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NaCl7 crystallizes in the cubic Pm-3 space group. The structure is three-dimensional and consists of one hydrochloric acid molecule and one NaCl6 framework. In the NaCl6 framework, Na is bonded to twelve equivalent Cl atoms to form edge-sharing NaCl12 cuboctahedra. All Na–Cl bond lengths are 3.24 Å. Cl is bonded in a 3-coordinate geometry to two equivalent Na and one Cl atom. The Cl–Cl bond length is 2.05 Å.
NaAuCl4 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are four inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to seven Cl1- atoms to form distorted corner-sharing NaCl7 pentagonal bipyramids. There are a spread of Na–Cl bond distances ranging from 2.95–3.09 Å. In the second Na1+ site, Na1+ is bonded to seven Cl1- atoms to form distorted corner-sharing NaCl7 pentagonal bipyramids. There are a spread of Na–Cl bond distances ranging from 2.89–3.15 Å. In the third Na1+ site, Na1+ is bonded to seven Cl1- atoms to form distorted corner-sharing NaCl7 pentagonal bipyramids. There are a spread of Na–Cl bond distances ranging from 2.94–3.10 Å. In the fourth Na1+ site, Na1+ is bonded to seven Cl1- atoms to form distorted corner-sharing NaCl7 pentagonal bipyramids. There are a spread of Na–Cl bond distances ranging from 2.86–3.27 Å. There are four inequivalent Au3+ sites. In the first Au3+ site, Au3+ is bonded in a rectangular see-saw-like geometry to four Cl1- atoms. There are one shorter (2.32 Å) and three longer (2.33 Å) Au–Cl bond lengths. In the second Au3+ site, Au3+ is bonded in a rectangular see-saw-like geometry to four Cl1- atoms. There are a spread of Au–Cl bond distances ranging from 2.31–2.33 Å. In the third Au3+ site, Au3+ is bonded in a rectangular see-saw-like geometry to four Cl1- atoms. There are two shorter (2.32 Å) and two longer (2.33 Å) Au–Cl bond lengths. In the fourth Au3+ site, Au3+ is bonded in a rectangular see-saw-like geometry to four Cl1- atoms. There are three shorter (2.32 Å) and one longer (2.33 Å) Au–Cl bond lengths. There are sixteen inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to two Na1+ and one Au3+ atom. In the second Cl1- site, Cl1- is bonded in a water-like geometry to one Na1+ and one Au3+ atom. In the third Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to two Na1+ and one Au3+ atom. In the fourth Cl1- site, Cl1- is bonded in a trigonal non-coplanar geometry to two Na1+ and one Au3+ atom. In the fifth Cl1- site, Cl1- is bonded in a trigonal non-coplanar geometry to two Na1+ and one Au3+ atom. In the sixth Cl1- site, Cl1- is bonded in a water-like geometry to one Na1+ and one Au3+ atom. In the seventh Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to two Na1+ and one Au3+ atom. In the eighth Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to two Na1+ and one Au3+ atom. In the ninth Cl1- site, Cl1- is bonded in a water-like geometry to one Na1+ and one Au3+ atom. In the tenth Cl1- site, Cl1- is bonded in a 3-coordinate geometry to two Na1+ and one Au3+ atom. In the eleventh Cl1- site, Cl1- is bonded in a distorted trigonal non-coplanar geometry to two Na1+ and one Au3+ atom. In the twelfth Cl1- site, Cl1- is bonded in a 3-coordinate geometry to two Na1+ and one Au3+ atom. In the thirteenth Cl1- site, Cl1- is bonded in a water-like geometry to one Na1+ and one Au3+ atom. In the fourteenth Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to two Na1+ and one Au3+ atom. In the fifteenth Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to two Na1+ and one Au3+ atom. In the sixteenth Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to two Na1+ and one Au3+ atom.