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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1225.
Published online 2008 June 7. doi:  10.1107/S1600536808014347
PMCID: PMC2961645

4-Hydr­oxy-1-oxo-1,2-dihydro­phthalazine-6,7-dicarboxylic acid dihydrate

Abstract

In the crystal structure of the title compound, C10H6N2O6·2H2O, the OH and NH groups each serve as a hydrogen-bond donor to one acceptor site whereas the water mol­ecules each serve as a hydrogen-bond donor to two acceptor sites. The hydrogen-bonding scheme gives rise to a three-dimensional network.

Related literature

For the structure of bis­(hydrazinium) 4-hydr­oxy-1-oxo-2H-phthalazine-6,7-dicarboxyl­ate, see: Benniston et al. (1999 [triangle]).

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Object name is e-64-o1225-scheme1.jpg

Experimental

Crystal data

  • C10H6N2O6·2H2O
  • M r = 286.20
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1225-efi1.jpg
  • a = 6.4069 (1) Å
  • b = 9.4254 (2) Å
  • c = 9.6922 (2) Å
  • α = 82.843 (2)°
  • β = 87.496 (1)°
  • γ = 73.451 (2)°
  • V = 556.65 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.15 mm−1
  • T = 100 (2) K
  • 0.33 × 0.31 × 0.09 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: none
  • 4702 measured reflections
  • 2530 independent reflections
  • 2160 reflections with I > 2σ(I)
  • R int = 0.017

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.105
  • S = 1.06
  • 2530 reflections
  • 221 parameters
  • 10 restraints
  • All H-atom parameters refined
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.24 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/S1600536808014347/tk2271sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014347/tk2271Isup2.hkl

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

Acknowledgments

We thank Northwest University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Benzene-1,2,4,5-tetracarboxylic acid reacts with hydrazine to form bis(hydrazinium) 4-hydroxy-1-oxo-2H-phthalazine-6,7-dicarboxylate, whose anion represents a ligand possesses a recognition site for metals as well as a rich hydrogen-bonding motif (Benniston et al., 1999). The neutral acid itself would be more useful for the synthesis of metal derivatives; the neutral acid has been unexpectedly obtained when the reaction was carried out in the presence of a cobaltous salt. The acid crystallizes as a dihydrate (Scheme I, Fig. 1). The –OH and –NH groups each serves as hydrogen-bond donor to one acceptor site whereas the water molecules each serves as hydrogen bond donor to two acceptor sites. The hydrogen bonding scheme gives rise to a three-dimensional network.

Experimental

Hydrazine hydrate (0.01 g, 0.2 mmol), pyromellitic acid (0.05 g, 0.2 mmol), cobaltous chloride hexahydrate (0.02 g, 0.1 mmol) and water (10 ml) were heated in a 25 ml, Teflon-lined Parr bomb at 433 K for 96 h. The bomb was cooled to room temperature at 10 K per hour.

Refinement

All hydrogen atoms were located in a difference Fouier map, and were refined with distance restraints (C–H 0.95±0.01, N–H 0.88±0.01 and O–H 0.84±0.01 Å). Temperature factors were freely refined.

Figures

Fig. 1.
Molecular structure of (I) showing atomic labelling scheme and displacement ellipsoids at the 70% probability level.

Crystal data

C10H6N2O6·2H2OZ = 2
Mr = 286.20F000 = 296
Triclinic, P1Dx = 1.708 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 6.4069 (1) ÅCell parameters from 2234 reflections
b = 9.4254 (2) Åθ = 2.9–28.2º
c = 9.6922 (2) ŵ = 0.15 mm1
α = 82.843 (2)ºT = 100 (2) K
β = 87.496 (1)ºPrism, colorless
γ = 73.451 (2)º0.33 × 0.31 × 0.09 mm
V = 556.65 (2) Å3

