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  • Title: Vibrational spectroscopy of the borate mineral henmilite Ca₂Cu[B(OH)₄]₂(OH)₄.
    Author: Frost RL, Xi Y.
    Journal: Spectrochim Acta A Mol Biomol Spectrosc; 2013 Feb 15; 103():356-60. PubMed ID: 23261634.
    Abstract:
    Henmilite is a triclinic mineral with the crystal structure consisting of isolated B(OH)(4) tetrahedra, planar Cu(OH)(4) groups and Ca(OH)(3) polyhedra. The structure can also be viewed as having dimers of Ca polyhedra connected to each other through 2B(OH) tetrahedra to form chains parallel to the C axis. The structure of the mineral has been assessed by the combination of Raman and infrared spectra. Raman bands at 902, 922, 951, and 984 cm(-1) and infrared bands at 912, 955 and 998 cm(-1) are assigned to stretching vibrations of tetragonal boron. The Raman band at 758 cm(-1) is assigned to the symmetric stretching mode of tetrahedral boron. The series of bands in the 400-600 cm(-1) region are due to the out-of-plane bending modes of tetrahedral boron. Two very sharp Raman bands are observed at 3559 and 3609 cm(-1). Two infrared bands are found at 3558 and 3607 cm(-1). These bands are assigned to the OH stretching vibrations of the OH units in henmilite. A series of Raman bands are observed at 3195, 3269, 3328, 3396, 3424 and 3501 cm(-1) are assigned to water stretching modes. Infrared spectroscopy also identified water and OH units in the henmilite structure. It is proposed that water is involved in the structure of henmilite. Hydrogen bond distances based upon the OH stretching vibrations using a Libowitzky equation were calculated. The number and variation of water hydrogen bond distances are important for the stability off the mineral.
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