Synthesis and crystal structure of Mn(II) and Zn(II) complexes with 1,3,5-tris(carboxymethoxyl)benzene ligand

Two complexes (H₂bipy)[M₂(TB)₂(H₂O)₈]·5H₂O (M = Mn 1, Zn 2) (bipy = 4,4′-bipyridine, H₃TB = 1,3,5-tris(carboxymethoxyl)benzene) were synthesized by the reaction of the corresponding metal salt with ligand H₃TB and 4,4′-bipy in an aqueous methanol solution at room temperature, respectively. Their structures were determined by single crystal X-ray diffraction analysis. Both complexes 1 and 2 crystallize in the triclinic space group with the crystal parameters of 1: a = 9.725(12) ?, b = 10.651(13) ?, c = 10.882(13) ?, α = 91.72(2)°, β = 96.41(2)°, γ = 97.72(2)°, V = 1109(2) ?³, Z = 1 and 2: a = 9.610(10) ?, b = 10.55(2) ?, c = 10.83(2) ?, α = 91.60(4)°, β = 95.32(2)°, γ = 97.73(4)°, V = 1082(3) ?³, Z = 1. Complexes 1 and 2 have the same dinuclear structure, in which each metal atom is six coordinated with distorted octahedral geometry by two oxygen atoms from two different TB³⁻ ligands and four ones from four coordinated water molecules. The dinuclear units are further linked by hydrogen bonding and π–π interactions to form the three-dimensional framework structure.     

Two new CrIII(bpb)(H2O)X complexes derived from [Cr(bpb)(N3)2]− or [Cr(bpb)(CN)2]− (bpb2− = 1,2-bis(pyridine-2-carboxamido)benzenate, X− = hydroxo or azide)

Two new Cr(III) complexes, [Cr(bpb)(H₂O)(OH)]·3H₂O (1) and [Cr(bpb)(H₂O)(N₃)]·H₂O (2) have been synthesized and structurally characterized. Both complexes were unexpectedly obtained as single crystals during the reactions of [Cr(bpb)(CN)₂]⁻ or [Cr(bpb)(N₃)₂]⁻ with [Ni(L)](ClO₄)₂ (L = 3,10-dimethyl-1,3,6,8,10,12-hexaazacyclotetradecane) or MX₂·nH₂O (M = Cu, Ni and Mn, X = Cl⁻ and ClO₄ ⁻). Complex 1 crystallizes in the triclinic system, space group P-1, formula CrC₁₈H₂₁N₄O₇ with a = 7.1543(17) ?, b = 12.420(3) ?, c = 12.955(3) ?, α = 115.021(5)°, β = 95.544(5)°, and γ = 101.575(5)°. Complex 2 crystallizes in the monoclinic system, space group P2₁/c, formula CrC₁₈H₁₆N₇O₄ with a = 11.7171(9) ?, b = 9.4999(7) ?, c = 16.8799(13) ?, and β = 97.449(2)°. Both complexes exhibit distorted octahedral coordination environment with four nitrogen atoms of bpb²⁻ situated at the equatorial plane (Cr–N bond distances range from 1.961(3) to 2.1088(15) ?), and the remaining two trans-positions occupied by terminal ligands H₂O/HO and H₂O/N₃ in 1 and 2, respectively. It is noteworthy that a hydrogen-bonded folded ladder-like structure involving twelve O atoms in 1 and a chair-like hexagonal hydrogen-bonded cluster containing six O atoms are formed.     

Synthesis and crystal structure of cobalt(III) complex with a Schiff base and azide

The cobalt(III) complex, [Co(L)₂(N₃)₂]₂(ClO₄)₂, L being a Schiff base N-[phenyl(pyridin-2-yl)methylene]aniline has been synthesized and the crystal structure determined using X-ray crystallography. The complex crystallizes in triclinic system, space group P-1 with unit cell parameters a=10.9367(9) ?, b=18.0817(17) ?, c=20.1629(16) ?, α=111.341(2)°, β=91.622(2)°, γ=107.5030(10)°, V=3499.1(5) ?³ and Z=2. It crystallizes with two independent molecules in the asymmetric unit. The two cobalt atoms are hexa-coordinate and have a distorted octahedral geometry, satisfied by four nitrogen atoms from two molecules of the Schiff base and two nitrogen atoms from the monodentate azide group. The perchlorate ions are non-coordinating.     

