metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 4| April 2011| Pages m425-m426

Poly[aqua­(μ3-pyridazine-4-carboxyl­ato-κ2O:O:O′)lithium]

aInstitute of Nuclear Chemistry and Technology, ul.Dorodna 16, 03-195 Warszawa, Poland
*Correspondence e-mail: j.leciejewicz@ichtj.waw.pl

(Received 2 March 2011; accepted 7 March 2011; online 12 March 2011)

The structure of the title compound, [Li(C5H3N2O2)(H2O)]n, is composed of centrosymmetric dimers in which two LiI ions are bridged by a carboxyl­ate O atom, each donated by a ligand, acting in a bidentate mode. The second carboxyl­ato O atoms bridge the dimers to LiI ions in adjacent dimers, forming mol­ecular layers parallel to (001). Each LiI ion is coordinated by two bridging carboxyl­ate O atoms, a bridging carboxyl­ate O atom donated by the adjacent dimer and an aqua O atom, resulting in a distorted tetra­hedral coordination geometry. The layers are held together by O—H⋯N hydrogen bonds in which coordinated water O atoms act as donors and ligand hetero-ring N atoms as acceptors.

Related literature

For the crystal structure of a Pb(II) complex with pyridazine-4-carboxyl­ate and water ligands, see: Starosta & Leciejewicz, (2009[Starosta, W. & Leciejewicz, J. (2009). Acta Cryst. E65, m1291.]) and for the structure of a Mg(II) complex, see: Starosta & Leciejewicz, (2011b[Starosta, W. & Leciejewicz, J. (2011b). Acta Cryst. E67, m316.]). For the structure of pyridazine-4-carb­oxy­lic acid hydro­chloride, see: Starosta & Leciejewicz, (2008[Starosta, W. & Leciejewicz, J. (2008). Acta Cryst. E64, o1553.]) and for the structure of a LiI complex with pyridazine-3-carboxyl­ate and water ligands, see: Starosta & Leciejewicz, (2011a[Starosta, W. & Leciejewicz, J. (2011a). Acta Cryst. E67, m202.]).

[Scheme 1]

Experimental

Crystal data
  • [Li(C5H3N2O2)(H2O)]

  • Mr = 148.05

  • Monoclinic, P 21 /c

  • a = 8.1673 (16) Å

  • b = 9.6908 (19) Å

  • c = 8.0248 (16) Å

  • β = 97.08 (3)°

  • V = 630.3 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.13 mm−1

  • T = 293 K

  • 0.30 × 0.28 × 0.12 mm

Data collection
  • Kuma KM-4 four-circle diffractometer

  • Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.] Tmin = 0.946, Tmax = 0.973

  • 1958 measured reflections

  • 1843 independent reflections

  • 1208 reflections with I > 2σ(I)

  • Rint = 0.077

  • 3 standard reflections every 200 reflections intensity decay: 2.1%

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.128

  • S = 1.02

  • 1843 reflections

  • 108 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.33 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Selected bond lengths (Å)

