Volume 62, Issue 6

Black plate-like single crystals of BaFe 3.39(5) Ru 2.61(5) O11 and BaCo 1.85(6) Ru 4.15(6) O 11 were grown from a BaCl 2 flux [hexagonal, space group P6 3 /mmc (No. 194), Fe: a = 5.856(1), c = 13.587(1) Å , R1 = 0.029, wR2 = 0.084; Co: a = 5.842(1), c = 13.573(3) Å, R1 = 0.033, wR2 = 0.075]. The crystal structures contain two crystallographic sites with mixed Ru and Fe/Co occupation of different level in octahedral coordination and one site purely occupied by the respective 3d metal. The latter position is in trigonal bipyramidal coordination, with some indication for a displacement of the metal atom towards tetrahedral coordination. According to the charge balance, the ruthenium atoms are incorporated with different electronic situations in the two Ru containing sites. The Co compound may be described as containing Co 2+ and Ru 5+ next to Ru 3+ . Magnetic susceptibility data support this assignment. According to magnetization measurements on oriented crystals, BaCo 1.85(6) Ru 4.15(6) O 11 is a soft ferromagnetic material with low coercive field and a spontaneous magnetization below T c = 105 K. It behaves as an electric conductor. However, BaFe 3.39(5) Ru 2.61(5) O 11 is a narrow band semiconductor material with ferrimagnetic ordering at T c = 440 K

The cerium meta-oxoborate δ -Ce(BO 2 ) 3 was synthesized under high-pressure / high-temperature conditions of 3.5 GPa and 1050 ° C in a Walker-type multianvil apparatus. The crystal structure was determined by single crystal X-ray diffraction data, collected at r. t. The compound crystallizes monoclinicly in the space group P2 1 /c with the lattice parameters a = 422.52(8), b = 1169.7(2), c = 725.2(2) pm, and β = 91.33(3)°. The structure is isotypic to the recently published high-pressure phase δ -La(BO 2 ) 3 , consisting exclusively of corner sharing [BO 4 ] 5− tetrahedra

The compounds β -RE(BO 2 ) 3 [RE = Nd (neodymium meta-borate), Sm (samarium meta-borate) and Gd (gadolinium meta-borate)] were synthesized under high-pressure and high-temperature conditions in a Walker-type multianvil apparatus at 3.5 GPa (Nd), 7.5 GPa (Sm, Gd) and 1050 °C. The crystal structures were determined by single crystal X-ray diffraction data collected at r. t. (Sm, Gd) and at−73°C (Nd), respectively. The structures are isotypic with the already known ambient-pressure phases β -RE(BO 2 ) 3 (RE = (Tb, Dy) and the high-pressure phases β -RE(BO 2 ) 3 (RE = Ho-Lu)

New and quick methods to synthesize Ce(CrO 4 ) 2 · 2H 2 O and Ce(CrO 4 )2 ·H 2 O, giving high yields, are described. The methods are based on exchange reactions by refluxing in water or on solid state reactions. The first crystal structure containing a chromatosulfato ion is presented. K 2 CrSO 7 belongs to space group P2 1 /n with a = 7.4024(1), b = 7.3908(1), c = 12.9883(2) Å , β = 90.021(1)° and Z = 4. The CrSO 7 2− ion, consisting of one chromate group sharing one oxygen atom with one sulfate group, has a pseudo syn-C2v conformation with eclipsed oxygen atoms. K 2 CrSO 7 forms a three dimensional network of CrSO 7 2− ions held together by the charge balancing potassium ions, with the general structural features common with dichromate-like structures. The redetermination of the structures of (NH 4 ) 2 Cr 2 O 7 (space group C2/c, with hydrogen atoms located) and Na 2 Cr 2 O 7 ·2H 2 O (space group P2 1 , with hydrogen atoms located and the absolute structure established) are reported

