3,5-Dimethyl-1H-pyrazole–2-hy­droxy-5-(phenyl­diazen­yl)benzoic acid (1/1)

Xu, Y.; Jin, S.; Zhu, J.; Liu, Y.-J.; Shi, C.-C.

doi:10.1107/S1600536811034970

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2528

doi:10.1107/S1600536811034970

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3,5-Dimethyl-1H-pyrazole–2-hydroxy-5-(phenyldiazenyl)benzoic acid (1/1)

Yichao Xu,^a Shouwen Jin,^a ^* Jianlong Zhu,^a Ying-Jia Liu ^a and Chuan-Chuan Shi ^a

^aTianmu college of ZheJiang A & F University, Lin'An 311300, People's Republic of China
^*Correspondence e-mail: JINSW@yahoo.cn

(Received 12 August 2011; accepted 25 August 2011; online 31 August 2011)

There are two independent 3,5-dimethylpyrazole and two independent 2-hydroxy-5-(phenyldiazenyl)benzoic acid molecules [in which intramolecular O—H⋯O bonds form S(6) graph-set motifs] in the asymmetric unit of the title compound, C₅H₈N₂·C₁₃H₁₀N₂O₃. In the crystal, the components are linked by intermolecular O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds, forming four-component clusters. Further stabilization is provided by weak C—H⋯π interactions.

Related literature

For general background to hydrogen-bonding interactions, see: Lam & Mak (2000 ); Desiraju (2002 ); Liu et al. (2008 ); Biswas et al. (2009 ); Jin et al. (2010 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₅H₈N₂·C₁₃H₁₀N₂O₃
M_r = 338.36
Triclinic, $[P \overline 1]$
a = 11.4871 (11) Å
b = 12.4746 (13) Å
c = 13.2235 (16) Å
α = 86.650 (2)°
β = 67.540 (1)°
γ = 77.715 (1)°
V = 1710.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.38 × 0.28 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.970, T_max = 0.982
8928 measured reflections
5945 independent reflections
2614 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.159
S = 0.99
5945 reflections
455 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C31–C36 and C25–C30 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6⋯O2ⁱ	0.82	2.43	3.019 (3)	129
O6—H6⋯O5	0.82	1.89	2.605 (3)	145
O4—H4A⋯N4ⁱⁱ	0.82	1.75	2.564 (3)	169
O3—H3A⋯O5ⁱⁱⁱ	0.82	2.45	3.019 (3)	128
O3—H3A⋯O2	0.82	1.85	2.574 (3)	147
O1—H1A⋯N1^iv	0.82	1.75	2.565 (3)	171
N3—H3⋯O3^v	0.86	2.17	3.008 (3)	165
N2—H2⋯O6^vi	0.86	2.15	3.002 (3)	170
C1—H1D⋯Cg1^vii	0.96	2.75	3.677 (4)	164
C5—H5B⋯Cg2^vii	0.96	2.96	3.840 (4)	153
Symmetry codes: (i) x, y-1, z-1; (ii) -x+2, -y+1, -z; (iii) x, y+1, z+1; (iv) x, y, z+1; (v) -x+2, -y+2, -z+1; (vi) x, y+1, z; (vii) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811034970/lh5315sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034970/lh5315Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811034970/lh5315Isup3.cml

checkCIF report

Comment top

Intermolecular interactions are responsible for crystal packing and gaining an understanding of these interactions allows the comprehension of the collective properties and permits the design of new crystals with specific physical and chemical properties (Lam & Mak, 2000). Hydrogen bonding is one of the most important noncovalent interactions that determines and controls the assembly of molecules and ions (Desiraju, 2002, Liu et al., 2008, Biswas et al., 2009). As an extension of our study concentrating on hydrogen bonded assembly of organic acids and organic bases (Jin et al., 2010), herein we report the crystal structure of the 1:1 adduct of 3,5-dimethyl pyrazole and 2-hydroxy-5-(phenyldiazenyl)benzoic acid.

The asymmetric unit of the compound consists of two independent 3,5-dimethyl pyrazole and two independent 2-hydroxy-5-(phenyldiazenyl)benzoic acid molecules (Fig. 1). Intramolecular hydrogen bonds between the phenol O—H groups and the carbonyl groups form S(6) graph motifs (Bernstein et al., 1995). The two independent carboxylic acid molecules form a dimer through O—H···O hydrogen bonds in which the phenol group is the donor and the carbonyl O atom acts as the acceptor. The two pyrazole molecules are linked to the carboxylic dimer through the N—H···O, and O—H···N hydrogen bonds to form a four component adduct containing R₂²(12) and R₃³(9) ring motifs (Fig. 2). Further stabilization is provided by weak C—H···π interactions.

Related literature top

For general background to hydrogen-bonding interactions, see: Lam & Mak (2000); Desiraju (2002); Liu et al. (2008); Biswas et al. (2009); Jin et al. (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A solution of 3,5-dimethyl pyrazole (19.2 mg, 0.2 mmol) in 5 ml of MeOH was added to a MeOH solution (3 ml) containing 2-hydroxy-5-(phenyldiazenyl)benzoic acid (48.4 mg, 0.2 mmol) under continuous stirring. The solution was stirred for about 1 h at room temperature, then the solution was filtered into a test tube. The solution was left standing at room temperature for several days, red block-shaped crystals were isolated after slow evaporation of the solution in air at ambient temperature.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.

3,5-Dimethyl-1H-pyrazole–2-hydroxy-5-(phenyldiazenyl)benzoic acid (1/1) top

Crystal data top

C₅H₈N₂·C₁₃H₁₀N₂O₃	Z = 4
M_r = 338.36	F(000) = 712
Triclinic, P1	D_x = 1.314 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.4871 (11) Å	Cell parameters from 1438 reflections
b = 12.4746 (13) Å	θ = 2.4–21.4°
c = 13.2235 (16) Å	µ = 0.09 mm⁻¹
α = 86.650 (2)°	T = 298 K
β = 67.540 (1)°	Block, red
γ = 77.715 (1)°	0.38 × 0.28 × 0.20 mm
V = 1710.5 (3) Å³

Data collection top

Bruker SMART CCD diffractometer	5945 independent reflections
Radiation source: fine-focus sealed tube	2614 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→13
T_min = 0.970, T_max = 0.982	k = −14→14
8928 measured reflections	l = −15→12

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0639P)²] where P = (F_o² + 2F_c²)/3
5945 reflections	(Δ/σ)_max < 0.001
455 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₅H₈N₂·C₁₃H₁₀N₂O₃	γ = 77.715 (1)°
M_r = 338.36	V = 1710.5 (3) Å³
Triclinic, P1	Z = 4
a = 11.4871 (11) Å	Mo Kα radiation
b = 12.4746 (13) Å	µ = 0.09 mm⁻¹
c = 13.2235 (16) Å	T = 298 K
α = 86.650 (2)°	0.38 × 0.28 × 0.20 mm
β = 67.540 (1)°

Data collection top

Bruker SMART CCD diffractometer	5945 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2614 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.982	R_int = 0.025
8928 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 0.99	Δρ_max = 0.21 e Å⁻³
5945 reflections	Δρ_min = −0.17 e Å⁻³
455 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
N1	0.4488 (2)	0.8896 (2)	0.1548 (2)	0.0495 (7)
N2	0.4409 (2)	0.9469 (2)	0.2418 (2)	0.0517 (7)
H2	0.4842	0.9967	0.2372	0.062*
N3	0.8917 (3)	0.8335 (2)	0.1146 (2)	0.0589 (8)
H3	0.9400	0.8778	0.1139	0.071*
N4	0.9161 (3)	0.7637 (2)	0.0310 (2)	0.0627 (8)
N5	0.8889 (2)	0.7607 (2)	0.5787 (2)	0.0552 (8)
N6	0.9694 (2)	0.7542 (2)	0.4833 (2)	0.0556 (8)
N7	0.6155 (3)	0.3798 (2)	0.5330 (2)	0.0520 (7)
N8	0.5186 (3)	0.4064 (2)	0.6184 (2)	0.0538 (7)
O1	0.61956 (19)	0.87430 (17)	0.95957 (16)	0.0598 (7)
H1A	0.5662	0.8861	1.0223	0.090*
O2	0.7063 (2)	0.99484 (18)	1.01085 (16)	0.0576 (6)
O3	0.9136 (2)	1.04618 (19)	0.87199 (18)	0.0731 (8)
H3A	0.8553	1.0448	0.9318	0.110*
O4	0.8984 (2)	0.25974 (19)	0.15689 (17)	0.0732 (8)
H4A	0.9552	0.2444	0.0962	0.110*
O5	0.8065 (2)	0.1510 (2)	0.09796 (19)	0.0806 (8)
O6	0.5691 (2)	0.13862 (17)	0.21526 (17)	0.0638 (7)
H6	0.6370	0.1266	0.1618	0.096*
C1	0.3553 (3)	0.7443 (3)	0.1208 (3)	0.0678 (11)
H1B	0.3986	0.7633	0.0464	0.102*
H1C	0.2657	0.7498	0.1353	0.102*
H1D	0.3928	0.6705	0.1323	0.102*
C2	0.3689 (3)	0.8209 (3)	0.1960 (3)	0.0491 (8)
C3	0.3104 (3)	0.8361 (3)	0.3096 (2)	0.0548 (9)
H3B	0.2508	0.7982	0.3576	0.066*
C4	0.3572 (3)	0.9167 (3)	0.3362 (2)	0.0492 (9)
C5	0.3317 (3)	0.9694 (3)	0.4430 (2)	0.0640 (10)
H5A	0.4039	0.9999	0.4373	0.096*
H5B	0.3187	0.9156	0.4989	0.096*
H5C	0.2559	1.0268	0.4615	0.096*
C6	0.7346 (3)	0.8921 (3)	0.3023 (3)	0.0678 (10)
H6A	0.7835	0.8618	0.3459	0.102*
H6B	0.6453	0.8916	0.3427	0.102*
H6C	0.7447	0.9662	0.2846	0.102*
C7	0.7820 (3)	0.8248 (3)	0.1991 (3)	0.0526 (9)
C8	0.7350 (3)	0.7468 (3)	0.1691 (3)	0.0580 (10)
H8	0.6600	0.7225	0.2106	0.070*
C9	0.8199 (3)	0.7099 (3)	0.0644 (3)	0.0576 (9)
C10	0.8155 (4)	0.6257 (3)	−0.0085 (3)	0.0884 (13)
H10A	0.8595	0.6427	−0.0835	0.133*
H10B	0.7275	0.6254	0.0044	0.133*
H10C	0.8569	0.5548	0.0066	0.133*
C11	0.7069 (3)	0.9320 (3)	0.9424 (2)	0.0466 (8)
C12	0.8086 (3)	0.9170 (2)	0.8312 (2)	0.0421 (8)
C13	0.9061 (3)	0.9767 (3)	0.8012 (3)	0.0527 (9)
C14	0.9967 (3)	0.9671 (3)	0.6950 (3)	0.0680 (11)
H14	1.0596	1.0091	0.6743	0.082*
C15	0.9950 (3)	0.8972 (3)	0.6202 (3)	0.0606 (10)
H15	1.0573	0.8911	0.5495	0.073*
C16	0.9007 (3)	0.8348 (3)	0.6493 (2)	0.0489 (8)
