16-[(E)-Benzyl­idene]-2-hy­droxy-12,13-diphenyl-1,11-diaza­penta­cyclo­[12.3.1.02,10.03,8.010,14]octa­deca-3(8),4,6-triene-9,15-dione

Kumar, R.S.; Osman, H.; Ali, M.A.; Goh, J.H.; Fun, H.-K.

doi:10.1107/S1600536810028345

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages o2084-o2085

https://doi.org/10.1107/S1600536810028345

Open

access

16-[(E)-Benzylidene]-2-hydroxy-12,13-diphenyl-1,11-diazapentacyclo[12.3.1.0^2,10.0^3,8.0^10,14]octadeca-3(8),4,6-triene-9,15-dione

Raju Suresh Kumar,^a Hasnah Osman,^a ‡ Mohamed Ashraf Ali,^b Jia Hao Goh ^c § and Hoong-Kun Fun ^c ^*¶

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bInstitute for Research in Molecular Medicine, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 12 July 2010; accepted 15 July 2010; online 24 July 2010)

In the title compound, C₃₅H₂₈N₂O₃, an intramolecular O—H⋯N hydrogen bonds generates a five-membered ring, producing an S(5) ring motif. The piperidone ring adopts a half-chair conformation and the two pyrrolidine rings adopt an envelope conformation. The dihedral angles formed between adjacent benzene rings are 74.39 (5) and 37.70 (6)°. In the crystal crystal, intermolecular C—H⋯O hydrogen bonds link molecules into dimers, which are further interconnected into two-dimensional networks parallel to the ac plane by intermolecular C—H⋯O hydrogen bonds. The crystal structure is consolidated by weak C—H⋯π interactions.

Related literature

For general background to and applications of the title compound, see: Daly et al. (1986 ); Monlineux & Pelletier (1987 ); Padwa (1984 ); Tsuge & Kanemasa (1989 ); Waldmann (1995 ). For ring puckering analysis, see: Cremer & Pople (1975 ). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ). For closely related structures, see: Kumar et al. (2010a ,b ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₃₅H₂₈N₂O₃
M_r = 524.59
Triclinic, $[P \overline 1]$
a = 8.6319 (2) Å
b = 11.8130 (2) Å
c = 14.3562 (3) Å
α = 75.395 (1)°
β = 72.876 (1)°
γ = 76.185 (1)°
V = 1332.18 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.32 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.973, T_max = 0.980
35745 measured reflections
10026 independent reflections
8085 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.136
S = 1.02
10026 reflections
369 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C30–C35 and C9–C14 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N1	0.862 (18)	1.999 (18)	2.6383 (12)	130.2 (15)
C7—H7A⋯O1ⁱ	0.98	2.49	3.4701 (13)	177
C10—H10A⋯O1ⁱ	0.93	2.44	3.3605 (13)	173
C35—H35A⋯O3ⁱⁱ	0.93	2.44	3.3424 (16)	163
C13—H13A⋯Cg1ⁱⁱⁱ	0.93	2.89	3.7470 (12)	155
C20—H20A⋯Cg2^iv	0.93	2.84	3.4275 (15)	122
C33—H33A⋯Cg2^v	0.93	2.96	3.7723 (15)	147
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x, -y+1, -z+1; (iii) x, y-1, z; (iv) x, y+1, z; (v) -x+1, -y+1, -z+1.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810028345/rz2477sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028345/rz2477Isup2.hkl

checkCIF report

Comment top

The 1,3-dipolar cycloaddition of azomethine ylides with olefinic dipolarophiles offers an excellent route for the construction of pyrrolidines (Tsuge & Kanemasa, 1989; Padwa, 1984). The chemistry of azomethine ylides has gained significance in recent years as it serves as an important route for the construction of nitrogen containing five-membered heterocycles, which are often central ring systems of numerous natural products (Daly et al., 1986; Waldmann, 1995). The pyrrolidine moiety is one of the significant core structures among the most extensively studied natural and synthetic heterocyclic compounds with remarkable medicinal activities (Monlineux & Pelletier, 1987).

In the title compound (Fig. 1), an intramolecular O1—H1O1···N1 hydrogen bond (Table 1) forms a five-membered ring, generating an S(5) hydrogen bond ring motif (Bernstein et al., 1995). The 4-piperidone ring (N2/C15/C25-C28) adopts a half-chair conformation, with puckering parameters Q = 0.6229 (10) Å, θ = 137.36 (9)° and φ = 236.70 (14)° (Cremer & Pople, 1975). The two fused pyrrolidine rings (N1/C7/C8/C15/C16 and N2/C15/C16/C17/C25) adopt an envelope conformation, with atoms C8 and C25 as the flap atoms, respectively. The puckering parameters are Q = 0.4071 (10) Å, φ = 248.43 (14)° for the N1/C7/C8/C15/C16 ring and Q = 0.4468 (10) Å, φ = 151.15 (13)° for the N2/C15/C16/C17/C25 pyrrolidine ring. The dihedral angles formed between benzene rings A/B and C/D are 74.39 (5) and 37.70 (6)°, respectively. The bond lengths and angles are comparable to those observed in closely related structures (Kumar et al., 2010a,b).

In the crystal structure (Fig. 2), intermolecular C35—H35A···O3 hydrogen bonds (Table 1) link neighbouring molecules into dimers. Intermolecular C7—H7A···O1 and C10—H10A···O1 hydrogen bonds (Table 1) further interconnect these dimers into two-dimensional networks parallel to the ac plane. The crystal structure is further stabilized by weak intermolecular C13—H13A···Cg1, C20—H20A···Cg2 and C33—H33A···Cg2 interactions, where Cg1 and Cg2 are the centroids of the C30-C35 and C9-C14 benzene rings, respectively.

Related literature top

For general background to and applications of the title compound, see: Daly et al. (1986); Monlineux & Pelletier (1987); Padwa (1984); Tsuge & Kanemasa (1989); Waldmann (1995). For ring puckering analysis, see: Cremer & Pople (1975). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995). For closely related structures, see: Kumar et al. (2010a,b). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

A mixture of 3,5-bis[(E)-phenylmethylidene]tetrahydro-4(1H)- pyridinone (0.100 g, 0.363 mmol), ninhydrin (0.065 g, 0.363 mmol) and phenylglycine (0.055 g, 0.363 mmol) were dissolved in methanol (10 ml) and refluxed for 1 h. After completion of the reaction as evident from TLC, the mixture was poured into water (50 ml). The solid precipitated was filtered and washed with water to afford the product which was recrystallized from ethyl acetate to reveal the title compound as colourless crystals.

Structure description top

For general background to and applications of the title compound, see: Daly et al. (1986); Monlineux & Pelletier (1987); Padwa (1984); Tsuge & Kanemasa (1989); Waldmann (1995). For ring puckering analysis, see: Cremer & Pople (1975). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995). For closely related structures, see: Kumar et al. (2010a,b). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30 % probability displacement ellipsoids for non-H atoms and the atom-numbering scheme. An intramolecular hydrogen bond is shown as dashed line.
	Fig. 2. The crystal structure of the title compound, viewed down the b axis, showing a two-dimensional hydrogen-bonded network parallel to the ac plane. H atoms not involved in intermolecular hydrogen bonds (dashed lines) have been omitted for clarity.

16-[(E)-Benzylidene]-2-hydroxy-12,13-diphenyl-1,11- diazapentacyclo[12.3.1.0^2,10.0^3,8.0^10,14]octadeca-3(8),4,6-triene- 9,15-dione top

Crystal data top

C₃₅H₂₈N₂O₃	Z = 2
M_r = 524.59	F(000) = 552
Triclinic, P1	D_x = 1.308 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6319 (2) Å	Cell parameters from 9908 reflections
b = 11.8130 (2) Å	θ = 2.5–33.0°
c = 14.3562 (3) Å	µ = 0.08 mm⁻¹
α = 75.395 (1)°	T = 100 K
β = 72.876 (1)°	Block, colourless
γ = 76.185 (1)°	0.32 × 0.30 × 0.25 mm
V = 1332.18 (5) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	10026 independent reflections
Radiation source: fine-focus sealed tube	8085 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 33.1°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→13
T_min = 0.973, T_max = 0.980	k = −15→18
35745 measured reflections	l = −21→22

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0752P)² + 0.3278P] where P = (F_o² + 2F_c²)/3
10026 reflections	(Δ/σ)_max < 0.001
369 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₃₅H₂₈N₂O₃	γ = 76.185 (1)°
M_r = 524.59	V = 1332.18 (5) Å³
Triclinic, P1	Z = 2
a = 8.6319 (2) Å	Mo Kα radiation
b = 11.8130 (2) Å	µ = 0.08 mm⁻¹
c = 14.3562 (3) Å	T = 100 K
α = 75.395 (1)°	0.32 × 0.30 × 0.25 mm
β = 72.876 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	10026 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	8085 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.980	R_int = 0.027
35745 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.51 e Å⁻³
10026 reflections	Δρ_min = −0.24 e Å⁻³
369 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1	0.37832 (9)	0.64683 (7)	0.04084 (5)	0.01893 (14)
O2	−0.08312 (9)	0.57843 (7)	0.29194 (6)	0.02456 (16)
O3	0.17358 (9)	0.37449 (7)	0.41701 (5)	0.01996 (15)
N1	0.15205 (10)	0.51021 (7)	0.10911 (6)	0.01565 (15)
N2	0.46901 (10)	0.57415 (7)	0.18617 (6)	0.01554 (15)
C1	0.20254 (13)	0.27449 (9)	−0.01412 (8)	0.02146 (19)
H1A	0.3056	0.2903	−0.0519	0.026*
C2	0.12201 (16)	0.20652 (10)	−0.04456 (10)	0.0284 (2)
H2A	0.1715	0.1772	−0.1027	0.034*
C3	−0.03146 (16)	0.18240 (10)	0.01147 (10)	0.0290 (2)
H3A	−0.0834	0.1350	−0.0080	0.035*
C4	−0.10753 (14)	0.22921 (10)	0.09674 (9)	0.0264 (2)
H4A	−0.2116	0.2145	0.1336	0.032*
C5	−0.02863 (12)	0.29778 (9)	0.12704 (8)	0.02011 (18)
H5A	−0.0808	0.3299	0.1836	0.024*
C6	0.12871 (11)	0.31887 (8)	0.07312 (7)	0.01559 (16)
C7	0.22380 (11)	0.38226 (8)	0.11019 (7)	0.01398 (16)
H7A	0.3361	0.3768	0.0674	0.017*
C8	0.23468 (11)	0.33085 (8)	0.21896 (7)	0.01388 (15)
H8A	0.1220	0.3279	0.2598	0.017*
C9	0.33395 (11)	0.20676 (8)	0.23764 (7)	0.01492 (16)
C10	0.47150 (12)	0.16476 (8)	0.16708 (8)	0.01862 (18)
H10A	0.5069	0.2147	0.1067	0.022*
C11	0.55647 (13)	0.04853 (9)	0.18631 (9)	0.0231 (2)
H11A	0.6488	0.0219	0.1390	0.028*
C12	0.50438 (14)	−0.02770 (9)	0.27554 (9)	0.0245 (2)
H12A	0.5611	−0.1052	0.2880	0.029*
C13	0.36703 (14)	0.01263 (9)	0.34600 (8)	0.0241 (2)
H13A	0.3310	−0.0381	0.4058	0.029*
C14	0.28311 (13)	0.12884 (9)	0.32735 (8)	0.01999 (18)
H14A	0.1916	0.1552	0.3753	0.024*
C15	0.29208 (11)	0.43124 (8)	0.24213 (7)	0.01354 (15)
C16	0.19664 (11)	0.54615 (8)	0.18681 (7)	0.01378 (15)
C17	0.32511 (11)	0.63251 (8)	0.14526 (7)	0.01468 (16)
C18	0.23354 (12)	0.74740 (8)	0.17864 (7)	0.01695 (17)
C19	0.28408 (14)	0.85751 (9)	0.15035 (9)	0.0227 (2)
H19A	0.3879	0.8663	0.1091	0.027*
C20	0.17512 (16)	0.95369 (10)	0.18545 (10)	0.0291 (2)
H20A	0.2058	1.0281	0.1666	0.035*
C21	0.01984 (16)	0.94031 (11)	0.24878 (11)	0.0319 (3)
H21A	−0.0508	1.0059	0.2718	0.038*
C22	−0.03022 (14)	0.83114 (10)	0.27771 (9)	0.0261 (2)
H22A	−0.1329	0.8220	0.3204	0.031*
C23	0.07820 (12)	0.73506 (9)	0.24084 (7)	0.01799 (17)
C24	0.04469 (11)	0.61565 (8)	0.24970 (7)	0.01689 (17)
C25	0.47371 (11)	0.44701 (8)	0.19245 (7)	0.01582 (16)
H25A	0.5466	0.3976	0.2328	0.019*
H25B	0.5099	0.4272	0.1269	0.019*
C26	0.45734 (12)	0.59095 (8)	0.28658 (7)	0.01673 (17)
H26A	0.4352	0.6756	0.2860	0.020*
H26B	0.5633	0.5584	0.3019	0.020*
C27	0.32554 (11)	0.53394 (8)	0.36921 (7)	0.01594 (16)
C28	0.25652 (11)	0.43883 (8)	0.35060 (7)	0.01509 (16)
C29	0.25868 (13)	0.56680 (9)	0.45800 (7)	0.01835 (17)
H29A	0.1739	0.5284	0.4999	0.022*
C30	0.30193 (13)	0.65502 (9)	0.49733 (7)	0.01963 (18)
C31	0.46073 (14)	0.68084 (9)	0.47512 (8)	0.0221 (2)
H31A	0.5459	0.6442	0.4295	0.027*
C32	0.49189 (15)	0.76115 (10)	0.52097 (9)	0.0255 (2)
H32A	0.5978	0.7772	0.5060	0.031*
C33	0.36614 (17)	0.81721 (10)	0.58864 (9)	0.0282 (2)
H33A	0.3873	0.8706	0.6192	0.034*
C34	0.20874 (18)	0.79293 (12)	0.61028 (9)	0.0321 (3)
H34A	0.1235	0.8313	0.6548	0.039*
C35	0.17695 (15)	0.71182 (11)	0.56616 (8)	0.0273 (2)
H35A	0.0711	0.6951	0.5827	0.033*
H1O1	0.306 (2)	0.6203 (15)	0.0257 (13)	0.039 (4)*
H1N1	0.0415 (18)	0.5227 (13)	0.1190 (11)	0.023 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0219 (3)	0.0209 (3)	0.0135 (3)	−0.0075 (3)	−0.0018 (2)	−0.0021 (2)
O2	0.0173 (3)	0.0246 (4)	0.0276 (4)	−0.0041 (3)	0.0013 (3)	−0.0054 (3)
O3	0.0236 (3)	0.0197 (3)	0.0165 (3)	−0.0087 (3)	−0.0021 (3)	−0.0024 (3)
N1	0.0182 (3)	0.0117 (3)	0.0182 (4)	−0.0011 (3)	−0.0068 (3)	−0.0038 (3)
N2	0.0160 (3)	0.0140 (3)	0.0167 (4)	−0.0034 (3)	−0.0031 (3)	−0.0037 (3)
C1	0.0224 (4)	0.0217 (5)	0.0223 (5)	0.0003 (3)	−0.0079 (4)	−0.0090 (4)
C2	0.0363 (6)	0.0234 (5)	0.0324 (6)	0.0040 (4)	−0.0186 (5)	−0.0148 (4)
C3	0.0388 (6)	0.0173 (4)	0.0413 (7)	−0.0053 (4)	−0.0270 (5)	−0.0041 (4)
C4	0.0266 (5)	0.0228 (5)	0.0340 (6)	−0.0103 (4)	−0.0164 (4)	0.0027 (4)
C5	0.0192 (4)	0.0204 (4)	0.0220 (5)	−0.0056 (3)	−0.0070 (3)	−0.0024 (4)
C6	0.0175 (4)	0.0125 (4)	0.0176 (4)	−0.0014 (3)	−0.0065 (3)	−0.0030 (3)
C7	0.0156 (4)	0.0118 (4)	0.0147 (4)	−0.0020 (3)	−0.0036 (3)	−0.0035 (3)
C8	0.0154 (4)	0.0116 (3)	0.0144 (4)	−0.0025 (3)	−0.0030 (3)	−0.0028 (3)
C9	0.0161 (4)	0.0115 (4)	0.0182 (4)	−0.0034 (3)	−0.0056 (3)	−0.0024 (3)
C10	0.0170 (4)	0.0131 (4)	0.0237 (5)	−0.0028 (3)	−0.0027 (3)	−0.0026 (3)
C11	0.0181 (4)	0.0151 (4)	0.0338 (6)	−0.0006 (3)	−0.0044 (4)	−0.0054 (4)
C12	0.0249 (5)	0.0130 (4)	0.0367 (6)	−0.0018 (3)	−0.0139 (4)	−0.0006 (4)
C13	0.0303 (5)	0.0168 (4)	0.0248 (5)	−0.0061 (4)	−0.0111 (4)	0.0034 (4)
C14	0.0244 (4)	0.0164 (4)	0.0182 (4)	−0.0046 (3)	−0.0053 (3)	−0.0007 (3)
C15	0.0151 (4)	0.0114 (3)	0.0141 (4)	−0.0021 (3)	−0.0033 (3)	−0.0031 (3)
C16	0.0149 (4)	0.0113 (4)	0.0145 (4)	−0.0020 (3)	−0.0024 (3)	−0.0030 (3)
C17	0.0165 (4)	0.0130 (4)	0.0139 (4)	−0.0037 (3)	−0.0020 (3)	−0.0027 (3)
C18	0.0212 (4)	0.0129 (4)	0.0184 (4)	−0.0027 (3)	−0.0076 (3)	−0.0031 (3)
C19	0.0280 (5)	0.0151 (4)	0.0281 (5)	−0.0056 (4)	−0.0122 (4)	−0.0023 (4)
C20	0.0376 (6)	0.0141 (4)	0.0421 (7)	−0.0027 (4)	−0.0198 (5)	−0.0074 (4)
C21	0.0360 (6)	0.0198 (5)	0.0449 (7)	0.0053 (4)	−0.0162 (5)	−0.0178 (5)
C22	0.0247 (5)	0.0238 (5)	0.0315 (6)	0.0038 (4)	−0.0078 (4)	−0.0149 (4)
C23	0.0203 (4)	0.0151 (4)	0.0196 (4)	−0.0001 (3)	−0.0061 (3)	−0.0067 (3)
C24	0.0169 (4)	0.0158 (4)	0.0167 (4)	−0.0004 (3)	−0.0035 (3)	−0.0040 (3)
C25	0.0145 (4)	0.0138 (4)	0.0186 (4)	−0.0019 (3)	−0.0024 (3)	−0.0047 (3)
C26	0.0170 (4)	0.0164 (4)	0.0181 (4)	−0.0048 (3)	−0.0048 (3)	−0.0036 (3)
C27	0.0177 (4)	0.0150 (4)	0.0163 (4)	−0.0036 (3)	−0.0057 (3)	−0.0027 (3)
C28	0.0161 (4)	0.0137 (4)	0.0157 (4)	−0.0020 (3)	−0.0042 (3)	−0.0037 (3)
C29	0.0236 (4)	0.0166 (4)	0.0162 (4)	−0.0060 (3)	−0.0053 (3)	−0.0030 (3)
C30	0.0279 (5)	0.0175 (4)	0.0154 (4)	−0.0071 (3)	−0.0066 (3)	−0.0024 (3)
C31	0.0258 (5)	0.0205 (4)	0.0238 (5)	−0.0030 (4)	−0.0134 (4)	−0.0033 (4)
C32	0.0321 (5)	0.0220 (5)	0.0288 (5)	−0.0077 (4)	−0.0184 (4)	−0.0005 (4)
C33	0.0472 (7)	0.0222 (5)	0.0221 (5)	−0.0146 (5)	−0.0132 (5)	−0.0032 (4)
C34	0.0446 (7)	0.0310 (6)	0.0240 (5)	−0.0169 (5)	0.0017 (5)	−0.0137 (5)
C35	0.0323 (5)	0.0302 (6)	0.0218 (5)	−0.0150 (4)	0.0031 (4)	−0.0121 (4)

