Syntheses and crystal structures of Zn(II) and Co(II) complexes with ofloxacin and enoxacin

[Zn(Ofl) · (H₂O)] · 2H₂O (1) and [Co(Enox)₂] · 4H₂O (2) were obtained by hydrothermal reactions. The solid-state structures have been characterized by IR spectroscopy and single crystal X-ray diffraction analyses. Complex 1 crystallizes in the triclinic system, space group P 1, with lattice parameters a = 9.2923(5), b = 11.3432(6), c = 17.7722(10) Å, α = 92.839(3), β = 94.826(3), γ = 91.909(3)°, V = 1863.01(18) ų, Z = 2, D _Calcd = 1.494 mg m^?3. The coordination environment around Zn²⁺ is a slightly distorted square pyramid. Complex 2 crystallizes in the triclinic system, space group P2(1)/c, with lattice parameters a = 5.97980(10), b = 21.4183(3), c = 13.1539(2) Å, V = 100.2810(10), Z = 2, D _Calcd = 1.526 mg m^?3, Co(II) ion is a distorted octahedral geometry.     

Syntheses and crystal structures of bis(4-dimethylaminopyridine) group 12 trifluoroacetates — M(OCOCF3)2·2DMAP (M=Zn, Cd, Hg)

Bis(4-dimethylaminopyridine) group 12 trifluoroacetates—M(OCOCF₃)₂·2DMAP (M=Zn, Cd, Hg) were prepared in quantitative yields from the anhydrous metal trifluoroacetates and DMAP. All compounds crystallize in the triclinic space group (no. 2) with two molecules per unit cell. While Zn(OCOCF₃)₂·2DMAP is built up by well-separated tetrahedral units exhibiting strongly covalent ZnO bonds to monodentate trifluoroactate groups, Cd(OCOCF₃)₂·2DMAP and Hg(OCOCF₃)₂·2DMAP form dimeric units. The metal centers are distorted octahedrally surrounded by two axial DMAP ligands, two ionic bridging and one chelating trifluoroacetate group.     

Two types of coordination polymers based on cluster anions [Re4Q4(CN)12] (Q = S, Se) and cations of rare-earth metals Ln: Syntheses and crystal structures

The reactions of aqueous solutions of the tetrahedral cluster anions [Re₄Q₄(CN)₁₂]⁴⁻ (Q = S, Se) with lanthanide chlorides resulted in the crystallization of the formed compounds into two main structural types [{Ln(H₂O)₄(H₂O)_2/3Cl_1/3}₃{Re₄Q₄(CN)₁₂}₂]·2H₂O (Ln = La-Gd, Q = S, Se) and K_0.5(H)_0.5[{Ln(H₂O)₄}{Re₄S₄(CN)₁₂}]·nH₂O or (H)[{Ln(H₂O)₄}{Re₄Se₄(CN)₁₂}]·nH₂O (Ln = Tb-Lu). Compounds of the first type crystallize in the hexagonal crystal system (space group Р6₃/m) and they have a three-dimensional polymeric structure; compounds of the second type crystallize in the orthorhombic crystal system (space group Cmcm) and they have a two-dimensional crystal structure due to the polymeric anion {[{Ln(H₂O)₄}{Re₄Q₄(CN)₁₂}]⁻}_∞∞.     

A NOVEL ONE-DIMENSIONAL CYANO-BRIDGED CHAIN COMPLEX [Gd(DMF)4(H2O)2Mn(CN)6 · H2O] n : SYNTHESIS,CRYSTAL STRUCTURE AND MAGNETOCHEMISTRY

Abstract

DMF (dimethylformamide) reacts with Gd(NO₃)₃6H₂O and K₃Mn(CN)₆ to afford a novel cyano-bridged complex [Gd(DMF)₄(H₂O)₂Mn(CN)₆] · H₂O] _n . The crystal structure of the complex (abbreviated as GdMn) has shown that it has a novel one-dimensional chain structure. The complex crystallizes in space group P2₁/c with a = 13.004(2), b = 12.762(2), c = 19.160(4) Å, β = 109.51(3)°, V = 2997.2(9) Å, D_x = 1.584 Mgm^?3, Z = 4. Variable temperature (1.5–300K) magnetism shows there exists weak antiferromagnetic interaction between Gd and Mn atoms across the cyano bridge.     

Telluro- and seleno-bridged TiIV-MII (M = Ni,Pd, Pt) heterobimetallic complexes

Summary Heterobimetallic complexes of the types [Cp₂Ti(-EAr)₂-M(dppe)] (ClO₄)₂ [(1)–(4); M, E = Ni, Te (1); Ni, Se (2); Pt, Te (3); Pt, Se (4); Ar = Ph (a), C₆H₄-4-Me (b), C₆H₄-4-OMe (c), C₆H₄-4-OEt (d)] and [Cp₂Ti(-TeAr)₂-MCl ₂] [M = Pd (5), Pt (6)] were obtained by the reactions of Cp₂Ti(EAr)₂ with M(dppe)(ClO₄)₂ and M(PhCN)₂Cl₂, respectively. While (1), (5) and (6) are stable in the solid state as well as in solution, (2)–(4) undergo dissociation to M(dppe)(EAr)₂ and Cp₂Ti(ClO₄)₂ in solution, as shown by multinuclear (³¹P{¹H},¹⁹⁵Pt{¹H}, ¹²⁵Te{¹H}) n.m.r. studies. The reaction of Cp₂Ti(SeAr)₂ with M(PhCN)₂Cl₂, however, leads to the formation of Cp₂TiCl₂ and a polymeric material [M(SeAr)₂] _n .     

Syntheses, crystal structures, thermal stabilities and luminescence of six M(II)-hydroxyphosphonoacetate materials

Hydrothermal reactions of Zn^II, Ba^II or Co^II ion with 2-hydroxyphosphonoacetic acid (H₃L) afforded six metal phosphonates, namely, [Zn₅(O₃PCH(OH)CO₂)₄(C₆H₉N₂)₂] (1), [(C₄H₁₂N₂)Zn₅(O₃PCH(OH)CO₂)₄(H₂O)₂] (2), [(C₃H₁₂N₂)_0.5Zn₅(HO₃PCH(OH)CO₂)(O₃PCH(OH)CO₂)₃(H₂O)₂]·0.75H₂O (3), [BaZn₂(O₃P CH(OH)CO₂)₂] (4), [Ba(HO₃PCH(OH)CO₂)] (5) and [(NH₄)₂Co₇(HO₃PCH(OH) CO₂)₆(HPO₄)₂(H₂O)₆]·4H₂O (6). In 1, zinc tetrahedra ([ZnO₄]) and octahedra ([ZnO₅N], [ZnO₆]) are bridged by 2-hydroxyphosphonoacetate with penta- and hexadendate modes into a hybrid layer, which is further pillared by the 3-picolylamines to form a 3D structure through Zn-N bonds and hydrogen bondings. Both 2 and 3 are 3D framework encapsulating piperazine and 1,2-propanediamine cations, respectively. In solids 4-6, the cross-linkages of [ZnO₄], [BaO₁₀] and [CoO₆] polyhedral with 2-hydroxyphosphonoacetate form 3D frameworks. Solids 3 and 4 behave thermally stable up to 250 and 300 °C under air atmosphere, respectively. It is interesting that the peak emission of solid 3 displays a 10 nm red-shift after simple heat-treatment.     

Syntheses,structures and luminescent properties of two Zn(II) complexes of N-2-nitrobenzenesulfonyl-glycine acid

Two luminescent zinc coordination complexes [Zn₂(2-NBS-gly)₄(H₂O)₄]?·?2H₂O (1), and Zn(Im)₂(2-NBS-gly)₂ (2), (2-NBS-glyH?=?N-2-nitrobenzenesulfonyl-glycine acid, Im?=?imidazole) have been synthesized and their crystal structures determined by X-ray crystallography. The Zn(II) in 1 is a five-coordinate geometry and can be described as a slightly distorted square-pyramid; complex 2 is four-coordinate, forming a distorted tetrahedron. Through hydrogen bonding, complex 1 forms a 2-D network and complex 2 forms a zigzag chain. Fluorescent analyses show that both 1 and 2 exhibit photoluminescence in the solid state and may be potential candidates for photoactive materials.     

M[B(CN)4]2: Zwei neue Tetracyanoborate mit zweiwertigen Kationen (M = Zn,Cu)

M[B(CN)₄]₂: Two new Tetracyanoborate Compounds with divalent Cations (M = Zn, Cu) The reaction of ZnO or CuO with [H₃O][B(CN)₄] in aqueous solution yielded single crystals of Zn[B(CN)₄]₂ and Cu[B(CN)₄]₂, respectively. The compounds were characterized by single‐crystal X‐ray diffraction. Zn[B(CN)₄]₂ ( (no. 164), a = b = 7.5092(9) Å, c = 6.0159(6) Å, Z = 1) crystallizes isotypic with Hg[B(CN)₄]₂. The structure of Cu[B(CN)₄]₂ (C2/m (no. 12), a = 13.185(3) Å, b = 7.2919(9) Å, c = 6.029(1) Å, β = 93.02(2)°, Z = 2) can be considered as a super‐structure, resulting from Jahn‐Teller distortion of the Cu²⁺ ions. Magnetic measurements were performed for the copper compound. Vibrational spectra and thermal stabilities were compared with the known mercury(II) tetracyanoborate.     

Syntheses,crystal structures,and antibacterial activities of two cobalt(III) complexes

Syntheses, structures, and antimicrobial activities of cobalt(III) complexes with two tetradentate Schiff-base ligands, (BA)₂en?=?bis(benzoylacetone)ethylenediimine dianion and (acac)₂en?=?bis(acetylacetone)ethylenediimine dianion, and two axial pyridines (py) have been investigated. These complexes were characterized by FT-IR, ¹H-NMR, UV-Vis spectroscopy, and elemental analysis. The crystal structures of the complexes were determined by X-ray crystallography. Single-crystal X-ray diffraction analyses revealed that both complexes have distorted octahedral environments, Schiff-base ligand coordinates cobalt in four equatorial positions, and the two axial positions are occupied by pyridines. The pyridines and Schiff-base ligands are involved in N–H···O hydrogen bonds with perchlorate. Biological activities of the ligands and metal complexes have been studied on Staphylococcus aureus, Escherichia coli, and Bacillus subtilis by the well diffusion method. The activity data show the metal complexes to be more potent than the parent ligand against two bacterial species.     

Tetracyanometallates with Complex Dien Cations: [Ni(dien)2][Ni(CN)4]·2H2O and [Ni(dien)2][Pd(CN)4]

The crystal structures of two square tetracyanocomplexes were determined. [Ni(dien)₂][Ni(CN)₄]·2H₂O (NDNCH) and [Ni‐(dien)₂][Pd(CN)₄] (NDPC) (dien = diethylene triamine) exhibit ionic structures consisting of mer‐[Ni(dien)₂]²⁺ cations and [Ni(CN)₄]^2‐ or [Pd(CN)₄]^2‐ anions, respectively. Moreover, the structure of NDNCH is completed by two water molecules of crystallisation. In both compounds hydrogen bonds contribute to the stabilisation of the structure. NDNCH dehydrates on air quickly yielding anhydrous [Ni(dien)₂][Ni(CN)₄] (NDNC). Its thermal decomposition proceeds in a complicated process followed by aerial oxidation of metallic nickel to NiO.     

Syntheses,crystal structures and thermal behavior of three Mn(II) complexes with 4-acyl pyrazolone derivatives

Three new manganese complexes, [Mn(PPeAP-INH)(CH₃OH)₂]_n(CHCl₃) (1) [PPeAP-INH=N-(1-phenyl-3-phenylethyl-4-ethylene-5-pyrazolone isoniazid, INH = isoniazid], [Mn₂(PM4MbP-INH)₂(CH₃OH)₄](CH₃OH) (2·CH₃OH), [PM4MbP-INH=N-(1-phenyl-3-methyl-4-(p-methylbenzoylene)-5-pyrazolone) isoniazid)] and [Mn₂(PPePeP-INH)₂(CH₃OH)₄] (3) [PPePeP-INH=N-(1-phenyl-3-phenylethyl-4-phenylethylene-5-pyrazolone) isoniazid] have been prepared, aiming at the formation of extended coordination polymer with Mn(II) ions. Formation of the corresponding manganese-ligand complexes has been monitored and characterized by chemical and spectroscopic techniques. X-ray diffraction analyses of available single crystals revealed 1D polymeric patterns of supramolecular system. Among them, the dimers of 2 and 3, bridged by two methanol molecules, are extended by hydrogen bond of O–H···N to form the 1D chain. In these three new complexes which are all octahedral coordination environments, the N(5) atom of the pyridine heterocycles plays a very important role in building the bridged polymeric chain.     

Syntheses, crystal structures and magnetic properties of Ni(II)–2,4-pyridine-dicarboxylates

Two new complexes [Ni(pydc)(H₂O)₂]_n (1) and [Ni₂(pydc)₂(H₂O)₅]_n (2) (H₂pydc = 2,4-pyridinedicarboxylic acid) have been obtained by hydrothermal synthetic method and characterized by single crystal X-ray analysis. In 1 six-coordinate Ni(II) ions are coordinated by pydc ligands to form 2-D layer structures; while in 2 six-coordinate Ni(II) ions are only connected into 1-D zigzag chains constructed by dinuclear nickel units. Although the coordination geometries around Ni(II) centers in both complexes are similar, their structure topologies are greatly tuned by coordination modes of pydc. Variable temperature magnetic susceptibility studies have shown that both compounds 1 and 2 may display antiferromagnetic coupling between paramagnetic metal centers mediated by bridging carboxylate groups.     

Synthesis,crystal structures and properties of five-coordinate Schiff-base Zn(II) complexes

Five-coordinate Schiff-base Zn complexes (1,2-cyclohexanediamino-N,N′-bis(salicylidene)) zinc-pyridine 1 and (1,2-cyclohexanediamino-N,N′-bis(3,5-di-tert-butylsalicylidene)) zinc-pyridine 2 were synthesized and the structures of 1 and 2 have been determined by single-crystal X-ray analysis. All Zn atoms are five-coordinate in both structures. Both complexes exhibit interesting structures based on intermolecular π–π stacking and hydrogen bond interactions. Complex 1 has a one-dimensional molecular chain structure via π–π stacking interaction, while complex 2 has an interesting lattice structure (with cavities with dimensions 10.9?×?6.9?Å) formed through intermolecular π–π stacking and hydrogen bond interactions. 1 and 2 are compared and characterized by MS, elemental analysis, IR, UV-Vis and Photoluminescence (PL). Fluorescence spectra show that the maximal emission wavelength of 1 and 2 are 454?nm, and 480?nm, respectively, upon radiation by UV light. Cyclic voltammetry performed on 1 and 2 indicate a dependence of the cathodic potentials upon conformational and electronic effects. Electronic spectral properties of 1 and 2 were studied by TD-DFT methods. The fluorescent emission of these complexes originates from ligand-centred π–π? transitions. The Zn (II) centres play a key role in enhancing the fluorescent emission of the ligands.     

一维链状冠醚配合物[k(18-C-6)]~2[M(NO~2)~4](H~2O)(M=Pd,Pt) 的合成与结构

研究了18-C-6分别与k~2[Pd(NO~2~4],k~2[Pt(NO~2)~4])的反应,并通过元素分析、红外光谱、单晶X射线衍射对生成的配合物[k(18-C-6)]~2[Pd(NO~2)~4](H~2O)~0.5(1)和[k(18-C-6)]~2,k~2[Pt(NO~2)~4])(H~2O)(2)进行了表征,两个配合匀匀为单斜晶系,空间P2~1/c.1的晶体学数据：α=1,7104(3),c=1,5763(3)nm,β=93.49(3)°,V=3.9987(14)nm^3,Z=4,D~c=1.507g/cm^3,F(000)=1880,R~1=0.0681,~wR~2=0.1004。2的晶体学数据：a=1.1312(3)nm,b=1.4227(2)nm,c=1.2266(3)nm,β93.141(10)°,V=1.9711(8)nm^3,Z=4,D~c=1.614g/cm^3,F(000)=936,R~1=0.0265,~wR~2=0.0721。在固态,配合物1具有[(18-c-6)]~2[Pd(NO~2)~4](H~2O)(1a)和[(18---c-6)]~2[Pd·(NO~2)~4](1b)两个分子,两者比例这1：1前者相邻的两个分子通过水分是的氧原子相连接形成一维链状结构,后者形面假一维链状结构,在配合物2中相邻的两个分子通过品分子中的氧原子相连接形成一维链状结构。     

Syntheses,crystal structures and magnetic properties of three new binuclear Ni(II) complexes derived from tripodal tetradentate (N4) ligands

Three new binuclear Ni(II) complexes [{Ni(L_22py)Cl}₂](ClO₄)₂ (1), [{Ni(L_23py)Cl}₂](ClO₄)₂ (2), and [{Ni(L_33py)Cl}₂](ClO₄)₂ (3), {L_22py = N-(2-pyridylmethyl)-N-(2-aminoethyl)-1,2-diaminoethane, L_23py = N-(2-pyridylmethyl)-N-(2-aminoethyl)-1,3-diaminopropane, L_33py = N-(2-pyridylmethyl)-N-(3-aminopropyl)-1,3-diaminopropane} have been synthesized. Single crystal X-ray structure analysis showed that in each complex two distorted octahedral Ni(II) ions are bridged asymmetrically by a pair of chloride anions. Variable temperature magnetic susceptibility measurements of 1 and 3 revealed dominant ferromagnetic exchange interactions.     

Trinuclear and dinuclear Ni(II) complexes constructed by bridging oxygen: crystal structures,magnetic, and thermal properties

The reaction of H₂L (N,N ′-bis(5-ethyl-1,3,4-thiadiazol-2-yl)-2,6-pyridinedicarboxamide) with Ni(II) salts gave crystals of two new complexes, [Ni₃(µ₃-O)(H₂L)(L)₂] · 2DMF (1) and [Ni₂(µ-H₂O)(CH₃OH)(DMF)(L)₂] · H₂O · CH₃OH (2). The complexes were characterized by elemental analysis, IR, thermal analysis, and X-ray single crystal diffraction. Complex 1 is a trinuclear complex containing a triangle frame in the center formed by three Ni(II) atoms with a bridging µ₃-O. Complex 2 is dinuclear formed by two Ni(II) atoms with a bridging H₂O. H₂L coordinates to metal centers as a pentadentate ligand in 1 and tetradentate in 2. Thermal analysis shows that the thermal stability of 1 is higher than that of 2. In addition, the magnetic properties of 2 are also reported.     

Syntheses, crystal structures and spectral properties of three chiral complexes [M((R, R)-et-pybox)Cl2] (M=Zn and Mn) and [Ni((R, R)-et-pybox)(H2O)2Cl]Cl

Three chiral complexes: [M((R, R)-et-pybox)Cl₂] (M=Zn, 1, and Mn, 2) and [Ni((R, R)-et-pybox)(H₂O)₂Cl]Cl (3) ((R, R)-et-pybox is C₂-symmetric 2,6-bis[4′-(R)-ethoxyoxazolin-2′-yl]pyridine) have been synthesized and characterized by elemental analysis, IR, UV, TG and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analyses show that 1 is isostructural to 2, the obtained complexes are of isolated mononuclear and the metal atoms of 1 and 2 have distorted trigonal bipyramidal coordination environment. A feature of interest is noted in the unit cell of 3, there exist two types of molecules, which similarly have a distorted octahedral geometry but only slightly differ in the orientation of the coordinated atoms to the central Ni atom. These two types of molecules interact with each other by O–H···Cl hydrogen bonds, giving rise to one-dimensional ribbon structure.     

Syntheses,crystal structures,and catalytic properties of dioxomolybdenum(VI) complexes with hydrazone ligands

Two new dioxomolybdenum(VI) complexes, [MoO₂L¹(CH₃OH)] (1) and [MoO₂L²(H₂O)] (2), where L¹ and L² are dianionic form of N′-(2-hydroxy-3-methoxybenzylidene)-4methoxybenzohydrazide and N′-(2-hydroxy-3methoxybenzylidene)-2-hydroxybenzohydrazide, respectively, have been synthesized and structurally characterized by spectroscopic methods and single-crystal X-ray determination. The complexes are mononuclear molybdenum(VI) compounds. Mo in each complex is octahedral. The difference in the substituent groups in the benzohydrazides leads to coordination of different solvent molecules. Crystals of the complexes are stabilized by hydrogen bonds. The complexes are effective catalysts for sulfoxidation.