Ortho­rhom­bic polymorph of 4-[(1H-benzimidazol-1-yl)meth­yl]benzoic acid

Kuai, H.-W.; Cheng, X.-C.

doi:10.1107/S1600536811042838

organic compounds

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Volume 67| Part 11| November 2011| Page o3014

doi:10.1107/S1600536811042838

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Orthorhombic polymorph of 4-[(1H-benzimidazol-1-yl)methyl]benzoic acid

Hai-Wei Kuai ^a ^* and Xiao-Chun Cheng ^a

^aFaculty of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaian 223003, People's Republic of China
^*Correspondence e-mail: hyitshy@126.com

(Received 13 August 2011; accepted 16 October 2011; online 22 October 2011)

We reported recently the first polymorph of the title compound [Kuai & Cheng (2011a ). Acta Cryst., E67, o2787]. A second polymorph of the title compound, C₁₅H₁₂N₂O₂, was unexpectedly obtained by the hydrothermal reaction of the title compound with manganese chloride in the presence of potassium hydroxide at 413 K. The benzimidazole ring system is almost planar, with a maximum deviation from the mean plane of 0.015 (2) Å. The benzimidazole and benzene rings are inclined at a dihedral angle of 79.00 (1)°. In the crystal, adjacent molecules are connected through O—H⋯N hydrogen bonds into a one-dimensional chain along the [001] direction.

Related literature

For the synthesis of 4-[(1H-benzo[d]imidazol-1-yl)methyl]benzoic acid, see: Hua et al. (2010 ). For two other polymorphs of the title compound, see: Kuai & Cheng (2011a,b ). For related structures, see Das & Bharadwaj (2009 ).

Experimental

Crystal data

C₁₅H₁₂N₂O₂
M_r = 252.27
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.6969 (15) Å
b = 12.657 (3) Å
c = 17.604 (5) Å
V = 1269.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.18 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.974, T_max = 0.984
7948 measured reflections
1786 independent reflections
1313 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.089
S = 0.99
1786 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H12⋯N12ⁱ	0.82	1.84	2.649 (3)	168
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811042838/aa2024sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042838/aa2024Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811042838/aa2024Isup4.cdx

Supporting information file. DOI: 10.1107/S1600536811042838/aa2024Isup4.cml

checkCIF report

Comment top

The title compound, C₁₅H₁₂N₂O₂ (I), is usually regarded as an excellent candidate for building block in molecular self-assembly engineering due to its variable conformation and coordination modes (Das & Bharadwaj, 2009). During assembly of a coordination polymer, we accidentally obtained three polymorphs of (I), which can be proved by different unit-cell parameters and space groups. Here, we are introducing one of them. The single crystals of (I) were accidentally obtained by the hydrothermal reaction at 413 K of (I) with manganese chloride in the presence of potassium hydroxide as alkaline medium for the deprotonation. As shown in Fig. 1, the asymmetric unit of (I) consists of only one molecule. Interestingly, though crystallizing from alkaline solution, (I) remains the intact carboxylic group in the crystal structure. The flexible benzimidazolyl arm is apt to rotate. As a result, the benzimidazolyl ring and central benzene rings are inclined at a dihedral angle of 79.00 (1) °; The torsion angles N11—C11—C1—C2 and N11—C11—C1—C6 are -61.8 (2) ° and 118.0 (2) °, respectively. Adjacent molecules are connected through O—H···N hydrogen bonds into a one-dimensional chain along [001] direction (Fig. 2, Table 1).

Related literature top

For the synthesis of 4-[(1H-benzo[d]imidazol-1-yl)methyl]benzoic acid, see: Hua et al. (2010). For two other polymorphs of the title compound, see: Kuai & Cheng (2011a,b). For related structures, see Das & Bharadwaj (2009).

Experimental top

Reaction mixture of MnCl₂ (21.5 mg, 0.1 mmol), 4-((1H-benzo[d]imidazol-1-yl)methyl)benzoic acid (25.2 mg, 0.1 mmol) and KOH (5.61 mg, 0.1 mmol) in 10 ml H₂O was sealed in a 16 ml Teflon-lined stainless steel container and heated to 413 K for 3 days. After cooling to the room temperature, colorless block crystals of the title compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. : The crystal structure of (I) showing 30% probability displacement ellipsoids.
	Fig. 2. : The packing diagram of (I). Hydrogen bonds are shown as dashed lines.

4-[(1H-benzimidazol-1-yl)methyl]benzoic acid top

Crystal data top

C₁₅H₁₂N₂O₂	F(000) = 528
M_r = 252.27	D_x = 1.320 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1326 reflections
a = 5.6969 (15) Å	θ = 2.3–19.9°
b = 12.657 (3) Å	µ = 0.09 mm⁻¹
c = 17.604 (5) Å	T = 293 K
V = 1269.4 (6) Å³	Block, colorless
Z = 4	0.30 × 0.18 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1786 independent reflections
Radiation source: fine-focus sealed tube	1313 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 28.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.974, T_max = 0.984	k = −14→16
7948 measured reflections	l = −23→20

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0455P)²] where P = (F_o² + 2F_c²)/3
1786 reflections	(Δ/σ)_max < 0.001
166 parameters	Δρ_max = 0.11 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₅H₁₂N₂O₂	V = 1269.4 (6) Å³
M_r = 252.27	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.6969 (15) Å	µ = 0.09 mm⁻¹
b = 12.657 (3) Å	T = 293 K
c = 17.604 (5) Å	0.30 × 0.18 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1786 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1313 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.984	R_int = 0.040
7948 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 0.99	Δρ_max = 0.11 e Å⁻³
1786 reflections	Δρ_min = −0.15 e Å⁻³
166 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 > σ(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. Absolute structure can not be determined in this case because of no heavy atoms present. Friedel-pair data are merged with the MERG 3 instruction. The number of Friedel pairs is 1229.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.3871 (4)	0.37836 (13)	1.03801 (9)	0.0731 (6)
H12	0.3280	0.3376	1.0688	0.088*
O2	0.0975 (4)	0.48320 (13)	1.07621 (9)	0.0650 (5)
N11	0.4456 (3)	0.78681 (13)	0.75703 (9)	0.0412 (4)
N12	0.2556 (4)	0.74457 (14)	0.65069 (10)	0.053
C4	0.3625 (4)	0.54619 (16)	0.98240 (11)	0.0390 (5)
C11	0.6074 (4)	0.77548 (17)	0.82087 (11)	0.0451 (5)
H6	0.6262	0.8434	0.8456	0.054*
H5	0.7598	0.7537	0.8019	0.054*
C13	0.1428 (4)	0.83025 (16)	0.68400 (11)	0.0417 (5)
C14	0.2622 (4)	0.85805 (15)	0.75045 (11)	0.0372 (5)
C6	0.6520 (4)	0.60602 (17)	0.89316 (11)	0.0458 (5)
H4	0.7940	0.5954	0.8682	0.055*
C5	0.5733 (4)	0.53174 (17)	0.94491 (11)	0.0473 (6)
H3	0.6627	0.4717	0.9545	0.057*
C41	0.2678 (5)	0.46665 (17)	1.03690 (11)	0.0472 (6)
C15	0.1919 (4)	0.94228 (17)	0.79536 (12)	0.0462 (6)
H8	0.2725	0.9610	0.8393	0.055*
C1	0.5221 (4)	0.69567 (16)	0.87823 (11)	0.0374 (5)
C17	−0.1262 (5)	0.9687 (2)	0.70573 (13)	0.0572 (7)
H10	−0.2587	1.0071	0.6920	0.069*
C12	0.4308 (5)	0.72183 (17)	0.69610 (12)	0.0510 (6)
H7	0.5348	0.6665	0.6873	0.061*
C16	−0.0036 (5)	0.99675 (19)	0.77139 (13)	0.0557 (6)
H9	−0.0557	1.0541	0.7998	0.067*
C2	0.3115 (4)	0.71014 (16)	0.91701 (11)	0.0437 (5)
H1	0.2224	0.7704	0.9081	0.052*
C3	0.2344 (4)	0.63641 (15)	0.96819 (11)	0.0426 (5)
H2	0.0936	0.6474	0.9937	0.051*
C18	−0.0555 (4)	0.88605 (18)	0.66126 (13)	0.0526 (6)
H11	−0.1370	0.8678	0.6174	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0997 (15)	0.0514 (10)	0.0681 (10)	0.0157 (11)	0.0362 (11)	0.0196 (8)
O2	0.0673 (13)	0.0707 (11)	0.0571 (9)	0.0034 (10)	0.0240 (10)	0.0109 (8)
N11	0.0449 (11)	0.0390 (9)	0.0396 (9)	−0.0030 (9)	−0.0010 (8)	0.0024 (8)
N12	0.072	0.044	0.042	−0.007	−0.005	−0.002
C4	0.0435 (13)	0.0422 (11)	0.0313 (10)	0.0001 (10)	0.0020 (10)	−0.0025 (8)
C11	0.0395 (13)	0.0473 (12)	0.0484 (12)	−0.0053 (11)	−0.0046 (11)	0.0069 (10)
C13	0.0494 (14)	0.0382 (11)	0.0375 (10)	−0.0108 (10)	−0.0017 (10)	0.0050 (9)
C14	0.0382 (12)	0.0354 (10)	0.0379 (10)	−0.0067 (9)	0.0022 (10)	0.0054 (9)
C6	0.0354 (13)	0.0556 (13)	0.0462 (12)	0.0063 (11)	0.0079 (11)	0.0022 (11)
C5	0.0509 (15)	0.0467 (12)	0.0442 (12)	0.0138 (11)	0.0048 (11)	0.0069 (10)
C41	0.0569 (15)	0.0505 (14)	0.0341 (10)	0.0001 (12)	0.0032 (12)	0.0005 (10)
C15	0.0542 (16)	0.0442 (12)	0.0404 (11)	−0.0009 (11)	−0.0001 (11)	0.0002 (10)
C1	0.0360 (12)	0.0400 (11)	0.0363 (10)	−0.0036 (9)	−0.0045 (9)	−0.0012 (9)
C17	0.0488 (15)	0.0614 (15)	0.0613 (15)	0.0054 (13)	−0.0005 (13)	0.0225 (13)
C12	0.0672 (17)	0.0371 (12)	0.0487 (12)	−0.0035 (12)	0.0066 (12)	−0.0026 (10)
C16	0.0621 (16)	0.0493 (13)	0.0557 (14)	0.0082 (12)	0.0102 (14)	0.0079 (11)
C2	0.0441 (14)	0.0394 (12)	0.0476 (11)	0.0064 (10)	0.0007 (11)	0.0004 (10)
C3	0.0395 (12)	0.0478 (12)	0.0403 (11)	0.0048 (10)	0.0054 (11)	−0.0039 (10)
C18	0.0535 (16)	0.0557 (14)	0.0487 (13)	−0.0134 (13)	−0.0128 (12)	0.0152 (12)

Geometric parameters (Å, º) top

O1—C41	1.308 (3)	C6—C1	1.380 (3)
O1—H12	0.8200	C6—C5	1.384 (3)
O2—C41	1.210 (3)	C6—H4	0.9300
N11—C12	1.354 (3)	C5—H3	0.9300
N11—C14	1.385 (3)	C15—C16	1.376 (3)
N11—C11	1.461 (3)	C15—H8	0.9300
N12—C12	1.311 (3)	C1—C2	1.392 (3)
N12—C13	1.390 (3)	C17—C18	1.367 (3)
C4—C3	1.378 (3)	C17—C16	1.396 (3)
C4—C5	1.382 (3)	C17—H10	0.9300
C4—C41	1.492 (3)	C12—H7	0.9300
C11—C1	1.509 (3)	C16—H9	0.9300
C11—H6	0.9700	C2—C3	1.369 (3)
C11—H5	0.9700	C2—H1	0.9300
C13—C18	1.391 (3)	C3—H2	0.9300
C13—C14	1.398 (3)	C18—H11	0.9300
C14—C15	1.386 (3)

C41—O1—H12	109.5	O2—C41—C4	122.8 (2)
C12—N11—C14	106.40 (18)	O1—C41—C4	113.5 (2)
C12—N11—C11	126.09 (19)	C16—C15—C14	116.4 (2)
C14—N11—C11	127.18 (16)	C16—C15—H8	121.8
C12—N12—C13	105.42 (18)	C14—C15—H8	121.8
C3—C4—C5	118.88 (19)	C6—C1—C2	118.50 (19)
C3—C4—C41	119.0 (2)	C6—C1—C11	120.3 (2)
C5—C4—C41	122.1 (2)	C2—C1—C11	121.2 (2)
N11—C11—C1	112.17 (17)	C18—C17—C16	121.4 (2)
N11—C11—H6	109.2	C18—C17—H10	119.3
C1—C11—H6	109.2	C16—C17—H10	119.3
N11—C11—H5	109.2	N12—C12—N11	113.4 (2)
C1—C11—H5	109.2	N12—C12—H7	123.3
H6—C11—H5	107.9	N11—C12—H7	123.3
N12—C13—C18	130.5 (2)	C15—C16—C17	122.1 (2)
N12—C13—C14	108.94 (19)	C15—C16—H9	119.0
C18—C13—C14	120.5 (2)	C17—C16—H9	119.0
N11—C14—C15	132.13 (19)	C3—C2—C1	120.6 (2)
N11—C14—C13	105.84 (17)	C3—C2—H1	119.7
C15—C14—C13	122.0 (2)	C1—C2—H1	119.7
C1—C6—C5	120.7 (2)	C2—C3—C4	121.0 (2)
C1—C6—H4	119.7	C2—C3—H2	119.5
C5—C6—H4	119.7	C4—C3—H2	119.5
C4—C5—C6	120.4 (2)	C17—C18—C13	117.6 (2)
C4—C5—H3	119.8	C17—C18—H11	121.2
C6—C5—H3	119.8	C13—C18—H11	121.2
O2—C41—O1	123.8 (2)

C12—N11—C11—C1	−80.9 (3)	N11—C14—C15—C16	−179.6 (2)
C14—N11—C11—C1	91.6 (2)	C13—C14—C15—C16	0.6 (3)
C12—N12—C13—C18	−178.9 (2)	C5—C6—C1—C2	0.7 (3)
C12—N12—C13—C14	1.0 (2)	C5—C6—C1—C11	−179.09 (19)
C12—N11—C14—C15	−179.4 (2)	N11—C11—C1—C6	118.0 (2)
C11—N11—C14—C15	7.0 (3)	N11—C11—C1—C2	−61.8 (2)
C12—N11—C14—C13	0.4 (2)	C13—N12—C12—N11	−0.7 (2)
C11—N11—C14—C13	−173.21 (18)	C14—N11—C12—N12	0.2 (2)
N12—C13—C14—N11	−0.9 (2)	C11—N11—C12—N12	173.93 (19)
C18—C13—C14—N11	179.04 (18)	C14—C15—C16—C17	0.4 (3)
N12—C13—C14—C15	179.0 (2)	C18—C17—C16—C15	−0.9 (4)
C18—C13—C14—C15	−1.1 (3)	C6—C1—C2—C3	−0.7 (3)
C3—C4—C5—C6	−1.0 (3)	C11—C1—C2—C3	179.11 (19)
C41—C4—C5—C6	178.2 (2)	C1—C2—C3—C4	−0.2 (3)
C1—C6—C5—C4	0.1 (3)	C5—C4—C3—C2	1.0 (3)
C3—C4—C41—O2	−9.2 (3)	C41—C4—C3—C2	−178.2 (2)
C5—C4—C41—O2	171.7 (2)	C16—C17—C18—C13	0.3 (3)
C3—C4—C41—O1	171.1 (2)	N12—C13—C18—C17	−179.5 (2)
C5—C4—C41—O1	−8.0 (3)	C14—C13—C18—C17	0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H12···N12ⁱ	0.82	1.84	2.649 (3)	168

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂N₂O₂
M_r	252.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	5.6969 (15), 12.657 (3), 17.604 (5)
V (Å³)	1269.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.18 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.974, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	7948, 1786, 1313
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.089, 0.99
No. of reflections	1786
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.15

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H12···N12ⁱ	0.82	1.84	2.649 (3)	168.1

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

Acknowledgements

The authors gratefully acknowledge the Natural Science Foundation of Jiangsu Province of China (grant No. BK2008195) for financial support of this work.

References

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