Supramolecular pseudometallacycles in a nickel compound with 4,4-diaminodiphenylmethane: Synthesis and structure of {Ni[(CH2(C6H4NH2)2]2(NO3)2(H2O)2}

The [Ni(DDM)₂(NO₃)₂(H₂O)₂] complex (DDM is 4,4-diaminodiphenylmethane [CH₂(C₆H₄NH₂)₂]) is synthesized, and its structure is determined. The crystals are triclinic, space group P , a = 5.846(1) ?, b = 9.450(2) ?, c = 13.390(3) ?, α = 105.63(3)°, β = 98.13(3)°, γ = 105.84(3)°, V = 666.6(2) ?³, ρ_calcd = 1.553 g/cm³, Z = 2. The Ni(II) ion (in the inversion center) is bound to a distorted octahedral array formed by the nitrogen atoms of the primary amino groups of the DDM molecules and the oxygen atoms of the monodentate nitrato groups and water molecules (Ni(1)-N(3) 2.119(2) ?, Ni(1)-O(1) 2.122(2) ?, Ni(1)-O(w) 2.047(2) ?, angles at the Ni atoms vary in the 85.08(9)°–94.92(9)° interval). The structure contains supramolecular metallacycles formed by the O(w)-H…N(2) hydrogen bonds between the coordinated H₂O molecules and the terminal amino groups of DDM. The metallacycles are joined by the Ni²⁺ ions into infinite chains running in the [111] direction. Original Russian Text ? Yu.V. Kokunov, V.V. Kovalev, Yu.E. Gorbunova, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 11, pp. 1838–1843.     

Syntheses and structural characterizations of Fe4S4 cubane-like cluster compounds containing cycloalkylthiolate ligands

In a reaction system consisting of FeCl₂, tetrathiometallate and cycloalkylthiolate, two Fe₄S₄ cubanelike cluster compounds were obtained with the following crystallographic data: (PhCH₂NMe₃)₂ [ Fe₄S₄ (SC₅H₉)₄] (I), monoclinic space groupP2₁/c,a = 1.632 7(4),b=1.122 9(3),c = 2. 802 5(10) nm, β= 94.63(2)°, Z=4, andR= 0.074; (Et₄N)₂[F₄S4(SC₆H_lI)₄] (II), tetragod space group ,a = l.167 05(9),b = 1.167 06(2),c = 2.063 26(5) nm,Z = 2, D_obs = 1. 28 g/cm³, andR = 0. 078. The participation of cycloalkylthiolate ligand does not obviously arouse the change of the Fe₄S₄ core structure. Meanwhile, the influence of the cation on the structural symmetry of the Fe₄S₄ cluster dianion is also discussed. Project supported by the National Natural Science Foundation of China and the Climbing Program Foundation of China.     

Dinuclear iron (III) complex with a bridging diphenylphosphate and two terminal diphenylphosphate ligands

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Synthesis and structure of [Ni(dien)2]3[W4S4(CN)2]·20H2O and [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O

[Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O and [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O were obtained by evaporating water-ammonia solutions containing K₆[W₄S₄(CN)₁₂]·2H₂O·2CH₃OH, diethylene triamine, and NiCl₂·6H₂O or CuCl₂·6H₂O. The crystals of the complex compounds were obtained within 3 days. The complex compounds were characterized by IR spectroscopy and by XRD and elemental analysis. XRD data for the complex [Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O are: triclinic system, , a = 14.671(2) Å, b = 16.448(3) Å, c = 19.814(3) Å, α = 67.841(3)°, β = 68.996(3)°, γ = 67.527(3)°, V = 3961.6(11) ų, Z = 2; for the complex [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O: monoclinic system, C2/c, a = 37.4290(1) Å, b = 17.7370(1) Å, c = 25.7370(2) Å, β = 105.3840(2)°, V = 16474.02(16) ų, Z = 12. Original Russian Text Copyright ? 2005 by I. V. Kalinina, D. G. Samsonenko, Z. A. Starikova, A. A. Korlyukov, J. Lipkowski, V. P. Fedin, and M. Yu. Antipin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 139–148, January–February, 2005.     

Crystal structure of (acetylacetonato) (dicarbonyl)iridium(I)

The structure of Ir(CO)₂(acac) is determined by XRD at room temperature. Crystallographic data for C₇H₇IrO₄ are: a = 6.4798(5) ?, b = 7.7288(5) ?, c = 9.1629(10) ?, α = 105.738(2)°, β = 90.467(3)°, γ = 100.658(2)°, space group 1, P , V= 433.24(6) ?³, Z = 2, d _calc = 2.662 g/cm³, R = 0.0167. The structure is built of isolated mononuclear molecules. The central iridium atom has a square coordination environment formed by two oxygen atoms that belong to the acetylacetonate ligand and two carbon atoms of carbonyl groups. The average Ir-O and Ir-C bond lengths are 2.045(3) ? and 1.832(6) ? respectively. Molecules are stacked in such a way that the planes of coordination squares turn out to be parallel to the Ir...Ir distances between the nearest neighbors in the stack of 3.242 ? and 3.260 ?. Original Russian Text Copyright ? 2009 by K. V. Zherikova, N. V. Kuratieva, and N. B. Morozova __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 595–597, May–June, 2009.     

Crystal structure of a new coordination polymer [LaAg(Pydc)(HPydc)(C2O4)0.5(H2O)2]n (H2Pydc = pyridine-3,5-dicarboxylic acid)

A new 3D coordination polymer, [LaAg(Pydc)(HPydc)(C₂O₄)_0.5(H₂O)₂] _n (I) (H₂Pydc = pyridine-3,5-dicarboxylic acid), has been hydrothermally synthesized and characterized by elemental analyses and single crystal X-ray diffraction. The X-ray diffraction analysis reveals that I (C₁₅H₁₁AgLaN₂O₁₂) crystallizes in triclinic space group P $ \bar 1 $ \bar 1 and features an interesting 3D framework constructed by 2D layers via strong Ag-Ag interactions. Unit cell parameters for I (n = 1): a = 7.749(2), b = 8.316(1), c = 14.239(3) ?, α = 97.64(2)°, β = 100.12(2)°, γ = 94.37(2)°, and Z = 2.     

Crystal structure of cadmium iodide complexes with acetamide and propaneamide [Cd(CH3CONH2)6][Cd2I6] and [Cd(C2H5CONH2)6][Cd2I6]

The complexes of CdI₂ with acetamide (AA) and propaneamide (PrA) of the composition [Cd(AA)₆][Cd₂I₆] (I) and [Cd(PrA)₆][Cd₂I₆] (II) were synthesized and studied by X-ray diffraction. Isostructural crystals I and II are triclinic: a = 7.285(3) and 8.066(6), b = 11.266(4) and 11.649(3), c = 11.554(3) and 12.063(2) ?, α = 100.96(2)° and 102.74(2)°, β = 91.59(2)° and 91.73(4)°, γ = 100.76(3)° and 101.05(4)°, V = 912.5 and 1081.9 ?³, respectively; space group , Z = 1. Original Russian Text ? I.A. Zamilatskov, E.V. Savinkina, D.V. Al’bov, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 6, pp. 407–410.     

Synthesis of heteroligand complex Nd(Phen){( iso -C4H9)2PS2}2(NO3). Crystal structure of [Nd(Phen){( iso -C4H9)2PS2}3] and luminescent properties of these compounds

The heteroligand complex Nd(Phen){(iso-C₄H₉)₂PS₂}₂(NO₃) (I) was synthesized and its IR spectrum was analyzed. The anions (iso-C₄H₉)₂PS_2/− and N_3/− act as bidentate cyclic ligands. The single crystals of [Nd(Phen){iso-C₄H₉)₂PS₂}₃] (II) were obtained on evaporation of a solution of complex I in a mixture CH₂Cl₂-hexane and were studied by X-ray diffraction. Crystals II are triclinic: a = 10.5509(5); b = 14.7432(8), c = 16.8503(10) ?; α = 102.882(2)°, β = 97.211(2)°, γ= 108.087(2)°, V = 2374(2) ?³, Z = 2, ρ(calcd.) = 1.332 g/cm³, space group . The coordination polyhedron of the Nd atom in a separate mononuclear molecule II is a distorted dodecahedron N₂S₆. The molecules are bound by weak van der Waals and π-π interactions. The photoluminescence spectra of complexes I, II were measured and interpreted. Original Russian Text ? S.V. Larionov, V.L. Varand, R.F. Klevtsova, T.G. Leonova, L.A. Glinskaya, E.M. Uskov, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 12, pp. 944–950.     

