Imidazolium 3-nitro­benzoate

Abstract

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,

• a = 12.209 (2) Å

• b = 12.081 (2) Å

• c = 7.3216 (15) Å

• β = 106.38 (3)°

• V = 1036.1 (3) ų

• 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[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

N-bound H atoms were located in a difference Fourier map and refined freely. Other H atoms are placed in calculated positions (C–H = 0.93 Å) and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

C3H5N2+·C7H4NO4−	F(000) = 488
Mr = 235.20	Dx = 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

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

Refinement

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(Fo2) + (0.0443P)2 + 0.1735P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2369 reflections	Δρmax = 0.20 e Å−3
163 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) −x, y+1/2, −z+1/2.