research papers
The crystal structure of the NaMnSO4F fluorosulfate phase prepared by low-temperature solid-state synthesis has been solved and refined by the Rietveld analysis of synchrotron X-ray powder diffraction data. Isostructural to the naturally occurring triplite family of minerals, this compound crystallizes in monoclinic C2/c symmetry (No. 15) with unit-cell parameters of a = 13.77027 (17), b = 6.63687 (8), c = 10.35113 (14) Å, β = 121.4795 (3)° and V = 806.78 (2) Å3. Its structure is built of edge-sharing chains of distorted MO4F2 octahedra, which are interconnected by constituent SO4 tetrahedra to form a robust three-dimensional polyanionic framework. MO4F2 octahedra are randomly occupied by Na and Mn with close to 1:1 occupancy. This random mixing of cations among polyhedral building blocks means that there are no channels for Na-ion conduction, rendering it electrochemically inactive. The structure is discussed and compared with other known alkali metal fluorosulfates as well as to naturally occurring triplite-type minerals.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2052519213024093/kd5072sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052519213024093/kd5072Isup2.hkl | |
Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052519213024093/kd5072Isup3.rtv | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2052519213024093/kd5072sup4.pdf |
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 1.
(I) top
Crystal data top
FMn1.00Na1.00O4S | V = 806.78 (2) Å3 |
Mr = 192.98 | Z = 8 |
Monoclinic, C2/c | F(000) = 744.0 |
a = 13.77027 (17) Å | ? radiation, λ = 0.58966 Å |
b = 6.63687 (8) Å | T = 298 K |
c = 10.35113 (14) Å | ?, ? × ? × ? mm |
β = 121.4795 (3)° |
Data collection top
Synchrotron diffractometer | Scan method: step |
Specimen mounting: quartz capillary | 2θmin = 5.184°, 2θmax = 55.00°, 2θstep = 0.004° |
Data collection mode: transmission |
Refinement top
Least-squares matrix: full | 21286 data points |
Rp = 0.037 | Profile function: CW Profile function number 2 with 18 terms Profile coefficients for Simpson's rule integration of pseudovoigt function C.J. Howard (1982). J. Appl. Cryst.,15,615-620. P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. #1(GU) = 0.620 #2(GV) = 0.920 #3(GW) = 0.371 #4(LX) = 0.250 #5(LY) = 18.708 #6(trns) = 0.000 #7(asym) = 0.2013 #8(shft) = 0.0000 #9(GP) = 0.000 #10(stec)= 3.35 #11(ptec)= 0.75 #12(sfec)= 0.00 #13(L11) = 0.000 #14(L22) = 0.000 #15(L33) = 0.000 #16(L12) = 0.000 #17(L13) = 0.000 #18(L23) = 0.000 Peak tails are ignored where the intensity is below 0.0001 times the peak Aniso. broadening axis 0.0 0.0 1.0 |
Rwp = 0.048 | 61 parameters |
Rexp = 0.022 | 0 restraints |
R(F2) = 0.04073 | (Δ/σ)max = 0.04 |
χ2 = 4.709 | Background function: GSAS Background function number 1 with 16 terms. Shifted Chebyshev function of 1st kind 1: 1907.05 2: -1516.50 3: 870.519 4: -447.604 5: 182.415 6: 2.97958 7: -125.918 8: 153.939 9: -123.451 10: 66.9678 11: -8.74399 12: -38.9879 13: 45.7531 14: -32.4665 15: 20.4485 16: -11.8987 |
Crystal data top
FMn1.00Na1.00O4S | β = 121.4795 (3)° |
Mr = 192.98 | V = 806.78 (2) Å3 |
Monoclinic, C2/c | Z = 8 |
a = 13.77027 (17) Å | ? radiation, λ = 0.58966 Å |
b = 6.63687 (8) Å | T = 298 K |
c = 10.35113 (14) Å | ?, ? × ? × ? mm |
Data collection top
Synchrotron diffractometer | Scan method: step |
Specimen mounting: quartz capillary | 2θmin = 5.184°, 2θmax = 55.00°, 2θstep = 0.004° |
Data collection mode: transmission |
Refinement top
Rp = 0.037 | χ2 = 4.709 |
Rwp = 0.048 | 21286 data points |
Rexp = 0.022 | 61 parameters |
R(F2) = 0.04073 | 0 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | Occ. (<1) | |
F | 0.51332 (19) | 0.0824 (4) | 0.3883 (3) | 0.0227 (7)* | |
Na1 | 0.64582 (9) | 0.09644 (17) | 0.33843 (12) | 0.0115 (4)* | 0.4326 (18) |
Mn1 | 0.64582 (9) | 0.09644 (17) | 0.33843 (12) | 0.0115 (4)* | 0.5674 (18) |
Na2 | 0.54839 (9) | 0.24073 (17) | 0.98754 (13) | 0.0103 (4)* | 0.5674 (18) |
Mn2 | 0.54839 (9) | 0.24073 (17) | 0.98754 (13) | 0.0103 (4)* | 0.4326 (18) |
O1 | 0.9103 (3) | 0.0192 (4) | 0.3509 (4) | 0.0370 (11)* | |
O2 | 0.7169 (2) | 0.1289 (4) | 0.1901 (3) | 0.0096 (9)* | |
O3 | 0.8655 (2) | 0.2585 (5) | 0.1544 (3) | 0.0155 (9)* | |
O4 | 0.6942 (2) | 0.4138 (5) | 0.4104 (3) | 0.0182 (9)* | |
S | 0.82345 (11) | 0.0821 (2) | 0.19515 (14) | 0.0158 (3)* |
Experimental details
Crystal data | |
Chemical formula | FMn1.00Na1.00O4S |
Mr | 192.98 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 13.77027 (17), 6.63687 (8), 10.35113 (14) |
β (°) | 121.4795 (3) |
V (Å3) | 806.78 (2) |
Z | 8 |
Radiation type | ?, λ = 0.58966 Å |
µ (mm−1) | ? |
Specimen shape, size (mm) | ?, ? × ? × ? |
Data collection | |
Diffractometer | Synchrotron diffractometer |
Specimen mounting | Quartz capillary |
Data collection mode | Transmission |
Scan method | Step |
Absorption correction | ? GSAS Absorption/surface roughness correction: function number 0 Debye-Scherrer absorption correction Term (= MU.r/wave) = 0.40700 Correction is not refined. |
Tmin, Tmax | 0.667, 0.672 |
2θ values (°) | 2θmin = 5.184 2θmax = 55.00 2θstep = 0.004 |
Refinement | |
R factors and goodness of fit | Rp = 0.037, Rwp = 0.048, Rexp = 0.022, R(F2) = 0.04073, χ2 = 4.709 |
No. of data points | 21286 |
No. of parameters | 61 |
Computer programs: GSAS.