2,6-Bis(4H-1,2,4-triazol-4-yl)pyridine dihydrate

Liu, S.Y.; Wang, Y.

doi:10.1107/S1600536811022215

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1631

doi:10.1107/S1600536811022215

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2,6-Bis(4H-1,2,4-triazol-4-yl)pyridine dihydrate

Shang Yuan Liu ^a and Ying Wang ^a ^*

^aTianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: wangying790601@163.com

(Received 16 May 2011; accepted 8 June 2011; online 11 June 2011)

In the asymmetric unit of the title compound, C₉H₇N₇·2H₂O, there are two formula units in which the two triazole rings of each of the organic component molecules form dihedral angles of 7.0 (4)/6.9 (4) and 2.7 (4)/3.6 (4)° with the respective central pyridine rings. The four water molecules of solvation form O—H⋯O hydrogen bonds among themselves and O—H⋯N bonds with the N-atom acceptors of the triazine rings, giving a three-dimensional framework structure.

Related literature

For the synthesis of the title compound, see: Wiley & Hart (1953 ). For properties of related compounds, see: Haasnoot (2000 ).

Experimental

Crystal data

C₉H₇N₇·2H₂O
M_r = 249.25
Monoclinic, P 2₁
a = 7.052 (8) Å
b = 17.862 (16) Å
c = 9.715 (8) Å
β = 111.158 (9)°
V = 1141.2 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.30 × 0.29 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.635, T_max = 1.000
6610 measured reflections
2096 independent reflections
1789 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.094
S = 1.19
2096 reflections
325 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1ⁱ	0.85	1.98	2.814 (5)	165
O1—H1B⋯N7ⁱⁱ	0.85	2.07	2.904 (5)	168
O2—H2A⋯O4	0.85	1.87	2.709 (5)	169
O2—H2B⋯O1	0.85	2.00	2.850 (6)	174
O3—H3A⋯O1ⁱⁱⁱ	0.85	2.05	2.888 (5)	169
O3—H3B⋯O2	0.85	2.07	2.916 (6)	170
O4—H4A⋯N13^iv	0.85	1.98	2.822 (5)	170
O4—H4B⋯N8^v	0.85	2.06	2.873 (5)	159
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (ii) x, y, z+1; (iii) x+1, y, z; (iv) $[-x, y-{\script{1\over 2}}, -z]$ ; (v) x-1, y, z-1.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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/S1600536811022215/zs2114sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022215/zs2114Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811022215/zs2114Isup3.cml

checkCIF report

Comment top

The field of molecular materials has known rapid development in recent years, with molecular-based compounds which exhibit interesting magnetic and luminescent properties having been described (Haasnoot, 2000). One of the requirements for producing such macroscopic properties is to create interactions between the molecular units and the active sites within the crystal lattices. 1,2,4-Triazole and in particular its derivatives are very interesting as bridging ligands. Here we report the synthesis and the crystal structure of the title compound, the dihydrate of 2,6-di(4H-1,2,4-triazol-4-yl)pyridine, C₉H₇N₇ . 2(H₂O) (I).

In the asymmetric unit of (I) there are two molecular units (Fig. 1) in which the two triazole rings of each of the organic component molecules form dihedral angles of 7.0, 6.9 (4)° and 2.7, 3.6 (4)° with the respective pyridine rings. The four water molecules of solvation form hydrogen bonds with the N atom acceptors only of the triazine rings (Table 1) giving a three-dimensional framework structure (Fig. 2).

Related literature top

For the synthesis of the title compound, see: Wiley & Hart (1953). For properties of related compounds, see: Haasnoot (2000).

Experimental top

A mixture of 1.3 g (0.012 mol) of 2,6-diaminopyridine and 2.0 g (0.023 mol) of diformylhydrazine was heated slowly to 160°C and held at 160-170°C for 30 min. The crystals, which separated on cooling, were collected and recrystallized from water to give 0.70 g of (I) (yield 13%). After several recrystallizations from water and from alcohol, the air-dried product was obtained as white needles, m.p. 325-327 K (placed in hot block at 320 K). The analysis was obtained on the air-dried sample. Anal. Calcd for C₉H11₁₁N₇O₂: C, 46.75; H, 3.92%. Found: C, 46.55; H, 3.96%.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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. Molecular conformation and atom numbering scheme for the two independent molecules of C₉H₇N₇ and the four water molecules of solvation in the asymmetric unit of (I). Probability spheres are drawn at the 15% level.
	Fig. 2. The packing of (I) in the unit cell showing hydrogen-bonding interactions.

