Gd4I6CN: Ein Carbidnitrid mit Ketten aus Gd6(C2)-Oktaedern und Gd6N2-Tetraederdoppeln

Gd₄I₆CN: A Carbide Nitride with Chains of Gd₆(C₂) Octahedra and Gd₆N₂ Double Tetrahedra The compound α-Gd₄I₆CN is prepared by reaction of Gd, GdI₃, C, and GdN (1:2:1:1 mole ratio) at 1 170 K in sealed Ta tubes. It is obtained as brown red, transparent needles which are air and moisture sensitive. The structure of α-Gd₄I₆CN contains Gd₆ octahedra centered by C₂ groups and double tetrahedra centered by N atoms. The units are alternatingly connected via common edges to form chains (Gd₂Gd_4/2C₂) (Gd_2/2Gd_2/2N)₂ parallel [001]. The linear chains are surrounded by I atoms above all free edges of the metal polyhedra and linked according to (Gd₂Gd_4/2C₂) (Gd₂Gd_4/2N₂)I_4/2I₈I₂ in the a – b plane. We also found β-Gd₄I₆CN, which is formed in a monotropic transition from the α-form. In the structure the chains of Gd octahedra and tetrahedra as described for α-Gd₄I₆CN are more densely packed. The structure of Y₆I₉C₂N is composed by chains of pairs of Y-octahedra and Y-tetrahedra, respectively. The octahedra are centered by C₂ groups, the tetrahedra by N-atoms. We also synthesized the compounds Gd₄Br₆CN und La₄I₆CN by tempering at 1 220 K. They are isotypic with α-Gd₄I₆CN.     

catena‐Poly­[[di­aqua­cobalt(II)]‐μ‐oxalato]

Single crystals of the title compound, [Co(C₂O₄)(H₂O)₂]_n, have been prepared by hydro­thermal methods and characterized by X‐ray diffraction analysis. The crystal structure consists of infinite one‐dimensional chains of di­aqua­cobalt(II) units bridged by oxalate groups. These chains lie on twofold symmetry axes parallel to the b axis, and the [Co(C₂O₄)]_n system is nearly planar within experimental error. The cobalt(II) coordination polyhedra are irregular octahedra, with oxalate O atoms at the equatorial positions and water mol­ecules at the axial positions. The chains are linked by hydrogen bonds via the water mol­ecules.     

Two drimane lactones,valdiviolide and 11‐epivaldiviolide,in the form of a 1:1 cocrystal obtained from Drimys winteri extracts

A cocrystal, C₁₅H₂₂O₃·C₁₅H₂₂O₃, (I), obtained from Drimys winteri, is composed of two isomeric drimane sesquiterpene lactones, namely valdiviolide, (Ia), and 11‐epivaldiviolide, (Ib), neither of which has been reported in the crystal form. Both diastereoisomers present three chiral centres at sites 5, 10 and 11, with an SSR sequence in (Ia) and an SSS sequence in (Ib). O—H...O hydrogen bonds bind molecules into chains running along [20] and the chains are in turn linked by π–π stacking interactions to define planar weakly interacting arrays parallel to (001).     

2,6‐Diiodo‐4‐nitrophenol, 2,6‐diiodo‐4‐nitrophenyl acetate and 2,6‐diiodo‐4‐nitroanisole: interplay of hydrogen bonds,iodo–nitro interactions and aromatic π–π‐stacking interactions to give supramolecular structures in one,two and three dimensions

In 2,6‐di­iodo‐4‐nitro­phenol, C₆H₃I₂NO₃, the mol­ecules are linked, by an O—H?O hydrogen bond and two iodo–nitro interactions, into sheets, which are further linked into a three‐dimensional framework by aromatic π–π‐stacking interactions. The mol­ecules of 2,6‐di­iodo‐4‐nitro­phenyl acetate, C₈H₅I₂NO₄, lie across a mirror plane in space group Pnma, with the acetyl group on the mirror, and they are linked by a single iodo–nitro interaction to form isolated sheets. The mol­ecules of 2,6‐di­iodo‐4‐nitro­anisole, C₇H₅I₂NO₃, are linked into isolated chains by a single two‐centre iodo–nitro interaction.     

