19-[(E)-4-Chloro­benzyl­idene]-16-(4-chloro­phen­yl)-2-hydr­oxy-1,11-diaza­hexa­cyclo­[15.3.1.02,10.03,8.010,17.011,15]henicosa-3(8),4,6-triene-9,18-dione

Kumar, R.S.; Osman, H.; Abdul Rahim, A.S.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536810018611

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages o1444-o1445

https://doi.org/10.1107/S1600536810018611

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19-[(E)-4-Chlorobenzylidene]-16-(4-chlorophenyl)-2-hydroxy-1,11-diazahexacyclo[15.3.1.0^2,10.0^3,8.0^10,17.0^11,15]henicosa-3(8),4,6-triene-9,18-dione

Raju Suresh Kumar,^a Hasnah Osman,^a ‡ Aisyah Saad Abdul Rahim,^b Madhukar Hemamalini ^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 7 May 2010; accepted 19 May 2010; online 26 May 2010)

In the title compound, C₃₂H₂₆Cl₂N₂O₃, the piperidone ring adopts a chair conformation and the proline and pyrrolidine rings adopt envelope conformations. The indane ring system is essentially planar with an r.m.s. deviation of 0.011 Å for the non-H atoms. The dihedral angle between the two chloro-substituted benzene rings is 63.69 (10)°. Intramolecular C—H⋯O and N—H⋯O hydrogen bonds may influence the molecular conformation. In the crystal structure, molecules are connected into layers by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For cycloaddition reactions, see: Dondas et al. (2004 ); Boruah et al. (2007 ). For applications of pyrrolizines, see: Boruah et al. (2007); Dimmock et al. (2001 ); El-Subbagh et al. (2000 ); Lee et al. (2001 ); Liddell (1998 ). 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

C₃₂H₂₆Cl₂N₂O₃
M_r = 557.45
Monoclinic, P 2₁ /c
a = 14.603 (2) Å
b = 10.5701 (14) Å
c = 21.808 (2) Å
β = 130.094 (6)°
V = 2575.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.34 × 0.19 × 0.11 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.906, T_max = 0.969
27859 measured reflections
7631 independent reflections
5380 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.186
S = 1.06
7631 reflections
356 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯N2	0.86 (5)	1.97 (5)	2.623 (3)	133 (5)
C1—H1A⋯O3ⁱ	0.93	2.44	3.305 (3)	155
C22—H22A⋯O3	0.97	2.51	3.186 (3)	126
C23—H23A⋯O2ⁱⁱ	0.97	2.59	3.506 (3)	158
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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/S1600536810018611/lh5043sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018611/lh5043Isup2.hkl

checkCIF report

Comment top

1,3-Dipolar cycloaddition of nonstabilized azomethine ylides with olefins represents one of the most convergent approaches for the construction of five membered heterocycles (Dondas et al., 2004; Boruah et al. 2007). The pyrrolizine substructure occurs in many natural products of potential use in medicine and agriculture (Liddell, 1998). Heterocycles with piperidine sub-structures display important biological activities, such as cytotoxic (Dimmock et al., 2001) and anticancer properties (El-Subbagh et al., 2000) besides being useful as synthons in the construction of alkaloid natural products (Lee et al., 2001). In view of the biological importance of aforementioned heterocycles, the crystal structure determination of the title compound was carried out and the results are presented herein.

The molecular structure of the title compound is shown in Fig.1. The piperidone (N1/C8–C12) ring adopts a chair conformation [Q = 0.608 (3) Å, Θ = 37.4 (3)°, φ= 59.8 (4)°; Cremer & Pople, 1975]. The proline ring (N2/C22–C25) and the five membered pyrrolidine ring (N1/C10/C11/C13/C14) adopt envelope conformations [puckering parameters Q = 0.398 (3) Å, φ = 269.4 (4)° and Q = 0.470 (3) Å, φ = 214.4 (3)° respectively]. The indane ring system is essentially planar with an rms deviation of 0.011 Å for the non-hydrogen atoms. The dihedral angle between the two chlorophenyl rings (C1–C6) and (C27–C32) is 63.69 (10)°. In the crystal structure, molecules are connected into layers by intermolecular weak C—H···O hydrogen bonds (Table 1, Fig. 2).

Related literature top

For cycloaddition reactions, see: Dondas et al. (2004); Boruah et al. (2007). For applications of pyrrolizines, see: Boruah et al. (2007); Dimmock et al. (2001); El-Subbagh et al. (2000); Lee et al. (2001); Liddell (1998). 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)-(4-chlorophenyl)methylidene] tetrahydro-4-(1H)-pyridinone (0.100 g, 0.291 mmol), ninhydrin (0.052 g, 0.291 mmol) and proline (0.033 g, 0.291 mmol) were dissolved in methanol (10 mL) and refluxed for 30 minutes. After completion of the reaction as evident from TLC, the mixture was poured into water (50 mL). The precipitated solid was filtered and washed with water to afford the product which was recrystallised from ethyl acetate to reveal the title compound as yellow crystals.

Structure description top

For cycloaddition reactions, see: Dondas et al. (2004); Boruah et al. (2007). For applications of pyrrolizines, see: Boruah et al. (2007); Dimmock et al. (2001); El-Subbagh et al. (2000); Lee et al. (2001); Liddell (1998). For puckering parameters, see: Cremer & Pople (1975). 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 asymmetric unit of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme (H atoms are omitted for clarity).
	Fig. 2. The crystal packing of the title compound, showing hydrogen-bonded (dashed lines) network. H atoms are not involing the hydrogen bond interactions are omitted for clarity.

19-[(E)-4-Chlorobenzylidene]-16-(4-chlorophenyl)-2-hydroxy-1,11-diazahexacyclo[15.3.1.0^2,10.0^3,8.0^10,17.0^11,15]henicosa-3(8),4,6-triene-9,18-dione top

Crystal data top

C₃₂H₂₆Cl₂N₂O₃	F(000) = 1160
M_r = 557.45	D_x = 1.438 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5137 reflections
a = 14.603 (2) Å	θ = 2.3–29.6°
b = 10.5701 (14) Å	µ = 0.29 mm⁻¹
c = 21.808 (2) Å	T = 100 K
β = 130.094 (6)°	Block, yellow
V = 2575.1 (5) Å³	0.34 × 0.19 × 0.11 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	7631 independent reflections
Radiation source: fine-focus sealed tube	5380 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
φ and ω scans	θ_max = 30.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −19→20
T_min = 0.906, T_max = 0.969	k = −14→14
27859 measured reflections	l = −30→30

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.1017P)² + 1.0123P] where P = (F_o² + 2F_c²)/3
7631 reflections	(Δ/σ)_max < 0.001
356 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

