Syntheses,Structures, and Magnetic Properties of Two Mn(II) Coordination Polymers Based on 4-Fluorocinnamic Acid and 1,10-Phenanthroline

Two Mn(II) coordination polymers, {[Mn₃ (Pfca)₆(Phen)₂] · 2DMF} _n (I) and [Mn(Pfca)₂(Phen)(H₂O)] _n (II) (HPfca = 4-fluorocinnamic acid, Phen = 1,10-phenanthroline), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and singlecrystal X-ray diffraction (CIF files CCDC nos. 967513 (I), 1542972 (II)). Complex I crystallizes in the triclinic crystal system, space group Pī with a = 11.0821(11), b = 12.2632(12), c = 15.0288(15) Å, α = 87.3760(10)°, β = 88.4610(10)°, γ = 81.2220(10)°, V = 2016.0(3) Å3, ρ_c = 1.369 g/cm³, M _r = 1662.25, Z = 1, F(000) = 853, μ = 0.543 mm^–1, the final R = 0.0592 and wR = 0.1681 for 15498 observed reflections with I > 2σ(I). Complex II is of monoclinic system, space group P2₁/c with a = 18.0539(19), b = 8.5806(9), c = 18.758(2) Å, β = 116.5700(10)°, V = 2599.0(5) ų, ρ_c = 1.491 g/cm³, M _r = 583.44, Z = 4, F(000) = 1196, μ = 0.567 mm^–1, the final R = 0.0337 and wR = 0.0853 for 18139 observed reflections with I > 2σ(I). Complex I features linear Mn(II)-trinuclear units, which form 1D chain structure through F···F weak interactions, and complex II is 1D polymeric Mn(II)-chains. Antiferromagnetic coupling interactions exist within Mn(II)- carboxylate trinuclear in I (J =–0.40 cm^–1) and Mn(II)-carboxylate chain in II (J =–0.45 cm^–1).     

Syntheses,characterization, and crystal structures of two dinuclear nickel(II) and copper(II) complexes with Schiff bases

The phenolic azide bridged dinuclear nickel(II) complex, [Ni₂(L¹)₂(N₃)(H₂O)(μ_1,1-N₃)] · EtOH (I), and the thiocyanate bridged dinuclear copper(II) complex, [Cu₂(L²)₂(μ_1,1-NCS)₂] (II), where L¹ and L² are the deprotonated forms of 2-mothoxy-6-[(2-piperidin-1-ylethylimino)methyl]phenol and 2,4-dichloro-6-[(2-methylaminoethylimino)methyl]phenol, respectively, were synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The crystal of I is orthorhombic: space group Pbca, a = 12.172(1), b = 20.953(1), c = 29.779(2) Å, V = 7594.8(9) ų, Z = 8. The crystal of II is monoclinic: space group P2₁/n, a = 8.7615(11), b = 19.672(2), c = 16.568(2) Å, β = 99.449(2)°, V = 2816.9(6) ų, Z = 4. The Ni atoms in I are in octahedral coordinations, and the Cu atoms in II are in square-pyramidal coordinations.     

Crystal structures of two new dinuclear Ag(I) complexes constructed from 4,4′-biphenyldicarboxylic acid and N-containing ligands

The reaction of silver 4,4′-biphenyldicarboxylate with 1,3-diaminopropane (DAP) and 2-amino-5-methylpyridine (AMP) respectively results in the formation of two dinuclear silver(I) complexes: [Ag₂(DAP)₂](BPC)·2H₂O (1) and [Ag₂(BPC)(AMP)₄]·2H₂O (2), where BPC is 4,4′-biphenyldicarboxylate. The complexes are characterized by elemental analysis and X-ray crystallography. Complex 1 crystallizes in the triclinic system, P-1 space group, a = 8.585(2) Å, b = 8.849(2) Å, c = 9.890(3) Å, α = 107.893(3)°, β = 94.139(3)°, γ = 113.202(3)°, V = 640.9(3) ų, Z = 1. Complex 2 crystallizes in the triclinic system, P-1 space group, a = 11.818(3) Å, b = 13.132(4) Å, c = 13.281(4) Å, α = 92.571(4)°, β = 96.425(3)°, γ = 102.142(4)°, V = 1997.5(10) ų, Z = 2. Complex 1 consists of a macrocyclic dinuclear silver(I) dication, a 4,4′-biphenyldicarboxylate anion, and two water molecules of crystallization. Each Ag atom is in a linear coordination. Complex 2 consists of a dinuclear silver(I) complex molecule and two water molecules of crystallization. Each Ag atom is in a T-shaped coordination. The Ag...Ag separations are 5.127(2) Å in 1 and 3.172(2) Å in 2.     

Spectral and thermal properties,and the crystal structure of 1,4,5,8-naphthalene-tetracarboxylate dinuclear Ni(II) complex

A novel dinuclear Ni^II complex, [Ni₂(ntc)(H₂O)₁₀]·7(H₂O) (1), with 1,4,5,8-naphthaenetetracarboxylate (ntc) has been synthesized and characterized by X-ray diffraction analysis, IR, UV-vis spectra and thermogravimetric analysis. Complex 1 crystallizes in triclinic system, space group P-1, a = 7.721(3) Å, b = 9.458(3) Å, c = 11.453(4) Å, α = 114.110(6)°, β = 92.184(6)°, γ = 107.472(6)°, V = 715.7(4) ų, Z = 1, final R = 0.048. Each nickel atom is octahedrally coordinated by five aqua ligands and one oxygen atom of the bridging ntc connecting two nickel atoms. The resulting dinuclear Ni^II complex forms a 3D H-bonded network.     

Crystal structures of copper(II) and zinc(II) complexes derived from 3-(2-pyridyl)pyrazole

Two dinuclear complexes [Zn(μ-L)(NO₃)(H₂O)]₂ (1) and [Cu₂(μ-L)₂(HL)₂](NO₃)₂(C₁₂H₈Br₂)_0.5·H₂O (2), (HL = 3-(2-pyridyl)pyrazole, C₁₂H₈Br₂ = 4,4′-dibromobiphenyl) are synthesized under hydrothermal conditions and characterized by elemental analysis and X-ray single crystal diffraction. Crystal data for 1: triclinic, \(P\bar 1\), a = 8.8478(7) Å, b = 15.0550(11) Å, c = 16.4310(12) Å, α = 107.588(4)°, β = 112.498(3)°, γ = 115.595(3)°, V = 2099.8(9) ų, Z = 2; for 2: triclinic, \(P\bar 1\), a = 7.2870(15) Å, b = 8.6840(17) Å, c = 9.3290(19) Å, α = 107.588(4)°, β = 112.498(3)°, γ = 115.595(3)°, V = 528.77(18) ų, Z = 1. Complex 1 and 2 are both dinuclear structures which are further packed into a 1D supramolecular chain and a 3D supramolecular framework via weak C–H…O hydrogen bond interactions respectively.     

Crystal structures of pyridine-4-aldehyde thiosemicarbazone perchlorate and trifluoromethane sulfonate

The new salts of pyridine-4-aldehyde thiosemicarbazone: perchlorate (I) and trifluoromethane sulfonate (II) HN⁺C₅H₄-CH=N-NH-C(S)-NH₂·X^? (X = ClO₄, CF₃SO₃) were synthesized and studied by IR and NMR spectroscopy and X-ray diffraction analysis. The compounds were synthesized by a reaction of pyridine-4-aldehyde thiosemicarbazone with chloric or trifluoromethane sulfonic acid, respectively. Compound I crystallized in the triclinic crystal system, space group P-1, a = 6.8691(2) Å, b = 9.5406(4) Å, c = 9.6348(4) Å, α = 78.838(1)°, β = 77.618(1)°, γ = 69.661(1)°, Z = 2. Compound II crystallized in the monoclinic crystal system, space group P2₁/c, a = 7.3149(8) Å, b = 11.9830(16) Å, c = 15.143(2) Å, β= 96.949(4)°, Z = 4. The structures are formed by hydrogen-bonded ions. Moreover, the cations are linked in “dimmers” due to the weak N-H...S hydrogen bonds.     

