| O,O'-diaryldithiophosphates:(p-MeC6H4O)2PS2NH2Et2,(PhCH2O)2PS2 -NH2Et2, (PhCH2CH2O)2PS2NH2Et2,(p-C6H4O2)PS2NHEt3, (p-C6H4O2)PS2NHEt3 and their 20 transition metal complexes were synthesised in this paper,and the single crystals of the 14 complexes were obtained. The complexes were characterized by elemental analysis, IR spectra, UV-vis spectra and thermogravimetry analysis, and the single crystals were characterized by X-ray diffraction analysis. The complexes have been synthesised includ: complexes with tetraaza-macrocycle: [Ni(hmtade)][S2P(OC6H4Me-p)2]2 (1), [Cu(hmtade)] [S2P(OC6H4Me-p)2]2(2), [Ni(hmta)][S2P(OC6H4Me-p)2]2 (3), [Cu(hmta)] [S2P(OC6H4Me-p)2]2 (4), [Ag(hmtade)][S2P(OC6H4Me-p)2] (5), [Ni(hmtade)] [S2P(OMe)(o-HOC6H4O)]2 (6), [Ni(hmtade)] [S2P(O2C6H4)-p]2 (7), [Ni(hmta)] [S2P(O2C6H4)-p]2(8), [Cu(hmtade){S2P(O2C6H4)-p}](ClO4) (9), [Cu(hmta)] [S2P(O2C6H4)-p]2 (10), [Ag(hmtade)][S2P(O2C6H4)-p] (11); octanuclear cluster [Ag8(μ6-S){S2P(OC6H4Me-p)2}6]·DMF (12); coordination polymer {[(p-MeC6H4O)PS2]2Ag}n (13); Binuclear Silver complexes: {Ag2[(p-MeC6H4O) -PS2]2·Phen2} (14), {Ag2[(PhCH2O)2 PS2]2·Phen2} (15), {Ag2[(PhCH2CH2O)2 -PS2]2·Phen2} (16); ternary complex {Ni[S2PO(C6H4 Me-p)2]2.(PyMe-p)2} (17); Cr complexes: [(PhCH2CH2O)2PS2]3Cr (18), [(p-MeC6H4O)2PS2]3Cr (19), and [(p-C6H4O2)PS2]3Cr (20). Where lingand hmtade is 5,5,7,12,14,14-hexamethyl-1, 4,8,1-tetrazacyclotetradeca-4,11-diene, ligand hmta is 5,7,7,12,12,14-hexamethyl -1,4,8,1-tetrazacyclotetradrane, phen is 1,10-Phenanthroline and DMF is N,N'-dimethylformamide.All of the complexes 1, 3, 5, 6, 7, 8 and 10 contain MN4 square-planar conformation. All of the tetraaza-macrocycles, hmtade and hmta, are mesomer conformation, there are no M-S coordinate bond, but N-H···S hydrogen bonding or other non-classical hydrogen bondings have been found between (RO)2PS2- and hmtade / hmta,which make the complexes form a 2-dimensional or 3- dimensional structure.In the complex 9, the Cu(II) ion assumes a five-coordinated square pyramidal environmentis of CuN4S, the ClO4- ion doesn't coordinate to Cu(Ⅱ) ion, and the (o-C6H4O2)PS2- ion is a monodentate ligand, which lies in the apical position of the square pyramidal. The bond length for Cu-S is 0.27395 (11)nm, while the Cu-N in the range of 0.1978(3)0.2014(3)nm. The traaza-macrocycles hmtade is racemism which is saddle configuration.The octanuclear cluster 12 consists of eight Ag atoms, six (p-MeC6H4O)2PS2-, one S atom and one DMF molecular. eight Ag atoms form an distorted cube, Ag atoms locate at the corners of the distorted hexahedron, S atom locate at the center of the cube, one-dimensional stack is formed by C35-H35…O3 hydrogen bonds between cluster structure.The coordination polymer 13 is a one-dimensional polymer, a S atom from (p-MeC6H4O)2PS2- coordinate one Ag atoms, and the another S atom bridges two Ag atoms. One-dimensional zigzag chain structure is formed along the a axis, and the all silver atoms of the one -dimensional zigzag chain locate in a plane.In the binuclear silver complexes 14, 15 and 16, the Ag atom is coordinated by two S atoms from two (p-MeC6H4O)2PS2- ligands and two N atoms from one phen ligand, which form an chair conformation of eight-membered Ag2S4P2 ring,Ag atom is in a AgS2N2 distorted tetrahedral geometry. And one-dimensional stack is formed vis intermolecularπ-πinteractions between the phen ligands, which is further linked into three-dimensional networks by weak intermolecular C-H···O or C-H···πinteractions.In the complex 17, the Ni atom is coordinated by four S atoms of two bidentate ligand (p-MeC6H4O)2PS2- and two N atoms of two monodentate ligand 4-methylpyridines forming a compressed octahedral. The extensive C-H···O non-classic hydrogen bonding and C-H···πstack interactions lead to a 2-dimensional network structure in the crystal structure of the complex.In the complex 18, the Cr atom is coordinated environment by six S atoms from three bidentate ligand (PhCH2CH2O)2PS2-, which formed an distorted octahedral, the bond length for Cr-S is in the range of 0.24202(9) 0.24476(9)nm.The synthesis condition, IR, UV-vis spectra and thermogravimetric analysis of the complexes are also discussed in this paper.
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