Geometric parameters (Å, º) top

O1—C17	1.4109 (11)	C15—C28	1.5175 (13)
O1—H1O1	0.863 (18)	C15—C25	1.5542 (13)
O2—C24	1.2171 (12)	C15—C16	1.5683 (12)
O3—C28	1.2214 (11)	C16—C24	1.5401 (13)
N1—C16	1.4636 (12)	C16—C17	1.5717 (13)
N1—C7	1.4883 (12)	C17—C18	1.5129 (13)
N1—H1N1	0.904 (15)	C18—C23	1.3926 (14)
N2—C25	1.4731 (12)	C18—C19	1.3955 (14)
N2—C26	1.4754 (13)	C19—C20	1.3887 (16)
N2—C17	1.4763 (12)	C19—H19A	0.9300
C1—C2	1.3933 (16)	C20—C21	1.3998 (19)
C1—C6	1.3969 (14)	C20—H20A	0.9300
C1—H1A	0.9300	C21—C22	1.3829 (17)
C2—C3	1.3857 (19)	C21—H21A	0.9300
C2—H2A	0.9300	C22—C23	1.3958 (14)
C3—C4	1.3892 (19)	C22—H22A	0.9300
C3—H3A	0.9300	C23—C24	1.4738 (14)
C4—C5	1.3874 (15)	C25—H25A	0.9700
C4—H4A	0.9300	C25—H25B	0.9700
C5—C6	1.3968 (14)	C26—C27	1.5242 (13)
C5—H5A	0.9300	C26—H26A	0.9700
C6—C7	1.5064 (13)	C26—H26B	0.9700
C7—C8	1.5482 (13)	C27—C29	1.3483 (14)
C7—H7A	0.9800	C27—C28	1.5012 (13)
C8—C9	1.5140 (12)	C29—C30	1.4666 (14)
C8—C15	1.5295 (13)	C29—H29A	0.9300
C8—H8A	0.9800	C30—C35	1.3970 (15)
C9—C10	1.3949 (13)	C30—C31	1.4025 (15)
C9—C14	1.4002 (13)	C31—C32	1.3953 (15)
C10—C11	1.3952 (13)	C31—H31A	0.9300
C10—H10A	0.9300	C32—C33	1.3859 (18)
C11—C12	1.3880 (16)	C32—H32A	0.9300
C11—H11A	0.9300	C33—C34	1.3847 (18)
C12—C13	1.3867 (17)	C33—H33A	0.9300
C12—H12A	0.9300	C34—C35	1.3886 (16)
C13—C14	1.3911 (14)	C34—H34A	0.9300
C13—H13A	0.9300	C35—H35A	0.9300
C14—H14A	0.9300

