Band 43, Heft 2

Ca 2 [Fe(CN) 6 ] · C 6 H 12 N 4 · 6H 2 O crystallizes in the monoclinic space group B2/b with a = 1130,2(4), b = 1373,5(4), c = 1353,0(4) pm and γ = 97,17°. The X-ray single crystal structure determination converged at R = 0.055 (2057 reflections). Each of the four Fe(CN) 6 octahedra (Z = 4) in the unit cell is coordinated by six Ca atoms with mean N CYAN - Ca distances of 253.5(3) pm. The Ca atoms are bridged by hexamethylenetetramine and water molecules

[Ph 3 PN(H)Ph][AuI 2 ] (2) is formed by the reaction of AuI with N-Phenyl-iminotriphenylphosphorane, Ph 3 PNPh in a toluene suspension. 2,3-Bis(triphenylphosphinimino)maleic acid-N-methylimide (3) has been prepared by the Staudinger reaction of 2,3-bis(azido)maleic acid-N-methylimide with PPh 3 in THF solution in the form of red crystals. Crystal structure determinations of three iminophosphoranes were carried out by X-ray methods. Ph 3 PNPh (1): space group P2 1 /c, Z = 4, 2176 independent observed reflexions, R = 0.057. Lattice dimensions (-30 °C): a = 1126.4, b = 1148.6, c = 1476.0 pm; β = 97.21°. The compound forms monomeric molecules with P=N = 160.2 pm and an PNC angle of 130.4°. [Ph 3 PN(H)Ph][AuI 2 ] (2): space group P1̄, Z = 2, 1780 independent observed reflexions, R = 0.057. Lattice dimensions (18 °C); a = 824.9, b = 1022, c = 1476.2 pm; α = 89.23°, β = 87.41°, γ = 85.65°. The compound consists of ions [Ph 3 PN(H)Ph] ⊕ with P=N = 162.4 pm and PNC = 129.3°, and anions [AuI 2 ] ⊖ with Au-I = 261.9 and 259.3 pm, IAuI = 176.8°. (Ph 3 P) 2 N 2 C 4 O 2 (NMe) (3): space group P1̄, Z = 2, 4972 independent observed reflexions, R = 0.050. Lattice dimensions (-90 °C): a = 904.7, b = 993.8, c = 2017.4 pm; α = 101.55°, β = 96.39°, γ = 105.81°. The compound forms monomeric molecules with syn-conformation of the two NPPh 3 groups. Bond lengths: P=N = 157.1; 155.3 pm, bond angles: PNC = 133°; 136°

The new compound K[I(CN) 2 ] can be prepared by addition of one formula unit of iodine to a concentrated aqueous solution of two mole equivalents of potassium cyanide. It crystallizes in the monoclinic space group C2/m with a = 736.4, b = 451.4, c = 908.0 pm, β = 92.56° and Z = 2. The crystal structure has been refined to R f = 0.020 for 301 observed reflections. The structure may be described as a layer-like package of cations K + and trihalide-analogous anions [I(CN) 2 ] - . The anions are strictly linear at the I atoms (symmetry 2/m) and nearly linear at the C atoms with φ (I-C-N) = 178.6° and d(I-C) = 229.8, d(C-N) = 112.9 pm. The cation is surrounded by a slightly distorted octahedron of nitrogen atoms with d(K···N) = 284.8,292.6 pm

Quaternary chalcogenide halides M 2 M′X 3 Y (M = Zn, Cd; M′ = Al, Ga, In; X = Se, Te; Y = Cl, Br, I) can be synthesized by heating stoichiometric amounts of the binary components MX. MY 2 , and M′ 2 X 3 in evacuated sealed quartz ampoules. In the case of aluminium and gallium compounds, a mixture of the M′ and X elements rather than the binary compounds has been used. The products are typical tetrahedral compounds, crystallizing with either the defect wurtzite-type or the defect zinc-blende-type structure. At 25 kbar, and 1400 °C, Cd 2 InSe 3 Cl, Cd 2 InSe 3 Br, and Cd 2 InSe 3 I transform from the defect wurtzite-type structure to quenchable high-pressure phases with defect NaCl-type structure. The retransformation to the ambient-pressure phases proceeds via intermediates having the defect zinc-blende-type structure. Some aspects of the apparent non-stoichiometry in the high-pressure phases are discussed

Discrete mononuclear TeCl - 5 anions were prepared for the first time in solid phase in association with bulky cations as tetrabutylammonium and tetraphenylphosphonium. The vibrational spectra imply tetragonal symmetry as for the isoelectronic TeF - 5 anion which is caused by a stereochemically active lone pair. A complete vibrational assignment is given and supported by a normal coordinate treatment for both ions. The significance of the resulting force constants is briefly discussed

The synthesis of trans-1.2-cyclohexanedioxydiacetamides starting with trans-1.2-cyclohexane-diol is described. Eleven of these compounds are characterized by IR, 1 H NMR, 13 C NMR and mass spectroscopy as well as elemental analyses. Most of these compounds are suitable ionophors for the cations K + and Ca 2+ . The coordination sites of these ligands in the 1:2 complexes were determined by IR and NMR spectroscopy

(Ph 4 P) 2 Mn 2 Br 6 (1) and (Ph 3 PCH 2 Ph) 2 Mn 2 I 6 (2) were prepared from the reaction of manganese dihalide with the corresponding phosphonium halide in CH 2 Cl 2 . The structures of 1 and 2 were determined from single crystal X-ray diffraction data. Both compounds crystallize in the triclinic space group P 1 with one formula unit per unit cell. 1:a = 998.1(1), b = 1005.7(1), c = 1313.3(2) pm, α = 108.51(1), β = 94.25(1), γ = 100.36(1)°. 2: a = 1058.6(2), b = 1236.3(2), c = 1248.4(3) pm, α = 63.53(1), β = 74.15(1), γ = 74.65(1)°. The structures of 1 and 2 exhibit discrete, dimeric anions formed by the fusion of two identical tetrahedral-like units with a common halogen-halogen edge. The mean Mn-Hal bond lengths were found to be 251.8 pm (Mn-Br) and 272.2 pm (Mn-I). The difference between the bridging and terminal Mn-Hal bond lengths is about 12-13 pm in both compounds

The compounds (Ph 4 P)MnI 3 L (1), MnI 2 L 3 (2), [MnIL 5 ]I 3 (3), and [MnL 6 ](I 3 ) 2 (4) (L = C 4 H 8 O, thf) were prepared in thf solution and their structures determined from single crystal X-ray diffraction data. 1 crystallizes in the monoclinic space group C2/c with a = 1743.6(1), b = 1985.8(1), c = 1806.7(1) pm, β = 98.74(1)°, Z = 8. The structure of 1 exhibits tetrahedral anions. The Mn-I distance was found to be 268.0 pm (mean). 2: monoclinic, C2/c with a = 1252.3(2), b = 1255.0(3), c = 1271.8(3) pm β = 113.88(2)°, Z = 4. The characteristic feature of the structure of 2 is the existence of neutral MnI 2 L 3 molecules with a distorted trigonal bipyramidal geometry and the iodine atoms in equatorial positions (Mn-I: 271.1 pm). The compound crystallizes from a solution of Mnl 2 in tetrahydrofuran. 3: monoclinic, C2/c with a = 1695.3(1), b = 1123.1(1), c = 1646.2(1̱) pm, β = 96.91(1)°, Z = 4. The preparation of 3 from 2 and iodine yields octahedral MnIL + 5 cations (Mn-I: 278.8̄ pm) and triiodide anions. 4: monoclinic, P2 1 /n with a = 1005.5(1). b = 1056.8(1), c =1835.6(2) pm, β = 91.16(1)°, Z = 2. 4 is prepared from 3 and iodine in thf solution, and shows octahedral MnL 6 2+ cations and triiodide anions

The binary system Al-Te contains the intermediate phases AlTe (m.p. 857 °C, syntectic). Al 2 Te 3 (α-phase stable up to 720 °C; β-phase: m.p. 903 °C, congruent) and Al 2 Te 5 (stable between 415 °C and 465 °C, incongruent). The crystal structure of α-Al 2 Te 3 is monoclinic (super-structure; a = 41.565(8) Å, b = 7.189(1) Å, c = 25.477(7) Å, β = 90.21(2)°. Z = 48. D x = 4.57g/cm 3 ). Te positions of the sub-cell (monoclinic P2 1 ; a/3, b, c/6, β) were determined by direct methods; Te atoms are arranged in close-packed layers which are stacked along [100] with the sequence ABCBA. A metastable cubic phase of composition Al 2 Te 3 (Zinc blende-type-structure; a = 5.949(1) Å; Al with random distribution) is obtained by thermal decomposition of ternary compounds AlTeX (X = Cl, Br, I)

