Crystals of the MnxBa12(BO3)(8-2x)F-8x phase were grown from a high-temperature solution. This new fluoride borate is built of positively charged [Ba-12(BO3)(6)](6+) blocks, the so-called "anti-zeolite" pattern. Using X-ray single-crystal diffraction, the bulk atomic arrangement in the centrosymmetric tetragonal unit cell in I4/mcm could be elucidated. Crystals of the (MnF6)(4-) group-containing solid solution MnxBa12(BO3)(8-2x)F-8x are dark brown in color in contrast to the differently colored crystals of (LiF4)(3-) group-containing "anti-zeolite" LiBa12(BO3)(7)F-4 (P4(2)bc). According to the electron spin resonance and optical spectroscopic investigation, the absorption spectrum of LiBa12(BO3)(7)F-4 crystals results from the absorption of light by both exciton and free charge carriers and can be tuned by varying the initial composition of the high-temperature solution.