1-[4-Bromo-2-(tri­fluoro­meth­oxy)phen­yl]-3-methyl-1H-1,2,4-triazole

Sandeep, C.; Padmashali, B.; Suchetan, P.A.; Kulkarni, R.S.

doi:10.1107/S1600536814010083

organic compounds

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Volume 70| Part 6| June 2014| Page o654

doi:10.1107/S1600536814010083

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1-[4-Bromo-2-(trifluoromethoxy)phenyl]-3-methyl-1H-1,2,4-triazole

C Sandeep,^a Basavaraj Padmashali,^a,^b ^* P. A. Suchetan ^c and Rashmi S. Kulkarni ^d

^aDepartment of Chemistry, Sahyadri Science College (Autonomous), Shimoga 577 203, Karnataka, India, ^bDepartment of Studies and Research in Chemistry, School of Basic Sciences, Rani Channamma University, Belagavi 591 156, Karnataka, India, ^cDepartment of Studies in Chemistry, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, and ^dPG Department of Chemistry, Jain University, Bangalore 560 019, Karnataka, India
^*Correspondence e-mail: basavarajpadmashali@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 23 April 2014; accepted 5 May 2014; online 10 May 2014)

In the title compound, C₁₀H₇BrF₃N₃O, the dihedral angle between the benzene and triazole rings is 23.17 (12)° and the C atom of the –CF₃ group deviates from its attached ring plane by 1.147 (3) Å. In the crystal, molecules are linked by C—H⋯N interactions, generating C(7) chains running along [010].

CCDC reference: 1000730

Related literature

For the antibacterial activity of 1,2,4-triazoles, see: Gabriela et al. (2009 ); Palekar et al. (2009 ). For their antiviral activity, see: Upmanyu et al. (2006 ). For antimicrobial agents, see: Badr & Barwa (2011 ), and for antimycotic activity such as voriconazole, see: Haber (2001 ).

Experimental

Crystal data

C₁₀H₇BrF₃N₃O
M_r = 322.10
Monoclinic, P 2₁ /n
a = 5.2389 (3) Å
b = 16.1548 (8) Å
c = 14.0315 (7) Å
β = 92.673 (3)°
V = 1186.24 (11) Å³
Z = 4
Mo Kα radiation
μ = 3.50 mm⁻¹
T = 293 K
0.33 × 0.21 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.419, T_max = 0.613
37092 measured reflections
3499 independent reflections
2373 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.135
S = 0.99
3499 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N3ⁱ	0.93	2.59	3.511 (3)	169
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 1000730

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814010083/hb7221sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814010083/hb7221Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814010083/hb7221Isup3.cml

checkCIF report

Introduction top

1,2,4-triazole containing ring system have been incorporated into a wide variety of therapeutically interesting drug candidates including anti-inflammatory, CNS stimulants sedatives, antibacterial (Gabriela et al., 2009, Palekar et al., 2009), antiviral (Upmanyu et al., 2006), antimicrobial agents (Badr et al., 2011) and antimycotic activity such as fluconazole, intraconazole and voriconazole (Haber et al., 2001). The search for new agent is one of the most challenging tasks to a medicinal chemist. The synthesis of high nitrogen containing heterocyclic systems has been attracting increasing interest over the past decade because of their utility in various applications. In recent years, the chemistry of triazoles and their fused heterocyclic derivatives has received considerable attention owing to their synthetic and effective biological importance. The presence of three nitrogen hetero-atoms in five membered ring system defines an interesting class of compounds. Keeping this in mind, we synthesized the title compound to study its crystal structure.

Experimental top

Synthesis and crystallization top

To a stirred solution of 4-bromo-1-iodo-2-(trifluoromethoxy)benzene (1 g, 2.73mmol) in N,N-Dimethyl Formamide (10 mL), was added potassium carbonate ( 0.41g , 3.0 mmol), followed by 3-methyl-1H-1,2,4-triazole (0.23g 2.73 mmol). The mixture was stirred at room temperature for 30 minutes. Completion of the reaction was monitored by TLC. The reaction mixture was poured to 100g of crushed ice and the separated solid was filtered off and dried under vaccum.

Single crystals of the title compound were obtained from hexane-ethyl acetate (1:1 v/v) solvent system.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

In the title compound, C₁₀H₇BrF₃N₃O, the dihedral angle between the two planes defined by the benzene ring and the triazole ring is 23.17 (12)°. In the crystal structure, the molecules are linked to one another through C2—H2···N3 interactions generating zig zag C(7) chains running along [010].

Related literature top

For the antibacterial activity of 1,2,4-triazoles, see: Gabriela et al. (2009); Palekar et al. (2009). For their antiviral activity, see: Upmanyu et al. (2006). For antimicrobial agents, see: Badr & Barwa (2011), and for antimycotic activity such as voriconazole, see: Haber (2001).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Linking of molecules in the crystal structure through C—H···N interactions into C(7) chains.

1-[4-Bromo-2-(trifluoromethoxy)phenyl]-3-methyl-1H-1,2,4-triazole top

Crystal data top

C₁₀H₇BrF₃N₃O	Prism
M_r = 322.10	D_x = 1.804 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 453 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 5.2389 (3) Å	Cell parameters from 25 reflections
b = 16.1548 (8) Å	θ = 1.9–30.1°
c = 14.0315 (7) Å	µ = 3.50 mm⁻¹
β = 92.673 (3)°	T = 293 K
V = 1186.24 (11) Å³	Prism, colourless
Z = 4	0.33 × 0.21 × 0.14 mm
F(000) = 632

Data collection top

Bruker APEXII CCD diffractometer	3499 independent reflections
Radiation source: fine-focus sealed tube	2373 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scans	θ_max = 30.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
T_min = 0.419, T_max = 0.613	k = −22→22
37092 measured reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.0871P)² + 0.1014P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
3499 reflections	Δρ_max = 0.41 e Å⁻³
165 parameters	Δρ_min = −0.68 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0045 (16)

Crystal data top

C₁₀H₇BrF₃N₃O	V = 1186.24 (11) Å³
M_r = 322.10	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.2389 (3) Å	µ = 3.50 mm⁻¹
b = 16.1548 (8) Å	T = 293 K
c = 14.0315 (7) Å	0.33 × 0.21 × 0.14 mm
β = 92.673 (3)°

Data collection top

Bruker APEXII CCD diffractometer	3499 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2373 reflections with I > 2σ(I)
T_min = 0.419, T_max = 0.613	R_int = 0.051
37092 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 0.99	Δρ_max = 0.41 e Å⁻³
3499 reflections	Δρ_min = −0.68 e Å⁻³
165 parameters

