Download citation
Download citation
link to html
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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810002199/kp2247sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536810002199/kp2247Isup2.hkl
Contains datablock I

CCDC reference: 724412

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.013 Å
  • R factor = 0.048
  • wR factor = 0.137
  • Data-to-parameter ratio = 19.6

checkCIF/PLATON results

No syntax errors found



Alert level C DIFMX01_ALERT_2_C The maximum difference density is > 0.1*ZMAX*0.75 _refine_diff_density_max given = 6.566 Test value = 6.150 DIFMX02_ALERT_1_C The maximum difference density is > 0.1*ZMAX*0.75 The relevant atom site should be identified. PLAT097_ALERT_2_C Large Reported Max. (Positive) Residual Density 6.57 eA-3 PLAT213_ALERT_2_C Atom N21 has ADP max/min Ratio ..... 3.30 prola PLAT213_ALERT_2_C Atom C24 has ADP max/min Ratio ..... 3.40 prola PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.87 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 13 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 10 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H14 .. O21 .. 2.76 Ang. PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 3
Alert level G PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c .... P21/n PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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.

Structure description 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).

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).

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 m3
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 mm1
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
Graphite monochromatorθmax = 30.1°, θmin = 2.5°
profile data from ω/2θ scansh = 011
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2008)
k = 014
Tmin = 0.284, Tmax = 0.379l = 1919
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 Å3
0 restraintsΔρmin = 4.30 e Å3
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 mm1
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 = 0.3793 standard reflections every 200 reflections
3587 measured reflections intensity decay: 1.3%
3365 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.05Δρmax = 6.57 e Å3
3365 reflectionsΔρmin = 4.30 e Å3
172 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
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)
O120.0827 (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*
C260.0251 (11)0.6477 (9)1.0961 (7)0.0311 (19)
H260.13580.62141.09590.037*
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, º) 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, º) 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) x1/2, y+3/2, z1/2; (v) x1, y, z; (vi) x+1/2, y1/2, z+3/2; (vii) x, y+1, z+2.

Experimental details

Crystal data
Chemical formula[Pb(C5H3N2O2)2]
Mr453.38
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)8.0336 (16), 10.386 (2), 13.766 (3)
β (°) 93.72 (3)
V3)1146.2 (4)
Z4
Radiation typeMo Kα
µ (mm1)14.74
Crystal size (mm)0.33 × 0.09 × 0.08
Data collection
DiffractometerKuma KM-4 four-circle
diffractometer
Absorption correctionAnalytical
(CrysAlis RED; Oxford Diffraction, 2008)
Tmin, Tmax0.284, 0.379
No. of measured, independent and
observed [I > 2σ(I)] reflections
3587, 3365, 2119
Rint0.040
(sin θ/λ)max1)0.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.137, 1.05
No. of reflections3365
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)6.57, 4.30

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

Selected bond lengths (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.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16···O12iii0.932.353.182 (12)148.5
C14—H14···O21iv0.932.763.489 (10)135.6
C26—H26···O22v0.932.423.201 (12)142.2
C15—H15···O11vi0.932.403.266 (10)155.4
C25—H25···O12vii0.932.423.328 (12)164.8
Symmetry codes: (iii) x+1, y, z; (iv) x1/2, y+3/2, z1/2; (v) x1, y, z; (vi) x+1/2, y1/2, z+3/2; (vii) x, y+1, z+2.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds