Poly[(μ4-pyridine-2,3-dicarboxyl­ato)lead(II)]

Shie Fu Lush; Fwu Ming Shen

doi:10.1107/S1600536811000419

. 2011 Jan 15;67(Pt 2):m163–m164. doi: 10.1107/S1600536811000419

Poly[(μ₄-pyridine-2,3-dicarboxylato)lead(II)]

Shie Fu Lush ^a, Fwu Ming Shen ^b,^*

PMCID: PMC3051456 PMID: 21522843

Abstract

In the title coordination polymer, [Pb(C₇H₃NO₄)]_n, the Pb^II ion is eight-coordinated in a distorted square-antiprismatic geometry formed by one pyridine N atom and seven carboxylate O atoms from four pyridine-2,3-dicarboxylate (pda) anions. In the pda anion, the dihedral angles between the pyridine ring and carboxylate groups are 19.5 (6) and 73.3 (6)°. The carboxylate groups of the pda anions bridge the Pb ions, forming a two-dimensional coordination polymer parallel to (100). Weak intermolecular C—H⋯O hydrogen boning is present in the crystal structure.

Related literature

For the coordination modes of the pyridine-2,3-dicarboxylate anion, see: Aghabozorg et al. (2007 ▶); Baruah et al. (2007 ▶); Li et al. (2006 ▶). For the biological activity of pyridine-2,3-dicarboxylic acid, see: Xiang et al. (2006 ▶); Yang et al. (2006 ▶); Zhang et al. (2008 ▶). For the inert lone-pair effect, see: Liat et al. (1998 ▶). For longer Pb—O bonds, see: Mao et al. (2006 ▶); Yang et al. (2010 ▶).

Experimental

Crystal data

[Pb(C₇H₃NO₄)]
M _r = 372.30
Monoclinic,
a = 11.6943 (9) Å
b = 4.5392 (4) Å
c = 14.1636 (12) Å
β = 90.046 (2)°
V = 751.84 (11) Å³
Z = 4
Mo Kα radiation
μ = 22.42 mm⁻¹
T = 297 K
0.54 × 0.23 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.659, T _max = 1.000
4013 measured reflections
1484 independent reflections
1336 reflections with I > 2σ(I)
R _int = 0.125

Refinement

R[F ² > 2σ(F ²)] = 0.073
wR(F ²) = 0.204
S = 1.13
1484 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 4.56 e Å⁻³
Δρ_min = −5.06 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000419/xu5124sup1.cif

e-67-0m163-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000419/xu5124Isup2.hkl

e-67-0m163-Isup2.hkl^{(73.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Pb—N	2.651 (7)
Pb—O1ⁱ	2.816 (7)
Pb—O1ⁱⁱ	2.911 (6)
Pb—O2	2.592 (7)
Pb—O2ⁱ	2.566 (9)
Pb—O3ⁱⁱⁱ	2.397 (9)
Pb—O3ⁱⁱ	2.754 (9)
Pb—O4ⁱⁱ	2.845 (7)

Open in a new tab

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O3ⁱⁱⁱ	0.93	2.57	3.164 (13)	122

Open in a new tab

Symmetry code: (iii) Inline graphic .

Acknowledgments

This work was supported financially by Yuanpei University, Taiwan.

supplementary crystallographic information

Comment

The pyridine-2,3-dicarboxylic acid (pdaH₂) is a typical chealated-form ligand. Its biological importance has been described in several literatures (Xiang et al., 2006; Yang et al., 2006; Zhang et al., 2008). Pda shows diverse coordination modes, such as monodentate (Baruah et al., 2007), µ₂-bridging (Aghabozorg et al., 2007), µ₃-bridging (Li et al., 2006). Here we describe the title compound in which the pda is a µ₄-bridging ligand (Fig. 1).

The structure of a coordination polymer [Pb(C₇H₃NO₄)]_n, the lead ion is eight-coordinated with a distorted square-antiprismatic geometry formed by one O-monodentate pda^-2 ligand, one N,O-bidentate pda^-2 ligand, one O,O'-bidentate pda^-2 ligand and one O,O',O''-tridentate pda^-2 ligand (Table 1). According to "inert-pair effect", the coordination number of Pb^II is variable, and the lengths of bonds to Pb^II vary in a wide range (Liat et al., 1998). Longer distance is observed between Pb and O1 (2.911 (6) Å); some long Pb—O weak bonds have also been reported in reported lead complexes (Mao et al., 2006; Yang et al., 2010). The carboxylate group of pda^-2ligand bridges four Pb^II ion forming a 2-D framework is constructed.

There are no classic intermolecular hydrogen-bonding in the title compound, but intermolecular C—H···O weak interaction (Table 2) and ring···metal interaction help to stabilize the crystal structure, the Cg3 (Pb/O1—O2—C6)···Pb interaction is 3.877 Å (symmetry code: 1 - x,-1/2 + y,3/2 - z).

Experimental

An aqueous solution (5 ml) containing Pb(NO₃)₂ (0.164 g, 0.50 mmol) and 1,2-bis(4-pyridyl)ethane (0.0934 g, 0.50 mmol) was added to an aqueous solution (5 ml) of pyridine-2,3-dicarboxylic acid (0.0838 g, 0.50 mmol), and the mixture was stirred for 30 minutes and then filtered. The solution was placed in a 23 ml Teflon-lined reactor, heated at 423 K for 3 days, then cooled slowly to room temperature. The colorless transparent single crystals of the title compound were obtained in 45.67% yield (based on Pb).