4-[5-(4-Pyrid­yl)-1,3,4-oxadiazol-2-yl]pyridine N-oxide–isophthalic acid (1/1)

Hou, G.-G.; Liu, L.-L.; Ma, J.-P.; Huang, R.-Q.; Dong, Y.-B.

doi:10.1107/S1600536808012622

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o997

doi:10.1107/S1600536808012622

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4-[5-(4-Pyridyl)-1,3,4-oxadiazol-2-yl]pyridine N-oxide–isophthalic acid (1/1)

Gui-Ge Hou,^a Li-Li Liu,^a Jian-Ping Ma,^a Ru-Qi Huang ^a and Yu-Bin Dong ^a ^*

^aCollege of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: yubindong@sdnu.edu.cn

(Received 6 March 2008; accepted 30 April 2008; online 7 May 2008)

The title compound, C₁₂H₈N₄O₂·C₈H₆O₄, was synthesized from 4-[5-(4-pyridyl)-1,3,4-oxadiazol-2-yl]pyridine N-oxide and isophthalic acid. The two molecules are linked through O—H⋯O and O—H⋯N hydrogen bonds. Weak intramolecular π–π interactions between the two hydrogen-bonded chains result in the formation a one-dimensional supramolecular curved tape (the face-to-face distance between the pyridine N-oxide ring and the benzene ring is 3.7 Å).

Related literature

For related literature, see: Beckmann & Jänicke (2006 ); Dong et al. (2003 ); Du et al. (2006 ); Hunter (1994 ); Kitagawa et al. (2004 ); Long et al. (2004 ); Lu et al. (1997 ); Ma et al. (2005 ); Ren et al. (1995 ); Tan et al. (2006 ).

Experimental

Crystal data

C₁₂H₈N₄O₂·C₈H₆O₄
M_r = 406.35
Triclinic, $[P \overline 1]$
a = 7.0993 (18) Å
b = 7.1770 (19) Å
c = 19.823 (5) Å
α = 93.003 (4)°
β = 98.481 (3)°
γ = 112.745 (4)°
V = 914.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 (2) K
0.30 × 0.15 × 0.06 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
4661 measured reflections
3189 independent reflections
1972 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.132
S = 0.98
3189 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N4	0.82	1.82	2.640 (2)	171
O3—H3⋯O5ⁱ	0.82	1.72	2.521 (3)	163
Symmetry code: (i) x+1, y+1, z+1.

Data collection: SMART (Bruker 2000 ); cell refinement: SMART; data reduction: SAINT (Bruker 2000); 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/S1600536808012622/bv2095sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012622/bv2095Isup2.hkl

checkCIF report

Comment top

Rigid pyridyl compounds have been considered as good hydrogen bond acceptors. These compounds include 4,4-bipyridine (Lu et al., 1997; Kitagawa et al., 2004; Tan et al., 2006), 1,2-bis(4-pyridyl)ethyne (Beckmann & Jänicke, 2006), 4,4'-bipyridine-N,N'-dioxide (Long et al., 2004; Ma et al., 2005), and other similar molecules. We recently prepared the rigid bent compound, 2-(4-pyridyl)-5-(4-pyridyl N-oxide)-1,3,4-oxadiazole, (L2). It has a rigid 144° angle because of the bridging five-membered oxadiazole ring. In addition, isophthalic acid is a good hydrogen-bonding donor and its two carboxylic acid moieties make an angle of 120°. Supramolecular systems with novel architecture may result because of their specific geometry. Accordingly, when L2 reacted with isophthalic acid in a mixed CH₂Cl₂/CH₃OH solution, yellow crystals formed and its structure is reported here.

The molecular structure of (1) is shown in Fig. 1. The asymmetric unit contains one L2 molecule and one isophthalic acid molecule. O···H—O and N···H—O hydrogen bonds (Fig. 3) are formed by the –COOH groups of the isophthalic acid and the pyridyl-N-oxide O atom and N_pyridine atom, (Table 1). The dihedral angles between the benzene ring of isophthalic acid and pyridyl-N-oxide ring and pyridyl ring are 1.4° and 7.0°, respectively, which are similar to previously reported experimental values (Du et al., 2006; Tan et al., 2006). In addition to the specific geometry of the oxadiazole-containing rigid curved organic ligand L2, the molecules in (1) connect with each other generating one-dimensional extended zigzag chains, which have not been obtained using normal linear rigid bidentate organic ligands (Dong & Ma, 2003).

