catena-Poly[μ-aqua-2:1′κ2 O:O-aqua-2κO-(2-fluoro­benzoato-1κ2 O,O′)(μ2-2-fluoro­benzoato-2′:1κ2 O:O′)bis­(μ3-2-fluoro­benzoato)-2′:1:2κ4 O:O,O′:O′;1:2:1′κ5 F,O:O,O′:O′-dilead(II)]

Bi-Song Zhang

doi:10.1107/S1600536808022678

. 2008 Jul 23;64(Pt 8):m1055–m1056. doi: 10.1107/S1600536808022678

catena-Poly[μ-aqua-2:1′κ² O:O-aqua-2κO-(2-fluorobenzoato-1κ² O,O′)(μ₂-2-fluorobenzoato-2′:1κ² O:O′)bis(μ₃-2-fluorobenzoato)-2′:1:2κ⁴ O:O,O′:O′;1:2:1′κ⁵ F,O:O,O′:O′-dilead(II)]

Bi-Song Zhang ^a,^*

PMCID: PMC2961970 PMID: 21203040

Abstract

In the title compound, [Pb₂(C₇H₄FO₂)₄(H₂O)₂]_n, one Pb^II atom is coordinated by seven O atoms and one F atom from five 2-fluorobenzoate ligands, and the other Pb^II atom is coordinated by five O atoms from four 2-fluorobenzoate ligands and three water molecules, resulting in distorted PbO₇F and PbO₈ polyhedra. The 2-fluorobenzoate ligands bridge Pb atoms, giving rise to a one-dimensional chain structure extending along the [100] direction. The polymeric chains are connected via C—H⋯O hydrogen bonds and π–π interactions, with an interplanar distance of 3.46 (1) Å. An intramolecular O—H⋯F interaction is also present.

Related literature

For related literature, see: Morsali & Mahjoub (2005 ▶); Xiao & Morsali (2007 ▶); Zhang (2004 ▶, 2005 ▶, 2006a ▶,b ▶,c ▶); Zhang et al. (2005 ▶); Zhu et al. (1999 ▶).

Experimental

Crystal data

[Pb₂(C₇H₄FO₂)₄(H₂O)₂]
M _r = 1006.84
Triclinic,
a = 7.1016 (14) Å
b = 14.794 (3) Å
c = 15.096 (3) Å
α = 111.56 (3)°
β = 95.32 (3)°
γ = 97.31 (3)°
V = 1446.2 (6) Å³
Z = 2
Mo Kα radiation
μ = 11.71 mm⁻¹
T = 290 (2) K
0.44 × 0.19 × 0.13 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.082, T _max = 0.223
14182 measured reflections
6646 independent reflections
5329 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.094
S = 1.03
6646 reflections
397 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 3.74 e Å⁻³
Δρ_min = −2.48 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808022678/hy2143sup1.cif

e-64-m1055-sup1.cif^{(22.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022678/hy2143Isup2.hkl

e-64-m1055-Isup2.hkl^{(316.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Pb1—O4	2.480 (6)
Pb1—O2	2.489 (5)
Pb1—O1	2.551 (6)
Pb1—O8	2.574 (5)
Pb1—O9	2.621 (6)
Pb1—O3	2.642 (6)
Pb1—O6ⁱ	2.766 (6)
Pb1—F3ⁱⁱ	2.856 (8)
Pb2—O2	2.517 (5)
Pb2—O7	2.534 (6)
Pb2—O5	2.592 (6)
Pb2—O10	2.599 (6)
Pb2—O8	2.603 (5)
Pb2—O9ⁱⁱ	2.670 (6)
Pb2—O7ⁱⁱⁱ	2.999 (6)
Pb2—O1ⁱⁱ	2.804 (5)

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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
O7—H7A⋯O6ⁱ	0.82	2.15	2.881 (8)	148
O7—H7B⋯O5ⁱⁱⁱ	0.82	2.66	3.360 (8)	144
O10—H10A⋯O3ⁱⁱ	0.82	2.07	2.892 (8)	174
O10—H10B⋯O4	0.82	2.22	2.856 (8)	135
O10—H10B⋯F2	0.82	2.44	3.161 (13)	147
C19—H19⋯O3^iv	0.93	2.56	3.364 (13)	145

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

Acknowledgments

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

supplementary crystallographic information

Comment

We have studied the metal complexes of halogen-substituted benzoic acid (X–C₆H₄COOH; X = F, Cl, Br and I) (Zhang, 2004, 2005; Zhang et al., 2005; Zhang, 2006a,b,c). The related crystal structures can be found, such as [Pb(phen)_n(NO₂)X] (phen = 1,10-phenanthroline; X = CH₃COO^-, NCS^- and ClO₄^-) (Morsali & Mahjoub, 2005), [Pb₃(bpy)(H₂O)₅(sip)₂].0.5bpy.2H₂O (sip = 5-sulfoisophthalate; bpy = 2,2'-bipyridine) (Xiao & Morsali, 2007) and PbI₂(L) (L = bpy, phen) (Zhu et al., 1999). We report here the synthesis and structure of the title compound, a new one-dimensional Pb^II coordination polymer.

In the title compound, the Pb1 atom is coordinated by seven O atoms and one F atom from five 2-fluorobenzoate ligands to complete a significantly distorted PbO₇F polyhedron. The Pb1—O bond lengths are in the range of 2.480 (6) to 2.766 (6) Å and the Pb1—F bond length is 2.856 (8)Å (Table 1). The Pb2 atom is coordinated by five O atoms from four 2-fluorobenzoate ligands and three water molecules to complete a significantly distorted PbO₈ polyhedron. The Pb2—O bond lengths are in the range of 2.517 (5) to 2.999 (6)Å (Table 1). The 2-fluorobenzoate ligands bridge the Pb atoms, giving rise to a one-dimensional chain structure extending along the [100] direction (Fig. 2). There are intrachain O—H···O hydrogen bonds between the coordinated water molecules and the carboxylate O atoms of the 2-fluorobenzoate ligands (Table 2). The polymeric chains are connected via C—H···O hydrogen bonds and π–π stacking interactions between the benzene rings, with an interplanar distance of 3.46 (1) Å, into a two-dimensional supramolecular structure (Fig. 3).

Experimental

Freshly prepared PbCO₃ (0.140 g, 0.52 mmol), 2-fluorobenzoic acid (0.035 g, 0.25 mmol) in CH₃OH/H₂O (15 ml; 1:2 v/v) were mixed and stirred for ca 2 h. Subsequently, the resulting suspension was heated in a 23 ml Teflon-lined stainless steel autoclave at 423 K for 5 d. After the autoclave was cooled to room temperature, the solid was filtered off. The resulting colorless filtrate was allowed to stand at room temperature for one month, affording colorless block crystals suitable for X-ray analysis.