Structural variation of babingtonite depending on cation distribution at the octahedral sites

Babingtonite, Ca₂Fe²⁺Fe³⁺[Si₅O₁₄(OH)] (Z?=?2, space group $ P\overline{1} $ ) from Yakuki mine (Japan), Grönsjöberget (Sweden), Kandivali Quarry (India), Baveno Quarry (Italy), Bråstad Mine (Norway), and Kouragahana (Japan), and manganbabingtonite, Ca₂(Mn²⁺, Fe²⁺)Fe³⁺[Si₅O₁₄(OH)], from Iron Cap mine (USA) were studied using electron-microprobe analysis (EMPA), ⁵⁷Fe Mössbauer analysis and single-crystal X-ray diffraction methods to determine the cation distribution at M1 and M2 and to analyze its effect on the crystal structure of babingtonite. Although all studied babingtonite crystals are relatively homogeneous, chemical zonation due to mainly Fe ? Mn substitution is observed in manganbabingtonite. Mössbauer spectra consist of two doublets with isomer shift (I.S.)?=?1.16–1.22 mm/s and quadrupole splitting (Q.S.)?=?2.33–2.50 mm/s and with I.S.?=?0.38–0.42 mm/s and Q.S.?=?0.82–0.90 mm/s, assigned to Fe²⁺ and Fe³⁺ at the M1 and M2 octahedral sites, respectively. The determined ratio of Fe²⁺/total Fe in manganbabingtonite (0.26) was smaller than that in the others (0.35–0.44) because of high Mn²⁺ content instead of Fe²⁺. The unit-cell parameters of babingtonite are a?=?7.466–7.478, b?=?11.624–11.642, c?=?6.681–6.690 Å, α?=?91.53–91.59, β?=?93.86–93.94, γ?=?104.20–104.34º, and V?=?560.2–562.3 Å³, and those of manganbabingtonite are a?=?7.4967(3), b?=?11.6632(4), c?=?6.7014(2) Å, α?=?91.602(2), β?=?93.989(2), γ?=?104.574(3)º, and V =565.09(5) ų. Structural refinements converged to R ₁ values of 1.64–3.16 %. The <M1-O> distance was lengthened due to the substitution of large octahedral cations such as Mn²⁺ for Fe²⁺. The increase of the M1-O8, M1-O8’ and M1-O13 lengths with mean ionic radii is slightly more pronounced than of the other M1-Oi lengths. The lengthened M1-O13 distance leads the positive correlation between Si5-O15-Si1 angle and M1-O13 distance. The increase of Si2-O3-Si1 and Si5-O12-Si4 angles due to the increase of mean ionic radius of M2 is also observed.