Syntheses, crystal structures and supramolecular topologies of copper(II)–main group metal complexes derived from N,N′-o-phenylenebis(3-ethoxysalicylaldimine)

The work in the present investigation reports the syntheses, crystal structures and supramolecular topologies of 11 copper(II)–main group metal ion complexes [CuIILNaI(NO3)(H2O)]·2CH3CN (1), [CuIILNaI(N3)(CH3OH)]·CH3OH (2), [CuIILNaI(ClO4)(CH3CN)]·0.5CH3CN (3), [CuIILNaI(BF4)(CH3OH)]·H2O (4), [{CuIILNaI(H2O)}2(CuIIL)](BPh4)2 (5), [CuIILKI(ClO4)(CH3COCH3)] (6), [CuIILCaII(ClO4)2(H2O)] (7), [{CuIILCaII(NO3)(μ-NO3)(H2O)}(CuIIL)]·H2O·CH3COCH3 (8), [(CuIIL)2BaII(NO3)2]·CH3OH (9), [CuIILPbII(NO3)2]·CH3OH (10) and [CuIILBiIII(NO3)3]·CH3COCH3 (11), where H2L = N,N′-o-phenylenebis(3-ethoxysalicylaldimine). Among these, eight (1–4, 6, 7, 10 and 11) are dinuclear compounds, one (9) is trinuclear double-decker sandwich compound, one (8) is a [2 × 1 + 1 × 1] trimetallic cocrystal of a dinuclear and a mononuclear units and the remaining (5) is a [2 × 2 + 1 × 1] pentametallic cocrystal of two dinuclear and one mononuclear units. All the 11 compounds 1–11 contain one or more deprotonated ligand, L2−, the salen type N2O2 compartment of each of which is occupied by a CuII ion to result in the formation of a [CuIIL] moiety. On the other hand, the larger and open O(phenoxo)2O(ethoxy)2 compartment of the ligand in one or more [CuIIL] moieties interact (s) with the metal ions NaI (1–5)/KI (6)/CaII (7 and 8)/BaII (9)/PbII (10)/BiIII (11) to produce the title compounds. It has been observed that the neighbouring di/trinuclear units in 1/3/4/6/9/10/11 are self-assembled to one-/two-dimensional topologies as a result of one or more CH⋯O/OH⋯O hydrogen bonding interaction (s). Following self-assemblies are observed: one-dimensional in 4, one-dimensional helical in 1, one-dimensional double-chain (ladder) in 3, 6 and 10, two-dimensional in 9 and 11.

► N,N′-o-phenylenebis(3-ethoxysalicylaldimine) is utilized as the blocking ligand. ► Eleven heterometallic CuIINaI/KI/CaII/BaII/PbII/BiIII complexes are described. ► All the 11 compounds are characterized by single-crystal X-ray structures. ► The complexes are di-/tri-/pentanuclear including [2 × 1 + 1 × 1]/[2 × 2 + 1 × 1] cocrystals. ► Weak interaction assisted one- or two-dimensional self-assemblies are generated.