Structure cristalline de type alluaudite KNa₅Mn₃(MoO₄)₆

In the new molybdenum oxide potassium penta­sodium trimanganese hexa­kis­(molybdate), KNa₅Mn₃Mo₆O₂₄, the structure is composed of M₂O₁₀ (M = Mn, Na) dimers and MoO₄ tetra­hedra sharing corners and forming layers which are linked via common corners of another type of MO₄ tetra­hedra, forming a three-dimensional structure with two types of large channels in which the Na⁺ and K⁺ cations are located.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](Mo-O) = 0.003 Å
• Disorder in main residue
• R factor = 0.021
• wR factor = 0.055
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT975_ALERT_2_C Check Calcd Residual Density  0.67A From      O4       0.45 eA-3

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
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  O5_g    ..        8.6 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  O2_i    ..        6.1 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  O3_i    ..        8.1 su
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =          9 Note
PLAT302_ALERT_4_G Anion/Solvent Disorder ............ Percentage =         27 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
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Potassium pentasodium trimanganese hexakis(molybdate)

Crystal data

KNa5Mn3(MoO4)6	F(000) = 1186
Mr = 1278.51	Dx = 3.640 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 12.8943 (8) Å	θ = 10–15°
b = 13.6295 (9) Å	µ = 5.05 mm^−1
c = 7.1809 (7) Å	T = 298 K
β = 112.437 (5)°	Prism, yellow
V = 1166.46 (16) Å^3	0.26 × 0.22 × 0.18 mm
Z = 2

Data collection

Enraf–Nonius CAD-4 diffractometer	1155 reflections with I > 2/s(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 27.0°, θmin = 2.3°
ω/2θ scans	h = −16→16
Absorption correction: ψ scan (North et al., 1968)	k = −2→17
Tmin = 0.303, Tmax = 0.413	l = −9→9
2955 measured reflections	2 standard reflections every 120 min
1266 independent reflections	intensity decay: 1.2%

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)] = 0.021	w = 1/[σ^2(Fo^2) + (0.0194P)^2 + 2.2536P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.055	(Δ/σ)max = 0.001
S = 1.13	Δρmax = 0.60 e Å^−3
1266 reflections	Δρmin = −0.57 e Å^−3
97 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00373 (18)

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	0.76468 (2)	0.61059 (2)	0.87380 (4)	0.01636 (12)
Mo2	0.0000	0.78727 (3)	0.7500	0.01521 (13)
Mn1	0.78663 (5)	0.65843 (5)	0.37656 (9)	0.01657 (15)	0.75
Na3	0.78663 (5)	0.65843 (5)	0.37656 (9)	0.01657 (15)	0.25
Na1	0.0000	0.76259 (17)	0.2500	0.0243 (5)
Na2	0.5000	0.5000	0.5000	0.0539 (8)
K1	0.0000	0.4921 (3)	0.2500	0.0512 (8)	0.50
O1	0.0426 (2)	0.7148 (2)	0.9703 (3)	0.0222 (5)
O2	0.8937 (2)	0.8681 (2)	0.7505 (4)	0.0311 (6)
O3	0.7807 (2)	0.6818 (2)	0.6776 (3)	0.0252 (6)
O4	0.8271 (2)	0.6698 (2)	1.1086 (3)	0.0251 (6)
O5	0.8292 (3)	0.4957 (2)	0.8897 (4)	0.0341 (7)
O6	0.6219 (2)	0.5916 (2)	0.8139 (4)	0.0322 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.02017 (18)	0.01682 (18)	0.01267 (16)	0.00076 (11)	0.00692 (12)	−0.00067 (10)
Mo2	0.0177 (2)	0.0147 (2)	0.0122 (2)	0.000	0.00450 (15)	0.000
Mn1	0.0184 (3)	0.0184 (3)	0.0144 (3)	−0.0002 (2)	0.0079 (2)	−0.0014 (2)
Na3	0.0184 (3)	0.0184 (3)	0.0144 (3)	−0.0002 (2)	0.0079 (2)	−0.0014 (2)
Na1	0.0219 (10)	0.0333 (12)	0.0226 (10)	0.000	0.0139 (8)	0.000
Na2	0.0668 (19)	0.0312 (14)	0.0380 (14)	−0.0041 (14)	−0.0087 (13)	0.0063 (13)
K1	0.0304 (14)	0.075 (2)	0.0439 (16)	0.000	0.0090 (12)	0.000
O1	0.0223 (12)	0.0297 (14)	0.0155 (11)	0.0005 (11)	0.0082 (10)	0.0052 (11)
O2	0.0264 (13)	0.0245 (14)	0.0383 (16)	0.0039 (12)	0.0076 (12)	−0.0082 (14)
O3	0.0325 (14)	0.0305 (15)	0.0148 (11)	0.0011 (12)	0.0115 (10)	0.0013 (11)
O4	0.0346 (14)	0.0256 (14)	0.0154 (11)	−0.0060 (12)	0.0099 (10)	−0.0020 (11)
O5	0.0415 (17)	0.0255 (15)	0.0358 (15)	0.0110 (13)	0.0154 (13)	−0.0015 (13)
O6	0.0263 (14)	0.0304 (15)	0.0404 (16)	−0.0051 (12)	0.0132 (12)	−0.0045 (13)

