Vibrational behavior of matrix-isolated ions in Tutton compounds. II. Infrared spectroscopic study of and ions included in copper sulfates and selenates

Vibrational behavior of matrix‐isolated ions in Tutton compounds IV. Infrared spectroscopic study of NH4+ and SO42‐ ions included in nickel sulfates and selenates

“…The inclusion of NH 4 + leads to the formation of new hydrogen bonds between the guest cations and the XO 4 2-host ions additionally to those with water molecules, thus resulting in the decrease of the proton acceptor capabilities of the anions (anticooperative or proton acceptor competitive effect). The same phenomenon was observed when ammonium ions are incorporated in the crystals of the respective magnesium and copper Tutton compounds [1,2]. It is worthy of note that the shifts of water librations in the mixed crystals K 2-x (NH 4 ) x Ni(XO 4 ) 2 ·6H 2 O are smaller than those in the respective magnesium compounds K 2-x (NH 4 ) x Mg(XO 4 ) 2 ·6H 2 O and larger than those in the respective copper ones K 2-x (NH 4 ) x Cu(SeO 4 ) 2 ·6H 2 O.…”

“…As figure 5d shows the inclusion of ammonium ions in the structure of K 2 Ni(SeO 4 ) 2 ·6H 2 O leads to the appearance of four infrared bands corresponding to matrix-isolated ammonium ions (the crystal field effect is ignored). As was commented in the Introduction this phenomenon was also observed when ammonium ions are included in the respective potassium copper selenate [2]. Taking into account all these considerations we believe that the four bands for ν 4 of the ammonium cations in the spectrum of (NH 4 ) 2 Ni(SeO 4 ) 2 ·6H 2 O as well as in the spectra of the K 2-x (NH 4 ) x Ni(SeO 4 ) 2 ·6H 2 O mixed crystals could be attributed to some kind of disorder of these ions, i.e.…”

“…Recently, we have published infrared spectra of SO 4 2-and NH 4 + ions included in the magnesium and copper Tutton salts [1,2]. The spectroscopic experiments allowed us to draw several main conclusions: (i) The matrixisolated SO 4 2-ions in the structures of the selenate compounds (concentration of the guest ions up to 5-7 mol%) exhibit three infrared bands for ν 3 and one band for ν 1 in good agreement with the low site symmetry C 1 of the host selenate ions.…”

Crystal growth, structure, crystalline perfection and characterization of zinc magnesium ammonium sulfate hexahydrate mixed crystals ZnxMg(1−x)(NH4)2(SO4)2·6H2O

“…The crystal structure of magnesium ammonium sulfate hexahydrate [1,2] and zinc ammonium sulfate hexahydrate [3] has been reported. Ballirano et al [4] have investigated the Rietveld refinement of the Tutton's salt Rb 2 [Cu(H 2 O) 6 ](SO 4 ) 2 by parallel-beam X-ray powder diffraction. Detailed studies on vibrational patterns of SO 4 2À and NH 4 þ ions in Tutton's salts have been carried out [5][6][7][8].…”

“…Ballirano et al [4] have investigated the Rietveld refinement of the Tutton's salt Rb 2 [Cu(H 2 O) 6 ](SO 4 ) 2 by parallel-beam X-ray powder diffraction. Detailed studies on vibrational patterns of SO 4 2À and NH 4 þ ions in Tutton's salts have been carried out [5][6][7][8]. The single crystal EPR studies on Fe(III) [9], Cr(III) [10], VO(II) [11], Cu(II) [12], and Mn(II) [13] doped Tutton's salts are studied.…”