Zur elektronischen Struktur von [Y9C4O]I8

On the Electronic Structure of [Y₉C₄O]I₈ The new [Y₉C₄O]I₈ structure exhibits striking similarities with layered structures of the well-known rare-earth metal carbide halides [M₂C]X₂ and [M₂C₂]X₂ (M = rare-earth metal, X = halide) which already have been studied concerning their electronic structures and conductivities. In contrast to the last compounds, [Y₉C₄O]I₈ formally contains one extra electron. This electron appears to be delocalized in various metallic orbitals. The oxygen atoms which are located in the bent sections in the metal double layers as well as the halide double layers in the structure are considered to act as barriers for electronic mobility. Therefore a one-dimensional metallic conductivity is expected to be dominant.     

The inner‐salt zwitterion,the dihydrochloride dihydrate and the dimethyl sulfoxide disolvate of 3,6‐bis(pyridin‐2‐yl)pyrazine‐2,5‐dicarboxylic acid

In the inner‐salt zwitterion of 3,6‐bis(pyridin‐2‐yl)pyrazine‐2,5‐dicarboxylic acid, (I), namely 5‐carboxy‐3‐(pyridin‐1‐ium‐2‐yl)‐6‐(pyridin‐2‐yl)pyrazine‐2‐carboxylate, [C₁₆H₁₀N₄O₄, (Ia)], the pyrazine ring has a twist–boat conformation. The opposing pyridine and pyridinium rings are almost perpendicular to one another, with a dihedral angle of 80.24 (18)°, and are inclined to the pyrazine mean plane by 36.83 (17) and 43.74 (17)°, respectively. The carboxy and carboxylate groups are inclined to the mean plane of the pyrazine ring by 43.60 (17) and 45.46 (17)°, respectively. In the crystal structure, the molecules are linked via N—H...O and O—H...O hydrogen bonds, leading to the formation of double‐stranded chains propagating in the [010] direction. On treating (Ia) with aqueous 1 M HCl, the diprotonated dihydrate form 2,2′‐(3,6‐dicarboxypyrazine‐2,5‐diyl)bis(pyridin‐1‐ium) dichloride dihydrate [C₁₆H₁₂N₄O₄²⁺·2Cl⁻·2H₂O, (Ib)] was obtained. The cation lies about an inversion centre. The pyridinium rings and carboxy groups are inclined to the planar pyrazine ring by 55.53 (9) and 19.8 (2)°, respectively. In the crystal structure, the molecules are involved in N—H...Cl, O—H...O_water and O_water—H...Cl hydrogen bonds, leading to the formation of chains propagating in the [010] direction. When (Ia) was recrystallized from dimethyl sulfoxide (DMSO), the DMSO disolvate 3,6‐bis(pyridin‐2‐yl)pyrazine‐2,5‐dicarboxylic acid dimethyl sulfoxide disolvate [C₁₆H₁₀N₄O₄·2C₂H₆OS, (Ic)] of (I) was obtained. Here, the molecule of (I) lies about an inversion centre and the pyridine rings are inclined to the planar pyrazine ring by only 23.59 (12)°. However, the carboxy groups are inclined to the pyrazine ring by 69.0 (3)°. In the crystal structure, the carboxy groups are linked to the DMSO molecules by O—H...O hydrogen bonds. In all three crystal structures, the presence of nonclassical hydrogen bonds gives rise to the formation of three‐dimensional supramolecular architectures.     

Bilayers in 4‐iodo‐N‐(2‐iodo‐4‐nitrophenyl)benzamide generated by a combination of an N—H⋯O=C hydrogen bond and two independent iodo–nitro interactions

Molecules of the title compound, C₁₃H₈I₂N₂O₃, are linked into C(4) chains by a single N—H⋯O=C hydrogen bond [H⋯O = 2.10 Å, N⋯O = 2.832 (5) Å and N—H⋯O = 140°]. Two independent two‐centre iodo–nitro interactions, both involving the same O atom but different I atoms [I⋯O = 3.205 (3) and 3.400 (3) Å, and C—I⋯O = 160.4 (2) and 155.7 (2)°], link the hydrogen‐bonded chains into bilayers.     

Amine-templated metal squarates

Two layered amine-templated cobalt squarates, [C₆N₂H₁₄]₂[Co₂(C₄O₄)₃(H₂O)₄], I, and [C₃N₂H₅]₂[Co₂(C₄O₄)₃(H₂O)₄], II, have been prepared under hydrothermal conditions. Both I and II contain chains formed by dimers comprising two cobalt atoms bound to the squarate units, the chains being connected through hydrogen bond interactions. An amine-templated cobalt squarate of the formula [C₄N₂H₁₂][Co(C₄O₄)₂(H₂O)₄][H₂O]₂, III, as well as its Ni, Zn and Cd analogues have been prepared by room temperature reactions. III has a layered architecture wherein the cobalt-squarate monomers are linked by the amine molecules. Co and Zn analogues of [Ni(C₄O₄)(H₂O)₂(C₃N₂H₄)] with ligating imidazole units have also been prepared and characterized.     

A three‐dimensional supramolecular vanadium hydroxylamide complex: poly[di‐μ2‐aqua‐bis(hydroxylamido)‐μ3‐malonato‐oxidosodiumvanadium(V)]

The crystal structure of the title compound, [NaV(C₃H₂O₄)(NH₂O)₂O(H₂O)₂], is built up of NaO₆ and VO₅N₂ polyhedra connected through malonate bridges. The NaO₆ octahedra are linked by edge sharing in the equatorial plane to form one‐dimensional infinite chains. These chains are linked together by the malonate bridges to form two‐dimensional layers. The distorted VO₅N₂ pentagonal bipyramid is grafted on to the layer by a malonate carboxylate O atom. Adjacent layers are connected through O—H...O and N—H...O hydrogen bonds to build up a three‐dimensional supramolecular structure.     

Gd12C6I17 – eine Verbindung mit kondensierten,C2-gefüllten Gd6I12-Clustern

Gd₁₂C₆I₁₇ — a Compound with Condensed, C₂-Containing Gd₆I₁₂ Clusters Gd₁₂C₆I₁₇ was isolated in black shining crystals from a reaction product of Gd, GdI₃ and graphite, heated in sealed tantalum capsules at 1170 K. The compound is monoclinic (C2/c; a = 1929.7(9), b = 1220.1(5), c = 1863.5(5) pm, = 90.37(3)°). The crystal structure is composed of linear units of 3 condensed Gd₆I₁₂ clusters (connection via trans-edges of the central Gd₆ octahedron), which are further linked via cis edges to form zig-zag chains. The centres of the Gd₆ octahedra are occupied by C₂ units. The distances d_{C? C} ≈ 145 pm correspond to a filling of the antibonding π* orbitals of the C₂ group, which, however, interact with empty d-orbitals of the metal atoms especially in the apices of the octahedra and thus loose their pure carbon character. The short Gd? C distances (d_{Gd? C} = 222 and 227 pm, respectively) are explained as due to multiple bonds. The occurrence of C₂ units and single C atoms, respectively, in lanthanide carbides and carbide halides is coupled to the electron concentration of the metal or cluster framework.     

一维双链镉(Ⅱ)配合物[Cd(C5H5N)CH2C(OH)(PO3)(PO3H)·3H2O]n的合成与晶体结构

A new cadmium complex [Cd(C₅H₅N)CH₂C(OH)(PO₃)(PO₃H)·3H₂O]_n((C₅H₄N)CH₂C(OH)(PO₃H₂)₂=1-hydroxy-2-(2-pyridyl)ethylidene-1,1-diphosphonate acid) has been synthesized under hydrothermal conditions. Single crystal structure determination reveals that the compound has a ladder-like chain structure in which the edge-shared {CdO₆} octahedra are linked by {CPO₃} tetrahedra through corner-sharing. The chains of {Cd(C₅H₅N)CH₂C(OH)(PO₃)(PO₃H)}_n are linked by inter-chain hydrogen bonds, forming a supramolecular layer. CCDC: 722396.     

Y16I19C8B4 – ein Yttriumboridcarbidhalogenid mit B2C4-Einheiten

Y₁₆I₁₉C₈B₄ – a Yttrium Boride Carbide Halide Containing B₂C₄ Units The new compound Y₁₆I₁₉C₈B₄ was prepared from Y, YI₃, C and B at 1050–1150 °C. The structure of a twinned crystal was determined by means of X-ray diffraction (space group P 1¯, a = 12.311(2) Å, b = 13.996(3) Å, c = 19.695(3) Å, α = 74.96(2)°, β = 89.51(2)°, γ = 67.03(2)°, Z = 2). Y₁₆I₁₉C₈B₄ is a semiconductor and contains nearly planar B₂C₄ units which are located in cages built up by 12 yttrium atoms. Assuming (B₂C₄)^12–, these units can be regarded as isoelectronic with B₂F₄. The yttrium cages are connected via faces to form rods, which are surrounded by iodine atoms. Bridging iodine atoms connect the rods so that layers are formed. The characteristic twinning observed can be understood from the geometry of the crystal structure.     

Di‐μ‐isopropoxy‐bis[bis(η5‐methyl­cyclopentadienyl)yttrium(III)]

The title complex, [Y₂(C₆H₇)₄(C₃H₇O)₂], is a centrosymmetric dimer bridged through the O atoms of the isopropoxide ligands. The Y₂O₂ unit is planar and the geometry around the eight‐coordinate Y atom is distorted pseudo‐tetrahedral. The Y—O distances are 2.2228 (19) and 2.2432 (19) Å, and the O—Y—O angle is 74.86 (7)°.     

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.     

Poly[propane‐1,3‐diammonium [tetra‐μ3‐oxo‐hexaoxotrimolybdenum(VI)] dihydrate]

The crystal structure of the title compound, {(C₃H₁₂N₂)[Mo₃O₁₀]·2H₂O}_n, is composed of [Mo₃O₁₀]²⁻ anionic chains, propane‐1,3‐diammonium cations and solvent water molecules. The [Mo₃O₁₀]²⁻ chain is constructed from edge‐sharing MoO₆ octahedra. The protonated propane‐1,3‐diamine cations and solvent water molecules are located between the chains and are linked to the O atoms of the inorganic chains by hydrogen bonds.     

Poly[nickel(II)‐di‐μ‐4,4′‐bipyridyl‐κ4N:N′‐μ‐dichromato‐κ2O:O′] and poly[copper(II)‐di‐μ‐4,4'‐bipyridyl‐κ4N:N′‐μ‐dichromato‐κ2O:O′]

The novel title hybrid isomorphous organic–inorganic mixed‐metal dichromates, [Ni(Cr₂O₇)(C₁₀H₈N₂)₂] and [Cu(Cr₂O₇)(C₁₀H₈N₂)₂], have been synthesized. A non‐centrosymmetric three‐dimensional (4,6)‐net is formed from a linear chain of vertex‐linked [Cr₂O]²⁻ and [MN₄O]²⁺ (M = Ni and Cu) units, which in turn are linked by the planar bidentate 4,4′‐­bipyridine ligand through the four remaining vertices of the [MN₄O]²⁺ octahedra. There are two such three‐dimensional nets that interpenetrate with inversion symmetry.     

Synthetic ferric sulfate trihydrate,Fe2(SO4)3·3H2O,a new ferric sulfate salt

Ferric sulfate trihydrate has been synthesized at 403 K under hydrothermal conditions. The structure consists of quadruple chains of [Fe₂(SO₄)₃(H₂O)₃] parallel to [010]. Each quadruple chain is composed of equal proportions of FeO₄(H₂O)₂ octahedra and FeO₅(H₂O) octahedra sharing corners with SO₄ tetrahedra. The chains are joined to each other by hydrogen bonds. This compound is a new hydration state of Fe₂(SO₄)₃·nH₂O; minerals with n = 0, 5, 7.25–7.75, 9 and 11 are found in nature.     

2‐(2,1‐Benzoxazol‐3‐yl)‐3,5‐di­methoxy­phenol and 3‐phenyl‐2,1‐benzoxazole

The title compounds, C₁₅H₁₃NO₄, (I), and C₁₃H₉NO, (II), are produced, along with the corresponding anilines, by the reduction of the appropriate o‐nitro­benzo­phenones. In (I), the planar benz­isoxazole and phenol fragments are tilted relative to one another by a rotation of 53.02 (14)° about the bond joining them, and the mol­ecules are linked into chains by phenol O—H...N and phenyl C—H...O_oxazole hydrogen bonds. The cell of (II) (space group I2/c) contains eight mol­ecules in general positions, four more in the 2b sites, with twofold axial symmetry that induces a degree of disorder, and a further four as centrosymmetric pairs of complete mol­ecules, each with an occupancy of one‐half. The relative tilt of the planar fragments varies slightly from one mol­ecule to another but is much less than that in (I), ranging from 8.8 (8) to 12.58 (15)°.     

A three‐dimensional supramolecular framework of silver(I), 2‐phenylquinoline‐4‐carboxylate and 4,4′‐bipyridine

A novel supramolecular framework, catena‐poly[[[aqua(2‐phenylquinoline‐4‐carboxylato‐κO)silver(I)]‐μ‐4,4′‐bipyridine‐κ²N:N′] dihydrate], {[Ag(C₁₆H₁₀NO₂)(C₁₀H₈N₂)(H₂O)]·2H₂O}_n, has been synthesized and structurally characterized. The Ag^I centres are four‐coordinated and bridged by 4,4′‐bipyridine (4,4′‐bipy) ligands to form a one‐dimensional Ag–bipy chain. The Ag–bipy chains are further linked together by intermolecular O—H...O and O—H...N hydrogen‐bonding interactions between adjacent chains, resulting in a three‐dimensional framework.     

Magnesium Hexafluoridozirconates MgZrF6·5H2O,MgZrF6·2H2O,and MgZrF6: Structures,Phase Transitions,and Internal Mobility of Water Molecules

The MgZrF₆ · n H₂O (n = 5, 2 and 0) compounds were studied by the methods of X‐ray diffraction and ¹⁹F, MAS ¹⁹F, and ¹H NMR spectroscopy. At room temperature, the compound MgZrF₆ · 5H₂O has a monoclinic C‐centered unit cell and is composed of isolated chains of edge‐sharing ZrF₈ dodecahedra reinforced with MgF₂(H₂O)₄ octahedra and uncoordinated H₂O molecules and characterized by a disordered system of hydrogen bonds. In the temperature range 259 to 255 K, a reversible monoclinic ? two‐domain triclinic phase transition is observed. The phase transition is accompanied with ordering of hydrogen atoms positions and the system of hydrogen bonds. The structure of MgZrF₆ · 2H₂O comprises a three‐dimensional framework consisting of chains of edge‐sharing ZrF₈ dodecahedra linked to each other through MgF₄(H₂O)₂ octahedra. The compound MgZrF₆ belongs to the NaSbF₆ type and is built from regular ZrF₆ and MgF₆ octahedra linked into a three‐dimensional framework through linear Zr–F–Mg bridges. The peaks in ¹⁹F MAS spectra were attributed to the fluorine structural positions. The motions of structural water molecules were studied by variable‐temperature ¹H NMR spectroscopy.