11-[(E)-4-Bromo­benzyl­idene]-8-(4-bromo­phen­yl)-14-hy­droxy-3,13-diaza­hepta­cyclo­[13.7.1.19,13.02,9.02,14.03,7.019,23]tetra­cosa-1(22),15,17,19(23),20-pentaen-10-one

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

doi:10.1107/S1600536810042091

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages o2926-o2927

https://doi.org/10.1107/S1600536810042091

Open

access

11-[(E)-4-Bromobenzylidene]-8-(4-bromophenyl)-14-hydroxy-3,13-diazaheptacyclo[13.7.1.1^9,13.0^2,9.0^2,14.0^3,7.0^19,23]tetracosa-1(22),15,17,19(23),20-pentaen-10-one

Raju Suresh Kumar,^a Hasnah Osman,^a ‡ Mohamed Ashraf Ali,^b Madhukar Hemamalini ^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 October 2010; accepted 17 October 2010; online 23 October 2010)

In the title compound, C₃₅H₂₈Br₂N₂O₂, the piperidone ring adopts a chair conformation and the five-membered ring of the pyrrolidine ring adopts an envelope conformation. The naphthalene ring system makes dihedral angles of 37.12 (8) and 50.62 (9)° with the terminal bromo-substituted benzene rings. The dihedral angle between the two bromo-substituted benzene rings is 72.54 (10)°. In the crystal, adjacent molecules are connected by a pair of intermolecular C—H⋯O hydrogen bonds, forming an inversion dimer. An intramolecular O—H⋯N hydrogen bond is also present.

Related literature

For details of cycloaddition, see: Babu & Raghunathan (2007 ); Boruah et al. (2007 ); Dondas et al. (2004 ); Hong et al. (2007 ); Karthikeyan et al. (2007 ); Liddell (1998 ); Ramesh et al. (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

C₃₅H₂₈Br₂N₂O₂
M_r = 668.41
Triclinic, $[P \overline 1]$
a = 8.4833 (10) Å
b = 11.8334 (13) Å
c = 14.8942 (17) Å
α = 79.868 (2)°
β = 80.705 (2)°
γ = 77.359 (2)°
V = 1424.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.88 mm⁻¹
T = 100 K
0.44 × 0.17 × 0.16 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.364, T_max = 0.657
14706 measured reflections
6459 independent reflections
5384 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.077
S = 1.07
6459 reflections
374 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯N2	0.81 (3)	2.01 (2)	2.578 (2)	127 (3)
C20—H20A⋯O2ⁱ	0.98	2.46	3.130 (3)	125
Symmetry code: (i) -x, -y+1, -z+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/S1600536810042091/is2614sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042091/is2614Isup2.hkl

checkCIF report

Comment top

1,3-Dipolar cycloadditions form a subject of intensive research in organic synthesis in view of their great synthetic potential (Karthikeyan et al., 2007; Hong et al., 2007). In particular, the 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). Acenaphthenequinone is a versatile precursor for azomethine ylide cycloaddition as it reacts with various l-amino acids generating reactive 1,3-dipoles (Babu & Raghunathan, 2007; Ramesh et al., 2007). The pyrrolidine substructure occurs in many natural products of potential use in medicine and agriculture (Liddell, 1998).

The molecular structure of the title compound is shown in Fig. 1. The piperidine (N1/C8–C12) ring adopts a chair conformation [Q = 0.611 (2) Å, Θ = 139.77 (19) °, φ = 241.0 (3) ° ; Cremer & Pople, 1975]. The pyrrolidine ring (N2/C20–C23) adopts an envelope conformation [puckering parameters Q = 0.385 (2) Å, Θ = 112.7 (3) °]. The naphthalene (C25–34) ring makes dihedral angles of 37.12 (8)° and 50.62 (9)° with the terminal bromo-substituted benzene (C1–C6) and (C13–C18) rings. The dihedral angle between the two bromo-substituted benzene (C1–C6) and (C13–C18) rings is 72.54 (10)°.

In the crystal packing (Fig. 2), adjacent molecules are connected by intermolecular C20—H20A···O2 hydrogen bonds, forming dimers arranged in sheets parallel to the bc-plane. An intramolecular O—H···N hydrogen bond is also present.

Related literature top

For details of cycloaddition, see: Babu & Raghunathan (2007); Boruah et al. (2007); Dondas et al. (2004); Hong et al. (2007); Karthikeyan et al. (2007); Liddell (1998); Ramesh et al. (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)-(4-bromophenyl)methylidene]tetrahydro-4(1H)-pyridinone (0.100 g, 0.231 mmol), acenaphthenequinone (0.042 g, 0.231 mmol) and proline (0.027 g, 0.231 mmol) were dissolved in methanol (5 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 colourless crystals.

Structure description top

For details of cycloaddition, see: Babu & Raghunathan (2007); Boruah et al. (2007); Dondas et al. (2004); Hong et al. (2007); Karthikeyan et al. (2007); Liddell (1998); Ramesh et al. (2007). 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) dimers. H atoms are not involving the hydrogen bond interactions are omitted for clarity.

11-[(E)-4-Bromobenzylidene]-8-(4-bromophenyl)-14-hydroxy-3,13- diazaheptacyclo[13.7.1.1^9,13.0^2,9.0^2,14.0^3,7.0^19,23]tetracosa- 1(22),15,17,19 (23),20-pentaen-10-one top

Crystal data top

C₃₅H₂₈Br₂N₂O₂	Z = 2
M_r = 668.41	F(000) = 676
Triclinic, P1	D_x = 1.559 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4833 (10) Å	Cell parameters from 6649 reflections
b = 11.8334 (13) Å	θ = 2.4–28.4°
c = 14.8942 (17) Å	µ = 2.88 mm⁻¹
α = 79.868 (2)°	T = 100 K
β = 80.705 (2)°	Block, colourless
γ = 77.359 (2)°	0.44 × 0.17 × 0.16 mm
V = 1424.4 (3) Å³

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	6459 independent reflections
Radiation source: fine-focus sealed tube	5384 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→10
T_min = 0.364, T_max = 0.657	k = −15→15
14706 measured reflections	l = −19→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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.030P)² + 0.5557P] where P = (F_o² + 2F_c²)/3
6459 reflections	(Δ/σ)_max = 0.003
374 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₃₅H₂₈Br₂N₂O₂	γ = 77.359 (2)°
M_r = 668.41	V = 1424.4 (3) Å³
Triclinic, P1	Z = 2
a = 8.4833 (10) Å	Mo Kα radiation
b = 11.8334 (13) Å	µ = 2.88 mm⁻¹
c = 14.8942 (17) Å	T = 100 K
α = 79.868 (2)°	0.44 × 0.17 × 0.16 mm
β = 80.705 (2)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	6459 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5384 reflections with I > 2σ(I)
T_min = 0.364, T_max = 0.657	R_int = 0.030
14706 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.45 e Å⁻³
6459 reflections	Δρ_min = −0.48 e Å⁻³
374 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
Br1	0.95912 (3)	0.70022 (2)	0.375928 (15)	0.03029 (7)
Br2	0.50038 (3)	0.80345 (2)	1.346623 (16)	0.03079 (8)
O1	0.36372 (17)	0.90896 (12)	0.88975 (10)	0.0203 (3)
O2	0.11709 (19)	0.50546 (13)	0.90383 (10)	0.0213 (3)
N1	0.3708 (2)	0.56045 (14)	0.88753 (11)	0.0159 (3)
N2	−0.02666 (19)	0.70855 (14)	0.94557 (11)	0.0157 (3)
C1	0.7446 (3)	0.66951 (19)	0.64742 (15)	0.0225 (4)
H1A	0.7501	0.6124	0.6990	0.027*
C2	0.8377 (3)	0.64507 (19)	0.56501 (15)	0.0254 (5)
H2A	0.9044	0.5720	0.5610	0.030*
C3	0.8299 (3)	0.7308 (2)	0.48903 (14)	0.0228 (4)
C4	0.7332 (3)	0.84159 (19)	0.49339 (14)	0.0225 (4)
H4A	0.7310	0.8990	0.4419	0.027*
C5	0.6406 (3)	0.86453 (18)	0.57587 (14)	0.0213 (4)
H5A	0.5758	0.9384	0.5794	0.026*
C6	0.6419 (2)	0.77957 (18)	0.65411 (13)	0.0182 (4)
C7	0.5367 (2)	0.81193 (17)	0.73743 (13)	0.0174 (4)
H7A	0.5086	0.8919	0.7400	0.021*
C8	0.4743 (2)	0.74428 (17)	0.81089 (13)	0.0157 (4)
C9	0.3618 (2)	0.80907 (17)	0.88225 (13)	0.0150 (4)
C10	0.2428 (2)	0.73992 (16)	0.94201 (13)	0.0136 (4)
C11	0.3388 (2)	0.61511 (16)	0.97163 (13)	0.0158 (4)
H11A	0.4399	0.6181	0.9929	0.019*
H11B	0.2746	0.5724	1.0203	0.019*
C12	0.4976 (2)	0.61138 (17)	0.82450 (13)	0.0168 (4)
H12A	0.5039	0.5869	0.7650	0.020*
H12B	0.6014	0.5787	0.8472	0.020*
C13	0.2392 (2)	0.70348 (18)	1.17155 (14)	0.0192 (4)
H13A	0.1953	0.6386	1.1697	0.023*
C14	0.3250 (3)	0.70395 (19)	1.24397 (14)	0.0217 (4)
H14A	0.3397	0.6396	1.2898	0.026*
C15	0.3874 (2)	0.80129 (18)	1.24641 (14)	0.0201 (4)
C16	0.3701 (3)	0.89758 (19)	1.17861 (14)	0.0228 (4)
H16A	0.4137	0.9624	1.1810	0.027*
C17	0.2856 (2)	0.89479 (18)	1.10674 (14)	0.0189 (4)
H17A	0.2737	0.9589	1.0605	0.023*
C18	0.2184 (2)	0.79958 (16)	1.10161 (13)	0.0151 (4)
C19	0.1330 (2)	0.80060 (16)	1.01924 (13)	0.0145 (4)
H19A	0.0937	0.8824	0.9940	0.017*
C20	−0.0118 (2)	0.73723 (17)	1.03739 (13)	0.0157 (4)
H20A	0.0135	0.6647	1.0802	0.019*
C21	−0.1792 (2)	0.80658 (19)	1.07021 (14)	0.0216 (4)
H21A	−0.1806	0.8900	1.0586	0.026*
H21B	−0.2099	0.7836	1.1354	0.026*
C22	−0.2933 (3)	0.7743 (2)	1.01281 (15)	0.0237 (4)
H22A	−0.3252	0.7005	1.0398	0.028*
H22B	−0.3904	0.8348	1.0072	0.028*
C23	−0.1894 (2)	0.76447 (19)	0.91974 (15)	0.0218 (4)
H23A	−0.2285	0.7163	0.8852	0.026*
H23B	−0.1884	0.8410	0.8836	0.026*
C24	0.1223 (2)	0.71519 (16)	0.88158 (13)	0.0137 (4)
C25	0.1053 (2)	0.78952 (17)	0.78823 (13)	0.0165 (4)
C26	0.0509 (3)	0.90806 (18)	0.76295 (15)	0.0220 (4)
H26A	0.0155	0.9579	0.8071	0.026*
C27	0.0505 (3)	0.9519 (2)	0.66793 (17)	0.0302 (5)
H27A	0.0114	1.0313	0.6507	0.036*
C28	0.1049 (3)	0.8824 (2)	0.60051 (16)	0.0333 (5)
H28A	0.1034	0.9152	0.5391	0.040*
C29	0.1642 (3)	0.7598 (2)	0.62403 (15)	0.0253 (5)
C30	0.2261 (3)	0.6766 (2)	0.56313 (15)	0.0330 (6)
H30A	0.2332	0.7008	0.5000	0.040*
C31	0.2762 (3)	0.5598 (2)	0.59660 (16)	0.0326 (6)
H31A	0.3143	0.5063	0.5554	0.039*
C32	0.2708 (3)	0.5194 (2)	0.69231 (15)	0.0257 (5)
H32A	0.3041	0.4404	0.7139	0.031*
C33	0.2154 (2)	0.59901 (18)	0.75230 (14)	0.0186 (4)
C34	0.1594 (2)	0.71801 (18)	0.71875 (14)	0.0187 (4)
C35	0.2080 (2)	0.58723 (16)	0.85513 (13)	0.0156 (4)
H1O2	0.035 (4)	0.538 (2)	0.9321 (19)	0.037 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02851 (13)	0.03823 (14)	0.02268 (12)	−0.00510 (10)	0.00563 (9)	−0.01058 (9)
Br2	0.03305 (14)	0.03556 (14)	0.02841 (13)	−0.00501 (10)	−0.01459 (10)	−0.00954 (10)
O1	0.0203 (8)	0.0184 (7)	0.0235 (7)	−0.0077 (6)	0.0010 (6)	−0.0048 (6)
O2	0.0213 (8)	0.0153 (7)	0.0275 (8)	−0.0092 (6)	0.0025 (6)	−0.0015 (6)
N1	0.0155 (8)	0.0147 (8)	0.0164 (8)	−0.0019 (6)	−0.0024 (6)	−0.0002 (6)
N2	0.0117 (8)	0.0177 (8)	0.0184 (8)	−0.0053 (6)	−0.0026 (6)	−0.0006 (6)
C1	0.0177 (11)	0.0235 (11)	0.0230 (10)	−0.0020 (8)	0.0011 (8)	−0.0004 (8)
C2	0.0218 (11)	0.0233 (11)	0.0289 (11)	−0.0033 (9)	0.0038 (9)	−0.0057 (9)
C3	0.0185 (10)	0.0330 (12)	0.0182 (10)	−0.0077 (9)	0.0028 (8)	−0.0084 (9)
C4	0.0254 (11)	0.0249 (11)	0.0177 (10)	−0.0079 (9)	−0.0022 (8)	−0.0017 (8)
C5	0.0228 (11)	0.0196 (10)	0.0216 (10)	−0.0051 (8)	−0.0021 (8)	−0.0031 (8)
C6	0.0154 (10)	0.0223 (10)	0.0179 (10)	−0.0068 (8)	−0.0007 (8)	−0.0032 (8)
C7	0.0161 (10)	0.0180 (9)	0.0192 (10)	−0.0049 (8)	−0.0027 (8)	−0.0032 (8)
C8	0.0095 (9)	0.0199 (10)	0.0182 (9)	−0.0022 (7)	−0.0028 (7)	−0.0041 (8)
C9	0.0129 (9)	0.0165 (9)	0.0161 (9)	−0.0025 (7)	−0.0050 (7)	−0.0011 (7)
C10	0.0118 (9)	0.0146 (9)	0.0142 (9)	−0.0021 (7)	−0.0031 (7)	−0.0014 (7)
C11	0.0156 (10)	0.0142 (9)	0.0164 (9)	−0.0012 (7)	−0.0037 (7)	−0.0002 (7)
C12	0.0136 (10)	0.0169 (9)	0.0194 (9)	−0.0018 (7)	−0.0022 (7)	−0.0029 (8)
C13	0.0195 (10)	0.0199 (10)	0.0189 (10)	−0.0065 (8)	−0.0011 (8)	−0.0032 (8)
C14	0.0222 (11)	0.0246 (11)	0.0166 (10)	−0.0020 (9)	−0.0030 (8)	−0.0010 (8)
C15	0.0162 (10)	0.0259 (11)	0.0195 (10)	−0.0018 (8)	−0.0032 (8)	−0.0090 (8)
C16	0.0216 (11)	0.0246 (11)	0.0250 (11)	−0.0071 (9)	−0.0034 (9)	−0.0076 (9)
C17	0.0181 (10)	0.0183 (10)	0.0201 (10)	−0.0042 (8)	−0.0012 (8)	−0.0027 (8)
C18	0.0119 (9)	0.0157 (9)	0.0165 (9)	−0.0011 (7)	0.0001 (7)	−0.0030 (7)
C19	0.0127 (9)	0.0128 (9)	0.0171 (9)	−0.0022 (7)	−0.0013 (7)	−0.0007 (7)
C20	0.0139 (10)	0.0157 (9)	0.0171 (9)	−0.0039 (8)	−0.0018 (7)	−0.0004 (7)
C21	0.0129 (10)	0.0273 (11)	0.0222 (10)	−0.0020 (8)	0.0011 (8)	−0.0026 (8)
C22	0.0135 (10)	0.0265 (11)	0.0298 (11)	−0.0034 (8)	−0.0023 (8)	−0.0021 (9)
C23	0.0127 (10)	0.0257 (11)	0.0282 (11)	−0.0029 (8)	−0.0063 (8)	−0.0046 (9)
C24	0.0120 (9)	0.0121 (9)	0.0172 (9)	−0.0037 (7)	−0.0031 (7)	0.0001 (7)
C25	0.0121 (9)	0.0200 (10)	0.0172 (9)	−0.0055 (8)	−0.0044 (7)	0.0029 (8)
C26	0.0199 (11)	0.0185 (10)	0.0263 (11)	−0.0045 (8)	−0.0043 (8)	0.0026 (8)
C27	0.0277 (13)	0.0243 (11)	0.0343 (13)	−0.0051 (10)	−0.0081 (10)	0.0109 (10)
C28	0.0298 (13)	0.0455 (15)	0.0213 (11)	−0.0106 (11)	−0.0075 (10)	0.0115 (10)
C29	0.0211 (11)	0.0355 (12)	0.0210 (10)	−0.0105 (9)	−0.0066 (9)	0.0009 (9)
C30	0.0293 (13)	0.0566 (16)	0.0163 (10)	−0.0149 (12)	−0.0037 (9)	−0.0050 (10)
C31	0.0305 (13)	0.0462 (15)	0.0266 (12)	−0.0114 (11)	−0.0012 (10)	−0.0172 (11)
C32	0.0251 (12)	0.0286 (12)	0.0270 (11)	−0.0082 (9)	−0.0037 (9)	−0.0095 (9)
C33	0.0143 (10)	0.0240 (10)	0.0194 (10)	−0.0072 (8)	−0.0029 (8)	−0.0031 (8)
C34	0.0165 (10)	0.0231 (10)	0.0185 (10)	−0.0081 (8)	−0.0060 (8)	0.0002 (8)
C35	0.0148 (10)	0.0139 (9)	0.0182 (9)	−0.0044 (7)	−0.0013 (7)	−0.0012 (7)

Geometric parameters (Å, º) top

Br1—C3	1.901 (2)	C15—C16	1.382 (3)
Br2—C15	1.9063 (19)	C16—C17	1.390 (3)
O1—C9	1.210 (2)	C16—H16A	0.9300
O2—C35	1.399 (2)	C17—C18	1.388 (3)
O2—H1O2	0.81 (3)	C17—H17A	0.9300
N1—C11	1.470 (2)	C18—C19	1.519 (3)
N1—C12	1.470 (3)	C19—C20	1.539 (3)
N1—C35	1.487 (2)	C19—H19A	0.9800
N2—C24	1.463 (2)	C20—C21	1.529 (3)
N2—C23	1.474 (2)	C20—H20A	0.9800
N2—C20	1.496 (2)	C21—C22	1.536 (3)
C1—C2	1.388 (3)	C21—H21A	0.9700
C1—C6	1.409 (3)	C21—H21B	0.9700
C1—H1A	0.9300	C22—C23	1.526 (3)
C2—C3	1.380 (3)	C22—H22A	0.9700
C2—H2A	0.9300	C22—H22B	0.9700
C3—C4	1.392 (3)	C23—H23A	0.9700
C4—C5	1.383 (3)	C23—H23B	0.9700
C4—H4A	0.9300	C24—C25	1.519 (3)
C5—C6	1.398 (3)	C24—C35	1.616 (3)
C5—H5A	0.9300	C25—C26	1.382 (3)
C6—C7	1.464 (3)	C25—C34	1.408 (3)
C7—C8	1.345 (3)	C26—C27	1.419 (3)
C7—H7A	0.9300	C26—H26A	0.9300
C8—C9	1.506 (3)	C27—C28	1.368 (4)
C8—C12	1.523 (3)	C27—H27A	0.9300
C9—C10	1.515 (3)	C28—C29	1.428 (3)
C10—C19	1.536 (2)	C28—H28A	0.9300
C10—C11	1.549 (3)	C29—C34	1.408 (3)
C10—C24	1.569 (2)	C29—C30	1.415 (3)
C11—H11A	0.9700	C30—C31	1.382 (4)
C11—H11B	0.9700	C30—H30A	0.9300
C12—H12A	0.9700	C31—C32	1.418 (3)
C12—H12B	0.9700	C31—H31A	0.9300
C13—C14	1.397 (3)	C32—C33	1.369 (3)
C13—C18	1.401 (3)	C32—H32A	0.9300
C13—H13A	0.9300	C33—C34	1.412 (3)
C14—C15	1.377 (3)	C33—C35	1.505 (3)
C14—H14A	0.9300

C35—O2—H1O2	110 (2)	C18—C19—C20	116.38 (16)
C11—N1—C12	108.25 (15)	C10—C19—C20	101.97 (14)
C11—N1—C35	102.77 (14)	C18—C19—H19A	108.0
C12—N1—C35	115.10 (15)	C10—C19—H19A	108.0
C24—N2—C23	122.19 (16)	C20—C19—H19A	108.0
C24—N2—C20	111.43 (14)	N2—C20—C21	105.40 (15)
C23—N2—C20	109.51 (15)	N2—C20—C19	104.64 (15)
C2—C1—C6	121.0 (2)	C21—C20—C19	117.58 (16)
C2—C1—H1A	119.5	N2—C20—H20A	109.6
C6—C1—H1A	119.5	C21—C20—H20A	109.6
C3—C2—C1	119.1 (2)	C19—C20—H20A	109.6
C3—C2—H2A	120.5	C20—C21—C22	103.60 (16)
C1—C2—H2A	120.5	C20—C21—H21A	111.0
C2—C3—C4	121.69 (19)	C22—C21—H21A	111.0
C2—C3—Br1	119.80 (16)	C20—C21—H21B	111.0
C4—C3—Br1	118.47 (16)	C22—C21—H21B	111.0
C5—C4—C3	118.6 (2)	H21A—C21—H21B	109.0
C5—C4—H4A	120.7	C23—C22—C21	103.12 (16)
C3—C4—H4A	120.7	C23—C22—H22A	111.1
C4—C5—C6	121.70 (19)	C21—C22—H22A	111.1
C4—C5—H5A	119.1	C23—C22—H22B	111.1
C6—C5—H5A	119.1	C21—C22—H22B	111.1
C5—C6—C1	117.91 (18)	H22A—C22—H22B	109.1
C5—C6—C7	117.39 (18)	N2—C23—C22	102.76 (16)
C1—C6—C7	124.70 (19)	N2—C23—H23A	111.2
C8—C7—C6	130.21 (19)	C22—C23—H23A	111.2
C8—C7—H7A	114.9	N2—C23—H23B	111.2
C6—C7—H7A	114.9	C22—C23—H23B	111.2
C7—C8—C9	115.48 (17)	H23A—C23—H23B	109.1
C7—C8—C12	126.23 (17)	N2—C24—C25	117.47 (15)
C9—C8—C12	118.14 (17)	N2—C24—C10	103.75 (14)
O1—C9—C8	122.78 (18)	C25—C24—C10	118.48 (16)
O1—C9—C10	122.87 (17)	N2—C24—C35	110.44 (15)
C8—C9—C10	114.33 (16)	C25—C24—C35	102.85 (15)
C9—C10—C19	115.73 (15)	C10—C24—C35	102.89 (14)
C9—C10—C11	107.62 (15)	C26—C25—C34	118.66 (18)
C19—C10—C11	115.94 (16)	C26—C25—C24	131.91 (18)
C9—C10—C24	109.71 (15)	C34—C25—C24	109.42 (17)
C19—C10—C24	104.93 (15)	C25—C26—C27	118.3 (2)
C11—C10—C24	101.86 (14)	C25—C26—H26A	120.8
N1—C11—C10	103.98 (14)	C27—C26—H26A	120.8
N1—C11—H11A	111.0	C28—C27—C26	122.9 (2)
C10—C11—H11A	111.0	C28—C27—H27A	118.6
N1—C11—H11B	111.0	C26—C27—H27A	118.6
C10—C11—H11B	111.0	C27—C28—C29	120.3 (2)
H11A—C11—H11B	109.0	C27—C28—H28A	119.8
N1—C12—C8	116.06 (16)	C29—C28—H28A	119.8
N1—C12—H12A	108.3	C34—C29—C30	116.9 (2)
C8—C12—H12A	108.3	C34—C29—C28	115.7 (2)
N1—C12—H12B	108.3	C30—C29—C28	127.4 (2)
C8—C12—H12B	108.3	C31—C30—C29	120.6 (2)
H12A—C12—H12B	107.4	C31—C30—H30A	119.7
C14—C13—C18	120.83 (19)	C29—C30—H30A	119.7
C14—C13—H13A	119.6	C30—C31—C32	121.6 (2)
C18—C13—H13A	119.6	C30—C31—H31A	119.2
C15—C14—C13	118.9 (2)	C32—C31—H31A	119.2
C15—C14—H14A	120.5	C33—C32—C31	118.6 (2)
C13—C14—H14A	120.5	C33—C32—H32A	120.7
C14—C15—C16	122.01 (18)	C31—C32—H32A	120.7
C14—C15—Br2	118.98 (16)	C32—C33—C34	120.08 (19)
C16—C15—Br2	119.01 (15)	C32—C33—C35	131.8 (2)
C15—C16—C17	118.09 (19)	C34—C33—C35	108.01 (16)
C15—C16—H16A	121.0	C29—C34—C25	124.07 (19)
C17—C16—H16A	121.0	C29—C34—C33	122.07 (19)
C18—C17—C16	122.2 (2)	C25—C34—C33	113.82 (17)
C18—C17—H17A	118.9	O2—C35—N1	108.74 (15)
C16—C17—H17A	118.9	O2—C35—C33	113.94 (15)
C17—C18—C13	117.91 (17)	N1—C35—C33	113.66 (16)
C17—C18—C19	119.40 (17)	O2—C35—C24	108.79 (15)
C13—C18—C19	122.62 (17)	N1—C35—C24	105.65 (14)
C18—C19—C10	113.92 (15)	C33—C35—C24	105.59 (15)

C6—C1—C2—C3	0.6 (3)	C23—N2—C24—C25	4.1 (2)
C1—C2—C3—C4	1.1 (3)	C20—N2—C24—C25	−128.02 (17)
C1—C2—C3—Br1	178.94 (16)	C23—N2—C24—C10	137.01 (17)
C2—C3—C4—C5	−1.3 (3)	C20—N2—C24—C10	4.87 (19)
Br1—C3—C4—C5	−179.23 (15)	C23—N2—C24—C35	−113.35 (18)
C3—C4—C5—C6	−0.1 (3)	C20—N2—C24—C35	114.51 (16)
C4—C5—C6—C1	1.7 (3)	C9—C10—C24—N2	−150.70 (15)
C4—C5—C6—C7	−178.66 (19)	C19—C10—C24—N2	−25.76 (18)
C2—C1—C6—C5	−2.0 (3)	C11—C10—C24—N2	95.48 (16)
C2—C1—C6—C7	178.4 (2)	C9—C10—C24—C25	−18.4 (2)
C5—C6—C7—C8	157.1 (2)	C19—C10—C24—C25	106.54 (18)
C1—C6—C7—C8	−23.3 (3)	C11—C10—C24—C25	−132.22 (17)
C6—C7—C8—C9	−176.58 (18)	C9—C10—C24—C35	94.16 (17)
C6—C7—C8—C12	−1.1 (3)	C19—C10—C24—C35	−140.89 (15)
C7—C8—C9—O1	−21.9 (3)	C11—C10—C24—C35	−19.66 (18)
C12—C8—C9—O1	162.27 (18)	N2—C24—C25—C26	63.1 (3)
C7—C8—C9—C10	156.46 (17)	C10—C24—C25—C26	−62.8 (3)
C12—C8—C9—C10	−19.4 (2)	C35—C24—C25—C26	−175.4 (2)
O1—C9—C10—C19	−5.1 (3)	N2—C24—C25—C34	−117.82 (18)
C8—C9—C10—C19	176.55 (15)	C10—C24—C25—C34	116.24 (18)
O1—C9—C10—C11	−136.63 (19)	C35—C24—C25—C34	3.7 (2)
C8—C9—C10—C11	45.05 (19)	C34—C25—C26—C27	0.7 (3)
O1—C9—C10—C24	113.3 (2)	C24—C25—C26—C27	179.7 (2)
C8—C9—C10—C24	−65.00 (19)	C25—C26—C27—C28	−1.6 (3)
C12—N1—C11—C10	73.46 (18)	C26—C27—C28—C29	0.7 (4)
C35—N1—C11—C10	−48.73 (18)	C27—C28—C29—C34	1.0 (3)
C9—C10—C11—N1	−72.90 (17)	C27—C28—C29—C30	−179.3 (2)
C19—C10—C11—N1	155.71 (15)	C34—C29—C30—C31	1.1 (3)
C24—C10—C11—N1	42.46 (18)	C28—C29—C30—C31	−178.6 (2)
C11—N1—C12—C8	−47.2 (2)	C29—C30—C31—C32	−1.3 (4)
C35—N1—C12—C8	67.1 (2)	C30—C31—C32—C33	−0.5 (3)
C7—C8—C12—N1	−155.72 (18)	C31—C32—C33—C34	2.4 (3)
C9—C8—C12—N1	19.6 (2)	C31—C32—C33—C35	−174.0 (2)
C18—C13—C14—C15	0.8 (3)	C30—C29—C34—C25	178.4 (2)
C13—C14—C15—C16	−1.1 (3)	C28—C29—C34—C25	−1.8 (3)
C13—C14—C15—Br2	178.65 (15)	C30—C29—C34—C33	0.8 (3)
C14—C15—C16—C17	0.5 (3)	C28—C29—C34—C33	−179.4 (2)
Br2—C15—C16—C17	−179.23 (15)	C26—C25—C34—C29	1.0 (3)
C15—C16—C17—C18	0.4 (3)	C24—C25—C34—C29	−178.22 (18)
C16—C17—C18—C13	−0.6 (3)	C26—C25—C34—C33	178.72 (18)
C16—C17—C18—C19	−177.76 (18)	C24—C25—C34—C33	−0.5 (2)
C14—C13—C18—C17	0.0 (3)	C32—C33—C34—C29	−2.6 (3)
C14—C13—C18—C19	177.05 (18)	C35—C33—C34—C29	174.52 (18)
C17—C18—C19—C10	94.5 (2)	C32—C33—C34—C25	179.59 (19)
C13—C18—C19—C10	−82.5 (2)	C35—C33—C34—C25	−3.3 (2)
C17—C18—C19—C20	−147.24 (18)	C11—N1—C35—O2	−81.90 (17)
C13—C18—C19—C20	35.7 (3)	C12—N1—C35—O2	160.66 (15)
C9—C10—C19—C18	−76.7 (2)	C11—N1—C35—C33	150.04 (16)
C11—C10—C19—C18	50.8 (2)	C12—N1—C35—C33	32.6 (2)
C24—C10—C19—C18	162.24 (15)	C11—N1—C35—C24	34.74 (18)
C9—C10—C19—C20	157.07 (15)	C12—N1—C35—C24	−82.70 (18)
C11—C10—C19—C20	−75.47 (19)	C32—C33—C35—O2	−58.7 (3)
C24—C10—C19—C20	36.01 (18)	C34—C33—C35—O2	124.68 (18)
C24—N2—C20—C21	142.38 (16)	C32—C33—C35—N1	66.7 (3)
C23—N2—C20—C21	4.1 (2)	C34—C33—C35—N1	−109.99 (18)
C24—N2—C20—C19	17.7 (2)	C32—C33—C35—C24	−178.0 (2)
C23—N2—C20—C19	−120.52 (17)	C34—C33—C35—C24	5.4 (2)
C18—C19—C20—N2	−157.36 (15)	N2—C24—C35—O2	−1.9 (2)
C10—C19—C20—N2	−32.76 (18)	C25—C24—C35—O2	−128.07 (16)
C18—C19—C20—C21	86.1 (2)	C10—C24—C35—O2	108.29 (16)
C10—C19—C20—C21	−149.26 (17)	N2—C24—C35—N1	−118.52 (16)
N2—C20—C21—C22	20.2 (2)	C25—C24—C35—N1	115.33 (16)
C19—C20—C21—C22	136.26 (18)	C10—C24—C35—N1	−8.31 (19)
C20—C21—C22—C23	−36.4 (2)	N2—C24—C35—C33	120.76 (16)
C24—N2—C23—C22	−159.72 (16)	C25—C24—C35—C33	−5.39 (19)
C20—N2—C23—C22	−26.8 (2)	C10—C24—C35—C33	−129.03 (16)
C21—C22—C23—N2	38.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···N2	0.81 (3)	2.01 (2)	2.578 (2)	127 (3)
C20—H20A···O2ⁱ	0.98	2.46	3.130 (3)	125

Symmetry code: (i) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₃₅H₂₈Br₂N₂O₂
M_r	668.41
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.4833 (10), 11.8334 (13), 14.8942 (17)
α, β, γ (°)	79.868 (2), 80.705 (2), 77.359 (2)
V (Å³)	1424.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.88
Crystal size (mm)	0.44 × 0.17 × 0.16

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.364, 0.657
No. of measured, independent and observed [I > 2σ(I)] reflections	14706, 6459, 5384
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.077, 1.07
No. of reflections	6459
No. of parameters	374
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.48

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	0.81 (3)	2.01 (2)	2.578 (2)	127 (3)
C20—H20A···O2ⁱ	0.98	2.46	3.130 (3)	125

Symmetry code: (i) −x, −y+1, −z+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 the University Research Grant No. 1001/PKIMIA/811133 and RSK thanks Universiti Sains Malaysia for the award of a 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.

References

Babu, A. R. S. & Raghunathan, R. (2007). Tetrahedron Lett. 48, 305–308. CAS Google Scholar
Boruah, M., Konwar, D. & Sharma, S. D. (2007). Tetrahedron Lett. 48, 4535–4537. Web of Science CrossRef CAS 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
Dondas, H. A., Fishwick, C. W. G., Grigg, R. & Kilner, C. (2004). Tetrahedron, 60, 3473–3485. Web of Science CSD CrossRef CAS Google Scholar
Hong, X., France, S. & Padwa, A. (2007). Tetrahedron, 63, 5962–5976. Web of Science CrossRef PubMed CAS Google Scholar
Karthikeyan, K., Perumal, P. T., Etti, S. & Shanmugam, G. (2007). Tetrahedron, 63, 10581–10586. Web of Science CSD CrossRef CAS Google Scholar
Liddell, J. R. (1998). Nat. Prod. Rep. 15, 363–370. CrossRef CAS PubMed Google Scholar
Ramesh, E., Kathiresan, M. & Raghunathan, R. (2007). Tetrahedron Lett. 48, 1835–1839. Web of Science CSD CrossRef CAS 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

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.