Solid solution investigations in the CsHSO4-CsH2PO4system, carried out as part of an ongoing effort to elucidate the relationship between proton conduction, hydrogen bonding, and phase transitions, yielded the new compound Cs5(HSO4)3(H2PO4) 2. Single-crystal X-ray diffraction methods revealed that Cs5(HSO4)3(H2PO4) 2crystallizes in space groupC2/c(or possiblyCc), has lattice parametersa=34.066(19) Å,b=7.661(4) Å,c=9.158(6) Å, andβ=90.44(6)°, a unit cell volume of 2389.9(24) Å3, a density of 3.198 Mg m-3, and four formula units in the unit cell. Sixteen non-hydrogen atoms and five hydrogen sites were located in the asymmetric unit, the latter on the basis of geometric considerations rather than from Fourier difference maps. Refinement using anisotropic temperature factors for all non-hydrogen atoms and fixed isotropic temperature factors for all hydrogen atoms yielded residuals based onF2(weighted) andFvalues, respectively, of 0.0767 and 0.0340 for observed reflections [F2>2σ(F2)]. The structure contains layers of (CsH2XO4)2that alternate with layers of (CsHXO4)3, whereXis P or S. The arrangement of Cs, H, andXO4groups within the two types of layers is almost identical to that in the end-member compounds, CsH2PO4and CsHSO4-II, respectively. Although P and S each reside on two of the threeXatom sites in Cs5(HSO4)3(H2PO4) 2, the number of protons in the structure appears fixed. In addition, the correlation of S-O and S-OH bond distances with O···O distances, where the latter represents the distance between two hydrogen-bonded oxygen atoms, was determined from a review of literature data.
ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Ceramics and Composites
- Condensed Matter Physics
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry