2-(5-Bromo-1H-indol-3-yl)-4-(4-bromophenyl)-5- (4-chlorobenzoyl)-1H-pyrrole-3-carbonitrile dimethyl sulfoxide monosolvate

Transcript

1 ISSN (5-Bromo-1H-indol-3-yl)-4-(4-bromophenyl)-5- (4-chlorobenzoyl)-1H-pyrrole-3-carbonitrile dimethyl sulfoxide monosolvate Y. AaminaNaaz, a Jayabal Kamalraja, b G. Vimala, a Paramasivam T. Perumal b and A. SubbiahPandi a * Received 3 July 2016 Accepted 22 July 2016 a Department of Physics, Presidency College (Autonomous), Chennai , India, and b Organic Chemistry Division, Central Leather Research Institute, Adyar, Chennai , India. *Correspondence aspandian59@gmail.com Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland Keywords: crystal structure; indole derivative; pyrrole-3-carbonitrile; N HO hydrogen bonding. CCDC reference: In the title solvated compound, C 26 H 14 Br 2 ClN 3 OC 2 H 6 OS, the indole ring is inclined to the central pyrrole ring by 25.7 (2). The chlorobenzene ring and the bromobenzene rings subtend dihedral angles of 56.5 (2) and 53.4 (2), respectively, with the central pyrrole ring. In the crystal, molecules are bridged by N HO hydrogen bonds, involving the dimethyl sulfoxide solvent molecule, forming chains along [010]. There are no other significant intermolecular interactions present. Structural data: full structural data are available from iucrdata.iucr.org Structure description Indole structures are considered to be privileged structural motifs due to their ability to bind many receptors within the body (Fuwa & Sasaki, 2009). Several indole derivatives are in clinical use, such as sunitinib as a tyrosine kinase inhibitor (Oudard et al., 2011) or delavirdine as a non-nucleoside reverse transcriptase inhibitor (Beale, 2011). Indole derivatives are known to exhibit biological activities such as anti-proliferative (Parrino et al., 2015), potential mushroom tyrosinase inhibition (Ferro et al., 2015), anti-inflammatory (Chen et al., 2015) and anti-tumor (Ma et al., 2015). As part of our studies of indole derivatives, we have synthesized the title compound and report herein on its crystal structure. In the title compound, Fig. 1, the indole ring system is twisted away from the central pyrrole ring by 25.7 (2). The C16 C17 N3 bond angle of (5) indicates the linear character of the cyano group, a feature observed in carbonitrile compounds. In the benzene ring of the indole ring system, the endocyclic angle at C26 is contracted to (4), while the angle at C21 is expanded to (4). This would appear to be a real 1of3

2 Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA N1 H1O (4) 143 N2 H2O2 i (4) 170 Symmetry code: (i) x þ 5 2 ; y 1 2 ; z þ 1 2. effect caused by the fusion of the pyrrole ring with the benzene ring resulting in an angular distortion. The chlorobenzene (C1 C6) and bromobenzene (C10 C15) rings subtend dihedral angles of 56.5 (2) and 53.4 (2), respectively, with the central pyrrole ring. In the crystal, molecules are bridged by N HO hydrogen bonds involving the dimethyl sulfoxide solvent molecule, forming chains along [010], see Table 1 and Fig. 2. There are no other significant intermolecular interactions present. Synthesis and crystallization To a stirred mixture of 4-bromobenzaldehyde 1 (1.0 mmol), 3- (5-bromo-1H-indol-3-yl)-3-oxopropanenitrile 2 (1.0 mmol) and 4-chlorophenacylazide 3 (1.0 mmol) in H 2 O (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 30 min. After completion of the reaction, as indicated by TLC, the solid was filtered and washed with a PE EtOAc mixture (1:1 ratio, v/v, 5 ml) to give the title compound (yield 91%), which was recrystallized from EtOH solution to give yellow crystals on slow evaporation of the solvent. Table 2 Experimental details. Crystal data Chemical formula C 26 H 14 Br 2 ClN 3 OC 2 H 6 OS M r Crystal system, space group Monoclinic, P2 1 /n Temperature (K) 293 a, b, c (Å) (12), (10), (17) ( ) (3) V (Å 3 ) (4) Z 4 Radiation type Mo K (mm 1 ) 3.07 Crystal size (mm) Data collection Diffractometer Bruker SMART APEXII CCD Absorption correction Multi-scan (SADABS; Bruker, 2008) T min, T max 0.547, No. of measured, independent and 29776, 4972, 3236 observed [I > 2(I)] reflections R int (sin /) max (Å 1 ) Refinement R[F 2 >2(F 2 )], wr(f 2 ), S 0.070, 0.107, 1.15 No. of reflections 4972 No. of parameters 334 H-atom treatment H-atom parameters constrained max, min (e Å 3 ) 0.59, 0.40 Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 and SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009). Refinement Crystal data, data collection and structure refinement details are summarized in Table 2. Figure 1 The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Figure 2 A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1), and for clarity C- bound H atoms have been omitted. 2of3 AaminaNaaz et al. C 26 H 14 Br 2 ClN 3 OC 2 H 6 OS

3 Acknowledgements The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection. References Beale, J. M. (2011). Wilson and Gisvold s Textbook of Organic Medicinal and Pharmaceutical Chemistry, 12th ed., edited by J. M. Beale & J. H. Block, pp Philadelphia: Lippincott Williams and Wilkins. Bruker (2008). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Chen, Y. R., Tseng, C. H., Chen, Y. L., Hwang, T. L. & Tzeng, C. C. (2015). Int. J. Mol. Sci. 16, Farrugia, L. J. (2012). J. Appl. Cryst. 45, Ferro, S., Certo, G., De Luca, L., Germanò, M. P., Rapisarda, A. & Gitto, R. (2015). J. Enzyme Inhib. Med. Chem. pp Fuwa, H. & Sasaki, M. (2009). J. Org. Chem. 74, Ma, J., Bao, G., Wang, L., Li, W., Xu, B., Du, B., Lv, J., Zhai, X. & Gong, P. (2015). Eur. J. Med. Chem. 96, Oudard, S., Beuselinck, B., Decoene, J. & Albers, P. (2011). Cancer Treat. Rev. 37, Parrino, B., Carbone, A., Di Vita, G., Ciancimino, C., Attanzio, A., Spano, V., Montalbano, A., Barraja, P., Tesoriere, L., Livera, M. A., Diana, P. & Cirrincione, G. (2015). Mar. Drugs, 13, Sheldrick, G. M. (2008). Acta Cryst. A64, Spek, A. L. (2009). Acta Cryst. D65, AaminaNaaz et al. C 26 H 14 Br 2 ClN 3 OC 2 H 6 OS 3of3

4 full crystallographic data [ 2-(5-Bromo-1H-indol-3-yl)-4-(4-bromophenyl)-5-(4-chlorobenzoyl)-1Hpyrrole-3-carbonitrile dimethyl sulfoxide monosolvate Y. AaminaNaaz, Jayabal Kamalraja, G. Vimala, Paramasivam T. Perumal and A. SubbiahPandi 2-(5-Bromo-1H-indol-3-yl)-4-(4-bromophenyl)-5-(4-chlorobenzoyl)-1H-pyrrole-3-carbonitrile dimethyl sulfoxide monosolvate Crystal data C 26 H 14 Br 2 ClN 3 O C 2 H 6 OS M r = Monoclinic, P2 1 /n Hall symbol: -P 2yn a = (12) Å b = (10) Å c = (17) Å β = (3) V = (4) Å 3 Z = 4 Data collection Bruker SMART APEXII CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω and φ scans Absorption correction: multi-scan (SADABS; Bruker, 2008) T min = 0.547, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 334 parameters 0 restraints Primary atom site location: structure-invariant direct methods F(000) = 1312 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 3236 reflections θ = µ = 3.07 mm 1 T = 293 K Block, yellow mm measured reflections 4972 independent reflections 3236 reflections with I > 2σ(I) R int = θ max = 25.0, θ min = 2.0 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0239P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.59 e Å 3 Δρ min = 0.40 e Å 3 data-1

