Synthese und Eigenschaften von cis-Diacidophthalocyaninato(2–)thallaten(III); Kristallstruktur von Tetra(n-butyl)ammonium-cisdinitrito(O,O′)- und -cis-dichlorophthalocyaninato(2–)thallat(III)

Syntheses and Properties of cis -Diacidophthalocyaninato(2–)thallates(III); Crystal Structure of Tetra(n-butyl)ammonium cis -dinitrito(O,O ′)- and cis -dichlorophthalocyaninato(2–)thallate(III) Blue green cis-diacidophthalocyaninato(2–)thallate(III), ^cis[Tl(X)₂pc^2–]^– (X = Cl, ONO′, NCO) is prepared from iodophthalocyaninato(2–)thallium(III) and the corresponding tetra(n-butyl)ammonium salt, (ⁿBu₄N)X in dichloromethane, and isolated as (ⁿBu₄N)^cis[Tl(X)₂pc^2–]. (ⁿBu₄N)^cis[Tl(ONO′)₂pc^2–] ( 1 ) and (ⁿBu₄N)^cis[Tl(X)₂pc^2–] · 0,5 (C₂H₅)₂O ( 2 ) crystallize in the monoclinic space group P2₁/n with cell parameters for 1: a = 14.496(2) Å, b = 17.293(5) Å, c = 18.293(2) Å, β = 98.76(1)° resp. for 2 : a = 13.146(1) Å, b = 14.204(5) Å, c = 24.900(3) Å, β = 93.88(1)°; Z = 4. In 1 , the octa-coordinated Tl atom is surrounded by four isoindole-N atoms (N_iso) and four O atoms of the bidental nitrito(O,O′) ligands in a distorted antiprism. The Tl–N_iso distances vary between 2.257(3) and 2.312(3) Å, the Tl–O distances between 2.408(3) and 2.562(3) Å. In 2 , the hexa-coordinated Tl atom ligates four N_iso atoms and two Cl atoms in a typical cis-arrangement. The average Tl–N_iso distance is 2.276 Å, the average Tl–Cl distance is 2.550 Å. In 1 and 2 , the Tl atom is directed out of the centre of the (N_iso)₄ plane (Ct_N) towards the acido ligands (d(Tl–Ct_N) = 1.144(1) Å in 1 , 1.116(2) Å in 2 ), and the phthalocyaninato ligand is concavely distorted. The vertical displacements of the periphereal C atoms amounts up to 0.82 Å. The optical and vibrational spectra as well as the electrochemical properties are discussed.     

Hexamincyclotriphosphazenhemiammoniakat,P3N3(NH2)6 · 0,5 NH3, ein Produkt der Hochdruckammonolyse von weißem Phosphor

Hexaminecyclotriphosphazenehemiammoniate, P₃N₃(NH₂)₆ · 0.5 NH₃, a Product of High Pressure Ammonolysis of White Phosphorus White phosphorus gives at NH₃-pressures ≥5 kbar and temperatures above 250°C in a disproportionation reaction P₃N₃(NH₂)₆ · 0.5 NH₃; besides these products red phosphorus is formed. The yield on P₃N₃(NH₂)₆ · 0.5 NH₃ increases with T and is about 70–80% at 400°C as to the disproportionation reaction of the amount of white phosphorus. X-ray structure determination was successful on single crystals of P₃N₃(NH₂)₆ · 0.5 NH₃. Pbca, N = 8 a = 11.395(3) Å, b = 12.935(4) Å, c = 12.834(4) Å R = 0.035, R_w = 0.041 with w = 1, N (F_o²) ≥ 3σ(F_o²) = 1371, N(Var.) = 166. The molecules are connected by N? H? N-bridgebonds with 3.04 Å ≤ d(N …? N) ≤ 3,19 Å and d (N? H) = 0.87 Å. The compound is furthermore characterized by IR-data and its thermical behaviour.     

Crystal structures of new isostructural oxovanadium(V) complexes with hydrazone ligands

Two new isostructural methoxide-bridged dimeric oxovanadium(V) complexes [VO(L¹)(OMe)]₂ (1) and [VO(L²)(OMe)]₂ (2), where L¹ and L² are the deprotonated forms of 3-bromo-N′-[1-(2-hydroxyphenyl)×ethylidene]benzohydrazide (H₂L¹) and 3-chloro-N′-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide (H₂L²) respectively, are synthesized and characterized by elemental analyses, IR spectra, and single crystal X-ray determination. Both crystals crystallize in the triclinic space group P-1. For 1, a = 7.5237(15) Å, b = 10.846(3) Å, c = 11.195(3) Å, α = 84.143(3)°, β = 72.244(3)°, γ = 77.869(3)°, V = 849.9(4) ų, Z = 1, R ₁ = 0.0634, wR ₂ = 0.1373. For 2, a = 7.493(2) Å, b = 10.740(3) Å, c = 11.109(3) Å, α = 84.569(2)°, β = 71.783(2)°, γ = 79.822(2)°, V = 835.0(4) ų, Z = 1, R ₁ = 0.0511, wR ₂ = 0.1076. Each V atom in the complexes is octahedrally coordinated.     

Microwave spectrum,structure and dipole moment of trimethylamine-borane

The ground state rotational spectra often isotopic species of trimethylamineborane, (CH₃)₃N¹⁰BH₃, (CH₃)₃N¹¹BH₃, (CH₃)₃N¹⁰BD₃, (CH₃)₃N¹¹BD₃, (CH₃)₃N¹¹BD₂H, (CD₃)₃N¹⁰BH₃, (CD₃)₃N¹¹BH₃, (CD₃)₃N¹⁰BD₃, (CD₃)₃N¹¹BD₃ and (¹³CH₃)(¹²CH₃)₂N¹¹BH₃, have been measured and the effective moments of inertia obtained. The utilization of Kraitchman's equations leads to an r_s value of the B-H distance of 1.211±0.003 Å and a NBH angle of 105.32±0.16°. By a least squares fit of the rotational constants the following structural parameters were obtained: r(NC) = 1.495 Å, r(BN) = 1.609 Å, and ∠BNC = 110.9°. The value of the dipole moment was found to be 4.59±0.13 D. A lower limit to the barrier to internal rotation of the BH₃ group was determined to be 3.4 kcal/mole.     

Syntheses and structural determination of binuclear nine-coordinate (NH4)4[SmIII2(Httha)2]·16H2O and 2-D ladder-like binuclear nine-coordinate (NH4)4[SmIII2(dtpa)2]·10H2O

Two rare-earth metal coordination compounds, (NH₄)₄[Sm^III₂(Httha)₂]·16H₂O (1) (H₆ttha?=?triethylenetetramine-N,N,N′,N′′,N′′′,N′′′-hexaacetic acid) and (NH₄)₄[Sm^III₂(dtpa)₂]·10H₂O (2) (H₅dtpa?=?diethylenetriamine-N,N,N′,N′′,N′′-pentaacetic acid), have been synthesized through reflux and characterized by FT-IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction techniques. Sm^III of (NH₄)₄[Sm^III₂(Httha)₂]·16H₂O (1) is nine-coordinate, forming tricapped trigonal prismatic coordination with three amine nitrogens and six oxygens, in which four oxygens are from one ttha and two from the other ttha. (NH₄)₄[Sm^III₂(Httha)₂]·16H₂O (1) crystallizes in the monoclinic crystal system with P2(1)/c space group. The crystal data are: a?=?13.9340(13) Å, b?=?22.890(3) Å, c?=?20.708(2) (14) Å, β?=?99.521(2)°, and V?=?6513.7(13) ų. There are two –NH⁺– groups in the [Sm^III₂(Httha)₂]^4?. The polymeric (NH₄)₄[Sm^III₂(dtpa)₂]·10H₂O (2) also is nine-coordinate with tricapped trigonal prismatic conformation and crystallizes in the triclinic crystal system with P–1 space group. The cell dimensions are: a?=?9.8240(8) Å, b?=?10.0329(9) Å, c?=?13.0941(11) Å, β?=?77.1640(10)°, and V?=?1227.30(18) ų. In (NH₄)₄[Sm^III₂(dtpa)₂]·10H₂O, there are two types of ammonium cations, which connect [Sm^III₂(dtpa)₂]^4? and lattice water through hydrogen bonds, leading to a 2-D ladder-like layer structure.     

Syntheses,structural determination,and binding studies of nine-coordinate multinuclear (mnH)2[EuIII(egta)]2·6H2O and binuclear (mnH)4[EuIII2(dtpa)2]·6H2O

Two lanthanide complexes, (mnH)₂[Eu^III(egta)]₂·6H₂O (1) (H₄egta = ethyleneglycol-bis-(2aminoethylether)-N,N,N′,N′-tetraacetic acid) and (mnH)₄[Eu^III₂(dtpa)₂]·6H₂O (2) (H₅dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), have been synthesized and characterized by FT-IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction. X-ray diffraction reveals that 1 is multinuclear nine-coordinate and crystallizes in the monoclinic crystal system with space group C2/c. The obtained cell dimensions are a = 38.513(3)?Å, b = 13.5877(8)?Å, c = 8.7051(5)?Å, β = 99.6780(10)°, and 4490.6(5)?ų. Each methylamine (mnH⁺) cation in 1, through hydrogen bonds, connects three adjacent [Eu^III(egta)]^? anions. The [Eu^III(egta)]^? anions connect one another forming a 1-D multinuclear zigzag chain structure along the c-axis. Complex 2 is nine-coordinate binuclear structure with tricapped trigonal prismatic conformation and crystallizing in the monoclinic crystal system, but with space group P2₁/n. The obtained cell dimensions are a = 9.9132(8)?Å, b = 24.1027(18)?Å, c = 10.7120(10)?Å, β = 109.1220(10)°, and 2418.2(3)?ų. For 2, there are two kinds of methylamine cations (mnH⁺) connecting [Eu^III₂(dtpa)₂]^4? complex anions and lattice waters through hydrogen bonds, leading to formation of a 2-D ladder-like layer structure.     

Hydrothermal Synthesis,Crystal Structures and Characterization of Two Hydrogen Phosphates Templated by 4-Amino-2,2,6,6-tetramethylpiperidine

Abstract

Chemical preparations, crystal structures, thermal analyses, and IR spectroscopic studies are given for two new hydrogen phosphates templated by 4-amino-2,2,6,6-tetramethylpiperidine: (C₉H₂₂N₂)₂·(H₂PO₄)·(HPO₄)·(F)·H₂O (I) and (C₉H₂₂N₂)·(H₂PO₄)₂(II). The structures are determined by single crystal X-ray diffraction. Both compounds crystallize in the P2₁/c (N°14) monoclinic space group with the unit cell parameters: a = 14.856 (1) Å, b = 14.092 (2) Å, c = 14.7166 (9) Å, β = 118.434 (7)°, V = 2709.2 (4) Å ³, and Z = 4 for (I) and a = 9.803 (2) Å, c = 0.466 (2) Å, c = 15.640 (8) Å, β = 94.990 (4), V = 1598.68 (7) ų, and Z = 4 for (II).

The structure of I, refined to R = 0.042 and R_w = 0.067 for 6009 reflections (I ≥ 2σ (I)), exhibits infinite inorganic chains _∞((H₂PO₄)·(HPO₄)·(F)·H₂O)^4? linked together through weak hydrogen bonds to form layers onto which the diprotonated [C₉H₂₂N₂]^{2 +} amine molecules are anchored.

The structure of II, refined to R = 0.060 and R_w = 0.086 for 1435 reflections (I ≥ 2σ (I)), consists of _∞(H₂PO₄)^? (100) layers between which [C₉H₂₂N₂]²⁺ cations are inserted. A network of hydrogen bonds connects the different components. IR spectra of I and II show the characteristic bands of amine groups and phosphate anions.     

A picosecond transient absorption study of the intramolecular excited state proton transfer in 3-hydroxyflavone: assignment of the observed bands

The time-resolved transient absorption and gain of 3-hydroxyflavone in ethanol ( T = 300 and 173 K) and MCH ( T = 300 and 198 K) has been investigated. Two absorption bands (A and B) and two gain bands (E₁ and E₂) have been observed. Band A (lying in the 5200 Å spectral region) appears during and just after the excitation step and is assigned to the normal excited form N_x Band B (lying in the 6050 Å spectral region) appears after band A and is assigned to the tautomer form T. A gain band E₂ (lying at λ=5400 Å) appears at the same time as the B band and is attributed to the T→T emission. A gain band E₁ (lying at λ = 5730 Å) appears earlier than the E₂ band. Its origin is discussed and two possible assignments are presented: vibronic progression of the emission spectrum of T or formation of an intermediate species on the proton transfer pathway from N_x to T.     

(12,17‐Diethoxy­carbonyl‐2,3,6,­7,11,­18‐hexa­methyl­corrphy­cenato‐­κ4N)iodoiron(III) chloro­form solvate

The title complex, (diethyl 3,4,8,15,19,20‐hexa­methyl‐21,22,23,24‐tetraazopenta­cyclo­[16.2.1.1^2,5.1^7,11.1^14,17]­tetracosa‐1(20),2(22),3,5,7,9,11,13(24),14,16,18‐undecaene‐9,14‐dicarb­oxyl­ate‐κ⁴N)­iodo­iron(III) chloro­form solvate, [Fe(C₃₂H₃₂­N₄O₄)I]·­CHCl₃, shows an almost planar arrangement of the corrphycene moiety with a slightly distorted trapezoid pyramidal core; the Fe^III atom is 0.416 (1) Å from the plane of the C₂₀N₄ system. The Fe—N distances are 2.049 (3), 2.044 (3), 2.079 (3) and 2.075 (3) Å. The solvated chloro­form forms a C—H?O hydrogen bond [C?O 3.107 (10) Å] to an adjacent carbonyl O atom. This is the first X‐ray structure analysis of a corrphycenatoiron(III) derivative.     

Molybdänhalogenidcluster mit zwei terminalen Alkoholatliganden: Synthese und Kristallstrukturen von (C18H36N2O6Na)2[Mo6Cl12(OCH3)2] und (C18H36N2O6Na)2[Mo6Cl12(OC15H11)2] · 2C4H6O3

Molybdenum(II) Halide Clusters with two Alcoholate Ligands: Syntheses and Crystal Structures of (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ . Reaction of Mo₆Cl₁₂ with two equivalents of sodium methoxide in the presence of 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] ( 1 ), which can be converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ ( 2 ) by metathesis with 9-Anthracenemethanole in propylene carbonate. As confirmed by X-ray single crystal structure determination ( 1 : C2/m, a=25.513(8) Å, b=13.001(3) Å, c=10.128(3) Å, β=100.204(12)°; : C2/c, a=15.580(5) Å, b=22.337(5) Å, c=27.143(8) Å, β=98.756(10)°) the compounds contain anionic cluster units [Mo₆ClCl(OR^a)₂]^2? with two alcoholate ligands in terminal trans positions ( 1 : d(Mo—Mo) 2.597(2) Å to 2.610(2) Å, d(Mo—Clⁱ) 2.471(3) Å to 2.493(4) Å, d(Mo—Cl^a) 2.417(8) Å and 2.427(8) Å, d(Mo—O) 2.006(13) Å; 2 : d(Mo—Mo) 2.599(3) Å to 2.628(3), d(Mo—Clⁱ) 2.468(8) Å to 2.506(7) Å, d(Mo—Cl^a) 2.444(8) Å and 2.445(7) Å, d(Mo—O) 2.012(19) Å).     

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.     

