Hydroxo‐bridged Tetranuclear CuII Complexes: {[Cu(bpy)(OH)]4Cl2}Cl2 · 6 H2O and {[Cu(phen)(OH)]4(H2O)2}]Cl4 · 4 H2O

The blue tetranuclear Cu^II complexes {[Cu(bpy)(OH)]₄Cl₂}Cl₂ · 6 H₂O ( 1 ) and {[Cu(phen)(OH)]₄(H₂O)₂}Cl₄ · 4 H₂O ( 2 ) were synthesized and characterized by single crystal X‐ray diffraction. ( 1 ): P 1 (no. 2), a = 9.240(1) Å, b = 10.366(2) Å, c = 12.973(2) Å, α = 85.76(1)°, β = 75.94(1)°, γ = 72.94(1)°, V = 1152.2(4) ų, Z = 1; ( 2 ): P 1 (no. 2), a = 9.770(3) Å, b = 10.118(3) Å, c = 14.258(4) Å, α = 83.72(2)°, β = 70.31(1)°, γ = 70.63(1)°, V = 1252.0(9) ų, Z = 1. The building units are centrosymmetric tetranuclear {[Cu(bpy)(OH)]₄Cl₂}²⁺ and {[Cu(phen)(OH)]₄(H₂O)₂}⁴⁺ complex cations formed by condensation of four elongated square pyramids CuN₂(OH)₂L^ap with the apical ligands L^ap = Cl, H₂O, OH. The resulting [Cu₄(μ₂‐OH)₂(μ₃‐OH)₂] core has the shape of a zigzag band of three Cu₂(OH)₂ squares. The cations exhibit intramolecular and intermolecular π‐π stacking interactions and the latter form 2D layers with the non‐bonded Cl^– anions and H₂O molecules in between (bond lengths: Cu–N = 1.995–2.038 Å; Cu–O = 1.927–1.982 Å; Cu–Cl^ap = 2.563; Cu–O^ap(OH) = 2.334–2.369 Å; Cu–O^ap(H₂O) = 2.256 Å). The Cu…Cu distances of about 2.93 Å do not indicate direct interactions, but the strongly reduced magnetic moment of about 2.74 B.M. corresponds with only two unpaired electrons per formula unit of 1 (1.37 B.M./Cu) and obviously results from intramolecular spin couplings (χ_m(T‐θ) = 0.933 cm³ · mol^–1 · K with θ = –0.7 K).     

A Hydrogen Adipato‐bridged Copper(II) Coordination Polymer: [Cu(bpy)(HL)]2L · 6H2O (bpy = 2, 2'‐Bipyridine,H2L = Adipic Acid)

Reaction of a fresh Cu(OH)_2x(CO₃)_1—x · yH₂O precipitate with adipic acid (H₂L) and 2, 2'—bipyridine (bpy) in ethanolic aqueous solution at room temperature afforded the hydrogen adipato bridged Cu^II coordination polymer [Cu(bpy)(HL)]₂L · 6H₂O consisting of double chains according to {[Cu(bpy)(HL)_2/2]₂L} and hydrogen bonded H₂O molecules. The chains result from [Cu(bpy)]²⁺ units bridged by bis—monodentate hydrogen adipato ligands and further crosslinked by bis—monodentate adipato ligands. Through the interchain π—π stacking interactions and interchain C(bpy)—H···O(adipato) hydrogen bonding interactions, the double chains are assembled into layers, between which the crystal H₂O molecules are located. The Cu atoms are square pyramidally coordinated by two N atoms of one bpy ligand and three O atoms of one adipato ligand and two hydrogen adipato ligands. The doubly bonded oxygen atom of the protonated carboxyl group occupies the apical position (Cu—N: 1.997, 2.005 Å; equatorial Cu—O: 1.925, 1.942 Å; apical Cu—O: 2.354 Å). Furthermore, the thermal behavior of the compound will be discussed. Crystal data: triclinic, P1¯ (no. 2), a = 9.618(1) Å, b = 9.933(1) Å, c = 12.782(2) Å, α = 70.88(1)°, β = 73.70(1)°, γ = 75.60(1)°, V = 1090.7(2) ų, Z = 1, R = 0.0453 and wR² = 0.1265 for 4643 observed reflections (F_o² > 2σ(F_o²)) out of 4985 unique reflections.     

