2-[4-(Trifluoro­meth­oxy)phen­yl]-1H-benzimidazole

Fathima, N.; Krishnamurthy, M.S.; Begum, N.S.

doi:10.1107/S1600536813001220

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o264

doi:10.1107/S1600536813001220

Open

access

2-[4-(Trifluoromethoxy)phenyl]-1H-benzimidazole

Nikhath Fathima,^a M. S. Krishnamurthy ^a and Noor Shahina Begum ^a ^*

^aDepartment of Studies in Chemistry, Bangalore University, Bangalore 560 001, India
^*Correspondence e-mail: noorsb@rediffmail.com

(Received 3 January 2013; accepted 12 January 2013; online 19 January 2013)

In the title compound, C₁₄H₉F₃N₂O, the best planes of the benzimidazole group and benzene ring form a dihedral angle of 26.68 (3)°. In the crystal, N—H⋯N hydrogen bonds link the molecules into infinite chains parallel to the c axis. Stacking interactions between the benzimidazole groups [centroid–centroid distance = 3.594 (5) Å] assemble the molecules into layers parallel to (100). The trifluoromethyl group is disordered over three sets of sites with site-occupancy factors of 0.787 (4), 0.107 (7) and 0.106 (7).

Related literature

For therapeutic and medicinal properties of benzimidazole derivatives, see: Chimirri et al. (1991 ); Benavides et al. (1995 ); Ishihara et al. (1994 ); Kubo et al. (1993 ). For related structures, see: Jian et al. (2006 ); Rashid, Tahir, Yusof et al. (2007 ); Rashid, Tahir, Kanwal et al. (2007 ).

Experimental

Crystal data

C₁₄H₉F₃N₂O
M_r = 278.23
Monoclinic, P 2₁ /c
a = 14.476 (6) Å
b = 9.312 (4) Å
c = 9.835 (4) Å
β = 108.192 (8)°
V = 1259.5 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 K
0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.978, T_max = 0.980
6284 measured reflections
2209 independent reflections
1333 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.157
S = 1.00
2209 reflections
210 parameters
21 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯N1ⁱ	0.86	2.07	2.864 (4)	154
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813001220/gk2550sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813001220/gk2550Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813001220/gk2550Isup3.cml

checkCIF report

Comment top

Benzimidazole and its derivatives are known to exhibit a wide variety of pharmacological activities such as anti-HIV (Chimirri et al., 1991), antihistaminic (Benavides et al., 1995), antiulcer (Ishihara et al., 1994), antihypertensive (Kubo et al., 1993). The benzimidazole and phenyl groups form a dihedral angle of 26.68 (3)°. The bond lengths and angles of the benzimidazole moiety in the title compound are in good agreement with those observed in other benzimidazole derivatives (Jian et al., 2006; Rashid, Tahir, Yusof et al., 2007; Rashid, Tahir, Kanwal et al., 2007). The N1—C8 and N2—C8 distances were found to be 1.338 (5) Å and 1.356 (5) Å, respectively. The trifluoromethyl group is disordered over three sites with occupancy factors 0.787 (4), 0.107 (7) and 0.106 (7). The molecules are linked by intermolecular N—H···N hydrogen bonds to form infinite chains parallel to the c axis. Additionally, the crystal packing is further stabilized by π -π stacking interactions between the benzimidazole groups [interplanar distance 3.594 (5) Å].

Related literature top

For therapeutic and medicinal properties of benzimidazole derivatives, see: Chimirri et al. (1991); Benavides et al. (1995); Ishihara et al. (1994); Kubo et al. (1993). For related structures, see: Jian et al. (2006); Rashid, Tahir, Yusof et al. (2007); Rashid, Tahir, Kanwal et al. (2007).

Experimental top

A mixture of 4-(trifluoromethoxy)benzaldehyde (10 mmol, 0.19 g) and o-phenyldiamine (10 mmol, 0.19 g) in benzene (2 ml) was refluxed for 6 h on a water bath. The reaction mixture was cooled. The solid separated, was filtered and dried (yield: 0.26 g, 75% and m.p. 503–508 K). Pale yellow crystals of the title compound were obtained by slow evaporation from a solution in ethyl acetate.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.The trifluoromethyl group is disordered over three sites.
	Fig. 2. A view of the intermolecular hydrogen bonds(dotted lines) in the crystal structure of the title compound. H atoms non participating in H-bonding and minor components of the disordered CF₃ group were omitted for clarity.

