2-Hy­droxy-16-[(E)-4-methyl­benzyl­idene]-13-(4-methyl­phen­yl)-12-phenyl-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.; Abdul Rahim, A.S.; Goh, J.H.; Fun, H.-K.

doi:10.1107/S1600536810028357

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages o2086-o2087

https://doi.org/10.1107/S1600536810028357

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2-Hydroxy-16-[(E)-4-methylbenzylidene]-13-(4-methylphenyl)-12-phenyl-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 ‡ Aisyah Saad Abdul Rahim,^b Jia Hao Goh ^c § and Hoong-Kun Fun ^c ^*¶

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSchool of Pharmaceutical Sciences, 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, C₃₇H₃₂N₂O₃, an intramolecular O—H⋯N hydrogen bond generates a five-membered ring, producing an S(5) motif. The piperidone ring adopts a half-chair conformation. The two fused pyrrolidine rings have similar envelope conformations. The interplanar angles between the benzene rings A/B and C/D are 75.68 (7) and 30.22 (6)°, respectively. In the crystal structure, adjacent molecules are interconnected into chains propagating along the [010] direction via intermolecular C—H⋯O hydrogen bonds. Further stabilization is provided by weak C—H⋯π interactions.

Related literature

For general background to and applications of related structures, see: Ban et al. (1974 ); De Amici et al. (1990 ); Howe & Shelton (1990 ); Kornet & Thio (1976 ); Kozikowski (1984 ); Li et al. (1996 ); Okita & Isobe (1994 ); Rosenmond et al. (1994 ); Southon & Buckingham (1989 ). 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 ,c ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₃₇H₃₂N₂O₃
M_r = 552.65
Monoclinic, C 2/c
a = 42.936 (5) Å
b = 7.3759 (9) Å
c = 17.990 (2) Å
β = 91.154 (2)°
V = 5696.0 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.48 × 0.15 × 0.12 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.962, T_max = 0.990
21929 measured reflections
7946 independent reflections
6021 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.139
S = 1.04
7946 reflections
389 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C9–C14 and C18–C23 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N1	0.98 (2)	1.94 (2)	2.6477 (15)	126.7 (18)
C22—H22A⋯O1ⁱ	0.93	2.42	3.2564 (16)	149
C3—H3A⋯Cg1ⁱⁱ	0.93	2.73	3.5620 (18)	150
C37—H37B⋯Cg2ⁱⁱⁱ	0.96	2.61	3.3932 (16)	139
Symmetry codes: (i) x, y-1, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{5\over 2}}, -z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536810028357/rz2478sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028357/rz2478Isup2.hkl

checkCIF report

Comment top

The versatility of 1,3-dipolar cycloadditions for the construction of five-membered heterocyclic rings is well established. The reaction of azomethine ylides with alkenes affords pyrrolidines which are present in numerous alkaloids (Southon & Buckingham, 1989) and physiologically active compounds (Li et al., 1996). Spiropyrrolidines have received considerable attention due to its biological activity (Kozikowski, 1984; Howe & Shelton, 1990; De Amici et al., 1990; Ban et al., 1974). They display interesting anti-microbial, anti-tumor and antibiotic properties besides acting as inhibitors of human NK-I receptor activity (Okita & Isobe, 1994; Rosenmond et al., 1994; Kornet & Thio, 1976). The biological significance of the above mentioned heterocycles, prompted us to synthesize the title compound whose crystal structure is presented here.

The molecular structure of the title compound is shown in 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 = 0.6128 (13) Å, θ = 36.28 (12)° and φ = 58.1 (2)° (Cremer & Pople, 1975). The two fused pyrrolidine rings with atom sequences C7/C8/C15/C16/N1 and C15/C16/C17/N2/C25, adopt similar envelope conformations, with atoms C8 and C25, respectively, as the flap atoms. The puckering parameters are Q = 0.3433 (14) Å, φ = 77.2 (2)° for the C7/C8/C15/C16/N1 pyrrolidine ring and Q = 0.4564 (13) Å, φ = 331.35 (17)° for the C15/C16/C17/N2/C25 pyrrolidine ring. The benzene rings A/B and C/D form interplanar angles of 75.68 (7) and 30.22 (6)°, respectively. The geometric parameters are consistent to those observed in closely related structures (Kumar et al., 2010a,b,c).

