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Mn3Zn9(PO4)8 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are three inequivalent Mn2+ sites. In the first Mn2+ site, Mn2+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of Mn–O bond distances ranging from 2.09–2.31 Å. In the second Mn2+ site, Mn2+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of Mn–O bond distances ranging from 2.10–2.30 Å. In the third Mn2+ site, Mn2+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of Mn–O bond distances ranging from 2.10–2.30 Å. There are five inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Zn–O bond distances ranging from 1.97–2.45 Å. In the second Zn2+ site, Zn2+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Zn–O bond distances ranging from 1.97–2.46 Å. In the third Zn2+ site, Zn2+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Zn–O bond distances ranging from 1.97–2.46 Å. In the fourth Zn2+ site, Zn2+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Zn–O bond distances ranging from 1.96–2.46 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 2.05–2.29 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 a cornercorner with one MnO6 octahedra and corners with two equivalent ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 35–57°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with three MnO6 octahedra. The corner-sharing octahedra tilt angles range from 36–58°. There are a spread of P–O bond distances ranging from 1.53–1.57 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one ZnO6 octahedra and corners with two equivalent MnO6 octahedra. The corner-sharing octahedra tilt angles range from 36–57°. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with three MnO6 octahedra. The corner-sharing octahedra tilt angles range from 36–58°. There are a spread of P–O bond distances ranging from 1.53–1.57 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mn2+, one Zn2+, and one P5+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mn2+, one Zn2+, and one P5+ atom. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one P5+ atom. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Mn2+, one Zn2+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Zn2+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to two 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 3-coordinate geometry to two Zn2+ and one P5+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to one Mn2+, one Zn2+, and one P5+ atom. In the eleventh O2- site, O2- is bonded in a 3-coordinate geometry to one Mn2+, one Zn2+, and one P5+ atom. In the twelfth O2- site, O2- is bonded in a 3-coordinate geometry to one Mn2+, one Zn2+, and one P5+ atom. In the thirteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Zn2+ and one P5+ atom. In the fourteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Mn2+, one Zn2+, and one P5+ atom. In the fifteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Mn2+, one Zn2+, and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Mn2+, one Zn2+, and one P5+ atom.

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