Bis[[(6-carb-oxy-pyridazine-3-carboxyl-ato-κN,O)lithium]-μ-penta-hydrogen-dioxy-gen(1+)].

The structure of the title compound, [Li(C(6)H(3)N(2)O(4))(2)(H(5)O(2))], is composed of centrosymmetric monomers in which an Li(I) ion is chelated by two N,O-bonding groups donated by two ligands. The Li(I) ion and both ligand mol-ecules are coplanar [r.m.s. deviation 0.0047 (2) Å] and water O atoms are in the axial positions. The second carboxyl group of each ligand remains protonated. An additional H atom, located between adjacent coordinated water mol-ecules and observed on Fourier maps, maintains the charge balance within the monomers and bridges them by short symmetric hydrogen bonds of 2.518 (3) Å to form catenated ribbons. The monomers also inter-act via hydrogen bonds in which water and carboxyl O atoms act as donors.

Related literature

For the crystal structures of 3d metal complexes with pyrid­azine-3,6-dicarboxyl­ate and water ligands, see: El Gueddi et al. (1996 ▶); Escuer et al. (1997 ▶); Gryz et al. (2006 ▶); Sun et al. (2007 ▶, 2008 ▶). For the structures of complexes with MgII, see: Gryz et al. (2004 ▶). For the structures of complexes with PbII, see: Sobanska et al. (1999 ▶). For the structures of both modifications of pyridazine-3,6-dicarb­oxy­lic acid, see: Suecur et al. (1987 ▶); Starosta & Leciejewicz (2004 ▶).

Experimental

Crystal data

[Li(C6H3N2O4)2(H5O2)]

M = 378.19

Monoclinic,

a = 4.903 (1) Å

b = 24.640 (5) Å

c = 6.6020 (13) Å

β = 111.60 (3)°

V = 741.6 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.15 mm−1

T = 295 K

0.42 × 0.39 × 0.07 mm

Data collection

Kuma KM-4 four-circle diffractometer

Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.961, T max = 0.999

4355 measured reflections

2181 independent reflections

1207 reflections with I > 2σ(I)

R int = 0.160

3 standard reflections every 200 reflections intensity decay: 0.8%

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.117

S = 1.01

2181 reflections

135 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.31 e Å−3

Data collection: KM-4 (Kuma, 1996 ▶); cell refinement: KM-4; data reduction: DATAPROC (Kuma, 2001 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810039176/rk2232sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039176/rk2232Isup2.hkl

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

[Li(C6H3N2O4)2(H5O2)]	F(000) = 388
Mr = 378.19	Dx = 1.694 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.903 (1) Å	Cell parameters from 25 reflections
b = 24.640 (5) Å	θ = 6–15°
c = 6.6020 (13) Å	µ = 0.15 mm−1
β = 111.60 (3)°	T = 295 K
V = 741.6 (3) Å3	Plate, colourless
Z = 2	0.42 × 0.39 × 0.07 mm

Kuma KM-4 four-circle diffractometer	1207 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.160
graphite	θmax = 30.1°, θmin = 1.7°
profile data from ω/2θ–scans	h = −6→6
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = 0→34
Tmin = 0.961, Tmax = 0.999	l = −9→9
4355 measured reflections	3 standard reflections every 200 reflections
2181 independent reflections	intensity decay: 0.8%

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0251P)2 + 0.0008P] where P = (Fo2 + 2Fc2)/3
2181 reflections	(Δ/σ)max < 0.001
135 parameters	Δρmax = 0.40 e Å−3
3 restraints	Δρmin = −0.31 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
N1	0.1189 (4)	0.08134 (5)	0.4137 (2)	0.0216 (3)
O1	−0.1491 (4)	0.04967 (4)	0.6760 (2)	0.0308 (3)
O3	0.5111 (3)	0.11620 (5)	0.0040 (2)	0.0288 (3)
O2	−0.2209 (3)	0.13593 (5)	0.7509 (2)	0.0297 (3)
C5	0.2683 (4)	0.14735 (6)	0.2292 (3)	0.0208 (4)
N2	0.2452 (4)	0.09550 (5)	0.2750 (2)	0.0215 (3)
C2	0.0209 (4)	0.11977 (6)	0.5110 (2)	0.0196 (3)
C7	−0.1279 (4)	0.10016 (6)	0.6606 (2)	0.0208 (4)
C8	0.4088 (4)	0.15946 (6)	0.0675 (3)	0.0226 (4)
O4	0.4208 (4)	0.20499 (4)	0.0057 (2)	0.0405 (4)
C4	0.1727 (5)	0.18911 (6)	0.3287 (3)	0.0264 (4)
H4	0.1930	0.2253	0.2965	0.032*
C3	0.0479 (5)	0.17513 (6)	0.4753 (3)	0.0253 (4)
H3	−0.0165	0.2014	0.5486	0.030*
Li1	0.0000	0.0000	0.5000	0.0588 (19)
O6	0.4949 (4)	−0.00562 (5)	0.8091 (2)	0.0415 (4)
H61	0.606 (6)	0.0181 (8)	0.792 (4)	0.062*
H62	0.558 (6)	−0.0364 (7)	0.807 (4)	0.062*
H31	0.617 (7)	0.1250 (8)	−0.089 (4)	0.042 (7)*
H63	0.5000	0.0000	1.0000	0.080 (14)*

