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The new polymorph of Na 2 Mn 3 (SO 4 ) 4  was prepared via solid state reaction route in a powder form and its crystals were grown by self-flux method. The crystal structure was determined from single crystal X-ray diffraction data. This polymorph crystallizes with an orthorhombic symmetry, space group  Pbca , with  a  = 9.8313(4),  b  = 8.7467(3),  c  = 29.6004(11) Å,  V  = 2545.38(17) Å 3 ,  Z  = 8. Its structure refinement yielded the residual factors  R ( F ) = 0.025 and  wR ( F  2 ) = 0.065 for 227 parameters and 2605 independent reflections at 2 σ(I)  level. The use of group-subgroup schemes in the Bärnighausen formalism enabled an accurate comparison of the  Pbca - and  Cmc  2 1 -polymorphs of Na 2 Mn 3 (SO 4 ) 4 . Both polymorphs contain similar [Mn 3 (SO 4 ) 4 ] 2−  building blocks formed of Mn 2 O 11  dimer units and MnO 5  trigonal pyramids that are interconnected by sharing corners with the SO 4  tetrahedra. However, the stacking of these building blocks along the longest axes of the  Pbca - and  Cmc  2 1 -structures is different. This induces differences in the coordination of the sodium atoms and in the orientation of the SO 4  tetrahedra.

Crystal structure of a new polymorphic modification of Na 2 Mn 3 (SO 4 ) 4