Role of Hydrogen-Bonding in the Formation of Polar Achiral and Nonpolar Chiral Vanadium Selenite Frameworks

Document Type

Journal Article

Role

Author

Published In

Inorganic Chemistry

Volume

51

Issue

20

First Page

11040

Last Page

11048

Publication Date

2012

Abstract

A series of organically templated vanadium selenites have been prepared under mild hydrothermal conditions. Single crystals were grown from mixtures of VOSO4, SeO2, and either 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, or 2-methylpiperazine in H2O. Each compound contains one-dimensional [VO(SeO3)(HSeO3)](n)(n-), secondary building units, which connect to form three-dimensional frameworks in the presence of 2,5-dimethylpiperazine or 2-methylpiperazine. Differences in composition and both intra-secondary building unit and organic-inorganic hydrogen-bonding between compounds dictate the dimensionality of the resulting inorganic structures. [1,4-dimethylpiperazineH(2)] [VO(SeO3)(HSeO3)](2) contains one-dimensional [VO(SeO3)(HSeO3)](n)(n-) chains, while [2,5-dimethylpiperazineH(2)] [VO(SeO3)(HSeO3)](2)center dot 2H(2)O contains a three-dimensional [VO(SeO3)(HSeO3)](n)(n-) framework. The use of racemic 2-methylpiperazine also results in a compound containing a three-dimensional [VO(SeO3)(HSeO3)](n)(n-) framework, crystallizing in the noncentrosymmetric polar, achiral space group Pca2(1) (no. 29), while analogous reactions containing either (R)-2-methylpiperazine or (S)-2-methylpiperazine result in noncentrosymmetric, nonpolar chiral frameworks that crystallize in P2(1)2(1)2 (no. 18). The formation of these noncentrosymmetric framework materials is dictated by the structure, symmetry, and hydrogen-bonding properties of the [2-methylpiperazineH(2)](2+) cations. --auhtor-supplied description

Share

COinS