C17	0.8081 (3)	0.8470 (2)	0.7541 (2)	0.0473 (8)
H17	0.7435	0.8070	0.7734	0.057*
C18	0.9564 (3)	0.6770 (3)	0.4144 (3)	0.0529 (9)
C19	1.0231 (3)	0.6814 (3)	0.3045 (3)	0.0679 (11)
H19	1.0742	0.7331	0.2772	0.081*
C20	1.0147 (4)	0.6087 (4)	0.2336 (3)	0.0809 (12)
H20	1.0599	0.6118	0.1586	0.097*
C21	0.9407 (4)	0.5330 (4)	0.2733 (4)	0.0923 (14)
H21	0.9358	0.4834	0.2260	0.111*
C22	0.8738 (5)	0.5302 (4)	0.3826 (4)	0.127 (2)
H22	0.8214	0.4793	0.4099	0.152*
C23	0.8823 (4)	0.6011 (3)	0.4529 (3)	0.1058 (17)
H23	0.8370	0.5973	0.5277	0.127*
C24	0.8065 (3)	0.2099 (3)	0.1692 (3)	0.0570 (9)
C25	0.6965 (3)	0.2315 (2)	0.2758 (2)	0.0465 (8)
C26	0.5819 (3)	0.1987 (2)	0.2917 (3)	0.0483 (8)
C27	0.4752 (3)	0.2303 (3)	0.3866 (3)	0.0560 (9)
H27	0.3980	0.2110	0.3956	0.067*
C28	0.4815 (3)	0.2895 (3)	0.4676 (2)	0.0528 (9)
H28	0.4090	0.3099	0.5312	0.063*
C29	0.5965 (3)	0.3193 (2)	0.4548 (3)	0.0468 (8)
C30	0.7017 (3)	0.2909 (2)	0.3588 (2)	0.0488 (8)
H30	0.7780	0.3121	0.3493	0.059*
C31	0.5405 (3)	0.4670 (2)	0.6963 (2)	0.0496 (9)
C32	0.6597 (4)	0.4840 (3)	0.6864 (3)	0.0624 (10)
H32	0.7329	0.4540	0.6266	0.075*
C33	0.6705 (4)	0.5451 (3)	0.7646 (3)	0.0713 (11)
H33	0.7504	0.5575	0.7569	0.086*
C34	0.5632 (4)	0.5873 (3)	0.8538 (3)	0.0774 (12)
H34	0.5703	0.6280	0.9071	0.093*
C35	0.4450 (4)	0.5699 (3)	0.8646 (3)	0.0725 (11)
H35	0.3724	0.5992	0.9252	0.087*
C36	0.4329 (3)	0.5094 (3)	0.7868 (3)	0.0613 (10)
H36	0.3527	0.4972	0.7951	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0481 (16)	0.0578 (18)	0.0385 (16)	−0.0182 (14)	−0.0075 (13)	−0.0027 (14)
N2	0.0525 (17)	0.0597 (18)	0.0410 (17)	−0.0227 (14)	−0.0094 (14)	−0.0031 (14)
N3	0.0597 (19)	0.073 (2)	0.0483 (18)	−0.0304 (16)	−0.0164 (16)	0.0005 (16)
N4	0.0631 (19)	0.079 (2)	0.0451 (18)	−0.0292 (17)	−0.0107 (15)	−0.0092 (16)
N5	0.0552 (17)	0.0649 (19)	0.0401 (17)	−0.0225 (15)	−0.0053 (15)	−0.0099 (14)
N6	0.0554 (18)	0.0650 (19)	0.0389 (17)	−0.0170 (15)	−0.0061 (15)	−0.0080 (14)
N7	0.0613 (18)	0.0526 (17)	0.0398 (17)	−0.0159 (14)	−0.0140 (15)	−0.0031 (14)
N8	0.0633 (18)	0.0515 (17)	0.0436 (18)	−0.0136 (15)	−0.0154 (16)	−0.0032 (14)
O1	0.0581 (14)	0.0766 (16)	0.0376 (13)	−0.0327 (13)	0.0008 (11)	−0.0085 (11)
O2	0.0603 (15)	0.0695 (16)	0.0400 (13)	−0.0207 (12)	−0.0098 (11)	−0.0132 (12)
O3	0.0655 (15)	0.0945 (19)	0.0567 (16)	−0.0406 (14)	−0.0035 (13)	−0.0268 (14)
O4	0.0658 (16)	0.0992 (19)	0.0498 (15)	−0.0391 (15)	−0.0022 (13)	−0.0172 (13)
O5	0.0840 (18)	0.101 (2)	0.0523 (16)	−0.0412 (16)	−0.0049 (14)	−0.0297 (14)
O6	0.0666 (15)	0.0741 (16)	0.0534 (15)	−0.0312 (13)	−0.0141 (12)	−0.0171 (12)
C1	0.081 (3)	0.065 (2)	0.051 (2)	−0.024 (2)	−0.010 (2)	−0.0082 (18)
C2	0.056 (2)	0.049 (2)	0.041 (2)	−0.0153 (17)	−0.0139 (17)	0.0006 (16)
C3	0.065 (2)	0.052 (2)	0.038 (2)	−0.0221 (18)	−0.0052 (18)	0.0043 (16)
C4	0.053 (2)	0.053 (2)	0.035 (2)	−0.0107 (17)	−0.0085 (17)	0.0008 (16)
C5	0.076 (2)	0.067 (2)	0.047 (2)	−0.018 (2)	−0.0182 (19)	−0.0062 (18)
C6	0.070 (2)	0.073 (3)	0.056 (2)	−0.011 (2)	−0.018 (2)	−0.0111 (19)
C7	0.053 (2)	0.058 (2)	0.045 (2)	−0.0157 (18)	−0.0140 (18)	0.0003 (17)
C8	0.050 (2)	0.066 (2)	0.053 (2)	−0.0246 (18)	−0.0064 (18)	−0.0033 (18)
C9	0.059 (2)	0.065 (2)	0.050 (2)	−0.0225 (19)	−0.0167 (19)	−0.0048 (18)
C10	0.092 (3)	0.099 (3)	0.071 (3)	−0.036 (3)	−0.014 (2)	−0.029 (2)
C11	0.049 (2)	0.054 (2)	0.037 (2)	−0.0130 (18)	−0.0145 (17)	−0.0024 (17)
C12	0.0398 (18)	0.0488 (19)	0.0351 (18)	−0.0133 (15)	−0.0085 (15)	−0.0032 (15)
C13	0.050 (2)	0.062 (2)	0.048 (2)	−0.0189 (18)	−0.0142 (18)	−0.0120 (17)
C14	0.053 (2)	0.084 (3)	0.060 (2)	−0.041 (2)	0.004 (2)	−0.019 (2)
C15	0.048 (2)	0.075 (3)	0.049 (2)	−0.0275 (19)	0.0019 (18)	−0.0128 (19)
C16	0.0465 (19)	0.054 (2)	0.040 (2)	−0.0152 (17)	−0.0064 (17)	−0.0090 (16)
C17	0.0467 (19)	0.053 (2)	0.041 (2)	−0.0220 (16)	−0.0085 (17)	−0.0013 (16)
C18	0.047 (2)	0.058 (2)	0.046 (2)	−0.0089 (17)	−0.0081 (17)	−0.0142 (18)
C19	0.067 (2)	0.082 (3)	0.044 (2)	−0.020 (2)	−0.005 (2)	−0.012 (2)
C20	0.093 (3)	0.096 (3)	0.048 (2)	−0.004 (3)	−0.025 (2)	−0.021 (2)
C21	0.083 (3)	0.102 (4)	0.087 (4)	−0.019 (3)	−0.019 (3)	−0.048 (3)
C22	0.142 (4)	0.140 (4)	0.081 (4)	−0.090 (4)	0.014 (3)	−0.048 (3)
C23	0.135 (4)	0.106 (4)	0.058 (3)	−0.075 (3)	0.013 (3)	−0.031 (2)
C24	0.062 (2)	0.064 (2)	0.046 (2)	−0.023 (2)	−0.0150 (19)	−0.0086 (18)
C25	0.052 (2)	0.049 (2)	0.0391 (19)	−0.0183 (16)	−0.0127 (17)	−0.0016 (16)
C26	0.057 (2)	0.048 (2)	0.044 (2)	−0.0199 (17)	−0.0167 (18)	−0.0067 (16)
C27	0.055 (2)	0.059 (2)	0.054 (2)	−0.0256 (18)	−0.0110 (19)	−0.0089 (18)
C28	0.056 (2)	0.055 (2)	0.042 (2)	−0.0190 (18)	−0.0075 (17)	−0.0059 (17)
C29	0.055 (2)	0.046 (2)	0.041 (2)	−0.0146 (17)	−0.0171 (18)	−0.0020 (16)
C30	0.052 (2)	0.052 (2)	0.043 (2)	−0.0195 (17)	−0.0147 (18)	−0.0019 (16)
C31	0.071 (2)	0.045 (2)	0.036 (2)	−0.0153 (18)	−0.0224 (19)	0.0015 (16)
C32	0.072 (3)	0.063 (2)	0.050 (2)	−0.018 (2)	−0.018 (2)	−0.0057 (18)
C33	0.079 (3)	0.079 (3)	0.064 (3)	−0.023 (2)	−0.030 (2)	−0.012 (2)
C34	0.099 (3)	0.077 (3)	0.062 (3)	−0.006 (3)	−0.041 (3)	−0.022 (2)
C35	0.083 (3)	0.077 (3)	0.052 (2)	−0.007 (2)	−0.022 (2)	−0.022 (2)
C36	0.067 (2)	0.062 (2)	0.050 (2)	−0.0120 (19)	−0.017 (2)	−0.0081 (18)

Geometric parameters (Å, º) top

N1—C2	1.331 (3)	C10—H10B	0.9600
N1—N2	1.353 (3)	C10—H10C	0.9600
N2—C4	1.345 (3)	C11—C12	1.480 (4)
N2—H2	0.8600	C12—C17	1.384 (4)
N3—C7	1.348 (4)	C12—C13	1.395 (4)
N3—N4	1.353 (3)	C13—C14	1.385 (4)
N3—H3	0.8600	C14—C15	1.365 (4)
N4—C9	1.333 (4)	C14—H14	0.9300
N5—N6	1.242 (3)	C15—C16	1.390 (4)
N5—C16	1.413 (4)	C15—H15	0.9300
N6—C18	1.430 (4)	C16—C17	1.379 (4)
N7—N8	1.245 (3)	C17—H17	0.9300
N7—C29	1.420 (4)	C18—C23	1.355 (4)
N8—C31	1.436 (4)	C18—C19	1.363 (4)
O1—C11	1.301 (3)	C19—C20	1.385 (5)
O1—H1A	0.8200	C19—H19	0.9300
O2—C11	1.228 (3)	C20—C21	1.353 (5)
O3—C13	1.351 (3)	C20—H20	0.9300
O3—H3A	0.8200	C21—C22	1.356 (5)
O4—C24	1.290 (4)	C21—H21	0.9300
O4—H4A	0.8200	C22—C23	1.363 (5)
O5—C24	1.228 (4)	C22—H22	0.9300
O6—C26	1.362 (3)	C23—H23	0.9300
O6—H6	0.8200	C24—C25	1.482 (4)
C1—C2	1.490 (4)	C25—C30	1.385 (4)
C1—H1B	0.9600	C25—C26	1.397 (4)
C1—H1C	0.9600	C26—C27	1.382 (4)
C1—H1D	0.9600	C27—C28	1.368 (4)
C2—C3	1.397 (4)	C27—H27	0.9300
C3—C4	1.357 (4)	C28—C29	1.395 (4)
C3—H3B	0.9300	C28—H28	0.9300
C4—C5	1.490 (4)	C29—C30	1.377 (4)
C5—H5A	0.9600	C30—H30	0.9300
C5—H5B	0.9600	C31—C36	1.380 (4)
C5—H5C	0.9600	C31—C32	1.386 (4)
C6—C7	1.495 (4)	C32—C33	1.377 (4)
C6—H6A	0.9600	C32—H32	0.9300
C6—H6B	0.9600	C33—C34	1.369 (5)
C6—H6C	0.9600	C33—H33	0.9300
C7—C8	1.352 (4)	C34—C35	1.372 (5)
C8—C9	1.390 (4)	C34—H34	0.9300
C8—H8	0.9300	C35—C36	1.376 (4)
C9—C10	1.487 (4)	C35—H35	0.9300
C10—H10A	0.9600	C36—H36	0.9300

C2—N1—N2	105.5 (2)	C15—C14—H14	119.5
C4—N2—N1	111.8 (3)	C13—C14—H14	119.5
C4—N2—H2	124.1	C14—C15—C16	120.2 (3)
N1—N2—H2	124.1	C14—C15—H15	119.9
C7—N3—N4	111.4 (3)	C16—C15—H15	119.9
C7—N3—H3	124.3	C17—C16—C15	118.7 (3)
N4—N3—H3	124.3	C17—C16—N5	116.2 (3)
C9—N4—N3	105.6 (3)	C15—C16—N5	125.1 (3)
N6—N5—C16	115.6 (3)	C16—C17—C12	122.0 (3)
N5—N6—C18	114.2 (3)	C16—C17—H17	119.0
N8—N7—C29	114.6 (3)	C12—C17—H17	119.0
N7—N8—C31	113.5 (3)	C23—C18—C19	119.2 (3)
C11—O1—H1A	109.5	C23—C18—N6	123.5 (3)
C13—O3—H3A	109.5	C19—C18—N6	117.3 (3)
C24—O4—H4A	109.5	C18—C19—C20	120.0 (4)
C26—O6—H6	109.5	C18—C19—H19	120.0
C2—C1—H1B	109.5	C20—C19—H19	120.0
C2—C1—H1C	109.5	C21—C20—C19	120.0 (4)
H1B—C1—H1C	109.5	C21—C20—H20	120.0
C2—C1—H1D	109.5	C19—C20—H20	120.0
H1B—C1—H1D	109.5	C20—C21—C22	119.5 (4)
H1C—C1—H1D	109.5	C20—C21—H21	120.3
N1—C2—C3	109.6 (3)	C22—C21—H21	120.3
N1—C2—C1	119.3 (3)	C21—C22—C23	120.7 (4)
C3—C2—C1	131.1 (3)	C21—C22—H22	119.6
C4—C3—C2	106.7 (3)	C23—C22—H22	119.6
C4—C3—H3B	126.6	C18—C23—C22	120.5 (4)
C2—C3—H3B	126.6	C18—C23—H23	119.7
N2—C4—C3	106.3 (3)	C22—C23—H23	119.7
N2—C4—C5	121.4 (3)	O5—C24—O4	123.6 (3)
C3—C4—C5	132.3 (3)	O5—C24—C25	121.4 (3)
C4—C5—H5A	109.5	O4—C24—C25	115.0 (3)
C4—C5—H5B	109.5	C30—C25—C26	118.6 (3)
H5A—C5—H5B	109.5	C30—C25—C24	121.0 (3)
C4—C5—H5C	109.5	C26—C25—C24	120.3 (3)
H5A—C5—H5C	109.5	O6—C26—C27	117.8 (3)
H5B—C5—H5C	109.5	O6—C26—C25	122.5 (3)
C7—C6—H6A	109.5	C27—C26—C25	119.7 (3)
C7—C6—H6B	109.5	C28—C27—C26	121.0 (3)
H6A—C6—H6B	109.5	C28—C27—H27	119.5
C7—C6—H6C	109.5	C26—C27—H27	119.5
H6A—C6—H6C	109.5	C27—C28—C29	120.0 (3)
H6B—C6—H6C	109.5	C27—C28—H28	120.0
N3—C7—C8	106.5 (3)	C29—C28—H28	120.0
N3—C7—C6	121.8 (3)	C30—C29—C28	119.0 (3)
C8—C7—C6	131.7 (3)	C30—C29—N7	115.7 (3)
C7—C8—C9	107.0 (3)	C28—C29—N7	125.3 (3)
C7—C8—H8	126.5	C29—C30—C25	121.6 (3)
C9—C8—H8	126.5	C29—C30—H30	119.2
N4—C9—C8	109.6 (3)	C25—C30—H30	119.2
N4—C9—C10	120.2 (3)	C36—C31—C32	119.4 (3)
C8—C9—C10	130.2 (3)	C36—C31—N8	115.9 (3)
C9—C10—H10A	109.5	C32—C31—N8	124.8 (3)
C9—C10—H10B	109.5	C33—C32—C31	120.4 (3)
H10A—C10—H10B	109.5	C33—C32—H32	119.8
C9—C10—H10C	109.5	C31—C32—H32	119.8
H10A—C10—H10C	109.5	C34—C33—C32	119.7 (4)
H10B—C10—H10C	109.5	C34—C33—H33	120.1
O2—C11—O1	124.0 (3)	C32—C33—H33	120.1
O2—C11—C12	121.9 (3)	C33—C34—C35	120.2 (3)
O1—C11—C12	114.1 (3)	C33—C34—H34	119.9
C17—C12—C13	118.5 (3)	C35—C34—H34	119.9
C17—C12—C11	121.6 (3)	C34—C35—C36	120.6 (4)
C13—C12—C11	119.9 (3)	C34—C35—H35	119.7
O3—C13—C14	118.4 (3)	C36—C35—H35	119.7
O3—C13—C12	122.0 (3)	C35—C36—C31	119.6 (3)
C14—C13—C12	119.6 (3)	C35—C36—H36	120.2
C15—C14—C13	121.1 (3)	C31—C36—H36	120.2

