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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): m1362–m1363.
Published online 2010 October 9. doi:  10.1107/S1600536810039176
PMCID: PMC3009182

Bis[[(6-carb­oxy­pyridazine-3-carboxyl­ato-κ2 N 2,O 3)lithium]-μ-penta­hydrogen­dioxy­gen(1+)]

Abstract

The structure of the title compound, [Li(C6H3N2O4)2(H5O2)], is composed of centrosymmetric monomers in which an LiI ion is chelated by two N,O-bonding groups donated by two ligands. The LiI ion and both ligand mol­ecules 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 mol­ecules 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 inter­act 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 [triangle]); Escuer et al. (1997 [triangle]); Gryz et al. (2006 [triangle]); Sun et al. (2007 [triangle], 2008 [triangle]). For the structures of complexes with MgII, see: Gryz et al. (2004 [triangle]). For the structures of complexes with PbII, see: Sobanska et al. (1999 [triangle]). For the structures of both modifications of pyridazine-3,6-dicarb­oxy­lic acid, see: Suecur et al. (1987 [triangle]); Starosta & Leciejewicz (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1362-scheme1.jpg

Experimental

Crystal data

  • [Li(C6H3N2O4)2(H5O2)]
  • M r = 378.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1362-efi1.jpg
  • 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 [triangle]) 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 [triangle]); cell refinement: KM-4; data reduction: DATAPROC (Kuma, 2001 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

supplementary crystallographic information

Comment

Studies of 3d metal complexes with pyridazine-3,6-dicarboxylate and water ligands revealed a variety of structures: from a monomeric anion in an ionic complex [Mg{C6H2N2O4)2(H2O)2}]2-(N2H6)2+ (Gryz et al., 2004) and dimeric molecules as in Ni, Co and Zn complexes (Escuer et al., 1997; Gryz et al., 2006; Sun et al., 2008) to coordination polymers as in MnII complexes (El Gueddi et al., 1996; Sun et al., 2007, 2008). The structure of a PbII complex shows also a polymeric pattern (Sobanska et al., 1999). The structure of the title compound is composed of monomers in which a LiI ion located in a centre of symmetry is chelated by two N,O bonding groups donated by two symmetry related ligand molecules and by two symmetry related aqua O atoms in axial positions. The coordination is slightly distorted octahedral. The ligand molecules and a LiI ion are coplanar [r.m.s. 0.0047 (2) Å]. The second carboxylic group of each ligand remains protonated and makes an angle of 5.9 (1)° with the pyridazine plane. Bond lengths and angles within the ligand ring are close to those reported earlier for both structures of the parent acid (Suecur et al., 1987; Starosta & Leciejewicz, 2004). An additional proton in a special position located between coordinated water molecules is clearly observed on Fourier maps. It maintains the charge balance within monomers and bridges them by short symmetric hydrogen bonds of 2.518 (3) Å with O6—H63—O6(ii) angle of 180° to form catenated ribbons. Symmetry code: (ii) -x + 1, -y, -z + 2. The latter are held together via hydrogen bonds in which water and protonated carboxylate O atoms act as donors and carboxylate O atoms and hetero-N atoms in adjacent ribbons as acceptors.

Experimental

The title compound was synthesized by mixing of boiling aqueous solutions, one containing 1 mmol of pyridazine-3,6-dicarboxylic acid, the other - 1 mmol of lithium hydroxide (Aldrich). The mixture was boiled under reflux for 3 h and after cooling to room temperature, filtered and left to crystallize. Few days later, colourless single crystals in the form of thin plates were found after evaporation to dryness. They were extracted, washed with cold ethanol and dried in the air.

Refinement

Water H atoms were located in a difference map and were allowed to ride on the parent atom with Uiso(H) = 1.5Ueq(O). H atoms attached to pyridazine-ring C atoms were located at calculated positions and treated as riding on the parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
A structural unit of title compound with atom labelling scheme. Displacement ellipsoids are drawn at 50% probability level. Symmetry codes: (i) -x, -y, -z + 1; (ii) -x + 1, -y, -z + 2.
Fig. 2.
Packing diagram of the structure.

Crystal data

[Li(C6H3N2O4)2(H5O2)]F(000) = 388
Mr = 378.19Dx = 1.694 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 4.903 (1) ÅCell parameters from 25 reflections
b = 24.640 (5) Åθ = 6–15°
c = 6.6020 (13) ŵ = 0.15 mm1
β = 111.60 (3)°T = 295 K
V = 741.6 (3) Å3Plate, colourless
Z = 20.42 × 0.39 × 0.07 mm

Data collection

Kuma KM-4 four-circle diffractometer1207 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.160
graphiteθmax = 30.1°, θmin = 1.7°
profile data from ω/2θ–scansh = −6→6
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)k = 0→34
Tmin = 0.961, Tmax = 0.999l = −9→9
4355 measured reflections3 standard reflections every 200 reflections
2181 independent reflections intensity decay: 0.8%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 1.01w = 1/[σ2(Fo2) + (0.0251P)2 + 0.0008P] where P = (Fo2 + 2Fc2)/3
2181 reflections(Δ/σ)max < 0.001
135 parametersΔρmax = 0.40 e Å3
3 restraintsΔρmin = −0.31 e Å3

Special details

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.

