The new heterometallic title complex, [Co(NCS)(2)(C(10)H(8)N(2))(NH(3))(2)][Cr(NCS)(4)(NH(3))(2)]·2CH(3)CN, has been prepared using the open-air reaction of cobalt powder, Reineckes salt and 2,2'-bipyridine (dpy) in acetonitrile. The crystal structure consists of discrete cationic [Co(NCS)(2)(NH(3))(2)(dpy)](+) and anionic [Cr(NCS)(4)(NH(3))(2)](-) building blocks, both with 2 symmetry, and acetonitrile solvent mol-ecules, which are linked together by N-H⋯N hydrogen bonds, forming extended supra-molecular chains. Furthermore, N-H⋯S, C-H⋯S and C-H⋯N hydrogen bonds inter-link neighbouring chains into a three-dimensional framework. The Co atom is in an elongated octa-hedral coordination environment with two N atoms from the dpy ligands and two NCS-groups in the equatorial plane and with two NH(3) mol-ecules at the axial positions. The Cr(III) ion is octa-hedraly coordinated by two NH(3) mol-ecules at the axial positions and four NCS-groups in the equatorial plane. Intensity statistics indicated non-merohedral twinning with the twin matrix [100; 0[Formula: see text]0; [Formula: see text]0[Formula: see text]]. The refined ratio of the twin components is 0.530 (1):0.470 (1).