C2—N1—N2—C4	−0.6 (3)	N5—N6—C18—C23	−13.3 (5)
C7—N3—N4—C9	−0.3 (4)	N5—N6—C18—C19	166.9 (3)
C16—N5—N6—C18	178.9 (3)	C23—C18—C19—C20	0.0 (6)
C29—N7—N8—C31	179.7 (2)	N6—C18—C19—C20	179.9 (3)
N2—N1—C2—C3	0.3 (3)	C18—C19—C20—C21	−0.3 (6)
N2—N1—C2—C1	−179.6 (3)	C19—C20—C21—C22	1.0 (7)
N1—C2—C3—C4	0.1 (4)	C20—C21—C22—C23	−1.4 (8)
C1—C2—C3—C4	180.0 (3)	C19—C18—C23—C22	−0.4 (7)
N1—N2—C4—C3	0.7 (3)	N6—C18—C23—C22	179.7 (4)
N1—N2—C4—C5	−179.4 (3)	C21—C22—C23—C18	1.1 (8)
C2—C3—C4—N2	−0.5 (4)	O5—C24—C25—C30	174.8 (3)
C2—C3—C4—C5	179.6 (3)	O4—C24—C25—C30	−7.0 (5)
N4—N3—C7—C8	0.3 (4)	O5—C24—C25—C26	−9.7 (5)
N4—N3—C7—C6	179.1 (3)	O4—C24—C25—C26	168.5 (3)
N3—C7—C8—C9	−0.1 (4)	C30—C25—C26—O6	−178.9 (3)
C6—C7—C8—C9	−178.8 (3)	C24—C25—C26—O6	5.5 (5)
N3—N4—C9—C8	0.2 (4)	C30—C25—C26—C27	3.1 (5)
N3—N4—C9—C10	179.7 (3)	C24—C25—C26—C27	−172.5 (3)
C7—C8—C9—N4	−0.1 (4)	O6—C26—C27—C28	179.2 (3)
C7—C8—C9—C10	−179.5 (4)	C25—C26—C27—C28	−2.8 (5)
O2—C11—C12—C17	−179.3 (3)	C26—C27—C28—C29	0.3 (5)
O1—C11—C12—C17	−0.1 (4)	C27—C28—C29—C30	1.8 (5)
O2—C11—C12—C13	−1.1 (5)	C27—C28—C29—N7	−179.5 (3)
O1—C11—C12—C13	178.1 (3)	N8—N7—C29—C30	178.8 (3)
C17—C12—C13—O3	−179.6 (3)	N8—N7—C29—C28	0.0 (4)
C11—C12—C13—O3	2.2 (5)	C28—C29—C30—C25	−1.4 (5)
C17—C12—C13—C14	2.0 (5)	N7—C29—C30—C25	179.7 (3)
C11—C12—C13—C14	−176.2 (3)	C26—C25—C30—C29	−1.0 (5)
O3—C13—C14—C15	179.1 (3)	C24—C25—C30—C29	174.5 (3)
C12—C13—C14—C15	−2.5 (5)	N7—N8—C31—C36	172.8 (3)
C13—C14—C15—C16	0.8 (6)	N7—N8—C31—C32	−7.7 (4)
C14—C15—C16—C17	1.3 (5)	C36—C31—C32—C33	−1.7 (5)
C14—C15—C16—N5	179.4 (3)	N8—C31—C32—C33	178.8 (3)
N6—N5—C16—C17	176.9 (3)	C31—C32—C33—C34	1.3 (6)
N6—N5—C16—C15	−1.2 (5)	C32—C33—C34—C35	−0.6 (6)
C15—C16—C17—C12	−1.7 (5)	C33—C34—C35—C36	0.4 (6)
N5—C16—C17—C12	−180.0 (3)	C34—C35—C36—C31	−0.7 (6)
C13—C12—C17—C16	0.1 (5)	C32—C31—C36—C35	1.4 (5)
C11—C12—C17—C16	178.3 (3)	N8—C31—C36—C35	−179.1 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C31–C36 and C25–C30 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O2ⁱ	0.82	2.43	3.019 (3)	129
O6—H6···O5	0.82	1.89	2.605 (3)	145
O4—H4A···N4ⁱⁱ	0.82	1.75	2.564 (3)	169
O3—H3A···O5ⁱⁱⁱ	0.82	2.45	3.019 (3)	128
O3—H3A···O2	0.82	1.85	2.574 (3)	147
O1—H1A···N1^iv	0.82	1.75	2.565 (3)	171
N3—H3···O3^v	0.86	2.17	3.008 (3)	165
N2—H2···O6^vi	0.86	2.15	3.002 (3)	170
C1—H1D···Cg1^vii	0.96	2.75	3.677 (4)	164
C5—H5B···Cg2^vii	0.96	2.96	3.840 (4)	153

Symmetry codes: (i) x, y−1, z−1; (ii) −x+2, −y+1, −z; (iii) x, y+1, z+1; (iv) x, y, z+1; (v) −x+2, −y+2, −z+1; (vi) x, y+1, z; (vii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₅H₈N₂·C₁₃H₁₀N₂O₃
M_r	338.36
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	11.4871 (11), 12.4746 (13), 13.2235 (16)
α, β, γ (°)	86.650 (2), 67.540 (1), 77.715 (1)
V (Å³)	1710.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.38 × 0.28 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.970, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	8928, 5945, 2614
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.159, 0.99
No. of reflections	5945
No. of parameters	455
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.17

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C31–C36 and C25–C30 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O2ⁱ	0.82	2.43	3.019 (3)	129.1
O6—H6···O5	0.82	1.89	2.605 (3)	145.4
O4—H4A···N4ⁱⁱ	0.82	1.75	2.564 (3)	168.8
O3—H3A···O5ⁱⁱⁱ	0.82	2.45	3.019 (3)	127.8
O3—H3A···O2	0.82	1.85	2.574 (3)	146.5
O1—H1A···N1^iv	0.82	1.75	2.565 (3)	170.7
N3—H3···O3^v	0.86	2.17	3.008 (3)	165.4
N2—H2···O6^vi	0.86	2.15	3.002 (3)	170.1
C1—H1D···Cg1^vii	0.96	2.75	3.677 (4)	164
C5—H5B···Cg2^vii	0.96	2.96	3.840 (4)	153

Symmetry codes: (i) x, y−1, z−1; (ii) −x+2, −y+1, −z; (iii) x, y+1, z+1; (iv) x, y, z+1; (v) −x+2, −y+2, −z+1; (vi) x, y+1, z; (vii) −x+1, −y+1, −z+1.

Acknowledgements

We gratefully acknowledge financial support by the Education Office Foundation of ZheJiang Province (project No. Y201017321) and the innovation project of ZheJiang A & F University.

References

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