A chiral salency complex,[Mn(Salency)(H2O)2](PF6)·2H2O 1(Salency =(R,R)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine),has been prepared by the reaction of Mn(CH3COO)3·2H2O with Salency and NH4PF6,and was established by X-ray diffraction techniques.The complex crystallizes in triclinic,space group P1 with a=9.299(8),b=10.012(8),c=13.461(11),α=92.037(15),β=92.974(12),γ=93.530(18)°,V=1248.3(18)3,C20H28F6MnN2O6P,Mr = 592.35,Z=2,Dc=1.038 g/cm3,F(000)=608,μ=0.676 mm-1,the final R=0.0651 and wR=0.1880 for 5260 observed reflections with I > 2σ(I).
Two one-dimensional chain-like cyanide-bridged compounds, [Fe(Phen)2(CN)2Ni-(Cyclam)](ClO4)2·DMF·2H2O 1 (Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, Phen = 1,10-phenan-throline, and DMF = N,N-dimethylformamide) and [Fe(Phen)2(CN)2Zn(Cyclam)](PF6)2·CH3CN 2, were prepared by the reaction of [Fe(Phen)2(CN)2]·2H2O with M(Cyclam)2+ (M = Ni, Zn). In complexes 1 and 2, the metal atoms are connected alternatively with CN groups. X-ray structure and IR analyses for 1 and 2 were performed. Structure analysis revealed that both complexes are centrosymmetric and the geometry around each metal atom is an octahedron. The two complexes crystallize in triclinic with space group of P1. For 1, a = 10.439(4), b = 14.976(7), c = 15.914(8) , α = 83.168(15), β = 74.338(15), γ = 78.023(15)°, V = 2338.3(18) 3, Z = 2, Mr = 1035.37, Dc = 1.471 g/cm3, F(000) = 1076, μ = 0.895 mm-1, the final R = 0.0616 and wR = 0.1414 for 5849 observed reflections (I > 2σ(I)). For 2, a = 9.656(6), b = 15.404(9), c = 15.822(10) , α = 78.68(2), β = 78.917(19), γ = 77.15(2)°, V = 2223(2) 3, Z = 2, Mr = 1064.87, Dc = 1.587 g/cm3, F(000) = 1078, μ = 1.032 mm-1, the final R = 0.0672 and wR = 0.1595 for 6819 observed reflections (I > 2σ(I)).
The title compound bis(1-(4-(dimethylamino)benzylidene)-4-phenylthiosemicar-bazato)-palladium(Ⅱ)(PdL2) was obtained by reacting 1-(4-(dimethylamino)benzylidene)-4-phenyl-thiosemicarbazide with dichlorobis(benzonitrile)palladium(Ⅱ) in methanol,and its structure was characterized by single-crystal X-ray diffraction.The crystal of PdL2 was obtained in dimethyl-formamide(DMF) solvent with solvent molecules involved in the cell and crystallizes in the monoclinic system,space group C2 with a = 18.485(15),b = 7.090(5),c = 17.595(11) ,β = 121.21(3)o,V = 1972(2) 3,Z = 2,Mr = 847.40,Dc = 1.427 g/cm3,μ = 0.624 mm-1,F(000) = 880,R = 0.0607 and wR = 0.1358.The Pd atom adopts a distorted square planar coordination geometry with two Pd-N and two Pd-S bonds.The ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via mercapto sulfur and the imine nitrogen atom,which binds to palladium as bidentate N,S-donors forming five-membered chelate rings.The complex formed hydrogen bonding interaction with solvent DMF molecules from the hydrogen of phenylamine to the oxygen of DMF and several intramolecular hydrogen bonds.Pd(Ⅱ) perturbed ligand π-π* transition and metal-to-ligand charge transfer(MLCT) transition are observed in its electronic absorption spectra.The complex exhibits intraligand 1π-π*(IL) state and MLCT state dual fluorescent emissions in organic solvent at room temperature.
A new thiostannate,[tmdpH2]Sn3S7 1(tmdp = 4,4'-trimethylenedipiperidine),has been synthesized under solvothermal conditions and characterized by elemental analysis,IR spectroscopy,and single-crystal X-ray diffraction analysis.In 1,the Sn3S4 secondary incomplete cubane-like building units are bridged by μ2-S atoms to form Sn12S12 rings which are then joined parallelly to the [001] plane,giving the final 2D(Sn3S72-)n layer of(6,3) network.The layers are stacked along the c axis so that 24-membered ring channels are generated,in which the organic cations are accommodated.The compound crystallizes in monoclinic,space group C2/c,with a=23.052(3),b=13.4039(12),c=18.412(2),β=120.112(4)°,V=4921.3(9)3,C13H28N2S7Sn3,Mr=792.86,Z=8,Dc=2.140 g/cm3,F(000)=3056,μ=3.619 mm-1,the final R=0.0488 and wR=0.1125 for 4607 observed reflections with I>2σ(I).
A dinuclear copper(Ⅱ) complex,[Cu2(HL)2(H2O)6] 1(H3L = 2,4,6-tri(3-carboxy-phenylthio)-1,3,5-triazine),was synthesized hydrothermally and characterized by single-crystal X-ray diffraction,IR and thermal analysis.Single-crystal X-ray diffraction reveals that complex 1 is a dinuclear copper(Ⅱ) complex,which is further extended to a 3D network by weak interactions such as O…H-O hydrogen bonds and noncovalent S...S interactions.The crystal of compound 1 belongs to monoclinic,space group C2/c,with a = 50.15(2),b = 6.789(3),c =15.667(8) ,β = 90.588(9)o,V = 5334(4) 3,Z = 4,C48H38Cu2N6O18S6,Mr = 1306.28,Dc = 1.627 g/cm3,F(000) = 2664,Rint = 0.0631,T = 293(2) K,μ = 1.112 mm-1,the final R = 0.0661 and wR = 0.1850 for 3782 observed reflections with I > 2σ(I).
2-Thioxo-1,2-dihydrobenzo[d][1,3]thiazin-4-one(TDBTO),a new thiazin-one derivative,was synthesized and investigated.The crystal structure of TDBTO(C8H5NOS2,Mr = 193.8) was determined by single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P1 with a = 6.946(3),b = 7.402(3),c = 8.954(4) ,α = 66.931(7)o,β = 89.866(7)o,γ = 72.289(7)o,V = 399.8(3) 3,Z = 2,Mr = 195.25,Dc = 1.622 g/cm3,μ = 0.606 mm-1,F(000) = 200,R = 0.0361 and wR = 0.1032.There exist intermolecular hydrogen bond of N(1)-H(1A)···O(1) and weak C(6)-H(6A)···O(1) contact in the structure as well as face-to-face π-π stacking interactions between the benzene ring and the thiazin ring of an adjacent benzo-thiazin unit.The photoinduced proton transfer reaction,transforming the initial thione into thiol form,was found,and the latter form was characterized by UV absorption spectra,fluo-rescence spectra and infrared spectra.
