Heterometallic Trinuclear Ni_2Zn and Ni_2Mn Complexes of Macrocyclic Oxamide: Synthesis and Crystal Structures

Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn（NiL）2（HBTC）H2O] （1） and [Zn（NiL）2（HBTC）H2O] （2） （NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid） have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595（5）, b = 23.1498（11）, c = 17.2558（8） and =101.2530（10）°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214（8）, b = 20.6566（14）, c = 18.4126（13） and = 92.6770（10）°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.

Synthesis,Structure and Luminescence of Zn_(4.5)Cu_3 Heteronuclear Coordination Polymer Comprising Macrocyclic Oxamide and 5-Sulfosalicylic Ion

The complex [Zn4.5（SSA）3（CuL）3（H2O）6]n was synthesized and structurally determined, where SSA is fully deprotonated 5-sulfosalicylic acid（CuL, H2L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca- 7,13-dien）. The title complex crystallized in the triclinic system with space group P1^-, a=1.19788（17） nm, b=1.4253（2） nm, c=2.2890（4） nm, α=90.211（2）°, ,β=93.076（2）°, γ=90.600（2）°. The complex displayed a 1D ladderlike chain. All these 1D chains were further interlinked via hydrogen bonds, resulting in a 2D architecture. The luminescent property of the compound was also discussed.

Syntheses and Structures of Two Coordination Polymers Containing Macrocyclic Oxamide and Isophthalic Acid Derivatives

Two novel coordination polymers [Cd（NiL）（aipt）]（1） and [Mn（nipt）（NiL）2]？H2O（2）（NiL, H2L=2,3-dioxo- 5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H2aipt=5-aminoisophthalic acid, H2nipt=5-nitroisoph- thalic acid） were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compounds 1 and 2 consist of different 1D chains including both oxamide and 5-aminoisophthalate or 5-nitroisophthalic bridge. And all these chains were further interlinked via hydrogen bonds, resulting in a 2D architecture in compounds 1 and 2.

Synthesis and Crystal Structure of Unprecedented Pentanuclear Cu_5~Ⅱ Complex Containing both Macrocyclic and Azido Ligands

The organic-inorganic hybrid complex with formula [（CuL）2Cu3（μ-1,1-N3）4（ClO4）2], complex 1, {CuL, [5,6：14,l5-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,3-diene-2,3-dione（2-）]copper（Ⅱ）}, has been synthesized and structurally determined. The crystals of complex 1 crystallize in the triclinic system with space group P1, a=0.92983（12） nm, b=1.09644（14） nm, c=1.27396（16） nm, α=70.782（2）°β=86.266（2）°,γ=78.284（2）°. In this complex, the five copper ions are bridged by macrocyclic oxamide groups and azido. Furthermore, C-H…O hydrogen bond interactions link the pentanuclear fragments to form a 2D supramolecular architecture.

Crystal Structure and Magnetic Properties of the Oxamidato-bridged Cu_3 Complex Containing Macrocyclic Ligands

One novel oxamido-bridged trinuclear complex [Cu（CuL）2（ClO4）2] has been syn-thesized and structurally determined.It crystallizes in the monoclinic system,space group P21/n with a = 10.636（4）,b = 11.645（4）,c = 16.038（6） ,β = 91.029（5）°,V = 1986.2（12） 3,C38H32Cl2Cu3N8O12,Mr = 1054.24,Dc = 1.763 Mg/m3,μ（MoKα） = 1.802 mm-1,F（000） = 1066,Z = 2,the final R = 0.0328 and wR = 0.0882 for 3152 observed reflections.The crystal structure is a trinuclear complex in which the CuII ions are bridged by macrocyclic oxamide groups.C-H···O hydrogen bonding interactions link the trinuclear fragment to form a 2D supramolecular architecture.Magnetic measurements indicate that the compound is moderately antiferromagnetically coupled.