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.     

Metall-Schwefelstickstoff-Verbindungen. 22. S4N3Cl als Ausgangsprodukt zur Herstellung von Komplexen mit dem S3N−-Liganden Die Komplexe [Ph6P2N][Cu3(S3N)2(CN)2]und [Ph4As][(CuS3N)2(CN)]

The reaction of S₄N₃Cl with metal salts leads to complexes containing the S₃N^?chelating ligand, a reaction which proceeds smoothly especially in an alkaline medium. Thus we were able to prepare, by the reaction of CuCN with S₄N₃Cl and [Ph₆P₂N]OH (Ph = phenyl), the salt [Ph₆P₂N][Cu₃(S₃N)₂(CN)₂], a compound in which the anions build a bidimensional network through supplementary Cu - S contact interactions. The salt is monoclinic, space group C2/c, a = 18.960, b = 14.651 and c = 15.400 Å, β = 101.03° and Z = 4. Metal Sulfur Nitrogen Compounds. 22. S₄N₃Cl as a Starting Compound for the Preparation of Complexes Containing the S₃N^? Ligand. Complexes [Ph₆P₂N] [Cu₃(S₃N)₂ (CN)₂] and [Ph₄As] [(CuS₃N)₂ (CN)] In contrast, the reaction of CuN with S₄N₃Cl and [Ph₄As]OH led to the compound [Ph₄As][(CuS₃N)₂(CN)], monoclinic, space group C2/c, a = 18.478, b = 6.405, c = 27.051 Å, β = 119.50°, Z = 4. In the centrosymmetric anion the two Cu(S₃N) groups are linked together by disordered CN^? groups. An additional linkage results from Cu - Cu contact interactions, with d = 2.84 Å.     

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.     

Metall-Schwefelstickstoff-Verbindungen. 19. Neue Komplexe von CuI mit dem S3N−-Chelatliganden Darstellung und Struktur von [Ph4As][Cu(S3N)(CN)], [(Ph3P)2N][Cu(S3N)(S7N)] und [Ph4As]2[(S3N)Cu(S2O3)Cu(S3N)]

Metal Sulfur-Nitrogen Compounds. 19. Novel Complexes of Cu^I with the S₃N^? Chelate Ligand. Preparation and Structure of [Ph₄As][Cu(S₃N)(CN)], [(Ph₃P)₂N][Cu(S₃N)(S₇N)], and [Ph₄As]₂[(S₃N)Cu(S₂O₃)Cu(S₃N)] In alkaline media S₇NH reacts with Cu salts to yield different products. With Cu(CN) the ion [Cu(S₃N)(CN)]^? is formed, which was isolated as the [Ph₄As]⁺ salt. The crystals are monoclinic, space group P2₁/c, a = 10.499(5), b = 13.418(6), c = 18.032(8) Å, β = 91.84°(3), Z = 4. Besides the known complex ions [Cu(S₃N)₂]^? and [Cu(S₃N)Cl]^? still some more may be obtained when CuCl₂ is reacted with S₇NH: Under special conditions the S₇N ring is partly preserved, and [Cu(S₃N)(S₇N)]^? is formed. Its sparingly soluble [(Ph₃P)₂N]⁺ salt is monoclinic, space group P2₁/n, a = 9.335(6), b = 30.984(11), c = 15.108(8) Å, β = 102.87°(4), Z = 4. Using a longer reaction time a dinuclear complex [(S₃N)Cu(S₂O₃)Cu(S₃N)]^{? ?} results from the reaction of CuCl₂ with S₇NH. The two Cu atoms are bridged by an S atom of the S₂O₃^{? ?} anion. The [Ph₄As]⁺ salt of the dinuclear complex anion is triclinic, space group P1 , a = 11.226(6), b = 12.423(6), c = 19.000(10) Å, β = 76.47°(4), β = 83.98°(4), γ = 84.71°(4), Z = 2. In all these compounds the coordination of Cu^I is trigonal-planar, the S₃N^? chelate group coordinates the Cu in the usual way by two S atoms.     

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.     