Special details top

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
C1	−0.1456 (5)	0.66662 (15)	0.14761 (15)	0.0523 (5)
C2	0.0451 (4)	0.63544 (14)	0.20903 (15)	0.0524 (5)
H2	0.1392	0.6703	0.2500	0.063*
C3	0.0922 (4)	0.55182 (13)	0.20808 (14)	0.0453 (4)
C4	−0.0376 (4)	0.49886 (12)	0.14480 (14)	0.0427 (4)
C5	−0.2245 (4)	0.53249 (14)	0.08273 (16)	0.0524 (5)
H5	−0.3122	0.4982	0.0392	0.063*
C6	−0.2820 (5)	0.61578 (15)	0.08462 (17)	0.0559 (5)
H6	−0.4107	0.6374	0.0441	0.067*
N1	0.0066 (3)	0.41252 (11)	0.14056 (12)	0.0446 (4)
C7	0.2131 (4)	0.36565 (15)	0.16360 (18)	0.0541 (5)
H7	0.3662	0.3859	0.1905	0.065*
C8	−0.0743 (4)	0.28860 (13)	0.10549 (17)	0.0508 (5)
C9	−0.2132 (6)	0.21249 (15)	0.0729 (3)	0.0708 (8)
H9A	−0.3924	0.2244	0.0646	0.106*
H9B	−0.1874	0.1697	0.1198	0.106*
H9C	−0.1494	0.1944	0.0134	0.106*
C10	0.2286 (6)	0.50572 (18)	0.36008 (19)	0.0688 (7)
N2	−0.1818 (3)	0.36208 (11)	0.10201 (14)	0.0492 (4)
N3	0.1693 (4)	0.28792 (12)	0.14296 (18)	0.0582 (5)
O1	0.2873 (3)	0.51928 (11)	0.26983 (13)	0.0592 (4)
F1	0.0294 (6)	0.45837 (17)	0.36571 (16)	0.1342 (11)
F2	0.4236 (6)	0.46877 (15)	0.40292 (16)	0.1310 (10)
F3	0.1867 (5)	0.57307 (12)	0.40782 (12)	0.0998 (6)
Br1	−0.22139 (7)	0.780974 (16)	0.14867 (2)	0.07657 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0645 (12)	0.0470 (11)	0.0453 (11)	0.0065 (9)	0.0010 (9)	0.0023 (8)
C2	0.0605 (12)	0.0480 (11)	0.0478 (11)	−0.0036 (9)	−0.0062 (9)	−0.0017 (8)
C3	0.0458 (10)	0.0467 (10)	0.0425 (10)	0.0017 (8)	−0.0066 (8)	0.0012 (8)
C4	0.0415 (9)	0.0416 (10)	0.0447 (10)	0.0022 (7)	−0.0012 (7)	−0.0007 (8)
C5	0.0536 (11)	0.0507 (11)	0.0514 (12)	0.0059 (9)	−0.0128 (9)	−0.0030 (9)
C6	0.0634 (13)	0.0511 (12)	0.0520 (12)	0.0118 (10)	−0.0099 (10)	0.0037 (9)
N1	0.0415 (8)	0.0438 (9)	0.0479 (9)	0.0036 (6)	−0.0040 (6)	−0.0028 (7)
C7	0.0411 (10)	0.0539 (12)	0.0664 (14)	0.0093 (9)	−0.0077 (9)	−0.0052 (10)
C8	0.0507 (11)	0.0471 (12)	0.0547 (12)	0.0030 (8)	0.0024 (9)	−0.0046 (9)
C9	0.0684 (16)	0.0487 (14)	0.095 (2)	−0.0032 (10)	0.0046 (14)	−0.0127 (12)
C10	0.0948 (19)	0.0510 (13)	0.0577 (15)	0.0047 (12)	−0.0265 (13)	0.0011 (10)
N2	0.0410 (8)	0.0462 (9)	0.0598 (10)	−0.0013 (7)	−0.0046 (7)	−0.0023 (8)
N3	0.0511 (10)	0.0518 (11)	0.0713 (14)	0.0114 (8)	−0.0016 (9)	−0.0039 (8)
O1	0.0567 (8)	0.0600 (9)	0.0589 (9)	0.0055 (7)	−0.0205 (7)	−0.0029 (7)
F1	0.181 (2)	0.139 (2)	0.0812 (14)	−0.080 (2)	−0.0096 (15)	0.0274 (13)
F2	0.177 (2)	0.1229 (19)	0.0866 (14)	0.0713 (17)	−0.0627 (15)	−0.0062 (13)
F3	0.1628 (19)	0.0694 (11)	0.0658 (10)	0.0264 (12)	−0.0112 (11)	−0.0113 (8)
Br1	0.1162 (3)	0.04531 (19)	0.0671 (2)	0.01567 (12)	−0.00788 (17)	0.00117 (10)

