metal-organic compounds
catena-Poly[lead(II)-bis(μ2-pyridazine-3-carboxylato-κ3N2,O:O)]
aInstitute of Nuclear Chemistry and Technology, ul.Dorodna 16, 03-195 Warszawa, Poland
*Correspondence e-mail: j.leciejewicz@ichtj.waw.pl
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.
Related literature
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
Crystal data
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Data collection
Refinement
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Data collection: KM-4 Software (Kuma, 1996); cell KM-4 Software; 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.
Supporting information
https://doi.org/10.1107/S1600536810002199/kp2247sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810002199/kp2247Isup2.hkl
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.
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
close to the Pb1 atom.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).
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).
Data collection: KM-4 Software (Kuma, 1996); cell
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).Fig. 1. A structural unit of (1) with atom labelling scheme and 50% probability displacement ellipsoids. | |
Fig. 2. The alignement of two ribbons in the structure. |
[Pb(C5H3N2O2)2] | F(000) = 832 |
Mr = 453.38 | Dx = 2.627 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0336 (16) Å | Cell parameters from 25 reflections |
b = 10.386 (2) Å | θ = 6–15° |
c = 13.766 (3) Å | µ = 14.74 mm−1 |
β = 93.72 (3)° | T = 293 K |
V = 1146.2 (4) Å3 | Blocks, colourless |
Z = 4 | 0.33 × 0.09 × 0.08 mm |
Kuma KM-4 four-circle diffractometer | 2119 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 30.1°, θmin = 2.5° |
profile data from ω/2θ scans | h = 0→11 |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008) | k = 0→14 |
Tmin = 0.284, Tmax = 0.379 | l = −19→19 |
3587 measured reflections | 3 standard reflections every 200 reflections |
3365 independent reflections | intensity decay: 1.3% |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H-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 parameters | Δρmax = 6.57 e Å−3 |
0 restraints | Δρmin = −4.30 e Å−3 |
[Pb(C5H3N2O2)2] | V = 1146.2 (4) Å3 |
Mr = 453.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.0336 (16) Å | µ = 14.74 mm−1 |
b = 10.386 (2) Å | T = 293 K |
c = 13.766 (3) Å | 0.33 × 0.09 × 0.08 mm |
β = 93.72 (3)° |
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 = 0.379 | 3 standard reflections every 200 reflections |
3587 measured reflections | intensity decay: 1.3% |
3365 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.05 | Δρmax = 6.57 e Å−3 |
3365 reflections | Δρmin = −4.30 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Pb1 | 0.25237 (3) | 1.03613 (3) | 1.006155 (19) | 0.02242 (12) | |
O11 | 0.0180 (7) | 0.9406 (6) | 0.8924 (4) | 0.0250 (12) | |
N12 | 0.3296 (8) | 0.8553 (6) | 0.8814 (5) | 0.0224 (13) | |
N22 | 0.1664 (8) | 0.8074 (6) | 1.0764 (5) | 0.0214 (13) | |
O21 | 0.4781 (8) | 0.9011 (6) | 1.0862 (5) | 0.0301 (13) | |
N21 | 0.0078 (8) | 0.7670 (7) | 1.0745 (5) | 0.0259 (15) | |
O12 | −0.0827 (8) | 0.7546 (6) | 0.8339 (6) | 0.0388 (17) | |
O22 | 0.5838 (9) | 0.7035 (7) | 1.1022 (7) | 0.052 (2) | |
N11 | 0.4876 (9) | 0.8212 (8) | 0.8732 (6) | 0.0291 (16) | |
C16 | 0.5237 (12) | 0.7161 (9) | 0.8257 (7) | 0.033 (2) | |
H16 | 0.6349 | 0.6937 | 0.8203 | 0.039* | |
C14 | 0.2380 (10) | 0.6694 (8) | 0.7923 (6) | 0.0257 (16) | |
H14 | 0.1517 | 0.6183 | 0.7656 | 0.031* | |
C26 | −0.0251 (11) | 0.6477 (9) | 1.0961 (7) | 0.0311 (19) | |
H26 | −0.1358 | 0.6214 | 1.0959 | 0.037* | |
C17 | 0.0322 (10) | 0.8273 (8) | 0.8564 (6) | 0.0207 (15) | |
C13 | 0.2049 (9) | 0.7810 (7) | 0.8424 (5) | 0.0182 (14) | |
C23 | 0.2885 (10) | 0.7262 (8) | 1.0976 (6) | 0.0260 (17) | |
C15 | 0.3974 (11) | 0.6369 (9) | 0.7831 (6) | 0.0316 (19) | |
H15 | 0.4240 | 0.5631 | 0.7492 | 0.038* | |
C27 | 0.4639 (10) | 0.7783 (8) | 1.0958 (6) | 0.0256 (17) | |
C24 | 0.2584 (14) | 0.5976 (9) | 1.1172 (9) | 0.047 (3) | |
H24 | 0.3460 | 0.5399 | 1.1286 | 0.056* | |
C25 | 0.1003 (13) | 0.5593 (10) | 1.1192 (9) | 0.045 (3) | |
H25 | 0.0747 | 0.4751 | 1.1357 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pb1 | 0.01425 (17) | 0.01657 (17) | 0.03658 (19) | −0.00057 (14) | 0.00282 (11) | −0.00095 (13) |
O11 | 0.016 (3) | 0.019 (3) | 0.041 (3) | 0.004 (2) | 0.008 (2) | 0.000 (2) |
N12 | 0.013 (3) | 0.018 (3) | 0.037 (3) | 0.001 (3) | 0.004 (3) | −0.005 (3) |
N22 | 0.018 (3) | 0.014 (3) | 0.032 (3) | 0.000 (3) | 0.005 (2) | 0.007 (2) |
O21 | 0.025 (3) | 0.018 (3) | 0.048 (3) | −0.008 (3) | 0.004 (3) | 0.004 (3) |
N21 | 0.006 (3) | 0.027 (4) | 0.045 (4) | −0.005 (3) | 0.003 (3) | 0.008 (3) |
O12 | 0.011 (3) | 0.027 (3) | 0.078 (5) | −0.006 (3) | 0.004 (3) | −0.010 (3) |
O22 | 0.024 (4) | 0.030 (4) | 0.101 (6) | 0.012 (3) | 0.002 (4) | 0.001 (4) |
N11 | 0.017 (4) | 0.030 (4) | 0.040 (4) | −0.004 (3) | 0.003 (3) | −0.012 (3) |
C16 | 0.022 (4) | 0.028 (5) | 0.048 (5) | 0.012 (4) | −0.001 (4) | −0.007 (4) |
C14 | 0.017 (4) | 0.020 (4) | 0.040 (4) | 0.000 (3) | 0.002 (3) | −0.007 (3) |
C26 | 0.019 (4) | 0.022 (4) | 0.051 (5) | −0.009 (4) | 0.000 (4) | 0.008 (4) |
C17 | 0.017 (4) | 0.016 (4) | 0.030 (4) | 0.005 (3) | 0.002 (3) | −0.002 (3) |
C13 | 0.013 (3) | 0.014 (3) | 0.027 (3) | −0.002 (3) | 0.000 (3) | −0.001 (3) |
C23 | 0.017 (4) | 0.017 (4) | 0.045 (4) | −0.004 (3) | 0.005 (3) | 0.007 (3) |
C15 | 0.022 (4) | 0.033 (5) | 0.040 (4) | 0.004 (4) | 0.009 (3) | −0.016 (4) |
C27 | 0.010 (4) | 0.024 (4) | 0.044 (4) | 0.001 (3) | 0.004 (3) | −0.002 (3) |
C24 | 0.031 (5) | 0.014 (4) | 0.093 (8) | 0.005 (4) | −0.008 (5) | 0.017 (5) |
C25 | 0.028 (6) | 0.017 (5) | 0.092 (8) | 0.001 (4) | 0.010 (5) | 0.012 (5) |
Pb1—O21 | 2.492 (7) | O22—C27 | 1.237 (10) |
Pb1—O11 | 2.569 (6) | N11—C16 | 1.315 (12) |
Pb1—N12 | 2.645 (7) | C16—C15 | 1.405 (12) |
Pb1—O21i | 2.662 (7) | C16—H16 | 0.9300 |
Pb1—O11ii | 2.669 (6) | C14—C15 | 1.338 (12) |
Pb1—N22 | 2.672 (6) | C14—C13 | 1.384 (11) |
O11—C17 | 1.285 (10) | C14—H14 | 0.9300 |
O11—Pb1ii | 2.669 (6) | C26—C25 | 1.385 (13) |
N12—N11 | 1.330 (10) | C26—H26 | 0.9300 |
N12—C13 | 1.348 (9) | C17—C13 | 1.493 (11) |
N22—C23 | 1.312 (10) | C23—C24 | 1.386 (12) |
N22—N21 | 1.340 (9) | C23—C27 | 1.511 (12) |
O21—C27 | 1.289 (10) | C15—H15 | 0.9300 |
O21—Pb1i | 2.662 (7) | C24—C25 | 1.334 (14) |
N21—C26 | 1.305 (11) | C24—H24 | 0.9300 |
O12—C17 | 1.217 (10) | C25—H25 | 0.9300 |