Synthesis of 1,2,4,5‐Benzenetetrasulfonic Acid (H4B4S) and its Implementation as a Linker for Building Metal‐Organic Frameworks on the Example of [Cu2(B4S)(H2O)8]·0.5H2O

Benzene 1,2,4,5‐tetrasulfonic acid (H₄B4S) was prepared in two steps starting from 1,2,4,5‐Tetrachlorobenzene. Slow evaporation of an aqueous reaction mixture of H₄B4S and Cu₂(OH)₂(CO₃) led to light green single crystals of [Cu₂(B4S)(H₂O)₈] · 0.5H₂O. X‐ray single crystal investigations revealed the compound to be triclinic [P , Z = 1, a = 710.0(1), b = 713.7(1), c = 1077.1(2) pm, α = 98.41(2)°, β = 102.91(2)°, γ = 100.69(2)°]. In the crystal structure the Cu²⁺ ions are coordinated by four water molecules and two monodentate sulfonate anions yielding a tetragonally distorted [CuO₆] octahedron. The anions are connected to further copper ions leading to ladder shaped chains running along the [100] direction. According to DTA/TG investigations the dehydration of the compound is finished at 240 °C and the decomposition of the anhydrous sulfonate starts at 340 °C.     

One‐dimensional Cadmium(II) Coordination Polymers: Syntheses and Crystal Structures of [Cd(H2O)3(C5H6O4)]·2H2O,Cd(H2O)2(C6H8O4), and Cd(H2O)2(C8H12O4)

[Cd(H₂O)₃(C₅H₆O₄)]·2H₂O ( 1 ) and Cd(H₂O)₂(C₆H₈O₄) ( 2 ) were prepared from reactions of fresh CdCO₃ precipitate with aqueous solutions of glutaric acid and adipic acid, respectively, while Cd(H₂O)₂(C₈H₁₂O₄) ( 3 ) crystallized in a filtrate obtained from the hydrothermal reaction of CdCl₂·2.5H₂O, suberic acid and H₂O. Compound 1 consists of hydrogen bonded water molecules and linear {[Cd(H₂O)₃](C₅H₆O₄)_2/2} chains, which result from the pentagonal bipyramidally coordinated Cd atoms bridged by bis‐chelating glutarato ligands. In 2 and 3 , the six‐coordinate Cd atoms are bridged by bis‐chelating adipato and suberato ligands into zigzag chains according to {[Cd(H₂O)₃](C₅H₆O₄)_2/2} and {[Cd(H₂O)₂](C₈H₁₂O₄)_2/2}, respectively. The hydrogen bonds between water and the carboxylate oxygen atoms are responsible for the supramolecular assemblies of the zigzag chains into 3D networks. Crystallographic data: ( 1 ) P1¯ (no. 2), a = 8.012(1), b = 8.160(1), c = 8.939(1) Å, α = 82.29(1)°, β = 76.69(1)°, γ = 81.68(1)°, U = 559.6(1) ų, Z = 2; ( 2 ) C2/c (no. 15), a = 16.495(1), b = 5.578(1), c = 11.073(1) Å, β = 95.48(1)°, U = 1014.2(1) ų, Z = 4; ( 3 ) P2/c (no. 13), a = 9.407(2), b = 5.491(1), c = 11.317(2) Å, β = 95.93(3)°, U = 581.4(2) ų, Z = 2.     

Crystal structures of the octahedral rhenium cluster compexes Cs4[Re6S8(OH)6]·6H2O and Cs4[Re6Se8(OH)6]·8H2O

The salts Cs₄[Re₆S₈(OH)₆]·6H₂O (1) and Cs₄[Re₆Se₈(OH)₆]·8H₂O (2) were obtained by the reactions of Re₆S₈Br₂ and Re₆Se₈Br₂ with a CsOH melt with further solution of the products in water and crystallization of 1 and 2 from the aqueous solutions. The structure of the compounds was established by X-ray single crystal diffraction analysis. Compound 1 crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 14.175(2) Å, b = 11.321(2) Å, c = 17.503(2) Å, V = 2808.5(7) ų, Z = 4, d _calc = 5.003 g/cm³; compound 2 crystallizes in the triclinic space group with unit cell parameters a = 9.020(4) Å, b = 9.127(4) Å, c = 10.289(4) Å, α = 79.589(7)°, β = 75.829(7)°, γ = 72.186(7)°, V = 776.8(6) ų, Z = 1, d _calc = 5.402 g/cm³. Original Russian Text Copyright ? 2007 by K. A. Brylev, Yu. V. Mironov, S.-J. Kim, and V. E. Fedorov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 6, pp. 1183–1188, November–December, 2007.     

