Metal-hydroxycarboxylate interactions: syntheses and structures of K2[VO2(C6H6O7)]2·4H2O and (NH4)2[VO2(C6H6O7)]2·2H2O

Potassium and ammonium dimeric (citrato)dioxovanadium(V) hydrate K₂[VO₂(H₂cit)]₂·4H₂O1 and (NH₄)₂[VO₂(H₂cit)]₂·2H₂O2 (H₄cit=citric acid) have been prepared and characterized by X-ray structure analyses. Vanadate1 crystallizes in the monoclinic space groupP2₁/n (No. 14) with unit cell parameters:a=9.304(2),b=11.756(2),c=11.911(2)Å, =111.72(3)°, andD _c=1.911 g/cm³,Z=2; Vanadate2 also crystallizes in the monoclinic space groupP2₁/n with unit cell parameters:a=9.719(2),b=11.111(3),c=11.294(2)Å, =109.03(2)°, andD _c=1.781 g/cm³,Z=2. Each dimer contains a centro-symmetric planar four-member V₂O₂ ring with two exocyclic citrate entities coordinated by the oxygen atoms of the hydroxy-and -carboxylate ligands, while the other two -carboxylate groups remain uncomplexed. Principal dimensions of the V–O bonds are 1.986(4)_av (hydroxy) and 1.980(3)Å(-carboxyl) for vanadate1, 1.988(2)_av (hydroxy) and 1.974(3)Å(-carboxyl) for vanadate2.     

Synthesis and crystal structure of [Cu(azpy)(H2O)4][Cu2(nta)2(azpy)]····6H2O: A two-dimensional network solid

The copper(II) complex [Cu(azpy)(H₂O)₄][Cu₂(nta)₂(azpy)]····6H₂O (nta = nitrilotriacetate, azpy = 4,4-azobispyridine) has been synthesized and structurally characterized. It crystallizes in the triclinic space group P , a = 8.6985(3) Å, b = 9.4776(3) Å, c = 14.6544(5) Å, = 71.5360(10)°, = 85.7600(10)°, = 88.1420(10)°, V = 1142.74(7) ų, Z = 1. The crystal structure consists of one-dimensional linear chain cations and dimeric anions. The copper centers in the anion possess distorted trigonal bipyramidal geometry, while Cu(2) has a distorted octahedral geometry in the cation. Coordinated water molecules in the one-dimensional chain form interionic hydrogen bonds with the oxygen atoms of the carboxylate of nta of the dimmer anion. These hydrogen bonds result in the formation of a two-dimensional network.     

Crystal structures of acid ethylenediaminetetraacetates [Cd(H2 Edta)(H2O)] · 2H2O and [Mn(H2O)4][Mn(HEdta)(H2O)]2 · 4H2O

The crystal structures of [Cd(H₂ Edta)(H₂O)] · 2H₂O (I) and [Mn(H₂O)₄][Mn(HEdta)(H₂O)]₂ · 4H₂O (II) are studied by X-ray diffraction [R ₁ = 0.0209 (0.0272), wR ₂ = 0.0571 (0.0730) for 2551 (4025) reflections with I > 2σ(I) in I (II), respectively]. Structure I contains mononuclear [Cd(H₂ Edta)(H₂O)] complexes with the C ₂ symmetry, and structure II contains centrosymmetric trinuclear [Mn(H₂O)₄][Mn(HEdta)(H₂O)]₂ complexes. In I and II, the protonated ligands are hexadentate (2N + 4O), and the water molecule increases the coordination number of the metal atom to seven. The acid protons participate in short intermolecular hydrogen bonds, which are symmetric in II and asymmetric in I.     

Crystal structure of dibarium (Ethylenediaminetetraacetato)cuprate(II) diperchlorate hexahydrate, Ba2[Cu(Edta)](ClO4)2 ⋅ 6H2O

Compound Ba₂[Cu(Edta)](ClO₄)₂ ? 6H₂O is synthesized and its crystal structure is determined [R = 0.0500 for 4439 reflections with I > 2σ(I)]. The structure consists of the [Cu(Edta)]^2? anionic complexes, hydrated barium cations, Cl ₄ ^? anions, and molecules of crystallization water, which are interlinked into a framework. The hexadentate Edta ^4? ligand coordinates the Cu atom forming the polyhedron in a shape of a tetragonal bipyramid, which is asymmetrically stretched along the OR-Cu-OR, axis (Cu-O, 2.262 and 2.532 Å). The mean lengths of the equatorial Cu-N and Cu-O bonds are 2.011 and 1.952 Å, respectively. The anionic complex is bound to six Ba atoms. Two independent Ba atoms have different environments; their coordination numbers are nine and ten. The Ba-O distances lie in the range 2.669–3.136 Å. Layers of Ba atoms parallel to the x0z plane are distinguished in the structure.     

