Crystal structures of the trifluoromethyl sulfonates M(SO₃CF₃)₂ (M = Mg, Ca, Ba, Zn, Cu) from synchrotron X-ray powder diffraction data

Abstract

The crystal structures of divalent metal salts of trifluoromethyl sulfonic acid ("trifluoromethyl sulfonates") M(SO(3)CF(3))(2) (M = Mg, Ca, Ba, Zn, Cu) were determined from high-resolution X-ray powder diffraction data. Magnesium, calcium and zinc trifluoromethyl sulfonate crystallize in the rhombohedral space group R(bar)3. Barium trifluoromethyl sulfonate crystallizes in the monoclinic space group I2/a(C2/c) and copper trifluoromethyl sulfonate crystallizes in the triclinic group P(bar)1. Within the crystal structures the trifluoromethyl sulfonate anions are arranged in double layers with the apolar CF(3) groups pointing towards each other. The cations are located next to the SO(3) groups. The symmetry relations between the different crystal structures have been analysed.

Silver(ii) triflate with one-dimensional [Ag(ii)(SO3CF3)4/2]∞ chains hosting antiferromagnetism

“…Indexation of the XRDP of Ag(OTf) 2 suggested its isomorphism with Cu(OTf) 2 . 23 The structure of Ag(II)(OTf) 2 was refined by the Rietveld method as applied in Jana2006 (ref. 24) with Cu(SO 3 CF 3 ) 2 used as a starting structure model.…”

Cation effect on the inorganic–organic layered structure of pyrazole-4-sulfonate networks and inhibitory effects on copper corrosion

“…31 The nature of the backbone of the sulfonate groups also affects the number of coordinated sulfonates and H 2 O molecules. For example, from the 22 Mg 2+ sulfonate structures found in the Cambridge Structural Database (CSD) 32 (with no other functional groups than sulfonate coordinating to Mg), 20 structures based on aromatic sulfonates contain [Mg(H 2 O) 6 ] 2+ and no sulfonate groups coordinating, while two structures containing the aliphatic hydroxymethyl-33 and trifluoromethyl-sulfonates 34 have two (Z 1 ) or even six (m 3 -Z 1 :Z 1 :Z 1 ) sulfonate groups coordinating, respectively. The non-coordination of the aromatic sulfonates can be attributed to the diminished negative charge on the sulfonate groups due to delocalization over the aromatic ring, which in turn participates in extended p-p interactions.…”

Water-Tolerant Trifloaluminate Ionic Liquids: New and Unique Lewis Acidic Catalysts for the Synthesis of Chromane

“…Indeed, no M(OTf) 3 crystal structures are known. The only single crystal structures recorded by conventional methods are these of Group 1, K(OTf) (Korus and Jansen, 2001 ) and Na(OTf) (Sofina et al, 2003 ), in addition to several M(OTf) 2 structures, recoded relatively recently by synchrotron X-ray powder diffraction data (Dinnebier et al, 2006 ). All of these feature triflate anions in complex binding modes, both terminal and bridging, with a single oxygen in triflate shared by one, two or three metal centers.…”