C17—O1—H1O1	103.4 (11)	O1—C17—N2	107.75 (7)
C16—N1—C7	108.20 (7)	O1—C17—C18	112.40 (8)
C16—N1—H1N1	110.8 (9)	N2—C17—C18	115.09 (8)
C7—N1—H1N1	110.8 (9)	O1—C17—C16	109.81 (7)
C25—N2—C26	107.71 (7)	N2—C17—C16	106.84 (7)
C25—N2—C17	102.98 (7)	C18—C17—C16	104.70 (7)
C26—N2—C17	115.82 (7)	C23—C18—C19	120.49 (9)
C2—C1—C6	120.09 (10)	C23—C18—C17	111.55 (8)
C2—C1—H1A	120.0	C19—C18—C17	127.87 (9)
C6—C1—H1A	120.0	C20—C19—C18	118.18 (11)
C3—C2—C1	120.29 (11)	C20—C19—H19A	120.9
C3—C2—H2A	119.9	C18—C19—H19A	120.9
C1—C2—H2A	119.9	C19—C20—C21	120.99 (11)
C2—C3—C4	119.84 (10)	C19—C20—H20A	119.5
C2—C3—H3A	120.1	C21—C20—H20A	119.5
C4—C3—H3A	120.1	C22—C21—C20	121.03 (10)
C5—C4—C3	120.16 (11)	C22—C21—H21A	119.5
C5—C4—H4A	119.9	C20—C21—H21A	119.5
C3—C4—H4A	119.9	C21—C22—C23	117.91 (11)
C4—C5—C6	120.41 (10)	C21—C22—H22A	121.0
C4—C5—H5A	119.8	C23—C22—H22A	121.0
C6—C5—H5A	119.8	C18—C23—C22	121.38 (10)
C5—C6—C1	119.14 (9)	C18—C23—C24	110.55 (8)
C5—C6—C7	121.33 (9)	C22—C23—C24	127.71 (10)
C1—C6—C7	119.45 (9)	O2—C24—C23	127.65 (9)
N1—C7—C6	113.67 (7)	O2—C24—C16	124.17 (9)
N1—C7—C8	104.17 (7)	C23—C24—C16	107.95 (8)
C6—C7—C8	114.21 (7)	N2—C25—C15	103.48 (7)
N1—C7—H7A	108.2	N2—C25—H25A	111.1
C6—C7—H7A	108.2	C15—C25—H25A	111.1
C8—C7—H7A	108.2	N2—C25—H25B	111.1
C9—C8—C15	117.66 (7)	C15—C25—H25B	111.1
C9—C8—C7	115.68 (7)	H25A—C25—H25B	109.0
C15—C8—C7	101.04 (7)	N2—C26—C27	114.98 (8)
C9—C8—H8A	107.3	N2—C26—H26A	108.5
C15—C8—H8A	107.3	C27—C26—H26A	108.5
C7—C8—H8A	107.3	N2—C26—H26B	108.5
C10—C9—C14	118.20 (9)	C27—C26—H26B	108.5
C10—C9—C8	122.50 (8)	H26A—C26—H26B	107.5
C14—C9—C8	119.25 (8)	C29—C27—C28	116.36 (9)
C9—C10—C11	120.58 (9)	C29—C27—C26	124.55 (9)
C9—C10—H10A	119.7	C28—C27—C26	119.00 (8)
C11—C10—H10A	119.7	O3—C28—C27	122.90 (9)
C12—C11—C10	120.53 (10)	O3—C28—C15	122.12 (9)
C12—C11—H11A	119.7	C27—C28—C15	114.94 (8)
C10—C11—H11A	119.7	C27—C29—C30	128.62 (9)
C13—C12—C11	119.47 (9)	C27—C29—H29A	115.7
C13—C12—H12A	120.3	C30—C29—H29A	115.7
C11—C12—H12A	120.3	C35—C30—C31	118.20 (10)
C12—C13—C14	120.07 (10)	C35—C30—C29	117.01 (9)
C12—C13—H13A	120.0	C31—C30—C29	124.68 (10)
C14—C13—H13A	120.0	C32—C31—C30	120.50 (10)
C13—C14—C9	121.14 (10)	C32—C31—H31A	119.8
C13—C14—H14A	119.4	C30—C31—H31A	119.8
C9—C14—H14A	119.4	C33—C32—C31	120.49 (11)
C28—C15—C8	117.35 (7)	C33—C32—H32A	119.8
C28—C15—C25	107.65 (7)	C31—C32—H32A	119.8
C8—C15—C25	116.98 (7)	C34—C33—C32	119.32 (10)
C28—C15—C16	108.88 (7)	C34—C33—H33A	120.3
C8—C15—C16	103.12 (7)	C32—C33—H33A	120.3
C25—C15—C16	101.25 (7)	C33—C34—C35	120.63 (11)
N1—C16—C24	110.58 (7)	C33—C34—H34A	119.7
N1—C16—C15	106.43 (7)	C35—C34—H34A	119.7
C24—C16—C15	117.72 (7)	C34—C35—C30	120.84 (11)
N1—C16—C17	113.59 (7)	C34—C35—H35A	119.6
C24—C16—C17	104.93 (7)	C30—C35—H35A	119.6
C15—C16—C17	103.62 (7)