2-[4-(Trifluoromethoxy)phenyl]-1H-benzimidazole top

Crystal data top

C₁₄H₉F₃N₂O	F(000) = 568
M_r = 278.23	D_x = 1.467 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2209 reflections
a = 14.476 (6) Å	θ = 2.6–25.0°
b = 9.312 (4) Å	µ = 0.13 mm⁻¹
c = 9.835 (4) Å	T = 296 K
β = 108.192 (8)°	Block, yellow
V = 1259.5 (9) Å³	0.18 × 0.16 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX CCD detector diffractometer	2209 independent reflections
Radiation source: fine-focus sealed tube	1333 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −17→15
T_min = 0.978, T_max = 0.980	k = −8→11
6284 measured reflections	l = −11→11

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0655P)²] where P = (F_o² + 2F_c²)/3
2209 reflections	(Δ/σ)_max = 0.001
210 parameters	Δρ_max = 0.26 e Å⁻³
21 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₄H₉F₃N₂O	V = 1259.5 (9) Å³
M_r = 278.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.476 (6) Å	µ = 0.13 mm⁻¹
b = 9.312 (4) Å	T = 296 K
c = 9.835 (4) Å	0.18 × 0.16 × 0.16 mm
β = 108.192 (8)°

Data collection top

Bruker SMART APEX CCD detector diffractometer	2209 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1333 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.980	R_int = 0.077
6284 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	21 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.00	Δρ_max = 0.26 e Å⁻³
2209 reflections	Δρ_min = −0.22 e Å⁻³
210 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	Occ. (<1)
C1	0.3459 (2)	0.8348 (3)	0.4611 (3)	0.0246 (8)
C2	0.3309 (2)	0.9562 (3)	0.3748 (3)	0.0297 (8)
H2	0.3786	0.9857	0.3359	0.036*
C3	0.2445 (2)	1.0344 (4)	0.3460 (4)	0.0361 (9)
H3	0.2352	1.1177	0.2912	0.043*
C4	0.1735 (2)	0.9856 (4)	0.4004 (4)	0.0333 (9)
C6	0.1860 (2)	0.8644 (3)	0.4854 (3)	0.0321 (9)
H6	0.1368	0.8332	0.5206	0.039*
C7	0.2734 (2)	0.7900 (3)	0.5172 (3)	0.0284 (8)
H7	0.2836	0.7097	0.5763	0.034*
C8	0.4390 (2)	0.7578 (3)	0.4969 (3)	0.0245 (8)
C9	0.5675 (2)	0.6361 (3)	0.6072 (3)	0.0260 (8)
C10	0.6411 (2)	0.5565 (3)	0.7050 (3)	0.0316 (9)
H10	0.6339	0.5228	0.7901	0.038*
C11	0.7245 (2)	0.5305 (3)	0.6695 (4)	0.0327 (9)
H11	0.7743	0.4778	0.7323	0.039*
C12	0.7367 (2)	0.5806 (3)	0.5422 (3)	0.0311 (8)
H12	0.7946	0.5624	0.5233	0.037*
C13	0.6639 (2)	0.6567 (3)	0.4443 (3)	0.0277 (8)
H13	0.6709	0.6883	0.3583	0.033*
C14	0.5804 (2)	0.6840 (3)	0.4794 (3)	0.0233 (8)
O1	0.08661 (17)	1.0648 (3)	0.3804 (3)	0.0460 (7)
N1	0.47847 (18)	0.6843 (3)	0.6176 (3)	0.0272 (7)
N2	0.49671 (18)	0.7606 (3)	0.4113 (3)	0.0260 (7)
H21	0.4836	0.8024	0.3295	0.031*
C5	0.0271 (4)	1.0787 (7)	0.2470 (6)	0.0534 (16)	0.787 (4)
F1	−0.0537 (4)	1.1368 (8)	0.2540 (9)	0.0740 (15)	0.787 (4)
F2	0.0616 (3)	1.1639 (8)	0.1658 (6)	0.0954 (17)	0.787 (4)
F3	0.0071 (4)	0.9548 (6)	0.1788 (7)	0.110 (2)	0.787 (4)
C51	0.0312 (14)	1.109 (2)	0.268 (3)	0.047 (6)*	0.107 (7)
F11	−0.0580 (16)	1.145 (3)	0.259 (7)	0.047 (6)*	0.107 (7)
F21	0.0781 (14)	1.2304 (19)	0.261 (3)	0.047 (6)*	0.107 (7)
F31	0.030 (3)	1.033 (3)	0.154 (4)	0.047 (6)*	0.107 (7)
C52	0.010 (2)	1.062 (3)	0.270 (3)	0.056 (7)*	0.106 (7)
F12	−0.066 (4)	1.144 (3)	0.251 (8)	0.056 (7)*	0.106 (7)
F22	−0.0187 (16)	0.928 (2)	0.282 (3)	0.056 (7)*	0.106 (7)
F32	0.037 (4)	1.064 (4)	0.154 (4)	0.056 (7)*	0.106 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0277 (18)	0.0240 (18)	0.0207 (17)	−0.0013 (14)	0.0055 (14)	−0.0033 (14)
C2	0.031 (2)	0.037 (2)	0.0256 (18)	0.0045 (15)	0.0146 (15)	0.0039 (16)
C3	0.040 (2)	0.038 (2)	0.033 (2)	0.0027 (17)	0.0134 (17)	0.0087 (17)
C4	0.030 (2)	0.035 (2)	0.032 (2)	0.0030 (16)	0.0069 (16)	−0.0047 (17)
C6	0.030 (2)	0.033 (2)	0.035 (2)	−0.0056 (15)	0.0115 (16)	−0.0059 (17)
C7	0.033 (2)	0.0275 (19)	0.0244 (18)	−0.0029 (15)	0.0087 (15)	−0.0031 (15)
C8	0.0320 (19)	0.0228 (18)	0.0204 (17)	−0.0048 (14)	0.0105 (15)	−0.0034 (14)
C9	0.0305 (19)	0.0217 (18)	0.0248 (18)	−0.0018 (14)	0.0069 (14)	−0.0029 (14)
C10	0.043 (2)	0.028 (2)	0.0243 (19)	0.0028 (16)	0.0104 (16)	−0.0006 (15)
C11	0.038 (2)	0.0272 (19)	0.030 (2)	0.0044 (16)	0.0060 (16)	−0.0005 (16)
C12	0.032 (2)	0.0268 (19)	0.034 (2)	0.0023 (15)	0.0106 (16)	−0.0014 (16)
C13	0.036 (2)	0.0242 (18)	0.0250 (18)	0.0006 (15)	0.0132 (15)	−0.0037 (15)
C14	0.0318 (19)	0.0179 (17)	0.0206 (17)	−0.0004 (14)	0.0087 (14)	−0.0005 (14)
O1	0.0353 (15)	0.0582 (18)	0.0454 (16)	0.0162 (12)	0.0137 (13)	0.0099 (13)
N1	0.0327 (16)	0.0248 (15)	0.0238 (15)	−0.0002 (12)	0.0085 (12)	−0.0020 (12)
N2	0.0335 (16)	0.0241 (15)	0.0207 (14)	0.0028 (12)	0.0089 (12)	0.0042 (12)
C5	0.038 (3)	0.065 (5)	0.054 (4)	0.012 (3)	0.010 (3)	0.003 (4)
F1	0.026 (2)	0.084 (3)	0.111 (3)	0.0205 (17)	0.021 (2)	0.043 (2)
F2	0.056 (2)	0.154 (5)	0.086 (3)	0.030 (3)	0.034 (2)	0.078 (3)
F3	0.076 (3)	0.085 (3)	0.116 (4)	0.016 (3)	−0.045 (3)	−0.042 (3)

Geometric parameters (Å, º) top

C1—C2	1.390 (4)	C11—C12	1.397 (5)
C1—C7	1.393 (4)	C11—H11	0.9300
C1—C8	1.469 (4)	C12—C13	1.380 (4)
C2—C3	1.397 (4)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.380 (4)
C3—C4	1.376 (5)	C13—H13	0.9300
C3—H3	0.9300	C14—N2	1.385 (4)
C4—C6	1.382 (4)	O1—C5	1.332 (6)
C4—O1	1.417 (4)	N2—H21	0.8600
C6—C7	1.391 (4)	C5—F1	1.309 (5)
C6—H6	0.9300	C5—F3	1.321 (7)
C7—H7	0.9300	C5—F2	1.329 (8)
C8—N1	1.334 (4)	C51—F11	1.309 (5)
C8—N2	1.358 (4)	C51—F31	1.321 (7)
C9—N1	1.399 (4)	C51—F21	1.329 (8)
C9—C14	1.400 (4)	C52—F12	1.309 (5)
C9—C10	1.403 (4)	C52—F32	1.321 (7)
C10—C11	1.379 (5)	C52—F22	1.329 (8)
C10—H10	0.9300

C2—C1—C7	119.5 (3)	C10—C11—H11	118.9
C2—C1—C8	120.0 (3)	C12—C11—H11	118.9
C7—C1—C8	120.4 (3)	C13—C12—C11	121.0 (3)
C1—C2—C3	120.5 (3)	C13—C12—H12	119.5
C1—C2—H2	119.8	C11—C12—H12	119.5
C3—C2—H2	119.8	C14—C13—C12	117.2 (3)
C4—C3—C2	118.6 (3)	C14—C13—H13	121.4
C4—C3—H3	120.7	C12—C13—H13	121.4
C2—C3—H3	120.7	C13—C14—N2	132.6 (3)
C3—C4—C6	122.1 (3)	C13—C14—C9	122.6 (3)
C3—C4—O1	120.8 (3)	N2—C14—C9	104.8 (3)
C6—C4—O1	116.9 (3)	C5—O1—C4	117.5 (3)
C4—C6—C7	118.7 (3)	C8—N1—C9	104.3 (3)
C4—C6—H6	120.6	C8—N2—C14	107.8 (3)
C7—C6—H6	120.6	C8—N2—H21	126.1
C6—C7—C1	120.4 (3)	C14—N2—H21	126.1
C6—C7—H7	119.8	F1—C5—F3	109.3 (5)
C1—C7—H7	119.8	F1—C5—F2	107.1 (5)
N1—C8—N2	112.7 (3)	F3—C5—F2	106.3 (6)
N1—C8—C1	124.7 (3)	F1—C5—O1	107.6 (5)
N2—C8—C1	122.5 (3)	F3—C5—O1	112.8 (5)
N1—C9—C14	110.4 (3)	F2—C5—O1	113.6 (5)
N1—C9—C10	129.7 (3)	F11—C51—F31	109.3 (5)
C14—C9—C10	119.9 (3)	F11—C51—F21	107.1 (5)
C11—C10—C9	117.1 (3)	F31—C51—F21	106.3 (6)
C11—C10—H10	121.4	F12—C52—F32	109.3 (5)
C9—C10—H10	121.4	F12—C52—F22	107.1 (5)
C10—C11—C12	122.2 (3)	F32—C52—F22	106.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···N1ⁱ	0.86	2.07	2.864 (4)	154

Symmetry code: (i) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₉F₃N₂O
M_r	278.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.476 (6), 9.312 (4), 9.835 (4)
β (°)	108.192 (8)
V (Å³)	1259.5 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.18 × 0.16 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.978, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	6284, 2209, 1333
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.157, 1.00
No. of reflections	2209
No. of parameters	210
No. of restraints	21
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.22

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and CAMERON (Watkin et al., 1996), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···N1ⁱ	0.86	2.066	2.864 (4)	154

Symmetry code: (i) x, −y+3/2, z−1/2.

Acknowledgements

NSB is thankful to the University Grants Commission (UGC), India, for financial assistance.

References

Benavides, J., Schoemaker, H., Dana, C., Clausture, Y., Delahaye, M., Prouteau, M., Manoury, P., Allen, J. V., Scatton, B., Langer, S. Z. & Arbilla, S. (1995). Arzneim. Forsch. (Drug. Res.), 45, 551—558. Google Scholar
Bruker. (1998). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chimirri, A., Grasso, S., Monforte, A. M., Monforte, P. & Zappala, M. (1991). Il Farmaco, 46, 925—933. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ishihara, K., Ichikawa, T., Komuro, Y., Ohara, S. & Hotta, K. (1994). Arzneim. Forsch. (Drug. Res.), 44, 827—830. Google Scholar
Jian, F.-F., Yu, H.-Q., Qiao, Y.-B., Zhao, P.-S. & Xiao, H.-L. (2006). Acta Cryst. E62, o5194–o5195. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Kubo, K., Kohara, Y., Imamia, E., Sugiura, Y., Inada, Y., Furukawa, Y., Nishikawa, K. & Naka, T. (1993). J. Med. Chem. 36, 2182–2195. CrossRef CAS PubMed Web of Science Google Scholar
Rashid, N., Tahir, M. K., Kanwal, S., Yusof, N. M. & Yamin, B. M. (2007). Acta Cryst. E63, o1402–o1403. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rashid, N., Tahir, M. K., Yusof, N. M. & Yamin, B. M. (2007). Acta Cryst. E63, o1260–o1261. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England. Google Scholar