The title compound 1 can be obtained from an aqueous solution of aquopentaammine rhodium(III) dithionate and hydroxopentaammine rhodium(III) dithionate. The crystal structure has been determined from single crystal X-ray diffraction data and refined to R = 0.035 for 4390 unique reflections. Crystal data: monoclinic, space group P2 1 /c, a = 1300.9(5) pm. b = 1472.3(6) pm. c = 1478.8(9) pm, β = 106.20(4)°, Z = 4. In the crystal dinuclear rhodium cations with point group symmetry 1 (C 1 ) are found. A central μ-H 3 O 2 -bridge is formed by strong hydrogen bonding between aquo and hydroxo ligands; this bridge is additionally coordinated by two molecules of water. The entire bridging system is therefore H 7 O 4 - (H 3 O 2 - · 2 H 2 O). O-O distances characterizing the strength of the three hydrogen bonds within this new kind of structural unit are O(H 2 O-Rh 1)-O(HO-Rh2): 248 pm. O(H 2 O-Rh 1)-O(H 2 O a ): 273 pm, O(HO-Rh2)-O(H 2 O b ): 287 pm. The hydrogen atoms involved in these bridges have been located. The small difference in the Rh 1-O(H 2 O) - (205.4(3) pm) and Rh2-O(OH)- (204.3(3) pm) distances indicates that the entire H 7 O 4 - - moiety serves as a μ-bridging unit between Rh 1 and Rh 2

The [2,2,2-trifluoro-1-(trifluoromethyl)-1-(trimethylsiloxy)ethyl]phosphonates 2a-g and/or the 4,4,5,5-tetrakis(trifluoromethyl)-1,3,2λ 5 σ 4 -dioxaphospholanes 4a-c, e were obtained from the silylphosphites 1a-g and hexafluoroacetone depending on the reaction conditions. Intermediates were the λ 5 σ 5 -phosphoranes 3a-e formed by an 1:2 oxidative addition of hexafluoroacetone whereas in the case of the cyclic phosphites 1f and g thermally stable phosphoranes, 3f, 6 and 3g were found to undergo no substituent exchange

Hydrophilic sulfur sols prepared from sodium thiosulfate and concentrated sulfuric acid and purified by repeated NaCl precipitation and peptization in water have been studied by chemical analysis, vibrational spectroscopy, ion-pair chromatography and reversed-phase HPLC. The composition of the sol is Na 1.64 S 28.6 O 6 · 5.9/n S n · 1.0 NaCl. The elemental sulfur S n (n = 6-14; mainly S 8 ) accounts for 17% the total sulfur; 83% of the S are present as long-chain polythionates which form micelles in which the S n molecules are dissolved. On aging of the sol at 20 °C the polythionate micelles decompose to give water-soluble short-chain polythionates and elemental sulfur which precipitates from the solution. The micelle structure of hydrophilic sulfur sols may serve as a model for the so-called sulfur globules (S°) formed intra- or extracellularly by many sulfur bacteria which oxidize reduced sulfur compounds to S°. - ᴛ ∙nfrared and Raman spectra of K 2 S m O 6 (m = 3-6) are reported. The photodecomposition of aqueous tetrathionate yields sulfite, thiosulfate, and polythionates with up to 9 sulfur atoms

The heptaarsanes(3) As 7 (Mme 3 ) 3 (M = Si, Ge, Sn) with nortricyclene structure have been synthesized by heterogeneous and homogeneous reactions from K 3 As 7 and Rb 3 As 7 , respectively, with Mme 3 Cl. The crystal structures have been determined. The compounds are isotypic and crystallize in unit cells of R3̄̄ symmetry, containing pairs of enantiomers. The bond lengths d(As-As) in the nortricyclene skeleton are nearly uneffected by the substituents and show the sequence typical for covalent nortricyclenes: d(basal) = 244.3 pm > d(basal-equatorial) = 242.7 pm > d(equatorial-apical) = 240.7 pm (mean values). The spread-off of the Mme, substituents decreases as going from P 7 to As 7 skeletons as well as with increasing size of M

