2-Bromo-1-[1-(4-bromo­phen­yl)-5-methyl-1H-1,2,3-triazol-4-yl]ethanone

Alexander S Bunev; Marina A Troshina; Gennady I Ostapenko; Andzhela P Pavlova; Victor N Khrustalev

doi:10.1107/S1600536814014603

. 2014 Jun 25;70(Pt 7):o818. doi: 10.1107/S1600536814014603

2-Bromo-1-[1-(4-bromophenyl)-5-methyl-1H-1,2,3-triazol-4-yl]ethanone

Alexander S Bunev ^a,^*, Marina A Troshina ^a, Gennady I Ostapenko ^a, Andzhela P Pavlova ^b, Victor N Khrustalev ^c

PMCID: PMC4120528 PMID: 25161595

Abstract

The asymmetric unit of the title compound, C₁₁H₉Br₂N₃O, contains two crystallographically independent molecules with similar geometries; the Br—C—C=O torsion angles are 1.2 (4) and −2.8 (4)°, and the benzene and triazole rings are inclined o one another by 51.90 (16) and 51.88 (16)°. The two molecules are related by a pseudo-screw 2₁ axis directed along [100]. In the crystal, molecules are linked into a three-dimensional network by weak C—H⋯O and C—H⋯N hydrogen bonds and secondary Br⋯Br [3.5991 (8) and 3.6503 (9) Å] interactions.

Keywords: crystal structure

Related literature

For applications of 1,2,3-triazoles, see recent reviews by Agalave et al. (2011 ▶); Thirumurugan et al. (2013 ▶). For the crystal structures of related compounds, see: Danence et al. (2011 ▶); Zeghada et al. (2011 ▶); Abdel-Wahab, Abdel-Latif et al. (2013 ▶); Abdel-Wahab, Mohamed et al. (2013 ▶). graphic file with name e-70-0o818-scheme1.jpg

Experimental

Crystal data

C₁₁H₉Br₂N₃O
M _r = 359.03
Monoclinic,
a = 3.9699 (10) Å
b = 19.437 (5) Å
c = 15.402 (4) Å
β = 90.908 (3)°
V = 1188.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 6.81 mm⁻¹
T = 100 K
0.30 × 0.03 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.235, T _max = 0.822
18272 measured reflections
6924 independent reflections
6426 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.067
S = 1.04
6924 reflections
309 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.59 e Å⁻³
Absolute structure: Flack (1983 ▶), 3428 Friedel pairs
Absolute structure parameter: 0.032 (7)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814014603/cv5467sup1.cif

e-70-0o818-sup1.cif^{(30.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814014603/cv5467Isup2.hkl

e-70-0o818-Isup2.hkl^{(338.8KB, hkl)}

Click here for additional data file.^{(4.5KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814014603/cv5467Isup3.cml

CCDC reference: 1009335

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1ⁱ	0.95	2.44	3.205 (4)	137
C13—H13B⋯N6ⁱⁱ	0.99	2.49	3.467 (4)	170
C21—H21⋯O2ⁱⁱⁱ	0.95	2.45	3.210 (4)	137
C24—H24B⋯N3	0.99	2.49	3.482 (4)	177

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors are grateful to the Ministry of Education and Science of the Russian Federation (State program No. 426).

supplementary crystallographic information

S1. Comment

1-H-1,2,3-Triazole occupies a special place in heterocyclic chemistry because it is the core structure of many agents of various interests (used as pharmaceuticals, afrochemicals etc.). These compounds and their derivatives demonstrate antiviral, antimicrobial, anticancer activities as well as the inhibition activity of VIM-2 Metallo-β-Lactamase, and α-Glucosidases (Agalave et al., 2011; Thirumurugan et al., 2013). In this work, the title compound was prepared by the reaction of 1-(1-(4-bromophenyl)-5-methyl-1H-1,2,3-triazol-4-yl)ethanone with bromine (Figure 1), and its structure was unambiguously established by the X-ray diffraction study.

The title compound (I) crystallizes in the non-centrosymmetric monoclinic space group Pn with two crystallographically independent molecules in the asymmetric unit (Figure 2). The two crystallographically independent molecules are related by pseudo-screw axis 2₁ directed in [100] and, consequently, have very similar geometries (Figure 3). The position of the pseudo-screw axis 2₁ with the approximate coordinates of (x, 0.75, 0.55) is shifted relative to the crystallographic position of (x, 0.75, 0.75) by ca. 0.20 Å towards the c axis, apparently, due to the formation of the more dense crystal packing as well as different non-valent intermolecular interactions.

The bond lengths and angles within the molecules of I are in a good agreement with those found in the related compounds (Danence et al. 2011; Zeghada et al. 2011; Abdel-Wahab, Abdel-Latif et al. 2013; Abdel-Wahab, Mohamed et al. 2013). The 2-bromo-1-ethanone substituent in the molecules of I has a significantly flattened conformation (the Br–C–C═O torsion angles are 1.2 (4) and -2.8 (4)° for the two independent molecules, respectively), with the carbonyl group directed toward the methyl substituent, and lies almost within the triazole plane (r.m.s. deviations are 0.037 and 0.023 Å for the two independent molecules, respectively) (Figure 2). The bromo-benzene substituent is twisted by 52.30 (6) and 51.81 (6)° (for the two independent molecules, respectively) relative to this main plane of the molecule.

In the crystal, the molecules of I are linked into three-dimensional framework by intermolecular C–H···O and C–H···N hydrogen bonds (Table 1) as well as secondary Br1···Br2ⁱ (3.5991 (8) Å) and Br3···Br4ⁱⁱ (3.6503 (9) Å) interactions [symmetry codes: (i) x, y, z+1; (ii) x, y, z-1].

S2. Experimental

Bromine (1.6 g, 10 mmol) was slowly added to a solution of 1-(1-(4-bromophenyl)-5-methyl-1H-1,2,3-triazol-4-yl)ethanone (2.8 g, 10 mmol) in AcOH (30 mL). The mixture was stirred at 80 ^oC for 20 min. Then the reaction mixture was cooled to room temperature. The crude precipitate formed was filtrated, washed with H₂O (20 mL), dried, and re-crystallized from EtOH. Yield is 83%. The single-crystals of the product I were obtained by slow crystallization from EtOH. M.p. = 398-399 K. IR (KBr), ν/cm^-1: 3301, 1693, 1550, 1495, 1181, 972, 872. ¹H NMR (600 MHz, DMSO-d₆, 304 K): 2.55 (s, 3H), 4.88 (s, 2H), 7.62 (d, 2H, J = 8.8), 7.87 (d, 2H, J = 8.8). Anal. Calcd for C₁₁H₉Br₂N₃O: C, 42.00; H, 2.88. Found: C, 42.07; H, 2.92.