C6—C1—C2—C3	−0.08 (16)	C24—C16—C17—C18	−5.11 (9)
C1—C2—C3—C4	1.96 (17)	C15—C16—C17—C18	−129.17 (7)
C2—C3—C4—C5	−1.43 (16)	O1—C17—C18—C23	124.98 (9)
C3—C4—C5—C6	−0.98 (16)	N2—C17—C18—C23	−111.16 (9)
C4—C5—C6—C1	2.83 (14)	C16—C17—C18—C23	5.82 (10)
C4—C5—C6—C7	−173.65 (9)	O1—C17—C18—C19	−51.54 (13)
C2—C1—C6—C5	−2.30 (15)	N2—C17—C18—C19	72.33 (13)
C2—C1—C6—C7	174.25 (9)	C16—C17—C18—C19	−170.69 (10)
C16—N1—C7—C6	152.42 (8)	C23—C18—C19—C20	−0.35 (15)
C16—N1—C7—C8	27.49 (9)	C17—C18—C19—C20	175.89 (10)
C5—C6—C7—N1	−68.57 (11)	C18—C19—C20—C21	1.03 (17)
C1—C6—C7—N1	114.96 (10)	C19—C20—C21—C22	−0.48 (19)
C5—C6—C7—C8	50.78 (11)	C20—C21—C22—C23	−0.74 (18)
C1—C6—C7—C8	−125.69 (9)	C19—C18—C23—C22	−0.89 (15)
N1—C7—C8—C9	−168.61 (7)	C17—C18—C23—C22	−177.70 (9)
C6—C7—C8—C9	66.82 (10)	C19—C18—C23—C24	172.68 (9)
N1—C7—C8—C15	−40.39 (8)	C17—C18—C23—C24	−4.13 (11)
C6—C7—C8—C15	−164.96 (7)	C21—C22—C23—C18	1.42 (17)
C15—C8—C9—C10	−86.52 (11)	C21—C22—C23—C24	−170.96 (11)
C7—C8—C9—C10	32.95 (12)	C18—C23—C24—O2	−174.10 (10)
C15—C8—C9—C14	96.07 (11)	C22—C23—C24—O2	−1.04 (18)
C7—C8—C9—C14	−144.46 (9)	C18—C23—C24—C16	0.55 (11)
C14—C9—C10—C11	−0.64 (15)	C22—C23—C24—C16	173.61 (10)
C8—C9—C10—C11	−178.07 (9)	N1—C16—C24—O2	55.00 (12)
C9—C10—C11—C12	0.76 (16)	C15—C16—C24—O2	−67.59 (13)
C10—C11—C12—C13	−0.23 (17)	C17—C16—C24—O2	177.86 (9)
C11—C12—C13—C14	−0.40 (17)	N1—C16—C24—C23	−119.88 (8)
C12—C13—C14—C9	0.51 (17)	C15—C16—C24—C23	117.52 (9)
C10—C9—C14—C13	0.01 (15)	C17—C16—C24—C23	2.98 (10)
C8—C9—C14—C13	177.53 (9)	C26—N2—C25—C15	75.74 (9)
C9—C8—C15—C28	−75.97 (10)	C17—N2—C25—C15	−47.14 (9)
C7—C8—C15—C28	157.10 (7)	C28—C15—C25—N2	−72.26 (9)
C9—C8—C15—C25	54.29 (11)	C8—C15—C25—N2	153.07 (8)
C7—C8—C15—C25	−72.63 (9)	C16—C15—C25—N2	41.91 (9)
C9—C8—C15—C16	164.38 (7)	C25—N2—C26—C27	−48.63 (10)
C7—C8—C15—C16	37.46 (8)	C17—N2—C26—C27	65.98 (10)
C7—N1—C16—C24	−132.42 (8)	N2—C26—C27—C29	−158.49 (9)
C7—N1—C16—C15	−3.45 (9)	N2—C26—C27—C28	18.05 (12)
C7—N1—C16—C17	109.92 (8)	C29—C27—C28—O3	−16.55 (14)
C28—C15—C16—N1	−147.40 (7)	C26—C27—C28—O3	166.63 (9)
C8—C15—C16—N1	−22.08 (9)	C29—C27—C28—C15	161.28 (8)
C25—C15—C16—N1	99.34 (8)	C26—C27—C28—C15	−15.54 (12)
C28—C15—C16—C24	−22.72 (11)	C8—C15—C28—O3	−6.06 (13)
C8—C15—C16—C24	102.61 (9)	C25—C15—C28—O3	−140.53 (9)
C25—C15—C16—C24	−135.97 (8)	C16—C15—C28—O3	110.49 (10)
C28—C15—C16—C17	92.55 (8)	C8—C15—C28—C27	176.10 (7)
C8—C15—C16—C17	−142.13 (7)	C25—C15—C28—C27	41.63 (10)
C25—C15—C16—C17	−20.70 (8)	C16—C15—C28—C27	−67.36 (9)
C25—N2—C17—O1	−84.81 (8)	C28—C27—C29—C30	178.98 (9)
C26—N2—C17—O1	157.91 (7)	C26—C27—C29—C30	−4.39 (16)
C25—N2—C17—C18	148.90 (8)	C27—C29—C30—C35	151.84 (11)
C26—N2—C17—C18	31.62 (11)	C27—C29—C30—C31	−32.02 (17)
C25—N2—C17—C16	33.14 (9)	C35—C30—C31—C32	0.05 (15)
C26—N2—C17—C16	−84.14 (9)	C29—C30—C31—C32	−176.05 (9)
N1—C16—C17—O1	−5.11 (10)	C30—C31—C32—C33	−0.44 (16)
C24—C16—C17—O1	−126.00 (8)	C31—C32—C33—C34	−0.13 (17)
C15—C16—C17—O1	109.94 (8)	C32—C33—C34—C35	1.09 (19)
N1—C16—C17—N2	−121.70 (8)	C33—C34—C35—C30	−1.5 (2)
C24—C16—C17—N2	117.40 (8)	C31—C30—C35—C34	0.91 (17)
C15—C16—C17—N2	−6.65 (9)	C29—C30—C35—C34	177.31 (11)
N1—C16—C17—C18	115.78 (8)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C30–C35 and C9–C14 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.862 (18)	1.999 (18)	2.6383 (12)	130.2 (15)
C7—H7A···O1ⁱ	0.98	2.49	3.4701 (13)	177
C10—H10A···O1ⁱ	0.93	2.44	3.3605 (13)	173
C35—H35A···O3ⁱⁱ	0.93	2.44	3.3424 (16)	163
C13—H13A···Cg1ⁱⁱⁱ	0.93	2.89	3.7470 (12)	155
C20—H20A···Cg2^iv	0.93	2.84	3.4275 (15)	122
C33—H33A···Cg2^v	0.93	2.96	3.7723 (15)	147

