Structure determination of phase II of the antifungal drug griseofulvin by powder X‐ray diffraction

Two new crystalline polymorphs of the widely used antifungal drug griseofulvin (phases II and III), which originate from the crystallization of the melt, have been detected recently. The crystal structure of phase II of griseofulvin {systematic name: (2S,6′R)‐7‐chloro‐2′,4,6‐trimethoxy‐6′‐methyl‐3H,4′H‐spiro[1‐benzofuran‐2,1′‐cyclohex‐2‐ene]‐3,4′‐dione}, C₁₇H₁₇ClO₆, has been solved by powder X‐ray diffraction (PXRD). The PXRD pattern of this new phase was recorded at room temperature using synchrotron radiation. The starting structural model was generated by a Monte Carlo simulated annealing method. The final structure was obtained through Rietveld refinement with soft restraints for interatomic bond lengths and angles, except for the aromatic ring, where a rigid‐body constraint was applied. The symmetry is orthorhombic (space group P2₁2₁2₁) and the asymmetric unit contains two molecules.     

Novel modification of anhydrous transition metal oxalates from powder diffraction

The known metal–C₂O₄ structures may be divided into two modifications, α and β. The α‐modification has an order–disorder struxture, revealing one‐dimensional disordering of the metal–oxalate chains, and the β‐modification is ordered. The crystal structures of orthorhombic γ‐MnC₂O₄ {poly[μ‐oxalato‐manganese(II)]; space group Pmna , a = 7.1333 (1), b = 5.8787 (1), c = 9.0186 (2) Å, V = 378.19 (1) ų, Z = 4 and D_x = 2.511 Mg m⁻³} and γ‐CdC₂O₄ {poly[μ‐oxalato‐cadmium(II)]; space group Pmna , a = 7.3218 (1), b = 6.0231 (1), c = 9.2546 (2) Å, V = 408.13 (1) ų, Z = 4 and D_x = 3.262 Mg m⁻³} have been obtained from powder diffraction patterns. The structures are isostructural. Each metal atom in each structure is coordinated by seven O atoms which belong to five oxalate ions. The crystal packing, which contains noticeable cavities in the [101] and [001] directions, is not close packed and essentially differs from the known disordered α‐ and ordered β‐modifications of transition metal oxalates. This modification seems to be metastable. It was found that a spontaneous γ→β phase transition takes place for γ‐CdC₂O₄.     

A low‐temperature modification of hexa‐tert‐butyldisilane and a new polymorph of 1,1,2,2‐tetra‐tert‐butyl‐1,2‐diphenyldisilane

Crystals of hexa‐tert‐butyldisilane, C₂₄H₅₄Si₂, undergo a reversible phase transition at 179 (2) K. The space group changes from Ibca (high temperature) to Pbca (low temperature), but the lattice constants a, b and c do not change significantly during the phase transition. The crystallographic twofold axis of the molecule in the high‐temperature phase is replaced by a noncrystallographic twofold axis in the low‐temperature phase. The angle between the two axes is 2.36 (4)°. The centre of the molecule undergoes a translation of 0.123 (1) Å during the phase transition, but the conformation angles of the molecule remain unchanged. Between the two tri‐tert‐butylsilyl subunits there are six short repulsive intramolecular C—H...H—C contacts, with H...H distances between 2.02 and 2.04 Å, resulting in a significant lengthening of the Si—Si and Si—C bonds. The Si—Si bond length is 2.6863 (5) Å and the Si—C bond lengths are between 1.9860 (14) and 1.9933 (14) Å. Torsion angles about the Si—Si and Si—C bonds deviate by approximately 15° from the values expected for staggered conformations due to intramolecular steric H...H repulsions. A new polymorph is reported for the crystal structure of 1,1,2,2‐tetra‐tert‐butyl‐1,2‐diphenyldisilane, C₂₈H₄₆Si₂. It has two independent molecules with rather similar conformations. The Si—Si bond lengths are 2.4869 (8) and 2.4944 (8) Å. The C—Si—Si—C torsion angles deviate by between −3.4 (1) and −18.5 (1)° from the values expected for a staggered conformation. These deviations result from steric interactions. Four Si—C(t‐Bu) bonds are almost staggered, while the other four Si—C(t‐Bu) bonds are intermediate between a staggered and an eclipsed conformation. The latter Si—C(t‐Bu) bonds are about 0.019 (2) Å longer than the staggered Si—C(t‐Bu) bonds.     

