Modulated structures in oxidized cerium niobates

Three previously reported oxidized cerium niobate phases CeNbO4+x (x = 0.08, 0.25, and 0.33) have been synthesized and characterized by X-ray powder and electron diffraction. All three phases display structures which are modulated variants of a parent fergusonite-type CeIIINbO4 structure (I2/a, a = 5.5342(2) angstrom, b = 11.4016(6) angstrom, c = 5.1583(3) angstrom, β = 94.600(5)degree). The x = 0.08 phase with parent unit cell (I2/a, a = 5.3029(8) angstrom, b = 11.483(2) angstrom, c = 5.2515(8) angstrom, β = 91.32(2)degree) is a two-dimensional, incommensurately modulated phase characterized by incommensurate primary modulation wavevectors q1 ∼ [0.345, 0, 0.138]p* and q2 ∼ [-0.069, 0, 0.172]p* (p for parent). The x = 0.25 phase with parent unit cell (I2/a, a = 5.3522(8) angstrom, b = 11.374(3) angstrom, c = 5.116(1) angstrom, β = 93.34(2)degree) is a commensurately modulated superstructure phase characterized by the reciprocal space unit cell ar* = 1/12[402]p*, br* = 1/4[020]p*, and cr* = 1/3[101]p* (r for resultant). The x = 0.33 phase with parent unit cell (I1, a = 5.4374(8) angstrom, b = 11.189(2) angstrom, c = 5.1458(8) angstrom, α = 90.56(1), β = 94.37(1), γ = 88.19(1)degree) is again commensurately modulated with q = 1/3[101]p*. The close structural relationship between the three oxidized phases and possible interstitial oxygen sites in the CeIIINbO4 structure are discussed