[PYH](2)[CU(PY)(4)(MX6)(2)] (MX6 = ZRF62-, NBOF52-, MOO2F42- - PY EQUALS PYRIDINE) - RARELY OBSERVED ORDERING OF METAL-OXIDE FLUORIDE ANIONS

Single crystals of [pyH](2)[Cu(py)(4)(MX6)(2)] (MX6 = ZrF62-, MoO2F42- ; py = pyridine), analogous to those of the previously reported [pyH]( 2)[Cu(py)(4)(NbOF5)(2)], were synthesized by reaction of the metal oxi des in (HF)(x) . pyridine/ pyridine/water solutions (150 degrees C, au togeneous pressure). The NbOF(5)(2-)and MoO2F42- anions generally crys tallize with orientational disorder masking the true coordination geom etry. The combination of the two different and strongly coordinating c ations tetrakis(pyridine)copper(ll) and pyridinium causes the anions t o adopt regular and ordered orientations. Crystal data: for [pyH](2)[C u(py)(4)(ZrF6)(2)], tetragonal, space group I4/mmm (No. 139), with a = 11.047(1) Angstrom, c = 16.763(3) Angstrom, and Z = 2; for [pyH](2)[C u(py)(4)(MoO2F4)(2)]; monoclinic, space group <C(2)over bar /c> (No. 1 5), with a = 19.195(4) Angstrom, b = 11.316(3) Angstrom, c = 18.920(5) Angstrom, beta = 107.68(2)degrees, and Z = 4.