Two New Polyoxovanadate‐supported Transition Metal Complexes: [Zn(en)2][Zn(en)2(H2O)2][{Zn(en)(enMe)}As6V15O42(H2O)]·4H2O and [Zn2(enMe)2(en)3][{Zn(enMe)2}As6V15O42(H2O)]·4H2O

Two novel As‐V‐O cluster supported transition metal complexes, [Zn(en)₂][Zn(en)₂(H₂O)₂][{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 1 ) and [Zn₂(enMe)₂(en)₃][{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 2 ), have been hydrothermally synthesized. The single X‐ray diffraction studies reveal that both compounds consist of discrete noncentral polyoxoanions [{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]^4? or [{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]^4? cocrystallized with respective zinc coordination complexes. Interestingly, compounds 1 and 2 exhibit the first two polyoxovanadates containing As₈V₁₅O₄₂‐(H₂O)]^6? cluster decorated by only one transition metal complex. Crystal data: 1 , monoclinic, P2₁/n, a = 14.9037(4) Å, b = 18.1243(5) Å, c = 27.6103(7) Å, β = 105.376(6)°, Z = 4; 2 monoclinic, P2₁/n, a = 14.9786(7) Å, b = 33.0534(16) Å, c = 14.9811(5) Å, Z = 4.     

The Cocrystallization of the Cubic [Ta6Br12(H2O)6][CuBr2X2]·10H2O and Triclinic [Ta6Br12(H2O)6]X2·trans‐[Ta6Br12(OH)4(H2O)2]·18H2O (X = Cl,Br, NO3) Phases with the Coexistence of [Ta6Br12]2+ and [Ta6Br12]4+ in the Latter

Cubic [Ta₆Br₁₂(H₂O)₆][CuBr₂X₂]·10H₂O and triclinic [Ta₆Br₁₂(H₂O)₆]X₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O (X = Cl, Br, NO₃) cocrystallize in aqueous solutions of [Ta₆Br₁₂]²⁺ in the presence of Cu²⁺ ions. The crystal structures of [Ta₆Br₁₂(H₂O)₆]Cl₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O ( 1 ) and [Ta₆Br₁₂(H₂O)₆]Br₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O ( 3 )have been solved in the triclinic space group P&1macr; (No. 2). Crystal data: 1 , a = 9.3264(2) Å, b = 9.8272(2) Å, c = 19.0158(4) Å, α = 80.931(1)?, β = 81.772(2)?, γ = 80.691(1)?; 3 , a = 9.3399(2) Å, b = 9.8796(2) Å, c = 19.0494(4) Å; α = 81.037(1)?, β = 81.808(1)?, γ = 80.736(1)?. 1 and 3 consist of two octahedral differently charged cluster entities, [Ta₆Br₁₂]²⁺ in the [Ta₆Br₁₂(H₂O)₆]²⁺ cation and [Ta₆Br₁₂]⁴⁺ in trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]. Average bond distances in the [Ta₆Br₁₂(H₂O)₆]²⁺ cations: 1 , Ta‐Ta, 2.9243 Å; Ta‐Brⁱ , 2.607 Å; Ta‐O, 2.23 Å; 3 , Ta‐Ta, 2.9162 Å; Ta‐Brⁱ , 2.603 Å; Ta‐O, 2.24 Å. Average bond distances in trans‐[Ta₆‐Br₁₂(OH)₄(H₂O)₂]: 1 , Ta‐Ta, 3.0133 Å; Ta‐Brⁱ, 2.586 Å; Ta‐O(OH), 2.14 Å; Ta‐O(H₂O), 2.258(9) Å; 3 , Ta‐Ta, 3.0113 Å; Ta‐Brⁱ, 2.580 Å; Ta‐O(OH), 2.11 Å; Ta‐O(H₂O), 2.23(1) Å. The crystal packing results in short O···O contacts along the c axes. Under the same experimental conditions, [Ta₆Cl₁₂]²⁺ oxidized to [Ta₆Cl₁₂]⁴⁺ , whereas [Nb₆X₁₂]²⁺ clusters were not affected by the Cu²⁺ ion.     

Zinc and Cobalt Complexes Derived from Tetradentate Tripodal Ligands with N2O2 Donorset as Model Compounds for Phosphatases

Starting from the tripodal tetradentate ligands ‐(3,5‐dibromo‐2‐hydroxybenzyl)(2‐hydroxybenzyl)(2‐pyridyl)methylamine (H₂L1), (3,5‐dibromo‐2‐hydroxybenzyl)(2‐hydroxy‐5‐nitrobenzyl)(2‐pyridyl)methylamine (H₂L2), and (3,5‐dichloro2‐hydroxybenzyl)(2‐hydroxy‐5‐nitrobenzyl)(2‐pyridyl)methylamine (H₂L3) the new isostructural dinuclear zinc compounds [Zn₂(L1)₂]·N(CH₂CH₃)₃ ( 1 ), [Zn₂(L2)₂]·2CH₃OH ( 2 ) and [Zn₂(L3)₂]·C₄H₁₀O ( 3 ) were synthesized. Due to their enzyme‐like trigonal bipyramidal N₂O₃ coordination environment of the zinc ions and the similar Zn···Zn distances the complexes can be considered to be structural models for the active sites in phospholipase C and nuclease P1. With H₂L3 also the dinuclear complex [Co₂(L2)₂(CH₃OH)]·2CH₃OH·0.5C₄H₁₀O ( 4 ) could be prepared. The new compounds were isolated and characterized by single crystal X‐ray crystallography as well as infrared spectroscopy. The cobalt compound 4 was additionally characterized by UV‐Vis spectroscopy and magnetic measurements. 1 crystallizes in the monoclinic space group P2₁/n with a = 11.2814(2), b = 28.6154(2), c = 13.1866(3) Å, β = 96.995(1)°, V = 4225.2(2) ų, Z = 4. 2 and 3 are monoclinic, space group C2/c with a = 23.084(5), b = 9.232(2), c = 21.849(4) Å, &β; = 96.83(3)°, V = 4623(2) ų, Z = 4, and a = 22.7834(3), b = 9.2463(1), c = 21.6351(3) Å, &β; = 97.592(1)°, V = 4517.7(2) ų, Z = 4, respectively. 4 crystallizes in the monoclinic space group I2/a with a = 22.4680(4), b = 20.5517(4), c = 22.8910(6) Å, &β; = 111.938(1)°, V = 9804.7(4) ų, Z = 8. 4 shows an effective magnetic moment of 6.72 μ_B at 300 K which clearly indicates the presence of two cobalt(II) high spin ions with Curie‐Weiss behaviour above 80 K. At lower temperatures a decrease of the effective magnetic moment was observed.     

A Novel 3D Framework Coordination Polymer based on Succinato bridged Helical Chains Connected by 4, 4' ‐ Bipyridine: [Cu(bpy)(H2O)2(C4H4O4)]?2H2O

Blue needle—shaped crystals of [Cu(bpy)(H₂O)₂(C₄H₄O₄)]· 2H₂O were obtained by slow evaporation of a methanolic aqueous solution containing a fresh Cu(C₄H₄O₄)· 2H₂O precipitate, 4, 4′—bipyridine, and ammonia. Within the complex, the six—coordinated Cu atoms are linked by bis—monodentate gauche succinate anions into chains propagating helically around the [001] axis. The chains are interconnected by 4, 4′—bipyridine ligands into a 3D framework with the crystal H₂O molecules located in the channels along the [100], [010] and [110] directions. The Cu²⁺ ions are in distorted octahedral coordination of two nitrogen and four oxygen atoms (equatorial bonds: Cu—N 1.986(5), 2.015(5)Å; Cu—O 1.950(6), 1.954(6)Å; axial bonds Cu—O: 2.524(9), 2.539(8)Å). Furthermore, the thermal and magnetic behavior of the compound will be discussed. Crystal data: hexagonal, P6₁ (no. 169), a = 11.066(2)Å, c = 24.965(5)Å, V = 2647.5(8)ų, Z = 6, R = 0.0528 and wR₂ = 0.1103 for 1426 observed reflections (F_o² > 2σ(F_o²)) out of 2170 unique reflections.     

Synthesis,Crystal Structure,and Magnetic Properties of {[Cu(phen)]2(C4H2O4)2} · 4.5H2O with C4H4O4 = Maleic Acid

Reaction of CuCl₂ · 2H₂O, phenanthroline, maleic acid and NaOH in CH₃OH/H₂O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]₂(C₄H₂O₄)₂} · 4.5H₂O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)ų, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]₂(C₄H₂O₄)₂} complex molecules and hydrogen bonded H₂O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H₂O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law _χm(T—θ) = 0.435 cm³ · mol^—1 · K with θ = 1.59 K.     

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).     

Synthese und Charakterisierung von Aquapentachloroplatinaten(IV) – Struktur von [K(18-Krone-6)][PtCl5(H2O)]

Synthesis and Characterization of Aquapentachloroplatinates(IV) – Structure of [K(18-crown-6)][PtCl₅(H₂O)] The crown ether complex of the aquapentachloroplatinic acid of the composition [H₁₃O₆][PtCl₅(H₄O₂)] · 2(18-cr-6) ( 2 ) reacts with K₂CO₃ and [NⁿBu₄]OH in aqueous solution to give [K(18-cr-6)][PtCl₅(H₂O)] ( 5 a ) and [NⁿBu₄][PtCl₅(H₂O)] · ¹/₂ (18-cr-6) · H₂O ( 5 b ), respectively. Both compounds were characterized by microanalysis, vibrational (IR, Raman) and NMR (¹H, ¹³C, ¹⁹⁵Pt) spectroscopy. The X-ray structure analysis of 5 a (orthorhombic, pnma; a = 16,550(4), b = 18,044(3), c = 7,415(1) Å; Z = 4; R1 = 0,0183; wR2 = 0,0414) reveals that the crystal is threaded by chains built up of [PtCl₅(H₂O)]^? and [K(18-cr-6)]⁺ units. There are tight K …? Cl contacts (d(K? Cl1)) = 3,0881(9) Å and O_W? H? O_cr hydrogen bridges (d(O1 …? O2) = 2,806(3) Å) between these units. The coordination polyhedron [PtCl₅O] has approximately C_4v symmetry.     

Aquabis(3,5-dimethyl-1H-pyrazole-κN2)(malonato-κ2O,O′)copper(II) ­dihydrate

In the neutral title complex, [Cu(C₃H₂O₄)(C₅H₈N₂)₂(H₂O)]·2H₂O or [Cu(mal)(dmp)₂(H₂O)]·2H₂O (mal is malon­ate and dmp is 3,5-di­methyl-1H-pyrazole), the Cu^II ion, in a slightly distorted square-pyramidal geometry, is coordinated by two O atoms of the bidentate malonate, the O atom of the water ligand and two N atoms from the two 3,5-di­methyl­pyrazole ligands. The mean Cu—N bond length is 2.007 (6) Å, longer than the Cu—O_mal bonds [1.950 (5) Å]. The apical position is occupied by a relatively strongly coordinated water mol­ecule [Cu—O_water 2.288 (5) Å]. The crystal structure is characterized by the layer motif of a hydrogen-bonded network.     

An Azelaato‐bridged Dinuclear Copper(II) Complex, [Cu2(phen)2(C9H14O4)2] · 6 H2O (phen = 1,10‐phenanthroline)

The title compound [Cu₂(phen)₂(C₉H₁₄O₄)₂] · 6 H₂O was prepared by the reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), azelaic acid and Na₂CO₃ in a CH₃OH/H₂O solution. The crystal structure (monoclinic, C2/c (no. 15), a = 22.346(3), b = 11.862(1), c = 17.989(3) Å, β = 91.71(1)°, Z = 4, R = 0.0473, wR² = 0.1344 for 4279 observed reflections) consists of centrosymmetric dinuclear [Cu₂(phen)₂(C₉H₁₄O₄)₂] complexes and hydrogen bonded H₂O molecules. The Cu atom is square‐planar coordinated by the two N atoms of the chelating phen ligand and two O atoms of different bidentate bridging azelaate groups with d(Cu–N) = 2.053, 2.122(2) Å and d(Cu–O) = 1.948(2), 2.031(2) Å. Two azelaate anions bridge two common Cu atoms via the terminal O atoms (d(C–O) = 1.29(2) Å; d(C–C) = 1.550(4)–1.583(4) Å). Phen ligands of adjacent complexes cover each other at distances of about 3.62 Å, indicating π‐π stacking interaction, by which the complexes are linked to 1 D bands.     