O1—Li1 1.967 (2)
Li1—O2i 1.909 (3)
Li1—O3 1.915 (3)
Li1—O1ii 1.946 (2)
Symmetry codes: (i) [x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) -x, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H32⋯N1iii 0.86 (3) 1.93 (3) 2.7910 (18) 175 (3)
O3—H31⋯N2iv 0.85 (3) 2.33 (3) 3.1272 (19) 155 (2)
Symmetry codes: (iii) x-1, y, z-1; (iv) [x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: KM-4 Software (Kuma, 1996[Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.]); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001[Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland.]); 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The structural unit of the title compound is a centrosymmetric dimer composed of two LiI ions bridged by a bidentate carboxylate O1 atom, each donated by one of two symmetry related ligands. The ligand carboxylate group C7/O1/O2 makes with the O1/Li1/O1(II)/Li1(II) plane a dihedral angle of 10.9 (1)°, while the dihedral angle between this carboxylate group and the pyridazine ring is 43.4 (2)°. The pyridazine ring is almost planar with r.m.s. of 0.0148 (2) Å. Both ligand's heterocyclic N atoms remain coordination inactive. Bond distances and bond angles within the ligand molecule fit the values reported earlier in the structures of pyridazine-4-carboxylic acid hydrochloride (Starosta & Leciejewicz, 2008) and other metal complexes with the title ligand. The LiI ion is coordinated by the bridging carboxylato O1 and O1(II)atoms, a bridging carboxylato O2(I) atom donated by the adjacent dimer and the aqua O3 atom resulting in a distorted tetrahedral coordination. The observed Li—O bond distances which fall in the range from 1.909 (3) to 1.946 (2)Å are characteristic for all LiI complexes with carboxylate ligands. Carboxylato O2 atoms bridge the dimers into molecular layers which are approximately parallel to the crystal bc plane. The structure of a layer can be visualized as composed of corrugated loops with four equal sides and the dimers at their apices. Hydrophobic parts of pairs of pyridazine rings are directed inside the loop with the closet distance of 4.91 (1)Å between the ring centers while the heterocyclic N atoms are directed outside and participate in a network of hydrogen bonds. The latter consists of coordinated water molecules acting as donors and the pyridazine N atoms in an adjacent layer as acceptors. They form centrosymmetric rings which give rise to a three-dimensional structure. Discrete dinuclear molecules were reported to constitute the structure of a Pb(II) complex with the title ligand, in which two symmetry related metal ions are bridged by a pair of ligands via their heterocyclic N atoms and two pairs of aqua O atoms. Each Pb(II) ion is also coordinated by two carboxylate O atoms of another ligand (Starosta & Leciejewicz, 2009). On the other hand, the structure of a Mg(II) complex is built of discrete centrosymmetric molecules in which the metal ion is coordinated by only one carboxylato O atom of two ligands and two pairs of aqua O atoms in octahedral geometry. Heterocyclic N atoms do not act in coordination mode (Starosta & Leciejewicz, 2011b). Discrete monomers have been also reported to constitute the structure of a LiI complex with the pyridazine-3-carboxylate and water ligands. A LiI ion is coordinated by ligand N,O chelating group and two aqua O atoms in a terahedral mode (Starosta & Leciejewicz, 2011a).

Related literature top

For the crystal structure of a Pb(II) complex with pyridazine-4-carboxylate and water ligands, see: Starosta & Leciejewicz, (2009) and for the structure of a Mg(II) complex, see: Starosta & Leciejewicz, (2011b). For the structure of pyridazine-4-carboxylic acid hydrochloride, see: Starosta & Leciejewicz, (2008) and for the structure of a LiI complex with pyridazine-3- carboxylate and water ligands, see: Starosta & Leciejewicz, (2011a).

Experimental top

The title compound was obtained by boiling under reflux with stirring 50 ml of an aqueous solution containig 1 mmol of pyridazine-4-carboxylic acid (Aldrich) and 1 mmol of LiOH (Aldrich). The solution was boiled for two h. After cooling to room temperature a 1 N solution of HCl was added dropwise until the pH reached the value of 5.5 and then left to crystallize. Ten days later, colourless crystalline plates were found after evaporating to dryness. They were recrystallized from water a couple of times until well formed single crystals were found. They were washed with cold ethanol and dried in air.

Refinement top

Water hydrogen atoms were located in a difference map and refined isotropically. H atoms arrached to pyridazine-ring C atoms were positioned at calculated positions and were treated as riding on the parent atoms, with C—H=0.93 Å and Uiso(H)=1.5Ueq(C).

