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Acta Cryst. (2010). E66, m192    [ doi:10.1107/S1600536810002199 ]

catena-Poly[lead(II)-bis([mu]2-pyridazine-3-carboxylato-[kappa]3N2,O:O)]

W. Starosta and J. Leciejewicz

Abstract top

In the title structure, [Pb(C5H3N2O2)2]n, the PbII ion is six-coordinated by two pyridazine-3-carboxylate ligands via N and O atoms, with the carboxylato O atoms acting as bidentate and bridging adjacent PbII ions, giving rise to catenated molecular ribbons propagating along the a-axis direction. The ribbons are connected by C-H...O hydrogen bonds and van der Waals interactions.

Comment top

In the structure of the title compound (I) each PbII ion is coordinated by two symmetry independent ligand molecules via N,O atoms; their O atoms act as bidentate and bridging to adjacent metal ions (Fig. 1) to form molecular ribbons extending in the a direction (Fig.2). The second O atom of each carboxylato group does not participate in coordination. The coordination environment of a PbII ion involving O11,N12, O21, N22 and two bridging carboxylate O11(I) and O21(II) atoms (Table 1) is highly distorted. Both pyridazine rings are planar with r.m.s. of 0.0037 (2)Å and 0.0120((2)Å. The dihedral angle between the rings is 45.2 (1)°. Carboxylato planes make dihedral angles with the respective rings of 9.7 (1)° (C13/O11/O12) and of 8.8 (2)° (C23/O21/22). Bond distances and bond angles within both ligand molecules are in fair agreement with those reported for pyridazine-3-carboxylic acid chloride and other metal complexes with this ligand. The ribbons are held together by weak interactions between ring carbon atoms and carboxylato O atoms belonging to adjacent ribbons (Table 2).

Related literature top

For the structures of 3d-metal and Mg(II) complexes with pyridazine-3-carboxylate and water ligands containing monomeric molecules with an octahedral enviroment for the metal ion, see: Ardiwinata et al. (1989), Gryz et al. (2003, 2004, 2006). Centrosymmetric dimeric molecules, each with a different bridging mode, have been reported in the structure of a calcium(II) complex (Starosta & Leciejewicz, 2007), a uranyl complex Leciejewicz & Starosta (2009) as well as in the structure of a lead(II) complex with pyridazine-4-carboxylate ligands (Starosta & Leciejewicz, 2009). For the structure of pyridazine-3-carboxylic acid hydrochloride, see: Gryz et al. (2003).

Experimental top

2 mmols of pyridazine-3-carboxylic acid dissolved in 50 ml of hot water were boiled under reflux for three hours with small excess of lead hydroxide. After cooling to room temperature the mixture was filtered and left for crystallization. After evaporation to dryness, colourless single crystals were found on the bottom of the reaction vessel. They were separated, washed with cold ethanol and dried in air.

Refinement top

H atoms attached to pyridazine-ring C atoms were positioned geometrically and refined with a riding model using AFIX43 instruction. A maximum peak of 6.566 e Å3 and a deepest hole of -4.302 e Å3(each at 0.80 Å) were found on the final electron density map close to the Pb1 atom.

