title: Anhydrous ammonioguanidinium(2+) and dihydrated bis[aminoguanidinium(1+)] hexafluorosilicates: new co-products of preparing ferroelectric ammonioguanidinium(2+) hexafluorozirconate.
abstract: Ammonioguanidinium hexafluorosilicate, CH8N4(2+).SiF6(2-), and bis(aminoguanidinium) hexafluorosilicate dihydrate, 2CH7N4+.SiF6(2-).2H2O, are new materials formed as by-products in course of preparing ferroelectric CH8N4ZrF6 in the presence of glassware. Their structures were determined for comparison with the corresponding hexafluorozirconates. All atoms including the eight H atoms in the CH8N4(2+) cation and the seven H atoms in the CH7N4+ cation have been located and refined with wR(F2) = 0.0653, R = 0.0255, S = 1.146 and wR(F2) = 0.0745, R = 0.0301, S = 1.065, respectively. The N2C-N-N backbone of the 2+ cation is close to planarity, while that of the 1+ cation does not differ significantly from planarity. The SiF6(2-) octahedron is nearly ideally regular in both materials, with < Si-F > = 1.684 (unbiassed estimator of standard uncertainty = 0.016) A in the anhydrous hexafluorosilicate and 1.6801 (unbiassed estimator of standard uncertainty = 0.0006) A in the dihydrate. The combination of coulombic and NH...F interactions in CH8N4SiF6 results in a relatively dense variant of the NaCl structure. In addition to similar forces, the dihydrate is also characterized by the role of the water molecule with its strong NH...O interactions; its packing efficiency is, however, appreciably less than that of the anhydrous hexafluorosilicate with an approximately 8% increase in void space. Cleaved crystals of the dihydrate are frequently twinned across the (001) composition plane, with a twofold rotation about the b axis as the twin operation.
authors.affiliation: Department of Structural Biology, St. Jude Children's Research Hospital, Memphis, TN 38105-2794, USA.
authors.forename: C R
authors.initials: CR
authors.lastname: Ross
authors.forename: M R
authors.initials: MR
authors.lastname: Bauer
authors.forename: R M
authors.initials: RM
authors.lastname: Nielson
authors.forename: S C
authors.initials: SC
authors.lastname: Abrahams
mesh_terms: D003460:Crystallization; D018360:Crystallography, X-Ray; D019791:Guanidine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure
chemical_list: C118966:anhydrous ammonioguanidinium(2+); C118968:dihydrated bis(aminoguanidinium(1+))hexafluorosilicate; C118967:ferroelectric ammonioguanidinium(2+)hexafluorozirconate; D019791:Guanidine