Treatment of [HNBu3](3)[Mo-V(CN)(8)] with manganese(II) p-toluenesulfonate in N, N'-dimethylformamide (DMF) affords {[Mn-II(DMF)(4)](3)[ Mo-V(CN)(8)] 2}(n) ( 1) as a two-dimensional network. The structure of 1 consists of [cis-Mn-II(DMF)(4)(mu-NC)(2)](2+) and [trans-Mn-II(DMF)(4)(mu-NC) (2)](2+) units that are linked via cyanides to three-connected [ Mo-V( CN)(5)(mu-CN)(3)](3-) centers in a 4: 2: 6 ratio, forming 12-membered rings. Magnetic measurements indicate that 1 is a ferrimagnet (T-N = 8 K) that exhibits frequency-dependent behavior in chi ''. Heating of 1 affords an additional magnetic phase (T-N = 21 K) that is absent of linkage isomerism.