Crystal structure of catena-Bis(2-thiobarbiturato-O,S)diaquacadmium

The crystal structure of catena-bis(2-thiobarbiturato-O,S)diaquacadmium (C₈H₁₀CdN₄O₆S₂) _n (I), [Cd(H₂O)₂(HTBA)₂] _n (C₄H₄N₂O₂S is 2-thiobarbituric acid, H₂TBA) has been determined. The crystals of compound I are triclinic, a = 6.9433(3) Å, b = 7.2257(3) Å, c = 7.4047(3) Å, α = 88.559(2)°, β = 75.346(2)°, γ = 111.687(1)°, V = 331.05(3) ų, space group $P\bar 1$ , Z = 1. The Cd²⁺ ion is coordinated to the two oxygen atoms of water molecules and the two oxygen and two sulfur atoms of four HTBA^? ions at the vertices of an octahedron. Octahedra are linked by bridging μ₂-HTBA^?-O,S ions into infinite chains. Intermolecular hydrogen bonds form infinite chains. The structure is also stabilized by the π-π interaction of HTBA^? ions.     

Copper(II)-assisted thorough hydrolysis of 2,4,6-tris(2-pyridyl)1,3,5-triazine (tptz). Crystal structures of bis(2-pyridylcarboxylato)-copper(II) dihydrate and bis(2-pyridylcarbonyl)-amido-2,4,6-tris(2-pyridyl)-1,3,5-triazine-copper(II) dicyanamide heptahydrate

2,4,6-Tris(2-pyridyl)-1,3,5-triazine (tptz) undergoes hydrolysis in the presence of copper(II) acetate affording bis(2-pyridylcarbonyl)amido-copper(II) and free 2-pyridylcarboxylic anion. Two compounds of formulas [Cu(NC₅H₄COO)₂]·2H₂O (1) and [Cu(NC₅H₄CO)₂N(tptz)](N(CN)₂)·7H₂O (2), where NC₅H₄COO^? and (NC₅H₄CO)₂N^? are 2-pyridylcarboxylate and bis(2-pyridylcarbonyl)amido-anion, respectively, were obtained from methanol/ethanol solution of tptz with copper acetate; they were characterized by element analysis and single crystal X-ray diffraction method. Single crystal XRD analysis shows that in complex 1 coordination number around Cu atom is 4 with distorted square-planar coordination geometry and in complex 2 coordination number around Cu atom is 6 with distorted octahedral geometry. Crystal data for 1: a = 5.1359(10) Å, b = 7.6471(15) Å, c = 9.2303(18) Å, α = 74.90(3)°, β = 84.36(3)°, γ = 71.37(3)°, space group P1, crystal system triclinic, Z = 1, V = 331.6(1) ų, d _calc = 1.721 g/cm³. Crystallographic data for 2: space group C2/c, crystal system monoclinic, a = 23.976(5) Å, b = 15.465(3) Å, c = 18.649(4) Å, β = 92.66(3)°, V = 6907(2) ų, d _calc = 1.0448 g/cm³, Z = 4.     

Synthesis and crystal structure of platinum(II) acetamidates [Pt(2,2′-bipy)(NHCOCH3)2] and [enPt(μ-NHCOCH3)(μ-OH)Pten](NO3)2

The diamines PtbipyCl₂, and PtenCl₂ and their aqua and hydroxy derivatives react with acetonitrile to give the Pt(II) acetamidates [Pt(2,2′-bipy)(NHCOCH₃)₂] · 4.125 H₂O (I) and [enPt(μ-NHCOCH₃(μ-OH)Pten](NO₃)₂ · H₂O (II), which are characterized by X-ray diffraction. The crystals of I are triclinic, a = 7.137(10) Å, b = 12.655(3) Å, c = 21.914(6) Å, α = 81.82(2)°, β = 82.12(2)°, γ = 77.72(2)°, V = 1908.6(7) ų, space group P $\overline 1 $ , Z = 4, R = 0.033 for 3700 reflections. Complex I is a mononuclear acetamidate with terminal (NHCOCH₃)^? ligands. The crystals of II are monoclinic, a = 11.413(2) Å, b = 10.981(2) Å, c = 14.385(3) Å, β = 105.90(3)°, V = 1733.8(6) ų, space group P2₁/n, R = 0.028 for 2797 reflections. Complex II is a dimer with bridging (NHCOCH₃)^? and (OH)^? groups. The Pt-Pt distance is 3.1667(7) Å.     

Syntheses, crystal structure, and fluorescent properties of a lanthanide complex

A new complex [Dy₂(Pht)₂(HPht)₂(Phen)₂(H₂O)₄] (I), where Pht^2? = dianion of o-phthalic acid; HPht^? = mono-anion of o-phthalic acid; Phen = 1,10-phenanthroline, has been synthesized and the crystal structure was determined by X-ray crystallography. The I crystallizes in the triclinic system, space group $P\bar 1$ with lattice parameters a =10.1126(3) Å, b =10.7029(3) Å, c = 11.9360(3) Å, α = 90.2260(10)°, β = 99.5340(10)°, γ = 100.9810(10)°, V = 1249.87(6) ų, Z = 2, ρ_calcd = 1.881 mg m^?3. The photophysical property of I has been studied with excitation and emission spectra.     

Crystal structure of polymer hexaaqua-hexakis(2-thiobarbiturato)dieuropium(III)

Complex [Eu₂(HTBA)₆(H₂O)₆] _n (I), where H₂TBA is 2-thiobarbituric acid C₄H₄N₂O₂S, is synthesized. Its structure is determined by X-ray diffraction analysis (CIF file CCDC 987519). The crystals of complex I are monoclinic: a = 14.1033(4) Å, b = 10.0988(4) Å, c = 15.4061(5) Å, β = 110.003(1)°, V = 2061.9(1) ų, space group P2/n, Z = 2. All three independent ligands HTBA^? are coordinated to Eu³⁺ through oxygen atoms. Six HTBA^? ions (two terminal and four bridging) and two water molecules are coordinated to one of the independent Eu³⁺ ions. The second Eu³⁺ ion is bound to four bridging HTBA^? ions and four water molecules. The coordination polyhedra are square antiprisms. The bridging HTBA^? ions join the antiprisms into layers. The structure is stabilized by numerous hydrogen bonds and the π-π interaction between HTBA^?.     

Ion-selective properties of 1,8-bis [2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H4L3), synthesis and vibrational spectra of copper and zinc complexes with H4L3, and crystal and molecular structure of [Cu(H4L3)(H2O)3][(H2L3)(H2O)]

The ion-selective properties of 1,8-bis[2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H₄L³) have been studied and its potentiometric selectivity coefficients have been determined. New complexes [Cu(H₄L³)(H₂O)₃][(H₂L³)(H₂O)] (I) and Zn(H₄L³)(H₂L³) · 3H₂O, and Cu(H₂L³) · 2(H₂O) have been synthesized and characterized. The crystal and molecular structure of I has been determined by X-ray crystallography and vibrational spectroscopy. The crystals are monoclinic, a = 10.279(5) Å, b = 26.532(13) Å, c = 8.399(4) Å, β = 99.270(8)°, V = 2260.8(7) ų, Z = 2, space group Cm, R = 0.0347 for 4325 reflections with I > 2σ(I). Ionic compound I is composed of the [Cu(H₄L³)(H₂O)₃]²⁺ complex cations and [(H₂L³)(H₂O)]^2? anions. In the cation, the Cu²⁺ cation located in the m plane is bound to a tetragonal pyramidal (TP) array. The equatorial plane of the TP is formed by two phosphoryl oxygen atoms of the podand (Cu(1)-O, 1.921(2) Å) and two O atoms of two water molecules (av. Cu(1)-O, 1.981(3) Å). The third water molecule is at the axial vertex of the TP at a considerably larger distance (Cu(1)-O, 2.139(3) Å). The anion is of the host-guest type. The host is the deprotonated podand (H₂L³)^2?, and the guest is the water molecule. The latter is bound to the terminal hydroxyl groups of two phosphoryl groups of the podand by two acceptor hydrogen bonds and to two central ether oxygen atoms of the (H₂L³)^2? anion by one donor bifurcated hydrogen bond. The cations and anions in the structure are linked by hydrogen bonds to form chains parallel to the c axis.     

