Rare-earth chromium borates RCr3(BO3)4, where R = La-Er, obtained as a result of spontaneous solutionmelt crystallization and belonging to two polytypic modifications (R32 (D 73 ) and C2/c (C62h ) space groups) are studied by infrared spectroscopy with the factor group analysis of vibrations. Borates with R = La-Nd are shown to crystallize in the monoclinic C2/c space group. Borates with R = Sm-Er in the 1:1 ratio of batch and solvent form rhombohedral (R32 space group) and monoclinic (C2/c space group) phases at the 2.3:1 ratio, except EuCr3(BO3)4 and GdCr3(BO3)4 that have the rhombohedral structure under all crystallization conditions. Both rhombohedral and monoclinic polytypes may contain oppositely ordered layers. Y-, Tm-, Yb-, Lu-chromium borates are not formed.
Rare-earth aluminum borates RAl3(BO3)4 (R = Y, Nd-Yb) obtained by spontaneous high-temperature flux crystallization form two polytype modifications described by the space groups R32 (D73 ) and C2/c (C62h ). They differ in the symmetry versions in mutual arrangement of layers. These borates have been investigated by mid- and far-IR spectroscopy in combination with factor-group analysis of the vibrations of BO 3−3 ions; translational motions of Al3+, R3+ (Y, Nd-Yb), and BO 3−3 ions; and BO 3−3 rotations. Rare-earth aluminum borates are assigned to different space groups according to their IR spectra. Borates with large rare-earth Nd and Pr cations are crystallized into the space group C2/c (C62h ), while borates with smaller (Y, Sm-Yb) ions are crystallized into the space group R32 (D73 ). The rhombohedral structure of the latter compounds includes monoclinically ordered domains, as is evidenced by the presence of monoclinic-phase bands in the IR spectrum. NdAl3(BO3)4 and SmAl3(BO3)4 can form both monoclinic and rhombohedral polytypes. The IR spectrum of the monoclinic SmAl3(BO3)4 phase contains bands due to the rhombohedral phase, while the IR spectrum of NdAl3(BO3)4 (which is described by the space group R32) contains bands due to the monoclinic polytype. The presence of domains with another arrangement of layers in the polytype structure is a characteristic sign that corresponds to the order-disorder theory; this theory explains the structure of polytypes.