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

Ling-Ling Liang; Jian-She Zhao; Seik Weng Ng

doi:10.1107/S1600536808014347

. 2008 Jun 7;64(Pt 7):o1225. doi: 10.1107/S1600536808014347

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

Ling-Ling Liang ^a, Jian-She Zhao ^a, Seik Weng Ng ^b,^*

PMCID: PMC2961645 PMID: 21202862

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 ▶).

Experimental

Crystal data

C₁₀H₆N₂O₆·2H₂O
M _r = 286.20
Triclinic,
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
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.24 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/S1600536808014347/tk2271sup1.cif

e-64-o1225-sup1.cif^{(17.3KB, cif)}

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

e-64-o1225-Isup2.hkl^{(124.2KB, 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
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⋯O6^iv	0.85 (1)	1.91 (1)	2.758 (1)	173 (2)
O1w—H12⋯O3^v	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⋯O2^vi	0.83 (1)	2.37 (2)	3.050 (1)	139 (2)

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

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.