Synthesis of chloroantimonates(III) with selected organic cations. X-ray studies of phase transition in ferroelectric tris(trimethylammonium) nonachlorodiantimonate(III) at 125K

Single crystal X-ray diffraction studies on [(CH3)nNH4–n]3[Sb2Cl9] (, 3) chloroantimonates(III) in their low-temperature ferroelectric phases—structures and phase transitions

“…A previous structure determination [5] has shown that at 165 K the N3B cation in TMACA is ordered and it remains so at 95 K. Our data at 15 K further confirm this Table 2 Atomic coordinates ( Â 10 4 ) and equivalent isotropic displacement parameters (Å 2 Â 10 3 ) for non-hydrogen atoms of DMACA at 100 and 15 K, and of TMACA at 15 K…”

“…2). The overall pattern of distortions and geometry of the Sb-Cl bond lengths and Cl-Sb-Cl angles within these anionic layers at 100 and 15 K are similar to those found at higher temperatures as well as other chloroantimonates(III) containing the same anionic layers [5,14,18,27,28,33,34]. The only difference is that one out of the three bridging chlorine atoms was found to be disordered in the structure of TMACA at 373 K. Its position is split between two sites with half occupancy [28].…”

“…1). As a result of the ordering, new and somewhat stronger hydrogen bonds are formed, as previously reported for TMACA [5]. These hydrogen bonds, as well as the inter-ionic interactions, cause a deformation of the inorganic [SbCl 6 ] 3-octahedra.…”

“…Differences in the size, symmetry and ability to form hydrogen bonds of the various possible organic cations, together with the many different possible metal-halogen atom configurations provide a rich family of compounds. The anionic structures which have been reported so far range from simple isolated [MX 6 ] 3-octahedra and [MX 5 ] 2-square pyramids (MSb III , Bi III ; X-Cl, Br, I) through isolated units containing octahedra/square pyramids, connected by corners, edges or faces, to infinite one-or two-dimensional polyanionic structures [1][2][3][4][5].…”

Synthesis and Crystal Structure of Penthylenediammonium pentabromobismutate(III) [NH3(CH2)5NH3]BiBr5

“…The anionic structures that have been reported so far range from simple isolated [MX6] 3-octahedra and [MX5] 2-square pyramids (M-Sb III , Bi III ; X-Br, Cl, I) through isolated units containing octahedra/square pyramids, connected by corners, edges or faces, to infinite one-or two-dimensional polyanionic structures. 1,2 Single crystals of [NH3(CH2)5NH3]BiBr5 were obtained in the reaction of Bi(NO3)3 with NH2(CH2)5NH2 with a large excess of HBr. The synthesized compound was purified by repeated crystallizations.…”