Zur Protonierung und Methylierung des 1, 1-Dicyanoethylen-2, 2-dithiolat Dianions: Präparative und strukturelle Untersuchungen

Protonation and Methylation of 1, 1-Dicyanoethylene-2, 2-dithiolate Dianion. Preparative and Structural Investigations Protonation of alkaline metal salts of [S₂C = C(CN)₂]^2? ( I ) in water yields a product of composition H₂S₂C₄N₂ ( II ). The species has to be formulated as dimere and crystallizes with two moles DMSO from DMSO solution with space group C2/c and a = 20.611(3), b = 4.800(1), c = 20.638(3) Å, β = 103.3(1)°, Z = 4. The X-ray structural analysis shows II to be a centrosymmetric 1, 3-Dithiacyclobutane system. On methylation of I with CH₃I in the molar ratio 1:1, the monomethylated anion III can be isolated as AsPh₄ salt. The compound crystallizes in the monoclinic space group P2₁/c, with a = 23.632(2), b = 14.304(1), c = 7.989(1) Å, β = 100.1(8)° and Z = 4. There are nearly planar anions [MeS(S)C?C(CN)₂]^? with an anti-conformation of the MeS group.     

Synthesis and Crystal Structures of the Novel Tetrameric Nitrido Complexes [{cyclo-ReN}4(S2CNEt2)6(MeOH)2(PPh3)2][BPh4]2 · CH2Cl2 · 2 H2O and [{cyclo-ReN}4(S2CNEt2)4Cl4(PMe2Ph)4] · 2 acetone

Novel tetrameric rhenium(V) complexes have been prepared from [ReNCl₂(PPh₃)₂] and [ReN(PMe₂Ph)(S₂CNEt)₂], respectively. [ReNCl₂(PPh₃)₂] reacts with 1.5 equivalents of KS₂CNEt₂ in methanol to yield the unusual dark red species [{cyclo-ReN}₄(S₂CNEt₂)₆(MeOH)₂(PPh₃)₂][BPh₄]₂ · CH₂Cl₂ · 2 H₂O ( 1 ). The crystal structure of the tetramer (triclinic, space group P1, a = 13.842(2), b = 15.213(2), c = 16.796(3) Å, α = 67.88(1), β = 70.90(1), γ = 88.05(1)°, U = 3080.2(8) ų, Z = 1) shows four rhenium atoms in a square configuration which are bridged via linear asymmetric Re≡N–Re groups with bond lengths of about 169 and 203 pm. The molecule contains a centre of symmetry with two distinct octahedral rhenium environments. The first rhenium environment contains two bidentate dithiocarbamate ligands which complete the octahedral geometry and the second contains a bidentate dithiocarbamate ligand, coordinated methanol and has retained a single phosphine coligand. A symmetric compound containing the {cyclo-ReN}₄ core is obtained from the reaction of [ReN(PMe₂Ph)(S₂CNEt₂)₂] with Al₂Cl₆ in acetone. [{cyclo-ReN}₄(S₂CNEt₂)₄Cl₄(PMe₂Ph)₄] · 2 acetone ( 2 ) forms red crystals (monoclinic, space group C2/c, a = 21.432(6), b = 13.700(3), c = 28.060(9) Å, β = 102.37(1)°, U = 8048(4) Å3, Z = 4) with each rhenium atom coordinated by a bidentate dithiocarbamato, a phosphine and a chloro ligand. The non-planar 8-membered {ReN}₄ ring contains asymmetric Re≡N–Re bridges (mean values: 1.69 Å and 2.029 Å, respectively). In contrast, reaction of [ReNCl(S₂CNEt₂)(PMe₂Ph)₂] with one equivalent of K[S₂CN(Me)CH₂CH₂NMe₃]I gave the mixed dithiocarbamato-cation [ReN(S₂CNEt₂)(S₂CN(Me)CH₂CH₂NMe₃)(PMe₂Ph)]⁺ ( 3 ) which was isolated as a tetraphenylborate salt.     

M[B(CN)4]2: Zwei neue Tetracyanoborate mit zweiwertigen Kationen (M = Zn,Cu)

M[B(CN)₄]₂: Two new Tetracyanoborate Compounds with divalent Cations (M = Zn, Cu) The reaction of ZnO or CuO with [H₃O][B(CN)₄] in aqueous solution yielded single crystals of Zn[B(CN)₄]₂ and Cu[B(CN)₄]₂, respectively. The compounds were characterized by single‐crystal X‐ray diffraction. Zn[B(CN)₄]₂ ( (no. 164), a = b = 7.5092(9) Å, c = 6.0159(6) Å, Z = 1) crystallizes isotypic with Hg[B(CN)₄]₂. The structure of Cu[B(CN)₄]₂ (C2/m (no. 12), a = 13.185(3) Å, b = 7.2919(9) Å, c = 6.029(1) Å, β = 93.02(2)°, Z = 2) can be considered as a super‐structure, resulting from Jahn‐Teller distortion of the Cu²⁺ ions. Magnetic measurements were performed for the copper compound. Vibrational spectra and thermal stabilities were compared with the known mercury(II) tetracyanoborate.     

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.     

Struktur und thermische Zersetzung von Bis(triethanolamin)kupfer(II)-acetat [Cu{N(CH2CH2OH)3}2](CH3COO)2

Structure and Thermal Decomposition of Bis(triethanolamine)copper(II) Acetate [Cu{N(CH₂CH₂OH)₃}₂](CH₃COO)₂ Bis(triethanolamine)copper(II) acetate [Cu{N · (CH₂CH₂OH)₃}₂](CH₃COO)₂ was prepared using the basic components; the structure was determined by single crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.101 Å, b = 13.136 Å, c = 9.819 Å, β = 111.63°. Details of the synthesis, X-ray data, and the thermal decomposition are reported.     

Synthese und Kristallstruktur des tetrameren Nitridokomplexes [Cu(CH3CN)4]2[W4N4Cl14(CH3CN)2]

Synthesis and Crystal Structure of the Tetrameric Nitrido Complex [Cu(CH₃CN)₄]₂[W₄N₄Cl₁₄(CH₃CN)₂] . The title compound has been prepared by the reaction of CuCl with WNCl₃ in acetonitrile solution, forming red, moisture sensitive crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group I2/a, Z = 4, 2 027 observed unique reflections, R = 0.049. Lattice dimensions at -80°C: a = 2 527.0, b = 971.9, c = 2 137.5 pm, β = 106.01°. The compound consists of [Cu(CH₃CN)₄]⁺ ions, which are arranged to form strands, and of anions [W₄N₄Cl₁₄(CH₃CN)₂]^2?, in which the tungsten atoms were located at the vertices of a square and are linked with one another via linear W?N? W bridges. Two of the four tungsten atoms have four chlorine atoms as terminal ligands, the other two tungsten atoms have three chlorine atoms and an acetonitrile molecule as terminal ligands.     

Synthese und Röntgenstrukturanalyse von S4N4-Derivaten mit drei- und vierfach koordinierten Schwefelatomen

CF₃SO₂N?SCl₂ reagiert mit (CH₃)₂S[NSi(CH₃)₃]₂, (C₄H₈)S[NSi(CH₃)₃]₂ oder (C₅H₁₀)S[NSi(CH₃)₃]₂ unter Trimethylchlorsilanabspaltung zu den achtgliedrigen S₄N₄-Derivaten S₄N₄(NSO₂CF₃)₂(CH₃)₄ 3 , S₄N₄(NSO₂CF₃)₂(C₄H₈)₂ 4a und S₄N₄(NSO₂CF₃)₂(C₅H_{1 0})₂ 4b . In den achtgliedrigen SN-Ringen haben die Schwefelatome die Koordinationszahl 3 und 4. Die Röntgenstrukturanalyse von 4a ergab eine Sessel-Konformation. 4a kristallisiert orthorhombisch in der Raumgruppe Pna2₁ mit a = 17,641(4), b = 6,406(2), c = 19,130(4) Å, d_x = 1,815 g cm^?3 und Z = 4. Die mittleren S? N-Abstände betragen an den vierfach koordinierten Schwefelatomen 1,597 Å und an den Schwefelatomen mit der Koordinationszahl 3 1,650 Å. CF₃SO₂N? SCl₂ reagiert mit trimethylzinnhaltigen S? N-Verbindungen zum bekannten CF₃SO₂N[Sn(CH₃)₃]S(CH₃)NSO₂CF₃ und Dimethylzinndichlorid. Synthesis and X-Ray Structure Analysis of S₄N₄-Derivatives with Threefold and Fourfold Coordinated Sulfur Atoms CF₃SO₂N?SCl₂ reacts with (CH₃)₂S[NSi(CH₃)₃]₂, (C₄H₈)S[NSi(CH₃)₃]₂ or (C₅H₁₀S[NSi(CH₃)₂]₂ under elimination of (CH₃)₃SiCl to yield the eight-membered S₄N₄ derivatives S₄N₄?NSO₂CF₃)₂(CH₃)₄, 3 , S₄N₄(NSO₂CF₃)₂(C₄H₈)₂ 4a und S₄N₄(NSO₂CF₃)₂(C₅H_{1 0})₂ 4b . In the eight-membered SN-rings the sulfur atoms have the coordination number 3 and 4. The X-ray structure analysis of 4a revealed a chair conformation. 4a crystallizes in the orthorhombic space group Pna2₁ with a = 17.641(4), b = 6.406(2), c = 19.130(4) Å, d_x = 1.815 g cm^?3, and Z = 4. The average S? N distance was found to be 1.597 Å at fourfold coordinated sulfur atoms and 1.650 Å at sulfur with coordination number 3. CF₃SO₂N=SCl₂ reacts with trimethyl tin-containing S? N compounds to the known CF₃SO₂N[Sn(CH₃)₃]S(CH₃)NSO₂CF₃ and dimethyl tin dichloride.     

