4-[4-(1H-Tetra­zol-5-yl)phen­oxy]benzaldehyde

Lu, J.; Xu, J.; Ni, L.-W.; Ma, W.-L.; Du, Z.-T.

doi:10.1107/S1600536811044254

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3106

doi:10.1107/S1600536811044254

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4-[4-(1H-Tetrazol-5-yl)phenoxy]benzaldehyde

Jing Lu,^a Jiao Xu,^a Li-Wei Ni,^a Wei-Li Ma ^a and Zhen-Ting Du ^a ^*

^aCollege of Science, Northwest A&F University, Yangling Shaanxi 712100, People's Republic of China
^*Correspondence e-mail: duzt@nwsuaf.edu.cn

(Received 19 October 2011; accepted 24 October 2011; online 29 October 2011)

The asymmetric unit of the title compound, C₁₄H₁₀N₄O₂, contains two independent molecules with similar structures. In one molecule, the tetrazole ring is oriented at dihedral angles of 17.71 (16) and 57.13 (17)°, respectively, to the central benzene ring and the terminal benzene ring; in the other molecule, the corresponding dihedral angles are 16.46 (18) and 75.87 (18)°. Intermolecular N—H⋯N hydrogen bonds and weak C—H⋯O and C—H⋯N hydrogen bonds occur in the crystal structure.

Related literature

For the synthesis of 5-substituted 1H-tetrazoles, see: Ostrovskii et al. (2008 ); Saikia & Phukan (2009 ); Nasrollahzadeh et al. (2009 ); Teimouri & Najafi Chermahini (2011 ). For related structures, see: Li et al. (2008 ); Hu et al. (2009 ); Xu et al. (2010 ); Deng et al. (2010 ).

Experimental

Crystal data

C₁₄H₁₀N₄O₂
M_r = 266.26
Triclinic, $[P \overline 1]$
a = 9.854 (4) Å
b = 9.948 (4) Å
c = 14.139 (6) Å
α = 98.537 (4)°
β = 106.668 (4)°
γ = 99.737 (4)°
V = 1279.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.23 × 0.21 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
9274 measured reflections
4683 independent reflections
2623 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.142
S = 1.01
4683 reflections
369 parameters
30 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N8ⁱ	0.91 (3)	1.94 (3)	2.849 (4)	174 (2)
N5—H2N⋯N4ⁱⁱ	0.90 (3)	2.03 (3)	2.924 (3)	176 (3)
C4—H4⋯O4	0.93	2.54	3.420 (4)	158
C17—H17⋯N3ⁱⁱ	0.93	2.58	3.365 (4)	143
C23—H23⋯O2ⁱⁱⁱ	0.93	2.42	3.262 (6)	151
Symmetry codes: (i) x+1, y-1, z+1; (ii) x-1, y, z-1; (iii) -x, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2001 ); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I, New_Global_Publ_Block. DOI: 10.1107/S1600536811044254/xu5357sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044254/xu5357Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811044254/xu5357Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536811044254/xu5357Isup4.cml

checkCIF report

Comment top

Tetrazoles play a variety of roles in coordination chemistry, medicinal chemistry, materials chemistry etc. (Ostrovskii et al., 2008). We intended to find a new way for preparation of tetrazoles using a new solid acid which is regarded as a green catalyst. In order to confirm the verity of the final product, the single crystal X-ray analysis was performed and the structure is reported here.

Compared with the other phenyltetrazole coplanar structures reported by Li et al. (2008) and Xu et al. (2010), there is torsion between tetrazole rings and neighboring phenyl rings, with a dihedral angle 17.7 (1)° and 16.4 (4)°, respectively.

Related literature top

For the synthesis of 5-substituted 1H-tetrazoles, see: Ostrovskii et al. (2008); Saikia & Phukan (2009); Nasrollahzadeh et al. (2009); Teimouri & Najafi Chermahini (2011). For related structures, see: Li et al. (2008); Hu et al. (2009); Xu et al. (2010); Deng et al. (2010).

Experimental top

A solution of 4-(4-formylphenoxy)benzonitrile (892 mg, 4 mmol) and sodium azide (780 mg, 12 mmol) in dry DMF (15 mL) at the presence of sulfuric acid on silica gel (5% load, 400 mg ) was heated to 80°C. When the reaction was completed, the solid acid was filtered, 2 mL water was added to the filtration, and then was extracted with ethyl acetate (20 mL × 3). The ethyl acetate layers were combined and washed by 20 mL water, and then 15 mL saturated sodium chloride and dried over anhydrous sodium sulfate. The solution was evaporated and the residue was separated on silica gel column chromatography with a gradient of petroleum ether and ethyl acetate as eluent to yield 570 mg the title compound. The compound was then dissolved in methanol, and colorless crystals were formed on slow evaporation at room temperature over one week.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

4-[4-(1H-Tetrazol-5-yl)phenoxy]benzaldehyde top

Crystal data top

C₁₄H₁₀N₄O₂	Z = 4
M_r = 266.26	F(000) = 552
Triclinic, P1	D_x = 1.382 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.854 (4) Å	Cell parameters from 1475 reflections
b = 9.948 (4) Å	θ = 2.2–21.0°
c = 14.139 (6) Å	µ = 0.10 mm⁻¹
α = 98.537 (4)°	T = 296 K
β = 106.668 (4)°	Block, colourless
γ = 99.737 (4)°	0.23 × 0.21 × 0.19 mm
V = 1279.8 (9) Å³

Data collection top

Bruker APEXII CCD diffractometer	2623 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 25.5°, θ_min = 2.2°
ϕ and ω scans	h = −11→11
9274 measured reflections	k = −10→12
4683 independent reflections	l = −17→17

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0462P)² + 0.4163P] where P = (F_o² + 2F_c²)/3
4683 reflections	(Δ/σ)_max < 0.001
369 parameters	Δρ_max = 0.41 e Å⁻³
30 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₄H₁₀N₄O₂	γ = 99.737 (4)°
M_r = 266.26	V = 1279.8 (9) Å³
Triclinic, P1	Z = 4
a = 9.854 (4) Å	Mo Kα radiation
b = 9.948 (4) Å	µ = 0.10 mm⁻¹
c = 14.139 (6) Å	T = 296 K
α = 98.537 (4)°	0.23 × 0.21 × 0.19 mm
β = 106.668 (4)°

Data collection top

Bruker APEXII CCD diffractometer	2623 reflections with I > 2σ(I)
9274 measured reflections	R_int = 0.035
4683 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	30 restraints
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.41 e Å⁻³
4683 reflections	Δρ_min = −0.30 e Å⁻³
369 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.8863 (3)	0.1795 (3)	1.0915 (2)	0.0414 (7)
C2	0.7457 (3)	0.1392 (3)	1.0126 (2)	0.0415 (7)
C3	0.6554 (3)	0.2318 (3)	1.0004 (2)	0.0514 (8)
H3	0.6862	0.3205	1.0416	0.062*
C4	0.5208 (3)	0.1945 (3)	0.9283 (2)	0.0602 (8)
H4	0.4598	0.2568	0.9209	0.072*
C5	0.4773 (3)	0.0638 (3)	0.8672 (2)	0.0543 (8)
C6	0.5645 (3)	−0.0298 (3)	0.8772 (2)	0.0597 (8)
H6	0.5335	−0.1177	0.8349	0.072*
C7	0.6986 (3)	0.0072 (3)	0.9504 (2)	0.0533 (8)
H7	0.7580	−0.0564	0.9583	0.064*
C8	0.3025 (3)	0.0912 (3)	0.7196 (2)	0.0558 (8)
C9	0.1567 (3)	0.0772 (4)	0.6724 (3)	0.0728 (10)
H9	0.0880	0.0209	0.6914	0.087*
C10	0.1142 (4)	0.1482 (4)	0.5964 (3)	0.0820 (11)
H10	0.0155	0.1401	0.5647	0.098*
C11	0.2142 (4)	0.2309 (4)	0.5662 (3)	0.0718 (9)
C12	0.3588 (4)	0.2389 (3)	0.6127 (2)	0.0668 (9)
H12	0.4274	0.2921	0.5918	0.080*
C13	0.4051 (3)	0.1701 (3)	0.6898 (2)	0.0629 (9)
H13	0.5037	0.1769	0.7208	0.075*
C14	0.1805 (5)	0.3200 (5)	0.4876 (3)	0.1064 (14)
H14	0.2555	0.3725	0.4720	0.128*
C15	−0.0013 (3)	0.7097 (3)	0.1508 (2)	0.0430 (7)
C16	0.1047 (3)	0.7403 (3)	0.2513 (2)	0.0455 (7)
C17	0.1222 (4)	0.6369 (3)	0.3065 (2)	0.0667 (9)
H17	0.0665	0.5468	0.2782	0.080*
C18	0.2201 (4)	0.6649 (3)	0.4020 (2)	0.0747 (11)
H18	0.2318	0.5936	0.4373	0.090*
C19	0.3005 (3)	0.7972 (3)	0.4453 (2)	0.0587 (8)
C20	0.2850 (3)	0.9026 (3)	0.3926 (2)	0.0606 (9)
H20	0.3397	0.9927	0.4219	0.073*
C21	0.1884 (3)	0.8738 (3)	0.2964 (2)	0.0530 (8)
H21	0.1788	0.9451	0.2609	0.064*
C22	0.4087 (4)	0.7458 (3)	0.6065 (2)	0.0612 (9)
C23	0.2899 (4)	0.7028 (3)	0.6363 (3)	0.0678 (9)
H23	0.2027	0.7280	0.6082	0.081*
C24	0.3016 (3)	0.6222 (3)	0.7079 (3)	0.0627 (9)
H24	0.2217	0.5927	0.7282	0.075*
C25	0.4307 (3)	0.5845 (3)	0.7501 (2)	0.0551 (8)
C26	0.5488 (4)	0.6304 (3)	0.7202 (3)	0.0644 (9)
H26	0.6365	0.6065	0.7489	0.077*
C27	0.5387 (4)	0.7110 (3)	0.6487 (3)	0.0663 (9)
H27	0.6189	0.7416	0.6290	0.080*
C28	0.4455 (4)	0.4991 (3)	0.8268 (3)	0.0734 (10)
H28	0.5360	0.4795	0.8538	0.088*
N1	0.9674 (3)	0.0935 (3)	1.12958 (18)	0.0499 (6)
N2	1.0895 (3)	0.1684 (2)	1.20221 (19)	0.0581 (7)
N3	1.0818 (3)	0.2977 (2)	1.20764 (19)	0.0584 (7)
N4	0.9565 (2)	0.3084 (2)	1.13952 (18)	0.0503 (6)
N5	−0.0625 (3)	0.5829 (2)	0.09329 (18)	0.0466 (6)
N6	−0.1563 (3)	0.5921 (2)	0.00568 (18)	0.0545 (6)
N7	−0.1514 (3)	0.7233 (2)	0.00983 (18)	0.0565 (7)
N8	−0.0556 (3)	0.7999 (2)	0.09919 (18)	0.0520 (6)
O1	0.3385 (2)	0.0200 (2)	0.79639 (17)	0.0707 (7)
O2	0.0601 (4)	0.3220 (4)	0.4469 (3)	0.1609 (14)
O3	0.4057 (2)	0.8339 (2)	0.53920 (17)	0.0789 (7)
O4	0.3497 (3)	0.4526 (3)	0.8575 (2)	0.0967 (9)
H2N	−0.053 (3)	0.499 (3)	0.107 (2)	0.058 (9)*
H1N	0.954 (3)	−0.001 (3)	1.117 (2)	0.081 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0474 (17)	0.0281 (14)	0.0483 (17)	0.0103 (13)	0.0123 (14)	0.0106 (13)
C2	0.0441 (16)	0.0303 (14)	0.0494 (17)	0.0101 (12)	0.0107 (14)	0.0121 (12)
C3	0.0529 (19)	0.0350 (15)	0.0599 (19)	0.0138 (14)	0.0082 (16)	0.0058 (14)
C4	0.0524 (19)	0.0473 (18)	0.076 (2)	0.0198 (16)	0.0077 (17)	0.0148 (17)
C5	0.0447 (18)	0.0490 (18)	0.0581 (19)	0.0046 (15)	0.0008 (15)	0.0153 (15)
C6	0.065 (2)	0.0373 (16)	0.061 (2)	0.0086 (15)	0.0021 (17)	0.0003 (14)
C7	0.0558 (19)	0.0388 (16)	0.0597 (19)	0.0161 (14)	0.0080 (16)	0.0082 (14)
C8	0.053 (2)	0.0499 (18)	0.0533 (19)	0.0130 (16)	0.0014 (16)	0.0058 (15)
C9	0.046 (2)	0.094 (3)	0.073 (2)	0.0132 (19)	0.0095 (18)	0.024 (2)
C10	0.052 (2)	0.119 (3)	0.070 (2)	0.031 (2)	0.004 (2)	0.022 (2)
C11	0.069 (2)	0.093 (3)	0.060 (2)	0.041 (2)	0.0175 (19)	0.0136 (18)
C12	0.071 (2)	0.069 (2)	0.061 (2)	0.0207 (19)	0.0215 (19)	0.0127 (18)
C13	0.0494 (19)	0.068 (2)	0.063 (2)	0.0149 (17)	0.0072 (17)	0.0101 (18)
C14	0.090 (3)	0.133 (3)	0.086 (3)	0.070 (2)	−0.007 (2)	0.011 (2)
C15	0.0487 (17)	0.0287 (14)	0.0513 (17)	0.0090 (13)	0.0157 (14)	0.0082 (13)
C16	0.0487 (17)	0.0318 (15)	0.0509 (17)	0.0096 (13)	0.0088 (14)	0.0062 (13)
C17	0.083 (2)	0.0308 (16)	0.062 (2)	−0.0002 (16)	−0.0051 (18)	0.0075 (15)
C18	0.096 (3)	0.0411 (18)	0.062 (2)	0.0041 (18)	−0.009 (2)	0.0154 (16)
C19	0.058 (2)	0.0500 (19)	0.0533 (19)	0.0019 (16)	0.0007 (16)	0.0103 (16)
C20	0.0534 (19)	0.0372 (17)	0.073 (2)	−0.0035 (14)	0.0022 (17)	0.0066 (16)
C21	0.0505 (18)	0.0336 (15)	0.067 (2)	0.0050 (14)	0.0064 (16)	0.0148 (14)
C22	0.059 (2)	0.0532 (19)	0.0505 (19)	−0.0055 (17)	−0.0011 (17)	0.0063 (16)
C23	0.053 (2)	0.065 (2)	0.071 (2)	0.0110 (17)	0.0019 (18)	0.0117 (19)
C24	0.053 (2)	0.061 (2)	0.071 (2)	0.0094 (17)	0.0178 (17)	0.0098 (18)
C25	0.058 (2)	0.0457 (18)	0.0545 (19)	0.0123 (16)	0.0111 (17)	0.0031 (15)
C26	0.053 (2)	0.062 (2)	0.070 (2)	0.0134 (17)	0.0078 (18)	0.0096 (18)
C27	0.051 (2)	0.072 (2)	0.068 (2)	0.0037 (17)	0.0157 (18)	0.0101 (19)
C28	0.085 (3)	0.060 (2)	0.080 (3)	0.026 (2)	0.030 (2)	0.011 (2)
N1	0.0518 (16)	0.0326 (14)	0.0574 (16)	0.0109 (12)	0.0044 (13)	0.0101 (12)
N2	0.0553 (16)	0.0395 (14)	0.0648 (17)	0.0116 (12)	−0.0032 (13)	0.0093 (12)
N3	0.0588 (17)	0.0371 (14)	0.0655 (17)	0.0109 (12)	−0.0001 (14)	0.0086 (12)
N4	0.0510 (15)	0.0313 (13)	0.0593 (15)	0.0086 (11)	0.0048 (13)	0.0077 (11)
N5	0.0557 (15)	0.0295 (13)	0.0505 (15)	0.0124 (12)	0.0078 (12)	0.0106 (11)
N6	0.0652 (17)	0.0411 (14)	0.0505 (16)	0.0131 (12)	0.0072 (13)	0.0103 (12)
N7	0.0693 (17)	0.0396 (14)	0.0541 (16)	0.0144 (13)	0.0083 (14)	0.0107 (12)
N8	0.0654 (16)	0.0334 (13)	0.0548 (15)	0.0156 (12)	0.0108 (13)	0.0132 (12)
O1	0.0513 (13)	0.0620 (14)	0.0781 (16)	−0.0014 (11)	−0.0063 (12)	0.0215 (12)
O2	0.142 (3)	0.222 (4)	0.138 (3)	0.066 (3)	0.038 (3)	0.081 (3)
O3	0.0761 (16)	0.0672 (15)	0.0615 (15)	−0.0176 (12)	−0.0099 (13)	0.0190 (12)
O4	0.129 (2)	0.0865 (19)	0.111 (2)	0.0483 (18)	0.071 (2)	0.0389 (17)

