Chloro- und Polyselenoselenate(II) Darstellung,Struktur und Eigenschaften von [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6] und [Ph4P]2[Se(Se5)2]

Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN, [Ph₄P]₂[Se₂Cl₆], and [Ph₄P]₂[Se(Se₅)₂] By symproportionation of elemental selenium and SeCl₄ in polar protic solvents the novel chloroselenates(+II), [SeCl₄]^2? and [Se₂Cl₆]^2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl₄]^2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph₄P]₂[Se₂Cl₆] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se₂Cl₆]^2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se₅)₂]^2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph₄P]₂[Se(Se₅)₂] (space group P2₁/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se₅)₂]^2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se₅]_2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.     

Transition metal complexes with bidentate ligands spanning trans-positions part XV X-ray structural and 31P-NMR solution studies of some three-coordinate silver complexes of 2,11-bis[di(tert-butyl)phosphinomethyl]benzo[c]phenathrene and related ligands

A series of three-coordinate bis(dialkylphosphinomethyl)benzo[c]phenanthrene Ag(I) complexes, alkyl= t-Bu, (1b) , and cyclohexyl, (1c) , anion = BF₄, CIO₄, CIO₄, NO₃, Cl, Br, I, have been prepared and thier ³¹ P-NMR characteristics recorded. The solid state structures of [Ag( 1b )Br], [Ag( 1b )Cl] and [Ag( 1b )CIO₄] have been determined by X-ray diffraction. The Ag atom in these complexes shows distorted trigonal geometry. Selected bond lengths and angles are as follows: Ag-P = 2.463(4) Å and 2.433(5) Å, P-Ag-P=141.6(2)° in the bromo complex, Ag-P = 2.457(2) Å and 2.427(2) Å, P-Ag-P = 142.6(1)° ion the chloro complex, and Ag-P = 2.394(2) and 2.393 (2) Å, P-AG-P = 161.5(1)° in the perchlorato complex.     

Synthetic and structural studies on some 1,3-diselena- and 1,3-dithia-[3]ferrocenophanes of germanium and tin. crystal and molecular structure of 1,3-diselena-2,2- dichlorogermyl-[3]ferrocenophane

A series of [3]ferrocenophanes of general formula Fe(C₅H₄X)₂YCl₂ and the spiro compounds [Fe(C₅H₄X)₂]₂Ge (X = S, Se; Y = Ge, Sn) have been prepared by the reaction of ferrocene 1,1′-dithiol and ferrocene 1,1′-diselenol with tetrahalides of germanium and tin. Spectroscopic properties of the compounds are reported. In solution, the compounds are fluxional by a bridge reversal process. The crystal structure of 1,3-diselena-2,2-dichlorogermyl-[3]ferrocenophane at 163 K. has been determined by X-ray diffraction methods. At that temperature, crystals have space group P2₁/n with a 6.222(3), b 16.156(13), c 12.968(4) Å, β 97.53(1)° and Z = 4. Least-squares refinement gave R = 0.033 for 2834 unique significant reflections whose intensities were measured by counter diffractometry. The two SeGe bond lengths are 2.323 and 2.325(1) Å, with GeCl 2.148 and 2.161(1) Å. The SeGeSe bond angle is 118.2(1)°, ClGeCl 104.7(1)°, and SeGeCl angles range from 106.2 to 109.8(1)°. The SeC bond lengths are 1.901 and 1.904(5) Å, with CSeGe angles of 95.8 and 96.5(2)°. The cyclopentadienyl rings are in an eclipsed conformation with a mean twist angle of 2.7°, and are inclined to one another at 6.1°. The Se atoms are displaced from the ring planes by 0.17 and 0.20 Å yielding a non-bonded intramolecular Se…Se contact of 3.99 Å.     

31P-NMR and X-Ray Studies of the Complexes [HgX2 (1)]. (1=2, 11-bis (diphenylphosphinomethyl)benzo [c]phenanthrene,X=Cl,I)

The ³¹P{¹H}-NMR characteristics of the complexes [HgX₂( 1 )] and [HgX₂-(PPh₂Bz)₂] (X = NO₃, Cl, Br, I, SCN, CN) and the solid state structures of the complexes [HgCl₂( 1 )] and [HgI₂( 1 )] ( 1 = 2,11-bis (diphenylphosphinomethyl)benzo-[c]phenanthrene) have been determined. The ¹J(¹⁹⁹Hg, ³¹P) values increase in the order CN < I < SCN < Br < Cl < NO₃. The two molecular structures show a distorted tetrahedral geometry about mercury. Pertinent bond lengths and bond angles from the X-ray analysis are as follows: Hg? P = 2.485(7) Å and 2.509 (8) Å, Hg? Cl = 2.525 (8) Å and 2.505 (10) Å, P? Hg? P = 125.6(3)°, Cl? Hg? Cl = 97.0(3)° for [HgCl₂( 1 )] and Hg? P = 2.491 (10) Å and 2.500(11) Å, Hg? I = 2.858(5) Å and 2.832(3) Å, P? Hg? P = 146.0(4)°, I? Hg? I = 116.9(1)° for [HgI₂( 1 )]. The equation, derived previously, relating ¹J(¹⁹⁹Hg, ³¹P) and the angles P? Hg? P and X? Hg? X is shown to be valid for 1 .     

4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]-hexacosane tetrachloromanganese(II) and tetrachlorozinc(II) hydrates: Synthesis and crystal structures

Two complex salts, i.e., 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane tetrachloromanganese(II) and tetrachlorozinc(II) hydrates, [H₂(Crypt-222)][MnCl₄] · 1.5H₂O (I) and [H₂(Crypt-222)][ZnCl₄] · 2H₂O (II) were synthesized and their crystal structures were studied by X-ray diffraction. Crystals I and II are trigonal (space group R \(\bar 3\) c, Z = 12); I: a = 11.033, c = 77.775 Å; II: a = 11.046, c = 77.555 Å (the structures were solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.056 (I) and 0.065 (II) for all 2634 (I) and 2636 (II) independent reflections; CAD-4 automated diffractometer, λMoK _α). The [MnCl₄]^2? or [ZnCl₄]^2? anion in structures I or II and the 2.2.2-cryptand dication (with two protonated N atoms) lie on crystal axis 3. The dication contains trifurcate hydrogen bonds N⁺-H(…O)₃. The bond lengths and bond angles in tetrahedral anions [MnCl₄]^2? or [ZnCl₄]^2? are disproportional, probably, due to the Jahn-Teller effect. The molecules of water of crystallization in crystals I, II are disordered over two positions.     

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.     

Mg2[BN2]Cl and Mg8[BN2]5I: Novel Magnesium Nitridoborate Halides — Syntheses,Crystal Structures,and Vibrational Spectra

The title compounds have been synthesized at 1473 K from stoichiometric mixtures of the binary components Mg₃N₂, MgX₂ (X = Cl, I) and BN in arc‐welded steel ampoules encapsulated in evacuated silica tubes. Mg₂[BN₂]Cl ( 1 ) and Mg₈[BN₂]₅I ( 2 ) crystallize in the orthorhombic space groups Pbca (no. 61) and Imma (no. 74), respectively, with a = 6.6139(8)Å, b = 9.766(1)Å, c = 10.600(1)Å, Z = 8 for 1 and a = 13.535(3)Å, b = 9.350(2)Å, c = 11.194(2)Å, Z = 4 for 2 . The crystal structures are characterized mainly by Mg₆ trigonal prisms which are condensed to 3D frameworks in different ways. Part of the trigonal prisms are centered by the [N—B—N]^3— anions and other voids in the framework by the X^— anions. The magnesium environment around Cl^— is a very distorted monocapped trigonal prism (CN = 6+1) and that of I^— is a bicapped heptagonal prism (CN = 14+2). The bond lengths and bond angles for the relevant [BN₂]^3— anions are d(B—N) = 1.330 — 1.338Å, ∠N—B—N = 175.8° in 1 and d(B—N) = 1.330 — 1.339Å, ∠N—B—N = 176.8° — 178.0° in 2 . The vibrational spectra of the title compounds have been recorded and interpreted based on the D_∞h symmetry of the relevant [N—B—N]^3— groups considering the site symmetry splitting.     

Direct Syntheses of Bis(tetraphenylphosphonium) and Bis(ethyltriphenylphosphonium) Hexabromo‐diselenates(II), [PPh4]2[Se2Br6] and [PEtPh3]2[Se2Br6]. The Crystal Structure of [PEtPh3]2[Se2Br6]

Brown crystals of [PPh₄]₂[Se₂Br₆] ( 1 ) and [PEtPh₃]₂[Se₂Br₆] ( 2 ) were obtained when selenium and bromine reacted in acetonitrile solution in the presence of tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide, respectively. The crystal structure of 2 has been determined by X‐ray methods and refined to R = 0.0420 for 4161 reflections. The crystals are monoclinic, space group P2₁/n with Z = 2 and a = 13.055(3) Å, b = 12.628(3) Å, c = 13.530(3) Å, β = 92.40(3)° (293(2) K). In the solid state structure of 2 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square‐planar SeBr₄ units sharing a common edge through two bridging Br atoms. The terminal Se^II–Br bond distances are found to be 2.419(1) and 2.445(1) Å, the bridging μBr–Se^II bond distances 2.901(1) and 2.802(1) Å.     

Reaction of Selenium with Bromine in the Presence of Methyltriphenylphosphonium Bromide: Syntheses and Crystal Structures of [PMePh3]2[Se2Br6] and [PMePh3]2[SeBr6(SeBr2)2]

The brown crystals of [PMePh₃]₂[Se₂Br₆] ( 1 ) and red crystals of [PMePh₃]₂[SeBr₆(SeBr₂)₂] ( 2 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of methyltriphenylphosphonium bromide. The crystal structures of 1 and 2 has been determined by the X‐ray methods and refined to R = 0.0373 for 2397 reflections and 0.0397 for 3417 reflections, respectively. The salt 1 crystallizes in the monoclinic space group P2₁/n with the cell dimensions a = 13.202(5) Å, b = 11.954(4) Å, c = 13.418(6) Å, β = 93.08(4)° (193(2)). The crystals of 2 are triclinic, space group with the cell dimensions a = 10.266(3) Å, b = 11.311(3) Å, c = 11.619(2) Å, α = 108.87(2)°, β = 105.72(2)°, γ = 99.40(2)° (193(2) K). In the solid state structure of 1 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square planar SeBr₄ units sharing a common edge through two μ‐bridging Br atoms. The terminal Se^II–Br bonds are 2.3984(11) and 2.4273(11) Å, whereas the bridging μBr–Se^II bonds are 2.7817(11) and 2.9081(12) Å. In the solid state the trinuclear [SeBr₆(SeBr₂)₂]^2? anion of 2 is centrosymmetric too and contains a nearly regular [SeBr₆] octahedron where the four equatorial bromo ligands each have developed bonds to the Se^II atoms of the SeBr₂ molecules. The contacts between the bridging bromo and the Se^II atoms of the SeBr₂ molecules are 3.0603(15) and 3.1043(12) Å, and can be interpreted as bonds of the donor‐acceptor type with the bridging bromo ligands as donors and the SeBr₂ molecules as acceptors. The Se^IV–Br distances are in the range 2.5570(9)–2.5773(11) Å and the Se^II–Br bond lengths in coordinated SeBr₂ molecules – 2.3411(12) and 2.3421(10) Å.     

