The iron jarosites, plumbojarosite, Pb0.5Fe3(OH)(6)(SO4)(2), argentojarosite, AgFe3(OH)(6)(SO4)(2), and thallium jarosite, TIFe3(OH)(6)(SO4)(2), along with the selenate-capped jarosite analogues of potassium, KFe3(OH)(6)(SeO4)(2), and rubidium, RbFe3(OH)(6)(SeO4)(2), have been prepared in their analytically pure forms by employing redox-based hydrothermal methods. The crystal structures of these materials have been determined, and all are found to be essentially isostructrual including Pb0.5Fe3(OH)(6)(SO4)(2), which is distinct from the structure reported for naturally mined samples. All iron jarosites show long-range order (LRO), signified by a sharp transition temperature, T-N, which falls in the narrow temperature range of 61.4 +/- 5 K. The mechanism responsible for this ordering has been established by examining magnetostructural correlations for the jarosites possessing various interlayer cation and capping groups. We show that all magnetic properties of jarosites, including LRO, find their origin in the basic magnetic unit, the intralayer Fe-3(mu-OH)(3) triangle. Field-dependent magnetization experiments are consistent with the antiferromagnetic stacking of an out of plane moment developed from spin canting within Fe-3(mu-OH)(3) triangles. Together with the previously reported AFe(3)(OH)(6)(SO4)(2) (A = Na+, K+, Rb+ and NH4+) jarosites, these compounds provide a framework for probing magnetic ordering in a spin frustrated lattice of the largest series of isoelectronic and isostructural kagome syste ms yet discovered.