Discrete Oligomers and Polymers of Chloride Monohydrate Can Form in Encapsulated Environments: Structures and Infrared Spectra of [Cl 4 (H 2 O) 4 ] 4− and {[Cl(H 2 O)] − } ∞

A discrete tetrachloride tetrahydrate cluster, [Cl 4 (H 2 O) 4 ] 4− , was obtained with a partially‐fluorinated triaminocyclopropenium cation, [C 3 (N(CH 2 CF 3 ) 2 )(NEt 2 )(NPr 2 )] + . The cluster consists of a [Cl 2 (H 2 O) 2 ] 2− square with each Cl − coordinated by another H 2 O bridged to another Cl − . A 1D polymer of chloride monohydrate, {[Cl(H 2 O)] − } ∞ , was obtained with [C 3 (N(CH 2 CF 3 ) 2 ) 2 (NBuMe)] + . The tetrameric and polymeric structures were found to be computationally‐unstable in the gas phase which indicates that an encapsulated environment is essential for their isolation. DFT and DFTB calculations were carried out on gas‐phase [Cl 4 (H 2 O) 4 ] 4− to assist the infrared assignments. Anharmonically‐corrected B3LYP transition frequencies were in close agreement with experiment, but DFTB models were only appropriate for qualitative interpretation. Solid‐state DFTB calculations allowed the vibrational modes to be assigned. The results found are consistent with “discrete” chloride hydrates.