Crystal Structure Features, Spectroscopic Characteristics and Thermal Conversions of Sulfur-Bearing Groups: New Natural Commensurately Modulated Haüyne Analogue, Na6Ca2−x(Si6Al6O24)(SO42−,HS−,S2●−,S4,S3●−,S52−)2−y

A multimethodic approach based on infrared, Raman, electron spin resonance and photoluminescence spectroscopy, absorption spectroscopy in near infrared, visible and ultraviolet regions, single-crystal X-ray diffraction as well as electron microprobe analyses was applied to the characterization of a new commensurately modulated cubic haüyne analogue with the modulation parameter of 0.2 and unit-cell parameter of 45.3629(3) Å (designated as haüyne-45Å) from the Malobystrinskoe lazurite deposit, in the Baikal Lake area, Siberia, Russia, as well as associated SO32−-bearing afghanite. Haüyne-45Å is the second member, after vladimirivanovite, of the sodalite group with a commensurately modulated structure. The average structure is based on the tetrahedral aluminosilicate sodalite-type framework with sodalite cages of different sizes. The simplified formula of haüyne-45Å is Na6Ca2−x(Si6Al6O24)(SO42−,HS−,S2●−,S4,S3●−,S52−)2−y. The structural modulations of the haüyne-45Å framework are presumably related to the regular alternation of SO42− anions with polysulfide S2●−, S3●−, S4, and S52− groups detected by the spectroscopic methods. Mechanisms of thermal conversions of S-bearing groups in haüyne-45Å under oxidizing and reducing conditions at temperatures up to 800 °C are studied, and their geochemical importance is discussed.