The name pyrrhotite is derived from Greek pyrrhos, flame-colored.
Pyrrhotite has a number of polytypes of hexagonal or monoclinic crystal symmetry; several polytypes often occur within the same specimen. Their crystalline structure is based on the NiAs unit cell, where metal occurs in octahedral coordination and anions in trigonal prismatic arrangement. An important feature of this structure is an ability to omit metal atoms with the total fraction up to 1/8, thereby creating iron vacancies. One of such structures is pyrrhotite-4C (Fe7S8). Here "4" indicates that iron vacancies form a superlattice which is 4 times larger than the unit cell in the "C" direction. The C direction is conventionally chosen parallel to the main symmetry axis of the crystal; this direction usually corresponds to the largest lattice spacing. Other polytypes include: pyrrhotite-5C (Fe9S10), 6C (Fec11S12), 7C (Fe9S10) and 11C (Fe10S11). Every polytype can have monoclinic (M) or hexagonal (H) symmetry, and therefore some sources label them, for example, not as 6C, but 6H or 6M depending on the symmetry. The monoclinic forms are stable at temperatures below 254 °C, whereas the hexagonal forms are stable above that temperature. The exception is for those with high iron content, close to the troilite composition (47 to 50 % atomic percent iron) which exhibit hexagonal symmetry.
The ideal FeS lattice, such as that of troilite, is non-magnetic. The ferromagnetism which is widely observed in pyrrhotite is therefore attributed to the presence of relatively large concentrations of iron vacancies (up to 20%) in the crystal structure. Vacancies lower the crystal symmetry. Therefore, monoclinic forms of pyrrhotite are in general more defect-rich than the more symmetrical hexagonal forms, and thus are more magnetic. Upon heating to 320 °C, pyrrhotite loses its magnetism, but also starts decomposing to magnetite. The saturation magnetization of pyrrhotite is 0.12 tesla.
Pyrrhotite is a rather common trace constituent of mafic igneous rocks especially norites. It occurs as segregation deposits in layered intrusions associated with pentlandite, chalcopyrite and other sulfides. It is an important constituent of the Sudbury intrusion where it occurs in masses associated with copper and nickel mineralisation. It also occurs in pegmatites and in contact metamorphic zones. Pyrrhotite is often accompanied by pyrite, marcasite and magnetite. Pyrrhotite does not have specific applications. It is mined primarily because it is associated with pentlandite, sulfide mineral that can contain significant amounts of nickel and cobalt.