Na2CuF4 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 7-coordinate geometry to three equivalent F(2) and four equivalent F(1) atoms. Cu(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form edge-sharing CuF6 octahedra. There are two inequivalent F sites. In the first F site, F(2) is bonded to three equivalent Na(1) and two equivalent Cu(1) atoms to form distorted FNa3Cu2 trigonal bipyramids that share corners with four equivalent F(1)Na4Cu trigonal bipyramids, corners with eight equivalent F(2)Na3Cu2 trigonal bipyramids, edges with two equivalent F(2)Na3Cu2 trigonal bipyramids, and edges with six equivalent F(1)Na4Cu trigonal bipyramids. In the second F site, F(1) is bonded to four equivalent Na(1) and one Cu(1) atom to form distorted FNa4Cu trigonal bipyramids that share corners with four equivalent F(2)Na3Cu2 trigonal bipyramids, corners with five equivalent F(1)Na4Cu trigonal bipyramids, edges with four equivalent F(1)Na4Cu trigonal bipyramids, and edges with six equivalent F(2)Na3Cu2 trigonal bipyramids.
Na2CuF4 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 7-coordinate geometry to three equivalent F(2) and four equivalent F(1) atoms. There are a spread of Na(1)-F(2) bond distances ranging from 2.27-2.61 Å. There are a spread of Na(1)-F(1) bond distances ranging from 2.26-2.34 Å. Cu(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form edge-sharing CuF6 octahedra. Both Cu(1)-F(1) bond lengths are 1.90 Å. There are two shorter (1.93 Å) and two longer (2.37 Å) Cu(1)-F(2) bond lengths. There are two inequivalent F sites. In the first F site, F(2) is bonded to three equivalent Na(1) and two equivalent Cu(1) atoms to form distorted FNa3Cu2 trigonal bipyramids that share corners with four equivalent F(1)Na4Cu trigonal bipyramids, corners with eight equivalent F(2)Na3Cu2 trigonal bipyramids, edges with two equivalent F(2)Na3Cu2 trigonal bipyramids, and edges with six equivalent F(1)Na4Cu trigonal bipyramids. In the second F site, F(1) is bonded to four equivalent Na(1) and one Cu(1) atom to form distorted FNa4Cu trigonal bipyramids that share corners with four equivalent F(2)Na3Cu2 trigonal bipyramids, corners with five equivalent F(1)Na4Cu trigonal bipyramids, edges with four equivalent F(1)Na4Cu trigonal bipyramids, and edges with six equivalent F(2)Na3Cu2 trigonal bipyramids.