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

Liang, L.-L.; Zhao, J.-S.; Ng, S.W.

doi:10.1107/S1600536808014347

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1225

doi:10.1107/S1600536808014347

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

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

^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 ).

Experimental

Crystal data

C₁₀H₆N₂O₆·2H₂O
M_r = 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)
R_int = 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
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.24 e Å⁻³

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)
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 ); 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014347/tk2271sup1.cif

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

checkCIF report

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.

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

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

C₁₀H₆N₂O₆·2H₂O	Z = 2
M_r = 286.20	F(000) = 296
Triclinic, P1	D_x = 1.708 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4069 (1) Å	Cell parameters from 2234 reflections
b = 9.4254 (2) Å	θ = 2.9–28.2°
c = 9.6922 (2) Å	µ = 0.15 mm⁻¹
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 tube	R_int = 0.017
Graphite monochromator	θ_max = 27.5°, θ_min = 2.1°
ω scans	h = −8→8
4702 measured reflections	k = −12→11
2530 independent reflections	l = −12→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.0657P)² + 0.0694P] where P = (F_o² + 2F_c²)/3
2530 reflections	(Δ/σ)_max = 0.001
221 parameters	Δρ_max = 0.43 e Å⁻³
10 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₀H₆N₂O₆·2H₂O	γ = 73.451 (2)°
M_r = 286.20	V = 556.65 (2) Å³
Triclinic, P1	Z = 2
a = 6.4069 (1) Å	Mo Kα radiation
b = 9.4254 (2) Å	µ = 0.15 mm⁻¹
c = 9.6922 (2) Å	T = 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 reflections	R_int = 0.017
2530 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	10 restraints
wR(F²) = 0.105	All H-atom parameters refined
S = 1.06	Δρ_max = 0.43 e Å⁻³
2530 reflections	Δρ_min = −0.24 e Å⁻³
221 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.92046 (15)	0.93958 (11)	0.64792 (10)	0.0166 (2)
O2	0.86240 (15)	0.86579 (11)	0.87194 (10)	0.0195 (2)
O3	0.44292 (15)	0.84970 (10)	1.00234 (9)	0.0155 (2)
O4	0.68492 (16)	0.62355 (11)	1.02233 (9)	0.0199 (2)
O5	0.10736 (15)	0.53241 (11)	0.66473 (9)	0.0180 (2)
O6	0.49784 (14)	0.82489 (10)	0.27322 (9)	0.0147 (2)
O1W	1.14691 (16)	1.06674 (12)	0.78414 (11)	0.0207 (2)
O2W	0.85169 (16)	0.35754 (12)	0.90954 (10)	0.0213 (2)
