Syntheses, Crystal Structures, and Properties of Two Quaternary Selenite/Tellurite‐Nitrates with Formula of Bi(SeO 3 )(NO 3 ) and Bi 3 (μ 3 ‐OH)(TeO 3 ) 3 (NO 3 ) 2

Abstract Here, we report the preparation and characterization of two quaternary selenite/tellurite‐nitrates, namely, Bi(SeO 3 )(NO 3 ) and Bi 3 (μ 3 ‐OH)(TeO 3 ) 3 (NO 3 ) 2 through a facile hydrothermal reaction. Bi(SeO 3 )(NO 3 ) crystallizes in the centrosymmetric space group C 2/c (No.15), which features a 2D [Bi(SeO 3 )] ∞ layer in the ab plane and NO 3 − anions are located between the neighboring [Bi(SeO 3 )] ∞ layers. Bi 3 (μ 3 ‐OH)(TeO 3 ) 3 (NO 3 ) 2 crystallizes in the noncentrosymmetric space group P ‐62 m (No.189), which exhibits a rare bismuth‐oxo‐tellurite 1D tube that are separated by nitrate groups. This rare bismuth‐oxo‐tellurite 1D tube is formed by the interconnection of hexanuclear [Bi 6 (μ 3 ‐OH) 2 O 24 ] cage clusters and 1D chain of [Te 3 O 10 ] ∞ . The nonlinear optical property of Bi 3 (μ 3 ‐OH)(TeO 3 ) 3 (NO 3 ) 2 has been studied and it produces a weak second harmonic generation (SHG) response that of 0.5×KDP (KH 2 PO 4 ) due to the effect of the stereo‐active lone‐pairs on Bi 3+ and Te 4+ cations and π‐conjugated NO 3 units in Bi 3 (μ 3 ‐OH)(TeO 3 ) 3 (NO 3 ) 2 . IR, UV‐vis spectra and thermogravimetric analysis (TGA) for the two compounds were also measured.