4-(Imidazol-1-yl)benzoic acid

Zheng, Z.; Geng, W.-Q.; Wu, Z.-C.; Zhou, H.-P.

doi:10.1107/S1600536811003345

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o524

doi:10.1107/S1600536811003345

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4-(Imidazol-1-yl)benzoic acid

Zheng Zheng,^a Wen-Qian Geng,^a Zhi-Chao Wu ^a and Hong-Ping Zhou ^a ^*

^aDepartment of Chemistry, Anhui University, Hefei 230039, People's Republic of China, and Key Laboratory of Functional Inorganic Materials Chemistry, Hefei 230039, People's Republic of China
^*Correspondence e-mail: zhpzhp@263.net

(Received 30 December 2010; accepted 25 January 2011; online 29 January 2011)

In the title molecule, C₁₀H₈N₂O₂, the imidazole and benzene rings form a dihedral angle of 14.5 (1)°. In the crystal, intermolecular O—H⋯N hydrogen bonds link the molecules into chains extending in [ $[\overline{1}]$ 01], which are further linked into sheets parallel to (102) through weak C—H⋯O interactions.

Related literature

The crystal structures of the Cd and Co complexes with the title molecule were described by Gao et al. (2009 ) and Zhang et al. (2007 ), respectively.

Experimental

Crystal data

C₁₀H₈N₂O₂
M_r = 188.18
Monoclinic, P c
a = 4.1443 (11) Å
b = 6.6561 (19) Å
c = 15.706 (4) Å
β = 101.023 (7)°
V = 425.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.969, T_max = 0.979
2483 measured reflections
782 independent reflections
626 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.104
S = 0.71
782 reflections
128 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.82	1.83	2.645 (5)	178
C9—H9⋯O2ⁱⁱ	0.93	2.42	3.332 (6)	168
Symmetry codes: (i) $[x-1, -y, z+{\script{1\over 2}}]$ ; (ii) $[x+1, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003345/cv5031sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003345/cv5031Isup2.hkl

checkCIF report

Comment top

The molecules of the title compound, (I), are often used as coordinating ligands in the metal complexes (Gao et al., 2009; Zhang et al., 2007). Herewith we presenet the crystal structure of (I).

In (I) (Fig.1), the imidazole ring is twisted out of the plane of benzene ring at 14.5 (1)°. In the crystal structure, intermolecular O—H···N hydrogen bonds (Table 1) link the molecules into chains extended in direction [-101]. These chains are further linked into sheets parallel to the plane (102) through the weak C—H···O interactions (Table 1).

Related literature top

The crystal structures of the Cd and Co complexes with the title molecule were described by Gao et al. (2009) and Zhang et al. (2007), respectively.

Experimental top

A 150 ml round-bottom flask was charged with a magnetic stirrer and a reflux condenser, iminazole (44 mmol), K₂CO₃ (6.00 g, 43 mmol), 30 ml DMSO and a little Aliquat 336 were added. 4-fluorobenzaldehyde (4.5 ml, 42 mmol) was added dropwise to the mixture at 363 K and stirred for 15 min. Then the reaction mixture was refluxed for 24 h at 353 K, cooled to room temperature, poured into 150 ml ice-water and filtered. The primrose yellow crude product was obtained, washed with distilled water, and dried in vacuo at room temperature, then purified by recrystallization with ethyl acetate to give the desired analytical pure intermediate products. Intermediate product (12.5 mmol) and 15 ml 20% (wt) NaOH (aq) were added to a round-bottom flask equipped with a magnetic stirrer and a reflux condenser at 333 K for 30 min. Then AgNO₃ (4.00 g, 24 mmol) was added to the mixture group by group. The reaction mixture was refluxed for 24 h at 333 K, cooled to room temperature and filtered. Excessive HCl (1 M) was added to the filtrate and adjust pH to 2, a great deal of sediments were obtained and then filtered. The crude product was recrystallized with ethanol. 4-imidazolylbenzoic acid: Yellow crystals. Weight: 1.44 g, Yield: 64%.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids.

4-(Imidazol-1-yl)benzoic acid top

Crystal data top

C₁₀H₈N₂O₂	F(000) = 196
M_r = 188.18	D_x = 1.470 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 4.1443 (11) Å	Cell parameters from 553 reflections
b = 6.6561 (19) Å	θ = 2.6–21.0°
c = 15.706 (4) Å	µ = 0.11 mm⁻¹
β = 101.023 (7)°	T = 296 K
V = 425.3 (2) Å³	Prism, yellow
Z = 2	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	782 independent reflections
Radiation source: fine-focus sealed tube	626 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −3→4
T_min = 0.969, T_max = 0.979	k = −7→8
2483 measured reflections	l = −18→19

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 0.71	w = 1/[σ²(F_o²) + (0.0601P)² + 0.4878P] where P = (F_o² + 2F_c²)/3
782 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.14 e Å⁻³
2 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₀H₈N₂O₂	V = 425.3 (2) Å³
M_r = 188.18	Z = 2
Monoclinic, Pc	Mo Kα radiation
a = 4.1443 (11) Å	µ = 0.11 mm⁻¹
b = 6.6561 (19) Å	T = 296 K
c = 15.706 (4) Å	0.30 × 0.20 × 0.20 mm
β = 101.023 (7)°

Data collection top

Bruker SMART CCD diffractometer	782 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	626 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.979	R_int = 0.032
2483 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	2 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 0.71	Δρ_max = 0.14 e Å⁻³
782 reflections	Δρ_min = −0.17 e Å⁻³
128 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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.

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

	x	y	z	U_iso*/U_eq
O1	0.4877 (9)	−0.2462 (5)	0.4370 (2)	0.0588 (9)
H1	0.4273	−0.2969	0.4789	0.088*
O2	0.5637 (9)	0.0207 (5)	0.52362 (19)	0.0599 (10)
N1	1.0752 (8)	0.3543 (5)	0.1902 (2)	0.0415 (9)
C9	1.2725 (12)	0.5824 (7)	0.1140 (3)	0.0569 (13)
H9	1.3408	0.7049	0.0952	0.068*
C2	0.7016 (11)	0.0470 (6)	0.3847 (3)	0.0413 (10)
C4	0.8260 (11)	0.0591 (6)	0.2410 (3)	0.0444 (11)
H4	0.8267	−0.0025	0.1878	0.053*
C7	0.8116 (11)	0.2437 (7)	0.3973 (3)	0.0499 (11)
H7	0.8012	0.3079	0.4493	0.060*
C3	0.7080 (10)	−0.0435 (7)	0.3054 (3)	0.0462 (11)
H3	0.6322	−0.1745	0.2954	0.055*
N2	1.2859 (9)	0.4028 (6)	0.0725 (2)	0.0518 (10)
C6	0.9360 (11)	0.3462 (7)	0.3342 (3)	0.0491 (12)
H6	1.0147	0.4766	0.3443	0.059*
C1	0.5766 (11)	−0.0580 (6)	0.4551 (3)	0.0465 (11)
C5	0.9428 (9)	0.2532 (6)	0.2556 (3)	0.0399 (10)
C8	1.1662 (11)	0.2706 (7)	0.1202 (2)	0.0466 (11)
H8	1.1463	0.1343	0.1071	0.056*
C10	1.1460 (13)	0.5559 (7)	0.1859 (3)	0.0548 (12)
H10	1.1128	0.6547	0.2252	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.088 (3)	0.047 (2)	0.0476 (17)	−0.0050 (18)	0.0288 (17)	−0.0015 (14)
O2	0.094 (3)	0.049 (2)	0.0417 (17)	0.0028 (19)	0.0252 (18)	−0.0047 (16)
N1	0.050 (2)	0.0351 (18)	0.041 (2)	0.0025 (17)	0.0151 (16)	−0.0019 (17)
C9	0.074 (4)	0.043 (3)	0.059 (3)	−0.003 (2)	0.025 (2)	0.006 (2)
C2	0.045 (2)	0.042 (3)	0.037 (2)	0.006 (2)	0.0100 (17)	−0.0013 (19)
C4	0.055 (3)	0.045 (3)	0.036 (2)	−0.001 (2)	0.0162 (19)	−0.0062 (19)
C7	0.068 (3)	0.041 (3)	0.042 (2)	0.004 (2)	0.014 (2)	−0.008 (2)
C3	0.056 (3)	0.040 (2)	0.045 (2)	−0.003 (2)	0.014 (2)	−0.0038 (19)
N2	0.063 (3)	0.048 (2)	0.047 (2)	−0.0019 (19)	0.0190 (17)	0.0003 (18)
C6	0.065 (3)	0.038 (2)	0.045 (3)	0.001 (2)	0.013 (2)	−0.006 (2)
C1	0.059 (3)	0.039 (3)	0.042 (2)	0.006 (2)	0.010 (2)	0.003 (2)
C5	0.042 (2)	0.040 (2)	0.038 (2)	0.0084 (18)	0.0089 (18)	0.0003 (19)
C8	0.059 (3)	0.041 (2)	0.042 (3)	0.002 (2)	0.015 (2)	−0.0038 (18)
C10	0.072 (3)	0.036 (2)	0.064 (3)	0.000 (2)	0.030 (3)	−0.003 (2)

Geometric parameters (Å, º) top

O1—C1	1.321 (6)	C4—C3	1.385 (5)
O1—H1	0.8200	C4—C5	1.384 (5)
O2—C1	1.207 (5)	C4—H4	0.9300
N1—C8	1.350 (5)	C7—C6	1.382 (6)
N1—C10	1.378 (5)	C7—H7	0.9300
N1—C5	1.423 (5)	C3—H3	0.9300
C9—C10	1.345 (6)	N2—C8	1.313 (5)
C9—N2	1.368 (6)	C6—C5	1.385 (5)
C9—H9	0.9300	C6—H6	0.9300
C2—C7	1.388 (6)	C8—H8	0.9300
C2—C3	1.388 (6)	C10—H10	0.9300
C2—C1	1.483 (6)

C1—O1—H1	109.5	C2—C3—H3	119.6
C8—N1—C10	105.5 (4)	C8—N2—C9	105.1 (4)
C8—N1—C5	126.9 (3)	C7—C6—C5	119.5 (4)
C10—N1—C5	127.7 (3)	C7—C6—H6	120.3
C10—C9—N2	110.1 (4)	C5—C6—H6	120.3
C10—C9—H9	124.9	O2—C1—O1	123.1 (4)
N2—C9—H9	124.9	O2—C1—C2	122.8 (4)
C7—C2—C3	118.4 (4)	O1—C1—C2	114.1 (4)
C7—C2—C1	119.3 (4)	C4—C5—C6	120.0 (4)
C3—C2—C1	122.3 (4)	C4—C5—N1	119.5 (4)
C3—C4—C5	120.0 (4)	C6—C5—N1	120.5 (4)
C3—C4—H4	120.0	N2—C8—N1	112.5 (4)
C5—C4—H4	120.0	N2—C8—H8	123.7
C6—C7—C2	121.3 (4)	N1—C8—H8	123.7
C6—C7—H7	119.3	C9—C10—N1	106.8 (4)
C2—C7—H7	119.3	C9—C10—H10	126.6
C4—C3—C2	120.8 (4)	N1—C10—H10	126.6
C4—C3—H3	119.6

C3—C2—C7—C6	−2.3 (7)	C7—C6—C5—C4	−0.1 (6)
C1—C2—C7—C6	178.7 (4)	C7—C6—C5—N1	−178.8 (4)
C5—C4—C3—C2	0.7 (6)	C8—N1—C5—C4	−14.9 (6)
C7—C2—C3—C4	1.0 (7)	C10—N1—C5—C4	167.0 (4)
C1—C2—C3—C4	179.9 (4)	C8—N1—C5—C6	163.9 (4)
C10—C9—N2—C8	0.1 (5)	C10—N1—C5—C6	−14.3 (7)
C2—C7—C6—C5	1.9 (7)	C9—N2—C8—N1	0.1 (5)
C7—C2—C1—O2	0.5 (7)	C10—N1—C8—N2	−0.3 (5)
C3—C2—C1—O2	−178.4 (5)	C5—N1—C8—N2	−178.7 (4)
C7—C2—C1—O1	−178.1 (5)	N2—C9—C10—N1	−0.3 (6)
C3—C2—C1—O1	3.0 (6)	C8—N1—C10—C9	0.4 (5)
C3—C4—C5—C6	−1.2 (6)	C5—N1—C10—C9	178.8 (4)
C3—C4—C5—N1	177.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.82	1.83	2.645 (5)	178
C9—H9···O2ⁱⁱ	0.93	2.42	3.332 (6)	168

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

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂O₂
M_r	188.18
Crystal system, space group	Monoclinic, Pc
Temperature (K)	296
a, b, c (Å)	4.1443 (11), 6.6561 (19), 15.706 (4)
β (°)	101.023 (7)
V (Å³)	425.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.969, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	2483, 782, 626
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.104, 0.71
No. of reflections	782
No. of parameters	128
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.17

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.82	1.83	2.645 (5)	178
C9—H9···O2ⁱⁱ	0.93	2.42	3.332 (6)	168

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21071001), the Education Committee of Anhui Province (KJ2009A52, KJ2010A30), the Team for Scientific Innovation Foundation of Anhui Province (2006 K J007TD), the Ministry of Education and Person with Ability Foundation of Anhui University, the Science and Technological Fund of Anhui Province for Outstanding Youth (10040606Y22) and the 211 Project of Anhui University.

References

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