In the solid state, the crystal packing view of (1) shows a pair of zigzag chains which stack via aromatic π-π interactions (Fig. 3). The face-to-face distance between the pyridine-N-oxide ring and benzene ring from isophthalic acid is 3.7 Å. The shortest close contact is 3.447 (6) Å. Although these values are typical for aromatic π-π stacking interactions, compared with the strong π-π interactions (Hunter, 1994) they are comparatively weak. Two adjacent chains are further linked via intramolecular π-π stacking interactions to construct a one-dimensional supramolecular curved tape (Fig. 3). These weak intramolecular π-π interactions and crucial hydrogen bonds enhance the stability of the compound (1).

Related literature top

For related literature, see: Beckmann & Jänicke (2006); Dong et al. (2003); Du et al. (2006); Hunter (1994); Kitagawa et al. (2004); Long et al. (2004); Lu et al. (1997); Ma et al. (2005); Ren et al. (1995); Tan et al. (2006).

Experimental top

L1 (2,5-bis(4-pyridyl)-1,3,4-oxadiazole) was prepared according to literature methods (Ren et al., 1995). L1 (1.1 g, 5 mmol), 1.0 ml hydrogen dioxide 30% solution and 3.0 ml acetic acid were mixed and refluxed at 343–353 K for 20 h. After removal of solvent under vacuum, the residue was purified on a silica gel column using CH₂Cl₂/CH₃OH (15:1, v/v) as the eluent to afford L2, Yield: 38%. Mp: 501–503 K. 1H NMR (DMSO, 300 MHz, p.p.m.): δ 8.89–8.91 (d, 2H, 2C₅H₄N), 8.34–8.37 (d, 2H, 2C₅H₄NO), 7.99–8.06 (m, 4H, 2C₅H₄N, 2C₅H₄NO). IR (KBr pellet cm^-1): 3423(s), 1620(m), 1563(m), 1537(m), 1475(s), 1439(s), 1407(s), 1272(s), 1174(s), 1111(m), 965(m), 848(m), 740(m), 703(s), 644(s), 509(m).

A CH₂Cl₂ and CH₃OH solution (10 ml, 1:1, v/v) of L2 (24 mg, 0.1 mmol) and isophthalic acid (16.6 mg, 0.1 mmol) kept at room temperature. After a few days yellow block crystals (1) were obtained (36 mg). Yield: 89%.

Computing details top

Data collection: SMART (Bruker 2000); cell refinement: SMART (Bruker 2000); data reduction: SAINT (Bruker 2000); 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 (1), with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).
	Fig. 2. : A view of the hydrogen-bonded chains observed in the crystal structure of (1).
	Fig. 3. : The crystal packing of (1) via weak π-π interactions, and the face-to-face distance is 3.7 Å.
	Fig. 4. The formation of L2.

4-[5-(4-pyridyl)-1,3,4-oxadiazol-2-yl]pyridine N-oxide–isophthalic acid (1/1) top

Crystal data top

C₁₂H₈N₄O₂·C₈H₆O₄	Z = 2
M_r = 406.35	F(000) = 420
Triclinic, P1	D_x = 1.475 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0993 (18) Å	Cell parameters from 893 reflections
b = 7.1770 (19) Å	θ = 3.2–21.1°
c = 19.823 (5) Å	µ = 0.11 mm⁻¹
α = 93.003 (4)°	T = 298 K
β = 98.481 (3)°	Bar, colourless
γ = 112.745 (4)°	0.30 × 0.15 × 0.06 mm
V = 914.6 (4) Å³

Data collection top

Bruker SMART APEX diffractometer	1972 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 25.0°, θ_min = 3.1°
ϕ and ω scans	h = −8→8
4661 measured reflections	k = −8→8
3189 independent reflections	l = −17→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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0637P)²] where P = (F_o² + 2F_c²)/3
3189 reflections	(Δ/σ)_max = 0.001
272 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₂H₈N₄O₂·C₈H₆O₄	γ = 112.745 (4)°
M_r = 406.35	V = 914.6 (4) Å³
Triclinic, P1	Z = 2
a = 7.0993 (18) Å	Mo Kα radiation
b = 7.1770 (19) Å	µ = 0.11 mm⁻¹
c = 19.823 (5) Å	T = 298 K
α = 93.003 (4)°	0.30 × 0.15 × 0.06 mm
β = 98.481 (3)°

Data collection top

Bruker SMART APEX diffractometer	1972 reflections with I > 2σ(I)
4661 measured reflections	R_int = 0.027
3189 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 0.98	Δρ_max = 0.30 e Å⁻³
3189 reflections	Δρ_min = −0.15 e Å⁻³
272 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	0.7708 (3)	0.9021 (3)	0.64281 (9)	0.0693 (6)
O2	1.0221 (3)	0.8709 (4)	0.59557 (10)	0.0861 (7)
O5	−0.2941 (3)	0.2221 (4)	−0.02763 (9)	0.0882 (8)
O3	0.8643 (3)	1.0843 (3)	0.88695 (9)	0.0738 (6)
H3	0.8309	1.1276	0.9203	0.111*
O4	1.1774 (3)	1.2181 (3)	0.95238 (9)	0.0726 (6)
C1	−0.4071 (4)	0.2792 (4)	0.06980 (13)	0.0592 (8)
H1A	−0.5408	0.2374	0.0446	0.071*
C2	−0.3697 (4)	0.3405 (4)	0.13821 (12)	0.0528 (7)
H2	−0.4781	0.3399	0.1595	0.063*
C3	−0.1721 (4)	0.4035 (4)	0.17649 (11)	0.0427 (6)
C4	−0.0155 (4)	0.4016 (4)	0.14322 (12)	0.0515 (7)
H4	0.1189	0.4429	0.1678	0.062*
C5	−0.0572 (4)	0.3385 (4)	0.07365 (12)	0.0558 (7)
H5A	0.0489	0.3375	0.0513	0.067*
C6	−0.1345 (4)	0.4706 (4)	0.24973 (12)	0.0436 (6)
C7	0.0337 (4)	0.5784 (4)	0.35129 (11)	0.0431 (6)
C8	0.2083 (4)	0.6463 (4)	0.40831 (11)	0.0415 (6)
C9	0.1803 (4)	0.7064 (4)	0.47216 (12)	0.0496 (7)
H9	0.0533	0.7076	0.4782	0.059*
C10	0.3421 (4)	0.7639 (4)	0.52633 (12)	0.0520 (7)
H10	0.3205	0.8000	0.5694	0.062*
C11	0.5555 (4)	0.7154 (4)	0.45907 (13)	0.0551 (7)
H11	0.6856	0.7205	0.4542	0.066*
C12	0.4001 (4)	0.6505 (4)	0.40169 (12)	0.0490 (7)
H12	0.4245	0.6105	0.3596	0.059*
C13	0.9602 (4)	0.9161 (4)	0.64414 (14)	0.0521 (7)
C14	1.0945 (4)	0.9948 (4)	0.71368 (11)	0.0453 (6)
C15	1.0149 (4)	1.0271 (4)	0.77116 (12)	0.0451 (6)
H15	0.8738	0.9975	0.7670	0.054*
C16	1.1455 (4)	1.1037 (4)	0.83507 (11)	0.0436 (6)
C17	1.3553 (4)	1.1470 (4)	0.84013 (13)	0.0533 (7)
H17	1.4443	1.1995	0.8822	0.064*
C18	1.4324 (4)	1.1130 (4)	0.78334 (13)	0.0577 (8)
H18	1.5734	1.1419	0.7874	0.069*
C19	1.3043 (4)	1.0369 (4)	0.72065 (13)	0.0542 (7)
H19	1.3586	1.0134	0.6827	0.065*
C20	1.0666 (4)	1.1418 (4)	0.89757 (13)	0.0509 (7)
N1	−0.2515 (3)	0.2788 (3)	0.03830 (10)	0.0569 (6)
N2	−0.2670 (3)	0.4826 (3)	0.28576 (10)	0.0511 (6)
N3	−0.1552 (3)	0.5550 (3)	0.35274 (10)	0.0529 (6)
N4	0.5295 (3)	0.7709 (3)	0.52071 (10)	0.0525 (6)
H1	0.7016	0.8526	0.6043	0.079*
O6	0.0597 (2)	0.5275 (2)	0.28698 (7)	0.0451 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0608 (14)	0.0982 (17)	0.0411 (11)	0.0313 (12)	−0.0073 (9)	−0.0095 (10)
O2	0.0854 (16)	0.128 (2)	0.0449 (12)	0.0492 (15)	0.0062 (11)	−0.0239 (12)
O5	0.0759 (15)	0.157 (2)	0.0339 (12)	0.0592 (15)	−0.0082 (10)	−0.0223 (12)
O3	0.0545 (13)	0.1118 (18)	0.0450 (12)	0.0277 (12)	0.0025 (9)	−0.0144 (11)
O4	0.0630 (13)	0.1144 (18)	0.0341 (11)	0.0374 (12)	−0.0070 (9)	−0.0135 (11)
C1	0.0494 (17)	0.077 (2)	0.0459 (17)	0.0259 (15)	−0.0048 (13)	−0.0079 (14)
C2	0.0514 (17)	0.0658 (19)	0.0379 (16)	0.0239 (14)	0.0000 (12)	−0.0024 (13)
C3	0.0490 (16)	0.0424 (16)	0.0352 (14)	0.0190 (12)	0.0020 (12)	0.0006 (11)
C4	0.0498 (17)	0.0596 (19)	0.0377 (16)	0.0182 (14)	−0.0013 (12)	−0.0006 (12)
C5	0.0523 (18)	0.075 (2)	0.0405 (16)	0.0282 (15)	0.0051 (13)	0.0002 (14)
C6	0.0501 (17)	0.0421 (16)	0.0331 (14)	0.0167 (13)	−0.0027 (12)	0.0002 (11)
C7	0.0534 (17)	0.0443 (16)	0.0326 (15)	0.0210 (13)	0.0079 (12)	0.0010 (11)
C8	0.0474 (16)	0.0436 (16)	0.0313 (14)	0.0182 (12)	0.0019 (11)	0.0009 (11)
C9	0.0487 (16)	0.0590 (18)	0.0375 (15)	0.0193 (14)	0.0060 (12)	−0.0018 (12)
C10	0.0591 (19)	0.0614 (19)	0.0319 (15)	0.0225 (15)	0.0052 (13)	−0.0025 (12)
C11	0.0491 (17)	0.066 (2)	0.0508 (18)	0.0258 (15)	0.0033 (14)	0.0032 (14)
C12	0.0551 (18)	0.0575 (18)	0.0338 (15)	0.0228 (14)	0.0073 (13)	−0.0006 (12)
C13	0.0625 (19)	0.0471 (18)	0.0468 (18)	0.0236 (14)	0.0068 (14)	0.0024 (13)
C14	0.0574 (17)	0.0467 (17)	0.0315 (14)	0.0233 (13)	0.0020 (12)	−0.0004 (11)
C15	0.0472 (15)	0.0468 (16)	0.0417 (15)	0.0221 (13)	0.0003 (12)	0.0039 (12)
C16	0.0492 (16)	0.0482 (16)	0.0329 (14)	0.0220 (13)	−0.0005 (12)	0.0029 (11)
C17	0.0537 (18)	0.0604 (19)	0.0428 (16)	0.0251 (15)	−0.0042 (13)	−0.0001 (13)
C18	0.0508 (17)	0.073 (2)	0.0485 (18)	0.0270 (16)	0.0037 (14)	0.0004 (15)
C19	0.0609 (19)	0.0605 (19)	0.0458 (17)	0.0285 (15)	0.0126 (14)	0.0029 (13)
C20	0.0509 (18)	0.0600 (19)	0.0408 (16)	0.0251 (14)	−0.0007 (13)	0.0014 (13)
N1	0.0585 (16)	0.0779 (18)	0.0301 (13)	0.0295 (13)	−0.0054 (11)	−0.0088 (11)
N2	0.0505 (14)	0.0635 (16)	0.0366 (13)	0.0230 (12)	0.0021 (10)	−0.0024 (10)
N3	0.0525 (15)	0.0684 (16)	0.0351 (13)	0.0244 (12)	0.0016 (10)	−0.0013 (10)
N4	0.0582 (15)	0.0540 (15)	0.0382 (13)	0.0189 (12)	−0.0012 (11)	0.0011 (10)
O6	0.0486 (11)	0.0548 (11)	0.0293 (9)	0.0211 (9)	0.0009 (8)	−0.0035 (7)

Geometric parameters (Å, º) top

O1—C13	1.306 (3)	C8—C12	1.377 (3)
O1—H1	0.8221	C8—C9	1.382 (3)
O2—C13	1.195 (3)	C9—C10	1.366 (3)
O5—N1	1.303 (2)	C9—H9	0.9300
O3—C20	1.312 (3)	C10—N4	1.333 (3)
O3—H3	0.8200	C10—H10	0.9300
O4—C20	1.205 (3)	C11—N4	1.326 (3)
C1—N1	1.347 (3)	C11—C12	1.380 (3)
C1—C2	1.358 (3)	C11—H11	0.9300
C1—H1A	0.9300	C12—H12	0.9300
C2—C3	1.381 (3)	C13—C14	1.497 (3)
C2—H2	0.9300	C14—C19	1.384 (3)
C3—C4	1.378 (3)	C14—C15	1.391 (3)
C3—C6	1.457 (3)	C15—C16	1.398 (3)
C4—C5	1.380 (3)	C15—H15	0.9300
C4—H4	0.9300	C16—C17	1.385 (3)
C5—N1	1.343 (3)	C16—C20	1.487 (3)
C5—H5A	0.9300	C17—C18	1.372 (3)
C6—N2	1.287 (3)	C17—H17	0.9300
C6—O6	1.358 (3)	C18—C19	1.372 (3)
C7—N3	1.290 (3)	C18—H18	0.9300
C7—O6	1.366 (3)	C19—H19	0.9300
C7—C8	1.454 (3)	N2—N3	1.400 (3)

C13—O1—H1	109.3	C8—C12—C11	118.4 (2)
C20—O3—H3	109.5	C8—C12—H12	120.8
N1—C1—C2	120.3 (2)	C11—C12—H12	120.8
N1—C1—H1A	119.8	O2—C13—O1	124.3 (3)
C2—C1—H1A	119.8	O2—C13—C14	122.8 (3)
C1—C2—C3	120.7 (2)	O1—C13—C14	112.8 (2)
C1—C2—H2	119.7	C19—C14—C15	119.2 (2)
C3—C2—H2	119.7	C19—C14—C13	118.7 (2)
C4—C3—C2	118.0 (2)	C15—C14—C13	122.0 (2)
C4—C3—C6	122.1 (2)	C14—C15—C16	120.4 (2)
C2—C3—C6	119.9 (2)	C14—C15—H15	119.8
C3—C4—C5	120.3 (2)	C16—C15—H15	119.8
C3—C4—H4	119.8	C17—C16—C15	118.9 (2)
C5—C4—H4	119.8	C17—C16—C20	119.1 (2)
N1—C5—C4	119.7 (2)	C15—C16—C20	122.0 (2)
N1—C5—H5A	120.1	C18—C17—C16	120.3 (2)
C4—C5—H5A	120.1	C18—C17—H17	119.8
N2—C6—O6	113.3 (2)	C16—C17—H17	119.8
N2—C6—C3	127.5 (2)	C19—C18—C17	120.8 (3)
O6—C6—C3	119.1 (2)	C19—C18—H18	119.6
N3—C7—O6	112.1 (2)	C17—C18—H18	119.6
N3—C7—C8	127.9 (2)	C18—C19—C14	120.2 (2)
O6—C7—C8	120.0 (2)	C18—C19—H19	119.9
C12—C8—C9	118.4 (2)	C14—C19—H19	119.9
C12—C8—C7	122.7 (2)	O4—C20—O3	123.4 (2)
C9—C8—C7	118.8 (2)	O4—C20—C16	123.4 (2)
C10—C9—C8	119.0 (2)	O3—C20—C16	113.2 (2)
C10—C9—H9	120.5	O5—N1—C5	120.9 (2)
C8—C9—H9	120.5	O5—N1—C1	118.2 (2)
N4—C10—C9	123.4 (2)	C5—N1—C1	120.9 (2)
N4—C10—H10	118.3	C6—N2—N3	105.6 (2)
C9—C10—H10	118.3	C7—N3—N2	106.81 (19)
N4—C11—C12	123.7 (2)	C11—N4—C10	117.1 (2)
N4—C11—H11	118.2	C6—O6—C7	102.14 (18)
C12—C11—H11	118.2