C₃₂H₂₆Cl₂N₂O₃	V = 2575.1 (5) Å³
M_r = 557.45	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.603 (2) Å	µ = 0.29 mm⁻¹
b = 10.5701 (14) Å	T = 100 K
c = 21.808 (2) Å	0.34 × 0.19 × 0.11 mm
β = 130.094 (6)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	7631 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5380 reflections with I > 2σ(I)
T_min = 0.906, T_max = 0.969	R_int = 0.045
27859 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.186	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.62 e Å⁻³
7631 reflections	Δρ_min = −0.58 e Å⁻³
356 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
Cl1	0.72105 (6)	0.37813 (6)	0.23348 (4)	0.03884 (18)
Cl2	0.28180 (6)	1.55604 (6)	0.30038 (4)	0.03719 (17)
O1	0.70242 (16)	1.14499 (14)	0.37668 (9)	0.0270 (3)
O2	0.75301 (15)	0.85624 (15)	0.61320 (9)	0.0248 (3)
O3	0.97349 (14)	1.06477 (14)	0.56290 (9)	0.0265 (3)
N1	0.62861 (16)	0.87558 (16)	0.47338 (10)	0.0205 (3)
N2	0.83265 (17)	1.08411 (16)	0.62301 (10)	0.0230 (4)
C1	0.8080 (2)	0.7298 (2)	0.31990 (13)	0.0278 (5)
H1A	0.8706	0.7859	0.3399	0.033*
C2	0.8108 (2)	0.6108 (2)	0.29435 (14)	0.0315 (5)
H2A	0.8744	0.5876	0.2966	0.038*
C3	0.7182 (2)	0.5272 (2)	0.26543 (13)	0.0273 (5)
C4	0.6213 (2)	0.5618 (2)	0.25928 (13)	0.0268 (5)
H4A	0.5591	0.5050	0.2393	0.032*
C5	0.6175 (2)	0.6819 (2)	0.28318 (12)	0.0245 (4)
H5A	0.5511	0.7065	0.2774	0.029*
C6	0.7127 (2)	0.76651 (19)	0.31604 (12)	0.0225 (4)
C7	0.71498 (19)	0.89214 (19)	0.34519 (11)	0.0221 (4)
H7A	0.7511	0.9561	0.3380	0.026*
C8	0.67102 (18)	0.92557 (18)	0.38095 (11)	0.0201 (4)
C9	0.69127 (19)	1.05940 (18)	0.40864 (11)	0.0210 (4)
C10	0.69859 (19)	1.08168 (18)	0.48066 (11)	0.0193 (4)
C11	0.59325 (19)	1.00825 (19)	0.46492 (12)	0.0214 (4)
H11A	0.5842	1.0307	0.5039	0.026*
H11B	0.5187	1.0251	0.4115	0.026*
C12	0.61408 (19)	0.83699 (19)	0.40280 (11)	0.0214 (4)
H12A	0.5292	0.8306	0.3573	0.026*
H12B	0.6486	0.7534	0.4126	0.026*
C13	0.80569 (19)	1.01008 (18)	0.55666 (11)	0.0198 (4)
C14	0.75404 (19)	0.87571 (19)	0.55007 (11)	0.0207 (4)
C15	0.8366 (2)	0.78312 (19)	0.55386 (12)	0.0222 (4)
C16	0.8318 (2)	0.6517 (2)	0.55102 (13)	0.0269 (5)
H16A	0.7728	0.6085	0.5472	0.032*
C17	0.9170 (2)	0.5864 (2)	0.55402 (14)	0.0317 (5)
H17A	0.9146	0.4985	0.5519	0.038*
C18	1.0055 (2)	0.6494 (2)	0.56008 (15)	0.0321 (5)
H18A	1.0621	0.6034	0.5625	0.039*
C19	1.0108 (2)	0.7800 (2)	0.56257 (13)	0.0275 (5)
H19A	1.0698	0.8228	0.5663	0.033*
C20	0.92553 (19)	0.84543 (19)	0.55940 (11)	0.0216 (4)
C21	0.91251 (19)	0.98351 (19)	0.56015 (11)	0.0209 (4)
C22	0.9558 (2)	1.0914 (2)	0.70050 (12)	0.0278 (5)
H22A	1.0140	1.0753	0.6936	0.033*
H22B	0.9675	1.0305	0.7383	0.033*
C23	0.9671 (2)	1.2266 (2)	0.72949 (13)	0.0307 (5)
H23A	1.0495	1.2555	0.7637	0.037*
H23B	0.9376	1.2333	0.7584	0.037*
C24	0.8886 (2)	1.3011 (2)	0.65101 (13)	0.0286 (5)
H24A	0.8644	1.3815	0.6580	0.034*
H24B	0.9298	1.3161	0.6303	0.034*
C25	0.7816 (2)	1.21395 (19)	0.59597 (12)	0.0237 (4)
H25A	0.7231	1.2278	0.6036	0.028*
C26	0.7192 (2)	1.22071 (18)	0.50652 (12)	0.0210 (4)
H26A	0.7777	1.2545	0.5025	0.025*
C27	0.6102 (2)	1.30567 (18)	0.45664 (12)	0.0221 (4)
C28	0.5997 (2)	1.39566 (19)	0.40587 (13)	0.0251 (4)
H28A	0.6608	1.4037	0.4036	0.030*
C29	0.4999 (2)	1.4740 (2)	0.35843 (13)	0.0281 (5)
H29A	0.4949	1.5344	0.3254	0.034*
C30	0.4084 (2)	1.46082 (19)	0.36103 (14)	0.0277 (5)
C31	0.4160 (2)	1.3725 (2)	0.41077 (16)	0.0322 (5)
H31A	0.3542	1.3645	0.4124	0.039*
C32	0.5155 (2)	1.2962 (2)	0.45792 (15)	0.0313 (5)
H32A	0.5202	1.2371	0.4914	0.038*
H1O2	0.782 (4)	0.925 (4)	0.640 (3)	0.077 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0295 (3)	0.0352 (3)	0.0469 (3)	−0.0032 (3)	0.0224 (3)	−0.0176 (2)
Cl2	0.0401 (4)	0.0299 (3)	0.0441 (3)	0.0115 (3)	0.0283 (3)	0.0032 (2)
O1	0.0343 (9)	0.0231 (7)	0.0303 (7)	0.0004 (7)	0.0238 (7)	0.0030 (6)
O2	0.0299 (8)	0.0265 (7)	0.0239 (7)	−0.0057 (7)	0.0199 (7)	−0.0006 (6)
O3	0.0230 (8)	0.0262 (7)	0.0299 (7)	−0.0067 (6)	0.0169 (7)	−0.0007 (6)
N1	0.0182 (8)	0.0210 (7)	0.0211 (7)	−0.0033 (7)	0.0121 (7)	−0.0020 (6)
N2	0.0238 (9)	0.0227 (8)	0.0191 (7)	−0.0050 (7)	0.0123 (7)	−0.0038 (6)
C1	0.0239 (11)	0.0296 (10)	0.0326 (10)	−0.0059 (9)	0.0195 (10)	−0.0061 (8)
C2	0.0252 (11)	0.0354 (12)	0.0370 (12)	−0.0043 (10)	0.0215 (11)	−0.0087 (9)
C3	0.0251 (11)	0.0282 (10)	0.0271 (10)	−0.0037 (9)	0.0161 (10)	−0.0078 (8)
C4	0.0225 (11)	0.0310 (10)	0.0256 (10)	−0.0063 (9)	0.0148 (9)	−0.0084 (8)
C5	0.0213 (10)	0.0292 (10)	0.0241 (9)	−0.0007 (9)	0.0151 (9)	−0.0035 (8)
C6	0.0213 (10)	0.0252 (9)	0.0198 (8)	−0.0007 (8)	0.0127 (8)	−0.0003 (7)
C7	0.0201 (10)	0.0222 (9)	0.0203 (8)	−0.0019 (8)	0.0114 (8)	−0.0008 (7)
C8	0.0171 (9)	0.0207 (8)	0.0173 (8)	−0.0009 (8)	0.0087 (8)	0.0004 (7)
C9	0.0185 (10)	0.0213 (9)	0.0191 (8)	0.0003 (8)	0.0103 (8)	−0.0001 (7)
C10	0.0198 (9)	0.0174 (8)	0.0206 (8)	−0.0017 (8)	0.0129 (8)	−0.0014 (6)
C11	0.0190 (10)	0.0217 (9)	0.0215 (9)	−0.0021 (8)	0.0121 (8)	−0.0017 (7)
C12	0.0189 (10)	0.0230 (9)	0.0197 (8)	−0.0031 (8)	0.0112 (8)	−0.0027 (7)
C13	0.0205 (10)	0.0180 (8)	0.0192 (8)	−0.0046 (8)	0.0120 (8)	−0.0017 (6)
C14	0.0205 (10)	0.0216 (9)	0.0206 (8)	−0.0049 (8)	0.0135 (8)	−0.0006 (7)
C15	0.0227 (10)	0.0212 (9)	0.0217 (9)	−0.0027 (8)	0.0138 (9)	0.0004 (7)
C16	0.0312 (12)	0.0218 (9)	0.0302 (10)	−0.0025 (9)	0.0209 (10)	0.0019 (8)
C17	0.0373 (13)	0.0221 (10)	0.0355 (11)	0.0032 (10)	0.0233 (11)	0.0025 (8)
C18	0.0318 (13)	0.0285 (10)	0.0381 (12)	0.0081 (10)	0.0235 (11)	0.0044 (9)
C19	0.0240 (11)	0.0299 (10)	0.0302 (10)	0.0031 (9)	0.0182 (10)	0.0047 (8)
C20	0.0195 (10)	0.0232 (9)	0.0196 (8)	−0.0006 (8)	0.0114 (8)	0.0020 (7)
C21	0.0175 (9)	0.0218 (9)	0.0181 (8)	−0.0003 (8)	0.0090 (8)	0.0021 (7)
C22	0.0248 (11)	0.0275 (10)	0.0207 (9)	−0.0058 (9)	0.0099 (9)	−0.0042 (8)
C23	0.0307 (12)	0.0320 (11)	0.0245 (10)	−0.0110 (10)	0.0155 (10)	−0.0087 (8)
C24	0.0311 (12)	0.0236 (9)	0.0283 (10)	−0.0085 (9)	0.0179 (10)	−0.0088 (8)
C25	0.0271 (11)	0.0212 (9)	0.0257 (9)	−0.0036 (8)	0.0184 (9)	−0.0041 (7)
C26	0.0229 (10)	0.0185 (8)	0.0241 (9)	−0.0028 (8)	0.0162 (9)	−0.0024 (7)
C27	0.0249 (10)	0.0178 (8)	0.0251 (9)	−0.0029 (8)	0.0168 (9)	−0.0032 (7)
C28	0.0296 (11)	0.0211 (9)	0.0316 (10)	−0.0019 (9)	0.0228 (10)	−0.0014 (7)
C29	0.0328 (12)	0.0220 (9)	0.0300 (10)	0.0007 (9)	0.0205 (10)	0.0023 (8)
C30	0.0308 (12)	0.0189 (9)	0.0344 (11)	0.0028 (9)	0.0214 (10)	−0.0028 (8)
C31	0.0331 (13)	0.0267 (10)	0.0492 (14)	0.0007 (10)	0.0322 (12)	0.0015 (9)
C32	0.0400 (14)	0.0227 (10)	0.0456 (13)	0.0027 (10)	0.0341 (12)	0.0068 (9)

Geometric parameters (Å, º) top

Cl1—C3	1.734 (2)	C13—C14	1.571 (3)
Cl2—C30	1.741 (2)	C14—C15	1.514 (3)
O1—C9	1.215 (2)	C15—C20	1.390 (3)
O2—C14	1.402 (2)	C15—C16	1.391 (3)
O2—H1O2	0.86 (4)	C16—C17	1.387 (4)
O3—C21	1.211 (3)	C16—H16A	0.9300
N1—C11	1.464 (3)	C17—C18	1.382 (4)
N1—C12	1.470 (3)	C17—H17A	0.9300
N1—C14	1.485 (3)	C18—C19	1.382 (3)
N2—C13	1.459 (2)	C18—H18A	0.9300
N2—C22	1.477 (3)	C19—C20	1.386 (3)
N2—C25	1.490 (3)	C19—H19A	0.9300
C1—C2	1.387 (3)	C20—C21	1.473 (3)
C1—C6	1.393 (3)	C22—C23	1.528 (3)
C1—H1A	0.9300	C22—H22A	0.9700
C2—C3	1.382 (3)	C22—H22B	0.9700
C2—H2A	0.9300	C23—C24	1.529 (3)
C3—C4	1.382 (3)	C23—H23A	0.9700
C4—C5	1.386 (3)	C23—H23B	0.9700
C4—H4A	0.9300	C24—C25	1.521 (3)
C5—C6	1.401 (3)	C24—H24A	0.9700
C5—H5A	0.9300	C24—H24B	0.9700
C6—C7	1.464 (3)	C25—C26	1.533 (3)
C7—C8	1.338 (3)	C25—H25A	0.9800
C7—H7A	0.9300	C26—C27	1.515 (3)
C8—C9	1.491 (3)	C26—H26A	0.9800
C8—C12	1.518 (3)	C27—C28	1.391 (3)
C9—C10	1.522 (3)	C27—C32	1.404 (3)
C10—C26	1.533 (3)	C28—C29	1.392 (3)
C10—C11	1.551 (3)	C28—H28A	0.9300
C10—C13	1.558 (3)	C29—C30	1.380 (4)
C11—H11A	0.9700	C29—H29A	0.9300
C11—H11B	0.9700	C30—C31	1.381 (3)
C12—H12A	0.9700	C31—C32	1.376 (3)
C12—H12B	0.9700	C31—H31A	0.9300
C13—C21	1.538 (3)	C32—H32A	0.9300

C14—O2—H1O2	103 (3)	C17—C16—C15	118.5 (2)
C11—N1—C12	109.42 (15)	C17—C16—H16A	120.8
C11—N1—C14	102.71 (15)	C15—C16—H16A	120.8
C12—N1—C14	114.90 (17)	C18—C17—C16	121.3 (2)
C13—N2—C22	120.99 (18)	C18—C17—H17A	119.3
C13—N2—C25	110.79 (15)	C16—C17—H17A	119.3
C22—N2—C25	109.58 (16)	C17—C18—C19	120.7 (2)
C2—C1—C6	121.0 (2)	C17—C18—H18A	119.7
C2—C1—H1A	119.5	C19—C18—H18A	119.7
C6—C1—H1A	119.5	C18—C19—C20	118.1 (2)
C3—C2—C1	119.3 (2)	C18—C19—H19A	121.0
C3—C2—H2A	120.4	C20—C19—H19A	121.0
C1—C2—H2A	120.4	C19—C20—C15	121.8 (2)
C2—C3—C4	121.0 (2)	C19—C20—C21	127.7 (2)
C2—C3—Cl1	119.65 (18)	C15—C20—C21	110.51 (19)
C4—C3—Cl1	119.31 (18)	O3—C21—C20	127.4 (2)
C3—C4—C5	119.4 (2)	O3—C21—C13	124.27 (19)
C3—C4—H4A	120.3	C20—C21—C13	108.33 (17)
C5—C4—H4A	120.3	N2—C22—C23	104.47 (19)
C4—C5—C6	120.7 (2)	N2—C22—H22A	110.9
C4—C5—H5A	119.7	C23—C22—H22A	110.9
C6—C5—H5A	119.7	N2—C22—H22B	110.9
C1—C6—C5	118.44 (19)	C23—C22—H22B	110.9
C1—C6—C7	119.0 (2)	H22A—C22—H22B	108.9
C5—C6—C7	122.6 (2)	C22—C23—C24	102.44 (16)
C8—C7—C6	127.4 (2)	C22—C23—H23A	111.3
C8—C7—H7A	116.3	C24—C23—H23A	111.3
C6—C7—H7A	116.3	C22—C23—H23B	111.3
C7—C8—C9	116.25 (19)	C24—C23—H23B	111.3
C7—C8—C12	125.83 (18)	H23A—C23—H23B	109.2
C9—C8—C12	117.63 (18)	C25—C24—C23	102.73 (17)
O1—C9—C8	122.60 (18)	C25—C24—H24A	111.2
O1—C9—C10	122.02 (18)	C23—C24—H24A	111.2
C8—C9—C10	115.37 (17)	C25—C24—H24B	111.2
C9—C10—C26	113.24 (16)	C23—C24—H24B	111.2
C9—C10—C11	107.07 (16)	H24A—C24—H24B	109.1
C26—C10—C11	119.53 (17)	N2—C25—C24	104.33 (18)
C9—C10—C13	112.20 (17)	N2—C25—C26	106.39 (15)
C26—C10—C13	104.45 (15)	C24—C25—C26	116.25 (18)
C11—C10—C13	99.52 (15)	N2—C25—H25A	109.9
N1—C11—C10	103.43 (16)	C24—C25—H25A	109.9
N1—C11—H11A	111.1	C26—C25—H25A	109.9
C10—C11—H11A	111.1	C27—C26—C10	115.95 (17)
N1—C11—H11B	111.1	C27—C26—C25	115.44 (17)
C10—C11—H11B	111.1	C10—C26—C25	103.79 (15)
H11A—C11—H11B	109.0	C27—C26—H26A	107.0
N1—C12—C8	114.75 (16)	C10—C26—H26A	107.0
N1—C12—H12A	108.6	C25—C26—H26A	107.0
C8—C12—H12A	108.6	C28—C27—C32	117.3 (2)
N1—C12—H12B	108.6	C28—C27—C26	120.2 (2)
C8—C12—H12B	108.6	C32—C27—C26	122.47 (18)
H12A—C12—H12B	107.6	C27—C28—C29	121.6 (2)
N2—C13—C21	115.59 (17)	C27—C28—H28A	119.2
N2—C13—C10	103.85 (16)	C29—C28—H28A	119.2
C21—C13—C10	115.64 (16)	C30—C29—C28	119.2 (2)
N2—C13—C14	112.50 (15)	C30—C29—H29A	120.4
C21—C13—C14	104.56 (16)	C28—C29—H29A	120.4
C10—C13—C14	104.36 (16)	C29—C30—C31	120.7 (2)
O2—C14—N1	108.68 (17)	C29—C30—Cl2	119.54 (17)
O2—C14—C15	111.33 (16)	C31—C30—Cl2	119.76 (19)
N1—C14—C15	114.98 (16)	C32—C31—C30	119.6 (2)
O2—C14—C13	110.56 (15)	C32—C31—H31A	120.2
N1—C14—C13	105.97 (15)	C30—C31—H31A	120.2
C15—C14—C13	105.12 (17)	C31—C32—C27	121.5 (2)
C20—C15—C16	119.7 (2)	C31—C32—H32A	119.2
C20—C15—C14	111.42 (17)	C27—C32—H32A	119.2
C16—C15—C14	128.9 (2)

