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Single crystals of Na 2 Cu + [Cu 2+  3 O](AsO 4 ) 2 Cl ( 1 ) and Cu 3 [Cu 3 O] 2 (PO 4 ) 4 Cl 2  ( 2 ) were prepared by chemical vapor transport reactions. Both crystal structures are based upon the same [O 2 Cu 6 ] 8+  chains formed by corner-sharing (OCu 4 ) 6+  tetrahedra and interconnected by ( T O 4 ) 3−  ( T  = P, As) tetrahedra into porous {[OCu 3 ]( T O 4 ) 2 Cl} 3−  frameworks. The channels within the frameworks are occupied by Na + , Cu +  and Cl −  ions in the crystal structure of  1 , whereas the channels in the structure of  2  contain edge-sharing CuO 4 Cl tetragonal pyramids. Both compounds are structurally related to the previously described synthetic Na 2 Cu + [Cu 2+  3 O](PO 4 ) 2 Cl and NaCu 2+ [Cu 2+  3 O](PO 4 ) 2 Cl. The compound  2  is structurally and chemically related to yaroshevskite, Cu 3 [Cu 3 O] 2 (VO 4 ) 4 Cl 2 , a mineral discovered in volcanic fumaroles, but the two structure types are drastically different. The crystal chemical analysis of the title and related compounds allows to recognize a family of at least four compounds based upon {[OCu 3 ]( T O 4 ) 2 Cl} 3−  frameworks with channels occupied by different chemical constituents.

Na 2 Cu + [Cu 2+ 3 O](AsO 4 ) 2 Cl and Cu 3 [Cu 3 O] 2 (PO 4 ) 4 Cl 2 : two new structure types based upon chains of oxocentered tetrahedra