	U11	U22	U33	U12	U13	U23
N1	0.0282 (8)	0.0198 (6)	0.0270 (7)	0.0007 (5)	0.0221 (6)	0.0017 (5)
O1	0.0433 (9)	0.0227 (5)	0.0420 (7)	−0.0012 (5)	0.0339 (6)	0.0023 (5)
O3	0.0415 (9)	0.0237 (5)	0.0362 (7)	0.0014 (5)	0.0319 (6)	0.0020 (5)
O2	0.0401 (9)	0.0289 (6)	0.0350 (7)	0.0004 (5)	0.0311 (5)	−0.0016 (4)
C5	0.0247 (9)	0.0204 (6)	0.0235 (7)	−0.0007 (7)	0.0160 (6)	0.0004 (5)
N2	0.0295 (9)	0.0200 (5)	0.0245 (7)	0.0004 (6)	0.0211 (6)	0.0018 (5)
C2	0.0234 (9)	0.0205 (6)	0.0215 (7)	−0.0009 (6)	0.0162 (6)	0.0000 (5)
C7	0.0215 (9)	0.0260 (7)	0.0221 (7)	−0.0010 (6)	0.0162 (6)	0.0000 (5)
C8	0.0289 (10)	0.0216 (7)	0.0243 (7)	−0.0016 (6)	0.0182 (7)	−0.0013 (5)
O4	0.0689 (11)	0.0230 (6)	0.0506 (8)	−0.0029 (7)	0.0465 (7)	0.0046 (5)
C4	0.0384 (12)	0.0187 (6)	0.0308 (9)	0.0008 (7)	0.0229 (8)	0.0013 (6)
C3	0.0352 (11)	0.0195 (7)	0.0312 (9)	0.0001 (7)	0.0239 (7)	−0.0029 (6)
Li1	0.108 (6)	0.0194 (19)	0.095 (4)	−0.006 (3)	0.091 (4)	−0.001 (2)
O6	0.0709 (13)	0.0209 (6)	0.0542 (9)	−0.0033 (6)	0.0484 (8)	0.0009 (5)

N1—N2	1.327 (2)	C2—C7	1.507 (3)
N1—C2	1.330 (2)	C8—O4	1.2024 (19)
N1—Li1	2.2194 (14)	C4—C3	1.366 (3)
O1—C7	1.2558 (18)	C4—H4	0.9300
O1—Li1	2.0019 (15)	C3—H3	0.9300
O3—C8	1.311 (2)	Li1—O1i	2.0020 (15)
O3—H31	0.96 (4)	Li1—N1i	2.2195 (14)
O2—C7	1.241 (2)	Li1—O6	2.535 (2)
C5—N2	1.3274 (19)	Li1—O6i	2.535 (2)
C5—C4	1.392 (2)	O6—H61	0.836 (18)
C5—C8	1.498 (3)	O6—H62	0.822 (16)
C2—C3	1.399 (2)	O6—H63	1.2600
N2—N1—C2	119.32 (13)	C2—C3—H3	121.3
N2—N1—Li1	130.38 (11)	O1—Li1—O1i	180.0
C2—N1—Li1	110.08 (12)	O1—Li1—N1	77.50 (6)
C7—O1—Li1	119.98 (14)	O1i—Li1—N1	102.50 (6)
C8—O3—H31	112.3 (14)	O1—Li1—N1i	102.50 (6)
N2—C5—C4	122.17 (19)	O1i—Li1—N1i	77.50 (6)
N2—C5—C8	117.00 (16)	N1—Li1—N1i	180.0
C4—C5—C8	120.82 (14)	O1—Li1—O6	90.68 (6)
C5—N2—N1	120.70 (16)	O1i—Li1—O6	89.32 (6)
N1—C2—C3	122.66 (18)	N1—Li1—O6	89.54 (5)
N1—C2—C7	115.88 (13)	N1i—Li1—O6	90.46 (5)
C3—C2—C7	121.45 (17)	O1—Li1—O6i	89.32 (6)
O2—C7—O1	127.48 (19)	O1i—Li1—O6i	90.68 (6)
O2—C7—C2	116.05 (14)	N1—Li1—O6i	90.46 (5)
O1—C7—C2	116.45 (16)	N1i—Li1—O6i	89.54 (5)
O4—C8—O3	125.3 (2)	O6—Li1—O6i	180.0
O4—C8—C5	121.33 (18)	Li1—O6—H61	109.5 (17)
O3—C8—C5	113.34 (14)	Li1—O6—H62	106.8 (17)
C3—C4—C5	117.69 (15)	H61—O6—H62	112 (3)
C3—C4—H4	121.2	Li1—O6—H63	117.00
C5—C4—H4	121.2	H61—O6—H63	107.00
C4—C3—C2	117.40 (17)	H62—O6—H63	104.00
C4—C3—H3	121.3

D—H···A	D—H	H···A	D···A	D—H···A
O6—H63···O6ii	1.26	1.26	2.518 (3)	180
O6—H61···O1iii	0.84 (2)	1.82 (2)	2.608 (2)	157 (3)
O3—H31···O2iv	0.96 (4)	1.56 (4)	2.525 (2)	176 (2)
O6—H62···O3v	0.82 (2)	2.42 (2)	2.9957 (19)	128 (3)
O6—H62···N2v	0.82 (2)	1.93 (2)	2.712 (2)	159 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H63⋯O6i	1.26	1.26	2.518 (3)	180
O6—H61⋯O1ii	0.84 (2)	1.82 (2)	2.608 (2)	157 (3)
O3—H31⋯O2iii	0.96 (4)	1.56 (4)	2.525 (2)	176 (2)
O6—H62⋯O3iv	0.82 (2)	2.42 (2)	2.9957 (19)	128 (3)
O6—H62⋯N2iv	0.82 (2)	1.93 (2)	2.712 (2)	159 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .