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)]nn- 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-dimethylpiperazineH2][VO(SeO3)(HSeO3)]2 contains one-dimensional [VO(SeO3)(HSeO3)]nn- chains, while [2,5-dimethylpiperazineH2][VO(SeO3)(HSeO3)]2�2H2O contains a three-dimensional [VO(SeO3)(HSeO3)]nn- framework.  The use of racemic 2-methylpiperazine also results in a compound containing a three-dimensional [VO(SeO3)(HSeO3)]nn- framework, crystallizing in the noncentrosymmetric polar, achiral space group Pca21 (no. 29), while analogous reactions containing either (R)-2-methylpiperazine or  (S)-2-methylpiperazine result in noncentrosymmetric, nonpolar chiral frameworks that crystallize in P21212 (no. 18).   The formation of these noncentrosymmetric framework materials is dictated by the structure, symmetry and hydrogen-bonding properties of the [2-methylpiperazineH2]2+ cations.

Centrosymmetric, polar, and chiral vanadium selenite frameworks

245th National Meeting (2013)

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