The unique enantiopure {[Lambda-Co-II((R)mpm)(2)](3)[W-V(CN)(8)](2)}center dot 9H(2)O [(R)-1] and {[Delta-Co-II((S)mpm)(2)}(3)[W-V(CN)(8)](2)}center dot 9H(2)O [(S)-1], where mpm = alpha-methylpyridinemethanol, magnetic spongelike materials, crystallizing in the chiral P2(1) space group, are constructed of cyanido-bridged {Co3W2} trigonal bipyramids with three cis[Co-II(mpm)(2)(mu-NC)(2)] moieties in equatorial sites and two [W-V(CN)(8)](3-) units in apical positions. The arrangement of {Co3W2} clusters in the crystal lattice is controlled by interactions with crystallization H2O molecules, resulting in two independent hydrogen-bonding systems: the first weaving along open channels in the a direction (weakly bonded H2O) and the second closed in the cages formed by the surrounding [W(CN)(8)](3-) and mpm fragments (strongly bonded H2O). The strong optical activity of (R)- and (S)-1 together with continuous chirality measure (CCM) analysis confirms the chirality transfer from enantiopure (R)- and (S)-mpm to [Co(mpm)(2)(mu-NC)(2)] units, a cyanido-bridged skeleton, and to the whole crystal lattice. Magnetic properties confronted with ab initio calculations prove the ferromagnetic couplings within Co-II-NC-W-V linkages inside {Co3W2} molecules, accompanied by weak antiferromagnetic intermolecular interactions. The reversible removal of wealdy bonded H2O above 50 degrees C induces the structural phase transition 1 reversible arrow 1deh and strongly affects the magnetic characteristics. The observed changes can be interpreted in terms of the combined effects of the decreasing strength of ferromagnetic Co-II-W-V coupling and the increasing role of antiferromagnetic intermolecular correlation, both connected with dehydration-induced structural modifications in the clusters' core and supramolecular network of