DOE OSTI2020
Na12MnH16(SO4)8(Cu)2 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional and consists of four copper molecules and one Na12MnH16(SO4)8 framework. In the Na12MnH16(SO4)8 framework, there are six inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Na–O bond distances ranging from 2.33–2.43 Å. In the second Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Na–O bond distances ranging from 2.33–2.55 Å. In the third Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.36–2.74 Å. In the fourth Na1+ site, Na1+ is bonded in a 6-coordinate geometry to one H1+ and five O2- atoms. The Na–H bond length is 2.47 Å. There are a spread of Na–O bond distances ranging from 2.38–2.60 Å. In the fifth Na1+ site, Na1+ is bonded in a trigonal bipyramidal geometry to five O2- atoms. There are a spread of Na–O bond distances ranging from 2.35–2.46 Å. In the sixth Na1+ site, Na1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Na–O bond distances ranging from 2.35–3.03 Å. Mn7+ is bonded in an octahedral geometry to six O2- atoms. There are a spread of Mn–O bond distances ranging from 2.20–2.23 Å. There are eight inequivalent H1+ sites. In the first 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 second H1+ site, H1+ is bonded in a distorted single-bond geometry to two O2- atoms. There is one shorter (1.00 Å) and one longer (1.69 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 0.99 Å. In the fourth 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 fifth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the sixth 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 seventh H1+ site, H1+ is bonded in a single-bond geometry to one Na1+ and one O2- atom. The H–O bond length is 0.99 Å. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. There are four inequivalent S3+ sites. In the first S3+ site, S3+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. There is two shorter (1.53 Å) and one longer (1.54 Å) S–O bond length. In the second S3+ site, S3+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. All S–O bond lengths are 1.53 Å. In the third S3+ site, S3+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. There are a spread of S–O bond distances ranging from 1.52–1.54 Å. In the fourth S3+ site, S3+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. There are a spread of S–O bond distances ranging from 1.50–1.55 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S3+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one H1+, and one S3+ atom. In the third O2- site, O2- is bonded in a distorted water-like geometry to one Na1+ and two H1+ atoms. In the fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Na1+ and one S3+ atom. In the fifth O2- site, O2- is bonded to three Na1+ and one S3+ atom to form distorted corner-sharing ONa3S tetrahedra. In the sixth O2- site, O2- is bonded in a 1-coordinate geometry to three Na1+ and one S3+ atom. In the seventh O2- site, O2- is bonded to three Na1+ and one S3+ atom to form distorted corner-sharing ONa3S tetrahedra. In the eighth O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+ and one S3+ atom. In the ninth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Na1+ and one S3+ atom. In the tenth O2- site, O2- is bonded to two Na1+, one Mn7+, and one S3+ atom to form distorted ONa2MnS trigonal pyramids that share corners with two equivalent ONa3S tetrahedra, corners with two ONa2MnS trigonal pyramids, and an edgeedge with one ONa2MnS trigonal pyramid. In the eleventh O2- site, O2- is bonded in a distorted water-like geometry to two Na1+ and two H1+ atoms. In the twelfth O2- site, O2- is bonded in a 4-coordinate geometry to two Na1+, one Mn7+, and one S3+ atom. In the thirteenth O2- site, O2- is bonded to two Na1+, one Mn7+, and one S3+ atom to form distorted ONa2MnS trigonal pyramids that share corners with two ONa3S tetrahedra, corners with two ONa2MnS trigonal pyramids, and an edgeedge with one ONa2MnS trigonal pyramid. In the fourteenth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two Na1+ and one S3+ atom. In the fifteenth O2- site, O2- is bonded in a water-like geometry to two Na1+ and two H1+ atoms. In the sixteenth O2- site, O2- is bonded in a distorted water-like geometry to two Na1+ and two H1+ atoms.