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Acid-based analogs of certain water tetramers: an examination of some crystal structures in the literature

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Abstract

Chemical clusters with composition (H2nOn), (H2n+1On)+, and (H2n−1On)− with n = 4 are crystallographically known. Moreover, for each of those classes, there are documented examples in more than one stereochemical conformation. In this study, we consider the relation between their stereochemical characteristics in the solid and in their free form as fluids, by calculating their energies as crystallographically reported, as well as by energy optimization. Also, since accurate crystallographic studies provided these species in more than one geometrical isomer, quantum mechanical comparisons of their energies in crystalline and free molecular form are herein reported. Finally, for those in which energy minimization(s) resulted in stereochemical rearrangements, the new stereoisomer resulting is herein described. Quantum calculations show the molecular energy increases from deprotonated, to neutral, to protonated fragments. Energy optimization was carried out for each of the crystal structures studied, which allowed us to determine the structural relationship between the crystalline and free form of these fragments. Among these aquo-fragments, the most frequent structures were quadrangular and triangular motifs with either four or three hydrogen bonds. The quantum chemical calculated energy of all crystal and optimized structures are reported.

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Authors and Affiliations

  1. Chemistry Department, Hunter College, CUNY, 695 Park Avenue, New York, NY, 10065, USA

    Hiroko Ajiki, Ivan Bernal & Lou Massa

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  1. Hiroko Ajiki
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  2. Ivan Bernal
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  3. Lou Massa
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All authors, HA, IB, LM, contributed equally to all sections of the paper.

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Correspondence to Lou Massa.

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Ajiki, H., Bernal, I. & Massa, L. Acid-based analogs of certain water tetramers: an examination of some crystal structures in the literature. Struct Chem 33, 1177–1188 (2022). https://doi.org/10.1007/s11224-022-01924-0

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