (11)	0.0376 (9)	0.0189 (7)	0.0181 (7)	0.0160 (7)

Geometric parameters (Å, º) top

C1—C2	1.497 (2)	C24—C25	1.379 (3)
C1—N12	1.505 (2)	C24—H24	0.9500
C1—C13	1.533 (2)	C25—C26	1.388 (3)
C1—H1	1.0000	C25—H25	0.9500
C2—C3	1.391 (2)	C26—H26	0.9500
C2—C7	1.396 (2)	C27—C32	1.384 (2)
C3—C4	1.382 (3)	C27—C28	1.400 (2)
C3—H3	0.9500	C28—O2	1.354 (2)
C4—C5	1.389 (3)	C28—C29	1.395 (2)
C4—H4	0.9500	O2—H2O	0.9659
C5—C6	1.382 (2)	C29—C30	1.376 (3)
C5—H5	0.9500	C29—H29	0.9500
C6—C7	1.383 (2)	C30—C31	1.385 (3)
C6—H6	0.9500	C30—H30	0.9500
C7—O8	1.3820 (19)	C31—C32	1.382 (3)
O8—C9	1.438 (2)	C31—H31	0.9500
C9—N1	1.439 (2)	C32—H32	0.9500
C9—C13	1.545 (2)	C33—C38	1.391 (3)
C9—C10	1.551 (2)	C33—C34	1.392 (3)
C10—C21	1.514 (2)	C34—C35	1.385 (3)
C10—C11	1.541 (2)	C34—H34	0.9500
C10—H10	1.0000	C35—C36	1.385 (3)
C11—N12	1.497 (2)	C35—H35	0.9500
C11—C27	1.516 (2)	C36—C37	1.382 (3)
C11—H11	1.0000	C36—H36	0.9500
N12—H12A	0.9347	C37—C38	1.386 (3)
N12—H12B	0.9381	C37—H37	0.9500
C13—C33	1.519 (2)	C38—H38	0.9500
C13—H13	1.0000	O5—C41	1.425 (2)
N1—C14	1.272 (2)	O5—H5O	0.9692
C14—C15	1.459 (2)	C41—C42	1.497 (3)
C14—H14	0.9500	C41—H41A	0.9900
C15—C16	1.400 (3)	C41—H41B	0.9900
C15—C20	1.400 (3)	C42—H42A	0.9800
C16—O1	1.360 (2)	C42—H42B	0.9800
C16—C17	1.385 (3)	C42—H42C	0.9800
O1—H1O	0.9389	O6—C43	1.422 (2)
C17—C18	1.375 (3)	O6—H6O	0.9752
C17—H17	0.9500	C43—C44	1.491 (3)
C18—C19	1.382 (3)	C43—H43A	0.9900
C18—H18	0.9500	C43—H43B	0.9900
C19—C20	1.377 (3)	C44—H44A	0.9800
C19—H19	0.9500	C44—H44B	0.9800
C20—H20	0.9500	C44—H44C	0.9800
C21—C22	1.390 (3)	C39—O4	1.246 (2)
C21—C26	1.394 (2)	C39—O3	1.261 (2)
C22—C23	1.385 (2)	C39—C40	1.509 (3)
C22—H22	0.9500	C40—H40A	0.9800
C23—C24	1.382 (3)	C40—H40B	0.9800
C23—H23	0.9500	C40—H40C	0.9800

C2—C1—N12	109.30 (14)	C24—C23—C22	120.32 (19)
C2—C1—C13	111.69 (14)	C24—C23—H23	119.8
N12—C1—C13	107.37 (13)	C22—C23—H23	119.8
C2—C1—H1	109.5	C25—C24—C23	119.36 (18)
N12—C1—H1	109.5	C25—C24—H24	120.3
C13—C1—H1	109.5	C23—C24—H24	120.3
C3—C2—C7	118.13 (16)	C24—C25—C26	120.58 (18)
C3—C2—C1	122.50 (16)	C24—C25—H25	119.7
C7—C2—C1	119.36 (15)	C26—C25—H25	119.7
C4—C3—C2	120.99 (18)	C25—C26—C21	120.53 (18)
C4—C3—H3	119.5	C25—C26—H26	119.7
C2—C3—H3	119.5	C21—C26—H26	119.7
C3—C4—C5	119.63 (17)	C32—C27—C28	119.04 (16)
C3—C4—H4	120.2	C32—C27—C11	121.92 (16)
C5—C4—H4	120.2	C28—C27—C11	119.03 (15)
C6—C5—C4	120.63 (18)	O2—C28—C29	122.43 (16)
C6—C5—H5	119.7	O2—C28—C27	118.04 (15)
C4—C5—H5	119.7	C29—C28—C27	119.53 (17)
C5—C6—C7	118.99 (17)	C28—O2—H2O	110.8
C5—C6—H6	120.5	C30—C29—C28	120.17 (18)
C7—C6—H6	120.5	C30—C29—H29	119.9
O8—C7—C6	116.05 (15)	C28—C29—H29	119.9
O8—C7—C2	122.28 (15)	C29—C30—C31	120.79 (18)
C6—C7—C2	121.61 (16)	C29—C30—H30	119.6
C7—O8—C9	119.13 (13)	C31—C30—H30	119.6
O8—C9—N1	109.09 (13)	C32—C31—C30	118.95 (18)
O8—C9—C13	111.85 (13)	C32—C31—H31	120.5
N1—C9—C13	108.96 (13)	C30—C31—H31	120.5
O8—C9—C10	110.38 (13)	C31—C32—C27	121.48 (18)
N1—C9—C10	107.26 (13)	C31—C32—H32	119.3
C13—C9—C10	109.18 (13)	C27—C32—H32	119.3
C21—C10—C11	110.40 (14)	C38—C33—C34	118.44 (17)
C21—C10—C9	113.29 (14)	C38—C33—C13	117.35 (16)
C11—C10—C9	112.37 (14)	C34—C33—C13	124.20 (16)
C21—C10—H10	106.8	C35—C34—C33	120.51 (18)
C11—C10—H10	106.8	C35—C34—H34	119.7
C9—C10—H10	106.8	C33—C34—H34	119.7
N12—C11—C27	109.93 (13)	C34—C35—C36	120.53 (19)
N12—C11—C10	110.66 (13)	C34—C35—H35	119.7
C27—C11—C10	112.63 (14)	C36—C35—H35	119.7
N12—C11—H11	107.8	C37—C36—C35	119.38 (19)
C27—C11—H11	107.8	C37—C36—H36	120.3
C10—C11—H11	107.8	C35—C36—H36	120.3
C11—N12—C1	113.59 (13)	C36—C37—C38	120.18 (19)
C11—N12—H12A	107.5	C36—C37—H37	119.9
C1—N12—H12A	108.1	C38—C37—H37	119.9
C11—N12—H12B	111.5	C37—C38—C33	120.95 (19)
C1—N12—H12B	106.5	C37—C38—H38	119.5
H12A—N12—H12B	109.5	C33—C38—H38	119.5
C33—C13—C1	115.72 (14)	C41—O5—H5O	114.3
C33—C13—C9	114.42 (14)	O5—C41—C42	111.77 (16)
C1—C13—C9	106.41 (13)	O5—C41—H41A	109.3
C33—C13—H13	106.6	C42—C41—H41A	109.3
C1—C13—H13	106.6	O5—C41—H41B	109.3
C9—C13—H13	106.6	C42—C41—H41B	109.3
C14—N1—C9	121.86 (15)	H41A—C41—H41B	107.9
N1—C14—C15	122.22 (16)	C41—C42—H42A	109.5
N1—C14—H14	118.9	C41—C42—H42B	109.5
C15—C14—H14	118.9	H42A—C42—H42B	109.5
C16—C15—C20	118.30 (17)	C41—C42—H42C	109.5
C16—C15—C14	121.47 (16)	H42A—C42—H42C	109.5
C20—C15—C14	120.21 (16)	H42B—C42—H42C	109.5
O1—C16—C17	118.54 (17)	C43—O6—H6O	112.5
O1—C16—C15	121.25 (16)	O6—C43—C44	111.19 (17)
C17—C16—C15	120.21 (18)	O6—C43—H43A	109.4
C16—O1—H1O	103.3	C44—C43—H43A	109.4
C18—C17—C16	119.89 (19)	O6—C43—H43B	109.4
C18—C17—H17	120.1	C44—C43—H43B	109.4
C16—C17—H17	120.1	H43A—C43—H43B	108.0
C17—C18—C19	121.22 (18)	C43—C44—H44A	109.5
C17—C18—H18	119.4	C43—C44—H44B	109.5
C19—C18—H18	119.4	H44A—C44—H44B	109.5
C20—C19—C18	118.95 (18)	C43—C44—H44C	109.5
C20—C19—H19	120.5	H44A—C44—H44C	109.5
C18—C19—H19	120.5	H44B—C44—H44C	109.5
C19—C20—C15	121.41 (18)	O4—C39—O3	122.28 (17)
C19—C20—H20	119.3	O4—C39—C40	119.18 (18)
C15—C20—H20	119.3	O3—C39—C40	118.54 (17)
C22—C21—C26	118.20 (17)	C39—C40—H40A	109.5
C22—C21—C10	121.76 (15)	C39—C40—H40B	109.5
C26—C21—C10	120.03 (16)	H40A—C40—H40B	109.5
C23—C22—C21	121.00 (17)	C39—C40—H40C	109.5
C23—C22—H22	119.5	H40A—C40—H40C	109.5
C21—C22—H22	119.5	H40B—C40—H40C	109.5

N12—C1—C2—C3	88.45 (19)	C20—C15—C16—O1	178.30 (18)
C13—C1—C2—C3	−152.89 (16)	C14—C15—C16—O1	−3.1 (3)
N12—C1—C2—C7	−90.60 (18)	C20—C15—C16—C17	−0.8 (3)
C13—C1—C2—C7	28.1 (2)	C14—C15—C16—C17	177.75 (18)
C7—C2—C3—C4	0.7 (3)	O1—C16—C17—C18	−178.2 (2)
C1—C2—C3—C4	−178.39 (16)	C15—C16—C17—C18	1.0 (3)
C2—C3—C4—C5	−0.3 (3)	C16—C17—C18—C19	−0.1 (3)
C3—C4—C5—C6	−0.6 (3)	C17—C18—C19—C20	−1.0 (3)
C4—C5—C6—C7	1.1 (3)	C18—C19—C20—C15	1.2 (3)
C5—C6—C7—O8	−178.01 (15)	C16—C15—C20—C19	−0.3 (3)
C5—C6—C7—C2	−0.6 (3)	C14—C15—C20—C19	−178.86 (18)
C3—C2—C7—O8	176.98 (15)	C11—C10—C21—C22	44.7 (2)
C1—C2—C7—O8	−3.9 (2)	C9—C10—C21—C22	−82.32 (19)
C3—C2—C7—C6	−0.2 (2)	C11—C10—C21—C26	−133.91 (16)
C1—C2—C7—C6	178.88 (15)	C9—C10—C21—C26	99.07 (18)
C6—C7—O8—C9	−173.46 (14)	C26—C21—C22—C23	1.3 (2)
C2—C7—O8—C9	9.2 (2)	C10—C21—C22—C23	−177.29 (16)
C7—O8—C9—N1	−158.67 (13)	C21—C22—C23—C24	−1.0 (3)
C7—O8—C9—C13	−38.05 (18)	C22—C23—C24—C25	0.0 (3)
C7—O8—C9—C10	83.72 (17)	C23—C24—C25—C26	0.8 (3)
O8—C9—C10—C21	57.51 (18)	C24—C25—C26—C21	−0.4 (3)
N1—C9—C10—C21	−61.23 (18)	C22—C21—C26—C25	−0.6 (3)
C13—C9—C10—C21	−179.16 (14)	C10—C21—C26—C25	178.05 (16)
O8—C9—C10—C11	−68.47 (17)	N12—C11—C27—C32	−70.3 (2)
N1—C9—C10—C11	172.79 (13)	C10—C11—C27—C32	53.6 (2)
C13—C9—C10—C11	54.86 (18)	N12—C11—C27—C28	109.50 (17)
C21—C10—C11—N12	−175.72 (13)	C10—C11—C27—C28	−126.60 (17)
C9—C10—C11—N12	−48.19 (18)	C32—C27—C28—O2	−178.12 (15)
C21—C10—C11—C27	60.78 (18)	C11—C27—C28—O2	2.1 (2)
C9—C10—C11—C27	−171.69 (14)	C32—C27—C28—C29	1.5 (3)
C27—C11—N12—C1	177.98 (13)	C11—C27—C28—C29	−178.31 (16)
C10—C11—N12—C1	52.95 (18)	O2—C28—C29—C30	178.19 (17)
C2—C1—N12—C11	58.31 (18)	C27—C28—C29—C30	−1.4 (3)
C13—C1—N12—C11	−63.00 (17)	C28—C29—C30—C31	−0.3 (3)
C2—C1—C13—C33	74.96 (19)	C29—C30—C31—C32	1.8 (3)
N12—C1—C13—C33	−165.24 (14)	C30—C31—C32—C27	−1.7 (3)
C2—C1—C13—C9	−53.37 (18)	C28—C27—C32—C31	0.1 (3)
N12—C1—C13—C9	66.44 (16)	C11—C27—C32—C31	179.82 (17)
O8—C9—C13—C33	−69.97 (18)	C1—C13—C33—C38	127.54 (18)
N1—C9—C13—C33	50.72 (19)	C9—C13—C33—C38	−108.19 (18)
C10—C9—C13—C33	167.57 (14)	C1—C13—C33—C34	−54.1 (2)
O8—C9—C13—C1	59.12 (16)	C9—C13—C33—C34	70.1 (2)
N1—C9—C13—C1	179.81 (13)	C38—C33—C34—C35	0.5 (3)
C10—C9—C13—C1	−63.34 (16)	C13—C33—C34—C35	−177.78 (18)
O8—C9—N1—C14	13.6 (2)	C33—C34—C35—C36	0.1 (3)
C13—C9—N1—C14	−108.74 (18)	C34—C35—C36—C37	−1.1 (4)
C10—C9—N1—C14	133.19 (16)	C35—C36—C37—C38	1.4 (4)
C9—N1—C14—C15	178.85 (16)	C36—C37—C38—C33	−0.7 (3)
N1—C14—C15—C16	1.3 (3)	C34—C33—C38—C37	−0.2 (3)
N1—C14—C15—C20	179.83 (17)	C13—C33—C38—C37	178.19 (19)

Hydrogen-bond geometry (Å, º) top

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

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

Experimental details

Crystal data
Chemical formula	C₃₆H₃₁N₂O₃⁺·C₂H₃O₂⁻·2C₂H₆O
M_r	690.81
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.5464 (10), 20.1124 (15), 14.2535 (11)
β (°)	105.118 (2)
V (Å³)	3749.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.28 × 0.15 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.977, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	35569, 7399, 4951
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.620

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.107, 1.01
No. of reflections	7399
No. of parameters	463
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.24

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SAINT-Plus (Bruker, 2001, SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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

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

References

Baliah, V., Jeyaraman, R. & Chandrasekaran, L. (1983). Chem. Rev. 83, 379–423. CrossRef CAS Web of Science Google Scholar
Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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. Google Scholar
Sheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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. CrossRef Google Scholar
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Volume 67| Part 3| March 2011| Pages o560-o561

doi:10.1107/S160053681100376X

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

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