Structure cristalline de type alluaudite K_0.4Na_3.6Co(MoO₄)₃

A new triple molybdate K_0.4Na_3.6Co(MoO₄)₃ was synthesized using solid-state reaction at 973 K and characterized by X-ray diffraction. The structure is characterized by M₂O₁₀ (M = Co/Na) dimers, which are linked by MoO₄ tetra­hedra, forming infinite layers. The latter are connected on one hand by insertion of Mo1O₄ tetra­hedra and secondly by sharing corners with Mo2O₄ tetra­hedra.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](Mo-O) = 0.003 Å
• Disorder in main residue
• R factor = 0.022
• wR factor = 0.056
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...     Please Check
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..     Please Check
PLAT241_ALERT_2_C High      Ueq as Compared to Neighbors for .....         O6 Check

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Dimension .......          2 Info
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT128_ALERT_4_G Alternate Setting for Input Space Group     C2/c       I2/a Note
PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ...          2 Units
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo1    --  O4      ..        5.9 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co1    --  O3      ..        5.7 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co1    --  O6      ..       15.3 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co1    --  O2_b    ..        5.6 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co1    --  O1_c    ..        9.7 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co1    --  O2_d    ..       16.9 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co1    --  O4_f    ..       20.9 su
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =          7 Note
PLAT302_ALERT_4_G Anion/Solvent Disorder ............ Percentage =         33 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note

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

   3 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
   2 ALERT type 3 Indicator that the structure quality may be low
   4 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: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Potassium sodium cobalt tris(molybdate)

Crystal data

K0.4Na3.6Co(MoO4)3	F(000) = 1185
Mr = 637.15	Dx = 3.670 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 12.8054 (8) Å	θ = 10–15°
b = 13.5328 (9) Å	µ = 4.94 mm^−1
c = 7.1888 (6) Å	T = 298 K
β = 112.239 (8)°	Prism, purple
V = 1153.10 (14) Å^3	0.22 × 0.16 × 0.12 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	1092 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 27.0°, θmin = 2.3°
ω/2θ scans	h = −16→13
Absorption correction: ψ scan (North et al., 1968)	k = −2→17
Tmin = 0.557, Tmax = 0.607	l = −9→9
2813 measured reflections	2 standard reflections every 120 min
1252 independent reflections	intensity decay: 1.4%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.0256P)^2 + 0.2937P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.056	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.47 e Å^−3
1252 reflections	Δρmin = −0.43 e Å^−3
99 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00215 (15)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mo1	0.5000	0.21535 (3)	0.2500	0.02386 (14)
Mo2	0.73366 (2)	0.60949 (2)	0.62347 (4)	0.02137 (12)
Co1	0.71350 (6)	0.33825 (6)	0.62440 (10)	0.01883 (17)	0.50
Na1	0.71350 (6)	0.33825 (6)	0.62440 (10)	0.01883 (17)	0.50
Na2	0.5000	0.23393 (16)	0.7500	0.0245 (4)
Na3	0.5000	0.0000	0.5000	0.0358 (5)
K4	0.5000	0.48817 (18)	0.2500	0.0434 (8)	0.402 (16)
Na4	0.5000	0.48817 (18)	0.2500	0.0434 (8)	0.597 (18)
O1	0.6713 (2)	0.6703 (2)	0.3919 (4)	0.0310 (6)
O2	0.7192 (2)	0.6791 (2)	0.8226 (4)	0.0367 (7)
O3	0.5413 (2)	0.2891 (2)	0.4691 (4)	0.0291 (6)
O4	0.6072 (3)	0.1336 (2)	0.2506 (5)	0.0461 (8)
O5	0.8768 (2)	0.5878 (2)	0.6818 (4)	0.0329 (6)
O6	0.6623 (3)	0.4960 (2)	0.6026 (5)	0.0438 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0371 (3)	0.0170 (2)	0.0127 (2)	0.000	0.00406 (17)	0.000
Mo2	0.02105 (18)	0.0256 (2)	0.01562 (17)	−0.00171 (12)	0.00482 (12)	0.00182 (11)
Co1	0.0207 (3)	0.0214 (4)	0.0145 (3)	0.0035 (3)	0.0068 (3)	0.0003 (3)
Na1	0.0207 (3)	0.0214 (4)	0.0145 (3)	0.0035 (3)	0.0068 (3)	0.0003 (3)
Na2	0.0237 (9)	0.0250 (11)	0.0276 (10)	0.000	0.0129 (8)	0.000
Na3	0.0478 (14)	0.0220 (11)	0.0246 (11)	−0.0008 (11)	−0.0011 (10)	0.0008 (9)
K4	0.0238 (10)	0.0710 (17)	0.0308 (10)	0.000	0.0051 (7)	0.000
Na4	0.0238 (10)	0.0710 (17)	0.0308 (10)	0.000	0.0051 (7)	0.000
O1	0.0330 (14)	0.0347 (16)	0.0204 (12)	0.0102 (13)	0.0046 (11)	0.0015 (12)
O2	0.0410 (16)	0.0462 (18)	0.0242 (14)	0.0009 (14)	0.0139 (12)	0.0005 (13)
O3	0.0328 (13)	0.0357 (15)	0.0189 (12)	−0.0025 (12)	0.0098 (10)	−0.0051 (11)
O4	0.058 (2)	0.0285 (16)	0.0375 (16)	0.0091 (15)	0.0012 (15)	−0.0093 (14)
O5	0.0270 (14)	0.0289 (15)	0.0400 (16)	0.0025 (12)	0.0096 (12)	0.0084 (13)
O6	0.0439 (18)	0.0396 (18)	0.0457 (18)	−0.0114 (15)	0.0145 (14)	0.0076 (15)

Geometric parameters (Å, º)

Mo1—O4^i	1.762 (3)	Na2—O1^vii	2.416 (3)
Mo1—O4	1.762 (3)	Na2—O5^viii	2.461 (3)
Mo1—O3	1.768 (2)	Na2—O5^v	2.461 (3)
Mo1—O3^i	1.768 (2)	Na3—O5^ix	2.530 (3)
Mo2—O5	1.744 (3)	Na3—O5^v	2.530 (3)
Mo2—O1	1.755 (3)	Na3—O4^i	2.554 (3)
Mo2—O6	1.764 (3)	Na3—O4^x	2.554 (3)
Mo2—O2	1.781 (3)	Na3—O5^ii	2.677 (3)
Co1—O4^ii	2.159 (4)	Na3—O5^viii	2.677 (3)
Co1—O3	2.166 (3)	K4—O6	2.602 (3)
Co1—O1^iii	2.188 (3)	K4—O6^i	2.602 (3)
Co1—O2^iv	2.211 (3)	K4—O6^iv	2.675 (3)
Co1—O6	2.222 (3)	K4—O6^vii	2.675 (3)
Co1—O2^v	2.298 (3)	K4—O3^i	3.064 (3)
Na2—O3^vi	2.392 (3)	K4—O3	3.064 (3)
Na2—O3	2.392 (3)	K4—O1	3.199 (4)
Na2—O1^iii	2.416 (3)	K4—O1^i	3.199 (4)
O4^i—Mo1—O4	102.2 (2)	O3—Co1—O1^iii	83.96 (10)
O4^i—Mo1—O3	109.06 (14)	O4^ii—Co1—O2^iv	90.15 (12)
O4—Mo1—O3	112.50 (13)	O3—Co1—O2^iv	82.34 (11)
O4^i—Mo1—O3^i	112.50 (13)	O1^iii—Co1—O2^iv	165.35 (11)
O4—Mo1—O3^i	109.06 (14)	O4^ii—Co1—O6	95.65 (12)
O3—Mo1—O3^i	111.26 (18)	O3—Co1—O6	92.46 (11)
O5—Mo2—O1	111.51 (13)	O1^iii—Co1—O6	87.03 (12)
O5—Mo2—O6	109.70 (15)	O2^iv—Co1—O6	98.70 (12)
O1—Mo2—O6	107.00 (15)	O4^ii—Co1—O2^v	79.83 (11)
O5—Mo2—O2	108.41 (14)	O3—Co1—O2^v	92.45 (11)
O1—Mo2—O2	111.48 (13)	O1^iii—Co1—O2^v	90.38 (11)
O6—Mo2—O2	108.69 (15)	O2^iv—Co1—O2^v	85.05 (11)
O4^ii—Co1—O3	169.69 (11)	O6—Co1—O2^v	174.18 (11)
O4^ii—Co1—O1^iii	102.76 (12)

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