Synthesis, crystal structure, and thermal stability of [Mo2O4(μ2-O)(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO₃ in acetic acid solution, a new compound, [Mo₂(μ₂-O)₂(C₆H₄O₂)₂(H₂O)] · (C₈H₉N₂)₂ · 2H₂O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P2₁/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρ_c = 1.665 g/cm³, μ(MoK _α) = 0.84 mm^?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R _int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.     

Synthesis,structure, and properties of a new trinuclear iron cluster, [(MeOH)(H2O)2Fe3(μ3-O)(μ-OOCC6H4OCH2C5H4NH)6] (ClO4)7 · · 8MeOH · 3.5H2O

Reactions of iron(m) salts with a new bidentate ligand, which is potentially capable of forming binuclear iron complexes upon complexation, were studied. Under various conditions, we succeeded in isolating only the trinuclear cationic complex (Fe^III ₃(O₂CR)6(₃-)17+ (1), where RCO₂ is 2-(pyrid-2-ylmethoxy)benzoic acid protonated at the pyridyl moiety. The structure of 1 was established by spectral, magnetic, and X-ray structural studies. Cyclic voltammetry in McCN in the temperature range from -35 to 20 °C demonstrated that 1 undergoes successive Fe^IIIFe^II reduction in three one-electron stages, which is indicative of the electronic interaction between iron atoms in the complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2086–2092, August, 1996.     

Synthesis and crystal structure of Cs2[(UO2)2(C2O4)3] and Cs2[UO2(C3H2O4)2] · H2O

Cs₂[(UO₂)₂(C₂O₄)₃] (I) and Cs₂[UO₂(C₃H₂O₄)₂] · H₂O (II) have been synthesized and studied by X-ray diffraction. The crystals of complexes I and II are monoclinic: a = 8.1453(2) Å, b = 8.9831(2) Å, c = 11.3897(4) Å, β = 104.0950(10)°, V = 808.29(4) ų, space group P2₁/n, Z = 2, and R ₁ = 0.0255 for I and a = 9.6998(2) Å, b = 17.8686(3) Å, c = 8.2074(2) Å, β = 97.5780(10)°, V = 1410.10(5) ų, space group P2₁/c, Z = 4, and R ₁ = 0.0287 for II. The uranium-containing structural units of complexes I and II are [(UO₂)₂(C₂O₄)₃]^2? chains and [UO₂(C₃H₂O₄)₂] ₂ ^4? dimers, which belong to the AK _0.5 ⁰² T¹¹ and AT¹¹B⁰¹ crystallochemical groups (A = UO ₂ ²⁺ , K⁰² and T¹¹ = C₂O ₄ ^2? , T¹¹ and B⁰¹ = C₃H₂O ₄ ^2? ) of uranyl complexes.     

Crystal and molecular structure of the [Nd2(H2O)8(C6F5COO)6]·2H2O Compound

A compound with the composition Nd(C₆F₅COO)₃· H₂O (I) is prepared. Single crystals are grown, and their single crystal XRD analysis of the Nd₂(H₂O)₈(C₆F₅COO)₆]·2H₂O (II) compound is performed. The crystals are triclinic: a = 7.693(2) Å, b = 9.394(2) Å, c = 18.203(4) Å, α = 81.91(3)°, β = 84.41(3)°, γ = 88.97(3)°, Z = 1, d _x = 2.223 g/cm³. The structure is composed of symmetrical molecules of the binuclear [Nd₂(H₂O)₈(C₆F₅COO)₆] complex and crystallization water molecules. The C₆F₅COO^- ligands are monodentate and tridentate bridging- chelating, which results in a closure of two four-membered chelate cycles NdO₂C and a four-membered metal cycle Nd₂O₂. The NdO₉ polyhedron is a distorted one-capped tetragonal antiprism.     

Syntheses and Structures of the Hexacoordinated Antimony Complexes: Ph3(C2H4O2)Sb⋅⋅⋅DMSO, (3-FC6H4)3(C2H4O2)Sb⋅⋅⋅DMSO,and (4-MeC6H4)3(C6H4O2)Sb⋅⋅⋅DMSO

Russian Journal of Coordination Chemistry - Complexes Ph3(C2H4O2)Sb???DMSO (I), (3-FC6H4)3(C2H4O2)Sb???DMSO (II), and...     

Synthesis and crystal structure of [Nd(C6NO2H5)3(H2O)2] n n[ZnCl4]·nCl·2.5nH2O with novel poly-cationic chain

The title complex, [Nd(C₆NO₂H₅)₃(H₂O)₂] _n n[ZnCl₄]·nCl·2.5nH₂O (1), was obtained by hydrothermal reactions and structurally characterized by X-ray diffraction. The crystal structure analysis reveals that the title complex is characteristic of a novel polycationic [Nd(C₆NO₂H₅)₃(H₂O)₂] _n ³ⁿ⁺ one-dimensional chain-like structure.     

Synthesis and structure of [UO2(SeO4)(C2H4N4)2] · 0.5H2O

The single-crystal X-ray diffraction analysis of [UO₂(SeO₄)(C₂H₄N₄)₂] · 0.5H₂O (I) is performed. The crystals are monoclinic: space group C2/c, Z = 8, a = 19.035(2), b = 7.1326(8), c = 21.477(2) Å, β = 109.683(4)°. The main structural units of the crystal are chains of [UO₂(SeO₄)(C₂H₄N₄)₂]. Compound I belongs to the crystal-chemical group AT³M ₂ ¹ (A = UO ₂ ²⁺ , T³ = SeO ₄ ^2? , M¹ is a cyanoguanidine molecule) of the uranyl complexes. The chains are united into three-dimensional framework through hydrogen bonds involving the oxygen atoms of the selenate and uranyl groups, the nitrogen atoms of cyanoguanidine, and the hydrogen atoms of the cyanoguanidine or water molecules.     

Synthesis and structure of antimony complexes [Ph3AmP] 2 + [Sb2I8 · 2DMSO]2−, [Ph3PrP] 2 + [Sb2I8 · C4H8O2]2−, and [(HOCH2CH2)3NH] 4 + [Sb4I16]4−

The reaction of equimolar amounts of triphenylamyl- and triphenylpropylphosphonium iodides and triethanolammonium iodide with antimony iodide in dimethyl sulfoxide, dioxane, or acetone gave complexes [Ph₃AmP] ₂ ⁺ [Sb₂I₈ · 2DMSO]^2?, [Ph₃PrP] ₂ ⁺ [Sb₂I₈ · C₄H₈O₂]^2?, and [(HOCH₂CH₂)₃NH] ₄ ⁺ [Sb₄I₁₆]^4?, the structure of which was established by X-ray diffraction analysis. The cations of all complexes have slightly distorted tetrahedral structure, and the antimony atoms in the anions are hexacoordinated. The crystals of the complexes have intra- and intermolecular contacts, which form the structure.     

Synthesis and structure assignment of vanadyl(iv) citrate [(VO)3(C6H5O7)2]·H2O

Pseudo-crystals of vanadyl(iv) citrate [(VO)₃(C₆H₅O₇)₂]·H₂O have been obtained after addition of V₂O₅ to citric acid solution. Composition of the compound has been established by thermal analysis and confirmed by IR, UV-VIS, Raman and ESR spectra.     

Synthesis and structure of bismuth complexes [Ph3MeP] 2 + [BiI3.5Br1.5(C5H5N)]2− · C5H5N, [Ph4Bi] 4 + [Bi4I16]4− · 2Me2C=O, and [Ph3(iso-Am)P] 4 + [Bi8I28]4− · 2Me2C=O