Synthese und Kristallstruktur des Nitridokomplexes [Na-15-Krone-5]2[MoNF4]2 · 2 CH3CN

Synthesis and Crystal Structure of the Nitrido Complex [Na-15-crown-5]₂[MoNF₄]₂ · 2 CH₃CN The title compound is synthesized by the reaction of [MoCl₄(NSCl)]₂ with excess NaF in boiling acetonitrile in the presence of the crown ether 15-crown-5. [Na-15-crown-5]₂[MoNF₄]₂ · 2 CH₃CN forms yellow crystals, which were characterized by an X-ray structure determination. Space group P1 , Z = 1. Lattice dimensions at ?90°C: a = 855.5, b = 1 069.9, C = 1 143.5 pm, α = 105.71°, β = 95.29°, γ = 102.25° (4 096 independent observed reflexions, R = 0.039). Short Na…?F contacts of 234 pm with the four axial fluoro ligands of the dimeric anion [MoNF₄]₂^2? allow formulation of a triple ion. The centrosymmetric anion is dimerized by bent fluoro bridges with Mo? F distances of 198 and 245 pm. The long Mo? F distances of the MoF₂Mo ring are in transposition to the nitrido ligands, the bond lengths of which (165 pm) correspond to triple bonds.     

Preparation and properties of dinitrogen trimethylphosphine complexes of molybdenum and tungsten—II: Synthesis and crystal structures of [MCl(N2)(PMe3)4] (M = Mo,W) and trans-[MoCl2(PMe3)4]

Sodium amalgam reduction of the complexes [MCl₃(PMe₃)₃] (M = Mo, W) in tetrahydrofuran, under dinitrogen, yields dark red-brown suspensions from which red-orange crystals of composition trans-[MCl(N₂)· (PMe₃)₄] can be collected. Spectroscopic and chemical evidence indicate the compounds are best formulated as mixtures of trans-[M(N₂)₂(PMe₃)₄] and trans-[MCl₂(PMe₃)₄] species, but attempts to isolate the pure bis(dinitro derivatives have proved unsuccessful. Single crystals of analytical composition [MCl(N₂)(PMe₃)₄] have been studied by X-ray crystallography, and the structure of trans-[MoCl₂(PMe₃)₄] has been determined for comparison. trans-[MCl(N₂)(PMe₃)₄] (M = Mo, W) and trans-[MoCl₂(PMe₃)₄] are all isostructural, crystallizing in the tetragonal space group I$\text{4}$2 trans-[MoCl(N₂)(PMe₃)₄] has a = 9.597(5), b = 12.294(6) Å, D_c = 1.36g cm^?3 Z = 2 and was refined to a final R value of 0.021 based on 319 independent observed reflections. The tungsten analogue has a = 9.573(4), b = 12.278(5) Å, D_c = 1.63g cm^?3 for Z = 2 and was refined to R = 0.19 with 322 independent observed reflections. trans-[MoCl₂(PMe₃)₄] has cell parameters a = 9.675(5), b = 12.311(6) Å D_c = 1.36 g cm^?3 for Z = 2 and was refined to R = 0.043 with 316 independent observed reflections. In each case the metal atom resides on a crystallographic $\text{4}$2m position. For trans-[MoCl(N₂)(PMe₃)₄] (M = Mo, W) the chlorine and dinitrogen ligands are disordered. M-N distances of 2.08(1) ? (M = Mo) and 2.04(2) ? (M = W) and M-Cl bond lengths of 2.415(8) Å (M = Mo) and 2.46(1) Å (M = W) are observed. In trans-[MoCl₂(PMe₃)₄], where there is no disorder, the Mo-Cl distance is 2.420(6) Å.     

Kristallstrukturen von Säurehydraten und Oxoniumsalzen. XX. Die Oxoniumtetrafluoroborate H3OBF4, [H5O2]BF4 und [H(CH3OH)2]BF4

Crystal Structures of Acid Hydrates and Oxonium Salts. XX. Oxonium Tetrafluoroborates H₃OBF₄, [H₅O₂]BF₄, and [H(CH₃OH)₂]BF₄ The crystal structures of three oxonium tetrafluoroborates were determined. H₃OBF₄, oxonium tetrafluoroborate proper, is triclinic with space group P1 , Z = 2 and the unit cell dimensions a = 4.758, b = 6.047, c = 6.352 Å and α = 80.40, β = 79.48, γ = 88.25° at ?26°C. Cations H₃O⁺ and anions BF₄^? are linked by hydrogen bonds O? H…?F into ribbons of condensed rings. In [H₅O₂]BF₄ (diaquohydrogen tetrafluoroborate, monoclinic, P2₁/c, Z = 4, a = 6.584, b = 9.725, c = 7.084 Å, β = 95.15° at ?100°C) the hydrogen bond in the cation H₅O₂⁺ is 2.412 Å short, asymmetric and approximately centered and the linking of cations and anions three-dimensional. In [H(CH₃OH)₂]BF₄ (Bis(methanol)hydrogen tetrafluoroborate, monoclinic, P2₁/c, Z = 4, a = 5.197, b = 14.458, c = 9.318 Å, β = 94.61° at ?50°C) the cation [H(CH₃OH)₂]⁺ is characterized for the first time in a crystal structure with an again very short (2.394 Å), asymmetric and effectively centered hydrogen bond. By further hydrogen bonds cations and anions form only dimers of the formula unit of centrosymmetric cyclic structure.     

Synthesis and crystal and molecular structure of μ-oxo-bis[trifluoroacetato(p-tolyl)iodine]

Crystal and molecular structure of μ-oxo-bis[trifluoroacetato(p-tolyl)iodine] (I) synthesized by a new procedure was determined by X-ray diffraction analysis. Crystals I are orthorhombic, unstable, space group Pbcn, a=17.684(3), b=8.453(3), c=30.560(4) Å, Z=8. The structure of I was solved by direct and Fourier methods and refined by the full-matrix least-squares procedure in an anisotropic-isotropic approximation to R=0.098 (CAD-4 automatic diffractometer, λCuK_α, 1200 observed reflections with I≥2σ). In molecule I, two iodine atoms have T-configuration of valence bonds with the average bond angles O?I?O 169(1) and O?I?C 86(2)°, average bond lengths I?O_μ 2.009(9), I?O_acet 2.269(9), and I?C_aryl 2.11(1) Å, and the bond angle I?O?I 118.1(5)°. In molecule I, two p-Tol substituents are directed to approximately the same side of the medium plane of the central O?I?O?I?O fragment. Crystal structure I has I...O type intra-and intermolecular nonvalent interactions (secondary bonds).     

Tripodal Ligands: Design of Distorted Coordination Polyhedra in Biomimetic Metal Complexes. Crystal structures of [Zn(SCN)(ntb)](SCN) · iPrpOH and [Fe(acac)(ntb)](ClO4)2 · 2CH2Cl2 · iPrpOH,ntb = N-tris(2-benzimidazolylmethyl)amine

The tripodal ligand N-tris(2-benzimidazolylmethyl)-amine (ntb) was used for the preparation of zinc(II) and iron(III) complexes, [Zn(SCN)(ntb)](SCN) · ⁱPrpOH ( 1 ) and [Fe(acac)(ntb)](ClO₄)₂ · 2CH₂Cl₂ · ⁱPrpOH ( 2 ). 1 has a highly distorted trigonal-bipyramidal ZnN₅ coordination geometry. The donor atoms are nitrogens of one amine, three benzimidazoles and one SCN^?. A striking feature of the complex is the length of the Zn? N_amine bond of 2.539(6)Å. The octahedral N₄O₂ coordination sphere of the iron in 2 is less distorted than that of the zinc in 1 . The metal is surrounded by an amine and three benzimidazole nitrogens of the ligand and two oxygens of the bidentate acetylacetonate co-ligand. The Fe? O bond lengths differ by about 0.1 Å. As for the unusual long Zn? N bond in 1 this is a result of a trans effect. 1 crystallizes in the space group P1 with: a = 9.530(1)Å, b = 13.402(1)Å, c = 13.578(2)Å, α = 98.83(1), β = 95.19(1), γ = 101.21(1)°, Z = 2; 2 is also triclinic, space group P1 , with: a = 9.875(6)Å, b = 12.929(10)Å, c = 18.635(15)Å, α = 94.95(8)°, β = 101.01(6)°, γ = 111.09(4)°, Z = 2.     

Characterization of copper(II) coordination compounds of 5,7-dimethyl[1,2,4]triazolo[1,5-a]pyrimidine: the crystal structure of diaquatetrakis(5,7-dimethyl[1,2,4]triazolo[1,5-a]pyrimidine-N3)-copper(II) hexafluorophosphate

Copper(II) coordination compounds of several CuA₂ salts (A = PF₆, BF₄, ClO₄, CF₃SO₃ or NO₃) with 5,7-dimethyl[1,2,4]triazolo[1,5-a]pyrimidine (dmtp) as a ligand have been studied. The crystal structure of [Cu(dmtp)₄(H₂O)₂](PF₆)₂ is described. This compound is monoclinic, space group P2₁/c, a = 11.826(2) Å, b = 9.463(2) Å, c = 17.673(3) Å, β = 97.50(1)°, Z = 2, d_calc. = 1.66 Mg m⁻³, and has been refined to a final discrepancy factor (R) of 0.0382 based on 2316 reflections. The structure consists of PF⁻₆ anions and centrosymmetric mononuclear [Cu(dmtp)₄(H₂O)₂]²⁺ cations, Cu₂₊ being coordinated by four equatorial N(3)-bonded dmtp molecules with CuN = 2.019 and 2.050 Å, and by two axial water molecules with CuO = 2.650 Å. The water molecules form intramolecular hydrogen bonds with the dmtp N(4) atoms.     

Fluorine Containing Coordination Compounds of CrIII. I. Crystal and Molecular Structure of trans-[Cr(en)2F2] · ClO4

Trans-[Cr(en)₂F₂]ClO₄ (en = 1,2-diaminoethane) has triclinic P1 space group with a = 5.633(1), b = 8.879(2), c = 11.686(2) Å, α = 99.92(2), β = 87.22(2), γ = 100.02(2)° and Z = 2. The unit cell contains two independent trans-Cr(en)₂F₂⁺ cations and ClO₄^? anion. Average Cr? F bond length is 1.88(1) Å. Cr? N bonding distances are from 2.05 to 2.10 Å. Mean Cl? O distance is 1.36 Å. 1,2-diaminoethans are in the gauche conformation. Trans-[Cr(en)₂F₂]Cl and [Cr(en)₂F₂]Br have monoclinic and orthorhombic space groups with four equivalent Cr(en)₂F₂⁺ cations. Trans-[Cr(en)₂F₂]I forms twinned crystals preventing further crystallographic investigation.     

Crystal structure of 6-ferrocenyl-3-phenyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole

A new compound of 6-ferrocenyl-3-phenyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole is synthesized and its single crystal structure is determined by X-ray diffraction method. The compound belongs to the monoclinic P2₁/c space group with cell parameters: a = 10.5523(12) Å, b = 13.8414(16) Å, c = 11.4303(13) Å, V = 1603.5(3) ų.     

Darstellung,Schwingungsspektren, Normalkoordinatenanalyse und Kristallstruktur von fac-(PPN)2[ReClBr2I3]

Preparation, Vibrational Spectra, Normal Coordinate Analysis, and Crystal Structure of fac-(PPN)₂[ReClBr₂I₃] By treatment of cis-[ReBr₂I₄]^2? with HCl fac-[ReClBr₂I₃]^2? is formed beside other mixed complex ions of the Type [ReCl_kBr_lI_m]^2?, k + l + m = 6, which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on single crystals of (PPN)₂[ReClBr₂I₃] (monoclinic, space group P2₁/c, a = 22.059(3), b = 13.569(2), c = 23.9679(2) Å, β = 106.194(4)°, Z = 4) reveals the complete ordering of the complex anions. Due to the different trans influence the bond lengths ReCl (2.39) and ReBr (2.50) are slightly increased, the average ReI distance (2.66 Å) is a little shortened as compared with corresponding homoleptic octahedral complexes. The well resolved low temperature (80 K) IR and Raman spectra exhibit rheniumhalogen stretching vibrations in characteristic regions. The assignment is confirmed by the normal coordinate analysis based on a general valence force field. Taking into account increments of the trans influence on the valence force constants of the structural groups an adjustment between calculated and observed frequencies within a few cm^?1 is achieved.     

