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NaIn2Sn crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two NaIn2Sn ribbons oriented in the (1, 0, 0) direction. Na is bonded in a linear geometry to two equivalent In atoms. Both Na–In bond lengths are 3.10 Å. In is bonded in a linear geometry to one Na and one Sn atom. The In–Sn bond length is 2.74 Å. Sn is bonded in a linear geometry to two equivalent In atoms.
NaInSn2 crystallizes in the orthorhombic P2_12_12_1 space group. The structure is three-dimensional. Na is bonded in a 12-coordinate geometry to three equivalent In and seven Sn atoms. There are a spread of Na–In bond distances ranging from 3.50–3.72 Å. There are a spread of Na–Sn bond distances ranging from 3.32–3.68 Å. In is bonded in a 7-coordinate geometry to three equivalent Na and four Sn atoms. There are a spread of In–Sn bond distances ranging from 2.91–2.93 Å. There are two inequivalent Sn sites. In the first Sn site, Sn is bonded in a 7-coordinate geometry to three equivalent Na, two equivalent In, and two equivalent Sn atoms. There are one shorter (2.92 Å) and one longer (2.94 Å) Sn–Sn bond lengths. In the second Sn site, Sn is bonded in a 8-coordinate geometry to four equivalent Na, two equivalent In, and two equivalent Sn atoms.
NaInSn4 crystallizes in the tetragonal I422 space group. The structure is three-dimensional. Na is bonded in a distorted q6 geometry to two equivalent In and eight equivalent Sn atoms. Both Na–In bond lengths are 3.08 Å. All Na–Sn bond lengths are 3.21 Å. In is bonded in a 10-coordinate geometry to two equivalent Na and eight equivalent Sn atoms. All In–Sn bond lengths are 3.21 Å. Sn is bonded in a 2-coordinate geometry to two equivalent Na, two equivalent In, and one Sn atom. The Sn–Sn bond length is 3.12 Å.