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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A structural unit of (1) with atom labelling scheme and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The alignement of two ribbons in the structure.
catena-Poly[lead(II)-bis(µ2-pyridazine-3-carboxylato- κ3N2,O:O)] top
Crystal data top
[Pb(C5H3N2O2)2]F(000) = 832
Mr = 453.38Dx = 2.627 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.0336 (16) ÅCell parameters from 25 reflections
b = 10.386 (2) Åθ = 6–15°
c = 13.766 (3) ŵ = 14.74 mm−1
β = 93.72 (3)°T = 293 K
V = 1146.2 (4) Å3Blocks, colourless
Z = 40.33 × 0.09 × 0.08 mm
Data collection top
Kuma KM-4 four-circle
diffractometer		2119 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.040
graphiteθmax = 30.1°, θmin = 2.5°
profile data from ω/2θ scansh = 0→11
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2008)		k = 0→14
Tmin = 0.284, Tmax = 0.379l = −19→19
3587 measured reflections3 standard reflections every 200 reflections
3365 independent reflections intensity decay: 1.3%
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0903P)2]
where P = (Fo2 + 2Fc2)/3
3365 reflections(Δ/σ)max = 0.002
172 parametersΔρmax = 6.57 e Å−3
0 restraintsΔρmin = −4.30 e Å−3
Crystal data top
[Pb(C5H3N2O2)2]V = 1146.2 (4) Å3
Mr = 453.38Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.0336 (16) ŵ = 14.74 mm−1
b = 10.386 (2) ÅT = 293 K
c = 13.766 (3) Å0.33 × 0.09 × 0.08 mm
β = 93.72 (3)°
Data collection top
Kuma KM-4 four-circle
diffractometer		2119 reflections with I > 2σ(I)
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2008)		Rint = 0.040
Tmin = 0.284, Tmax = 0.379θmax = 30.1°
3587 measured reflections3 standard reflections every 200 reflections
3365 independent reflections intensity decay: 1.3%
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.137Δρmax = 6.57 e Å−3
S = 1.05Δρmin = −4.30 e Å−3
3365 reflectionsAbsolute structure: ?
172 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Pb10.25237 (3)1.03613 (3)1.006155 (19)0.02242 (12)
O110.0180 (7)0.9406 (6)0.8924 (4)0.0250 (12)
N120.3296 (8)0.8553 (6)0.8814 (5)0.0224 (13)
N220.1664 (8)0.8074 (6)1.0764 (5)0.0214 (13)
O210.4781 (8)0.9011 (6)1.0862 (5)0.0301 (13)
N210.0078 (8)0.7670 (7)1.0745 (5)0.0259 (15)
O12−0.0827 (8)0.7546 (6)0.8339 (6)0.0388 (17)
O220.5838 (9)0.7035 (7)1.1022 (7)0.052 (2)
N110.4876 (9)0.8212 (8)0.8732 (6)0.0291 (16)
C160.5237 (12)0.7161 (9)0.8257 (7)0.033 (2)
H160.63490.69370.82030.039*
C140.2380 (10)0.6694 (8)0.7923 (6)0.0257 (16)
H140.15170.61830.76560.031*
C26−0.0251 (11)0.6477 (9)1.0961 (7)0.0311 (19)
H26−0.13580.62141.09590.037*
C170.0322 (10)0.8273 (8)0.8564 (6)0.0207 (15)
C130.2049 (9)0.7810 (7)0.8424 (5)0.0182 (14)
C230.2885 (10)0.7262 (8)1.0976 (6)0.0260 (17)
C150.3974 (11)0.6369 (9)0.7831 (6)0.0316 (19)
H150.42400.56310.74920.038*
C270.4639 (10)0.7783 (8)1.0958 (6)0.0256 (17)
C240.2584 (14)0.5976 (9)1.1172 (9)0.047 (3)
H240.34600.53991.12860.056*
C250.1003 (13)0.5593 (10)1.1192 (9)0.045 (3)
H250.07470.47511.13570.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb10.01425 (17)0.01657 (17)0.03658 (19)−0.00057 (14)0.00282 (11)−0.00095 (13)
O110.016 (3)0.019 (3)0.041 (3)0.004 (2)0.008 (2)0.000 (2)
N120.013 (3)0.018 (3)0.037 (3)0.001 (3)0.004 (3)−0.005 (3)
N220.018 (3)0.014 (3)0.032 (3)0.000 (3)0.005 (2)0.007 (2)
O210.025 (3)0.018 (3)0.048 (3)−0.008 (3)0.004 (3)0.004 (3)
N210.006 (3)0.027 (4)0.045 (4)−0.005 (3)0.003 (3)0.008 (3)
O120.011 (3)0.027 (3)0.078 (5)−0.006 (3)0.004 (3)−0.010 (3)
O220.024 (4)0.030 (4)0.101 (6)0.012 (3)0.002 (4)0.001 (4)
N110.017 (4)0.030 (4)0.040 (4)−0.004 (3)0.003 (3)−0.012 (3)
C160.022 (4)0.028 (5)0.048 (5)0.012 (4)−0.001 (4)−0.007 (4)
C140.017 (4)0.020 (4)0.040 (4)0.000 (3)0.002 (3)−0.007 (3)
C260.019 (4)0.022 (4)0.051 (5)−0.009 (4)0.000 (4)0.008 (4)
C170.017 (4)0.016 (4)0.030 (4)0.005 (3)0.002 (3)−0.002 (3)
