Über Chalkogenolate. 168. Reaktion von N,N′-Diphenylformamidin mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von N,N′-Diphenyl-N-form-imidoyldithiocarbamaten

On Chalcogenolates. 168. Reaction of N,N′-Diphenyl Formamidine with Carbon Disulfide. 1. Synthesis and Properties of N,N′-Diphenyl N-Formimidoyl Dithiocarbamates N,N′-Diphenyl formamidine H? N(C₆H₅)? CH?NC₆H₅ reacts in different solvents with CS₂ in the presence of an alkali metal hydroxide to produce N,N′-diphenyl N-formimidoyl dithiocarbamate solvates. The properties of the prepared compounds (L = H₂O, acetonitrile, dioxane, dimethoxyethane, acetone, and mixed solvates) and of the Tl, Ba, and Pb salts are described.     

[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.     

Über Chalkogenolate. 152. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure. 2. Kristallstruktur von Tetra-n-butylammonium-N-thioformyldithiocarbamat

On Chalcogenolates. 152. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 2. Crystal Structure of Tetra-n-butylammonium N-Thioformyl Dithiocarbamate The title compound [N(ⁿC₄H₉)₄][S₂C? NH? CS? H] crystallizes with Z = 2 in the triclinic space group P1 with cell dimensions a = 9.694(2) Å, b = 11.478(3) Å, c = 12.551(6) Å, α = 63.03(3)°, β = 66.42(2)°, γ = 85.60(2)°. The crystal structure has been determined from single crystal X-ray data measured at 20°C and refined to a conventional R of 0.061 for 2249 independent reflections (R_w = 0.042). The structure is built up of dimeric aggregates consisting of 2[N(ⁿC₄H₉)₄]⁺ cations and 2[S₂C? NH? CS? H]^? anions. The two anions are linked together by ? CS? S…?H? N bridges. To make possible a space saving stacking of the dimeric aggregates in the crystal, one methyl group in terminal position of one n-butyl chain in the cation has gauche conformation.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): a finite cyclic 1:1 adduct with 2,2′‐dipyridyl­amine

In ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–2,2′‐dipyridyl­amine (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₀H₉N₃, (I), there is an intramolecular O—H?O hydrogen bond [H?O 2.03 Å, O?O 2.775 (2) Å and O—H?O 147°] in the ferrocenediol component, and the two neutral molecular components are linked by one O—H?N hydrogen bond [H?N 1.96 Å, O?N 2.755 (2) Å and O—H?N, 157°] and one N—H?O hydrogen bond [H?O 2.26 Å, N?O 3.112 (2) Å and N—H?O 164°] forming a cyclic R(8) motif. One of the pyridyl N atoms plays no part in the intermolecular hydrogen bonding, but participates in a short intramolecular C—H?N contact [H?N 2.31 Å, C?N 2.922 (2) Å and C—H?N 122°].     

N,N′,N′′,N′′′‐Tetraethylterephthalamidinium bis(tetrazolate)

The crystal structure of the title 2:1 salt of tetrazole and a substituted terephthal­amidine, C₁₆H₂₈N₄²⁺·2CHN₄^?, contains an infinite network of hydrogen bonds, with short N?N distances of 2.820 (2) and 2.8585 (19) Å between the tetrazolate anion and the amidinium cation. Involvement of the lateral N atoms of the tetrazole in the hydrogen bonding appears to be a typical binding pattern for the tetrazolate anion.     

Die Chelatbildung von N-Tris(2-aminoethyl)amin-N′,N′,N″,N″,N‴,N‴-hexaessigsäure (H6TTAHA) und N-(Pyrid-2-yl-methyl)ethylendiamin-N,N′,N′-triessigsäure (H3PEDTA) mit Gadolinium(III) – Synthesen,Komplexstabilität und NMR-Relaxivität

Chelate Formation of N-Tris(2-aminoethyl)amine-N′,N′,N″,N″,N?,N?-hexaacetic Acid (H₆TTAHA) and N-(Pyrid-2-yl-methyl)ethylenediamine-N,N′,N′-triacetic Acid (H₃PEDTA) with Gadolinium(III) – Syntheses, Stability Constants, and NMR-Relaxivities The chelate formation of N-tris(2-aminoethyl)amine-N′,N′,N″,N″,N?,N?-hexaacetic acid (H₆TTAHA) and N-(pyrid-2-yl-methyl)ethylenediamine-N,N′,N′-triacetic acid (H₃PEDTA) with gadolinium(III) has been studied potentiometrically in aqueous solution at 25°C and μ = 0.1 (KCl). [Gd(TTAHA)]^3?: 1gβ_M/ML = 19.0; {H[Gd(TTAHA)]}^2?: 1gK_H/MHL = 8.30; [Gd(PEDTA)]: 1gβ_M/ML = 15.56. Both 1 : 1 gadolinium(III) complexes were isolated as Na₂H[Gd(C₁₈H₂₄N₄O₁₂)] · 3.5 H₂O and [Gd(C₁₄H₁₆N₃O₆)] · 3 H₂O, respectively. Their ¹H-NMR relaxivities [1 · mmol^?1 · s^?1] ({H[Gd(TTAHA)]}^2?: 9.5; [Gd(PEDTA)]: 8.8) offer promising applications for ¹H-NMR imaging.     

Beiträge zum thermischen Verhalten von Sulfaten. II. Zur thermischen Dehydratisierung des ZnSO4 · 7 H2O und zum Hochtemperaturverhalten von wasserfreiem ZnSO4

Contributions to the Thermal Behaviour of Sulfates. II. On the Thermal Dehydration of ZnSO₄ · 7 H₂O and the Effect of High Temperature upon Anhydrous ZnSO₄ The dehydration of ZnSO₄ · 7 H₂O and effect of high temperature upon unhydrous ZnSO₄ was examined by means of continous high temperature Guinier photographs. On heating in air ZnSO₄ · 7 H₂O decomposes stepwise to ZnSO₄ · 6 H₂O, to an unknown hydrate, to the monohydrate and finally to N? ZnSO₄, which is the thermodynamically stable modification at S.T.P. At about 700°C a reversible transformation to H-ZnSO₄ can be observed which can start from N? ZnSO₄ or H-ZnSO₄, proceeds to the oxide sulfate Zn₃O(SO₄)₂ and finally to ZnO. ZnSO₄ · 6 H₂O crystallizes monoclinically in the hexahydrite structure with a_25°C = 9.981 Å, b_25°C = 7.250 Å, c_25°C = 24.280 Å, β_25°C = 98.45°, Z = 8, space group: C 2/c. Cubic H-ZnSO₄ is the first A²⁺B⁶⁺O₄ compound of H-Cristobalit structure; probable space group F 4 3 m with a_700°C = 7.18 Å, Z =4, N-Zn₃O(SO₄)₂ is monoclinic probable space group B 2 with a_25°c=13.987 Å, b_25°c=6.706 Å, c_25°c =7.379 Å β_25°c=90.69°, Z=4, Above 420°C N-Zn₃(SO₄)₂ becomes orthorhombic where at first of all H′-Zn₃O(SO₄)₂ which has a reversible transformation point to H-Zn₃O(SO₄)₂ at 655°C is formed. The probable space group of H-Zn₂O(SO₄)₂ is C 222₁ with a _850°C = 7.36 Å, b_350°C = 13.96 Å, c_850°C = 6.79 Å Z = 4, The solid solution N? Cu_1,5Zn_1,5O(SO₄)₂ is isotypic with N? Zn₃O(SO₄)₂ and has the lattice constants a_25°C = 14.03 Å, b_25°C = 6.62 Å, c_25°C = 7.33 Å, β_25°C = 90.58°, Transoformations into the non quenchable high temperature modifications H-ZnSO₄, H′-Zn₃O(SO₄)₂ and H-Zn₃O(SO₄)₂ are displacive. The thermal expansion of N-ZnSO₄ and H-ZnSO₄ and H-ZnSO₄ has been exa-mined.     