Crystal structure of [Cu2(Edta)(Py)2(H2O)2] · 2H2O and [Cu(Im)6]{;Cu(Im)4[Cu(Edta)(Im)]2} · 6H2O, Products of the interaction of (Ethylenediaminetetraacetato)diaquadicopper(II) with pyridine and imidazole

The crystals of [Cu₂(Edta)(Py)₂(H₂O)₂] · 2H₂O (I) and [Cu(Im)₆]{;Cu(Im)₄[Cu(Edta)(Im)]₂} · 6H₂O (II) were isolated as a result of the reaction of an aqueous solutions of Cu₂(Edta) · 4H₂O with pyridine or imidazole, respectively. The crystals were studied by X-ray diffraction. The crystals of I are monoclinic, a = 12.682 Å, b = 6.788 Å, c = 14.834 Å, β = 91.44°, Z = 2, space group P2₁/n. The crystals of II are triclinic, a = 9.118 Å, b = 14.889 Å, c = 15.130 Å, α = 72.59°, β = 72.94°, γ = 82.54°, Z = 1, space group P{ie241-1}. In the centrosymmetric binuclear complex molecule of I, an N atom and two O atoms of the Edta ligand are coordinated to each Cu atom (Cu-N, 2.046 Å; Cu-O, 1.941 and 1.954 Å). The N atom of the pyridine molecule (Cu-N, 1.993 Å) completes the base of an elongated tetragonal pyramid (4 + 1) with the O atom of the H₂O molecule in the apex (Cu-O(w), 2.244 Å). The crystals of II are built of centrosymmetric complex cations [Cu(Im)₆]²⁺ (Cu(1)-N, 2.469, 2.021, and 2.056 Å), centrosymmetric trinuclear complex anions {;Cu(Im)₄[Cu(Edta)(Im)]₂}^2?, and crystal water molecules. In the anion, the central fragment [Cu(Im)₄]²⁺ (Cu(2)-N, 1.985 and 2.023 Å) is bonded to two peripheral complexes [Cu(Edta)(Im)]^2? through atoms O of the Edta ligand (Cu(2)-O, 2.615 Å). In the [Cu(Edta)(Im)]^2? fragment of the complex anion, the Cu(3) atom is bonded to the Edta ligand through the two N atoms and three O atoms (Cu(3)-N, 1.970 and 2.071 Å; Cu(3)-O, 1.966, 1.969, and 2.238 Å) and with the imidazole molecule, through an N atom (Cu(3)-N, 2.397 Å). The coordination polyhedra of the three copper atoms (Cu(1)-Cu(3)) in the structure of II are elongated tetragonal bipyramids (4 + 2). In the structures studied, Edta^4? is a hexadentate chelating/bridging ligand. However, the coordination mode of the ligand in these structures is different: in the binuclear complex I, the Edta ligand is coordinated to each Cu atom through an N atom and two O atoms with the formation of two chelate rings (symmetric (trans) coordination mode), whereas, in the trinuclear complex II, the Edta ligand is coordinated to the Cu(2) atom through an O atom and to the Cu(3) atom through the two N atoms and three O atoms with the formation of three chelate rings (asymmetric (cis) coordination mode).     

Structures of bis(2-thiobarbiturato-O)tetraaquamagnesium and catena-[(μ2-2-thiobarbiturato-O,O)(2-thiobarbiturato-O) bis(μ2-aqua)diaquastrontium] monohydrate

The crystal structures of bis(2-thiobarbiturato-O)tetraaquamagnesium Mg(H₂O)₄(HTBA-O)₂ I and catena-[(μ₂-2-thiobarbiturato-O,O)(2-thiobarbiturato-O)bis(μ₂-aqua)diaquastrontium] monohydrate catena-[Sr(μ₂-H₂O)₂(H₂O)₂(μ₂-HTBA-O,O)(HBTA-O)] _n · nH₂O (II), where H₂TBA is 2-thiobarbituric acid C₄H₄N₂O₂S, have been determined. Crystal data for a=6.7598(2) Å, b = 7.6060(2) Å, c = 8.5797(2) Å, α = 79.822(2)°, β = 76.622(1)°, γ = 69.124(1)°, V = 398.82(2) ų, space group P $\bar 1$ , Z = 1; for II: a = 20.8499(4) Å, b = 19.2649(5) Å, c = 4.14007(9) Å, β = 92.023(2)°, V = 1661.91(7) ų, space group P2₁/n, Z = 4. The Mg²⁺ ion in I is bonded to six O atoms of two HTBA^? ions and four water molecules that form a nearly regular octahedron. Each Sr²⁺ ion in II is coordinated to three oxygen atoms of three HTBA^? ions and six water molecules that form an almost ideal tricapped trigonal prism. These polyhedra share edges to form infinite chains. Intermolecular hydrogen bonds create layered structures of I and II.     