Cobalt(II) and cadmium(II) square grids supported with 4,4′‐bipyrazole and accommodating 3‐carboxyadamantane‐1‐carboxylate

In poly[[bis(μ‐4,4′‐bi‐1H‐pyrazole‐κ²N²:N^2′)bis(3‐carboxyadamantane‐1‐carboxylato‐κO¹)cobalt(II)] dihydrate], {[Co(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (I), the Co²⁺ cation lies on an inversion centre and the 4,4′‐bipyrazole (4,4′‐bpz) ligands are also situated across centres of inversion. In its non‐isomorphous cadmium analogue, {[Cd(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (II), the Cd²⁺ cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co—N = 2.156 (2) and 2.162 (2) Å; Cd—N = 2.298 (2) and 2.321 (2) Å] and two axial carboxylate O atoms [Co—O = 2.1547 (18) Å and Cd—O = 2.347 (2) Å]. In both structures, interligand hydrogen bonding [N...O = 2.682 (3)–2.819 (3) Å] is essential for stabilization of the MN₄O₂ environment with its unusually high (for bulky adamantanecarboxylates) number of coordinated N‐donor co‐ligands. The compounds adopt two‐dimensional coordination connectivities and exist as square‐grid [M(4,4′‐bpz)₂]_n networks accommodating monodentate carboxylate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565 (3) and 2.616 (3) Å] to the carboxylate groups in the next layer [O...O = 2.717 (3)–2.841 (3) Å], thereby extending the structures in the third dimension.     

Zinc(II) complexes with the tetradentate schiff base ligand N,N′-bis(1-pyridin-2-yl-ethylidene)propane-1,3-diamine: Synthesis and crystal structures

Two new zinc(II) complexes [ZnL(N₃)]·BF₄ (1) and [ZnBrL]·BF₄ (2), derived from the tetradentate Schiff base ligand N,N′-bis(1-pyridin-2-yl-ethylidene)propane-1,3-diamine (L), are prepared and characterized by physicochemical methods and single crystal X-ray crystallography. The crystal of (1) is triclinic: space group P-1, a = 8.593(1) Å, b = 8.752(1) Å, c = 13.393(2) Å, α = 97.153(1)°, β = 93.046(1)°, γ = 91.577(1)°, V = 997.4(2) ų, Z = 2. The crystal of (2) is triclinic: space group P-1, a = 8.351(1) Å, b = 8.956(1) Å, c = 13.139(2) Å, α = 92.716(1)°, β = 94.241(2)°, γ = 95.016(1)°, V = 974.8(2) ų, Z = 2. The geometries of the penta-coordinated zinc atoms in both complexes are intermediate between the square pyramid and the trigonal bipyramid having the Addison parameters of 0.39 and 0.47 respectively. The syntheses of the complexes show distinct preference for the anions in the order Br^? > N ₃ ^? > CH₃COO^?.     

Syntheses and structures of two new M6Li8(N3)a6 cluster-unit based compounds: Cs4Re6S8(N3)6·H2O and Na2Mo6Br8(N3)6·2H2O

The two new cluster compounds, Cs₄Re₆S₈(N₃)₆·H₂O (1) and Na₂Mo₆Br₈(N₃)₆·2H₂O (2), have been prepared via solution chemistry route, starting from the Cs₄Re₆S₈Br₆CsBr and Mo₆Br₁₂ precursors synthesized by solid state chemistry techniques, and structurally characterized (crystal data: Cs₄Re₆S₈(N₃)₆·H₂O (1): Orthorhombic, space group Pnam, a=10.0651(1) Å, b=15.8856(2) Å, c=20.1714(3) Å, V=3225.2(7) Å³, Z=4, d_calc=4.48 g cm⁻³, μ=27.43 mm⁻¹; Na₂Mo₆Br₈(N₃)₆·2H₂O (2): Orthorhombic, space group Ibam, a=11.5643(3) Å, b=14.3959(5) Å, c=17.0340(7) Å, V=2835.8(2) ų, Z=4, d_calc=3.63 g cm⁻³, μ=13.91 mm⁻¹). Their structures revealed that in both cases, the M₆Lⁱ₈ cluster core remains unchanged in the starting and final compounds whereas the bromine apical ligands (Br^a) are substituted by N₃ azide groups leading to M₆Lⁱ₈(N₃)^a₆ cluster unit. The new Cs₄Re₆S₈(N₃)₆·H₂O is the first example of a compound containing an octahedral rhenium cluster coordinated to azide groups.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

Synthese von Cadmiumnitrid Cd3N2 durch thermischen Abbau von Cadmiumazid Cd(N3)2 und Kristallstrukturbestimmung aus Röntgen‐Pulverbeugungsdaten

Synthesis of Cadmium Nitride Cd₃N₂ by Thermolysis of Cadmium Azide Cd(N₃)₂ and Crystal Structure Determination from X‐ray Powder Diffraction Data Cadmium nitride Cd₃N₂ was obtained by thermolysis of cadmium azide Cd(N₃)₂ at 2·10^?6 mbar and 210 °C. It was obtained as a black, crystalline powder which becomes brown in air due to formation of cadmium amide Cd(NH₂)₂. The crystal structure of Cd₃N₂ was determined from X‐ray powder diffraction data and refined by the Rietveld method ( , a = 10.829(9) Å, V = 1270(3) ų, Z = 16, R(F²) = 0.1196). Cd₃N₂ crystallizes in the anti‐bixbyite structure type and is isotypic to Ca₃N₂.     

Bis(bis(triphenylphosphin)iminium)-μ-nitrido-bis(azidophthalocyaninato(2–)ferrat(IV))-Triiodid Diethylether-Disolvat: Synthese,Eigenschaften und Kristallstruktur

Bis(bis(triphenylphosphine)iminium) μ-Nitrido-bis(azidophthalocyaninato(2–)ferrate(IV)) Triiodide Diethylether Di-Solvate: Synthesis, Properties, and Crystal Structure Bis(bis(triphenylphosphine)iminium) μ-nitrido-bis(azidophthalocyaninato(2–)ferrate(IV)) triiodide is prepared as a diethylether di-solvate by substitution of μ-nitrido-bis(pyridinephthalocyaninato(2–)iron(IV)) pentaiodide with bis(triphenylphosphine)iminium azide in acetone and precipitation by slow diffusion of diethylether. The doublesalt crystallizes monoclinically in the space group C12/c1 with cell parameters: a = 34.567(9) Å, b = 20.237(9) Å, c = 21.251(5) Å, β = 119.79(2)°; Z = 4. The Fe atoms are located almost in the centre (Ct) of the (N_iso)₄ planes (d(Fe–Ct) = 0.080(1) Å; N_iso: isoindoline N atom). The average Fe–N_iso distance is 1.947(5) Å, the Fe-(μ-N) distance 1.650(1) Å. The Fe-(μ-N)–Fe skeleton is linear (177.4(4)°). Both waving pc^2– ligands are in a staggered conformation (skew angle φ = 38.5(5)°). Fe coordinates linear azide (d(Fe–N_azide) = 2.152(7) Å) with an angle of 121.2(6)°. The isolated triiodide ion is almost linear (d(I–I) = 2.936(2) Å). The PNP cation obtains an hybrid conformation (∠(P–N–P) = 157.4(2)°). The asymmetrical Fe-(μ-N)–Fe stretching vibration is observed in the IR spectrum at 997 cm^–1, the symmetrical one is selectively enhanced in the resonance Raman (RR) spectrum at 478 cm^–1. The corresponding I–I stretching vibrations of the triiodide ion are present in the actual spectra at 134 (IR) and 115 cm^–1 (RR). An IR band at 334 cm^–1 is attributed to the asymmetrical Fe–N_azide stretching vibration.     

Bis(triphenylphosphin)iminium-bis(methoxo)phthalocyaninato(2–)ferrat(III) – Synthese und Kristallstruktur

Bis(triphenylphosphine)iminium Bis(methoxo)phthalocyaninato(2–)ferrate(III) – Synthesis and Crystal Structure Chlorophthalocyaninato(2–)ferrate(III) reacts with bis(triphenylphosphine)iminium hydroxide in methanol/acetone solution to yield blue crystals of bis(triphenylphosphine)iminium bis(methoxo)phthalocyaninato(2–)ferrate(III). The complex salt crystallizes as an acetone/methanol solvate (^bPNP)[Fe(OCH₃)₂pc^2–] · (CH₃)₂CO · 1.5 CH₃OH in the triclinic space group P 1 (no. 2) with the cell parameters a = 13.160(5) Å, b = 15.480(5) Å, c = 17.140(5) Å, α = 97.54(5)°, β = 91.79(5)°, γ = 95.44(5)°. The Fe atom is located in the centre of the pc^2– ligand coordinating four isoindole N atoms (N_iso) of the pc^2– ligand and two O atoms of the methoxo ligands in a mutual trans arrangement. The average Fe–O and Fe–N_iso distances are 1.887 and 1.943 Å, respectively. The cation adopts the bent conformation (< P–N–P = 140.4(2)°) with P–N distances of 1.579(3) and 1.575(3) Å.     

Darstellung und Eigenschaften von (Acido)(pyridin)phthalocyaninato(2–)ruthenaten(II); Kristallstruktur von Tetra(n-butyl)ammonium(cyano)(pyridin)phthalocyaninato(2–)ruthenat(II)

Syntheses and Properties of (Acido)(pyridine)phthalocyaninato(2–)ruthenates(II); Crystal Structure of Tetra(n-butyl)ammonium (Cyano)(pyridine)phthalocyaninato(2–)ruthenate(II) Bis(tetra(n-butyl)ammonium bis(acido)phthalocyaninato(2–)ruthenate(II) reacts in boiling pyridine to yield blue purple, diamagnetic tetra(n-butyl)ammonium (acido)(pyridine)phthalocyaninato(2–)ruthenate(II), (ⁿBu₄N)[Ru(X)(py)pc^2–] (X = CN, N₃, NCS, NCO, NO₂). (ⁿBu₄N)[Ru(CN)(py)pc^2–] crystallizes in the orthorhombic space group Pca2₁ (no. 29) with cell parameters a = 28.319(5) Å, b = 29.850(3) Å, c = 24.566(7) Å, Z = 16, with four crystallographically independent complex anions present in the unit cell. Each Ru atom is located outside the centre (Ct) of the corresponding (N_iso)₄ plane (N_iso: isoindoline N atom) and coordinates axially pyridine and cyanide in a mutual trans position. The largest vertical displacement of the Ru atom from the (N_iso)₄ plane towards cyanide (d(Ru–Ct)) is 0.020 Å. The Ru–N_iso distance varies from 1.947(2) to 1.992(2) Å. The average Ru–C and Ru–N_py distance is 2.00 Å and 2.19 Å, respectively. The pc^2– ligand ist slightly distorted towards the cyanide. The cyclic and differential pulse voltammograms of (ⁿBu₄N)[Ru(X)(py)pc^2–] exhibit the first quasi-reversible one electron process (in V) at 0.46 (X = CN), 0.34 (N₃), 0.40 (NCO), 0.47 (NO₂), 0.50 V (NCS) and the second, independent of X, at approximately 1.05 V. The first process is metal directed, the second ring directed. The electronic absorption spectra and the vibrational spectra of (ⁿBu₄N)[Ru(X)(py)pc^2–] are discussed.     

The structure of di-μ-chloro- bis - {chloro( N,N -diethylethane-1,2-diamine-κ 2)copper(II)}

Dichloro(N,N-diethyl-ethane-1,2-diamine)copper(II) has copper(II) ions in square pyramidal coordination. The two nitrogen atoms of the diamine {Cu–N_primary?=?1.979(3), Cu–N_tertiary?=?2.108(2)?Å} and two chloride ions are in the basal plane {Cu–Cl1?=?2.2680(9), Cu–Cl2?=?2.2989(8)?Å}. A centrosymmetrical dimer di-μ-chloro-bis{chloro(N,N-diethylethane-1,2-diamine-κ²)copper(II)}, C₆H1₆Cl₂CuN₂, is formed by axial coordination by Cl2, trans to the tertiary nitrogen, to a second copper(II) ion, with Cu?···?Cuⁱ?=?3.4855(9) and Cl2–Cuⁱ?=?2.7860(8)?Å. The dimer is also linked by H-bond N1–H?···?Cl1ⁱ.