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

Jiao, D.; Han, X.T.; Zhou, Q.; Wang, Y.

doi:10.1107/S1600536811041687

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2944

doi:10.1107/S1600536811041687

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

De-quan Jiao,^a Xiao Tong Han,^a Qiong Zhou ^a and Ying Wang ^a ^*

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

(Received 8 September 2011; accepted 10 October 2011; online 12 October 2011)

The asymmetric unit of the title compound, C₉H₇N₇·2H₂O, comprises three formula units. The dihedral angles between the triazole rings and the respective central pyridine rings are 4.87 (16)/1.39 (17), 6.46 (16)/7.61 (16) and 7.00 (16)/3.77 (17)°. The water molecules form O—H⋯O hydrogen bonds between themselves and O—H⋯N hydrogen bonds with the N-atom acceptors of the triazole rings, producing a three-dimensional framework.

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 /c
a = 9.7211 (17) Å
b = 17.921 (3) Å
c = 19.603 (4) Å
β = 91.333 (3)°
V = 3414.2 (10) Å³
Z = 12
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 566 K
0.32 × 0.16 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.966, T_max = 0.991
19614 measured reflections
6030 independent reflections
3151 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.133
S = 1.00
6030 reflections
523 parameters
18 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯N21ⁱ	0.86 (1)	1.95 (1)	2.801 (3)	172 (3)
O6—H6B⋯N1ⁱⁱ	0.86 (1)	2.04 (1)	2.878 (3)	166 (3)
O5—H5A⋯O6	0.87 (1)	1.86 (2)	2.707 (3)	166 (4)
O5—H5B⋯O1ⁱⁱⁱ	0.86 (1)	2.01 (1)	2.864 (4)	171 (4)
O4—H4A⋯N14^iv	0.86 (1)	1.95 (1)	2.808 (3)	173 (4)
O4—H4B⋯N8^v	0.86 (1)	2.09 (2)	2.907 (3)	160 (3)
O3—H3B⋯O5	0.86 (1)	2.03 (2)	2.868 (4)	166 (4)
O3—H3A⋯O4	0.85 (1)	2.01 (1)	2.855 (3)	173 (3)
O2—H2B⋯O4	0.86 (1)	2.00 (1)	2.851 (4)	172 (4)
O2—H2A⋯O1	0.87 (1)	2.03 (1)	2.886 (3)	171 (3)
O1—H1B⋯N15^vi	0.86 (1)	2.05 (2)	2.861 (3)	158 (3)
O1—H1A⋯N7	0.86 (1)	1.97 (1)	2.820 (3)	171 (3)
Symmetry codes: (i) x-1, y, z; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) x+1, y, z; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (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/S1600536811041687/go2026sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041687/go2026Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811041687/go2026Isup3.cml

checkCIF report

Comment top

Many molecular-based compounds exhibit interesting magnetic and luminescent properties, (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 interesting bridging ligands.

The asymmetric unit of (I) comprises three C₉H₇N₇.2H₂O components of those ilustrated in Figure 1. The dihedral angles between the triazole rings and the respective central pyridine rings are (atoms named indicate the relevant rings) N3/N4 4.87 (16)°, N4/N5 1.39 (17)°, N10/N11 6.46 (16)°, N11/N12 7.61 (16)°, N17/N18 7.00 (16)° and N18/N19 3.77 (17)°. The water molecules form O—H···O hydrogen bonds between themselves and O—H···N bonds with the N-atom acceptors of the triazole rings, producing a three-dimensional framework. (Table 1, Figure 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 160–170 °C for 30 min. The crystals, which separated on cooling, were collected and recrystallized form water and acetonitrile to give 0.8 g of (I) (yield 20%). After several recrystallizations from water, the air-dried product was obtained as white needles, m.p. 325–327 K (placed in hot bolck at 320 K). The analysis was obtained on the air-dried sample. Anal. Calc. for C₉H₁₁N₇O₂ (%): C, 46.75; H, 3.92. Found (%): C, 46.89; H, 4.00.

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing for (I), with the H bond interactions shown as dashed lines.