Geometric parameters (Å, º) top

C1—C6	1.381 (3)	N1—N2	1.372 (2)
C1—C2	1.383 (3)	C7—N3	1.307 (3)
C1—Br1	1.890 (2)	C7—H7	0.9300
C2—C3	1.373 (3)	C8—N2	1.314 (3)
C2—H2	0.9300	C8—N3	1.358 (3)
C3—C4	1.388 (3)	C8—C9	1.490 (3)
C3—O1	1.410 (2)	C9—H9A	0.9600
C4—C5	1.390 (3)	C9—H9B	0.9600
C4—N1	1.416 (3)	C9—H9C	0.9600
C5—C6	1.379 (3)	C10—F1	1.299 (4)
C5—H5	0.9300	C10—F2	1.306 (3)
C6—H6	0.9300	C10—F3	1.302 (3)
N1—C7	1.347 (3)	C10—O1	1.335 (3)

C6—C1—C2	121.3 (2)	N3—C7—N1	110.9 (2)
C6—C1—Br1	118.93 (17)	N3—C7—H7	124.6
C2—C1—Br1	119.80 (17)	N1—C7—H7	124.6
C3—C2—C1	118.5 (2)	N2—C8—N3	114.54 (19)
C3—C2—H2	120.8	N2—C8—C9	122.1 (2)
C1—C2—H2	120.8	N3—C8—C9	123.3 (2)
C2—C3—C4	121.97 (18)	C8—C9—H9A	109.5
C2—C3—O1	119.08 (18)	C8—C9—H9B	109.5
C4—C3—O1	118.86 (18)	H9A—C9—H9B	109.5
C5—C4—C3	118.01 (19)	C8—C9—H9C	109.5
C5—C4—N1	118.07 (18)	H9A—C9—H9C	109.5
C3—C4—N1	123.91 (18)	H9B—C9—H9C	109.5
C4—C5—C6	121.1 (2)	F1—C10—F2	108.4 (3)
C4—C5—H5	119.4	F1—C10—F3	107.8 (3)
C6—C5—H5	119.4	F2—C10—F3	107.0 (2)
C1—C6—C5	119.0 (2)	F1—C10—O1	112.0 (2)
C1—C6—H6	120.5	F2—C10—O1	107.6 (3)
C5—C6—H6	120.5	F3—C10—O1	113.8 (2)
C7—N1—N2	108.42 (17)	C8—N2—N1	102.87 (16)
C7—N1—C4	132.43 (18)	C7—N3—C8	103.32 (18)
N2—N1—C4	119.06 (16)	C10—O1—C3	116.85 (18)

C6—C1—C2—C3	−1.7 (3)	C3—C4—N1—N2	157.37 (19)
Br1—C1—C2—C3	178.63 (17)	N2—N1—C7—N3	−0.5 (3)
C1—C2—C3—C4	2.8 (3)	C4—N1—C7—N3	−176.8 (2)
C1—C2—C3—O1	179.54 (19)	N3—C8—N2—N1	−0.3 (3)
C2—C3—C4—C5	−1.6 (3)	C9—C8—N2—N1	178.3 (2)
O1—C3—C4—C5	−178.29 (19)	C7—N1—N2—C8	0.4 (2)
C2—C3—C4—N1	179.3 (2)	C4—N1—N2—C8	177.29 (19)
O1—C3—C4—N1	2.6 (3)	N1—C7—N3—C8	0.3 (3)
C3—C4—C5—C6	−0.8 (3)	N2—C8—N3—C7	0.0 (3)
N1—C4—C5—C6	178.4 (2)	C9—C8—N3—C7	−178.5 (3)
C2—C1—C6—C5	−0.6 (4)	F1—C10—O1—C3	55.1 (3)
Br1—C1—C6—C5	179.06 (18)	F2—C10—O1—C3	174.1 (2)
C4—C5—C6—C1	1.9 (4)	F3—C10—O1—C3	−67.6 (3)
C5—C4—N1—C7	154.2 (2)	C2—C3—O1—C10	81.4 (3)
C3—C4—N1—C7	−26.6 (3)	C4—C3—O1—C10	−101.8 (2)
C5—C4—N1—N2	−21.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N3ⁱ	0.93	2.59	3.511 (3)	169

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N3ⁱ	0.93	2.59	3.511 (3)	169

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

References

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doi:10.1107/S1600536814010083

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