The crystal-structure of synthetic NaNa(2)Mg(5)Si(8)O(21)(OH)(3), a triclinic C(1)over bar amphibole with a triple-cell and excess hydrogen

Synthetic NaNa2Mg5Si8O21(OH)(3) is the first triclinic member of the amphibole group, and has a tripling of the unit cell in the b direction. The space group is C1 and the triple-b repeat gives Z = 6. The unit-cell parameters are: a = 9.883(2), b = 54.082(9), and c = 5.277(1) Angstrom, alpha = 90.045(4)degrees, beta = 103.068(3)degrees, gamma = 89.960(4)degrees, and V = 2748(1) Angstrom(3). The crystal structure has been refined to R-1 = 7.6 and wR(2) = 16.7% for the 1835 reflections with F-o > 4sigma(F) and for 4832 supercell reflections in the 2theta range 2-25degrees, respectively. The structure is pseudo-monoclinic, but both the intensity distribution and refined model indicate space group C1. Compared with the common C2/m amphibole structure, the two halves of an I-beam unit are no longer mirror-related, and the overall structure can be rationalized in terms of two different types of I-beam occurring in the unit cell. The first (with multiplicity 2) is centrosymmetric, and the second (with multiplicity 4) is non-centrosymmetric. There are also significant displacements of the cations, especially at the M4 sites, from their corresponding locations in the C2/m structure. The correlated displacements of Na atoms at the M4 sites permit incorporation of excess protons in pseudo-tetrahedral cavities between two adjacent chains of tetrahedra belonging to different I-beams. Bond-valence calculations and crystal-chemical analysis suggest that excess protons are bonded to O atoms at the O4 sites, and are hydrogen bonded to O atoms at adjacent O2 sites. The infrared spectrum of the amphibole in the principal OH-stretching region has a triplet of sharp bands at 3740, 3727, and 3711 cm(-1), which are assigned to the three independent "normal" O3-H groups in the triclinic structure. There is an additional intense and very broad absorption at 3430 cm(-1) that is resolved only when adsorbed moisture is removed. This band is assigned to the extra H in the structure. All the details provided by structure refinement and the proposed location of the excess H atoms is in accord with previous HRTEM and Si-29- and H-1 MAS NMR studies of this amphibole.