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Acta Cryst. (2008). E64, o1701    [ doi:10.1107/S1600536808024604 ]

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

Y. Li, P. Li, Q.-P. Zhou, G.-F. Zhang and S. W. Ng

Abstract top

The three independent organic molecules of 3,5-dinitropyridin-4(1H)-one monohydrate, C5H3N3O5·H2O, each feature an N-H...Owater 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.

Comment top

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···Owater 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.

Related literature top

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

Experimental top

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.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the refinement using a riding model approximation, with U(H) 1.2Ueq(C). The amino and water H-atoms were refined with distance restraints of O–H = N–H 0.85 (1) and H···H 1.39 (1) Å; their temperature factors Uiso were freely refined.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) plot of the three independent molecules of C5H3N3O5.H2O at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
3,5-Dinitropyridin-4(1H)-one monohydrate top
Crystal data top
C5H3N3O5·H2OF000 = 1664
Mr = 203.12Dx = 1.746 Mg m−3
Orthorhombic, PbcnMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 6494 reflections
a = 21.728 (2) Åθ = 2.7–27.9º
b = 21.654 (2) ŵ = 0.16 mm−1
c = 6.5713 (5) ÅT = 293 (2) K
V = 3091.7 (4) Å3Block, colorless
Z = 160.45 × 0.45 × 0.20 mm
Data collection top
Bruker APEXII
diffractometer		3555 independent reflections
Radiation source: fine-focus sealed tube2852 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.022
Detector resolution: 9 pixels mm-1θmax = 27.5º
T = 293(2) Kθmin = 2.7º
φ and ω scansh = −28→27
Absorption correction: nonek = −28→27
21800 measured reflectionsl = −8→8
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.123  w = 1/[σ2(Fo2) + (0.0528P)2 + 1.6904P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
3555 reflectionsΔρmax = 0.35 e Å−3
281 parametersΔρmin = −0.31 e Å−3
10 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C5H3N3O5·H2OV = 3091.7 (4) Å3
Mr = 203.12Z = 16
Orthorhombic, PbcnMo Kα
a = 21.728 (2) ŵ = 0.16 mm−1
b = 21.654 (2) ÅT = 293 (2) K
c = 6.5713 (5) Å0.45 × 0.45 × 0.20 mm
Data collection top
Bruker APEXII
diffractometer		3555 independent reflections
Absorption correction: none2852 reflections with I > 2σ(I)
21800 measured reflectionsRint = 0.022
Refinement top
R[F2 > 2σ(F2)] = 0.04010 restraints
wR(F2) = 0.123H atoms treated by a mixture of
independent and constrained refinement
S = 1.08Δρmax = 0.35 e Å−3
3555 reflectionsΔρmin = −0.31 e Å−3
281 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.69961 (7)0.46193 (6)0.2892 (3)0.0552 (4)
O20.62136 (6)0.50982 (6)0.4163 (3)0.0464 (4)
O30.60319 (6)0.62125 (6)0.2292 (2)0.0431 (4)
O40.61633 (6)0.73545 (6)0.0695 (3)0.0486 (4)
O50.70310 (8)0.77792 (8)0.1081 (6)0.1176 (12)
O60.60858 (6)0.75858 (6)0.5467 (3)0.0496 (4)
O70.65774 (6)0.67898 (7)0.6579 (3)0.0562 (4)
O80.50000.77618 (7)0.75000.0389 (4)
O90.65904 (7)0.92189 (7)0.1991 (3)0.0659 (5)
O100.61401 (6)1.00203 (6)0.0759 (3)0.0482 (4)
O110.50001.02039 (7)0.25000.0357 (4)
O1W0.91543 (6)0.62174 (6)0.2293 (3)0.0507 (4)
O2W0.50000.46255 (9)0.75000.0627 (7)
O3W0.50000.70522 (8)0.25000.0416 (5)
N10.67114 (7)0.50953 (7)0.3278 (3)0.0360 (3)
N20.67066 (7)0.73271 (7)0.1089 (3)0.0435 (4)
N30.79137 (7)0.61956 (8)0.1992 (3)0.0434 (4)
N40.61008 (6)0.70807 (7)0.6311 (3)0.0357 (3)
N50.50000.58686 (9)0.75000.0376 (5)
N60.50000.83100 (9)0.25000.0384 (5)
N70.61264 (7)0.95139 (7)0.1582 (3)0.0377 (4)
C10.76100 (8)0.56854 (9)0.2549 (3)0.0390 (4)
H1A0.78290.53290.28570.047*
C20.69872 (8)0.56805 (8)0.2672 (3)0.0315 (4)
C30.65995 (8)0.62114 (7)0.2208 (3)0.0302 (4)
C40.69804 (8)0.67347 (8)0.1610 (3)0.0337 (4)
C50.76066 (8)0.67135 (9)0.1539 (3)0.0405 (4)
H5A0.78250.70650.11690.049*
C60.55166 (8)0.61756 (8)0.7027 (3)0.0345 (4)
H6A0.58740.59570.67330.041*
C70.55244 (7)0.68038 (7)0.6972 (3)0.0290 (4)
C80.50000.71922 (10)0.75000.0269 (5)
C90.55223 (9)0.86172 (8)0.2128 (3)0.0360 (4)
H90.58840.83980.18930.043*
C100.55324 (8)0.92451 (7)0.2090 (3)0.0301 (4)
C110.50000.96327 (10)0.25000.0278 (5)
H110.9376 (8)0.6540 (6)0.220 (4)0.059 (7)*
H120.9385 (8)0.5898 (6)0.218 (4)0.053 (7)*
H210.4680 (2)0.4409 (7)0.757 (4)0.055 (7)*
H310.5318 (3)0.6832 (7)0.236 (4)0.058 (7)*
H30.8306 (5)0.6181 (10)0.199 (4)0.057 (7)*
H50.50000.5477 (5)0.75000.051 (9)*
H60.50000.7915 (5)0.25000.051 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0543 (9)0.0322 (7)0.0790 (12)0.0112 (6)0.0045 (8)0.0018 (7)
O20.0369 (7)0.0417 (7)0.0607 (9)−0.0020 (6)0.0068 (7)0.0077 (7)
O30.0218 (6)0.0344 (7)0.0730 (10)0.0014 (5)0.0029 (6)0.0061 (6)
O40.0381 (7)0.0401 (7)0.0676 (10)0.0086 (6)−0.0039 (7)0.0016 (7)
O50.0504 (10)0.0435 (10)0.259 (4)−0.0121 (8)−0.0082 (15)0.0441 (15)
O60.0415 (7)0.0392 (7)0.0681 (10)−0.0090 (6)0.0128 (7)0.0059 (7)
O70.0273 (7)0.0575 (9)0.0837 (12)0.0076 (6)0.0053 (7)−0.0044 (8)
O80.0326 (9)0.0211 (8)0.0631 (13)0.0000.0069 (8)0.000
O90.0304 (7)0.0501 (9)0.1171 (16)0.0104 (6)0.0009 (8)0.0031 (9)
O100.0399 (7)0.0372 (7)0.0673 (10)−0.0056 (6)0.0073 (7)0.0088 (7)
