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

Bi-Song Zhang

doi:10.1107/S1600536809035016

. 2009 Sep 5;65(Pt 10):m1167–m1168. doi: 10.1107/S1600536809035016

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

Bi-Song Zhang ^a,^*

PMCID: PMC2970442 PMID: 21577705

Abstract

In the title compound, [Pb(C₇H₄FO₂)₂(C₁₂H₈N₂)₂]·2H₂O, the Pb^II atom is coordinated by four N atoms from two bidentate chelating 1,10-phenanthroline (phen) ligands and four O atoms from two 2-fluorobenzoate ligands in an irregular polyhedral coordination geometry. Two carboxylate O atoms and one F atom are each disordered over two sites with occupancy factors of 0.60 and 0.40. The dihedral angle between the two phen ligands is 89.9 (1)°. The mean interplanar distances are alternatively of 3.44 (3) and 3.45 (3) Å, indicating π–π stacking interactions between the neighboring phen ligands. In the crystal, O—H⋯O, O—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: Ye & Zhang (2009 ▶); Zhang et al. (2005 ▶). For related structures, see: Zhang (2004 ▶, 2005 ▶, 2006a ▶,b ▶,c ▶).

Experimental

Crystal data

[Pb(C₇H₄FO₂)₂(C₁₂H₈N₂)₂]·2H₂O
M _r = 881.83
Triclinic,
a = 11.406 (2) Å
b = 12.510 (3) Å
c = 13.771 (3) Å
α = 95.11 (3)°
β = 114.39 (3)°
γ = 101.72 (3)°
V = 1719.0 (9) Å³
Z = 2
Mo Kα radiation
μ = 4.97 mm⁻¹
T = 290 K
0.29 × 0.18 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.353, T _max = 0.428
13556 measured reflections
6018 independent reflections
4795 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.136
S = 1.22
6018 reflections
484 parameters
H-atom parameters constrained
Δρ_max = 2.12 e Å⁻³
Δρ_min = −2.69 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; 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/S1600536809035016/hy2223sup1.cif

e-65-m1167-sup1.cif^{(26.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035016/hy2223Isup2.hkl

e-65-m1167-Isup2.hkl^{(294.6KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Pb1—N1	2.675 (9)
Pb1—N2	2.644 (8)
Pb1—N3	2.622 (9)
Pb1—N4	2.566 (8)
Pb1—O1	2.788 (16)
Pb1—O1′	2.95 (3)
Pb1—O2	2.880 (18)
Pb1—O2′	2.77 (3)
Pb1—O3	2.670 (8)
Pb1—O4	2.777 (9)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O1′ⁱ	0.85	2.34	3.027 (4)	138
O5—H5A⋯F1ⁱⁱ	0.85	2.33	2.801 (5)	116
O5—H5A⋯O2′ⁱ	0.85	2.51	3.313 (6)	158
O5—H5B⋯O2′ⁱⁱ	0.85	2.05	2.789 (3)	146
O5—H5B⋯O1ⁱⁱ	0.85	1.99	2.792 (6)	158
O6—H6A⋯O4	0.85	2.08	2.807 (11)	143
O6—H6B⋯O2ⁱⁱⁱ	0.85	2.03	2.795 (5)	149
O6—H6B⋯O1′ⁱⁱⁱ	0.85	2.17	2.889 (5)	143
O7—H7A⋯O5	0.85	1.97	2.75 (2)	152
O7—H7B⋯O6^iv	0.85	2.29	2.810 (2)	120
C8—H8⋯O5	0.93	2.54	3.344 (34)	145
C16—H16⋯O3^v	0.93	2.54	3.422 (19)	158
C21—H21⋯O1	0.93	2.44	3.106 (82)	127

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

Acknowledgments

The author gratefully acknowledges financial support from the Education Office of Zhejiang Province (grant No. 20051316).

supplementary crystallographic information

Comment

The synthesis was originally directed to repeat the synthesis of [Pb(C₇H₄FO₂)₂(C₁₂H₈N₂)₂(H₂O)_0.5].2H₂O, (I), (Ye & Zhang, 2009). The title compound was unintentionally obtained and structurally related to (I).

The title compound (Fig .1) shows a structure similar to (I) and to those of the 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] complex molecule and two uncoordinated water molecules. The Pb^II atom is coordinated by four N atoms from two bidentate chelating phen ligands and four O atoms from two 2-fluorobenzoate ligands in an irregular polyhedral coordination geometry, with Pb—N bond lengths in the range of 2.566 (8) to 2.675 (9)Å and Pb—O bond lengths in the range of 2.670 (8) to 2.95 (3)Å (Table 1). The dihedral angle of the two phen ligands is 89.9 (1)°, as distinct from (I) (0.0 (2)°). The mean interplanar distances are alternatively of 3.44 (3) and 3.45 (3) Å, indicating π–π stacking interactions between the neighboring phen ligands (Fig. 2). O—H···O, O—H···F and C—H···O hydrogen bonds are present (Table 2 ). A combination of the π–π stacking interactions and hydrogen bonds leads to a supramolecular network.

Experimental

Pb(NO₃)₂ (0.331 g, 1.00 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 (0.050 g, 0.25 mmol), 2-fluorobenzoic acid (0.036 g, 0.25 mmol), CH₃OH/H₂O (v/v = 1:2, 15 ml) were mixed and stirred for 2 h. Subsequently, the resulting cream suspension was heated in a 23 ml Teflon-lined stainless steel autoclave at 433 K for 5 d. 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 2 weeks afforded colorless transparent block single crystals.