Elaboration, structural study and validation of a new NASICON-type structure, Na_0.72(Cr_0.48,Al_1.52)(Mo_2.77,Al_0.23)O₁₂

A new NASICON-type phase, Na_0.72(Cr_0.48,Al_1.52)(Mo_2.77,Al_0.23)O₁₂, was synthesized by solid-state reaction. The structural unit consists of one octa­hedron M1O₆ (M1 = Cr1/Al2) and one tetra­hedron M2O₄ (M2 = Mo1/Al1) sharing corners. The charge compensation is provided by Na⁺ cations.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma]() = 0.000 Å
• Disorder in main residue
• R factor = 0.013
• wR factor = 0.024
• Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ     Please Check
PLAT077_ALERT_4_C Unitcell Contains Non-integer Number of Atoms ..     Please Check
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of         O1 Check
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of         O2 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.369 Check

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          2 Info
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT045_ALERT_1_G Calculated and Reported Z Differ by a Factor ...       0.67 Check
PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ...          2 Units
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          2 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Mo1      --O1        .       11.1 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Mo1      --O2        .        9.9 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Cr1      --O2        .       15.3 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Al2      --O2        .       15.3 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Al1      --O1        .       11.1 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Al1      --O2        .        9.9 s.u.
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        34% Note
PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd  2  )       100% Note
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  15 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Sodium chromium/aluminium molybdenum/aluminium dodecaoxide

Crystal data

Na0.72(Cr0.48·Al1.52)(Mo2.77·Al0.23)O12	Dx = 3.267 Mg m^−3
Mr = 546.34	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 25 reflections
a = 9.217 (2) Å	θ = 12.1–14.8°
c = 22.646 (2) Å	µ = 3.74 mm^−1
V = 1666.1 (7) Å^3	T = 298 K
Z = 6	Prism, red
F(000) = 1526	0.24 × 0.21 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.026
Radiation source: fine-focus sealed tube	θmax = 26.9°, θmin = 3.1°
ω/2θ scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = −2→11
Tmin = 0.491, Tmax = 0.599	l = −28→28
2878 measured reflections	2 standard reflections every 120 reflections
414 independent reflections	intensity decay: 0.8%
401 reflections with I > 2σ(I)

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + 4.1215P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.013	(Δ/σ)max = 0.001
wR(F^2) = 0.024	Δρmax = 0.23 e Å^−3
S = 1.25	Δρmin = −0.42 e Å^−3
414 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
35 parameters	Extinction coefficient: 0.00046 (6)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mo1	0.28488 (2)	0.0000	0.7500	0.01214 (9)	0.921 (6)
Al1	0.28488 (2)	0.0000	0.7500	0.01214 (9)	0.080 (10)
Cr1	0.0000	0.0000	0.63854 (3)	0.0109 (2)	0.238 (11)
Al2	0.0000	0.0000	0.63854 (3)	0.0109 (2)	0.761 (19)
Na1	0.0000	0.0000	0.5000	0.0259 (9)	0.724 (8)
O1	0.48491 (19)	0.17851 (19)	0.74736 (7)	0.0326 (4)
O2	0.1686 (2)	−0.0152 (2)	0.68761 (6)	0.0376 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01265 (11)	0.01229 (13)	0.01137 (12)	0.00614 (6)	0.00085 (4)	0.00169 (8)
Al1	0.01265 (11)	0.01229 (13)	0.01137 (12)	0.00614 (6)	0.00085 (4)	0.00169 (8)
Cr1	0.0117 (3)	0.0117 (3)	0.0092 (3)	0.00587 (14)	0.000	0.000
Al2	0.0117 (3)	0.0117 (3)	0.0092 (3)	0.00587 (14)	0.000	0.000
Na1	0.0322 (11)	0.0322 (11)	0.0132 (12)	0.0161 (6)	0.000	0.000
O1	0.0254 (8)	0.0218 (8)	0.0442 (9)	0.0071 (7)	−0.0038 (6)	0.0003 (7)
O2	0.0364 (9)	0.0446 (11)	0.0278 (8)	0.0172 (8)	−0.0093 (7)	0.0015 (7)

Geometric parameters (Å, º)

Mo1—O2^i	1.7358 (15)	Na1—O1^ii	2.4987 (15)
Mo1—O2	1.7359 (15)	Na1—O1^vii	2.4987 (15)
Mo1—O1	1.7540 (16)	Na1—O1^iii	2.4987 (15)
Mo1—O1^i	1.7540 (15)	Na1—O1^viii	2.4987 (15)
Cr1—O1^ii	1.9668 (16)	Na1—O1^iv	2.4987 (15)
Cr1—O1^iii	1.9668 (16)	Na1—O1^ix	2.4987 (15)
Cr1—O1^iv	1.9669 (16)	Na1—Al2^x	3.1373 (7)
Cr1—O2	1.9720 (16)	Na1—Cr1^x	3.1373 (7)
Cr1—O2^v	1.9721 (16)	O1—Al2^iii	1.9668 (16)
Cr1—O2^vi	1.9721 (16)	O1—Cr1^iii	1.9668 (16)
Cr1—Na1	3.1374 (7)	O1—Na1^xi	2.4987 (15)
O2^i—Mo1—O2	109.56 (11)	O1^iii—Na1—O1^iv	65.74 (6)
O2^i—Mo1—O1	107.85 (8)	O1^viii—Na1—O1^iv	114.26 (6)
O2—Mo1—O1	111.40 (8)	O1^ii—Na1—O1^ix	114.26 (6)
O2^i—Mo1—O1^i	111.40 (8)	O1^vii—Na1—O1^ix	65.74 (6)
O2—Mo1—O1^i	107.86 (8)	O1^iii—Na1—O1^ix	114.26 (6)
O1—Mo1—O1^i	108.80 (11)	O1^viii—Na1—O1^ix	65.74 (6)
O1^ii—Cr1—O1^iii	87.18 (7)	O1^iv—Na1—O1^ix	180.0
O1^ii—Cr1—O1^iv	87.18 (7)	O1^ii—Na1—Al2^x	141.20 (4)
O1^iii—Cr1—O1^iv	87.18 (7)	O1^vii—Na1—Al2^x	38.80 (4)
O1^ii—Cr1—O2	92.79 (7)	O1^iii—Na1—Al2^x	141.19 (4)
O1^iii—Cr1—O2	88.68 (7)	O1^viii—Na1—Al2^x	38.81 (4)
O1^iv—Cr1—O2	175.86 (7)	O1^iv—Na1—Al2^x	141.19 (4)
O1^ii—Cr1—O2^v	88.68 (7)	O1^ix—Na1—Al2^x	38.81 (4)
O1^iii—Cr1—O2^v	175.86 (7)	O1^ii—Na1—Cr1^x	141.20 (4)
O1^iv—Cr1—O2^v	92.79 (7)	O1^vii—Na1—Cr1^x	38.80 (4)
O2—Cr1—O2^v	91.35 (7)	O1^iii—Na1—Cr1^x	141.19 (4)
O1^ii—Cr1—O2^vi	175.85 (7)	O1^viii—Na1—Cr1^x	38.81 (4)
O1^iii—Cr1—O2^vi	92.79 (7)	O1^iv—Na1—Cr1^x	141.19 (4)
O1^iv—Cr1—O2^vi	88.68 (7)	O1^ix—Na1—Cr1^x	38.81 (4)
O2—Cr1—O2^vi	91.35 (7)	Al2^x—Na1—Cr1^x	0.0
O2^v—Cr1—O2^vi	91.35 (7)	O1^ii—Na1—Cr1	38.80 (4)
O1^ii—Cr1—Na1	52.76 (5)	O1^vii—Na1—Cr1	141.20 (4)
O1^iii—Cr1—Na1	52.76 (5)	O1^iii—Na1—Cr1	38.81 (4)
O1^iv—Cr1—Na1	52.76 (5)	O1^viii—Na1—Cr1	141.19 (4)
O2—Cr1—Na1	124.30 (5)	O1^iv—Na1—Cr1	38.81 (4)
O2^v—Cr1—Na1	124.30 (5)	O1^ix—Na1—Cr1	141.19 (4)
O2^vi—Cr1—Na1	124.30 (5)	Al2^x—Na1—Cr1	180.0
O1^ii—Na1—O1^vii	180.0	Cr1^x—Na1—Cr1	180.0
O1^ii—Na1—O1^iii	65.74 (6)	Mo1—O1—Al2^iii	144.66 (9)
O1^vii—Na1—O1^iii	114.26 (6)	Mo1—O1—Cr1^iii	144.66 (9)
O1^ii—Na1—O1^viii	114.26 (6)	Al2^iii—O1—Cr1^iii	0.0
O1^vii—Na1—O1^viii	65.74 (6)	Mo1—O1—Na1^xi	126.81 (8)
O1^iii—Na1—O1^viii	180.0	Al2^iii—O1—Na1^xi	88.43 (6)
O1^ii—Na1—O1^iv	65.74 (6)	Cr1^iii—O1—Na1^xi	88.43 (6)
O1^vii—Na1—O1^iv	114.26 (6)	Mo1—O2—Cr1	158.35 (10)

Symmetry codes: (i) x−y, −y, −z+3/2; (ii) x−y−1/3, x−2/3, −z+4/3; (iii) −x+2/3, −y+1/3, −z+4/3; (iv) y−1/3, −x+y+1/3, −z+4/3; (v) −x+y, −x, z; (vi) −y, x−y, z; (vii) −x+y+1/3, −x+2/3, z−1/3; (viii) x−2/3, y−1/3, z−1/3; (ix) −y+1/3, x−y−1/3, z−1/3; (x) −x, −y, −z+1; (xi) x+2/3, y+1/3, z+1/3.