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF TRIS(DIMETHYLDITHIOCARBAMATE) INDIUM(III), In[S2CN(CH3)2]3

Abstract

The synthesis and structure of the indium dithiocarbamate, In[S₂CN(CH₃)₂]₃·(1/2) 4-mepy (4-mepy=4-methylpyridine), is described. Indium metal was oxidized by tetramethylthiuram disulfide in 4-methylpyridine at 25°C to form a new, homoleptic indium(III) dithiocarbamate in yields exceeding 60%. In[S₂CN(CH₃)₂]₃ exists as a discrete molecule with a distorted-octahedral geometry. The compound crystallizes in the P 1 (No. 2) space group with a=9.282(1)Å, b=10.081(1)Å, c=12.502Å, α=73.91(1)°, β=70.21(1)°, γ=85.84(1)°, Z=2, V(Å)=1057.3(3), R=0.046 and R_w =0.061.     

Stabilization of Highly Reactive “Naked Anions”: Synthesis,Crystal Structure and Vibrational Spectrum of [Na(12‐crown‐4)2]2 [P2S6] · CH3CN

The novel thiodiphosphate, [Na(12‐crown‐4)₂]₂[P₂S₆] · CH₃CN, bis[di(12‐crown‐4)sodium] hexathiodiphosphate(V) acetonitrile solvate ( 1 ) has been synthesized by the reaction of Na₂[P₂S₆] with 12‐crown‐4 in dry acetonitrile. The title compound crystallizes in the tetragonal space group P4₂/mbc (no. 135), with a = 15.184(1) Å, c = 21.406(2) Å and Z = 4 and final R1 = 0.0671 and wR2 = 0.0809. The crystal structure is characterized by discrete sodium‐bound crown‐ether sandwich cations, [Na(12‐crown‐4)₂]⁺ and [P₂S₆]^2? ions with D_2h symmetry. Sodium ion is coordinated by the eight oxygen atoms of two crown‐ether molecules to form a square antiprisma. Solvent molecules of CH₃CN are statistically disordered. Distances and angles of the [P₂S₆]^2? unit are similar to those in [K(18‐crown‐6)]₂ [P₂S₆] · 2 CH₃CN, and in K₂[P₂S₆] and Cs₂[P₂S₆]. The FT‐Raman and FT‐IR spectrum of the title compound has been recorded and interpreted, especially with respect to the P₂S₆ group and in comparison to the few known metal hexathiodiphosphates(V).     

Low‐dimensional compounds containing cyano groups. XVI. (Dicyanamido‐κN1)bis(1,10‐phenanthroline‐κ2N,N′)copper(II) tetrafluoridoborate

The title compound, [Cu{N(CN)₂}(C₁₂H₈N₂)₂]BF₄, was prepared as part of our study of the shape of coordination polyhedra in five‐coordinated copper(II) complexes. Single‐crystal X‐ray analysis reveals that the structure consists of [Cu{N(CN)₂}(phen)₂]⁺ cations (phen is 1,10‐phenanthroline) and BF₄⁻ anions. The Cu centre is five‐coordinated in a distorted trigonal bipyramidal manner by four N atoms of two phen ligands and one N atom of a dicyanamide anion, which is coordinated in the equatorial plane at a distance of 1.996 (2) Å. The two axial Cu—N_phen distances have similar values [average 1.994 (6) Å] and are shorter than the two equatorial Cu—N_phen bonds [average 2.09 (6) Å]. This work demonstrates the effect of ligand rigidity on the shape of coordination polyhedra in five‐coordinated copper(II) complexes.     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).     

