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Tychite, hexa­sodium dimagnesium sulfate tetra­carbonate, is a member of the northupite [Na3Mg(CO3)2Cl] group and has a framework structure consisting of four basic units: CO32− groups (3 symmetry), SO42− tetra­hedra (23 symmetry), MgO6 (\overline{3} symmetry) and NaO6 octa­hedra (2 symmetry). Among them, the CO32−, SO42−, and MgO6 units are regular in shape, but the NaO6 octa­hedron, showing three different Na—O bond lengths, is considerably distorted. The Na atoms in tychite are slightly overbonded relative to those in northupite. The Raman spectroscopic data show three and four vibration modes for the CO32− and SO42− groups, respectively; these are comparable to the corresponding Raman modes observed in other carbonates and sulfates.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680603491X/wm2032sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680603491X/wm2032Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](S-O) = 0.001 Å
  • R factor = 0.023
  • wR factor = 0.076
  • Data-to-parameter ratio = 23.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT040_ALERT_1_C No H-atoms in this Carbon Containing Compound .. ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT127_ALERT_1_C Implicit Hall Symbol Inconsistent with Explicit -F 2uv 2vw
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 36.59 From the CIF: _reflns_number_total 570 From the CIF: _diffrn_reflns_limit_ max hkl 23. 15. 23. From the CIF: _diffrn_reflns_limit_ min hkl -23. -14. -23. TEST1: Expected hkl limits for theta max Calculated maximum hkl 23. 23. 23. Calculated minimum hkl -23. -23. -23.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XtalDraw (Downs & Hall-Wallace, 2003); software used to prepare material for publication: SHELXTL (Bruker, 1997.

hexasodium dimagnesium sulfate tetracarbonate top
Crystal data top
Na6Mg2(SO4)(CO3)4Dx = 2.583 Mg m3
Mr = 522.66Mo Kα radiation, λ = 0.71073 Å
Cubic, Fd3Cell parameters from 3000 reflections
Hall symbol: -F 2uv 2vwθ = 2.5–36.6°
a = 13.9038 (2) ŵ = 0.63 mm1
V = 2687.82 (7) Å3T = 298 K
Z = 8Block, colourless
F(000) = 20640.10 × 0.10 × 0.08 mm
Data collection top
Bruker SMART APEX-II CCD
diffractometer
570 independent reflections
Radiation source: fine-focus sealed tube505 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
φ and ω scansθmax = 36.6°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2005)
h = 2323
Tmin = 0.939, Tmax = 0.951k = 1415
12979 measured reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023 w = 1/[σ2(Fo2) + (0.0575P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.076(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.41 e Å3
570 reflectionsΔρmin = 0.39 e Å3
24 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: none
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S0.12500.12500.12500.01191 (15)
Mg1.00000.50000.00000.00903 (15)
C1.03207 (5)0.71793 (5)0.03207 (5)0.0087 (2)
Na0.34379 (4)0.12500.12500.01915 (16)
O10.26626 (4)0.22529 (4)0.35333 (4)0.01226 (14)
O20.06362 (4)0.06362 (4)0.06362 (4)0.0195 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.01191 (15)0.01191 (15)0.01191 (15)0.0000.0000.000
Mg0.00903 (15)0.00903 (15)0.00903 (15)0.00030 (11)0.00030 (11)0.00030 (11)
C0.0087 (2)0.0087 (2)0.0087 (2)0.00005 (19)0.00005 (19)0.00005 (19)
Na0.0139 (2)0.0229 (3)0.0206 (3)0.0000.0000.00774 (17)
O10.0149 (2)0.0117 (2)0.0102 (2)0.00012 (16)0.00191 (16)0.00302 (16)
O20.0195 (2)0.0195 (2)0.0195 (2)0.00351 (18)0.00351 (18)0.00351 (18)
Geometric parameters (Å, º) top
S—O2i1.4782 (10)Mg—Naxvi3.2799 (3)
S—O21.4782 (10)Mg—Naxvii3.2799 (3)
S—O2ii1.4782 (10)Mg—Naxviii3.2799 (3)
S—O2iii1.4782 (10)Mg—Naxix3.2799 (3)
S—Naiv3.0421 (5)C—O1xx1.2857 (5)
S—Na3.0421 (5)C—O1xxi1.2857 (5)
S—Nav3.0421 (5)C—O1ix1.2857 (5)
S—Navi3.0421 (5)Na—O1xxii2.3915 (7)
S—Nai3.0421 (5)Na—O1xxiii2.3915 (7)
S—Navii3.0421 (5)Na—O1iv2.4124 (5)
Mg—O1viii2.0804 (5)Na—O1vii2.4124 (5)
Mg—O1ix2.0804 (5)Na—O2i2.4994 (5)
Mg—O1x2.0804 (5)Na—O2ii2.4994 (5)
Mg—O1xi2.0804 (5)Na—Mgxxiv3.2799 (3)
Mg—O1xii2.0804 (5)Na—Mgxxv3.2799 (3)
Mg—O1xiii2.0804 (5)Na—Naxxiii3.5297 (1)
Mg—Naxiv3.2799 (3)Na—Naxxvi3.5297 (1)
Mg—Naxv3.2799 (3)Na—Naxxvii3.5297 (1)
O2i—S—O2109.5O1xxiii—Na—O1iv102.758 (16)
O2i—S—O2ii109.5O1xxii—Na—O1vii102.757 (16)
O2—S—O2ii109.5O1xxiii—Na—O1vii72.25 (2)
O2i—S—O2iii109.5O1iv—Na—O1vii173.70 (3)
O2—S—O2iii109.5O1xxii—Na—O2i158.180 (15)
O2ii—S—O2iii109.5O1xxiii—Na—O2i114.24 (3)
O1viii—Mg—O1ix94.20 (2)O1iv—Na—O2i88.136 (16)
O1viii—Mg—O1x94.20 (2)O1vii—Na—O2i97.396 (17)
O1ix—Mg—O1x94.20 (2)O1xxii—Na—O2ii114.24 (3)
O1viii—Mg—O1xi85.80 (2)O1xxiii—Na—O2ii158.180 (15)
O1ix—Mg—O1xi85.80 (2)O1iv—Na—O2ii97.396 (17)
O1x—Mg—O1xi180.00 (3)O1vii—Na—O2ii88.136 (16)
O1viii—Mg—O1xii85.80 (2)O2i—Na—O2ii57.75 (5)
O1ix—Mg—O1xii180.00 (3)Cxxviii—O1—Mgxxix132.27 (5)
O1x—Mg—O1xii85.80 (2)Cxxviii—O1—Naxxvi117.29 (3)
O1xi—Mg—O1xii94.20 (2)Mgxxix—O1—Naxxvi94.096 (19)
O1viii—Mg—O1xiii180.0Cxxviii—O1—Nav116.85 (6)
O1ix—Mg—O1xiii85.80 (2)Mgxxix—O1—Nav93.49 (2)
O1x—Mg—O1xiii85.80 (2)Naxxvi—O1—Nav94.57 (2)
O1xi—Mg—O1xiii94.20 (2)S—O2—Navi96.39 (2)
O1xii—Mg—O1xiii94.20 (2)S—O2—Nai96.39 (2)
O1xx—C—O1xxi119.993 (2)Navi—O2—Nai118.778 (9)
O1xx—C—O1ix119.993 (2)S—O2—Navii96.39 (2)
O1xxi—C—O1ix119.993 (2)Navi—O2—Navii118.778 (9)
O1xxii—Na—O1xxiii80.27 (3)Nai—O2—Navii118.778 (9)
O1xxii—Na—O1iv72.25 (2)
Symmetry codes: (i) x+1/4, y+1/4, z; (ii) x+1/4, y, z+1/4; (iii) x, y+1/4, z+1/4; (iv) z, x, y; (v) y, z, x; (vi) y+1/4, z, x+1/4; (vii) z, x+1/4, y+1/4; (viii) z+3/2, x+1/4, y1/4; (ix) y+3/4, z+1, x1/4; (x) x+3/4, y+1/4, z+1/2; (xi) x+5/4, y+3/4, z1/2; (xii) y+5/4, z, x+1/4; (xiii) z+1/2, x+3/4, y+1/4; (xiv) y+1, z+1/2, x1/2; (xv) z+1, x+1, y; (xvi) z+1, x, y; (xvii) x+3/2, y+1/2, z; (xviii) x+1/2, y+1/2, z; (xix) y+1, z+1/2, x+1/2; (xx) z+3/4, x+1, y1/4; (xxi) x+3/4, y+1, z1/4; (xxii) y+1/4, z1/4, x+1/2; (xxiii) y+1/4, z+1/2, x1/4; (xxiv) x1/2, y+3/4, z+1/4; (xxv) x1/2, y1/2, z; (xxvi) z+1/2, x1/4, y+1/4; (xxvii) z+1/2, x+1/2, y; (xxviii) x3/4, y+1, z+1/4; (xxix) x+5/4, y+3/4, z+1/2.
Comparison of bond distances (Å) between tychite (M = Mg; this work) and ferrotychite (M = Fe; Malinovskii et al., 1979) top
BondsTychiteFerrotychite
S-O (x4)1.4782 (10)1.483 (1)
C-O (x3)1.2857 (5)1.287 (1)
Na-O1 (x2)2.4994 (5)2.485 (1)
Na-O2 (x2)2.3915 (7)2.388 (1)
Na-O2 (x2)2.4124 (5)2.409 (1)
M-O (x6)2.0804 (5)2.132 (1)
Raman peak assignments for selected vibrational modes observed in tychite top
Peak Positions (cm-1)Mode Assignments
144, 360Lattice Vibrations
493.8ν2 SO4 symmetric bend
629.7ν4 SO4 antisymmetric bending
708.7ν4 CO3 in-plane bending
859.2ν2 CO3 out-of-plane bending
967.1ν1 SO4 primary internal stretching mode
1108.1ν1 CO3 primary internal stretching mode
1136.6ν3 SO4 antisymmetric stretching
 

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