2,6-Bis(4H-1,2,4-triazol-4-yl)pyridine dihydrate top

Crystal data top

C₉H₇N₇·2H₂O	F(000) = 520
M_r = 249.25	D_x = 1.451 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1604 reflections
a = 7.052 (8) Å	θ = 2.3–23.1°
b = 17.862 (16) Å	µ = 0.11 mm⁻¹
c = 9.715 (8) Å	T = 293 K
β = 111.158 (9)°	Block, colorless
V = 1141.2 (19) Å³	0.30 × 0.29 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2096 independent reflections
Radiation source: fine-focus sealed tube	1789 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
T_min = 0.635, T_max = 1.000	k = −20→21
6610 measured reflections	l = −11→9

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.02P)²] where P = (F_o² + 2F_c²)/3
2096 reflections	(Δ/σ)_max < 0.001
325 parameters	Δρ_max = 0.13 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₉H₇N₇·2H₂O	V = 1141.2 (19) Å³
M_r = 249.25	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 7.052 (8) Å	µ = 0.11 mm⁻¹
b = 17.862 (16) Å	T = 293 K
c = 9.715 (8) Å	0.30 × 0.29 × 0.10 mm
β = 111.158 (9)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2096 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1789 reflections with I > 2σ(I)
T_min = 0.635, T_max = 1.000	R_int = 0.028
6610 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	1 restraint
wR(F²) = 0.094	H-atom parameters constrained
S = 1.19	Δρ_max = 0.13 e Å⁻³
2096 reflections	Δρ_min = −0.19 e Å⁻³
325 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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	0.8333 (4)	0.57130 (16)	0.3342 (3)	0.0478 (9)
N2	0.7010 (5)	0.60054 (15)	0.2019 (3)	0.0486 (9)
N3	0.7201 (4)	0.47959 (13)	0.1779 (2)	0.0362 (8)
N4	0.5316 (4)	0.40426 (13)	−0.0145 (2)	0.0346 (8)
N5	0.3281 (4)	0.33831 (14)	−0.2179 (2)	0.0361 (7)
N6	0.1060 (4)	0.37967 (15)	−0.4259 (3)	0.0441 (9)
N7	0.0990 (4)	0.30183 (16)	−0.4263 (3)	0.0481 (9)
C1	0.8413 (5)	0.49967 (18)	0.3165 (3)	0.0397 (10)
C2	0.6375 (5)	0.54465 (17)	0.1118 (3)	0.0438 (10)
C3	0.6778 (4)	0.40638 (17)	0.1168 (3)	0.0349 (9)
C4	0.7786 (5)	0.34433 (19)	0.1922 (3)	0.0439 (10)
C5	0.7209 (5)	0.27547 (18)	0.1262 (3)	0.0454 (11)
C6	0.5697 (5)	0.27085 (18)	−0.0111 (3)	0.0426 (10)
C7	0.4817 (4)	0.33686 (17)	−0.0757 (3)	0.0342 (9)
C8	0.2312 (5)	0.27945 (18)	−0.3025 (3)	0.0448 (11)
C9	0.2422 (5)	0.39963 (17)	−0.3011 (3)	0.0400 (10)
N8	0.9611 (4)	0.38269 (15)	0.9078 (3)	0.0438 (9)
N9	0.9503 (4)	0.46049 (16)	0.9104 (3)	0.0476 (10)
N10	0.7369 (4)	0.41986 (14)	0.6977 (2)	0.0359 (7)
N11	0.5207 (4)	0.48637 (13)	0.5001 (3)	0.0349 (8)
N12	0.3162 (4)	0.56230 (14)	0.3130 (2)	0.0373 (8)
N13	0.1657 (5)	0.65496 (17)	0.1704 (3)	0.0554 (10)
N14	0.2856 (5)	0.68389 (16)	0.3071 (3)	0.0569 (10)
C10	0.8165 (5)	0.48092 (18)	0.7842 (3)	0.0451 (11)
C11	0.8331 (5)	0.36112 (17)	0.7816 (3)	0.0399 (10)
C12	0.5915 (4)	0.41913 (18)	0.5521 (3)	0.0343 (9)
C13	0.5325 (5)	0.35351 (17)	0.4748 (3)	0.0436 (11)
C14	0.3899 (5)	0.35832 (18)	0.3354 (3)	0.0477 (11)
C15	0.3103 (5)	0.42704 (18)	0.2768 (3)	0.0426 (10)
C16	0.3835 (4)	0.48866 (17)	0.3647 (3)	0.0339 (9)
C17	0.1877 (5)	0.58319 (18)	0.1776 (3)	0.0450 (11)
C18	0.3716 (5)	0.62737 (18)	0.3880 (3)	0.0507 (11)
O1	0.0057 (4)	0.16140 (14)	0.4125 (2)	0.0636 (9)
O2	0.3057 (5)	0.15947 (15)	0.2795 (3)	0.0725 (10)
O3	0.6429 (5)	0.08242 (16)	0.2340 (3)	0.0749 (10)
O4	0.1440 (4)	0.24252 (14)	0.0311 (2)	0.0625 (8)
H1	0.91930	0.46660	0.38870	0.0480*
H2	0.54740	0.54870	0.01480	0.0530*
H4	0.88170	0.34870	0.28420	0.0530*
H5	0.78400	0.23220	0.17450	0.0540*