Synthesis and structure of copper(II) trans-diaqua-bis(3-hydroxybenzoylhydrazine) nitrate dihydrate [Cu(C7H8O2N2)2(OH2)2](NO3)22H2O

Synthesis of [Cu(m-HBH)₂(OH₂)₂](NO₃)₂·2H₂O, where m-HBH = C₇H₈O₂N₂ (3-hydroxybenzoylhydrazine), is described. The structure of the compound was studied by X-ray phase analysis and IR spectroscopy; crystal data are a = 57.415(6) Å, b = 19.760(2) Å, c = 7.586(2) Å; Fdd 2, Z = 16, R(F) = 0.053. The compound consists of [Cu(m-HBH)₂(OH₂)₂]²⁺ complex cations, NO ₃ ^? anions, and two water molecules. The similarity between the IR spectra of Cu(m-HBH)₂(NO₃)₂·nH₂O and Co(m-HBH)₂(NO₃)₂·5H₂O, element analysis data, and crystal data obtained at the first stage of X-ray analysis show that the structures and compositions of these compounds are identical relative to the type of surroundings of the central atom. In contrast to the cobalt compound [Co(m-HBH)₂(OH₂)₂](NO₃)₂·3H₂O, in which the cobalt atom has a nearly regular octahedron as a coordination polyhedron, the copper(II) compound has a square bipyramid around the copper atom; c.n. is 6 = 4 + 2 (planar distances: 2.013(2) Å, 2.021(2) Å, 2.033(3) Å, 2.087(3) Å; axial distances: 2.367(3) Å, 2.374(3) Å) and lacks one crystallization water molecule.     

Zur Koordinationschemie von cis-Trioxowolfram(VI)-Komplexen. Die Kristallstrukturen von LWO3 · 3 H2O, [L′WO2(OH)]Br, [LWO2Br]Br, [L2W2O5](S2O6) · 4 H2O und [LWO2(μ-O)WO(O2)2(OH2)] (L = 1,4,7-Triazacyclononan; L′ = 1,4,7-Trimethyl-1,4,7-triazacyclononan)

Coordination-chemistry of cis-Trioxotungsten(VI) Complexes. Crystal Structures of LWO₃ · 3 H₂O, [L′WO₂(OH)]Br, [LWO₂Br]Br, [L₂W₂O₅](S₂O₆) · 4 H₂O and [LWO₂(μ-O)WO(O₂)₂(OH₂)] (L = 1,4,7-Triazacyclonane; L′ = 1,4,7-Trimethyl-1,4,7-triazacyclononane) The cyclic triamines 1,4,7-triazacyclononane (L; C₆H₁₅N₃) and 1,4,7-trimethyl-1,4,7-triazacyclononane (L′; C₉H₂₁N₃) react in aqueous solution with WO₃ affording LWO₃ · 3 H₂O, 1 , and L′WO₃ · 3 H₂O, respectively, which yield [L′WO₂(OH)]Br, 2 , and [LWO₂Br]Br, 3 , in concentrated HBr solutions. In aqueous CH₃SO₃H solution 1 dimerizes. The iodide and dithionate 4 salts of [L₂W₂O₅]²⁺ have been isolated. In 35% H₂O₂ complex 1 yields the neutral species [LWO₂(μ-O)WO(O₂)₂(H₂O)] 5 . The crystal structures of 1 – 5 have been determined by X-ray analysis. Crystal data: 1 : P2₁/c; a = 7.729(2), b = 14.887(3), c = 10.774(2) Å, β = 90.77(2)°, Z = 4; 2 : Cc; 8.910(3), b = 12.220(6), c = 13.279(6) Å, β = 101.31(3)°, Z = 4; 3 : Cmc2₁, a = 8.857(5), b = 12.062(7), c = 11.218(7) Å, Z = 4; 4 : Cc, a = 17.601(7), b = 12.906(7), c = 14.107(8) Å, β = 124.08(4)°, Z = 4; 5 : P2₁2₁2₁; a = 8.452(4), b = 11.301(6), c = 13.750(6) Å, Z = 4.     