5 Special details 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq C (3) (3) (3) (12) H1A * C (4) (4) (3) (13) H2A * C (4) (4) (4) (14) C (4) (4) (3) (15) H * C (4) (4) (3) (13) H * C (3) (3) (3) (11) C (3) (3) (3) (11) C (3) (3) (2) (10) C (3) (3) (2) (10) C (3) (3) (2) (10) C (3) (3) (3) (11) H * C (4) (4) (3) (13) H * C (4) (4) (3) (13) C (3) (4) (3) (13) H * C (3) (3) (3) (12) H * C (3) (3) (2) (10) C (4) (4) (3) (12) C (3) (3) (2) (10) C (3) (3) (2) (10) C (3) (3) (2) (11) H * C (3) (3) (2) (11) C (3) (3) (2) (10) C (3) (3) (2) (11) H * C (3) (4) (3) (12) C (4) (4) (3) (13) data-2

6 H * C (4) (3) (3) (12) H * C (5) (5) (4) (2) H27A * H27B * H27C * C (5) (6) (4) (3) H28A * H28B * H28C * N (3) (2) (19) (9) H * N (3) (3) (2) (10) H * N (3) (3) (3) (14) O (3) (3) (2) (11) O (2) (2) (17) (8) Cl (14) (10) (10) (6) Br (4) (5) (4) (2) Br (5) (5) (4) (3) S (9) (11) (8) (4) Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (3) (3) (3) C (3) (3) (4) (2) (3) (3) C (3) (3) (4) (3) (3) (3) C (3) (3) (4) (2) (2) (3) C (2) (2) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (2) (3) (19) (2) (2) C (2) (3) (3) (19) (2) (2) C (2) (2) (3) (19) (2) (2) C (3) (3) (3) (2) (2) (3) C (3) (3) (3) (3) (3) (3) C (3) (3) (4) (2) (3) (3) C (3) (3) (4) (2) (2) (3) C (3) (3) (3) (2) (2) (2) C (2) (2) (3) (19) (19) (2) C (3) (3) (3) (2) (2) (2) C (2) (2) (3) (2) (19) (2) C (2) (2) (3) (19) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (2) (3) (19) (2) (2) data-3

7 C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (3) C (3) (3) (4) (2) (3) (3) C (3) (3) (3) (2) (3) (2) C (4) (5) (5) (4) (4) (4) C (4) (7) (6) (4) (4) (5) N (18) (2) (2) (16) (16) (17) N (2) (2) (2) (18) (19) (18) N (3) (3) (4) (2) (3) (3) O (2) (2) (3) (17) (2) (2) O (17) (19) (2) (14) (15) (16) Cl (13) (8) (14) (8) (11) (8) Br (3) (4) (5) (3) (3) (4) Br (5) (5) (6) (4) (4) (4) S (7) (9) (9) (6) (6) (7) Geometric parameters (Å, º) C1 C (6) C16 C (6) C1 C (6) C17 N (5) C1 H1A C18 N (5) C2 C (7) C18 C (6) C2 H2A C19 C (5) C3 C (7) C19 C (5) C3 Cl (5) C20 N (5) C4 C (6) C20 H C4 H C21 N (5) C5 C (6) C21 C (6) C5 H C21 C (6) C6 C (6) C22 C (5) C7 O (5) C23 C (6) C7 C (6) C23 H C8 N (5) C24 C (6) C8 C (5) C24 Br (4) C9 C (6) C25 C (6) C9 C (6) C25 H C10 C (6) C26 H C10 C (6) C27 S (6) C11 C (6) C27 H27A C11 H C27 H27B C12 C (6) C27 H27C C12 H C28 S (6) C13 C (6) C28 H28A C13 Br (4) C28 H28B C14 C (6) C28 H28C C14 H N1 H C15 H N2 H C16 C (5) O2 S (3) data-4

8 C6 C1 C (4) N1 C18 C (3) C6 C1 H1A N1 C18 C (4) C2 C1 H1A C16 C18 C (4) C3 C2 C (5) C20 C19 C (4) C3 C2 H2A C20 C19 C (4) C1 C2 H2A C22 C19 C (4) C2 C3 C (4) N2 C20 C (4) C2 C3 Cl (5) N2 C20 H C4 C3 Cl (4) C19 C20 H C3 C4 C (5) N2 C21 C (4) C3 C4 H N2 C21 C (4) C5 C4 H C26 C21 C (4) C4 C5 C (5) C23 C22 C (4) C4 C5 H C23 C22 C (4) C6 C5 H C21 C22 C (3) C1 C6 C (4) C24 C23 C (4) C1 C6 C (4) C24 C23 H C5 C6 C (4) C22 C23 H O1 C7 C (4) C23 C24 C (4) O1 C7 C (4) C23 C24 Br (4) C8 C7 C (4) C25 C24 Br (3) N1 C8 C (3) C26 C25 C (4) N1 C8 C (4) C26 C25 H C9 C8 C (4) C24 C25 H C8 C9 C (3) C25 C26 C (4) C8 C9 C (4) C25 C26 H C16 C9 C (4) C21 C26 H C11 C10 C (4) S C27 H27A C11 C10 C (4) S C27 H27B C15 C10 C (4) H27A C27 H27B C10 C11 C (4) S C27 H27C C10 C11 H H27A C27 H27C C12 C11 H H27B C27 H27C C13 C12 C (5) S C28 H28A C13 C12 H S C28 H28B C11 C12 H H28A C28 H28B C14 C13 C (4) S C28 H28C C14 C13 Br (4) H28A C28 H28C C12 C13 Br (4) H28B C28 H28C C13 C14 C (4) C18 N1 C (3) C13 C14 H C18 N1 H C15 C14 H C8 N1 H C14 C15 C (4) C20 N2 C (3) C14 C15 H C20 N2 H C10 C15 H C21 N2 H C18 C16 C (3) O2 S C (3) C18 C16 C (4) O2 S C (2) data-5

9 C9 C16 C (4) C28 S C (3) N3 C17 C (5) C6 C1 C2 C3 0.6 (7) C8 C9 C16 C (4) C1 C2 C3 C4 3.0 (7) C10 C9 C16 C (7) C1 C2 C3 Cl (3) C18 C16 C17 N3 59 (18) C2 C3 C4 C5 2.4 (8) C9 C16 C17 N3 114 (18) Cl1 C3 C4 C (4) C9 C16 C18 N1 2.5 (5) C3 C4 C5 C6 0.5 (7) C17 C16 C18 N (4) C2 C1 C6 C5 2.3 (7) C9 C16 C18 C (4) C2 C1 C6 C (4) C17 C16 C18 C (7) C4 C5 C6 C1 2.8 (7) N1 C18 C19 C (4) C4 C5 C6 C (4) C16 C18 C19 C (7) C1 C6 C7 O (5) N1 C18 C19 C (7) C5 C6 C7 O (7) C16 C18 C19 C (4) C1 C6 C7 C (6) C22 C19 C20 N2 0.1 (5) C5 C6 C7 C (4) C18 C19 C20 N (4) O1 C7 C8 N (7) N2 C21 C22 C (4) C6 C7 C8 N (4) C26 C21 C22 C (6) O1 C7 C8 C (5) N2 C21 C22 C (5) C6 C7 C8 C (8) C26 C21 C22 C (4) N1 C8 C9 C (5) C20 C19 C22 C (5) C7 C8 C9 C (5) C18 C19 C22 C (8) N1 C8 C9 C (4) C20 C19 C22 C (5) C7 C8 C9 C (8) C18 C19 C22 C (4) C8 C9 C10 C (6) C21 C22 C23 C (6) C16 C9 C10 C (5) C19 C22 C23 C (5) C8 C9 C10 C (5) C22 C23 C24 C (7) C16 C9 C10 C (6) C22 C23 C24 Br (3) C15 C10 C11 C (7) C23 C24 C25 C (7) C9 C10 C11 C (4) Br1 C24 C25 C (4) C10 C11 C12 C (7) C24 C25 C26 C (7) C11 C12 C13 C (7) N2 C21 C26 C (4) C11 C12 C13 Br (3) C22 C21 C26 C (7) C12 C13 C14 C (7) C16 C18 N1 C8 2.2 (5) Br2 C13 C14 C (3) C19 C18 N1 C (4) C13 C14 C15 C (7) C9 C8 N1 C (5) C11 C10 C15 C (7) C7 C8 N1 C (4) C9 C10 C15 C (4) C19 C20 N2 C (5) C8 C9 C16 C (5) C26 C21 N2 C (4) C10 C9 C16 C (4) C22 C21 N2 C (5) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A N1 H1 O (4) 143 data-6

10 N2 H2 O2 i (4) 170 Symmetry code: (i) x+5/2, y 1/2, z+1/2. data-7