Syntheses and structural characterizations of the first coordination polymers assembled from the Ni(cyclam)(2+) cation and the benzene-1,3,5-tri­carboxyl­ate linker

The asymmetric unit of catena-poly[[[(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ(4) N (1),N (4),N (8),N (11))nickel(II)]-μ(2)-5-carb­oxy­benzene-1,3-di­carboxyl­ato-κ(2) O (1):O (3)] octa­hydrate], {[Ni(C(9)H(4)O(6))(C(10)H(24)N(4))]·8H(2)O}( n ) (I), consists of a macrocyclic Ni(2+) cation, a carboxyl­ate dianion and eight highly disordered water mol­ecules of crystallization. The components of the compound catena-poly[[[(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ(4) N (1),N (4),N (8),N (11))nickel(II)]-μ(2)-5-carb­oxy­benzene-1,3-di­carboxyl­ato-κ(2) O (1):O (3)] monohydrate], {[Ni(C(9)H(4)O(6))(C(10)H(24)N(4))]·H(2)O}( n ) (II), are two crystallographically unique centrosymmetric macrocyclic dications, a carboxyl­ate dianion and one water mol­ecule of crystallization. In each compound, the metal ion is coordinated in the equatorial plane by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable trans-III conformation, and two mutually trans O atoms of the carboxyl­ate anions in a slightly tetra­gonally distorted trans-NiN(4)O(2) octa­hedral geometry. The crystals of both compounds are composed of parallel coordination polymeric chains running along the [010] direction in I and the [110] and [1 [Image: see text] 0] directions in II. The bridging carboxyl­ate anions display different modes of coordination connected with the relative orientation of coordinated O atoms, i.e., remote in I and inter­mediate in II, thus resulting in essentially different distances between the Ni atoms in the chains [11.0657 (4) and 8.9089 (2) Å in I and II, respectively]. As a result of hydrogen-bonding inter­actions, the chains are joined together in sheets oriented parallel to the (10 [Image: see text] ) and (001) planes in I and II, respectively.