The structure of orange HgI2. I. Polytypic layer structure.

The metastable orange crystals of HgI(2) comprise three different crystal structures, all of which are built from corner-linked Hg(4)I(10) supertetrahedra. Two of them are end members with the maximum degree of order (MDO) of a polytypic layer structure; the third shows a three-dimensional linkage. This paper presents the determination from X-ray diffraction data of the tetragonal polytypic structures and their stacking disorder. Diffraction patterns show sharp Bragg reflections and rods of diffuse intensity with pronounced maxima. In a first step, the diffuse intensity was neglected and all maxima were treated as Bragg reflections. The crystal was supposed to be a conglomerate of the two MDO structures diffracting independently, and their parameters and volume ratio were refined against the single data set. The geometries and anisotropic displacement parameters of the layers in the two structures are shown to be nearly identical. Layer contacts in the two stacking modes are identical. The structures are fractal complications of the stable red form of HgI(2). In a second step, the stacking disorder has been quantitatively analyzed with a Markov chain model. Two probabilities describing next-nearest-layer interactions were visually adjusted to observed intensity profiles extracted from image-plate detector data. Results consistently show that the crystal comprises nearly equal volumes of MDO structures with an average domain thickness of about 5 layers or 30 A