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

Crystal data top

C₉H₇N₇·2H₂O	F(000) = 1560
M_r = 249.25	D_x = 1.455 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.7211 (17) Å	Cell parameters from 1505 reflections
b = 17.921 (3) Å	θ = 2.4–21.4°
c = 19.603 (4) Å	µ = 0.11 mm⁻¹
β = 91.333 (3)°	T = 566 K
V = 3414.2 (10) Å³	PLATE, colorless
Z = 12	0.32 × 0.16 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	6030 independent reflections
Radiation source: fine-focus sealed tube	3151 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.966, T_max = 0.991	k = −21→21
19614 measured reflections	l = −23→18

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0378P)² + 0.9562P] where P = (F_o² + 2F_c²)/3
6030 reflections	(Δ/σ)_max < 0.001
523 parameters	Δρ_max = 0.17 e Å⁻³
18 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₉H₇N₇·2H₂O	V = 3414.2 (10) Å³
M_r = 249.25	Z = 12
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.7211 (17) Å	µ = 0.11 mm⁻¹
b = 17.921 (3) Å	T = 566 K
c = 19.603 (4) Å	0.32 × 0.16 × 0.08 mm
β = 91.333 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6030 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3151 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.991	R_int = 0.057
19614 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	18 restraints
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.17 e Å⁻³
6030 reflections	Δρ_min = −0.25 e Å⁻³
523 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	0.7154 (2)	0.78220 (11)	0.96334 (15)	0.0661 (7)
H1A	0.654 (3)	0.7512 (12)	0.9490 (19)	0.099*
H1B	0.694 (3)	0.8260 (8)	0.9486 (19)	0.099*
O2	0.9471 (3)	0.69444 (15)	0.92087 (15)	0.0823 (8)
H2A	0.879 (3)	0.719 (2)	0.9382 (16)	0.123*
H2B	0.943 (4)	0.701 (2)	0.8775 (6)	0.123*
O3	0.7061 (3)	0.61811 (12)	0.72477 (16)	0.0778 (8)
H3A	0.777 (3)	0.6395 (18)	0.7419 (18)	0.117*
H3B	0.673 (4)	0.6445 (18)	0.6918 (15)	0.117*
O4	0.9378 (2)	0.70073 (12)	0.77552 (15)	0.0677 (7)
H4A	1.004 (2)	0.6707 (13)	0.7666 (19)	0.102*
H4B	0.960 (3)	0.7445 (8)	0.762 (2)	0.102*
O5	0.6322 (3)	0.69516 (15)	0.60102 (15)	0.0821 (8)
H5A	0.558 (3)	0.719 (2)	0.6101 (18)	0.123*
H5B	0.648 (4)	0.701 (2)	0.5583 (8)	0.123*
O6	0.4062 (2)	0.78247 (12)	0.60995 (15)	0.0728 (8)
H6A	0.341 (3)	0.7504 (13)	0.606 (2)	0.109*
H6B	0.375 (3)	0.8260 (8)	0.600 (2)	0.109*
N1	−0.2572 (2)	0.41842 (13)	0.91734 (13)	0.0467 (7)
N2	−0.2565 (2)	0.49602 (13)	0.91358 (13)	0.0471 (7)
N3	−0.0433 (2)	0.45570 (11)	0.91796 (12)	0.0364 (6)
N4	0.1588 (2)	0.52262 (11)	0.91983 (11)	0.0339 (6)
N5	0.3497 (2)	0.59867 (12)	0.92021 (12)	0.0386 (6)
N6	0.3602 (3)	0.72068 (13)	0.92221 (15)	0.0541 (8)
N7	0.4924 (2)	0.69199 (13)	0.91984 (15)	0.0578 (8)
N8	0.0804 (2)	0.83897 (12)	0.74510 (14)	0.0474 (7)
N9	0.0826 (2)	0.91653 (12)	0.74574 (13)	0.0448 (7)
N10	0.2947 (2)	0.87465 (11)	0.75369 (12)	0.0352 (6)
N11	0.4984 (2)	0.94024 (11)	0.75457 (12)	0.0337 (6)
N12	0.6900 (2)	1.01533 (11)	0.75413 (12)	0.0362 (6)
N13	0.7018 (2)	1.13674 (13)	0.74646 (13)	0.0490 (7)
N14	0.8339 (2)	1.10798 (13)	0.74444 (13)	0.0477 (7)
N15	0.4265 (2)	0.41749 (12)	0.57083 (13)	0.0453 (7)
N16	0.4285 (2)	0.49419 (12)	0.58098 (13)	0.0444 (7)
N17	0.6411 (2)	0.45391 (11)	0.57956 (12)	0.0339 (6)
N18	0.8443 (2)	0.52004 (12)	0.58430 (12)	0.0355 (6)
N19	1.0366 (2)	0.59472 (12)	0.58859 (12)	0.0391 (6)
N20	1.0484 (3)	0.71698 (13)	0.58745 (16)	0.0625 (8)
N21	1.1808 (3)	0.68779 (14)	0.58657 (14)	0.0560 (8)
C1	−0.1310 (3)	0.39664 (15)	0.92001 (16)	0.0433 (8)
H1	−0.1034	0.3470	0.9230	0.052*
C2	−0.1282 (3)	0.51609 (15)	0.91468 (15)	0.0419 (8)
H2	−0.0981	0.5653	0.9134	0.050*
C3	0.1020 (3)	0.45514 (14)	0.91807 (15)	0.0352 (7)
C4	0.1745 (3)	0.38948 (15)	0.91611 (16)	0.0484 (9)
H4	0.1304	0.3434	0.9150	0.058*
C5	0.3165 (3)	0.39510 (16)	0.91587 (18)	0.0543 (9)
H5	0.3698	0.3521	0.9145	0.065*
C6	0.3790 (3)	0.46336 (14)	0.91766 (16)	0.0470 (9)
H6	0.4743	0.4679	0.9178	0.056*
C7	0.2948 (3)	0.52521 (14)	0.91926 (14)	0.0344 (7)
C8	0.2778 (3)	0.66368 (15)	0.92221 (16)	0.0462 (8)
H8	0.1824	0.6669	0.9234	0.055*
C9	0.4838 (3)	0.61994 (16)	0.91853 (16)	0.0486 (9)
H9	0.5583	0.5875	0.9167	0.058*
C10	0.2067 (3)	0.81618 (15)	0.74954 (16)	0.0457 (8)
H10	0.2334	0.7663	0.7498	0.055*
C11	0.2113 (3)	0.93586 (15)	0.75085 (14)	0.0398 (7)
H11	0.2424	0.9849	0.7524	0.048*
C12	0.4406 (2)	0.87350 (14)	0.75887 (14)	0.0334 (7)
C13	0.5117 (3)	0.80762 (15)	0.76775 (16)	0.0452 (8)
H13	0.4666	0.7620	0.7705	0.054*
C14	0.6524 (3)	0.81262 (15)	0.77231 (17)	0.0488 (9)
H14	0.7046	0.7696	0.7787	0.059*
C15	0.7168 (3)	0.88044 (15)	0.76760 (16)	0.0430 (8)
H15	0.8122	0.8845	0.7698	0.052*
C16	0.6338 (3)	0.94236 (14)	0.75953 (14)	0.0347 (7)
C17	0.6190 (3)	1.08051 (15)	0.75224 (16)	0.0437 (8)
H17	0.5238	1.0843	0.7548	0.052*
C18	0.8236 (3)	1.03616 (15)	0.74905 (15)	0.0426 (8)
H18	0.8976	1.0033	0.7489	0.051*
C19	0.5535 (3)	0.39572 (15)	0.57048 (16)	0.0436 (8)
H19	0.5810	0.3465	0.5647	0.052*
C20	0.5561 (3)	0.51389 (15)	0.58591 (15)	0.0408 (8)
H20	0.5861	0.5626	0.5929	0.049*
C21	0.7878 (3)	0.45277 (14)	0.58206 (14)	0.0326 (7)
C22	0.8581 (3)	0.38678 (15)	0.58217 (15)	0.0401 (8)
H22	0.8129	0.3411	0.5804	0.048*
C23	0.9995 (3)	0.39140 (15)	0.58510 (16)	0.0443 (8)
H23	1.0520	0.3480	0.5854	0.053*
C24	1.0638 (3)	0.45981 (15)	0.58760 (15)	0.0413 (8)
H24	1.1592	0.4639	0.5896	0.050*
C25	0.9809 (3)	0.52181 (14)	0.58709 (15)	0.0358 (7)
C26	0.9662 (3)	0.66025 (16)	0.58895 (18)	0.0559 (10)
H26	0.8709	0.6639	0.5901	0.067*
C27	1.1704 (3)	0.61615 (16)	0.58718 (16)	0.0482 (8)
H27	1.2446	0.5835	0.5867	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0398 (13)	0.0492 (13)	0.109 (2)	0.0011 (10)	−0.0098 (13)	−0.0046 (14)
O2	0.0740 (18)	0.0638 (16)	0.109 (2)	0.0206 (13)	0.0131 (17)	0.0014 (18)
O3	0.0645 (17)	0.0626 (16)	0.106 (3)	−0.0161 (13)	−0.0046 (15)	0.0018 (15)
O4	0.0360 (13)	0.0498 (13)	0.118 (2)	−0.0005 (10)	0.0105 (13)	−0.0040 (15)
O5	0.0698 (18)	0.0691 (17)	0.107 (2)	0.0234 (14)	0.0024 (16)	0.0062 (18)
O6	0.0393 (13)	0.0498 (13)	0.129 (2)	0.0028 (10)	−0.0090 (14)	−0.0066 (16)
N1	0.0353 (15)	0.0441 (15)	0.061 (2)	−0.0023 (12)	0.0029 (13)	−0.0056 (13)
N2	0.0373 (15)	0.0420 (15)	0.062 (2)	0.0040 (11)	−0.0004 (13)	−0.0034 (13)
N3	0.0310 (13)	0.0298 (12)	0.0484 (18)	0.0015 (11)	0.0026 (11)	−0.0044 (11)
N4	0.0298 (13)	0.0309 (12)	0.0412 (17)	−0.0004 (10)	0.0012 (11)	0.0022 (11)
N5	0.0317 (13)	0.0319 (13)	0.0520 (18)	−0.0016 (10)	−0.0013 (12)	0.0042 (11)
N6	0.0444 (16)	0.0377 (14)	0.080 (2)	−0.0068 (12)	0.0027 (14)	0.0004 (14)
N7	0.0389 (16)	0.0442 (16)	0.090 (2)	−0.0045 (12)	0.0004 (15)	0.0004 (15)
N8	0.0336 (14)	0.0402 (14)	0.068 (2)	−0.0001 (11)	0.0041 (13)	−0.0020 (13)
N9	0.0315 (14)	0.0442 (15)	0.0587 (19)	0.0024 (11)	0.0030 (12)	0.0008 (13)
N10	0.0274 (12)	0.0296 (12)	0.0487 (17)	0.0001 (10)	0.0022 (11)	−0.0013 (11)
N11	0.0267 (12)	0.0322 (12)	0.0421 (16)	0.0026 (10)	−0.0008 (10)	−0.0003 (11)
N12	0.0276 (12)	0.0301 (12)	0.0509 (18)	−0.0025 (10)	0.0005 (11)	−0.0002 (12)
N13	0.0429 (15)	0.0376 (14)	0.067 (2)	−0.0027 (12)	0.0027 (13)	0.0070 (13)
N14	0.0407 (15)	0.0441 (15)	0.058 (2)	−0.0089 (12)	0.0003 (13)	0.0015 (13)
N15	0.0320 (14)	0.0385 (14)	0.065 (2)	−0.0043 (11)	−0.0005 (13)	0.0064 (13)
N16	0.0321 (14)	0.0437 (15)	0.058 (2)	0.0009 (11)	0.0023 (12)	0.0012 (13)
N17	0.0287 (12)	0.0302 (12)	0.0429 (17)	−0.0002 (10)	0.0000 (11)	0.0018 (11)
N18	0.0299 (13)	0.0345 (13)	0.0423 (17)	0.0015 (10)	0.0019 (11)	0.0015 (11)
N19	0.0303 (13)	0.0348 (13)	0.0522 (18)	−0.0024 (11)	−0.0019 (12)	−0.0010 (12)
N20	0.0495 (17)	0.0432 (16)	0.095 (3)	−0.0043 (14)	0.0004 (16)	−0.0010 (15)
N21	0.0435 (16)	0.0473 (16)	0.077 (2)	−0.0086 (13)	−0.0016 (14)	0.0052 (15)
C1	0.0402 (17)	0.0327 (16)	0.057 (2)	−0.0018 (14)	0.0015 (15)	−0.0022 (15)
C2	0.0384 (17)	0.0344 (16)	0.053 (2)	0.0030 (14)	−0.0020 (15)	−0.0015 (15)
C3	0.0323 (16)	0.0302 (15)	0.043 (2)	−0.0007 (12)	0.0024 (14)	0.0019 (13)
C4	0.0411 (18)	0.0290 (16)	0.075 (3)	0.0002 (13)	0.0042 (17)	−0.0064 (15)
C5	0.0389 (18)	0.0368 (17)	0.087 (3)	0.0104 (14)	0.0042 (17)	−0.0047 (17)
C6	0.0314 (16)	0.0366 (17)	0.073 (3)	0.0040 (13)	0.0050 (16)	−0.0012 (16)
C7	0.0360 (16)	0.0276 (14)	0.039 (2)	−0.0016 (12)	0.0019 (14)	0.0005 (13)
C8	0.0403 (18)	0.0357 (17)	0.063 (2)	0.0020 (14)	−0.0007 (16)	0.0036 (16)
C9	0.0364 (17)	0.0409 (18)	0.068 (3)	−0.0007 (14)	−0.0032 (16)	0.0034 (16)
C10	0.0327 (17)	0.0329 (16)	0.072 (3)	0.0004 (13)	0.0010 (16)	−0.0039 (15)
C11	0.0348 (17)	0.0376 (16)	0.047 (2)	0.0049 (13)	0.0031 (14)	0.0011 (14)
C12	0.0251 (14)	0.0335 (15)	0.041 (2)	0.0015 (12)	−0.0003 (13)	−0.0058 (13)
C13	0.0380 (17)	0.0311 (15)	0.066 (2)	0.0011 (13)	−0.0020 (16)	−0.0004 (15)
C14	0.0388 (18)	0.0360 (17)	0.071 (3)	0.0123 (13)	−0.0063 (16)	−0.0029 (16)
C15	0.0273 (15)	0.0428 (17)	0.059 (2)	0.0034 (13)	−0.0029 (14)	−0.0045 (16)
C16	0.0302 (16)	0.0332 (15)	0.041 (2)	0.0008 (12)	−0.0011 (13)	−0.0064 (14)
C17	0.0350 (16)	0.0382 (17)	0.058 (2)	0.0014 (14)	0.0019 (15)	0.0013 (15)
C18	0.0334 (17)	0.0452 (18)	0.049 (2)	−0.0012 (14)	0.0000 (15)	−0.0014 (16)
C19	0.0383 (17)	0.0314 (15)	0.061 (2)	−0.0043 (13)	−0.0044 (15)	−0.0010 (15)
C20	0.0377 (17)	0.0342 (16)	0.051 (2)	0.0031 (14)	0.0024 (15)	−0.0023 (15)
C21	0.0273 (15)	0.0339 (15)	0.0368 (19)	−0.0003 (12)	0.0017 (13)	0.0016 (13)
C22	0.0384 (17)	0.0305 (15)	0.051 (2)	−0.0015 (13)	0.0012 (15)	−0.0026 (14)
C23	0.0401 (18)	0.0321 (16)	0.061 (2)	0.0073 (13)	0.0020 (16)	−0.0006 (15)
C24	0.0238 (15)	0.0435 (17)	0.057 (2)	0.0048 (13)	−0.0017 (14)	−0.0008 (15)
C25	0.0342 (16)	0.0325 (15)	0.041 (2)	−0.0018 (13)	0.0011 (14)	−0.0011 (14)
C26	0.0396 (18)	0.0373 (18)	0.091 (3)	−0.0021 (15)	−0.0006 (18)	0.0027 (18)
C27	0.0360 (18)	0.0460 (19)	0.062 (2)	−0.0037 (14)	−0.0041 (16)	0.0043 (16)