In the crystal structure, adjacent molecules are interconnected into one-dimensional chains propagating along the [010] direction via intermolecular C22—H22A···O1 hydrogen bonds (Fig. 2, Table 1). Further stabilization is provided by weak intermolecular C3—H3A···Cg1 and C37—H37B···Cg2 interactions involving the C9-C14 (Cg1) and C18-C23 (Cg2) benzene rings.

Related literature top

For general background to and applications of the title compound, see: Ban et al. (1974); De Amici et al. (1990); Howe & Shelton (1990); Kornet & Thio (1976); Kozikowski (1984); Li et al. (1996); Okita & Isobe (1994); Rosenmond et al. (1994); Southon & Buckingham (1989). 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,c). 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)-(4-methylphenyl)methylidene]tetrahydro-4(1H)-pyridinone (0.100 g, 0.330 mmol), ninhydrin (0.059 g, 0.330 mmol) and phenylglycine (0.050 g, 0.330 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

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 20 % 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 c axis, showing infinite chains propagating along the [010] direction. H atoms not involved in intermolecular hydrogen bonds (dashed lines) have been omitted for clarity.

2-Hydroxy-16-[(E)-4-methylbenzylidene]-13-(4-methylphenyl)-12-phenyl- 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

C₃₇H₃₂N₂O₃	F(000) = 2336
M_r = 552.65	D_x = 1.289 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5678 reflections
a = 42.936 (5) Å	θ = 2.4–29.4°
b = 7.3759 (9) Å	µ = 0.08 mm⁻¹
c = 17.990 (2) Å	T = 100 K
β = 91.154 (2)°	Block, colourless
V = 5696.0 (12) Å³	0.48 × 0.15 × 0.12 mm
Z = 8

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	7946 independent reflections
Radiation source: fine-focus sealed tube	6021 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 29.6°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −59→57
T_min = 0.962, T_max = 0.990	k = −10→10
21929 measured reflections	l = −17→24

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.075P)² + 2.0745P] where P = (F_o² + 2F_c²)/3
7946 reflections	(Δ/σ)_max < 0.001
389 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₃₇H₃₂N₂O₃	V = 5696.0 (12) Å³
M_r = 552.65	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 42.936 (5) Å	µ = 0.08 mm⁻¹
b = 7.3759 (9) Å	T = 100 K
c = 17.990 (2) Å	0.48 × 0.15 × 0.12 mm
β = 91.154 (2)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	7946 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	6021 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.990	R_int = 0.034
21929 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.44 e Å⁻³
7946 reflections	Δρ_min = −0.23 e Å⁻³
389 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	0.18627 (2)	1.03210 (12)	0.30204 (5)	0.01996 (19)
O2	0.13482 (2)	0.48587 (12)	0.29378 (6)	0.0250 (2)
O3	0.08307 (2)	0.67065 (13)	0.41752 (5)	0.0241 (2)
N1	0.13953 (3)	0.86274 (16)	0.23346 (6)	0.0199 (2)
N2	0.15966 (2)	1.00834 (14)	0.41487 (6)	0.0178 (2)
C1	0.08158 (3)	1.0494 (2)	0.10439 (8)	0.0304 (3)
H1A	0.0854	1.1698	0.1171	0.036*
C2	0.06469 (4)	1.0090 (3)	0.03965 (9)	0.0421 (5)
H2A	0.0569	1.1022	0.0098	0.050*
C3	0.05942 (4)	0.8310 (3)	0.01968 (9)	0.0442 (5)
H3A	0.0482	0.8042	−0.0237	0.053*
C4	0.07088 (4)	0.6919 (3)	0.06415 (9)	0.0379 (4)
H4A	0.0676	0.5719	0.0502	0.046*
C5	0.08731 (3)	0.7314 (2)	0.12971 (8)	0.0287 (3)
H5A	0.0946	0.6377	0.1599	0.034*
C6	0.09286 (3)	0.9115 (2)	0.15028 (7)	0.0220 (3)
C7	0.10909 (3)	0.95777 (18)	0.22299 (7)	0.0192 (3)
H7A	0.1129	1.0888	0.2242	0.023*
C8	0.08979 (3)	0.90609 (17)	0.29166 (7)	0.0177 (2)
H8A	0.0808	0.7859	0.2824	0.021*
C9	0.06333 (3)	1.03429 (18)	0.30922 (7)	0.0200 (3)
C10	0.06675 (3)	1.22327 (19)	0.30781 (8)	0.0242 (3)
H10A	0.0857	1.2737	0.2944	0.029*
C11	0.04219 (3)	1.3357 (2)	0.32621 (9)	0.0287 (3)
H11A	0.0451	1.4607	0.3255	0.034*
C12	0.01336 (3)	1.2665 (2)	0.34572 (8)	0.0293 (3)
C13	0.00988 (3)	1.0786 (2)	0.34639 (8)	0.0291 (3)
H13A	−0.0092	1.0286	0.3590	0.035*
C14	0.03436 (3)	0.9650 (2)	0.32861 (8)	0.0238 (3)
H14A	0.0314	0.8401	0.3296	0.029*
C15	0.11491 (3)	0.88589 (16)	0.35278 (7)	0.0170 (2)
C16	0.14402 (3)	0.81013 (16)	0.31136 (7)	0.0168 (2)
C17	0.17248 (3)	0.90762 (16)	0.35090 (7)	0.0167 (2)
C18	0.19448 (3)	0.75676 (17)	0.37353 (7)	0.0171 (2)
C19	0.22436 (3)	0.77126 (18)	0.40446 (7)	0.0198 (3)
H19A	0.2335	0.8841	0.4125	0.024*
C20	0.24021 (3)	0.61228 (19)	0.42312 (7)	0.0223 (3)
H20A	0.2603	0.6194	0.4432	0.027*
C21	0.22647 (3)	0.44229 (19)	0.41226 (8)	0.0229 (3)
H21A	0.2372	0.3384	0.4271	0.027*
C22	0.19708 (3)	0.42651 (17)	0.37970 (8)	0.0213 (3)
H22A	0.1880	0.3135	0.3715	0.026*
C23	0.18143 (3)	0.58607 (17)	0.35960 (7)	0.0181 (2)
C24	0.15120 (3)	0.60572 (17)	0.31985 (7)	0.0183 (2)
C25	0.12859 (3)	1.06363 (17)	0.38670 (7)	0.0188 (2)
H25A	0.1302	1.1574	0.3492	0.023*
H25B	0.1158	1.1079	0.4267	0.023*
C26	0.15543 (3)	0.89938 (17)	0.48297 (7)	0.0184 (2)
H26A	0.1486	0.9792	0.5223	0.022*
H26B	0.1755	0.8498	0.4983	0.022*
C27	0.13222 (3)	0.74384 (17)	0.47496 (7)	0.0181 (2)
C28	0.10700 (3)	0.75907 (17)	0.41627 (7)	0.0183 (2)
C29	0.13492 (3)	0.58452 (18)	0.51089 (7)	0.0201 (3)
H29A	0.1197	0.4982	0.5001	0.024*
C30	0.15930 (3)	0.53178 (18)	0.56535 (7)	0.0199 (3)
C31	0.17147 (3)	0.35579 (18)	0.56138 (8)	0.0231 (3)
H31A	0.1635	0.2751	0.5261	0.028*
C32	0.19527 (3)	0.30077 (18)	0.60963 (8)	0.0228 (3)
H32A	0.2030	0.1834	0.6061	0.027*
C33	0.20786 (3)	0.41771 (18)	0.66347 (7)	0.0203 (3)
C34	0.19511 (3)	0.59187 (19)	0.66842 (7)	0.0232 (3)
H34A	0.2027	0.6713	0.7046	0.028*
C35	0.17126 (3)	0.64854 (18)	0.62047 (7)	0.0225 (3)
H35A	0.1632	0.7649	0.6250	0.027*
C36	−0.01298 (4)	1.3907 (3)	0.36736 (11)	0.0440 (4)
H36A	−0.0091	1.5106	0.3490	0.066*
H36B	−0.0143	1.3941	0.4205	0.066*
H36C	−0.0322	1.3462	0.3463	0.066*
C37	0.23421 (3)	0.35823 (19)	0.71403 (8)	0.0234 (3)
H37A	0.2320	0.2315	0.7250	0.035*
H37B	0.2338	0.4266	0.7594	0.035*
H37D	0.2537	0.3786	0.6900	0.035*
H1O1	0.1756 (5)	1.015 (3)	0.2538 (13)	0.056 (6)*
H1N1	0.1405 (4)	0.767 (3)	0.2071 (10)	0.032 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0211 (5)	0.0179 (4)	0.0209 (5)	−0.0028 (3)	0.0006 (4)	0.0031 (4)
O2	0.0225 (5)	0.0194 (4)	0.0330 (5)	−0.0036 (4)	−0.0018 (4)	−0.0046 (4)
O3	0.0216 (5)	0.0251 (5)	0.0254 (5)	−0.0044 (4)	−0.0012 (4)	0.0033 (4)
N1	0.0183 (5)	0.0239 (6)	0.0177 (5)	0.0019 (4)	0.0002 (4)	−0.0017 (4)
N2	0.0192 (5)	0.0162 (5)	0.0179 (5)	0.0014 (4)	0.0002 (4)	−0.0006 (4)
C1	0.0224 (7)	0.0431 (9)	0.0257 (7)	0.0004 (6)	0.0035 (5)	0.0129 (6)
C2	0.0246 (8)	0.0774 (14)	0.0242 (8)	0.0027 (8)	0.0005 (6)	0.0195 (8)
C3	0.0224 (7)	0.0920 (15)	0.0181 (7)	−0.0063 (8)	−0.0005 (6)	−0.0006 (8)
C4	0.0241 (7)	0.0609 (11)	0.0289 (8)	−0.0092 (7)	0.0039 (6)	−0.0152 (8)
C5	0.0242 (7)	0.0367 (8)	0.0252 (7)	−0.0022 (6)	−0.0008 (5)	−0.0033 (6)
C6	0.0162 (6)	0.0316 (7)	0.0183 (6)	−0.0003 (5)	0.0019 (5)	0.0031 (5)
C7	0.0176 (6)	0.0207 (6)	0.0193 (6)	0.0006 (5)	0.0002 (5)	0.0016 (5)
C8	0.0167 (6)	0.0184 (6)	0.0179 (6)	0.0002 (4)	−0.0002 (4)	0.0005 (5)
C9	0.0180 (6)	0.0239 (6)	0.0179 (6)	0.0028 (5)	−0.0020 (5)	−0.0006 (5)
C10	0.0210 (6)	0.0236 (6)	0.0279 (7)	0.0015 (5)	−0.0027 (5)	0.0018 (5)
C11	0.0270 (7)	0.0250 (7)	0.0338 (8)	0.0057 (6)	−0.0063 (6)	−0.0032 (6)
C12	0.0222 (7)	0.0371 (8)	0.0282 (7)	0.0091 (6)	−0.0058 (6)	−0.0090 (6)
C13	0.0182 (6)	0.0400 (8)	0.0291 (8)	0.0011 (6)	0.0000 (5)	−0.0057 (6)
C14	0.0207 (6)	0.0272 (7)	0.0236 (7)	−0.0004 (5)	−0.0003 (5)	−0.0027 (5)
C15	0.0156 (6)	0.0176 (5)	0.0178 (6)	0.0005 (4)	0.0008 (4)	0.0005 (5)
C16	0.0158 (6)	0.0169 (5)	0.0176 (6)	−0.0004 (4)	−0.0002 (4)	−0.0009 (4)
C17	0.0169 (6)	0.0150 (5)	0.0183 (6)	−0.0017 (4)	0.0004 (4)	−0.0006 (4)
C18	0.0181 (6)	0.0168 (5)	0.0162 (6)	0.0008 (4)	0.0008 (4)	−0.0008 (4)
C19	0.0205 (6)	0.0200 (6)	0.0188 (6)	−0.0008 (5)	−0.0012 (5)	−0.0018 (5)
C20	0.0209 (6)	0.0269 (7)	0.0189 (6)	0.0035 (5)	−0.0027 (5)	−0.0017 (5)
C21	0.0255 (7)	0.0219 (6)	0.0213 (6)	0.0067 (5)	−0.0002 (5)	−0.0002 (5)
C22	0.0237 (6)	0.0160 (6)	0.0242 (7)	0.0014 (5)	0.0022 (5)	−0.0019 (5)
C23	0.0181 (6)	0.0179 (6)	0.0184 (6)	0.0002 (4)	0.0015 (5)	−0.0019 (5)
C24	0.0172 (6)	0.0175 (6)	0.0202 (6)	−0.0003 (4)	0.0020 (5)	−0.0019 (5)
C25	0.0188 (6)	0.0168 (6)	0.0208 (6)	0.0008 (4)	0.0007 (5)	−0.0002 (5)
C26	0.0203 (6)	0.0175 (6)	0.0175 (6)	−0.0006 (5)	0.0003 (5)	−0.0008 (5)
C27	0.0191 (6)	0.0193 (6)	0.0160 (6)	0.0001 (5)	0.0012 (4)	−0.0005 (5)
C28	0.0189 (6)	0.0167 (5)	0.0193 (6)	0.0017 (4)	0.0016 (5)	−0.0013 (5)
C29	0.0202 (6)	0.0211 (6)	0.0191 (6)	−0.0018 (5)	0.0004 (5)	0.0017 (5)
C30	0.0219 (6)	0.0201 (6)	0.0178 (6)	−0.0014 (5)	0.0012 (5)	0.0027 (5)
C31	0.0268 (7)	0.0179 (6)	0.0245 (7)	−0.0031 (5)	−0.0027 (5)	−0.0001 (5)
C32	0.0258 (7)	0.0173 (6)	0.0253 (7)	0.0013 (5)	0.0009 (5)	0.0014 (5)
C33	0.0199 (6)	0.0226 (6)	0.0184 (6)	−0.0004 (5)	0.0024 (5)	0.0030 (5)
C34	0.0281 (7)	0.0242 (6)	0.0172 (6)	0.0006 (5)	−0.0007 (5)	−0.0016 (5)
C35	0.0284 (7)	0.0203 (6)	0.0189 (6)	0.0041 (5)	0.0003 (5)	−0.0005 (5)
C36	0.0301 (8)	0.0494 (10)	0.0524 (11)	0.0153 (7)	−0.0035 (8)	−0.0168 (9)
C37	0.0223 (6)	0.0272 (7)	0.0205 (6)	0.0019 (5)	−0.0003 (5)	0.0018 (5)

Geometric parameters (Å, º) top

O1—C17	1.4095 (15)	C16—C24	1.5458 (17)
O1—H1O1	0.98 (2)	C16—C17	1.5753 (17)
O2—C24	1.2176 (15)	C17—C18	1.5101 (17)
O3—C28	1.2175 (16)	C18—C19	1.3922 (18)
N1—C16	1.4631 (17)	C18—C23	1.3986 (17)
N1—C7	1.4914 (17)	C19—C20	1.3935 (18)
N1—H1N1	0.853 (19)	C19—H19A	0.9300
N2—C25	1.4748 (16)	C20—C21	1.3978 (19)
N2—C26	1.4795 (16)	C20—H20A	0.9300
N2—C17	1.4848 (16)	C21—C22	1.3851 (19)
C1—C6	1.391 (2)	C21—H21A	0.9300
C1—C2	1.392 (2)	C22—C23	1.3992 (17)
C1—H1A	0.9300	C22—H22A	0.9300
C2—C3	1.379 (3)	C23—C24	1.4766 (18)
C2—H2A	0.9300	C25—H25A	0.9700
C3—C4	1.385 (3)	C25—H25B	0.9700
C3—H3A	0.9300	C26—C27	1.5248 (17)
C4—C5	1.393 (2)	C26—H26A	0.9700
C4—H4A	0.9300	C26—H26B	0.9700
C5—C6	1.398 (2)	C27—C29	1.3451 (18)
C5—H5A	0.9300	C27—C28	1.5012 (18)
C6—C7	1.5090 (18)	C29—C30	1.4717 (18)
C7—C8	1.5490 (18)	C29—H29A	0.9300
C7—H7A	0.9800	C30—C31	1.4016 (18)
C8—C9	1.5162 (18)	C30—C35	1.4028 (19)
C8—C15	1.5321 (17)	C31—C32	1.3880 (19)
C8—H8A	0.9800	C31—H31A	0.9300
C9—C14	1.3953 (19)	C32—C33	1.3976 (19)
C9—C10	1.4019 (19)	C32—H32A	0.9300
C10—C11	1.3867 (19)	C33—C34	1.4000 (19)
C10—H10A	0.9300	C33—C37	1.5027 (19)
C11—C12	1.391 (2)	C34—C35	1.3898 (19)
C11—H11A	0.9300	C34—H34A	0.9300
C12—C13	1.394 (2)	C35—H35A	0.9300
C12—C36	1.512 (2)	C36—H36A	0.9600
C13—C14	1.387 (2)	C36—H36B	0.9600
C13—H13A	0.9300	C36—H36C	0.9600
C14—H14A	0.9300	C37—H37A	0.9600
C15—C28	1.5202 (18)	C37—H37B	0.9600
C15—C25	1.5562 (17)	C37—H37D	0.9600
C15—C16	1.5708 (17)

C17—O1—H1O1	105.8 (13)	C19—C18—C23	120.23 (11)
C16—N1—C7	110.12 (10)	C19—C18—C17	128.13 (11)
C16—N1—H1N1	107.8 (12)	C23—C18—C17	111.64 (11)
C7—N1—H1N1	111.8 (12)	C18—C19—C20	118.25 (12)
C25—N2—C26	108.03 (10)	C18—C19—H19A	120.9
C25—N2—C17	102.65 (10)	C20—C19—H19A	120.9
C26—N2—C17	115.06 (10)	C19—C20—C21	121.22 (12)
C6—C1—C2	120.58 (17)	C19—C20—H20A	119.4
C6—C1—H1A	119.7	C21—C20—H20A	119.4
C2—C1—H1A	119.7	C22—C21—C20	120.86 (12)
C3—C2—C1	120.15 (16)	C22—C21—H21A	119.6
C3—C2—H2A	119.9	C20—C21—H21A	119.6
C1—C2—H2A	119.9	C21—C22—C23	117.85 (12)
C2—C3—C4	120.01 (15)	C21—C22—H22A	121.1
C2—C3—H3A	120.0	C23—C22—H22A	121.1
C4—C3—H3A	120.0	C18—C23—C22	121.48 (12)
C3—C4—C5	120.16 (17)	C18—C23—C24	110.10 (11)
C3—C4—H4A	119.9	C22—C23—C24	128.36 (12)
C5—C4—H4A	119.9	O2—C24—C23	127.63 (12)
C4—C5—C6	120.23 (15)	O2—C24—C16	123.90 (12)
C4—C5—H5A	119.9	C23—C24—C16	108.36 (10)
C6—C5—H5A	119.9	N2—C25—C15	103.50 (10)
C1—C6—C5	118.85 (14)	N2—C25—H25A	111.1
C1—C6—C7	119.87 (13)	C15—C25—H25A	111.1
C5—C6—C7	121.18 (12)	N2—C25—H25B	111.1
N1—C7—C6	113.04 (11)	C15—C25—H25B	111.1
N1—C7—C8	105.38 (10)	H25A—C25—H25B	109.0
C6—C7—C8	112.98 (10)	N2—C26—C27	114.92 (10)
N1—C7—H7A	108.4	N2—C26—H26A	108.5
C6—C7—H7A	108.4	C27—C26—H26A	108.5
C8—C7—H7A	108.4	N2—C26—H26B	108.5
C9—C8—C15	115.52 (10)	C27—C26—H26B	108.5
C9—C8—C7	115.34 (11)	H26A—C26—H26B	107.5
C15—C8—C7	102.47 (10)	C29—C27—C28	117.22 (11)
C9—C8—H8A	107.7	C29—C27—C26	124.19 (12)
C15—C8—H8A	107.7	C28—C27—C26	118.11 (11)
C7—C8—H8A	107.7	O3—C28—C27	122.95 (12)
C14—C9—C10	117.58 (12)	O3—C28—C15	123.02 (12)
C14—C9—C8	119.93 (12)	C27—C28—C15	113.92 (11)
C10—C9—C8	122.49 (12)	C27—C29—C30	127.18 (12)
C11—C10—C9	120.66 (13)	C27—C29—H29A	116.4
C11—C10—H10A	119.7	C30—C29—H29A	116.4
C9—C10—H10A	119.7	C31—C30—C35	118.24 (12)
C10—C11—C12	121.71 (14)	C31—C30—C29	118.15 (12)
C10—C11—H11A	119.1	C35—C30—C29	123.61 (12)
C12—C11—H11A	119.1	C32—C31—C30	120.62 (13)
C11—C12—C13	117.58 (13)	C32—C31—H31A	119.7
C11—C12—C36	121.11 (15)	C30—C31—H31A	119.7
C13—C12—C36	121.29 (15)	C31—C32—C33	121.50 (12)
C14—C13—C12	121.15 (14)	C31—C32—H32A	119.2
C14—C13—H13A	119.4	C33—C32—H32A	119.2
C12—C13—H13A	119.4	C32—C33—C34	117.64 (12)
C13—C14—C9	121.31 (14)	C32—C33—C37	121.02 (12)
C13—C14—H14A	119.3	C34—C33—C37	121.34 (12)
C9—C14—H14A	119.3	C35—C34—C33	121.39 (13)
C28—C15—C8	115.74 (10)	C35—C34—H34A	119.3
C28—C15—C25	108.19 (10)	C33—C34—H34A	119.3
C8—C15—C25	117.02 (10)	C34—C35—C30	120.57 (12)
C28—C15—C16	109.24 (10)	C34—C35—H35A	119.7
C8—C15—C16	104.45 (10)	C30—C35—H35A	119.7
C25—C15—C16	100.84 (9)	C12—C36—H36A	109.5
N1—C16—C24	112.06 (10)	C12—C36—H36B	109.5
N1—C16—C15	105.61 (10)	H36A—C36—H36B	109.5
C24—C16—C15	117.32 (10)	C12—C36—H36C	109.5
N1—C16—C17	113.43 (10)	H36A—C36—H36C	109.5
C24—C16—C17	104.44 (10)	H36B—C36—H36C	109.5
C15—C16—C17	103.93 (9)	C33—C37—H37A	109.5
O1—C17—N2	108.92 (10)	C33—C37—H37B	109.5
O1—C17—C18	112.33 (10)	H37A—C37—H37B	109.5
N2—C17—C18	113.54 (10)	C33—C37—H37D	109.5
O1—C17—C16	110.32 (10)	H37A—C37—H37D	109.5
N2—C17—C16	106.38 (10)	H37B—C37—H37D	109.5
C18—C17—C16	105.11 (10)