O21—Pb1—O11 | 122.4 (2) | N11—C16—H16 | 119.4 |
O21—Pb1—N12 | 72.1 (2) | C15—C16—H16 | 119.4 |
O11—Pb1—N12 | 61.55 (19) | C15—C14—C13 | 118.4 (8) |
O21—Pb1—O21i | 76.0 (2) | C15—C14—H14 | 120.8 |
O11—Pb1—O21i | 112.9 (2) | C13—C14—H14 | 120.8 |
N12—Pb1—O21i | 68.4 (2) | N21—C26—C25 | 121.8 (9) |
O21—Pb1—O11ii | 114.4 (2) | N21—C26—H26 | 119.1 |
O11—Pb1—O11ii | 76.4 (2) | C25—C26—H26 | 119.1 |
N12—Pb1—O11ii | 129.6 (2) | O12—C17—O11 | 125.6 (8) |
O21i—Pb1—O11ii | 160.5 (2) | O12—C17—C13 | 117.6 (7) |
O21—Pb1—N22 | 62.5 (2) | O11—C17—C13 | 116.8 (7) |
O11—Pb1—N22 | 71.4 (2) | N12—C13—C14 | 121.1 (7) |
N12—Pb1—N22 | 71.4 (2) | N12—C13—C17 | 115.9 (6) |
O21i—Pb1—N22 | 128.9 (2) | C14—C13—C17 | 123.0 (7) |
O11ii—Pb1—N22 | 69.7 (2) | N22—C23—C24 | 121.7 (8) |
C17—O11—Pb1 | 120.6 (5) | N22—C23—C27 | 116.8 (7) |
C17—O11—Pb1ii | 112.3 (5) | C24—C23—C27 | 121.5 (8) |
Pb1—O11—Pb1ii | 103.6 (2) | C14—C15—C16 | 118.9 (8) |
N11—N12—C13 | 120.1 (7) | C14—C15—H15 | 120.6 |
N11—N12—Pb1 | 120.6 (5) | C16—C15—H15 | 120.6 |
C13—N12—Pb1 | 117.8 (5) | O22—C27—O21 | 123.7 (8) |
C23—N22—N21 | 119.9 (7) | O22—C27—C23 | 119.8 (8) |
C23—N22—Pb1 | 116.4 (5) | O21—C27—C23 | 116.5 (7) |
N21—N22—Pb1 | 122.6 (5) | C25—C24—C23 | 118.0 (9) |
C27—O21—Pb1 | 122.4 (5) | C25—C24—H24 | 121.0 |
C27—O21—Pb1i | 111.8 (6) | C23—C24—H24 | 121.0 |
Pb1—O21—Pb1i | 104.0 (2) | C24—C25—C26 | 118.5 (9) |
C26—N21—N22 | 120.0 (8) | C24—C25—H25 | 120.8 |
C16—N11—N12 | 120.4 (7) | C26—C25—H25 | 120.8 |
N11—C16—C15 | 121.1 (8) |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···O12iii | 0.93 | 2.35 | 3.182 (12) | 149 |
C14—H14···O21iv | 0.93 | 2.76 | 3.489 (10) | 136 |
C26—H26···O22v | 0.93 | 2.42 | 3.201 (12) | 142 |
C15—H15···O11vi | 0.93 | 2.40 | 3.266 (10) | 155 |
C25—H25···O12vii | 0.93 | 2.42 | 3.328 (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. |
Experimental details
Crystal data | |
Chemical formula | [Pb(C5H3N2O2)2] |
Mr | 453.38 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.0336 (16), 10.386 (2), 13.766 (3) |
β (°) | 93.72 (3) |
V (Å3) | 1146.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 14.74 |
Crystal size (mm) | 0.33 × 0.09 × 0.08 |
Data collection | |
Diffractometer | Kuma KM-4 four-circle diffractometer |
Absorption correction | Analytical (CrysAlis RED; Oxford Diffraction, 2008) |
Tmin, Tmax | 0.284, 0.379 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3587, 3365, 2119 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.137, 1.05 |
No. of reflections | 3365 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 6.57, −4.30 |
Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Pb1—O21 | 2.492 (7) | Pb1—O21i | 2.662 (7) |
Pb1—O11 | 2.569 (6) | Pb1—O11ii | 2.669 (6) |
Pb1—N12 | 2.645 (7) | Pb1—N22 | 2.672 (6) |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···O12iii | 0.93 | 2.35 | 3.182 (12) | 148.5 |
C14—H14···O21iv | 0.93 | 2.76 | 3.489 (10) | 135.6 |
C26—H26···O22v | 0.93 | 2.42 | 3.201 (12) | 142.2 |
C15—H15···O11vi | 0.93 | 2.40 | 3.266 (10) | 155.4 |
C25—H25···O12vii | 0.93 | 2.42 | 3.328 (12) | 164.8 |
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. |
References
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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).