Powder neutron diffraction and magnetic susceptibility measurements at 10-300 K have been used to determine the crystal and magnetic structures of brownmillerite type Ca(2)Cr(2)O(5), which was obtained by reduction of the high pressure phase CaCrO(3) through hard-soft chemistry. The ambient temperature crystal structure of Ca(2)Cr(2)O(5) is refined in space group I2mb and the unusual tetrahedral coordination of Cr(3+) results in local structural distortions. Cr(3+) spins order antiferromagnetically below 220 K and a substantial observed canting of moments shows that Heisenberg exchange is weak or frustrated and competes with antisymmetric Dzialoshinskii-Moriya interactions.