(TTM-TTF)(CuI) 2 . {TTM-TTF = Tetra(methylthio)-tetrathiafulvalene}. the product of the reaction of TTM-TTF with CuI in an I 2 , atmosphere, is monoclinic C2/m, a = 7.928(2). b = 13.272(1), c = 10.523(2) Å, β 107.82(2)° V = 1054 Å 3 Z = 2, d c = 2.42 g cm -3 , μ = 56.8 cm -1 , final R w = 0.027 for 964 reflections and 59 variables. The donor acts as a bridging chelate ligand by coordination of the SCH 3- groups to Cu. (TTM-TTF) + (CuCl 2 ] - is triclinic P1̄, a = 7.253(1), b = 7.657(1), c = 10.256(1) Å, α = 89.63(1), β = 89.98(1), 3̄̄μ1̄γ = 73.26(1)°, V = 470 Å 3 Z = 1, d c = 2.07 g cm -1 , μ = 22.95 cm -1 , final R w = 0.029 for 1871 reflections and 104 variables. Stacks of the (TTM-TTF) + radical cations with intrastack S···S-contacts of 3.792(2) Å. (TTM-TTF) 2+ [AuCl 4 ] 2 - and C 4 H 6 S 4 AuCl 2 were obtained as products of the reaction of TTM-TTF with AuCl 3 in acetonitrile. (TTM-TTF) 2+ [AuCl 4 ] 2 - is monoclinic, C2, a = 14.799(2), b = 11.513(2), c = 8.034(3) Å, β = 97.05(3)°, V = 1359 Å 3 , Z = 2, d c = 2.61 g cm -3 , μ = 121.6 cm -1 , final R w = 0.028 for 1581 reflections and 140 variables. Stacks of the oxidized donor with intrastack S···S-contacts of 3.683(6) Å. C 4 H 6 S 4 AuCl 2 is monoclinic. P2 1 /n, a = 10.722(2), b = 14.054(3), c = 14.877(2) Å, β = 108.03(2)°, V = 2132 Å 3 , Z = 8, d c = 2.80 g cm -3 , μ = 149.8 cm -1 , final R w = 0.029 for 3053 reflections and 212 variables. The molecules are arranged in stacks which shortest S···S-contacts of 3.269(3) Å

Ph 2 PC 5 H 4 FeC 5 H 4 PPh 2 (1) reacts with Me 3 SiN 3 with evolution of nitrogen to yield (Me 3 SiN = PPh 2 C 5 H 4 ) 2 Fe (2). Treatment of 2 with WF 6 results in the formation of (C 5 H 4 PPh 2 N) 2 FeWF 4 (3). 3 is a rare example of a metal complex containing two metal atoms in very different oxidation states

The impact of change only in one heteroatom in the substituent at position 5(6) of methyl benzimidazole-2-carbamates on the profile of anthelmintic activity against intestinal worms Ancylostoma ceylanicum (hookworm), Nippostrongylus brasiliensis (trichostrongylid), Syphacia obvelata (oxyurid) and Hymenolepis nana (cestode) has been studied. The observations made are likely to evoke interest for understanding the SAR in methyl benzimidazole-2-carbamates anthelmintics at a molecular level

The colourless compounds Na 3 OCl and Na 3 OBr have been prepared and characterized by X-ray diffraction techniques. Na 3 OCl crystallizes in a cubic primitive lattice with a = 450.0(3) pm (Z = 1). Na 3 OBr is isotypic with Na 3 OCl and its lattice constant is a = 457.3(5) pm. The structures are related to the anti-perowskitetype

New quaternary compounds AgIn 2 X 3 Y (X = Se, Te; Y = Br, I) could be synthesized from AgY-In 2 X 3 -mixtures at atmospheric pressure. The crystal structures are defect-wurtzite (AgIn 2 S 3 Br) or defect-zinc-blende (AgIn 2 Te 3 Br, AgIn 2 Te 3 I). A transformation to high-pressure phases with spinel structure (AgIn 2 Se 3 Br, AgIn 2 Se 3 I) or defect-NaCl-structure (AgIn 2 Te 3 Br, AgIn 2 Te 3 I) takes place at 20 and 40 kbar.,respectively. AgIn 2 S 3 I with spinel structure could by synthesized from AgI and In 2 S 3 at 40 kbar, 500 °C

The crystal structure of CuSe 2 Cl has been determined by single-crystal X-ray diffraction. CuSe 2 Cl crystallizes monoclinically in space group P2 1 /c with the lattice parameters a = 768.3(9) pm, b = 462.5(5) pm and c = 1455.2(3) pm, β = 135.2(4)°, Z = 4. The structure could be shown to be isotypic with CuTe 2 Cl

The 77 Se NMR spectrum of 1,2-Se 2 S 5 exhibits one singlet at 1077.3 ppm indicating pseudorotation in solution; the same conclusion is reached from the solution Raman spectrum of S 7 showing characteristic line broadening compared to the solid state spectrum