DOE OSTI2020
K3Mn4P5H3O20 crystallizes in the monoclinic Cc space group. The structure is three-dimensional. there are three inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a 12-coordinate geometry to two H1+ and ten O2- atoms. There are one shorter (2.89 Å) and one longer (2.90 Å) K–H bond lengths. There are a spread of K–O bond distances ranging from 2.70–3.32 Å. 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 2.70–2.93 Å. In the third K1+ site, K1+ is bonded in a 6-coordinate geometry to one H1+ and six O2- atoms. The K–H bond length is 2.87 Å. There are a spread of K–O bond distances ranging from 2.70–2.87 Å. There are four inequivalent Mn+2.25+ sites. In the first Mn+2.25+ site, Mn+2.25+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Mn–O bond distances ranging from 2.07–2.32 Å. In the second Mn+2.25+ site, Mn+2.25+ is bonded in a 5-coordinate geometry to six O2- atoms. There are a spread of Mn–O bond distances ranging from 2.04–2.77 Å. In the third Mn+2.25+ site, Mn+2.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent MnO6 octahedra and corners with six PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 68–70°. There are a spread of Mn–O bond distances ranging from 1.92–2.36 Å. In the fourth Mn+2.25+ site, Mn+2.25+ is bonded to six O2- atoms to form distorted MnO6 octahedra that share corners with two equivalent MnO6 octahedra, corners with four PO4 tetrahedra, and an edgeedge with one PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 68–70°. There are a spread of Mn–O bond distances ranging from 2.16–2.32 Å. There are five inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent MnO6 octahedra and an edgeedge with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 39–40°. There is two shorter (1.56 Å) and two longer (1.57 Å) P–O bond length. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two MnO6 octahedra. The corner-sharing octahedra tilt angles range from 38–58°. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two MnO6 octahedra. The corner-sharing octahedra tilt angles range from 39–58°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two MnO6 octahedra. The corner-sharing octahedra tilt angles range from 46–50°. There are a spread of P–O bond distances ranging from 1.54–1.60 Å. In the fifth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two MnO6 octahedra. The corner-sharing octahedra tilt angles range from 46–50°. There are a spread of P–O bond distances ranging from 1.54–1.60 Å. There are three inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a distorted linear geometry to one K1+ and two O2- atoms. There is one shorter (1.05 Å) and one longer (1.50 Å) H–O bond length. In the second H1+ site, H1+ is bonded in a distorted linear geometry to two K1+ and two O2- atoms. There is one shorter (1.05 Å) and one longer (1.50 Å) H–O bond length. In the third H1+ site, H1+ is bonded in a linear geometry to two O2- atoms. There is one shorter (1.10 Å) and one longer (1.35 Å) H–O bond length. There are twenty inequivalent O2- sites. In the first O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, one Mn+2.25+, and one P5+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, two Mn+2.25+, and one P5+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one K1+, two Mn+2.25+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one K1+, two Mn+2.25+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Mn+2.25+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Mn+2.25+ and one P5+ atom. In the seventh O2- site, O2- is bonded in a distorted water-like geometry to two K1+, one P5+, and one H1+ atom. In the eighth O2- site, O2- is bonded in a distorted water-like geometry to two K1+, one P5+, and one H1+ atom. In the ninth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two K1+, one P5+, and one H1+ atom. In the tenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two K1+, one P5+, and one H1+ atom. In the eleventh O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, one Mn+2.25+, one P5+, and one H1+ atom. In the twelfth O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, one Mn+2.25+, one P5+, and one H1+ atom. In the thirteenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Mn+2.25+ and one P5+ atom. In the fourteenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Mn+2.25+ and one P5+ atom. In the fifteenth O2- site, O2- is bonded to two K1+, one Mn+2.25+, and one P5+ atom to form distorted corner-sharing OK2MnP tetrahedra. In the sixteenth O2- site, O2- is bonded to two K1+, one Mn+2.25+, and one P5+ atom to form distorted corner-sharing OK2MnP tetrahedra. In the seventeenth O2- site, O2- is bonded in a 1-coordinate geometry to one K1+, two Mn+2.25+, and one P5+ atom. In the eighteenth O2- site, O2- is bonded in a 1-coordinate geometry to one K1+, two Mn+2.25+, and one P5+ atom. In the nineteenth O2- site, O2- is bonded in a 3-coordinate geometry to one K1+, one Mn+2.25+, and one P5+ atom. In the twentieth O2- site, O2- is bonded in a 3-coordinate geometry to one K1+, one Mn+2.25+, and one P5+ atom.