Metall-Schwefelstickstoff-Verbindungen. 17. Die Verbindungen HgN2S · NH3 und 2Hg(NH3)2I2 · S4N4

Metal Sulphur Nitrogen Compounds. 17. Compounds HgN₂S · NH₃ and Hg(NH₃)₂I₂ · S₄N₄ The crystal and molecular structures of the known compounds HgN₂S · NH₃ and of the new inclusion compound 2Hg(NH₃)₂I₂ · S₄N₄ are reported. HgN₂S · NH₃ is orthorhombic, space group Pbca with a = 5.548, b = 10.158, c = 14.919 Å, Z = 8. In the dimeric molecules two Hg atoms are bridged to form eight-membered rings . In addition, each Hg is coordinated by an NH₃ molecule and by an N atom of an adjacent ring. This results in a two-dimensional network. 2Hg(NH₃)₂I₂ · S₄N₄ is tetragonal, space group P4₂/nmc, a = 8.948, c = 13.188 Å, Z = 2. It is an inclusion compound with S₄N₄ molecules in the holes of the lattice of the large Hg(NH₃)₂I₂ tetrahedra.     

Die Kristall- und MolekülStruktur von S4N4·2C7H8

Crystal and Molecular Structure, of S₄N₄ · 2C₇H₈ The structure of the title compound has been determined from threedimensional X-ray data. Crystals are monoclinic, with unit cell dimenions a = 16.532 Å, b = 8.563 Å, c = 10.880 Å, β = 103.2°, space group C? C2/c and Z = 4. Least squares refinement, by use of 1132 independent reflections measured on a diffractometer has reached 3.9%. In the S₄N₄·2C₇H₈ molecules the organic components are linked to two sulfur atoms of the S₄N₄, ring each.     

S4N4 und seine Derivate: β-FeCl3 · S4N4, ein Übergangsmetallkomplex mit dem S4N4-Ligand

S₄N₄ and its Derivatives: β-FeCl₃ · S₄N₄, a Transition Metal Complex with the S₄N₄ Ligand The reaction of FeCl₃ with S₄N₄ in CCl₄ yields among other products two modifications of FeCl₃ · S₄N₄. The β-modification crystallizes in the monoclinic space group P2₁/c with Z = 4 and the lattice parameters a = 6.803(3), b = 11.312(4), c = 13.784(5) Å and β 95.02(3)º. An X-ray analysis shows that the S₄N₄ ligand is bonded via one of its N atoms and completes the coordination tetrahedron around the Fe atom, like in the α-modification investigated earlier.     

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.     

Polyhydrogenchloride: Bildung und Kristallstruktur der tiefschmelzenden Addukte Me2S · 4HCl und Me2S · 5HCl

Poly(hydrogen chlorides): Formation and Crystal Structure of the Low-melting Adducts Me₂S · 4HCl and Me₂S · 5HCl The melting diagram of the system dimethylsulfide-hydrogen chloride has been determined using difference thermal analysis. It shows the existence of three adducts Me₂S · nHCl with n = 1, 4 and 5 as well as melting points of ?91, ?53 and ?80°C (decomposition), respectively. The two phases richest in HCl have been further characterized by crystal structure analysis. Me₂S · 4HCl is orthorhombic with space group Pnma and Z = 4 formula units per unit cell of dimensions a = 14.842, b = 9.747 and c = 6.652 Å at ?150°C. Me₂S · 5HCl is monoclinic with P2₁/n and Z = 4 as well as a = 7.292, b = 12.537, c = 12.479 Å and β = 92.73° at ?168°C. The R values obtained with 1737 and 3047 independent observed reflections are 0.039 and 0.045, respectively. Both structures are ionic, according to [Me₂SH][Cl(HCl)_n?1], and shaped by hydrogen bonding.     

Chalkogenohalogenogallate(III) und -indate(III): Eine neue Verbindungsklasse in der dritten Hauptgruppe. Synthese und Struktur von [Ph4P]2[In2SX6], [Et4N]3[In3E3Cl6] · MeCN und [Et4N]3[Ga3S3Cl6] · THF (X = Cl,Br; E = S,Se)

Chalcogenohalogenogallates(III) and -indates(III): A New Class of Compounds for Elements of the Third Main Group. Preparation and Structure of [Ph₄P]₂[In₂SX₆], [Et₄N]₃[In₃E₃Cl₆] · MeCN and [Et₄N]₃[Ga₃S₃Cl₆] · THF (X = Cl, Br; E = S, Se) [In₂SCl₆]^2?, [In₂SBr₆]^2?, [In₃S₃Cl₆]^3?, [In₃Se₃Cl₆]^3?, and [Ga₃S₃Cl₆]^3? were synthesised as the first known chalcogenohalogeno anions of main group 3 elements. [Ph₄P]₂[In₂SCl₆] ( 1 ) (P1 ; a = 10.876(4) Å, b = 12.711(6) Å, c = 19.634(7) Å, α = 107.21(3)°, β = 96.80(3)°, γ = 109.78(3)°; Z = 2) and [Ph₄P]₂[In₂SBr₆] ( 2 ) (C2/c; a = 48.290(9) Å, b = 11.974(4) Å, c = 17.188(5) Å, β = 93.57(3)°, Z = 8) were prepared by reaction of InX₃, (CH₃)₃SiSSi(CH₃)₃ and Ph₄PX (X = Cl, Br) in acetonitrile. The reaction of MCl₃ (M = Ga, In) with Et₄NSH/Et₄NSeH in acetonitrile gave [Et₄N]₃[In₃S₃Cl₆] · MeCN ( 3 ) (P2₁/c; a = 17.328(4) Å, b = 12.694(3) Å, c = 21.409(4) Å, β = 112.18(1)°, Z = 4), [Et₄N]₃[In₃Se₃Cl₆] · MeCN ( 4 ) (P2₁/c; a = 17.460(4) Å, b = 12.816(2) Å, c = 21.513(4) Å, β = 112.16(2)°, Z = 4), and [Et₄N]₃[Ga₃S₃Cl₆] · THF ( 5 ) (P2₁/n; a = 11.967(3) Å, b = 23.404(9) Å, c = 16.260(3) Å, β = 90.75(2)°, Z = 4). The [In₂SX₆]^2? anions (X = Cl, Br) in 1 and 2 consist of two InSX₃ tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternating metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.     

Synthese,Kristallstruktur und Eigenschaften der käfigartigen,sechsbasigen Säure P12S12N8(NH)6 · 14 H2O sowie ihrer Salze Li6[P12S12N14] · 26 H2O, (NH4)6[P12S12N14] · 10 H2O und K6[P12S12N14] · 8 H2O

Syntheses, Crystal Structure, and Properties of the Cage‐like, Hexaacidic P₁₂S₁₂N₈(NH)₆ · 14 H₂O and its Salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O, (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O, and K₆[P₁₂S₁₂N₁₄] · 8 H₂O The cage‐like acid P₁₂S₁₂N₈(NH)₆ · 14 H₂O was obtained by the reaction of KSCN with P₄S₁₀ via the formation of K₆[P₁₂S₁₂N₁₄] · 8 H₂O and subsequent ion exchange reactions in aqueous solution. Starting from the acid the salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O and (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O were synthesized. According to X‐ray single‐crystal structure analyses the compounds are built up by isosteric P–N cages [P₁₂S₁₂N^[3]₈N^[2]₆]^6–. Each of them is made up of twelve P₃N₃ rings, which exclusively exhibit the boat conformation. The cages have the idealized symmetry 2/m3; P₁₂S₁₂N₈(NH)₆ · 14 H₂O: P1, a = 1119.11(7), b = 1123.61(7), c = 1125.80(6) pm, α = 80.186(4), β = 60.391(4), γ = 60.605(4)°, Z = 1; Li₆[P₁₂S₁₂N₁₄] · 26 H₂O: Fm3, a = 1797.4(1) pm, Z = 4; (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O: P6₃, a = 1153.2(1), c = 2035.6(2) pm, Z = 2; K₆[P₁₂S₁₂N₁₄] · 8 H₂O: R3c, a = 1142.37(5), c = 6009.6(3) pm, Z = 6. In the crystal the cages of the acid are crosslinked via hydrate molecules by hydrogen bonds. The cations in the salts show a high‐mobility and are located between the cages.     

S4N4 und seine Derivate: [Cu(CH3CN)Cl2]2S2N2, ein Übergangsmetallkomplex mit dem S2N2-Ligand

S₄N₄ and its Derivatives: [Cu(CH₃CN)CL₂]₂S₂N₂, a Transition Metal Complex with the S₂N₂ Ligand S₄N₄ reacts with CuCl₂ · 2H₂O in acetonitrile to give among other products the polymer copper(II) complex [Cu(CH₃CN)Cl₂]₂S₂N₂, This complex crystallizes in the space group P2₁/c with a = 9.635(4), b = 7.270(4), c = 10.009(6) Å, β = 93.16(6)°, and Z = 2. An X-ray structure analysis (R = 0,065) shows the crystal to.contain parallel chains with copper atoms bridged by Cl and S₂N₂ bridges. The coordination of the Cu atom is square pyramidal. The S₂N₂ ring is planar. The SN bond distances are 1.633 and 1.641 Å.     

Hydrate schwacher und starker Basen. XI. Die Kristallstrukturen von NaOH · 3,5H2O und NaOH · 7 H2O. Eine Präzisierung

Hydrates of Weak and Strong Bases. XI. The Crystal Structures of NaOH · 3,5H₂O and NaOH · 7 H₂O. A Refinement The crystal structures of the hydrates NaOH · 3,5 H₂O (space group P2₁/c, Z = 8 formula units per unit cell; lattice parameters: a = 6.481, b = 12.460, c = 11.681 Å, β = 104.12° at ?100°C) and NaOH · 7 H₂O (P2₁/c, Z = 4; a = 7.344, b = 16.356, c = 6.897 Å, β = 92.91° at ?150°C) have been redetermined using MoKα diffractometer data. The obtained refinement of the structures, including the localization also of the H atoms for the first time, has led to new findings with respect to the H bonds. In particular, in both hydrates there is one such interaction of the rare type OH^? …? OH₂, from an OH^? ion to an H₂O molecule, i. e. with the OH^? ion as the proton donor.     

Metall-Schwefelstickstoff-Verbindungen. 20. Reaktionsprodukte von PdCl2 und Pd(CN)2 mit S7NH. Darstellung und Struktur der Komplexe [Ph6P2N][Pd(S3N)(S5)] und X[Pd(S3N)(CN)2] (X = [Me4N]+, [Ph4P]+)

Metal Sulfur Nitrogen Compounds. 20. Reaction Products of PdCl₂ and Pd(CN)₂ with S₇NH. Preparation and Structure of the Complexes [Ph₆P₂N][Pd(S₃N)(S₅)] and X[Pd(S₃N)(CN)₂] X = [Me₄N]⁺, [Ph₄P]⁺ With PdCl₂ and [Ph₆P₂N]OH S₇NH forms the complex salt [Ph₆P₂N][Pd(S₃N)(S₅)], which could be isolated in two modifications (α- and β-form). The α-form is triclinic, a = 9.347(4), b = 14.410(8), c = 15.440(11) Å, α = 76.27°(5), β = 77.06°(4), γ = 76.61α(4), Z = 2, space group P1 . The β-form is orthorhombic, a = 9.333(2), b = 17.659(4), c = 23.950(6) Å, Z = 4. The structure of the metal complex is the same in the two modifications. One S₃N^? and one S₅^2? are coordinate as chelate ligands to Pd. From S₇NH, Pd(CN)₂, and XOH X = [(CH₃)₄N]⁺ and [(C₆H₅)₄P]⁺ the salts X[Pd(S₃N)(CN)₂] were formed. The (CH₃)₄N-salt is isomorphous with the analogous Ni compound described earlier, the (C₆H₅)₄P-salt is triclinic, a = 9.372(4), b = 10.202(5), c = 13.638(6) Å, α = 86.36α(4), β = 85.66°(4), γ = 88.71°(4), Z = 2, space group P1 . One S₃N^? chelate ligand and two CN^? ions are bound to Pd. In all these complexes the coordination of Pd is nearly square planar.     

Die Kristall- und MolekülStruktur von (S4N3)2SbCI5

The structure of (S₄N₃)₂SbCI₅ has been determined by X-ray methods using least-squares′ refinement. The compound crystallises monoclinic; C–P2₁/c, a = 9.24 Å, b = 17.77 Å, c = 11.29 Å, β = 110.06°, Z = 4. The antimony atom has a fivefold coordination the geometry being derived from a deformed octahedron, the S₄N-rings retained their planar shape.     

Hydrate schwacher und starker Basen. VII. Zum System Caesiumhydroxid-Wasser: Die Kristallstrukturen von CsOH · 2H2O und CsOH · 3H2O

Hydrates of Weak and Strong Bases. VII. Concerning the System Cesium Hydroxide—Water: The Crystal Structures of CsOH · 2H₂O and CsOH · 3H₂O In the context of structural studies of hydrates of the alkali metal hydroxide the crystal structure of CsOH · 2H₂O and CsOH · 3H₂O have been determined for the first time. The diffractometer data, obtained at -150 · C,made it possible to locate and refine also all the H-atoms. The dihydrate was found to probably form only one phase, melting incongruently at 2,5 · C. It is orthorhombic with space group Pca2₁ and Z = 8 formula units per unit cell. The lattice constants are a = 13.238, b = 6.747 and c = 9.121 A. With 1870 independent observed reflection a final R value of 0.013 was obtained. The trihydrate, melting congruently et -5.5 ·C, is monoclinic with space group P2₁/n,Z = 4 and lattice constants a = 8.637, b = 5.984, c = 10.061 Å and ß = 96.57 ·. With 2098 independent observed reflection the final R is 0.026. In both hydrate structures there are no simple characteristic coordination polyhedra for the cations; in each case it is rather the hydrogen-bonded and fully ordered anionic water structure which shows up as the determining building principle. Both these water structures are altogether three-dimensional, but primarily contain layers. The anionic layers are formed by condensation of small and medium rings, namely four-, five- and seven-membered rings in CsOH · 2H₂O and four-, five- and six membered ones in CsOH · 3H₂O. They are linked together by one set each of extra H₂O molecules between the layers as well as by the Cs⁺ ions.     

Mehrkernige Kobaltkomplexe. IV. Darstellung und Struktur von [(papd)Co(O2)Co(papd)](S2O6)(NO3)2 · 4 H2O1)

Polynuclear Cobalt Complexes. IV. Preparation and Structure of [(papd)Co(O₂)Co(papd)](S₂O₆)(NO₃)₂ · 4 H₂O The binuclear peroxo complex [(papd)Co(O₂)Co(papd)](S₂O₆)(NO₃)₂ · 4 H₂O I crystallizes in the triclinic space group P1 . Lattice constants are a = 9.405(4), b = 9.270(4), c = 12.218(6)Å, α = 89.58(5), β = 99.08(6), γ = 114.79(5)° for Z = 1. The binuclear cation has a center of symmetry, so the Co? O? O? Co unit is planar. Three chelate rings have a common plane, the ligand configuration is δ.     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

Über Chalkogenolate. 111. Untersuchungen über Perthiocyansäure. 4. Kristall- und Molekülstruktur von Dimethylperthiocyanat

On Chalcogenolates. 111. Studies on Perthiocyanic Acid. 4. Crystal and Molecular Structure of Dimethyl Perthiocyanate (CH₃)₂C₂N₂S₃ crystallizes with Z = 4 in the monoclinic space group P2₁/c with cell dimensions a = 7.661(4) Å, b = 11.675(5) Å, c = 9.549(5) Å, β = 116.7(3)·. The crystal and molecular structure has been determined from single X-ray data at 20°C and refined to a conventional R of 0.062. The structure consists of isolated 3,5-bis(methylmercapto)-1,2,4-thiadiazole molecules. The 1,2,4-thiadiazole ring is plane and stabilized by mesomerism.     

Präparation und Charakterisierung von PbBr2·C4H10O3 (Diethylenglykol)

Structural Chemistry of PbBr₂·C₄H₁₀O₃ (Diethyleneglycol) Crystals of PbBr₂·C₄H₁₀O₃ have been synthesized and structurally characterized by single‐crystal X‐ray diffraction. PbBr₂·C₄H₁₀O₃ crystallizes monoclinic in space group P2₁/n (No. 14) with a = 9.370(1)Å, b = 10.045(1)Å, c = 21.090(1)Å, β = 98.98(1)° and Z = 8. The compound contains compact Pb—Br groups, which build colums parallel to [0 1 0] direction by Hydrogen Bonding.     

Selenostannate aus wäßriger Lösung: Darstellung und Struktur von Na4SnSe4 · 16 H2O

Selenostannates from Aqueous Solutions: Preparation and Structure of Na₄SnSe₄ · 16 H₂0 Pure selenostannates(IV) are prepared from aqueous solutions by reaction of SnSe₂, with alkali selenides, strictly excluding oxygen. Na₄SnSe₄ · 16 H₂O, being obtained from stoicheo-metric 1:2 quantities, is characterized by a complete X-ray structure analysis and by vibrational spectra. The compound is monoclinic (P2₁/m) with a = 8.673(3), b = 16.563(4), c = 8.647(2) Å, β = 92.10(2)°, Z = 2; it contains isolated tetrahedral SnSe₄^4? ions [Sn? Se 2.504(2)?2.527(2) Å, Se? Sn? Se 106.6(1)?111.1(1)°] which are in contact to the hydrated octahedral [Na(OH₂)₆]⁺ ions through Se…?H? O bridges within an extensive hydrogen bridge system. The stretching vibrations of the SnSe₄^4? ion are observed at 195 (n?₁) and 252 cm^?1 (n?₃). The stretching force constant is approximately 1.59 mdyn/Å.     

Zur Darstellung und Kristallstruktur von CrSO4 · 3 H2O

Preparation and Crystal Structure of CrSO₄ · 3 H₂O Evaporating a solution of Cr²⁺ in dilute sulphuric acid at 70°C light blue crystals of CrSO₄ · 3 H₂O were grown. Its x-ray powder diffraction pattern is quite similar to that of CuSO₄ · 3 H₂O. The crystal structure refinement of CrSO₄ · 3 H₂O (space group Ce, a = 5.7056(8) Å, b = 13.211(2) Å, c = 7.485(1) Å, β = 96.73(1)°, Z = 4) from single crystal data, using the parameters of the copper compound as starting values, results in a final R-value of R = 3.8%. The surrounding of the Cr²⁺ ion can be described as a strongly elongated octahedron. The basal plane of the CrO₆-octahedron consists of three hydrate oxygen atoms and one sulphate oxygen atom. The two more distant axial oxygen atoms also belong to sulphate groups. Thus they are forming chains of alterning CrO₆-octahedra and SO₄-tetrahedra along [110] and [1–10] linked via common corners. These chains are connected via sulphate groups and by bridging hydrogen bonds to a 3-dimensional network.     

Die Kristallstruktur des SrHg(SCN)4 · 3 H2O

Crystal Structure of SrHg(SCN)₄ · 3 H₂O SrHg(SCN)₄ · 3 H₂O is orthorhombic, space group Pcca, with a = 19.476(7), b = 8.150(1), c = 8.991(3) Å, V = 1427.1 ų, Z = 4, d_c = 2.67 g · cm^?3, μ(AgKα) = 77.95 cm^?1. The salt consists of nearly tetrahedral Hg(SCN)₄ groups, Sr has a tricapped trigonal prismatic coordination: four N and five O atoms. The thiocyanate groups form end-to-end bridges and connect the Hg and Sr coordination polyhedra.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.