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NaIn is Zintl Phase structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional and consists of two NaIn frameworks. Na is bonded to four equivalent In atoms to form distorted corner-sharing NaIn4 tetrahedra. All Na–In bond lengths are 3.23 Å. In is bonded to four equivalent Na atoms to form distorted corner-sharing InNa4 tetrahedra.
Na2In crystallizes in the orthorhombic C222_1 space group. The structure is three-dimensional. there are five inequivalent Na sites. In the first Na site, Na is bonded in a 4-coordinate geometry to two equivalent Na and four In atoms. Both Na–Na bond lengths are 3.41 Å. There are two shorter (3.34 Å) and two longer (3.44 Å) Na–In bond lengths. In the second Na site, Na is bonded in a 12-coordinate geometry to six Na and six In atoms. There are a spread of Na–Na bond distances ranging from 3.33–3.58 Å. There are a spread of Na–In bond distances ranging from 3.32–3.61 Å. In the third Na site, Na is bonded in a 1-coordinate geometry to eight Na and five In atoms. There are a spread of Na–Na bond distances ranging from 3.55–3.99 Å. There are a spread of Na–In bond distances ranging from 3.39–3.72 Å. In the fourth Na site, Na is bonded in a 4-coordinate geometry to three Na and four In atoms. There are a spread of Na–In bond distances ranging from 3.21–3.33 Å. In the fifth Na site, Na is bonded in a 3-coordinate geometry to four Na and three In atoms. There are a spread of Na–In bond distances ranging from 3.33–3.48 Å. There are two inequivalent In sites. In the first In site, In is bonded to nine Na and three In atoms to form a mixture of distorted face and corner-sharing InNa9In3 cuboctahedra. There are two shorter (3.12 Å) and one longer (3.21 Å) In–In bond lengths. In the second In site, In is bonded in a 11-coordinate geometry to eight Na and three In atoms. The In–In bond length is 3.19 Å.
NaIn3 is Uranium Silicide-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Na is bonded to twelve equivalent In atoms to form a mixture of face and corner-sharing NaIn12 cuboctahedra. There are six shorter (3.33 Å) and six longer (3.40 Å) Na–In bond lengths. In is bonded to four equivalent Na atoms to form a mixture of distorted edge, face, and corner-sharing InNa4 cuboctahedra.
Na3In is Uranium Silicide-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Na sites. In the first Na site, Na is bonded to eight Na and four equivalent In atoms to form distorted NaNa8In4 cuboctahedra that share corners with twelve equivalent NaNa8In4 cuboctahedra, edges with eight equivalent NaNa8In4 cuboctahedra, edges with eight equivalent InNa12 cuboctahedra, faces with four equivalent InNa12 cuboctahedra, and faces with ten equivalent NaNa8In4 cuboctahedra. There are four shorter (3.46 Å) and four longer (3.50 Å) Na–Na bond lengths. All Na–In bond lengths are 3.50 Å. In the second Na site, Na is bonded in a distorted square co-planar geometry to eight equivalent Na and four equivalent In atoms. All Na–In bond lengths are 3.46 Å. In is bonded to twelve Na atoms to form InNa12 cuboctahedra that share corners with four equivalent InNa12 cuboctahedra, edges with eight equivalent InNa12 cuboctahedra, edges with sixteen equivalent NaNa8In4 cuboctahedra, faces with four equivalent InNa12 cuboctahedra, and faces with eight equivalent NaNa8In4 cuboctahedra.
NaIn3 is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Na is bonded to twelve equivalent In atoms to form a mixture of face and corner-sharing NaIn12 cuboctahedra. All Na–In bond lengths are 3.35 Å. In is bonded in a distorted square co-planar geometry to four equivalent Na atoms.
Na3In is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. there are two inequivalent Na sites. In the first Na site, Na is bonded to four equivalent Na and four equivalent In atoms to form a mixture of distorted face, edge, and corner-sharing NaNa4In4 tetrahedra. All Na–Na bond lengths are 3.38 Å. All Na–In bond lengths are 3.38 Å. In the second Na site, Na is bonded in a body-centered cubic geometry to eight equivalent Na atoms. In is bonded in a body-centered cubic geometry to eight equivalent Na atoms.