New binuclear complex of bis(2,4,6,8-tetramethyl-2,4,6,8- tetraazabicyclo(3.3.0)octane-3,7-dione-<Emphasis Type="Italic">O,O</Emphasis>')-diaquatetrakis(nitrato-<Emphasis Type="Italic">O,O</Emphasis>')-dimanganese(II) monohydrate: Synthesis and crystal structure

The centrosymmetric binuclear manganese(II) nitrate complex with a bicyclic bis-carbamide, namely, 2,4,6,8-tetramethyl-2,4,6,8-tetraazabicyclo(3.3.0)octane-3,7-dione, or mebicar (Mk) [Mn(C₈H₁₄N₄O₂)(H₂O)(NO₃)₂]₂ · H₂O (I), has been synthesized for the first time. The structure of complex I has been solved (CCDC no. 1435139). Crystals of complex I are monoclinic, space group P2₁/c, a = 12.8108(11) Å, _b = 10.0662(2) Å, c = 18.6367(17) Å, β = 136.512(16)°, V = 1654.0(4) ų, ρcalcd = 1.659 g/cm³, Z = 2. Each manganese atom is coordinated to the two oxygen atoms of two Mk molecules related by the symmetry codes (1–x, 2–y, 1–z) and to two bidentate nitrate anions and one water molecule. The coordination polyhedron of the manganese atom is a strongly distorted pentagonal bipyramid. The Mn···Mn distance in the complex is 8.7261(9) Å.     

New complex of manganese(II) with schiff base derived from furaldehyde and diethylenetriamine

A new manganeses(II) complex MnLCl₂ · CH₃OH (L = N,N′-bis(furaldehyde)diethylenetriamine) was synthesized and characterized by X-ray crystallographic analysis. The crystals are orthorhombic, space group Pnma with cell parameters a = 20.998(6), b = 13.314(5), c = 6.785(8) Å, Z = 4, R ₁ = 0.0609, and wR₂ = 0.2116. The coordination geometry around Mn(II) atom is a trigonal-bipyramidic containing one tridenate ligand L and two Cl^? ions.     

Crystal structures of <Emphasis Type="Italic">trans</Emphasis>-[Re<Subscript>6</Subscript>S<Subscript>8</Subscript>(CN)<Subscript>2</Subscript>L<Subscript>4</Subscript>] complexes,L = pyridine or 4-methylpyridine

The structures of three novel octahedral rhenium cluster compounds [Re₆S₈(CN)₂(py)₄]·H₂O (1), [Re₆S₈(CN)₂(4-Mepy)₄] (2), [Re₆S₈(CN)₂(4-Mepy)₄]·4-Mepy (3) (py = pyridine, 4-Mepy = 4-methylpyridine) are determined by X-ray crystallography. Crystal data are: C2/m space group, a = 14.813(1) Å, b = 14.772(1) Å, c = 9.2122(6) Å, β = 119.085(2)°, V = 1761.7(2) ų, d _x = 3.318 g/cm³, R = 0.0585 (1); I4₁/amd space group, a = 16.0018(3) Å, c = 14.7186(5) Å, V = 3768.81(16) ų, d _x = 3.169 g/cm³, R = 0.0489 (2); P2₁/c space group, a = 9.0452(4) Å, b = 15.8065(7) Å, c = 15.2951(6) Å, β = 103.700(2)°, V = 2124.57(16) ų, d _x = 2.957 g/cm³, R = 0.0245 (3). Molecular cluster complexes interact via π-π stacking affording 3D frameworks in 1 and 2 and chains in 3.     

