Polysulfonylamine. XL Darstellung von Silber(I)-disulfonylamid-Acetonitril-Komplexen. Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetraacetonitrilsilber(I)-bis(dimesylamido)argentat(I) und von (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilsilber(I)

Polysulfonyl Amines. XL. Preparation of Silver(I) Disulfonylamide Acetonitrile Complexes. Characterization of Tetraacetonitrilesilver(I) bis(dimesylamido)argentate(I) and (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilesilver(I) by X-Ray Diffractometry and Thermal Analysis The following silver(I) disulfonylamides were prepared for the first time or by improved procedures: AgN(SO₂CH₃)₂ ( 2a ); AgN(SO₂C₆H₄-4-X)₂ with X = F ( 2b ), Cl ( 2c ), Br ( 2d ), CH₃ ( 2e ); silver(I) 1,2-benzenedisulfonimide AgN(SO₂)₂C₆H₄ ( 2f ). With acetonitrile, the salts 2a to 2e form (1/2) complexes AgN(SO₂R)· 2 CH₃CN ( 4a to 4e ), whereas 2f gives the (1/1) complex AgN(SO₂)₂C₆H · CH₃CN ( 4f ). The crystallographic data (at - 95°C) for the title compounds 4a and 4f are: 4a , space group C2/c, a = 1 967.6(4), b = 562.2(1), c = 2 353.0(5) pm, β = 102.21(2)°, V = 2.5440 nm³, Z = 4, D_x = 1.891 Mg m^?3; 4f , space group P2₁/m, a = 741.5(3), b = 980.4(4), c = 756.6(3) pm, β = 99.28(2)°, V = 0.5428 nm³, Z = 2, D_x = 2.246 Mg m^?3. 4a forms an ionic crystal [Ag(NCCH₃)₄]^⊕[Ag{N(SO₂CH₃)₂}₂]^? with a tetrahedrally coordinated silver atom (lying on a twofold axis) in the cation (225.3/225.7 pm for the two independent Ag? N distances, N? Ag? N 106.2—114.5°) and a linear-dicoordinated silver atom in the centrosymmetric anion (Ag? N 213.9 pm, two intraionic secondary Ag…O contacts 303.4 pm). 4f consists of uncharged molecules [C₆H₄(SO₂)₂N¹AgN²CCH₃] with crystallographic mirror symmetry (Ag? N¹ 218.8, Ag? N² 216.1 pm, N¹? Ag? N² 174.3°), associated into strands by intermolecular secondary silver-oxygen contacts (Ag…O 273.8 pm, O…Ag…O 175.6, N? Ag…O 91.9/88.2°). The thermochemical behaviour of 4f was investigated using thermogravimetry, differential scanning calorimetry (DSC), time- and temperature-resolved X-ray diffractometry (TXRD), and solution calorimetry. The desolvation process occurs in the temperature range from 60 to 200°C and appears to be complex, although no crystalline intermediate could be detected. The desolvation enthalpy at 298 K was found to be + 26.8(4) kJ mol^?1. 4a is desolvated in two steps at - 15 to 60°C and 60 to 95°C (DSC), suggesting the formation of AgN(SO₂CH₃) · CH₃CN as an intermediate.     

Polysulfonylamine. LVII. Zwei Silber(I)-di(organosulfonyl)-amide mit einer Silber-η2-Aryl- beziehungsweise einer Silber-Silber-Wechselwirkung: Kristallstrukturen von Silberdi(benzolsulfonyl)-amid-Wasser (1/0,5) und von wasserfreiem Silberdi(4-toluolsulfonyl)-amid

Polysulfonyl Amines. LVII. Two Silver(I) Di(organosulfonyl)-amides with Silver-η²-Aryl or Silver-Silver Interactions: Crystal Structures of Silver Di(benzenesulfonyl)amide-Water (1/0.5) and of Anhydrous Silver Di(4-toluenesulfonyl)-amide Crystals of [(PhSO₂)₂NAg(μ-H₂O)AgN(SO₂Ph)₂]_n ( 5 ) and [(4-Me? C₆H₄SO₂)₂NAgAgN(SO₂C₆H₄-4-Me)₂]_n ( 6 ) were obtained from aqueous solutions. The crystallographic data are for 5 (at ?95°C): monoclinic, space group C2/c, a = 2 743.8(5), b = 600.49(12), c = 1 664.5(3) pm, β = 101.143(15)°, V = 2.6908 nm³, Z = 8, D_x = 2.040 Mg m^?3; for 6 (at ?130°C): monoclinic, space group P2₁/n, a = 1 099.8(5), b = 563.7(3), c = 2 487.7(13) pm, β = 99.68(4)°, V = 1.5203 nm³, Z = 4, D_x = 1.888 Mg m^?3. In both crystals, the silver atom has a fivefold coordination. The structure of 5 displays [(RSO₂)₂N? Ag(μ-H₂O)Ag′? N(SO₂R)₂] units with Ag? N 226.9 pm, Ag? O 236.7 pm and Ag? O? Ag′ 95.3°; the water oxygen lies on a crystallographic twofold axis. These units are extended to two fused six-membered rings by intramolecular dative bonds (S)O → Ag′ and S(O)′ → Ag (249.3 pm). One phenyl group from each (PhSO₂)₂N moiety is η²-coordinated with its p-C and one m-C atom to a silver atom of a neighbouring bicyclic unit related by a glide plane to form infinite parallel strands (p-C? Ag 252.2, m-C? Ag 263.9 pm). The strands are interconnected into parallel layers through hydrogen bonds between H₂O and sulfonyl oxygens [O …? O(S) 276.1 pm]. These layers consist of a hydrophilic inner region containing metal ions, N(SO₂)₂ fragments and water molecules, and hydrophobic surfaces formed by phenyl groups. The structure of 6 features centrosymmetric [(RSO₂)₂N? Ag? Ag′? N(SO₂R)₂] units with two intramolecular dative bonds (S)O → Ag′ and (S)O′ → Ag (Ag? Ag′ 295.4, Ag? N 226.0, Ag? O 229.4 pm). These bi-pentacyclic units are associated by translation parallel to y into infinite strands by two dative (S)O → Ag bonds per silver atom (Ag? O 243.2 and 253.3 pm).     

Polysulfonylamine. XLII. Ein Aquasilber(I)-Komplex mit einem Ag(m̈-H2O)2Ag-Strukturmotiv: Röntgenstrukturanalytische und thermoanalytische Charakterisierung von Aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silber(I)

Polysulfonyl Amines. XLII. An Aquasilver(I) Complex with an Ag(m?-H₂O)₂Ag Structural Unit: Characterization of Aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silver(I) by X-Ray Diffractometry and Thermal Analysis The title compound C₆H₄(SO₂)₂NAg · H₂O, where C₆H₄(SO₂)₂N^º is the anion of 1,2-benzenedisulfonimide, crystallizes in the monoclinic space group C2/m with (at ?95°C) a = 1 129,7(3), b = 1 196.1(3), c = 810.7(2) pm, β = 124.25(2)°, V = 0.9055 nm³, Z = 4, D_x = 2.524 Mg m^?3. The crystal packing consists of [Ag(m?-H₂O)₂Ag{m?-C₆H₄(SO₂)₂N}₂]_n bands with crystallographic mirror symmetry, associated into layers by H-bonds with O(W)—O(S) 289.7 pm. The Ag(m?-H₂O)₂Ag moiety forms a planar four-membered ring with Ag? O(W)? Ag 97.3°, O(W)? Ag? O(W) 82.7° and Ag°Ag 372.1 pm. In the Ag{C₆H₄(SO₂)₂N}₂Ag′ unit, the anions act as tridentate (N, 1-O, 3-O)-ligands: One is N-bonded to Ag and O,O-chelated to Ag′, the other N-bonded to Ag′ and O,O-chelated to Ag. The silver atoms are (O₄N)-pentacoordinate, with nitrogen in the apical position of a distorted square pyramid [Ag? N 223.6, Ag? O(W) 247.8, Ag? O(S) 259.4 pm]. The thermochemical behaviour of the hydrate was investigated by thermal analysis and calorimetry. Water is only released at temperatures above 220°C. The dehydration enthalpy at 298 K is + 13.9 kJ mol^?1.     

Polysulfonylamine. LXI [1]. Silber(I) in einer neuartigen N-Donor-Umgebung: Darstellung und Struktur von catena-Poly[(dimesylamido-N)(acetonitril)(μ-pyrazin)silber(I)]

Polysulfonyl Amines. LXI. Silver(I) in a Novel N-Donor Environment: Synthesis and Structure of catena-Poly[(dimesylamido-N)(acetonitrile)(μ-pyrazine)silver(I)] The complex [Ag{N(SO₂Me)₂}(μ-pz)(MeCN)]_∞ is precipitated upon adding pyrazine to an acetonitrile solution of AgN(SO₂Me)₂. Crystallographic data (at ?100°C); monoclinic, space group P2₁/c, a = 912.3(2), b = 1 396.5(3), c = 1 151.7(3) pm, β = 97.20(2)°, U = 1.4557 nm³, Z = 4. The structure consists of infinite zigzag chains in the z-direction. The chain backbone is composed of silver atoms linked by pyrazine ligands (N? Ag? N 99.4°, Ag? N 232.4 und 234.0 pm). The severely distorted tetrahedral environment of Ag is completed by an N-bonded dimesylamide anion (Ag? N 224.3 pm) and an acetonitrile molecule (Ag? N 240.9 pm). The N? Ag? N angles vary from 97.5 bis 125.7°.     

Polysulfonylamine. XXXVII. Darstellung von Quecksilberdimesylamiden. Kristall- und Molekülstrukturen von Hg[N(SO2CH3)2]2, Hg[{N(SO2CH3)2}2(DMSO)2] und Hg[{N(SO2CH3)2}2(HMPA)]

Polysulfonyl Amines. XXXVII. Preparation of Mercury Dimesylamides. Crystal and Molecular Structures of Hg[N(SO₂CH₃)₂]₂, Hg[{N(SO₂CH₃)₂}₂(DMSO)₂], and Hg[{N(SO₂CH₃)₂}₂(HMPA)] Hg[N(SO₂CH₃)₂]₂ ( 1 ) and Hg₂[N(SO₂CH₃)₂]₂ ( 2 a ) are formed as colourless, sparingly soluble precipitates when solutions of Hg(NO₃)₂ or Hg₂(NO₃)₂ in dilute nitric acid are added to an aqueous HN(SO₂CH₃)₂ solution. By a similar reaction, Hg₂[N(SO₂C₆H₄ ? Cl? 4)₂]₂ is obtained. 1 forms isolable complexes of composition Hg[N(SO₂CH₃)₂]₂ · 2 L with L = dimethyl sulfoxide (complex 3 a ), acetonitrile, dimethyl formamide, pyridine or 1,10-phenanthroline and a (1/1) complex Hg[N(SO₂CH₃)₂]₂ · HMPA ( 4 ) with hexamethyl phosphoramide. Attempted complexation of 2 a with some of these ligands induced formation of Hg⁰ and the corresponding Hg^II complexes. Crystallographic data (at -95°C) are for 1: space group 14₁/a, a = 990.7(2), c = 2897.7(8) pm, V = 2.844 nm³, Z = 8, D_x = 2.545Mgm^?3; for 4a: space group P1 , a = 767.8(2), b = 859.2(2), c = 925.2(2)pm α = 68.44(2), β = 86.68(2), γ = 76.24(2)°, V = 0.551nm³, Z = 1, D_x = 2.113 Mgm^?3; for 4: space group P2₁/c, a = 1041.3(3), b = 1545.4(3), c = 1542.5(3) pm, β = 100.30(2)°, V = 2.474nm³, Z = 4, D_x = 1.944Mgm³. The three compounds form molecular crystals. The molecular structures contain a linear or approximately linear, covalent NHgN moiety; the Hg? N distances and N? Hg? N angles are 206.7(4) pm and 176.3(2)° for 1, 207.2(2) pm and 180.0° for 3a, 205.7(4)/206.7(4) pm and 170.5(1)° for 4. In the complexes 3a and 4, the 0-ligands are bonded to the Hg atoms perpendicularly to the N? Hg? N axes, leading in 3a to a square-planar trans-(N₂O₂) coordination with Hg? 0 261.2(2) pm and N? Hg? O 92.3(1)/87.7(1)°, in 4 to a slightly distorted T-shaped (N₂O) geometry with Hg? 0 246.2(4)pm and N? Hg? 0 96.7(1)/92.0(1)°. In all three structures, the primary coordination is extended to a severely distorted (N₂O₄) hexacoordination by the appropriate number of secondary, inter- and/or intramolecular Hg…?0 inter-actions (0 atoms from sulfonyl groups, Hg…?O distances in the range 280—300pm). The intramolecular Hg…?O interactions give rise to nearly planar four-membered [HgNSO] rings. The molecule of 1 has a two-fold axis through the bisector of the N? Hg? N angle, the molecule of 3a an inversion center at the Hg atom. The molecule of 4 has no symmetry.     

Polysulfonylamine. XLVI Molekülkomplexe von Di(organosulfonyl)aminen mit Dimethylsulfoxid und Triphenylphosphinoxid. Röntgenstrukturanalyse von Di(4-fluorbenzolsulfonyl)amin-Dimethylsulfoxid(2/1)

Polysulfonyl Amines. XLVI. Molecular Adducts of Di(organosulfonyl)amines with Dimethyl Sulfoxide and Triphenylphosphine Oxide. X-Ray Structure Determination of Di(4-fluorobenzenesulfonyl)amine-Dimethyl Sulfoxide(2/1) From equimolar solutions of the respective components in CH₂Cl₂/petroleum ether, the following crystalline addition compounds were obtained: (X? C₆H₄SO₂)₂NH …? OS(CH₃)₂, where X = H, 4? CH₃, 4? Cl, 4? Br, 4? I, 4? NO₂ or 3? NO₂; [(4? F? C₆H₄SO₂)₂NH]₂ · (OS(CH)₃)₂ ( 8 ); (4? I? C₆H₄SO₂)₂NH · OP(C₆H₅)₃. A (2/1) complex of (4? F? C₆H₄SO₂)₂NH with OP(C₆H₅)₃ could not be isolated. The solid-state structure of the (2/1) compound 8 is compared with the known structure of the (1/1) complex (CH₃SO₂)₂NH · OS(CH₃)₂. The crystallographic data for 8 at ?95°C are: monoclinic, space group C2/c, a = 2 369.9(13), b = 1 006.8(4), c = 2 772.6(13) pm, β = 110.71(4)°, U = 6.187 nm³, Z = 8. Two N? H …? O hydrogen bonds with N …? O 275 and 280 pm connect the disulfonylamine molecules with the dimethyl sulfoxide molecule. The O atom of the latter has a trigonal-planar environment consisting of the S atom and the two hydrogen bond H atoms.     

Polysulfonylamine. LXIX. Neuartige Pniktogendisulfonylamide: Synthese von Bismutdimesylamiden und Kristallstrukturen des zwölfgliedrigen Cyclodimers [Ph2BiN(SO2Me)2]2 und des ionischen Komplexes [H(OAsPh3)2]⊕(MeSO2)2N⊖

Polysulfonyl Amines. LXIX. Novel Pnictogen Disulfonylamides: Synthesis of Bismuth Dimesylamides and Crystal Structures of the Twelve-Membered Cyclodimer [Ph₂BiN(SO₂Me)₂]₂ and of the Ionic Complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? The novel bismuth(III or V) disulfonylamides Ph₂BiN(SO₂Me)₂ ( 1 ), PhBi[N(SO₂Me)₂]₂ ( 2 ), PhBi[N(SO₂Me)₂]Br ( 3 ), Bi[N(SO₂Me)₂]₂Cl ( 4 ), Bi[N(SO₂Me)₂]Cl₂ · 12-crown-4 ( 5 ) and Ph₃Bi[N(SO₂Me)₂]Cl ( 6 ) were obtained by acidolysis of Ph₃Bi with HN(SO₂Me)₂ (→ 1 ), by metathesis of AgN(SO₂Me)₂ with Ph₂BiCl (→ 1 ) or PhBiBr₂ (→ 2, 3 ), by condensation of BiCl₃ with Me₃SiN(SO₂Me)₂ (→ 4 ; in presence of 12-crown-4: → 5 ), or by oxidative addition of ClN(SO₂Me)₂ to Ph₃Bi (→ 6 ). Independently of the molar ratio employed, triphenylarsane oxide and dimesylamine form the crystalline 2/1 complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? ( 7 ). The crystal packing of 7 (monoclinic, space group C2/c) consists of discrete cations displaying crystallographic C_i symmetry and a strong O …? H …? O hydrogen bond (H atom located on a centre of symmetry, O …? O′ 241.2 pm, As? O …? O′ 120°, As? O 168.3 pm), and chiral anions with crystallographic C₂ symmetry (N? S 157.3 pm, S? N? S 122,9°). In the solid state, the bismuth(III) compound 1 (triclinic, space group P1 ) is a cyclodimer with crystallographic C_i symmetry, in which two Ph₂Bi^⊕ cations are connected through two (α-O, ω-O)-donating dimesylamide ligands to form a roughly twelve-membered [BiOSNSO]₂ ring (Bi? O 239.7 and 246.6, O? S 148.0 and 145.4, S? N 157.7 and 159.2 pm, Bi? O? S 126.6 and 127.5°). The bismuth atom adopts a pseudo-trigonal-bipyramidal geometry (O? Bi? O 165.4, C? Bi? C 93.0, O? Bi? C 83.8 to 86.5°). The essentially similar conformations of the discrete anion in 7 and of the bidentate bridging ligand in 1 are discussed in detail.     

Silber(I)‐di(arensulfonyl)amide und ein Silber(I)‐(arensulfonyl)(alkansulfonyl)amid: Von Bändern zu lamellaren Schichten mit kurzen Zwischenschichtkontakten C–H…Hal–C oder C–Br…Br–C

Structures of Ionic Di(arenesulfonyl)amides. 2. Silver(I) Di(arenesulfonyl)amides and a Silver(I) (Arenesulfonyl)(alkanesulfonyl)amide: From Ribbons to Lamellar Layers Exhibiting Short C–H…Hal–C or C–Br…Br–C Interlayer Contacts Low‐temperature X‐ray crystal structures are reported for AgN(SO₂C₆H₄‐4‐X)₂ · H₂O, where X is Cl ( 4 ) or Br ( 5 ), and for AgN(SO₂Ph)(SO₂Me) ( 6 ). Compounds 4 and 5 and the previously described F analogue ( 3 ) are isotypic, though not strictly isostructural (monoclinic, space group P2₁/c, Z = 4, but egregiously large discrepancies of x and z coordinates for corresponding atoms). Throughout this triad, glide‐plane related formula units are linked along the z axis to form infinite ribbons [(ArSO₂)₂N–Ag(μ‐H₂O)]_∞, in which Ag extends its coordination number to five by accepting one Ag–O bond from each of the (ArSO₂)₂N^⊖ ligands in the adjacent units. By means of O–H…O(S) hydrogen bonds, the ribbons are associated into lamellar layers parallel to the xz plane. Owing to the folded conformation of the anions, the layers display an inner polar region of Ag atoms, H₂O molecules and N(SO₂)₂ groups, outer apolar regions of stacked pairs of aryl rings, and interlayer regions hosting the halogen atoms. Inspection of the latter areas provides sound evidence that the distinct juxtapositions of adjacent layers arise from specific interlamellar attractions and repulsions ( 3 : two C–H…F, all F…F beyond the van der Waals limit d_W; 4 : one C–H…Cl, close packing of Cl atoms at Cl…Cl ≈ d_W; 5 : one C–H…Br, one short Br…Br contact < d_W, all other Br…Br > d_W). Structure 6 (monoclinic, P2₁/n, Z = 4) consists of a lamellar coordination polymer, in which the cation accepts one Ag–N and three Ag–O bonds drawn from four different anions. On account of crystal symmetry, the extended ligand has its Ph and Me groups distributed on both sides of the sheet, the phenyl rings forming the apolar regions of the lamella, whereas the smaller methyl groups are integrated into the corrugated inorganic region by means of weak C–H…O hydrogen bonds.     

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.     

Polysulfonylamine. LXXII [1]. Triphenylcarbenium- und Triphenylphosphonium-di(fluorsulfonyl)amid: Zwei Kristallstrukturen mit geordneten (FSO2)2N⊖-Lagen

Polysulfonyl Amines. LXXII. Triphenylcarbenium and Triphenylphosphonium Di(fluorosulfonyl)amides: Two Crystal Structures with Ordered (FSO₂)₂N^? Sites Treatment of HN(SO₂F)₂ in CH₂Cl₂ with Ph₃P, Ph₃PO or collidine (=B) affords the compounds Ph₃PH^⊕[(FSO₂)₂N]^? ( 3 ), Ph₃PO · HN(SO₂F)₂, and BH^⊕[(FSO₂)₂N]^? ( 7 ). The carbenium salt Ph₃C^⊕[(FSO₂)₂N]^? ( 5 ), obtained by metathesis of Ph₃CBr with [(C₆H₆)AgN(SO₂F)₂] in CH₂Cl₂, crystallizes from chloroform/petroleum ether as a monosolvate Ph₃C^⊕[(FSO₂)₂N]^? · CHCl₃ ( 6 ). In presence of a sterically hindered base, viz. collidine, 5 is a suitable reagent for the tritylation of molecules containing weakly activated H atoms (e. g.: MeCN → Ph₃CCH₂CN, acetone → tritylacetone; co-product: 7 ). The crystal structures of the ionic solids 3 (monoclinic, space group P2₁/n) and 6 (monoclinic, P2₁/c) were determined by X-ray diffraction at ?130°C; the structure refinements were not impaired by the notorious tendency of the (FSO₂)₂N moiety towards crystallographic disorder. As in the known structure of the tetraphenylarsonium salt, the anion of 3 and 6 adopts a staggered conformation of approximately C₂ symmetry (averages of all values: S? N? S 121.4°, N? S 156.2, S? O 141.6, S? F 156.6 pm). The crystal packing of 6 displays a three-centre C? H(…?O)₂ hydrogen bond between the CHCl₃ molecule and two oxygen atoms of a single anion, resulting in a six-membered ring [R₁²(6) pattern; H …? O 234 and 262 pm]. The crystal of 3 contains one-dimensional arrays of alternating cations and anions connected by a three-centre P? H(…?O)₂ bond [C(6) pattern; H …? O 237 and 254 pm]. The Ph₃C^⊕ cation of 6 is propeller-shaped, with three coplanar central bonds (mean C? C 144.5 pm) and interplanar angles of 52.7, 56.4 and 60.1° between the phenyl groups.     

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).     

Zum Reaktionsverhalten der Tris(dialkylthiophosphinyl)phosphane – Die Kristallstruktur von [Ag{O[P(S)Me2]2}2] [AsF6]

Reactivity of Tris(dialkylthiophosphinyl)phosphines – Crystal Structure of [Ag{O[P(S)Me₂]₂}₂][AsF₆] In contrast to tris(dialkylphosphoryl)phosphines the reaction of tris(dimethylthiophosphinyl)phosphine with transition metal hexafluoroarsenates of the type [M(SO₂)_m [AsF₆]_n (M = Ag, m = 0, n = 1; M = Fe, Cd, m = n = 2) forms no molecular 2 : 1-complexes but polymeric products. The silver polymer is transformed into [Ag{O[P(S)Me₂]₂}₂][AsF₆], which is also formed by the reaction of Ag[AsF₆] with O[P(S)Me₂]₂. It crystallizes in the space group P1 with a = 862.5(2), b = 1 241.4(2), c = 1 254.0(3)pm, α = 80.34(1), β = 101.99(6), γ= 73.75(1)° (at 20°C) and Z = 2. The central silver atom is surrounded by four sulphur atoms in a slighly distorted tetrahedron. The average (Ag? S) and (P? S) bond lengthes are 259.4(2) pm and 194.9(2)pm, respectively.     