Geometric parameters (Å, º) top

C1—N4	1.325 (3)	C16—C21	1.388 (4)
C1—N1	1.335 (3)	C17—C18	1.373 (4)
C1—C2	1.455 (4)	C17—H17	0.9300
C2—C3	1.381 (3)	C18—C19	1.366 (4)
C2—C7	1.389 (4)	C18—H18	0.9300
C3—C4	1.372 (4)	C19—C20	1.378 (4)
C3—H3	0.9300	C19—O3	1.381 (3)
C4—C5	1.373 (4)	C20—C21	1.374 (4)
C4—H4	0.9300	C20—H20	0.9300
C5—C6	1.366 (4)	C21—H21	0.9300
C5—O1	1.396 (3)	C22—C27	1.375 (4)
C6—C7	1.374 (4)	C22—C23	1.378 (4)
C6—H6	0.9300	C22—O3	1.384 (4)
C7—H7	0.9300	C23—C24	1.374 (4)
C8—C13	1.375 (4)	C23—H23	0.9300
C8—C9	1.372 (4)	C24—C25	1.381 (4)
C8—O1	1.378 (3)	C24—H24	0.9300
C9—C10	1.377 (4)	C25—C26	1.378 (4)
C9—H9	0.9300	C25—C28	1.464 (4)
C10—C11	1.380 (5)	C26—C27	1.373 (4)
C10—H10	0.9300	C26—H26	0.9300
C11—C12	1.369 (4)	C27—H27	0.9300
C11—C14	1.520 (5)	C28—O4	1.200 (4)
C12—C13	1.381 (4)	C28—H28	0.9300
C12—H12	0.9300	N1—N2	1.349 (3)
C13—H13	0.9300	N1—H1N	0.91 (3)
C14—O2	1.166 (4)	N2—N3	1.294 (3)
C14—H14	0.9300	N3—N4	1.363 (3)
C15—N8	1.325 (3)	N5—N6	1.343 (3)
C15—N5	1.332 (3)	N5—H2N	0.90 (3)
C15—C16	1.455 (4)	N6—N7	1.291 (3)
C16—C17	1.385 (4)	N7—N8	1.362 (3)

N4—C1—N1	107.5 (2)	C18—C17—H17	119.4
N4—C1—C2	126.2 (2)	C16—C17—H17	119.4
N1—C1—C2	126.3 (2)	C19—C18—C17	120.1 (3)
C3—C2—C7	119.0 (3)	C19—C18—H18	119.9
C3—C2—C1	119.8 (2)	C17—C18—H18	119.9
C7—C2—C1	121.1 (2)	C18—C19—C20	120.1 (3)
C4—C3—C2	120.8 (3)	C18—C19—O3	124.1 (3)
C4—C3—H3	119.6	C20—C19—O3	115.7 (3)
C2—C3—H3	119.6	C21—C20—C19	119.7 (3)
C5—C4—C3	119.0 (3)	C21—C20—H20	120.1
C5—C4—H4	120.5	C19—C20—H20	120.1
C3—C4—H4	120.5	C20—C21—C16	121.2 (3)
C6—C5—C4	121.5 (3)	C20—C21—H21	119.4
C6—C5—O1	117.8 (3)	C16—C21—H21	119.4
C4—C5—O1	120.6 (3)	C27—C22—C23	120.9 (3)
C5—C6—C7	119.3 (3)	C27—C22—O3	117.3 (3)
C5—C6—H6	120.3	C23—C22—O3	121.6 (3)
C7—C6—H6	120.3	C24—C23—C22	119.3 (3)
C6—C7—C2	120.3 (3)	C24—C23—H23	120.4
C6—C7—H7	119.8	C22—C23—H23	120.4
C2—C7—H7	119.8	C23—C24—C25	120.7 (3)
C13—C8—C9	121.2 (3)	C23—C24—H24	119.6
C13—C8—O1	122.7 (3)	C25—C24—H24	119.6
C9—C8—O1	116.1 (3)	C24—C25—C26	119.1 (3)
C8—C9—C10	118.7 (3)	C24—C25—C28	121.5 (3)
C8—C9—H9	120.7	C26—C25—C28	119.4 (3)
C10—C9—H9	120.7	C27—C26—C25	120.9 (3)
C9—C10—C11	121.6 (3)	C27—C26—H26	119.5
C9—C10—H10	119.2	C25—C26—H26	119.5
C11—C10—H10	119.2	C26—C27—C22	119.2 (3)
C12—C11—C10	118.1 (3)	C26—C27—H27	120.4
C12—C11—C14	115.6 (4)	C22—C27—H27	120.4
C10—C11—C14	126.3 (4)	O4—C28—C25	124.9 (4)
C11—C12—C13	121.7 (3)	O4—C28—H28	117.5
C11—C12—H12	119.2	C25—C28—H28	117.5
C13—C12—H12	119.2	C1—N1—N2	109.5 (2)
C8—C13—C12	118.6 (3)	C1—N1—H1N	133 (2)
C8—C13—H13	120.7	N2—N1—H1N	117 (2)
C12—C13—H13	120.7	N3—N2—N1	106.1 (2)
O2—C14—C11	119.7 (5)	N2—N3—N4	110.5 (2)
O2—C14—H14	120.2	C1—N4—N3	106.4 (2)
C11—C14—H14	120.2	C15—N5—N6	109.9 (2)
N8—C15—N5	107.1 (2)	C15—N5—H2N	129.8 (18)
N8—C15—C16	127.5 (2)	N6—N5—H2N	120.1 (18)
N5—C15—C16	125.4 (2)	N7—N6—N5	106.0 (2)
C17—C16—C21	117.8 (3)	N6—N7—N8	110.5 (2)
C17—C16—C15	120.6 (2)	C15—N8—N7	106.5 (2)
C21—C16—C15	121.6 (3)	C8—O1—C5	118.2 (2)
C18—C17—C16	121.2 (3)	C19—O3—C22	119.9 (2)

N4—C1—C2—C3	−17.7 (4)	C19—C20—C21—C16	0.5 (5)
N1—C1—C2—C3	161.4 (3)	C17—C16—C21—C20	−0.1 (4)
N4—C1—C2—C7	163.8 (3)	C15—C16—C21—C20	178.0 (3)
N1—C1—C2—C7	−17.1 (4)	C27—C22—C23—C24	−1.0 (5)
C7—C2—C3—C4	0.3 (4)	O3—C22—C23—C24	−176.1 (3)
C1—C2—C3—C4	−178.3 (3)	C22—C23—C24—C25	0.1 (5)
C2—C3—C4—C5	−0.8 (5)	C23—C24—C25—C26	0.8 (5)
C3—C4—C5—C6	0.5 (5)	C23—C24—C25—C28	179.7 (3)
C3—C4—C5—O1	176.9 (3)	C24—C25—C26—C27	−0.8 (5)
C4—C5—C6—C7	0.3 (5)	C28—C25—C26—C27	−179.8 (3)
O1—C5—C6—C7	−176.1 (3)	C25—C26—C27—C22	−0.1 (5)
C5—C6—C7—C2	−0.9 (5)	C23—C22—C27—C26	1.0 (5)
C3—C2—C7—C6	0.6 (4)	O3—C22—C27—C26	176.3 (3)
C1—C2—C7—C6	179.1 (3)	C24—C25—C28—O4	1.9 (5)
C13—C8—C9—C10	−2.4 (5)	C26—C25—C28—O4	−179.2 (3)
O1—C8—C9—C10	178.8 (3)	N4—C1—N1—N2	0.0 (3)
C8—C9—C10—C11	0.8 (6)	C2—C1—N1—N2	−179.2 (3)
C9—C10—C11—C12	1.3 (5)	C1—N1—N2—N3	0.0 (3)
C9—C10—C11—C14	−176.4 (3)	N1—N2—N3—N4	−0.1 (3)
C10—C11—C12—C13	−1.8 (5)	N1—C1—N4—N3	−0.1 (3)
C14—C11—C12—C13	176.1 (3)	C2—C1—N4—N3	179.1 (3)
C9—C8—C13—C12	1.9 (5)	N2—N3—N4—C1	0.1 (3)
O1—C8—C13—C12	−179.4 (3)	N8—C15—N5—N6	−0.5 (3)
C11—C12—C13—C8	0.3 (5)	C16—C15—N5—N6	179.3 (3)
C12—C11—C14—O2	−177.7 (4)	C15—N5—N6—N7	0.3 (3)
C10—C11—C14—O2	0.0 (7)	N5—N6—N7—N8	−0.1 (3)
N8—C15—C16—C17	162.4 (3)	N5—C15—N8—N7	0.4 (3)
N5—C15—C16—C17	−17.4 (4)	C16—C15—N8—N7	−179.4 (3)
N8—C15—C16—C21	−15.7 (5)	N6—N7—N8—C15	−0.2 (3)
N5—C15—C16—C21	164.5 (3)	C13—C8—O1—C5	21.7 (4)
C21—C16—C17—C18	−0.8 (5)	C9—C8—O1—C5	−159.5 (3)
C15—C16—C17—C18	−178.9 (3)	C6—C5—O1—C8	−120.5 (3)
C16—C17—C18—C19	1.4 (6)	C4—C5—O1—C8	63.0 (4)
C17—C18—C19—C20	−1.0 (5)	C18—C19—O3—C22	−17.6 (5)
C17—C18—C19—O3	−177.2 (3)	C20—C19—O3—C22	166.1 (3)
C18—C19—C20—C21	0.1 (5)	C27—C22—O3—C19	128.5 (3)
O3—C19—C20—C21	176.6 (3)	C23—C22—O3—C19	−56.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N8ⁱ	0.91 (3)	1.94 (3)	2.849 (4)	174 (2)
N5—H2N···N4ⁱⁱ	0.90 (3)	2.03 (3)	2.924 (3)	176 (3)
C4—H4···O4	0.93	2.54	3.420 (4)	158
C17—H17···N3ⁱⁱ	0.93	2.58	3.365 (4)	143
C23—H23···O2ⁱⁱⁱ	0.93	2.42	3.262 (6)	151

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀N₄O₂
M_r	266.26
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.854 (4), 9.948 (4), 14.139 (6)
α, β, γ (°)	98.537 (4), 106.668 (4), 99.737 (4)
V (Å³)	1279.8 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.23 × 0.21 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9274, 4683, 2623
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.142, 1.01
No. of reflections	4683
No. of parameters	369
No. of restraints	30
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.30

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N8ⁱ	0.91 (3)	1.94 (3)	2.849 (4)	174 (2)
N5—H2N···N4ⁱⁱ	0.90 (3)	2.03 (3)	2.924 (3)	176 (3)
C4—H4···O4	0.93	2.54	3.420 (4)	158
C17—H17···N3ⁱⁱ	0.93	2.58	3.365 (4)	143
C23—H23···O2ⁱⁱⁱ	0.93	2.42	3.262 (6)	151

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

Acknowledgements

Financial support from the Fundamental Research Funds for the Central Universities in NWSUAF (No. QN2009048) and the opening project of Xinjiang Production & Construction Corps Key Laboratory of Protection and Utilization of Biological Resources in Tarim Basin (BRTD1004) as well as the National Natural Science Foundation of China (20802058) are greatly appreciated.

References

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