Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052519213024093/kd5072sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052519213024093/kd5072Isup2.hkl
Contains datablock I

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052519213024093/kd5072Isup3.rtv
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052519213024093/kd5072sup4.pdf
SEM image and electrochemical performance of NaMnSO4F triplite phase

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Computing details top

Program(s) used to refine structure: GSAS.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
(I) top
Crystal data top
FMn1.00Na1.00O4SV = 806.78 (2) Å3
Mr = 192.98Z = 8
Monoclinic, C2/cF(000) = 744.0
a = 13.77027 (17) Å? radiation, λ = 0.58966 Å
b = 6.63687 (8) ÅT = 298 K
c = 10.35113 (14) Å?, ? × ? × ? mm
β = 121.4795 (3)°
Data collection top
Synchrotron
diffractometer
Scan method: step
Specimen mounting: quartz capillary2θmin = 5.184°, 2θmax = 55.00°, 2θstep = 0.004°
Data collection mode: transmission
Refinement top
Least-squares matrix: full21286 data points
Rp = 0.037Profile 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 = 0.04861 parameters
Rexp = 0.0220 restraints
R(F2) = 0.04073(Δ/σ)max = 0.04
χ2 = 4.709Background 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
FMn1.00Na1.00O4Sβ = 121.4795 (3)°
Mr = 192.98V = 806.78 (2) Å3
Monoclinic, C2/cZ = 8
a = 13.77027 (17) Å? radiation, λ = 0.58966 Å
b = 6.63687 (8) ÅT = 298 K
c = 10.35113 (14) Å?, ? × ? × ? mm
Data collection top
Synchrotron
diffractometer
Scan method: step
Specimen mounting: quartz capillary2θmin = 5.184°, 2θmax = 55.00°, 2θstep = 0.004°
Data collection mode: transmission
Refinement top
Rp = 0.037χ2 = 4.709
Rwp = 0.04821286 data points
Rexp = 0.02261 parameters
R(F2) = 0.040730 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
F0.51332 (19)0.0824 (4)0.3883 (3)0.0227 (7)*
Na10.64582 (9)0.09644 (17)0.33843 (12)0.0115 (4)*0.4326 (18)
Mn10.64582 (9)0.09644 (17)0.33843 (12)0.0115 (4)*0.5674 (18)
Na20.54839 (9)0.24073 (17)0.98754 (13)0.0103 (4)*0.5674 (18)
Mn20.54839 (9)0.24073 (17)0.98754 (13)0.0103 (4)*0.4326 (18)
O10.9103 (3)0.0192 (4)0.3509 (4)0.0370 (11)*
O20.7169 (2)0.1289 (4)0.1901 (3)0.0096 (9)*
O30.8655 (2)0.2585 (5)0.1544 (3)0.0155 (9)*
O40.6942 (2)0.4138 (5)0.4104 (3)0.0182 (9)*
S0.82345 (11)0.0821 (2)0.19515 (14)0.0158 (3)*

Experimental details

Crystal data
Chemical formulaFMn1.00Na1.00O4S
Mr192.98
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)13.77027 (17), 6.63687 (8), 10.35113 (14)
β (°) 121.4795 (3)
V3)806.78 (2)
Z8
Radiation type?, λ = 0.58966 Å
µ (mm1)?
Specimen shape, size (mm)?, ? × ? × ?
Data collection
DiffractometerSynchrotron
diffractometer
Specimen mountingQuartz capillary
Data collection modeTransmission
Scan methodStep
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, Tmax0.667, 0.672
2θ values (°)2θmin = 5.184 2θmax = 55.00 2θstep = 0.004
Refinement
R factors and goodness of fitRp = 0.037, Rwp = 0.048, Rexp = 0.022, R(F2) = 0.04073, χ2 = 4.709
No. of data points21286
No. of parameters61

Computer programs: GSAS.

 

Subscribe to Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. B
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds