Na2Cu3(GeO3)4 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(6), and two equivalent O(5) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(6) atom. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(6) atoms. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form corner-sharing GeO4 tetrahedra. In the second Ge site, Ge(2) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form corner-sharing GeO4 tetrahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one Ge(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Cu(1), and one Ge(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cu(1), one Cu(2), and one Ge(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Ge(1), and one Ge(2) atom. In the fifth O site, O(5) is bonded to two equivalent Na(1), one Ge(1), and one Ge(2) atom to form distorted ONa2Ge2 trigonal pyramids that share corners with three equivalent O(6)NaCu2Ge trigonal pyramids and  an edgeedge with one O(5)Na2Ge2 trigonal pyramid. In the sixth O site, O(6) is bonded to one Na(1), one Cu(1), one Cu(2), and one Ge(2) atom to form distorted ONaCu2Ge trigonal pyramids that share  a cornercorner with one O(6)NaCu2Ge trigonal pyramid and corners with three equivalent O(5)Na2Ge2 trigonal pyramids.
Na2Cu3(GeO3)4 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(6), and two equivalent O(5) atoms. The Na(1)-O(1) bond length is 2.35 Å. The Na(1)-O(2) bond length is 2.80 Å. The Na(1)-O(4) bond length is 2.43 Å. The Na(1)-O(6) bond length is 2.36 Å. There is one shorter (2.35 Å) and one longer (2.69 Å) Na(1)-O(5) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(6) atom. The Cu(1)-O(1) bond length is 1.93 Å. The Cu(1)-O(2) bond length is 1.92 Å. The Cu(1)-O(3) bond length is 1.96 Å. The Cu(1)-O(6) bond length is 1.99 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(6) atoms. Both Cu(2)-O(3) bond lengths are 1.97 Å. Both Cu(2)-O(6) bond lengths are 1.95 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form corner-sharing GeO4 tetrahedra. The Ge(1)-O(2) bond length is 1.74 Å. The Ge(1)-O(3) bond length is 1.77 Å. The Ge(1)-O(4) bond length is 1.81 Å. The Ge(1)-O(5) bond length is 1.81 Å. In the second Ge site, Ge(2) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form corner-sharing GeO4 tetrahedra. The Ge(2)-O(1) bond length is 1.75 Å. The Ge(2)-O(4) bond length is 1.78 Å. The Ge(2)-O(5) bond length is 1.80 Å. The Ge(2)-O(6) bond length is 1.78 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one Ge(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Cu(1), and one Ge(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Cu(1), one Cu(2), and one Ge(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Ge(1), and one Ge(2) atom. In the fifth O site, O(5) is bonded to two equivalent Na(1), one Ge(1), and one Ge(2) atom to form distorted ONa2Ge2 trigonal pyramids that share corners with three equivalent O(6)NaCu2Ge trigonal pyramids and  an edgeedge with one O(5)Na2Ge2 trigonal pyramid. In the sixth O site, O(6) is bonded to one Na(1), one Cu(1), one Cu(2), and one Ge(2) atom to form distorted ONaCu2Ge trigonal pyramids that share  a cornercorner with one O(6)NaCu2Ge trigonal pyramid and corners with three equivalent O(5)Na2Ge2 trigonal pyramids.