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The crystal structure of 1,3-di-thiane 1,1,3,3-tetra-oxide, C 4 H 8 O 4 S 2 , has been determined to examine the inter-molecular C-H⋯O hydrogen bonds in a small mol-ecule with highly polarized hydrogen atoms. The crystals are monoclinic, space group P n, with a = 4.9472 (5), b = 9.9021 (10), c = 7.1002 (7) Å and β = 91.464 (3)° with Z = 2. The mol-ecules form two stacks parallel to the a axis with the molecules being one a translation distance from each other. This stacking involves axial hydrogen atoms on one mol-ecule and the axial oxygen atoms on the adjacent mol-ecule in the stack. None of these C-H⋯O contacts is particularly short (all are > 2.4 Å). The many C-H⋯O contacts between the two stacks involve at least one equatorial hydrogen or oxygen atom. Again, no unusually short contacts are found. The whole crystal structure basically consists of a complex network of C-H⋯O contacts with no single, linear C-H⋯O contacts, only contacts that involve two (bifurcated), and mostly three or four neighbors., (© Harlow et al. 2021.)

The crystal structures of two crystalline phases of 1,4-di-thiane 1,1,4,4-tetra-oxide, C 4 H 8 O 4 S 2 , have been determined in order to examine the nature of possible inter-molecular hydrogen bonds. Phase 1 is monoclinic, space group C 2/ m , with unit-cell dimensions of a = 9.073 (8), b = 7.077 (6), c = 5.597 (5) Å and β = 105.89 (1)°. The mol-ecule adopts 2/ m symmetry and all of the mol-ecules are related by translation and thus have the same orientation. Phase 2 is also monoclinic but in space group P 2 1 / n with unit-cell dimensions of a = 7.1305 (5), b = 5.7245 (4), c = 8.3760 (6) Å and β = 91.138 (2)°. In this phase, the mol-ecule sits on an inversion center and the mol-ecules within the unit cell adopt quite different orientations. In both phases, examination of the potential C-H⋯O hydrogen bonds around each of the independent oxygen atoms (one axial and the other equatorial) shows the general O⋯H patterns to be quite similar with each oxygen atom in contact with four neighboring H atoms, and each H atom contacting two neighboring O atoms. While none of the H⋯O contacts is particularly short (all are greater than 2.5 Å), each mol-ecule has 32 such contacts that form an extensive inter-molecular network. A 1 H NMR spectrum of the compound dissolved in DMSO shows a singlet of 8H at δ 3.677 which indicates that the C-H bonds are only moderately polarized by the single adjacent -SO 2 - moiety: strongly polarized C-H bonds have δ values in the 5-6 range [Li & Sammes (1983 ▸). J. Chem. Soc. Perkin Trans. 1 , pp. 1303-1309]. The phase 1 crystal studied was non-merohedrally twinned.

Electron diffraction has been recently used in the pharmaceutical industry to study the polymorphism in crystalline drug substances. While conventional X-ray diffraction patterns could not be used to determine the cell parameters of two forms of the microcrystalline GP IIb/IIIa receptor antagonist roxifiban, a combination of electron single-crystal and synchrotron powder diffraction techniques were able to clearly distinguish the two polymorphs. The unit-cell parameters of the two polymorphs were ultimately determined using new software routines designed to take advantage of each technique's unique capabilities. The combined use of transmission electron microscopy (TEM) and synchrotron patterns appears to be a good general approach for characterizing complex (low-symmetry, large-unit-cell, micron-sized) polymorphic pharmaceutical compounds.

In the course of the development of Lumaxistrade mark (roxifiban), the physical state of XP280 (the besylate salt of the active metabolites of roxifiban) and SC887 (the mesylate salt of the free base of roxifiban) were characterized. Powder X-ray diffraction patterns of XP280 were ambiguous in that a high degree of background signal was present and potentially indicative of the existence of an amorphous phase. Herein the results of combined synchrotron X-ray diffraction and electron microscopy (diffraction and imaging) studies on XP280 and SC887 are reported. The combination of these two techniques allowed an unambiguous assessment of the crystallinity, as well as determination of four of the unit cell parameters of XP280 and complete determination of the unit cell parameters for SC887., (Copyright 2000 Wiley-Liss, Inc. and the American Pharmaceutical Association J Pharm Sci 89: 1237-1242, 2000)

Unit cell parameters of two polymorphs of roxifiban have been determined by a combination of transmission electron microscopy (TEM) single-crystal and synchrotron X-ray powder diffraction techniques. While it was difficult to differentiate the two forms by their standard X-ray diffraction patterns, the high-resolution synchrotron patterns clearly showed striking differences. Unit cells for the two forms required the use of cell parameters derived from TEM diffraction patterns. The two unit cells are, not surprisingly, very similar except for a doubling of one of the axes for form II. The combined use of TEM and synchrotron patterns appears to be a good general approach for characterizing complex (low-symmetry, large unit cell) polymorphs.

A large number of incorrect crystal structures is being published today. These structures are proving to be a particular problem to those of us who are interested in comparing structural moieties found in the databases in order to develop structure-property relationships. Problems can reside in the input data, e.g., wrong unit cell or low quality intensity data, or in the structural model, e.g., wrong space group or atom types. Many of the common mistakes are, however, relatively easy to detect and thus should be preventable; at the very least, suspicious structures can be flagged, if not by the authors then by the referees and, ultimately, the crystallographic databases. This article describes some of the more common mistakes and their effects on the resulting structures, lists a series of tests that can be used to detect incorrect structures, and makes a strong plea for the publication of higher quality structures.

C(60) and liquid bromine react to form C(60)Br(24), a crystalline compound isolated as a bromine solvate, C(60)Br(24)(Br(2))(x), The x-ray crystal structure defines a new pattern of addition to the carbon skeleton that imparts a rare high symmetry. The parent C(60) framework is recognizable in C(60)Br(24), but sp(3) carbons at sites of bromination distort the surface, affecting conformations of all of the hexagonal and pentagonal rings. Twenty-four bromine atoms envelop the carbon core, shielding the 18 remaining double bonds from addition. At 150 degrees to 200 degrees C there is effectively quantitative reversion of C(60)Br(24) to C(60) and Br(2).

The oxygen isotope effect on the superconducting transition temperature (alpha(o)) varies as a function of x in La2-xSrxCuO(4) and La2-xBaxCuO(4), with the maximum alpha(o) values (alpha(o) >/= 0.5) found for x near 0.12. This unusual x dependence implies that the isotope effect is influenced by proximity to the Abma --> P4(2)/ncm structural phase transition in these systems. Synchrotron x-ray difaction measurements reveal little change in lattice parameters or orthorhombicity due to isotope exchange in strontium-doped materials where alpha(o) > 0.5, eliminating static structural distortion as a cause of the large isotope effects. The anomalous behavior of alpha(o) in both strontium- and barium-doped materials, in combination with the previously discovered Abma --> P4(2)/ncm structural phase-transition in La(1.88)B(0.12)CuO(4), suggests that an electronic contribution to the lattice instability is present and maximizes at approximately 1/8 hole per copper atom. These observations indicate a dose connection between hole doping of the Cu-O sheets, tilting instabilities of the CuO(6) octahedra, and superconductivity in La(2)CuO(4)-based superconductors.