Über Zinn-haltige Heterocyclen. VIII. 2-Chlor-2-phenyl-1,3,6-trithia-2-stannocan Kristallstruktur und Schwingungsspektren

On Heterocyclic Systems Containing Tin. VIII. 2-Chloro-2-phenyl-1,3,6-trithia-2-stannocane, Crystal Structure and Vibrational Spectra The crystal structure of the title compound has been determined and refined until R = 0.040. The coordination around tin is trigonal bipyramidal (equatorial ligands 2 × S and Ph; axial ligands Sn? Cl 245.3(2) and 1,5-transannular Sn…?S 280.6(2) pm). The eight-membered ring has boat-chair conformation. The vibrational spectra of the title compound and of five analogues with donor O or S and substitution Cl, Ph are given and discussed. The three compounds with donor S have nearly identical aliphatic ring modes (3 × boat-chair conformation), whereas these modes exhibit a conformational change for the case of donor O in the series Cl₂, Ph₂, ClPh substituted tin. The stretching vibrations of the coordination polyhedron Cl_nSnS₂ are in the range 400 to 340 cm^?1. The strong 1,5-transannular Sn…?O or Sn…?S interactions in the cases of Cl substituted Sn are correlated with strong and broad transitions in the range 330 to 280 cm^?1; an extended distance of 5 pm is in correspondence with an approximate decrease of energy by 40 cm^?1.     

Ein neues Bleistrontiumferrat(III): Die Kristallstruktur der Phase Pb4Sr2Fe6O15

A New Lead Strontium Ferrate(III): The Crystal Structure of the Phase Pb₄Sr₂Fe₆O₁₅ At orthorhombic single crystals of Pb₄Sr₂Fe₆O₁₅ (a = 568.73(8), b = 392.03(4), c = 2107.5(3) pm; Z = 4/3, space group Pnma) a X-ray structure determination has been performed (R₁ = 0,036 for 488 ?observed”? resp. wR₂ = 0,073 for all 643 independent reflexions). It revealed a framework of polyhedra related to perovskite, in which chains of edgesharing pyramids [FeO₅] (average Fe1? O: 197 pm; Fe1? Fe1: 305.5 pm) are linked via apices with corner-sharing [FeO₆] octahedra (Fe2? O: 201 pm). 12–fold, strongly distorted cuboctahedrally coordinated ?perovskite positions”? show mixed occupancy by 2/3 Sr + 1/3 Pb (= Sr2; Sr2? O: 287 pm). More spacy channels, running parallel to the chains of pyramids along [010] of the structure, contain lead atoms only. The double occupancy of the corresponding cages results in short distances Pb1? Pb1 (355.9 pm) and Pb1? Fe2 (314.4 pm), as well as in a very asymmetric [PbO₆] coordination (Pb1? O: 253 pm), in the opposite hemisphere of which the lone electron pair s² is supposed to be located. Details are communicated and structural relations discussed.     

Deprotonierte Dithiocarbaminsäureester als Thiolat-S-Donor-Liganden. Strukturen von Ph(H)NC(S)SMe,Co(PhNC(S)SMe)3 und Cu6(PhNC(S)SMe)6

Deprotonated Dithiocarbamic Acid Esters as Thiolate S-Donor Ligands. Structures of Ph(H)NC(S)SMe, Co(PhNC(S)SMe)₃, and Cu₆(PhNC(S)SMe)₆ The reaction of N-phenyl-S-methyldithiocarbamate, PhN(H)C(?S)SMe, ( 1 ) with cobalt(II) and copper(II) salts yields the monomeric compound Co^III(PhNC(S)SMe)₃ ( 2 ) and the hexameric compound Cu₆^I(PhNC(S)SMe)₆ ( 3 ). These complexes contain the negatively charged imino-thiolate ligand PhN?C(? S)SMe, which has been formed by deprotonation of 1 . The crystal structures of 1 – 3 have been determined. 1 forms centrosymmetrical dimers through N? H …? S bridge bonds, the conformation in the solid state and in solution is Z,E′. Co^III shows in 2 a trigonal-antiprismatic coordination, with the ligands acting as N,S-chelates. 3 contains an octahedral Cu₆-core with Cu …? Cu-distances ranging from 276.3(5) to 305.7(4) pm. Each copper center is trigonally coordinated to one nitrogen and two sulfur atoms of three different ligands. Crystal data: 1 , triclinic, space group P1 , a = 590.5(6), b = 869.0(1), c = 968.5(9) pm, α = 67.29(8), β = 78.44(8), γ = 81.64(9)°, Z = 2, 1 775 reflections, R(R_w) = 0.0317(0.032). 2 , orthorhombic, space group Pbca, a = 978.0(2), b = 1 842.9(4), c = 3 059.7(6) pm, Z = 8, 1 129 reflections, R(R_w) = 0.0997(0.0886). 3 , monoclinic, space group P2₁/c, a = 1 363.1(3), b = 1 342.8(3), c = 1 671.9(3) pm, β = 103.48°, Z = 2, 1 374 reflections, R(R_w) = 0.0708(0.0617).     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XXXIX. Blei(II)-bis-tri-tert-butoxysilanthiolat

Contributions to the Chemistry of Silicon Sulfur Compounds. XXXIX. Lead(II)-bis-tritertbutoxysilanethiolate The title compound 1 is formed from (t-C₄H₉O)₃SiSH and PbO by an exothermic reaction. In benzene solution 1 is monomeric, whereas a solvated dimer the structure of which was determined crystallizes from glyme solutions. The F.I. mass spectrum only shows the mass of the monomeric unit. The ²⁹Si n.m.r. spectrum shows only one sharp signal at δ = ?68.33 ppm. The central four-membered (Pb₂S₂) ring of the dimer is puckered (butterfly; 51.2°). The folding takes place at the Pb atoms. The Pb atoms are threefold coordinated by S atoms (d_endo = 278.9 pm; d_exo = 258.6 pm) whereas the S atoms are bonded to two Pb atoms and one Si atom (208.8–214.3 pm).     

Zur Konstitution von ‚KPbO2’︁

On the Constitution of ‘KPbO₂’ Transparent, orangered single crystals of K₂Pb₂O₄ have been obtained by heating mixtures of K₂O₂ and PbO (K:Pb = 1:1) [Ag-cylinders, 560°C, 40 d, after cooling (15°C/h)]. The space group is P1 , a = 1295.94(9), b = 753.35(7), c = 697.12(8) pm, α = 118.00(1)°, β = 106.15(1)°, γ = 93.44(1)°, Z = 4, d_x = 6.573 und d_pyk = 6.54 g · cm³. The structure is characterized by rutilanalogous chains of edge-connected [PbO₆] octahedra along [001] according to [PbO_4/2O_2/1] = PbO₄. On both sides of such a chain there are respectively three O^2?, which belong to two octahedra, alternating capped with Pb²⁺ or not capped, corresponding to [PbO₄]Pb₂[PbO₄]□₂… = Pb₂O₄. Those capped chains are held together by K(1)…K(4), each of them with C.N. 6. The order of the chains corresponds to the motive of a closest packing. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Darstellung von Organylquecksilber(II)‐di(methansulfonyl)amiden und Kristallstruktur von Ph–Hg–N(SO2Me)2

Polysulfonylamines. CXXIV. Preparation of Organylmercury(II) Di(methanesulfonyl)amides and Crystal Structure of Ph–Hg–N(SO₂Me)₂ Four N,N‐disulfonylated organylmercury(II) amides R–Hg–N(SO₂Me)₂, where R is Me, ⁱPr, Me₃SiCH₂ or Ph, were obtained on treating the appropriate chlorides RHgCl with AgN(SO₂Me)₂, and characterized by ¹H and ¹³C NMR spectra. In the crystal structure of the phenyl compound (orthorhombic, space group Pbca, Z = 8, X‐ray diffraction at –95 °C), the molecule exhibits a covalent and significantly bent C–Hg–N grouping [bond angle 172.7(3)°; Hg–C 204.0(8), Hg–N 209.1(7) pm]. One sulfonyl oxygen atom forms a short intramolecular Hg…O contact [296.1(5) pm] and simultaneously catenates glide‐plane related molecules via a second Hg…O interaction 297.6(5) pm], thus conferring upon Hg^II the effective coordination number 4 and a geometrically irregular coordination polyhedron (bond angles from 173 to 54°).     

KCuMIVF7 (MIV = Zr4+, Hf 4+), ein neuer Strukturtyp

KCuM^IVF₇ (M^IV = Zr⁴⁺, Hf ⁴⁺) a New Type of Structure KCuZrF₆ (colourless, orthorhombic, Cmcm – D (No. 63); a = 829,6 pm, b = 1276,5 pm, c = 1011,6 pm, Z = 8) and KCuHfF₇ (colourless, orthorhombic, Cmcm – D (Nr. 63); a = 829,6 pm, b = 1276,5 pm, c = 1011,6 pm, Z = 8) could be prepared by heating up in a goldtube at 700 °C for 3 weeks a mixture of KF, CuF₂, and ZrF₄ or HfF₄, respectively. Both compounds crystallize isotypic in a previous unknown structure.     

Chloroantimonate(III): Die Kristallstruktur des 4,4′-Dipyridylium-pentachloroantimonats, (C10H8N2H2)SbCl5

Chloroantimonates(III): Crystal Structure of 4,4′-Dipyridylium Pentachloroantimonate, (C₁₀H₈N₂H₂)SbCl₅ (C₁₀H₈N₂H₂)SbCl₅ crystallizes in the triclinic space group P1 with a= 843.1(5), b = 958.6(8), c = 1098.0(10) pm, α = 112.45(6), β = 101.95(6), γ = 97.78(6)° and Z = 2. The structure is built up of 4,4 °-dipyridylium cations and pentachloroantimonate anions. The Sb atoms are distorted octahedrally coordinated. Mean distances are Sb? Cl = 242 pm (1×), Sb? Cl = 255 pm (2×), Sb ? Cl = 275 pm (2×) and Sb…?Cl.= 319 pm (1× ). The anions build up dimers.     

Über Zinn-haltige Heterocyclen. III. 2,2-Dimethyl-1,3,2-dithiastannolan,eine linear vernetzte Molekülstruktur mit trigonal-bipyramidal-koordiniertem Zinn

On Heterocyclic Systems Containing Tin. III. 2,2-Dimethyl-1,3,2-dithiastannolane, Trigonal-Bipyramidal Coordinated Tin by Linear Connected Molecules The crystal structure of the title compound has been determined and refined to a R of 0.028. The molecules are arranged in chains by intermolecular S…?Sn contacts (318 pm) resulting in trigonal bipyramidal 5-coordinated Sn (intramolecular S? Sn distances axial 247, equatorial 241 pm). The 5-membered cycle SnS₂C₂ contains a chiral envelope conformation with methylen top. Earlier spectroscopic discussions of the compound assumed tetrahedral 4-coordination at tin and C_s symmetry of the 5-membered ring. A revised interpretation is needed.     

Synthese und Kristallstruktur von Silber(II)‐Fluoriden AgMIVF6 (MIV = Sn,Ti, Pb,Pd, Pt,Rh)

Synthesis and Crystal Structure of Silver(II) Fluorides AgM^IVF₆ (M^IV = Sn, Ti, Pb, Pd, Pt, Rh) For the first time single crystals of AgSnF₆ (light blue, triclinic with a = 519.93(7) pm, b = 524.96(10) pm, c = 563.13(9) pm, α = 115.66(2)°, β = 89.28(2)°, γ = 118.77(2)°, spcgr. P1–C ; (No. 2), Z = 1) and AgPdF₆ (brown green, triclinic with a = 501.5(2) pm, b = 508.7(2) pm, c = 996.4(2) pm, α = 89.58(2)°, β = 103.10(2)°, γ = 120.88(2)°, spcgr. P1–C , (No. 2), Z = 2) have been synthesized and investigated. Other compounds of this type, like AgTiF₆ and AgPbF₆ (isotypic to AgSnF₆) or AgPtF₆ and AgRhF₆ (isotypic to AgPdF₆) have been synthesized in form of microcrystalline powders, their lattice parameters have been determined by Guinier data. All compounds are structure variants oft the LiSbF₆‐type and isotypic with CuMF₆ (M = Ti, Sn, Pb and Pd, Pt, respectively).     

Das erste gemischtvalente Oxoplumbat mit „isolierten”︁ Baugruppen: KNa7[PbIVO4][PbIIO3]

The First Mixed-valent Oxoplumbate with Isolated Anions. On KNa₇[Pb^IVO₄][Pb^IIO₃] For the first time KNa₇Pb₂O₇ has been prepared by reaction of K and Na Oxides with ?PbO₂”? rsp. PbO_red [e. g.: KO_0.48:NaO_0.36:?PbO₂”? = 1:7:2 (Ag-cylinders, reduced Ar-pressure, sealed in supremax-glas ampoules, 600°C, 14 d): redorange single crystals of plated shape]. The structure determination [3269 I_o(hkl), four-circle diffractometer PW 1100 (Fa. Philips), ω-scan, MoKα, R = 9.52%, R_w = 7.67%, absorption not considered] proves the space group P2₁/c with a = 1758.48(10), b = 596.76(3), c = 1066.46(8) pm, β = 90.682(8)°, Z = 4, d_x = 4.311, d_pyk = 4.28 g/cm³. The structure is characterized by isolated [Pb^IVO₄] (symmetry nearly T_d) and [Pb^IIO₃] groups (symmetry nearly C_3v), the latter connected by cations to double-layers. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Strukturen ladungsgestörter oder räumlich überfüllter Moleküle. 15. Tetracyanethen-Natrium-Dimethoxyethan

Structures of Charge-Perturbed or Sterically Overcrowded Molecules. 16. Tetracyanoethylene Sodium Dimethoxyethane The Single crystal structure of [(NC)₂C? C(CN)₂?·Na⊕(H₃CO? CH₂CH₂? OCH₃)]∞ reveals two formula units within the triclinic (P1 ) unit cell. The tetracyanoethylene radical anions are arranged along parallel double layers, which are shifted relative to each other, and in between which are interspersed the sodium counter cations and their dimethoxyethane ligands. The distances within the double layers amount to 300 pm and the ones between them to 385 pm. The six-fold coordinated Na⊕ centers are surrounded by four radical anions with contact distances Na…?N between 250 and 254 pm as well as by a twofold solvent ligand with Na…?O of 238 and 241 pm. Due to the electron transfer to the acceptor molecule, its (NC)₂C-halves twist by 8° and the bond lengths of the N?C? C subunits, bent by each 3°, are shortened up to 2 pm. The structural parameters are compared to those of the analogous potassium salt [TCNE^?K^⊕DME], of the dianion , of the sodium salts [(NC)₃C^?Na^⊕]∞ as well as [(NC)₂C? C(CHCH)₂? C(CN)₂^?Na^⊕]_∞ and, in addition, are discussed based on geometry-optimized MNDO calculations.     

Über gemischtvalente Oxoplumbate. Zur Kenntnis von Rb2Pb4O7 = Rb2PbPbO7

On Mixed-valent Oxoplumbates. On Rb₂Pb₄O₇ = Rb₂Pb Pb O₇ For the first time, Rb₂Pb₄O₇ has been prepared by annealing mixtures of Rb₂O₃ and PbO with Rb:Pb = 1:2 [Ag-cylinders, sealed under vacuum in Duran-glass ampoule, 450°C, 30 d (single crystals)]. The rubin red single crystals are of longish [001] shape. The structure determination [5162 symmetry independent hkl, four-circle-diffractometer CAD 4 (Fa. Enraf-Nonius), ω-2Θ—scan, AgKα, ψ-scan absorption correction, R = 7.54%, R_W = 7.71%] confirms the space group P1 with a = 1036.00(10), b = 733.72(8), c = 663.54(10) pm, α = 90.049(12)°, β = 99.236(12)°, γ = 101.641(12)°, Z = 2, d_rö = 7,58 g · cm^?3, d_pyk = 7,55 g · cm^?3. The structure is characterized by a layer-lattice. The coordination number is three for Pb²⁺, six for Pb⁴⁺. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Effective Ionic Radii, MEFIR, are calculated.     

Group 13 Ligand Supported Heavy‐Metal Complexes: First Structural Evidence for Gallium–Lead and Gallium–Mercury Bonds

Heavy‐metal complexes of lead and mercury stabilized by Group 13 ligands were derived from the oxidative addition of Ga(ddp) (ddp=HC(CMeNC₆H₃‐2,6‐iPr₂)₂, 2‐diisopropylphenylamino‐4‐diisopropyl phenylimino‐2‐pentene) with corresponding metal precursors. The reaction of Me₃PbCl and Ga(ddp) afforded compound [{(ddp)Ga(Cl)}PbMe₃] ( 1 ) composed of Ga? Pb^IV bonds. In addition, the monomeric plumbylene‐type compound [{(ddp)Ga(OSO₂CF₃)}₂Pb(thf)] ( 2 a ) with an unsupported Ga‐Pb^II‐Ga linkage was obtained by the reaction of [Pb(OSO₂CF₃)₃] with Ga(ddp) (2 equiv). Compound 2 a falls under the rare example of a discrete plumbylene‐type compound supported by a nonclassical ligand. Interesting structural changes were observed when [Pb(OSO₂CF₃)₃] ? 2 H₂O was treated with Ga(ddp) in a 1:2 ratio to yield [{(ddp)Ga(μ‐OSO₂CF₃)}₂(OH₂)Pb] ( 2 b ) at below ?10 °C. Compound 2 b consists of a bent Ga‐Pb‐Ga backbone with a bridging triflate group between the Ga? Pb bond and a weakly interacting water molecule at the gallium center. Similarly, the reaction of mercury thiolate Hg(SC₆F₅) with Ga(ddp) (2 equiv) produced the bimetallic homoleptic compounds anti‐[{(ddp)Ga(SC₆F₅)}₂Hg] ( 3 a ) and gauche‐[{(ddp)Ga(SC₆F₅)}₂Hg] ( 3 b ), respectively, with a linear Ga‐Hg‐Ga linkage. Compounds 1 – 3 were structurally characterized and these are the first examples of compounds comprised of Ga? Pb^II, Ga? Pb^IV, and Ga? Hg bonds.     

Metallkomplexe von Phenylenbistriazeniden: Synthese und Kristallstrukturen von [Cp(CO)2M]2(1,2-PhN3C6H4N3Ph) (M = Mo,W)

Metal Complexes of Phenylenebistriazenides: Synthesis and Crystal Structures of [Cp(CO)₂M]₂(1,2-PhN₃C₆H₄N₃Ph) (M = Mo, W) [Cp(CO)₂M]₂(1,2-PhN₃C₆H₄N₃Ph) [(M = Mo( 1 ), M = W( 2 )] is formed in the reaction of Cp(CO)₃MCl with PhN₃(H)C₆H₄N₃(H)Ph and C₂H₅ONa in a THF/ethanol mixture. 1 crystallizes from toluene as dark red crystals (triclinic, P1 , a = 1 499.3(9) pm, b = 1 734.0(7) pm, c = 1 852.8(8) pm, α = 66.84(3)°, β = 78.25(4)°, γ = 77.19(4)°). The unit cell contains four complexes with two independent complexes in the asymmetric unit, and eight solvent molecules. 2 crystallizes from THF as yellow crystals free from solvent molecules (triclinic, P1 , a = 979.0(5) pm, b = 1 152.8(5) pm, c = 1 475.8(5) pm, α = 98.26(4)°, β = 104.93(4)°, γ = 101.03(4)°, Z = 2). 1 and 2 are discrete molecular complexes with a 1,2-bis(phenyltriazenido)phenylligand, (PhN₃C₆H₄N₃Ph)^2?, chelating the metal atoms of two Cp(CO)₂M units with the N atoms N1 and N3 of both N₃ groups. Due to the sterical pretension of the Cp(CO)₂M units the phenylenebistriazenido ligand deviates strongly from planarity that is found in the metal complexes characterized so far.     

Synthese und Kristallstruktur von Cu4[PhN3C6H4N3(H)Ph]4(μ2-O)2, einem vierkernigen Kupfer(II)-Komplex mit 1-Phenyltriazenido-2-phenyltriazenobenzol als Ligand

Synthesis and Crystal Structure of Cu₄[PhN₃C₆H₄N₃(H)Ph]₄(μ₂-O)₂, a Tetranuclear Copper(II) Complex with 1-Phenyltriazenido-2-phenyltriazeno-benzene as Ligand Cu₄[PhN₃C₆H₄N₃(H)Ph]₄(μ-O)₂ ( 1 ) results from the reaction of an aqueous solution of [Cu(NH₃)₄]²⁺ with 1,2-bis(phenyltriazeno)benzene in ether. 1 crystallizes in the orthorhombic space group Pba2 with the lattice parameters a = 1661.5(5), b = 1914.7(7), c = 1269.2(5) pm; Z = 2. In the tetrameric complex with the symmetry C₂ the Cu²⁺ cations form a tetrahedron (Cu? Cu: 298.3(1)?337.1(1) pm). The μ₂-oxo ligands occupy the twofold axis and bridge two opposite edges of the Cu₄ tetrahedron (Cu? O: 190.0(3) and 192.5(4) pm). The 1-phenyltriazenido-2-phenyltriazeno benzene anions bridge two Cu²⁺ ions chelating one metal ion and coordinating monodentate the neighbouring one (Cu? N: 191.0(5)–204.1(4) pm).     

Between MOFs and molecules: organolead(IV) compounds with chain structures

Organolead compounds are of interest mainly as catalysts and organolead halides have proved to be very efficient materials for solar cells. Two organolead(IV) dimethylarsinates, namely catena‐poly[[triphenyllead(IV)]‐μ‐chlorido‐[triphenyllead(IV)]‐μ‐dimethylarsinato‐κ²O:O′], [Pb₂(C₆H₅)₆(C₂H₆AsO₂)Cl]_n or [(Ph₃Pb)₂Cl(O₂AsMe₂)], ( 1 ), and poly[chlorido(μ₃‐dimethylarsinato‐κ³O:O,O′:O′)diphenyllead(IV)], [Pb(C₆H₅)₂(C₂H₆AsO₂)Cl]_n or [(Ph₂ClPb)(O₂AsMe₂)], ( 2 ), together with the triphenyllead(IV) diphenylphosphinate catena‐poly[[triphenyllead(IV)]‐μ‐diphenylphosphinato‐κ²O:O′], [Pb(C₆H₅)₃(C₁₂H₁₀O₂P)]_n or [(Ph₃Pb)(O₂PPh₂)], ( 3 ), have been synthesized and characterized by single‐crystal X‐ray diffraction, IR spectroscopy and mass spectrometry. In ( 1 ), a chain structure was found with alternating chloride and Pb—O—As—O—Pb arsinate bridges between five‐coordinate Pb^IV atoms. In ( 2 ), bidentate and chelate‐like bonded dimethylarsinate ligands form double chains with heptacoordinated Pb^IV atoms. In ( 3 ), a pentacoordinated Pb^IV atom is connected by Pb—O—P—O—Pb phosphinate bridges to form a linear chain. Obviously, the steric demand of the phenyl ligands at Pb^IV reduces the possibility of interconnections via polydentate ligands to one dimension only. Thus, no metal–organic frameworks (MOF) are formed but instead various chain structures are observed.     

Zur Oxydation intermetallischer Phasen: Die Oxoplumbate(II) K6[Pb2O5] [1] und K4[PbO3] [2]

On the Oxidation of Intermetallic Phases: The Oxoplumbates(II) K₆[Pb₂O₅] [1] and K₄[PbO₃] [2] Very pale yellow crystals of K₆[Pb₂O₅] were obtained by heating a wellground mixture of LiPb und K₂O₂ (K₂O₂: LiPb = 2.5:1) in Ag-tubes (550°C; 40 d). The crystal structure, triclinic, space group P1 , a = 1 326.7(6); b = 758.8(4); c = 637.0(3) pm; α = 92.17(3)°; β = 94.41(3)°; γ = 112.85(4)°; Z = 2 was determined (four-circle diffractometer data, Mo? K, 3 270 I_o(hkl), R = 8.0%, R_w = 3.5%, parameters see text). The pale yellow crystals of K₄[PbO3] were received by heating KPb and K₂O₂ (K₂O₂: KPb = 3.3:2) in Ni-tubes (450°C; 17 d). The crystal structure (orthorhombic, space group Pbca with a = 658.2(1); b = 1 131.8(4); c = 1 872.2(6) pm; Z = 8) was refined (four-circle diffractometer data, Mo? K, 2 003 I_o(hkl), R = 4.9%, R_w = 2.8%). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), the Mean Fictive Ionic Radii (MEFIR) and the Charge Distribution (CHARDI) are being calculated for both oxides.     

Über Polystannane. III. 1,2-Dichlortetramethyldistannan,eine Sn?Sn-verknüpfte helicale Bandstruktur [(…︁SnMe2?Cl…︁SnMe2?Cl…︁)∞]2

On Polystannanes. III. 1,2-Dichloro-tetramethyl-distannane. Forming a Sn? Sn-connected Helical Double Chain Structure [(…?SnMe₂Cl…?SnMe₂? Cl…?)_∞]₂ The crystal structure of the title compound has been determined at ?160°C and refined to R = 0.071 (bond lengths Sn? Sn 277.0(2), Sn? Cl 244.2(3) and 244.8(3), Sn? C 214(2) pm). Intermolecular Sn…?Cl connection (324.0(3) and 329.2(3) pm) results in a double chain structure. ¹¹⁹Sn-NMR spectra in CH₂Cl₂ and acetone exhibit a movable temperature dependent coordination of acetone at the distannane (¹J(¹¹⁹Sn? ¹¹⁹Sn) 8000 to 9000 Hz; appr. 5000 Hz in CH₂Cl₂).     

Synthesis,Characterization and Crystal Structures of new Palladium(II) Complexes and the first Platinum(III) Complex Containing ATT (ATT = 6‐Aza‐2‐thiothymine)

Treatment of the ligand 6‐aza‐2‐thiothymine (ATT, HL, 1 ) with palladium chloride in methanol forms the ionic complex [(HL)₄Pd]Cl₂·8MeOH ( 2 ), while its reaction with palladium iodide in same solvent produces the neutral complex trans‐[(HL)₂PdI₂]·2MeOH ( 3 ) in high yields. The reaction of 1 with Na₂[PdCl₄] in the presence of sodium acetate in a molar ratio of 2:1:2 and with platinum(II) chloride in presence of sodium acetate led to the dimer tetranuclear complexes [(L₄Pd₂)NaCl]₂·8MeOH ( 4 ) and [L₄Pt₂Cl₂]·6MeOH·H₂O ( 5 ). The latter is the first Pt^III complex of the ligand. All complexes were characterized by elemental analyses and IR spectroscopy and the crystal structures of 2 , 3 , 4 and 5 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: triclinic space group , a = 1006.6(1), b = 1006.9(1), c = 1158.1(1) pm, α = 85.20(1)°, β = 83.84(1)°, γ = 88.91(1)°, Z = 1, R₁ = 0.0278; for 3 at ?80 °C: triclinic space group , a = 490.5(1), b = 977.2(2), c = 1116.8(2) pm, α = 90.26(1)°, β = 102.33(1)°, γ = 96.08(1)°, Z = 1, R₁ = 0.0394; for 4 at ?80 °C: orthorhombic space group Ccca, a = 1791.7(2), b = 1874.1(2), c = 2044.0(1) pm, Z = 4, R₁ = 0.0341 and for 5 at ?80 °C: monoclinic space group P2₁/c, a = 1464.3(1), b = 2003.7(1), c = 1368.5(1) pm, β = 95.66(1)°, Z = 4, R₁ = 0.0429.