Volume 57, Issue 12

By crystallisation from a strongly acidic aqueous solution calciumtetrahydrogen-hexaoxo-diperiodatetetrahydrate CaH 4 I 2 O 10 ∙ 4 H2O has been obtained. In the structure of this compound (S.G. C2/c, Nr. 15), Z = 4, a = 1986,6(4), b = 564,2(1), c = 1149,4(20) pm, β = 120,62(3)°) centrosymmetric H 4 I 2 O 10 2− anions in the form of edge-sharing octahedra form layers via hydrogen bonds originating from the acidic, trans-configurated OH groups of the anions. IR and Raman spectra are analysed with respect to the hydrogen bond system and the internal vibrations of the periodate anion. The dehydration of the compound takes place via Ca(IO 4 ) 2 ∙ 5 H 2 O and Ca(IO 4 ) 2 ∙2H 2 O leading at 143°C to the anhydrous metaperiodate Ca(IO 4 ) 2 which decomposes above 248°C to Ca(IO 3 ) 2 .

The ternary silicides Mg 5 Pd 10 Si 16 and Mg 5 Pt 10 Si 16 have been prepared by reaction of magnesium with the binary platinum-metal silicides in sealed tantalum containers (Pt-compound: 1200°C, 3 d, up 20 °/h, down 5 °/h; Pd-compound: 1000°C, 2 d, up and down 50 °/h). In the case of the Pd-compound contact with the tantalum had to be avoided by using a boron nitride crucible. The isotypic compounds crystallize in the cubic space group F4̄3m with 4 formula units per unit cell. The crystal structures were determined from single crystal data, lattice constants from Guinier patterns. The following data were obtained: a = 1258.81(8) pm for Mg 5 Pd 10 Si 16 and a = 1256.94(9) pm for Mg 5 Pt 10 Si 16 . Short distances in the three-dimensional platinum-metal silicon network indicate strong, covalent Pd(Pt)-Si-bonding (d(Pd-Si) = 240.2 to 256.1 pm; d(Pt-Si) = 237.1 to 258.5 pm). In addition, homonuclear bonding seems to be important, resulting in the formation of Si 4 -tetrahedra (d(Si-Si) = 250.4 pm (Mg 5 Pd 10 Si 16 ) and 255 pm (Mg 5 Pt 10 Si 16 )), empty Si 12- polyhedra with the shape of truncated tetrahedra (d(Si- Si): 234.5 and 248.2 pm (Mg 5 Pd 10 Si 16 ); 236 and 248.2 pm (Mg 5 Pt 10 Si 16 )), and Mg-centered Pd(Pt)10-clusters with the shape of adamantane (d(Pd-Pd) = 282.3 pm; d(Pt-Pt) = 284.5 pm). Furthermore, Mg 4 -tetrahedra with Mg-Mg-distances of 360 pm are formed. The structure may be described by an expanded cubic “close” packing of MgPd(Pt) 10 -units in which the Si 4 -tetrahedra occupy the octahedral holes while the Si 12 -polyhedra and the Mg 4 -tetrahedra reside in one half of the tetrahedral holes each.

The ternary indides Zr 5 Rh 2 In 4 and Hf 5 Rh 2 In 2 were synthesized by high-frequency melting of the elements in glassy carbon crucibles in a water-cooled sample chamber. Both compounds have been investigated by X-ray diffraction on powders and single crystals: Lu 5 Ni 2 In 4 type, Pbam, a = 1739.8(2), b = 758.3(1), c = 337.42(5) pm, wR2 = 0.0420, 1015 F 2 values for Zr 5 Rh 2 In 4 , and a = 1732.1(3), b = 757.5(2), c = 333.36(7) pm, wR2 = 0.0534, 739 F 2 values for Hf 5 Rh 2 In 4 with 36 variables per refinement. The structures contain three crystallographically different zirconium(hafnium) siteswith coordination numbers 12, 14, and 16. Striking structural motifs are distorted rhodium-centered trigonal prisms formed by the zirconium(hafnium) atoms and CuAu related distorted cubes of zirconium (hafnium) and indium atoms. The shortest interatomic distances occur for Zr-Rh and Hf-Rh followed by Rh-In. Chemical bonding in these intermetallics is briefly discussed.

A new ternary intermetallic has been obtained in the Ce-Ni-As system, the composition of which is CeNi 1.91 As 1.94 from X-ray single crystal structure determination. The structure is derived from the CaBe 2 Ge 2 type with the following relations between the vectors a, b, and c of the cell and a 0 , b 0 , and c 0 of the subcell: a = 2a 0 - 2b 0 ; b = 2a 0 + 2b 0 and c = 2c 0 (V = 16 V 0 ). The structure takes its origin from compositional and displacive mechanisms. The major structural modifications occur in the nickel-arsenic layers (two per cell) where the nickel atoms are in “square” pyramidal As sites. Moreover, the slight atomic displacements in these layers that develop in the ab plane, lead to As 8 clusters, each formed by a central part As 4 linked by four apical As ligands. These clusters constrain arsenic to adopt a valence state higher than -3 which in turn involves the lowering of the counterbalancing charge from the nickel substructure. The structure of CeNi 1.91 As 1.94 is compared in details with that of the previously reported URh 1.6 As 1.9 .

Single crystals of the intercalation compounds Ge 1/3 NbS 2 andGe 1/4 NbS 2 have been prepared by heating of the elements at 1073 K and by chemical transport with iodine at 923 to 1073 K. Their crystal structures were determined by single crystal X-ray methods.Ge 1/3 NbS 2 (P6 3 /mcm, a=5.767(1), c=13.518(3) Å, Z = 6) crystallizes with a superstructureof 2H-NbS 2 , characterized by layers of edge-sharing NbS 6 trigonal prisms. The Ge atoms in the octahedral voids of the van der Waals gap are sixfold coordinated by sulfur. The NbS2-sublattice of Ge 1/4 NbS 2 (P6 3 /mmc, a = 3.339(1), c = 37.326(7) Å , Z = 6) represents a new 6H-polymorph. Herein, the Ge atoms are located either in the centers of the octahedral voids (c. n. = 6) or shifted from this position along [001] (c. n. = 3 + 3). The unusual electronic state and the bonding situation of germanium in the van der Waal gaps of NbS 2 and the metal-metal bonding are studied in detail by using DFT band structure calculations.

From a solution of Ni(CH 3 COO) 2 ∙ 4 H 2 O and acetylenedicarboxylic acid in deionized water single crystals of Ni(C 2 (COO) 2 )(H 2 O) 4 ∙ 2 H 2 O(P2 1 /a, Z = 2, isotypic to Co(C 2 (COO) 2 )(H 2 O) 4 ∙ 2 H 2 O) were obtained by slow evaporation of the solvent. In the solid state structure nickel is octahedrally surrounded by four water molecules and two oxygen atoms of the carboxylate anions. These octahedra are connected to chains by the dicarboxylates. Heating the hexahydrate to 100 °C in a stream of argon leads to Ni(C 2 (COO) 2 )(H 2 O) 2 (C2/c, Z = 4, isotypic to Mn[C 2 (COO) 2 ] ∙ 2 H 2 O). Here, the NiO 6 octahedron is built by two water molecules and four oxygen atoms of the dicarboxylate ligands, which connect the Ni octahedra to a three-dimensional network. Thermoanalytical investigations show another mass loss at about 200 °C, which leads to non-crystalline products. Finally, at about 400 °C NiO is formed. Measurements of the magnetic susceptibilities result in the expected behaviour for Ni 2+ in an octahedral co-ordination ( 3 A 2 ground state). The effective magnetic moment at room temperature is μ eff = 3.20 μ B .

The reactions of potassium polysulfides with elemental Nb were investigated with different analytical techniques. The amount of the polysulfide applied has no influence onto product formation, i. e. the ratio K 2 S x : Nb is not important. The length of the polsysulfide chain, i. e. the value of x in K 2 S x determines what product is formed. In sulfur-poor melts, K 3 NbS 4 is observed. Increasing x to 5 - 6, K 4 Nb 2 S 11 is formed with a structure containing S 2 2− anions. Finally, applying a melt with x > 6, K6Nb4S25 is found as the product with a crystal structure containing the S 5 2− polysulfide anion. When K 2 S x (x < 5) is heated with sulfur in the first step the pentasulfide K 2 S 5 is formed. Immediately after melting of K 2 S 5 a reaction with elemental Nb occurs. The results of FT-IR and X-ray investigations have demonstrated that after oxidation the anion [Nb 2 S 11 ] 4− is formed relatively fast, and after a short time crystalline K 4 Nb 2 S 11 can be detected. After 24 h the reaction is complete.

Thiotrithiazyl iododichloride, S 4 N 3 ICl 2 , has been synthesized from molecular S 4 N 4 and liquid ICl and structurally characterized by an X-ray Rietveld refinement. S 4 N 3 ICl 2 crystallizes in the monoclinic system (P2 1 /c, a = 611.548(7), b = 877.336(8), c = 1770.12(2) pm, β = 92.3357(7)°, Z = 4), follows the crystal-chemical motif (S 4 N 3 + )(ClICl − ), and is thus isotypic with (S 4 N 3 + )(Br 3 − ). The crystal structure contains a planar S 4 N 3 + ring and a linear ClICl − unit.

The reaction of rhodium(III) chloride trihydrate with 1,3-diaminopropane and 1,4-diaminobutane in concentrated hydrobromic acid results in the formation of the bis(α,ω-diammonioalkane) diaquahydrogen(1+) hexabromorhodate(III) dibromides [H 3 N(CH 2 ) x NH 3 ] 2 [H 5 O 2 ][RhBr 6 ]Br 2 (x = 3, 4). Dark red single crystals were obtained by diffusion-controlled crystallization at room temperature. Both compounds crystallize in space group type P1̄ and their structures are closely related. In view of crystal engineering they are inorganic-organic hybrid materials built up from octahedral [RhBr 6 ] 3− , simple Br − and flexible chain-like [H 3 N(CH 2 ) x NH 3 ] 2+ ions with the [H 5 O 2 ] + and further Br − ions incorporated and thus might be considered as addition compounds [H 3 N(CH 2 ) x NH 3 ] 2 [RhBr 6 ]Br ∙ [H 5 O 2 ]Br. Cationic and anionic moieties in the crystal are held together by a complex system of N-H∙∙∙Br and O-H∙∙∙Br hydrogen bonds. Geometric features of O-H∙∙∙Br hydrogen bonding as well as the pronounced disorder of the [H 5 O 2 ] + ions in the diammoniopropane salt indicate the weak association of these species in the solids. Weak association of the ions is also documented by difference ATR-FT-IR spectra of the compounds and related diammonioalkane dibromides that show the stretching modes of the terminal O-H bonds above 3300 cm −1 . Further characteristic bands are recognized at ca. 1635 (s), 985 (vs), and 670 (m) cm −1 .

The ortho-lithiation of benzene-1,2-dithiol with three equivalents of nBuLi afforded monoas well as di-C-lithiated intermediates. The surprising kinetically controlled formation of di- C-lithiated species offers the opportunity to obtain dimercaptobenzoic and -terephthalic acid derivatives in a onepot synthesis in reasonable yields. Both compounds are versatile building blocks for the synthesis of macrocycles containing arylenedithiol units. Focusing on novel terephthalic acid derivatives, two preparation routes, via amide and via alkyl linkage, respectively, have been elaborated. The reaction sequence (i) sulfur protection using either isopropyl or benzyl groups, (ii) transformation of the carboxylic function into an amide or an alkyl group and (iii) subsequent removal of the protection groups afforded the terephthaldiamidedithiol 6 and the 1,2-bis(2,3-dimercaptophenyl)ethane 11.

The title compound was prepared from elements by sintering in the temperature region between 1073 and 1473 K. The monoclinic structure of La 7 Pd 17 P 12 was solved and refined from X-ray single crystal data: space group C2/m, a = 24.519(1), b = 4.0859(5), c = 13.6106(8)Å , β = 112.129(3)°, Z = 2, R F = 0.025 for 1065 unique of 4877 measured reflections and 112 refined parameters. Main structural motif of the new phosphide are condensed blocks of trigonal prisms around phosphorus atoms connected to infinite chains via lanthanum atoms. The structural features of La 7 Pd 17 P 12 are discussed in comparison with some representatives of a large family of structures with metal / non-metal ratio close to 2 : 1.

Violet single crystals of NdClSeO 3 (Pnma, Z = 8, a = 1115.3(2), b = 535.19(6), c = 1356.8(1) pm, R all = 0.0281) were obtained from the reaction of Nd 2 O 3 , NdCl 3 , and SeO 2 in evacuated silica ampoules. The analogous procedure using Er 2 O 3 and ErCl 3 led to pink single crystals of ErClSeO 3 (Pnma, Z = 4, a = 721.8(1), b = 692.2(1), c = 874.3(2) pm, R all = 0.0305). The crystal structure of NdClSeO 3 contains two crystallographically different neodymium ions. Nd(2) 3+ is coordinated by four oxygen atoms and four chloride ions while eight oxygen atoms and one Cl − ion are connected to Nd(1) 3+ . The linkage of the polyhedra leads to a three-dimensional structure. In the structure of ErClSeO 3 the Er 3+ ion is coordinated by two Cl − ions, three O-monodentate SeO 3 2− and one O,O-chelating SeO 3 2− groups. The [ErO 5 Cl 2 ] polyhedra can be seen as pentagonal bipyramids, which are connected in the [010] direction via opposite edges of oxygen atoms to infinite chains. These are further linked via chloride ions to give a three-dimensional network. In both crystal structures a prominent stereochemical activity of the lone electron pairs of the selenite ions can be observed.

The dehydration of Ca(SCN) 2 ∙4H 2 O yields single crystals of Ca(SCN) 2 ∙ 2 H 2 O as well as of Ca(SCN) 2 . Ca(SCN) 2 ∙ 2 H 2 O crystallizes with a hitherto unknown structure (orthorhombic, Pnma, Z = 4, a = 1280.1(2), b = 790.3(1), c = 726.9(1) pm, R all = 0.0430). The Ca 2+ ions are surrounded by four SCN − ions and four water molecules. The polyhedra are connected to chains along [010] via common oxygen atoms. The SCN − ions connect these chains to a three-dimensional network so that each thiocyanate group is linked to two Ca 2+ ions. Hydrogen bonding with sulfur atoms as acceptors is observed. The crystal structure of Ca(SCN) 2 (monoclinic, C2/c, Z = 4, a = 961.7(2), b = 642.4(2), c = 787.2(2) pm, R all = 0.0673) consists of alternating layers of Ca 2+ and SCN − ions. The cations are surrounded by four sulfur and four nitrogen atoms in form of a square antiprism. According to 3 ∞ [Ca(SCN) 8/4 ] each SCN − ion connects four Ca 2+ ions with each other. Thermal investigations show a phase transition of Ca(SCN) 2 ∙ 4 H 2 O followed by dehydration to Ca(SCN) 2 which finally decomposes yielding CaS. IR and Raman measurements have been performed and the resulting frequencies assigned and discussed.

The sulfide derivatized oxodisilicates M 4 S 3 [Si 2 O 7 ] of the heavy lanthanides (M = Gd - Tm) have been synthesized by reaction of M, M 2 O 3 , S, and SiO 2 using MCl 3 as flux in evacuated silica tubes at 850 °C for 7 d. The title compounds crystallize tetragonally in the space group I4 1 /amd with 8 formula units per unit cell. Their crystal structure contains isolated [Si 2 O 7 ] 6− pyroanions of two vertex-sharing [SiO 4 ] tetrahedra in eclipsed conformation with Si-O-Si bridging angles of about 130°. The two crystallographically independent lanthanide cations (M 3+ ) both reside in tricapped trigonal prismatic environments of chalcogen ligands. In the case of M1 five S 2− and three plus one O 2− anions (CN = 8+1), for M2 three S 2− and six O 2− anions (CN = 9) fill the coordination spheres. Two of the three different sulfide anions are surrounded by four M 3+ cations forming a seesaw (S2) and a square (S3), respectively. The third one (S1) is coordinated by six lanthanide cations in the form of a distorted octahedron. The whole structure is basically built up of cationic lanthanide silicate layers which are threaded by sulfide anions.

The new compounds Li 2 CsBS 3 and Cs 3 BS 3 were prepared from the metal sulfide(s), amorphous boron and sulfur in solid state reactions at high temperatures. The crystal structures were determined by single crystal X-ray diffraction experiments. The purity of the products was proved by powder diffraction. Li 2 CsBS 3 crystallizes in the orthorhombic space group Pnma (no. 62) with a = 10.004(2), b = 8.000(2), c = 8.082(2) Å , and Z = 4, while Cs 3 BS 3 is isotypic to Rb 3 BS 3 in the monoclinic space group P2 1 /c (no. 14) with a = 10.397(1), b = 6.660(1), c = 13.618(1) Å , β = 101.31(1) °, and Z = 4. Both compounds contain isolated [BS 3 ] 3− anions with boron in a trigonal-planar coordination.

Both title compounds were found to crystallize from the system ScCl 3 / K 2 CO 3 / H 2 O and their crystal structures have been determined: K 5 [Sc(CO 3 ) 4 ] ∙ 5 H 2 O is monoclinic, space group P2 1 /n with a = 883,06(13), b = 1826,2(2), c = 1113,2(2) pm, β = 93,28(2)°, V = 1792,3(4) ∙ 10 6 pm 3 , Z = 4), while K 7 [Sc(CO 3 ) 4 ]CO 3 ∙ 9 H 2 O is monoclinic, space group C2 with a = 1395,98(13), b = 1081,35(7), c = 3378,1(4) pm, β = 93,76(1)°, V EZ = 5088,4(8) ∙ 10 6 pm 3 , Z = 8). Both compounds contain discrete [Sc(CO 3 ) 4 ] anions.

Na 6 [Al 6 (Gal 1 ,6A 2 1,2,5,6H −4 )4(OH) 8 ] ∙ 21 H 2 O (1) crystallizes from alkaline aqueous solutions of galactaric acid (Gal1,6A 2 ) and aluminium nitrate. Crystal structure analysis (P1̄, a = 9.09950(10), b = 15.1996(2), c = 21.9667(3) Å , α = 96.6190(5), β = 90.5307(4), γ = 103.5658(5)°, V = 2931.66(6) Å 3 , Z = 2) and solid state 27 Al NMR spectroscopy reveal rings of six edge-sharing AlO 6 octahedra, the O-atoms stemming from four galactarato and eight hydroxo ligands. The potassium homologue K 6 [Al 6 (Gal 1 ,6A 2 1,2,5,6H −4 ) 4 (OH) 8 ] ∙ 23 H 2 O (2) is not isotypic (P2 1 /c, a = 9.7604(6), b = 22.0843(17), c = 30.1534(17) Å , β = 95.970(7)°, V = 6464.4(7) Å 3 , Z = 4), but the anion structure is the same. Pure polyolato coordination of entirely deprotonated galactarate has been found in Na 4 [Cu(Gal 1 ,6A 2 H −6 )]] ∙ 12 H 2 O (3). In 3, a coordination polymer is formed by the copper atoms and the erythro-bis-diolate ligand (P1̄, a = 5.9711(2), b = 9.5319(3), c = 9.7794(3) Å , α = 99.883(2), β = 100.807(2), γ = 105.9182(11)°, V = 510.90(3) Å 3 , Z = 1).

The synthesis of the Mannich base N,N’-bis(antipyryl-4-methyl)-piperazine (BAMP) (1), its crystal structure as well as the synthesis and the crystal structure of the copper complex Cu(BAMP)(ClO 4 ) 2 (2) are reported. C 28 H 34 N 6 O 2 ∙ 4H 2 O (BAMP ∙ 4H 2 O) crystallizes with triclinic symmetry, space group P1̄, lattice parameters: a = 704,9(2), b = 983,4(2), c = 1198,9(3) pm, α = 68,72°, β = 73,62°, γ = 78,49°. The copper-complex Cu(BAMP)(ClO 4 ) 2 crystallizes with tetragonal symmetry, space group P4 2 /n, lattice parameters: a = 2295,1(3), c = 1412,2(2) pm. The copper(II) atom is five-coordinate by the two nitrogen atoms belonging to the piperazine ring and the oxygen atoms of the antipyrinemoieties. The geometry of the copper(II) atom can be described as a square-based pyramid with the N 2 O 2 donor atoms of BAMP forming the basal plane and an oxygen atom of the neighbouring complex molecule occupying the apical position. BAMP acts as a tetradentate ligand, which incorporates a piperazine-fused ring. The structural parameters illustrate well the reinforcing effect exerted by the double “straps” of the piperazine molecule.

Na 5 [CoO 2 ]CO 3 was prepared via the azide/nitrate route. Stoichiometric mixtures of the precursors (Co 3 O 4 , NaN 3 , NaNO 3 and Na 2 CO 3 ) were heated in a special regime up to 500 °C and annealed at this temperature for 50 h in silver crucibles. Single crystals have been grown by subsequent annealing of the powder at 500 °C for 2000 h in silver crucibles, which were sealed in glass ampoules under dry Ar. According to the X-ray analysis of the crystal structure (P4/mmm, Z = 1, a = 4.6467(4), c = 8.2577(6) Å ). Na 5 [CoO 2 ]CO 3 is isostructural with Na 5 [NiO 2 ]CO 3 and contains Co 1+ , which is coordinated by two oxygen atoms forming a dumb-bell. Na 5 CoCO 5 decomposes at 600 °C to Na 3 CoO 2 and Na 2 CO 3 .