Syntheses,crystal structures,and antimicrobial activities of nickel(II) and cadmium(II) complexes with 4-methylsulfonyl cinnamate and diamines

Two metal complexes, [Ni^II(mscinn)₂(pda)₂] (1) and [Cd^II(mscinn)₂(dmeda)₂·2H₂O] (2) (mscinn?=?4-methylsulfonyl cinnamate, pda?=?propane-1,3-diamine, dmeda?=?N′,N′-dimethylethane-1,2-diamine), were synthesized by reacting 4-methylsulfonyl cinnamate with the diamines and metal salts. Their structures were determined by single-crystal X-ray diffraction analysis. Crystal parameters of 1: C₂₆H₃₈N₄NiO₈S₂, M?=?657.43, monoclinic, P2₁/c, a?=?16.6123(8)?Å, b?=?8.5956(4)?Å, c?=?11.2047(5)?Å, β?=?107.423(1)°, V?=?1526.54(12)?ų, Z?=?2, D _calcd?=?1.430?g?cm^?3, F(000)?=?692, μ?=?0.825?mm^?1, R ₁?=?0.0257, wR ₂?=?0.0669. Crystal data of 2: C₂₈H₄₂CdN₄O₈S_2?·?2(H₂O), M?=?775.24, monoclinic, P2₁/c, a?=?9.8278(4)?Å, b?=?11.6611(5)?Å, c?=?15.3972(7)?Å, β?=?96.195(1)°, V?=?1754.26(13)?ų, Z?=?2, D _calcd?=?1.468?g?cm^?3, F(000)?=?804, μ?=?0.798?mm^?1, R ₁?=?0.0299, wR ₂?=?0.0770. Antimicrobial activities for 1 and 2 against Escherichia coli, Pseudomonas putida, Bacillus subtilis, and Bacillus cereus had better antibacterial activity than their parent carboxylic acid against Gram-positive bacteria (B. subtilis and B. cereus). The cadmium complex of the cinnamate displayed high inhibitory activity with an MIC value of 5?µg?mL^?1 against P. putida, while the nickel complex also exhibited good inhibitory potency with an MIC value of 5?µg?mL^?1 against B. subtilis.     

A dimeric luminescent lanthanide complex [Eu(PAA)2(phen)(NO3)]2: hydrothermal synthesis,crystal structure and fluorescence

A lanthanide coordination complex [Eu(PAA)₂(phen)(NO₃)]₂ (PAA?=?phenylacetic acid, phen?=?1,10-phenanthroline) has been synthesized by the hydrothermal method. Single crystal X-ray diffractions show that it forms a dimeric molecular structure. The title complex crystallizes in the triclinic system, space group P 1, with lattice parameters a?=?8.9473(8)?Å, b?=?13.3659(12)?Å, c?=?13.4745(12)?Å, α?=?60.7590(10)°, β?=?89.5100(10)°, γ?=?71.9850(10)°, V?=?1317.3(2)?ų, D _c?= 1.675?Mg?m^?3, Z?=?1, F(000)?=?660, GOF?=?1.003, R ₁?=?0.0206, wR ₂?=?0.0575. The fluorescence excitation and emission spectra have been investigated.     

Aquachloro[N,N′‐ethylenebis(salicylideneiminato)]manganese(III)

The title compound, aqua­chloro{2,2′‐[1,2‐ethanediyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴O,N,N′,O′}manganese(III),[MnCl(C₁₆H₁₄N₂O₂)(H₂O)], is a neutral manganese(III) complex with a pseudo‐octahedral metal centre. The equatorial plane comprises the four donor atoms of the tetradentate Schiff base ligand [Mn—O 1.886 (4) and 1.893 (4) Å, and Mn—N 1.978 (5) and 1.982 (5) Å], with a water mol­ecule [Mn—O 2.383 (4) Å] and a Cl^? ligand [Mn—Cl 2.4680 (16) Å] completing the coordination sphere. The distorted geometry is highlighted by the marked displacement of the Mn^III ion out of the least‐squares plane of the four Schiff base donor atoms by 0.165 (2) Å. These monomeric Mn^III centres are then linked into a polymeric array via hydrogen bonds between the coordinated water mol­ecule and the phenolic O‐atom donors of an adjacent Mn^III centre [O—H?O 2.789 (5) and 2.881 (5) Å].     

