Band 59, Heft 10

Crystals of 1,4,7,10-tetrathiacyclododecane silver(I) trifluoromethanesulfonate, Ag(C 8 H 16 S 4 )- (CF 3 SO 3 ), 1,4,7,10-tetrathiacyclododecane iodo mercury(II) hexaiododimercurate(II)methylene chloride [HgI(C 8 H 16 S 4 )][Hg 2 I 6 ] · CH 2 Cl 2 , 1,4,7,10,13,16-hexathiacyclooctadecane silver(I) trifluoromethanesulfonate [Ag(C 12 H 24 S 6 )](CF 3 SO 3 ), 1,4,7,10,13,16-hexathiacyclooctadecane diiodocadmium, [Cd(C 12 H 24 S 6 )I 2 ], and bis-3,6,9,14-tetrathiabicyclo[9.2.1]tetradeca-11-13-diene silver(I) trifluoromethanesulfonate [Ag(C 10 H 14 S 4 ) 2 ](CF 3 SO 3 ) were obtained by reaction of solutions of the ligands and the appropriate metal salts and their X-ray crystal structures determined.

Three new tetrathiomolybdates (pipH 2 )[MoS 4 ] (1), (trenH 2 )[MoS 4 ]·H 2 O (2) and [(prop) 4 N] 2 - [MoS 4 ] (3) (pip = piperazine, tren = tris(2-aminoethyl)amine and prop = n-propyl) were synthesized and characterized by elemental analysis, infrared spectroscopy, single crystal X-ray crystallography, and thermoanalysis. All compounds were prepared by the base promoted cation exchange method, i.e. by the reaction of the ammonium salt of [MoS 4 ] 2− with the corresponding organic amine or organic ammonium hydroxide. In the compounds 1 and 2 the organic amines pip and tren are diprotonated and they are linked to the tetrahedral [MoS 4 ] 2− dianions through weak hydrogen bonding interactions. The strength and number of these hydrogen bonds affect the Mo-S bond lengths and a relatively long Mo-S bond of 2.2114(8) Å is observed in 1 while the longest Mo-S bond in 2 is 2.1951(5) Å . In compound 3 no S···H-N interactions are possible and the Mo-S bond lengths scatter in a more narrow range compared to those in compounds 1 and 2. The thermal behavior was investigated using differential thermal analysis and thermogravimetry. On heating compound 1 decomposes in two closely related steps while 2 loses first the crystal water followed by the decomposition of the tetrathiomolybdate. The final products are amorphous molybdenum sulfides. The decomposition of compound 3 yields a very porous material with sponge-like morphology.

The reaction of diastereomeric methyl rhenium complexes [CpRe(NO)(NMDPP)(CH 3 )] (NMDPP = neomenthyl-diphenylphosphine) and [CpRe(NO)(PAMP)(CH 3 )] (PAMP = phenyl-2- anisyl-methylphosphine) with thiols in the presence of HBF 4 gave thiolate complexes [CpRe(NO)(NMDPP)(SCH 2 Ph)] and [CpRe(NO)(PAMP)(SCH 2 R)] (R = Ph, 4-C 6 H 4 Cl, 4-C 6 H 4 OMe, 2-C 4 H 3 O, CH 3 , CH=CH 2 ). Treatment of [CpRe(NO)(PAMP)(THF)]BF 4 with the thiols and Na 2 CO 3 gave the same compounds under neutral conditions. Similarly, the reaction of the chelate complex {CpRe(NO)[κP(Ph)(Me)(CH 2 C 4 H 3 κS)]}BF 4 with thiols and NaOEt yielded the ring-opened products {CpRe(NO)[P(Ph)(Me)(CH 2 C 4 H 3 S)](SCH 2 R)} (R = Ph, 4-C 6 H 4 Cl, 4-C 6 H 4 OMe). One of the benzylic hydrogen atoms can be abstracted with [Ph 3 C]BF 4 to give the diastereomeric thiobenzaldehyde complexes [CpRe(NO)(PAMP)(S=CHR)]BF 4 (R = Ph, 4-C 6 H 4 Cl, 4-C 6 H 4 OMe) and {CpRe(NO)[P(Ph)(Me)(CH 2 C 4 H 3 S)](S=CHPh)}BF 4 . In these products, the thioformyl group is predominantly η 2 (C,S) coordinated to rhenium, but in a few cases the corresponding η 1 (S) isomers were also detected by IR and NMR spectroscopy.

The title compound was prepared from the elements by arc-melting followed by annealing in silica tubes at 1070 K for 3 months. The orthorhombic structure of LaNi 5 As 3 was solved and refined from X-ray single crystal data: space group Pnma, a = 11.179(2), b = 3.9133(5), c = 24.443(3) Å , Z = 8, R = 0.040, Rw = 0.039 for 1045 unique reflections with I > 2σ (I) and 110 parameters. It is a new structure type, which can be described by condensed units of trigonal prisms around the arsenic atoms linked together to infinite zigzag chains. The structural features of LaNi 5 As 3 are discussed in comparison with some representatives of a large family of structures with a metal/non-metal ratio equal or close to 2:1.

The 1:2 and 1:1 mixed-ligand mercury(II) complexes with 2,2’-bipyridine (bpy) containing two different anions, Hg(bpy) n (SCN)X (X= CH3COO−, NO 3 − and ClO 4 −), have been synthesized and characterized by elemental analysis, and IR, 1 H and 13 C NMR spectroscopy. The structure of [Hg(bpy) 2 (SCN)]NO 3 was confirmed by X-ray crystallography. The complex is monomeric and the Hg atom has an unsymmetrical five-coordinate geometry, with four nitrogen atoms of two bpy ligands and one sulfur atom of the thiocyanate ligand as donor atoms. This is in contrast to lead(II) complexes, [Pb(phen) 2 (NO 3 )(NCS)], [Pb(phen)(O 2 CCH 3 )(NCS)] where the thiocyanate ligands are coordinated to the lead atom via the nitrogen atom. There is a π −π stacking interaction between the parallel aromatic rings.

