Poly[[diaqua­(μ2-1,4-dioxane-κ2 O:O′)(μ2-2,3,5,6-tetra­fluoro­benzene-1,4-dicarboxyl­ato-κ2 O 1:O 4)copper(II)] 1,4-dioxane disolvate dihydrate]

Jing Yu; Yi-Feng Zhang; Fu-An Sun; Qun Chen

doi:10.1107/S1600536811009755

. 2011 Apr 7;67(Pt 5):m527–m528. doi: 10.1107/S1600536811009755

Poly[[diaqua(μ₂-1,4-dioxane-κ² O:O′)(μ₂-2,3,5,6-tetrafluorobenzene-1,4-dicarboxylato-κ² O ¹:O ⁴)copper(II)] 1,4-dioxane disolvate dihydrate]

Jing Yu ^a, Yi-Feng Zhang ^a, Fu-An Sun ^a, Qun Chen ^a,^*

PMCID: PMC3089286 PMID: 21754269

Abstract

In the title complex, {[Cu(C₈F₄O₄)(C₄H₈O₂)(H₂O)₂]·2C₄H₈O₂·2H₂O}_n, the Cu^II ion is six-coordinated by two oxygen donors from two trans 2,3,5,6-tetrafluoro-1,4-dicarboxylate (BDC-F₄) ligands, two O atoms from two chair 1,4-dioxane ligands and two O atoms from two terminal water molecules, adopting a distorted octahedral coordinated geometry. Each BDC-F₄ anion bridges two Cu^II ions in a bis-monodentate fashion, forming a [Cu(BDC-F₄)]_n chain. These chains are further linked by bridging 1,4-dioxane ligands, generating a two-dimensional net with approximately rectangular grids of 11.253 × 7.654 Å. Such adjacent parallel layers are connected by O—H⋯O hydrogen bonds between guest water molecules and the uncoordinated carboxylate O atoms and coordinated water molecules into the final three-dimensional supramolecular network.

Related literature

For the solvent template effect of 1,4-dioxane in the construction of coordination polymers, see: Chen et al. (2008 ▶); He et al. (2009 ▶).

Experimental

Crystal data

[Cu(C₈F₄O₄)(C₄H₈O₂)(H₂O)₂]·2C₄H₈O₂·2H₂O
M _r = 636.00
Monoclinic,
a = 7.654 (2) Å
b = 11.253 (3) Å
c = 16.126 (4) Å
β = 99.634 (6)°
V = 1369.4 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 297 K
0.20 × 0.15 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.842, T _max = 0.901
7646 measured reflections
2536 independent reflections
2011 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.182
S = 1.07
2536 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2 and SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 2005 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009755/jj2078sup1.cif

e-67-0m527-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009755/jj2078Isup2.hkl

e-67-0m527-Isup2.hkl^{(124.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B⋯O7	0.82	1.92	2.670 (5)	152
O4—H4A⋯O1ⁱ	0.82	1.85	2.641 (3)	162
O7—H7C⋯O6ⁱⁱ	0.82	2.03	2.807 (7)	158
O7—H7D⋯O1ⁱⁱⁱ	0.82	2.09	2.797 (5)	144

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

supplementary crystallographic information

Comment

Recently, our group has been engaged in studying the influence that a range of solvent species have on the structures of a series of Mn^II—BDC-Cl₄ polymers with 2,3,5,6-tetracholorobenzene-1,4-dicarboxylate (BDC-Cl₄) ligand (Chen et al., 2008; He et al.., 2009). Among them, the 1,4-dioxane (dioxane) solvent molecule may serve as a solvent template to play a key role in controlling the resulting polymeric network. To further understand the solvent template effect of 1,4-dioxane, we employed the tetrafluorinated benzene-1,4-dicarboxylic acid (H₂BDC-F₄) ligand to assemble with a copper(II) ion in the presence of dioxane and obtained the title two-dimensional coordination polymer {[Cu(BDC-F₄)(dioxane)(H₂O)₂].(dioxane)₂(H₂O)₂}_n, (I).

The asymmetric unit of (I) is composed of one Cu^II center, one 2,3,5,6-tetrafluoro-1,4-dicarboxylate (BDC-F₄) anion, one dioxane ligand, two coordinated water molecules, and two lattice dioxane as well as two water moieties (Fig. 1). Each Cu^II ion is six-coordinated by two oxygen donors from two trans 2,3,5,6-tetrafluoro-1,4-dicarboxylate (BDC-F₄) ligands, two oxygen atoms from two chair dioxane ligands, and two oxygen atoms from two terminal water molecules, adopting a distorted octahedral coordinated geometry. Each BDC-F₄ anion bridges two Cu^II ions in a bis-monodentate fashion to form a one-dimensional [Cu(BDC-F₄)]_n chain, which is further joined together by bridging dioxane ligands to generate a two-dimensional net with approximately rectangular grids of 11.253 Å × 7.654 Å (Cu···Cu nucleus-to-nucleus), where the Cu···Cu···Cu angles are 90.8 and 89.2°, respectively (Fig. 2). Such adjacent parallel layers are connected by O—H···O hydrogen bonds between guest water molecules with the uncoordinated carboxylate oxygen atoms and coordinated water molecules to fulfill the final three-dimensional supramolecular network.

Experimental

An aqueous solution (2 ml) of Cu(ClO₄)₂.6H₂O (37.1 mg, 0.10 mmol) was added to a dioxane solution (4 ml) of H₂BDC-F₄ (23.8 mg, 0.10 mmol) with stirring for 15 min. Then, the reaction mixture was filtered and left to stand at room temperature. After 3 days, well blue block crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of the solvents in 52% yield (33.1 mg, based on H₂BDC-F₄).