Synthesis and structure of (NH4)3[UO2(C3H2O4)2(NCS)] · 2H2O

Malonate-thiocyanate complex (NH₄)₃[UO₂(C₃H₂O₄)₂(NCS)] · 2H₂O is synthesized and studied by X-ray diffraction. The compound crystallizes in the monoclinic system: a = 13.9983(4) Å, b = 8.1947(2) Å, c = 16.4678(4) Å, β = 100.846(1)°, space group Cc, Z = 4, and R = 0.0158. The main structural units of the crystal are mononuclear [UO₂(C₃H₂O₄)₂(NCS)]^3? groups belonging to the AB ₂ ⁰¹ M ₁ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₂O ₄ ^2? , M ¹ = NCS^?). Discrete uranium-containing groups are connected by electrostatic interactions with ammonium ions and by hydrogen bonds. Some specific structural features of crystals containing [UO₂(L)₂(NCS)]^3? complexes, where L is the oxalate or malonate ion, are discussed.     

Synthesis and structural characterization of [Co(tren)(Tsal)]ClO4·H2O and [Ni(pn)(py)2(NCS)2]

Complexes [Co(tren)(Tsal)]ClO₄·H₂O 1 and [Ni(pn)(py)₂(NCS)₂] 2, (tren = tris(2-aminoethyl)amine, Tsal = thiosalicylate ion, pn = 1, 2-diamino propane and py = pyridine) have been synthesized and structurally characterized. Both complexes crystallize in the monoclinic space group C2/c with a = 21.3340(6), b = 11.7754(2), c = 14.8076(5) Å, = 100.3831(10)°, Z = 8 (1), and a = 7.2573(8), b = 17.8810(11), c = 15.2681(12) Å, = 101.170(2)°, Z = 4 (2). The metal atoms in both cases have distorted octahedral geometry. In 1, the tren ligand is quadridentate and Tsal is bidentate chelate. In 2, the pn ligand forms a bidentate chelate with the NCS ligands in trans positions. Complex 1 is diamagnetic whereas 2 shows paramagnetism with a magnetic moment of 3.10 B. M.     

Structure of a Cu(II)-containing peptide,diaquo-gly-l-tyr Cu(II) dihydrate, [Cu(C11N2O4H13)(H2O)2·2H2O

The structure of the Cu(II) complex of gly-l-tyr [Cu(C₁₁N₂O₄H₁₃) (H₂O)₂]·2H₂O has been solved by X-ray diffraction methods. The compound crystallizes in the orthorhombic space groupP2₁2₁2₁ witha=11.970(2) Å,b=12.485(2) Å andc=10.418(3) Å, respectively, (MoK)=0.710 Å,D _c =1.59 Mgm^–3,D _m =1.59 Mgm^–3, finalR=0.04. The structure was solved by heavy atom (Cu) phased Fourier and refined by full-matrix least squares methods. The coordination geometry of the ligand around the Cu(II) ion has been established as a distorted tetragonal pyramid. The peptide molecule behaves as a tridentate ligand via its amino (N2), amido (N1) nitrogens and carboxyl (O2) oxygens. The peptide nitrogen is found to be deprotonated.     

Synthesis, crystal structure, and thermal analyses of triaqua-(1,10-phenanthroline-N,N′) succinatomanganese(II) dihydrate, [Mn(H2O)3(phen)(C4H4O4)]·2H2O

[Mn(H₂O)₃(phen)(C₄H₄O₄)]·2H₂O was obtained by reaction of freshly prepared MnCO₃, phen and succinic acid in CH₃OH/H₂O (1:1 v/v), and its crystal structure has been determined by single crystal X-ray diffraction methods. The title mixed ligand complex crystallizes in the triclinic space group with cell dimensions a = 7.590(1) Å, b = 9.324(1) Å, c = 13.917(1) Å, = 85.64(1)°, = 74.56(1)°, = 77.10(1)°, and D _calc = 1.584 g/cm³ for Z = 2. The crystal structure consists of the [Mn(H₂O)₃(phen)(C₄H₄O₄)] complex molecules and lattice H₂O molecules. The Mn atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three H₂O molecules and one succinato ligand with d(Mn—N) = 2.271 and 2.299 Å, and d(Mn—O) = 2.133–2.239 Å. Through intermolecular hydrogen bondings, the complex molecules are interlinked to form 2D layers, which are assembled by – stacking interactions into 3D framework with tunnels occupied by the lattice H₂O molecules. Thermal analyses showed that the title compound decomposes in two steps over the range 25–600°C upon heating in flowing Ar.     

Structures and properties of layered barium borates Ba0.975[B6O9(OH)(O0.975Br0.025) · B2O(OH)3], Ba2[B5O8(OH)2](OH), Na2Ba2[B20O34(OH)4], and Ba5[B20O33(OH)4]H2O

A new hexaborate, Ba_0.975[B₆O₉(OH)(O_0.975Br_0.025) · B₂O(OH)₃], was synthesized under hydrothermal conditions. This compound is structurally similar to tunnelite and the synthetic borates Pb[B₆O₁₀(OH) · B₂O(OH)₃], Pr[B₆O₁₀(OH) · B₂O(OH)₄], and Nd[B₆O₁₀ · B₃O₃(OH)₄] · H₂O studied earlier. In the new hexaborate and the refined pentaborate Ba₂[B₅O₈(OH)₂]OH, in which the polyanions adopt an orientation in layers unusual for pentaborates, thermal vibrations of the terminal groups were revealed. This fact reflects the real crystal structure. The nonlinear optical properties of the crystals of the polar pentaborate Na₄Ba₄[B₂₀O₃₄(OH)₄] were determined. The crystal structure of the related pentaborate Ba₅[B₂₀O₃₃(OH)₄]H₂O was considered. The factors most likely responsible for the difference in the second-harmonic generation signal for this pair were revealed.     

Synthesis and crystal structure of a tetranuclear manganese(IV) cluster [L4Mn4O6](ClO4)4·2H2O (L = 1,4,7-triazacyclononane)

A tetranuclear manganese (IV) complex, [L₄Mn₄O₆](ClO₄)₄·2H₂O (1), with 1,4,7-triazacyclononane (L) as the capping ligands, has been synthesized and characterized by X-ray diffraction; monoclinic, space group P2₁/n with a = 21.335(6) Å, b = 11.387(3) Å, c = 21.788 (6) Å, = 111.410 (6)°, V = 4928 (2) Å, Z = 4. Each manganese atom has a distorted octahedral environment comprised of three facially coordinated amine nitrogen atoms and three oxygen atoms, and the cation is an idealized tetrahedron. The Mn₄O₆ ⁴⁺ cation corresponds to an adamantane skeleton.     

Structural and spectroscopic characterization of the macrocyclic complex: [Tb(CrO4)(H2O)(C22H26N6)] ·0.5(Cr2O7)·(H2O)

The title complex was obtained by anion metathesis from [Tb(CH₃COO)₂(C₂₂H₂₆N₆)] (CH₃COO)·4H₂O and K₂CrO₄ in aqueous solution. The compound crystallizes in the triclinic space group witha=8.384(2),b=10.425(2)c=15.752(2)Å, =98.82(2), =93.52(2), =97.22(2)°, andZ=2. The structure is ionic and consists of a (+1) complex cation balanced in a 21 ratio by a disordered dichromate ion. The 9-coordinate Tb(III) is linked to the six nitrogen atoms of the macrocyclic ligand L=C₂₂H₂₆N₆, as well as to a water molecule and a bidentate chelating chromate situated on opposite sides of the macrocycle. The infrared spectrum shows, in addition to the pattern of the macrocyclic ligand, the absorptions arising from the stretching modes of the bidentate chelating CrO₄ ^2– ligand and of the Cr₂O₇ ^2– counterion.     

Crystal structure of strontium aqua(ethylenediaminetetraacetato)cobaltate(II) tetrahydrate Sr[CoEdta(H2O)] · 4H2O

The complex Sr[Co^II Edta] · 5H₂O (I) (where Edta ^4? is the ethylenediaminetetraacetate ion) has been synthesized. The crystal structure of this compound is determined by X-ray diffraction. Crystals are monoclinic, a = 7.906(2) Å, b = 12.768(2) Å, c = 18.254(3) Å, β = 95.30(3)°, V = 1834.8 ų, space group P2₁/n, Z = 4, and R = 0.036. The structure is built up of the binuclear complex fragments {Sr(H₂O)₃[CoEdta(H₂O)]}, which consist of the anionic [CoEdta(H₂O)]^2? and cationic [Sr(H₂O)₃]²⁺ units linked by the Sr-O bonds into a three-dimensional framework. The coordination polyhedra of the Co and Sr atoms are mono-and bicapped trigonal prisms. The coordination sphere of the Co atom (the coordination number is equal to 6 + 1) involves six donor atoms (2N and 4O) of the Edta ^4? ligand and the O_w atom of water molecule. One of the Co-O distances (2.718 Å) is considerably longer than the other Co-O_lig distances (2.092–2.190 Å) and the Co-O_w(1) distance (2.079 Å). The Sr coordination polyhedron (the coordination number is eight) contains three water molecules, three carbonyl O atoms of the three different anionic complexes, and two O atoms of one acetate group of the fourth anionic complex. The Sr-O distances fall in the range 2.535–2.674 Å. The structural formula of the compound is {Sr(H₂O)₃[CoEdta(H₂O)]}_3∞ · H₂O.     

[Co(H2O)6](C18H15O4SO3)2·4H2O的合成和晶体结构

以芒柄花素为先导化合物,合成了水溶性的[Co(H2O)6](C18H15O4SO3)2·4H2O,并采用IR, 1H NMR, TG-DTA, XRD和单晶X射线衍射法对其结构进行了表征.单晶X射线衍射结果表明:[Co(H2O)6]2+、C18H15O4SO 3和H2O之间存在多种氢键,形成晶体结构中的亲水区.异黄酮骨架间反平行排列,面对面和边对面芳香堆积作用同时存在于其中,构成晶体结构中的疏水区.磺酸根是连接亲水区和疏水区的桥梁.氢键、芳香堆积作用以及阴阳离子之间的静电引力共同将标题化合物组装成具有三维网络结构的超分子.     

Syntheses and Crystal Structures of Two CuII Coordination Isomers [Cu(pmt)2] · 4H2O (1) and {[Cu(pmt)2] · 2H2O} n (2)

Abstract  A pair of Cu^II coordination isomers [Cu(pmt)₂] · 4H₂O (1) and {[Cu(pmt)₂] · 2H₂O} _n (2) [Hpmt = 2-(2-pyridylmethylamino) ethanesulfonic acid] have been prepared by reaction of the same proportion CuCl₂ · 2H₂O and Hpmt but with different experimental methods in water–methanol mixed solution, and were characterized by X-ray diffraction, elemental analysis, IR spectrum. X-ray analysis indicates that complex (1) is a mononuclear complex in which two deprotonated pmt ligands coordinate in a facial tridentate arrangement about the Cu^II atom. While complex (2) is a coordination polymer, in which four N atoms of pmt ligands coordinate to one Cu^II atom but its sulfonate O atoms bond to adjacent Cu^II atom. Thus 12-membered rings (–Cu–N–C–C–S–O–)₂ are obtained between two neighbouring Cu^II atoms and they connect one another to form this new polymer. Crystal data: [Cu(pmt)₂] · 4H₂O (1), Mr = 566.10, monoclinic, P2 ₁/c, a = 9.1950(8) ?, b = 11.5093(10) ?, c = 11.2304(10) ?, β  = 105.5550(10)°, Z = 2, V = 1144.96(17) ?³, R ₁  = 0.0407, wR ₂  = 0.1242 [I > 2σ (I)]; {[Cu(pmt)₂] · 2H₂O} _n (2), Mr = 530.07, triclinic, P-1, a = 7.6165(19) ?, b = 8.806(2) ?, c = 9.592(4) ?, α = 104.933(4)°, β = 106.732(4)°, γ = 109.503(3)°, Z = 1, V = 534.2(3) ?³, R ₁ = 0.0470, wR ₂ = 0.1082 [I > 2σ(I)]. Index Abstract  A pair of Cu^II coordination isomers [Cu(pmt)₂] · 4H₂O (1) and {[Cu(pmt)₂] · 2H₂O} _n (2) [Hpmt = 2-(2-pyridylmethylamino) ethanesulfonic acid] have been prepared by reaction of the same proportion CuCl₂ · 2H₂O and Hpmt but with different experimental methods in water–methanol mixed solution.      

Crystal structure of {NH2C(NHC6H5)2}3[UO2(C2O4)2(NCS)] · 1.25H2O

Synthesis and X-ray diffraction study of {NH₂C(NHC₆H₅)₂}₃[UO₂(C₂O₄)₂(NCS)] · 1.25H₂O single crystals have been performed. This compound is crystallized in the orthorhombic system, with the unit-cell parameters a = 45.2646(8) Å, b = 57.7359(11) Å, c = 7.9244(3) Å, sp. gr. Fdd2, Z = 16, V = 20 709.6(10) ų, and R = 0.0477. The uranium-containing structural units of the crystals are one-core groups of the [UO₂(C₂O₄)₂(NCS)]^3? composition, belonging to the crystallochemical group AB ₂ ⁰¹ M ¹ (A = UO ₂ ⁺² , B ⁰¹ = C₂O ₄ ^2? , M ¹ = NCS^?) of uranyl complexes. The uranium-containing complexes are connected into a three-dimensional framework owing to the electrostatic interactions with the outer-sphere cations and a system of hydrogen bonds.     

[Co(dmg)2Cl2]3·[Co(dmg)2Cl(OH)]·[Co(dmg)(phen)]·(H2O)4的合成和晶体结构

本文合成了一个复杂的单核配合物 [Co(H2dmg)2Cl2]3·[Co(H2dmg)2Cl(OH)]·[Co(Hdmg)(phen)]·(H2O)4 (H2dmg＝dimethylglyoxime, phen＝1,10-Phenanthroline).通过X射线衍射技术获得其单晶结构.在单晶结构中,每五个单核钴(II)的配位结构形成一个重复单元,是一个较为复杂的单晶.其空间群为P-1,晶胞参数为a＝1.3738nm;b＝1.4396nm;c＝1.8656nm.本文中我们将讨论该化合物的分子结构及相关光谱性质.     

Six-coordinated zinc complexes: [Zn(H2O)4(phen)] (NO3)2·H2O and [ZnNO3(H2O)(bipy)(Him)]NO3 (phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine, and Him = imidazole)

Two novel six-coordinated zinc complexes, tetra-aqua(1,10-phenanthroline)zinc dinitrate monohydrate, [Zn(H₂O)₄(phen)](NO₃)₂·H₂O (1) and aqua(2,2-bipyridine)(imidazole)-nitratozinc nitrate, [ZnNO₃(H₂O)(bipy)(Him)]NO₃ (2) were prepared. Compound 1 crystallizes in the monoclinic space group P2₁/c with a = 8.780(4), b = 13.609(4), c = 15.368(5) Å, = 93.86(2)°C, V = 1832.1(12) ų. In 1, a phenanthroline molecule chelates the zinc atom and four water molecules complete the octahedral geometry around the metal. Compound 2 crystallizes in the monoclinic space group P2₁/n with a = 7.250(1), b = 24.554(4), c = 10.258(2) Å, = 107.880(10)°, V = 1737.9(5) ų. In 2, a bipyridine molecule and a nitrate anion chelate the zinc atom. An imidazole molecule and a water molecule then complete the six-coordinated geometry around zinc. The intermolecular packing is controlled by hydrogen bonding, especially in 1 and by stacking. The thermal stability of the compounds and the loss of water molecules and ligands was monitored by a thermogravimetric study.     

Synthesis and structure determination of a new layered zincophosphate: [H2N2C6H16]0.5[Zn2(PO4)(HPO4)(H2O)]·H2O

The synthesis and crystal structure of a new microporous zincophosphate are described. [H₂N₂C₆H₁₆]_0.5[Zn₂(PO₄)(HPO₄)(H₂O)]·H₂O crystallizes in the triclinic space group P1¯ with a = 8.822(4), b = 9.236(4), c = 8.451(3) Å, = 67.19(3), = 91.32(3), = 111.10(3)°, V = 586.7(4) ų and Z = 2. This new material consists of infinite two-dimensional anionic layers alternated with planes containing organic diprotonated templates, N, N, N, N-tetramethylethylenediamine [H₂N₂C₆H₁₆]²⁺ molecules. The framework structure is built up of ZnO₄, ZnO₃OH₂, PO₄, and PO₃OH tetrahedra, linked through oxygen vertices. The presence of terminal OH₂ and OH groups, leads to an open structure containing four- and eight-rings. The organic molecules are interconnected to the framework through hydrogen bonds.     

Synthesis, properties, and crystal structure of barium 1-oxyethylidenediphosphonatohydroxogermanate(IV) polyhydrate Ba3[Ge(μ-OH)(μ-Oedph)]6 · 25H2O

The barium salt of 1-oxyethylidenediphosphonatohydroxogermanium acid Ba₃[Ge(μ-OH)(μ-Oedph)]₆ · 25H₂O (I) (H₄Oedph is 1-oxyethylidenediphosphonic acid) was synthesized and studied by X-ray diffraction. The complex was characterized by elemental analysis, thermogravimetry, and IR spectroscopy. The hexanuclear cyclic complex anions [Ge(μ-OH)(μ-Oedph)] ₆ ^6-t- ] cations, and water molecules of crystallization are the structural units of the crystal of I.