Polymorphism and optical properties in [NH4][InSe2]

The solvothermal synthesis and characterization of two indium selenides with stoichiometry [NH4][InSe2] is described. Yellow [NH4][InSe2] (1), which exhibits a layered structure, was initially prepared in an aqueous solution of trans-1,4-diaminocyclohexane, and subsequently using a concentrated ammonia solution. A red polymorph of one-dimensional character, [NH4][InSe2] (2), was obtained using 3,5-dimethylpyridine as solvent. [NH4][InSe2] (1) crystallizes in the non-centrosymmetric space group Cc (a=11.5147(6), b=11.3242(6), c=15.9969(9) Å and β=100.354(3)°). The structural motif of the layers is the In4Se10 adamantane unit, composed of four corner-linked InSe4 tetrahedra. These units are linked by their corners, forming [InSe2]− layers which are stacked back to back along the c-direction, and interspaced by [NH4]+cations. The one-dimensional polymorph, (2), crystallizes in the tetragonal space group, I4/mcm (a=8.2519(16), c=6.9059 (14) Å). This structure contains infinite chains of edge-sharing InSe4 tetrahedra separated by [NH4]+ cations. - Graphical abstract: Two polymorphic forms of [NH4][InSe2], which are yellow and red, have been prepared and their optical properties investigated. Highlights: • Two new indium selenides prepared by a solvothermal method. • Depending on synthesis conditions, two polymorphic forms of [NH4][InSe2] prepared. • Layered polymorph contains In4Se10 adamantane clusters, linked by their corners. • One-dimensional polymorph contains [InSe2]− chains of edge-sharing tetrahedra. • Non-centrosymmetric layered polymorph shows a second harmonic generation response