catena-Poly[[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/S1600536811046691

. 2011 Nov 9;67(Pt 12):m1727–m1728. doi: 10.1107/S1600536811046691

catena-Poly[[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: PMC3238641 PMID: 22199532

Abstract

The Pb^II atom in the polymeric title compound, {[Pb(C₁₃H₁₁N₄O)]ClO₄}_n, is coordinated by the N′-[1-(pyridin-2-yl-κN)ethylidene]isonicotinohydrazidate ligand via its O,N,N′-donors and simultaneously bridged by a neighbouring ligand via the pyridin-2-yl N atom. The resultant supramolecular chain is a zigzag along the a axis. The stereochemistry of the Pb^II atom is defined by an N₃OE donor set (E = lone pair of electrons), which results in a Ψ-trigonal–bipyramidal coordination with the O and pyridin-2-yl N atoms in axial positions. The dihedral angle between the pyridine rings of the ligand is 6.3 (3)°. The supramolecular cationic chains are linked into a three-dimensional array via secondary Pb⋯O [3.133 (6) and 3.28 (7) Å] and Pb⋯N [3.028 (4) Å] interactions. Weak C—H⋯O interactions and aromatic π–π stacking [centroid–centroid separation = 3.693 (2) Å] also occur in the crystal.

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 ▶). For specialized crystallization techniques, see: Harrowfield et al. (1996 ▶).

Experimental

Crystal data

[Pb(C₁₃H₁₁N₄O)]ClO₄
M _r = 545.90
Monoclinic,
a = 10.0620 (6) Å
b = 14.4431 (8) Å
c = 11.1456 (7) Å
β = 99.174 (1)°
V = 1599.03 (16) Å³
Z = 4
Mo Kα radiation
μ = 10.75 mm⁻¹
T = 293 K
0.29 × 0.11 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.691, T _max = 1.000
8396 measured reflections
2811 independent reflections
2392 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.056
S = 1.07
2811 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.45 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/S1600536811046691/hb6465sup1.cif

e-67-m1727-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046691/hb6465Isup2.hkl

e-67-m1727-Isup2.hkl^{(135.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Pb—O1	2.405 (3)
Pb—N1	2.597 (4)
Pb—N2	2.456 (4)
Pb—N4ⁱ	2.472 (4)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3ⁱⁱ	0.93	2.53	3.422 (10)	160
C4—H4⋯O1ⁱⁱⁱ	0.93	2.45	3.277 (7)	148
C10—H10⋯O2^iv	0.93	2.57	3.485 (8)	170

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Symmetry codes: (ii) Inline graphic ; (iii) ; (iv) .

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 the title lead(II) complex, (I), all four donor atoms participate in coordination of the Pb atom.

The asymmetric unit of (I), Fig. 1, comprises a Pb atom, a N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide anion and a perchlorate anion. 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.

The resultant N₃O donor set plus the lone pair of electrons is based on a trigonal bipyramid with the O1 and N1 atoms in axial positions [O1—Pb—N1 = 126.27 (12)°] and the remaining N atoms [N2—Pb—N4ⁱ = 90.17 (13)°] and lone pair in equatorial positions; symmetry operation i: -1/2 + x, 1.5 - y, -1/2 + z. The µ₂-bridging mode of the tetradentate N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand leads to a zigzag chain along the a axis, Fig. 2. The considerable distortions from the ideal geometry arise from the acute chelate angles (O1—Pb—N2 = 64.75 (12)° and N1—Pb—N2 = 63.45 (12)°) as well as the close approach of other donor atoms. Most notable amongst the latter are Pb···O(perchlorate) interactions with the two shortest contacts being Pb···O4ⁱⁱ of 3.133 (6) Å and Pb···O5ⁱⁱⁱ = 3.287 (7) Å for i: -1 + x, y, z and ii: 1 - x, 1 - y, 2 - z. These interactions along with Pb···N3ⁱⁱⁱ contacts of 3.028 (4) Å [iii: 1 - x, 1 - y, 2 - z] generate a three-dimensional architecture, Fig. 3.

Experimental

A solution of methyl 2-pyridyl ketone (10 mmol) in MeOH (25 ml) was added drop wise to a solution of 4-pyridinecarboxylic acid hydrazide (10 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 ligand (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 1 week, yellow needles of (I) had deposited in the arm held at ambient temperature. They were then filtered off, washed with acetone and ether, and air dried. Yield: 75%. M.pt.: 506 K