[en] Four isostructural one-dimensional polymeric iron(II) spin crossover materials containing the ligand 2-chloro-4,6-bis(dipyrid-2-ylamino)-1,3,5-triazine (cddt) have been synthesized and magnetically and structurally characterized. The polymeric material Fe(NCS)2(cddt)·n(guest) (1), self assembles into three crystallographically distinct phases; the compounds 1b and 1c, [Fe(NCS)2(cddt)]·2(CH3OH), are polymorphs, however, 1a, [Fe(NCS)2(cddt)]·1/2(CHCl3)·(H2O) contains a different solvent system. Each phase shows very different magnetic behavior; phases 1a and 1b remain high spin over all temperatures, whilst phase 1c undergoes a half spin crossover between 225 and 125 K. The structural consequences of the spin transition in 1c have been followed using variable temperature synchrotron powder X-ray diffraction techniques. Variation of the chalcogenide ligand in the complex [Fe(NCSe)2(cddt)]·2(CH3OH), 2, leads to a full one-step spin crossover with a T1/2 of 200 K. Structural analysis of 1c below the transition temperature reveals alternating, crystallographically distinct, HS and LS iron(II) centers (HS: high spin, LS: low spin) along the chain, and structural analysis of 2 below the transition temperature reveals all LS iron(II) centers. Also reported are the structural characterizations of two dinuclear materials, containing the ligand 2,4,6-tris(dipyridin-2-ylamino)-1,3,5-triazine (tdt), of the formula [Fe(tdt)(X)2]2·(ClO4)·(solvent) (X = H2O, Cl- for 3a, 3b) which are analogous to those recently reported by Gamez et al. In addition, the structural characterizations are described for dinuclear materials, containing the ligand cddt, of the formula [Fe(cddt)(Cl)(X)]2·(Y)2·n(solvent) (X: H2O or NCCH3, Y: ClO4-, BF4- 4a, 4b and 4d) and for a cobalt(II) analogue, [Co(cddt)(Cl)(H2O)]2·(BF4)2·n(solvent) (4c)