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CuIn2n+1 S3n+2 crystals were synthesized by horizontal Bridgman method using high purity copper, indium, sulfur elements. The phases and crystallographic structure of the CuIn2n+1S3n+2 crystals were analyzed by X-ray diffraction (XRD) and the composition of the material powders was determined using the energy dispersive X-ray analysis (EDX). Measurement data revealed that CuIn2n+1S3n+2 materials have not the same structure. In fact, CuInS2 and CuIn3S5 crystallize in the chalcopyrite structure whereas CuIn5S8, CuIn7S11 and CuIn11S17 crystallize in the cubic spinel structure.