N1—C1—C2—C3	0.2 (4)	C14—C15—C16—C20	179.5 (2)
C1—C2—C3—C4	−0.2 (4)	C15—C16—C17—C18	−0.7 (4)
C1—C2—C3—C6	179.4 (2)	C20—C16—C17—C18	179.9 (2)
C2—C3—C4—C5	0.1 (4)	C16—C17—C18—C19	0.4 (4)
C6—C3—C4—C5	−179.5 (2)	C17—C18—C19—C14	0.6 (4)
C3—C4—C5—N1	0.0 (4)	C15—C14—C19—C18	−1.2 (4)
C4—C3—C6—N2	178.5 (3)	C13—C14—C19—C18	178.7 (2)
C2—C3—C6—N2	−1.1 (4)	C17—C16—C20—O4	3.7 (4)
C4—C3—C6—O6	−2.0 (4)	C15—C16—C20—O4	−175.7 (3)
C2—C3—C6—O6	178.4 (2)	C17—C16—C20—O3	−176.5 (2)
N3—C7—C8—C12	174.8 (2)	C15—C16—C20—O3	4.1 (4)
O6—C7—C8—C12	−4.2 (4)	C4—C5—N1—O5	178.7 (2)
N3—C7—C8—C9	−4.2 (4)	C4—C5—N1—C1	0.0 (4)
O6—C7—C8—C9	176.9 (2)	C2—C1—N1—O5	−178.8 (2)
C12—C8—C9—C10	−1.1 (4)	C2—C1—N1—C5	0.0 (4)
C7—C8—C9—C10	177.9 (2)	O6—C6—N2—N3	0.5 (3)
C8—C9—C10—N4	2.0 (4)	C3—C6—N2—N3	−179.9 (2)
C9—C8—C12—C11	−0.3 (4)	O6—C7—N3—N2	0.4 (3)
C7—C8—C12—C11	−179.3 (2)	C8—C7—N3—N2	−178.6 (2)
N4—C11—C12—C8	1.2 (4)	C6—N2—N3—C7	−0.5 (3)
O2—C13—C14—C19	6.8 (4)	C12—C11—N4—C10	−0.5 (4)
O1—C13—C14—C19	−173.4 (2)	C9—C10—N4—C11	−1.1 (4)
O2—C13—C14—C15	−173.3 (3)	N2—C6—O6—C7	−0.3 (3)
O1—C13—C14—C15	6.5 (4)	C3—C6—O6—C7	−179.9 (2)
C19—C14—C15—C16	0.9 (4)	N3—C7—O6—C6	0.0 (3)
C13—C14—C15—C16	−179.0 (2)	C8—C7—O6—C6	179.0 (2)
C14—C15—C16—C17	0.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N4	0.82	1.82	2.640 (2)	171
O3—H3···O5ⁱ	0.82	1.72	2.521 (3)	163

Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₈N₄O₂·C₈H₆O₄
M_r	406.35
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.0993 (18), 7.1770 (19), 19.823 (5)
α, β, γ (°)	93.003 (4), 98.481 (3), 112.745 (4)
V (Å³)	914.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.15 × 0.06

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4661, 3189, 1972
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.132, 0.98
No. of reflections	3189
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.15

Computer programs: SMART (Bruker 2000), SAINT (Bruker 2000), 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—H1···N4	0.82	1.82	2.640 (2)	171.0
O3—H3···O5ⁱ	0.82	1.72	2.521 (3)	163.4

Symmetry code: (i) x+1, y+1, z+1.

Acknowledgements

The authors thank the National Natural Science Foundation of China (grant No. 20671060) and Shangdong Natural Science Foundation (grant Nos. J06D05 and 2006BS04040) for support.

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