Metall-Schwefelstickstoff-Verbindungen. 16. Reaktionsprodukte von Blei- und Zinnsalzen mit S4N4 Die Strukturen von PbN2S2 · NH3, PbN2S2 und SnCl4 · 2S4N4

Metal Sulfur Nitrogen Compounds. 16. Products of the Reaction of Lead- and Tin Salts with S₄N₄. Structures of PbN₂S₂ · NH₃, PbN₂S₂, and SnCl₄ · 2S₄N₄ PbN₂S₂ · NH₃ is monoclinic, P2₁/a, a = 5.671, b = 16.123, c = 6.102 Å, β = 95.12°, Z = 4, PbN₂S₂, however, orthorhombic, P2₁2₁2₁, a = 4.375, b = 7.654, c = 12.274 Å, Z = 4. The planar five-membered PbN₂S₂ rings in both compounds show no remarkable differences. In PbN₂S₂ · NH₃, the NH₃ molecule is bound to Pb perpendicularly to the plane of the ring. The structure of the long known addition compound SnCl₄ · 2S₄N₄ was determined. It is orthorhombic, Pc2₁b, a = 11.467, b = 11.995, c = 12.374 Å, Z = 4. Sn shows sixfold coordination, the two S₄N₄ rings are attached to Sn trans to each other via a N atom.     

Crystal structure of the dichlorobis(1-allyltetrazole-N4)copper(II) complex [Cu(1-CH2=CHCH2−N4CH)2Cl4/2]∞∞

The crystal structure of the dichlorobis(1-allyltetrazole-N⁴)copper(II) complex was determined by X-ray diffraction analysis. The crystals are monoclinic, a=14.233(3), b=6.755(1), c=7.273(1) Å, β=104.63(3)°, V_cell=676.6(2), ų, space group P2₁/c, Z=4, d_calc=1.741g/cm³, d_msd=1.69 g/cm³, CAD-4, λMoK_α radiation, R_F=0.0377 for 520 F_hkl>4σ(F_hkl) and 0.0560 for all 872 independent reflections. The structure is layered; the coordination polyhedron of copper is a square bipyramid, in which the equatorial positions are occupied by two chlorine atoms (Cu?Cl 2.27(2)–2.31(2) Å) and two N⁴ atoms of planar tetrazole ligands, whereas the axial positions are occupied by two chlorine atoms of the neighboring molecules of the complex (Cu?Cl 2.97(2)–3.01(2) Å). The sublattice of chlorine atoms is disordered in such a way that the [CuCl_4/2]_∞∞ layer is a superposition of two variants with weights 61(3) and 39(3)% and with similar geometrical characteristics: the equatorial chlorine atoms in variant A are replaced by the axial atoms in variant B and vice versa. The tetrazole ligand has the same position in both variants. In general, the crystal is a polytype with random alternation of A and B type blocks. It is shown that the compound is isostructural to the complex with 1-ethyltetrazole [Cu(ettz)₂Cl₂], in which only variant B is realized.     

New Thioantimonates(III) with Different Sb:S Ratios: Solvothermal Syntheses and Crystal Structures of [(C3H10NO)(C3H10N)][Sb8S13], [(C2H8NO)(C2H8N)(CH5N)][Sb8S13], [(C6H16N2)(C6H14N2)][Sb6S10], and [C8H22N2][Sb4S7]

Four new thioantimonates(III) with compositions [(C₃H₁₀NO)(C₃H₁₀N)][Sb₈S₁₃] ( 1 ) (C₃H₉NO = 1‐amino‐3‐propanol, C₃H₉N = propylamine), [(C₂H₈NO)(C₂H₈N)(CH₅N)][Sb₈S₁₃] ( 2 ) (C₂H₇NO = ethanolamine, C₂H₇N = ethylamine, CH₅N = methylamine), [(C₆H₁₆N₂)(C₆H₁₄N₂)][Sb₆S₁₀] ( 3 ) (C₆H₁₄N₂ = 1,2‐diaminocyclohexane) and [C₈H₂₂N₂][Sb₄S₇] ( 4 ) (C₈H₂₀N₂ = 1,8‐diaminooctane) were synthesized under solvothermal conditions. Compound 1 : triclinic space group P$\bar{1}$ , a = 6.9695(6) Å, b = 13.8095(12) Å, c = 18.0354(17) Å, α = 98.367(11), β = 96.097(11) and γ = 101.281(11)°; compound 2 : monoclinic space group P2₁/m, a = 7.1668(5), b = 25.8986(14), c = 16.0436(11) Å, β = 96.847(8)°; compound 3 : monoclinic space group P2₁/n, a = 11.6194(9), b = 10.2445(5) Å, c = 27.3590(18) Å, β = 91.909(6)°; compound 4 : triclinic space group P$\bar{1}$ , a = 7.0743(6), b = 12.0846(11), c = 13.9933(14) Å, α = 114.723(10), β = 97.595(11), γ = 93.272(11)°. The main structural feature of the two atoms thick layered [Sb₈S₁₃]^2– anion in 1 are large nearly rectangular pores with dimensions 11.2 × 11.7 Å. The layers are stacked perpendicular to [100] to form tunnels being directed along [100]. In contrast to 1 the structure of 2 contains a [Sb₈S₁₃]^2– chain anion with Sb₁₂S₁₂ pores measuring about 8.9 × 11.5 Å. Only if longer Sb–S distances are considered as bonding interactions a layered anion is formed. The chain anion [Sb₆S₁₀]^2– in compound 3 is unique and is constructed by corner‐sharing SbS₃ pyramids. Two symmetry‐related single chains consisting of alternating SbS₃ units and Sb₃S₃ rings are bound to Sb₄S₄ rings in chair conformation. Finally, in the structure of 4 the SbS₃ and SbS₄ moieties are joined corner‐linked to form a chain of alternating SbS₄ units and (SbS₃)₃ blocks. Neighboring chains are connected into sheets that contain relatively large Sb₁₀S₁₀ heterorings. The sheets are further connected by sulfur atoms generating four atoms thick double sheets.     

Die Reaktionen von M[BF4] (M = Li,K) und (C2H5)2O·BF3 mit (CH3)3SiCN. Bildung von M[BFx>(CN)4—x] (M = Li,K; x = 1, 2) und (CH3)3SiNCBFx(CN)3—x, (x = 0, 1)

The Reactions of M[BF₄] (M = Li, K) and (C₂H₅)₂O·BF₃ with (CH₃)₃SiCN. Formation of M[BF_x(CN)_4—x] (M = Li, K; x = 1, 2) and (CH₃)₃SiNCBF_x(CN)_3—x, (x = 0, 1) The reaction of M[BF₄] (M = Li, K) with (CH₃)₃SiCN leads selectively, depending on the reaction time and temperature, to the mixed cyanofluoroborates M[BF_x(CN)_4—x] (x = 1, 2; M = Li, K). By using (C₂H₅)₂O·BF₃ the synthesis yields the compounds (CH₃)₃SiNCBF_x(CN)_3—x x = 0, 1. The products are characterized by vibrational and NMR‐spectroscopy, as well as by X‐ray diffraction of single‐crystals: Li[BF₂(CN)₂]·2Me₃SiCN Cmc2₁, a = 24.0851(5), b = 12.8829(3), c = 18.9139(5) Å V = 5868.7(2) ų, Z = 12, R₁ = 4.7%; K[BF₂(CN)₂] P4₁2₁2, a = 13.1596(3), c = 38.4183(8) Å, V = 6653.1(3) ų, Z = 48, R₁ = 2.5%; K[BF(CN)₃] P1¯, a = 6.519(1), b = 7.319(1), c = 7.633(2) Å, α = 68.02(3), β = 74.70(3), γ = 89.09(3)°, V = 324.3(1) ų, Z = 2, R₁ = 3.6%; Me₃SiNCBF(CN)₂ Pbca, a = 9.1838(6), b = 13.3094(8), c = 16.840(1) Å, V = 2058.4(2) ų, Z = 8, R₁ = 4.4%