4-Nitro­benzoic acid–N-(pyrimidin-2-yl)aniline (1/1)

Aznan, A.M.A.; Abdullah, Z.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811044175

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages o3080-o3081

doi:10.1107/S1600536811044175

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4-Nitrobenzoic acid–N-(pyrimidin-2-yl)aniline (1/1)

Aina Mardia Akhmad Aznan,^a Zanariah Abdullah,^a ‡ Seik Weng Ng ^a,^b and Edward R. T. Tiekink ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^bChemistry Department, Faculty of, Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 6 October 2011; accepted 24 October 2011; online 29 October 2011)

Four independent molecules comprise the asymmetric unit of the title co-crystal, C₁₀H₉N₃·C₇H₅NO₄, two for each component. Small conformational differences are noted for the benzoic acid derivatives, notably in the twists of the carboxylic acid residue out of the plane of the benzene ring to which it is connected [torsion angles = 167.62 (17) and 174.54 (17)°]. In the aniline derivative, the major difference is observed in the dihedral angles formed between the CN₃ and phenyl least-squares planes [1.51 (5) and 6.25 (6)°]. Pairs of molecules associate via O—H⋯N and N—H⋯O hydrogen bonds leading to eight-membered {⋯HOCO⋯HNCN} hetero-synthons. The two-molecule aggregates are consolidated in the crystal structure by C—H⋯O(nitro) and π–π interactions [shortest centroid–centroid distance between benzene rings = 3.6242 (10) Å].

Related literature

For related studies in co-crystal formation, see: Wardell & Tiekink (2011 ). For the structure of N-(pyrimidin-2-yl)aniline, see: Badaruddin et al. (2009 ). For the structure of 4-nitrobenzoic acid, see: Tonogaki et al. (1993 ).

Experimental

Crystal data

C₁₀H₉N₃·C₇H₅NO₄
M_r = 338.32
Monoclinic, P 2₁ /c
a = 12.7754 (4) Å
b = 25.7788 (8) Å
c = 9.5813 (3) Å
β = 104.209 (4)°
V = 3058.92 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.35 × 0.30 × 0.25 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.856, T_max = 1.000
15808 measured reflections
6818 independent reflections
5093 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.118
S = 1.03
6818 reflections
463 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2o⋯N2	0.87 (1)	1.70 (1)	2.5581 (18)	171 (2)
O6—H6o⋯N5	0.85 (1)	1.78 (1)	2.6230 (18)	171 (2)
N1—H1n⋯O1	0.88 (1)	2.15 (1)	3.0217 (18)	176 (2)
N4—H4n⋯O5	0.88 (1)	2.14 (1)	3.0190 (19)	180 (2)
C2—H2⋯O8	0.95	2.41	3.201 (2)	141
C12—H12⋯O4	0.95	2.43	3.106 (2)	128
C18—H18⋯O7ⁱ	0.95	2.56	3.330 (2)	138
C19—H19⋯O3ⁱⁱ	0.95	2.60	3.518 (2)	163
C31—H31⋯O8ⁱⁱⁱ	0.95	2.55	3.238 (2)	129
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ), QMol (Gans & Shalloway, 2001 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811044175/ez2266sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044175/ez2266Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811044175/ez2266Isup3.cml

checkCIF report

Comment top

In continuation of recent studies into the phenomenon of co-crystal formation (Wardell & Tiekink, 2011), the title 1:1 carboxylic acid–secondary amine co-crystal, (I), was prepared. There are two independent molecules of each of 4-nitrobenzoic acid and N-(pyrimidin-2-yl)aniline comprising the crystallographic asymmetric unit of (I), Fig. 1.

The two independent molecules of 4-nitrobenzoic acid differ from each other marginally, and from the conformation found in the crystal structure of 4-nitrobenzoic acid (Tonogaki et al., 1993), Fig. 2. In each molecule of (I) there are small twists of the carboxylic acid residue out of the plane of the benzene ring to which it is connected, i.e. the O1—C21—C22—C23 and O5—C28—C29—C30 torsion angles are 167.62 (17) and 174.54 (17)°, respectively, and deviate from planarity compared with the equivalent torsion angle of 178.39 (4)° found in the literature structure (Tonogaki et al., 1993). Less variation is noted for the relative orientation of the nitro groups in (I). Thus, the O3—N7—C25—C26 and O7—N8—C32—C33 torsion angles of 2.7 (3) and -3.0 (2) °, respectively, indicate a similarity in their orientations in (I), and smaller deviations from co-planarity than observed in the literature structure [torsion angle = -14.78 (7)°].