C130.013 (3)0.014 (3)0.027 (3)−0.002 (3)0.000 (3)−0.001 (3)
C230.017 (4)0.017 (4)0.045 (4)−0.004 (3)0.005 (3)0.007 (3)
C150.022 (4)0.033 (5)0.040 (4)0.004 (4)0.009 (3)−0.016 (4)
C270.010 (4)0.024 (4)0.044 (4)0.001 (3)0.004 (3)−0.002 (3)
C240.031 (5)0.014 (4)0.093 (8)0.005 (4)−0.008 (5)0.017 (5)
C250.028 (6)0.017 (5)0.092 (8)0.001 (4)0.010 (5)0.012 (5)
Geometric parameters (Å, °) top
Pb1—O212.492 (7)O22—C271.237 (10)
Pb1—O112.569 (6)N11—C161.315 (12)
Pb1—N122.645 (7)C16—C151.405 (12)
Pb1—O21i2.662 (7)C16—H160.9300
Pb1—O11ii2.669 (6)C14—C151.338 (12)
Pb1—N222.672 (6)C14—C131.384 (11)
O11—C171.285 (10)C14—H140.9300
O11—Pb1ii2.669 (6)C26—C251.385 (13)
N12—N111.330 (10)C26—H260.9300
N12—C131.348 (9)C17—C131.493 (11)
N22—C231.312 (10)C23—C241.386 (12)
N22—N211.340 (9)C23—C271.511 (12)
O21—C271.289 (10)C15—H150.9300
O21—Pb1i2.662 (7)C24—C251.334 (14)
N21—C261.305 (11)C24—H240.9300
O12—C171.217 (10)C25—H250.9300
O21—Pb1—O11122.4 (2)N11—C16—H16119.4
O21—Pb1—N1272.1 (2)C15—C16—H16119.4
O11—Pb1—N1261.55 (19)C15—C14—C13118.4 (8)
O21—Pb1—O21i76.0 (2)C15—C14—H14120.8
O11—Pb1—O21i112.9 (2)C13—C14—H14120.8
N12—Pb1—O21i68.4 (2)N21—C26—C25121.8 (9)
O21—Pb1—O11ii114.4 (2)N21—C26—H26119.1
O11—Pb1—O11ii76.4 (2)C25—C26—H26119.1
N12—Pb1—O11ii129.6 (2)O12—C17—O11125.6 (8)
O21i—Pb1—O11ii160.5 (2)O12—C17—C13117.6 (7)
O21—Pb1—N2262.5 (2)O11—C17—C13116.8 (7)
O11—Pb1—N2271.4 (2)N12—C13—C14121.1 (7)
N12—Pb1—N2271.4 (2)N12—C13—C17115.9 (6)
O21i—Pb1—N22128.9 (2)C14—C13—C17123.0 (7)
O11ii—Pb1—N2269.7 (2)N22—C23—C24121.7 (8)
C17—O11—Pb1120.6 (5)N22—C23—C27116.8 (7)
C17—O11—Pb1ii112.3 (5)C24—C23—C27121.5 (8)
Pb1—O11—Pb1ii103.6 (2)C14—C15—C16118.9 (8)
N11—N12—C13120.1 (7)C14—C15—H15120.6
N11—N12—Pb1120.6 (5)C16—C15—H15120.6
C13—N12—Pb1117.8 (5)O22—C27—O21123.7 (8)
C23—N22—N21119.9 (7)O22—C27—C23119.8 (8)
C23—N22—Pb1116.4 (5)O21—C27—C23116.5 (7)
N21—N22—Pb1122.6 (5)C25—C24—C23118.0 (9)
C27—O21—Pb1122.4 (5)C25—C24—H24121.0
C27—O21—Pb1i111.8 (6)C23—C24—H24121.0
Pb1—O21—Pb1i104.0 (2)C24—C25—C26118.5 (9)
C26—N21—N22120.0 (8)C24—C25—H25120.8
C16—N11—N12120.4 (7)C26—C25—H25120.8
N11—C16—C15121.1 (8)
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x, −y+2, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C16—H16···O12iii0.932.353.182 (12)149
C14—H14···O21iv0.932.763.489 (10)136
C26—H26···O22v0.932.423.201 (12)142
C15—H15···O11vi0.932.403.266 (10)155
C25—H25···O12vii0.932.423.328 (12)165
Symmetry codes: (iii) x+1, y, z; (iv) x−1/2, −y+3/2, z−1/2; (v) x−1, y, z; (vi) −x+1/2, y−1/2, −z+3/2; (vii) −x, −y+1, −z+2.
Table 1
Selected geometric parameters (Å) top
Pb1—O212.492 (7)Pb1—O21i2.662 (7)
Pb1—O112.569 (6)Pb1—O11ii2.669 (6)
Pb1—N122.645 (7)Pb1—N222.672 (6)
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x, −y+2, −z+2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C16—H16···O12iii0.932.353.182 (12)149
C14—H14···O21iv0.932.763.489 (10)136
C26—H26···O22v0.932.423.201 (12)142
C15—H15···O11vi0.932.403.266 (10)155
C25—H25···O12vii0.932.423.328 (12)165
Symmetry codes: (iii) x+1, y, z; (iv) x−1/2, −y+3/2, z−1/2; (v) x−1, y, z; (vi) −x+1/2, y−1/2, −z+3/2; (vii) −x, −y+1, −z+2.
Acknowledgements top

no acknowledgements

references
References top

Ardiwinata, E. S., Craig, D. C. & Philips, D. J. (1989). Inorg. Chim. Acta, 166, 233–238.

Gryz, M., Starosta, W. & Leciejewicz, J. (2004). Acta Cryst. E60, m1481–m1483.

Gryz, M., Starosta, W. & Leciejewicz, J. (2006). Acta Cryst. E62, m123–m124.

Gryz, M., Starosta, W., Ptasiewicz-Bąk, H. & Leciejewicz, J. (2003). J. Coord. Chem. 56, 1505-1511.

Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.

Kuma (2001). DATAPROC. Version 10.0.7. Kuma Diffraction Ltd, Wrocław, Poland.

Leciejewicz, J. & Starosta, W. (2009). Acta Cryst. E65, m94.

Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Starosta, W. & Leciejewicz, J. (2007). Acta Cryst. E63, m1662–m1663.

Starosta, W. & Leciejewicz, J. (2009). Acta Cryst. E65, m1291.