3-Amino­benzonitrile–3,5-dinitro­benzoic acid (1/1)

Xuehua Ding; Shi Wang; Wenrui He; Wei Huang

doi:10.1107/S1600536811039870

. 2011 Oct 5;67(Pt 11):o2833. doi: 10.1107/S1600536811039870

3-Aminobenzonitrile–3,5-dinitrobenzoic acid (1/1)

Xuehua Ding ^a, Shi Wang ^a,^*, Wenrui He ^a, Wei Huang ^a

PMCID: PMC3247572 PMID: 22219877

Abstract

The asymmetric unit of the title co-crystal, C₇H₆N₂·C₇H₄N₂O₆, contains two formula units of both components. The crystal structure is stabilized by intermolecular O—H⋯O, N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds, generating a two-dimensional wave-like network. π–π stacking interactions [centroid–centroid distances = 3.702 (2), 3.660 (2)and 3.671 (2) Å] stabilize the crystal packing.

Related literature

For general background to hydrogen bonding, see: Desiraju (2002 ▶); Prins et al. (2001 ▶); Steiner (2002 ▶). For background to the applications of co-crystals, see: Bhatt & Desiraju (2008 ▶); Etter & Baures (1988 ▶); Gao et al. (2004 ▶); Hori et al. (2009 ▶); Weyna et al. (2009 ▶). For the synthesis of co-crystals by complementary functional groups, see: Li et al. (2006 ▶); Roy et al. (2009 ▶); Wei (2007 ▶).

Experimental

Crystal data

C₇H₆N₂·C₇H₄N₂O₆
M _r = 330.26
Triclinic,
a = 7.4547 (15) Å
b = 14.260 (3) Å
c = 14.845 (3) Å
α = 108.01 (3)°
β = 91.90 (3)°
γ = 93.37 (3)°
V = 1496.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.35 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.969, T _max = 0.977
15550 measured reflections
6830 independent reflections
3195 reflections with I > 2σ(I)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.159
S = 0.99
6830 reflections
461 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811039870/kp2355sup1.cif

e-67-o2833-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811039870/kp2355Isup2.hkl

e-67-o2833-Isup2.hkl^{(334.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811039870/kp2355Isup3.cml

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
O1—H1A⋯O2ⁱ	1.18 (4)	1.41 (4)	2.590 (2)	173 (3)
N6—H6A⋯N7ⁱⁱ	0.92 (3)	2.32 (4)	3.232 (5)	169 (3)
N6—H6B⋯O12ⁱⁱⁱ	0.90 (3)	2.57 (3)	2.953 (4)	107 (2)
N8—H8A⋯N5^iv	0.91 (3)	2.37 (3)	3.262 (5)	170 (3)
N8—H8B⋯O5ⁱⁱⁱ	0.85 (3)	2.48 (4)	3.286 (4)	157 (3)
O7—H9A⋯O8^iv	1.23 (5)	1.38 (5)	2.608 (2)	174 (4)
C5—H5A⋯O4^v	0.93	2.44	3.321 (3)	158
C12—H12A⋯O11ⁱⁱ	0.93	2.50	3.352 (3)	153
C18—H18A⋯O2^vi	0.96 (3)	2.58 (3)	3.421 (4)	147 (2)
C21—H21A⋯O10^vii	0.93	2.60	3.451 (3)	153

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

This work was supported by NJ210003, BJ211008 and in part by the National Basic Research Program of China (2009CB930601).

supplementary crystallographic information

Comment

The self-assembly of two or more different types of molecules to form a multi-component crystal is greatly fascinating to chemists, known as cocrystals. The considerable effort has been devoted to cocrystal formation over decades, due to its extensive applications in construction of organic solid-state materials, such as in the pharmaceutical industry (Weyna et al., 2009), in organic synthesis (Gao et al., 2004), for promoting crystal growth (Etter & Baures, 1988), as luminescent materials (Hori et al., 2009), and for absolute structure determination (Bhatt & Desiraju, 2008). One of the important ways is the utilisation of self-assembly of small molecules through intermolecular interactions to construct cocrystals, which are one-, two- or three-dimensional networks. In the study of intermolecular interactions the central role is the hydrogen bond. The simple way of preparation of cocrystals is to employ the components containing functional groups with hydrogen bonding capability (Li et al., 2006; Roy et al., 2009; Wei, 2007), such as –COOH and –NH₂, which can easily result in O—H···N and N—H···O hydrogen bonds.

In this report we have established unambiguously the structure of the cocrystal 3,5-dinitrobenzoic acid with 3-aminobenzonitrile in the solid state by X-ray diffraction analysis. An asymmetric unit of the title compound contains two 3,5-dinitrobenzoic acid and two 3-aminobenzonitrile (Fig. 1). Intermolecular O—H···O, N—H···O, N—H···N and C—H···O hydrogen bonds are observed (Fig. 2, Table 1). The hydrogen bonds O—H···O between carboxyl groups results in the dimerization of 3,5-dinitrobenzoic acid. Extensive hydrogen-bonding interactions generate a two-dimensional wave-like network (Fig. 3).

Additionally, the crystal packing is stabilised by aromatic π–π stacking interactions involving the rings of the asymmetric unit with separation distances between their centroids: Cg1(C2→ C7)···Cg3 (C16→ C21) of 3.702 (2) Å, Cg2(C9→ C14)··· Cg3(C16→ C21) of 3.660 (2)Å, and Cg2(C9→ C14)···Cg4(C23→ C28) of 3.671 (2) Å.

Experimental

The cocrystals were prepared from stoichiometric amounts of components in water mixed with metanol (in volume ratio 1:1) and left to evaporate slowly at room temperature.