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A dimeric structural unit of the title compound with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (I) x, -y + 1/2, z - 1/2. (II) -x, -y + 1, -z.
[Figure 2] Fig. 2. Molecular layer composed of dimeric structural units.
[Figure 3] Fig. 3. The packing of layers viewed along the c axis.
Poly[aqua(µ3-pyridazine-4-carboxylato- κ2O:O:O')lithium] top
Crystal data top
[Li(C5H3N2O2)(H2O)]F(000) = 304
Mr = 148.05Dx = 1.560 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 8.1673 (16) Åθ = 6–15°
b = 9.6908 (19) ŵ = 0.13 mm1
c = 8.0248 (16) ÅT = 293 K
β = 97.08 (3)°Plates, colourless
V = 630.3 (2) Å30.30 × 0.28 × 0.12 mm
Z = 4
Data collection top
Kuma KM-4 four-circle
diffractometer
1208 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.077
Graphite monochromatorθmax = 30.1°, θmin = 2.5°
profile data from ω/2θ scansh = 011
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2008)
k = 130
Tmin = 0.946, Tmax = 0.973l = 1111
1958 measured reflections3 standard reflections every 200 reflections
1843 independent reflections intensity decay: 2.1%
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0832P)2 + 0.0472P]
where P = (Fo2 + 2Fc2)/3
1843 reflections(Δ/σ)max < 0.001
108 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
[Li(C5H3N2O2)(H2O)]V = 630.3 (2) Å3
Mr = 148.05Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.1673 (16) ŵ = 0.13 mm1
b = 9.6908 (19) ÅT = 293 K
c = 8.0248 (16) Å0.30 × 0.28 × 0.12 mm
β = 97.08 (3)°
Data collection top
Kuma KM-4 four-circle
diffractometer
1208 reflections with I > 2σ(I)
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2008)
Rint = 0.077
Tmin = 0.946, Tmax = 0.9733 standard reflections every 200 reflections
1958 measured reflections intensity decay: 2.1%
1843 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.33 e Å3
1843 reflectionsΔρmin = 0.28 e Å3
108 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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) top
xyzUiso*/Ueq
O10.03194 (12)0.42855 (10)0.15091 (11)0.0264 (2)
C40.18403 (15)0.37648 (13)0.41306 (14)0.0210 (2)
O20.03510 (14)0.24156 (11)0.28565 (13)0.0369 (3)
N20.40511 (15)0.28845 (14)0.60951 (16)0.0334 (3)
C70.04912 (15)0.34645 (12)0.27196 (15)0.0210 (3)
C60.33735 (19)0.51936 (16)0.61350 (17)0.0316 (3)
H60.35510.60580.66290.038*
N10.42945 (15)0.41548 (14)0.67579 (15)0.0334 (3)
C30.28349 (16)0.26953 (14)0.48590 (16)0.0263 (3)
H30.26330.18040.44550.032*
C50.21451 (17)0.50626 (14)0.47709 (16)0.0262 (3)
H50.15590.58250.43160.031*
Li10.1023 (3)0.3958 (2)0.0663 (3)0.0264 (5)
O30.33301 (14)0.39117 (15)0.04432 (15)0.0415 (3)
H310.389 (4)0.354 (3)0.027 (3)0.075 (8)*
H320.403 (4)0.403 (3)0.133 (4)0.075 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0337 (5)0.0224 (5)0.0208 (4)0.0029 (3)0.0062 (3)0.0050 (3)
C40.0245 (5)0.0214 (5)0.0163 (5)0.0005 (4)0.0008 (4)0.0011 (4)
O20.0491 (6)0.0269 (5)0.0311 (5)0.0160 (4)0.0099 (4)0.0068 (4)
N20.0301 (6)0.0370 (7)0.0308 (6)0.0046 (5)0.0057 (4)0.0065 (5)
C70.0259 (6)0.0182 (6)0.0178 (5)0.0004 (4)0.0019 (4)0.0000 (4)
C60.0357 (7)0.0332 (7)0.0241 (6)0.0053 (6)0.0035 (5)0.0046 (5)
N10.0302 (6)0.0422 (7)0.0255 (6)0.0032 (5)0.0057 (4)0.0016 (5)
C30.0289 (6)0.0249 (6)0.0240 (6)0.0022 (5)0.0009 (5)0.0023 (5)
C50.0308 (6)0.0231 (6)0.0230 (6)0.0007 (5)0.0036 (4)0.0006 (5)
Li10.0312 (11)0.0179 (10)0.0278 (11)0.0006 (8)0.0057 (8)0.0018 (8)
O30.0282 (5)0.0601 (8)0.0336 (6)0.0048 (5)0.0066 (4)0.0073 (5)
Geometric parameters (Å, º) top
O1—C71.2501 (15)C6—C51.3965 (18)
O1—Li1i1.946 (2)C6—H60.9300
O1—Li11.967 (2)C3—H30.9300
C4—C51.3697 (18)C5—H50.9300
C4—C31.3995 (17)Li1—O2iii1.909 (3)
C4—C71.5078 (17)Li1—O31.915 (3)
O2—C71.2398 (16)Li1—O1i1.946 (2)
O2—Li1ii1.909 (3)Li1—Li1i2.751 (4)
N2—C31.3272 (18)O3—H310.85 (3)
N2—N11.3460 (19)O3—H320.86 (3)
C6—N11.318 (2)
C7—O1—Li1i144.92 (11)C4—C3—H3118.2
C7—O1—Li1125.64 (11)C4—C5—C6117.21 (12)
Li1i—O1—Li189.33 (10)C4—C5—H5121.4
C5—C4—C3117.00 (11)C6—C5—H5121.4
C5—C4—C7122.76 (11)O2iii—Li1—O3113.75 (12)
C3—C4—C7120.23 (11)O2iii—Li1—O1i105.83 (12)
C7—O2—Li1ii146.29 (11)O3—Li1—O1i112.89 (12)
C3—N2—N1118.83 (12)O2iii—Li1—O1119.50 (12)
O2—C7—O1125.47 (12)O3—Li1—O1111.69 (13)
O2—C7—C4116.99 (11)O1i—Li1—O190.67 (10)
O1—C7—C4117.54 (11)O2iii—Li1—Li1i123.03 (16)
N1—C6—C5123.32 (13)O3—Li1—Li1i122.65 (15)
N1—C6—H6118.3O1i—Li1—Li1i45.65 (7)
C5—C6—H6118.3O1—Li1—Li1i45.02 (7)
C6—N1—N2119.95 (12)Li1—O3—H31133.5 (19)
N2—C3—C4123.52 (13)Li1—O3—H32118.7 (18)
N2—C3—H3118.2H31—O3—H32104 (3)
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z+1/2; (iii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H32···N1iv0.86 (3)1.93 (3)2.7910 (18)175 (3)
O3—H31···N2v0.85 (3)2.33 (3)3.1272 (19)155 (2)
Symmetry codes: (iv) x1, y, z1; (v) x1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula[Li(C5H3N2O2)(H2O)]
Mr148.05
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)8.1673 (16), 9.6908 (19), 8.0248 (16)
β (°) 97.08 (3)
V3)630.3 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.30 × 0.28 × 0.12
Data collection
DiffractometerKuma KM-4 four-circle
diffractometer
Absorption correctionAnalytical
(CrysAlis RED; Oxford Diffraction, 2008)
Tmin, Tmax0.946, 0.973
No. of measured, independent and
observed [I > 2σ(I)] reflections
1958, 1843, 1208
Rint0.077
(sin θ/λ)max1)0.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.128, 1.02
No. of reflections1843
No. of parameters108
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.33, 0.28

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
O1—Li11.967 (2)Li1—O31.915 (3)
Li1—O2i1.909 (3)Li1—O1ii1.946 (2)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H32···N1iii0.86 (3)1.93 (3)2.7910 (18)175 (3)
O3—H31···N2iv0.85 (3)2.33 (3)3.1272 (19)155 (2)
Symmetry codes: (iii) x1, y, z1; (iv) x1, y+1/2, z1/2.
 

References

First citationKuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.  Google Scholar
First citationKuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland.  Google Scholar
First citationOxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStarosta, W. & Leciejewicz, J. (2008). Acta Cryst. E64, o1553.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationStarosta, W. & Leciejewicz, J. (2009). Acta Cryst. E65, m1291.  Web of Science CrossRef IUCr Journals Google Scholar
First citationStarosta, W. & Leciejewicz, J. (2011a). Acta Cryst. E67, m202.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationStarosta, W. & Leciejewicz, J. (2011b). Acta Cryst. E67, m316.  Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 4| April 2011| Pages m425-m426
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds