4,4′-Bipyridine–pyridine-3,5-dicarb­oxy­lic acid (3/4)

Liu, S.-B.; Xu, C.; Duan, T.; Chen, Q.; Zhang, Q.-F.

doi:10.1107/S160053681102719X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2033

doi:10.1107/S160053681102719X

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4,4′-Bipyridine–pyridine-3,5-dicarboxylic acid (3/4)

Sheng-Bo Liu,^a Chao Xu,^a Taike Duan,^a Qun Chen ^b and Qian-Feng Zhang ^a,^b ^*

^aInstitute of Molecular Engineering and Applied Chemsitry, Anhui University of Technology, Ma'anshan, Anhui 243002, People's Republic of China, and ^bDepartment of Applied Chemistry, School of Petrochemical Engineering, Changzhou University, Jiangsu 213164, People's Republic of China
^*Correspondence e-mail: zhangqf@cczu.edu.cn

(Received 20 June 2011; accepted 7 July 2011; online 13 July 2011)

In the title compound, 3C₁₀H₈N₂·4C₇H₅NO₄, the asymmetric unit contains two molecules of pyridine-3,5-dicarboxylic acid and one molecule of 4,4′-bipyridine in general positions together with one molecule of 4,4′-bipyridine lying across a centre of inversion, thus giving a 4:3 molar ratio of pyridine-3,5-dicarboxylic acid to 4,4′-bipyridine. The dihedral angle between the bipyridine rings on general positions is 21.2 (2)°. These molecular units are linked by O—H⋯N hydrogen bonds forming an extended two-dimensional framework in the crystal.

Related literature

For structures and properties of self-assembled supermolecular compounds, see: Lehn (1990 ). For hydrogen bonds and π–π stacking interactions in supermolecular compounds, see: Roesky & Andruh (2003 ). For related structures, see: Soleimannejad et al. (2009 ); Jiang et al. (2010 ).

Experimental

Crystal data

3C₁₀H₈N₂·4C₇H₅NO₄
M_r = 1137.04
Monoclinic, P 2₁ /n
a = 13.8461 (4) Å
b = 11.0564 (3) Å
c = 18.1060 (4) Å
β = 110.511 (1)°
V = 2596.09 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.14 × 0.12 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.985, T_max = 0.995
24265 measured reflections
5918 independent reflections
4086 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.118
S = 1.03
5918 reflections
379 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N5ⁱ	0.82	1.80	2.5928 (17)	162
O4—H4⋯N4ⁱⁱ	0.82	1.79	2.6037 (18)	172
O5—H5⋯N3ⁱⁱⁱ	0.82	1.78	2.5956 (17)	173
O7—H7⋯N2ⁱⁱ	0.82	1.83	2.5862 (16)	152
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); 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/S160053681102719X/bx2358sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102719X/bx2358Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681102719X/bx2358Isup3.cml

checkCIF report

Comment top

In the past decades, the field of self-assembled supermolecular chemistry attracted increasing concerns due to their interesting structures and unique properties (Lehn, 1990). Hydrogen-bonds and pi—pi stacking are the most two important interactions in supermolecular compounds (Roesky & Andruh, 2003). As well known, many organic molecules with N– and O-donors such as bipyridine and pyridine-carboxylate acid have been wildly employed for constructing supermolecular complexes. In this paper, we report the hydrothermal synthesis and co-crystal structure of a two-dimensional framework of 4,4'-bipyridine (4,4'-bipy) and pyridine-3,5-dicarboxylic acid (3,5-pydcH₂) assembled by the intermolecular hydrogen-bonding interactions. In the title compound, the asymmetric unit is formed by two molecules of pyridine-3,5-dicarboxylic acid and one molecule of 4,4'-bipyridine lying in general positions, together with one molecule of 4,4'-bipyridine lying across a centre of inversion, thus giving a 4:3 molar ratio of pyridine-3,5-dicarboxylic acid to 4,4'-bipyridine. These molecular units are linked by O—H···N hydrogen-bonds forming an extended two-dimensional framework, Table 1, Fig.2. The geometric parameters are in normal range.

Related literature top

For structures and properties of self-assembled supermolecular compounds, see: Lehn (1990). For hydrogen bonds and pi–pi stacking interactions in supermolecular compounds, see: Roesky & Andruh (2003). For related structures, see: Soleimannejad et al. (2009); Jiang et al. (2010).

Experimental top

4, 4'-bipyridine (31.2 mg, 0.2 mmol) and 3, 5-pyridinedicarboxylic acid (50.1 mg, 0.3 mmol) were mixed in 2.5 ml water solution and the mixture was stirred for a while. The solution was transferred to a 23 ml Teflon-lined stainless autoclave. The vessel was sealed and heated to 110 C° for 2 days. The autoclave was cooled to ambient temperature. Colorless flake crystals of title co-crystal compound were obtained and air dried. Yield: 43.2 mg, ca 67%. Anal. Calcd. for C₂₉H₂₁O₈N₅: C, 61.4; H, 3.71; N, 12.3%. Found: C, 61.1; H, 3.65; N, 12.1%.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 structure of the title co-crystal compound, showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. Packing diagram of the title compound viewed along b-axis showing hydrogen bonds as dash lines.

4,4'-Bipyridine–pyridine-3,5-dicarboxylic acid (3/4) top

Crystal data top

3C₁₀H₈N₂·4C₇H₅NO₄	F(000) = 1180
M_r = 1137.04	D_x = 1.455 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.8461 (4) Å	Cell parameters from 6026 reflections
b = 11.0564 (3) Å	θ = 2.3–27.4°
c = 18.1060 (4) Å	µ = 0.11 mm⁻¹
β = 110.511 (1)°	T = 296 K
V = 2596.09 (12) Å³	Bar, colourless
Z = 2	0.14 × 0.12 × 0.05 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	5918 independent reflections
Radiation source: fine-focus sealed tube	4086 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
phi and ω scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −17→17
T_min = 0.985, T_max = 0.995	k = −14→14
24265 measured reflections	l = −19→23

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.058P)² + 0.3037P] where P = (F_o² + 2F_c²)/3
5918 reflections	(Δ/σ)_max = 0.001
379 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

3C₁₀H₈N₂·4C₇H₅NO₄	V = 2596.09 (12) Å³
M_r = 1137.04	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.8461 (4) Å	µ = 0.11 mm⁻¹
b = 11.0564 (3) Å	T = 296 K
c = 18.1060 (4) Å	0.14 × 0.12 × 0.05 mm
β = 110.511 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	5918 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	4086 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.995	R_int = 0.031
24265 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.03	Δρ_max = 0.19 e Å⁻³
5918 reflections	Δρ_min = −0.22 e Å⁻³
379 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
O1	0.89232 (10)	0.36614 (11)	1.13048 (7)	0.0566 (4)
O2	0.91840 (11)	0.19752 (11)	1.20316 (7)	0.0556 (4)
H2	0.9475	0.2439	1.2395	0.083*
O3	0.74670 (12)	0.28184 (12)	0.82900 (7)	0.0623 (4)
O4	0.71741 (11)	0.08686 (12)	0.79668 (7)	0.0619 (4)
H4	0.7058	0.1124	0.7519	0.093*
O5	0.87147 (10)	0.21216 (11)	0.58878 (6)	0.0513 (3)
H5	0.8940	0.2100	0.6371	0.077*
O6	0.91991 (11)	0.01904 (12)	0.60066 (7)	0.0624 (4)
O7	0.79322 (9)	−0.10426 (10)	0.23327 (6)	0.0469 (3)
H7	0.7969	−0.1689	0.2123	0.070*
O8	0.84624 (11)	−0.21541 (11)	0.34327 (7)	0.0577 (4)
N1	0.75488 (11)	−0.01589 (13)	1.02110 (8)	0.0448 (4)
N2	0.76208 (10)	0.19983 (11)	0.34879 (7)	0.0357 (3)
N3	1.06273 (12)	0.77515 (15)	0.25843 (8)	0.0504 (4)
N4	0.83365 (12)	0.65049 (16)	−0.14945 (8)	0.0520 (4)
N5	0.51891 (10)	0.82688 (12)	0.16936 (7)	0.0391 (3)
C1	0.88290 (13)	0.25840 (16)	1.13706 (9)	0.0403 (4)
C2	0.82884 (12)	0.17824 (14)	1.06824 (9)	0.0360 (4)
C3	0.79903 (13)	0.06220 (15)	1.07946 (9)	0.0412 (4)
H3	0.8105	0.0371	1.1309	0.049*
C4	0.74003 (12)	0.02231 (15)	0.94810 (9)	0.0399 (4)
H4A	0.7118	−0.0317	0.9067	0.048*
C5	0.76425 (12)	0.13790 (15)	0.93021 (9)	0.0365 (4)
C6	0.80869 (12)	0.21694 (15)	0.99183 (9)	0.0387 (4)
H6	0.8249	0.2955	0.9819	0.046*
C7	0.74147 (13)	0.17741 (17)	0.84653 (9)	0.0435 (4)
C8	0.88248 (12)	0.10611 (15)	0.56092 (9)	0.0387 (4)
C9	0.84316 (11)	0.10225 (13)	0.47271 (8)	0.0326 (3)
C10	0.79689 (12)	0.20178 (14)	0.42774 (9)	0.0341 (3)
H10	0.7897	0.2724	0.4533	0.041*
C11	0.77338 (12)	0.09854 (14)	0.31231 (9)	0.0351 (4)
H11	0.7507	0.0980	0.2575	0.042*
C12	0.81732 (11)	−0.00551 (13)	0.35251 (8)	0.0333 (3)
C13	0.85226 (12)	−0.00289 (14)	0.43401 (9)	0.0353 (4)
H13	0.8818	−0.0715	0.4628	0.042*
C14	0.82183 (12)	−0.11939 (14)	0.30945 (9)	0.0365 (4)
C15	1.05291 (14)	0.66299 (18)	0.23018 (10)	0.0517 (5)
H15	1.0778	0.5997	0.2656	0.062*
C16	1.00790 (13)	0.63556 (17)	0.15141 (10)	0.0468 (4)
H16	1.0007	0.5554	0.1348	0.056*
C17	0.97328 (12)	0.72881 (15)	0.09689 (9)	0.0377 (4)
C18	0.92417 (12)	0.70293 (16)	0.01128 (9)	0.0380 (4)
C19	0.88180 (13)	0.58973 (16)	−0.01519 (9)	0.0444 (4)
H19	0.8830	0.5294	0.0209	0.053*
C20	0.83816 (14)	0.56738 (18)	−0.09498 (10)	0.0501 (5)
H20	0.8107	0.4911	−0.1115	0.060*
C21	0.87225 (15)	0.75957 (19)	−0.12476 (10)	0.0557 (5)
H21	0.8684	0.8187	−0.1622	0.067*
C22	0.91764 (14)	0.78877 (17)	−0.04623 (10)	0.0484 (4)
H22	0.9439	0.8660	−0.0317	0.058*
C23	0.98663 (14)	0.84544 (17)	0.12672 (10)	0.0505 (5)
H23	0.9666	0.9110	0.0926	0.061*
C24	1.02949 (15)	0.86454 (18)	0.20685 (11)	0.0553 (5)
H24	1.0354	0.9435	0.2256	0.066*
C25	0.48131 (13)	0.77880 (15)	0.09709 (9)	0.0407 (4)
H25	0.4599	0.6985	0.0919	0.049*
C26	0.47296 (12)	0.84300 (14)	0.02999 (9)	0.0376 (4)
H26	0.4469	0.8057	−0.0191	0.045*
C27	0.50350 (11)	0.96381 (14)	0.03536 (8)	0.0323 (3)
C28	0.54147 (13)	1.01290 (15)	0.11086 (9)	0.0438 (4)
H28	0.5624	1.0933	0.1180	0.053*
C29	0.54790 (13)	0.94206 (16)	0.17488 (9)	0.0444 (4)
H29	0.5740	0.9767	0.2248	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0855 (9)	0.0374 (7)	0.0412 (7)	−0.0112 (6)	0.0149 (6)	−0.0045 (6)
O2	0.0860 (9)	0.0441 (7)	0.0262 (6)	−0.0050 (6)	0.0065 (6)	−0.0053 (5)
O3	0.0973 (11)	0.0522 (9)	0.0348 (7)	−0.0113 (7)	0.0198 (7)	0.0069 (6)
O4	0.0973 (10)	0.0599 (9)	0.0235 (6)	−0.0126 (7)	0.0148 (6)	−0.0025 (6)
O5	0.0793 (9)	0.0441 (7)	0.0249 (6)	0.0074 (6)	0.0109 (6)	−0.0062 (5)
O6	0.1012 (10)	0.0483 (8)	0.0291 (6)	0.0213 (7)	0.0123 (6)	0.0055 (6)
O7	0.0818 (9)	0.0287 (6)	0.0277 (6)	−0.0007 (5)	0.0160 (6)	−0.0037 (5)
O8	0.0974 (10)	0.0319 (7)	0.0366 (7)	0.0155 (6)	0.0147 (7)	0.0028 (5)
N1	0.0630 (9)	0.0356 (8)	0.0315 (8)	−0.0053 (6)	0.0110 (7)	−0.0003 (6)
N2	0.0488 (8)	0.0287 (7)	0.0277 (7)	0.0007 (6)	0.0111 (6)	0.0008 (5)
N3	0.0596 (9)	0.0583 (10)	0.0293 (8)	0.0016 (8)	0.0105 (7)	−0.0065 (7)
N4	0.0595 (9)	0.0672 (11)	0.0277 (8)	0.0081 (8)	0.0129 (7)	−0.0009 (8)
N5	0.0472 (8)	0.0396 (8)	0.0284 (7)	0.0025 (6)	0.0104 (6)	0.0056 (6)
C1	0.0531 (10)	0.0393 (10)	0.0283 (8)	−0.0024 (8)	0.0141 (7)	−0.0041 (7)
C2	0.0427 (9)	0.0362 (9)	0.0284 (8)	0.0006 (7)	0.0114 (7)	−0.0014 (7)
C3	0.0583 (10)	0.0381 (9)	0.0255 (8)	0.0010 (8)	0.0125 (7)	0.0009 (7)
C4	0.0486 (9)	0.0390 (9)	0.0286 (8)	−0.0021 (7)	0.0092 (7)	−0.0044 (7)
C5	0.0425 (9)	0.0409 (9)	0.0250 (8)	−0.0014 (7)	0.0104 (7)	−0.0001 (7)
C6	0.0487 (9)	0.0363 (9)	0.0313 (9)	−0.0033 (7)	0.0141 (7)	0.0013 (7)
C7	0.0491 (10)	0.0525 (11)	0.0278 (9)	−0.0062 (8)	0.0119 (7)	0.0005 (8)
C8	0.0488 (9)	0.0392 (10)	0.0271 (8)	0.0020 (7)	0.0121 (7)	−0.0024 (7)
C9	0.0404 (8)	0.0315 (8)	0.0256 (8)	0.0001 (6)	0.0112 (6)	−0.0005 (6)
C10	0.0441 (9)	0.0297 (8)	0.0288 (8)	−0.0016 (7)	0.0131 (7)	−0.0032 (6)
C11	0.0473 (9)	0.0323 (8)	0.0241 (8)	−0.0019 (7)	0.0106 (6)	−0.0005 (6)
C12	0.0420 (8)	0.0290 (8)	0.0278 (8)	−0.0015 (6)	0.0110 (6)	−0.0020 (6)
C13	0.0464 (9)	0.0305 (8)	0.0267 (8)	0.0030 (7)	0.0100 (7)	0.0022 (6)
C14	0.0489 (9)	0.0304 (9)	0.0284 (8)	0.0010 (7)	0.0113 (7)	−0.0006 (6)
C15	0.0652 (12)	0.0530 (12)	0.0299 (9)	0.0009 (9)	0.0080 (8)	0.0027 (8)
C16	0.0588 (11)	0.0435 (10)	0.0340 (9)	−0.0013 (8)	0.0112 (8)	−0.0023 (8)
C17	0.0393 (8)	0.0444 (10)	0.0292 (8)	0.0030 (7)	0.0116 (7)	−0.0020 (7)
C18	0.0388 (8)	0.0477 (10)	0.0279 (8)	0.0066 (7)	0.0119 (7)	0.0006 (7)
C19	0.0513 (10)	0.0498 (11)	0.0298 (9)	0.0020 (8)	0.0114 (7)	0.0000 (7)
C20	0.0586 (11)	0.0560 (12)	0.0330 (9)	0.0013 (9)	0.0129 (8)	−0.0066 (8)
C21	0.0693 (13)	0.0634 (13)	0.0351 (10)	0.0069 (10)	0.0190 (9)	0.0098 (9)
C22	0.0583 (11)	0.0500 (11)	0.0370 (10)	0.0004 (8)	0.0166 (8)	0.0020 (8)
C23	0.0645 (11)	0.0435 (11)	0.0372 (10)	0.0082 (9)	0.0097 (8)	0.0006 (8)
C24	0.0693 (12)	0.0499 (11)	0.0409 (11)	0.0036 (9)	0.0119 (9)	−0.0121 (9)
C25	0.0529 (10)	0.0320 (9)	0.0353 (9)	−0.0008 (7)	0.0130 (8)	0.0026 (7)
C26	0.0496 (9)	0.0319 (9)	0.0276 (8)	−0.0005 (7)	0.0088 (7)	−0.0018 (7)
C27	0.0361 (8)	0.0317 (8)	0.0268 (8)	0.0015 (6)	0.0080 (6)	0.0016 (6)
C28	0.0607 (11)	0.0354 (9)	0.0306 (9)	−0.0111 (8)	0.0104 (8)	−0.0024 (7)
C29	0.0583 (10)	0.0442 (10)	0.0258 (8)	−0.0061 (8)	0.0086 (7)	−0.0013 (7)

Geometric parameters (Å, º) top

O1—C1	1.209 (2)	C9—C13	1.386 (2)
O2—C1	1.310 (2)	C10—H10	0.9300
O2—H2	0.8200	C11—C12	1.383 (2)
O3—C7	1.206 (2)	C11—H11	0.9300
O4—C7	1.311 (2)	C12—C13	1.383 (2)
O4—H4	0.8200	C12—C14	1.494 (2)
O5—C8	1.3063 (19)	C13—H13	0.9300
O5—H5	0.8200	C15—C16	1.375 (2)
O6—C8	1.2049 (19)	C15—H15	0.9300
O7—C14	1.3056 (18)	C16—C17	1.391 (2)
O7—H7	0.8200	C16—H16	0.9300
O8—C14	1.2129 (19)	C17—C23	1.385 (2)
N1—C4	1.333 (2)	C17—C18	1.486 (2)
N1—C3	1.335 (2)	C18—C22	1.388 (2)
N2—C11	1.3370 (19)	C18—C19	1.394 (2)
N2—C10	1.3391 (19)	C19—C20	1.379 (2)
N3—C24	1.326 (2)	C19—H19	0.9300
N3—C15	1.330 (2)	C20—H20	0.9300
N4—C21	1.331 (2)	C21—C22	1.376 (2)
N4—C20	1.333 (2)	C21—H21	0.9300
N5—C29	1.328 (2)	C22—H22	0.9300
N5—C25	1.337 (2)	C23—C24	1.378 (2)
C1—C2	1.498 (2)	C23—H23	0.9300
C2—C6	1.380 (2)	C24—H24	0.9300
C2—C3	1.384 (2)	C25—C26	1.377 (2)
C3—H3	0.9300	C25—H25	0.9300
C4—C5	1.388 (2)	C26—C27	1.394 (2)
C4—H4A	0.9300	C26—H26	0.9300
C5—C6	1.380 (2)	C27—C28	1.391 (2)
C5—C7	1.500 (2)	C27—C27ⁱ	1.484 (3)
C6—H6	0.9300	C28—C29	1.376 (2)
C8—C9	1.496 (2)	C28—H28	0.9300
C9—C10	1.385 (2)	C29—H29	0.9300

