One-dimensional magnetic materials have been widely studied due to their often remarkable ground states and excitations. Recent study of the triclinic form of CoV2O6 brannerite showed how a period three exchange modulation dramatically alters the ground state of a ferromagnetic Ising spin chain, leading to a rich excitation spectrum. We are now studying the monoclinic and a new, high pressure, orthorhombic polymorph of CoV2O6. These can be prepared as phase pure powders. Low temperature spin orderings are clearly very sensitive to the lattice symmetry; triclinic, monoclinic and orthorhombic CoV2O6 have magnetic transition temperatures of 6, 16, and ~<2 K respectively. Neutron beamtime is requested to refine the structures of the monoclinic and the new, high pressure, orthorhombic form of CoV2O6, and to investigate their low temperature spin orderings.