Synthesis and structure of the first water-soluble chiral monomeric MnIV complex: [Δ-MnIV(biguanide)3] (ClO4)4·H2O

The reaction of KMnO₄ with alkaline biguanide sulfate solution, followed by acidification of the resulting stable filtrate with concentrated HClO₄, led to the title complex, 1. The crystal structure of the [Δ-Mn^IV(bigH)₃](ClO₄)₄·H₂O (1, bigH: biguanide, C₂H₇N₅) has a tetragonal chiral P4 ₁ 2 ₁ 2 space group with a = b = 11.416(3) ?, c = 20.742(7) ?, Z = 4. The complex consists of one chiral [Δ-Mn^IV(bigH)₃] tetracation, four ClO₄ ⁻ anions, and one water molecule. In the tetracation, six N atoms from three neutral biguanide chelate coordinate to the Mn^IV cation, forming an octahedron with Δ-optical activity. The [Δ-Mn^IV(bigH)₃] tetracation interconnects each other by numerous hydrogen bonds with N–H···O and O–H···O between biguanide moieties of the [Δ-Mn^IV(bigH)₃] tetracations and counter-anions as well as water molecules, to construct a three-dimensional network.     

Persistence of layer motifs in the crystal structures of [1,4-bis-(2-methoxy-2-carbonylethyl)piperazinium (2’)] chloride and [1,4-bis-(2-amidoethyl)piperazinium (2’)] perchlorate

Two structures of the closely related piperazinium salts, [1,4-bis-(2-methoxy-2-carbonylethyl)piperazinium (2+)] chloride (1) and [1,4-bis-(2-amidoethyl)piperazinium (2+)] perchlorate (2) reveal the persistence of a layer structure, interspersed with anions, held in place by N–H···Cl, C–H···O and C–H···Cl interactions in the case of 1, and N–H···O and C–H···O interactions in the case of 2. Compound 1 crystallizes in the triclinic space group P-1 with a=6.7667(6) ?, b = 6.9467(6) ?, c=9.3880(18) ?, α=105.845(9)°, β=99.896(16)°, γ=103.600(9)°, and Z=1. Compound 2 crystallizes in the monoclinic space group P2₁/c with a = 9.0930(8) ?, b=10.0525(11) ? c=10.2104(13) ?, β=114.279(9)°, and Z=2.     

Supramolecular Network via Hydrogen Bonding and π–π Stacking in 4,4′-Bipyridin-1-ium Perchlorate Dihydrate

Abstract The crystal structure of 4,4′-bipyridin-1-ium perchlorate dihydrate, [C₁₀H₉N₂](ClO₄) · 2H₂O, is determined by room temperature X-ray diffraction. The compound crystallizes in the triclinic space group P-1 with a = 8.122(3) ?, b = 9.726(3) ?, c = 17.648(6) ?, α = 78.181(4)°, β = 82.797(5)°, γ = 67.439(4)°, Z = 2, V = 1258.4(7) ?³. In the compound, monoprotonated 4,4′-bipyridin-1-ium cations are self-assembled into supramolecular chains along the a-axis through N–H···N hydrogen bonds in a head-to-tail fashion. The chains are stacked via π–π stacking interactions to create two-dimensional sheets. The interlayer space is occupied by the hydrogen-bonded water chains that are linked to the organic sheets via C–H···O interactions and the perchlorate anions that are linked to the water chains and the organic sheets via O–H···O and C–H···O hydrogen bonds, respectively, thus generating a three-dimensional supramolecular architecture. Index Abstract Supramolecular Network via Hydrogen Bonding and π–π Stacking in 4,4′-Bipyridin-1-ium perchlorate dihydrate Jian-Yong Zhang, Ai-Ling Cheng and En-Qing Gao* Monoprotonated 4,4′-bipyridin-1-ium cations are self-assembled into supramolecular chains along the a-axis through N–H···N hydrogen bonds, and these chains are stacked via π–π stacking and hydrogen bond interactions involving water molecules and perchlorate anions.      

Copper(II) and lead(II) complexes of 4,4′-bipyridine-<Emphasis Type="Italic">N,N</Emphasis>′-dioxide

Cu(II) and Pb(II) complexes of 4,4′-bipyridine-N,N′-dioxide have been prepared using a solvent-layering system. [Cu₂Cl₄(bpdo)₃(H₂O)₂] . 2(CH₃)₂SO (1) crystallises in P-1, a=8.731(2), b=8.943(2), c=14.408(3) ?, α=102.85(3), β=97.49(3), γ=109.77(3)°. The Cu(II) complex is a z-shaped discrete molecule with a DMSO molecule hydrogen bonded to the host through coordinated water molecule. Crystallisation of PbCl₂, PbBr₂ and PbI₂ with bpdo afforded isostructural 2D coordination polymers. [PbCl₂(bpdo)]_n is monoclinic, C2/c with a=16.3274(7), b=4.0708(1), c=18.6146(8) ?, β=93.73(1)°; [PbBr₂(bpdo)]_n is monoclinic, C2/c with a=16.403(3), b=4.2412(8), c=18.846(4) ?, β=92.59(3)° and [PbI₂(bpdo)]_n is monoclinic, C2/c with a=16.438(3), b=4.538(1), c=18.973(4) ?, β=91.04(3)°. The adjacent metal centres of these polymers are bridged by coordinated Cl⁻, Br⁻ or I⁻ anions as well as by bpdo ligands. These polymers possess no conventional hydrogen bonds.     

Syntheses and crystal structures of an organometallic thiosemicarbazone and an organometallic enehydrazide

Reactions of ferrocenoylacetone with thiosemicarbazide and isonicotinic acid hydrazide generate an organometallic thiosemicarbazone 1 and enehydrazide 2, respectively. The complexes 1 and 2, which can be formulated as [C₅H₅FeC₅H₄C(O)CH₂C(=NNHCSNH₂)CH₃] and [C₅H₅FeC₅H₄C(O)CH=C(NHNHCOC₅H₄N-4)CH₃], have been characterized by elemental analyses, IR, NMR, UV and were structurally characterized by single-crystal X-ray crystallography. Complex 1 (C₁₅H₁₇FeN₃OS) crystallizes in the monoclinic space group P2₁/c, with lattice constants: a = 13.939(3) ?, b = 8.2600(17) ?, c = 13.176(3) ?, β = 94.83(3)°, V = 1511.7(6) ?³, Z = 4, D _c = 1.508 g cm⁻³, F(000) = 712, R ₁ = 0.0602, wR ₂ = 0.1526. Two intermolecular hydrogen bonds N–H···S (N···S = 3.356(8) and 3.499(7) ?, N–H···S = 168 and 170°) form a chain in the [010] direction. The intermolecular hydrogen bond C–H···O (C···O = 3.432(10) ?, C–H···O = 151°) leads to a [010] double-chain through each unit cell. The intermolecular hydrogen bond C–H···O (C···O = 3.359(10) ?, C–H···O = 173°) makes the [010] double-chain pack along the c axis to result in a two-dimensional network. Complex 2 (C₂₀H₁₉FeN₃O₂) crystallizes in the monoclinic space group P2₁/c, with lattice constants: a = 14.091(2) ?, b = 10.024(2) ?, c = 13.806(2) ?, β = 112.41(2)°, V = 1802.8(6) ?³, Z = 4, D _c = 1.434 g cm⁻³, F(000) = 808, R ₁ = 0.0576, wR ₂ = 0.1593. The strong intramolecular hydrogen bond N–H···O from the enamine N atom and carbonyl O atom stabilizes the enehydrazide. The intermolecular hydrogen bonds N–H···O and C–H···O (N···O = 2.906(6) ?, N–H···O = 155° C···O = 3.364(6) ?, C–H···O = 153°) generate a [010] chain. The intermolecular hydrogen bond N–H···O (N···O = 2.989(6) ?, N–H···O = 128°) forms a [010] double-chain through each unit cell. The π···π stacking interation involving the pyridyl groups makes the [010] double-chain pack along the c axis to lead to a two-dimensional network.     