Sc(III), Eu(III), and Gd(III) Complexes with Macrocyclic Cavitand Cucurbit[6]uril: Synthesis and Crystal Structures

Slow evaporation of solutions of Sc and Eu nitrates with macrocyclic cavitand cucurbit[6]uril gives crystals of isostructural complexes [Sc(NO₃)(H₂O)₄(C₃₆H₃₆N₂₄O₁₂)](NO₃)₂ ? 8.5H₂O (space group Pna2₁, a = 32.0065(18) Å, b = 14.7904(8) Å, c = 11.5774(6) Å, V = 5480.6(5) ų, Z = 4) and [Eu(NO₃)(H₂O)₄(C₃₆H₃₆N₂₄O₁₂)](NO₃)₂ ? 6.75H₂O (space group Pna2₁, a = 31.9525(17) Å, b = 14.7203(8) Å, c = 11.8592(6) Å, V = 5578.0(5) ų, Z = 4). The metal to ligand ratio in these complexes is 1 : 1; the complexes are obtained at 0.025–0.1 mol/l concentrations of the metals in solutions. With higher lanthanide concentrations (0.7–1 mol/l), the 2 : 1 complex with cucurbit[6]uril is formed of the composition [{ Gd(NO₃)(H₂O)₅}₂(C₃₆H₃₆N₂₄O₁₂)](NO₃)₄ ? 6.5H₂O (space group \(P\bar 1\), a = 13.3972(6) Å, b = 14.4994(5) Å, c = 18.3290(8) Å, α = 73.5610(10)°, β = 87.2590(10)°, γ = 87.5540(10)°, V = 3409.4(2) ų, Z = 2) and isotypical complex [{Gd(NO₃)(H₂O)₅}₂{(C₅H₅N) ? (C₃₆H₃₆N₂₄O₁₂)}](NO₃)₄ ? 8H₂O with a pyridine molecule inside the cucurbit[6]uril cavity (space group P2₁/n, a = 14.8263(6) Å, b = 13.3688(7) Å, c = 18.5970(9) Å, β = 107.5860(10)°, V = 3513.8(3) ų, Z = 2). According to X-ray diffraction data, the metal atoms of the title complexes coordinate the O atoms in portals of cucurbit[6]uril molecules.     

Darstellung und Kristallstruktur von (n-Bu4N)3[Ir(NCS)(SCN)5]

Preparation and Crystal Structure of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] The evaporated ethanolic extrakt of the reaction product of K₃[IrCl₆] and HNO₃, refluxed with an aqueous KSCN solution yields a mixture of the linkage isomers [Ir(NCS)_n(SCN)_6?-n]^3?, n = 0? 2, and small amounts of linkage isomeric chloropentarhodanoiridates(III), from which [Ir(NCS)(SCN)₅]^3? has been isolated by ion exchange chromatography on DEAE-cellulose. The X-Ray structure determination on a single crystal of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] (monoclinic, space group P 2₁/a, a = 17.513(5), b = 32.607(5), c = 23.661(5) Å, β = 94.757(5)°, Z = 8) confirms the existance of a heteroleptic hexakis(thiocyanato(N)-thiocyanato(S))iridate(III) with an Ir? N distance of 2.03 Å and Ir? S bond lengths between 2.29 and 2.38 Å. The SCN groups with angles between 166 and 175° are nearly linear with Ir? S? C angles from 99.9 to 109.4°. The Ir? N? C angles of the two crystallographic independent anions are 166 and 174°.