Geometric parameters (Å, º) top

O1—H1A	0.857 (10)	N17—C20	1.363 (3)
O1—H1B	0.859 (10)	N17—C21	1.425 (3)
O2—H2A	0.868 (10)	N18—C21	1.325 (3)
O2—H2B	0.858 (10)	N18—C25	1.329 (3)
O3—H3A	0.854 (10)	N19—C27	1.357 (3)
O3—H3B	0.856 (10)	N19—C26	1.359 (3)
O4—H4A	0.861 (10)	N19—C25	1.414 (3)
O4—H4B	0.856 (10)	N20—C26	1.294 (3)
O5—H5A	0.868 (10)	N20—N21	1.390 (3)
O5—H5B	0.861 (10)	N21—C27	1.288 (3)
O6—H6A	0.861 (10)	C1—H1	0.9300
O6—H6B	0.858 (10)	C2—H2	0.9300
N1—C1	1.288 (3)	C3—C4	1.373 (3)
N1—N2	1.393 (3)	C4—C5	1.384 (4)
N2—C2	1.298 (3)	C4—H4	0.9300
N3—C1	1.360 (3)	C5—C6	1.366 (4)
N3—C2	1.361 (3)	C5—H5	0.9300
N3—C3	1.413 (3)	C6—C7	1.379 (3)
N4—C7	1.323 (3)	C6—H6	0.9300
N4—C3	1.329 (3)	C8—H8	0.9300
N5—C9	1.359 (3)	C9—H9	0.9300
N5—C8	1.359 (3)	C10—H10	0.9300
N5—C7	1.421 (3)	C11—H11	0.9300
N6—C8	1.298 (3)	C12—C13	1.377 (3)
N6—N7	1.386 (3)	C13—C14	1.371 (4)
N7—C9	1.294 (3)	C13—H13	0.9300
N8—C10	1.295 (3)	C14—C15	1.371 (4)
N8—N9	1.390 (3)	C14—H14	0.9300
N9—C11	1.300 (3)	C15—C16	1.379 (3)
N10—C10	1.354 (3)	C15—H15	0.9300
N10—C11	1.364 (3)	C17—H17	0.9300
N10—C12	1.420 (3)	C18—H18	0.9300
N11—C16	1.318 (3)	C19—H19	0.9300
N11—C12	1.325 (3)	C20—H20	0.9300
N12—C18	1.357 (3)	C21—C22	1.366 (3)
N12—C17	1.357 (3)	C22—C23	1.377 (4)
N12—C16	1.422 (3)	C22—H22	0.9300
N13—C17	1.296 (3)	C23—C24	1.376 (4)
N13—N14	1.385 (3)	C23—H23	0.9300
N14—C18	1.294 (3)	C24—C25	1.373 (3)
N15—C19	1.295 (3)	C24—H24	0.9300
N15—N16	1.389 (3)	C26—H26	0.9300
N16—C20	1.291 (3)	C27—H27	0.9300
N17—C19	1.356 (3)