Complexes [Ph₃MeP] ₂ ⁺ [BiI_3.5Br_1.5(C₅H₅N)]^2? · C₅H₅N(I), [Ph₄Bi] ₄ ⁺ [Bi₄I₁₆]^4? · 2Me₂C=O (II), and [Ph₃(iso-Am)P] ₄ ⁺ [Bi₈I₂₈]^4? · 2Me₂C=O (III) were synthesized by reactions of bismuth iodide with triphenylmethylphosphonium bromide, triphenylbismuthonium sulfosalicylate, and triphenylisoamylphosphonium iodide, respectively. The crystal structures of complexes I–III were determined by X-ray crystallography. The complexes contain, in addition to cations and solvent molecules, mono-, tetra-, and octanuclear anions, in which bismuth atoms are in octahedral coordination.     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Syntheses and structures of nine-coordinate NH4[HoIII(Edta)(H2O)3] · 1.5H2O, (NH4)4[Ho 2 III (Dtpa)2] · 9H2O, and (NH4)3[HoIII(Ttha)] · 5H2O complexes

The three title complexes, NH₄[Ho^III(Edta)(H₂O)₃] · 1.5H₂O (I) (H₄Edta = ethylenedianine-N,N,N′,N′-tetraacetic acid), (NH₄)₄[Ho ₂ ^III (Dtpa)₂] · 9H₂O (II) (H₅Dtpa = diethylenetriamine-N,N,N′,N″,N″-entaacetic acid), and (NH₄)₃[Ho^III(Ttha)] · 5H₂O (III) (H₆ Ttha = triethylenetetramine-N,N,N′,N″,N?,N?-hexaacetic acid), have been prepared and characterized by FT-IR, elemental analyses, and single-crystal X-ray diffraction technique. Complex I has a nine-coordinate mononuclear structure with distorted monocapped square antiprismatic conformation and its crystal structure belongs to orthorhombic system and Fdd2 space group. The crystal data are as follows: a = 19.343(9), b = 35.125(17), c = 12.364(6) Å, V = 8400(7) ų, Z = 16, M = 552.26, ρ_calcd = 1.747 g cm^?3 μ = 3.828 mm^?1, and F(000) = 4368. Complex II has a binuclear nine-coordinate pseudomonocapped square antiprismatic conformation and its crystal structure belongs to triclinic system and space P1 group. The crystal data are as follows: a = 9.7637(16), b = 9.9722(16), c = 12.945(2) Å, α= 85.853(2)°, β = 77. 140(2)°, γ = 77.140(2)°, V = 1198.4(3) ų, Z = 1, M = 1340.80, ρ_calcd = 1.858 g cm^?3, μ = 3.380 mm^?1, and F(000) = 674. As for complex III, it also has nine-coordinate mononuclear structure with distorted tricapped trigonal prism and its crystal structure belongs to monoclinic system andP2₁/c space group. The crystal data are as follows: a = 10.349(3), b = 12.760(4), c = 23.142(7) Å, β = 91.020(6)°, V = 3055.6(16) ų, Z = 2, M = 797.55, ρ_calcd = 1.734 g cm^?3, μ = 2.674 mm^?1, and F(000) = 1624. The results showed that although the ligands are different from one another in the shape and the numbers of coordination atoms, they all have nine-coordinate structures. However, one of them has binuclear structure and the other two have mononuclear structures because of the difference of the ligands.     

Synthesis and structure of tetra-p-tolylantimony complexes [(4-MeC6H4)4Sb] 2 + [Hg2I6]2−, [(4-MeC6H4)4Sb] 2 + [HgI4]2−, [(4-MeC6H4)4Sb] 3 + [Sb3I12]2−, and [(4-MeC6H4)4Sb]+[ReO4]−