Differences are also noted in the relative conformations found for the N-(pyrimidin-2-yl)aniline molecules in (I) and with those found in the crystal structure of N-(pyrimidin-2-yl)aniline (Badaruddin et al., 2009), Fig. 3. For the two independent molecules in (I), one of the pyrazinyl rings is twisted out of the CN₃ plane [the C4—N3—C1—N1 torsion angle is -174.73 (16)°] whereas the other sees both least-squares planes co-planar; the C14—N6—C11—N4 torsion angle is -0.4 (3)°. In the literature structure, the two planes are effectively co-planar with the greatest deviation in the comparable C—N—C—N torsion angles being 177.12 (10)°. Significantly greater differences are noted in the twists between the CN₃ and benzene least-squares planes. Thus, in (I), the two dihedral angles indicate a close to co-planar relationship between these residues, i.e. 1.51 (5) and 6.25 (6)°. By contrast, in the literature structure of N-(pyrimidin-2-yl)aniline (Badaruddin et al., 2009), the equivalent dihedral angles are 31.47 (4) and 29.59 (4)°, i.e. indicating significant twisting in the molecules.

In the crystal structure, two pairs of the four independent molecules comprising the asymmetric unit are connected into two molecule aggregates, Table 1 and Fig. 4. Eight-membered hetero-synthons are formed as the each carboxylic acid residue forms hydrogen bonds with the amino-H and one of the pyrazinyl-N atoms. The two molecular aggregates are connected into the three-dimensional architecture via C—H···O(nitro) interactions, Table 1, and several π–π interactions. The shortest of the latter, 3.6242 (10) Å, occurs between centrosymmetrically related (C22–C27)ⁱ rings; symmetry operation i: 2 - x, 1 - y, 1 - z. A view of the unit cell contents is shown in Fig. 5.

Related literature top

For related studies in co-crystal formation, see: Wardell & Tiekink (2011). For the structure of N-(pyrimidin-2-yl)aniline, see: Badaruddin et al. (2009). For the structure of 4-nitrobenzoic acid, see: Tonogaki et al. (1993).

Experimental top

N-(Pyrimidin-2-yl)aniline (0.05 g, 0.00029 mol) and 4-nitrobenzoic acid (0.048 g, 0.00029 mol) were refluxed in a solution comprising ethyl acetate (3 ml) and tetrahydrofuran (3 ml) for 2.5 h at 333 K. The mixture was then stirred overnight and left for crystallization. Yellow crystals formed after three to four days; M.pt: 397–398 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structures of the four molecules comprising the asymmetric unit in (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. An overlay diagram of the two 4-nitrobenzoic acid molecules in (I) with the literature structure (see text). The red and blue images illustrate the O1- and O5-containing molecules of (I), respectively, and the green image illustrates the literature structure.
	Fig. 3. An overlay diagram of the two N-(pyrimidin-2-yl)aniline molecules in (I) with the literature structure which also contains two independent molecules (see text). The red and blue images illustrate the N1- and N4-containing molecules of (I), respectively. The green and black images illustrate the two molecules in the literature structure.
	Fig. 4. Two supramolecular two molecule aggregates in (I) mediated by O—H···N and N—H···O hydrogen bonds shown as orange and blue dashed lines, respectively.
	Fig. 5. A view in projection down the c axis of the unit-cell contents of (I). The O—H···N, N—H···O and C—H···O interactions are shown as orange, blue and green dashed lines, respectively.

4-Nitrobenzoic acid–N-(pyrimidin-2-yl)aniline (1/1) top

Crystal data top

C₁₀H₉N₃·C₇H₅NO₄	F(000) = 1408
M_r = 338.32	D_x = 1.469 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5286 reflections
a = 12.7754 (4) Å	θ = 2.3–29.3°
b = 25.7788 (8) Å	µ = 0.11 mm⁻¹
c = 9.5813 (3) Å	T = 100 K
β = 104.209 (4)°	Block, colourless
V = 3058.92 (17) Å³	0.35 × 0.30 × 0.25 mm
Z = 8

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	6818 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	5093 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.031
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.3°
ω scan	h = −16→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −25→33
T_min = 0.856, T_max = 1.000	l = −12→11
15808 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0435P)² + 1.2445P] where P = (F_o² + 2F_c²)/3
6818 reflections	(Δ/σ)_max < 0.001
463 parameters	Δρ_max = 0.26 e Å⁻³
4 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₀H₉N₃·C₇H₅NO₄	V = 3058.92 (17) Å³
M_r = 338.32	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.7754 (4) Å	µ = 0.11 mm⁻¹
b = 25.7788 (8) Å	T = 100 K
c = 9.5813 (3) Å	0.35 × 0.30 × 0.25 mm
β = 104.209 (4)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	6818 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	5093 reflections with I > 2σ(I)
T_min = 0.856, T_max = 1.000	R_int = 0.031
15808 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	4 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.26 e Å⁻³
6818 reflections	Δρ_min = −0.28 e Å⁻³
463 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.85371 (10)	0.60855 (5)	0.50402 (13)	0.0228 (3)
O2	0.73858 (10)	0.55038 (5)	0.55581 (14)	0.0244 (3)
H2O	0.7228 (17)	0.5752 (6)	0.608 (2)	0.037*
O3	1.04527 (12)	0.41493 (6)	0.13302 (18)	0.0414 (4)
O4	0.95094 (12)	0.35836 (5)	0.21412 (17)	0.0382 (4)
O5	0.60266 (10)	0.23665 (5)	0.43762 (14)	0.0236 (3)
O6	0.67258 (11)	0.29895 (5)	0.32451 (14)	0.0264 (3)
H6O	0.7045 (17)	0.2740 (6)	0.294 (2)	0.040*
O7	0.39904 (11)	0.43347 (5)	0.78791 (14)	0.0292 (3)
O8	0.48451 (11)	0.49026 (5)	0.69235 (14)	0.0268 (3)
N1	0.75301 (12)	0.69124 (6)	0.65279 (16)	0.0184 (3)
H1N	0.7837 (14)	0.6684 (6)	0.6080 (19)	0.022*
N2	0.67877 (11)	0.61741 (5)	0.71728 (15)	0.0179 (3)
N3	0.63472 (12)	0.69905 (5)	0.80552 (15)	0.0182 (3)
N4	0.74841 (12)	0.15764 (6)	0.34898 (16)	0.0206 (3)
H4N	0.7060 (13)	0.1808 (6)	0.375 (2)	0.025*
N5	0.78776 (12)	0.22892 (6)	0.23078 (16)	0.0195 (3)
N6	0.87374 (12)	0.14807 (6)	0.20705 (16)	0.0208 (3)
N7	0.97993 (13)	0.40311 (6)	0.20136 (18)	0.0272 (4)
N8	0.45857 (12)	0.44542 (6)	0.71057 (15)	0.0196 (3)
C1	0.68704 (14)	0.66985 (7)	0.72861 (18)	0.0168 (4)
C2	0.62103 (14)	0.59339 (7)	0.79624 (19)	0.0201 (4)
H2	0.6140	0.5567	0.7900	0.024*
C3	0.57137 (14)	0.61991 (7)	0.88640 (19)	0.0206 (4)
H3	0.5336	0.6025	0.9466	0.025*
C4	0.57942 (14)	0.67334 (7)	0.88454 (18)	0.0191 (4)
H4	0.5435	0.6928	0.9429	0.023*
C5	0.78214 (14)	0.74334 (7)	0.63821 (18)	0.0173 (4)
C6	0.85205 (14)	0.75203 (7)	0.54896 (19)	0.0191 (4)
H6	0.8780	0.7234	0.5047	0.023*
C7	0.88375 (14)	0.80179 (7)	0.52446 (19)	0.0213 (4)
H7	0.9305	0.8072	0.4625	0.026*
C8	0.84778 (15)	0.84381 (7)	0.58981 (19)	0.0212 (4)
H8	0.8695	0.8780	0.5731	0.025*
C9	0.77973 (15)	0.83529 (7)	0.67983 (19)	0.0214 (4)
H9	0.7554	0.8640	0.7257	0.026*
C10	0.74631 (15)	0.78552 (7)	0.70434 (19)	0.0202 (4)
H10	0.6992	0.7803	0.7660	0.024*
C11	0.80609 (14)	0.17769 (7)	0.25915 (18)	0.0183 (4)
C12	0.84094 (14)	0.25086 (7)	0.14286 (19)	0.0211 (4)
H12	0.8299	0.2867	0.1210	0.025*
C13	0.91108 (15)	0.22362 (7)	0.0826 (2)	0.0233 (4)
H13	0.9477	0.2395	0.0186	0.028*
C14	0.92555 (14)	0.17199 (7)	0.11999 (19)	0.0214 (4)
H14	0.9750	0.1524	0.0818	0.026*
C15	0.74319 (14)	0.10683 (7)	0.40058 (19)	0.0187 (4)
C16	0.68064 (15)	0.10025 (7)	0.50034 (19)	0.0222 (4)
H16	0.6465	0.1294	0.5308	0.027*
C17	0.66824 (15)	0.05151 (7)	0.5550 (2)	0.0233 (4)
H17	0.6251	0.0474	0.6222	0.028*
C18	0.71820 (15)	0.00886 (7)	0.51246 (19)	0.0228 (4)
H18	0.7098	−0.0246	0.5500	0.027*
C19	0.78049 (15)	0.01546 (7)	0.4146 (2)	0.0253 (4)
H19	0.8151	−0.0138	0.3854	0.030*
C20	0.79362 (15)	0.06385 (7)	0.3581 (2)	0.0228 (4)
H20	0.8368	0.0676	0.2909	0.027*
C28	0.61670 (14)	0.28223 (7)	0.41411 (18)	0.0192 (4)
C29	0.57437 (14)	0.32553 (7)	0.48937 (18)	0.0180 (4)
C30	0.59992 (14)	0.37699 (7)	0.46832 (19)	0.0196 (4)
H30	0.6429	0.3850	0.4032	0.023*
C31	0.56314 (14)	0.41665 (7)	0.54154 (19)	0.0196 (4)
H31	0.5808	0.4518	0.5282	0.023*
C32	0.50015 (14)	0.40359 (7)	0.63449 (18)	0.0177 (4)
C33	0.47428 (15)	0.35275 (7)	0.65914 (19)	0.0209 (4)
H33	0.4316	0.3449	0.7249	0.025*
C34	0.51214 (14)	0.31377 (7)	0.58564 (19)	0.0213 (4)
H34	0.4955	0.2786	0.6010	0.026*
C21	0.81529 (14)	0.56496 (7)	0.49520 (18)	0.0183 (4)
C22	0.85442 (14)	0.52222 (7)	0.41378 (18)	0.0183 (4)
C23	0.82458 (14)	0.47097 (7)	0.42781 (19)	0.0207 (4)
H23	0.7765	0.4629	0.4862	0.025*
C24	0.86457 (15)	0.43168 (7)	0.35713 (19)	0.0217 (4)
H24	0.8444	0.3966	0.3659	0.026*
C25	0.93451 (14)	0.44478 (7)	0.27357 (19)	0.0204 (4)
C26	0.96440 (15)	0.49535 (7)	0.2557 (2)	0.0227 (4)
H26	1.0115	0.5033	0.1958	0.027*
C27	0.92389 (14)	0.53422 (7)	0.32744 (19)	0.0198 (4)
H27	0.9437	0.5693	0.3175	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0274 (7)	0.0153 (7)	0.0280 (7)	−0.0011 (5)	0.0110 (6)	−0.0024 (5)
O2	0.0285 (7)	0.0200 (7)	0.0293 (7)	−0.0027 (6)	0.0161 (6)	−0.0074 (6)
O3	0.0402 (9)	0.0332 (9)	0.0613 (10)	−0.0049 (7)	0.0326 (8)	−0.0181 (8)
O4	0.0361 (9)	0.0197 (8)	0.0628 (10)	−0.0052 (6)	0.0197 (8)	−0.0163 (7)
O5	0.0260 (7)	0.0173 (7)	0.0293 (7)	0.0011 (5)	0.0105 (6)	−0.0013 (5)
O6	0.0329 (8)	0.0208 (7)	0.0309 (7)	0.0078 (6)	0.0181 (6)	0.0019 (6)
O7	0.0396 (8)	0.0246 (7)	0.0313 (7)	−0.0007 (6)	0.0238 (7)	−0.0013 (6)
O8	0.0359 (8)	0.0134 (7)	0.0336 (8)	−0.0042 (6)	0.0136 (6)	−0.0028 (6)
N1	0.0219 (8)	0.0140 (8)	0.0229 (8)	0.0011 (6)	0.0120 (7)	−0.0021 (6)
N2	0.0186 (7)	0.0150 (7)	0.0209 (7)	0.0002 (6)	0.0061 (6)	−0.0003 (6)
N3	0.0188 (8)	0.0173 (8)	0.0195 (7)	0.0015 (6)	0.0068 (6)	−0.0011 (6)
N4	0.0210 (8)	0.0176 (8)	0.0266 (8)	0.0034 (6)	0.0122 (7)	0.0006 (6)
N5	0.0206 (8)	0.0167 (8)	0.0217 (8)	−0.0009 (6)	0.0063 (6)	0.0000 (6)
N6	0.0184 (8)	0.0213 (8)	0.0246 (8)	0.0013 (6)	0.0087 (7)	0.0000 (6)
N7	0.0209 (8)	0.0244 (9)	0.0369 (10)	−0.0021 (7)	0.0082 (7)	−0.0117 (7)
N8	0.0230 (8)	0.0172 (8)	0.0191 (8)	−0.0007 (6)	0.0058 (7)	−0.0013 (6)
C1	0.0159 (8)	0.0175 (9)	0.0167 (8)	0.0007 (7)	0.0033 (7)	0.0007 (7)
C2	0.0191 (9)	0.0184 (9)	0.0227 (9)	−0.0005 (7)	0.0051 (8)	0.0009 (7)
C3	0.0206 (9)	0.0216 (9)	0.0211 (9)	−0.0002 (8)	0.0081 (8)	0.0028 (7)
C4	0.0191 (9)	0.0206 (9)	0.0189 (9)	0.0009 (7)	0.0072 (7)	−0.0002 (7)
C5	0.0177 (9)	0.0159 (9)	0.0180 (9)	−0.0004 (7)	0.0041 (7)	0.0006 (7)
C6	0.0195 (9)	0.0186 (9)	0.0207 (9)	0.0020 (7)	0.0076 (8)	−0.0001 (7)
C7	0.0195 (9)	0.0226 (10)	0.0234 (9)	−0.0009 (8)	0.0085 (8)	0.0024 (8)
C8	0.0219 (9)	0.0173 (9)	0.0232 (9)	−0.0030 (8)	0.0035 (8)	0.0019 (7)
C9	0.0261 (10)	0.0172 (9)	0.0211 (9)	0.0008 (8)	0.0061 (8)	−0.0024 (7)
C10	0.0226 (9)	0.0196 (9)	0.0199 (9)	0.0004 (8)	0.0083 (8)	0.0006 (7)
C11	0.0176 (9)	0.0188 (9)	0.0180 (9)	−0.0022 (7)	0.0034 (7)	−0.0015 (7)
C12	0.0201 (9)	0.0191 (9)	0.0237 (9)	−0.0036 (8)	0.0044 (8)	0.0000 (7)
C13	0.0205 (9)	0.0231 (10)	0.0279 (10)	−0.0032 (8)	0.0090 (8)	0.0015 (8)
C14	0.0179 (9)	0.0251 (10)	0.0226 (9)	−0.0014 (8)	0.0075 (8)	−0.0023 (8)
C15	0.0166 (9)	0.0190 (9)	0.0196 (9)	−0.0014 (7)	0.0030 (7)	0.0005 (7)
C16	0.0213 (9)	0.0232 (10)	0.0234 (9)	0.0026 (8)	0.0082 (8)	−0.0003 (8)
C17	0.0212 (9)	0.0274 (10)	0.0222 (9)	−0.0010 (8)	0.0074 (8)	0.0034 (8)
C18	0.0222 (10)	0.0213 (10)	0.0240 (9)	−0.0042 (8)	0.0038 (8)	0.0026 (8)
C19	0.0270 (10)	0.0205 (10)	0.0296 (10)	0.0003 (8)	0.0091 (9)	−0.0012 (8)
C20	0.0234 (10)	0.0222 (10)	0.0258 (10)	−0.0018 (8)	0.0115 (8)	−0.0006 (8)
C28	0.0182 (9)	0.0203 (10)	0.0188 (9)	0.0038 (7)	0.0037 (7)	0.0016 (7)
C29	0.0174 (9)	0.0180 (9)	0.0174 (8)	0.0012 (7)	0.0022 (7)	0.0005 (7)
C30	0.0182 (9)	0.0213 (9)	0.0201 (9)	0.0006 (7)	0.0064 (7)	0.0009 (7)
C31	0.0207 (9)	0.0157 (9)	0.0223 (9)	−0.0002 (7)	0.0053 (8)	0.0021 (7)
C32	0.0174 (9)	0.0176 (9)	0.0177 (8)	0.0015 (7)	0.0036 (7)	−0.0013 (7)
C33	0.0239 (10)	0.0189 (9)	0.0222 (9)	−0.0025 (8)	0.0101 (8)	0.0003 (7)
C34	0.0232 (9)	0.0159 (9)	0.0253 (9)	0.0000 (8)	0.0065 (8)	0.0015 (7)
C21	0.0183 (9)	0.0198 (9)	0.0163 (8)	0.0030 (7)	0.0034 (7)	0.0013 (7)
C22	0.0169 (9)	0.0177 (9)	0.0181 (8)	0.0021 (7)	0.0002 (7)	−0.0011 (7)
C23	0.0206 (9)	0.0198 (9)	0.0221 (9)	−0.0002 (8)	0.0059 (8)	−0.0007 (7)
C24	0.0211 (9)	0.0177 (9)	0.0250 (9)	0.0004 (8)	0.0034 (8)	−0.0013 (7)
C25	0.0171 (9)	0.0193 (9)	0.0238 (9)	0.0023 (7)	0.0027 (8)	−0.0069 (7)
C26	0.0192 (9)	0.0234 (10)	0.0270 (10)	−0.0031 (8)	0.0085 (8)	−0.0046 (8)
C27	0.0188 (9)	0.0165 (9)	0.0233 (9)	0.0003 (7)	0.0039 (7)	−0.0022 (7)

Geometric parameters (Å, º) top

O1—C21	1.221 (2)	C9—H9	0.9500
O2—C21	1.311 (2)	C10—H10	0.9500
O2—H2O	0.866 (9)	C12—C13	1.372 (3)
O3—N7	1.219 (2)	C12—H12	0.9500
O4—N7	1.227 (2)	C13—C14	1.379 (3)
O5—C28	1.218 (2)	C13—H13	0.9500
O6—C28	1.317 (2)	C14—H14	0.9500
O6—H6O	0.853 (9)	C15—C20	1.392 (2)
O7—N8	1.2243 (18)	C15—C16	1.399 (2)
O8—N8	1.2267 (18)	C16—C17	1.385 (3)
N1—C1	1.357 (2)	C16—H16	0.9500
N1—C5	1.410 (2)	C17—C18	1.382 (3)
N1—H1N	0.876 (9)	C17—H17	0.9500
N2—C2	1.332 (2)	C18—C19	1.381 (2)
N2—C1	1.358 (2)	C18—H18	0.9500
N3—C4	1.332 (2)	C19—C20	1.386 (3)
N3—C1	1.341 (2)	C19—H19	0.9500
N4—C11	1.365 (2)	C20—H20	0.9500
N4—C15	1.407 (2)	C28—C29	1.500 (2)
N4—H4N	0.881 (9)	C29—C34	1.391 (2)
N5—C12	1.331 (2)	C29—C30	1.393 (2)
N5—C11	1.357 (2)	C30—C31	1.386 (2)
N6—C14	1.336 (2)	C30—H30	0.9500
N6—C11	1.338 (2)	C31—C32	1.380 (2)
N7—C25	1.472 (2)	C31—H31	0.9500
N8—C32	1.472 (2)	C32—C33	1.386 (2)
C2—C3	1.373 (2)	C33—C34	1.381 (2)
C2—H2	0.9500	C33—H33	0.9500
C3—C4	1.382 (2)	C34—H34	0.9500
C3—H3	0.9500	C21—C22	1.505 (2)
C4—H4	0.9500	C22—C27	1.389 (2)
C5—C10	1.391 (2)	C22—C23	1.391 (2)
C5—C6	1.398 (2)	C23—C24	1.384 (2)
C6—C7	1.382 (2)	C23—H23	0.9500
C6—H6	0.9500	C24—C25	1.380 (2)
C7—C8	1.385 (2)	C24—H24	0.9500
C7—H7	0.9500	C25—C26	1.381 (3)
C8—C9	1.384 (2)	C26—C27	1.385 (2)
C8—H8	0.9500	C26—H26	0.9500
C9—C10	1.390 (2)	C27—H27	0.9500

C21—O2—H2O	110.5 (14)	C20—C15—C16	119.11 (16)
C28—O6—H6O	111.2 (15)	C20—C15—N4	124.96 (15)
C1—N1—C5	130.82 (15)	C16—C15—N4	115.93 (15)
C1—N1—H1N	113.6 (12)	C17—C16—C15	120.40 (16)
C5—N1—H1N	115.5 (12)	C17—C16—H16	119.8
C2—N2—C1	117.41 (15)	C15—C16—H16	119.8
C4—N3—C1	116.00 (15)	C18—C17—C16	120.40 (16)
C11—N4—C15	130.81 (15)	C18—C17—H17	119.8
C11—N4—H4N	112.5 (13)	C16—C17—H17	119.8
C15—N4—H4N	116.6 (13)	C19—C18—C17	119.15 (17)
C12—N5—C11	116.77 (15)	C19—C18—H18	120.4
C14—N6—C11	115.72 (15)	C17—C18—H18	120.4
O3—N7—O4	123.48 (16)	C18—C19—C20	121.40 (17)
O3—N7—C25	118.09 (15)	C18—C19—H19	119.3
O4—N7—C25	118.42 (15)	C20—C19—H19	119.3
O7—N8—O8	123.56 (14)	C19—C20—C15	119.55 (16)
O7—N8—C32	117.95 (14)	C19—C20—H20	120.2
O8—N8—C32	118.48 (14)	C15—C20—H20	120.2
N3—C1—N1	121.65 (16)	O5—C28—O6	124.38 (16)
N3—C1—N2	124.28 (15)	O5—C28—C29	122.83 (15)
N1—C1—N2	114.06 (15)	O6—C28—C29	112.76 (15)
N2—C2—C3	122.12 (17)	C34—C29—C30	119.75 (16)
N2—C2—H2	118.9	C34—C29—C28	119.25 (15)
C3—C2—H2	118.9	C30—C29—C28	120.96 (15)
C2—C3—C4	116.16 (16)	C31—C30—C29	120.58 (16)
C2—C3—H3	121.9	C31—C30—H30	119.7
C4—C3—H3	121.9	C29—C30—H30	119.7
N3—C4—C3	123.71 (16)	C32—C31—C30	118.07 (16)
N3—C4—H4	118.1	C32—C31—H31	121.0
C3—C4—H4	118.1	C30—C31—H31	121.0
C10—C5—C6	118.98 (16)	C31—C32—C33	122.79 (16)
C10—C5—N1	125.10 (15)	C31—C32—N8	118.63 (15)
C6—C5—N1	115.92 (15)	C33—C32—N8	118.57 (14)
C7—C6—C5	120.68 (16)	C34—C33—C32	118.24 (16)
C7—C6—H6	119.7	C34—C33—H33	120.9
C5—C6—H6	119.7	C32—C33—H33	120.9
C6—C7—C8	120.36 (16)	C33—C34—C29	120.54 (16)
C6—C7—H7	119.8	C33—C34—H34	119.7
C8—C7—H7	119.8	C29—C34—H34	119.7
C9—C8—C7	119.11 (16)	O1—C21—O2	124.39 (16)
C9—C8—H8	120.4	O1—C21—C22	122.06 (15)
C7—C8—H8	120.4	O2—C21—C22	113.54 (15)
C8—C9—C10	121.17 (16)	C27—C22—C23	119.97 (16)
C8—C9—H9	119.4	C27—C22—C21	119.21 (16)
C10—C9—H9	119.4	C23—C22—C21	120.78 (15)
C9—C10—C5	119.69 (16)	C24—C23—C22	120.34 (16)
C9—C10—H10	120.2	C24—C23—H23	119.8
C5—C10—H10	120.2	C22—C23—H23	119.8
N6—C11—N5	125.17 (15)	C25—C24—C23	118.30 (17)
N6—C11—N4	121.16 (16)	C25—C24—H24	120.8
N5—C11—N4	113.68 (15)	C23—C24—H24	120.8
N5—C12—C13	122.43 (17)	C24—C25—C26	122.76 (16)
N5—C12—H12	118.8	C24—C25—N7	118.70 (16)
C13—C12—H12	118.8	C26—C25—N7	118.54 (16)
C12—C13—C14	116.37 (16)	C25—C26—C27	118.24 (16)
C12—C13—H13	121.8	C25—C26—H26	120.9
C14—C13—H13	121.8	C27—C26—H26	120.9
N6—C14—C13	123.53 (16)	C26—C27—C22	120.37 (17)
N6—C14—H14	118.2	C26—C27—H27	119.8
C13—C14—H14	118.2	C22—C27—H27	119.8

C4—N3—C1—N1	−174.73 (16)	C16—C15—C20—C19	0.4 (3)
C4—N3—C1—N2	6.1 (3)	N4—C15—C20—C19	−178.62 (18)
C5—N1—C1—N3	1.1 (3)	O5—C28—C29—C34	−3.0 (3)
C5—N1—C1—N2	−179.67 (17)	O6—C28—C29—C34	178.90 (16)
C2—N2—C1—N3	−5.1 (3)	O5—C28—C29—C30	174.54 (17)
C2—N2—C1—N1	175.71 (15)	O6—C28—C29—C30	−3.6 (2)
C1—N2—C2—C3	−0.1 (3)	C34—C29—C30—C31	−0.5 (3)
N2—C2—C3—C4	3.6 (3)	C28—C29—C30—C31	−178.06 (16)
C1—N3—C4—C3	−2.2 (3)	C29—C30—C31—C32	−0.5 (3)
C2—C3—C4—N3	−2.4 (3)	C30—C31—C32—C33	1.2 (3)
C1—N1—C5—C10	0.3 (3)	C30—C31—C32—N8	−178.68 (15)
C1—N1—C5—C6	−179.26 (17)	O7—N8—C32—C31	176.93 (16)
C10—C5—C6—C7	−1.1 (3)	O8—N8—C32—C31	−2.5 (2)
N1—C5—C6—C7	178.48 (16)	O7—N8—C32—C33	−3.0 (2)
C5—C6—C7—C8	0.9 (3)	O8—N8—C32—C33	177.59 (16)
C6—C7—C8—C9	0.0 (3)	C31—C32—C33—C34	−0.9 (3)
C7—C8—C9—C10	−0.6 (3)	N8—C32—C33—C34	178.98 (16)
C8—C9—C10—C5	0.4 (3)	C32—C33—C34—C29	−0.1 (3)
C6—C5—C10—C9	0.5 (3)	C30—C29—C34—C33	0.8 (3)
N1—C5—C10—C9	−179.09 (17)	C28—C29—C34—C33	178.42 (17)
C14—N6—C11—N5	−0.4 (3)	O1—C21—C22—C27	−10.3 (3)
C14—N6—C11—N4	179.87 (16)	O2—C21—C22—C27	170.65 (16)
C12—N5—C11—N6	0.7 (3)	O1—C21—C22—C23	167.62 (17)
C12—N5—C11—N4	−179.51 (16)	O2—C21—C22—C23	−11.4 (2)
C15—N4—C11—N6	−1.8 (3)	C27—C22—C23—C24	0.6 (3)
C15—N4—C11—N5	178.41 (17)	C21—C22—C23—C24	−177.32 (17)
C11—N5—C12—C13	0.1 (3)	C22—C23—C24—C25	0.2 (3)
N5—C12—C13—C14	−1.2 (3)	C23—C24—C25—C26	−1.2 (3)
C11—N6—C14—C13	−0.8 (3)	C23—C24—C25—N7	178.25 (16)
C12—C13—C14—N6	1.5 (3)	O3—N7—C25—C24	−176.83 (18)
C11—N4—C15—C20	−5.3 (3)	O4—N7—C25—C24	2.5 (3)
C11—N4—C15—C16	175.72 (18)	O3—N7—C25—C26	2.7 (3)
C20—C15—C16—C17	−0.6 (3)	O4—N7—C25—C26	−178.00 (18)
N4—C15—C16—C17	178.45 (17)	C24—C25—C26—C27	1.4 (3)
C15—C16—C17—C18	0.5 (3)	N7—C25—C26—C27	−178.10 (16)
C16—C17—C18—C19	−0.1 (3)	C25—C26—C27—C22	−0.5 (3)
C17—C18—C19—C20	−0.2 (3)	C23—C22—C27—C26	−0.4 (3)
C18—C19—C20—C15	0.0 (3)	C21—C22—C27—C26	177.51 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···N2	0.87 (1)	1.70 (1)	2.5581 (18)	171 (2)
O6—H6o···N5	0.85 (1)	1.78 (1)	2.6230 (18)	171 (2)
N1—H1n···O1	0.88 (1)	2.15 (1)	3.0217 (18)	176 (2)
N4—H4n···O5	0.88 (1)	2.14 (1)	3.0190 (19)	180 (2)
C2—H2···O8	0.95	2.41	3.201 (2)	141
C12—H12···O4	0.95	2.43	3.106 (2)	128
C18—H18···O7ⁱ	0.95	2.56	3.330 (2)	138
C19—H19···O3ⁱⁱ	0.95	2.60	3.518 (2)	163
C31—H31···O8ⁱⁱⁱ	0.95	2.55	3.238 (2)	129

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₉N₃·C₇H₅NO₄
M_r	338.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.7754 (4), 25.7788 (8), 9.5813 (3)
β (°)	104.209 (4)
V (Å³)	3058.92 (17)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.856, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15808, 6818, 5093
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.118, 1.03
No. of reflections	6818
No. of parameters	463
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.28

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···N2	0.866 (9)	1.698 (10)	2.5581 (18)	171 (2)
O6—H6o···N5	0.853 (9)	1.777 (10)	2.6230 (18)	171 (2)
N1—H1n···O1	0.876 (9)	2.147 (10)	3.0217 (18)	176.3 (17)
N4—H4n···O5	0.881 (9)	2.138 (10)	3.0190 (19)	179.6 (19)
C2—H2···O8	0.95	2.41	3.201 (2)	141
C12—H12···O4	0.95	2.43	3.106 (2)	128
C18—H18···O7ⁱ	0.95	2.56	3.330 (2)	138
C19—H19···O3ⁱⁱ	0.95	2.60	3.518 (2)	163
C31—H31···O8ⁱⁱⁱ	0.95	2.55	3.238 (2)	129

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.

Footnotes

‡Additional correspondence author, e-mail: zana@um.edu.my.

Acknowledgements

The Ministry of Higher Education, Malaysia, is thanked for research grants (FP047/2008 C & FP001/2010 A to ZA and RG125 to ERTT). The authors are also grateful to the University of Malaya for support of the crystallographic facility.

References

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