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

Ding, X.; Wang, S.; He, W.; Huang, W.

doi:10.1107/S1600536811039870

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2833

doi:10.1107/S1600536811039870

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

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

^aJiangsu Key Laboratory of Organic Electronics & Information Displays, Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications, Nanjing 210046, People's Republic of China
^*Correspondence e-mail: iamswang@njupt.edu.cn

(Received 21 September 2011; accepted 28 September 2011; online 5 October 2011)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.062
wR(F²) = 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

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
Symmetry codes: (i) -x+1, -y, -z; (ii) -x, -y+1, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y+1, -z; (v) -x, -y, -z+1; (vi) x-1, y, z; (vii) x+1, y, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811039870/kp2355sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811039870/kp2355Isup3.cml

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title cocrystal with the numbering scheme and 30% probability displacement ellipsoids.
	Fig. 2. The packing diagram of the molecules viewed along the b axis. Hydrogen bonds are drawn as dashed lines.
	Fig. 3. Packing diagram of the molecules. Hydrogen bonds are drawn as dashed lines.

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

Crystal data top

C₇H₆N₂·C₇H₄N₂O₆	Z = 4
M_r = 330.26	F(000) = 680
Triclinic, P1	D_x = 1.466 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4547 (15) Å	Cell parameters from 6830 reflections
b = 14.260 (3) Å	θ = 3.0–27.5°
c = 14.845 (3) Å	µ = 0.12 mm⁻¹
α = 108.01 (3)°	T = 293 K
β = 91.90 (3)°	Block, colorless
γ = 93.37 (3)°	0.35 × 0.22 × 0.20 mm
V = 1496.0 (5) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	6830 independent reflections
Radiation source: fine-focus sealed tube	3195 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
Detector resolution: 8.366 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −18→18
T_min = 0.969, T_max = 0.977	l = −19→19
15550 measured reflections

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0591P)²] where P = (F_o² + 2F_c²)/3
6830 reflections	(Δ/σ)_max < 0.001
461 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₇H₆N₂·C₇H₄N₂O₆	γ = 93.37 (3)°
M_r = 330.26	V = 1496.0 (5) Å³
Triclinic, P1	Z = 4
a = 7.4547 (15) Å	Mo Kα radiation
b = 14.260 (3) Å	µ = 0.12 mm⁻¹
c = 14.845 (3) Å	T = 293 K
α = 108.01 (3)°	0.35 × 0.22 × 0.20 mm
β = 91.90 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6830 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3195 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.977	R_int = 0.056
15550 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.16 e Å⁻³
6830 reflections	Δρ_min = −0.19 e Å⁻³
461 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	0.4080 (3)	0.01643 (18)	0.11993 (16)	0.0553 (6)
C2	0.3392 (3)	0.02905 (17)	0.21487 (15)	0.0490 (6)
C3	0.1637 (3)	−0.00114 (17)	0.22396 (15)	0.0490 (6)
H3A	0.0862	−0.0291	0.1707	0.059*
C4	0.1058 (3)	0.01088 (17)	0.31324 (16)	0.0506 (6)
C5	0.2159 (3)	0.05067 (18)	0.39350 (16)	0.0578 (6)
H5A	0.1751	0.0569	0.4534	0.069*
C6	0.3888 (3)	0.08091 (18)	0.38155 (16)	0.0544 (6)
C7	0.4516 (3)	0.07230 (17)	0.29418 (16)	0.0555 (6)
H7A	0.5686	0.0953	0.2884	0.067*
O1	0.3036 (2)	−0.03099 (14)	0.04900 (12)	0.0726 (6)
H1A	0.363 (5)	−0.035 (3)	−0.025 (3)	0.160 (14)*
O2	0.5615 (2)	0.05235 (14)	0.11410 (11)	0.0736 (5)
N1	−0.0818 (3)	−0.01956 (18)	0.32279 (18)	0.0721 (6)
O3	−0.1815 (2)	−0.04676 (16)	0.25263 (16)	0.0915 (7)
O4	−0.1288 (3)	−0.0171 (2)	0.40020 (16)	0.1302 (10)
N2	0.5102 (3)	0.12590 (18)	0.46559 (15)	0.0768 (7)
O5	0.4669 (3)	0.11480 (19)	0.53961 (14)	0.1112 (8)
O6	0.6490 (3)	0.16961 (19)	0.45609 (15)	0.1188 (9)
C8	0.3501 (3)	0.50842 (18)	0.10190 (17)	0.0544 (6)
C9	0.2362 (3)	0.50677 (16)	0.18160 (15)	0.0488 (6)
C10	0.0604 (3)	0.46720 (17)	0.16271 (16)	0.0536 (6)
H10A	0.0117	0.4431	0.1007	0.064*
C11	−0.0412 (3)	0.46423 (18)	0.23756 (17)	0.0527 (6)
C12	0.0242 (3)	0.49980 (17)	0.33016 (16)	0.0544 (6)
H12A	−0.0470	0.4979	0.3800	0.065*
C13	0.1991 (3)	0.53816 (17)	0.34579 (15)	0.0527 (6)
C14	0.3074 (3)	0.54240 (17)	0.27369 (16)	0.0517 (6)
H14A	0.4260	0.5687	0.2868	0.062*
N3	−0.2260 (3)	0.41929 (18)	0.21744 (18)	0.0714 (6)
O7	0.2803 (2)	0.47150 (15)	0.01875 (13)	0.0800 (6)
H9A	0.379 (6)	0.469 (3)	−0.047 (3)	0.203 (18)*
O8	0.5087 (2)	0.54478 (14)	0.12114 (12)	0.0714 (5)
O9	−0.2761 (2)	0.37659 (17)	0.13605 (16)	0.0941 (7)
O10	−0.3199 (2)	0.42753 (18)	0.28450 (15)	0.1015 (7)
O11	0.1742 (3)	0.58417 (17)	0.50753 (13)	0.1032 (7)
O12	0.4324 (3)	0.6007 (2)	0.45542 (14)	0.1205 (9)
N4	0.2750 (3)	0.57692 (17)	0.44339 (15)	0.0744 (6)
N5	0.3740 (4)	0.2057 (2)	−0.0240 (2)	0.1150 (10)
C15	0.2997 (4)	0.2144 (2)	0.0436 (2)	0.0796 (9)
C16	0.2076 (3)	0.22522 (19)	0.12900 (18)	0.0599 (7)
C17	0.0298 (4)	0.1905 (2)	0.1228 (2)	0.0735 (8)
H17A	−0.0302	0.1603	0.0641	0.088*
C18	−0.0566 (4)	0.2014 (2)	0.2050 (2)	0.0765 (8)
H18A	−0.180 (4)	0.1780 (19)	0.2036 (17)	0.086 (9)*
C19	0.0298 (4)	0.24544 (19)	0.2909 (2)	0.0685 (7)
H19A	−0.0323	0.2521	0.3456	0.082*
C20	0.2079 (3)	0.28052 (17)	0.29893 (18)	0.0596 (7)
C21	0.2961 (3)	0.27005 (18)	0.21579 (18)	0.0610 (7)
H21A	0.4159	0.2936	0.2189	0.073*
N6	0.2934 (5)	0.3273 (2)	0.3859 (2)	0.0891 (8)
H6A	0.240 (5)	0.317 (3)	0.437 (3)	0.127 (14)*
H6B	0.410 (4)	0.341 (2)	0.378 (2)	0.109 (13)*
N7	−0.1478 (4)	0.7302 (2)	0.4340 (2)	0.1190 (11)
C22	−0.0799 (4)	0.7346 (2)	0.3675 (2)	0.0822 (9)
C23	0.0139 (3)	0.73855 (18)	0.28564 (19)	0.0606 (7)
C24	−0.0753 (4)	0.7084 (2)	0.1977 (2)	0.0732 (8)
H24A	−0.1966	0.6869	0.1906	0.088*
C25	0.0187 (4)	0.7110 (2)	0.1210 (2)	0.0771 (8)
H25A	−0.0403	0.6921	0.0613	0.093*
C26	0.1980 (4)	0.74096 (19)	0.13031 (18)	0.0664 (7)
H26A	0.2596	0.7403	0.0767	0.080*
C27	0.2891 (3)	0.77223 (18)	0.21843 (18)	0.0584 (6)
C28	0.1939 (3)	0.76999 (17)	0.29630 (17)	0.0588 (6)
H28A	0.2519	0.7899	0.3563	0.071*
N8	0.4678 (4)	0.8027 (2)	0.2284 (3)	0.0883 (8)
H8A	0.524 (4)	0.806 (2)	0.176 (2)	0.103 (12)*
H8B	0.517 (5)	0.825 (3)	0.284 (3)	0.126 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0514 (14)	0.0662 (17)	0.0432 (14)	−0.0022 (12)	0.0060 (12)	0.0104 (13)
C2	0.0527 (14)	0.0535 (15)	0.0398 (13)	0.0060 (11)	0.0078 (11)	0.0119 (11)
C3	0.0552 (14)	0.0509 (14)	0.0424 (13)	0.0036 (11)	0.0047 (10)	0.0165 (11)
C4	0.0527 (13)	0.0536 (15)	0.0512 (15)	0.0053 (11)	0.0119 (11)	0.0233 (12)
C5	0.0707 (17)	0.0647 (17)	0.0426 (14)	0.0115 (13)	0.0127 (12)	0.0215 (13)
C6	0.0657 (15)	0.0574 (16)	0.0389 (13)	0.0058 (12)	0.0027 (11)	0.0129 (12)
C7	0.0528 (14)	0.0614 (16)	0.0509 (15)	0.0007 (12)	0.0048 (12)	0.0158 (13)
O1	0.0636 (10)	0.1044 (15)	0.0372 (10)	−0.0161 (10)	0.0058 (8)	0.0072 (10)
O2	0.0595 (11)	0.1067 (15)	0.0433 (10)	−0.0163 (10)	0.0104 (8)	0.0101 (10)
N1	0.0651 (15)	0.0872 (17)	0.0704 (17)	−0.0002 (12)	0.0185 (13)	0.0335 (14)
O3	0.0583 (11)	0.1231 (18)	0.0878 (15)	−0.0115 (11)	0.0058 (11)	0.0283 (14)
O4	0.0954 (16)	0.225 (3)	0.0855 (16)	−0.0204 (16)	0.0314 (13)	0.0746 (18)
N2	0.0839 (17)	0.0953 (19)	0.0439 (14)	−0.0009 (14)	−0.0024 (12)	0.0128 (13)
O5	0.1111 (17)	0.174 (2)	0.0451 (12)	−0.0154 (15)	−0.0068 (11)	0.0355 (14)
O6	0.1040 (17)	0.166 (2)	0.0704 (14)	−0.0510 (17)	−0.0168 (12)	0.0260 (15)
C8	0.0540 (15)	0.0601 (16)	0.0460 (15)	0.0010 (12)	0.0094 (12)	0.0121 (12)
C9	0.0539 (14)	0.0493 (14)	0.0433 (13)	0.0032 (11)	0.0108 (11)	0.0140 (11)
C10	0.0548 (14)	0.0584 (16)	0.0475 (14)	0.0034 (12)	0.0030 (11)	0.0163 (12)
C11	0.0449 (13)	0.0606 (16)	0.0584 (16)	0.0046 (11)	0.0109 (11)	0.0260 (13)
C12	0.0607 (15)	0.0575 (16)	0.0506 (15)	0.0067 (12)	0.0184 (12)	0.0231 (13)
C13	0.0616 (15)	0.0559 (15)	0.0408 (14)	−0.0003 (12)	0.0070 (11)	0.0157 (12)
C14	0.0508 (13)	0.0543 (15)	0.0487 (14)	−0.0002 (11)	0.0077 (11)	0.0143 (12)
N3	0.0505 (13)	0.0916 (18)	0.0756 (17)	0.0002 (12)	0.0066 (13)	0.0320 (15)
O7	0.0728 (12)	0.1110 (16)	0.0450 (11)	−0.0172 (10)	0.0127 (9)	0.0115 (11)
O8	0.0577 (11)	0.0959 (14)	0.0535 (11)	−0.0099 (10)	0.0156 (8)	0.0143 (10)
O9	0.0639 (12)	0.1283 (19)	0.0836 (15)	−0.0143 (11)	−0.0095 (11)	0.0288 (14)
O10	0.0590 (12)	0.158 (2)	0.0921 (16)	−0.0105 (12)	0.0214 (11)	0.0475 (15)
O11	0.1285 (17)	0.132 (2)	0.0450 (11)	−0.0182 (14)	0.0226 (12)	0.0245 (12)
O12	0.0902 (15)	0.187 (3)	0.0614 (13)	−0.0423 (16)	−0.0114 (11)	0.0159 (14)
N4	0.0881 (17)	0.0858 (18)	0.0440 (13)	−0.0099 (14)	0.0041 (13)	0.0154 (12)
N5	0.121 (2)	0.157 (3)	0.080 (2)	0.017 (2)	0.0235 (18)	0.053 (2)
C15	0.085 (2)	0.091 (2)	0.070 (2)	0.0088 (17)	0.0048 (17)	0.0367 (19)
C16	0.0650 (16)	0.0612 (17)	0.0546 (16)	0.0017 (13)	0.0008 (13)	0.0205 (14)
C17	0.0744 (18)	0.0696 (19)	0.0684 (19)	−0.0075 (15)	−0.0126 (15)	0.0137 (15)
C18	0.0634 (18)	0.075 (2)	0.087 (2)	−0.0125 (15)	0.0020 (17)	0.0222 (18)
C19	0.0726 (18)	0.0608 (18)	0.0721 (19)	0.0004 (14)	0.0124 (15)	0.0207 (15)
C20	0.0746 (17)	0.0462 (15)	0.0561 (17)	0.0016 (13)	−0.0079 (13)	0.0148 (13)
C21	0.0554 (14)	0.0606 (17)	0.0694 (18)	−0.0029 (12)	−0.0033 (13)	0.0258 (14)
N6	0.107 (2)	0.093 (2)	0.0613 (18)	−0.0088 (18)	−0.0128 (17)	0.0202 (15)
N7	0.146 (3)	0.112 (3)	0.107 (2)	0.0211 (19)	0.064 (2)	0.039 (2)
C22	0.091 (2)	0.071 (2)	0.087 (2)	0.0170 (16)	0.0310 (18)	0.0229 (18)
C23	0.0673 (16)	0.0535 (16)	0.0616 (17)	0.0104 (13)	0.0117 (14)	0.0168 (13)
C24	0.0606 (16)	0.0712 (19)	0.083 (2)	0.0050 (14)	−0.0036 (15)	0.0177 (17)
C25	0.090 (2)	0.076 (2)	0.0602 (18)	0.0097 (16)	−0.0166 (16)	0.0141 (16)
C26	0.0819 (19)	0.0663 (18)	0.0503 (16)	0.0071 (15)	0.0052 (14)	0.0169 (14)
C27	0.0653 (16)	0.0498 (15)	0.0593 (17)	0.0047 (12)	0.0038 (13)	0.0156 (13)
C28	0.0711 (17)	0.0541 (16)	0.0477 (15)	0.0046 (13)	−0.0056 (12)	0.0117 (13)
N8	0.0720 (18)	0.102 (2)	0.084 (2)	−0.0103 (15)	0.0072 (17)	0.0221 (19)

Geometric parameters (Å, º) top

C1—O2	1.243 (3)	N3—O10	1.216 (3)
C1—O1	1.271 (3)	O7—H9A	1.23 (5)
C1—C2	1.478 (3)	O11—N4	1.216 (3)
C2—C7	1.376 (3)	O12—N4	1.194 (3)
C2—C3	1.377 (3)	N5—C15	1.139 (3)
C3—C4	1.371 (3)	C15—C16	1.433 (4)
C3—H3A	0.9300	C16—C21	1.374 (3)
C4—C5	1.370 (3)	C16—C17	1.377 (3)
C4—N1	1.464 (3)	C17—C18	1.370 (4)
C5—C6	1.369 (3)	C17—H17A	0.9300
C5—H5A	0.9300	C18—C19	1.356 (4)
C6—C7	1.366 (3)	C18—H18A	0.96 (3)
C6—N2	1.466 (3)	C19—C20	1.379 (3)
C7—H7A	0.9300	C19—H19A	0.9300
O1—H1A	1.18 (4)	C20—N6	1.371 (3)
N1—O4	1.203 (3)	C20—C21	1.389 (3)
N1—O3	1.206 (3)	C21—H21A	0.9300
N2—O5	1.209 (3)	N6—H6A	0.92 (3)
N2—O6	1.211 (3)	N6—H6B	0.90 (3)
C8—O8	1.250 (3)	N7—C22	1.140 (3)
C8—O7	1.263 (3)	C22—C23	1.437 (4)
C8—C9	1.484 (3)	C23—C24	1.376 (4)
C9—C14	1.378 (3)	C23—C28	1.377 (3)
C9—C10	1.380 (3)	C24—C25	1.365 (4)
C10—C11	1.375 (3)	C24—H24A	0.9300
C10—H10A	0.9300	C25—C26	1.369 (4)
C11—C12	1.371 (3)	C25—H25A	0.9300
C11—N3	1.466 (3)	C26—C27	1.384 (3)
C12—C13	1.368 (3)	C26—H26A	0.9300
C12—H12A	0.9300	C27—N8	1.365 (3)
C13—C14	1.376 (3)	C27—C28	1.384 (3)
C13—N4	1.462 (3)	C28—H28A	0.9300
C14—H14A	0.9300	N8—H8A	0.91 (3)
N3—O9	1.208 (3)	N8—H8B	0.85 (3)

O2—C1—O1	124.3 (2)	O9—N3—C11	118.6 (2)
O2—C1—C2	118.9 (2)	O10—N3—C11	117.5 (2)
O1—C1—C2	116.8 (2)	C8—O7—H9A	116.9 (18)
C7—C2—C3	120.3 (2)	O12—N4—O11	123.8 (2)
C7—C2—C1	119.4 (2)	O12—N4—C13	118.0 (2)
C3—C2—C1	120.3 (2)	O11—N4—C13	118.3 (2)
C4—C3—C2	118.5 (2)	N5—C15—C16	179.5 (3)
C4—C3—H3A	120.8	C21—C16—C17	120.7 (2)
C2—C3—H3A	120.8	C21—C16—C15	120.2 (2)
C5—C4—C3	122.7 (2)	C17—C16—C15	119.1 (3)
C5—C4—N1	119.0 (2)	C18—C17—C16	118.5 (3)
C3—C4—N1	118.4 (2)	C18—C17—H17A	120.7
C6—C5—C4	117.1 (2)	C16—C17—H17A	120.7
C6—C5—H5A	121.5	C19—C18—C17	121.1 (3)
C4—C5—H5A	121.5	C19—C18—H18A	118.0 (15)
C7—C6—C5	122.4 (2)	C17—C18—H18A	120.9 (15)
C7—C6—N2	118.6 (2)	C18—C19—C20	121.4 (3)
C5—C6—N2	118.9 (2)	C18—C19—H19A	119.3
C6—C7—C2	119.0 (2)	C20—C19—H19A	119.3
C6—C7—H7A	120.5	N6—C20—C19	121.1 (3)
C2—C7—H7A	120.5	N6—C20—C21	121.1 (3)
C1—O1—H1A	113.5 (16)	C19—C20—C21	117.7 (2)
O4—N1—O3	123.0 (2)	C16—C21—C20	120.5 (2)
O4—N1—C4	118.5 (3)	C16—C21—H21A	119.7
O3—N1—C4	118.5 (2)	C20—C21—H21A	119.7
O5—N2—O6	124.3 (2)	C20—N6—H6A	116 (2)
O5—N2—C6	117.6 (2)	C20—N6—H6B	109 (2)
O6—N2—C6	118.1 (2)	H6A—N6—H6B	129 (3)
O8—C8—O7	124.3 (2)	N7—C22—C23	177.1 (4)
O8—C8—C9	118.2 (2)	C24—C23—C28	121.0 (2)
O7—C8—C9	117.5 (2)	C24—C23—C22	119.8 (3)
C14—C9—C10	120.4 (2)	C28—C23—C22	119.2 (3)
C14—C9—C8	120.0 (2)	C25—C24—C23	118.4 (3)
C10—C9—C8	119.6 (2)	C25—C24—H24A	120.8
C11—C10—C9	118.6 (2)	C23—C24—H24A	120.8
C11—C10—H10A	120.7	C24—C25—C26	121.3 (3)
C9—C10—H10A	120.7	C24—C25—H25A	119.3
C12—C11—C10	122.8 (2)	C26—C25—H25A	119.3
C12—C11—N3	118.6 (2)	C25—C26—C27	120.9 (3)
C10—C11—N3	118.6 (2)	C25—C26—H26A	119.5
C13—C12—C11	116.8 (2)	C27—C26—H26A	119.5
C13—C12—H12A	121.6	N8—C27—C26	121.3 (3)
C11—C12—H12A	121.6	N8—C27—C28	120.8 (3)
C12—C13—C14	122.9 (2)	C26—C27—C28	117.8 (2)
C12—C13—N4	118.8 (2)	C23—C28—C27	120.6 (2)
C14—C13—N4	118.2 (2)	C23—C28—H28A	119.7
C13—C14—C9	118.5 (2)	C27—C28—H28A	119.7
C13—C14—H14A	120.7	C27—N8—H8A	118 (2)
C9—C14—H14A	120.7	C27—N8—H8B	118 (2)
O9—N3—O10	123.9 (2)	H8A—N8—H8B	123 (3)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) −x, −y, −z+1; (vi) x−1, y, z; (vii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₇H₆N₂·C₇H₄N₂O₆
M_r	330.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.4547 (15), 14.260 (3), 14.845 (3)
α, β, γ (°)	108.01 (3), 91.90 (3), 93.37 (3)
V (Å³)	1496.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.35 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.969, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	15550, 6830, 3195
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.159, 0.99
No. of reflections	6830
No. of parameters	461
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.19

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), 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
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)	158.4
C12—H12A···O11ⁱⁱ	0.93	2.50	3.352 (3)	152.7
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)	152.5

Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) −x, −y, −z+1; (vi) x−1, y, z; (vii) x+1, y, z.

Acknowledgements

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

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