Kristall- und Molekülstruktur von Tetra-n-butylammonium-N-methyl-N-thioformyldithiocarbamat

Crystal and Molecular Structure of Tetra-n-butylammonium N-Methyl-N-Thioformyl Dithiocarbamate [N(n-C₄H₉)₄][S₂C? N(CH₃)? CS? H] crystallizes in the triclinic space group P1 (Z = 2) with cell dimensions (?45°C) a = 9.185(2) Å, b = 10.263(3) Å, c = 13.301(3) Å, α = 101.73(2)°, ß = 99.59(2)°, γ 100.57(2)°. The crystal structure was solved by means of direct methods and refined to a conventional reliability index R = 0.066 (R_ω = 0.070). 5945 independent intensities being measured.     

5‐Ethyl‐2′‐deoxy‐4′‐thiouridine (R)‐S‐oxide monohydrate

The pyrimidine ring of the title compound, C₁₁H₁₆N₂O₅S·H₂O, is planar to within 0.026 (1) Å and makes an angle of 77.73 (8)° with the mean plane of the thiosugar ring. In terms of standard nucleoside nomenclature, this ring has a C1′‐exo,C2′‐endo conformation. The O5′—C5′—C4′—C3′ torsion angle is ?167.4 (2)° and the glycosidic S4′—C1′—N1—C2 torsion angle is ?101.8 (2)° (anti).     

Die Kristallstruktur von Bis(N,N-diethyl-N′ -benzoylselenoureato)nickel(II)

The Crystal Structure of Bis(N,N-diethyl-N′ -benzoylselenoureato)nickel(II) Ni(C₁₂H₁₅N₂OSe)₂ crystallizes in the monoclinic space group P2₁/c. The cell parameters are a = 11.399(3), b = 16.016(4), c = 14.910(6) Å, β = 104.64(3)° and Z = 4. The structure was solved with Patterson and direct methods and was refined to a final R-value of 5.43%. Nickel is coordinated to two N,N-diethyl-N′ -benzoylselenourea molecules to form a bidentally coordinated chelate complex with cis arrangement of the donor atoms. Coordinaton around the nickel atom is planar while the chelate rings diverge from planarity. The ethyl groups of one diethylamino group are disordered. The Ni? Se bond lengths are 2.244(1) and 2.264(1) Å, the Ni? O bond lengths are 1.871(4) and 1.883(4) Å, respectively.     

Die Kristallstruktur von Tris(N,N-Diethyl-N′-benzoylselenoureato)indium(III)

The Crystal Structure of Tris(N,N-Diethyl-N′-benzoylselenoureato)indium(III) In(C₁₂H₁₅N₂OSe)₃ crystallizes in the monoclinic space group P2₁/c. The cell parameters are a = 11.792(2), b = 36.797(4), c = 18.574(2) Å, β = 92.15(2)° and Z = 4. The structure was solved with Patterson and direct methods and was refined to a final R-value of 3.41%. The asymmetric unit contains two complex molecules. The indium atoms are bidentally coordinated by three N,N-Diethyl-N′-benzoylselenourea molecules to form distorted octahedra with facial arrangement of the selenium and oxygen donor atoms. The chelate rings diverge strongly from planarity. The In? Se bond lengths vary from 2.643(1) to 2.657(1) Å, the In? O bond lengths from 2.179(4) to 2.203(4) Å, respectively.     

Über Chalkogenolate. 114. Kristallstruktur von Kalium-N-cyanodithiocarbimat-Monohydrat K2[S2CN ? CN] · H2O

On Chalcogenolates. 114. Crystal Structure of Potassium N-Cyanodithiocarbimate Monohydrate K₂[S₂C?N ? CN] · H₂O The crystal structure of the title compound has been determined and refined to R = 0.0287. K₂[S₂C?N ? CN] · H₂O crystallizes in the orthorhombic space group Pnma with a = 10.336(1) Å, b = 7.862(1) Å, c = 9.882(1) Å Z = 4. The structure is built up from layers of cations and anions. The potassium ion is coordinated by O, N, S atoms. The coordination polyhedron is a quadratic antiprism. ¹³C and ¹⁵N NMR data are reported and discussed.     

1:1 Complex of 4‐nitro­benzoic acid and 4‐nitro­pyridine N‐oxide

In the title co‐crystal, C₇H₅NO₄·C₅H₄N₂O₃, the two components are linked by an intermolecular hydrogen bond between the O—H and N—O groups [O?O 2.577 (3) Å]. The interplanar angle between the planes of the rings of the mol­ecules is 5.3 (2)°. The rings are stacked in the crystal with a mean interplanar distance of 3.279 (3) Å.     

Die Kristallstruktur von (N,N-Diethyl-N′-benzoylselenoureato)thallium(I)

The Crystal Structure of (N,N-Diethyl-N′-benzoylselenoureato)thallium(I) . Tl(C₁₂H₁₅N₂OSe) exists in a dimeric form and crystallizes in the triclinic space group P-1. The cell parameters are a = 6.501(6), b = 9.901(7), c = 12.233(9) Å, α = 91.59(2), β = 80.11(6), γ = 85.28(5)° and Z = 2. The structure was solved with Patterson and direct methods and was refined to a final R-value of 5.30%. Two complex molecules are connected by Tl? Se bonds to form a planar four membered ring with diagonally arranged Tl and Se atoms. The considerably bended chelate rings are nearly at right angle to the central four membered ring. The Tl? Se bond lengths are 3.105(3) and 3.118(3) Å, the Tl? O bond length is 2.532(9) Å.     

A dimeric heteroleptic five‐coordinate zinc(II) complex containing a non‐motionally restricted N,N′‐heterocyclic ligand

The title compound, bis(μ‐1,2‐benzene­thiol­ato)‐1:2κ³S,S′:S′;2:1κ³S,S′:S′‐bis­[(2,2′‐bi­pyridine‐κ²N,N′)­zinc(II)], [Zn₂(μ‐C₆H₄S₂)₂(C₁₀H₈N₂)₂], crystallizes with the dinuclear mol­ecule located on a center of symmetry. The coordination geometry about the Zn atom is a modestly distorted trigonal bipyramid, with the axial ligating atoms at an angle of 170.81 (4)° and the angles in the equatorial plane in the range 112.94 (4)–129.95 (4)°. Weak π‐stacking interactions between bi­pyridine ligands on adjacent mol­ecules [interplanar spacing = 3.315 (3) Å] and a possible weak intermolecular C—H⋯S hydrogen bond (H⋯S = 2.84 Å) are seen in the crystal.     

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.     

N,N′‐Di­methyl­piperazinium(2+) phos­phonoacetate: hydrogen‐bonded anion sheets containing cation‐templated R66(28) rings

In the title compound, C₆H₁₆N₂²⁺·2C₂H₄O₅P^?, the cations lie across centres of inversion; in the anions, two of the H‐atom sites have 0.50 occupancy. The anions are linked by short O—H?O hydrogen bonds [O?O 2.465 (3)–2.612 (3) Å and O—H?O 165–171°] into sheets of alternating R(12) and R(28) rings, both of which are centrosymmetric; the cations lie at the centres of the larger rings linked to the anion sheet by N—H?O hydrogen bonds [N?O 2.642 (2) Å and N—H?O 176°].     