Complexes [(4-MeC₆H₄)₄Sb] ₂ ⁺ [Hg₂I₆]^2? (I), [(4-MeC₆H₄)₄Sb] ₂ ⁺ [HgI₄]^2? (II), [(4-MeC₆H₄)₄Sb] ₃ ⁺ [Sb₃I₁₂]^2? (III), were synthesized by reactions of tetra-p-tolylantimony iodide with mercury iodide and antimony iodide, respectively. Tetra-p-tolylantimony perrhenate [(4-MeC₆H₄)₄Sb]⁺[ReO₄]^? (IV) was prepared from tetra-p-tolylantimony chloride and sodium perrhenate in acetone. Crystal structures of complexes I, II, and IV were determined by X-ray crystallography. Mercury and rhenium atoms have tetrahedral coordinations in these complexes. The Hg-I and Re-O distances in the structures of I, II, and IV vary within 2.7719(13)–2.7908(12)Å, 2.7028(3)–2.9163(3) Å, and 1.693(3)–1.744(3) Å, respectively. Antimony atoms in two crystallographically independent trinuclear centrosymmetric [Sb₃I₁₂]^2? anions of complex III have an octahedral environment. Each terminal SbI₃ fragment (Sb-I_t, 2.8265(9)–2.8333(10)Å) is bound to the central atom through tree bridging iodine atoms (Sb(2)-I_br, 3.2275(9)–3.3620(10)Å). The distances between the central Sb atom and bridging iodine atoms are much shorter (Sb(1)-I_br, 3.0153(6)–3.0316(6) Å; Sb(3)-I_br, 2.9926(6)–3.0074(6) Å).     

4[CuCl(C5H5N)4]·[W10O32]·2(C5H5N)·3H2O的合成及晶体结构

标题化合物是通过(NH_4)_2WS_4, CuCl_2·2H_2O在吡咤溶液中反应制得。晶体呈蓝色, 属三斜晶系, 空间群P1, 晶胞参数为:a=1.3555(7), b=1.3666(5), c=1.7860(13) nm, α=69.08(4)°, β=87.39(5)°, γ=70.72(4)。V=2.907(3) nm, Z=1, D_m=2.56 g cm~(-3)。结构由Patterson法和Fourier法测出。对5692个收集到的独立衍射数据进行计算, 最后R=0.046。结构测定表明, 晶体由W_(10)O_(32)~(4-), [CuCl(C_5H_5N)_4]~+, C_5H_5N和H_2O所组成。W_(10)O_(32)~(4-)的结构见图1, W原子处在O原子的八面体配位中, 彼此共边和共顶点相连。[CuCl(C_5H_5N)_4]~+的结构见图2, Cu原子由1个Cl和4个N原子配位, 呈略有变形的四方锥形, 这种离子是首次报导。C_5H_5N和H_2O填入正负离子堆积的空隙中。     

Synthesis,Crystal Structure,and Properties of [Dy(p-ABA)3Phen · H2O] · 1.5H2O1

(1.10-Phenanthroline)-tris(4-amidobenzoate)dysprosium, [Dy(p-ABA)₃Phen · H₂O] · 1.5H₂O (where p-ABA = p-amidobenzoate and Phen = 1.10-phenanthroline) has been synthesized. The complex was characterized by elemental analysis, UV, IR spectroscopy, and molar conductance. The crystal structure was determined by X-ray crystallography. The coordination number of the mononuclear complex is nine. The crystals are triclinic, space group P1 with a = 10.4484(13) Å, b = 12.2015(15) Å, c = 14.0170(17) Å; α = 92.800(2)°, β = 102.7220(10)°, γ = 108.880(2)°. Z = 2, d _c = 1.617 mg m^?3, F(000) = 786. R1 = 0.0327, and wR2 = 0.0911.     

Syntheses and Crystal Structures of Two Trinuclear Iron(Ⅲ) Carboxylate Complexes: [Fe3(μ3-O)(μ-O2CEt)6(H2O)3]Cl.3H2O and [Fe3(μ3-O)(μ-O2CEt)6Py3]Cl(Py=pyridine)

Two new oxo-centered trinuclear iron complexes [Fe3(μ3-O)(μ-O2CEt)6(H2O)3]Cl.3H2O 1 and [Fe3(μ3-O)(μ-O2CEt)6Py3]Cl 2 were prepared in non-aqueous solvent and their crystal structures have been determined. Crystal 1 is monoclinic, space group P21/n, a=9.909(3), b=24.467(8), c=14.542(7)(), β=107.85(4)° V=3356(4)()3, Z=4, Mr=765.52, Dc=1.52 g/cm3, μ=14.28 cm-1, F(000)=1588 and R=0.059, Rw=0.071 for 3745 unique reflections with I>3σ(I). Crystal 2 belongs to the monoclinic system with space group C2/c, a=13.750(3), b=18.439(4), c=16.696(3)(), β=93.42(3)°, V=4226(3)()3, Z=4, Mr=894.73, Dc=1.41 g/cm3, μ=11.4 cm-1, F(000)=2322 and R=0.058, Rw=0.062 for 2272 unique reflections with I>3σ(I). The two structures contain the same trimetal framework in which three iron(Ⅲ) atoms form a nearly equilateral triangle with a μ3-oxygen atom in the centre.     

Calixarenes as second-sphere ligands for transition metal ions. Synthesis and crystal structure of [(H2O)5 Ni(NC5H5)]2(Na)[calix[4]arene sulfonate] · 3.5 H2O and [(H2O)4Cu(NC5H5)2]-(H3O)3 [calix[4]arene sulfonate] · 10 H2O

The title compounds crystallize such that bilayers of calixarenes are separated by hydrophilic layers. In each case the transition metal has, in addition to a primary sphere of ligands, a second-sphere coordination by a calixarene. [(H₂O)₅Ni(NC₅H₅)]₂(Na)[calix[4]arene sulfonate]·3.5 H₂O,1, crystallizes in the triclinic space groupP \(\bar 1\) witha = 12.487(4),b = 14.281(2),c = 15.055(5) Å, α = 85.66(2), β = 80.07(2), γ = 80.48(2)°, andD _c = 1.64 g cm^?3 forZ = 2. Refinement based on 2441 observed reflections led to a finalR value of 0.066. There are two different environments for the nickel-containing cations: one is positioned within the hydrophilic layer with the pyridine ligand intercalated into the hydrophobic calixarene bilayer and the other is also positioned within the hydrophilic layer, but the pyridine ligand is inserted into the hydrophobic cavity of the calix[4]arene. [(H₂O)₄Cu(NC₅HS)₂](H₃O)₃[calix[4]arene sulfonate]·10 H₂O,2, crystallizes in the triclinic space groupP \(\bar 1\) witha = 15.438(4),b = 15.727(6),c = 12.121(9) Å, α = 112.74(4), β = 102.02(4), γ = 85.34(4)°, andD _c = 1.57 g cm^?3 forZ = 2. Refinement based on 3925 observed reflections led to a finalR value of 0.107. The structure is similar to that of 1 except that the one copper-containing cation spans the hydrophilic layer and is intercalated into the bilayer of calixarenes on one side and positioned into the calixarene cavity on the other.     

Crystal,molecular, and electronic structure of carboxylate [Fe3O(CH3COO)6(H2O)3]NO3·4H2O

Results of X-ray structural analysis, IR spectroscopy, and quantum chemical study of the [Fe₃O(CH₃COO)₆(H₂O)₃]NO₃·4H₂O complex are reported. The crystal belongs to the monoclinic system with a=15.688(3), b=11.767(2), c=15.318(4) Å, γ=92.54(3)^o, space group P2₁/a, R=0.078. The molecule has a trinuclear structure: three iron atoms occupy the vertices of an equilateral, triangle with an Fe−Fe distance of 3.29 Å and are bonded by the μ₃-oxo and μ-CH₃COO⁻ (O,O′) ligands. To each iron atom, one water molecule is coordinated. Using the obtained values of populations on 3d AO of Fe (d _xy ^1.34 ; d _xz ^1.39 ; d _yz ^1.46 ; ; ) and charges on oxygen atoms (O _c ^−0.5 ; O _ac ^−0.31 ; O _w ^−0.31 ), we estimated the values of isomeric shift and quadrupole splitting (0.75 and 0.70 mm/sec, respectively; these are close to the experimental values of 0.75 and 0.58 mm/sec, (300 K)). Institute of Chemistry, Moldovian Academy of Sciences. Moldovian State University. Institute of Applied Physics, Moldovian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii., Vol. 35, No. 2, pp. 112–120, March–April, 1994. Translated by T. Yudanova