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A new hybrid perovskite of [FCH2CH2NH3][Mn(HCOO)3] has been successfully prepared by utilizing the ammonium of FCH2CH2NH3+, and it is the first example incorporating F‐substituted ammonium in the class of ammonium metal formate framework. The compound crystallizes in polar, orthorhombic space group Pna21, and the cell parameters are a=8.5901(3)–8.7158(6), b=8.4613(3)–8.5216(6), c=12.4837(4)–12.6106(9)...