Magnetically ordered Prussian blue analogues with the general formulation of M[Mn(CN)(6)] (M = V, Cr, Mn, Co, Ni) were made in aprotic media utilizing [Mn-IV(CN)(6)](2-). These analogs are valence-ambiguous, as they can be formulated as M-II[Mn-IV(CN)(6)] or M-III[Mn-III(CN)(6)]. The X-ray powder diffraction of each member of this family can be indexed to the face-centered cubic (fcc) Prussian blue structure type, with atypically reduced unit cell parameters (a approximate to 9.25 +/- 0.25 Angstrom) with respect to hydrated Prussian blue structured materials (a greater than or equal to 10.1 Angstrom). The reduced a-values are attributed to a contraction of the lattice in the absence of water or coordinating solvent molecule (i.e., MeCN) that is necessary to help stabilize the structure during lattice formation. Based on nu(CN) LR absorptions, X-ray photoelectron spectra, and magnetic data, the following oxidation state assignments are made: M-II[Mn-IV(CN)(6)] (M = Co, Ni) and M-III[Mn-III(CN)(6)] (M = V, Cr, Mn). Formation of Mn-III[Mn-III(CN)(6)] is in contrast to Mn-II[Mn-IV(CN)(6)] prepared from aqueous media. Above 250 K, the magnetic susceptibilities of M[Mn(CN)(6)] (M = V, Cr, Mn, Co, Ni) can be fit to the Curie-Weiss equation with theta = -370, -140, -105, -55, and -120 K, respectively, suggesting strong antiferromagnetic coupling. The room temperature effective moments, respectively, are 3.71, 4.62, 5.66, 4.54, and 4.91 mu(B), consistent with the above oxidation state assignments. All compounds do not exhibit magnetic saturation at 50 kOe, and exhibit frequency-dependent chi'(T) and chi "(T) responses characteristic of spin-glass-like behavior. M[Mn(CN)(6)] order as ferrimagnets, with T-c's taken from the peak in the 10 Hz chi'(T) data, of 19, 16, 27.1, <1.75, and 4.8 K for M = V, Cr, Mn, Co, and Ni, respectively. The structural and magnetic disorder prevents Ni-II[Mn-IV(CN)(6)] from ordering as a ferromagnet as anticipated, and structural inhomogeneities allow Co-II[Mn-IV(CN)(6)] and Vm[Mn-III(CN)(6)] to unexpectedly order as ferrimagnets. Also, Mn-III[Mn(CN)(6)] behaves as a reentrant spin glass showing two transitions at 20 and 27.1 K, and similar behavior is evident for Crm[Mn-III(CN)(6)]. Hysteresis with coercive fields of 340, 130, 8, 9, and 220 Oe and remanent magnetizations of 40, 80, 1500, 4, and 250 emuOe/mol are obsen;ed for M = V, Cr, Mn, Co, and Ni, respectively.