Protein-induced, previously unidentified twin form of calcite.

Using single-crystal x-ray diffraction, we found a formerly unknown twin form in calcite crystals grown from solution to which a mollusc shell-derived 17-kDa protein, Caspartin, was added. This intracrystalline protein was extracted from the calcitic prisms of the Pinna nobilis shells. The observed twin form is characterized by the twinning plane of the (108)-type, which is in addition to the known four twin laws of calcite identified during 150 years of investigations. The established twin forms in calcite have twinning planes of the (001)-, (012)-, (104)-, and (018)-types. Our discovery provides additional evidence on the crucial role of biological macromolecules in biomineralization.

Two separable conformers of TATP and analogues exist at room temperature.

[reaction: see text] TATP gives rise to two separable conformations because the barrier for interconversion between them is relatively high at room temperature. This kind of behavior is rare in cyclic organic systems and is the result of poor overlap in the "flip-flop" transition state. The crystal structure of the analogous tricyclohexanone triperoxide also indicates the presence of two conformers.

Irreversible single-crystal to polycrystal and reversible single-crystal to single-crystal phase transformations in cyanurates.

4,6-Dimethoxy-3-methyldihydrotriazine-2-one (1) undergoes a single-crystal to single-crystal reversible phase transformation at 319 K. The low-temperature phase crystallizes in monoclinic space group P2(1)/n with two crystallographically independent molecules in the asymmetric unit. The high-temperature phase is obtained by heating a single crystal of the low-temperature phase. This phase is orthorhombic, space group Pnma, with the molecules occupying a crystallographic mirror plane. The enthalpy of the transformation is 1.34 kJ mol(-1). The small energy difference between the two phases and the minimal atomic movement facilitate the single-crystal to single-crystal reversible phase transformation with no destruction of the crystal lattice. On further heating, the high-temperature phase undergoes methyl rearrangement in the solid state. 2,4,6-Trimethoxy-1,3,5-triazine (3), on the other hand, undergoes an irreversible phase transformation from single-crystal to polycrystalline material at 340 K with an enthalpy of 3.9 kJ mol(-1); upon further heating it melts and methyl rearrangement takes place.

Determination of the structure of 2(benzene-1,3,5-tricarboxylic acid)-1.5(pyrene)-2(methanol) and comparison with that of 2(benzene-1,3,5-tricarboxylic acid)-pyrene-2(ethanol).

The structure of the title methanol complex (P1;, Z = 2) has been determined and compared with that of the title ethanol complex (C2/c, Z = 8) using published data. Both complexes have layer structures, the (essentially planar) layers being constructed from rings of six TMA molecules, hydrogen bonded through four 'carboxyl dimers' and two 'interrupted dimers', where methanol (ethanol) is included in the R4(4)(12) (graph set) ring. The packing of the layers differs in the two complexes, leading to different three-dimensional structures. In the methanol complex, one pyrene molecule is located within the layer and the other, at a centre of symmetry, between the layers in one type of interlayer space, while the methyls of methanol protrude into the other type of interlayer space. In the ethanol complex, the superpositioning of the layers is such that two types of stack are formed; one of these is mixed, containing pyrene and one of the independent TMA molecules in alternating sequence, while the other stack contains only the second type of TMA. Spectroscopic study is needed to establish whether the partial mixed stack arrangement in the crystalline ethanol complex implies donor-acceptor interaction.

Site effects in controlling the chemical reactivity in crystals: solid-state photochromism of N-(n-propyl)nitrospiropyrane.

The dynamics of decay of the photoproducts of the two non equivalent molecules of N-(n-propyl) nitrospiropyrane in the crystalline state is significantly different due to the effect of the specific site where each of the molecules is located in the crystal latice.

Determining the crystal structure of twinned 2-methylpyrazine.

Although systematic absences and symmetry relations among reflections pointed to space group I4(1)22 (one molecule in the asymmetric unit), a direct methods solution could only be obtained in I(-)4 (two molecules in the asymmetric unit). Refinement in I(-)4 was unsatisfactory until merohedral twinning was taken into account. The resulting molecular dimensions are in excellent agreement with analogous values in the literature. The molecular arrangement is described.

X-ray and neutron diffraction study of benzoylacetone in the temperature range 8-300 K: comparison with other cis-enol molecules.

The crystal structure of benzoylacetone (1-phenyl-1,3-butanedione, C(10)H(10)O(2); P2(1)/c, Z = 4) has been determined at 300, 160 (both Mo Kalpha X-ray diffraction, XRD), 20 (lambda = 1.012 Å neutron diffraction, ND) and 8 K (Ag Kalpha XRD), to which should be added earlier structure determinations at 300 (Mo Kalpha XRD and ND, lambda = 0.983 Å) and 143 K (Mo Kalpha XRD). Cell dimensions have been measured over the temperature range 8-300 K; a first- or second-order phase change does not occur within this range. The atomic displacement parameters have been analyzed using the thermal motion analysis program THMA11. The most marked change in the molecular structure is in the disposition of the methyl group, which has a librational amplitude of approximately 20 degrees at 20 K and is rotationally disordered at 300 K. The lengths of the two C-O bonds in the cis-enol ring do not differ significantly, nor do those of the two C-C bonds, nor do these lengths change between 8 and 300 K. An ND difference synthesis (20 K) shows a single enol hydrogen trough (rather than two half H atoms), approximately centered between the O atoms; analogous results were obtained by XRD (8 K). It is inferred that the enol hydrogen is in a broad, flat-bottomed single-minimum potential well between the O atoms, with a libration amplitude of approximately 0.30 Å at 8 K. These results suggest that at 8 K the cis-enol ring in benzoylacetone has quasi-aromatic character, in agreement with the results of high-level ab initio calculations made for benzoylacetone [Schiøtt et al. (1998). J. Am. Chem. Soc. 120, 12117-12124]. Application [in a related paper by Madsen et al. (1998). J. Am. Chem. Soc. 120, 10040-10045] of multipolar analysis and topological methods to the charge density obtained from the combined lowest temperature X-ray and neutron data provides evidence for an intramolecular hydrogen bond with partly electrostatic and partly covalent character, and large p-delocalization in the cis-enol ring. This is in good agreement with what is expected from the observed bond lengths. Analysis of the total available (through the Cambridge Structural Database, CSD) population of cis-enol ring geometries confirms earlier reports of correlation between the degree of bond localization in the pairs of C-C and C-O bonds, but does not show the dependence of bond localization on d(O.O) that was reported earlier for a more restricted sample. It is suggested that the only reliable method of determining whether the enol hydrogen is found in a single or double potential well is by low-temperature X-ray or (preferably) neutron diffraction.