title: Molecular and supramolecular ionic aggregates H(x)O(y)(z) in organic and organometallic crystalline hydrates.
abstract: Ionic aggregates of the form H(x)O(y)(z) (z ≠ 0) have been characterized during an analysis of 245 crystal structures extracted from the Cambridge Structural Database [Allen (2002). Acta Cryst. B58, 380-388]. A systematic nomenclature is proposed for these species. Three modes of hydrogen bonding are described, characterized in part by the distance between contiguous O atoms: normal (NHB; O···O = 2.6-3.0 Å), charge assisted (CAHB; O···O = 2.5 Å) and molecular (MHB; O···O = 2.4 Å). The three modes are consistent with previous reports, our experimental results, and quantum-chemical-optimized geometries and energetics. No evidence is presented concerning the possible existence or stability of these aggregates in solution. Rather, emphasis is placed on the necessity in crystal structure analysis to develop thoroughly existing hydrogen-bonded networks, ignorance of which can lead to erroneous crystal structure models and other physico-chemical data associated with composition and charge balance.
authors.affiliation: Chemistry Department, Hunter College, City University of New York, New York, NY 10021, USA.
authors.forename: Ivan
authors.initials: I
authors.lastname: Bernal
authors.affiliation: Chemistry Department, Louisiana State University, Baton Rouge, LA 70803, USA.
authors.forename: Steven F
authors.initials: SF
authors.lastname: Watkins
keywords: Cambridge Structural Database search; hydrogen-bonding modes; hydroxonane; hydroxonate; hydroxone; hydroxonium; molecular ionic aggregates; organic crystalline hydrates; organometallic crystalline hydrates; supramolecular ionic aggregates; systematic nomenclature