Synthesis, structure and characterization of five new organically templated metal sulfates with 2‐aminopyridinium

The chemistry of organically templated metal sulfates has attracted interest from the materials science community and the development of synthetic strategies for the preparation of organic–inorganic hybrid materials with novel structures and special properties is of current interest. Sulfur–oxygen–metal linkages provide the possibility of using sulfate tetrahedra as building units to form new solid‐state materials. A series of novel organically templated metal sulfates of 2‐aminopyridinium (2ap) with aluminium(III), cobalt(II), magnesium(II), nickel(II) and zinc(II) were obtained from the respective aqueous solutions and studied by single‐crystal X‐ray diffraction. The compounds crystallize in centrosymmetric triclinic unit cells in three structure types: type 1 for 2‐aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate, (C 5 H 7 N 2 )[Al(H 2 O) 6 ](SO 4 ) 2 ·4H 2 O, (I); type 2 for bis(2‐aminopyridinium) tris[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate, (C 5 H 7 N 2 ) 2 [Co(H 2 O) 6 ] 3 (SO 4 ) 4 ·2H 2 O, (II), and bis(2‐aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis(sulfate) dihydrate, (C 5 H 7 N 2 ) 2 [Mg(H 2 O) 6 ] 3 (SO 4 ) 4 ·2H 2 O, (III); and type 3 for bis(2‐aminopyridinium) hexaaquanickel(II) bis(sulfate), (C 5 H 7 N 2 ) 2 [Ni(H 2 O) 6 ](SO 4 ) 2 , (IV), and bis(2‐aminopyridinium) hexaaquazinc(II) bis(sulfate), (C 5 H 7 N 2 ) 2 [Zn(H 2 O) 6 ](SO 4 ) 2 , (V). The templating role of the 2ap cation in all of the reported crystalline substances is governed by the formation of characteristic charge‐assisted hydrogen‐bonded pairs with sulfate anions and the presence of π–π interactions between the cations. Additionally, both coordinated and uncoordinated water molecules are involved in hydrogen‐bond formation. As a consequence, extensive three‐dimensional hydrogen‐bonding patterns are formed in the reported crystal structures.