Poly[[μ-chlorido-μ-[2-(2,4-di­fluoro­phen­yl)-1,3-bis­(1,2,4-triazol-1-yl)propan-2-ol-κ2 N 4:N 4′]-zinc] chloride dihydrate]

Gang-Hong Pan; Jin-Niu Tang; Shi-Hua Xu; Zhong-Jing Huang; Bo-Fa Mo

doi:10.1107/S1600536813026524

. 2013 Oct 2;69(Pt 11):m573. doi: 10.1107/S1600536813026524

Poly[[μ-chlorido-μ-[2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)propan-2-ol-κ² N ⁴:N ^4′]-zinc] chloride dihydrate]

Gang-Hong Pan ^a, Jin-Niu Tang ^a, Shi-Hua Xu ^a, Zhong-Jing Huang ^a,^*, Bo-Fa Mo ^a

PMCID: PMC3884242 PMID: 24454018

Abstract

The title compound, {[ZnCl(C₁₃H₁₂F₂N₆O)₂]Cl·2H₂O}_n, is a two-dimensional coordination polymer. The Zn^II atom is six-coordinated by four N atoms from four 2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)propan-2-ol (HFlu) ligands and by two Cl atoms in a distorted octahedral geometry. Two Cl atoms bridge two Zn^II atoms, forming a centrosymmetric dinuclear unit. The HFlu ligands connect the dinuclear units into a 4⁴ net parallel to (001) when the dinuclear unit is considered as a node. O—H⋯O and O—H⋯Cl hydrogen bonds link the cationic layer, free chloride anions and lattice water molecules. Intralayer π–π interactions between the triazole rings are observed [centroid–centroid distance = 3.716 (6) Å].

Related literature

For background to this class of compounds, see: Han et al. (2006a ▶,b ▶). For related structures, see: Gao et al. (2001 ▶); Zhang et al. (2007 ▶). graphic file with name e-69-0m573-scheme1.jpg

Experimental

Crystal data

[ZnCl(C₁₃H₁₂F₂N₆O)₂]Cl·2H₂O
M _r = 784.89
Triclinic,
a = 10.2310 (6) Å
b = 11.8118 (6) Å
c = 14.3588 (9) Å
α = 91.191 (7)°
β = 107.481 (5)°
γ = 106.074 (6)°
V = 1580.11 (18) Å³
Z = 2
Mo Kα radiation
μ = 1.03 mm⁻¹
T = 296 K
0.25 × 0.25 × 0.21 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.784, T _max = 0.813
8374 measured reflections
5465 independent reflections
3137 reflections with I > 2σ(I)
R _int = 0.064

Refinement

R[F ² > 2σ(F ²)] = 0.080
wR(F ²) = 0.306
S = 1.07
5465 reflections
444 parameters
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −1.09 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: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813026524/hy2637sup1.cif

e-69-0m573-sup1.cif^{(24.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026524/hy2637Isup2.hkl

e-69-0m573-Isup2.hkl^{(267.6KB, 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
O1—H1⋯Cl2ⁱ	0.82	2.29	3.103 (7)	172
O2—H2⋯O4ⁱ	0.82	1.87	2.653 (9)	160
O3—H3A⋯Cl2ⁱⁱ	0.85	2.32	3.163 (11)	170
O3—H3B⋯Cl1ⁱⁱⁱ	0.85	2.38	3.221 (10)	170
O4—H4A⋯O2^iv	0.85	2.24	2.784 (9)	122
O4—H4B⋯Cl2	0.85	2.29	3.101 (8)	160

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

Acknowledgments

This work was supported by the Innovation Project of Guangxi University for Nationalities.

supplementary crystallographic information

1. Comment

Fluconazole 2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl) propan-2-ol, which is a 1,2,4-triazole derivative, is not only a widely used antifungal medicine but also a good flexible ligand to construct metal-organic polymers with optical properties and medical applications (Han et al., 2006a,b). Fluconazole can coordinate to metal ions in different configurations. We here report a new coordination polymer based on fluconazole.

The asymmetric unit of the title compound contains one Zn^II ion, two 2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)propan-2-ol (HFlu) ligands, one coordinated Cl^-1 anion, one free Cl^-1 anion and two free water molecules. As shown in Fig. 1, the Zn^II ion is six-coordinated by four N atoms from four HFlu ligands and two bridging Cl^-1 anions. The Zn—N bond lengths range from 2.127 (8) to 2.197 (7) Å, and the Zn—Cl bond distances are 2.418 (3) and 2.732 (3) Å. The Zn—N bond lengths are in the normal range as observed in other Zn(II) complexes (Zhang et al., 2007). However, the Zn—Cl bond distances are longer than those as observed in other Zn(II) complexe (Gao et al., 2001). Two Zn^II ions are connected by two HFlu ligands, forming a Zn₂(HFlu)₂ macrocycle, in which the Zn···Zn distance is 11.297 (2)Å. The other two HFlu ligands link the macrocycle along the a axis with a Zn···Zn distance of 10.231 (2) Å to form a grid unit with dimensions of 11.30 × 10.23 Å² (Fig. 2a). These grid units are further connected by two Cl^-1 anions with a Zn···Zn distance of 3.879 (1) Å into a two-dimensional structure (Fig. 2b), in which another type of grid with dimensions of 10.231 (2) × 3.879 (1) Å² is formed.

Free water molecules and free Cl^-1 anions are accommodated in the residual empties to shrink the void space and stabilize the structure. Moreover, there are intermolecular O—H···O and O—H···Cl hydrogen bonds involving the cationic layer, free Cl^-1 anions and water molecules (Table 1, Fig. 3). These interactions further stabilize the structural framework.

2. Experimental

A mixture of fluconazole (153 mg, 0.5 mmol), ZnCl₂ (136 mg, 1.0 mmol), 15 ml H₂O, and 3 ml ethanol was placed in a Parr Teflon-lined stainless steel vessel (30 ml), and then the vessel was sealed and heated at 423 K for 3 days. After the mixture was slowly cooled to room temperature, colorless block-shaped crystals of the title compound was obtained. Analysis, calculated for C₂₆H₂₈Cl₂F₄N₁₂O₄Zn: C 39.79, H 3.60, N 21.42%; found: C 39.66, H 3.52, N 21.28%.