catena-Poly[[bis­(4-methyl­benzoato-κ2 O:O′)lead(II)]-μ-nicotinamide-κ2 N 1:O]

Tuncer Hökelek; Hakan Dal; Barış Tercan; Efdal Çimen; Hacali Necefoğlu

doi:10.1107/S1600536810028126

. 2010 Jul 17;66(Pt 8):m953–m954. doi: 10.1107/S1600536810028126

catena-Poly[[bis(4-methylbenzoato-κ² O:O′)lead(II)]-μ-nicotinamide-κ² N ¹:O]

Tuncer Hökelek ^a,^*, Hakan Dal ^b, Barış Tercan ^c, Efdal Çimen ^d, Hacali Necefoğlu ^d

PMCID: PMC3007553 PMID: 21588183

Abstract

In the title compound, [Pb(C₈H₇O₂)₂(C₆H₆N₂O)]_n, the Pb^II ion is coordinated by two 4-methylbenzoate (PMB) and one nicotinamide (NA) ligands while symmetry-related NA ligands bridge adjacent Pb^II ions, forming polymeric chains along the c axis. The carboxylate groups in the two PMB ions are twisted away from the attached benzene ring by 22.9 (2) and 4.6 (2)°. The two benzene rings of the PMB ions are oriented at a dihedral angle of 83.7 (1)°. In a polymeric chain, the NA ligands are linked to PMB ions through intramolecular N—H⋯O hydrogen bonds. In the crystal structure, adjacent polymeric chains interact via N—H⋯O and C—H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane.

Related literature

For niacin, see: Krishnamachari (1974 ▶) and for N,N-diethylnicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Greenaway et al. (1984 ▶); Hökelek & Necefoğlu (1996 ▶); Hökelek et al. (2009a ▶,b ▶,c ▶,d ▶).

Experimental

Crystal data

[Pb(C₈H₇O₂)₂(C₆H₆N₂O)]
M _r = 599.60
Monoclinic,
a = 14.1146 (3) Å
b = 7.7431 (2) Å
c = 19.2165 (4) Å
β = 102.322 (2)°
V = 2051.81 (8) Å³
Z = 4
Mo Kα radiation
μ = 8.26 mm⁻¹
T = 100 K
0.34 × 0.32 × 0.13 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.074, T _max = 0.342
19461 measured reflections
5143 independent reflections
4669 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.020
wR(F ²) = 0.050
S = 1.03
5143 reflections
281 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.08 e Å⁻³
Δρ_min = −1.03 e Å⁻³

Data collection: APEX2 (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: Mercury (Macrae et al., 2006 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028126/ci5133sup1.cif

e-66-0m953-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028126/ci5133Isup2.hkl

e-66-0m953-Isup2.hkl^{(246.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Pb1—O1	2.7594 (19)
Pb1—O2	2.3141 (17)
Pb1—O3	2.4824 (18)
Pb1—O4	2.5672 (19)
Pb1—O5	2.6800 (16)
Pb1—N1ⁱ	2.661 (2)

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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
N2—H2A⋯O3	0.86 (3)	2.02 (3)	2.835 (3)	158 (3)
N2—H2B⋯O2ⁱⁱ	0.86 (3)	2.11 (3)	2.946 (3)	167 (3)
C4—H4⋯O1ⁱⁱⁱ	0.93	2.53	3.431 (3)	165
C11—H11⋯O1	0.93	2.59	3.253 (3)	129
C17—H17⋯O2ⁱⁱ	0.93	2.41	3.317 (3)	166

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

Acknowledgments

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of X-ray diffractometer. This work was supported financially by Kafkas University Research Fund (grant No. 2009-FEF-03).

supplementary crystallographic information

Comment

As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.

In the crystal structure of the title compound, each Pb^II ion is coordinated by two 4-methylbenzoate (PMB) and one nicotinamide (NA) ligands (Fig. 1), while symmetry related NA ligands bridge the Pb^II ions forming polymeric chains along the c axis (Fig. 2). The two PMB ions act as bidentate ligands, while the NA is monodentate ligand (Fig. 1). The crystal structures of similar complexes of Cd^II, Co^II, Mn^II and Zn^II ions, [Cd(C₈H₅O₃)₂(C₆H₆N₂O)₂(H₂O)].H₂O, (II) (Hökelek et al., 2009a), [Co(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂], (III) (Hökelek et al., 2009b), [Mn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂], (IV) (Hökelek et al., 2009c), [Zn₂(DENA)₂(C₇H₅O₃)₄].2H₂O, (V) (Hökelek & Necefoğlu, 1996) and [Zn(C₈H₈NO₂)₂(C₆H₆N₂O)₂].H₂O, (VI) (Hökelek et al., 2009d) have also been reported. In (II), the two benzoate ions are coordinated to the Cd atom as bidentate ligands. In the other structures one of the benzoate ligands acts as a bidentate ligand, while the other is monodentate ligand.

The average Pb—O bond length (Table 1) is 2.5606 (18) Å and the Pb1 atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O3/C9/O4) by -0.096 (10) Å and 0.403 (10) Å, respectively. The O1/C1/O2 and O3/C9/O4 carboxylate planes form dihedral angles of 22.9 (2)° and 4.6 (2)°, respectively, with benzene rings A(C2-C7) and B(C10-C15), while the angles between rings A, B and C (N1/C17-C21) are A/B = 83.7 (1), A/C = 65.4 (1) and B/C = 20.9 (1)°. An intramolecular N—H···O hydrogen bond (Table 2) links the NA ligand to one of the carboxylate groups of the PMB ions acting as a bidentate ligand. In (I), the O1—Pb1—O2 and O3—Pb1—O4 angles are 51.09 (6)° and 51.71 (5)°, respectively. The corresponding O—M—O (where M is a metal) angles are 52.91 (4)° and 53.96 (4)° in (II), 60.70 (4)° in (III), 58.45 (9)° in (IV), 58.3 (3)° in (V), 60.03 (6)° in (VI) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) [(VII); Greenaway et al., 1984].

In the crystal structure, N—H···O and C—H···O hydrogen bonds (Table 2) link adjacent chains into a two-dimensional network parallel to the bc plane (Fig.2).

Experimental

The title compound was prepared by the reaction of Pb(NO₃)₂ (1.656 g, 5 mmol) in H₂O (50 ml) and nicotinamide (1.220 g, 10 mmol) in H₂O (10 ml) with sodium 4-methylbenzoate (1.580 g, 10 mmol) in H₂O (160 ml). The mixture was filtered and set aside to crystallize at ambient temperature for four weeks, giving colourless single crystals.