Synthesis and Structures of [Mo12E16(PEt3)10] (E = S,Se)

Dodecanuclcar cluster complexes [Mo₁₂S₁₆(PEt₃)₁₀] 1 and [Mo₁₂Se₁₆(PEt₃)₁₀] 2 have been prepared by the reactions of [Mo₆S₈(PEt₃)₆] with sulfur or [Mo₆Se₈(PEt₃)₆] with Cp₂TiSe₅, respectively, in toluene at refluxing temperature. The structures have been determined at 173 K by X-ray crystallography. The compound 1 ·3CHCl₃ crystallizes in the triclinic space group $ {\rm P}\bar 1 $, with a = 14.859(5) Å, b = 15.868(4) Å, c = 14.200(7) Å, α = 100.58(3)°, β = 117.58(3)°, γ = 79.53(2)°, V = 2899(1) ų, and Z = 1. Full-matrix least-squares refinement using 9016 observed reflections (I_o > 2σ(I_o)) gave R = 0.056, and R_w = 0.045. The data for 2 ·2CHCl₃ are: triclinic, $ {\rm P}\bar 1 $, a = 15.737(4) Å, b = 18.763(9) Å, c = 13.062(4) Å, α = 102.45(3)°, β = 128.54(2)°, γ = 69.49(3)°, V = 2825 ų, Z = 1, R = 0.096, and R_w = 0.120 for 5922 reflections (I_o > 2σ(I_o)). The cluster complexes 1 and 2 have two octahedral molybdenum cluster units linked by the rhomboidal intercluster Mo₂(μ₄-E)₂ bonding. The intercluster Mo—Mo distances in 1 are 3.419 Å and 2 3.551 Å. The cyclic voltammetry of 1 and 2 shows two oxidation and two reduction steps separated as large as 380–490 mV. The UV-Vis spectra of the dodecanuclear cluster complexes 1 and 2 have an extra weak band at around 744 nm which is absent in the starting octahedral cluster complexes.     

Crystal structure of [Mn(1,10-C12H8N2)3](B6H7)2

A new compound [MN^II(Phen)₃]²⁺(B₆H₇)₂⁻ is synthesized; its crystal structure is studied by XRD at 100 K. Crystallographic data: C₃₆H₃₈B₁₂N₆Mn, M = 739.39, triclinic symmetry, space group P , unit cell parameters: a = 10.3131(3) ?, b = 13.4839(4) ?, c = 15.1132(4) ?; α = 97.696(1)°, β = 108.324(1)°, γ = 102.211(1)°; V = 1903.9(1) ?³, Z = 2, d _calc = 1.290 g/cm³. The structure is solved by direct and Fourier methods and refined by full-matrix LSM in the anisotropic (isotropic for hydrogen atoms) approximation to the final factor R ₁ = 0.036 for 10169 I _hkl ≥ 2σ _I (Bruker-Nonius X8 APEX CCD diffractometer, λMoK _α). The structure contains two crystallographically different anions. Original Russian Text Copyright ? 2009 by T. M. Polyanskaya, M. K. Drozdova, V. V. Volkov, and K. G. Myakishev __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 381–385, March–April, 2009.     

Molecular and crystal structure of 4-trifluoro-2-[2-(4-fluorophenyl)hydrazine-1-ylidene]-1-(thiophen -2-yl)butane-1,3-dione

Single crystal X-ray diffraction is used to determine the crystal and molecular structure of 4-trifluoro-2-[2-(4-fluorophenyl)hydrazine-1-ylidene]-1-(thiophen-2-yl)butane-1,3-dione. Crystallographic data for C₁₄H₈F₄N₂O₂S are as follows: a = 8.2723(6) ?, b = 9.3009(7) ?, c = 9.9895(7) ?; α = 79.224(2)°, β = 75.851(2)°, γ = 72.337(2)°. Triclinic crystal system, P-1 space group, d _x = 1.622 g/cm³, V = 704.83(9) ?³, μ = 0.286 mm⁻¹, crystal size 0.30×0.20×0.20 mm, R1 = 0.0891, wR2 = 0.1989.     

Crystal and molecular structure and properties of [Ni(4-NH2Py)2(iso-Bu2PS2)2] and [Co(4-NH2Py)(iso-Bu2PS2)2]

The interaction of the Co(iso-Bu₂PS₂)₂ chelate with 4-NH₂Py afforded a paramagnetic complex [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (μ_eff = 4.53 BM). Single crystals of [Ni(4-NH₂Py)₂(iso-Bu₂PS₂)₂] (I) and [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (II) were grown and used for X-ray diffraction investigation (X8 APEX diffractometer, MoK _α radiation). Crystals I are monoclinic with unit cell parameters a = 12.5336(5) Å, b = 9.4356(4) Å, c = 16.4095(6) Å; β = 111.351(1)°; V = 1807.4(1) ų; Z = 2, ρ = 1.223 g/cm³, space group P2₁/n. Crystals II are triclinic with unit cell parameters a = 8.7572(4) Å, b = 9.6934(6) Å, c = 18.665(1) Å; α = 79.374(2)°, β = 87.049(2)°, γ = 75.640(2)°; V = 1508.6(1) ų; Z = 2, ρ = 1.259 g/cm³; space group . The structures of I and II are formed by isolated mononuclear molecules. The coordination unit is NiN₂S₄ (octahedron) in I and CoNS₄ (tetragonal pyramid) in II. The 4-NH₂Py molecule is coordinated through the N atom of the heterocycle. Electronic spectroscopy data for II agree with the symmetry of the NS₄ polyhedron found by X-ray diffraction (XRD) analysis. The noncoordinated amine groups link the complex molecules via N-H...S hydrogen bonds. __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp.1072–1080, November–December, 2005. Original Russian Text Copyright ? 2005 by T. E. Kokina, L. A. Glinskaya, E. A. Sankova, R. F. Klevtsova, and S. V. Larionov     

1-Allyl derivatives: Synthesis and crystal structures for [(NH2C5H4N(C3H5))2Cu3Cl3(NO3)2] and [C9H7N(C3H5)Cu(NO3)2]

1-Allyl-4-aminopyridinium chloride reacts with Cu(NO₃)₂ · 3H₂O in an ethanolic solution under the conditions of ac electrochemical synthesis at copper electrodes to form crystals of compound [(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂] (I). The crystals of compound I are monoclinic: space group P2₁/c, Z = 4, a = 25.770(7), b = 7.230(4), c = 12.505(5) ?, β = 92.58(3)°, V = 2328(2) ?³. The direct interaction of 1-allylquinolinium nitrate with Cu(NO₃)₂ · 3H₂O in a methanolic solution in the presence of metallic copper yields crystals of compound [C₉H₇N(C₃H₅)Cu(NO₃)₂] (II). The crystals of compound II are triclinic: space group P , a = 6.756(3), b = 8.391(4), c = 12.489(5) ?, α = 77.18(3)°, β = 89.48(4)°, γ = 73.32(3)°, V = 662.0(5) ?³. The structure of compound I is built of infinite linear anions: polymeric fragments {(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂} _n . Each of two copper atoms (Cu(1) and Cu(2)) π-coordinates the C=C bonds of the allyl groups of the 1-allyl-4-aminopyridinium cations, the oxygen atom of the nitrate ions, and two chlorine atoms. The third copper atom Cu(3) is linearly linked with two chlorine atoms. Particular polymeric fragments are additionally joined by the N-H…O, C-H…O, C-H…Cl hydrogen bonds. The crystal structure of compound II is built-up of the isolated L₂Cu₂(NO₃)₄ fragments (L is the 1-allylquinolinium cation). The metal atom is localized in the trigonal pyramidal coordination environment of three oxygen atoms of the nitrate ions and of the C=C bond of the allyl group of the cation. The particular L₂Cu₂(NO₃)₄ fragments are additionally joined by the C-H…O hydrogen bonds. Original Russian Text ? A.V. Pavlyuk, T. Lis, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 6, pp. 458–462.     

Interrupted super framework of the crystal structure of Cs[Be2(PO4)(PO4H)] cesium diberyllium phosphate hydrophosphate

The crystal structure of cesium diberyllium phosphate hydrophosphate Cs[Be₂(PO₄)(PO₄H)] obtained hydrothermally is analyzed. Unit cell parameters are: a = 4.8860(5) ?, b = 10.7330(11) ?, c = 13.0061(15) ?, α = 92.540(10)°, β = 92.451(9)°, γ = 90.948(9)°, space group P . In the structural motif consisting of PO₄ and BeO₄ tetrahedra, Be,P two-link chains and ribbons are distinguished, typical of a short a-translation of ≈4.9 ?. The presence of ternary and terminal O ligands along with bridging ones determines the term interrupted super framework. The group of two Be tetrahedra with a common edge is detected for beryllium phosphates for the first time. Original Russian Text Copyright ? 2009 by V. V. Bakakin, Yu. V. Seretkin, and S. P. Demin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 369–373, March–April, 2009.