Home Crystal Structure of 1,1′-dimethyl-[4,4′-bipyridine]-1,1′-diium tetrachloridozincate(II), C12H14Cl4N2Zn
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Crystal Structure of 1,1′-dimethyl-[4,4′-bipyridine]-1,1′-diium tetrachloridozincate(II), C12H14Cl4N2Zn

  • Qingmei Song and Lijun Song EMAIL logo
Published/Copyright: April 7, 2017

Abstract

C12H14Cl4N2Zn, orthorhombic, Pbcn (no. 60), a = 12.7029(6) Å, b = 16.0791(8) Å, c = 7.7171(4) Å, V = 1576.23(14) Å3, Z = 4, Rgt(F) = 0.0316, wRref(F2) = 0.0988, T = 293 K.

CCDC no.:: 1465342

The crystal structure is shown in the figure. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Colourless prism
Size:0.12 × 0.08 × 0.06 mm3
Wavelength:Mo Kα radiation (0.71073 Å)
μ:22.2 cm−1
Diffractometer, scan mode:Bruker APEXII, φ and ω
2θmax, completeness:55°, >99%
N(hkl)measured, N(hkl)unique, Rint:21243, 1804, 0.027
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 1525
N(param)refined:88
Programs:Bruker [1], SHELX [2]
Table 2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
Cl20.11390(5)0.19641(4)0.60754(9)0.0486(2)
Cl1−0.09894(6)0.36382(4)0.57337(11)0.0572(2)
N10.26600(16)0.41035(12)0.5091(3)0.0433(5)
C30.4009(2)0.48441(14)0.6519(3)0.0426(6)
H3a0.43110.53610.68460.051*
C20.45014(19)0.41020(13)0.6999(3)0.0363(5)
C50.3116(2)0.33850(16)0.5522(4)0.0489(6)
H5a0.28060.28760.51590.059*
C40.3091(2)0.48304(15)0.5579(3)0.0451(6)
H4a0.27580.53380.52710.054*
C10.4024(2)0.33687(15)0.6480(4)0.0446(6)
H1a0.43290.28500.67910.054*
C60.1677(2)0.4088(2)0.4055(5)0.0625(8)
H6a0.14770.35110.38200.094*
H6b0.17910.43810.29570.094*
H6c0.11130.43640.47040.094*
Zn10.00000.28192(2)0.75000.03919(19)

Source of material

ZnCl2 (0.068 g, 0.20 mmol), methyl viologen chloride (0.054 g, 0.1 mmol) and HCl (1.0 mL) in ethanol (10.0 mL) were mixed and stirred for 10 min, and then sealed in an autoclave equipped with a Teflon liner (20.0 mL) and heated at 120 °C for 3 days. The colorless block crystals were obtained and dried in air.

Experimental details

H atoms were generated geometrically, with C—H = 0.98 and 0.95 Å for methyl and aromatic H, respectively, and constrained to ride their parent atoms with Uiso(H) = x Ueq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Discussion

Organically templated inorganic hybrid materials have attracted much interest due to their intriguing architectures and topologies as well as fascinating physical properties [3], [4], [5], [6]. Viologen and related derivatives have been widely used as templates to construct metal-halide-viologen complexes with various structure types because of their application in biology, electrochemistry and photochemistry [7], [8], [9], [10]. In order to find new organic-inorganic hybrid materials based on methyl viologen (MV), the title compound has been prepared and its crystal structure has also been determined by X-ray single crystal diffractions.

The title compound features a zero-dimensional discrete structure, including the inorganic anion [ZnCl4]2− anion and MV2+ organic cation.

The asymmetric unit includes one half of a [ZnCl4]2− and one half of a MV2+ cation. The cation is located around a twofold axis, whereas the anion is located at a twofold axis of the orthorhombic space group. The Zn(II) is four-coordinated by four chlorido ligands in a tetrahedral geometry. The bond lengths of Zn—Cl are 2.2741(7) Å and 2.2787(6) Å, respectively, which are within the normal range [10]. The bond angles of Cl—Zn—Cl are in the range of 105.77(3)° to 114.28(3)°, which deviates slightly from an ideal tetrahedron. Very weak C—H⋯Cl hydrogen bonds between MV2+ and [ZnCl4]2− lead to a three dimensional supramolecular structure.

Acknowledgement

I acknowledge support by the Innovation Program of Xiamen (No. 3502Z20162016).

References

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Received: 2016-11-25
Accepted: 2017-3-23
Published Online: 2017-4-7
Published in Print: 2017-5-24

©2017 Qingmei Song et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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