organic compounds
5-Benzoyl-2-(5-bromo-1H-indol-3-yl)-4-(4-methoxyphenyl)-1H-pyrrole-3-carbonitrile
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
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
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).
In the crystal, molecules are linked by pairs of Ni—H⋯Nc (i = indole and c = carbonitrile) classical hydrogen bonds, forming inversion dimers with (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].
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 .
details are summarized in Table 2Structural data
CCDC reference: 1477342
10.1107/S2414314616007240/su4044sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616007240/su4044Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616007240/su4044Isup3.cml
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%).
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).
In the crystal, molecules are linked by pairs of Ni—H···Nc (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].
Data collection: APEX2 (Bruker, 2004); cell
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).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. |
C27H18BrN3O2 | F(000) = 1008 |
Mr = 496.35 | Dx = 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 |
Bruker Kappa APEXII CCD diffractometer | 3823 independent reflections |
Radiation source: fine-focus sealed tube | 2582 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω and φ scan | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −17→17 |
Tmin = 0.636, Tmax = 0.680 | k = −11→11 |
26857 measured reflections | l = −18→18 |
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(Fo2) + (0.1132P)2 + 1.1029P] where P = (Fo2 + 2Fc2)/3 |
3823 reflections | (Δ/σ)max = 0.001 |
298 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
C27H18BrN3O2 | V = 2169.33 (15) Å3 |
Mr = 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)° |
Bruker Kappa APEXII CCD diffractometer | 3823 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2582 reflections with I > 2σ(I) |
Tmin = 0.636, Tmax = 0.680 | Rint = 0.047 |
26857 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 0.78 | Δρmax = 0.27 e Å−3 |
3823 reflections | Δρmin = −0.55 e Å−3 |
298 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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. |
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 |
Mr | 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) |
Tmin, Tmax | 0.636, 0.680 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26857, 3823, 2582 |
Rint | 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 |
Δρmax, Δρmin (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.
References
Amal Raj, A., Raghunathan, R., SrideviKumari, M. R. & Raman, N. (2003). Bioorg. Med. Chem. 11, 407–419. Web of Science PubMed Google Scholar
Andreani, A., Granaiola, M., Leoni, A., Locatelli, A., Morigi, R., Rambaldi, M., Giorgi, G., Salvini, L. & Garaliene, V. (2001). Anticancer Drug. Des. 16, 167–174. Web of Science PubMed CAS Google Scholar
Barden, T. C. (2011). Top. Heterocycl. Chem. 26, 31–46. CrossRef Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chai, H., Zhao, C., Zhao, C. & Gong, P. (2006). Bioorg. Med. Chem. 14, 911–917. Web of Science CrossRef PubMed CAS Google Scholar
Inglebert, S. A., Arun, Y., Sethusankar, K. & Perumal, P. T. (2013). Acta Cryst. E69, o1585. CSD CrossRef IUCr Journals Google Scholar
Rajeswaran, W. G., Labroo, R. B., Cohen, L. A. & King, M. M. (1999). J. Org. Chem. 64, 1369–1371. Web of Science CrossRef CAS Google Scholar
Rodriguez, J. G., Temprano, F., Esteban-Calderon, C., Martinez-Ripoll, M. & Garcia-Blanco, S. (1985). Tetrahedron, 41, 3813–3823. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Singh, U. P., Sarma, B. K., Mishra, P. K. & Ray, A. B. (2000). Fol. Microbiol. 45, 173–176. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stevenson, G. I., Smith, A. L., Lewis, S. G., Michie, S. G., Neduvelil, J. G., Patel, S., Marwood, R., Patel, S. & Castro, J. L. (2000). Bioorg. Med. Chem. Lett. 10, 2697–2699. Web of Science CrossRef PubMed CAS Google Scholar
Vimala, G., Raja, J. K., Naaz, Y. A., Preumal, P. T. & SubbiahPandi, A. (2015). Acta Cryst. E71, o335–o336. Web of Science CSD CrossRef 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.