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

De-quan Jiao; Xiao Tong Han; Qiong Zhou; Ying Wang

doi:10.1107/S1600536811041687

. 2011 Oct 12;67(Pt 11):o2944. doi: 10.1107/S1600536811041687

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

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

PMCID: PMC3247355 PMID: 22219973

Abstract

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,
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[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 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

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.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811041687/go2026sup1.cif

e-67-o2944-sup1.cif^{(29.4KB, cif)}

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

e-67-o2944-Isup2.hkl^{(295.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811041687/go2026Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

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).

supplementary crystallographic information

Comment

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).

Experimental

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.