Coordination polymers of silver with piperazine and uncoordinated anions: Syntheses and crystal structures of [Ag(C4H10N2)]CH3SO3 and [Ag(C4H10N2)]PO2F2

The coordination polymers [Ag(C₄H₁₀N₂)]CH₃SO₃ (I) and [Ag(C₄H₁₀N₂)]PO₂F₂ (II) (C₄H₁₀N₂ is piperazine (Ppz)) are synthesized, and their structures are determined. The crystals of I are monoclinic, space group P2₁/c, a = 6.280(1) Å, b = 11.781(1) Å, c = 12.112(1) Å, β = 97.21(1)°, V = 889.0(2) ų, ρ_calcd = 2.160 g/cm³, and Z = 4. The crystals of II are orthorhombic, space group Cmca, a = 13.039(1) Å, b = 10.450(1) Å, c = 12.837(1) Å, V = 1749.1(3) ų, ρ_calcd = 2.240 g/cm³, and Z = 8. Structure I contains cationic polymer chains [Ag(Ppz)] _∞ ⁺ . The silver atom bound to two nitrogen atoms of two Ppz ligands has an almost linear coordination mode (Ag-N_average 2.197 Å, angle NAgN 161.2(1)°). The structure includes supramolecular layers due to weak interactions Ag…O(CH₃SO₃). Structure II is built of zigzag polymer chains [Ag(Ppz)]⁺ and tetrahedral cations PO₂F ₂ ^? . The Ag⁺ ion has a linear coordination mode (Ag-N 2.220(3) Å, and the NAgN angle is 164.3(2)°). The tetrahedral anions PO₂F ₂ ^? having weak contacts with the silver ions (Ag…O 2.630(3)Å) join the [Ag(Ppz)] _∞ ⁺ chains into wavy layers.     

New fluorochromatouranylates of alkali metals: Synthesis and structure

Four new fluorochromatouranylates, namely, K[UO₂(CrO₄)F] · 1.5H₂O (I), Rb[UO₂(CrO₄)F] · 1.5H₂O (II), Rb[UO₂(CrO₄)F] · 0.5H₂O (III), and Cs[UO₂(CrO₄)F] · 0.5H₂O (IV), have been synthesized, and their crystallographic characteristics have been determined. All the compounds crystallize in monoclinic system, space group P2₁/c, with the unit cell parameters a = 13.1744(5) Å, b = 9.4598(3) Å, c = 13.0710(4) Å, β = 103.746(1)°, Z = 4, R = 0.0235 (I); a = 13.5902(7) Å, b = 9.5022(4) Å, c = 13.2271(6) Å, β = 102.914(2)°, Z = 4, R = 0.0247 (II); a = 24.7724(8) Å, b = 12.6671(4) Å, c = 9.4464(3) Å, β = 97.661(1)°, Z = 8, R = 0.0448 (III); a = 25.725(1) Å, b = 12.8261(5) Å, c = 9.4929(4) β = 97.208(1)°, Z = 8 (IV). The pairs of compounds I and II and compounds III and IV are isostructural. Crystals of compounds I–III have been subjected to complete X-ray diffraction study. It has been established that the structures of compounds I–III are built of [UO₂(CrO₄)F] _n ^n? layers, which are parallel to the (100) plane and linked into a framework by alkali-metal cations located between layers, together with water molecules. The effect of topological and geometric isomerism on the structural features of 34 known uranyl compounds of the AT³M² crystallochemical group, to which the studied compounds I–III also belong, is discussed.     

Silver complexes with 2-amino-4-methylpyrimidine: Synthesis, crystal structure, and luminescent properties

Reactions of AgReO₄ and AgCH₃SO₃ with L = 2-amino-4-methylpyrimidine (Ampym, C₅H₇N₃) in a ratio of 1: 2 in acetonitrile gave the complexes [AgL₂(ReO₄)] (I) and [AgL₂(CH₃SO₃)] (II). Their structures were determined. The crystals of complex I are monoclinic, space group C2/c, a = 5.985(1), b = 3.465(1), c = 19.071(1) Å, β = 96.52(1)°, V = 1527.0(3) ų, ρ_calcd = 2.507 g/cm³, Z = 4. The crystals of complex II are orthorhombic, space group Pbca, a = 14.784(1), b = 11.991(1), c = 17.711(1) Å, V = 3139.7(4) ų, ρ_calcd= 1.782 g/cm³, Z = 8. Structure I shows discrete cationic complexes [AgL₂]⁺. The silver atom is virtually linearly coordinated to two N atoms of crystallographically equivalent ligands L (Ag-N, 2.156(4) Å; the angle NAgN, 174.7(4)°). The complex cations are united into zigzag chains through the hydrogen bonds N-H...N. The resulting chains are linked by the hydrogen bonds N-H...O to uncoordinated perrhenate anions to form 2D supramolecular layers. In structure II, the Ag⁺ ion is coordinated by two crystallographically non-equivalent ligands L in a distorted linear fashion: Ag(1)-N(1), 2.166(7) Å;Ag(1)-N(4), 2.181(6) Å; the angle NAgN, 157.2(2)°. The anions CH₃SO₃ ^? are weakly linked to the Ag⁺ ions (Ag...O 2.72 Å) and are hydrogen-bonded to the complex cations [AgL₂]⁺, uniting them into supramolecular ribbons.     

Synthesis and crystal structures of two azido-bridged copper(II) complexes with schiff bases

Two new end-on azido-bridged dinuclear copper(II) complexes with the formula [Cu(μ_1,1-N₃)₂(IEP)₂] (I) and [Cu(μ_1,1-N₃)₂(EMP)₂] (II), where IEP and EMP are the deprotonated forms of 2-[1-(2-isopropylaminoethylimino)ethyl]phenol and 2-ethoxy-6-[(2-methylaminoeth-ylimino)methyl]phenol, respectively, were synthesized. Both complexes were characterized by elemental analyses and IR spectra. The crystal structures were determined by the X-ray diffraction. The crystal of I is monoclinic: space group P2₁/c, a = 9.662(2), b = 15.282(3), c = 10.639(2) Å, β = 115.418(10)°, V = 1418.9(5) ų, Z = 2. The crystal of II is monoclinic: space group P2₁/n, a = 12.588(2), b = 7.705(1), c = 14.481(2), β = 91.736(5)°, V = 1403.9(2) ų, Z = 2. The two Cu atoms in each complex are bridged by two end-on azide groups. Each Cu atom is in a square pyramidal coordination. The Cu…Cu distances are 3.230(2) Å in I and 3.150(2) Å in II.     

Syntheses and structures of mononuclear eight-coordinate Na[ErIII(Cydta)(H2O2]·5H2O (Cydta = trans-1,2-cyclohexanediaminetetraacetic acid) and binuclear nine-coordinate Na2[SmIII(Cydta)][SmIII(Cydta)(H2O)3] · 11H2O

The title complexes, Na[Er^III(Cydta)(H₂O)₂] · 5H₂O (I) and Na₂[Sm^III(Cydta)][Sm^III(Cydta)(H₂O)₃] · 11H₂O (II) (Cydta is trans-1,2-cyclohexanediaminetetraacetic acid), are prepared and characterized using IR, elemental analyses, and single-crystal X-ray diffraction techniques. Crystal I belongs to triclinic system (space group P1), which has a mononuclear eight-coordinate slightly distorted square antiprismatic conformation. The crystal data are as follows: a = 8.371(12) Å, b = 9.952(14) Å, c = 14.74(2) Å, α = 88.32(2)°, β = 76.30(2)°, γ = 87.87(2)°, V = 1192(3) ų, Z = 1, ρ = 1.835 g/cm³, μ = 3.612 mm^?1, F(000) = 658, R = 0.0194, and wR = 0.0520 for 4130 observed reflections with I≥2σ(I). Crystal II belongs to monoclinic system (space group P2₁/n), which has the binuclear nine-coordinate structure with tricapped trigonal prismatic conformation for Sm(1) and the pseudomonocapped square antiprismatic conformation for Sm(2). The crystal data are as follows: a = 12.283(6) Å, b = 15.626(7) Å, c = 25.875(12) Å, β = 97.962(7)°, V = 4919(4) ų, Z = 4, ρ = 1.717 g/cm³, μ = 2.476 mm^?1, F(000) = 2536, R = 0.0781, and wR = 0.1745 for 8554 observed reflections with I ≥ 2σ(I).     

Copper complexes with N-allylisoquinolinium halides: Synthesis and crystal structures of [C9H7N(C3H5)]2CuIICl2.86Br1.14, [C9H7N(C3H5)CuIBr2] · H2O, and [C9H7N(C3H5)CuIBr2]

Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C₉H₇N(C₃H₅)]₂Cu^IICl_2.86Br_1.14 (I), [C₉H₇N(C₃H₅)]Cu^IBr₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^IBr₂ (III) are prepared by ac electrochemical synthesis, and their structures are studied by X-ray diffraction analysis (DARCh-1 (for I) and KUMA/CCD (for II and III) diffractometers). The crystals of compound I are monoclinic: space group P2₁/n, a = 15.053(5) Å, b = 10.486(4) Å, c = 17.179(10) Å, γ = 109.77(3)°, V = 2552(4) ų, Z = 4. The crystals of complex II are triclinic: space group P $\overline 1 $ , a = 7.040(1) Å, b = 7.610(2) Å, c = 12.460(2) Å, α = 79.54(3)°, β = 86.73(3)°, γ = 89.51(1)°, V = 655.4(2) ų, Z = 2. The crystals of complex III are monoclinic: space group P2₁/n, a = 12.799(1) Å, b = 7.692(1) Å, c = 13.491(1) Å, β = 111.08(1)°, V = 1239.3(2) ų, Z = 4. The structure of compound I is built of the Cu^IIX ₄ ^2? tetrahedra and N-allylisoquinolinium cations united by the C-H···X contacts into corrugated layers. The crystal structure of π-complex II is formed of dimers of the composition [C₉H₇(C₃H₅)]₂ Cu ₂ ^I Br₄ forming layers in the direction of the z axis due to the C-H···X contacts. An important role in structure formation belongs to water molecules that cross-link the organometallic layers through the O-H···X contacts into a three-dimensional framework. When kept in the mother liquor for 6 months, the crystals of compound II transformed into crystals of compound III, whose structure consists of {[C₉H₇(C₃H₅)]₂Cu ₂ ^I Br₄} _n columns united through the C-H···Br contacts (H···Br 2.84(3)?2.92(4) Å) into a three-dimensional framework.     

Coordination behavior of 1,4-diallylpiperazinium and 1-allyloxybenzotriazole toward silver(I) in the crystalline π-complexes [Ag2(C4H8N2(C3H5)2(H+)2)(H2O)2(NO3)2](NO3)2 and [Ag(C6H4N3(OC3H5)(NO3))]

Reactions of a solution of AgNO₃ in aqueous methanol with solutions of 1,4-diallylpiperazine (acidified with HNO₃ to pH = 4) and 1-allyloxybenzotriazole in ethanol gave the crystalline silver(I) π-complexes [Ag₂(C₄H₈N₂(C₃H₅)₂(H⁺)₂)(H₂O)₂(NO₃)₂](NO₃)₂ (I) and [Ag(C₆H₄N₃(OC₃H₅)(NO₃))] (II). Their crystal structures were determined by X-ray diffraction. Crystals of complexes I and II are monoclinic, space group P2₁/c; for I: a = 7.053(3)Å, b = 9.389(3)Å, c = 15.488(4)Å, β = 91.60°, V = 1025.3(6)ų, Z = 4; for II: a = 10.650(4)Å, b = 15.062(5)Å, c = 7.412(4)Å, β = 104.20(3)°, V = 1152.6(8)ų, Z = 4. In both structures, the organic components act as bidentate ligands forming with AgNO₃ 34- and 14-membered topological rings, respectively. In complex I, the nearly tetrahedral environment of the Ag(I) atom is made up of the olefinic C=C bond, the O atoms of the nitrate anions, and the water molecule. 1-Allyloxybenzotriazole in structure II causes the deformation of the coordination polyhedron of Ag into a trigonal pyramid via inclusion of the ligand N atom in its coordination sphere. The topological units of the complexes form infinite polymer layers linked by anionic NO ₃ ^? bridges. In structure I, these layers are united through a system of hydrogen bonds into a three-dimensional framework.     

Crystal structures of cesium and rubidium 2-thiobarbiturates

The crystal structures of cesium 2-thiobarbiturate C₄H₃CsN₂O₂S (I) and rubidium 2-thiobarbiturate C₄H₃N₂O₂RbS (II) (C₄H₄N₂O₂S is 2-thiobarbituric acid, H₂TBA) have been determined. Isostructural crystals are monoclinic; a = 7.9609(3) Å,b = 11.8474(3) Å, c = 7.7317(2) Å, β = 101.285(3)°, V = 715.13(4) ų, space group C2/m, Z = 4 for I and a = 7.6369(2) Å, b = 11.7690(3) Å, c = 7.5568(2) Å, β = 100.212(1)°, V = 668.44(3) ų, space group C2/m, Z = 4 for II. Each metal ion in complexes I and II is bonded to four oxygen atoms and two sulfur atoms at the vertices of a six-vertex polyhedron. N-H…O hydrogen bonds link HTBA-ions into chains. The structure is also stabilized by the “head-to-tail” π-π interaction of HTBA-ions.     

Synthesis and characterization of cobalt(II) and manganese(II) xylaratogermanates: The molecular and crystal structures of the [M(H2O)6][Ge(μ3-L)2{M(H2O)2}2] · 4H2O · nCH3CN Complexes (M = Co, n = 0; M = Mn, n = 1)

A synthetic procedure was developed, and heteropolynuclear coordination compounds—the products of the interaction of germanium tetrachloride with xylaric (trihydroxyglutaric) acid HOOC-CH(OH)-CH(OH)-CH(OH)-COOH (H₅L) and the acetates of the 3d metals Mn(II) and Co(II)—were prepared. The compounds were characterized by elemental analysis, thermogravimetry, and IR spectroscopy. The X-ray diffraction analysis of the [M(H₂O)₆][Ge(μ₃-L)₂{M(H₂O)₂}₂] · 4H₂O · nCH₃CN complexes, where M = Co, n = 0 (I) and M = Mn, n = 1 (II), was performed. The crystals of I are monoclinic, a = 10.752(2) Å, b = 11.830(2) Å, and c = 10.772(2) Å, β = 94.741(3)°, V = 1365.4(5) ų, Z = 2, space group P2₁/n, R1 = 0.0309 for 3200 reflections with I > 2σ(I). The crystals of II are triclinic, a = 9.5330(17) Å, b = 9.7415(17) Å, and c = 10.3935(18) Å, α = 115.024(2)°, β = 97.580(3)°, γ = 111.535(3)°, V = 764.9(2)ų, Z = 1, space group $P\bar 1$ , R1 = 0.0621 for 3028 reflections with I > 2σ(I). The bimetallic anions [Ge(μ₃-L)₂{M(H₂O)₂}₂]^2?, the cations [M(H₂O)₆]²⁺, and crystal water molecules form the basis of compounds I and II (the acetonitrile molecule is also a constituent of compound II). In the centrally symmetrical trinuclear complex anion, the Ge(1) atom is bound to two M(1) atoms through two completely deprotonated bridging ligands. The Ge(1) atom is coordinated to the six alcohol oxygen atoms of two ligands L^5? at the apexes of a distorted octahedron (the average Ge(1)-O distances in I and II are 1.8858(14) and 1.892(3)Å, respectively). The coordination polyhedron of the M(1) atom in the complex anion is a strongly distorted octahedron. The base of the coordination polyhedron is formed by the two bridging alcohol oxygen atoms (the average M(1)-O distances in I and II are 2.1756(14) and 2.255(3) Å, respectively) of two L^5? ligands and by the oxygen atoms of two water molecules (the average M(1)-O distances in I and II are 2.0693(17) and 2.175(4) Å, respectively). In the centrally symmetrical complex cation, the coordination polyhedron of the M(2) atom is a somewhat distorted octahedron. The M(2)-O(H₂O) bond lengths in I and II vary in the ranges of 2.0137(17)-2.1555(17) and 2.140(5)-2.172(4) Å, respectively (the average lengths are 2.0375(17) and 2.166(4) Å, respectively). The cations and anions are joined by a branched system of hydrogen bonds.     

Synthesis,crystal structures,and biological property of dinuclear oxovanadium(V) complexes derived from tridentate Schiff bases

A pair of structurally similar dinuclear oxovanadium(V) complexes, [VO₂L¹]₂ (I) and [VO₂L²]₂ (II), where L¹ and L² are the mono-anionic form of 2-[(2-isopropylaminoethylimino)methyl]-4-methylphenol (HL¹) and 4-fluoro-2-[(2-isopropylaminoethylimino)methyl]phenol (HL²), respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination. The crystal of I is monoclinic: space group P2₁/c, a = 12.528(1), b = 12.266(1), c = 9.432(1) Å, β = 104.814(3)°, V = 1401.2(3) ų, Z = 2. The crystal of I is monoclinic: space group P2₁/n, a = 12.3128(5), b = 6.5124(3), c = 17.1272(7) Å, β = 105.863(1)°, V = 1321.1(1) ų, Z = 2. The V…V distances are 3.210(1) Å in I and 3.219(1) Å in II. The V atoms in the complexes are in octahedral coordination. Biological assay indicates that complex II, bearing fluoro-substitute groups, has stronger antimicrobial activity against most bacteria than complex I which bearing methyl-substitute groups.     

Cu(I) cloride complexes with 4,5-(2-pyridylethylene)dithio-1,3-dithiol-2-thione and triphenylphosphine

Heteroligand binuclear complexes of CuCl with triphenylphosphine and 5-pyridine-2-yl-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione (L¹) of the compositions [CuCl(PPh₃)(L¹)]₂ (I) and [CuCiL¹]₂ (II) are synthesized and studied by X-ray diffraction method. Crystals I are monoclinic; space group P2₁/n, a=8.9520(18) Å, b=18.926(4) Å, c=16.841(3) Å, β=94.96(3)°, Z=2. The Cu(I) atom has a quasi-tetrahedral surrounding involving the tetraphenylphosphine P atom, the pyridyl N atom of the molecule L¹, and two bridging Cl atoms. Crystals II are monoclinic; space group P2₁/c, a=9.3520(19) Å, b=8.1490(16) Å, c=18.660(4) A, β = 104.43(3)°, Z = 2. Both L¹ ligands in complex II act as bridges. The Cu(I) atom also has a quasi-tetrahedral surrounding formed by the Cl atoms, the pyridyl N atoms and thiol S atom of one L¹ ligand, and the thione S atom of the second L¹ ligand. Similar binuclear complexes with the bridging function of the L¹ ligand were also detected in a solution of II by the ESI method.     

Coordination compounds of cobalt(II) and cadmium(II) with 2-amino-4-methylpyrimidine: Synthesis, crystal structure, and luminescent properties

The coordination compounds [CoL₂Cl₂] (I) and [CdL₂(H₂O)₂(NO₃)₂] (II) have been synthesized by the reaction of CoCl₂ · 6H₂O and Cd(NO₃)₂ · 4H₂O with L = 2-amino-4-methylpyrimidine (Ampym, C₅H₇N₃), and their structures have been solved. The crystals of complex I are triclinic, space group $P\bar 1$ , a = 5.627(1) Å, b = 11.191(1) Å, c = 12.445(1) Å, α = 81.00(1)°, β = 77.21(1)°, γ = 76.18(1)°, V = 737.7(2) ų, ρ_calcd = 1.567 g/cm³, Z = 2. The crystals of complex II are monoclinic, space group P2₁/c, a = 10.390(1) Å, b = 11.982(1) Å, c = 7.624(1) Å, β = 102.61(1)°, V = 926.1(2) ų, ρ_calcd = 1.760 g/cm³, Z = 2. Discrete [CoL₂Cl₂] moieties are realized in the structure of complex I. The cobalt atom is tetrahedrally coordinated to the two nitrogen atoms of crystallographically nonequivalent ligands L and two chlorine atoms (Co(1)-N_avg, 2.051(4)Å; Co(1)-Cl(1), 2.241(1) Å; Co(1)-Cl(2), 2.263 Å; bond angles at the cobalt atom lie within a range of 102.1°–118.6°). The complexes are linked into supramolecular zigzag chains by N-H...N(Cl) hydrogen bonds. In the structure of complex II, the Cd²⁺ ion (at the inversion center) is coordinated in pairs to the nitrogen atoms of ligand L and the O(NO₃) and O(H₂O) oxygen atoms. The coordination of the Cd²⁺ ion is distorted octahedral (Cd(1)-N(1), 2.341Å; Cd(1)-O(1), 2.340(4) Å; Cd(1)-O(4), 2.327(3) Å; bond angles at the cadmium atom lie within a range of 79.1°–100.9°). N-H...N hydrogen bonds link the complexes into supramolecular chains. These chains are linked into a supramolecular framework by the O-H...O hydrogen bonds between water molecules and NO₃ groups.