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

Experimental details

Crystal data
Chemical formula	C₃₅H₂₈N₂O₃
M_r	524.59
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.6319 (2), 11.8130 (2), 14.3562 (3)
α, β, γ (°)	75.395 (1), 72.876 (1), 76.185 (1)
V (Å³)	1332.18 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.30 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.973, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	35745, 10026, 8085
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.768

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.136, 1.02
No. of reflections	10026
No. of parameters	369
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.24

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C30–C35 and C9–C14 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.862 (18)	1.999 (18)	2.6383 (12)	130.2 (15)
C7—H7A···O1ⁱ	0.9800	2.4900	3.4701 (13)	177.00
C10—H10A···O1ⁱ	0.9300	2.4400	3.3605 (13)	173.00
C35—H35A···O3ⁱⁱ	0.9300	2.4400	3.3424 (16)	163.00
C13—H13A···Cg1ⁱⁱⁱ	0.9300	2.89	3.7470 (12)	155
C20—H20A···Cg2^iv	0.9300	2.84	3.4275 (15)	122
C33—H33A···Cg2^v	0.9300	2.96	3.7723 (15)	147

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

Footnotes

‡Additional correspondence author, e-mail: ohasnah@usm.my.

§Thomson Reuters ResearcherID: C-7576-2009.

¶Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The synthetic chemistry work was funded by Universiti Sains Malaysia (USM) under the University Research Grant (No. 1001/PKIMIA/811016). HKF and JHG thank USM for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). RSK thanks USM for the award of a post doctoral fellowship and JHG also thanks USM for the award of a USM fellowship.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Daly, J. W., Spande, T. W., Whittaker, N., Highet, R. J., Feigl, D., Noshimori, N., Tokuyama, T. & Meyers, C. W. (1986). J. Nat. Prod. 49, 265–280. CrossRef CAS PubMed Web of Science Google Scholar
Kumar, R. S., Osman, H., Abdul Rahim, A. S., Hemamalini, M. & Fun, H.-K. (2010b). Acta Cryst. E66, o1444–o1445. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kumar, R. S., Osman, H., Ali, M. A., Hemamalini, M. & Fun, H.-K. (2010a). Acta Cryst. E66, o1370–o1371. Web of Science CSD CrossRef IUCr Journals Google Scholar
Monlineux, R. J. & Pelletier, S. (1987). Alkaloids Chemical and Biological Perspectives. New York: Wiley. Google Scholar
Padwa, A. (1984). 1,3-Dipolar Cycloaddition Chemistry. New York: Wiley. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tsuge, O. & Kanemasa, S. (1989). Adv. Heterocycl. Chem. 45, 231–349. CrossRef CAS Google Scholar
Waldmann, H. (1995). Synlett, pp. 133–141. CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages o2084-o2085

https://doi.org/10.1107/S1600536810028345

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

16-[(E)-Benzyl­­idene]-2-hy­dr­oxy-12,13-di­phenyl-1,11-di­aza­penta­cyclo­[12.3.1.02,10.03,8.010,14]octa­deca-3(8),4,6-triene-9,15-dione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

16-[(E)-Benzylidene]-2-hydroxy-12,13-diphenyl-1,11-diazapentacyclo[12.3.1.0^2,10.0^3,8.0^10,14]octadeca-3(8),4,6-triene-9,15-dione