An Orthorhombic Modification of KCoPO Stabilized under Hydrothermal Conditions: Crystal Chemistry and Magnetic Behavior.

A novel modification of the KCoPO, δ-phase has been prepared by hydrothermal synthesis at 553 K. The compound crystallizes in the orthorhombic system with the unit-cell parameters = 8.5031(8), = 10.2830(5), = 54.170(4) Å. The crystal structure was determined based on synchrotron low-temperature single-crystal X-ray diffraction data obtained from an inversion twin in the space group 222 and refined to = 0.077 for 5156 reflections with > 3σ(). The δ-KCoPO possesses a new structure type which is based on a framework built from sharing vertices Co- and P-centered tetrahedra. The {CoPO} construction of tetrahedra may be described as assembled from networks formed by two topologically diverse six-membered rings of tetrahedra stacked together through vertex-bridging contacts along the axis. The ratio of the (UUUDDD) and (UUDUDD) rings, where (U) and (D) denote the orientation of the tetrahedra in the six-membered rings up and down relative to the plane grids, is equal to 5:1. The (UUDUDD) rings form bands parallel to the [010] direction each surrounded from both sides along the axis by slabs of five ribbons width having alternative (UUUDDD) topology. Open in the [100] direction channels incorporate K ions; this structural feature permits to suppose ion-conductive and/or electrochemical properties of the title compound. The possible mechanism of the δ → γ phase transition is discussed on the basis of the crystal chemical analysis of the KCoPO polymorphs. The title compound orders magnetically at = 24.8 K.