Volume 51, Issue 4

The title systems have been investigated on samples quenched at 700, 800 and 1000 °C. Five new compounds have been obtained and characterized by X-ray powder diffraction: Spinel type MgGa 0.2 Cr 1.8 S 4 , two compounds crystallizing in the olivine structure, MgGaCrS 4 and MgGaInS 4 , and two layered materials, MgGa 1.5 Cr 0.5 S 4 and MgGa 1.5 In 0.5 S 4 . Lattice para­ meters and phase widths of the compounds are given.

New compounds of the composition BaPdLn 2 O 5 (Ln = Eu, Gd, Dy, Ho) have been prepared by crystallization from flux. They crystallize isotypic to BaPtLn 2 O 5 , space group D 5 4h -P4/ mbm. Eu: a = 6.6359(6), c = 5.885(3) Å ; Gd: a = 6.608(3), c = 5.873(3) Å ; Dy: a = 6.5431(7), c = 5.8574(8) Å ; Ho: a = 6.522(4), c = 5.855(5) A , Z = 2. The crystal structure is characterized by isolated planar PdO 4 polygons incorporated into a framework of edge-and corner-sharing doubly capped BaO 8 cubes and edge-and face-sharing LnO 6 prisms.

Single crystals of BaCuTeO 3 TeO 4 have been prepared by crystallisation from melts. X-ray investigations lead to orthorhombic symmetry, space group C 16 2v -Ama2, a = 5.4869(8), b = 15.412(1), c = 7.2066(4) Å , Z = 4. This compound represents a new structure type, containing BaO 10 , CuO 5 , TeO 6 and TeO 4 polyhedra. The lone pair (E) of Te IV completes the Te IV O 4 polyhedron to a trigonal TeO 4 E bipyramid. The Te to E distance is estimated by calculations of the Coulomb terms of lattice energy to 1.43 Å .

Single crystals of Zn 2.28 Mg 0.72 (AsO 4 ) 2 have been prepared by CO 2 LASER techniques. The compound crystallizes with monoclinic symmetry space group C 5 2h -P2 1 /n and the lattice parameters a = 5.292(2), b = 8.450(3), c = 7.737(3) Å , β = 96.33(3)°, Z = 2. Zn 2.28 Mg 0.72 (AsO 4 ) 2 is isotypic to β-Zn 3 (AsO 4 ) 2 . The formation of the β-Zn 3 (AsO 4 ) 2 struc­ture instead of other possible orthoarsenates is discussed.

Single crystals of K Ca 10 V 7 O 28 have been prepared by crystallization from flux. The yellow-green crystals show rhombohedral symmetry (trigonal space group C 6 3V -R3c, a = 10.830(1), c = 37.860(1) Å , Z = 6). The differences of the crystal chemistry are discussed with respect to the isotypic compound Ca 3 (VO 4 ) 2 . K + replaces exclusively Ca 2+ ions at one deficient point position.

Single crystals of KBaVO 4 (I) and KSrVO 4 (II) have been prepared by crystallization from V 2 O 5 flux. The yellowish crystals show orthorhombic symmetry, space group D 16 2h -Pnma with (I): a = 7.774(2), b = 5.899(1), c = 10.375(2) Å , (II): a = 7.400(2), b = 5.812(1), c -9.961(1), Z = 4. Both compounds show an ordered distribution of K + and Ba 2+ and Sr 2+ respectively. The different sizes of the KO 10 and BaO 9 (SrO 9 ) polyhedra are discussed with respect to those of the β-K 2 SO4 structure, considering the calculations of the Coulomb terms of lattice energy.

Tantalum, Germanium, Cluster Bronze coloured, rod-shaped crystals of Ta 5 Ge 3 B y have been prepared by CO 2 -LASER-techniques. X-ray-methods confirm the well known hexagonal Mn 5 Si 3 type, space-group D 3 6h -P6 3 /mcm, a = 7.6276(6) and c = 5.2781(9) Å . The Ta 6 -clusters are centred by boron atoms.

Single crystals of Ag 0.4 Na 2.3 Ca 4.3 RuO 8 have been prepared by heating Na 2 O 2 , CaO and ruthenium in closed silver tubes. Silver took part in the reaction. The crystal structure was investigated by X-ray techniques. AgO 4 Na 2.3 Ca 4.3 RuO 8 crystallizes with orthorhombic symmetry, space group D 19 2h -Cmmm ; a = 9.255(1), b = 6.683(1), c = 6.696(3) Å , Z = 2. It shows relations to the sodium chloride structure. A statistical distribution of Ag + and Na + can be separated in micro space by splitting one oxygen position to give a dumb-bell like O-Ag-O and an octahedral NaO 6 coordination.

Single crystals of Ba 2 (VO)V 2 O 8 have been prepared by solid state reactions of Ba 2 V 2 O 7 , V 2 O 3 and V 2 O 5 in sealed silica tubes. This compound crystallizes with monoclinic symmetry, space group C 2 2 -P2 1 , a = 8.1174(9), b = 5.9699(9), c = 9.2903(9) Å , β = 113.94(1)°, Z = 2. V 5+ shows tetrahedral coordination. V 4+ inside 1 ∞ [V (3)O 4 ] chains is characterized by a square pyramidal coordination with a short apical V-O distance of 1.6 Å typically for vanadyl groups. Ba 2 (VO)V 2 O 8 represents a new structure type and is not isotypic to Sr 2 (VO)V 2 O 8 .

Single crystals of K 4 CdV 5 O 15 Cl have been prepared by crystallization from melts. The yellow crystals show tetragonal symmetry, space group C 1 4 -P4, a = 9.097(1), c = 5.331(2) Å, Z = 1. K 4 CdV 5 O 15 Cl belongs to the K 4 CuV 5 O 3 Cl type. V (l) forms V 2 O 7 double tetrahedra connected by square V(2)O 5 pyramids and CdO 4 Cl 2 octahedra. The crystal structure is dis­cussed with respect to the isotypic compound K 4 CuV 5 O 15 Cl considering a short V(2)-O distance indicative of a vanadinyl group.

The reaction of tert-butyltrichlorosilane with an excess of ammonia leads to the formation of a tetrasilabicyclo[3.3.1.]nonane, an NH-bridged cyclotetrasilazane. The crystal structure of the compound (Me 3 CSi) 4 Cl 2 (NH) 5 is described.

The 1-alkyne-1-thiolates R-C ≡C-SLi [1a: R = C(CH 3 ) 3 , 1b: R = C 6 H 11 ] react with L 2 PtCl 2 (L = PPh 3 , 1/2 dppe) and CpRu(PPh 3 ) 2 Cl, respectively to give the complexes trans-(Ph 3 P) 2 Pt[S-C ≡C-C(CH 3 ) 3 ] 2 (2a), cis-dppePt[S-C≡C-C(CH 3 ) 3 ] 2 (2b), and CpRu(PPh 3 ) 2 -(S-C ≡ C-R) [3a: R = C(CH 3 ) 3 , 3b: R = C 6 H 11 ]. 2a has been characterized by 31 P CP/MAS NM R spectroscopy and its crystal structure determined by X-ray diffraction.

TiCl 4 (THF) 2 reacts with two equivalents of sodium in THF to afford the soluble TiCl 2 (THF)n (1), which has been characterized analytically and by spectroscopic and magnetic measurements. By redox reactions. TiCl 2 (THF) n gives TiCl 2 (9,10-C 10 H 8 O 2 ) (2), or TiCl 2 (benzoate) 2 .(3), with 9,10-phenanthrenequinone or dibenzoylperoxide in toluene, respectively. By operating in 1,2-dimethoxyethane (DME), Na(DME) 1.5 [TiCl 4 (DME)] (4), or NaTiCl 3 (DME) 2 have been isolated from the reaction of TiCl 4 (DME) with one or two equivalents of sodium, respectively. From 4, by cation exchange, PPN[TiCl 4 (DME)] [PPN = bis(triphenylphosphine)iminium] (5), has been obtained and characterized analytically, spectroscopically and by X-ray diffraction methods. Crystal data: C 40 HCl 4 NO 2 P 2 Ti. MW = 818.4, space group: Pna2 1 (N° 33). a = 14.445(2), b = 15.690(2), c = 17.544(2) Å . V = 3976(2) Å 3 , Z = 4, F(000) = 1692, R = 0.041, Rw = 0.0420. The titanium(III) atom in the anion has the expected cis-octahedral, slightly distorted, geometry. By reaction of TiBr 4 (DME) 0.5 with sodium in DME, TiBr 3 (DME) 1.5 .1.5 DM E (7), is the product. Bis(mesitylene)vanadium(0), Vmes 2 , reacts with two equivalents of CPh 3 Cl in DME, to give VCl 2 (DME) n .

trans-(NH 4 ) 2 [Ru(SO 3 ) 2 (NH 3 ) 4 ]·4H 2 O(1) (monoclinic, P2 1 /n; a = 629.8(3), b = 1000.6(2), c = 1345.7(5) pm, β = 112.25(4)°, Z = 2; R = 0.021; Rw = 0.017) is obtained as pale greenish-yellow crystals by reaction of trans-[Ru(SO 3 H) 2 (NH 3 ) 4 ] (2) with aqueous ammonia, and crystallization at +5 °C. The compound, when isolated, is stable at room temperature for only a few days even under inert gas, but persists under the mother liquor. In the centrosymmetric anion trans-[Ru(SO 3 ) 2 (NH 3 ) 4 ]2 - the bonds Ru-S = 230.5(1) pm are significantly longer than in the neutral complex 2 (227.6(1) pm), whereas the Ru-N bonds are the same in both com­plexes within experimental error (averages 214.1 and 214.0 pm). Hence, the mutual trans-influence of the sulfite ligands is weakened on protonation; the bonding of the co-ligands in cis-position is not affected. The internal structure of the sulfite ligand in 1 with long S-O bonds (average 151.2(5) pm) and small angles O-S-O (average 106.1(6)°) and the weakened Ru-S bond are a good match. The structure of 1 is held together by a complex network of hydrogen bonds, in which all potential hydrogen-bond donors (OH 2 , NH 4 + , NH 3 ) and acceptors (H 2 O ,SO 3 ) are involved. The structural findings are reflected in the vibrational spectra.

Single phase Li 6 NBr 3 was prepared by the reaction of Li 3 N and dry, OH-free LiBr at 450°C. It is the most bromide rich compound in the quasi binary system Li 3-2x N 1-x Br x . The crystal structures of Li 6 NBr 3 and of isotypic Li 6 NI 3 , have been redetermined from neutron powder diffraction data. Both compounds crystallize in the cubic space group Fm3m (No. 225), a(Li 6 NBr 3 ) = 894.18(7), a(Li 6 NI 3 ) = 951.7(1) pm with 4 formula units per unit cell. The anion sublattice comprises a rock salt like arrangement of N with one of the three halogen atoms (Hal1), with the remaining halogen atoms in the resulting N 4 Hal 4 cubes. The structure may be regarded as an ordered AX 3 variation of a body-centered packing. The lithium atoms are disordered over the 96 (distorted) tetrahedral NX 3 holes in such a way that of the four neighbouring, face-sharing NBr 3 tetrahedra along an N-H all-connection line only one is occupied. The resulting Li coordination polyhedron around N (and Hal1) is a distorted octahedron with 6 equidistant Li atoms. Hal2 is surrounded by 12 Li atoms. The Li 6 NHal 3 structure may be regarded as an anti-form of the cryolite structure.

[DyCl 3 (DME) 2 ] (DME = 1,2-dimethoxyethane) has been prepared from the known tetrahy-drofuran complex [Dy 2 Cl 6 (THF) 7 ] in boiling DME. Both complexes were characterized by structure determinations. [DyCl 3 (DME) 2 ]: Space group P2 1 /c, Z = 4, lattice dimensions at -70 °C: a = 1141.9(6), b = 884.2(4), c = 1558.3(6) pm, β = 104.83(4)°. The complex has a molecular structure with a distorted pentagonal bipyramidal geometry in which the oxygen atoms of the chelating DME molecules and one chlorine atom occupy the pentagonal plane. [DyCl 2 (THF) 5 ] + [DyCl 4 (THF) 2 ] - : Space group C2/c, Z = 4, lattice dimensions at -70 °C: a -1241.4(9), b = 1139.4(6), c = 2735.1(19) pm, β = 91.19(4)°. The complex contains a seven-coordinate cation with axial chloride ligands in a pentagonal bipyramidal structure and a six-coordinate anion with a trans octahedral geometry.

Hydrate formation of haloacetic acids CCl n F 3-n COOH (n = 1, 2, 3) has been studied by DTA and temperature-dependent X-ray powder diffraction, and evidence obtained for five phases, all melting at temperatures below ambient. The hydrates have been confirmed and further characterized by their crystal structures at -150 °C. Three lower hydrates, CCl 2 FCOOH· 0.5H 2 O (space group P2 1 /c and Z = 8 formula unites per unit cell), CClF 2 COOHH 2 O (P2 1 /c, Z = 4), and CClF 2 COOH ·4H 2 O (P1̄, Z = 2), have molecular structures with the acid and water molecules hydrogen-bonded in two-dimensional arrays. The structures of the remaining hydrates, CCl 2 FCOOH·6H 2 O and CCl 3 COOH · 6H 2O (similar, but not isotypic, both P1̄ and Z = 2), are ionic, as (H 5 O 2 + )(CX 3 COO - ) · 4H 2 O , and three-dimensional. The neutral water molecules are hydrogen-bonded in ice-like layers rare in crystal chemistry. Also, CCl 2 FCOOH is established only as the second acid of which a lower hydrate is molecular and a higher one ionic.

By reaction of [B 6 H 6 ] 2- with dibromomethane in acetonitrile μ-Methylene-bis-hexahydro-closo-hexaborate, [B 6 H 6 (CH 2 )B 6 H 6 ] 2- , is formed which can be separated from excess [B 6 H 6 ] 2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of [As(C 6 H 5 ) 4 ] 2 [B 6 H 6 (C H 2 )B 6 H 6 ] · (CH 3 ) 2 CO has been determined by single crystal X-ray analysis: triclinic, space group P1 with a = 10.779(2), b = 10.8003(12) and c = 23.077(3) Å, a = 99.147(10), β = 91.569(13) and y = 91.288(11)°. The 11 B NMR spectrum reveals the features of a monosubstituted octahedral B 6 cage. The 13 C NMR spectrum exhibits a multiplet at -5.44 ppm. In the 1 H NM R spectrum a singlet of the methylene protons at 0.23 ppm and two singlets at 1.97 and -4.52 ppm of the BH fragments are observed. The IR and Raman spectra exhibit strong CH stretching bands between 2873 and 2762 cm -1 , BH stretching bands between 2443 and 2403 cm -1 , and a BC stretching vibration at 1138 cm -1 in the Raman spectrum.

By reaction of [B 6 H 6 ] 2- with a solution of (SCN) 2 in dichloromethane in the presence of solid KOH the hexaisothiocyanatodiborate anion [B 2 (NCS) 6 ] 2- is formed and can be isolated by fractionated crystallization. The crystal structure of (PNP) 2 [B 2 (NCS) 6 ] has been determined by single crystal X-ray diffraction analysis; triclinic space group P1̄ with a=12,282(5), b=12,416(5), c=14,155(5)Å, a=68,36(5), β=70,59(5), γ=80,93(5)°.The [B 2 (NCS) 6 ] 2- anion reveals a staggered conformation with nearly local D 3d symmetry and a B-B bond length of 1,73(2) Å. Using the crystallographic data a normal coordinate analysis has been performed. With a set of 12 force constants (e.g. f d (BB)=3,62, f d (BN)=4,21 mdyn/Å) a good agreement between observed and calculated frequencies for the 10 B and 11 B isotopomers has been achieved. The potential energy distribution on the force constants reveals strong vibrational couplings within the B 2 N 6 framework.

The reaction of Trifluoronitrosomethan with (CH 3 ) 2 NS(O) 2 NH 2 in THF and Na 2 CO 3 as

The reaction of trifluoroacetylacetone with salicylhydrazone gives acetone salicylhydra­ zone besides the expected trifluoroacetylacetone salicylhydrazone. The resulting mixture was analyzed by mass spectroscopy. The structure of acetone salicylhydrazone was determined by X-ray analysis. Crystal data: a = 12,8493(12) Å, b = 6,1084(8) Å, c = 12,757(3) Å; space group Pna2 1 ; Z = 4; R = 0,051 ; 750 unique reflexions.

Ring oxidized green Cerium(IV)diphthalocyanines, [Ce(Pc) 2 ]X (X = (poly)halide, NO 3 - ) are prepared by chemical oxidation of ( n Bu 4 N)[Ce(Pc 2- ) 2 ] with the corresponding halogen in solution or of solid [Ce(Pc 2- ) 2 ] with aqueous HNO 3 Electrochemical oxidation of (nBu 4 N)[Ce(Pc 2- ) 2 ] in solution in the presence of ( n Bu 4 N)BF 4 yields [Ce(Pc) 2 ](BF 4 ) 0.33 , which crystallizes in the tetragonal space group P4/nnc (a, b = 19.643(3) Å, c = 6.525(3) A, Z = 2). The Ce IV ion is eightfold coordinated by the isoindole N atoms (N iso ) of the two staggered (ca. 41°), slightly distorted Pc ligands. The “[Ce(Pc) 2 ] 0.33+ ” subunits are arranged in infinite columns along [001] with the Ce atoms statistically disordered over two positions and Ce - N iso bond lengths of 2.45(1) and 2.69(1) A, respectively The UV-VIS spectrum is dominated by the transitions of the Pc 2- ligand at ca. 15,000 (B band), 30,000 and 36,000 cm -1 (Q, N region). A low energy (“metallic”) band at ca. 2800 cm -1 typical for partially oxidized systems is present. The UV-VIS-NIR spectrum of [Ce(Pc) 2 ]NO 3 indicates a cofacial Pc 2- - P c - complex. In addition to the π-π’ transitions of the Pc 2- moiety at ca. 14,000, 30,000 and 36,000 cm -1 , the Ch transition of the Pc- ring is observed at ca. 19,200 cm -1 and the typical NIR band at 6380 cm -1 . Oxidation of a thin film of (PNP)[Ce(Pc 2- )2] with dry Br 2 / N 2 gas yields purple [Ce(Pc - ) 2 ]Br x , whose UV-VIS-NIR spectrum shows the diagnostic features of dimeric Pc - radicals with intense bands at ca. 14,000 and 18,000 cm -1 assigned as B and Q 1 bands, respectively. At ca. 9000 cm -1 the typical Q D absorption is observed. The vibrational spectra are dominated by the transitions of the Pc - ligand at 1305/1445 cm -1 (IR) and 560/1120/1172/1591 cm -1 (resonance Raman). Excitation with 1064 nm strongly enhances the sym. C e-N stretch at 163 c m -1 .

Palladium(II), Platinum(II), 2-Hydroxyiminocarboxylate, Oximes of Pyruvoyl a-Amino Acids The synthesis and spectroscopic properties of palladium(II) and platinum (II) chelate com­ plexes with carboxylates of 2-hydroxyiminopropionic, 2-hydroxyimino-3-phenylpropionic acids, with the amide and N-methylamide of 2-hydroxyiminopropionic acid, and with oximes of pyruvoylglycine and pyruvoyl-L-phenylalanine are reported.

Chelate complexes of 5-phenyl-isoxazole-3-carboxylate (L 1 ) and 5-phenyl-isoxazoline-3-carboxylate (L 2 ) ligands were prepared: Pd(L 1 ) 2 . Cp*(Cl)Ir(L 1 ), (p-cymene)(Cl)Ru(L 1 ), Pd(L 2 ) 2 , (Et 3 P)(Cl)Pd(L 2 ), , Cp*(I)Co(L 2 ), Cp*(Cl)Ir(L 2 ) (10), and (p-cymene)(Cl)Ru(L 2 ) (Cp* = C 5 Me 5 ). The structure of 10 was determined by X-ray diffraction.

From thirty three new optically active 1,5-benzodiazepine derivatives the UV and CD data are reported and the bands discussed related to corresponding electronic transitions respectively stereochemical features.

The crystal structure of {[N(CH 3 ) 4 + Cl] 2 }·CH 3 CN · H 2 O is reported. Crystalls are orthorhombic, space group Pnma, with a = 1622.9(15), b = 671.3(6), c = 1511.2(11) pm, V = 1646(2) 106 pm 3 and Z = 4.

The crystal structure of the title com pound has been determined by X-ray methods. Space group C2/c, Z = 4, lattice dimensions at -80 °C: a = 1343.8(2), b = 1031.6(1), c = 1669.4(1) pm, β = 96.47(1)°. The compound forms an ion pair in which the lithium atom is coordinated in a distorted tetrahedral geometry by two THF molecules and by two chlorine atoms. The halide atoms have a μ 2 -bridging function, coordinating the lithium and the titanium center. The titanium atom possesses a distorted octahedral environment with two THF ligands in trans-position.

The dark green compound CsNaTe has been prepared. The characterization by X-ray powder methods leads to a tetragonal lattice (P4/nmm) with a = 530.8 (4), c = 853.2 (1) pm and Z = 2. The structure ist related to the PbFCl structure type.

The optical absorption of the aurides M 3 AuO (M = K, Rb, Cs) and CsAu has been determ inated by UV/VIS spectroscopy. The band gaps have been found to be 2,35(2) eV (Cs 3 AuO) and 2,30(2) eV (CsAu). This corresponds to a more pronounced anionic character of gold in Cs 3 AuO as compared to CsAu. In the case of K 3 AuO and Rb 3 AuO no band gap was detectable.