catena-Poly[[[bis­(methanol-κO)lead(II)]-μ-N′-[1-(pyridin-2-yl-κN)ethyl­idene]isonicotinohydrazidato-κ3 N′,O:N 1] perchlorate]

Gholam Hossein Shahverdizadeh; Edward R T Tiekink; Babak Mirtamizdoust

doi:10.1107/S1600536811046769

. 2011 Nov 9;67(Pt 12):m1729–m1730. doi: 10.1107/S1600536811046769

catena-Poly[[[bis(methanol-κO)lead(II)]-μ-N′-[1-(pyridin-2-yl-κN)ethylidene]isonicotinohydrazidato-κ³ N′,O:N ¹] perchlorate]

Gholam Hossein Shahverdizadeh ^a,^‡, Edward R T Tiekink ^b,^*, Babak Mirtamizdoust ^c

PMCID: PMC3238642 PMID: 22199533

Abstract

The Pb^II atom in the polymeric title compound, {[Pb(C₁₃H₁₁N₄O)(CH₃OH)₂]ClO₄}_n, is coordinated by an N′-[1-(pyridin-2-yl-κN)ethylidene]isonicotinohydrazidate ligand via O,N,N′-donors and simultaneously bridged by a neighbouring ligand via the isonicotinoyl N atom; two additional sites are occupied by methanol O atoms. The resultant supramolecular chain is a zigzag along the c axis. The Pb^II atom is seven-coordinated within an N₃O₃ donor set and a lone pair of electrons, which defines a Ψ-pentagonal–bipyramidal coordination geometry with the pyridine N and lone pair in axial positions. The supramolecular chains are linked into the two-dimensional array via intermolecular Pb⋯N [3.020 (4) Å] interactions. Layers stack along the a axis, being connected by O—H⋯O hydrogen bonds formed between the coordinated methanol molecules and perchlorate anions.

Related literature

For the structures of metal complexes containing the N′-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand, see: Maurya et al. (2002 ▶); Abboud et al. (2007 ▶); Zhang & Liu (2009 ▶); Hao et al. (2010 ▶); Shahverdizadeh et al. (2011 ▶). For specialized crystallization techniques, see: Harrowfield et al. (1996 ▶).

Experimental

Crystal data

[Pb(C₁₃H₁₁N₄O)(CH₄O)₂]ClO₄
M _r = 609.98
Monoclinic,
a = 11.2122 (14) Å
b = 13.4644 (17) Å
c = 14.1451 (18) Å
β = 111.906 (2)°
V = 1981.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 8.70 mm⁻¹
T = 173 K
0.46 × 0.43 × 0.37 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.108, T _max = 0.141
10367 measured reflections
3492 independent reflections
2641 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.066
S = 1.05
3492 reflections
255 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.98 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811046769/hg5133sup1.cif

e-67-m1729-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046769/hg5133Isup2.hkl

e-67-m1729-Isup2.hkl^{(167.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Pb—O1	2.415 (3)
Pb—O2	2.733 (4)
Pb—O3	2.891 (4)
Pb—N1	2.669 (4)
Pb—N2	2.493 (4)
Pb—N4ⁱ	2.477 (4)

Open in a new tab

Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2o⋯O4	0.84	2.16	2.909 (7)	149
O3—H3o⋯O5ⁱⁱ	0.84	2.11	2.930 (7)	166

Open in a new tab

Symmetry code: (ii) Inline graphic .

Acknowledgments

The authors thank the Islamic Azad University for support.

supplementary crystallographic information

Comment

Structural studies of coordination complexes containing the N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand are rare (Maurya et al., 2002; Abboud et al., 2007; Zhang & Liu, 2009; Hao et al., 2010). In each of these, the ligand coordinates in a tridentate mode with the terminal 4-pyridyl-N atom being non-coordinating. In a recently reported Pb^II structure, all four donor atoms were involved in coordination leading to a zigzag chain (Shahverdizadeh et al., 2011). A similar mode of coordination was found in the title lead(II) complex, (I), with complete details described herein.

The crystallographic asymmetric unit of (I), Fig. 1, comprises a Pb^II atom, an N'-1-(2-pyridyl)ethylidene]isonicotinohydrazide anion, a perchlorate anion, and two methanol molecules. The N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand coordinates a lead atom in a tridentate mode, via the N1, N2 and O1 atoms, and simultaneously bridges a symmetry related lead atom via the 4-pyridyl-N4 atom., Table 1. Both methanol molecules are connected to the Pb^II atom. The resulting N₃O₃ donor set, along with a stereochemically active lone pair of electrons, define a pentagonal bipyramidal geometry with the pyridyl-N4 atom lone pair of electrons occupying axial positions. The µ₂-bridging mode of the tetradentate N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand leads to a zigzag chain (glide symmetry) along the c axis, Fig. 2.

In the crystal packing, centrosymmetrically related supramolecular chains are linked into a two-dimensional array by Pb···N interactions [Pb···N3ⁱ = 3.020 (4) Å for i: 1 - x, 1 - y, 1 - z]. The layers thus formed in the bc plane are connected into a three-dimensional architecture via O—H···O hydrogen bonds involving the coordinated methanol molecules and the perchlorate anions, Fig. 4 and Table 2.

Experimental

A solution of methyl 2-pyridyl ketone (15 mmol) in MeOH (25 ml) was added drop-wise to a solution of 4-pyridinecarboxylic acid hydrazide (15 mmol) in MeOH (15 ml). The mixture was refluxed for 6 h. The white precipitate was removed by filtration and recrystallized from MeOH solution. Then the compound (1 mmol) was placed in one arm of a branched tube (Harrowfield et al., 1996) and a mixture of lead(II) acetate (1 mmol) and sodium perchlorate (1 mmol) in the other. Methanol was then added to fill both arms, the tube sealed and the ligand-containing arm immersed in a bath at 333 K, while the other was left at ambient temperature. After 2 weeks, crystals had deposited in the arm held at ambient temperature. They were filtered off, washed with acetone and ether, and air dried. Yield: 66%; M.pt.: 516 K.