5-[(E)-Benzyl­idene]-2-hy­droxy-10-methyl-8-phenyl-3,10-diazahexa­cyclo­[10.7.1.13,7.02,11.07,11.016,20]henicosa-1(19),12(20),13,15,17-pentaen-6-one ethanol 0.25-solvate 0.6-hydrate

Kumar, R.S.; Osman, H.; Perumal, S.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536810039310

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages o2736-o2737

https://doi.org/10.1107/S1600536810039310

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5-[(E)-Benzylidene]-2-hydroxy-10-methyl-8-phenyl-3,10-diazahexacyclo[10.7.1.1^3,7.0^2,11.0^7,11.0^16,20]henicosa-1(19),12(20),13,15,17-pentaen-6-one ethanol 0.25-solvate 0.6-hydrate

Raju Suresh Kumar,^a Hasnah Osman,^a Subbu Perumal,^b Madhukar Hemamalini ^c and Hoong-Kun Fun ^c ^*‡

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 31 August 2010; accepted 1 October 2010; online 9 October 2010)

In the title compound, C₃₃H₂₈N₂O₂·0.25C₂H₆O·0.6H₂O, the piperidone ring adopts a chair conformation and the pyrrolidine ring adopts an envelope conformation. The dihedral angle between the two phenyl rings is 70.83 (16)°. One of the N atoms of the organic molecule is disordered over two positions in a 0.52 (4):0.48 (4) ratio and the two solvent molecules are partially occupied and show high displacement parameters. In the crystal, molecules are connected by intermolecular O—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For details of 1,3-dipolar cycloaddition reactions, see: Lown (1984 ); Tsuge & Kanemasa (1989 ); Williams & Fegley (1992 ); Periyasami et al. (2009 ); Suresh Babu & Raghunathan (2007 ). For puckering parameters, see: Cremer & Pople (1975 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₃₃H₂₈N₂O₂·0.25C₂H₆O·0.6H₂O
M_r = 506.90
Tetragonal, $[P \overline 42_1 c ]$
a = 19.3839 (3) Å
c = 14.0757 (2) Å
V = 5288.74 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.19 × 0.18 × 0.15 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.985, T_max = 0.988
23186 measured reflections
4230 independent reflections
3388 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.148
S = 1.03
4230 reflections
387 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O1ⁱ	0.66 (4)	2.48 (4)	3.117 (5)	164 (5)
C17—H17A⋯O2ⁱⁱ	0.93	2.57	3.287 (6)	134
Symmetry codes: (i) -x+1, -y, z; (ii) y, -x+1, -z.

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/S1600536810039310/hb5631sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039310/hb5631Isup2.hkl

checkCIF report

Comment top

Intermolecular 1,3-dipolar cycloadditions are one of the most useful processes for the construction of five-membered heterocycles containing the pyrrolidine structural unit (Lown, 1984; Tsuge et al., 1989). This method is widely used for the synthesis of natural products such as alkaloids and pharmacologically important compounds (Williams et al., 1992). 1,3-Dipolar cycloaddition of azomethine ylides with definite dipolarophiles provides a way for the synthesis of many dispiroheterocyclic systems (Periyasami et al., 2009; Suresh Babu & Raghunathan, 2007). In view of their biological importance, herein we present the results of the crystal structure determination of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The piperidone (N1/C8/C9/C23–C25) ring adopts a chair conformation [Q = 0.610 (3) Å, θ = 37.6 (3)°, φ = 57.8 (4)° ; Cremer & Pople, 1975]. The pyrrolidine ring N atom disordered over two sites with a refined occupancy ratio of 0.52 (4):0.48 (4). The major (C7/C8/C21/C22/N2A) and minor (C7/C8/C21/C22/N2B) disordered pyrrolidine rings adopt the same envelope conformation with puckering parameters Q(2) = 0.349 (5) Å, φ = 73.0 (15)° for major disordered component and Q(2) = 0.459 (6) Å, φ = 332.4 (10) for minor disordered component. The dihedral angle between the two phenyl rings (C1–C6 and C27–C32) is 70.80 (16)°.

In the crystal packing (Fig. 2), molecules are connected by intermolecular O1—H1O1···O1 and C17—H17A···O2 (Table 1) hydrogen bonds to form a three-dimensional network.

Related literature top

For details of 1,3-dipolar cycloaddition reactions, see: Lown (1984); Tsuge et al. (1989); Williams et al. (1992); Periyasami et al. (2009); Suresh Babu & Raghunathan (2007). For puckering parameters, see: Cremer & Pople (1975). 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, 0.364 mmol), acenaphthenequinone (0.066 g, 0.364 mmol), and sarcosine (0.032 g, 0.272 mmol) were dissolved in methanol (5 mL) and refluxed for 1 hour. After completion of the reaction as evident from TLC, the mixture was poured into water (50 mL). The precipitated solid was filtered, washed with water and recrystallised from pet.ether-ethyl acetate mixture (1:1) to reveal pale yellow blocks of (I).

Structure description top

In the crystal packing (Fig. 2), molecules are connected by intermolecular O1—H1O1···O1 and C17—H17A···O2 (Table 1) hydrogen bonds to form a three-dimensional network.

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 asymmetric unit of (I), showing 30% probability displacement ellipsoids (H atoms are omitted for clarity). All disorder components are shown.
	Fig. 2. The crystal packing of (I), showing hydrogen-bonded (dashed lines) network. Solvent molecules, minor disorder components and H atoms are not involing the hydrogen bond interactions are omitted for clarity.

5-[(E)-Benzylidene]-2-hydroxy-10-methyl-8-phenyl-3,10- diazahexacyclo[10.7.1.1^3,7.0^2,11.0^7,11.0^16,20]henicosa- 1(19),12 (20),13,15,17-pentaen-6-one ethanol 0.25-solvate 0.6-hydrate top

Crystal data top

C₃₃H₂₈N₂O₂·0.25C₂H₆O·0.6H₂O	D_x = 1.273 Mg m⁻³
M_r = 506.90	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42₁c	Cell parameters from 5795 reflections
Hall symbol: P -4 2n	θ = 2.6–29.9°
a = 19.3839 (3) Å	µ = 0.08 mm⁻¹
c = 14.0757 (2) Å	T = 100 K
V = 5288.74 (14) Å³	Block, pale yellow
Z = 8	0.19 × 0.18 × 0.15 mm
F(000) = 2148

Data collection top

Bruker SMART APEXII CCD diffractometer	4230 independent reflections
Radiation source: fine-focus sealed tube	3388 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
φ and ω scans	θ_max = 30.1°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −23→24
T_min = 0.985, T_max = 0.988	k = −8→27
23186 measured reflections	l = −17→19

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0762P)² + 1.6944P] where P = (F_o² + 2F_c²)/3
4230 reflections	(Δ/σ)_max < 0.001
387 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₃₃H₂₈N₂O₂·0.25C₂H₆O·0.6H₂O	Z = 8
M_r = 506.90	Mo Kα radiation
Tetragonal, P42₁c	µ = 0.08 mm⁻¹
a = 19.3839 (3) Å	T = 100 K
c = 14.0757 (2) Å	0.19 × 0.18 × 0.15 mm
V = 5288.74 (14) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	4230 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3388 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.988	R_int = 0.041
23186 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.35 e Å⁻³
4230 reflections	Δρ_min = −0.21 e Å⁻³
387 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 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	Occ. (<1)
O1	0.44856 (11)	0.06178 (12)	−0.00668 (19)	0.0410 (6)
O2	0.54102 (12)	0.33051 (11)	−0.07672 (15)	0.0416 (5)
N1	0.55166 (11)	0.12176 (11)	−0.02818 (15)	0.0242 (4)
N2A	0.3846 (4)	0.1607 (11)	−0.0740 (5)	0.029 (3)	0.52 (4)
N2B	0.3748 (4)	0.1934 (11)	−0.0633 (5)	0.025 (3)	0.48 (4)
C1	0.48583 (15)	0.19294 (15)	−0.33651 (18)	0.0302 (6)
H1A	0.4671	0.1504	−0.3200	0.036*
C2	0.51981 (16)	0.20036 (17)	−0.42318 (19)	0.0364 (7)
H2A	0.5236	0.1628	−0.4639	0.044*
C3	0.54775 (18)	0.26274 (19)	−0.4490 (2)	0.0442 (8)
H3A	0.5709	0.2674	−0.5065	0.053*
C4	0.5409 (2)	0.3187 (2)	−0.3882 (2)	0.0526 (9)
H4A	0.5592	0.3613	−0.4054	0.063*
C5	0.50702 (19)	0.31165 (17)	−0.3015 (2)	0.0421 (8)
H5A	0.5027	0.3496	−0.2615	0.050*
C6	0.47963 (14)	0.24860 (15)	−0.27427 (18)	0.0277 (6)
C7	0.44519 (14)	0.24214 (15)	−0.17726 (18)	0.0284 (6)
H7A	0.4283	0.2879	−0.1591	0.034*
C8	0.49319 (14)	0.21656 (14)	−0.09800 (17)	0.0262 (5)
C9	0.53559 (14)	0.15141 (15)	−0.12184 (17)	0.0268 (5)
H9A	0.5088	0.1194	−0.1599	0.032*
H9B	0.5774	0.1633	−0.1559	0.032*
C10	0.48373 (13)	0.12174 (14)	0.02031 (19)	0.0260 (5)
C11	0.48822 (14)	0.13202 (16)	0.12660 (18)	0.0292 (6)
C12	0.51434 (18)	0.0923 (2)	0.1980 (2)	0.0499 (9)
H12A	0.5325	0.0489	0.1852	0.060*
C13	0.51320 (18)	0.1187 (3)	0.2928 (2)	0.0662 (14)
H13A	0.5295	0.0912	0.3421	0.079*
C14	0.48900 (18)	0.1825 (3)	0.3127 (2)	0.0621 (13)
H14A	0.4901	0.1984	0.3751	0.075*
C15	0.46233 (16)	0.2252 (2)	0.2412 (2)	0.0434 (8)
C16	0.4376 (2)	0.2932 (2)	0.2503 (3)	0.0632 (12)
H16A	0.4376	0.3143	0.3096	0.076*
C17	0.4135 (2)	0.3288 (2)	0.1732 (3)	0.0681 (13)
H17A	0.3979	0.3737	0.1812	0.082*
C18	0.41177 (19)	0.29897 (19)	0.0814 (3)	0.0497 (9)
H18A	0.3945	0.3237	0.0300	0.060*
C19	0.43589 (15)	0.23323 (16)	0.0697 (2)	0.0314 (6)
C20	0.46115 (14)	0.19742 (16)	0.14849 (18)	0.0300 (6)
C21	0.44354 (14)	0.18916 (15)	−0.01883 (18)	0.0271 (5)
C22	0.38450 (14)	0.19137 (16)	−0.16933 (18)	0.0298 (6)
H22A	0.3413	0.2154	−0.1802	0.036*
H22B	0.3890	0.1555	−0.2169	0.036*
C23	0.54231 (15)	0.26973 (15)	−0.05562 (19)	0.0294 (6)
C24	0.59090 (14)	0.24127 (14)	0.01748 (19)	0.0284 (5)
C25	0.60533 (13)	0.16417 (14)	0.01602 (19)	0.0265 (5)
H25A	0.6483	0.1564	−0.0176	0.032*
H25B	0.6118	0.1486	0.0809	0.032*
C26	0.61200 (15)	0.28449 (15)	0.0862 (2)	0.0316 (6)
H26A	0.5984	0.3303	0.0798	0.038*
C27	0.65392 (16)	0.26835 (16)	0.17032 (19)	0.0335 (6)
C28	0.70345 (16)	0.21629 (16)	0.1728 (2)	0.0375 (7)
H28A	0.7123	0.1908	0.1181	0.045*
C29	0.73987 (19)	0.20185 (18)	0.2554 (3)	0.0470 (9)
H29A	0.7719	0.1662	0.2561	0.056*
C30	0.7285 (2)	0.2406 (2)	0.3369 (3)	0.0536 (10)
H30A	0.7526	0.2307	0.3924	0.064*
C31	0.6811 (2)	0.2939 (2)	0.3350 (2)	0.0508 (10)
H31A	0.6741	0.3207	0.3890	0.061*
C32	0.64365 (17)	0.30786 (18)	0.2528 (2)	0.0393 (7)
H32A	0.6116	0.3436	0.2524	0.047*
C33	0.31851 (14)	0.15983 (19)	−0.0249 (2)	0.0404 (7)
H33A	0.3259	0.1550	0.0422	0.061*
H33B	0.3011	0.1173	−0.0502	0.061*
H33C	0.2857	0.1960	−0.0362	0.061*
O3	0.4685 (12)	0.459 (2)	0.8576 (13)	0.22 (2)	0.25
H1O3	0.4747	0.4920	0.9015	0.330*	0.25
C34	0.4750 (7)	0.4887 (8)	0.7781 (11)	0.046 (3)	0.25
H34A	0.4975	0.5271	0.8080	0.055*	0.25
H34B	0.4290	0.5052	0.7671	0.055*	0.25
C35	0.5000	0.5000	0.6848 (14)	0.097 (6)	0.50
H35A	0.4911	0.5467	0.6656	0.145*	0.25
H35B	0.5488	0.4916	0.6841	0.145*	0.25
H35C	0.4776	0.4689	0.6416	0.145*	0.25
O1W	0.4432 (8)	0.4776 (9)	0.629 (2)	0.270 (14)	0.40
H1W1	0.4418	0.4711	0.5691	0.405*	0.40
H2W1	0.4181	0.4646	0.6761	0.405*	0.40
O2W	0.5000	0.5000	0.9514 (16)	0.199 (13)	0.40
H1W2	0.5293	0.5433	0.9884	0.298*	0.40
H1O1	0.468 (2)	0.035 (2)	−0.017 (3)	0.068 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0307 (11)	0.0319 (11)	0.0604 (15)	−0.0074 (9)	0.0121 (11)	−0.0197 (11)
O2	0.0553 (14)	0.0358 (11)	0.0336 (11)	−0.0011 (10)	−0.0114 (10)	−0.0023 (9)
N1	0.0237 (10)	0.0298 (11)	0.0190 (10)	−0.0030 (8)	0.0026 (8)	−0.0070 (8)
N2A	0.018 (2)	0.048 (8)	0.021 (2)	0.000 (3)	0.0007 (18)	−0.009 (3)
N2B	0.027 (3)	0.040 (7)	0.009 (2)	0.005 (3)	0.0024 (19)	−0.007 (3)
C1	0.0362 (15)	0.0344 (14)	0.0200 (11)	−0.0052 (12)	0.0008 (11)	−0.0015 (11)
C2	0.0403 (16)	0.0482 (17)	0.0209 (12)	−0.0027 (14)	−0.0006 (11)	−0.0063 (13)
C3	0.0462 (18)	0.060 (2)	0.0263 (13)	−0.0122 (16)	0.0040 (13)	0.0040 (14)
C4	0.069 (2)	0.051 (2)	0.0378 (17)	−0.0256 (19)	0.0058 (17)	0.0069 (15)
C5	0.059 (2)	0.0383 (17)	0.0290 (14)	−0.0090 (15)	0.0011 (14)	−0.0021 (13)
C6	0.0293 (13)	0.0344 (14)	0.0193 (11)	−0.0014 (11)	−0.0038 (10)	−0.0013 (11)
C7	0.0307 (13)	0.0357 (14)	0.0187 (11)	0.0024 (11)	0.0007 (10)	−0.0061 (11)
C8	0.0297 (13)	0.0333 (14)	0.0157 (10)	−0.0008 (11)	−0.0011 (10)	−0.0047 (10)
C9	0.0243 (12)	0.0395 (14)	0.0165 (11)	−0.0004 (11)	0.0025 (9)	−0.0071 (10)
C10	0.0265 (12)	0.0277 (12)	0.0237 (11)	−0.0002 (10)	0.0042 (10)	−0.0054 (11)
C11	0.0240 (12)	0.0414 (15)	0.0223 (11)	0.0022 (11)	0.0072 (10)	0.0011 (11)
C12	0.0389 (18)	0.073 (2)	0.0373 (16)	0.0196 (18)	0.0158 (14)	0.0229 (17)
C13	0.0286 (17)	0.142 (4)	0.0275 (15)	0.022 (2)	0.0098 (13)	0.030 (2)
C14	0.0296 (16)	0.141 (4)	0.0155 (12)	0.004 (2)	0.0011 (12)	−0.007 (2)
C15	0.0315 (15)	0.073 (2)	0.0254 (14)	−0.0031 (15)	0.0050 (12)	−0.0205 (15)
C16	0.061 (2)	0.080 (3)	0.049 (2)	−0.005 (2)	0.019 (2)	−0.041 (2)
C17	0.074 (3)	0.049 (2)	0.081 (3)	0.011 (2)	0.033 (3)	−0.033 (2)
C18	0.0487 (19)	0.0463 (19)	0.054 (2)	0.0187 (16)	0.0187 (17)	−0.0037 (17)
C19	0.0309 (13)	0.0386 (15)	0.0246 (13)	0.0063 (11)	0.0069 (11)	−0.0057 (11)
C20	0.0282 (13)	0.0411 (15)	0.0208 (12)	0.0005 (12)	0.0009 (10)	−0.0090 (11)
C21	0.0274 (12)	0.0368 (14)	0.0172 (10)	0.0037 (11)	0.0007 (10)	−0.0053 (11)
C22	0.0296 (13)	0.0415 (15)	0.0183 (11)	0.0030 (12)	−0.0026 (10)	−0.0027 (11)
C23	0.0317 (14)	0.0368 (15)	0.0196 (11)	−0.0014 (11)	−0.0018 (10)	−0.0048 (11)
C24	0.0306 (13)	0.0342 (14)	0.0204 (11)	−0.0058 (11)	−0.0015 (11)	−0.0033 (11)
C25	0.0274 (12)	0.0316 (13)	0.0204 (11)	−0.0038 (10)	−0.0005 (10)	−0.0048 (10)
C26	0.0353 (14)	0.0341 (14)	0.0255 (12)	−0.0071 (12)	−0.0003 (11)	−0.0021 (11)
C27	0.0392 (16)	0.0364 (15)	0.0247 (13)	−0.0181 (12)	−0.0049 (12)	−0.0007 (11)
C28	0.0391 (16)	0.0344 (15)	0.0389 (16)	−0.0152 (12)	−0.0100 (14)	−0.0003 (13)
C29	0.0495 (19)	0.0395 (17)	0.0520 (19)	−0.0211 (15)	−0.0214 (17)	0.0140 (16)
C30	0.064 (2)	0.062 (2)	0.0350 (16)	−0.034 (2)	−0.0179 (16)	0.0168 (16)
C31	0.062 (2)	0.068 (2)	0.0221 (13)	−0.030 (2)	−0.0047 (15)	−0.0038 (15)
C32	0.0433 (17)	0.0459 (18)	0.0288 (14)	−0.0172 (14)	−0.0016 (13)	−0.0051 (13)
C33	0.0262 (13)	0.070 (2)	0.0254 (13)	0.0016 (14)	0.0034 (11)	−0.0101 (15)
O3	0.17 (2)	0.42 (6)	0.063 (9)	0.21 (3)	0.005 (11)	−0.045 (17)
C34	0.045 (8)	0.045 (8)	0.048 (8)	0.008 (6)	−0.007 (6)	−0.004 (6)
C35	0.132 (16)	0.048 (8)	0.111 (14)	0.029 (10)	0.000	0.000
O1W	0.118 (12)	0.157 (16)	0.54 (4)	−0.033 (11)	−0.04 (2)	0.00 (2)
O2W	0.25 (3)	0.19 (2)	0.16 (2)	0.16 (2)	0.000	0.000

Geometric parameters (Å, º) top

O1—C10	1.400 (3)	C17—H17A	0.9300
O1—H1O1	0.66 (4)	C18—C19	1.367 (4)
O2—C23	1.215 (4)	C18—H18A	0.9300
N1—C25	1.465 (3)	C19—C20	1.397 (4)
N1—C9	1.472 (3)	C19—C21	1.518 (4)
N1—C10	1.483 (3)	C22—H22A	0.9700
N2A—C33	1.456 (9)	C22—H22B	0.9700
N2A—C22	1.469 (7)	C23—C24	1.500 (4)
N2A—C21	1.487 (8)	C24—C26	1.344 (4)
N2B—C33	1.381 (7)	C24—C25	1.521 (4)
N2B—C21	1.474 (8)	C25—H25A	0.9700
N2B—C22	1.505 (8)	C25—H25B	0.9700
C1—C2	1.394 (4)	C26—C27	1.470 (4)
C1—C6	1.395 (4)	C26—H26A	0.9300
C1—H1A	0.9300	C27—C28	1.393 (5)
C2—C3	1.374 (5)	C27—C32	1.404 (4)
C2—H2A	0.9300	C28—C29	1.389 (4)
C3—C4	1.389 (5)	C28—H28A	0.9300
C3—H3A	0.9300	C29—C30	1.389 (6)
C4—C5	1.393 (5)	C29—H29A	0.9300
C4—H4A	0.9300	C30—C31	1.384 (6)
C5—C6	1.386 (4)	C30—H30A	0.9300
C5—H5A	0.9300	C31—C32	1.393 (5)
C6—C7	1.525 (4)	C31—H31A	0.9300
C7—C8	1.535 (4)	C32—H32A	0.9300
C7—C22	1.538 (4)	C33—H33A	0.9600
C7—H7A	0.9800	C33—H33B	0.9598
C8—C23	1.525 (4)	C33—H33C	0.9601
C8—C9	1.544 (4)	O3—C34	1.27 (3)
C8—C21	1.565 (4)	O3—C34ⁱ	1.87 (3)
C9—H9A	0.9700	O3—H1O3	0.9000
C9—H9B	0.9700	C34—C34ⁱ	1.06 (3)
C10—C11	1.512 (4)	C34—C35	1.42 (2)
C10—C21	1.618 (4)	C34—O3ⁱ	1.87 (3)
C11—C12	1.363 (4)	C34—H34A	0.9596
C11—C20	1.406 (4)	C34—H34B	0.9599
C12—C13	1.430 (6)	C35—C34ⁱ	1.42 (2)
C12—H12A	0.9300	C35—H35A	0.9600
C13—C14	1.353 (7)	C35—H35B	0.9600
C13—H13A	0.9300	C35—H35C	0.9600
C14—C15	1.401 (6)	O1W—H35C	0.7091
C14—H14A	0.9300	O1W—H1W1	0.8579
C15—C16	1.410 (6)	O1W—H2W1	0.8566
C15—C20	1.412 (4)	O2W—O2Wⁱⁱ	1.37 (5)
C16—C17	1.367 (6)	O2W—H1O3	0.8695
C16—H16A	0.9300	O2W—H1W2	1.1395
C17—C18	1.415 (6)

C10—O1—H1O1	116 (5)	C19—C21—C10	102.8 (2)
C25—N1—C9	108.2 (2)	C8—C21—C10	102.7 (2)
C25—N1—C10	115.81 (19)	N2A—C22—N2B	26.4 (2)
C9—N1—C10	103.0 (2)	N2A—C22—C7	109.0 (4)
C33—N2A—C22	115.9 (8)	N2B—C22—C7	98.7 (4)
C33—N2A—C21	115.6 (9)	N2A—C22—H22A	109.9
C22—N2A—C21	109.1 (6)	N2B—C22—H22A	92.1
C33—N2B—C21	121.5 (7)	C7—C22—H22A	109.9
C33—N2B—C22	118.3 (7)	N2A—C22—H22B	109.9
C21—N2B—C22	107.8 (7)	N2B—C22—H22B	135.7
C2—C1—C6	120.7 (3)	C7—C22—H22B	109.9
C2—C1—H1A	119.7	H22A—C22—H22B	108.3
C6—C1—H1A	119.7	O2—C23—C24	122.5 (2)
C3—C2—C1	120.6 (3)	O2—C23—C8	123.2 (3)
C3—C2—H2A	119.7	C24—C23—C8	114.3 (2)
C1—C2—H2A	119.7	C26—C24—C23	117.1 (3)
C2—C3—C4	119.1 (3)	C26—C24—C25	124.5 (3)
C2—C3—H3A	120.4	C23—C24—C25	117.9 (2)
C4—C3—H3A	120.4	N1—C25—C24	115.3 (2)
C3—C4—C5	120.6 (3)	N1—C25—H25A	108.5
C3—C4—H4A	119.7	C24—C25—H25A	108.5
C5—C4—H4A	119.7	N1—C25—H25B	108.5
C6—C5—C4	120.6 (3)	C24—C25—H25B	108.5
C6—C5—H5A	119.7	H25A—C25—H25B	107.5
C4—C5—H5A	119.7	C24—C26—C27	128.0 (3)
C5—C6—C1	118.4 (3)	C24—C26—H26A	116.0
C5—C6—C7	119.2 (3)	C27—C26—H26A	116.0
C1—C6—C7	122.4 (3)	C28—C27—C32	118.2 (3)
C6—C7—C8	114.3 (2)	C28—C27—C26	123.7 (3)
C6—C7—C22	116.9 (2)	C32—C27—C26	118.1 (3)
C8—C7—C22	101.8 (2)	C29—C28—C27	121.1 (3)
C6—C7—H7A	107.8	C29—C28—H28A	119.4
C8—C7—H7A	107.8	C27—C28—H28A	119.4
C22—C7—H7A	107.8	C30—C29—C28	120.1 (4)
C23—C8—C7	116.4 (2)	C30—C29—H29A	119.9
C23—C8—C9	107.8 (2)	C28—C29—H29A	119.9
C7—C8—C9	115.4 (2)	C31—C30—C29	119.6 (3)
C23—C8—C21	109.6 (2)	C31—C30—H30A	120.2
C7—C8—C21	104.7 (2)	C29—C30—H30A	120.2
C9—C8—C21	101.8 (2)	C30—C31—C32	120.5 (3)
N1—C9—C8	103.74 (19)	C30—C31—H31A	119.8
N1—C9—H9A	111.0	C32—C31—H31A	119.8
C8—C9—H9A	111.0	C31—C32—C27	120.5 (3)
N1—C9—H9B	111.0	C31—C32—H32A	119.8
C8—C9—H9B	111.0	C27—C32—H32A	119.8
H9A—C9—H9B	109.0	N2B—C33—N2A	27.6 (3)
O1—C10—N1	107.9 (2)	N2B—C33—H33A	108.3
O1—C10—C11	114.0 (2)	N2A—C33—H33A	109.7
N1—C10—C11	113.8 (2)	N2B—C33—H33B	122.5
O1—C10—C21	110.1 (2)	N2A—C33—H33B	98.2
N1—C10—C21	105.7 (2)	H33A—C33—H33B	109.5
C11—C10—C21	105.0 (2)	N2B—C33—H33C	96.6
C12—C11—C20	119.1 (3)	N2A—C33—H33C	119.8
C12—C11—C10	132.5 (3)	H33A—C33—H33C	109.5
C20—C11—C10	108.3 (2)	H33B—C33—H33C	109.5
C11—C12—C13	118.7 (4)	C34—O3—C34ⁱ	33.2 (13)
C11—C12—H12A	120.6	C34—O3—H1O3	105.4
C13—C12—H12A	120.6	C34ⁱ—O3—H1O3	86.8
C14—C13—C12	121.7 (3)	C34ⁱ—C34—O3	106.1 (16)
C14—C13—H13A	119.1	C34ⁱ—C34—C35	67.9 (7)
C12—C13—H13A	119.1	O3—C34—C35	157.4 (16)
C13—C14—C15	121.3 (3)	C34ⁱ—C34—O3ⁱ	40.7 (9)
C13—C14—H14A	119.4	O3—C34—O3ⁱ	77 (2)
C15—C14—H14A	119.4	C35—C34—O3ⁱ	105.7 (12)
C14—C15—C16	127.8 (3)	C34ⁱ—C34—H34A	42.8
C14—C15—C20	116.4 (3)	O3—C34—H34A	90.7
C16—C15—C20	115.8 (3)	C35—C34—H34A	97.5
C17—C16—C15	121.0 (3)	O3ⁱ—C34—H34A	17.8
C17—C16—H16A	119.5	C34ⁱ—C34—H34B	135.3
C15—C16—H16A	119.5	O3—C34—H34B	101.7
C16—C17—C18	121.8 (3)	C35—C34—H34B	96.8
C16—C17—H17A	119.1	O3ⁱ—C34—H34B	117.4
C18—C17—H17A	119.1	H34A—C34—H34B	103.7
C19—C18—C17	118.8 (4)	C34—C35—C34ⁱ	44.1 (13)
C19—C18—H18A	120.6	C34—C35—H35A	110.1
C17—C18—H18A	120.6	C34ⁱ—C35—H35A	100.2
C18—C19—C20	119.1 (3)	C34—C35—H35B	108.7
C18—C19—C21	131.1 (3)	C34ⁱ—C35—H35B	72.4
C20—C19—C21	109.7 (2)	H35A—C35—H35B	109.5
C19—C20—C11	113.9 (2)	C34—C35—H35C	109.6
C19—C20—C15	123.4 (3)	C34ⁱ—C35—H35C	147.0
C11—C20—C15	122.7 (3)	H35A—C35—H35C	109.5
N2B—C21—N2A	26.5 (2)	H35B—C35—H35C	109.5
N2B—C21—C19	103.2 (7)	H35C—O1W—H1W1	103.6
N2A—C21—C19	124.2 (7)	H35C—O1W—H2W1	106.1
N2B—C21—C8	103.6 (3)	H1W1—O1W—H2W1	134.2
N2A—C21—C8	103.1 (3)	O2Wⁱⁱ—O2W—H1O3	143.8
C19—C21—C8	117.0 (2)	O2Wⁱⁱ—O2W—H1W2	62.8
N2B—C21—C10	128.7 (8)	H1O3—O2W—H1W2	141.4
N2A—C21—C10	104.3 (8)

C6—C1—C2—C3	−0.1 (5)	C18—C19—C21—N2A	−69.1 (8)
C1—C2—C3—C4	−0.9 (5)	C20—C19—C21—N2A	113.4 (7)
C2—C3—C4—C5	0.8 (6)	C18—C19—C21—C8	61.8 (4)
C3—C4—C5—C6	0.2 (6)	C20—C19—C21—C8	−115.8 (3)
C4—C5—C6—C1	−1.1 (5)	C18—C19—C21—C10	173.4 (3)
C4—C5—C6—C7	177.7 (3)	C20—C19—C21—C10	−4.1 (3)
C2—C1—C6—C5	1.1 (4)	C23—C8—C21—N2B	132.1 (9)
C2—C1—C6—C7	−177.7 (3)	C7—C8—C21—N2B	6.6 (9)
C5—C6—C7—C8	−93.8 (3)	C9—C8—C21—N2B	−114.0 (9)
C1—C6—C7—C8	85.0 (3)	C23—C8—C21—N2A	159.4 (9)
C5—C6—C7—C22	147.5 (3)	C7—C8—C21—N2A	33.8 (9)
C1—C6—C7—C22	−33.7 (4)	C9—C8—C21—N2A	−86.7 (9)
C6—C7—C8—C23	78.6 (3)	C23—C8—C21—C19	19.4 (3)
C22—C7—C8—C23	−154.5 (2)	C7—C8—C21—C19	−106.2 (3)
C6—C7—C8—C9	−49.3 (3)	C9—C8—C21—C19	133.3 (2)
C22—C7—C8—C9	77.7 (3)	C23—C8—C21—C10	−92.4 (2)
C6—C7—C8—C21	−160.3 (2)	C7—C8—C21—C10	142.1 (2)
C22—C7—C8—C21	−33.3 (3)	C9—C8—C21—C10	21.5 (2)
C25—N1—C9—C8	−74.5 (2)	O1—C10—C21—N2B	9.4 (6)
C10—N1—C9—C8	48.6 (2)	N1—C10—C21—N2B	125.7 (6)
C23—C8—C9—N1	71.6 (2)	C11—C10—C21—N2B	−113.7 (6)
C7—C8—C9—N1	−156.3 (2)	O1—C10—C21—N2A	−2.6 (5)
C21—C8—C9—N1	−43.6 (2)	N1—C10—C21—N2A	113.7 (4)
C25—N1—C10—O1	−157.8 (2)	C11—C10—C21—N2A	−125.6 (4)
C9—N1—C10—O1	84.4 (3)	O1—C10—C21—C19	128.2 (2)
C25—N1—C10—C11	−30.3 (3)	N1—C10—C21—C19	−115.5 (2)
C9—N1—C10—C11	−148.1 (2)	C11—C10—C21—C19	5.1 (3)
C25—N1—C10—C21	84.4 (2)	O1—C10—C21—C8	−109.9 (2)
C9—N1—C10—C21	−33.4 (2)	N1—C10—C21—C8	6.4 (2)
O1—C10—C11—C12	57.4 (4)	C11—C10—C21—C8	127.0 (2)
N1—C10—C11—C12	−67.0 (4)	C33—N2A—C22—N2B	61.8 (13)
C21—C10—C11—C12	178.0 (3)	C21—N2A—C22—N2B	−70.8 (14)
O1—C10—C11—C20	−125.1 (3)	C33—N2A—C22—C7	132.3 (10)
N1—C10—C11—C20	110.5 (3)	C21—N2A—C22—C7	−0.3 (14)
C21—C10—C11—C20	−4.6 (3)	C33—N2B—C22—N2A	−71.7 (15)
C20—C11—C12—C13	0.0 (5)	C21—N2B—C22—N2A	71.1 (13)
C10—C11—C12—C13	177.3 (3)	C33—N2B—C22—C7	172.7 (13)
C11—C12—C13—C14	−2.1 (6)	C21—N2B—C22—C7	−44.5 (12)
C12—C13—C14—C15	1.6 (6)	C6—C7—C22—N2A	146.6 (9)
C13—C14—C15—C16	−177.7 (4)	C8—C7—C22—N2A	21.3 (9)
C13—C14—C15—C20	1.0 (5)	C6—C7—C22—N2B	171.7 (8)
C14—C15—C16—C17	179.4 (4)	C8—C7—C22—N2B	46.4 (8)
C20—C15—C16—C17	0.7 (6)	C7—C8—C23—O2	5.6 (4)
C15—C16—C17—C18	0.5 (7)	C9—C8—C23—O2	137.1 (3)
C16—C17—C18—C19	−1.0 (6)	C21—C8—C23—O2	−112.9 (3)
C17—C18—C19—C20	0.3 (5)	C7—C8—C23—C24	−176.6 (2)
C17—C18—C19—C21	−177.1 (3)	C9—C8—C23—C24	−45.1 (3)
C18—C19—C20—C11	−176.4 (3)	C21—C8—C23—C24	64.8 (3)
C21—C19—C20—C11	1.5 (4)	O2—C23—C24—C26	27.3 (4)
C18—C19—C20—C15	1.0 (5)	C8—C23—C24—C26	−150.5 (3)
C21—C19—C20—C15	178.9 (3)	O2—C23—C24—C25	−160.3 (3)
C12—C11—C20—C19	−180.0 (3)	C8—C23—C24—C25	21.9 (3)
C10—C11—C20—C19	2.2 (3)	C9—N1—C25—C24	50.7 (3)
C12—C11—C20—C15	2.6 (5)	C10—N1—C25—C24	−64.2 (3)
C10—C11—C20—C15	−175.3 (3)	C26—C24—C25—N1	147.8 (3)
C14—C15—C20—C19	179.7 (3)	C23—C24—C25—N1	−24.0 (4)
C16—C15—C20—C19	−1.5 (5)	C23—C24—C26—C27	173.9 (3)
C14—C15—C20—C11	−3.2 (5)	C25—C24—C26—C27	2.1 (5)
C16—C15—C20—C11	175.7 (3)	C24—C26—C27—C28	30.3 (5)
C33—N2B—C21—N2A	73.1 (17)	C24—C26—C27—C32	−150.0 (3)
C22—N2B—C21—N2A	−68.3 (12)	C32—C27—C28—C29	2.5 (4)
C33—N2B—C21—C19	−72.3 (16)	C26—C27—C28—C29	−177.8 (3)
C22—N2B—C21—C19	146.3 (10)	C27—C28—C29—C30	−1.6 (5)
C33—N2B—C21—C8	165.3 (13)	C28—C29—C30—C31	−0.5 (5)
C22—N2B—C21—C8	23.9 (13)	C29—C30—C31—C32	1.6 (5)
C33—N2B—C21—C10	46.4 (18)	C30—C31—C32—C27	−0.6 (5)
C22—N2B—C21—C10	−95.0 (8)	C28—C27—C32—C31	−1.5 (4)
C33—N2A—C21—N2B	−59.1 (13)	C26—C27—C32—C31	178.8 (3)
C22—N2A—C21—N2B	73.7 (13)	C21—N2B—C33—N2A	−70.6 (17)
C33—N2A—C21—C19	−17.1 (16)	C22—N2B—C33—N2A	66.9 (14)
C22—N2A—C21—C19	115.6 (8)	C22—N2A—C33—N2B	−67.3 (13)
C33—N2A—C21—C8	−153.3 (10)	C21—N2A—C33—N2B	62.2 (14)
C22—N2A—C21—C8	−20.5 (13)	C34ⁱ—O3—C34—C35	71 (5)
C33—N2A—C21—C10	99.6 (12)	C34ⁱ—O3—C34—O3ⁱ	−28.9 (19)
C22—N2A—C21—C10	−127.6 (11)	O3—C34—C35—C34ⁱ	−79 (5)
C18—C19—C21—N2B	−51.2 (7)	O3ⁱ—C34—C35—C34ⁱ	15.4 (12)
C20—C19—C21—N2B	131.2 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O1ⁱⁱⁱ	0.66 (4)	2.48 (4)	3.117 (5)	164 (5)
C17—H17A···O2^iv	0.93	2.57	3.287 (6)	134

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

Experimental details

Crystal data
Chemical formula	C₃₃H₂₈N₂O₂·0.25C₂H₆O·0.6H₂O
M_r	506.90
Crystal system, space group	Tetragonal, P42₁c
Temperature (K)	100
a, c (Å)	19.3839 (3), 14.0757 (2)
V (Å³)	5288.74 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.19 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.985, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	23186, 4230, 3388
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.148, 1.03
No. of reflections	4230
No. of parameters	387
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.21

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O1ⁱ	0.66 (4)	2.48 (4)	3.117 (5)	164 (5)
C17—H17A···O2ⁱⁱ	0.93	2.57	3.287 (6)	134.3

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

Footnotes

‡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. RSK thanks Universiti Sains Malaysia for the award of post doctoral fellowship. HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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