Die Kristallstruktur von Bis(N,N-Diethyl-N′-benzoylselenoureato)cadmium(II)

The Crystal Structure of Bis(N,N-Diethyl-N′-benzoylselenoureato)cadmium(II) . Cd(C₁₂H₁₅N₂OSe)₂ exists in a dimeric oxygen bridged form and crystallized in the monoclinic space group P2₁/n. The cell parameters are a = 12.506(3), b = 11.563(2), c = 18.924(4) Å, β = 91.59(3)°, Z = 4. The structure was solved with Patterson and direct methods and was refined to a final R-value of 6.58%. Cadmium is coordinated by 3 oxygen and 2 selenium atoms and exhibits the unusual coordination number 5. The coordination polyhedron is a distorted trigonal bipyramid, to bipyramids are connected by a common edge. The Cd? Se bond lengths are 2.591(1) and 2.565(1) Å, the Cd? O bond lengths are 2.263(6), 2.272(5) und 2.438(5) Å.     

Rhenium(V) Complexes of N,N′-Ethylenebis(2-mercaptopropanamide). Synthesis,Characterization, and X-ray Crystal Structures

The preparation of benzoyl-protectcd N,N′-ethylenebis(2-mercaptopropanamide) (H₄emp) and its ligand-exchange reaction with ReO₂(en)₂Cl are described. Three diastereomers, [syn-ReO(meso-emp)]; [anti-ReO(meso-emp)]-, and a pair of cnantiomers, [ReO(rac-emp)]-, were formed due to syn and anti orientation of the two methyl groups of the ligand relative to the ReO core. The diastereomers were separated by reverse phase C₁₈ semipreparative HPLC and isolated as salts of [Ph₄As][ReO-(emp)]. The structures of [Ph₄ As][ReO(meso-emp)] were determined by single-crystal X-ray analyses. [Ph₄As][syn-ReO(mesocmp)]H₂O crystallizes in triclinic space group Pl with a = 10.326(3) Å, b = 13.672(4) A, c = 14.023(5) Å, α = 61.20(2)°, β =74.74(3)°, γ= 75.68(2)° V = 1656.6(8) ų, Z = 2, Dc = 1.676 gmL^?1, F(000) = 824 and R = 0.0329 for 5877 unique reflections. For (he complex [Ph₄As][anti-ReO(meso-emp)], the crystal data are: monoclinic, space group P2₁/n, a = 9.128(2) Å, b = 24.284(7) Å, c = 14.112(4) Å, β = 93.41(2)° V = 3122.5(15) À³, Z = 4, Dc = 1.740 gmL^?1, F(000) = 1608 and R = 0.0361 for 5487 unique reflections. In both structures the rhenium atom is penta-coordinated and in an approximately square pyramidal environment.     

Crystal Structure of the [(C5H4BMe2)2Fe]‐4,4′‐bipyridine Polymer from High Resolution X‐Ray Powder Diffraction

The crystal structure of [(C₅H₄BMe₂)₂Fe]‐4,4′‐bipyridine [ 2 · bipy]_n has been determined by the method of simulated annealing from high resolution X‐ray powder diffraction at room temperature. The compound is of interest, because it proves that highly ordered organometallic macromolecules can be formed in the solid state via the self‐assembly of N–B‐donor‐acceptor bonds. [ 2 · bipy]_n crystallizes in the triclinic space group, P 1, Z = 2, with unit cell parameters of a = 8.3366(2) Å, b = 11.4378(3) Å, c = 12.6740(5) Å, α = 112.065(2)°, β = 108.979(1)°, γ = 90.551(2)°, and V = 1047.06(6) ų. For the structure solution of [ 2 · bipy]_n 11 degrees of freedom (3 translational, 3 orientational, 5 torsion angles) were determined within several hours, demonstrating that the crystal packing and the molecular conformation of medium sized (< 50 non‐hydrogen atoms) coordination compounds can nowadays be solved routinely from high resolution powder diffraction data.