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

xyzUiso*/Ueq
N10.1189 (4)0.08134 (5)0.4137 (2)0.0216 (3)
O1−0.1491 (4)0.04967 (4)0.6760 (2)0.0308 (3)
O30.5111 (3)0.11620 (5)0.0040 (2)0.0288 (3)
O2−0.2209 (3)0.13593 (5)0.7509 (2)0.0297 (3)
C50.2683 (4)0.14735 (6)0.2292 (3)0.0208 (4)
N20.2452 (4)0.09550 (5)0.2750 (2)0.0215 (3)
C20.0209 (4)0.11977 (6)0.5110 (2)0.0196 (3)
C7−0.1279 (4)0.10016 (6)0.6606 (2)0.0208 (4)
C80.4088 (4)0.15946 (6)0.0675 (3)0.0226 (4)
O40.4208 (4)0.20499 (4)0.0057 (2)0.0405 (4)
C40.1727 (5)0.18911 (6)0.3287 (3)0.0264 (4)
H40.19300.22530.29650.032*
C30.0479 (5)0.17513 (6)0.4753 (3)0.0253 (4)
H3−0.01650.20140.54860.030*
Li10.00000.00000.50000.0588 (19)
O60.4949 (4)−0.00562 (5)0.8091 (2)0.0415 (4)
H610.606 (6)0.0181 (8)0.792 (4)0.062*
H620.558 (6)−0.0364 (7)0.807 (4)0.062*
H310.617 (7)0.1250 (8)−0.089 (4)0.042 (7)*
H630.50000.00001.00000.080 (14)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0282 (8)0.0198 (6)0.0270 (7)0.0007 (5)0.0221 (6)0.0017 (5)
O10.0433 (9)0.0227 (5)0.0420 (7)−0.0012 (5)0.0339 (6)0.0023 (5)
O30.0415 (9)0.0237 (5)0.0362 (7)0.0014 (5)0.0319 (6)0.0020 (5)
O20.0401 (9)0.0289 (6)0.0350 (7)0.0004 (5)0.0311 (5)−0.0016 (4)
C50.0247 (9)0.0204 (6)0.0235 (7)−0.0007 (7)0.0160 (6)0.0004 (5)
N20.0295 (9)0.0200 (5)0.0245 (7)0.0004 (6)0.0211 (6)0.0018 (5)
C20.0234 (9)0.0205 (6)0.0215 (7)−0.0009 (6)0.0162 (6)0.0000 (5)
C70.0215 (9)0.0260 (7)0.0221 (7)−0.0010 (6)0.0162 (6)0.0000 (5)
C80.0289 (10)0.0216 (7)0.0243 (7)−0.0016 (6)0.0182 (7)−0.0013 (5)
O40.0689 (11)0.0230 (6)0.0506 (8)−0.0029 (7)0.0465 (7)0.0046 (5)
C40.0384 (12)0.0187 (6)0.0308 (9)0.0008 (7)0.0229 (8)0.0013 (6)
C30.0352 (11)0.0195 (7)0.0312 (9)0.0001 (7)0.0239 (7)−0.0029 (6)
Li10.108 (6)0.0194 (19)0.095 (4)−0.006 (3)0.091 (4)−0.001 (2)
O60.0709 (13)0.0209 (6)0.0542 (9)−0.0033 (6)0.0484 (8)0.0009 (5)

Geometric parameters (Å, °)

N1—N21.327 (2)C2—C71.507 (3)
N1—C21.330 (2)C8—O41.2024 (19)
N1—Li12.2194 (14)C4—C31.366 (3)
O1—C71.2558 (18)C4—H40.9300
O1—Li12.0019 (15)C3—H30.9300
O3—C81.311 (2)Li1—O1i2.0020 (15)
O3—H310.96 (4)Li1—N1i2.2195 (14)
O2—C71.241 (2)Li1—O62.535 (2)
C5—N21.3274 (19)Li1—O6i2.535 (2)
C5—C41.392 (2)O6—H610.836 (18)
C5—C81.498 (3)O6—H620.822 (16)
C2—C31.399 (2)O6—H631.2600
N2—N1—C2119.32 (13)C2—C3—H3121.3
N2—N1—Li1130.38 (11)O1—Li1—O1i180.0
C2—N1—Li1110.08 (12)O1—Li1—N177.50 (6)
C7—O1—Li1119.98 (14)O1i—Li1—N1102.50 (6)
C8—O3—H31112.3 (14)O1—Li1—N1i102.50 (6)
N2—C5—C4122.17 (19)O1i—Li1—N1i77.50 (6)
N2—C5—C8117.00 (16)N1—Li1—N1i180.0
C4—C5—C8120.82 (14)O1—Li1—O690.68 (6)
C5—N2—N1120.70 (16)O1i—Li1—O689.32 (6)
N1—C2—C3122.66 (18)N1—Li1—O689.54 (5)
N1—C2—C7115.88 (13)N1i—Li1—O690.46 (5)
C3—C2—C7121.45 (17)O1—Li1—O6i89.32 (6)
O2—C7—O1127.48 (19)O1i—Li1—O6i90.68 (6)
O2—C7—C2116.05 (14)N1—Li1—O6i90.46 (5)
O1—C7—C2116.45 (16)N1i—Li1—O6i89.54 (5)
O4—C8—O3125.3 (2)O6—Li1—O6i180.0
O4—C8—C5121.33 (18)Li1—O6—H61109.5 (17)
O3—C8—C5113.34 (14)Li1—O6—H62106.8 (17)
C3—C4—C5117.69 (15)H61—O6—H62112 (3)
C3—C4—H4121.2Li1—O6—H63117.00
C5—C4—H4121.2H61—O6—H63107.00
C4—C3—C2117.40 (17)H62—O6—H63104.00
C4—C3—H3121.3

Symmetry codes: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O6—H63···O6ii1.261.262.518 (3)180
O6—H61···O1iii0.84 (2)1.82 (2)2.608 (2)157 (3)
O3—H31···O2iv0.96 (4)1.56 (4)2.525 (2)176 (2)
O6—H62···O3v0.82 (2)2.42 (2)2.9957 (19)128 (3)
O6—H62···N2v0.82 (2)1.93 (2)2.712 (2)159 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2232).

References

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