Abstract
The results of in‐situ energy‐dispersive X‐ray diffraction under solvothermal conditions performed on isostructural, layered thioantimonates Mn~2~Sb~2~S~5~·L (L = amine) demonstrate the great potential of the method. When the synthesis was carried out at low temperatures with L being 1,3‐diaminopropane (DAP), two crystalline intermediate phases were detected which then grew and disappeared when product growth started. Surprisingly, when N‐methyl‐1,3‐diaminopropane (MDAP) was used, no crystalline intermediates could be detected and the induction time was significantly shorter than for DAP. For reactions up to 100 °C and for higher temperatures with α < 0.8 (α is the extent of reaction), the crystallisation is predominantly controlled by nucleation. Further progress of crystallisation (α > 0.8) leads to a change of the dominant process and a diffusion‐controlled mechanism is observed. During the reaction with diethylenetriamine (DIEN), three crystalline intermediates were detected prior to product growth. The induction time is longer than for the other two compounds. The crystallisation seems to be diffusion‐controlled and is faster than for the DAP and MDAP compounds. In a solution of DIEN, the crystalline phases Mn~2~Sb~2~S~5~·L (L = DAP or MDAP) are transformed into the DIEN product under solvothermal conditions, and a rigorous analysis of the intensities of the reflections suggests a partial dissolution of the crystalline starting materials followed by crystallisation of the DIEN material. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)