Hemiaqua­bis(2-fluoro­benzoato-κ2 O,O′)bis­(1,10-phenanthroline-κ2 N,N′)lead(II) dihydrate

Su-Fang Ye; Bi-Song Zhang

doi:10.1107/S1600536809027524

. 2009 Jul 18;65(Pt 8):m936–m937. doi: 10.1107/S1600536809027524

Hemiaquabis(2-fluorobenzoato-κ² O,O′)bis(1,10-phenanthroline-κ² N,N′)lead(II) dihydrate

Su-Fang Ye ^a, Bi-Song Zhang ^a,^*

PMCID: PMC2977250 PMID: 21583389

Abstract

In the title compound, [Pb(C₇H₄FO₂)₂(C₁₂H₈N₂)₂(H₂O)_0.5]·2H₂O, the Pb^II atom is coordinated by four N atoms from two bidentate chelating 1,10-phenanthroline (phen) ligands, four O atoms from two 2-fluorobenzoate ligands and a half-occupied water molecule in an irregular coordination geometry. One carboxylate O atom and two F atoms are each disordered over two sites with occupancy factors of 0.558 (6) and 0.442 (6). The two crystallographically independent phen ligands are co-planar [dihedral angle 0.0 (2)°]. Centroid–centroid distances of 3.659 (7) and 3.687 (7) Å indicate π–π stacking interactions between neighboring phen ligands. In the crystal, O—H⋯O, C—H⋯F and C—H⋯O hydrogen bonds link the complex molecules and uncoordinated water molecules into a supramolecular network.

Related literature

For other complexes with a 2(or 4)-fluorobenzoate ligand, see: Zhang et al. (2005 ▶). For related structures, see: Zhang (2004 ▶, 2005 ▶, 2006a ▶,b ▶,c ▶).

Experimental

Crystal data

[Pb(C₇H₄FO₂)₂(C₁₂H₈N₂)₂(H₂O)_0.5]·2H₂O
M _r = 890.84
Triclinic,
a = 9.833 (2) Å
b = 11.568 (2) Å
c = 15.766 (3) Å
α = 81.11 (3)°
β = 77.23 (3)°
γ = 86.20 (3)°
V = 1727.0 (6) Å³
Z = 2
Mo Kα radiation
μ = 4.95 mm⁻¹
T = 290 K
0.34 × 0.19 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.330, T _max = 0.448
28426 measured reflections
10232 independent reflections
7916 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.078
S = 1.02
10232 reflections
466 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 1.33 e Å⁻³
Δρ_min = −0.77 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027524/hy2206sup1.cif

e-65-0m936-sup1.cif^{(26.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027524/hy2206Isup2.hkl

e-65-0m936-Isup2.hkl^{(500.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Pb1—O1	2.957 (8)
Pb1—O1′	2.866 (9)
Pb1—O2	2.631 (3)
Pb1—O3	2.575 (3)
Pb1—O4	2.570 (3)
Pb1—N1	2.796 (3)
Pb1—N2	2.656 (3)
Pb1—N3	2.768 (3)
Pb1—N4	2.906 (3)
Pb1—O7W	2.965 (7)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5W—H5WA⋯O2	0.85	1.98	2.796 (4)	162
O5W—H5WB⋯O6W	0.85	1.97	2.757 (5)	153
O6W—H6WA⋯O5Wⁱ	0.85	1.98	2.809 (6)	163
O6W—H6WB⋯O4	0.85	1.97	2.818 (3)	175
O6W—H6WA⋯O5Wⁱ	0.85	1.98	2.809 (6)	163
O7W—H7WA⋯O1′	0.85	1.98	2.496 (5)	118
O7W—H7WB⋯O1′ⁱⁱ	0.85	1.99	2.565 (2)	124
C8—H8⋯F1ⁱⁱⁱ	0.93	2.54	3.310 (7)	141
C30—H30⋯F1′ⁱⁱ	0.93	2.50	3.032 (12)	115
C29—H29⋯O3^iv	0.93	2.46	3.311 (5)	153

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

Acknowledgments

The authors gratefully acknowledge financial support from the Jinhua Municipal Science and Technology (grant No. 2003-01-179).

supplementary crystallographic information

Comment

We have prepared the title complex by the hydrothermal reaction of freshly prepared PbCO₃ with 1,10-phenanthroline (phen) and 2-fluorobenzoic acid in CH₃OH/H₂O, and report here its crystal structure (Fig. 1). The title compound has a structure similar to those of complexes with halobenzoate ligands, X–C₆H₄COO^-, where X is F, Cl, Br and I (Zhang, 2004, 2005, 2006a,b,c; Zhang et al., 2005). The asymmetric unit of the title compound consists of a [Pb(C₇H₄FO₂)₂(C₁₂H₈N₂)₂(H₂O)_0.5] complex molecule and two uncoordinated water molecules. The Pb^II atom is coordinated by four N atoms from two bidentate chelating phen ligands, four O atoms from two 2-fluorobenzoate ligands and a half-occupied water molecule in an irregular coordination geometry, with Pb—N bond lengths in the range of 2.656 (3) to 2.906 (3)Å and Pb—O bond lengths in the range of 2.570 (3) to 2.965 (7)Å (Table 1). The centroid–centroid distances of 3.659 (7) and 3.687 (7) Å indicate π–π stacking interactions between the neighboring phen ligands (Fig. 2). O—H···O, C—H···F and C—H···O hydrogen bonds are also present (Table 2 and Fig. 3). A combination of the π–π stacking interactions and hydrogen bonds leads to a supramolecular network.

Experimental

Pb(CH₃COO)₂.3H₂O (0.17 g, 0.45 mmol) was dissolved in appropriate amount of water, and then 1M Na₂CO₃ solution was added. PbCO₃ was obtained by filtration, which was then washed with distilled water for 5 times. The freshly prepared PbCO₃, phen (0.05 g, 0.25 mmol), 2-fluorobenzoic acid (0.04 g, 0.29 mmol), CH₃OH/H₂O (v/v = 1:2, 15 ml) were mixed and stirred for 1.5 h. Subsequently, the resulting cream suspension was heated in a 23 ml Teflon-lined stainless steel autoclave at 423 K for one week. After the autoclave was cooled to room temperature, the solid was filtered off. The resulting filtrate was allowed to stand at room temperature, and evaporation for 3 weeks afforded colorless transparent pillar-like single crystals. Analysis calculated for C₃₈H₂₉F₂N₄O_6.5Pb: C 51.19, H 3.26, N 6.28%; found: C 51.06, H 3.06, N 6.13%.