H6	0.52900	0.22510	−0.05800	0.0510*
H8	0.25680	0.22950	−0.27490	0.0530*
H9	0.27680	0.44890	−0.27220	0.0480*
H10	0.78000	0.53030	0.75650	0.0540*
H11	0.81000	0.31140	0.75220	0.0480*
H13	0.58720	0.30770	0.51560	0.0520*
H14	0.34610	0.31510	0.27950	0.0570*
H15	0.21210	0.43130	0.18270	0.0510*
H17	0.12400	0.55040	0.10040	0.0540*
H18	0.46030	0.63090	0.48550	0.0610*
H1A	0.04450	0.12750	0.47830	0.0760*
H1B	0.02170	0.20560	0.44750	0.0760*
H2A	0.26290	0.18190	0.19670	0.0870*
H2B	0.22270	0.15830	0.32480	0.0870*
H3A	0.75790	0.10000	0.28750	0.0900*
H3B	0.53790	0.10490	0.23620	0.0900*
H4A	0.06240	0.21210	−0.02880	0.0750*
H4B	0.11000	0.28830	0.01600	0.0750*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0556 (17)	0.0435 (18)	0.0387 (14)	−0.0044 (14)	0.0102 (13)	−0.0062 (12)
N2	0.0578 (18)	0.0382 (16)	0.0420 (15)	−0.0014 (13)	0.0087 (13)	−0.0034 (12)
N3	0.0405 (14)	0.0313 (14)	0.0313 (12)	0.0007 (11)	0.0065 (11)	0.0000 (10)
N4	0.0365 (13)	0.0302 (15)	0.0320 (13)	0.0022 (10)	0.0061 (10)	0.0011 (10)
N5	0.0399 (13)	0.0300 (13)	0.0325 (12)	0.0003 (12)	0.0058 (10)	−0.0001 (11)
N6	0.0450 (15)	0.0418 (18)	0.0363 (15)	0.0030 (13)	0.0037 (13)	0.0064 (11)
N7	0.0549 (17)	0.0401 (18)	0.0361 (14)	−0.0026 (13)	0.0007 (13)	−0.0027 (11)
C1	0.0438 (17)	0.0359 (19)	0.0329 (16)	−0.0033 (15)	0.0060 (14)	−0.0015 (13)
C2	0.0513 (18)	0.0361 (19)	0.0365 (16)	−0.0009 (16)	0.0069 (14)	−0.0024 (14)
C3	0.0423 (17)	0.0285 (17)	0.0321 (15)	0.0009 (13)	0.0113 (13)	0.0007 (12)
C4	0.0451 (18)	0.0398 (18)	0.0367 (16)	0.0028 (15)	0.0026 (14)	0.0019 (14)
C5	0.0510 (19)	0.0327 (18)	0.0453 (18)	0.0074 (14)	0.0088 (15)	0.0118 (13)
C6	0.0530 (19)	0.0283 (17)	0.0399 (17)	0.0025 (14)	0.0090 (15)	0.0006 (12)
C7	0.0378 (16)	0.0309 (16)	0.0306 (14)	−0.0009 (14)	0.0085 (12)	0.0004 (13)
C8	0.053 (2)	0.0309 (18)	0.0411 (19)	−0.0016 (14)	0.0058 (16)	−0.0023 (13)
C9	0.0444 (17)	0.0328 (18)	0.0389 (17)	0.0037 (13)	0.0105 (14)	0.0047 (13)
N8	0.0491 (16)	0.0393 (17)	0.0369 (15)	0.0010 (12)	0.0082 (13)	0.0032 (11)
N9	0.0524 (17)	0.0416 (18)	0.0373 (15)	0.0004 (13)	0.0022 (13)	−0.0022 (12)
N10	0.0393 (13)	0.0306 (13)	0.0305 (12)	0.0007 (12)	0.0038 (10)	−0.0002 (11)
N11	0.0371 (14)	0.0328 (15)	0.0318 (12)	−0.0036 (11)	0.0088 (11)	−0.0003 (10)
N12	0.0427 (14)	0.0308 (15)	0.0307 (13)	0.0007 (11)	0.0039 (11)	0.0011 (10)
N13	0.0616 (18)	0.0407 (18)	0.0473 (16)	0.0017 (14)	−0.0004 (14)	0.0062 (12)
N14	0.070 (2)	0.0359 (16)	0.0506 (17)	0.0075 (14)	0.0045 (15)	0.0061 (13)
C10	0.051 (2)	0.0343 (19)	0.0425 (17)	−0.0004 (15)	0.0077 (16)	−0.0026 (14)
C11	0.0459 (17)	0.0308 (17)	0.0377 (16)	−0.0008 (13)	0.0087 (14)	0.0012 (12)
C12	0.0378 (15)	0.0316 (16)	0.0316 (14)	−0.0007 (13)	0.0102 (12)	0.0014 (13)
C13	0.054 (2)	0.0283 (18)	0.0412 (17)	0.0043 (14)	0.0083 (15)	−0.0008 (13)
C14	0.058 (2)	0.035 (2)	0.0407 (17)	−0.0034 (15)	0.0066 (16)	−0.0083 (14)
C15	0.0457 (18)	0.0387 (18)	0.0355 (15)	−0.0011 (15)	0.0050 (14)	−0.0013 (14)
C16	0.0363 (16)	0.0315 (17)	0.0316 (14)	−0.0002 (13)	0.0096 (13)	0.0021 (12)
C17	0.050 (2)	0.0362 (19)	0.0370 (17)	−0.0035 (15)	0.0014 (14)	0.0027 (14)
C18	0.064 (2)	0.0342 (19)	0.0401 (16)	0.0020 (17)	0.0021 (15)	−0.0022 (14)
O1	0.0880 (18)	0.0428 (14)	0.0407 (12)	−0.0062 (13)	0.0001 (12)	−0.0008 (10)
O2	0.0855 (19)	0.0621 (18)	0.0589 (15)	0.0193 (15)	0.0128 (14)	0.0157 (13)
O3	0.0718 (18)	0.0639 (17)	0.0754 (18)	−0.0105 (14)	0.0103 (14)	−0.0183 (14)
O4	0.0628 (15)	0.0468 (15)	0.0571 (13)	−0.0005 (12)	−0.0034 (12)	0.0059 (11)