Addition of anhydrous InCl 3 to a THF solution of CuCl and dppe (dppe = Ph 2 PCH 2 CH 2 PPh 2 ), or CuCl and PPh 3 , resulted in the formation of the crystalline heterometallic copper(I)/indium(III) complexes [(dppeCu) 2 (μ-Cl)(μ-dppe)][InCl 4 ]·THF (1·THF) and [{Cu(PPh 3 ) 2 } 2 (μ-Cl) 4 (InCl)]·THF (2·THF), respectively, which have been characterized by X-ray diffraction. Compound 1 is composed of a dinuclear copper(I) complex cation and a mononuclear tetrahedral indium(III) complex anion. Complex 2 comprises an indium center in a quasi square-pyramidal chloride-coordination environment connected to two Cu(PPh) 3 fragments via Cu(μ-Cl) 2 In bridges

Reaction of the doubly deprotonated pyridine 2,6-dicarboxamido ligand (1) with (PCy 3 ) 2 Cl 2 Ru=CHPh (3a) in THF gave a mixture of (lig)(PCy 3 )Ru=CHPh isomers (4). The pentane soluble N,N,O-4 isomer was isolated by extraction and characterized by X-ray diffraction. The O,N, O-4 isomer was identified in the residue. Single crystals of the closely related complex (lig)(NHC) Ru=CHPh, O,N,O-5, were obtained from the reaction of 1 with (NHC)(PCy 3 )Cl 2 Ru=CHPh (3b) and used for the X-ray crystal structure analysis of the system Keywords Chelate Ligand, Salt Metathesis, Ruthenium Carbene Complexes, Isomeric Coordination Compounds

Substitution reactions of the bis(benzylthio)acetylene complexes [Tp′Nb(BnSC 2 SBn)Cl 2 ] and [Tp′Mo(BnSC 2 SBn)(CO) 2 ](PF6) (Tp′ = hydro-tris(3,5-dimethyl)pyrazolylborate, Bn = benzyl) have been investigated. The coordination of the alkyne ligand turned out to be very stable, while one chloride ion in [Tp′Nb(BnSC 2 SBn)Cl 2 ], and either one or both of the CO ligands in [Tp′Mo(BnSC 2 SBn)(CO) 2 ](PF 6 ) can be substituted. The dissociative mechanism of the reactions with [Tp′Mo(BnSC 2 SBn)(CO) 2 ](PF 6 ) and [Tp′ Mo(BnSC 2 SBn)(CO)Cl] leads to the primary and exclusive reaction with the solvent. In the course of these studies the structures of [Tp′Nb(BnSC 2 SBn)Cl 2 ], [Tp′Mo(BnSC 2 SBn)(CO)(MeCN)](PF 6 ), [Tp′Mo(BnSC 2 SBn)(CO)Cl] and [Tp′Mo(BnSC 2 SBn)Cl 2 ][Tp′Mo(BnSC 2 SBn)ClF] have been determined by X-ray diffraction. Comparison of the closely related compounds allows conclusions how the number of d electrons and the character of the co-ligands influence the alkyne bonding

Reaction of [Cu 2 (H 3 CCN) 2 (μ-pydz) 3 ][PF 6 ] 2 (1) with an excess of pyridazine or phthalazine yielded the novel dinuclear complexes [Cu 2 (μ-pydz) 3 (pydz) 2 ][PF 6 ] 2 (2) and [Cu 2 (μ- pydz)(μ-phtz) 2 (phtz) 2 ][PF 6 ] 2 (5), respectively. Depolymerisation of the coordination polymer 1 ∞ {[Cu(μ-pydz) 2 ][PF 6 ]} (3) in dichloromethane by addition of an excess of benzo[c]cinnoline afforded the dinuclear copper(I) salt [Cu 2 (μ-pydz) 2 (pydz) 2 (benzo[c]cinnoline) 2 ][PF 6 ] 2 (4). Furthermore, a new route for the preparation of bis(benzonitrile)tris(μ-phthalazine)dicopper(I) bis(trifluoromethanesulfonate), [Cu 2 (C 6 H 5 CN) 2 (μ-phtz) 3 ][CF 3 SO 3 ] 2 (7), was established from {[Cu(CF 3 SO 3 )] 2 ・C 6 H 5 Me}, phthalazine and benzonitrile via the very air-sensitive intermediate [Cu 2 (CF 3 SO 3 ) 2 (μ-phtz) 3 ] (6). Copper(I) compounds 2, 4, and 7 were completely characterised and the molecular structures confirmed in the solid state by single-crystal X-ray structure determination. The analysis of the packing of the molecules in crystals of 4 and 7 revealed a self-assembly of oneand three-dimensional frameworks, respectively, resulting from intermolecular π-π stacking interactions between pyridazine-type ligands

Condensation of salicylaldehyde with enantiopure (R)-(1-aryl-ethyl)amines yields the enantiopure Schiff bases (R)-N-(1-aryl-ethyl)salicylaldimine (HSB*; aryl = phenyl, 2-methoxyphenyl, 3- methoxyphenyl, 4-methoxyphenyl (4), 4-bromophenyl (5), 2-naphthyl). These Schiff bases readily react with dinuclear (acetato)(η4-cycloocta-1,5-diene)rhodium(I), [Rh(μ-O 2 CMe)(η 4 -cod)] 2 , to afford the mononuclear complexes, cyclooctadiene-((R)-N-(1-aryl-ethyl)salicylaldiminato-κ 2 N,O)- rhodium(I), [Rh(SB ∗ )(η 4 -cod)] (SB* = deprotonated chiral Schiff base = salicylaldiminate; aryl = phenyl (7), 2-methoxyphenyl, 4-methoxyphenyl, 4-bromophenyl, 2-naphthyl). The complexes have been characterized by IR, UV/vis, 1 H/ 13 C NMR and mass spectrometry, optical rotation as well as by single-crystal X-ray structure determination for 4, 5 and 7. The structure of 5 shows C-Br· · ·π contacts. Compound 7 is only the second example of a Rh(η 4 -cod) complex with a six-membered Rh-N,O-chelate ring

The mer-bis(2-aminothiazole)diaqua-orotato-nickel(II) complex, mer-[Ni(HOr)(H 2 O) 2 (ata) 2 ] (1), was synthesized and characterized by spectral (IR and UV/vis) and thermal studies. In addition, the crystal structure of the complex was determined by single crystal X-ray diffraction. The complex crystallizes in the triclinic system, space group P1̅. The orotate ligand is coordinated to the nickel(II) atom through a nitrogen atom of the pyrimidine ring and an oxygen atom of the carboxylate group as a bidentate dianion. The coordination of the Ni(II) ion is extended to six by the two 2-aminothiazoles (ata) and two water molecules. The thermal decomposition has been studied in a static air atmosphere

New salts of 2-hydroxyaniline and 2-amino-3-hydroxypyridine with squaric acid were synthesized and characterized by elemental analyses, IR spectroscopy and thermal analyses (TG, DTG and DTA). The crystal structures of bis(2-hydroxyanilinium) squarate, [(C 6 H 8 NO + ) 2 (C 4 O 4 ) 2− ] (1) and bis(2- amino-3-hydroxy-pyridinium) squarate dihydrate, [(C 5 H 7 N 2 O + ) 2 (C 4 O 4 ) 2− ] · 2 H 2 O (2) were determined by single crystal X-ray diffraction. Both compounds crystallize in the monoclinic system, space group P2 1 /c. The organic ammonium squarates decompose in two thermal steps

A one-pot synthesis of sterically congested N-vinyl imides in fairly high yields by the reaction of ethyl 3-phenyl-2-propynoate, imides and triphenylphosphine is reported. The structures of these compounds were confirmed by IR, 1 H, and 13 C NMR spectroscopy, and by a single crystal X-ray structure determination. The structural analysis of the products indicated that the reaction is regioand stereoselective

Reaction of 2-aminobenzoic acid with (N-isocyanimino)triphenylphosphorane proceeds smoothly at r. t. to afford 2-(1,3,4-oxadiazol-2-yl)aniline in high yield. The structure of this compound was confirmed by IR, 1 H, and 13 C NMR spectroscopy, mass spectrometry, and single crystal X-ray structure determination. The X-ray structural analysis of the product indicated that its aromatic rings are approximately co-planar

Mercury(II)-induced dehydrogenation of α-(2-phenylpiperidin-1-yl)-acetophenone oximes 7 gives rise to two different iminium compounds which subsequently react with the neighbouring oxime group. With the mercury(II)-EDTA reagent, (E)-7 forms the cyclic nitrones 9 and 11a, b, whereas (Z)-7 is transformed into oxadiazines 12 and 13a, b. The pairs of diastereomers 11a, b and 13a, b result from the equilibrium involving an iminium oximate species. The introduction of electron donor or acceptor groups into the phenyl substituent in (E)-15 and (E)-16 does not influence significantly the direction of dehydrogenation. With mercury(II) acetate in dilute acetic acid no specifity of the oxime configuration is observed, and the nitrones and oxadiazines are produced together. This may be explained by a reaction with the acetate ion at the iminium oxime stage. NMR experiments in CDCl 3 have shown that treatment of nitrone 2 and oxadiazine 3 with CF 3 COOD causes ring cleavage by prototropy and after longer reaction times generates the same imidazole 23

A new phenolic glycoside, 2,6-dimethoxy-4-(3-hydroxy-propen-1-yl)phenyl-4-O-α-L-rhamnopyranosyl-( 1 → 6)-β -D-glucopyranoside (1) and a new D-ribono-γ -lactone derivative, 3-O-β -D-glucopyranosyl- 2-hydroxymethyl-D-ribono-γ -lactone (3), together with thirteen known compounds have been isolated from the roots and rhizomes of Clematis hexapetala Pall. The characterization of these compounds was achieved by various chromatographic and spectroscopic methods

A new mexicanolide and a new phragmalin, named 30α-hydroxyl xylogranatin A and xylogranatin E 2 , respectively, have been isolated from the seeds of a Chinese mangrove Xylocarpus granatum. Their structures were identified on the basis of spectroscopic data. Each of them has a 3-O-β -tigloyl group. The first complete assignments of 1 H and 13 C NMR data for these limonoids were achieved by means of 2D NMR techniques, including 1 H- 1 H COSY, HSQC, HMBC and NOESY spectra

The new triterpenoidal and flavonone glycosides atriplisides A and B have been isolated from the ethyl acetate fraction of the whole plant of Perovskia atriplicifolia. Their structures were elucidated on the basis of spectroscopic data, especially 2D NMR techniques including 1 H-COSY, HMQC, HMBC, and NOESY

1-Butyl-2,3-dimethylimidazolium bromide {(bdmim)Br} (1) and iodide {(bdmim)I} (2) were prepared conveniently by the reaction of 1,2-dimethylimidazole and the corresponding 1-halobutane. The compounds were characterized by 1 H and 13 C{ 1 H} NMR spectroscopy as well as by X-ray single crystal crystallography. 1 crystallizes in the monoclinic crystal system, space group P2 1 /n, with Z = 4, and unit cell dimensions a = 8.588(2), b = 11.789(1), c = 10.737(2) Å, β = 91.62(3) ° . Compound 2 crystallizes in the monoclinic crystal system, space group P21/c, with Z = 8, and unit cell dimensions a = 10.821(2), b = 14.221(3), c = 15.079(2) Å , β = 90.01(3)°. The lattices of the salts are built up of 1-butyl-2,3- dimethylimidazolium cations and halide anions. The cations of 1 form a double layer with the imidazolium rings stacked together due to π interactions. The Br − anions lie approximately in the plane of the imidazolium ring, and the closest interionic Br···H contacts span a range of 2.733(1) - 2.903(1) Å. Compound 2 shows no π stacking interactions. The closest interionic I···H contacts are 2.914(1) - 3.196(1) Å

The crystal structure of trimethyl(4-iodophenyl)ammonium iodide (2), obtained from 4-iodo-N,N-dimethylaniline and methyl iodide, reveals the presence of weak hypervalent bonding of the iodine atom