(3 + 1)-dimensional crystal and antiferromagnetic structures in CeRuSn.

At 320 K, the crystal structure of CeRuSn is commensurate with the related CeCoAl-type of structure by the doubling of the c lattice parameter. However, with lowering the temperature it becomes incommensurate with x and z position parameters at all three elemental sites being modulated as one moves along the c-axis. The resulting crystal structure can be conveniently described within the superspace formalism in (3 + 1) dimensions. The modulation vector, after initially strong temperature dependence, approaches a value close to qnuc = (0 0 0.35). Below TN = 2.8 (1) K, CeRuSn orders antiferromagnetically with a propagation vector qmag = (0 0 0.175), i.e. with the magnetic unit cell doubled along the c-axis direction with respect to the incommensurate crystal structure. Ce moments appear to be nearly collinear, confined to the a-c plane, forming ferromagnetically coupled pairs. Their magnitudes are modulated between 0.11 and 0.95 µB as one moves along the c-axis.

Orthonitridoborate ions [BN3]6- in oxonitridosilicate cages: synthesis, crystal structure, and magnetic properties of Ba4Pr7[Si12N23O][BN3], Ba4Nd7[Si12N23O][BN3], and Ba4Sm7[Si12N23O][BN3].

The isotypic title compounds Ba4Pr7[Si12N23O][BN3], Ba4Nd7[Si12N23O][BN3], and Ba4Sm7[Si12N23O][BN3] were prepared by reaction of Pr, Nd, or Sm, with barium, BaCO3, Si(NH)2, and poly(boron amide imide) in nitrogen atmosphere in tungsten crucibles using a radiofrequency furnace at temperatures up to 1650 C. They were obtained as main products (approximately 70%) embedded in a very hard glass matrix in the form of intense dark green (Pr), orange-brown (Sm), or dark red (Nd) large single crystals, respectively. The stoichiometric composition of Ba4Sm7[Si12N23O][BN3] was verified by a quantitative elemental analysis. According to the single-crystal X-ray structure determinations (Ba4Ln7[Si12N23][BN3], Z= , P6 with Ln = Pr: a = 1225.7(1), c = 544.83(9) pm, R1 = 0.013, wR2 = 0.030; Ln = Nd: a = 1222.6(1), c = 544.6(1) pm, R1 = 0.017, wR2 = .039; Ln = Sm: a = 1215.97(5), c = 542.80(5) pm, R1 = 0.047, wR2 = 0.099) all three compounds are built up by a framework structure [Si12N23O]23- of corner-sharing SiX4 tetrahedrons (X = O, N). The oxygen atoms are randomly distributed over the X positions. The trigonal-planar orthonitridoborate ions [BN3]6- and also the Ln(3)3+ are situated in hexagonal cages of the framework (bond lengths Si-(N/O) 169-179 pm for Ln=Pr). The remaining Ba2+ and Ln3- ions are positioned in channels of the large-pored network. The trigonal-planar [BN3]6- ions have a B-N distance of 147.1(6) pm (for Ln = Pr). Temperature-dependent susceptibility measurements for Ba4Nd7[Si12N23O][BN3] revealed Curie-Weiss behavior above 60 K with an experimental magnetic moment of muexp = 3.36(5) microB/Nd. The deviation from Curie-Weiss behavior below 60 K may be attributed to crystal field splitting of the J = 9/2 ground state of the Nd3+ ions. No magnetic ordering is evident down to 4.2 K.

Virtual screening: an effective tool for lead structure discovery?

Different methods of virtual screening as a tool for lead structure discovery are described. They range from structure based docking procedures to ligand based methods such as the chemical features based pharmacophore hypothesis approach. A review on several successful applications of virtual screening is given. Different approaches have been described to derive pharmacophore models, which were subsequently used for 3D database searching. The studies so far published cover a wide range of pharmacological applications. The results hereby obtained clearly indicate that focused assessment of corporate databases by virtual screening using well validated pharmacophore models yield to a significant improvement in lead structure determination compared to high throughput screening.