C6—C1—C2—C3	−0.7 (4)	C10—C13—C14—C15	124.24 (16)
C1—C2—C3—C4	2.1 (4)	O2—C14—C15—C20	−121.38 (18)
C1—C2—C3—Cl1	−179.90 (18)	N1—C14—C15—C20	114.48 (19)
C2—C3—C4—C5	−0.6 (3)	C13—C14—C15—C20	−1.6 (2)
Cl1—C3—C4—C5	−178.64 (17)	O2—C14—C15—C16	59.9 (3)
C3—C4—C5—C6	−2.3 (3)	N1—C14—C15—C16	−64.2 (3)
C2—C1—C6—C5	−2.1 (3)	C13—C14—C15—C16	179.6 (2)
C2—C1—C6—C7	178.8 (2)	C20—C15—C16—C17	0.1 (3)
C4—C5—C6—C1	3.6 (3)	C14—C15—C16—C17	178.8 (2)
C4—C5—C6—C7	−177.36 (19)	C15—C16—C17—C18	0.3 (3)
C1—C6—C7—C8	−146.5 (2)	C16—C17—C18—C19	−0.6 (4)
C5—C6—C7—C8	34.5 (3)	C17—C18—C19—C20	0.5 (3)
C6—C7—C8—C9	176.88 (19)	C18—C19—C20—C15	0.0 (3)
C6—C7—C8—C12	3.3 (3)	C18—C19—C20—C21	−179.2 (2)
C7—C8—C9—O1	27.9 (3)	C16—C15—C20—C19	−0.3 (3)
C12—C8—C9—O1	−158.0 (2)	C14—C15—C20—C19	−179.13 (18)
C7—C8—C9—C10	−151.40 (19)	C16—C15—C20—C21	179.02 (18)
C12—C8—C9—C10	22.7 (3)	C14—C15—C20—C21	0.2 (2)
O1—C9—C10—C26	0.8 (3)	C19—C20—C21—O3	0.8 (3)
C8—C9—C10—C26	−179.89 (18)	C15—C20—C21—O3	−178.47 (19)
O1—C9—C10—C11	134.7 (2)	C19—C20—C21—C13	−179.31 (19)
C8—C9—C10—C11	−46.0 (2)	C15—C20—C21—C13	1.4 (2)
O1—C9—C10—C13	−117.1 (2)	N2—C13—C21—O3	−58.2 (3)
C8—C9—C10—C13	62.2 (2)	C10—C13—C21—O3	63.4 (3)
C12—N1—C11—C10	−74.00 (18)	C14—C13—C21—O3	177.57 (18)
C14—N1—C11—C10	48.50 (18)	N2—C13—C21—C20	121.89 (17)
C9—C10—C11—N1	71.07 (18)	C10—C13—C21—C20	−116.49 (17)
C26—C10—C11—N1	−158.51 (16)	C14—C13—C21—C20	−2.35 (19)
C13—C10—C11—N1	−45.81 (17)	C13—N2—C22—C23	144.02 (19)
C11—N1—C12—C8	50.1 (2)	C25—N2—C22—C23	13.2 (2)
C14—N1—C12—C8	−64.8 (2)	N2—C22—C23—C24	−33.2 (2)
C7—C8—C12—N1	150.2 (2)	C22—C23—C24—C25	40.6 (2)
C9—C8—C12—N1	−23.3 (3)	C13—N2—C25—C24	−123.78 (18)
C22—N2—C13—C21	−21.8 (3)	C22—N2—C25—C24	12.2 (2)
C25—N2—C13—C21	108.51 (19)	C13—N2—C25—C26	−0.3 (2)
C22—N2—C13—C10	−149.50 (18)	C22—N2—C25—C26	135.68 (18)
C25—N2—C13—C10	−19.2 (2)	C23—C24—C25—N2	−32.7 (2)
C22—N2—C13—C14	98.2 (2)	C23—C24—C25—C26	−149.45 (19)
C25—N2—C13—C14	−131.49 (18)	C9—C10—C26—C27	78.5 (2)
C9—C10—C13—N2	154.42 (16)	C11—C10—C26—C27	−49.1 (2)
C26—C10—C13—N2	31.4 (2)	C13—C10—C26—C27	−159.14 (17)
C11—C10—C13—N2	−92.63 (17)	C9—C10—C26—C25	−153.81 (18)
C9—C10—C13—C21	26.7 (2)	C11—C10—C26—C25	78.6 (2)
C26—C10—C13—C21	−96.33 (19)	C13—C10—C26—C25	−31.4 (2)
C11—C10—C13—C21	139.66 (17)	N2—C25—C26—C27	148.12 (18)
C9—C10—C13—C14	−87.54 (19)	C24—C25—C26—C27	−96.2 (2)
C26—C10—C13—C14	149.42 (16)	N2—C25—C26—C10	20.1 (2)
C11—C10—C13—C14	25.41 (18)	C24—C25—C26—C10	135.8 (2)
C11—N1—C14—O2	88.01 (18)	C10—C26—C27—C28	−108.6 (2)
C12—N1—C14—O2	−153.27 (16)	C25—C26—C27—C28	129.7 (2)
C11—N1—C14—C15	−146.47 (17)	C10—C26—C27—C32	70.1 (3)
C12—N1—C14—C15	−27.7 (2)	C25—C26—C27—C32	−51.6 (3)
C11—N1—C14—C13	−30.83 (19)	C32—C27—C28—C29	0.4 (3)
C12—N1—C14—C13	87.89 (19)	C26—C27—C28—C29	179.10 (19)
N2—C13—C14—O2	−3.6 (2)	C27—C28—C29—C30	−0.9 (3)
C21—C13—C14—O2	122.61 (17)	C28—C29—C30—C31	0.9 (3)
C10—C13—C14—O2	−115.52 (18)	C28—C29—C30—Cl2	−178.67 (17)
N2—C13—C14—N1	114.01 (18)	C29—C30—C31—C32	−0.4 (4)
C21—C13—C14—N1	−119.79 (16)	Cl2—C30—C31—C32	179.21 (19)
C10—C13—C14—N1	2.1 (2)	C30—C31—C32—C27	−0.2 (4)
N2—C13—C14—C15	−123.83 (18)	C28—C27—C32—C31	0.2 (3)
C21—C13—C14—C15	2.37 (18)	C26—C27—C32—C31	−178.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···N2	0.86 (5)	1.97 (5)	2.623 (3)	133 (5)
C1—H1A···O3ⁱ	0.93	2.44	3.305 (3)	155
C22—H22A···O3	0.97	2.51	3.186 (3)	126
C23—H23A···O2ⁱⁱ	0.97	2.59	3.506 (3)	158

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

Experimental details

Crystal data
Chemical formula	C₃₂H₂₆Cl₂N₂O₃
M_r	557.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.603 (2), 10.5701 (14), 21.808 (2)
β (°)	130.094 (6)
V (Å³)	2575.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.34 × 0.19 × 0.11

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.906, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	27859, 7631, 5380
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.710

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.186, 1.06
No. of reflections	7631
No. of parameters	356
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.58

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
O2—H1O2···N2	0.86 (5)	1.97 (5)	2.623 (3)	133 (5)
C1—H1A···O3ⁱ	0.9300	2.4400	3.305 (3)	155.00
C22—H22A···O3	0.9700	2.5100	3.186 (3)	126.00
C23—H23A···O2ⁱⁱ	0.9700	2.5900	3.506 (3)	158.00

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

Footnotes

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

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The synthetic chemistry work was funded by Universiti Sains Malaysia (USM) under University Research grant No. 1001/PKIMIA/8111016 and 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 Golden Goose grant No. 1001/PFIZIK/811012. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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