C1—O2—H2	109.5	O8—C14—O7	124.97 (15)
C7—O4—H4	109.5	O8—C14—C12	121.98 (14)
C8—O5—H5	109.5	O7—C14—C12	113.00 (13)
C14—O7—H7	109.5	N3—C15—C16	123.54 (17)
C4—N1—C3	116.65 (14)	N3—C15—H15	118.2
C11—N2—C10	118.70 (13)	C16—C15—H15	118.2
C24—N3—C15	117.42 (15)	C15—C16—C17	119.38 (17)
C21—N4—C20	117.81 (15)	C15—C16—H16	120.3
C29—N5—C25	117.28 (13)	C17—C16—H16	120.3
O1—C1—O2	125.29 (15)	C23—C17—C16	116.58 (15)
O1—C1—C2	122.74 (15)	C23—C17—C18	122.40 (15)
O2—C1—C2	111.97 (14)	C16—C17—C18	121.02 (15)
C6—C2—C3	117.94 (15)	C22—C18—C19	116.55 (15)
C6—C2—C1	121.12 (15)	C22—C18—C17	122.44 (16)
C3—C2—C1	120.93 (14)	C19—C18—C17	121.01 (15)
N1—C3—C2	124.09 (15)	C20—C19—C18	119.88 (17)
N1—C3—H3	118.0	C20—C19—H19	120.1
C2—C3—H3	118.0	C18—C19—H19	120.1
N1—C4—C5	123.85 (15)	N4—C20—C19	122.77 (18)
N1—C4—H4A	118.1	N4—C20—H20	118.6
C5—C4—H4A	118.1	C19—C20—H20	118.6
C6—C5—C4	118.04 (14)	N4—C21—C22	122.94 (17)
C6—C5—C7	120.54 (15)	N4—C21—H21	118.5
C4—C5—C7	121.41 (14)	C22—C21—H21	118.5
C2—C6—C5	119.35 (15)	C21—C22—C18	120.04 (18)
C2—C6—H6	120.3	C21—C22—H22	120.0
C5—C6—H6	120.3	C18—C22—H22	120.0
O3—C7—O4	125.04 (15)	C24—C23—C17	120.18 (17)
O3—C7—C5	122.25 (16)	C24—C23—H23	119.9
O4—C7—C5	112.70 (15)	C17—C23—H23	119.9
O6—C8—O5	124.79 (15)	N3—C24—C23	122.84 (18)
O6—C8—C9	122.28 (15)	N3—C24—H24	118.6
O5—C8—C9	112.93 (14)	C23—C24—H24	118.6
C10—C9—C13	118.32 (14)	N5—C25—C26	122.83 (15)
C10—C9—C8	121.67 (14)	N5—C25—H25	118.6
C13—C9—C8	120.00 (13)	C26—C25—H25	118.6
N2—C10—C9	122.28 (14)	C25—C26—C27	120.19 (14)
N2—C10—H10	118.9	C25—C26—H26	119.9
C9—C10—H10	118.9	C27—C26—H26	119.9
N2—C11—C12	122.87 (14)	C28—C27—C26	116.31 (14)
N2—C11—H11	118.6	C28—C27—C27ⁱ	121.69 (17)
C12—C11—H11	118.6	C26—C27—C27ⁱ	122.00 (17)
C13—C12—C11	117.97 (14)	C29—C28—C27	119.75 (15)
C13—C12—C14	120.78 (14)	C29—C28—H28	120.1
C11—C12—C14	121.17 (13)	C27—C28—H28	120.1
C12—C13—C9	119.84 (14)	N5—C29—C28	123.63 (15)
C12—C13—H13	120.1	N5—C29—H29	118.2
C9—C13—H13	120.1	C28—C29—H29	118.2

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N5ⁱⁱ	0.82	1.80	2.5928 (17)	162
O4—H4···N4ⁱⁱⁱ	0.82	1.79	2.6037 (18)	172
O5—H5···N3^iv	0.82	1.78	2.5956 (17)	173
O7—H7···N2ⁱⁱⁱ	0.82	1.83	2.5862 (16)	152

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

Experimental details

Crystal data
Chemical formula	3C₁₀H₈N₂·4C₇H₅NO₄
M_r	1137.04
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	13.8461 (4), 11.0564 (3), 18.1060 (4)
β (°)	110.511 (1)
V (Å³)	2596.09 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.14 × 0.12 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.985, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	24265, 5918, 4086
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.118, 1.03
No. of reflections	5918
No. of parameters	379
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.22

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), 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
O2—H2···N5ⁱ	0.82	1.80	2.5928 (17)	161.9
O4—H4···N4ⁱⁱ	0.82	1.79	2.6037 (18)	171.5
O5—H5···N3ⁱⁱⁱ	0.82	1.78	2.5956 (17)	172.6
O7—H7···N2ⁱⁱ	0.82	1.83	2.5862 (16)	152.0

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

Acknowledgements

This project was supported by the Program for New Century Excellent Talents in Universities of China (NCET-08–0618).

References

Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jiang, X.-R., Wang, X.-J. & Feng, Y.-L. (2010). Acta Cryst. E66, o3308. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lehn, M.-L. (1990). Angew. Chem. Int. Ed. 29, 1304–1319. CrossRef Google Scholar
Roesky, H. W. & Andruh, M. (2003). Coord. Chem. Rev. 236, 91–119. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1997). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Soleimannejad, J., Aghabozorg, H., Morsali, A., Hemmati, F. & Manteghi, F. (2009). Acta Cryst. E65, o153. Web of Science CSD CrossRef IUCr Journals Google Scholar