3,5-Dinitro­pyridin-4(1H)-one monohydrate

Ying Li; Ping Li; Qiu-Ping Zhou; Guo-Fang Zhang; Seik Weng Ng

doi:10.1107/S1600536808024604

. 2008 Aug 6;64(Pt 9):o1701. doi: 10.1107/S1600536808024604

3,5-Dinitropyridin-4(1H)-one monohydrate

Ying Li ^a, Ping Li ^a, Qiu-Ping Zhou ^b, Guo-Fang Zhang ^b, Seik Weng Ng ^c,^*

PMCID: PMC2960580 PMID: 21201690

Abstract

The three independent organic molecules of 3,5-dinitropyridin-4(1H)-one monohydrate, C₅H₃N₃O₅·H₂O, each feature an N—H⋯O_water hydrogen bond. Each water molecule serves as hydrogen-bond donor to two carbonyl O atoms; these hydrogen bonds give rise to a layer motif. Two of the three formula units lie on special positions of site symmetry 2.

Related literature

The parent pyridin-4-one homolog crystallizes with five pyridone and six water molecules in the asymmetric unit; see: Jones (2001 ▶).

Experimental

Crystal data

C₅H₃N₃O₅·H₂O
M _r = 203.12
Orthorhombic,
a = 21.728 (2) Å
b = 21.654 (2) Å
c = 6.5713 (5) Å
V = 3091.7 (4) Å³
Z = 16
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 (2) K
0.45 × 0.45 × 0.20 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: none
21800 measured reflections
3555 independent reflections
2852 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.123
S = 1.08
3555 reflections
281 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024604/pk2110sup1.cif

e-64-o1701-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024604/pk2110Isup2.hkl

e-64-o1701-Isup2.hkl^{(174.4KB, hkl)}

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
N3—H3⋯O1w	0.85 (1)	1.86 (1)	2.703 (2)	172 (2)
N5—H5⋯O2w	0.85 (1)	1.84 (1)	2.692 (3)	180
N6—H6⋯O3w	0.85 (1)	1.87 (1)	2.723 (3)	180
O1w—H11⋯O8ⁱ	0.85 (1)	2.04 (1)	2.878 (2)	168 (2)
O1w—H12⋯O11ⁱⁱ	0.86 (1)	2.02 (1)	2.866 (2)	168 (2)
O2w—H21⋯O3ⁱⁱⁱ	0.84 (1)	2.05 (1)	2.888 (2)	173 (1)
O3w—H31⋯O3	0.84 (1)	2.05 (1)	2.890 (2)	172 (2)

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

Acknowledgments

We thank Jingning Normal College, Shaanxi Normal University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

3,5-Dinitro-4-pyridinol, a specialty chemical, is assumed in chemical catalogs to exist in the enol form. The homolog, 4-pyridinol, is in fact 4-pyridinone^.6/5hydrate. It has five independent pyridone and six water molecules that are hydrogen bonded to form layers (Jones, 2001). The presence of two electron-withdrawing groups in the title compound should enhance its propensity to form hydrogen bonds, and this is borne out in the present study. The three independent molecules of 3,5-dinitro-1H-pyridin-4-one hydrate (Fig. 1) each feature an N–H···O_water hydrogen bond; each water molecule serves as hydrogen-bond donor to two carbonyl oxygen atoms, and these hydrogen bonds give rise to a layered structure.

Experimental

4-Hydroxy-3-pyridine (19 g, 0.02 mol) was dissolved in fuming sulfuric acid (50% by SO₃ content) (60 ml), and to the solution was added an oleum-fuming nitric acid (1/3) mixture (50 ml). The temperature was kept at 0°C for an hour. The temperature was raised to 413 K over a period of one hour, and then held at 403 K for another 16 h. The mixture was poured into ice (200 g) to quench the reaction. Some 27 g of material was isolated. Crystals were obtained by recrystallization from water.