5-Benzoyl-2-(5-bromo-1H-indol-3-yl)-4-(4-meth­oxy­phen­yl)-1H-pyrrole-3-carbo­nitrile

Vimala, G.; Raja, J.K.; Perumal, P.T.; SubbiahPandi, A.

doi:10.1107/S2414314616007240

organic compounds

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ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160724

doi:10.1107/S2414314616007240

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5-Benzoyl-2-(5-bromo-1H-indol-3-yl)-4-(4-methoxyphenyl)-1H-pyrrole-3-carbonitrile

G. Vimala,^a J. Kamal Raja,^b P. T. Perumal ^b and A. SubbiahPandi ^a ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and ^bOrganic Chemistry, CSIR–Central Leather Research Institute, Adyar, Chennai 600 020, India
^*Correspondence e-mail: aspandian59@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 25 April 2016; accepted 29 April 2016; online 6 May 2016)

In the title compound, C₂₇H₁₈BrN₃O, the indole and central pyrrole ring systems are inclined to one another by 13.15 (15)°. The carbonitrile group is almost coplanar with its attached pyrrole ring, the C≡N bond making a dihedral angle of 1.9 (2)° with the ring plane. The 4-methoxybenzene ring and the benzoyl ring are inclined to the central pyrrole ring by 55.1 (2) and 51.5 (2)°, respectively. The dihedral angle between these two benzene rings is 37.68 (17)°. In the crystal, molecules are linked by pairs of N—H⋯N hydrogen bonds, forming inversion dimers with an R₂²(16) ring motif. The dimers are linked by offset π–π interactions [intercentroid distance = 3.614 (2) Å], which leads to the formation of chains propagating in the [010] direction.

Keywords: crystal structure; indole; naphthalene; carbonitrile-pyrrole; inversion dimers; hydrogen bonding.

CCDC reference: 1477342

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Chemical scheme

Structure description

Indole-containing compounds are best known for their medicinal properties in the pharmaceutical industry. Today, analogues based on indole are significant players in a diverse array of markets such as dyes, plastics, agriculture, vitamin supplements, over-the-counter drugs, flavour enhancers and perfumery (Barden, 2011 ). Indole derivatives exhibit antibacterial, antifungal (Singh et al. 2000 ), antitumor (Andreani et al., 2001 ), antihepatitis B virus (Chai et al., 2006 ) and anti-inflammatory (Rodriguez et al., 1985 ) activities. They are also used as bioactive drugs (Stevenson et al., 2000 ) and exhibit high aldose reductase inhibitory (Rajeswaran et al., 1999 ) and antimicrobial activities (Amal Raj et al., 2003 ). Against this background, we synthesized the title compound and report herein on its crystal structure.

The molecular structure of the title indole derivative is illustrated in Fig. 1. The central pyrrole ring is substituted with an indole ring, a 4-methoxybenzene ring and a benzoyl group. The indole and central pyrrole rings are inclined to one another by 13.1 (2)°. The carbonitrile group is almost coplanar with its attached pyrrole ring, as indicated by the dihedral angle of 1.9 (2)° between the C11≡N3 bond and the ring plane. The central pyrrole ring makes dihedral angles of 55.1 (2) and 51.5 (2)° with the 4-methoxybenzene ring and the benzoyl ring, respectively. The dihedral angle between these two benzene rings is 37.68 (17)°. The molecular dimensions in the title compound are in agreement with those reported for closely related compounds (Vimala et al., 2015 ; Inglebert et al., 2013 ).

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

In the crystal, molecules are linked by pairs of N_i—H⋯N_c (i = indole and c = carbonitrile) classical hydrogen bonds, forming inversion dimers with $[R_{2}^{2}]$ (16) loops (Table 1 and Fig. 2). The molecules are also linked via slipped parallel π–π interactions, forming chains propagating along the b-axis direction [Cg2⋯Cg3ⁱ = 3.614 (2) Å; inter-planar distance = 3.535 (1) Å, slippage = 0.525 Å; Cg2 and Cg3 are the centroids of the N2/C9/C10/C12/C19 and C2–C7 rings; symmetry code: (i) −x + 1, −y, −z + 1].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3ⁱ	0.86	2.21	2.916 (4)	140
Symmetry code: (i) -x+1, -y+1, -z+1.

Figure 2
The crystal packing of the title compound, viewed along the normal to (011). Hydrogen bonds are shown as dashed lines (see Table 1

) and C-bound H atoms have been omitted for clarity.

Synthesis and crystallization

To a stirred mixture of 4-methoxybenzaldehyde (1.0 mmol), 3-(5-bromo-1H-indol-3-yl)-3-oxopropanenitrile (1.0 mmol) and phenacylazide (1.0 mmol) in water (3 ml), piperidine (0.25 mmol) was added at 353 K. The turbid solution slowly turned into a clear solution, followed by the formation of a solid after 1.5 h. After completion of the reaction, as indicated by TLC, the solid was filtered and washed with a petroleum ether-EtOAc mixture (1:1 ratio, v/v, 5 ml) to give title compound. It was recrystallized from ethanol by using slow evaporation, giving yellow block-like crystals (yield 85%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₇H₁₈BrN₃O₂
M_r	496.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	14.6503 (6), 9.6974 (3), 15.2946 (7)
β (°)	93.284 (2)
V (Å³)	2169.33 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.93
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.636, 0.680
No. of measured, independent and observed [I > 2σ(I)] reflections	26857, 3823, 2582
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.139, 0.78
No. of reflections	3823
No. of parameters	298
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.55
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1477342

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616007240/su4044sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616007240/su4044Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616007240/su4044Isup3.cml

checkCIF report

Experimental top

Structure description top

Indole-containing compounds are best known for their medicinal properties in the pharmaceutical industry. Today, analogues based on indole are significant players in a diverse array of markets such as dyes, plastics, agriculture, vitamin supplements, over-the-counter drugs, flavour enhancers and perfumery (Barden, 2011). Indole derivatives exhibit antibacterial, antifungal (Singh et al. 2000), antitumor (Andreani et al., 2001), antihepatitis B virus (Chai et al., 2006) and anti-inflammatory (Rodriguez et al., 1985) activities. They are also used as bioactive drugs (Stevenson et al., 2000) and exhibit high aldose reductase inhibitory (Rajeswaran et al., 1999) and antimicrobial activities (Amal Raj et al., 2003). Against this background, we synthesized the title compound and report herein on its crystal structure.

In the crystal, molecules are linked by pairs of N_i—H···N_c (i = indole and c = carbonitrile) classical hydrogen bonds, forming inversion dimers with R₂²(16) loops (Table 1 and Fig. 2). The molecules are also linked via slipped parallel π–π interactions, forming chains propagating along the b-axis direction [Cg2···Cg3ⁱ = 3.614 (2) Å; inter-planar distance = 3.535 (1) Å, slippage = 0.525 Å; Cg2 and Cg3 are the centroids of the N2/C9/C10/C12/C19 and C2–C7 rings; symmetry code: (i) -x + 1, -y, -z + 1].

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound, viewed along the normal to (011). Hydrogen bonds are shown as dashed lines (see Table 1) and C-bound H atoms have been omitted for clarity.

5-Benzoyl-2-(5-bromo-1H-indol-3-yl)-4-(4-methoxyphenyl)-1H-pyrrole-3-carbonitrile top

Crystal data top

C₂₇H₁₈BrN₃O₂	F(000) = 1008
M_r = 496.35	D_x = 1.520 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2582 reflections
a = 14.6503 (6) Å	θ = 1.9–25.0°
b = 9.6974 (3) Å	µ = 1.93 mm⁻¹
c = 15.2946 (7) Å	T = 293 K
β = 93.284 (2)°	Block, yellow
V = 2169.33 (15) Å³	0.24 × 0.22 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	3823 independent reflections
Radiation source: fine-focus sealed tube	2582 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ω and φ scan	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −17→17
T_min = 0.636, T_max = 0.680	k = −11→11
26857 measured reflections	l = −18→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 0.78	w = 1/[σ²(F_o²) + (0.1132P)² + 1.1029P] where P = (F_o² + 2F_c²)/3
3823 reflections	(Δ/σ)_max = 0.001
298 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₂₇H₁₈BrN₃O₂	V = 2169.33 (15) Å³
M_r = 496.35	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.6503 (6) Å	µ = 1.93 mm⁻¹
b = 9.6974 (3) Å	T = 293 K
c = 15.2946 (7) Å	0.24 × 0.22 × 0.20 mm
β = 93.284 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3823 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2582 reflections with I > 2σ(I)
T_min = 0.636, T_max = 0.680	R_int = 0.047
26857 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 0.78	Δρ_max = 0.27 e Å⁻³
3823 reflections	Δρ_min = −0.55 e Å⁻³
298 parameters

Special details top

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
Br	0.30324 (3)	−0.25826 (4)	0.72049 (3)	0.0638 (2)
O2	1.10059 (16)	0.3663 (2)	0.55850 (18)	0.0562 (7)
N1	0.3744 (2)	0.2552 (2)	0.5243 (2)	0.0454 (7)
H1	0.3391	0.3156	0.4989	0.055*
N2	0.63376 (17)	0.0077 (2)	0.62556 (17)	0.0380 (6)
H2	0.6021	−0.0643	0.6364	0.046*
O1	0.73519 (18)	−0.2198 (2)	0.66235 (19)	0.0591 (7)
C6	0.4113 (2)	−0.0522 (3)	0.6453 (2)	0.0382 (7)
H6	0.4609	−0.1028	0.6683	0.046*
C13	0.8450 (2)	0.2048 (3)	0.6045 (2)	0.0341 (7)
C7	0.4242 (2)	0.0693 (3)	0.5988 (2)	0.0345 (7)
C2	0.3459 (2)	0.1408 (3)	0.5665 (2)	0.0393 (8)
C17	0.9914 (2)	0.1932 (3)	0.5422 (2)	0.0442 (8)
H17	1.0320	0.1457	0.5087	0.053*
C9	0.5976 (2)	0.1268 (3)	0.5936 (2)	0.0354 (7)
C18	0.9077 (2)	0.1372 (3)	0.5559 (2)	0.0409 (8)
H18	0.8927	0.0515	0.5318	0.049*
C21	0.8702 (2)	−0.0997 (3)	0.7049 (2)	0.0408 (8)
N3	0.6659 (2)	0.4599 (3)	0.5252 (3)	0.0697 (10)
C4	0.2471 (2)	−0.0223 (4)	0.6240 (2)	0.0451 (8)
H4	0.1886	−0.0547	0.6331	0.054*
C10	0.6715 (2)	0.2150 (3)	0.5857 (2)	0.0360 (7)
C20	0.7756 (2)	−0.1084 (3)	0.6680 (2)	0.0406 (8)
C12	0.7530 (2)	0.1458 (3)	0.6133 (2)	0.0353 (7)
C15	0.9552 (2)	0.3886 (3)	0.6267 (2)	0.0444 (8)
H15	0.9710	0.4735	0.6515	0.053*
C14	0.8703 (2)	0.3318 (3)	0.6391 (2)	0.0437 (8)
H14	0.8292	0.3803	0.6716	0.052*
C19	0.7273 (2)	0.0155 (3)	0.6386 (2)	0.0372 (7)
C5	0.3234 (2)	−0.0953 (3)	0.6562 (2)	0.0422 (8)
C16	1.0161 (2)	0.3191 (3)	0.5777 (2)	0.0406 (8)
C3	0.2583 (2)	0.0967 (4)	0.5790 (2)	0.0464 (9)
H3	0.2080	0.1472	0.5572	0.056*
C22	0.9322 (3)	−0.2039 (4)	0.6870 (2)	0.0512 (9)
H22	0.9132	−0.2779	0.6518	0.061*
C26	0.8999 (2)	0.0074 (3)	0.7592 (2)	0.0464 (8)
H26	0.8597	0.0776	0.7724	0.056*
C1	0.4662 (3)	0.2596 (3)	0.5283 (2)	0.0441 (9)
H1A	0.5008	0.3284	0.5038	0.053*
C8	0.5016 (2)	0.1482 (3)	0.5737 (2)	0.0368 (7)
C25	0.9885 (3)	0.0102 (4)	0.7935 (3)	0.0573 (10)
H25	1.0076	0.0816	0.8309	0.069*
C24	1.0489 (3)	−0.0906 (5)	0.7736 (3)	0.0643 (11)
H24	1.1093	−0.0861	0.7958	0.077*
C11	0.6677 (2)	0.3509 (3)	0.5522 (2)	0.0456 (8)
C27	1.1307 (3)	0.4935 (4)	0.5947 (3)	0.0597 (10)
H27A	1.1907	0.5138	0.5760	0.090*
H27B	1.1326	0.4879	0.6574	0.090*
H27C	1.0892	0.5652	0.5752	0.090*
C23	1.0206 (3)	−0.1980 (4)	0.7209 (3)	0.0630 (11)
H23	1.0616	−0.2673	0.7080	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0542 (3)	0.0555 (3)	0.0818 (4)	−0.01062 (17)	0.0039 (2)	0.02027 (19)
O2	0.0395 (14)	0.0513 (14)	0.0787 (18)	−0.0067 (11)	0.0114 (13)	−0.0024 (13)
N1	0.0445 (18)	0.0371 (15)	0.0539 (18)	0.0096 (12)	−0.0047 (14)	0.0085 (12)
N2	0.0366 (15)	0.0292 (13)	0.0484 (17)	−0.0014 (11)	0.0045 (12)	0.0051 (11)
O1	0.0560 (17)	0.0371 (13)	0.083 (2)	−0.0042 (12)	−0.0047 (14)	0.0106 (12)
C6	0.0348 (18)	0.0372 (17)	0.042 (2)	0.0037 (14)	−0.0001 (14)	0.0013 (14)
C13	0.0371 (18)	0.0303 (15)	0.0353 (18)	0.0019 (13)	0.0035 (14)	0.0028 (13)
C7	0.0352 (17)	0.0335 (16)	0.0349 (18)	0.0049 (13)	0.0030 (13)	−0.0003 (13)
C2	0.042 (2)	0.0361 (17)	0.0397 (19)	0.0036 (14)	−0.0005 (15)	−0.0030 (14)
C17	0.0365 (19)	0.0405 (18)	0.057 (2)	0.0061 (15)	0.0120 (16)	−0.0051 (16)
C9	0.0394 (18)	0.0328 (16)	0.0346 (18)	0.0045 (14)	0.0074 (14)	−0.0004 (13)
C18	0.042 (2)	0.0319 (16)	0.049 (2)	0.0008 (14)	0.0069 (16)	−0.0046 (14)
C21	0.044 (2)	0.0342 (17)	0.044 (2)	0.0043 (14)	0.0062 (15)	0.0113 (15)
N3	0.059 (2)	0.0448 (19)	0.107 (3)	0.0062 (15)	0.020 (2)	0.0261 (18)
C4	0.0330 (19)	0.054 (2)	0.048 (2)	0.0005 (15)	0.0032 (15)	−0.0014 (16)
C10	0.0372 (18)	0.0324 (15)	0.0390 (19)	0.0033 (13)	0.0076 (14)	0.0031 (13)
C20	0.044 (2)	0.0326 (17)	0.045 (2)	0.0013 (15)	0.0078 (16)	0.0032 (14)
C12	0.0395 (18)	0.0317 (15)	0.0352 (18)	0.0004 (13)	0.0068 (14)	−0.0010 (13)
C15	0.048 (2)	0.0341 (17)	0.052 (2)	−0.0073 (15)	0.0062 (16)	−0.0064 (15)
C14	0.043 (2)	0.0388 (18)	0.051 (2)	0.0026 (15)	0.0121 (16)	−0.0063 (15)
C19	0.0353 (18)	0.0347 (16)	0.042 (2)	0.0007 (13)	0.0036 (14)	0.0016 (13)
C5	0.044 (2)	0.0406 (18)	0.042 (2)	−0.0012 (15)	0.0031 (15)	−0.0001 (14)
C16	0.0329 (18)	0.0396 (18)	0.049 (2)	0.0024 (14)	0.0003 (15)	0.0053 (15)
C3	0.0358 (19)	0.052 (2)	0.051 (2)	0.0076 (16)	−0.0049 (16)	−0.0040 (17)
C22	0.056 (2)	0.0422 (19)	0.056 (2)	0.0091 (17)	0.0079 (19)	0.0051 (16)
C26	0.050 (2)	0.0430 (18)	0.047 (2)	0.0057 (16)	0.0055 (17)	0.0042 (15)
C1	0.046 (2)	0.0381 (19)	0.048 (2)	−0.0013 (15)	0.0048 (17)	0.0071 (15)
C8	0.0403 (19)	0.0304 (15)	0.0398 (19)	0.0042 (13)	0.0041 (14)	0.0013 (13)
C25	0.056 (3)	0.066 (2)	0.049 (2)	−0.006 (2)	−0.0010 (19)	0.0026 (19)
C24	0.047 (2)	0.087 (3)	0.059 (3)	0.004 (2)	−0.0001 (19)	0.021 (2)
C11	0.040 (2)	0.043 (2)	0.056 (2)	0.0024 (15)	0.0120 (16)	0.0042 (16)
C27	0.049 (2)	0.055 (2)	0.076 (3)	−0.0152 (18)	0.004 (2)	0.0027 (19)
C23	0.047 (2)	0.065 (2)	0.078 (3)	0.023 (2)	0.008 (2)	0.013 (2)

Geometric parameters (Å, º) top

Br—C5	1.893 (3)	N3—C11	1.134 (4)
O2—C16	1.368 (4)	C4—C3	1.358 (5)
O2—C27	1.411 (4)	C4—C5	1.390 (5)
N1—C1	1.343 (5)	C4—H4	0.9300
N1—C2	1.361 (4)	C10—C12	1.412 (4)
N1—H1	0.8600	C10—C11	1.415 (4)
N2—C9	1.350 (4)	C20—C19	1.452 (4)
N2—C19	1.376 (4)	C12—C19	1.380 (4)
N2—H2	0.8600	C15—C16	1.374 (5)
O1—C20	1.233 (4)	C15—C14	1.383 (4)
C6—C5	1.373 (4)	C15—H15	0.9300
C6—C7	1.394 (4)	C14—H14	0.9300
C6—H6	0.9300	C3—H3	0.9300
C13—C18	1.380 (4)	C22—C23	1.369 (5)
C13—C14	1.383 (4)	C22—H22	0.9300
C13—C12	1.477 (4)	C26—C25	1.373 (5)
C7—C2	1.406 (4)	C26—H26	0.9300
C7—C8	1.438 (4)	C1—C8	1.369 (4)
C2—C3	1.376 (5)	C1—H1A	0.9300
C17—C18	1.368 (4)	C25—C24	1.364 (6)
C17—C16	1.376 (5)	C25—H25	0.9300
C17—H17	0.9300	C24—C23	1.367 (6)
C9—C10	1.391 (4)	C24—H24	0.9300
C9—C8	1.437 (4)	C27—H27A	0.9600
C18—H18	0.9300	C27—H27B	0.9600
C21—C26	1.384 (5)	C27—H27C	0.9600
C21—C22	1.395 (5)	C23—H23	0.9300
C21—C20	1.469 (5)

C16—O2—C27	118.3 (3)	C14—C15—H15	120.1
C1—N1—C2	109.8 (3)	C15—C14—C13	121.7 (3)
C1—N1—H1	125.1	C15—C14—H14	119.1
C2—N1—H1	125.1	C13—C14—H14	119.1
C9—N2—C19	111.9 (3)	N2—C19—C12	107.1 (3)
C9—N2—H2	124.1	N2—C19—C20	117.6 (3)
C19—N2—H2	124.1	C12—C19—C20	135.1 (3)
C5—C6—C7	118.4 (3)	C6—C5—C4	122.9 (3)
C5—C6—H6	120.8	C6—C5—Br	119.5 (2)
C7—C6—H6	120.8	C4—C5—Br	117.6 (3)
C18—C13—C14	117.2 (3)	O2—C16—C15	125.2 (3)
C18—C13—C12	120.2 (3)	O2—C16—C17	115.7 (3)
C14—C13—C12	122.4 (3)	C15—C16—C17	119.1 (3)
C6—C7—C2	117.7 (3)	C4—C3—C2	118.4 (3)
C6—C7—C8	135.9 (3)	C4—C3—H3	120.8
C2—C7—C8	106.4 (3)	C2—C3—H3	120.8
N1—C2—C3	129.3 (3)	C23—C22—C21	120.5 (4)
N1—C2—C7	107.6 (3)	C23—C22—H22	119.7
C3—C2—C7	123.1 (3)	C21—C22—H22	119.7
C18—C17—C16	120.7 (3)	C25—C26—C21	120.1 (3)
C18—C17—H17	119.7	C25—C26—H26	119.9
C16—C17—H17	119.7	C21—C26—H26	119.9
N2—C9—C10	105.4 (3)	N1—C1—C8	110.3 (3)
N2—C9—C8	124.0 (3)	N1—C1—H1A	124.8
C10—C9—C8	130.6 (3)	C8—C1—H1A	124.8
C17—C18—C13	121.6 (3)	C1—C8—C9	124.0 (3)
C17—C18—H18	119.2	C1—C8—C7	105.9 (3)
C13—C18—H18	119.2	C9—C8—C7	130.0 (3)
C26—C21—C22	118.4 (3)	C24—C25—C26	120.7 (4)
C26—C21—C20	122.0 (3)	C24—C25—H25	119.6
C22—C21—C20	119.6 (3)	C26—C25—H25	119.6
C3—C4—C5	119.6 (3)	C25—C24—C23	120.0 (4)
C3—C4—H4	120.2	C25—C24—H24	120.0
C5—C4—H4	120.2	C23—C24—H24	120.0
C9—C10—C12	109.3 (3)	N3—C11—C10	179.0 (4)
C9—C10—C11	126.1 (3)	O2—C27—H27A	109.5
C12—C10—C11	124.5 (3)	O2—C27—H27B	109.5
O1—C20—C19	118.7 (3)	H27A—C27—H27B	109.5
O1—C20—C21	121.1 (3)	O2—C27—H27C	109.5
C19—C20—C21	120.2 (3)	H27A—C27—H27C	109.5
C19—C12—C10	106.2 (3)	H27B—C27—H27C	109.5
C19—C12—C13	130.1 (3)	C24—C23—C22	120.2 (4)
C10—C12—C13	123.3 (3)	C24—C23—H23	119.9
C16—C15—C14	119.7 (3)	C22—C23—H23	119.9
C16—C15—H15	120.1

C5—C6—C7—C2	0.5 (4)	O1—C20—C19—N2	15.1 (5)
C5—C6—C7—C8	179.6 (3)	C21—C20—C19—N2	−164.1 (3)
C1—N1—C2—C3	179.3 (3)	O1—C20—C19—C12	−159.6 (4)
C1—N1—C2—C7	0.0 (4)	C21—C20—C19—C12	21.3 (6)
C6—C7—C2—N1	179.6 (3)	C7—C6—C5—C4	−0.8 (5)
C8—C7—C2—N1	0.3 (3)	C7—C6—C5—Br	−179.0 (2)
C6—C7—C2—C3	0.2 (5)	C3—C4—C5—C6	0.4 (5)
C8—C7—C2—C3	−179.1 (3)	C3—C4—C5—Br	178.7 (3)
C19—N2—C9—C10	0.1 (4)	C27—O2—C16—C15	3.1 (5)
C19—N2—C9—C8	180.0 (3)	C27—O2—C16—C17	−178.5 (3)
C16—C17—C18—C13	0.7 (5)	C14—C15—C16—O2	177.8 (3)
C14—C13—C18—C17	−0.1 (5)	C14—C15—C16—C17	−0.4 (5)
C12—C13—C18—C17	176.0 (3)	C18—C17—C16—O2	−178.8 (3)
N2—C9—C10—C12	0.3 (3)	C18—C17—C16—C15	−0.4 (5)
C8—C9—C10—C12	−179.6 (3)	C5—C4—C3—C2	0.3 (5)
N2—C9—C10—C11	177.9 (3)	N1—C2—C3—C4	−179.9 (3)
C8—C9—C10—C11	−2.0 (6)	C7—C2—C3—C4	−0.7 (5)
C26—C21—C20—O1	−140.4 (3)	C26—C21—C22—C23	−1.6 (5)
C22—C21—C20—O1	37.9 (5)	C20—C21—C22—C23	−179.9 (3)
C26—C21—C20—C19	38.7 (5)	C22—C21—C26—C25	0.5 (5)
C22—C21—C20—C19	−143.0 (3)	C20—C21—C26—C25	178.8 (3)
C9—C10—C12—C19	−0.6 (4)	C2—N1—C1—C8	−0.3 (4)
C11—C10—C12—C19	−178.2 (3)	N1—C1—C8—C9	−176.5 (3)
C9—C10—C12—C13	173.3 (3)	N1—C1—C8—C7	0.4 (4)
C11—C10—C12—C13	−4.3 (5)	N2—C9—C8—C1	−168.9 (3)
C18—C13—C12—C19	51.9 (5)	C10—C9—C8—C1	11.0 (5)
C14—C13—C12—C19	−132.2 (4)	N2—C9—C8—C7	15.1 (5)
C18—C13—C12—C10	−120.4 (3)	C10—C9—C8—C7	−165.0 (3)
C14—C13—C12—C10	55.5 (4)	C6—C7—C8—C1	−179.6 (4)
C16—C15—C14—C13	1.0 (5)	C2—C7—C8—C1	−0.4 (3)
C18—C13—C14—C15	−0.8 (5)	C6—C7—C8—C9	−3.0 (6)
C12—C13—C14—C15	−176.8 (3)	C2—C7—C8—C9	176.2 (3)
C9—N2—C19—C12	−0.4 (4)	C21—C26—C25—C24	1.2 (6)
C9—N2—C19—C20	−176.5 (3)	C26—C25—C24—C23	−2.0 (6)
C10—C12—C19—N2	0.6 (4)	C9—C10—C11—N3	−169 (100)
C13—C12—C19—N2	−172.7 (3)	C12—C10—C11—N3	8 (24)
C10—C12—C19—C20	175.6 (4)	C25—C24—C23—C22	0.9 (6)
C13—C12—C19—C20	2.3 (6)	C21—C22—C23—C24	0.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.86	2.21	2.916 (4)	140

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.86	2.21	2.916 (4)	140

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₇H₁₈BrN₃O₂
M_r	496.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	14.6503 (6), 9.6974 (3), 15.2946 (7)
β (°)	93.284 (2)
V (Å³)	2169.33 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.93
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.636, 0.680
No. of measured, independent and observed [I > 2σ(I)] reflections	26857, 3823, 2582
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.139, 0.78
No. of reflections	3823
No. of parameters	298
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.55

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

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