Syntheses,crystal structures and magnetic study of two binuclear manganese(II) complexes with aromatic N-oxide as bridging ligand

Two new binuclear complexes, [Mn₂(μ-dmpo)₂(SCN)₄(H₂O)₂] (1) (where dmpo?=?3,5-dimethylpyridine N-oxide), [Mn₂(μ-po)₂(H₂O)₆I₂]I₂ (2) (where po?=?pyridine N-oxide), have been synthesized and their crystal structures determined by X-ray crystallography. Complexes 1 and 2 crystallize in monoclinic, space group P2₁/c, with unit cell dimensions a?=?8.8836(18)?Å, b?=?15.450(3)?Å, c?=?15.484(3)?Å, β?=?91.020(3)° for 1, and a?=?8.8352(13)?Å, b?=?17.927(3)?Å, c?=?8.3338(12)?Å, β?=?103.765(2)° for 2. In each binuclear complex two Mn(II) were bridged by two 3,5-dimethylpyridine N-oxides or by two pyridine N-oxides and the distances between the bridged Mn(II) ions are 3.599?Å for 1 and 3.552?Å for 2. Variable temperature (4–300?K) magnetic measurements were performed for 1 and the susceptibility data were fitted by using a binuclear Mn(II) magnetic coupling formula producing the 2J?=??2.17?cm^?1.     

Synthesis and crystal structure of a novel three-dimensional inorganic open-framework: Cd8(OH)8(SO4)4

The title compound Cd₈(OH)₈(SO₄)₄ (1) obtained under hydrothermal conditions by reacting Cd(OH)₂ with 4-aminobenzenesulfonic acid in an aqueous ethanol solution was confirmed by single-crystal X-ray diffraction. Crystal data: P2₁/c with a?=?6.8984(4), b?=?7.5640(4), c?=?11.3919(5)?Å, β?=?119.763(2)°, V?=?516.01(5)?ų, H₈Cd₈O₂₄S₄, M _r ?=?1419.50, Z?=?1, D _c ?=?4.568?Mg?m^?3, μ?=?8.595?mm^?1, F(000)?=?648, R?=?0.023, wR?=?0.060 for 1208 observed reflections [I?>?2σ(I?)]. The crystal structure of complex 1 forms a three-dimensional (3-D) framework.     

Hydrothermal syntheses,crystal structures,and thermal stability of two new 3D open-framework metal(II) phosphonates

This article reports the hydrothermal synthesis and characterization of two new phosphonate compounds NaCo[O₃PCH(OH)CO₂] (1) and NaMn[O₃PCH(OH)CO₂] (2) based on 2-hydroxyphosphonoacetic acid (H₃L). Their structures have been characterized by single-crystal X-ray diffraction as well as with elemental analysis, infrared spectroscopy and thermogravimetric analysis. The two isomorphous compounds crystalline in the orthorhombic, space group Pbca: Crystal data for 1: a?=?10.1827(8)?Å, b?=?9.6673(8)?Å, c?=?10.7853(9)?Å, V?=?1061.70(15)?ų, Z?=?8, R ₁?=?0.0252, wR ₂?=?0.0577; Crystal data for 2: a?=?10.4309(18)?Å, b?=?9.7913(17)?Å, c?=?10.9012(19)?Å, V?=?1113.4(3)?ų, Z?=?8, R ₁?=?0.0194, wR ₂?=?0.0536. In the two compounds, the metal atoms are octahedrally coordinated; all oxygen atoms from the H₃L ligand are involved in coordination. The overall structures can be described as a 3D open framework with channels running along the a axis and the charge-compensating Na⁺ cations being located at the intersections of these channels.     

Syntheses,crystal structures,and catalysis by polymeric dioxomolybdenum(VI) complexes with similar (iso)nicotinohydrazones

Polymeric dioxomolybdenum(VI) complexes, [MoO₂L]_n (L?=?L¹?=?N′-(2-hydroxybenzylidene)nicotinohydrazide for 1, L?=?L²?=?N′-(2-hydroxy-5-methoxybenzylidene)isonicotinohydrazide for 2), were prepared and characterized by physico-chemical, spectroscopic methods, and single-crystal X-ray determination. Complex 1 crystallizes in the orthorhombic space group P2₁2₁2₁ with a?=?7.6568(4), b?=?11.6315(7), c?=?15.2211(9)?Å, V?=?1355.59(13)?ų, Z?=?4, R ₁?=?0.0181, wR ₂?=?0.0464, and S?=?1.097. Complex 2 crystallizes in the monoclinic space group P2 ₁ /n with a?=?11.2516(6), b?=?11.8134(7), c?=?12.4371(6)?Å, β?=?116.2210(10)°, V?=?1483.02(14)?ų, Z?=?4, R ₁?=?0.0399, wR ₂?=?0.0874, and S?=?1.096. X-ray analysis indicates that Mo in each complex is octahedral with two oxo groups and N₂O₂ donor set of the nicotinohydrazone or isonicotinohydrazone. The complexes are efficient catalysts for oxidation of olefins.     

Crystal structure,thermal and magnetic studies of a dinuclear Mn(II) complex with decadentate picolinate based ligand

The reaction of the decadentate ligand tpmen (H₄tpmen?=?N,N,N′N′-tetrakis[(6-carboxypyridin-2-yl)methyl]ethylenediamine) with MnCl₂·4H₂O in aqueous solution gives a homodinuclear complex [Mn₂(H₂O)₂(tpmen)]·16H₂O, which has been characterized by elemental analysis, thermal gravimetric and single-crystal X-ray diffraction analysis. The complex crystallizes in the orthorhombic system, space group Cmca, a?=?28.786(5) Å, b?=?11.5033(19) Å, c?=?14.437(2) Å, Z?=?8, R ₁?=?0.0432, wR ₂?=?0.0786. The tpmen ligand contains four picolinate groups, two of which bind each Mn(II) to form a dinuclear complex. The geometry around the Mn(II) is distorted octahedral with two nitrogen and two oxygen atoms from the picolinate groups and two oxygen atoms from coordinated water. The variable-temperature (2–300?K) magnetic susceptibilities shows an antiferromagnetic interaction between Mn(II) ions.     

Solid state structures of the chiral heterobimetallic complexes [Cu(dach)2][Pt(CN)4] · 2H2O, [Ni(dach)3][Pt(CN)4] · 2DMF · H2O,and [Pd(dach)2][Pt(CN)4] · H2O (dach = 1 R , 2 R -diaminocyclohexane)

The chiral dinuclear heterometallic complexes [Cu(dach)₂][Pt(CN)₄]?·?2H₂O (1), [Ni(dach)₃][Pt(CN)₄]?·?2DMF?·?H₂O (2), and [Pd(dach)₄][Pt(CN)₄]?·?H₂O (3) (dach?=?1R,2R-cyclohexanediamine) have been prepared and characterized by X-ray diffraction analysis. Crystal data: 1, monoclinic, P2₁, a?=?8.108(3), b?=?15.552(6), c?=?9.914(4)?Å, β?=?110.931(6)°, V?=?1167.6(8)?ų, Z?=?2, R ₁?=?0.0420, wR ₂?=?0.1122; 2, monoclinic, P2₁, a?=?13.264(11), b?=?9.285(7), c?=?16.211(13)?Å, β?=?111.640(9)°, V?=?1856(3)?ų, Z?=?2, R ₁?=?0.0276, wR ₂?=?0.0698; 3, monoclinic, P2₁, a?=?6.887(2), b?=?12.809(4), c?=?12.975(4)?Å, β?=?94.865(4)°, V?=?1140.6(6)?ų, Z?=?2, R ₁?=?0.057, wR ₂?=?0.156. In complex 1, the Pt and Cu atoms are linked by a CN bridge that presents a very bent C=N–Cu angle [136.8(8)°].     

Synthesis and structures of two molybdenum(VI) complexes derived from similar benzohydrazone ligands with catalytic properties

Two new structurally similar molybdenum(VI) complexes, [MoO₂L¹(CH₃OH)] (1) and [MoO₂L²(CH₃OH)] (2), where L¹ is the dianionic form of N′-(2-hydroxy-5-nitrobenzylidene)-2-methylbenzohydrazide and L² is the dianionic form of N′-(2-hydroxy-4-methoxybenzylidene)-2-methylbenzohydrazide, were prepared and structurally characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. 1 crystallizes in the monoclinic space group P2₁/c, with unit cell dimensions a?=?7.941(1), b?=?14.337(2), c?=?15.141(2)?Å, β?=?92.782(2)°, V?=?1721.8(4)?ų, Z?=?4, R₁?=?0.0286, wR₂?=?0.0650, GOOF?=?1.028. 2 crystallizes in the triclinic space group P-1, with unit cell dimensions a?=?8.003(1), b?=?10.608(1), c?=?10.880(1)?Å, α?=?95.745(2)°, β?=?97.627(2)°, γ?=?105.762(2)°, V?=?872.0(2)?ų, Z?=?2, R₁?=?0.0226, wR₂?=?0.0595, GOOF?=?1.116. X-ray analysis indicates that Mo in the complexes are coordinated by the phenolate oxygen, imino nitrogen, and enolate oxygen of the benzohydrazone, methanol, and two oxo groups, generating octahedral coordination. The oxidation of olefins with the complexes as catalysts was evaluated, indicating that the complexes showed excellent catalytic efficiency in oxidation of most aliphatic and aromatic substrates under mild conditions using tert-butyl hydrogen peroxide as oxidant.     

Synthesis,structure and characterization of copper(II) and zinc(II) complexes based on 3-carboxyl-1,2,4-triazole

Two complexes [CuL₂(H₂O)₂] (1) and [ZnL₂(H₂O)₂] (2) (L?=?3-carboxyl-1,2,4-triazole (L)) have been synthesized and characterized by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic space group P ₂(1)/n, a?=?8.632(8)?Å, b?=?9.153(8)?Å, c?=?6.991(7)?Å, β?=?94.279(12)°, Z?=?2, R ₁?=?0.0296, wR ₂?=?0.0918. Compound 2 also crystallizes in the monoclinic space group P ₂(1)/n, a?=?4.937(3)?Å, b?=?18.107(10)?Å, c?=?6.344(4)?Å, β?=?106.839(7)°, Z?=?2, R ₁?=?0.0230, wR ₂?=?0.0556. Extensive intermolecular hydrogen bonds assemble 1 and 2 into three-dimensional (3D) supramolecular architectures, with eight-member H-bonded synthons. Compounds 1 and 2 were also characterized by element analysis, FT–IR, luminescence and EPR studies.     

Solid state structure of a rhenium bibenzimidazole complex

Re(CO)₅Br readily forms a complex with 2,2′-bibenzimidazole (bbimH₂) of the general composition (bbimH₂)Re(CO)₃Br, 1. The complex was characterized by NMR, IR, electronic and emission spectroscopy. The orange-brown compound is sparingly soluble in apolar solvents but could be crystallized from a DMF/toluene mixture. An X-ray structural investigation shows that the rhenium ion has a distorted octahedral geometry. Nitrogen atoms of the bibenzimidazole are trans to two carbonyl ligands. The secondary amine protons of the bibenzimidazole ligand form a hydrogen bond to the amide oxygen of a DMF molecule; N3–O4 2.725(7)?Å, N4–O4 2.761(7)?Å. The bending angle of the two benzimidazole units is 168°; the greatest deviation from planarity within the ligand is 0.14?Å. Crystal data: monoclinic, space group P2₁/n, a?=?10.9743(2), b?=?12.9182(2), c?=?15.1864(3)?Å, β?=?91.647(1)°, V?=?2152.06(7)?ų, T?=??90°C, Z?=?4, R ₁?=?0.025, wR ₂?=?0.062 for 4296 reflections with F _o?> 4σ(F _o) out of 4886 independent reflections.     

Synthesis,crystal structure,and spectral analysis of a 1-D Mn(II) coordination polymer

A manganese(II) coordination polymer [Mn(TMB)₂?·?H₂O] _n (1) (HTMB?=?3,4,5-trimethoxybenzoic acid) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, powder X-ray diffraction analysis, spectroscopic (IR, solid state UV-Vis), and thermal methods. The crystal belongs to orthorhombic system, space group P2₁2₁2₁, with cell parameters a?=?7.3001(8), b?=?11.4146(13), c?=?27.053(3)?Å, α?=?β?=?γ?=?90°, V?=?2254.3(4)?ų, Z?=?4. In 1, TMB in two different coordination modes bridges six-coordinate manganese(II) centers forming a 1-D infinite chain coordination framework. The spectral and thermal properties of the complexes have also been studied.     

Synthesis,crystal structure and magnetism of 1D cobalt(II) coordination polymer with thiocyanate as bridging ligand

A one-dimensional coordination polymer [Co(μ _1,3-NCS)₂(npdo)₂] _n (npdo?=?4-nitropyridine N-oxide) has been synthesized and structurally determined by X-ray crystallography. The complex crystallizes in the orthorhombic space group of Pbcn with a?=?22.688(5)?Å, b?=?7.2636(17)?Å, c?=?10.299(2)?Å. Adjacent Co(II) ions are coordinated by two μ _1,3-SCN^? bridging ligands, forming a one-dimensional chain along the c axis and the npdo coordinates to Co(II) ion as a terminal ligand. The thermal variation of the magnetic moments of the complex reflects the antiferromagnetic interaction between the bridged Co(II) ions above 20?K and the ferromagnetic transition or the strong short-range spin interaction below 20?K.     

Synthesis of the monosubstituted arylcyanoxime and its Na,Tl(I) and Ag(I) compounds

Nitrosation of 2-chlorophenyl acetonitrile with t-butylnitrite under basic conditions (Meyer reaction) resulted in a high-yield preparation of the first substituted arylcyanoxime, 2-chlorophenyl(oximino)acetonitrile, H(2Cl–PhCO) (HL). The obtained cyanoxime is readily deprotonated in solution by metal hydroxides or carbonates with the formation of yellow sodium, tetrabutylammonium, thallium(I) and silver(I) derivatives. The crystal structure of the Tl(I) complex was determined. Thallium(I) salt (TlL) crystallizes in the monoclinic space group P2₁ n with a?=?3.8382(7), b?=?11.0065(18), c?=?20.901(4)?Å, and β?=?92.447(3)°, V?=?882.2(3) ų, Z?=?4; T?=?193?K (Mo?Kα radiation). The structure was solved by direct methods to a final R of 0.0689 (wR2?=?0.1650) for I?>?2σ(I). The crystal structure of the complex is a one-dimensional coordination polymer that consists of centrosymmetric [TlL]₂ dimers in which Tl₂O₂ rhombohedra are connected to each other at 90.72°. The crystal structure of TlL is an interesting example of the ruffled metal-organic network composed of Tl–O–Tl–O zigzag chains with close (3.838?Å) intermetallic distances comparable to those in metallic thallium (3.42?Å). The cyanoxime anion bridges metal centers and acts as a tridentate ligand where oxygen atoms of the oxime group bond to three different Tl(I) cations with three different bond lengths.     

Malonato-bridged hexamethylenetetramine coordination polymers containing Mn(II) and Cu(II)

Two malonato-bridged hexamethylenetetramine coordination polymers, M₂(hmt)(H₂O)₂(mal)₂ [hmt?=?hexamethylenetetramine, mal?=?malonate(2-), M?=?Mn (1), Cu (2)] were prepared and structurally characterized. The isostructural complexes are orthorhombic, space group Imm2, with a?=?7.104(1), b?=?15.982(3), c?=?7.702(1)?Å, Z?=?2, D _calc?=?1.862?g?cm^?3(1) and a?=?6.962(3), b?=?15.500(7), c?=?7.627(3)?Å, Z?=?2, D _calc?=?2.047?g?cm^?3for 2. The transition metals are octahedrally coordinated by one nitrogen atom of an hmt ligand and five oxygen atoms of a water molecule and three malonate anions. The latter coordinate in chelating/bis-monodentate mode to give 2D layers with a (4,?4) topology, and which are pillared by bridging bidentate hmt ligands to generate an open 3D framework with channels extending in the [001] direction. Over the temperature range 5–300?K, 2 behaves paramagnetically, following the Curie–Weiss law χ_m(T???θ)?=?4.521(6)?cm³mol^?1K with a Weiss constant θ?=??4.8(2)?K.     

Synthesis,molecular structure,DNA binding and cleavage properties of a novel ternary Cu(II) complex containing dipyrido[3,2-a : 2′3′-c]phenazine and L-tryptophanate

A ternary Cu(II) complex with dipyrido[3,2-a?:?2′3′-c]phenazine(dppz) and L-tryptophanate (L-trp) has been synthesized and investigated by elemental analysis, molar conductivity, IR and X-ray diffraction. The complex crystallizes in the monoclimic space group P2₁ with two molecules in a unit cell of dimensions, a?=?7.949(2)?Å, b?=?10.724(3)?Å, c?=?18.580(5)?Å, β?=?93.697(5)°, V?=?1580.7(8)?ų, R ₁?=?0.0310, and wR ₂?=?0.0382. The central copper(II) ion has a distorted square-pyramidal geometry, in which the N,O-donor tryptophanate and N,N-donor heterocyclic base dppz are in the basal plane and a water molecule is coordinated at the axial site. DNA binding properties of the complex were studied by electronic absorption spectroscopy, fluorescence spectroscopy, and viscosity measurement. The DNA cleavage of the complex was investigated by agarose gel electrophoresis. The results show that the complex can bind DNA by intercalation and cleave pBR322 DNA in the presence of ascorbate.     

Synthesis and characterization of a dinuclear (Hedta)Ru(III) complex

A ruthenium(III) complex containing ethylenediaminetetraacetate (edta), [{Ru(Hedta)}₂(Pyz)]?·?8H₂O (1) (Pyz?=?pyrazine), has been synthesized by the reaction between K[Ru(Hedta)Cl]?·?1.5H₂O and pyrazine. The structure of the complex was determined by single X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 with a?=?7.293(9)?Å, b?=?10.575(14)?Å, c?=?12.742(16)?Å, α?=?104.044(19)°, β?=?91.893(19)°, γ?=?93.35(2)°, Z?=?1. The product was also characterized by IR, UV-Vis, EPR spectrum and magnetic techniques.     

Crystal structure,DNA interaction,and antiproliferative activity of the cobalt(II) complex of demethylcantharate and imidazole

A new cobalt(II) complex, [Co(C₃H₄N₂)(C₈H₈O₅)(H₂O)₂]·2H₂O, of demethylcantharate(7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, C₈H₈O₅) with imidazole has been synthesized from cobalt chloride, demethylcantharidin (NCTD) and imidazole. The complex was characterized by elemental analysis, IR, and X-ray single crystal diffraction. The complex crystallized in the monoclinic crystal system and P2₁/m space group with a?=?0.634790(10)?nm, b?=?0.963030(10)?nm, c?=?1.221770(10)?nm, α?=?90°, β?=?95.9700(10)°, γ?=?90°, V?=?0.742844(15)?nm³, M_r ?=?383.22, D_c ?=?1.713?g?cm^?3, Z?=?2, F(0?0?0)?=?398, μ?=?1.206?mm^?1, the final R?=?0.0291, and wR?=?0.0837 [I?>?2σ(I?)]. The interaction of the complex with deoxyribonucleic acid (DNA) was studied by electronic absorption spectra, fluorescence spectra, and viscosity measurements, which indicate that the complex binds to calf thymus DNA through a partially intercalative mode. The binding constant K _b for the complex was 2.62?×?10⁴?L?mol^?1. The antiproliferation activity test showed that the complex has high antiproliferative ability against human hepatoma cells SMMC7721 (with IC₅₀ being 42.8?±?0.9?µmol?L^?1) and human lung cancer cells A549 (with IC₅₀ being 65.1?±?3.2?µmol?L^?1). The inhibition rates of the complex are much higher than those of NCTD.