O110.0305 (9)0.0199 (8)0.0567 (12)0.0000.0020 (8)0.000
O1W0.0263 (7)0.0294 (7)0.0962 (13)0.0008 (5)−0.0054 (7)0.0013 (7)
O2W0.0296 (10)0.0253 (9)0.133 (2)0.000−0.0014 (12)0.000
O3W0.0286 (9)0.0244 (8)0.0719 (14)0.0000.0004 (9)0.000
N10.0345 (8)0.0322 (8)0.0414 (9)0.0028 (6)−0.0042 (7)0.0014 (6)
N20.0356 (8)0.0335 (8)0.0614 (11)−0.0008 (6)0.0060 (8)0.0067 (7)
N30.0206 (7)0.0488 (10)0.0608 (11)0.0008 (6)−0.0006 (7)0.0012 (8)
N40.0275 (7)0.0353 (8)0.0442 (9)−0.0025 (6)0.0039 (6)−0.0084 (7)
N50.0434 (12)0.0192 (9)0.0503 (14)0.0000.0058 (10)0.000
N60.0460 (13)0.0188 (9)0.0504 (13)0.0000.0006 (10)0.000
N70.0293 (7)0.0333 (8)0.0505 (10)0.0011 (6)0.0040 (7)−0.0052 (7)
C10.0282 (9)0.0412 (10)0.0476 (11)0.0067 (7)−0.0031 (8)−0.0008 (8)
C20.0270 (8)0.0305 (8)0.0371 (9)0.0010 (6)−0.0011 (7)−0.0017 (7)
C30.0237 (8)0.0296 (8)0.0374 (9)0.0006 (6)0.0012 (7)−0.0023 (7)
C40.0264 (8)0.0324 (9)0.0424 (10)0.0001 (7)0.0008 (7)0.0007 (7)
C50.0288 (9)0.0410 (10)0.0517 (12)−0.0062 (7)0.0027 (8)0.0011 (9)
C60.0339 (9)0.0289 (8)0.0406 (10)0.0063 (7)0.0034 (7)−0.0019 (7)
C70.0261 (8)0.0269 (8)0.0339 (9)−0.0002 (6)0.0009 (7)−0.0015 (6)
C80.0258 (11)0.0233 (10)0.0316 (12)0.000−0.0020 (9)0.000
C90.0387 (10)0.0270 (8)0.0421 (10)0.0055 (7)0.0003 (8)−0.0018 (7)
C100.0296 (8)0.0239 (8)0.0369 (9)0.0001 (6)−0.0006 (7)−0.0009 (6)
C110.0281 (11)0.0228 (10)0.0323 (12)0.000−0.0021 (9)0.000
Geometric parameters (Å, °) top
O1—N11.2285 (19)N5—C61.341 (2)
O2—N11.228 (2)N5—C6i1.341 (2)
O3—C31.235 (2)N5—H50.848 (10)
O4—N21.210 (2)N6—C91.338 (2)
O5—N21.206 (2)N6—C9ii1.338 (2)
O6—N41.227 (2)N6—H60.854 (10)
O7—N41.225 (2)N7—C101.455 (2)
O8—C81.233 (3)C1—C21.356 (2)
O9—N71.223 (2)C1—H1A0.9300
O10—N71.223 (2)C2—C31.457 (2)
O11—C111.237 (3)C3—C41.457 (2)
O1W—H110.851 (9)C4—C51.362 (2)
O1W—H120.858 (9)C5—H5A0.9300
O2W—H210.840 (8)C6—C71.361 (2)
O3W—H310.844 (8)C6—H6A0.9300
N1—C21.457 (2)C7—C81.458 (2)
N2—C41.455 (2)C8—C7i1.458 (2)
N3—C11.338 (3)C9—C101.360 (2)
N3—C51.338 (3)C9—H90.9300
N3—H30.853 (10)C10—C111.454 (2)
N4—C71.455 (2)C11—C10ii1.454 (2)
H11—O1W—H12109.1 (14)O3—C3—C4125.31 (15)
O2—N1—O1123.08 (16)O3—C3—C2124.72 (15)
O2—N1—C2119.15 (14)C4—C3—C2109.97 (14)
O1—N1—C2117.76 (15)C5—C4—N2115.48 (16)
O5—N2—O4121.96 (17)C5—C4—C3123.38 (16)
O5—N2—C4118.53 (17)N2—C4—C3121.12 (15)
O4—N2—C4119.51 (15)N3—C5—C4121.24 (17)
C1—N3—C5120.47 (16)N3—C5—H5A119.4
C1—N3—H3117.6 (16)C4—C5—H5A119.4
C5—N3—H3121.8 (16)N5—C6—C7120.80 (16)
O7—N4—O6123.11 (15)N5—C6—H6A119.6
O7—N4—C7118.20 (15)C7—C6—H6A119.6
O6—N4—C7118.66 (14)C6—C7—N4115.51 (15)
C6—N5—C6i120.6 (2)C6—C7—C8124.09 (16)
C6—N5—H5119.71 (10)N4—C7—C8120.39 (14)
C6i—N5—H5119.71 (10)O8—C8—C7i125.23 (9)
C9—N6—C9ii120.4 (2)O8—C8—C7125.23 (9)
C9—N6—H6119.82 (11)C7i—C8—C7109.54 (19)
C9ii—N6—H6119.82 (10)N6—C9—C10120.94 (17)
O10—N7—O9123.05 (16)N6—C9—H9119.5
O10—N7—C10118.79 (14)C10—C9—H9119.5
O9—N7—C10118.16 (16)C9—C10—C11124.11 (16)
N3—C1—C2120.99 (17)C9—C10—N7114.74 (15)
N3—C1—H1A119.5C11—C10—N7121.15 (14)
C2—C1—H1A119.5O11—C11—C10ii125.25 (9)
C1—C2—N1115.69 (15)O11—C11—C10125.25 (9)
C1—C2—C3123.94 (16)C10ii—C11—C10109.50 (19)
N1—C2—C3120.36 (14)
C5—N3—C1—C2−0.1 (3)C6i—N5—C6—C7−1.47 (13)
N3—C1—C2—N1179.48 (18)N5—C6—C7—N4−176.15 (14)
N3—C1—C2—C30.5 (3)N5—C6—C7—C83.0 (3)
O2—N1—C2—C1152.19 (18)O7—N4—C7—C6−26.7 (2)
O1—N1—C2—C1−27.0 (3)O6—N4—C7—C6151.55 (18)
O2—N1—C2—C3−28.8 (3)O7—N4—C7—C8154.12 (15)
O1—N1—C2—C3151.95 (18)O6—N4—C7—C8−27.7 (2)
C1—C2—C3—O3179.23 (19)C6—C7—C8—O8178.50 (13)
N1—C2—C3—O30.3 (3)N4—C7—C8—O8−2.34 (18)
C1—C2—C3—C4−0.1 (3)C6—C7—C8—C7i−1.50 (13)
N1—C2—C3—C4−179.00 (16)N4—C7—C8—C7i177.66 (18)
O5—N2—C4—C5−16.1 (3)C9ii—N6—C9—C10−0.98 (13)
O4—N2—C4—C5164.46 (19)N6—C9—C10—C112.0 (3)
O5—N2—C4—C3162.5 (3)N6—C9—C10—N7−177.52 (15)
O4—N2—C4—C3−16.9 (3)O10—N7—C10—C9152.08 (18)
O3—C3—C4—C5179.9 (2)O9—N7—C10—C9−27.5 (3)
C2—C3—C4—C5−0.7 (3)O10—N7—C10—C11−27.5 (2)
O3—C3—C4—N21.4 (3)O9—N7—C10—C11152.96 (17)
C2—C3—C4—N2−179.23 (17)C9—C10—C11—O11179.01 (13)
C1—N3—C5—C4−0.7 (3)N7—C10—C11—O11−1.48 (19)
N2—C4—C5—N3179.75 (19)C9—C10—C11—C10ii−0.99 (13)
C3—C4—C5—N31.2 (3)N7—C10—C11—C10ii178.52 (19)
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1w0.85 (1)1.86 (1)2.703 (2)172 (2)
N5—H5···O2w0.85 (1)1.84 (1)2.692 (3)180
N6—H6···O3w0.85 (1)1.87 (1)2.723 (3)180
O1w—H11···O8iii0.85 (1)2.04 (1)2.878 (2)168 (2)
O1w—H12···O11iv0.86 (1)2.02 (1)2.866 (2)168 (2)
O2w—H21···O3v0.84 (1)2.05 (1)2.888 (2)173 (1)
O3w—H31···O30.84 (1)2.05 (1)2.890 (2)172 (2)
Symmetry codes: (iii) −x+3/2, −y+3/2, z−1/2; (iv) x+1/2, y−1/2, −z+1/2; (v) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1w0.85 (1)1.86 (1)2.703 (2)172 (2)
N5—H5···O2w0.85 (1)1.84 (1)2.692 (3)180
N6—H6···O3w0.85 (1)1.87 (1)2.723 (3)180
O1w—H11···O8i0.85 (1)2.04 (1)2.878 (2)168 (2)
O1w—H12···O11ii0.86 (1)2.02 (1)2.866 (2)168 (2)
O2w—H21···O3iii0.84 (1)2.05 (1)2.888 (2)173 (1)
O3w—H31···O30.84 (1)2.05 (1)2.890 (2)172 (2)
Symmetry codes: (i) −x+3/2, −y+3/2, z−1/2; (ii) x+1/2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.
Acknowledgements top

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

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Jones, P. G. (2001). Acta Cryst. C57, 880–882.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2008). publCIF. In preparation.