Geometric parameters (Å, º)

Mo1—O6	1.743 (3)	Na1—O4^i	2.424 (3)
Mo1—O5	1.757 (3)	Na1—O6^viii	2.466 (4)
Mo1—O4	1.762 (2)	Na1—O6^ix	2.466 (4)
Mo1—O3	1.787 (3)	Na2—O6^x	2.531 (3)
Mo2—O2^i	1.759 (3)	Na2—O6	2.531 (3)
Mo2—O2^ii	1.759 (3)	Na2—O2^viii	2.538 (3)
Mo2—O1^iii	1.766 (2)	Na2—O2^xi	2.538 (3)
Mo2—O1	1.766 (2)	Na2—O6^iv	2.724 (3)
Mn1—O5^iv	2.164 (3)	Na2—O6^i	2.724 (3)
Mn1—O2^v	2.180 (3)	K1—O5^i	2.683 (3)
Mn1—O4^vi	2.182 (3)	K1—O5^vii	2.683 (3)
Mn1—O1^i	2.191 (3)	K1—O5^x	2.751 (3)
Mn1—O3	2.215 (2)	K1—O5^xii	2.751 (3)
Mn1—O3^v	2.321 (3)	K1—O1^xiii	3.177 (5)
Na1—O1^vi	2.367 (2)	K1—O1^iv	3.177 (5)
Na1—O1^iii	2.367 (2)	K1—O4^i	3.184 (4)
Na1—O4^vii	2.424 (3)	K1—O4^vii	3.184 (4)
O6—Mo1—O5	108.25 (14)	O2^v—Mn1—O4^vi	102.61 (11)
O6—Mo1—O4	110.96 (14)	O5^iv—Mn1—O1^i	97.38 (11)
O5—Mo1—O4	108.31 (14)	O2^v—Mn1—O1^i	167.33 (11)
O6—Mo1—O3	108.39 (13)	O4^vi—Mn1—O1^i	83.41 (9)
O5—Mo1—O3	109.94 (14)	O5^iv—Mn1—O3	101.53 (11)
O4—Mo1—O3	110.96 (12)	O2^v—Mn1—O3	90.23 (11)
O2^i—Mo2—O2^ii	102.44 (19)	O4^vi—Mn1—O3	163.52 (11)
O2^i—Mo2—O1^iii	108.96 (13)	O1^i—Mn1—O3	82.06 (10)
O2^ii—Mo2—O1^iii	112.10 (12)	O5^iv—Mn1—O3^v	171.99 (11)
O2^i—Mo2—O1	112.10 (12)	O2^v—Mn1—O3^v	79.30 (10)
O2^ii—Mo2—O1	108.96 (13)	O4^vi—Mn1—O3^v	89.19 (10)
O1^iii—Mo2—O1	111.93 (18)	O1^i—Mn1—O3^v	89.75 (10)
O5^iv—Mn1—O2^v	93.99 (11)	O3—Mn1—O3^v	83.02 (10)
O5^iv—Mn1—O4^vi	88.00 (11)

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