N→Sn-Coordinated Stannaoxidoborates Containing a SnB4O6 Unit.

We report here the synthesis of new N→Sn-coordinated stannaoxidoborates H[LSnB4O6R4] {L = [2,6-(Me2NCH2)C6H3](-) and R = Ph (6), 4-Br-Ph (7), 3,5-(CF3)2-Ph (8), and 4-CHO-Ph (9)} containing a nonsymmetric SnB4O6 unit. Compounds 6-9 represent new derivatives of the pentaborates [B5O6R4](-) in which the central boron is substituted by a tin atom. Compounds 6-9 were characterized by means of elemental analysis, electrospray ionization mass spectrometry, and NMR spectroscopy and in the case of 6-8 also by single-crystal X-ray diffraction analysis. The structures of N→Sn-coordinated stannaoxidoborates 6-8 consist of a spirobicyclic arrangement, with two six-membered SnB2O3 rings at the tin atom providing the new stannaoxidoborate [LSnB4O6R4](-) motif, which is compensated for by the proton atom coordinated to the Me2N group of the ligand L. The linear and thermal properties of 6-9 were studied with the help of electronic absorption spectra and differential scanning calorimetry. In addition, the presence of the nonsymmetric stannaoxidoborate SnB4O6 unit in 6, 7, and 9 prompted us to investigate their second-order nonlinear-optical properties.