Geometric parameters (Å, º) top

O1—H1A	0.8500	N11—C12	1.329 (4)
O1—H1B	0.8500	N12—C18	1.352 (4)
O2—H2B	0.8500	N12—C16	1.427 (4)
O2—H2A	0.8500	N12—C17	1.353 (4)
O3—H3A	0.8500	N13—C17	1.290 (5)
O3—H3B	0.8500	N13—N14	1.391 (4)
N1—N2	1.389 (4)	N14—C18	1.289 (4)
N1—C1	1.295 (5)	C3—C4	1.376 (5)
N2—C2	1.296 (4)	C4—C5	1.379 (5)
N3—C1	1.357 (4)	C5—C6	1.377 (4)
N3—C3	1.423 (4)	C6—C7	1.374 (5)
N3—C2	1.354 (4)	C1—H1	0.9300
N4—C3	1.320 (4)	C2—H2	0.9300
N4—C7	1.333 (4)	C4—H4	0.9300
N5—C9	1.366 (4)	C5—H5	0.9300
N5—C8	1.357 (4)	C6—H6	0.9300
N5—C7	1.415 (4)	C8—H8	0.9300
N6—N7	1.391 (4)	C9—H9	0.9300
N6—C9	1.296 (4)	C12—C13	1.373 (5)
N7—C8	1.291 (4)	C13—C14	1.367 (4)
O4—H4A	0.8500	C14—C15	1.384 (5)
O4—H4B	0.8500	C15—C16	1.374 (5)
N8—C11	1.291 (4)	C10—H10	0.9300
N8—N9	1.393 (4)	C11—H11	0.9300
N9—C10	1.301 (4)	C13—H13	0.9300
N10—C12	1.416 (4)	C14—H14	0.9300
N10—C10	1.368 (4)	C15—H15	0.9300
N10—C11	1.351 (4)	C17—H17	0.9300
N11—C16	1.323 (4)	C18—H18	0.9300

