Structural characterization, molecular dynamics, dielectric and spectroscopic properties of tetrakis(pyrazolium) bis(μ2-bromo-tetrabromobismuthate(III)) dihydrate, [C3N2H5]4[Bi2Br10]·2H2O

Abstract: The structure of [C3N2H5]4[Bi2Br10]·2H2O, (PBB) was determined by single crystal X-ray diffraction at 100K. It crystallizes in the monoclinic space group C2/m, with a =12.992(4)Å, b =16.326(5)Å, c =8.255(3)Å, β =108.56°(3), V =1659.9(9)Å3 and Z =2. The structure consists of discrete binuclear [Bi2Br10]4− anions, ordered pyrazolium cations and water molecules. The crystal packing is governed by strong N–H⋯O and weak O–H⋯Br hydrogen bonds. A sequence of structural phase transitions in PBB was established on the basis of differential scanning calorimetry and dilatometric studies. Two reversible first-order phase transitions were found: (I→II) at 381/371K (on heating/cooling) and (II→III) at 348/338K. Dielectric response near both phase transitions is characteristic of crystals with the “plastic-like” phases. Over the phase III a low frequency dielectric relaxator is disclosed. The possible molecular motions in the PBB compound are characterized by the 1H NMR studies. The infrared spectra of polycrystalline compound in the temperature range 300–380K are reported for the region 4000–400cm−1. The observed spectral changes through the structural phase transition III→II are attributed to an onset of motion both of the pyrazolium cations and water molecules. [Copyright &y& Elsevier]