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Using solution evaporation techniques, we succeeded in preparation of new members essentially extending the layered copper hydrogen selenite family, ( AX )[Cu(HSeO 3 ) 2 ] with  A  = Na, K, Rb, Cs, and NH 4 , and  X  = Cl and Br. Bromides and chlorides are isostructural in the family of described new compounds crystallizing in three different structure types. (Na X )[Cu(HSeO 3 ) 2 ] and (K X )[Cu(HSeO 3 ) 2 ] ( X  = Cl, Br) are monoclinic, whereas ( AX )[Cu(HSeO 3 ) 2 ] ( A  = NH 4 , Rb, Cs;  X  = Cl, Br) are orthorhombic. Upon the enlargement of the  A  +  ionic radii inserted in the interlayer between the neighboring [Cu(HSeO 3 ) 2 ] slabs, the effective distance is increasing and results in essential elongation of the apical Cu- X  ( X  = Cl, Br) distances. Three different types of CuO 4  X  n  ( n  = 0–2) polyhedra are formed. The observed trend is an interesting example of the chemical tuning of the Cu 2+  coordination environments.

zeitschrift für kristallographie - crystalline materials 

Influence of the alkali cation size on the Cu 2+  coordination environments in ( AX )[Cu(HSeO 3 ) 2 ] ( A =Na, K, NH 4 , Rb, Cs;  X =Cl, Br) layered copper hydrogen selenite halides