H1A—O1—H1B	108.9 (16)	N6—C8—N5	110.9 (3)
H2A—O2—H2B	107.5 (16)	N6—C8—H8	124.5
H3A—O3—H3B	109.4 (16)	N5—C8—H8	124.5
H4A—O4—H4B	108.5 (16)	N7—C9—N5	109.9 (2)
H5A—O5—H5B	107.8 (16)	N7—C9—H9	125.0
H6A—O6—H6B	109.3 (16)	N5—C9—H9	125.0
C1—N1—N2	107.4 (2)	N8—C10—N10	110.9 (2)
C2—N2—N1	106.4 (2)	N8—C10—H10	124.6
C1—N3—C2	103.9 (2)	N10—C10—H10	124.6
C1—N3—C3	128.4 (2)	N9—C11—N10	111.0 (2)
C2—N3—C3	127.6 (2)	N9—C11—H11	124.5
C7—N4—C3	116.5 (2)	N10—C11—H11	124.5
C9—N5—C8	104.7 (2)	N11—C12—C13	124.7 (2)
C9—N5—C7	128.3 (2)	N11—C12—N10	114.0 (2)
C8—N5—C7	127.0 (2)	C13—C12—N10	121.3 (2)
C8—N6—N7	106.3 (2)	C14—C13—C12	116.7 (3)
C9—N7—N6	108.1 (2)	C14—C13—H13	121.7
C10—N8—N9	107.5 (2)	C12—C13—H13	121.7
C11—N9—N8	106.4 (2)	C13—C14—C15	120.7 (3)
C10—N10—C11	104.2 (2)	C13—C14—H14	119.7
C10—N10—C12	128.4 (2)	C15—C14—H14	119.7
C11—N10—C12	127.3 (2)	C14—C15—C16	117.0 (3)
C16—N11—C12	116.5 (2)	C14—C15—H15	121.5
C18—N12—C17	104.4 (2)	C16—C15—H15	121.5
C18—N12—C16	128.9 (2)	N11—C16—C15	124.5 (2)
C17—N12—C16	126.7 (2)	N11—C16—N12	113.9 (2)
C17—N13—N14	106.9 (2)	C15—C16—N12	121.6 (2)
C18—N14—N13	107.2 (2)	N13—C17—N12	110.8 (2)
C19—N15—N16	106.8 (2)	N13—C17—H17	124.6
C20—N16—N15	107.0 (2)	N12—C17—H17	124.6
C19—N17—C20	103.8 (2)	N14—C18—N12	110.7 (2)
C19—N17—C21	128.2 (2)	N14—C18—H18	124.6
C20—N17—C21	128.0 (2)	N12—C18—H18	124.6
C21—N18—C25	115.9 (2)	N15—C19—N17	111.4 (2)
C27—N19—C26	103.8 (2)	N15—C19—H19	124.3
C27—N19—C25	128.9 (2)	N17—C19—H19	124.3
C26—N19—C25	127.3 (2)	N16—C20—N17	111.2 (2)
C26—N20—N21	106.1 (2)	N16—C20—H20	124.4
C27—N21—N20	107.6 (2)	N17—C20—H20	124.4
N1—C1—N3	111.1 (2)	N18—C21—C22	125.5 (2)
N1—C1—H1	124.4	N18—C21—N17	113.7 (2)
N3—C1—H1	124.4	C22—C21—N17	120.9 (2)
N2—C2—N3	111.2 (2)	C21—C22—C23	116.6 (3)
N2—C2—H2	124.4	C21—C22—H22	121.7
N3—C2—H2	124.4	C23—C22—H22	121.7
N4—C3—C4	124.6 (2)	C24—C23—C22	120.5 (3)
N4—C3—N3	114.1 (2)	C24—C23—H23	119.8
C4—C3—N3	121.3 (2)	C22—C23—H23	119.8
C3—C4—C5	116.8 (3)	C25—C24—C23	117.0 (2)
C3—C4—H4	121.6	C25—C24—H24	121.5
C5—C4—H4	121.6	C23—C24—H24	121.5
C6—C5—C4	120.6 (3)	N18—C25—C24	124.6 (2)
C6—C5—H5	119.7	N18—C25—N19	113.9 (2)
C4—C5—H5	119.7	C24—C25—N19	121.6 (2)
C5—C6—C7	117.1 (3)	N20—C26—N19	111.6 (3)
C5—C6—H6	121.4	N20—C26—H26	124.2
C7—C6—H6	121.4	N19—C26—H26	124.2
N4—C7—C6	124.5 (2)	N21—C27—N19	111.0 (3)
N4—C7—N5	114.0 (2)	N21—C27—H27	124.5
C6—C7—N5	121.5 (2)	N19—C27—H27	124.5

C1—N1—N2—C2	−0.4 (3)	N11—C12—C13—C14	0.0 (5)
C8—N6—N7—C9	0.0 (4)	N10—C12—C13—C14	−179.9 (3)
C10—N8—N9—C11	−0.2 (3)	C12—C13—C14—C15	−0.5 (5)
C17—N13—N14—C18	0.0 (3)	C13—C14—C15—C16	1.2 (5)
C19—N15—N16—C20	0.2 (3)	C12—N11—C16—C15	1.1 (4)
C26—N20—N21—C27	0.4 (4)	C12—N11—C16—N12	179.6 (2)
N2—N1—C1—N3	−0.3 (3)	C14—C15—C16—N11	−1.6 (5)
C2—N3—C1—N1	0.8 (3)	C14—C15—C16—N12	180.0 (3)
C3—N3—C1—N1	−178.3 (3)	C18—N12—C16—N11	−171.5 (3)
N1—N2—C2—N3	0.9 (3)	C17—N12—C16—N11	7.8 (4)
C1—N3—C2—N2	−1.1 (3)	C18—N12—C16—C15	7.1 (5)
C3—N3—C2—N2	178.1 (3)	C17—N12—C16—C15	−173.7 (3)
C7—N4—C3—C4	0.4 (4)	N14—N13—C17—N12	0.0 (3)
C7—N4—C3—N3	−179.3 (2)	C18—N12—C17—N13	0.0 (3)
C1—N3—C3—N4	−176.2 (3)	C16—N12—C17—N13	−179.4 (3)
C2—N3—C3—N4	4.9 (4)	N13—N14—C18—N12	0.0 (3)
C1—N3—C3—C4	4.2 (5)	C17—N12—C18—N14	0.0 (3)
C2—N3—C3—C4	−174.7 (3)	C16—N12—C18—N14	179.4 (3)
N4—C3—C4—C5	−0.1 (5)	N16—N15—C19—N17	−0.3 (3)
N3—C3—C4—C5	179.5 (3)	C20—N17—C19—N15	0.3 (3)
C3—C4—C5—C6	0.1 (5)	C21—N17—C19—N15	−179.8 (3)
C4—C5—C6—C7	−0.4 (5)	N15—N16—C20—N17	0.0 (3)
C3—N4—C7—C6	−0.7 (4)	C19—N17—C20—N16	−0.2 (3)
C3—N4—C7—N5	179.1 (2)	C21—N17—C20—N16	180.0 (3)
C5—C6—C7—N4	0.7 (5)	C25—N18—C21—C22	−0.2 (4)
C5—C6—C7—N5	−179.1 (3)	C25—N18—C21—N17	179.6 (2)
C9—N5—C7—N4	−178.5 (3)	C19—N17—C21—N18	173.2 (3)
C8—N5—C7—N4	0.6 (4)	C20—N17—C21—N18	−7.0 (4)
C9—N5—C7—C6	1.3 (5)	C19—N17—C21—C22	−7.0 (5)
C8—N5—C7—C6	−179.6 (3)	C20—N17—C21—C22	172.9 (3)
N7—N6—C8—N5	0.2 (4)	N18—C21—C22—C23	0.2 (5)
C9—N5—C8—N6	−0.4 (4)	N17—C21—C22—C23	−179.6 (3)
C7—N5—C8—N6	−179.7 (3)	C21—C22—C23—C24	−0.1 (5)
N6—N7—C9—N5	−0.2 (4)	C22—C23—C24—C25	0.0 (5)
C8—N5—C9—N7	0.4 (4)	C21—N18—C25—C24	0.1 (4)
C7—N5—C9—N7	179.7 (3)	C21—N18—C25—N19	179.3 (2)
N9—N8—C10—N10	0.5 (4)	C23—C24—C25—N18	−0.1 (5)
C11—N10—C10—N8	−0.5 (3)	C23—C24—C25—N19	−179.1 (3)
C12—N10—C10—N8	−179.7 (3)	C27—N19—C25—N18	−175.5 (3)
N8—N9—C11—N10	0.0 (3)	C26—N19—C25—N18	1.5 (4)
C10—N10—C11—N9	0.3 (3)	C27—N19—C25—C24	3.7 (5)
C12—N10—C11—N9	179.5 (3)	C26—N19—C25—C24	−179.3 (3)
C16—N11—C12—C13	−0.3 (4)	N21—N20—C26—N19	−0.5 (4)
C16—N11—C12—N10	179.6 (2)	C27—N19—C26—N20	0.4 (4)
C10—N10—C12—N11	173.0 (3)	C25—N19—C26—N20	−177.2 (3)
C11—N10—C12—N11	−6.0 (4)	N20—N21—C27—N19	−0.1 (4)
C10—N10—C12—C13	−7.1 (5)	C26—N19—C27—N21	−0.1 (4)
C11—N10—C12—C13	173.8 (3)	C25—N19—C27—N21	177.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···N21ⁱ	0.86 (1)	1.95 (1)	2.801 (3)	172 (3)
O6—H6B···N1ⁱⁱ	0.86 (1)	2.04 (1)	2.878 (3)	166 (3)
O5—H5A···O6	0.87 (1)	1.86 (2)	2.707 (3)	166 (4)
O5—H5B···O1ⁱⁱⁱ	0.86 (1)	2.01 (1)	2.864 (4)	171 (4)
O4—H4A···N14^iv	0.86 (1)	1.95 (1)	2.808 (3)	173 (4)
O4—H4B···N8^v	0.86 (1)	2.09 (2)	2.907 (3)	160 (3)
O3—H3B···O5	0.86 (1)	2.03 (2)	2.868 (4)	166 (4)
O3—H3A···O4	0.85 (1)	2.01 (1)	2.855 (3)	173 (3)
O2—H2B···O4	0.86 (1)	2.00 (1)	2.851 (4)	172 (4)
O2—H2A···O1	0.87 (1)	2.03 (1)	2.886 (3)	171 (3)
O1—H1B···N15^vi	0.86 (1)	2.05 (2)	2.861 (3)	158 (3)
O1—H1A···N7	0.86 (1)	1.97 (1)	2.820 (3)	171 (3)

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

Experimental details

Crystal data
Chemical formula	C₉H₇N₇·2H₂O
M_r	249.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	566
a, b, c (Å)	9.7211 (17), 17.921 (3), 19.603 (4)
β (°)	91.333 (3)
V (Å³)	3414.2 (10)
Z	12
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.32 × 0.16 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.966, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	19614, 6030, 3151
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.133, 1.00
No. of reflections	6030
No. of parameters	523
No. of restraints	18
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.25

Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), 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
O6—H6A···N21ⁱ	0.861 (10)	1.946 (12)	2.801 (3)	172 (3)
O6—H6B···N1ⁱⁱ	0.858 (10)	2.038 (14)	2.878 (3)	166 (3)
O5—H5A···O6	0.868 (10)	1.856 (15)	2.707 (3)	166 (4)
O5—H5B···O1ⁱⁱⁱ	0.861 (10)	2.011 (12)	2.864 (4)	171 (4)
O4—H4A···N14^iv	0.861 (10)	1.951 (11)	2.808 (3)	173 (4)
O4—H4B···N8^v	0.856 (10)	2.089 (16)	2.907 (3)	160 (3)
O3—H3B···O5	0.856 (10)	2.029 (15)	2.868 (4)	166 (4)
O3—H3A···O4	0.854 (10)	2.006 (12)	2.855 (3)	173 (3)
O2—H2B···O4	0.858 (10)	1.999 (12)	2.851 (4)	172 (4)
O2—H2A···O1	0.868 (10)	2.026 (13)	2.886 (3)	171 (3)
O1—H1B···N15^vi	0.859 (10)	2.048 (17)	2.861 (3)	158 (3)
O1—H1A···N7	0.857 (10)	1.970 (12)	2.820 (3)	171 (3)

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

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