Reactions of MnX2. nH(2)O with tris(N-(D-mannosyl)-2-aminoethyl)amine ((D-Man)(3)-tren), which was formed from D-mannose and tris(2-aminoethyl)amine (tren) in situ, afforded colorless crystals of [Mn((D-Man)(3)-tren)]X-2 (3a, X = Cl; 3b, X = Br; 3c, X = NO3; 3d, X = 1/2SO(4)). The similar reaction of MnSO4. 5H(2)O with tris(N-(L-rhamnosyl)-2-aminoethyl)amine ((L-Rha)(3)-tren) gave [Mn((L-Rha)(3)-tren)]SO4 (4d), where L-rhamnose is 6-deoxy-L-mannose. The structures of 3b and 4d were determined by X-ray crystallography to have a seven-coordinate Mn(II) center ligated by the N-glycoside ligand, (aldose)(3)-tren, with a C-3 helical structure. Three D-mannosyl residues of 3b are arranged in a Delta(ob(3)) configuration around the metal, leading to formation of a cage-type sugar domain in which a water molecule is trapped. in 4d, three L-rhamnosyl moieties are in a Delta(lel(3)) configuration to form a facially opened sugar domain on which a sulfate anion is capping through hydrogen bonding. These structures demonstrated that a configurational switch around the seven-coordinate manganese(II) center occurs depending on its counteranion. Reactions of 3a, 3b, and 4d with 0.5 equiv of Mn(II) salt in the presence of triethylamine yielded reddish orange crystals formulated as [{Mn((aldose)(3)-tren)}(2)Mn(H2O)]X-3. nH(2)O (5a, aldose = D-Man, X = Cl: 5b, aldose = D-Man, X = Br; 6d, aldose = L-Rha, X = 1/2SO(4)). The analogous trinuclear complexes 6a (aldose = L-Rha, X = Cl), 6b (aldose = L-Rha, X = Br), and 6c (aldose = L-Rha, X = NO3) were prepared by the one-pot reaction of Mn(II) salts with (L-Rha)(3)-tren without isolation of the intermediate Mn(II) complexes. X-ray crystallographic studies revealed that 5a, 5b, 6c, and 6d have a linearly ordered trimanganese core, (MnMnMnII)-Mn-II-Mn-III, bridged by two carbohydrate residues with Mn-Mn separations of 3.845(2)-3.919(4) Angstrom and Mn-Mn-Mn angles of 170.7(1)-173.81(7)degrees. The terminal Mn(II) atoms are seven-coordinate with a distorted mono-face-capped octahedral geometry ligated by the (aldose)(3)-tren ligand through three oxygen atoms of C-2 hydroxyl groups, three N-glycosidic nitrogen atoms, and a tertiary amino group. The central Mn(III) atoms are five-coordinate ligated by four oxygen atoms of carbohydrate residues in the (aldose)(3)-tren ligands and one water molecule, resulting in a square-pyramidal geometry. In the bridging part, a beta-aldopyranosyl unit with a chair conformation bridges the two (MnMnIII)-Mn-II ions with the C-2 mu-alkoxo group and with the C-1 N-glycosidic amino and the C-3 alkoxo groups coordinating to each metal center. These structures could be very useful information in relation to xylose isomerases which promote aldose-ketose isomerization by using divalent dimetal centers such as Mn2+, Mg2+, and Co2+.