Structure-based focusing using pharmacophores derived from the active site of 17beta-hydroxysteroid dehydrogenase.

Structure-based focusing constitutes a powerful approach to design libraries of compounds with a given biological profile. Computers with special software can be used to analyse the large amount of data usually available for the compounds. Pharmacophores can be used to identify new compounds that present a specific arrangement of features responsible for a certain type of activity. When available, information about the 3D structure of a biological target can also be included in the building of pharmacophore models. These pharmacophores can then be used as queries to search and/or focus large compound libraries. Multiple pharmacophores were generated from the 3D structure 17beta-hydroxystreoid dehydrogenase type1 complexed with different inhibitors. The validity of these pharmacophores was assessed against a test database containing known active and inactive 17beta-hydroxystreoid dehydrogenase type1 inhibitors. The most selective models were then used to search commercial databases for new structural lead molecules. This approach has allowed us to identify a few new compounds possessing structural features common to flavonoids, a structural class of compounds known to contain good inhibitors of 17beta-hydroxystreoid dehydrogenase type1 enzyme. A structure-based focusing approach is demonstrated to be a meaningful and powerful technique for identifying new lead candidates, which can be taken into the lead optimization process.

Two-dimensional [TIn2] polyanions in BaTIn2 (T=Rh, Pd, Ir, Pt)--the collapse of the three-dimensional indium polyanion of BaIn2.

The title compounds were prepared from the elements by reactions in sealed tantalum tubes in a high-frequency furnace. The four compounds were investigated by X-ray diffraction both on powders and single crystals, and the structures of the rhodium and platinum compounds were refined from single-crystal data: Cmcm, a = 447.68(8), b = 1131.1(2), c = 805.6(2) pm, wR2 = 0.0561, 354 F2 values for BaRhIn2; a = 452.06(8), b = 1162.4(2). c = 801.5(1) pm, wR2 = 0.1427, 362 F2 values, for BaPtIn2: with 16 variables for each refinement. The structures are isopointal to MgCuAl2 and can be considered to be a transition metal (T) filled CaIn2 type, in which the indium atoms form a distorted network like hexagonal diamond (lonsdaleite). The indium substructure is cut apart in BaTIn2 and resembles together with the transition metal atoms a two-dimensional polyanion rather than a three-dimensional polyanion as found in the compounds CaTIn2, CaTSn2, and SrTIn2. Semiempirical band structure calculations support the assumption of a two-dimensional polyanion in which the strongest interactions are found for the T-In contacts.

A new 1 --> infinity [Ni7] cluster in LaNi7In6 and distorted bcc indium cubes in LaNiIn4.

LaNiIn4 and LaNi7In, were prepared by reaction of the elements in an arc melting furnace and subsequent annealing at 870 K for five weeks. Both compounds were investigated by X-ray diffraction on powders and single crystals and the structures were refined from single-crystal data: Cmcm, a = 448.2(1), b = 1689.5(4). c = 722.1(1) pm, wR2 = 0.0340, 472 F2 values, 24 variables for LaNiIn4, and Ibam, a = 806.6(2). b = 924.8(2). c = 1246.5(2) pm. wR2 = 0.0681. 726 F2 values and 40 variables for LaNi7In,. LaNiIn4 adopts the YNiAl4-type structure. The nickel and indium atoms form a three-dimensional infinite [NiIn4] polyanion in which the lanthanum atoms fill distorted hexagonal channels. No Ni-Ni contacts occur. The indium substructure consists of distorted bcc-like indium cubes. LaNi7In6 crystallizes with a peculiar new structure type. The nickel atoms build a 1 --> infinity [Ni7] cluster unit with Ni-Ni distances ranging from 249 to 269 pm. The cluster units are enveloped by indium atoms. These larger units show an orthorhombic rod packing with the lanthanum atoms filling the space between the rods. Several nickel clusters in ternary rare earth metal nickel indides and the structural relations of the LaNi7In6 structure with the cubic NaZn13 type are discussed.