Na2CaGe6O14 is Esseneite-like structured and crystallizes in the monoclinic C2 space group. Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(5), one O(7), two equivalent O(4), and two equivalent O(6) atoms. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(7) atoms. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form GeO4 tetrahedra that share corners with two equivalent Ge(3)O6 octahedra and corners with two equivalent Ge(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 60-62°. In the second Ge site, Ge(2) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form GeO4 tetrahedra that share corners with two equivalent Ge(3)O6 octahedra and corners with two equivalent Ge(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 61°. In the third Ge site, Ge(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form corner-sharing GeO6 octahedra. In the fourth Ge site, Ge(4) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form corner-sharing GeO4 tetrahedra. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Ge(2), and one Ge(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Ge(1), and one Ge(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ge(1), and one Ge(3) atom. In the fourth O site, O(4) is bonded to two equivalent Na(1), one Ca(1), and one Ge(4) atom to form distorted corner-sharing ONa2CaGe tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Ge(2), and one Ge(4) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ge(1), and one Ge(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Ge(1), and one Ge(4) atom.
Na2CaGe6O14 is Esseneite-like structured and crystallizes in the monoclinic C2 space group. Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(5), one O(7), two equivalent O(4), and two equivalent O(6) atoms. The Na(1)-O(1) bond length is 2.46 Å. The Na(1)-O(2) bond length is 2.47 Å. The Na(1)-O(5) bond length is 2.90 Å. The Na(1)-O(7) bond length is 2.54 Å. Both Na(1)-O(4) bond lengths are 2.69 Å. There is one shorter (2.52 Å) and one longer (2.90 Å) Na(1)-O(6) bond length. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(7) atoms. Both Ca(1)-O(3) bond lengths are 2.44 Å. Both Ca(1)-O(4) bond lengths are 2.46 Å. Both Ca(1)-O(5) bond lengths are 2.48 Å. Both Ca(1)-O(7) bond lengths are 2.79 Å. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form GeO4 tetrahedra that share corners with two equivalent Ge(3)O6 octahedra and corners with two equivalent Ge(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 60-62°. The Ge(1)-O(2) bond length is 1.77 Å. The Ge(1)-O(3) bond length is 1.78 Å. The Ge(1)-O(6) bond length is 1.80 Å. The Ge(1)-O(7) bond length is 1.80 Å. In the second Ge site, Ge(2) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form GeO4 tetrahedra that share corners with two equivalent Ge(3)O6 octahedra and corners with two equivalent Ge(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 61°. Both Ge(2)-O(1) bond lengths are 1.77 Å. Both Ge(2)-O(5) bond lengths are 1.81 Å. In the third Ge site, Ge(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form corner-sharing GeO6 octahedra. Both Ge(3)-O(1) bond lengths are 1.92 Å. Both Ge(3)-O(2) bond lengths are 1.93 Å. Both Ge(3)-O(3) bond lengths are 1.95 Å. In the fourth Ge site, Ge(4) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form corner-sharing GeO4 tetrahedra. The Ge(4)-O(4) bond length is 1.70 Å. The Ge(4)-O(5) bond length is 1.81 Å. The Ge(4)-O(6) bond length is 1.79 Å. The Ge(4)-O(7) bond length is 1.81 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Ge(2), and one Ge(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Ge(1), and one Ge(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ge(1), and one Ge(3) atom. In the fourth O site, O(4) is bonded to two equivalent Na(1), one Ca(1), and one Ge(4) atom to form distorted corner-sharing ONa2CaGe tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Ge(2), and one Ge(4) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ge(1), and one Ge(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Ge(1), and one Ge(4) atom.