2-(4-Fluoro­phen­yl)-1-phenyl-1H-benzimidazole

Jayamoorthy, K.; Rosepriya, S.; Thiruvalluvar, A.; Jayabharathi, J.; Butcher, R.J.

doi:10.1107/S1600536812035155

2-(4-Fluorophenyl)-1-phenyl-1H-benzimidazole

K. Jayamoorthy, S. Rosepriya, A. Thiruvalluvar, J. Jayabharathi and R. J. Butcher

In the title molecule, C₁₉H₁₃FN₂, the benzimidazole unit is close to planar [maximum deviation = 0.0342 (9) Å] and forms dihedral angles of 58.94 (3) and 51.43 (3)° with the phenyl and fluorobenzene rings, respectively; the dihedral angle between the phenyl and fluorobenzene rings is 60.17 (6)°. In the crystal, three C—H

F hydrogen bonds and two weak C—H

π interactions involving the fused benzene ring lead to a three-dimensional architecture.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812035155/tk5141sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536812035155/tk5141Isup2.hkl Contains datablock I
	Chemdraw file https://doi.org/10.1107/S1600536812035155/tk5141Isup3.cdx Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536812035155/tk5141Isup4.cml Supplementary material

CCDC reference: 899696

checkCIF report

Key indicators

Single-crystal X-ray study
T = 123 K
Mean (C-C) = 0.002 Å
R factor = 0.063
wR factor = 0.160
Data-to-parameter ratio = 36.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.35
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      8.620
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.125
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT022_ALERT_3_G Ratio Unique / Expected Reflections (too) Low ..      0.946
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        407

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Benzimidazole based chromophores have received increasing attention due to their distinctive linear, non-linear optical properties and also due to their excellent thermal stability in guest-host systems (Cross et al., 1995). The imidazole ring can be easily tailored to accommodate functional groups, which allows the covalent incorporation of the NLO chromophores into polyamides leading to NLO side chain polymers (Bu et al., 1996). Most π-conjugated systems play a major role in determining second-order NLO response (Dirk et al., 1990). Since our group is doing research in organic light emitting devices (OLEDs), we are interested in using the title compound as a ligand in the preparation of Ir(III) complexes and in studying the photophysical properties of these complexes. Rosepriya et al. (2011) have reported a related crystal structure, namely 1-(4-Methylbenzyl)-2-(4-methylphenyl)-1H-benzimidazole.

In the title molecule, C₁₉H₁₃FN₂ (Fig. 1), the benzimidazole unit is almost planar [maximum deviation = 0.0342 (9) Å for C6]. The dihedral angles between the planes of the benzimidazole and the phenyl and the fluorobenzene groups are 58.94 (3) and 51.43 (3)°, respectively. The dihedral angle between the planes of the phenyl and the fluorobenzene rings is 60.17 (6)°. Intermolecular C4—H4···F4, C7—H7···F4 and C26—H26···F4 hydrogen bonds and weak C16—H16···π and C22—H22···π interactions involving the fused benzene ring are found in the crystal structure (Fig. 2, Table 1).

Related literature top

For linear and non-linear optical properties of benzimidazole compounds, see: Cross et al. (1995); Bu et al. (1996); Dirk et al. (1990). For a related structure, see: Rosepriya et al. (2011).

Experimental top

To N-phenyl-o-phenylenediamine (3.128 g, 17 mmol) in ethanol (10 ml) was added 4-fluorobenzaldehyde (1.9 ml, 17 mmol) and ammonium acetate (3 g) over about 1 h while maintaining the temperature at 353 K. The reaction mixture was refluxed until the completion of reaction, as monitored by TLC. The reaction mixture was extracted with dichloromethane. The solid that separated out was purified by column chromatography using petroleum ether: ethyl acetate as the eluent. Yield: 2.47 g (50%). The title compound was dissolved in acetonitrile and allowed to slowly evaporate for two days to obtain crystals suitable for X-ray diffraction studies.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.

The packing of the title compound, viewed down the b axis. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.

2-(4-Fluorophenyl)-1-phenyl-1H-benzimidazole top

Crystal data top

C₁₉H₁₃FN₂	F(000) = 600
M_r = 288.31	D_x = 1.308 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 369 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.7527 (4) Å	Cell parameters from 3202 reflections
b = 10.1342 (4) Å	θ = 3.1–37.6°
c = 17.0211 (6) Å	µ = 0.09 mm⁻¹
β = 104.187 (4)°	T = 123 K
V = 1463.75 (11) Å³	Plate, colourless
Z = 4	0.47 × 0.42 × 0.15 mm

Data collection top

Agilent Xcalibur Ruby Gemini diffractometer	7347 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5352 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 10.5081 pixels mm^-1	θ_max = 37.7°, θ_min = 3.1°
ω scans	h = −12→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −12→17
T_min = 0.961, T_max = 1.000	l = −28→24
13721 measured reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0685P)² + 0.2726P] where P = (F_o² + 2F_c²)/3
7347 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₉H₁₃FN₂	V = 1463.75 (11) Å³
M_r = 288.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.7527 (4) Å	µ = 0.09 mm⁻¹
b = 10.1342 (4) Å	T = 123 K
c = 17.0211 (6) Å	0.47 × 0.42 × 0.15 mm
β = 104.187 (4)°

Data collection top

Agilent Xcalibur Ruby Gemini diffractometer	7347 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	5352 reflections with I > 2σ(I)
T_min = 0.961, T_max = 1.000	R_int = 0.031
13721 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.04	Δρ_max = 0.52 e Å⁻³
7347 reflections	Δρ_min = −0.22 e Å⁻³
199 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
F4	0.45822 (10)	−0.05502 (7)	0.23042 (4)	0.0296 (2)
N1	0.25329 (11)	0.44506 (9)	−0.01000 (5)	0.0181 (2)
N3	0.32447 (11)	0.53932 (9)	0.11392 (5)	0.0204 (2)
C2	0.30699 (12)	0.42744 (10)	0.07314 (6)	0.0181 (2)
C4	0.27719 (14)	0.77382 (11)	0.06432 (7)	0.0224 (3)
C5	0.22041 (14)	0.84918 (11)	−0.00490 (7)	0.0241 (3)
C6	0.16727 (14)	0.79006 (11)	−0.08140 (7)	0.0242 (3)
C7	0.17379 (14)	0.65470 (11)	−0.09192 (6)	0.0227 (3)
C8	0.23331 (12)	0.57999 (10)	−0.02222 (6)	0.0184 (2)
C9	0.28005 (12)	0.63684 (10)	0.05527 (6)	0.0192 (2)
C11	0.21724 (12)	0.34608 (10)	−0.07164 (6)	0.0181 (2)
C12	0.29236 (14)	0.34944 (12)	−0.13497 (6)	0.0250 (3)
C13	0.25650 (17)	0.25270 (14)	−0.19472 (7)	0.0326 (4)
C14	0.14865 (18)	0.15428 (13)	−0.19126 (7)	0.0342 (4)
C15	0.07463 (16)	0.15197 (12)	−0.12781 (8)	0.0296 (3)
C16	0.10831 (13)	0.24826 (11)	−0.06771 (6)	0.0222 (3)
C21	0.34251 (12)	0.29683 (10)	0.11128 (6)	0.0184 (2)
C22	0.43985 (13)	0.20730 (11)	0.08453 (6)	0.0207 (3)
C23	0.47933 (13)	0.08832 (11)	0.12460 (6)	0.0226 (3)
C24	0.41834 (13)	0.06137 (11)	0.19050 (6)	0.0216 (3)
C25	0.31950 (14)	0.14570 (11)	0.21819 (6)	0.0240 (3)
C26	0.28287 (14)	0.26534 (11)	0.17816 (6)	0.0224 (3)
H4	0.31207	0.81317	0.11491	0.0269*
H5	0.21753	0.94056	−0.00049	0.0289*
H6	0.12661	0.84318	−0.12621	0.0290*
H7	0.14030	0.61573	−0.14271	0.0273*
H12	0.36522	0.41522	−0.13727	0.0299*
H13	0.30549	0.25419	−0.23741	0.0391*
H14	0.12581	0.08983	−0.23133	0.0410*
H15	0.00225	0.08581	−0.12547	0.0355*
H16	0.05837	0.24707	−0.02538	0.0266*
H22	0.47838	0.22748	0.03966	0.0248*
H23	0.54500	0.02834	0.10762	0.0271*
H25	0.27886	0.12332	0.26204	0.0288*
H26	0.21808	0.32514	0.19596	0.0269*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F4	0.0397 (4)	0.0227 (3)	0.0241 (3)	0.0008 (3)	0.0033 (3)	0.0082 (3)
N1	0.0235 (4)	0.0161 (3)	0.0140 (3)	−0.0019 (3)	0.0035 (3)	−0.0001 (3)
N3	0.0259 (4)	0.0195 (4)	0.0158 (3)	−0.0011 (3)	0.0051 (3)	−0.0005 (3)
C2	0.0208 (4)	0.0193 (4)	0.0144 (3)	−0.0009 (3)	0.0047 (3)	0.0010 (3)
C4	0.0266 (5)	0.0188 (4)	0.0221 (4)	−0.0028 (4)	0.0065 (4)	−0.0029 (4)
C5	0.0275 (5)	0.0183 (4)	0.0280 (5)	−0.0008 (4)	0.0096 (4)	0.0009 (4)
C6	0.0279 (5)	0.0209 (5)	0.0235 (4)	0.0007 (4)	0.0059 (4)	0.0055 (4)
C7	0.0279 (5)	0.0217 (5)	0.0174 (4)	−0.0007 (4)	0.0032 (3)	0.0028 (3)
C8	0.0214 (4)	0.0170 (4)	0.0167 (4)	−0.0021 (3)	0.0045 (3)	0.0002 (3)
C9	0.0214 (4)	0.0197 (4)	0.0167 (4)	−0.0021 (3)	0.0048 (3)	−0.0003 (3)
C11	0.0203 (4)	0.0186 (4)	0.0148 (3)	0.0007 (3)	0.0030 (3)	−0.0010 (3)
C12	0.0285 (5)	0.0289 (5)	0.0192 (4)	0.0028 (4)	0.0091 (4)	0.0010 (4)
C13	0.0437 (7)	0.0362 (7)	0.0192 (4)	0.0128 (6)	0.0102 (5)	−0.0029 (4)
C14	0.0464 (8)	0.0263 (6)	0.0244 (5)	0.0114 (5)	−0.0017 (5)	−0.0089 (4)
C15	0.0329 (6)	0.0203 (5)	0.0307 (5)	0.0001 (4)	−0.0017 (4)	−0.0051 (4)
C16	0.0236 (5)	0.0207 (4)	0.0211 (4)	−0.0011 (4)	0.0034 (3)	−0.0015 (4)
C21	0.0211 (4)	0.0194 (4)	0.0144 (3)	−0.0013 (3)	0.0039 (3)	0.0009 (3)
C22	0.0230 (4)	0.0222 (5)	0.0180 (4)	0.0003 (4)	0.0073 (3)	0.0027 (3)
C23	0.0244 (5)	0.0219 (5)	0.0218 (4)	0.0019 (4)	0.0062 (4)	0.0024 (4)
C24	0.0266 (5)	0.0189 (4)	0.0170 (4)	−0.0022 (4)	0.0010 (3)	0.0042 (3)
C25	0.0322 (5)	0.0244 (5)	0.0167 (4)	−0.0023 (4)	0.0086 (4)	0.0027 (4)
C26	0.0278 (5)	0.0233 (5)	0.0178 (4)	0.0009 (4)	0.0090 (4)	0.0008 (3)

Geometric parameters (Å, º) top

F4—C24	1.3633 (13)	C21—C22	1.3952 (15)
N1—C2	1.3890 (13)	C21—C26	1.4005 (15)
N1—C8	1.3877 (14)	C22—C23	1.3867 (15)
N1—C11	1.4298 (13)	C23—C24	1.3825 (15)
N3—C2	1.3186 (13)	C24—C25	1.3787 (16)
N3—C9	1.3908 (13)	C25—C26	1.3893 (15)
C2—C21	1.4735 (14)	C4—H4	0.9300
C4—C5	1.3897 (16)	C5—H5	0.9300
C4—C9	1.3976 (15)	C6—H6	0.9300
C5—C6	1.4050 (16)	C7—H7	0.9300
C6—C7	1.3864 (16)	C12—H12	0.9300
C7—C8	1.3961 (14)	C13—H13	0.9300
C8—C9	1.4052 (14)	C14—H14	0.9300
C11—C12	1.3939 (15)	C15—H15	0.9300
C11—C16	1.3883 (15)	C16—H16	0.9300
C12—C13	1.3919 (17)	C22—H22	0.9300
C13—C14	1.384 (2)	C23—H23	0.9300
C14—C15	1.3891 (19)	C25—H25	0.9300
C15—C16	1.3920 (17)	C26—H26	0.9300

C2—N1—C8	106.15 (8)	F4—C24—C25	118.13 (9)
C2—N1—C11	128.03 (9)	C23—C24—C25	123.67 (10)
C8—N1—C11	125.75 (8)	C24—C25—C26	117.52 (10)
C2—N3—C9	104.91 (8)	C21—C26—C25	120.69 (10)
N1—C2—N3	113.10 (9)	C5—C4—H4	121.00
N1—C2—C21	123.13 (9)	C9—C4—H4	121.00
N3—C2—C21	123.76 (9)	C4—C5—H5	119.00
C5—C4—C9	117.69 (10)	C6—C5—H5	119.00
C4—C5—C6	121.32 (10)	C5—C6—H6	119.00
C5—C6—C7	121.80 (10)	C7—C6—H6	119.00
C6—C7—C8	116.45 (10)	C6—C7—H7	122.00
N1—C8—C7	131.97 (9)	C8—C7—H7	122.00
N1—C8—C9	105.45 (8)	C11—C12—H12	121.00
C7—C8—C9	122.51 (9)	C13—C12—H12	121.00
N3—C9—C4	129.50 (9)	C12—C13—H13	120.00
N3—C9—C8	110.38 (9)	C14—C13—H13	120.00
C4—C9—C8	120.12 (9)	C13—C14—H14	120.00
N1—C11—C12	119.29 (10)	C15—C14—H14	120.00
N1—C11—C16	119.75 (9)	C14—C15—H15	120.00
C12—C11—C16	120.96 (10)	C16—C15—H15	120.00
C11—C12—C13	118.90 (11)	C11—C16—H16	120.00
C12—C13—C14	120.69 (12)	C15—C16—H16	120.00
C13—C14—C15	119.87 (12)	C21—C22—H22	120.00
C14—C15—C16	120.29 (12)	C23—C22—H22	120.00
C11—C16—C15	119.30 (10)	C22—C23—H23	121.00
C2—C21—C22	121.34 (9)	C24—C23—H23	121.00
C2—C21—C26	118.84 (9)	C24—C25—H25	121.00
C22—C21—C26	119.75 (10)	C26—C25—H25	121.00
C21—C22—C23	120.23 (10)	C21—C26—H26	120.00
C22—C23—C24	118.14 (10)	C25—C26—H26	120.00
F4—C24—C23	118.21 (10)

C8—N1—C2—N3	−0.88 (13)	C6—C7—C8—N1	178.40 (12)
C8—N1—C2—C21	179.88 (10)	C6—C7—C8—C9	1.94 (17)
C11—N1—C2—N3	−178.02 (10)	N1—C8—C9—N3	−1.25 (12)
C11—N1—C2—C21	2.74 (17)	N1—C8—C9—C4	178.72 (10)
C2—N1—C8—C7	−175.66 (12)	C7—C8—C9—N3	176.02 (10)
C2—N1—C8—C9	1.24 (12)	C7—C8—C9—C4	−4.00 (17)
C11—N1—C8—C7	1.56 (19)	N1—C11—C12—C13	−179.97 (12)
C11—N1—C8—C9	178.46 (10)	C16—C11—C12—C13	0.00 (17)
C2—N1—C11—C12	−123.95 (12)	N1—C11—C16—C15	−179.68 (10)
C2—N1—C11—C16	56.07 (16)	C12—C11—C16—C15	0.33 (17)
C8—N1—C11—C12	59.44 (15)	C11—C12—C13—C14	−0.32 (19)
C8—N1—C11—C16	−120.54 (12)	C12—C13—C14—C15	0.3 (2)
C9—N3—C2—N1	0.11 (13)	C13—C14—C15—C16	0.1 (2)
C9—N3—C2—C21	179.34 (10)	C14—C15—C16—C11	−0.36 (18)
C2—N3—C9—C4	−179.25 (12)	C2—C21—C22—C23	176.01 (10)
C2—N3—C9—C8	0.72 (12)	C26—C21—C22—C23	−0.90 (16)
N1—C2—C21—C22	50.81 (15)	C2—C21—C26—C25	−177.04 (10)
N1—C2—C21—C26	−132.26 (11)	C22—C21—C26—C25	−0.06 (17)
N3—C2—C21—C22	−128.35 (12)	C21—C22—C23—C24	0.67 (16)
N3—C2—C21—C26	48.58 (16)	C22—C23—C24—F4	−179.40 (10)
C9—C4—C5—C6	0.15 (18)	C22—C23—C24—C25	0.53 (17)
C5—C4—C9—N3	−177.21 (11)	F4—C24—C25—C26	178.48 (10)
C5—C4—C9—C8	2.83 (17)	C23—C24—C25—C26	−1.45 (17)
C4—C5—C6—C7	−2.2 (2)	C24—C25—C26—C21	1.18 (17)
C5—C6—C7—C8	1.13 (18)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the fused benzene ring (C4–C9).

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···F4ⁱ	0.93	2.46	3.3640 (14)	164
C7—H7···F4ⁱⁱ	0.93	2.43	3.3058 (13)	157
C26—H26···F4ⁱⁱⁱ	0.93	2.52	3.4348 (14)	166
C16—H16···Cg2^iv	0.93	2.75	3.5443 (12)	144
C22—H22···Cg2^v	0.93	2.80	3.5245 (13)	136

Symmetry codes: (i) x, y+1, z; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) −x, −y+1, −z; (v) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₃FN₂
M_r	288.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	123
a, b, c (Å)	8.7527 (4), 10.1342 (4), 17.0211 (6)
β (°)	104.187 (4)
V (Å³)	1463.75 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.47 × 0.42 × 0.15

Data collection
Diffractometer	Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.961, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13721, 7347, 5352
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.859

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.160, 1.04
No. of reflections	7347
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.22

Computer programs: CrysAlis PRO (Agilent, 2012), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), PLATON (Spek, 2009).