Darstellung und Kristallstruktur von Kupfer(II)-monofluorophosphat-Dihydrat CuPO3F · 2H2O

Salts of Halogenophosphoric Acids. XVII. Preparation and Crystal Structure of Copper(II) Monofluorophosphate Dihydrate CuPO₃F · 2H₂O Copper(II) monofluorophosphate dihydrate, CuPO₃F · 2H₂O 1 was obtained by the reaction of aqueous NH₄HPO₃F and acid (NH₄)₂PO₃F solutions, respectively, using acetone or ethanol as precipitating agents. The thermal dehydration of 1 gives the water-free copper monofluorophosphate CuPO₃F ( 2 ). 1 crystallizes in the monoclinic space group P2₁/c with a = 761,44, b = 780,97, c = 921,02 pm, β = 112,94° and Z = 4.     

Das erste KEGGIN-Anion mit tetraedrischer. Kupfer(II)—Sauerstoff-Koordination: [α-Cu0,4(H2)0,6O4W12O36]6−

The First KEGGIN-Anion with Tetrahedral Coordination of Copper(II)-Oxygen: [α-Cu_0,4(H₂)_0.6O₄W₁₂O₃₆]^6? The solution of the Cu^II-containing heteropolyanion was prepared starting from an aqueous solution of Na₂WO₄, adjusting to pH 5–6 by adding slowly a solution of Cu(NO₃)₂ in HNO₃. The addition of the corresponding amount of N(CH₃)₄Br to the concentrated solution led to the crystallization of the greenish-yellow mixed crystals (TMA)₆[α-Cu_0.4(H₂)_0.6O₄W₁₂O₃₆] · 9 H₂O. After repeated recrystallization it has been investigated by chemical, spectroscopic (IR/Raman, UV, ¹⁸³W/¹H-NMR, ESR) and X-ray diffraction methods (monoclinic; space group P2₁; a = 13.117(4), b = 21.466(4), c = 13.223(3) Å, β = 91.60°; Z = 2; D_c = 3.041 g · cm^?3; R = 8.0%). The distances of the four “tetrahedral” oxygen atoms to the position (0, 0, 0) range from 1.67 to 1.93 Å. The alternative occupation of the central KEGGIN position with copper(II) and two protons, respectively, accounts for the different distances. The prepared solid solution represents the first example for the tetrahedral copper(II)-oxygen coordination in any heteropolyanion compound.     

Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

Die Reaktion des Rhenium(VII)-oxides mit 1,4-Dioxan Re2O6(μ2-OH)2 · 3 C4H8O2 – ein neues Oxidhydroxid mit Metall-(1,4-Dioxan)-Bindung

Reaction of Rhenium(VII) Oxide with 1,4-Dioxane. Re₂O₆(μ₂-OH)₂ · 3 C₄H₈O₂— a Novel Oxide Hydroxide with Metal-(1,4-Dioxane) Bonds The reaction of Re₂O₇ with 1,4-dioxane in the presence of small amounts of H₂O yields the compound Re₂O₆(OH)₂ · 3(1,4-dioxane). It crystallizes in the triclinic space group P¯1 with a = 10.907(3), b = 12.875(4), c = 7.943(2) Å; α = 108.64(2), β = 103.00(2), γ = 102.29(2)°; Z = 2. The complete X-ray structure analysis (R = 2.9? ) shows the crystals to contain dimeric centrosymmetric Re₂O₆(OH)₂-units with two bridging μ₂-OH groups. The ligand spheres around Re are completed towards distorted octahedra by coordinated 1,4-dioxane molecules (one O donor per Re), the latter linking the dimeric units to endless chains. The rest of the 1,4-dioxane molecules are bonded to the OH-groups through hydrogen bridges and have no contact to Re. Mean bond distances are: Re? O(bridge) 2.065 (2.059…2.070(4)) Å, Re? O(1,4-dioxane) 2.478 (2.469 and 2.486(5)) Å, Re? O (terminal) 1.707 (1.694…1.720(5)) Å.     

Salze von Halogenophosphorsäuren. XIV. Darstellung und Kristallstruktur von Kalium-dikupferhydroxid-bis(monofluorophosphat)-Monohydrat Cu2K(OH)(PO3F)2 · H2O

Salts of Halogenophosphoric Acids. XIV. Preparation and Crystal Structure of Dicopper-potassium-hydroxide-bis(monofluorophosphate) Monohydrate Cu₂K(OH)(PO₃F)₂ · H₂O By the reaction of potassium monofluorophosphate and copper(II) salts in aqueous medium a crystalline, insoluble basic copper potassium monofluorophosphate Cu₂K(OH)(PO₃F)₂ · H₂O 1 is formed. The thermal decomposition of 1 has been studied. 1 crystallizes in the monoclinic space group B2/m with a = 9.094 Å, b = 7.755 Å, c = 6.333 Å, α = β = 90°; γ = 117.55°, and Z = 2.     

Synthesis and characterization of copper(II) complexes with 3-methylpicolinic acid. Crystal and molecular structure of bis (3-methylpicolinato- N,O )(4-picoline)copper(II)

Copper(II) complexes of 3-methylpicolinic acid (3-MepicH), namely [Cu(3-Mepic)₂] · 2H₂O (1) and [Cu(3-Mepic)₂(4-pic)] (2) were prepared and characterized by IR spectroscopy and thermal analysis (TGA/DTA). Crystal structure for 2 was determined by X-ray crystal structure analysis. 1 was prepared by reaction of copper(II) sulfate pentahydrate and 3-methylpicolinic acid in aqueous solution, while 2 was prepared by recrystallization of 1 from 4-picoline solution. Structure analysis revealed square-pyramidal copper(II) coordination and N,O-chelating mode of 3-methylpicolinic acid in 2. Copper(II) is coordinated by two 3-Mepic ligands in the basal plane of a square pyramid and by 4-picoline in the apical position. Crystal packing of 2 is dominated by weak intermolecular C–H ··· O hydrogen bonds and π ··· π stacking interactions forming a complex three-dimensional supramolecular architecture.     

Die ersten Hydrogencarbonate mit einer trimeren [H2(CO3)3]4−-Baugruppe: Zur Darstellung und Kristallstruktur von Rb4H2(CO3)3 · H2O und K4H2(CO3)3 · 1,5 H2O

The First Hydrogencarbonates with a Trimeric [H₂(CO₃)₃]^4? Group: Preparation and Crystal Structure of Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1.5 H₂O Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1,5 H₂O were prepared by means of the reaction of (CH₃)₂CO₃ with RbOH resp. KOH in aqueous methanole. Trimer [H₂(CO₃)₃]^4?-anions were found in the crystal structure of Rb₄H₂(CO₃)₃ · H₂O (orthorhombic, Pnma (no. 62), a = 1 218.0(1) pm, b = 1 572.3(6) pm, c = 615.9(1) pm, V_EZ = 1 179.5(5) · 10⁶ pm³, Z = 4, R1(I ≥ 2σ(I)) = 0.027, wR2(I ≥ 2σ(I)) = 0.055). K₄H₂(CO₃)₃ · 1,5 H₂O crystallizes in an OD-structure. The determined superposition structure (orthorhombic, Pbam (no. 55), a = 1 161.8(1) pm, b = 597.0(1) pm, c = 383.85(3) pm, V_EZ = 266.3(1) · 10⁶ pm³, Z = 1, R1(I ≥ 2σ(I)) = 0.035, wR2(I ≥ 2σ(I)) = 0.074) can be derived from the structure of the rubidium compound. The thermal decomposition of the substances is discussed.     

Präparation,Kristallstruktur, Schwingungsspektren und thermische Analyse von Kupfer‐tetrahydrogen‐decaoxo‐diperiodat‐hexahydrat CuH4I2O10·6H2O

On Copper‐tetrahydrogen‐decaoxo‐diperiodate‐hexahydrate CuH₄I₂O₁₀·6H₂O: Crystal Structure, Vibrational Spectroscopy and Thermal Analysis By crystallization from a strongly acidic aqueous solution copper‐tetrahydrogen‐decaoxodiperiodate‐hexahydrate CuH₄I₂O₁₀· 6H₂O has been obtained. In the structure of this compound (S.G. P 2₁/c, Nr.14), Z = 2, a = 1060.2(2) pm, b = 551.1(1) pm, c = 1164.7(2) pm, β = 111, 49(3)°) centrosymmetric [H₄I₂O₁₀]^2— anions in the form of two edge sharing octahedra form layers via hydrogen bonds originating from the acidic, trans‐configurated OH groups of the anions. Raman spectra are given and analyzed with respect to the internal vibrations of the periodate anion. The dehydration of the compound takes place via CuH₄I₂O₁₀·3H₂O and Cu(H₂IO₅)₂ which decomposes at 170 °C to Cu(IO₃)₂.     

Zur Reaktion des Rhenium(VII)-oxids mit 1,4-Dioxan – Kristallstruktur von Re2O7(OH2)2 · 2(1,4-Dioxan)

Reaction of Rhenium(VII) Oxide with 1,4-Dioxane – Crystal Structure of Re₂O₇(OH₂)₂ · 2(1,4-Dioxane) By solvolysis of polymeric Re₂O₇ with 1,4-dioxane in the presence of small amounts of H₂O two products of compositions Re₂O₆(OH)₂ · 3(1,4-dioxane) ( 1 ) and Re₂O₇ · 2H₂O · 2(1,4-dioxane) ( 2 ) are formed. From a complete X-ray single-crystal structure analysis 2 could now be characterized structurally (monoclinic, space group P2₁/c, a = 6.828(3) Å, b = 9.530(2) Å, c = 26.421(8) Å, β = 91.71(3)°, Z = 4). The compound is important as a convenient precursor for the preparation of pure rhenium trioxide. It is to be formulated as Re₂O₇(OH₂)₂ · 2(1,4-dioxane) and contains, contrary to 1 , no 1,4-dioxane coordinated to Re. The crystalline phase consists of a supramolecular arrangement of Re₂O₇(OH₂)₂ units as in “solid perrhenic acid” and of 1,4-dioxane molecules associated through O? H …? O hydrogen bridges. Analogous to dirhenium heptoxide and to solid perrhenic acid one of the rhenium atoms is in tetrahedral, the other is in distorted octahedral coordination.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Hydrothermal synthesis and crystal structures of Mn(II) and Cd(II) aminophosphonates with a layered structure

Two new divalent metal aminodiphosphonates with a layered structure, Mn₂[(HL)(H₂O)F]·H₂O (1) and Cd_3.5[(HL)L] (2) (H₄L =?CH₃CH₂CH₂N(CH₂PO₃H₂)₂), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. In 1, two MnO₄F₂ and two MnO₅F polyhedra are interconnected via edge-sharing into a tetramer, and such tetramers are bridged by the diphosphonate ligands into a Mn(II) phosphonate layer in the ab-plane. The structure of 2 also features a 2D layered structure, in which the CdO₅N and CdO₆ polyhedra are interconnected into a 1D chain. The chains are then cross-linked via phosphonate oxygen atoms to form Cd(II) phosphonate layers in the ab-plane.     

Synthesis and Crystal Structure of Copper(II) Trifluoroacetates,Cu2(CF3COO)4 · 2 CH3CN and Cu(CF3COO)2(H2O)4

Cu₂(CF₃COO)₄ · 2 CH₃CN ( I ) and Cu(CF₃COO)₂(H₂O)₄ ( II ) have been prepared by concentrating of acetonitrile and aqueous solutions respectively. According to X-ray data, the complex I consists of binuclear molecules with Cu–O 1.969 Å, Cu–N 2.114 Å. The Cu…Cu distance was found to be 2.766 Å, one of the longest for dimeric structures, apparently, due to the high acidity of trifluoroacetic acid. The coordination environment of Cu atom in II can be described as 4 + 2: 2 Cu–O (H₂O) 1.937 Å, 2 Cu–O (CF₃COO) 1.985 Å, 2 Cu–O (H₂O) 2.447 Å. The mononuclear structure is stabilized by formation of two intra- and six intermolecular hydrogen bonds.     

Über das Tri(phosphorano)borazinium-Monokation [H3B3(NPEt3)3Cl2]+. Kristallstrukturen von Me3SiNPR3 · BH3 (R = Et,Ph), [H3B3(NPEt3)3Cl1,85Br0,15]Br · CCl4 und des Hydrolyseproduktes NH4[B5O6(OH)4] · 2 H2O

On the Tri(phosphorano)borazinium Monocation [H₃B₃(NPEt₃)₃Cl₂]⁺. Crystal Structures of Me₃SiNPR₃ · BH₃ (R = Et, Ph), [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄, and of the Product of Hydrolysis NH₄[B₅O₆(OH)₄] · 2 H₂O The crystal structures of the donor-acceptor complexes of the silylated phosphanimines with borane which are suitable as educts for the synthesis of tri(phosphorano)borazinium ions, Me₃SiNPR₃ · BH₃ (R = Et, Ph), are described. After addition of CCl₄ the reaction of Me₃SiNPEt₃ with HBBr₂ · SMe₂ in CH₂Cl₂ leads to the tri(phosphorano)borazinium monocation [H₃B₃(NPEt₃)₃Cl₂]⁺, which is characterized crystallographically as [H₃B₃ · (NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄. It complements the series of the tri(phosphorano) cations [H₃B₃(NPEt₃)₃]³⁺ and [H₄B₃(NPEt₃)₃]²⁺ by the monocation. NH₄[B₅O₆(OH)₄] · 2 H₂O can be isolated as product of hydrolysis of the tri(phosphorano)borazinium ions; its crystal structure is redetermined, because in the literature it is based on a wrong space group. Me₃SiNPEt₃ · BH₃ ( 1 ): Space group P1, Z = 4, lattice dimensions at 213 K: a = 710.9(4), b = 1465.9(3), c = 1536.0(3) pm, α = 107.05°, β = 99.40(3)°, γ = 97.41(3)°; R = 0.0740. Me₃SiNPPh₃ · BH₃ ( 2 ): Space group P2₁/c, Z = 4, lattice dimensions at 203 K: a = 934.6(1), b = 1398.6(1), c = 1626.1(1) pm, β = 103.52(1)°; R = 0.0556. [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄ ( 3 ): Space group P2₁/n, Z = 4, lattice dimensions at 223 K: a = 1237.9(3), b = 1214.1(3), c = 2402.4(4) pm, β = 93.52(1)°. 3 holds a B₃N₃ six-membered ring in a distorted boat conformation. NH₄[B₅O₆(OH)₄] · 2 H₂O ( 4 ): Space group Aba2, Z = 4, lattice dimensions at 273 K: a = 1131.3(1), b = 1103.0(1), c = 923.0(1) pm; R = 0.0564.     

Zur Struktur des Isopropylammonium-trichloro-Managanats (II) (CH3)2CHNH3MnCl3 · 2 H2O

On the Structure of Isopropylammonium Trichloro Manganate(II) (CH₃)₂CHNH₃MnCl₃ · 2 H₂O The crystal structure of (i-C₃H₇NH₃)MnCl₃ · 2 H₂O has been determined by X-ray diffraction and the parameters refined by leastsquares calculations. (i-C₃H₇NH₃)MnCl₃ · 2 H₂O is monoclinic, space group P2_1/c with a = 1410(3), b = 584(1) and c = 1299(2) pm, β = 110.5(1)°. There are four formula units per unit cell. The manganese is octahedrally coordinated by four chlorine atoms and two water molecules in “trans” position. The structure contains discrete dioctahedra Mn₂Cl₆(H₂O)₄^2?.     

A Novel Adipate Bridged Supramolecular Layer: Crystal Structure of the Cobalt(II) Complex [(μ‐C6H8O4)4/2Co(μ‐H2O)2Co(H2O)4] · 4 H2O

The pale‐rose compound [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] · 4 H₂O was prepared from adipic acid and CoCO₃ in aqueous solution. The crystal structure (monoclinic, P2₁/n (no. 14), a = 8.061(1), b = 15.160(2), c = 9.708(2) Å, β = 90.939(7)°, Z = 2, R = 0.0405, wR² = 0.0971) consists of adipate bridged supramolecular [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] layers and hydrogen bonded H₂O molecules. The cobalt atoms Co1 and Co2 are distorted octahedrally coordinated by the O atoms of two bridging trans‐H₂O molecules and four bidentate adipate anions (Co1) and by the O atoms of two bridging trans‐H₂O molecules and four monodentate H₂O molecules (Co2), respectively. Equatorial bonds: d(Co1–O) = 2.048 Å (2 × ), 2.060 Å (2 × ); d(Co2–O) = 2.057 Å (2 × ), 2.072 Å (2 × ). Axial bonds: d(Co1–O) = 2.235 Å (2 × ); d(Co2–O) = 2.156 Å (2 × ).     

Synthese von Kupfer- und Silberkomplexen mit fünfzähnigen N,S- und sechszähnigen N,O-Chelatliganden – Charakterisierung und Kristallstrukturen von {Cu2[C6H4(SO2)NC(O)]2(C5H5N)4}, {Cu2[C5H3N(CHNC6H4SCH3)2]2}(PF6)2 und {Ag[C5H3N(CHNC6H4SCH3)2]}PO2F2

Synthesis of Copper and Silver Complexes with Pentadentate N,S and Hexadentate N,O Chelate Ligands – Characterization and Crystal Structures of {Cu₂[C₆H₄(SO₂)NC(O)]₂(C₅H₅N)₄}, {Cu₂[C₅H₃N(CHNC₆H₄SCH₃)₂]₂}(PF₆)₂, and {Ag[C₅H₃N(CHNC₆H₄SCH₃)₂]}PO₂F₂ In the course of the reaction of copper(II)-acetate monohydrate with 2,2′-bisbenzo[d][1,3]thiazolidyl in methanol the organic component is transformed to N,N′-bis-(2-thiophenyl)ethanediimine and subsequently oxidized to the N,N′-bis-(2-benzenesulfonyl)ethanediaciddiamide H₄BBSED, which coordinates in its deprotonated form two Cu²⁺ ions. Crystallisation from pyridine/n-hexane yields [Cu₂(BBSED)(py)₄] · MeOH. It forms triclinic crystals with the space group P1 and a = 995.5(2) pm, b = 1076.1(3) pm, c = 1120.7(2) pm, α = 104.17(1)°, β = 105.28(1)°, γ = 113.10(1)° and Z = 1. In the centrosymmetrical dinuclear complex the copper ions are coordinated in a square-pyramidal arrangement by three nitrogen and two oxygen atoms. The Jahn-Teller effect causes an elongation of the axial bond by approximately 30 pm. The reactions of the pentadentate ligand 2,6-Bis-[(2- methylthiophenyl)-2-azaethenyl]pyridine BMTEP with salts of copper(I), copper(II) and silver(I) yield the complexes [CU₂(BMTEP)₂](PF₆)₂, [Cu(BMTEP)]X₂ (X = BF, C1O) and [Ag(BMTEP)]X (X = PO₂F, ClO). [Cu₂(BMTEP)₂](PF₆)₂ crystallizes from acetone/diisopropyl- ether in form of monoclinic crystals with the space group C2/c, and a = 1833.2(3) pm, b = 2267.30(14) pm, c = 1323.5(2) pm, β= 118.286(5)°, and 2 = 4. In the dinuclear complex cation with the symmetry C₂ the copper ions are tetrahedrally coordinated by two bridging BMTEP ligands. The Cu? Cu distance of 278.3pm can be interpreted with weak Cu? Cu interactions which also manifest itself in a temperature independent paramagnetism of 0.45 B.M. The monomeric silver complex [Ag(BMTEP)]PO₂F₂ crystallizes from acetone/thf in the triclinic space group P1 with a = 768.7(3) pm, b = 1074.0(5) pm, c = 1356.8(5) pm, α = 99.52(2)°, β = 96.83(2)°, γ = 99.83(2)° and Z = 2. The central silver ion is coordinated by one sulfur and three nitrogen atoms of the ligand in a planar, semicircular arrangement. The bond lengths Ag? N = 240.4–261.7 and Ag? S = 257.2 pm are significantly elongated in comparison with single bonds.     

SYNTHESIS OF NOVEL BIDENTATE (Te,N) LIGANDS-2-ARYLTELLUROETHYLAMINES AND THEIR COMPLEXATION WITH MERCURY (II)

Abstract

Sodium aryltellurolate (ArTe^?Na⁺, where Ar = 4-MeOC₆H₄ or 4-EtOC₆H₄) reacts with 2- bromoethylamine resulting in the (Te, N) ligands 2-aryltelluroethylamine (ArTeCH₂CH₂NH₂, 1) which have been characterized by elemental analyses, molecular weight, IR, ¹H and ¹³C NMR spectra. With HgCI₂, they form HgC1₂·1 type of complexes. IR, ¹H and ¹³C NMR spectra of the complexes suggest that 1 ligates as a bidentate ligand with respect to Hg(II). Osmometric molecular weight measurements suggest that on heating the mercury complex HgCl₂·lb (Ar = 4-EtOC₆H₄) in solution, relatively less soluble species result. It seems to have two Hg atoms bridged by two (Te, N) ligands. The HgC₂·la (Ar = 4-MeOC₆H₄) has very low solubility in organic solvents and. therefore, seems to be dimerized or polymerized during the synthesis. Analysis of CH₂ rocking bands in IR spectra suggests that two CH₂ groups of the ligands are most probably in a gauche conformation in the mercury complexes.     

Syntheses,crystal structures and thermal behavior of three Mn(II) complexes with 4-acyl pyrazolone derivatives

Three new manganese complexes, [Mn(PPeAP-INH)(CH₃OH)₂]_n(CHCl₃) (1) [PPeAP-INH=N-(1-phenyl-3-phenylethyl-4-ethylene-5-pyrazolone isoniazid, INH = isoniazid], [Mn₂(PM4MbP-INH)₂(CH₃OH)₄](CH₃OH) (2·CH₃OH), [PM4MbP-INH=N-(1-phenyl-3-methyl-4-(p-methylbenzoylene)-5-pyrazolone) isoniazid)] and [Mn₂(PPePeP-INH)₂(CH₃OH)₄] (3) [PPePeP-INH=N-(1-phenyl-3-phenylethyl-4-phenylethylene-5-pyrazolone) isoniazid] have been prepared, aiming at the formation of extended coordination polymer with Mn(II) ions. Formation of the corresponding manganese-ligand complexes has been monitored and characterized by chemical and spectroscopic techniques. X-ray diffraction analyses of available single crystals revealed 1D polymeric patterns of supramolecular system. Among them, the dimers of 2 and 3, bridged by two methanol molecules, are extended by hydrogen bond of O–H···N to form the 1D chain. In these three new complexes which are all octahedral coordination environments, the N(5) atom of the pyridine heterocycles plays a very important role in building the bridged polymeric chain.     

Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.     

Synthesis of Ammonium‐ and 4‐Dimethylaminopyridinium Amidofluorophosphates and Crystal Structure of [DMAPH][PO2F(NH2)]

NH₄[PO₂F(NH₂)] has been prepared by the reaction of a betaine py·PO₂F with excess ammonia in acetonitrile solution, while the ammonolysis of DMAP·PO₂F with a stoichiometric amount of NH₃ yields [DMAPH][PO₂F(NH₂)]. The crystal structure of the latter was determined by single‐crystal X‐ray diffraction, which revealed that the anions [PO₂F(NH₂)]^— are linked to infinite chains by double N—H···O bridges. Additional strong N—H···O bridging bonds connect each anion with its [DMAPH]⁺ counterion. The formation of a new betaine NH₃·PO₂F in the solution of py·PO₂F in liquid ammonia was proved by ³¹P NMR spectroscopy and by identification of its hydrolysis products.