The structure of the intercalation complex (ND4 +)0.22(ND3)0.34 TiS2 0.22- has been determined by Rietveld refinement of time-of-flight neutron powder diffraction data taken at 298 and 12 K. This compound belongs to space group R3̄m, and the lattice parameters are a = 3.4170(3) A ̊ and c = 26.723(4) A ̊ at 298 K. No phase change was observed on cooling to 12 K. However, the c lattice parameter was observed to contract about 1.2%. Both ND4 + and ND3 occupy trigonal prismatic interlayer sites, with ND4 + exhibiting random spherical disorder and ND3 adopting a planar geometry. Two of the ND3 deuterium atoms are hydrogen bonded to host TiS2 sulfur atoms, whereas the third is found in the interlayer midplane and is not hydrogen bonded. The implications of this structure for the properties of such intercalation compounds is discussed.
Bibliographical noteFunding Information:
This study has benefited from the use of the Intense Pulsed Neutron Source at Argonne National Laboratory, which is funded by the U.S. Department of Energy, BES-Malerials Science, under contract U-31-109-Eng-38. We wish to thank R. L. Hitterman and J. Faber for data collection assistance. We a~ g~=~u~ io ~-= National Science Foundation for support through grant D~IR-841364102 and DMR-8605937, ~rizona Stale University for the necessary computer time, the Center for Solid State Science for the use of its Materials Preparation Facility and M. Wheeler and W. O~Neill for expert assistance in glassblowing.