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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1701.
Published online 2008 August 6. doi:  10.1107/S1600536808024604
PMCID: PMC2960580

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

Abstract

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.

Related literature

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

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Object name is e-64-o1701-scheme1.jpg

Experimental

Crystal data

  • C5H3N3O5·H2O
  • M r = 203.12
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1701-efi1.jpg
  • 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
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.31 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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···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.

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.

Refinement

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.

Figures

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.

Crystal data

C5H3N3O5·H2OF000 = 1664
Mr = 203.12Dx = 1.746 Mg m3
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 mm1
c = 6.5713 (5) ÅT = 293 (2) K
V = 3091.7 (4) Å3Block, colorless
Z = 160.45 × 0.45 × 0.20 mm

Data collection

Bruker APEXII diffractometer3555 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
[var phi] and ω scansh = −28→27
Absorption correction: nonek = −28→27
21800 measured reflectionsl = −8→8

Refinement

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 Å3
281 parametersΔρmin = −0.31 e Å3
10 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2110).

References

  • 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. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography