Darstellung und Kristallstruktur der Addukte [DB-18C6] · CH3CN · CH3CSOH und [DC-18C6](CH3CSOH)2 sowie der salzartigen Verbindungen [Cs(B-15C5)2]CH3CSS und [Cs(DB-18C6)]2S5(DMF)21)

Synthesis and Crystal Structure of the Adducts [DB-18C6] · CH₃CN · CH₃CSOH and [DC-18C6](CH₃CSOH)₂ as well as of the Salt-like Compounds [Cs(B-15C5)₂]CH₃CSS and [Cs(DB-18C6)]₂S₅(DMF)₂¹) The reaction products of crown ethers, cesium, and sulfur in aprotic solvents like acetonitrile and dimethylformamide strongly depend on the reaction conditions. Using CH₃CN as a solvent, sometimes neutral host-guest adducts crystallize only, e.g., [dibenzo-18C6] · CH₃CN · CH₃CSOH (monoclinic, S. G. P2₁/c, Z = 4, a = 9.73(1) Å, b = 22.03(1) Å, c = 11.86(1) Å, β = 91.8(1)°) or [dicyclohexyl-18C6](CH₃CSOH)₂ (monoclinic, S. G. P2₁/n, Z = 2, a = 7.75(1) Å, b = 10.32(1) Å, c = 17.73(1) Å, β = 95.7(1)°). The monothioacetic acid, CH₃CSOH, must be regarded as the first product of the hydrolysis of CH₃CN. Furthermore, another product of this kind of hydrolysis, CH₃CSSH, is obtained too. Therefore, we also obtain the salt-like compound [Cs(benzo-15C5)₂]CH₃CSS (monoclinic, S. G. C2/c, Z = 4, a = 16.05(1) Å, b = 16.73(1) Å, c = 13.11(1) Å, β = 106.3(1)°). If the solvent DMF is used, the pentasulfide [Cs(dibenzo-18C6)]₂S₅(DMF)₂ crystallizes (monoclinic, S. G. P2₁/n, Z = 4, a = 14.79(1) Å, b = 14.24(1) Å, c = 25.74(1) Å, β = 92.7(1°. The S₅^2? anions show the cis-conformation.     

Röntgenstrukturanalysen von Cyclododekaschwefel (S12) und Cyclododekaschwefel-1-Kohlendisulfid (S12 · CS2) [1]

X-Ray Structural Analyses of Cyclododecasulfur (S₁₂) and Cyclododecasulfur-1-Carbon-disulfide (S₁₂ · CS₂) S₁₂ · CS₂ crystallizes in space group R&3macr;m–D with hexagonal lattice constants a = 1066.8(3), c = 1155.1(4) pm, Z = 3, d_calc. = 2.04 g · cm^?3. The S₁₂ molecules occupy sites of D_3d symmetry with bond distance (d_ss) of 205.4(1) pm, bond angles (α) of 105.80(5) and 106.65(6)º and torsional angle (τ) of 87.20(7)º. The CS₂ molecule interacts only very weakly with the S₁₂ units. S₁₂ crystallizes in space group Pnnm–D with lattice constants a = 472.5(2), b = 910.4(3), c = 1453.2(3) pm, Z = 2, d_calc = 2.045 g · cm^?3. The molecules with mean parameters d = 205.2 pm, α 106.6º, τ 88.0º occupy sites of C_2h symmetry.     

Beiträge zur Chemie des Phosphors. 66. Kristall- und Molekülstrukturen von 1,2,3,4-Tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphan, (PC6H5)4CH2, und 1,4-Dithio-1,2,3,4-tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphan, (PC6H5)4CH2S2

Contributions to the Chemistry of Phosphorus. 66. Crystal and Molecular Structure of 1,2,3,4-Tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphane, (PC₆H₅)₄CH₂, and 1,4-Dithio-1,2,3,4-tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphane, (PC₆H₅)₄CH₂S₂ The following results were achieved by X-ray structure analyses of 1,2,3,4-Tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphane 1 and 1,4-Dithio-1,2,3,4-tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphane 2 :

• crystallises in the monoclinic space group Cc with a = 22.272, b = 13.726, c = 7.492 Å, β = 96.82° and Z = 4. The P₄C-ring has an envelope conformation. The phenyl groups are arranged alternately on both sides of the ring.
• forms triclinic crystals, space group P1 , with a = 10.900, b = 10.663, c = 12.233 Å, α = 106.26, β = 100.04, γ = 70.65°, Z = 2. The P₄C-ring has twist conformation, the carbon atom lies almost in the mean plane of the ring. The sulfur atoms are bonded in exo position to the phosphorus atoms neighbouring the carbon atom and in trans position to each other.

     

Volatile ZnPhen(S2CNEt2)2 and MnPhen(S2CNEt2)2 complexes and the MnZn2Phen3(S2CNEt2)6 phase: Thermal behavior and crystal and molecular structures of two modifications of ZnPhen(S2CNEt2)2

Two crystal modifications, I and II, of the ZnPhen(S₂CNEt₂)₂ complex have been isolated. According to XRD data, the single crystals of I are triclinic with a=9.745(2), b=10.252(2), c=14.331(3) Å, α=99.18(2), β=91.01(2), γ=113.28(2)°, V=1293.2(4) ų, space group P1, Z=2, d_calc=1.401 g/cm³. The crystals of II are monoclinic with a=7.220(6), b=18.095(2), c=19.050(4) Å, β=95.85(2)°, V=2475.8(7) ų, space group C2/c, Z=4, d_calc=1.461 g/cm³. In both modifications, the structure is formed by monomer molecules with a distorted octahedral environment of the zinc atom. All atoms in I are in the general position; in II, the atoms are linked by the twofold rotation axis. It is shown by X-ray phase analysis (XRPA) that the MnPhen(S₂CNEt₂)₂ complexes (III) are isostructural to modification I of the ZnPhen(S₂CNEt₂)₂ complex, which underlies the synthesis of a solid solution of these complexes, MnZn₂Phen₃(S₂CNEt₂)₆ (phase IV). It is found that MPhen(S₂CNEt₂)₂ (M=Zn²⁺, Mn²⁺) and phase IV quantitatively sublime when heated in vacuum. Thermolysis of III in argon yields manganese(II) sulfide of cubic modification; the main product of thermolysis of phase IV is a solid solution of Zn_xMn_1?xS of hexagonal modification.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

Neue Benzylkomplexe der Lanthanoiden. Darstellung und Kristallstrukturen von [(C5Me5)2Y(CH2C6H5)(thf)], [(C5Me5)2Sm(CH2C6H5)2K(thf)2]∞ und [(C5Me5)Gd(CH2C6H5)2(thf)]

New Benzyl Complexes of the Lanthanides. Synthesis and Crystal Structures of [(C₅Me₅)₂Y(CH₂C₆H₅)(thf)], [(C₅Me₅)₂Sm(CH₂C₆H₅)₂K(thf)₂]_∞, and [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] YBr₃ reacts with potassium benzyl and [K(C₅Me₅)] in THF to give KBr and the monobenzyl compound [(C₅Me₅)₂ · Y(CH₂C₆H₅)(thf)] 1 . The analogous reaction with SmBr₃ in THF leads to the polymeric product [(C₅Me₅)₂Sm(CH₂C₆H₅)₂ ∞ K(thf)₂]_∞ 2 , with GdBr₃ to [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] 3 . The structures of 1–3 were determined by X-ray single crystal structure analysis:

• Space group P1 , Z = 2, a = 851.2(4) pm, b = 952.7(4) pm, c = 1858.6(8) pm, α = 79.90(4)°, β = 77.35(4)°, γ = 73.30(3)°.
• Space group P1 , Z = 2, a = 903.3(2) pm, b = 1375.9(3) pm, c = 1801.1(4) pm, α = 100.92(3)°, β = 100.77°, γ = 98.25(3)°.
• Space group P2₁/n, Z = 8, a = 1458.2(5) pm, b = 927.8(3) pm, c = 3792.9(15) pm, β = 96.83(3)°.