A new cyanobridged one-dimensional coordination polymer based on the octahedral rhenium cluster [Re6Se8(CN)6]4−: Synthesis and crystal structure of [{Cu(H2O)0.5(en)2} {Cu(en)2}Re6Se8(CN)6]·3H2O

The rhenium cluster complex [{Cu(H₂O)_0.5(en)₂} {Cu(en)₂} Re₆Se₈(CN)₆]·3H₂O has been obtained by the reaction of an aqueous solution of K₄[Re₆Se₈(CN)₆]·3.5H₂O with an aqueous solution of Cu(en)₂Cl₂ using cross diffusion through a gel. The structure of the compound has been characterized by a single-crystal X-ray diffraction method (a = 10.690(3) Å, b = 15.035(5) Å, c = 25.847(8) Å, V = 4154(2) ų, Z = 4, space group P2₁2₁2₁, R = 0.0651). Cluster anions [Re₆Se₈(CN)₆]^4? in the complex are connected with Cu²⁺ cations by cyano bridges resulting in zigzag chains. Coordination environment of cations is completed by ethylenediamine molecules. Additionally each cluster anion is coordinated by one terminal fragment {Cu(H₂O)_0.5(en)₂}.     

Nine-coordinate rare earth metal complexes with aminopolycarboxylic acids: Mononuclear (NH4)3[TbIII(ttha)]·5H2O and binuclear (NH4)4[Tb 2 III (dtpa)2]·9H2O

The two title coordination compounds, (NH₄)₃[Tb^III(ttha)]·5H₂O (ttha = triethylenetetramine-N,N,N′,N″,N‴,N‴-hexaacetic acid) and (NH₄)₄[Tb ₂ ^III (ttha)]·9H₂O (dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), have been prepared and characterized by FT-IR, elemental analyses, TG-DTA and single crystal X-ray diffraction techniques. The (NH₄)₃[Tb^III(ttha)]·5H₂O compound is monoclinic, P2₁/c; a = 10.398(1) Å, b = 12.791(1) Å, c = 23.199(2) Å; β = 90.914(2)°; V = 3084.9(5) ų; Z = 4; D _calc = 1.704 g/cm³; μ(MoK _α ) = 2.376 mm^™; R = 0.023 and wR ² = 0.049 for 5429 observed reflections with I ≥ 2σ(I). The [Tb^III(ttha)]³⁻ complex anion in the crystal has a nine-coordinate mononuclear molecular structure with pseudo-monocapped square-antiprismatic configuration. The (NH₄)₄[Tb ₂ ^III (dtpa)₂]·9H₂O compound is triclinic, P-1; a = 9.739(1) Å, b = 10.010(1) Å, c = 12.968(2) Å; α= 85.890(2)°, β = 77.338(2)°, γ = 77.587(2)°; V = 1204.2(2) ų; Z = 1; D _calc = 1.832 g/cm³; μ(MoK _α ) = 3.015 mm^™; R = 0.024 and wR ² = 0.060 for 4750 observed reflections with I ≥ 2σ(I). The [Tb ₂ ^III (dtpa)₂]₄₋ complex anion has a binuclear structure in the crystal; the two Tb^III centers are equivalent and have a nine-coordinate environment with the same pseudo-tricapped trigonal-prismatic configuration. The thermal analysis revealed that the coordination cores of the (NH₄)₃[Tb^III(ttha)]·5H₂O and (NH₄)₄[Tb ₂ ^III (dtpa)₂]·9H₂O compounds are stable up to 221°C and 252°C, respectively. Original Russian Text Copyright ? 2008 by J. Wang, X. Zh. Liu, X. F. Wang, G. R. Gao, Zh. Q. Xing, X. D. Zhang, and R. Xu The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 81–89, January–February, 2008.     

Syntheses and Structures of Coordination Polymers Constructed by Semi‐Rigid Bicarboxylic Acid Ligands

The complexes [Co(L¹)(mpy)] ( 1 ), [Ni(L¹)(mpy)] ( 2 ), [Co(L¹)(tbpy)] · 2H₂O ( 3 ), [Ni₂(L¹)₂(tbpy)₂] · 5H₂O ( 4 ), [Mn₂(L¹)₂(tbpy)₂] · 3H₂O ( 5 ), [Mn(L¹)(biim‐3)] ( 6 ), [Ni₂(L¹)₂(btb)₂(H₂O)] · 2H₂O ( 7 ), [Cu(L²)(mpy)] · 7H₂O ( 8 ), [Co(L²)(tbpy)(H₂O)] ( 9 ), [Ni(L²)(tbpy)(H₂O)] · H₂O ( 10 ), [Cu(L²)(bib)] · 2H₂O ( 11 ), and [Cu(L²)(btb)] · 2H₂O ( 12 ) [H₂L¹ = (3‐carboxyl‐phenyl)‐(4‐(2′‐carboxyl‐phenyl)‐benzyl)ether, H₂L² = 3‐carboxy‐1‐(4′‐carboxybenzyl)‐2‐oxidopyridinium, mpy = 2‐(4‐(4′‐methylphenyl)‐6‐(pyrindin‐2‐yl)pyridin‐2‐yl)pyridine), tbpy = 2‐(4‐(4′‐tert‐butylphenyl)‐6‐(pyrindin‐2‐yl)pyridin‐2‐yl)pyridine), biim‐3 = 1,3‐bis(imidazol‐1′‐yl)propane, btb = 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene, bib = 1,4‐bis(imidazol‐1′‐ylmethyl)benzene] were synthesized. Compounds 1 – 6 have similar 1D chain structures, which are further linked by π–π interactions to generate supramolecular double chains for 1 and 2 , and supramolecular layers for 3 – 6 . Compound 7 displays a 3D 6‐connected framework with (4⁴ · 6¹¹) topology. Compound 8 features a monomolecular structure, which is further linked by hydrogen bonds between the lattice water molecules and carboxylate oxygen atoms of L² anions to form a 2D supramolecular layer. The monomolecular structures of 9 and 10 are connected by hydrogen bonds and π–π interactions simultaneously to generate supramolecular layers. Compounds 11 and 12 show layer structures.     

Synthesis,Structure, and Polarized Optical Spectra of a New Fluoromanganate(III): [(H3N(CH2)2)2NH2]2[MnF5(H2O)]3

The synthesis and crystal structure of a new fluoromanganate(III), [(H₃N(CH₂)₂)₂NH₂]₂[MnF₅(H₂O)]₃, is reported. The unit cell is unusually large: monoclinic, P2₁/c (no. 14), a = 41.0512(13) Å; b = 9.6469(4) Å; c = 12.8021(7) Å; β = 91.927(4)°; Z = 8, R = 0.0627 and wR₂ = 0.1347. The [MnF₅(H₂O)]^2– anions are octahedral with a strong distortion along the F–Mn OH₂ axes due to the Jahn-Teller effect. A very rich intermolecular hydrogen bond framework is present, leading to chains of octahedra linked by double-hydrogen bonds. The polarized optical spectra on single crystals are explained in terms of the intraconfigurational d⁴ transitions split by a ligand field of C_4v symmetry.     

Crystal structure of [{Cu(H2O)(en)2}{Cu(en)2}Re6Te8(CN)6]·3H2O

The reaction of Cs₄[Re₆Te₈(CN)₆]·2H₂O with Cu(en)₂Cl₂ in water affords crystals of a cluster complex [{Cu(H₂O)(en)₂}{Cu(en)₂}Re₆Te₈(CN)₆]·3H₂O. The structure of the compound is determined by single crystal X-ray diffraction (a = 10.8082(4) Å, b = 16.5404(6) Å, c = 24.6480(7) Å, β = 92.696(1)°, V = 4401.5(3) ų, Z = 4, space group P2₁/n, R ₁ = 0.0331, wR ₂ (all data) = 0.0652). In the complex, cluster [Re₆Te₈(CN)₆]^4? anions are linked by Cu²⁺ cations into zigzag chains through cyanide bridges. The coordination environment of the copper cations is complemented by ethylenediamine molecules. Each of the cluster anions is additionally coordinated by a terminal fragment {Cu(H₂O)(en)₂}.     

A Zipper‐like Supramolecular Double‐Chain based on 1 D π‐π Stacking Interactions: Synthesis and Crystal Structure of [Cu(phen)(C4H4O4)(H2O)]2 · C4H6O4 (phen = 1,10‐phenanthroline)

[Cu(C₁₂H₈N₂)(C₄H₄O₄)(H₂O)]₂ · C₄H₆O₄ was prepared by the reaction of succinic acid, CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen = C₁₂H₈N₂), and Na₂CO₃ in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 7.493(1), b = 9.758(1), c = 13.517(1) Å; α = 68.89(1)°, β = 88.89(1)°, γ = 73.32(1)°, Z = 1, R = 0.0308, wR² = 0.0799 for 3530 observed reflections (F ≥ 2σ(F ) out of 3946 unique reflections) consists of hydrogen bonded succinic acid molecules and succinato bridged 1 D zipperlike supramolecular [Cu(phen)(C₄H₄O₄)_2/2(H₂O)]₂ double chains based on 1 D π‐π stacking interactions between the chelating phen systems at distances of 3.71 Å and 3.79 Å. The Cu atoms are fivefold trigonal bipyramidally coordinated by two N atoms of the bidentate chelating phen ligand and three O atoms of one water molecule and two bidentate bridging succinate ligands. The water O atom and one phen N atom are at the apical positions (equatorial: d(Cu–O) = 1.945, 2.254(2) Å, d(Cu–N) = 2.034(2) Å; axial: d(Cu–O) = 1.971(2) Å, d(Cu–N) = 1.995 Å).     

Two Novel CuII Phenanthroline Adipato Complexes with π‐π Stacking Interactions: [Cu(phen)2(C6H8O4)] · 4.5 H2O and [(Cu2(phen)2Cl2)(C6H8O4)] · 4 H2O

The blue copper complex compounds [Cu(phen)₂(C₆H₈O₄)] · 4.5 H₂O ( 1 ) and [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)] · 4 H₂O ( 2 ) were synthesized from CuCl₂, 1,10‐phenanthroline (phen) and adipic acid in CH₃OH/H₂O solutions. [Cu(phen)₂‐ (C₆H₈O₄)] complexes and hydrogen bonded H₂O molecules form the crystal structure of ( 1 ) (P1 (no. 2), a = 10.086(2) Å, b = 11.470(2) Å, c = 16.523(3) Å, α = 99.80(1)°, β = 115.13(1)°, γ = 115.13(1)°, V = 1617.5(5) ų, Z = 2). The Cu atoms are square‐pyramidally coordinated by four N atoms of the phen ligands and one O atom of the adipate anion (d(Cu–O) = 1.989 Å, d(Cu–N) = 2.032–2.040 Å, axial d(Cu–N) = 2.235 Å). π‐π stacking interactions between phen ligands are responsible for the formation of supramolecular assemblies of [Cu(phen)₂(C₆H₈O₄)] complex molecules into 1 D chains along [111]. The crystal structure of ( 2 ) shows polymeric [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains (P1 (no. 2), a = 7.013(1) Å, b = 10.376(1) Å, c = 11.372(3) Å, α = 73.64(1)°, β = 78.15(2)°, γ = 81.44(1)°, V = 773.5(2) ų, Z = 1). The Cu atoms are fivefold coordinated by two Cl atoms, two N atoms of phen ligands and one O atom of the adipate anion, forming [CuCl₂N₂O] square pyramids with an axial Cl atom (d(Cu–O) = 1.958 Å, d(Cu–N) = 2.017–2.033 Å, d(Cu–Cl) = 2.281 Å; axial d(Cu–Cl) = 2.724 Å). Two square pyramids are condensed via the common Cl–Cl edge to centrosymmetric [Cu₂Cl₂N₄O₂] dimers, which are connected via the adipate anions to form the [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains. The supramolecular 3 D network results from π‐π stacking interactions between the chains. H₂O molecules are located in tunnels.