Large single crystals of A 2 Mn 2 V 2 O 7 F 2 (A = Rb, Cs) and Mn 2 VO 4 F were grown using a hightemperature (~600˚C) hydrothermal technique. Single crystal X-ray diffraction and powder Xray diffraction were utilized to characterize the structures, which both possess MnO 4 F 2 building blocks. The A 2 Mn 2 V 2 O 7 F 2 series crystallizes as a new structure type in space group Pbcn (no. 60), Z = 4 (Rb 2 Mn 2 V 2 O 7 F 2 : a = 7.4389(17) Å, b = 11.574(3) Å, c = 10.914(2) Å; Cs 2 Mn 2 V 2 O 7 F 2 : a = 7.5615(15) Å, b = 11.745(2) Å, c = 11.127(2) Å). The structure is composed of zigzag chains of edge-sharing MnO 4 F 2 units running along the a-axis, and interconnected through V 2 O 7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn 2+ indicated that Cs 2 Mn 2 V 2 O 7 F 2 is antiferromagnetic with a Neél temperature, T N = ~ 3 K a Weiss constant, θ, of-11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V-O vibrational modes in Cs 2 Mn 2 V 2 O 7 F 2. Mn 2 (VO 4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z = 8 with unit cell parameters of a = 13.559(2) Å, b = 6.8036(7) Å, c = 10.1408(13) Å and β = 116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and sixcoordinate Mn 2+. These interpenetrating chains are additionally connected through isolated VO 4 tetrahedra to form the condensed structure.