C6—C1—C2—C3	−1.1 (2)	C24—C16—C17—C18	4.01 (12)
C1—C2—C3—C4	0.2 (2)	C15—C16—C17—C18	127.53 (10)
C2—C3—C4—C5	1.0 (2)	O1—C17—C18—C19	53.74 (17)
C3—C4—C5—C6	−1.2 (2)	N2—C17—C18—C19	−70.41 (16)
C2—C1—C6—C5	0.9 (2)	C16—C17—C18—C19	173.73 (12)
C2—C1—C6—C7	−175.58 (13)	O1—C17—C18—C23	−126.08 (11)
C4—C5—C6—C1	0.3 (2)	N2—C17—C18—C23	109.78 (12)
C4—C5—C6—C7	176.70 (13)	C16—C17—C18—C23	−6.09 (14)
C16—N1—C7—C6	−142.49 (11)	C23—C18—C19—C20	−2.07 (19)
C16—N1—C7—C8	−18.64 (13)	C17—C18—C19—C20	178.13 (12)
C1—C6—C7—N1	−130.42 (13)	C18—C19—C20—C21	−0.9 (2)
C5—C6—C7—N1	53.20 (17)	C19—C20—C21—C22	2.7 (2)
C1—C6—C7—C8	110.02 (14)	C20—C21—C22—C23	−1.3 (2)
C5—C6—C7—C8	−66.36 (16)	C19—C18—C23—C22	3.43 (19)
N1—C7—C8—C9	158.63 (11)	C17—C18—C23—C22	−176.73 (12)
C6—C7—C8—C9	−77.49 (14)	C19—C18—C23—C24	−174.12 (11)
N1—C7—C8—C15	32.27 (12)	C17—C18—C23—C24	5.71 (15)
C6—C7—C8—C15	156.15 (11)	C21—C22—C23—C18	−1.68 (19)
C15—C8—C9—C14	−103.93 (14)	C21—C22—C23—C24	175.39 (13)
C7—C8—C9—C14	136.68 (13)	C18—C23—C24—O2	173.47 (13)
C15—C8—C9—C10	75.22 (16)	C22—C23—C24—O2	−3.9 (2)
C7—C8—C9—C10	−44.16 (17)	C18—C23—C24—C16	−2.83 (14)
C14—C9—C10—C11	0.9 (2)	C22—C23—C24—C16	179.82 (13)
C8—C9—C10—C11	−178.22 (12)	N1—C16—C24—O2	−54.22 (17)
C9—C10—C11—C12	−0.8 (2)	C15—C16—C24—O2	68.20 (17)
C10—C11—C12—C13	0.2 (2)	C17—C16—C24—O2	−177.41 (12)
C10—C11—C12—C36	178.59 (15)	N1—C16—C24—C23	122.25 (11)
C11—C12—C13—C14	0.3 (2)	C15—C16—C24—C23	−115.33 (12)
C36—C12—C13—C14	−178.10 (14)	C17—C16—C24—C23	−0.94 (13)
C12—C13—C14—C9	−0.2 (2)	C26—N2—C25—C15	−73.87 (11)
C10—C9—C14—C13	−0.5 (2)	C17—N2—C25—C15	48.11 (11)
C8—C9—C14—C13	178.72 (13)	C28—C15—C25—N2	71.91 (12)
C9—C8—C15—C28	80.11 (14)	C8—C15—C25—N2	−155.19 (10)
C7—C8—C15—C28	−153.65 (10)	C16—C15—C25—N2	−42.68 (11)
C9—C8—C15—C25	−49.30 (15)	C25—N2—C26—C27	51.24 (13)
C7—C8—C15—C25	76.94 (12)	C17—N2—C26—C27	−62.74 (14)
C9—C8—C15—C16	−159.75 (10)	N2—C26—C27—C29	146.41 (12)
C7—C8—C15—C16	−33.51 (12)	N2—C26—C27—C28	−25.38 (16)
C7—N1—C16—C24	126.20 (11)	C29—C27—C28—O3	27.66 (18)
C7—N1—C16—C15	−2.66 (13)	C26—C27—C28—O3	−159.97 (12)
C7—N1—C16—C17	−115.84 (11)	C29—C27—C28—C15	−148.73 (12)
C28—C15—C16—N1	147.51 (10)	C26—C27—C28—C15	23.64 (15)
C8—C15—C16—N1	23.11 (12)	C8—C15—C28—O3	3.79 (18)
C25—C15—C16—N1	−98.70 (11)	C25—C15—C28—O3	137.36 (12)
C28—C15—C16—C24	21.84 (15)	C16—C15—C28—O3	−113.72 (13)
C8—C15—C16—C24	−102.57 (12)	C8—C15—C28—C27	−179.82 (10)
C25—C15—C16—C24	135.63 (11)	C25—C15—C28—C27	−46.25 (13)
C28—C15—C16—C17	−92.83 (11)	C16—C15—C28—C27	62.67 (13)
C8—C15—C16—C17	142.76 (10)	C28—C27—C29—C30	174.18 (12)
C25—C15—C16—C17	20.96 (11)	C26—C27—C29—C30	2.3 (2)
C25—N2—C17—O1	85.20 (11)	C27—C29—C30—C31	−138.76 (14)
C26—N2—C17—O1	−157.73 (10)	C27—C29—C30—C35	40.5 (2)
C25—N2—C17—C18	−148.83 (10)	C35—C30—C31—C32	−1.6 (2)
C26—N2—C17—C18	−31.75 (14)	C29—C30—C31—C32	177.71 (12)
C25—N2—C17—C16	−33.71 (12)	C30—C31—C32—C33	0.0 (2)
C26—N2—C17—C16	83.36 (12)	C31—C32—C33—C34	1.5 (2)
N1—C16—C17—O1	3.03 (14)	C31—C32—C33—C37	−178.33 (13)
C24—C16—C17—O1	125.32 (10)	C32—C33—C34—C35	−1.5 (2)
C15—C16—C17—O1	−111.16 (10)	C37—C33—C34—C35	178.38 (13)
N1—C16—C17—N2	121.02 (11)	C33—C34—C35—C30	−0.1 (2)
C24—C16—C17—N2	−116.69 (10)	C31—C30—C35—C34	1.7 (2)
C15—C16—C17—N2	6.83 (12)	C29—C30—C35—C34	−177.62 (13)
N1—C16—C17—C18	−118.28 (11)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C9–C14 and C18–C23 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.98 (2)	1.94 (2)	2.6477 (15)	126.7 (18)
C22—H22A···O1ⁱ	0.93	2.42	3.2564 (16)	149
C3—H3A···Cg1ⁱⁱ	0.93	2.73	3.5620 (18)	150
C37—H37B···Cg2ⁱⁱⁱ	0.96	2.61	3.3932 (16)	139

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+5/2, −z−1/2; (iii) −x+1/2, y+3/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₃₇H₃₂N₂O₃
M_r	552.65
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	42.936 (5), 7.3759 (9), 17.990 (2)
β (°)	91.154 (2)
V (Å³)	5696.0 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.48 × 0.15 × 0.12

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.962, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	21929, 7946, 6021
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.139, 1.04
No. of reflections	7946
No. of parameters	389
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.23

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 C9–C14 and C18–C23 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.98 (2)	1.94 (2)	2.6477 (15)	126.7 (18)
C22—H22A···O1ⁱ	0.9300	2.4200	3.2564 (16)	149.00
C3—H3A···Cg1ⁱⁱ	0.9300	2.73	3.5620 (18)	150
C37—H37B···Cg2ⁱⁱⁱ	0.9600	2.61	3.3932 (16)	139

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+5/2, −z−1/2; (iii) −x+1/2, y+3/2, −z+1/2.

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.

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages o2086-o2087

https://doi.org/10.1107/S1600536810028357

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

2-Hy­dr­oxy-16-[(E)-4-methyl­benzyl­­idene]-13-(4-methyl­phen­yl)-12-phenyl-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

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