Inorganic Chemistry, Vol.59, No.12, 8620-8628, 2020
Synthesis and Characterization of SF4 Adducts with Polycyclic Amines
Chalcogen-bonding interactions of SF4 with the polycyclic amines DABCO (C6H12N2) and HMTA (C6H12N4) were studied by low-temperature Raman spectroscopy and X-ray crystallography, revealing the 2:1 adducts C6H12N2 center dot 2SF(4 )and C6H12N4 center dot 2SF(4) obtained from SF4 solvent. In C6H12N2 center dot 2SF(4), the sulfur in each SF4 molecule is pentacoordinate with each SF4 coordinated by a single amine group, whereas C6H12N4 center dot 2SF(4) forms a one-dimensional coordination polymer with three of the four nitrogen atoms in HMTA exhibiting N---S chalcogen bonds: one terminal N---SF4 and one experimentally unprecedented bridging N---(SF4)---N moiety. Solvolysis of C(6)H(1)2N(2)center dot 2S(4) by HF yielded crystals of [C6H12N2H]F-+(2)-[SF5](-)center dot 6SF(4), in which SF4 acts as a chalcogen-bond donor toward N as well as F. Solvolysis of C6H12N4 center dot 2SF(4) resulted in the formation of the monoprotonated HMTA salt [C6H12N4H](+)[HF2](-)center dot SF4. Excess HF also led to isolation of monoprotonated HTMA, as seen in the crystal structure of the [C6H12N4H](+)[H2F3]-(HF)-H-center dot salt. The reaction of bicyclic, monobasic quinuclidine with SF4 and HF gave [C7H13NH](+)F(-)3.5SF(4), which contains N-H---F----SF4 interactions, as well as an interstitial, disordered SF4 molecule.