H1A—O1—H1B	114.00	N3—C1—H1	125.00
H2A—O2—H2B	115.00	N2—C2—H2	125.00
H3A—O3—H3B	117.00	N3—C2—H2	125.00
N2—N1—C1	107.2 (3)	C3—C4—H4	121.00
N1—N2—C2	106.8 (3)	C5—C4—H4	121.00
C1—N3—C2	104.7 (2)	C4—C5—H5	120.00
C1—N3—C3	128.3 (2)	C6—C5—H5	120.00
C2—N3—C3	127.0 (2)	C5—C6—H6	121.00
C3—N4—C7	116.5 (2)	C7—C6—H6	121.00
C8—N5—C9	104.1 (2)	N5—C8—H8	124.00
C7—N5—C8	128.2 (3)	N7—C8—H8	124.00
C7—N5—C9	127.7 (3)	N6—C9—H9	125.00
N7—N6—C9	106.9 (3)	N5—C9—H9	125.00
N6—N7—C8	107.1 (3)	N9—C10—N10	110.7 (3)
H4A—O4—H4B	115.00	N8—C11—N10	111.6 (3)
N9—N8—C11	106.9 (3)	N10—C12—C13	121.4 (3)
N8—N9—C10	106.8 (3)	N11—C12—C13	124.5 (3)
C10—N10—C12	127.6 (3)	N10—C12—N11	114.1 (3)
C10—N10—C11	104.1 (2)	C12—C13—C14	117.2 (3)
C11—N10—C12	128.3 (3)	C13—C14—C15	120.5 (3)
C12—N11—C16	116.5 (3)	C14—C15—C16	116.7 (3)
C17—N12—C18	104.4 (2)	N11—C16—C15	124.7 (3)
C16—N12—C17	128.1 (2)	N12—C16—C15	121.1 (2)
C16—N12—C18	127.4 (2)	N11—C16—N12	114.2 (2)
N14—N13—C17	107.3 (3)	N12—C17—N13	110.6 (3)
N13—N14—C18	106.3 (3)	N12—C18—N14	111.3 (3)
N1—C1—N3	110.5 (3)	N10—C10—H10	125.00
N2—C2—N3	110.9 (3)	N9—C10—H10	125.00
N3—C3—C4	121.9 (3)	N10—C11—H11	124.00
N4—C3—C4	124.4 (3)	N8—C11—H11	124.00
N3—C3—N4	113.7 (2)	C14—C13—H13	121.00
C3—C4—C5	117.5 (3)	C12—C13—H13	121.00
C4—C5—C6	120.0 (3)	C13—C14—H14	120.00
C5—C6—C7	117.1 (3)	C15—C14—H14	120.00
N4—C7—N5	113.9 (2)	C14—C15—H15	122.00
N5—C7—C6	121.5 (3)	C16—C15—H15	122.00
N4—C7—C6	124.6 (3)	N13—C17—H17	125.00
N5—C8—N7	111.2 (3)	N12—C17—H17	125.00
N5—C9—N6	110.7 (3)	N12—C18—H18	124.00
N1—C1—H1	125.00	N14—C18—H18	124.00

C1—N1—N2—C2	−0.3 (4)	C12—N10—C10—N9	−178.3 (3)
N2—N1—C1—N3	0.0 (4)	C11—N10—C12—N11	178.5 (3)
N1—N2—C2—N3	0.4 (4)	C11—N10—C12—C13	−1.4 (5)
C2—N3—C1—N1	0.2 (4)	C10—N10—C12—N11	−3.5 (5)
C3—N3—C1—N1	−176.3 (3)	C10—N10—C12—C13	176.5 (3)
C1—N3—C2—N2	−0.3 (4)	C16—N11—C12—N10	−179.6 (3)
C3—N3—C2—N2	176.2 (3)	C12—N11—C16—C15	0.5 (5)
C1—N3—C3—N4	170.9 (3)	C16—N11—C12—C13	0.4 (5)
C1—N3—C3—C4	−7.3 (5)	C12—N11—C16—N12	−178.6 (3)
C2—N3—C3—N4	−4.9 (5)	C17—N12—C16—C15	−3.5 (5)
C2—N3—C3—C4	176.9 (3)	C18—N12—C16—N11	−2.4 (5)
C7—N4—C3—N3	−178.4 (3)	C18—N12—C16—C15	178.5 (3)
C7—N4—C3—C4	−0.2 (5)	C16—N12—C17—N13	−178.6 (3)
C3—N4—C7—N5	−178.4 (3)	C18—N12—C17—N13	−0.2 (4)
C3—N4—C7—C6	0.8 (5)	C16—N12—C18—N14	178.5 (3)
C8—N5—C7—N4	−173.2 (3)	C17—N12—C16—N11	175.6 (3)
C8—N5—C7—C6	7.6 (5)	C17—N12—C18—N14	0.1 (4)
C9—N5—C7—N4	6.3 (5)	C17—N13—N14—C18	−0.2 (4)
C9—N5—C7—C6	−172.9 (3)	N14—N13—C17—N12	0.3 (4)
C7—N5—C8—N7	179.9 (3)	N13—N14—C18—N12	0.1 (4)
C9—N5—C8—N7	0.3 (4)	N3—C3—C4—C5	177.4 (3)
C7—N5—C9—N6	−180.0 (3)	N4—C3—C4—C5	−0.7 (5)
C8—N5—C9—N6	−0.5 (4)	C3—C4—C5—C6	1.0 (5)
C9—N6—N7—C8	−0.2 (4)	C4—C5—C6—C7	−0.5 (5)
N7—N6—C9—N5	0.4 (4)	C5—C6—C7—N4	−0.4 (5)
N6—N7—C8—N5	−0.1 (4)	C5—C6—C7—N5	178.6 (3)
N9—N8—C11—N10	0.5 (4)	N10—C12—C13—C14	179.4 (3)
C11—N8—N9—C10	−0.5 (4)	N11—C12—C13—C14	−0.6 (5)
N8—N9—C10—N10	0.3 (4)	C12—C13—C14—C15	0.0 (5)
C11—N10—C10—N9	0.0 (4)	C13—C14—C15—C16	0.7 (5)
C10—N10—C11—N8	−0.3 (4)	C14—C15—C16—N11	−1.0 (5)
C12—N10—C11—N8	178.0 (3)	C14—C15—C16—N12	178.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1ⁱ	0.85	1.98	2.814 (5)	165
O1—H1B···N7ⁱⁱ	0.85	2.07	2.904 (5)	168
O2—H2A···O4	0.85	1.87	2.709 (5)	169
O2—H2B···O1	0.85	2.00	2.850 (6)	174
O3—H3A···O1ⁱⁱⁱ	0.85	2.05	2.888 (5)	169
O3—H3B···O2	0.85	2.07	2.916 (6)	170
O4—H4A···N13^iv	0.85	1.98	2.822 (5)	170
O4—H4B···N8^v	0.85	2.06	2.873 (5)	159

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

Experimental details

Crystal data
Chemical formula	C₉H₇N₇·2H₂O
M_r	249.25
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	7.052 (8), 17.862 (16), 9.715 (8)
β (°)	111.158 (9)
V (Å³)	1141.2 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.29 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.635, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6610, 2096, 1789
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.19
No. of reflections	2096
No. of parameters	325
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.19

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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—H1A···N1ⁱ	0.85	1.98	2.814 (5)	165
O1—H1B···N7ⁱⁱ	0.85	2.07	2.904 (5)	168
O2—H2A···O4	0.85	1.87	2.709 (5)	169
O2—H2B···O1	0.85	2.00	2.850 (6)	174
O3—H3A···O1ⁱⁱⁱ	0.85	2.05	2.888 (5)	169
O3—H3B···O2	0.85	2.07	2.916 (6)	170
O4—H4A···N13^iv	0.85	1.98	2.822 (5)	170
O4—H4B···N8^v	0.85	2.06	2.873 (5)	159

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

Acknowledgements

This work was supported financially by Tianjin Normal University (grant No. 5RL090), the Natural Science Foundation of Tianjin (grant No. 11JCYBJC03600) and the Young Scientist Fund (grant No. 52 G10005).

References

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Haasnoot, J. G. (2000). Coord. Chem. Rev. 200, 131–185. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (1996). 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
Wiley, R. H. & Hart, A. J. (1953). J. Org. Chem. 18, 1368–1371. CrossRef CAS Web of Science Google Scholar