The compounds [Mn-2(bpm)(3)(NCS)(4)] (1), [Mn(bpm)(NCO)(2)] (2), and [Mn-2(bpm)(N-3)(4)] (3) (where bpm=2,2'-bipyrimidine) have been synthesized and characterized. Compound 1 crystallizes in the triclinic P (1) over bar space group, with a = 9.122(1) Angstrom, b = 9.229(1) Angstrom, c = 11.710(2) Angstrom, alpha = 74.89(1)degrees, beta = 80.30(1)degrees, gamma = 61.04(1)degrees, V = 831.7(2) Angstrom(3), Z = 2, R(F-o) = 0.029, and wR(F-o(2)) = 0.078. Compound 2 crystallizes in the monoclinic C2/c space group, with a = 7.309(1) Angstrom, b = 14.498(2) Angstrom, c = 10.740(4) Angstrom, beta = 99.93(4)degrees, V = 1121.0(5) Angstrom(3), Z = 4, R = 0.025, and wR(F-o(2)) = 0.060. In the case of compound 3, the crystal parameters of the monoclinic C2/m space group are a = 6.206(2) Angstrom, b = 15.084(2) Angstrom, c = 8.909(1) Angstrom, beta = 95.75(2)degrees, V = 829.8(3) Angstrom(3), Z = 4, R = 0.029, and wR(F-o(2))= 0.069. The pseudohalide ions have a dramatic influence in the molecular structures of the three compounds. Compound 1 is dinuclear, with the manganese(II) ions bridged by bpm ligands and with terminal bpm and NCS groups; compound 2 is a linear chain of manganese(II) ions bridged by bpm ligands in cis conformation, with terminal cyanate groups; compound 3 shows a two-dimensional honeycomb like structure, where the sheets consist of an infinite hexagonal array of manganese(II) ions bridged by bischelating bpm ligands and double end-on azido bridges. The manganese(II) ions have octahedral environments in all cases. Magnetic susceptibility measurements show antiferromagnetic couplings for compounds 1 and 2, while alternating ferro-antiferromagnetism is observed for compound 3. The obtained exchange parameters are J = -0.72 K and J = -0.78 K for compounds 1 and 2, respectively. No theoretical model is available for compound 3, which represent the first two-dimensional honeycomb-like compound showing alternating signs in the magnetic interactions.