Lead lanthanum and strontium lanthanum germanovanadates with apatite and oxyapatite structures

New compounds Pb₄La(GeO₄)₂(VO₄)(I) and Sr₅La₅(GeO₄)₅(VO₄)O(II) were prepared and identified. Compound I has the structure of apatite, a = 10.108(1) Å, c = 7.369(1) Å, V = 652.1(2) ų. Compound II has the structure of oxyapatite, a = 9.9028(5) Å, c = 7.3162(4) Å, V = 621.34(6) ų.     

Synthesis and crystal structures of two Schiff base copper(II) complexes derived from 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol

A centrosymmetric mononuclear copper(II) complex, [Cu(L¹)₂] (I), and a phenolate oxygen-bridged dinuclear copper(II) complex, [Cu₂(L²)₄] (II) (HL¹ = 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol, HL² = 4-chloro-2-(cyclohexylimino-methyl)phenol), were synthesized and characterized by elemental analyses, IR, and single crystal X-ray diffraction. The crystal of I is monoclinic: space group {ITP}2₁/n, a = 13.396(3), b = 5.339(1), c = 19.740(4) Å, β = 108.64(3), V = 1337.8(5) ų, {ITZ} = 2. The crystal of II is monoclinic: space group P2₁, a = 9.157(2), b = 22.715(4), c = 12.169(2) Å, = 95.28(3), {ITV} = 2520.4(8) Å3, {ITZ}= 2. The Cu atom in I, lying on the inversion center, is four-coordinate in a square planar geometry with two phenolate oxygen and two imine nitrogen atoms. Each Cu atom in II is five-coordinate in a square pyramidal geometry with two phenolate oxygen and two imine nitrogen atoms from two L² ligands defining the basal plane and with one phenolate oxygen atom of another L² ligand occupying the apical position.     

Synthesis and Structure of a New Cu(II) Complex with 2-Benzoylpyridine and Its Hydrolyzed Derivative H<Subscript>2</Subscript>bpd as Ligands

A new Cu(II) complex, [Cu₂(bzpy)₂(Hbpd)₂(H₂O)](ClO₄)₂·H₂O (1) based on bzpy (bzpy = 2-benzoylpyridine) and H₂bpd (benzyl-2-pyridylmethanediol) mixing ligands, was synthesized and characterized by IR, UV–Vis spectra, TGA and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P2(1)/n with a = 18.7790(2), b = 14.4609(3), c = 18.9434(4) Å, β = 102.17°, V = 5028.63(16) ų, Z = 4. The complex bears a dinuclear structure in which two Cu(II) atoms adopt elongated square pyramidal (SP) and octahedral geometry, respectively, and two intramolecular π…π interactions are also observed. Then with the help of intermolecular π…π and CH…π interactions, a 1D chain structure is formed based on the dinuclear unit. Thermal stability of 1 was studied.     

Synthesis and crystal structures of cobalt(III) and zinc(II) complexes derived from 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol with urease inhibitory activity

A new mononuclear cobalt(III) complex, [CoL₂(N₃)]₂ · CH₃OH (I), and a new mononuclear zinc(II) complex, [ZnLCl(CH₃OH)] (II) (HL = 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol), were prepared and structurally characterized by elemental analyses, infrared spectroscopy, and single- crystal X-ray diffraction. The crystal of I is monoclinic: space group P2₁/c, a = 18.742(2) Å, b = 15.197(2) Å, c = 25.646(2) Å, β = 125.996(3)°, V = 5909.8(11) ų, Z = 4. The crystal of II is monoclinic: space group P2₁/c, a = 7.257(1) Å, b = 24.707(2) Å, c = 9.637(1) Å, β = 101.557(2)°, V = 1692.9(3) ų, Z = 4. The Co atom in I is in an octahedral coordination, and the Zn atom in II is in a trigonal-bipyramidal coordination. The urease inhibitory test shows that complex I has strong urease inhibitory activity, while complex II has no activity.     

Synthesis and characterization of a novel coordination polymer {[Mn(L)(Phen)<Subscript>2</Subscript>] · 2H<Subscript>2</Subscript>O}<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript><Superscript>1</Superscript>

A novel coordination polymer {[Mn(L)(Phen)₂] · 2H₂O} _n (I) has been synthesized by the reaction of Mn(CH₃COO)₂, 2,2′-bipyridine-5,5′-dicarboxylic acid (HL) and 1,10-phenanthroline (Phen). The structure of the complex was charactered by single-crystal X-ray diffractometry. The unit cell parameters for complex I: a = 11.796(3), b = 17.837(5), c = 15.081(4) Å; β = 101.804(5)°; V = 3106.0(15) ų; Z = 4; space group C2/c. The Mn(II) atom is coordinated by four nitrogen atoms from two Phen molecules and two oxygen atoms from two molecules L with a distorted octahedral geometry. Complex was dibridged by the L ligand forming a 1D infinite chain. Intramolecular weak interactions, such as hydrogen bonds and π...π-stacking, were found in the title complex, and 3D supramolecular framework was constructed by intermolecular weak interactions mentioned above.     

Tetramminenickel hydrogen hexamolybdometalates(III)

Tetramminenickel hydrogen hexamolybdoaluminate and hexamolybdogallate(III) of compositions [Ni(NH₃)₄] · H[AlMo₆O₁₈(OH)₆] · 10H₂O (I) and [Ni(NH₃)₄] · H[GaMo₆O₁₈(OH)₆] · 10H₂O (II) were synthesized and characterized by mass spectrometry, thermogravimetry, X-ray powder diffraction, and IR spectroscopy. Their crystals are triclinic. For compound I, a= 17.30 Å, b= 14.69 Å, c= 10.45 Å, α = 129.07, β = 65.91°, γ = 138.01°, V = 1338.7l ų, ρ_calcd = 2.75g/cm³, Z = 2; for compound II, a = 17.38 Å, b= 14.75 Å, c= 10.51 Å, α = 131.38°, β= 65.96°, γ = 138.09, V = 1338.15 ų, ρ_calcd = 2.68 g/cm³, Z = 2.     

Synthesis and structure of bis(1,2-diaminoethane) copper(II) bis(<Emphasis Type="Italic">o</Emphasis>-hydroxybenzoate) monohydrate and <Emphasis Type="Italic">trans</Emphasis>-diaquabis(1,2-diaminoethane)copper(II) bis(<Emphasis Type="Italic">o</Emphasis>-aminobenzoate)

X-ray structural analysis has been performed for two complex compounds: Cu(en)₂(o-HB)₂H₂O (I) (a = 16.873(4) Å, b = 8.713(2) Å, c = 14.803(3) Å, β = 91.15(2)°, V = 2175.8(8) ų, C2/c, Z = 4, R(F) = 0.0263, 1516 reflections with I > 3σ (I)) and [Cu(en)₂(OH₂)₂]²⁺(o-AB^?)₂ (II) (a = 7.488(5) Å, b = 22.122(8) Å, c = 7.856(5) Å, β = 118.77(2)°, V = 1140.7(11) ų, P2₁/n, Z = 2, R(F) = 0.0432, 1684 reflections with I > 3σ(I)) synthesized under identical conditions (en is ethylenediamine, o-HB is o-hydroxybenzoate, and o-AB is o-aminobenzoate). Although the compounds were assumed to have similar structures and the Cu-Lig bond lengths and the cis and trans angles are acceptable for an octahedral structure, the geometric parameters of o-HB suggest that the copper atom has a plane square environment.     

Manganese(II) 9-Molybdomanganate(IV), [Mn(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>]<Subscript>3</Subscript> · [MnMo<Subscript>9</Subscript>O<Subscript>32</Subscript>] · 2H<Subscript>2</Subscript>O: Synthesis,thermal analysis,IR spectra,and crystal structure

The [Mn(H₂O)₄]₃ · [MnMo₉O₃₂] · 2H₂O complex was synthesized and studied by X-ray diffraction, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are trigonal: space group R32, a = 14.811(2) Å, c = 14.232(2) Å, V = 2703.7(8) ų, M = 1848.5, Z = 3, ρ(calcd.) = 3.419 g/cm³.     

Synthesis and crystal structure of a new Schiff base ligand and its cobalt(II) complex

The crystal structures of cobalt(II) Schiff base complex (Co^IIL₂ · H₂O) and Schiff base ligand 3,5-dichlorosalicylidene-2-chlorophenylmethylamine (HL) have been determined by single-crystal X-ray analysis. The geometry around cobalt in Co^IIL₂ · H₂O is distorted tetrahedral. Co^IIL₂ · H₂O crystallizes in the monoclinic system, in space group C2/c, with crystallographic parameters: a = 12.9143(16) Å, b = 8.8326(16) Å, c = 25.115(3) Å, β = 92.791(10)°, V = 2861.4(7) ų, Z = 4, F(000) = 1420, and the final R indices (I > 2σ(I)) are R ₁ = 0.0440, wR ₂ = 0.1272. HL crystallizes in the monoclinic system, in space group P2₁/c, with crystallographic parameters: a = 11.9764(15), b = 8.2331(10), c = 14.2211(17) Å, β = 98.723(6)°, V = 1386.0(3) ų, Z = 4, F(000) = 640, and the final R indices (I > 2σ(I)) are R ₁ = 0.0397, wR ₂ = 0.1018.     

Crystal structure and antitumor activities of a dinuclear cobalt(II) complex based on <Emphasis Type="Italic">meso</Emphasis>-1,2,3,4-tetra(1H-benzo[<Emphasis Type="Italic">d</Emphasis>]imidazol-2-yl)butane

The [Co₂(tbb)Cl₄]?4DMF complex, where tbb is meso-1,2,3,4-tetra(1H-benzo[d]imidazol-2-yl)butane, is synthesized and characterized by single crystal X-ray diffraction. For the complex: C₄₄H₅₄Co₂C_l4N₁₂O₄, M_r = 1074.65, monoclinic crystal system, space group P21/n, a = 9.2350(13) Å, b = 11.3566(15) Å, c = 23.879(3) Å, β = 90.547(2)°, V = 2504.3(6) ų, Z = 2, D_c = 1.425 g/cm³, λ = 0.71073 Å, μ(MoK_α) = = 0.929 mm^–1, F(000) = 1112, S = 1.047, R = 0.0765, and wR = 0.2110 for 13668 observed reflections with I > 2σ(I). It is a neutral dinuclear complex. One meso-1,2,3,4-tetra(1H-benzo[d]imidazol-2-yl)butane coordinates two cobalt(II) ions. Each cobalt(II) ion is formed by two tbb nitrogen atoms and two chloride ions. The antiproliferative activities of the complex are screened by MTT assay against Eca109 cancer cells. The complex exhibits inhibition on the growth of Eca109 cancer cells with IC₅₀ of 22.1±6.7 μM after 48 h treatment. The cobalt complex has potential application in treatment of Eca109 cancer. CCDC 1015791.     

Binuclear copper(II) complexes with acyldihydrazones of benzenedicarboxylic acids with pyrrolidine or piperidine

The adducts of binuclear copper(II) complexes with acyldihydrazones formed by 1,3- or 1,4-benzenedicarboxylic acid and some nitrogen-containing Lewis bases (pyrrolidine, piperidine) were synthesized and studied. The structure of copper(II) complex with bis(salicylidene)hydrazone of terephthalic acid (H₄L), [Cu₂L(Pirr)₄] · CH₃OH, was determined by X-ray diffraction data. The crystals are monoclinic: a = 15.5142(7) Å, b = 13.8784(6) Å, c = 17.8873(8) Å; β = 91.990(2)°, space group C2/c, Z = 4. The number of symmetrically independent reflections was 4269, R = 0.0303, R _w = 0.0827. The complex contains two equivalent copper atoms located at a 11.021 Å is a tetragonal pyramid. EPR spectral features of the adducts were studied.