N1	0.16571 (17)	0.60686 (12)	0.43675 (11)	0.0136 (2)
N2	0.27394 (17)	0.68218 (12)	0.34120 (11)	0.0134 (2)
C1	0.5698 (2)	0.73086 (14)	0.95287 (13)	0.0129 (3)
C2	0.54372 (19)	0.73590 (14)	0.79857 (13)	0.0120 (3)
C3	0.39766 (19)	0.66628 (14)	0.75724 (13)	0.0126 (3)
C4	0.35973 (19)	0.67201 (13)	0.61528 (12)	0.0116 (3)
C5	0.20578 (19)	0.60273 (14)	0.56725 (13)	0.0126 (3)
C6	0.41699 (19)	0.75457 (14)	0.36872 (13)	0.0117 (3)
C7	0.46733 (19)	0.74720 (14)	0.51629 (12)	0.0114 (3)
C8	0.61956 (19)	0.81353 (14)	0.55846 (13)	0.0119 (3)
C9	0.65794 (19)	0.80760 (14)	0.69923 (12)	0.0117 (3)
C10	0.8230 (2)	0.87406 (14)	0.74930 (13)	0.0137 (3)
H10	0.998 (3)	0.980 (2)	0.6878 (19)	0.042 (6)*
H30	0.458 (3)	0.838 (2)	1.0895 (10)	0.036 (5)*
H50	0.026 (3)	0.496 (2)	0.622 (2)	0.048 (6)*
H11	1.253 (2)	1.101 (2)	0.760 (2)	0.044 (6)*
H12	1.180 (3)	1.0209 (19)	0.8645 (12)	0.034 (5)*
H21	0.824 (3)	0.4435 (13)	0.9343 (19)	0.034 (5)*
H22	0.975 (2)	0.314 (3)	0.942 (3)	0.074 (8)*
H2	0.241 (3)	0.681 (2)	0.2530 (11)	0.037 (5)*
H3	0.320 (2)	0.6187 (16)	0.8236 (13)	0.017 (4)*
H8	0.693 (2)	0.8618 (17)	0.4898 (14)	0.019 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0159 (4)	0.0209 (5)	0.0166 (5)	−0.0107 (4)	0.0004 (4)	−0.0025 (4)
O2	0.0220 (5)	0.0270 (6)	0.0137 (5)	−0.0129 (4)	−0.0045 (4)	−0.0019 (4)
O3	0.0206 (5)	0.0168 (5)	0.0094 (4)	−0.0052 (4)	−0.0009 (3)	−0.0032 (4)
O4	0.0267 (5)	0.0175 (5)	0.0140 (5)	−0.0033 (4)	−0.0056 (4)	−0.0007 (4)
O5	0.0223 (5)	0.0245 (5)	0.0128 (5)	−0.0160 (4)	−0.0010 (4)	−0.0007 (4)
O6	0.0173 (4)	0.0192 (5)	0.0096 (4)	−0.0085 (4)	0.0005 (3)	−0.0015 (4)
O1W	0.0195 (5)	0.0238 (6)	0.0217 (5)	−0.0118 (4)	−0.0040 (4)	0.0009 (4)
O2W	0.0232 (5)	0.0215 (6)	0.0187 (5)	−0.0019 (4)	−0.0073 (4)	−0.0075 (4)
N1	0.0151 (5)	0.0144 (5)	0.0128 (5)	−0.0068 (4)	−0.0008 (4)	−0.0009 (4)
N2	0.0175 (5)	0.0161 (6)	0.0083 (5)	−0.0074 (4)	−0.0015 (4)	−0.0013 (4)
C1	0.0152 (6)	0.0155 (6)	0.0108 (6)	−0.0088 (5)	−0.0009 (4)	−0.0011 (5)
C2	0.0128 (6)	0.0120 (6)	0.0102 (6)	−0.0013 (5)	−0.0017 (4)	−0.0016 (5)
C3	0.0143 (6)	0.0139 (6)	0.0101 (6)	−0.0050 (5)	−0.0001 (4)	−0.0007 (5)
C4	0.0122 (6)	0.0104 (6)	0.0120 (6)	−0.0025 (5)	−0.0011 (4)	−0.0025 (5)
C5	0.0143 (6)	0.0115 (6)	0.0123 (6)	−0.0038 (5)	−0.0012 (5)	−0.0017 (5)
C6	0.0120 (5)	0.0123 (6)	0.0108 (6)	−0.0025 (5)	−0.0001 (4)	−0.0031 (4)
C7	0.0119 (5)	0.0113 (6)	0.0102 (6)	−0.0014 (4)	−0.0005 (4)	−0.0023 (5)
C8	0.0125 (6)	0.0120 (6)	0.0107 (6)	−0.0031 (5)	0.0009 (4)	−0.0009 (5)
C9	0.0120 (6)	0.0120 (6)	0.0109 (6)	−0.0026 (5)	−0.0012 (4)	−0.0020 (5)
C10	0.0126 (6)	0.0134 (6)	0.0147 (6)	−0.0025 (5)	−0.0004 (5)	−0.0025 (5)

Geometric parameters (Å, º) top

O1—C10	1.3235 (15)	N2—C6	1.3415 (16)
O1—H10	0.84 (1)	N2—H2	0.89 (1)
O2—C10	1.2143 (16)	C1—C2	1.5054 (17)
O3—C1	1.3139 (15)	C2—C3	1.3838 (17)
O3—H30	0.84 (1)	C2—C9	1.4061 (16)
O4—C1	1.2121 (16)	C3—C4	1.3993 (17)
O5—C5	1.3265 (15)	C3—H3	0.941 (9)
O5—H50	0.85 (1)	C4—C7	1.3961 (16)
O6—C6	1.2511 (15)	C4—C5	1.4487 (16)
O1W—H11	0.85 (1)	C6—C7	1.4688 (17)
O1W—H12	0.85 (1)	C7—C8	1.3983 (17)
O2W—H21	0.84 (1)	C8—C9	1.3884 (17)
O2W—H22	0.83 (1)	C8—H8	0.942 (9)
N1—C5	1.2953 (16)	C9—C10	1.4981 (17)
N1—N2	1.3794 (14)

C10—O1—H10	105.3 (14)	C3—C4—C5	121.13 (11)
C1—O3—H30	107.8 (13)	N1—C5—O5	120.97 (11)
C5—O5—H50	106.0 (15)	N1—C5—C4	122.70 (11)
H11—O1W—H12	104.8 (18)	O5—C5—C4	116.32 (11)
H21—O2W—H22	104 (2)	O6—C6—N2	121.07 (11)
C5—N1—N2	117.77 (10)	O6—C6—C7	123.23 (11)
C6—N2—N1	126.82 (10)	N2—C6—C7	115.70 (11)
C6—N2—H2	119.3 (12)	C4—C7—C8	119.99 (11)
N1—N2—H2	113.9 (12)	C4—C7—C6	118.67 (11)
O4—C1—O3	125.08 (12)	C8—C7—C6	121.35 (11)
O4—C1—C2	122.51 (12)	C9—C8—C7	119.53 (11)
O3—C1—C2	112.24 (10)	C9—C8—H8	121.9 (10)
C3—C2—C9	120.51 (11)	C7—C8—H8	118.6 (10)
C3—C2—C1	116.41 (11)	C8—C9—C2	120.16 (11)
C9—C2—C1	123.07 (11)	C8—C9—C10	121.46 (11)
C2—C3—C4	119.19 (11)	C2—C9—C10	118.37 (11)
C2—C3—H3	120.6 (9)	O2—C10—O1	124.29 (11)
C4—C3—H3	120.2 (10)	O2—C10—C9	122.03 (11)
C7—C4—C3	120.56 (11)	O1—C10—C9	113.68 (11)
C7—C4—C5	118.31 (11)

C5—N1—N2—C6	−0.85 (19)	C3—C4—C7—C6	−177.98 (11)
O4—C1—C2—C3	81.31 (15)	C5—C4—C7—C6	0.97 (17)
O3—C1—C2—C3	−94.09 (13)	O6—C6—C7—C4	176.75 (11)
O4—C1—C2—C9	−99.19 (15)	N2—C6—C7—C4	−2.25 (17)
O3—C1—C2—C9	85.40 (14)	O6—C6—C7—C8	−3.27 (19)
C9—C2—C3—C4	−1.98 (19)	N2—C6—C7—C8	177.73 (11)
C1—C2—C3—C4	177.53 (11)	C4—C7—C8—C9	−1.82 (19)
C2—C3—C4—C7	−0.12 (19)	C6—C7—C8—C9	178.19 (11)
C2—C3—C4—C5	−179.04 (11)	C7—C8—C9—C2	−0.26 (19)
N2—N1—C5—O5	179.93 (10)	C7—C8—C9—C10	178.62 (11)
N2—N1—C5—C4	−0.70 (18)	C3—C2—C9—C8	2.19 (19)
C7—C4—C5—N1	0.56 (19)	C1—C2—C9—C8	−177.29 (11)
C3—C4—C5—N1	179.50 (12)	C3—C2—C9—C10	−176.73 (11)
C7—C4—C5—O5	179.95 (11)	C1—C2—C9—C10	3.80 (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—O2	1.06 (19)
N1—N2—C6—C7	2.30 (18)	C8—C9—C10—O1	1.46 (17)
C3—C4—C7—C8	2.03 (19)	C2—C9—C10—O1	−179.64 (10)
C5—C4—C7—C8	−179.02 (11)

Hydrogen-bond geometry (Å, º) top

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)

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 formula	C₁₀H₆N₂O₆·2H₂O
M_r	286.20
Crystal system, space group	Triclinic, 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)
V (Å³)	556.65 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.33 × 0.31 × 0.09

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4702, 2530, 2160
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.105, 1.06
No. of reflections	2530
No. of parameters	221
No. of restraints	10
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	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···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)

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

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Benniston, 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
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar