Na4Cu7P4(O9Cl)2 crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(6), one O(7), and one Cl(2) atom. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(4), one O(8), two equivalent O(1), and two equivalent O(5) atoms to form distorted CuO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Cu(2)ClO4 trigonal bipyramids, and edges with two equivalent Cu(3)ClO4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 61-63°. In the second Cu site, Cu(2) is bonded to one O(3), one O(4), two equivalent O(5), and one Cl(1) atom to form distorted CuClO4 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Cu(2)ClO4 trigonal bipyramid. In the third Cu site, Cu(3) is bonded to one O(6), one O(8), two equivalent O(1), and one Cl(2) atom to form distorted CuClO4 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Cu(3)ClO4 trigonal bipyramid. In the fourth Cu site, Cu(4) is bonded in a distorted T-shaped geometry to two equivalent O(7) and one Cl(2) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Cu(2)ClO4 trigonal bipyramid, and corners with two equivalent Cu(3)ClO4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. In the second P site, P(2) is bonded to one O(6), one O(7), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Cu(3)ClO4 trigonal bipyramid, and corners with two equivalent Cu(2)ClO4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 46°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(3), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one P(1) atom. In the third O site, O(3) is bonded to two equivalent Na(1), one Cu(2), and one P(1) atom to form distorted ONa2CuP tetrahedra that share  a cornercorner with one O(4)Cu4 tetrahedra and corners with two equivalent O(7)Na2CuP tetrahedra. In the fourth O site, O(4) is bonded to two equivalent Cu(1) and two equivalent Cu(2) atoms to form OCu4 tetrahedra that share corners with two equivalent O(8)Cu4 tetrahedra and corners with two equivalent O(3)Na2CuP tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Cu(3), and one P(2) atom. In the seventh O site, O(7) is bonded to two equivalent Na(1), one Cu(4), and one P(2) atom to form distorted corner-sharing ONa2CuP tetrahedra. In the eighth O site, O(8) is bonded to two equivalent Cu(1) and two equivalent Cu(3) atoms to form corner-sharing OCu4 tetrahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 2-coordinate geometry to two equivalent Cu(2) atoms. In the second Cl site, Cl(2) is bonded in a 7-coordinate geometry to four equivalent Na(1), one Cu(4), and two equivalent Cu(3) atoms.
Na4Cu7P4(O9Cl)2 crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(6), one O(7), and one Cl(2) atom. The Na(1)-O(2) bond length is 2.23 Å. The Na(1)-O(3) bond length is 2.41 Å. The Na(1)-O(6) bond length is 2.51 Å. The Na(1)-O(7) bond length is 2.38 Å. The Na(1)-Cl(2) bond length is 3.24 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(4), one O(8), two equivalent O(1), and two equivalent O(5) atoms to form distorted CuO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Cu(2)ClO4 trigonal bipyramids, and edges with two equivalent Cu(3)ClO4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 61-63°. The Cu(1)-O(4) bond length is 1.87 Å. The Cu(1)-O(8) bond length is 1.89 Å. Both Cu(1)-O(1) bond lengths are 2.21 Å. Both Cu(1)-O(5) bond lengths are 2.22 Å. In the second Cu site, Cu(2) is bonded to one O(3), one O(4), two equivalent O(5), and one Cl(1) atom to form distorted CuClO4 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Cu(2)ClO4 trigonal bipyramid. The Cu(2)-O(3) bond length is 1.95 Å. The Cu(2)-O(4) bond length is 1.96 Å. Both Cu(2)-O(5) bond lengths are 2.10 Å. The Cu(2)-Cl(1) bond length is 2.44 Å. In the third Cu site, Cu(3) is bonded to one O(6), one O(8), two equivalent O(1), and one Cl(2) atom to form distorted CuClO4 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Cu(1)O6 octahedra, and  an edgeedge with one Cu(3)ClO4 trigonal bipyramid. The Cu(3)-O(6) bond length is 1.92 Å. The Cu(3)-O(8) bond length is 1.92 Å. Both Cu(3)-O(1) bond lengths are 2.05 Å. The Cu(3)-Cl(2) bond length is 2.63 Å. In the fourth Cu site, Cu(4) is bonded in a distorted T-shaped geometry to two equivalent O(7) and one Cl(2) atom. Both Cu(4)-O(7) bond lengths are 1.95 Å. The Cu(4)-Cl(2) bond length is 2.27 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Cu(2)ClO4 trigonal bipyramid, and corners with two equivalent Cu(3)ClO4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(3) bond length is 1.58 Å. Both P(1)-O(1) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(6), one O(7), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Cu(3)ClO4 trigonal bipyramid, and corners with two equivalent Cu(2)ClO4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 46°. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.57 Å. Both P(2)-O(5) bond lengths are 1.55 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(3), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one P(1) atom. In the third O site, O(3) is bonded to two equivalent Na(1), one Cu(2), and one P(1) atom to form distorted ONa2CuP tetrahedra that share  a cornercorner with one O(4)Cu4 tetrahedra and corners with two equivalent O(7)Na2CuP tetrahedra. In the fourth O site, O(4) is bonded to two equivalent Cu(1) and two equivalent Cu(2) atoms to form OCu4 tetrahedra that share corners with two equivalent O(8)Cu4 tetrahedra and corners with two equivalent O(3)Na2CuP tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Cu(3), and one P(2) atom. In the seventh O site, O(7) is bonded to two equivalent Na(1), one Cu(4), and one P(2) atom to form distorted corner-sharing ONa2CuP tetrahedra. In the eighth O site, O(8) is bonded to two equivalent Cu(1) and two equivalent Cu(3) atoms to form corner-sharing OCu4 tetrahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 2-coordinate geometry to two equivalent Cu(2) atoms. In the second Cl site, Cl(2) is bonded in a 7-coordinate geometry to four equivalent Na(1), one Cu(4), and two equivalent Cu(3) atoms.