Imidazolium 3-nitro­benzoate

Hou, G.-Y.; Zhou, L.-N.; Yin, Q.-X.; Su, W.-Y.; Mao, H.-L.

doi:10.1107/S1600536809013142

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1038

doi:10.1107/S1600536809013142

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Imidazolium 3-nitrobenzoate

Guang-Yang Hou,^a Li-Na Zhou,^a Qiu-Xiang Yin,^a ^* Wei-Yi Su ^a and Hui-Lin Mao ^a

^aSchool of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: hougy@tju.edu.cn

(Received 24 March 2009; accepted 7 April 2009; online 18 April 2009)

In the title compound, C₃H₅N₂⁺·C₇H₄NO₄⁻, the benzene ring forms a dihedral angle of 40.60 (5)° with the imidizolium ring. The nitrobenzoate anion is approximately planar: the benzene ring makes dihedral angles of 3.8 (3) and 3.2 (1)° with the nitro and carboxylate groups, respectively. In the crystal structure, the cations and anions are linked by intermolecular N—H⋯O hydrogen bonds, forming a zigzag chain along the b axis.

Related literature

For general background to the physical and biological properties of imidazoles, see: Bunnage & Owen (2008 ); Ganellin & Fkyerat (1996 ); Weinreb (2007 ). For related structures of salts of imidazole with carboxylic acid derivatives, see: Mcdonald & Dorrestein (2001 ).

Experimental

Crystal data

C₃H₅N₂⁺·C₇H₄NO₄⁻
M_r = 235.20
Monoclinic, P 2₁ /c
a = 12.209 (2) Å
b = 12.081 (2) Å
c = 7.3216 (15) Å
β = 106.38 (3)°
V = 1036.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 K
0.38 × 0.21 × 0.13 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.956, T_max = 0.984
10057 measured reflections
2369 independent reflections
1571 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.108
S = 1.02
2369 reflections
163 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 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
N3—H1⋯O2	0.99 (2)	1.66 (2)	2.6502 (18)	177 (2)
N2—H2⋯O1ⁱ	0.94 (2)	1.74 (2)	2.677 (2)	175 (2)
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku/MSC, 2004 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013142/is2403sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013142/is2403Isup2.hkl

checkCIF report

Comment top

Imidazole is a commonly utilized substructure within the pharmaceutical industry, as the imidazole ring impart unique physical and biological properties to compounds of interest (Weinreb, 2007; Bunnage & Owen, 2008; Ganellin & Fkyerat, 1996). Synthetic imidazoles are always present in many fungicides and antifungal antiprotozoal, and antihypertensive medications. The crystal structures of salts between nitrobenzoic acids and imidazoles have been analyzed (Mcdonald & Dorrestein, 2001). As an extension study of hydrogen bonding pattern of nitrobenzoic acids and imidazoles herein we report the crystal structure of the title compound, (I).

The structure of the crystal is shown in Fig. 1. The asymmetric unit of the title compund contains one 3-nitrobenzote anion and one imidazolium cation. A proton transfer from the carboxyl group of 3-nitrobenzoic acid to atom N3 of imidazole. The corresponding C8—N3—C9 angle of the imidazole ring is 108.11 (15)°. The dihedral angle between the benzene ring of 3-nitrobenzote and imidazole ring is 40.60 (5)°. And the dihedral angles of the benzene with the nitro and carboxyl groups are 3.8 (3) and 3.2 (1)°, respectively. In the crystal structure, the crystal packing is consolidated by N—H···O intermolecular hydrogen bond.

Related literature top

For general background to the physical and biological

properties of imidazoles, see: Bunnage & Owen (2008); Ganellin & Fkyerat (1996); Weinreb (2007). For related structures of salts of imidazole with carboxylic acid derivatives, see: Mcdonald & Dorrestein (2001).

Experimental top

3-Nitrobenzoic acid and imidazole were mixed in water in a 1:1 molar ratio, then the suspension was heated to 343 K. The clear colourless solution obtained was cooled naturally to room temperature. Colourless crystals were obtained. Then the product was taken out from the solvent by tweezers, and dried in the air at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku/MSC, 2004); cell refinement: RAPID-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I). Dashed lines show N—H···O hydrogen bonds.

Imidazolium 3-nitrobenzoate top

Crystal data top

C₃H₅N₂⁺·C₇H₄NO₄⁻	F(000) = 488
M_r = 235.20	D_x = 1.508 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6213 reflections
a = 12.209 (2) Å	θ = 3.4–27.5°
b = 12.081 (2) Å	µ = 0.12 mm⁻¹
c = 7.3216 (15) Å	T = 298 K
β = 106.38 (3)°	Block, colourless
V = 1036.1 (3) Å³	0.38 × 0.21 × 0.13 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	2369 independent reflections
Radiation source: rotating anode	1571 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −15→14
T_min = 0.956, T_max = 0.984	k = −15→15
10057 measured reflections	l = −9→9

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)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0443P)² + 0.1735P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2369 reflections	Δρ_max = 0.20 e Å⁻³
163 parameters	Δρ_min = −0.17 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: 0.019 (3)

Crystal data top

C₃H₅N₂⁺·C₇H₄NO₄⁻	V = 1036.1 (3) Å³
M_r = 235.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.209 (2) Å	µ = 0.12 mm⁻¹
b = 12.081 (2) Å	T = 298 K
c = 7.3216 (15) Å	0.38 × 0.21 × 0.13 mm
β = 106.38 (3)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	2369 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1571 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.984	R_int = 0.051
10057 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.20 e Å⁻³
2369 reflections	Δρ_min = −0.17 e Å⁻³
163 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
C1	0.25763 (13)	0.52628 (15)	0.1825 (3)	0.0382 (4)
C2	0.35926 (13)	0.45955 (14)	0.1673 (2)	0.0337 (4)
C3	0.34637 (15)	0.36098 (15)	0.0674 (3)	0.0409 (4)
H3A	0.2733	0.3348	0.0082	0.049*
C4	0.44008 (17)	0.30055 (16)	0.0538 (3)	0.0470 (5)
H4A	0.4294	0.2345	−0.0142	0.056*
C5	0.54890 (16)	0.33750 (16)	0.1401 (3)	0.0463 (5)
H5A	0.6125	0.2971	0.1332	0.056*
C6	0.56048 (14)	0.43670 (15)	0.2374 (2)	0.0373 (4)
C7	0.46907 (13)	0.49843 (14)	0.2524 (2)	0.0352 (4)
H7A	0.4804	0.5652	0.3183	0.042*
C8	0.05956 (14)	0.80035 (16)	0.3479 (3)	0.0417 (4)
H8	0.1048	0.8624	0.3490	0.050*
C9	0.00096 (16)	0.63117 (17)	0.3339 (3)	0.0509 (5)
H9	−0.0009	0.5545	0.3227	0.061*
C10	−0.08242 (16)	0.69552 (17)	0.3607 (3)	0.0485 (5)
H10	−0.1528	0.6721	0.3719	0.058*
N1	0.67578 (12)	0.48134 (15)	0.3229 (2)	0.0460 (4)
H1	0.160 (2)	0.670 (2)	0.304 (3)	0.084 (8)*
H2	−0.0847 (18)	0.865 (2)	0.384 (3)	0.066 (6)*
N2	−0.04454 (13)	0.80152 (14)	0.3686 (2)	0.0432 (4)
N3	0.08885 (12)	0.69827 (13)	0.3259 (2)	0.0423 (4)
O1	0.16009 (9)	0.48714 (11)	0.1101 (2)	0.0507 (4)
O2	0.27753 (10)	0.61707 (11)	0.2665 (2)	0.0510 (4)
O3	0.68555 (10)	0.56865 (13)	0.4101 (2)	0.0574 (4)
O4	0.75732 (11)	0.42975 (14)	0.3012 (2)	0.0721 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0339 (8)	0.0330 (10)	0.0495 (11)	−0.0009 (7)	0.0148 (8)	0.0051 (8)
C2	0.0350 (8)	0.0296 (9)	0.0380 (9)	0.0006 (7)	0.0129 (7)	0.0043 (7)
C3	0.0442 (9)	0.0352 (10)	0.0444 (10)	−0.0038 (8)	0.0143 (8)	0.0009 (8)
C4	0.0624 (12)	0.0311 (10)	0.0527 (11)	0.0026 (8)	0.0246 (10)	−0.0023 (9)
C5	0.0506 (11)	0.0402 (11)	0.0548 (12)	0.0155 (8)	0.0256 (9)	0.0076 (9)
C6	0.0340 (8)	0.0392 (10)	0.0406 (10)	0.0064 (7)	0.0139 (7)	0.0082 (8)
C7	0.0363 (8)	0.0310 (9)	0.0411 (9)	0.0023 (7)	0.0157 (8)	0.0010 (7)
N1	0.0340 (8)	0.0561 (11)	0.0499 (10)	0.0087 (7)	0.0152 (7)	0.0108 (8)
O1	0.0309 (6)	0.0412 (8)	0.0769 (10)	−0.0044 (5)	0.0100 (6)	−0.0008 (7)
O2	0.0354 (6)	0.0370 (8)	0.0836 (10)	−0.0003 (5)	0.0215 (7)	−0.0128 (7)
O3	0.0398 (7)	0.0578 (10)	0.0742 (10)	−0.0063 (6)	0.0154 (7)	−0.0032 (8)
O4	0.0378 (7)	0.0952 (14)	0.0870 (12)	0.0218 (8)	0.0234 (8)	−0.0012 (10)
C8	0.0346 (9)	0.0400 (11)	0.0514 (11)	−0.0031 (7)	0.0137 (8)	−0.0015 (9)
C9	0.0518 (11)	0.0373 (11)	0.0667 (13)	−0.0075 (9)	0.0221 (10)	−0.0067 (10)
C10	0.0375 (9)	0.0534 (13)	0.0583 (12)	−0.0082 (8)	0.0194 (9)	−0.0060 (10)
N2	0.0373 (8)	0.0435 (10)	0.0500 (9)	0.0054 (7)	0.0144 (7)	−0.0031 (7)
N3	0.0352 (8)	0.0413 (9)	0.0523 (9)	0.0039 (7)	0.0153 (7)	−0.0048 (7)

Geometric parameters (Å, º) top

C8—N3	1.307 (2)	C2—C3	1.383 (2)
C8—N2	1.322 (2)	C2—C7	1.391 (2)
C8—H8	0.9300	C3—C4	1.384 (3)
C9—C10	1.339 (3)	C3—H3A	0.9300
C9—N3	1.359 (2)	C4—C5	1.375 (3)
C9—H9	0.9300	C4—H4A	0.9300
C10—N2	1.357 (2)	C5—C6	1.381 (2)
C10—H10	0.9300	C5—H5A	0.9300
N2—H2	0.94 (2)	C6—C7	1.372 (2)
N3—H1	0.99 (2)	C6—N1	1.472 (2)
C1—O2	1.247 (2)	C7—H7A	0.9300
C1—O1	1.252 (2)	N1—O3	1.221 (2)
C1—C2	1.510 (2)	N1—O4	1.2223 (19)

N3—C8—N2	109.25 (16)	C7—C2—C1	119.68 (15)
N3—C8—H8	125.4	C2—C3—C4	121.27 (17)
N2—C8—H8	125.4	C2—C3—H3A	119.4
C10—C9—N3	107.59 (17)	C4—C3—H3A	119.4
C10—C9—H9	126.2	C5—C4—C3	120.45 (18)
N3—C9—H9	126.2	C5—C4—H4A	119.8
C9—C10—N2	106.85 (16)	C3—C4—H4A	119.8
C9—C10—H10	126.6	C4—C5—C6	117.64 (16)
N2—C10—H10	126.6	C4—C5—H5A	121.2
C8—N2—C10	108.20 (16)	C6—C5—H5A	121.2
C8—N2—H2	125.1 (14)	C7—C6—C5	123.07 (17)
C10—N2—H2	126.7 (14)	C7—C6—N1	117.95 (16)
C8—N3—C9	108.11 (15)	C5—C6—N1	118.93 (15)
C8—N3—H1	128.8 (14)	C6—C7—C2	118.93 (16)
C9—N3—H1	123.1 (14)	C6—C7—H7A	120.5
O2—C1—O1	124.82 (16)	C2—C7—H7A	120.5
O2—C1—C2	117.12 (14)	O3—N1—O4	123.05 (17)
O1—C1—C2	118.06 (16)	O3—N1—C6	118.65 (14)
C3—C2—C7	118.62 (15)	O4—N1—C6	118.29 (17)
C3—C2—C1	121.69 (15)

N3—C9—C10—N2	0.1 (2)	C3—C4—C5—C6	−0.8 (3)
N3—C8—N2—C10	0.5 (2)	C4—C5—C6—C7	0.5 (3)
C9—C10—N2—C8	−0.4 (2)	C4—C5—C6—N1	−176.88 (16)
N2—C8—N3—C9	−0.4 (2)	C5—C6—C7—C2	0.5 (3)
C10—C9—N3—C8	0.2 (2)	N1—C6—C7—C2	177.96 (14)
O2—C1—C2—C3	−176.11 (16)	C3—C2—C7—C6	−1.3 (2)
O1—C1—C2—C3	3.7 (3)	C1—C2—C7—C6	179.92 (15)
O2—C1—C2—C7	2.6 (2)	C7—C6—N1—O3	3.0 (2)
O1—C1—C2—C7	−177.59 (16)	C5—C6—N1—O3	−179.45 (16)
C7—C2—C3—C4	1.0 (3)	C7—C6—N1—O4	−176.07 (16)
C1—C2—C3—C4	179.79 (16)	C5—C6—N1—O4	1.5 (2)
C2—C3—C4—C5	0.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O2	0.99 (2)	1.66 (2)	2.6502 (18)	177 (2)
N2—H2···O1ⁱ	0.94 (2)	1.74 (2)	2.677 (2)	175 (2)

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₃H₅N₂⁺·C₇H₄NO₄⁻
M_r	235.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.209 (2), 12.081 (2), 7.3216 (15)
β (°)	106.38 (3)
V (Å³)	1036.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.38 × 0.21 × 0.13

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.956, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	10057, 2369, 1571
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.108, 1.02
No. of reflections	2369
No. of parameters	163
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17

Computer programs: RAPID-AUTO (Rigaku/MSC, 2004), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O2	0.99 (2)	1.66 (2)	2.6502 (18)	177 (2)
N2—H2···O1ⁱ	0.94 (2)	1.74 (2)	2.677 (2)	175 (2)

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

The authors gratefully acknowledge financial support from the SRCICT of Tianjin University.

References

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