A gem-quality purplish-red tourmaline sample of alleged liddicoatitic composition from the Anjanabonoina pegmatite, Madagascar, has been fully characterised using a multi-analytical approach to define its crystal-chemical identity. Single-crystal X-ray diffraction, chemical and spectroscopic analysis resulted in the formula: X(Na0.41□0.35Ca0.24)Σ1.00Y(Al1.81Li1.00Fe3+0.04Mn3+0.02Mn2+0.12Ti0.004)Σ3.00ZAl6 [T(Si5.60B0.40)Σ6.00O18] (BO3)3 (OH)3 W[(OH)0.50F0.13O0.37]Σ1.00 which corresponds to the tourmaline species elbaite having the typical space group R3m and relatively small unit-cell dimensions, a = 15.7935(4) Å, c = 7.0860(2) Å and V = 7.0860(2) Å3.
Optical absorption spectroscopy showed that the purplish-red colour is caused by minor amounts of Mn3+ (Mn2O3 = 0.20 wt.%). Thermal treatment in air up to 750°C strongly intensified the colour of the sample due to the oxidation of all Mn2+ to Mn3+ (Mn2O3 up to 1.21 wt.%). Based on infrared and Raman data, a crystal-chemical model regarding the electrostatic interaction between the X cation and W anion, and involving the Y cations as well, is proposed to explain the absence or rarity of the mineral species ‘liddicoatite’.