The Synthesis And Crystal Structure Research Of Acylthiourea And Its Coordination Compounds

The research of thiourea coordination compound with trans metal got progress rapidly in recent year. The coordination compounds of thiourea show good bioactivities and may be used in pharmacy industry to produce antitumor and antifungal drug, and thin films can be prepared by spray pyrolysis method using thiourea coordination compounds as starting materials. Some carbonyl thiourea coordination compounds can be self-assembled into supramolecular ring structure, and also could be applied in the design and synthesis of three-dimension supramolecular cage structure. Relying on the good chelate ability, thiourea coordination compound also could be used in the extraction of trace metal and the separation of platinum group metal, and may be applied in the anion acceptor recognition etc. In order to research the coordination activity of acylthiourea and trans metal ions, thirteen acylthiourea ligands and thirty-five Cu(II) coordination compounds were synthesized and characterized, and their crystal structures and characters were discussed herein.1. A brief review of the research situations of the synthesis of thiourea ligands and crystal structures of acylthiourea coordination compounds, and the applications of thiourea coordination compounds was given here.2. Thirteen acylthiourea ligands and thirty-five Cu(II/I) coordination compounds were synthesized and characterized by element analysis, IR and 'H NMR etc. There are two series of thiourea ligands: N-benzoyl-N'-(bis)hydroxyethyl-thiourea (N1, N2) and N-ethoxycarbonyl-N'-substituted- phenylthiourea (L^L11) as show below:N1: N-benzoyl-N'-(2-hydroxyethyl)thiourea;N2: N-benzoyl-N'-(2,2-bishydroxyethyl) thiourea;L1: N-ethoxycarbonyl-N'-o-nitrophenylthiourea;L2: N-ethoxycarbonyl-N'-m-nitrophenylthiourea;L3: N-ethoxycarbonyl-N'-p-nitrophenylthiourea; L4: N-ethoxycarbonyl-N'-o-methylphenylthiourea; L5: N-ethoxycarbonyl-N'-m-methylphenylthiourea; L6: N-ethoxycarbonyl-N'-p-methylphenylthiourea;L7L9N-ethoxycarbonyl-N'-o-chlorophenylthiourea; L8 :N-ethoxycarbonyl-N'-p-chlorophenylthiourea;N-ethoxycarbonyl-N'-p-methyloxyphenylthiourea; L10: N-ethoxycarbonyl-N'-o-methyloxyphenylthiourea; L11: N-ethoxycarbonyl-N'-phenylthiourea.The corresponding coordination compounds [N12X(X=A, B, C), L1-10X(X=A, B, C)] were obtained by the reaction of thiourea ligands with CuSO45H2O (No. A), Cu(NO3)2 3H2O(No. B) and CuCl2 2H2O(No. C).The experiment affirmed that in the coordination reaction of N-substituted-phenyl-N'-ethoxycarbonylthiourea with Cu(II), Cu(II) is reduced into Cu(I) by one part of thiourea, and another part of thiourea is coordinated with Cu(I) and formed 1:2 coordination compound.The experiment also found that in the coordination reaction of N-benzoyl-N1-hydroxyethyl thiourea with cupric chloride, the desulfurisation of thiourea ligand results in oxazoline ring coordinated with central ion, and this synthesis method of oxazoline coordination compound is not reported by previous literatures.3. The following crystal structures of two thiourea ligands and four coordination compounds were analyzed:In the crystal structures of N-benzoyl-N'-hydroxyethyl thiourea and N-ethoxy-carbonyl-N'-phenylthiourea, the six-membered hydrogen ring structure is formed by the attraction of acyloxygen atom to thioamino H atom, and one-dimension supramolecular long chain structures are formed by intermolecular hydrogen bonds.In the crystal structure of trans-bis(2-benzamido)oxazoline copper (II) coordination compound, acyl oxygen atom and nitrogen atom of oxazoline ringcoordinate with central Cu(II), and the 1:2 coordination compound is formed. The coordination structure of central Cu(II) is planar square.cis-bis[N-ethoxycarbonyl-N-(o-methylphenyl)thiourea]copper(I) chloride,cis-bis[N-ethoxy-carbonyl-N-(m-methylphenyl)thiourea]copper(I) chloride and cis-bis[N-ethoxycarbonyl-N-(p- methylphenyl)thiourea]copper(I) chloride are all 1:2 coordination compounds. The coordination structures of central Cu(I) is plan...