DOE OSTI2020
K4Tm(PO4)8(N2)3(NO)2 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional and consists of twenty-four ammonia molecules, eight nitroxyl molecules, and one K4Tm(PO4)8 framework. In the K4Tm(PO4)8 framework, there are three inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a square co-planar geometry to four O2- atoms. There are two shorter (2.72 Å) and two longer (2.98 Å) K–O bond lengths. In the second K1+ site, K1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of K–O bond distances ranging from 2.65–3.39 Å. In the third K1+ site, K1+ is bonded in a 1-coordinate geometry to eight O2- atoms. There are a spread of K–O bond distances ranging from 2.58–3.30 Å. Tm3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Tm–O bond distances ranging from 2.27–2.51 Å. There are four inequivalent P5+ sites. In the first P5+ site, P5+ is bonded in a distorted bent 120 degrees geometry to two O2- atoms. There is one shorter (1.48 Å) and one longer (1.51 Å) P–O bond length. In the second P5+ site, P5+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.51 Å) and one longer (1.55 Å) P–O bond length. In the third P5+ site, P5+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.51 Å) and one longer (1.56 Å) P–O bond length. In the fourth P5+ site, P5+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.48 Å) and one longer (1.53 Å) P–O bond length. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted L-shaped geometry to one K1+ and one O2- atom. The O–O bond length is 1.24 Å. In the second O2- site, O2- is bonded in a 2-coordinate geometry to two K1+ and one O2- atom. The O–O bond length is 1.24 Å. In the third O2- site, O2- is bonded in a water-like geometry to one K1+ and one O2- atom. The O–O bond length is 1.24 Å. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to one O2- atom. The O–O bond length is 1.23 Å. In the fifth O2- site, O2- is bonded in a single-bond geometry to one O2- atom. In the sixth O2- site, O2- is bonded in a 2-coordinate geometry to one Tm3+ and one P5+ atom. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to one K1+, one Tm3+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a 1-coordinate geometry to two K1+, one Tm3+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a 1-coordinate geometry to one K1+, one Tm3+, and one P5+ atom. In the tenth O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the eleventh O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one P5+ atom. In the twelfth O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the thirteenth O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the fourteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two equivalent K1+ and one O2- atom. In the fifteenth O2- site, O2- is bonded in a 2-coordinate geometry to one K1+ and one O2- atom. In the sixteenth O2- site, O2- is bonded in a bent 150 degrees geometry to one K1+ and one O2- atom.