The reaction of 1,9-diaminononane with hydroiodic acid in the presence of iodine gave a compound best described as 1,9-diammoniononane bis-triiodide iodine, (H 3 N-(CH 2 ) 9 -NH 3 )[I 3 ] 2 · I 2 . The structure is built from two crystallographically independent I 3 − anions, which are connected via secondary I···I interactions to the iodine molecules, and the 1,9-diammonioalkane cations are connected via weak hydrogen bonds to neighbouring iodine atoms. By a cooperative phenomenon, the shape and the functionality of the cation lead to a solid state structure that includes a polyiodide substructure with the formula 2 ∞ [I 8 ] 2− or 2 ∞ [I 3 · I 2 · I 3 ] 2− , is best described as a brick-shaped layered array. Its rectangular pores fit excellently with the hydrogen bonding functionality as well as with the conformational needs of the 1,9-diammoniononane template. The Raman spectrum shows typical bands of coordinated triiodide anions and iodine molecules. The thermal analysis (DSC/TG) of the title compound indicates decomposition at temperatures above 210°C.

Methyl 7-(5’,5’-dimethyltetrahydrofuran-2’-yl)-3-methylocta-2,6-dieneoate (cazolobine), a new sesquiterpene derivative was isolated from the root of Isolona hexaloba (Annonaceae) collected in Gabon. The structure of cazolobine was elucidated on the basis of its spectral data, mainly MS and multiple-pulse NMR.

A series of 3-cyano-pyridones carrying a variety of alkyl substituents at C-5 and C-6 has been synthesized and their solid-state structures have been studied. Hydrogen bonding interactions between individual pyridone molecules lead either to the formation of symmetric dimers of the R 2 2 (8) type or to helical chains of the C(4) type. Based on known and calculated structures for the 2-pyridone parent system, the solid-state structures can be divided in two groups representing cases with little external influence on the hydrogen bonding array (group A) and those with a larger external influence (group B).

The reaction of nitrile imines, generated in situ, from hydrazonoyl halides 3a - e with enamines 2a - c affords pyrazoles 8a - g. These pyrazoles have been used to prepare condensed pyrazoles.

5,5’-Dimethoxy-3,3’-methanediyl-bis-indole (3) was synthesized in a reductive cyclisation process from (E)-5-methoxy-2-nitro-β -morpholinestyrene. The solid state structure was probed by single crystal X-ray diffraction and 13 C CP/MAS NMR methods. The results of the X-ray analysis indicate insignificantly different structure of both methoxyindole fragments of the molecule, and this is the main reason for the appearance of the double resonances in the solid state NMR spectrum. Interesting N-H· · ·π interactions were observed which may have a functional role in biological features of 3. 5,5’- Dimethoxy-3,3’-methanediyl-bis-indole at conc. 1 · 10 −4 M reduces the growth of MCF7 (breast), NCI-H460 (lung), and SF-268 (NCS) cells to 21, 0, and 48%, respectively.

Treatment of vic-dihydroxyindeno[1,2-d]imidazoles with N,N,N’,N’-tetraalkyl sulfurous diamides yields indeno[1,2-d]imidazoles by deoxygenation. Isochromeno[3,4-d]imidazoles are formed as byproducts. An X-ray crystal structure analysis confirmed the structure of deoxygenated products. The ratio of products depending on the reaction conditions was analyzed. A mechanism of the reaction is discussed.

High-resolution gas phase measurements of 1 H NMR spectra at 400 MHz and atmospheric pressure of seven small hydrocarbons are presented. The developed new method and the experimental set-up are described. Ab initio GIAO MO calculations of 1 H and 13 C NMR absolute shieldings on the HF, MP2 and B3LYP levels using 25 standard gaussian basis sets are reported for these hydrocarbons, based on experimental re distances. The measured gas phase 1 H chemical shifts have been converted to an absolute σ 0 shielding scale by use of the literature shielding of methane. These and gas phase 13 C literature values have been transferred with literature ZPV data to estimated σ e exp shieldings which are used to evaluate the basis set dependence of the calculated σ e shieldings utilizing linear least squares regressions. Exponential extrapolations of Dunning basis set calculations allow the determination of basis set limits for 1 H and 13 C shieldings. 1 H and 13 C chemical shifts have been derived from the HF calculated shieldings with shieldings of TMS which has been geometry optimized and GIAO calculated in each basis. Standard deviations (esd) as low as 0.09 ppm for 1 H and 0.76 ppm for 13 C calculations have been obtained. The statistically best basis set for simultaneous calculation of 1 H and 13 C absolute shieldings or relative shifts is 6-311G* within the HF and B3LYP methods. Aiming for highest accuracy and precision, 1 H and 13 C have to be treated separately. In this case, best results are obtained using MP2/6-311G** or higher for 1 H shieldings and MP2/cc-pVTZ for 13 C shieldings.

The reaction of β-himachalene with dichlorocarbene followed by ruthenium catalyzed oxidation under Sharpless conditions yields 8,8-dichloro-3,3,7-trimethyl-1(3-oxobutyl)bicyclo[5.1.0]octane-2- carboxylic acid (3). The absolute configuration was determined crystallographically to be (1S, 2R, 7R).