Data collection

Bruker SMART APEX diffractometer2160 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
Monochromator: graphiteθmax = 27.5º
T = 100(2) Kθmin = 2.1º
ω scansh = −8→8
Absorption correction: Nonek = −12→11
4702 measured reflectionsl = −12→11
2530 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035All H-atom parameters refined
wR(F2) = 0.105  w = 1/[σ2(Fo2) + (0.0657P)2 + 0.0694P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2530 reflectionsΔρmax = 0.43 e Å3
221 parametersΔρmin = −0.24 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
O10.92046 (15)0.93958 (11)0.64792 (10)0.0166 (2)
O20.86240 (15)0.86579 (11)0.87194 (10)0.0195 (2)
O30.44292 (15)0.84970 (10)1.00234 (9)0.0155 (2)
O40.68492 (16)0.62355 (11)1.02233 (9)0.0199 (2)
O50.10736 (15)0.53241 (11)0.66473 (9)0.0180 (2)
O60.49784 (14)0.82489 (10)0.27322 (9)0.0147 (2)
O1W1.14691 (16)1.06674 (12)0.78414 (11)0.0207 (2)
O2W0.85169 (16)0.35754 (12)0.90954 (10)0.0213 (2)
N10.16571 (17)0.60686 (12)0.43675 (11)0.0136 (2)
N20.27394 (17)0.68218 (12)0.34120 (11)0.0134 (2)
C10.5698 (2)0.73086 (14)0.95287 (13)0.0129 (3)
C20.54372 (19)0.73590 (14)0.79857 (13)0.0120 (3)
C30.39766 (19)0.66628 (14)0.75724 (13)0.0126 (3)
C40.35973 (19)0.67201 (13)0.61528 (12)0.0116 (3)
C50.20578 (19)0.60273 (14)0.56725 (13)0.0126 (3)
C60.41699 (19)0.75457 (14)0.36872 (13)0.0117 (3)
C70.46733 (19)0.74720 (14)0.51629 (12)0.0114 (3)
C80.61956 (19)0.81353 (14)0.55846 (13)0.0119 (3)
C90.65794 (19)0.80760 (14)0.69923 (12)0.0117 (3)
C100.8230 (2)0.87406 (14)0.74930 (13)0.0137 (3)
H100.998 (3)0.980 (2)0.6878 (19)0.042 (6)*
H300.458 (3)0.838 (2)1.0895 (10)0.036 (5)*
H500.026 (3)0.496 (2)0.622 (2)0.048 (6)*
H111.253 (2)1.101 (2)0.760 (2)0.044 (6)*
H121.180 (3)1.0209 (19)0.8645 (12)0.034 (5)*
H210.824 (3)0.4435 (13)0.9343 (19)0.034 (5)*
H220.975 (2)0.314 (3)0.942 (3)0.074 (8)*
H20.241 (3)0.681 (2)0.2530 (11)0.037 (5)*
H30.320 (2)0.6187 (16)0.8236 (13)0.017 (4)*
H80.693 (2)0.8618 (17)0.4898 (14)0.019 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0159 (4)0.0209 (5)0.0166 (5)−0.0107 (4)0.0004 (4)−0.0025 (4)
O20.0220 (5)0.0270 (6)0.0137 (5)−0.0129 (4)−0.0045 (4)−0.0019 (4)
O30.0206 (5)0.0168 (5)0.0094 (4)−0.0052 (4)−0.0009 (3)−0.0032 (4)
O40.0267 (5)0.0175 (5)0.0140 (5)−0.0033 (4)−0.0056 (4)−0.0007 (4)
O50.0223 (5)0.0245 (5)0.0128 (5)−0.0160 (4)−0.0010 (4)−0.0007 (4)
O60.0173 (4)0.0192 (5)0.0096 (4)−0.0085 (4)0.0005 (3)−0.0015 (4)
O1W0.0195 (5)0.0238 (6)0.0217 (5)−0.0118 (4)−0.0040 (4)0.0009 (4)
O2W0.0232 (5)0.0215 (6)0.0187 (5)−0.0019 (4)−0.0073 (4)−0.0075 (4)
N10.0151 (5)0.0144 (5)0.0128 (5)−0.0068 (4)−0.0008 (4)−0.0009 (4)
N20.0175 (5)0.0161 (6)0.0083 (5)−0.0074 (4)−0.0015 (4)−0.0013 (4)
C10.0152 (6)0.0155 (6)0.0108 (6)−0.0088 (5)−0.0009 (4)−0.0011 (5)
C20.0128 (6)0.0120 (6)0.0102 (6)−0.0013 (5)−0.0017 (4)−0.0016 (5)
C30.0143 (6)0.0139 (6)0.0101 (6)−0.0050 (5)−0.0001 (4)−0.0007 (5)
C40.0122 (6)0.0104 (6)0.0120 (6)−0.0025 (5)−0.0011 (4)−0.0025 (5)
C50.0143 (6)0.0115 (6)0.0123 (6)−0.0038 (5)−0.0012 (5)−0.0017 (5)
C60.0120 (5)0.0123 (6)0.0108 (6)−0.0025 (5)−0.0001 (4)−0.0031 (4)
C70.0119 (5)0.0113 (6)0.0102 (6)−0.0014 (4)−0.0005 (4)−0.0023 (5)
C80.0125 (6)0.0120 (6)0.0107 (6)−0.0031 (5)0.0009 (4)−0.0009 (5)
C90.0120 (6)0.0120 (6)0.0109 (6)−0.0026 (5)−0.0012 (4)−0.0020 (5)
C100.0126 (6)0.0134 (6)0.0147 (6)−0.0025 (5)−0.0004 (5)−0.0025 (5)

Geometric parameters (Å, °)

O1—C101.3235 (15)N2—C61.3415 (16)
O1—H100.84 (1)N2—H20.89 (1)
O2—C101.2143 (16)C1—C21.5054 (17)
O3—C11.3139 (15)C2—C31.3838 (17)
O3—H300.84 (1)C2—C91.4061 (16)
O4—C11.2121 (16)C3—C41.3993 (17)
O5—C51.3265 (15)C3—H30.941 (9)
O5—H500.85 (1)C4—C71.3961 (16)
O6—C61.2511 (15)C4—C51.4487 (16)
O1W—H110.85 (1)C6—C71.4688 (17)
O1W—H120.85 (1)C7—C81.3983 (17)
O2W—H210.84 (1)C8—C91.3884 (17)
O2W—H220.83 (1)C8—H80.942 (9)
N1—C51.2953 (16)C9—C101.4981 (17)
N1—N21.3794 (14)
C10—O1—H10105.3 (14)C3—C4—C5121.13 (11)
C1—O3—H30107.8 (13)N1—C5—O5120.97 (11)
C5—O5—H50106.0 (15)N1—C5—C4122.70 (11)
H11—O1W—H12104.8 (18)O5—C5—C4116.32 (11)
H21—O2W—H22104 (2)O6—C6—N2121.07 (11)
C5—N1—N2117.77 (10)O6—C6—C7123.23 (11)
C6—N2—N1126.82 (10)N2—C6—C7115.70 (11)
C6—N2—H2119.3 (12)C4—C7—C8119.99 (11)
N1—N2—H2113.9 (12)C4—C7—C6118.67 (11)
O4—C1—O3125.08 (12)C8—C7—C6121.35 (11)
O4—C1—C2122.51 (12)C9—C8—C7119.53 (11)
O3—C1—C2112.24 (10)C9—C8—H8121.9 (10)
C3—C2—C9120.51 (11)C7—C8—H8118.6 (10)
C3—C2—C1116.41 (11)C8—C9—C2120.16 (11)
C9—C2—C1123.07 (11)C8—C9—C10121.46 (11)
C2—C3—C4119.19 (11)C2—C9—C10118.37 (11)
C2—C3—H3120.6 (9)O2—C10—O1124.29 (11)
C4—C3—H3120.2 (10)O2—C10—C9122.03 (11)
C7—C4—C3120.56 (11)O1—C10—C9113.68 (11)
C7—C4—C5118.31 (11)
C5—N1—N2—C6−0.85 (19)C3—C4—C7—C6−177.98 (11)
O4—C1—C2—C381.31 (15)C5—C4—C7—C60.97 (17)
O3—C1—C2—C3−94.09 (13)O6—C6—C7—C4176.75 (11)
O4—C1—C2—C9−99.19 (15)N2—C6—C7—C4−2.25 (17)
O3—C1—C2—C985.40 (14)O6—C6—C7—C8−3.27 (19)
C9—C2—C3—C4−1.98 (19)N2—C6—C7—C8177.73 (11)
C1—C2—C3—C4177.53 (11)C4—C7—C8—C9−1.82 (19)
C2—C3—C4—C7−0.12 (19)C6—C7—C8—C9178.19 (11)
C2—C3—C4—C5−179.04 (11)C7—C8—C9—C2−0.26 (19)
N2—N1—C5—O5179.93 (10)C7—C8—C9—C10178.62 (11)
N2—N1—C5—C4−0.70 (18)C3—C2—C9—C82.19 (19)
C7—C4—C5—N10.56 (19)C1—C2—C9—C8−177.29 (11)
C3—C4—C5—N1179.50 (12)C3—C2—C9—C10−176.73 (11)
C7—C4—C5—O5179.95 (11)C1—C2—C9—C103.80 (18)
C3—C4—C5—O5−1.10 (18)C8—C9—C10—O2−177.84 (12)
N1—N2—C6—O6−176.72 (11)C2—C9—C10—O21.06 (19)
N1—N2—C6—C72.30 (18)C8—C9—C10—O11.46 (17)
C3—C4—C7—C82.03 (19)C2—C9—C10—O1−179.64 (10)
C5—C4—C7—C8−179.02 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1o···O1w0.84 (1)1.78 (1)2.615 (1)175 (2)
O3—H3o···O6i0.84 (1)1.79 (1)2.637 (1)176 (2)
O5—H5o···N1ii0.85 (1)1.91 (1)2.744 (1)168 (2)
N2—H2···O2wiii0.89 (1)1.82 (1)2.695 (1)167 (2)
O1w—H11···O6iv0.85 (1)1.91 (1)2.758 (1)173 (2)
O1w—H12···O3v0.85 (1)2.31 (1)3.052 (1)146 (2)
O2w—H21···O40.84 (1)1.96 (1)2.771 (1)162 (2)
O2w—H22···O2vi0.83 (1)2.37 (2)3.050 (1)139 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2271).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Benniston, A. C., Yufit, D. S. & Howard, J. A. K. (1999). Acta Cryst. C55, 1535–1536.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

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