DOE OSTI2020
Zn6P4H10O21(H2O)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional and consists of four water molecules and one Zn6P4H10O21 framework. In the Zn6P4H10O21 framework, there are six inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share a cornercorner with one ZnO6 octahedra, corners with four PO4 tetrahedra, and edges with two ZnO6 octahedra. The corner-sharing octahedral tilt angles are 64°. There are a spread of Zn–O bond distances ranging from 2.04–2.36 Å. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with four PO4 tetrahedra, a cornercorner with one ZnO5 trigonal bipyramid, and edges with two ZnO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.04–2.21 Å. In the third Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share a cornercorner with one ZnO6 octahedra, a cornercorner with one ZnO4 tetrahedra, corners with four PO4 tetrahedra, and an edgeedge with one ZnO6 octahedra. The corner-sharing octahedral tilt angles are 64°. There are a spread of Zn–O bond distances ranging from 2.06–2.19 Å. In the fourth Zn2+ site, Zn2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Zn–O bond distances ranging from 2.01–2.56 Å. In the fifth Zn2+ site, Zn2+ is bonded to four O2- atoms to form distorted ZnO4 tetrahedra that share a cornercorner with one ZnO6 octahedra, corners with four PO4 tetrahedra, and an edgeedge with one ZnO5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 75°. There are a spread of Zn–O bond distances ranging from 1.96–2.02 Å. In the sixth Zn2+ site, Zn2+ is bonded to five O2- atoms to form ZnO5 trigonal bipyramids that share a cornercorner with one ZnO6 octahedra, corners with four PO4 tetrahedra, and an edgeedge with one ZnO4 tetrahedra. The corner-sharing octahedral tilt angles are 71°. There are a spread of Zn–O bond distances ranging from 1.98–2.22 Å. There are four inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four ZnO6 octahedra and a cornercorner with one ZnO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 45–58°. There is three shorter (1.56 Å) and one 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 three ZnO6 octahedra, a cornercorner with one ZnO4 tetrahedra, and a cornercorner with one ZnO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 41–57°. There are a spread of P–O bond distances ranging from 1.54–1.58 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with three ZnO6 octahedra, corners with two equivalent ZnO4 tetrahedra, and a cornercorner with one ZnO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 50–57°. 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 equivalent ZnO6 octahedra, a cornercorner with one ZnO4 tetrahedra, and a cornercorner with one ZnO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 46–57°. There are a spread of P–O bond distances ranging from 1.55–1.57 Å. There are ten inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a distorted linear geometry to two O2- atoms. There is one shorter (1.04 Å) and one longer (1.55 Å) H–O bond length. In the second H1+ site, H1+ is bonded in a distorted single-bond geometry to two O2- atoms. There is one shorter (1.01 Å) and one longer (1.64 Å) H–O bond length. In the third H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.00 Å. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to two O2- atoms. There is one shorter (1.01 Å) and one longer (1.70 Å) H–O bond length. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.00 Å. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.00 Å. In the seventh H1+ site, H1+ is bonded in a distorted linear geometry to two O2- atoms. There is one shorter (1.03 Å) and one longer (1.57 Å) H–O bond length. In the eighth H1+ site, H1+ is bonded in a distorted single-bond geometry to two O2- atoms. There is one shorter (1.02 Å) and one longer (1.64 Å) H–O bond length. In the ninth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the tenth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. There are twenty-one inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Zn2+ and one P5+ atom. In the second O2- site, O2- is bonded in a trigonal non-coplanar geometry to one P5+ and two H1+ atoms. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Zn2+ and one P5+ atom. In the fourth O2- site, O2- is bonded in a bent 120 degrees geometry to one Zn2+ and one P5+ atom. In the fifth O2- site, O2- is bonded in a 3-coordinate geometry to one Zn2+, one P5+, and one H1+ atom. In the sixth O2- site, O2- is bonded in a water-like geometry to one Zn2+ and one P5+ atom. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one P5+ atom. In the eighth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one P5+ atom. In the ninth O2- site, O2- is bonded in a 2-coordinate geometry to one Zn2+ and one P5+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to two Zn2+ and one P5+ atom. In the eleventh O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one P5+ atom. In the twelfth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one P5+ atom. In the thirteenth O2- site, O2- is bonded in a trigonal non-coplanar geometry to one P5+ and two H1+ atoms. In the fourteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Zn2+ and one P5+ atom. In the fifteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Zn2+ and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one P5+ atom. In the seventeenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Zn2+ and two H1+ atoms. In the eighteenth O2- site, O2- is bonded in a distorted water-like geometry to two Zn2+ and two H1+ atoms. In the nineteenth O2- site, O2- is bonded in a distorted water-like geometry to two Zn2+ and two H1+ atoms. In the twentieth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Zn2+ and two H1+ atoms. In the twenty-first O2- site, O2- is bonded in a distorted water-like geometry to one Zn2+ and two H1+ atoms.