LiLa2F3(SO4)2 und LiEr2F3(SO4)2: Fluoridsulfate der Selten‐Erd‐Elemente mit Lithium

LiLa₂F₃(SO₄)₂ and LiEr₂F₃(SO₄)₂: Fluoride‐Sulfates of the Rare‐Earth Elements with Lithium The reaction of LiF with the anhydrous sulfates M₂(SO₄)₃ (M = La, Er) in sealed gold ampoules yields single crystals of the pseudo quaternary compounds LiLa₂F₃(SO₄)₂ and LiEr₂F₃(SO₄)₂. According to X‐ray single crystal investigations, LiLa₂F₃(SO₄)₂ crystallizes with the monoclinic (I2/a, Z = 4, a = 828.3(2), b = 694.7(1), c = 1420.9(3) pm, β = 95.30(2)°, R_all = 0.0214) and LiEr₂F₃(SO₄)₂ with the orthorhombic crystal system (Pbcn, a = 1479.1(2), b = 633.6(1), c = 813.7(1) pm, R_all = 0.0229). A common feature of both structures is a dimeric unit of metal atoms connected via three fluoride ions. This leads to relatively short metal‐metal distances (La³⁺–La³⁺: 389 pm, Er³⁺–Er³⁺: 355 pm). In LiLa₂F₃(SO₄)₂, Li⁺ is surrounded by four oxygen atoms of four sulfate groups and one fluoride ion in form of a trigonal bipyramid, in LiEr₂F₃(SO₄)₂ two further fluoride ligands are attached.     

Zur Kenntnis der Hydrate M(HSeO3)2 · 4H2O (M = Mg,Co, Ni,Zn). Röntgenstrukturanalytische,schwingungsspektroskopische und thermoanalytische Untersuchungen

On the Hydrates M(HSeO₃)₂ · 4H₂O (M = Mg, Co, Ni, Zn) – Crystal Structures, IR, Raman, and Thermoanalytical Investigations From aqueous solutions of M(HSeO₃)₂ single crystals of Mg(HSeO₃)₂ · 4H₂O and of the hitherto unknown compounds Co(HSeO₃)₂ · 4H₂O, Ni(HSeO₃)₂ · 4H₂O and Zn(HSeO₃)₂ · 4H₂O could be obtained. The crystal structures, X-ray powder, IR, Raman and thermoanalytical (DTA, TG, Raman heating) data are presented and discussed. The crystal data of the isotypic compounds are: monoclinic, space group C2/c, Z = 4, Mg: a = 1 464.6(2), b = 755.3(1), c = 1 099.9(1) pm, β = 126.59(1)°, V = 0.9769(1) nm³, Co: a = 1 462.5(2), b = 756.5(2), c = 1 102.2(2) pm, β = 126.53(1)°, V = 0.9798(2) nm³, Ni: a = 1 452.2(2), b = 751.0(1), c = 1 091.5(1) pm, β = 126.28(1)°, V = 0.9595(1) nm³, Zn: a = 1 468.3(2), b = 755.8(1), c = 1 103.1(1) pm, β = 126.79(1)°, V = 0.9804(2) nm³. The crystal structures consist of hexagonal packed [M(HSeO₃)₂ · 2H₂O]_n chains of [MO₄(H₂O)₂] octahedra linked by Se atoms. They contain trigonal pyramidal SeO₂OH^?ions with “free” hydroxyl groups and also “free” molecules of water of crystallization. The hydroxyl groups build strong H-bonds (O? H …? O distances: 265–268 pm). The IR spectra show AB doublett bands in the OH stretching mode region of the hydroxyl groups. The water molecules of crystallization are linked to planar (H₂O)₄ tetramers by H-bonds with unusually short O? H …? O bond distances of 271–273 pm. DTA and TG measurements indicate that thermal decomposition results in the direct formation of the respective diselenite MSe₂O₅. Raman heating measurements show under quasi static conditions the intermediate formation of the anhydrous hydrogen selenites.     

Darstellung und Kristallstrukturen von Ag[N(CN)2](PPh3)2, Cu[N(CN)2](PPh3)2 und Ag[N(CN)2](PPh3)3

Preparation and Crystal Structures of Ag[N(CN)₂](PPh₃)₂, Cu[N(CN)₂](PPh₃)₂, and Ag[N(CN)₂](PPh₃)₃ The coordination compounds Ag[N(CN)₂](PPh₃)₂ ( 1 ), Cu[N(CN)₂](PPh₃)₂ ( 2 ), and Ag[N(CN)₂](PPh₃)₃ ( 3 ) are obtained by the reaction of AgN(CN)₂ or CuN(CN)₂ with triphenylphosphane in CH₂Cl₂. X‐ray structure determinations were performed on single crystals of 1 , 2 , and 3 · C₆H₅Cl. The three compounds crystallize monoclinic in the space group P2₁/n with the following unit cell parameters. 1 : a = 1216.07(9), b = 1299.5(2), c = 2148.4(3) pm, β = 99.689(13)°, Z = 4; 2 : a = 1369.22(10), b = 1257.29(5), c = 1888.04(15) pm, β = 94.395(7)°, Z = 4; 3 · C₆H₅Cl: a = 1276.6(4), b = 1971.7(3), c = 2141.3(5) pm, β = 98.50(3)°, Z = 4. In all structures the metal atoms have a distorted tetrahedral coordination. The crystal structure of 3 · C₆H₅Cl shows monomeric molecular units with terminal coordinated dicyanamide. The crystal structure of 1 is built up by dinuclear units, which are bridged by dicyanamide ligands. However, the crystal structure of 2 corresponds to a onedimensional coordination polymer, bridged by dicyanamide anions.     

Clusteraufbau durch Photolyse von R3PAuN3. VIII. Synthese und Kristallstruktur von [(Ph3PAu)5Mo(CO)4]PF6 · CH2Cl2 und (Ph3PAu)3Co(CO)3

Cluster Synthesis by Photolysis of R₃PAuN₃. VIII. Synthesis and Crystal Structure of [(Ph₃PAu)₅Mo(CO)₄]PF₆ · CH₂Cl₂ and (Ph₃PAu)₃Co(CO)₃ Photolysis of a mixture of Ph₂PAuN₃ and Mo(CO)₆ in THF yields [(Ph₃PAu)₅Mo(CO)₄]⁺ (1), which can be crystallized from CH₂Cl₂/diisopropylether as orange 1 · PF₆ · CH₂Cl₂ with the space group P2₁/c and a = 1681.4(5), b = 2215.6(12), c = 2761.5(9) pm, β = 91.54(3)°, Z = 4. The Au₅Mo center of cluster 1 forms a capped trigonal bipyramid with the Mo atom in equatorial position and almost equal Mo? Au distances between 279.9(5) and 284.6(7) pm to all five Au atoms. The Au? Au distances range from 272.2(4) to 301.3(4) pm. The Mo(CO)₄ group causes three v(C0) at 1975, 1915 and 1890cm^?1. Reaction of Ph₃PAuCo(CO)₄ with Ph₃PAuPF₆ affords the known cluster cation [(Ph₃PAu)₄Co(CO)₃]⁺ in high yield. It can be degraded with C1^? to the neutral cluster (Ph₃PAu)₃Co(CO)₃ (2). 2 forms air stable, yellow crystals with the space group P2₁/n and a = 1359.4(4), b = 2041.0(5), c = 1853.2(6)pm, β = 91.47(1)°, Z = 4. The Au₃Co core of 2 has a tetrahedral structure with distances Co? Au between 250.4(1) and 254.0(2) pm and Au? Au between 279.5(1) and 285.1(1) pm. v(C0) are observed at 1963, 1905 and 1891 cm^?1. Reaction of 2 with [(Ph₃PAu)₄Co(CO)₃]⁺ yields the condensed cluster [(Ph₃PAu)₆AuCo₂(CO)₆]⁺.     

Clusteraufbau durch Photolyse von Azidokomplexen des Platins und Golds. Synthesen und Kristallstrukturen von [(Ph3PAu)6(AuCl)3Pt(CO)], [(dppe)PtCo2(CO)7] und [(Ph3PAu)4Pt(dppe)](PF6)2

Cluster Synthesis by Photolysis of Azido Complexes of Platinum and Gold. Syntheses and Crystal Structures of [(Ph₃PAu)₆(AuCl)₃Pt(CO)], [(dppe)PtCo₂(CO)₇] and [(Ph₃PAu)₄Pt(dppe)](PF₆)₂ Photolysis of a mixture of Ph₃PAuN₃, Ph₃PAuCl and (Ph₃P)₂Pt(N₃)₂ in THF yields after chromatographic separation with CH₂Cl₂/EtOH as eluens the cluster [(Ph₃PAu)₆(AuCl)₃Pt(CO)] ( 1 ). It crystallizes in the triclinic space group P1 with the lattice parameters a = 2 139.3(4), b = 2 457.1(4), c = 2 561.9(1) pm, α = 79.74(9)°, β = 80.06(6)°, γ = 66.05(5)°, Z = 4. The nine gold atoms form a fragment of an icosahedron with the platinum atom in its center. Upon photolysis of (dppe)Pt(N₃)₂ with Co₂(CO)₈ in THF one m?₂-CO ligand of the cobalt carbonyl is substituted by a (dppe)Pt group. The resulting cluster [(dppe)PtCo₂(CO)₇] ( 2 ) crystallizes monoclinically in the space group P2₁/n with a = 1 303.9(3), b = 1 768.1(8), c = 1 461.4(4) pm, β = 102.81(1)°, Z = 4. Photolysis of 2 with excess Ph₃PAuN₃ affords the clusters [(Ph₃PAu)₄Pt(dppe)]²⁺ ( 3 ), and [(Ph₃PAu)₆AuCo₂(CO)₆]⁺. 3 crystallizes with PF as counterions in the triclinic space group P1 with a = 1 369.1(4), b = 1 505.0(4), c = 2 773.0(8) pm, α = 84.74(1)°, β = 87.37(2)°, γ = 65.94(2)°, Z = 2. The Au₄Pt skeleton of 3 forms a trigonal bipyramid with the platinum atom in equatorial position.     

Kristall- und Molekülstruktur von fac-Trichloro-tris(dimethylsulfoxid)bismut(III) BiCl3(DMSO)3

Crystal and Molecular Structure of fac-Trichloro-tris(dimethyl sulfoxide)bismuth(III) BiCl₃(DMSO)₃ Crystals of the known, although structurally not characterized title compound were fortuitously obtained from a reaction mixture containing (CH₃)₃SiN(SO₂CH₃)₂, BiCl₃, DMSO, CH₂Cl₂ and CH₃NO₂. Crystallographic data (at ?130°C): triclinic, space group P1 1, a = 816.1(5), b = 885.1(6), c = 1 360.6(8) pm, α = 77.58(3), β = 77.39(3), γ = 64.42(3)°, U = 0.8569 nm³, Z = 2. The DMSO ligands are bound through oxygen to the Bi atom. Important bond distances and angles in the resulting fac-octahedral complex are as follows: Bi? Cl 258.9, 261.0, 263.0, Bi? O 242.6, 245.7, 246.1 pm; Cl? Bi? O (trans) 170.3, 170.6, 176.9, Cl? Bi? Cl 94.6, 94.7, 96.0, O? Bi? O 81.7, 85.4, 87.9, Cl? Bi? O (cis) in the range 87.2–92.6, Bi? O? S 123.4, 126.1, 129.6°.     

Synthese,Strukturen und Reaktivität von [(2,4,6-Ph3C6H2)Te(μ2-O)X]2 (X  Br und I)

Synthesis, Structures, and Reactivity of [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)X]₂ (X ? Br, I) [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with iodine affording the aryltellurenic halide (2,4,6-Ph₃C₆H₂)TeI, which is oxidized by oxygen to yield [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂. It crystallizes with two molecules of dichloromethane in the monoclinic space group P2₁/c with a unit cell of the dimensions a = 911.3(4); b = 1153.3(2); c = 2244.1(9) pm; β = 93.53(2)°, Z = 2). The analogues bromo compound [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)Br]₂ is obtained by the reaction of [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂ with NH₄Br. It crystallizes with two molecules of xylene in the monoclinic space group P2₁/n (a = 1067.5(5); b = 1018.4(4); c = 2486.5(8) pm; β = 101.71(2)°; Z = 2). Both compounds are built up by two (2,4,6-Ph₃C₆H₂)TeX units (X ? Br, I) which are linked by two oxgen bridges to form centrosymmetric molecules. The Te? O? Te angles are 102°. Distinct Te? O bond lengths have been found (191.4(2) and 208.6(2) pm in [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂ and 189.8(4)/208.4(5 pm in the bromo compound).     

Neutrale Thiolate und ein Iodidthiolat von Antimon(III). Die Kristallstrukturen von Sb(SC6H5)3, Sb(SC6H2Me3-2,4,6)3 und SbI(SC6H2Me3-2,4,6)2

Neutral Thiolates and a Iodothiolate of Antimony(III). Crystal Structures of Sb(SC₆H₅)₃, Sb(SC₆H₂Me₃-2,4,6)₃, and SbI(SC₆H₂Me₃-2,4,6)₂ The crystal structures of Sb(SC₆H₅)₃ ( 1 ), Sb(SC₆ · H₂Me₃-2,4,6)₃ ( 2 ), and the novel compound SbI(SC₆H₂Me₃-2,4,6)₂ ( 3 ) have been determined by X-ray crystallography. In addition to the expected trigonal pyramidal coordination of antimony intermolecular interactions are observed for 1 (Sb … O: 363.3 pm) and 3 (Sb … S: 2 × 369.4 pm) but not for 2 . The reasons for these differences are discussed.