Two-dimensional Hofmann-type coordination polymers of type Mn(H2O)(2)[Pd(CN)(4)]center dot xH(2)O (1 center dot xH(2)O; x = 0, 1, and 4), Mn(H2O)-(MeOH)[Pd(CN)(4)]center dot 2MeOH (2.2MeOH), and Mn(MeOH)(2) [Pd(CN)(4)]center dot MeOH (3 center dot MeOH) have been synthesized. The homosolvent-bound 1.4H(2)O, 1.H2O, and 3 center dot MeOH polymers consist of undulating layer structures, whereas the structure of heterosolvent-bound 2.2MeOH consists of "Janus-like" flat layers in which water-bound and MeOH-bound-sides are present. 1.4H(2)O and 1 center dot H2O exhibited anisotropic two-dimensional thermal expansions involving structural transformations of the undulating layers; one layer axis expands while the other contracts. 2.2MeOH exhibits anisotropic thermal expansion in which the flat layers shift sideways as the temperature is increased, with colossal interlayer expansion occurring (alpha(c) = +200 MK-1 over 140-180 K, alpha(c)= +16S MK-1 over 200-280 K). 3 center dot MeOH also showed colossal interlayer expansion (alpha(c)= +216 MK-1) together with expansion of the undulating layers.