Structure determination from powder diffraction data and thermal behaviour of layered lead nitrate oxalate hydrate, Pb2(NO3)2(C2O4).2H2O

The mixed lead nitrate oxalate, Pb₂(NO₃)₂(C₂O₄).2H₂O, has been obtained in a polycrystalline form in the course of a study on precursors of nanocrystalline PZT-type oxides. Its crystal structure has been solved from powder diffraction data collected using a monochromatic radiation from a conventional X-ray source. The symmetry is monoclinic, space group P2₁/c (No. 14), the cell dimensions are a=10.623(2) Å, b=7.9559(9) Å, c=6.1932(5) Å, β=104.49(1)° and Z=4. The structure consists of a stacking of complex double sheets parallel to (1 0 0), forming layers held together by hydrogen bonds. The sheets result from the condensation of PbO₁₀ polyhedra, in which the oxalate and nitrate groups, as well as water molecules, play a major role. The structure is discussed in terms of Pb---O distances, polyhedra shape and lead coordination, with emphasis on the dimensional polymerisation role of water molecules. The thermal behaviour of this layered compound is carefully described from temperature-dependent powder diffraction and thermogravimetric measurements. The enthalpy, Δ_rH=232(3) kJ mol⁻¹, and entropy, Δ_rS=532(8) J K⁻¹ mol⁻¹, of the dehydration reaction have been determined. The high value of Δ_rH demonstrates that the water molecules are strongly bonded in the structure. The complex decomposition proceeds through the crystallisation and decomposition of Pb(NO₃)₂(C₂O₄) into Pb(NO₃)₂ and PbC₂O₄, and, finally, various lead oxides.     

Structural investigation of water‐induced phase transitions of poly(ethylene imine). III. The thermal behavior of hydrates and the construction of a phase diagram

The thermal behavior of poly(ethylene imine) (PEI) hydrates in a water vapor atmosphere was investigated through temperature‐dependent measurements of infrared spectra and X‐ray diffraction. Almost perfectly dried anhydrate melted at about 60 °C during the heating process. Anhydrate containing a small amount of water showed a phase transition to a mixture of hemihydrate and sesquihydrate around 40 °C, at which point the ethylene imine (EI)/water ratio was 1/0.5 in the hemihydrate and 1/1.5 in the sesquihydrate. The hemihydrate transferred to the sesquihydrate around 60 °C, and the latter melted above 80 °C. When the starting PEI sample contained a greater amount of water and consisted of hemihydrate and sesquihydrate, the hemihydrate transferred to the sesquihydrate via heating, and the latter melted around 75 °C. For a sample of dihydrate (EI/water ratio = 1/2) containing an appreciably large amount of water, it transferred to the sesquihydrate around 65 °C, and the latter melted above 90 °C. A sample of dihydrate with a much higher water content existed up to 110 °C and then melted; during this period, no transition to the sesquihydrate was observed. In this way, the starting crystalline phases were found to change for anhydrate and various types of hydrates. Their transition behaviors varied according to the water content. From these data, a phase diagram was successfully derived as a function of the temperature and water content. This phase diagram allowed us to predict the transition behavior during the hydration process at various constant temperatures. For example, at 60 °C, a molten sample should crystallize into a mixture of hemihydrate and sesquihydrate at first, and the hemihydrate should transfer to the sesquihydrate with increasing water content. The latter should change to the dihydrate in the final stage. This prediction was checked with time‐resolved measurements of X‐ray diffraction and infrared spectra during the hydration process at the corresponding temperature; this led to the establishment of the phase diagram. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2937–2948, 2003     

Synthesis and structure determination of Ce6Cd23Te: a new chalcogen‐containing member of the RE6Cd23T family (RE is a rare‐earth metal and T is a late group 14, 15 and 16 element)

The ternary phase hexacerium tricosacadmium telluride, Ce₆Cd₂₃Te, was synthesized by a high‐temperature reaction of the elements in sealed Nb ampoules and was structurally characterized by powder and single‐crystal X‐ray diffraction. The structure, established from single‐crystal X‐ray diffraction methods, is isopointal with the Zr₆Zn₂₃Si structure type (Pearson symbol cF 120, cubic space group Fm m ), a filled version of the Th₆Mn₂₃ structure with the same space group and Pearson symbol cF 116. Though no Cd‐containing rare‐earth metal binaries are known to form with this structure, it appears that the addition of small amounts of a p‐block element allows the formation of such interstitially stabilized ternary compounds. Temperature‐dependent direct current (dc) magnetization measurements suggest local‐moment magnetism arising from the Ce³⁺ ground state, with possible valence fluctuations at low temperature, inferred from the deviations from the Curie–Weiss law.