N-Iodosaccharin-pyridine co-crystal system under pressure: experimental evidence of reversible twinning.

This work presents a single-crystal X-ray diffraction study of an organic co-crystal composed of N-iodosaccharin and pyridine (NISac·py) under hydrostatic pressure ranging from 0.00 (5) GPa to 4.5 (2) GPa. NISac·py crystallizes in the monoclinic system (space group B21/e). The unconventional setting of the space group is adopted (the conventional setting is P21/c, No. 14) to emphasise the strongly pseudo-orthorhombic symmetry of the lattice, with a ß angle very close to 90°. The crystal structure contains one molecule each of N-iodosaccharin (NISac) and pyridine (py) in the asymmetric unit (Z' = 1), linked via an Nsac...I...N'py halogen-bonding motif. A gradual modification of this motif is observed under pressure as a result of changes in the crystalline environment. Mechanical twinning is observed under compression and the sample splits into two domains, spanning an unequal volume that is mapped by a twofold rotation about the [100] direction of the B21/e unit cell. The twinning is particularly significant at high pressure, being reversible when the pressure is released. The structure of the twinned sample reveals the continuity of a substantial substructure across the composition plane. The presence of this common substructure in the two orientations of the twinned individuals can be interpreted as a structural reason for the formation of the twin and is the first observed example in a molecular crystal. These results indicate that the anisotropy of intermolecular interactions in the crystal structure results in an anisotropic strain generated upon the action of hydrostatic compression. Periodic density functional theory calculations were carried out by considering an isotropic external pressure, the results showing good agreement with the experimental findings. The bulk modulus of the crystal was obtained from the equations of state, being 7 (1) GPa for experimental data and 6.8 (5) GPa for theoretical data.

Grazing-angle reflectivity setup for the low-temperature infrared spectroscopy of two-dimensional systems.

A new optical setup is described that allows the reflectivity at grazing incidence to be measured, including ultrathin films and two-dimensional electron systems (2DES) down to liquid-helium temperatures, by exploiting the Berreman effect and the high brilliance of infrared synchrotron radiation. This apparatus is well adapted to detect the absorption of a 2DES of nanometric thickness, namely that which forms spontaneously at the interface between a thin film of LaAlO3 and its SrTiO3 substrate, and to determine its Drude parameters.

First spin-resolved electron distributions in crystals from combined polarized neutron and X-ray diffraction experiments.

Since the 1980s it has been possible to probe crystallized matter, thanks to X-ray or neutron scattering techniques, to obtain an accurate charge density or spin distribution at the atomic scale. Despite the description of the same physical quantity (electron density) and tremendous development of sources, detectors, data treatment software etc., these different techniques evolved separately with one model per experiment. However, a breakthrough was recently made by the development of a common model in order to combine information coming from all these different experiments. Here we report the first experimental determination of spin-resolved electron density obtained by a combined treatment of X-ray, neutron and polarized neutron diffraction data. These experimental spin up and spin down densities compare very well with density functional theory (DFT) calculations and also confirm a theoretical prediction made in 1985 which claims that majority spin electrons should have a more contracted distribution around the nucleus than minority spin electrons. Topological analysis of the resulting experimental spin-resolved electron density is also briefly discussed.

Experimental determination of spin-dependent electron density by joint refinement of X-ray and polarized neutron diffraction data.

New crystallographic tools were developed to access a more precise description of the spin-dependent electron density of magnetic crystals. The method combines experimental information coming from high-resolution X-ray diffraction (XRD) and polarized neutron diffraction (PND) in a unified model. A new algorithm that allows for a simultaneous refinement of the charge- and spin-density parameters against XRD and PND data is described. The resulting software MOLLYNX is based on the well known Hansen-Coppens multipolar model, and makes it possible to differentiate the electron spins. This algorithm is validated and demonstrated with a molecular crystal formed by a bimetallic chain, MnCu(pba)(H(2)O)(3)·2H(2)O, for which XRD and PND data are available. The joint refinement provides a more detailed description of the spin density than the refinement from PND data alone.

d-Orbital orientation in a dimer cobalt complex: link to magnetic properties?

The experimental charge-density distribution of the dinuclear cobalt(II) complex [Co(2)(sym-hmp)(2)](BPh(4))(2)·2H(2)O·2C(3)H(6)O was determined at 100 K. When decreasing the temperature, the magnetic susceptibility of this complex deviates from Curie law because of anti-ferromagnetic exchange interactions, but the susceptibility increases sharply at low temperature (< 20 K). To explain this magnetic behaviour a tilt angle between the Co-atom environments was previously theoretically predicted. The structure and experimental charge density determined in this study show a tilt angle. The calculated value, based on the 100 K experimental d-orbital model, is in agreement with the theoretical one.