A new polymorph of MnP4 was prepared by reaction of the elements via chemical vapor transport with iodine as transporting agent. The crystal structure was refined using single-crystal diffraction data (space group Cc, no. 9, a = 5.1049(8) Å, b = 10.540(2) Å, c = 10.875(2) Å, β = 93.80(2)°). The phase is called γ-MnP4 as it is isostructural with γ-FeP4. It is the fourth reported binary polymorph in the MnP4 system, all of which are stacking variants of nets built with manganese and phosphorus atoms. In γ-MnP4, there are two Mn-Mn distances (2.93 and 3.72 Å) arising from a Peierls-like distortion effectively forming Mn2 dumbbells in the structure. Magnetic and electrical conductivity measurements show diamagnetism and a small anisotropic band gap (100-200 meV) with significantly enhanced conductivity along the crystallographic a axis. Calculations of the electronic and vibrational (phonon) structures show the P-P and Mn-P bonds within the nets are mainly responsible for the stability of the phase. The similar bonding motifs of the polymorphs give rise to the existence of numerous dynamically stable variants. The calculated Helmholtz energy shows the polymorph formation to be closely tied to temperature with the 6-MnP4 structure favorable at low temperatures, the 2-MnP4 favorable between approximately 800 and 2000 K, and 8-MnP4 preferred at high temperatures.

Discovery of -MnP 4 and the Polymorphism of Manganese Tetraphosphide. -The new title polymorph of MnP 4 is synthesized by chemical vapor transport of a stoichiometric mixture of manganese and red phosphorus using iodine as transporting agent (evacuated silica tubes, temperature gradient 1073923 K, 14 d). -MnP 4 crystallizes in the monoclinic space group Cc with Z = 8 (single crystal XRD) and is isostructural with -FeP 4. All four binary polymorphs in the MnP4 system are stacking variants of nets built of Mn and P atoms. Mn 2 dumbbells exist in the structure of -MnP4. Magnetic and electrical conductivity measurements show diamagnetism and a small anisotropic band gap of 100-200 meV. DFT calculations show that all known stacking variants of MnP 4 exhibit similar bonding, energy, and thermodynamic properties. -(HENGE, D. B.; HERMUS, M.; LITTERSCHEID, C. F.; WAGNER, N.; BECK, J.; ALBERT*, B.; BRGOCH, J.; Inorg. Chem. 54 (2015) 17, 8761-8768, http://dx.doi.org/10.1021/acs.inorgchem.5b01372 ; Eduard-Zintl-Inst. Anorg. Phys. Chem., TH Darmstadt, D-64287 Darmstadt, Germany; Eng.) -W. Pewestorf 46-016