Understanding the adsorption mechanism of noble gases Kr and Xe in CPO-27-Ni, CPO-27-Mg, and ZIF-8.

An experimental study of Xe and Kr adsorption in metal-organic frameworks CPO-27-Ni, CPO-27-Mg, and ZIF-8 was carried out. In situ synchrotron X-ray powder diffraction experiments allowed precise determination of the adsorption sites and sequence of their filling with increasing of gas pressure at different temperatures. Structural investigations were used for interpretation of gas adsorption measurements.

High-pressure crystal structure of the non-linear optical compound BiB(3)O(6) from two-dimensional powder diffraction data.

Our recently proposed method for automatic detection, calibration and evaluation of Debye-Scherrer ellipses using pattern-recognition techniques and advanced signal filtering was applied to the two-dimensional powder diffraction data of the non-ferroelectric, non-centrosymmetric non-linear optical (NLO) compound alpha-BiB(3)O(6) as a function of pressure. At ambient conditions, alpha-BiB(3)O(6) crystallizes in the space group C2 (phase I). In the pressure range between P = 6.09 and 6.86 GPa, it exhibits a first-order phase transition into a structure with the space group C1 (P1) [phase II at P = 8.34 GPa: a = 7.4781 (6), b = 3.9340 (4), c = 6.2321 (6) A, alpha = 93.73 (1), beta = 102.93 (1), gamma = 90.76 (1) degrees , and V = 178.24 (3) A(3)]. Non-linear compression behaviour over the entire pressure range is observed, which can be described by two Vinet relations in the ranges from P = 0.0 to 6.09 GPa, and from P = 6.86 to 11.6 GPa. The extrapolated bulk moduli of the high-pressure phases were determined to be K(0) = 38 (1) GPa for phase I, and K(0) = 114 (10) GPa for phase II. The crystal structures of both phases were refined against X-ray powder diffraction data measured at several pressures between 0.0 and 11.6 GPa. The structural phase transition of alpha-BiB(3)O(6) is mainly characterized by a reorientation of the [BO(3)](3-) triangles, the [BO(4)](5-) tetrahedra and the lone electron pair which is localized at Bi(3+), in order to optimize crystal packing.

Advances in data reduction of high-pressure x-ray powder diffraction data from two-dimensional detectors: a case study of schafarzikite (FeSb(2)O(4)).

Methods have been developed to facilitate the data analysis of multiple two-dimensional powder diffraction images. These include, among others, automatic detection and calibration of Debye-Scherrer ellipses using pattern recognition techniques, and signal filtering employing established statistical procedures like fractile statistics.All algorithms are implemented in the freely available program package Powder3D developed for the evaluation and graphical presentation of large powder diffraction data sets.As a case study, we report the pressure dependence of the crystal structure of iron antimony oxide FeSb(2)O(4) (p≤21 GPa, T = 298 K) using high-resolution angle dispersive x-ray powder diffraction. FeSb(2)O(4) shows two phase transitions in the measured pressure range. The crystal structures of all modifications consist of frameworks of Fe(2+)O(6) octahedra and irregular Sb(3+)O(4) polyhedra. At ambient conditions, FeSb(2)O(4) crystallizes in space group P4(2)/mbc (phase I). Between p = 3.2 GPa and 4.1 GPa it exhibits a displacive second order phase transition to a structure of space group P 2(1)/c (phase II, a = 5.7792(4) Å, b = 8.3134(9) Å, c = 8.4545(11) Å, ß = 91.879(10)°, at p = 4.2 GPa). A second phase transition occurs between p = 6.4 GPa and 7.4 GPa to a structure of space group P4(2)/m (phase III, a = 7.8498(4) Å, c = 5.7452(5) Å, at p = 10.5 GPa). A nonlinear compression behaviour over the entire pressure range is observed, which can be described by three Vinet equations in the ranges from p = 0.52 GPa to p = 3.12 GPa, p = 4.2 GPa to p = 6.3 GPa and from p = 7.5 GPa to p = 19.8 GPa. The extrapolated bulk moduli of the high-pressure phases were determined to K(0) = 49(2) GPa for phase I, K(0) = 27(3) GPa for phase II and K(0) = 45(2) GPa for phase III. The crystal structures of all phases are refined against x-ray powder data measured at several pressures between p = 0.52 GPa, and 10.5 GPa.

Novel Alkali-Metal Coordination in Phenoxides: Powder Diffraction Results on C(6)H(5)OM (M = Li, Na, K, Rb, Cs).

We report the ab initio structure solutions of C(6)H(5)OM (M = K, Rb, Cs) by high-resolution powder X-ray diffraction. The compounds, which are of interest for reactions of the Kolbe-Schmitt type, are isostructural. The crystal structures are orthorhombic, space group Pna2(1), Z = 12, with lattice parameters (a, b, c in Å) 14.1003(1), 17.9121(1), and 7.16475(1) for the K compound, 14.4166(2), 18.2028(2), and 7.4009(1) for the Rb compound, and 14.8448(2), 18.5070(2), and 7.6306(1) for the Cs compound. They have a chain structure [M([6])] along the crystallographic c axis. This is a very unusual arrangement in which two different alkali-metal coordination spheres are observed: a distorted octahedron and a 3-fold oxygen coordination. In the latter, the 3-fold-coordinated unsaturated alkali metals additionally show weak interactions with phenyl rings. We also give powder patterns for the compounds with M = Li, Na. The former crystallizes in the monoclinic space group P2(1)/a with lattice parameters a = 22.594 Å, b = 4.7459 Å, c= 10.053 Å, and beta = 97.82 degrees with Z = 8, but no structure solution was possible. The powder pattern for the Na phenolate is in agreement with the earlier single-crystal structure.

Powder Structure Solutions of the Compounds Potassium Phenoxide-Phenol: C(6)H(5)OK.xC(6)H(5)OH (x = 2, 3).

We report the ab initio structure solutions of two solvent containing potassium phenoxides by high-resolution powder X-ray diffraction. Both compounds are of interest for the classification of the mechanism of Kolbe-Schmitt type reactions. C(6)H(5)OK.2C(6)H(5)OH crystallizes in space group Abm2, Z = 4, with unit cell parameters a = 10.12458(4) Å, b = 21.2413(1) Å, c = 7.89784(3) Å. C(6)H(5)OK.3C(6)H(5)OH crystallizes in space group Pbca, Z = 8, with unit cell parameters a = 22.7713(1) Å, b = 25.4479(2) Å, c = 7.75549(4) Å. Both compounds show polymeric zigzag chains [K([6])O(2)([2])O([1])pi(phenyl)([1])] aligned along the c-axis. The coordination of the potassium ions is similar for both compounds. They lie at the center of distorted octahedra of five oxygen atoms and one phenyl ring, which donates its pi electrons. The distortion decreases as the number of free phenol increases.

Structural characterization of three crystalline modifications of telmisartan by single crystal and high-resolution X-ray powder diffraction.

Three crystalline modifications (A, B, and C) of 4'-[[2-n-propyl-4-methyl-6-(1-methyl-benzimidazol-2-yl)benzi midazol-1-yl]methyl]biphenyl-2-carboxylic acid (INN name, telmisartan) have been detected and their crystal structures have been determined by single-crystal X-ray diffraction (pseudopolymorph C) and the method of simulated annealing from high-resolution X-ray powder diffraction data (polymorphs A and B). The compound is of interest because of its use as an angiotensin II receptor antagonist. Polymorph A crystallizes in space group P2(I)/c, Z = 4, with unit cell parameters a = 18.7798(3), b = 18.1043(2), and c = 8.00578(7) A, beta = 97.066(1) degrees, and V = 2701.31 A(3). Polymorph B crystallizes in space group P2(I)/a, Z = 4, with unit cell parameters a = 16.0646(5), b = 13.0909(3), and c = 13.3231(3) A, beta = 99.402(1) degrees, and V = 2764.2(1) A(3). The solvated form C crystallizes in space group C2/c, Z = 8, with unit cell parameters a = 30.990(5), b = 13.130(3), and c = 16.381(3) A, beta = 95.02(2) degrees, and V = 6639(2) A(3). For the structure solutions of polymorphs A and B, 13 degrees of freedom (3 translational, 3 orientational, 7 torsion angles) were determined in approximately 2 h of computer time, demonstrating that the crystal packing and the molecular conformation of medium-sized (MW approximately 500) pharmaceutical compounds can now be solved quickly and routinely from high-resolution X-ray powder diffraction data.

Effect of crystal packing on the structures of polymeric metallocenes.

The pressure dependencies of the crystal structures of the polymeric metallocenes lithium cyclopentadienide (LiCp) and potassium cyclopentadienide (KCp) have been determined by synchrotron X-ray powder diffraction. The decrease of the volume of LiCp by 34% up to a pressure of p = 12.2 GPa and of KCp by 23% at p = 5.3 GPa as well as the bulk moduli of K = 7.7 GPa for LiCp and 4.9 GPa for KCp indicate a high compressibility for these compounds. The crystal structures of KCp have been determined up to p = 3.9 GPa. An increase of the bend angle is found from 45 degrees at p = 0 GPa up to 51 degrees at p = 3.9 GPa. This variation is completely explained by a model invoking attractive K+ Cp- interaction and repulsive nonbonded carbon-carbon interactions. It is proposed that the bend angle in the polymeric alkali metal metallocenes is the result of the optimization of the crystal packing.

Characterization of the products of the heme detoxification pathway in malarial late trophozoites by X-ray diffraction.

In a process inhibited by the quinoline antimalarial drugs, Plasmodia detoxify heme released during the degradation of hemoglobin by aggregating it into malarial pigment, an insoluble crystalline heme coordination polymer. Synchrotron x-ray powder diffraction patterns for intact desiccated malarial trophozoites and synthetic beta-hematin have been measured; both materials correspond to a single crystalline triclinic lattice with unit cell parameters a = 12.2176(4), b = 14.7184(5), c = 8.0456(3) A; alpha = 90.200(2), beta = 96.806(3), gamma = 97.818(3) degrees and Z = 2. These results unambiguously demonstrate that hemozoin crystallites are identical to synthetic beta-hematin.

Bulk modulus and non-uniform compression of Nb3Te4 and InxNb3Te4 (x < 1) channel compounds.

The crystal structures of Nb3Te4 and InxNb3Te4 [x = 0.539 (4)] are reported for a series of pressures between 0 and 40 GPa. Both compounds crystallize in space group P6(3)/m with a = b = 10.671 and c = 3.6468 A for Nb3Te4, and a = b = 10.677 and c = 3.6566 A for InxNb3Te4 at ambient conditions. Phase transitions were not observed. High-pressure X-ray powder diffraction was measured using a diamond anvil cell and synchrotron radiation. Full Rietveld refinements provided the values of the lattice parameters and the values of the atomic coordinates at each pressure. The bulk modulus is found as K(0) = 70 (5) GPa for Nb3Te4 and as K(0) = 73 (4) GPa for InxNb3Te4. The analysis of the pressure dependences of the detailed crystal structures shows that the compression along c involves the folding up of the quasi-one-dimensional zigzag chains of Nb. The compression perpendicular to c is entirely due to the reduction of the diameter of the channels. The presence of intercalated In atoms is found to have hardly any influence on the compression behaviour up to 40 GPa.

Disordered crystal structure of pentamethylcyclopentadienylsodium as seen by high-resolution X-ray powder diffraction.

The crystal structure of pentamethylcyclopentadienylsodium, [NaC10H15] (NaCp*), has been determined from high-resolution X-ray powder diffraction. The compound crystallizes in space group Cmcm with lattice parameters a = 4.61030 (3), b = 16.4621 (3), c = 14.6751 (2) A, V = 1113.77 (4) A(3) (Z = 4). NaCp* forms polymeric multidecker chains along the a axis. The Rietveld refinement (R(p) = 0.050 and R(F) = 0.163) shows that the Cp* moieties occupy, with disorder, two different orientations rotated away from the eclipsed conformation by +/-13.8 degrees.