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ISSN: 2056-9890

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

aDepartment of Chemistry, Shaanxi Key Laboratory for Physico-Inorganic Chemistry, Northwest University, Xi'an 710069, People's Republic of China, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 12 May 2008; accepted 13 May 2008; online 7 June 2008)

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[Benniston, A. C., Yufit, D. S. & Howard, J. A. K. (1999). Acta Cryst. C55, 1535-1536.]).

[Scheme 1]

Experimental

Crystal data
  • C10H6N2O6·2H2O

  • Mr = 286.20

  • Triclinic, [P \overline 1]

  • 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)

  • Rint = 0.017

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1o⋯O1w 0.84 (1) 1.78 (1) 2.615 (1) 175 (2)
O3—H3o⋯O6i 0.84 (1) 1.79 (1) 2.637 (1) 176 (2)
O5—H5o⋯N1ii 0.85 (1) 1.91 (1) 2.744 (1) 168 (2)
N2—H2⋯O2wiii 0.89 (1) 1.82 (1) 2.695 (1) 167 (2)
O1w—H11⋯O6iv 0.85 (1) 1.91 (1) 2.758 (1) 173 (2)
O1w—H12⋯O3v 0.85 (1) 2.31 (1) 3.052 (1) 146 (2)
O2w—H21⋯O4 0.84 (1) 1.96 (1) 2.771 (1) 162 (2)
O2w—H22⋯O2vi 0.83 (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.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2008[Westrip, S. P. (2008). publCIF. In preparation.]).

Supporting information


Comment top

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.

Related literature top

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

Experimental top

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 top

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.

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. Molecular structure of (I) showing atomic labelling scheme and displacement ellipsoids at the 70% probability level.
4-Hydroxy-1-oxo-1,2-dihydrophthalazine-6,7-dicarboxylic acid dihydrate top
Crystal data top
C10H6N2O6·2H2OZ = 2
Mr = 286.20F(000) = 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 = 2.9–28.2°
c = 9.6922 (2) ŵ = 0.15 mm1
α = 82.843 (2)°T = 100 K
β = 87.496 (1)°Prism, colorless
γ = 73.451 (2)°0.33 × 0.31 × 0.09 mm
V = 556.65 (2) Å3
Data collection top
Bruker SMART APEX
diffractometer
2160 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
Graphite monochromatorθmax = 27.5°, θmin = 2.1°
ω scansh = 88
4702 measured reflectionsk = 1211
2530 independent reflectionsl = 1211
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105All H-atom parameters refined
S = 1.06 w = 1/[σ2(Fo2) + (0.0657P)2 + 0.0694P]
where P = (Fo2 + 2Fc2)/3
2530 reflections(Δ/σ)max = 0.001
221 parametersΔρmax = 0.43 e Å3
10 restraintsΔρmin = 0.24 e Å3
Crystal data top
C10H6N2O6·2H2Oγ = 73.451 (2)°
Mr = 286.20V = 556.65 (2) Å3
Triclinic, P1Z = 2
a = 6.4069 (1) ÅMo Kα radiation
b = 9.4254 (2) ŵ = 0.15 mm1
c = 9.6922 (2) ÅT = 100 K
α = 82.843 (2)°0.33 × 0.31 × 0.09 mm
β = 87.496 (1)°
Data collection top
Bruker SMART APEX
diffractometer
2160 reflections with I > 2σ(I)
4702 measured reflectionsRint = 0.017
2530 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03510 restraints
wR(F2) = 0.105All H-atom parameters refined
S = 1.06Δρmax = 0.43 e Å3
2530 reflectionsΔρmin = 0.24 e Å3
221 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, º) top
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—C60.85 (19)C3—C4—C7—C6177.98 (11)
O4—C1—C2—C381.31 (15)C5—C4—C7—C60.97 (17)
O3—C1—C2—C394.09 (13)O6—C6—C7—C4176.75 (11)
O4—C1—C2—C999.19 (15)N2—C6—C7—C42.25 (17)
O3—C1—C2—C985.40 (14)O6—C6—C7—C83.27 (19)
C9—C2—C3—C41.98 (19)N2—C6—C7—C8177.73 (11)
C1—C2—C3—C4177.53 (11)C4—C7—C8—C91.82 (19)
C2—C3—C4—C70.12 (19)C6—C7—C8—C9178.19 (11)
C2—C3—C4—C5179.04 (11)C7—C8—C9—C20.26 (19)
N2—N1—C5—O5179.93 (10)C7—C8—C9—C10178.62 (11)
N2—N1—C5—C40.70 (18)C3—C2—C9—C82.19 (19)
C7—C4—C5—N10.56 (19)C1—C2—C9—C8177.29 (11)
C3—C4—C5—N1179.50 (12)C3—C2—C9—C10176.73 (11)
C7—C4—C5—O5179.95 (11)C1—C2—C9—C103.80 (18)
C3—C4—C5—O51.10 (18)C8—C9—C10—O2177.84 (12)
N1—N2—C6—O6176.72 (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—O1179.64 (10)
C5—C4—C7—C8179.02 (11)
Hydrogen-bond geometry (Å, º) top
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.

Experimental details

Crystal data
Chemical formulaC10H6N2O6·2H2O
Mr286.20
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)6.4069 (1), 9.4254 (2), 9.6922 (2)
α, β, γ (°)82.843 (2), 87.496 (1), 73.451 (2)
V3)556.65 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.33 × 0.31 × 0.09
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4702, 2530, 2160
Rint0.017
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.105, 1.06
No. of reflections2530
No. of parameters221
No. of restraints10
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.43, 0.24

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top
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.
 

Acknowledgements

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

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBenniston, A. C., Yufit, D. S. & Howard, J. A. K. (1999). Acta Cryst. C55, 1535–1536.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2008). publCIF. In preparation.  Google Scholar

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