     

Darstellung,spektroskopische Charakterisierung und Kristallstrukturen von [(C5H5N)2CH2][PtCl5(SCN)] und cis-[(C5H5N)2CH2][PtCl4(SCN)2]

Preparation, Spectroscopic Characterization, and Crystal Structures of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] and cis -[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] By treatment of [PtCl₆]^2– with SCN^– in aqueous solution a mixture of chlorothiocyanatoplatinates(IV) is formed, from which [PtCl₅(SCN)]^2– and cis-[PtCl₄(SCN)₂]^2– have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-Ray structure determinations on single crystals of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] ( 1 ) (tetragonal, space group P 4₃, a = 7.687(1), c = 29.698(4), Z = 4) and cis-[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] ( 2 ) (monoclinic, space group P 2₁/n, a = 11.2467(9), b = 15.0445(10), c = 11.3179(13), β = 92.840(9)°, Z = 4) show, that the thiocyanate groups are coordinated via S atoms with average Pt–S distances of 2.339 Å and Pt–S–C angles of 104.7° up to 107.1°. Using the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra have been assigned by normal coordinate analyses. The valence force constants of the S–Pt–Cl˙ axes are f_d(PtS) = 1.81 ( 1 ) and 1.87 ( 2 ), f_d(PtCl ^× ) = 1.77 ( 1 ) and 1.81 ( 2 ), of the Cl–Pt–Cl axes are f_d(PtCl) = 1.93 ( 1 ) and 1.90 mdyn/Å ( 2 ). The ¹⁹⁵Pt NMR spectra from dichlormethane solutions exhibit each one sharp signal at 3975.6 ( 1 ) and 3231.6 ppm ( 2 ), respectively.     

Aminoguanidinium cations and the square-bipyramidal hexachlorocuprate(II) anion in the (CH8N4)2[CuCl6] crystal structure

Synthesis and structure of a novel thermochromic complex (CH₈N₄)₂[CuCl₆] are reported. X-ray analysis of the compound was carried out for a single crystal 0.4×0.2×0.05 mm in size (a bright-yellow plate). The monoclinic unit cell parameters are a=7.167(1), b=15.561(3), c=7.328(1) Å, β=118.73(3)°, V=716.7(2) ų, space group P2₁, Z=2 (CH₈N₄)₂[CuCl₆] d_calc=1.99 g/cm³, μ(MoK_α)=2.65 mm^?1, R=0.0264, and R_w=0.0290 for 1411 I_hkl>2σ_I.     

The Crystal Structure of Binuclear Metal Complexes of 7-Azaindole: Cu2 (CH3CO2)2 (C7H5N2)2(C7H6N2)2 AND Ni2(C7H5N2)4.2DMF

The crystal and molecular structures have been determined by single-crystal X-ray methods for the binuclear metal ions (II) complexes of 7-azaindole (1H-pyrrolo [2,3-b] pyridine, C₇H₆N₂ denoted by HL), Cu₂(CH₃CO₂)₂.·L₂(HL)₂ and Ni₂L₄.2DMF. The dark green crystal of Cu₂(CH₃CO₂)₂L₂(HL)₂ was found to crystallize in the monoclinic space group P 2₁/n with a = 9.566(2), b = 12.752(2), c = 12.852(4) Å, β = 99.23(3)⁰, V = 1547 Å, Z = 2, the final R = 0.062 and Rw = 0.053 for 1488 observations from 2722 unique reflections. The Cu-Cu distance is 2.747(2), Cu-N (L^?, bridge) is 1.966(7), Cu-N (HL, axial) is 2.229(8), and Cu-O is 2.031(6)Å. The red crystal of Ni₂L₄.2DMF was was found to crystallize in the triclinic space group \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm P \bar 1} $$\end{document} with a = 8.907(5), b = 9.462(2), c = 10.217(2) Å, α = 90.48(2), β = 91.09(3), γ = 110.69(3)⁰, V =805 ų, Z = 1, the final R = 0.063 and Rw = 0.069 for 1489 observations from 2834 unique reflections. The Ni-Ni distance is 2.594(2), Ni-N is 1.905(7) Å. These two molecules lie on crystllographic inversion centers and exhibit ligand disorder.     

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.     

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.     

Bipy,Phen und P(C6H4CH2NMe2‐2)3 in der Synthese kationischer Silber(I)‐Komplexe; die Festkörperstrukturen von [P(C6H4CH2NMe2‐2)3]AgOTf und [Ag(phen)2]OTf

Bipy, Phen, and P(C₆H₄CH₂NMe₂‐2)₃ in the Synthesis of Cationic Silver(I) Complexes; the Solid‐State Structures of [P(C₆H₄CH₂NMe₂‐2)₃]AgOTf and [Ag(phen)₂]OTf The reaction of [P(C₆H₄CH₂NMe₂‐2)₃]AgX ( 1a , X = OTf; 1b , X = OClO₃) with equimolar amounts of L^capL ( 2a , L^capL = 2, 2′‐bipyridine, bipy; 2b , L^capL = 4, 4′‐dimethyl‐2, 2′‐bipyridine, bipy′; 2c , L^capL = 1, 10‐phenanthroline, phen) leads to the formation of the cationic complexes {[P(C₆H₄CH₂NMe₂‐2)₃]Ag(L^capL)}⁺X^— (L^capL = bipy: 3a , X = OTf; 3b , X = ClO₄; L^capL = bipy′: 3c , X = OTf; 3d , X = ClO₄; L^capL = phen: 3e , X = OTf; 3f , X = ClO₄) in which the building blocks L^capL and P(C₆H₄CH₂NMe₂‐2)₃ act as bidentate chelating ligands and are datively‐bound to the silver atom. Spectroscopic studies reveal that on the NMR time‐scale the phosphane group is dynamic with exchanging the respective Me₂NCH₂ built‐in arms. While complex 3e is stable in the solid‐state, it appeared that solutions of 3e start to decompose upon precipitation of colloidal silver when they are heated or irradiated with light, respectively. Appropriate work‐up of the reaction mixture allows the isolation of the phosphane P(C₆H₄CH₂NMe₂‐2)₃ ( 5 ) along with [Ag(phen)₂]OTf ( 4 ). The solid‐state structures of neutral 1a and cationic 4 are reported. Mononuclear 1a crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 16.7763(2), b = 14.7892(2), c = 25.44130(10)Å, β = 106.1260(10), V = 6063.83(11)ų and Z = 4 with 8132 observed unique reflections (R₁ = 0.0712), while 4 crystallizes in the monoclinic space group C2/c with the cell parameters a = 26.749(3), b = 7.1550(10), c = 26.077(3)Å, β = 113.503(2), V = 4576.8(10)ų and Z = 4 with 6209 observed unique reflections (R₁ = 0.0481). The unit cell of 1a consists of two independent molecules. In both molecules the silver atom possesses a distorted tetrahedral coordination sphere and a boat‐like conformation for the six‐membered AgPNCH₂C_2/phenyl cycles is found. In 4 , as typical for 1a , the silver atom possesses the coordination number 4. The two phen ligands are tilted by 40.63°. The OTf group is acting as non‐coordinating counter ion.     

Primitive cubic packing of anions in Cs4[Re6Te8(CN)6]· 2H2O and Ba2[Re6Te8(CN)6] · 12H2O crystals

Crystal structures of Cs₄[Re₆Te₈(CN)₆]·2H₂O (1) and Ba₂[Re₆Te₈(CN)₆]· 12H₂O (2) are determined. Crystals 1 are orthorhombic, a = 14,282(1), b = 12.910(1), c = 18.040(1) Å, V_cell = 3326.3(8) ų, space group Pbcn, Z = 4, d_calc = 5.715 g/cm³, R(F) = 0.0482 for 3193 F_hkl > 4σ(F). Crystals 2 are triclinic, a = 9.671(3), b = 9.697(4), c = 11.039(4) Å, α = 89.86(3), β = 72.34(3), γ = 82.46(3)°, V_cell = 977.2(6) ų, space group P1, Z = 1, d^calc = 4.733 g/cm³, R(F) = 0.0490 for 3226 F_hkl > 4σ(F). In both structures, the [Re₆Te₈(CN)₆]^4? anions form a distorted primitive cubic packing with distances between the centers 9.02-9.63 Å in 1 and 9.70-11.04 Å in 2. The Cs⁺ cations in 1 lie near the face centers of the cubes formed by the onions. In 2, cation pairs (Ba²⁺)₂ bonded to two solvate water molecules are formed; the pairs lie at the centers of the anion cubes. In structures 1 and 2, there are shortened contacts between the tellurium atoms belonging to the neighboring anions (3.75-4.09 and 3.95-4.22 Å, respectively).     

Synthesis and crystal structure of bis (2-phenylethylammonium) dihydrogendimphosphate, [C6H5(CH2)2NH3]2H2P2O7

Chemical preparation, crystal structure and infrared absorption spectra are given for a new organic cation dihydrogendiphosphate. The new synthesized compound [C₆H₅(CH₂)₂NH₃]₂H₂P₂O₇; crystallized in the monoclinic system (P2_1/c space group) with Z = 4 and with the following unit-cell dimensions: a = 19.006(3); b = 10.718(2), c = 10.996(3) Å and β = 98.99(2) °. Its crystal structure was determined and refined down to R = 0,056 by using 3278 independent reflections. As in all atomic arrangements including acidic diphosphate groups; we can observe the formation of an infinite network of anions connected by strong H-bonds.     

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.     

Optically active transition-metal compounds: XXII. Stereochemistry and crystal structure determination of (η5-C5H5)CoI(NC4H3C(R)=N(S)-CH(CH3)(C6H5)) (R = H,CH3)

The crystal structures and absolute configurations of (η⁵-C₅H₅)-CoI(NC₄H₃-C(R)=N(S)-CH(CH₃)(C₆H₅)) (R = H, compound I; R = CH₃, compound II) have been determined by single crystal X-ray diffraction. Crystals of compound I are orthorhombic, with a 11.084(6), b 12.107(6) and c 13.121(7) Å, space group ^P2₁2₁2₁ and d (calcd, Z = 4) 1.69 g cm^?3 The structure was solved by the Patterson technique and refined with use of full matrix least-squares methods to R(F) = 0.031 and R_w(F) = 0.028. Compound II is nearly isomorphous and isostructural; a 11.246(6), b 11.923(6) and c 13.370(7) Å, d(calc., Z = 4) 1.71 g cm^?3 and was refined to the final agreement factors of R(F) = 0.044 and R_w(F) = 0.035. The Co atom has a distorted tetrahedral coordination, with Co-I 2.595(2) for I and 2.607(2) Å for II; Co-(η⁵-C₅H₅ ring centroid) 1.681(4) and 1.703(5) Å; Co-N(pyrrole) 1.905(9) and 1.885(9) Å; Co-N(imine) 1.971(8) and 2.003(9) Å, all the parameters being well within values found in the literature. The configuration around the chiral carbon of the phenylethylamine is S for both compounds, whereas the configuration around the metal is R in I and S in II. The different metal configurations in I and II have their origin in the two different substituents (R = H, CH₃) at the imine carbon atoms of the chelate ring, which induce completely different conformations of the (S)-CH(CH₃)(C₆H₅) moiety in the two complexes. For both compounds the thermodynamically less stable isomer is enriched upon crystallization. Also, for compound I the solution and solid state conformations are almost opposite to each other, the conformation in the solid reflecting intramolecular interactions (phenyl/C₅H₅ attraction).     

Cumulative subject index: Vol. 126(1977)–150(1978)

1,3-Cyclooctadiene reacts with trimethylaluminum and potassium according to the equation 4K + 4Al(CH₃)₃ + 2C₈H₁₂

3K[Al(CH₃)₄]+K[(C₈H₁₂)₂Al] to give potassium bis(3,8-cis-cyclooctenyl) aluminate. The compound can be described as a bicyclo derivative of cyclooctene formed by the 1,4 addition to 1,3-cyclooctadiene. The structure of the complex was determined from 4500 unique data measured by single crystal X-ray diffractometer techniques. Full matrix least squares refinement gave final agreement factors of R₁ = 0.043 (observed data) and R₂ = 0.045 (all data) in the monoclinic space group P2₁/c (a = 9.658(6), b = 12.220(8) and c = 14.150(9)Å; β = 113.85(1)°; V = 1527.43 Å; Z = 4 for ?_calc = 1.23 g cm^?3).     

Halogenomercurate: Darstellung und Strukturen von [Cu(en)2][Hg2Cl6], [Cu(en)2][Hg2Br6] und [Cu(en)2][HgBr4]

Halomercurates: Syntheses and Crystal Structures of [Cu(en)₂][Hg₂Cl₆], [Cu(en)₂][Hg₂Br₆], and [Cu(en)₂][HgBr₄] Crystals of [Cu(en)₂][Hg₂Cl₆] ( 1 ) have been obtained by layering a solution of Hg(NO₃)₂ and NaCl with a solution of [Cu(en)₂]SO₄. An analogous procedure, using NaBr instead of NaCl, gave crystals of [Cu(en)₂][HgBr₄] ( 3 ). Crystals of [Cu(en)₂][Hg₂Br₆] ( 2 ) were obtained by gel crystallization using the same starting materials as for 3 . The complexes show very low solubility. The dinuclear anions of 1 consist of two nearly planar HgCl₃ units related by a center of symmetry. In 2 infinite anionic chains are present, made up of parallel HgBr₃ units. These units are packed in such a way as to produce a trigonal bipyramidal configuration around the Hg atoms. 3 contains mononuclear deformed tetrahedral [HgBr₄]^2– anions. In all three complexes the packing of the ions is such that halogen atoms of halomercurate anions complete a tetragonal bipyramidal coordination at Cu. The resulting Cu–Halogen distances are 2.924 Å for 1 , 3.036 Å for 2 and 3.085 and 3.119 Å for 3 . 1 : Space group P 1, Z = 1, lattice constants at 20 °C: a = 7.000(2), b = 7.526(2), c = 8.239(2) Å; α = 88.39(2), β = 86.06(2), γ = 86.10(3)°; R₁ = 0.040. 2 : Space group P2₁/c, Z = 2, lattice constants at –50 °C: a = 7.185(1), b = 16.338(2), c = 7.814(1) Å; β = 94.88(2)°; R₁ = 0.033. 3 : Space group P2₁/n, Z = 4, lattice constants at 20 °C: a = 8.055(3), b = 13.101(3), c = 13.814(3) Å; β = 91.24(3)°; R₁ = 0.092.     

Nonvalent interactions in the crystal structures of (Et4N)2[Mo3S7Br6] and (Et4N)(H9O4)[Mo3S7Cl6] clusters

Crystal structures of (Et₄N)₂[Mo₃S₇Br₆] (I) and (Et₄N)(H₉O₄)[Mo₃S₇Cl₆] (II) clusters belonging to the class of Mo₃S ₇ ⁴⁺ were determined by X-ray diffraction analysis. Crystals I are orthorhombic a=19.106(3), b=12.930(2), c=29.887(5) Å, V=7383(2) ų, space group Pbca, Z=8, d_calc=2.253 g/cm³, R(F)=0.0402, wR(F²)=0.0587 for 2493 F_hkl>4σ. Crystals II are monoclinic, a=17.106(3), b=18.882(4), c=11.006(2), Å, β=126.13(3)°, V=2871.2(9) ų, space group Cc, Z=4, d_calc=2.147 g/cm³, R(F)=0.0181, wR(F²)=0.0445 for 2307 F_hkl>4σ. Structure I has an anion dimer with 3S_ax…Cl=3.258(4)–3.404(4) Å; the dimer is similar to that observed in the structures of A₂[M₃X₇Hal₆], A=Ph₄P⁺, Ph₃EtP⁺, and PPN⁺. In structure II, infinite chains of anions bonded by 3S_ax…Cl contacts of 3.183(3)–3.394(3) Å were found. A similar phenomenon was established earlier for the structure of (Et₄N)(H₉O₄)[Mo₃S₇Br₆] (III), which is not isostructural to II. Compounds II and III also differ in the structure of the H₉O₄ ⁺ cation: infinite helix in II and pyramid in III.     

Crystal and Molecular Structure of Bis(η5-methylcyclopentadienyl)titana(IV)-cyclohexasulfane Ti(η5-C5H4CH3)2S5

The crystal and molecular structure of Ti(n⁵-C₅H₄CH₃)₂S₅has been determined by X-ray diffraction studies. The substance crystallizes in the monoclinic crystal system [a = 6.8642(5), b = 16.507(1), c = 13.074(1) Å, β = 82.407(3)°, space group P2₁/n, Z = 4]. The geometry about the titanium atom is a distorted tetrahedron, with a (centroid)-Ti-(centroid) angle of 131.29° and a S? Ti? S angle of 93.38°. The six-membered ring TiS₅ has a cyclohexane-like chair configuration. The structural results are compared to those for similar type titanium complexes.