Scolecite, Part I: Refinement of high-order data, separation of internal and external vibrational amplitudes from displacement parameters

A single crystal of scolecite, CaAl₂Si₃O₁₀· 3H₂O, was studied by X-ray diffraction methods at room temperature. The intensities were measured with MoKα radiation (λ=0.71069?Å) in a complete sphere of reflection up to sinθ/λ=0.9?Å^?1. The structure was refined in the pseudo-orthorhombic setting of space group F1d1 instead of the conventional setting Cc for better comparison with natrolite (Fdd2). The cell parameters are: a=18.502(1)?Å, b=18.974(2)?Å, c=6.525(1)?Å, β=90.615(7)°, V=2290.6(3)?ų, Z=8. A refinement of high-order diffraction data yielded residuals of R(F)=0.9%, R _w (F)=0.9%, GoF=1.73 for 1831 high-angle reflections (0.7≤sinθ/λ≤0.9?Å^?1) and R(F)=1.2%, R _w (F)=1.4%, GoF=3.22 for all 3478 independent reflections. In comparison with natrolite, the replacement of 2 Na⁺ by 1 Ca²⁺ and 1 H₂O leads to a reduction of symmetry from Fdd2 to F1d1. Each general atomic position in natrolite (except of Na) splits into two crystallographically independent positions in scolecite. The T?O distances and T?O?T angles of these two sites differ distinctly from each other due to the influence of the calcium ions on the framework. An unexpected result of our detailed analysis of the data is that the additional water molecule (O7) disturbs the symmetry of the framework to a greater extent than the replacement of Na⁺ by Ca²⁺. As a comparison of the displacement parameters indicates, the bonds within the tetrahedral framework and to the extraframework cations are stronger in scolecite than in natrolite. The isotropic U(equ) values of the framework atoms and extraframework cations are about 10% smaller in scolecite compared to natrolite. The same tendency is shown by the analysis of the internal vibrational amplitudes ΔU. The corresponding force constants are in the range of F=358 to 3367?Nm^?1 for the T?O bonds in scolecite (in natrolite: F=354 to 824?Nm^?1). The values of the force constants which determine the vibrations of the Ca ions and water molecules against the framework oxygen atoms lie in the range of F=33 to 1757?Nm^?1 (in natrolite: F=57 to 293?Nm^?1).