Supramolecular Cobalt(II), Copper(II) and Cadmium(II) Complexes Obtained from a Proton Transfer Compound including Pyridine-2,6-dicarboxylate and Propane-1,3-diaminium Ions; Synthesis,Characterization and Crystal Structure

Abstract The three complexes (pnH₂)[Co(pydc)₂]·4H₂O 1, (pnH₂)[Cu(pydc)₂]·4H₂O 2, and (pnH₂)[Cd(pydc)₂]·3.5H₂O 3 (pn: propane-1,3-diamine, pydc: pyridine-2,6-dicarboxylate) were prepared using a proton transfer compound (pnH₂)(pydc)·(pydcH₂)·2.5H₂O, LH ₂ and corresponding metallic salts. The characterization was carried out using elemental analysis, IR and NMR spectroscopy, and single crystal X-ray diffraction. Complexes 1 and 2 crystallize in space group P , but complex 3 crystallizes in space group P2/c. Cell parameters of the complexes are a = 8.449(1) ?, b = 11.668(1) ?, c = 12.801(1) ?, α = 115.748(2)°, β = 93.038(2)°, γ = 97.867(2)° for 1; a = 7.973(2) ?, b = 16.632(2) ?, c = 25.280(5) ?, α = 94.178(6)°, β = 95.186(6)°, γ = 91.603(5)° for 2 and a = 20.055(1) ?, b = 13.8161(9) ?, c = 8.2418(5) ?, β = 100.086(1)° for 3. The three crystal structures illustrate that the metal ion is six-coordinated by two pydc’s. In structures of 2 and 3, it can be seen that propane-1,3-diaminium fragments have different conformations. The complexes have ion-pairing interactions, O–H···O, N–H···O and C–H···O hydrogen bonds, π–π stacking as well as van der Waals forces as the main factors in formation of their supramolecular structures. Index Abstract Supramolecular Cobalt(II), Copper(II) and Cadmium(II) Complexes Obtained from a Proton Transfer Compound including Pyridine-2,6-dicarboxylate and Propane-1,3-diaminium Ions; Synthesis, Characterization and Crystal Structure Hossein Aghabozorg, Mohammad Ghadermazi,Bahar Nakhjavan, Faranak Manteghi The synthesis, characterization, crystal structure and non-covalent interactions of three supramolecular complexes of Co(II), Cu(II) and Cd(II) obtained by the reaction of a proton transfer compound i.e. (pnH₂)(pydc)·(pydcH₂)·2.5H₂O with the corresponding metallic salts are reported. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal Structure of bis(18-Crown-6)-bis(formato-O) dicaesium dihydrate

Abstract  The crystal structure of the title compound, [2Cs⁺(C₁₂H₂₄O₆)₂(CHO₂ ⁻)₂(H₂O)₂], was determined by an X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P2₁ /n with cell parameters a = 10.4278(7) ?, b = 10.0183(5) ?, c = 18.2383(12) ?, β = 93.723(5)°, V = 1910.3(2) ?³ and Z = 2. The Cs cations are bonded to each of the six O atoms of a crown ether ring, two water molecules, and one O atom of a formato anion. As a result of that, a centrosymmetric dimeric dinuclear complex is formed. The two halves of the dimer are connected by a ring of formato anions and water molecules which are linked by O–H···O hydrogen bonds. Index Abstract  The title compound, bis(18-crown-6)-bis(formato-O), caesium dihydrate, features a centrosymmetric dimeric dinuclear complex where two Cs cations are coordinated by six O atoms of a crown ether ring. The two halves of this complex are held together by a ring of formato anions and water molecules which are linked by hydrogen bonds.      

Supramolecular Association in the Structure of 2,9-<Emphasis Type="Italic">C</Emphasis>-<Emphasis Type="Italic">meso</Emphasis>-2,5,5,7,9,12,12,14-Octamethyl-1,8-diaza-4,11-diazoniacyclotetradecane as its Bis(nitrate) and Bis(acetate) Trihydrate

Abstract In the crystal structure of the nitrate salt, columns of di-cationic macrocycles, each disposed about a center of inversion, are interspersed by pairs of nitrate anions that form charged-assisted N–H···O hydrogen-bonding interactions, reinforced by C–H···O contacts. The topology of the resulting supramolecular architecture is that of a linear chain and these associate via further weak C–H···O contacts. In the structure of the acetate trihydrate, di-cationic macrocycles are circumscribed by 32-membered rings defined by O–H···O interactions, involving the acetate anions and solvent water molecules. Systematic variations in the geometric parameters in the molecular structures are correlated with the influence of intermolecular interactions. The nitrate crystallizes in the monoclinic space group P2₁/n with a = 8.3524(11) ?, b = 12.5497(16) ?, c = 11.1208(16) ?, β = 103.180(3)°, and Z = 2. The acetate trihydrate also crystallizes in the monoclinic space group P2₁/n with a = 9.6679(15) ?, b = 15.278(2) ?, c = 9.8376(18) ?, β = 106.068(5)°, and Z = 2. Index Abstract Supramolecular Association in the Structure of 2,9- C-meso -2,5,5,7,9,12,12,14-Octamethyl-1,8-diaza-4,11- diazoniacyclotetradecane as its Bis(nitrate) and Bis(acetate) Trihydrate Saroj K. S. Hazari, ⁽¹⁾ Tapashi G. Roy, ^(1)* Kanak K. Barua ⁽¹⁾ and Edward R. T. Tiekink ^(2)* A linear supramolecular chain stabilized by charge-assisted N–H···O hydrogen-bonding interactions is found in the nitrate salt. In the acetate trihydrate, di-cationic macrocycles are circumscribed by 32-membered rings constructed by O–H···O hydrogen-bonds. Supramolecular Association in the Structure of 2,9- C-meso -2,5,5,7,9,12,12,14-Octamethyl-1,8-diaza-4,11- diazoniacyclotetradecane as its Bis(nitrate) and Bis(acetate) Trihydrate Saroj K. S. Hazari, ⁽¹⁾ Tapashi G. Roy, ^(1)* Kanak K. Barua ⁽¹⁾ and Edward R. T. Tiekink ^{(2)* (1)}Department of Chemistry, University of Chittagong, Chittagong-4331, Bangladesh ⁽²⁾Department of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698 Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

Metal Ion Interactions with Pyridinecarboxylates in Tripodal tris(2-Aminoethyl)amine Ligand System: Crystal Structures of [Ni(tren)(pic)]2(ClO4)2·CH3OH and [Co(tren)(dipic)]ClO4·CH3OH

Abstract  

Two new complexes [Ni(tren)(pic)]₂(ClO₄)₂·CH₃OH (1) and [Co(tren)(dipic)]ClO₄·CH₃OH (2), (tren is tris(2-aminoethyl)amine, pic is the anion of picolinic acid, dipic is the dianion of 2,6-pyridinedicarboxylic acid) have been synthesized and structurally characterized. X-ray analysis indicates that the two complexes are mononuclear with tren acting as a quadridentate ligand. In complex 1, the nickel(II) ion is further coordinated with picolinate in μ₂-N, O bidentate chelating mode. In complex 2, the cobalt(III) ion is coordinated with the pyridine nitrogen and one carboxylic oxygen of 2,6-pyridinedicarboxylate in μ₂-N, O chelating form. The metal atoms in both cases have distorted octahedral geometry. Crystal data: [Ni(tren)(pic)]₂(ClO₄)₂·CH₃OH (1), Mr = 869.03, monoclinic, C2/c, a = 26.354(5) ?, b = 10.407(2) ?, c = 25.839(5) ?, β = 96.24(3)°, Z = 8, V = 7045(2) ?³, R ₁ = 0.0418, wR ₂ = 0.1063 [I > 2σ(I)]; [Co(tren)(dipic)]ClO₄·CH₃OH (2), Mr = 501.77, Triclinic, P-1, a = 8.3667(2) ?, b = 10.4434(2) ?, c = 11.9431(16) ?, α = 73.9590(10)°, β = 88.0240(10)°, γ = 75.5890°, Z = 2, V = 969.97(4) ?³, R ₁ = 0.0408, wR ₂ = 0.1063 [I > 2σ(I)].     

Synthesis and Crystal Structure of a One-Dimensional Chain Cadmium Coordination Polymer Bridged Through 1,2-bis(imidazol-1-yl)ethane

Abstract The cadmium(II) complex [Cd(phba)₂(bim)(H₂O)₂]_n (1) (phba = 4-hydroxybenzoate, bim = 1,2-bis(imidazol-1-yl)ethane) has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in the monoclinic space group C2/c, a = 23.820(4) ?, b = 9.5331(14) ?, c = 11.1086(19) ?, β = 111.519(4)°, V = 2346.7(7) ?³, Z = 4. The coordination geometry of Cd(II) atom is distorted octahedral; it is coordinated by two nitrogen atoms from the imidazole rings of two symmetry-related bim molecules, and four oxygen atoms from two symmetry-related phba anions and two water molecules. The Cd(II) atoms are bridged by bim molecules to form a one-dimensional chain. Graphical abstract Synthesis and crystal structure of a one-dimensional chain cadmium coordination polymer bridged through 1,2-bis(imidazol-1-yl)ethane Yuping Zhang, Liyan Wang, Shouwu Wang, Baolong Li, Yong Zhang The cadmium(II) complex [Cd(phba)2(bim)(H2O)2]n (1) has been synthesized and structurally characterized by X-ray diffraction analysis. The coordination geometry of Cd(II) atom is distorted octahedral; it is coordinated by two nitrogen atoms from the imidazole rings of two symmetry-related bim ligands, and four oxygen atoms from two symmetry-related phba anions and two water molecules. The Cd(II) atoms are bridged by bim ligands to form a one-dimensional chain.     

Crystal Structures of (2-oxo-2H-Quinaxalin-1-yl)-acetic Acid and its Cobalt and Nickel Complexes and Their Comparison with (1,3-Dioxo-1,3-dihydro-isoindol-2-yl)-acetic Acid

Abstract The crystal structures of (2-oxo-2H-quinaxalin-1-yl)-acetic acid and its cobalt and nickel complexes are determined. The (2-oxo-2H-quinaxalin-1-yl)-acetic acid (1) crystallizes in orthorhombic, Pbca, a = 12.8571(11) ?, b = 9.4267(8) ?, c = 15.0095(13) ?, the cobalt complex of (2-oxo-2H-quinaxalin-1-yl)-acetic acid (2) crystallizes as dihydrate in triclinic, P-1 space group with a = 4.81150(10) ?, b = 11.8631(2) ?, c = 12.4867(3) ?, α = 71.7800(10)°, β = 79.2490(10)°, γ = 84.9020(10)° whereas the nickel complex of (2-oxo-2H-quinaxalin-1-yl)-acetic acid (3) crystallizes in monoclinic, P2₁/c space group with a = 14.9210(5) ?, b = 4.81730(10) ?, c = 15.7672(5) ?. and β = 99.823(2)°. The crystal structure of the ligand and the complexes are compared with structures of (1,3-dioxo-1,3-dihydro-isoindol-2-yl)-acetic acid and its cobalt and nickel complexes. Index Abstract The crystal structures of (2-oxo-2H-quinaxalin-1-yl)-acetic acid and its nickel and cobalt complexes are compared with (1,3-dioxo-1,3-dihydro-isoindol-2-yl)-acetic acid and its corresponding complexes with nickel(II) and cobalt(II).      

Synthesis and structure of a (4,4′-bipyridine) lanthanide(III) complex with tetraimine (2+2) macrocycle from 2,6-diformyl-4-chlorophenol and 1,3-diamino-2-hydroxypropane

A novel (2+2) macrocyclic Schiff base lanthanide(III) complex [La(H₄L)(NO₃)₃]·(4,4-bipy)·2H₂O has been synthesized by template condensation of 1,3-diamino-2-hydroxypropane and 2,6-diformyl-4-chlorophenol. The compound crystallizes in the orthorhombic space group Pnma with a = 16.400(3), b = 12.985(3), c = 19.118(4) Å, and Z = 4. In the macrocycle, La³⁺ was coordinated by two imino nitrogen atoms, two phenolic oxygen atoms, one pedant alcoholic oxygen atom, and six nitrate oxygen atoms. It is interesting that the neutral lanthanide macrocyle forms a saddlelike supramolecule with 4,4-bipyridine.     

Syntheses,characterization and crystal structures of two structurally similar Schiff bases isonicotinic acid [1-(3-methoxy-2-hydroxyphenyl)methylidene]hydrazide and isonicotinic acid [1-(4-dimethylaminophenyl)methylidene]hydrazide monohydrate

The Schiff base compounds, isonicotinic acid [1-(3-methoxy-2-hydroxyphenyl) methylidene]hydrazide (C₁₄H₁₃N₃O₃, 1) and isonicotinic acid [1-(4-dimethylaminophenyl) methylidene]hydrazide monohydrate (C₁₅H₁₆N₄O·H₂O, 2) have been synthesized by the condensation of equimolar 3-methoxysalicylaldehyde or 4-dimethylaminobenzaldehyde with isonicotinic acid hydrazide in MeOH or EtOH. The compounds were characterized by elemental analysis, IR, ¹HNMR spectra, and single crystal X-ray diffractions. Compound 1 crystallizes in the monoclinic space group P-1 with unit cell dimensions a = 7.662(1) ?, b = 16.249(2) , c = 10.874(2) ?, β = 110.426(3)°, V = 1268.7(3) ′³, Z = 4, R ₁ = 0.0644, and wR ₂ = 0.1283. Compound 2 crystallizes in the orthorhombic space group P2₁2₁2₁ with unit cell dimensions a = 7.388(1) ?, b = 11.812(1) ?, c = 17.197(2) ?, V = 1500.7(2) ′³, Z = 4, R ₁ = 0.0585, and wR ₂ = 0.1143. X-ray structure determinations revealed that the molecules of both compounds display trans configurations with respect to the C=N double bonds. In the crystal structure of 1, molecules are linked through N–H···N intermolecular hydrogen bonds, forming layers parallel to the bc plane, while in the crystal structure of 2, molecules are linked through N–H···O, O–H···O, and O–H···N intermolecular hydrogen bonds, forming a network. Supplementary material CCDC-615072 and 620235 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at http://www.ccdccam. ac.uk/const/retrieving.html or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223–336033 or e-mail: deposit@ccdc.cam.ac.uk.     

Complexes formed by the reactions of fluorinated and non-fluorinated organonitriles with [Zn(SO2)2][AsF6]2: A structural study

[Zn(SO₂)₂][AsF₆]₂ (1) has been prepared from zinc metal and AsF₅ in liquid sulfur dioxide, and crystallized from sulfur dioxide giving crystals of [Zn(SO₂)₄(AsF₆)₂] (1a). The compound 1 forms the homoleptic complexes [Zn(NCR)₆](AsF₆)₂ (R: CH₃ (2a), C₆H₅ (3a), C₆F₅ (3b)) with the corresponding nitriles. In these complexes, the metal center is octahedrally surrounded by six ligands (average Zn–N 2.13 ?). Reaction of 1 with the weaker ligand F₃CCN results in dicoordination at the metal center complemented by a two-dimensional polymeric network (2b) containing bridging AsF₆ ⁻ anions. [Zn(SO₂)₄(AsF₆)₂] (1a): monoclinic, P2₁/c, a=8.5176(8) ?, b=13.5787(14) ?, c=14.7661(15) ?, β=99.296(2)°; [Zn(NCCH₃)₆][AsF₆]₂ (2a): rhombohedral, R-3, a=11.2225(8) ?, b=11.2225(8) ?, c=16.9393(14) ?; [Zn (NCCF₃)₂][μ-FAsF₅)₂( (2b): monoclinic, P2₁/c, a=11.226(3) ?, b=6.6147(19) ?, c=10.460(3) ?, β=104.028(5)°; [Zn(NCC₆H₅)₆][AsF₆]₂ (3a): monoclinic, P2₁/n, a=13.7968(10) ?, b=19.8861(15) ?, c=16.1692(12) ?, β=91.563(2)°; [Zn(NCC₆F₅)₆][AsF₆]₂·2SO₂ (3b): monoclinic, P2₁/n, a=10.8448(9) ?, b=154456(13) ?, c=17.5206(15) ?, β=104.158(1)°.     

Synthesis and structure of a novel copper (II) nitrate complex of 2,4-dioxo-4-phenylbutanoic acid

2,4-Dioxo-4-phenylbutanoic acid, 1, was synthesized as a biproduct of the attempted synthesis of 1,6-bisphenyl-1,3,4,6-hexanetetrone. Crystals of [Cu(H2O)(bipy) (L)][Cu(bipy)(L)(NO3)] (H2O)(NO3) (L = 2,4-dioxolato-4-phenylbutanoic acid and bipy = 2,2′-bipyridine), 2, were grown by slow evaporation of a solution of Cu(NO₃)₂·3 H₂O, 2,2′-bipyridine, and 1 in a mixture of ethanol and water. The compound crystallized in the triclinic space group P-1 and is made up of two distinct molecular units each with approximately square pyramidal geometry: a = 10.663(2) ?, b = 13.275(3) ?, c = 15.071(3) ?, α = 80.26(3)°, β = 74.13(3)°, γ = 89.12(3)°. The copper ions are chelated by molecules of 1 and molecules of bipyridine. The molecular units are arrayed in rows held together by pi-stacking interactions and hydrogen bonding.     

Synthesis and crystal structure of a macrocyclic azidotetraamine copper(II) complex

The complex [Cu(L)N₃](H₂O)(ClO₄) (1) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18, 0^7.12]docosane) has been prepared and characterized by X-ray crystallography. 1 crystallizes in the monoclinic space group P2₁/c, with a = 8.907(5), b = 20.036(3), c = 14.773(2) Å, = 103.78(2)°, V = 2560.6(15) ų, and Z = 4. The coordination geometry around the Cu(II) ion is a distorted square-pyramidal with four nitrogen atoms of the macrocycle and one nitrogen atom of the axial azido group.     

Synthesis and Crystal Structure of One-Dimensional Carboxylate-Bridged Copper(II) Complex with 2-Pyridylmethylamino-3-butyric acid

Abstract The tridentate Schiff base carboxylate-containing ligand 2-pyridylmethylamino-3-butyric acid (Hpaba) reacts with copper(II) perchlorate to give the one-dimensional chain complex {[Cu(μ-paba)](ClO₄)·H₂O} _n (1). The coordination geometry of each copper(II) ion is best described as a square-plane with two nitrogen atoms and one carboxylate oxygen atom of the ligand, and one carboxylate oxygen atom belong to another ligand. It crystallizes in the monoclinic system P2₁/c with a = 12.717(2), b = 7.9163(15), c = 14.981(2) ?, β = 111.14(1)°, V = 1406.8(4) ?³, Z = 4. Cyclic voltammogram of 1 undergoes the reversible one-electron oxidation to the Cu(III) and the reversible one-electron reduction to the Cu(I) state. Graphical Abstract Crystal structure of 1 reveals a syn-anti carboxylate-bridged one dimensional chain complex in which the coordination environment around each copper(II) ion exhibits a distorted square plane.