The crystallizied Inactions of the two metastable phases in the glasses of plagioclase compositions were estimated by x-ray diffraction method. The orthorhombic metastable phase is easily drystaliized in the composition range of 70 to 80 mol% of albite, whereas the hexagonal metastable phase is mostly crystallized in the anonhite-rich side. For the purpose of refining the orthorhombic metastable structure some single crystal fragments of the composition Na,17ca‥‥All Isi2 nn were separated Som the crystallized glasses. The cell parameters of this crystal are a=8.237(1)A. b=8.644(1)A c=4.818(1)A. The space group of this crystal is Pn,2, Final atomic coordinates give R value of 0.040 and Rw of 0.028 with anisotropic thermal parameters. The position of Na and Ca atoms statistically distributed is splitted in two points with the occupancy of 0.5. The Si and Al atoms are statistically distributed in the six-membered ring of the Immm-type framework.