Crystal structure of alluaudite-type Na4Co(MoO4)3.

The title compound, tetra-sodium cobalt(II) tris-[molyb-date(IV)], was prepared by solid-state reactions. The structure is isotypic with Na3In2(AsO4)3 and Na3In2(PO4)3. The main structural feature is the presence of infinite chains of edge-sharing X 2O10 (X = Co/Na) dimers, which are linked by MoO4 tetra-hedra, forming a three-dimensional framework enclosing two types of hexa-gonal tunnels in which Na(+) cations reside. In this alluaudite structure, Co and Na atoms are located at the same general site with occupancies of 0.503 (5) and 0.497 (6), respectively. The other three Na and one of the two Mo atoms lie on special positions (site symmetries 2, -1, 2 and 2, respectively). The structure is compared with similar structures and other members of alluaudite family.

Related literature

For the bond-valance-sum method, see: Brown & Altermatt (1985 ▶). For related structures, see: Chaalia et al. (2012 ▶); Engel et al. (2005 ▶); Frigui et al. (2012 ▶); Hatert (2006 ▶); Hidouri et al. (2006 ▶); Kabbour et al. (2011 ▶); Kelvtsova et al. (1991 ▶); Lii & Ye (1997 ▶); Marzouki et al. (2013 ▶); Mikhailova et al. (2010 ▶); Moore (1971 ▶); Namsaraeva et al. (2011 ▶); Solodovnikov et al. (1988 ▶); Yakubovich et al. (2005 ▶).

Experimental

Crystal data

Na4Co(MoO4)3

M = 630.71

Monoclinic,

a = 12.8770 (8) Å

b = 13.4384 (9) Å

c = 7.1292 (7) Å

β = 112.072 (6)°

V = 1143.27 (15) Å3

Z = 4

Mo Kα radiation

μ = 4.85 mm−1

T = 298 K

0.84 × 0.28 × 0.22 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.214, T max = 0.344

2898 measured reflections

1242 independent reflections

1156 reflections with I > 2σ(I)

R int = 0.036

2 standard reflections every 120 min intensity decay: 1.4%

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.065

S = 1.12

1242 reflections

95 parameters

Δρmax = 1.14 e Å−3

Δρmin = −0.81 e Å−3

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; 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 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814016729/br2240sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016729/br2240Isup2.hkl

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asym 4 4 3 Code de symétrie x y z x y z x y z x y z x y z x y z . DOI: 10.1107/S1600536814016729/br2240fig1.tif

Unité asymétrique dans Na4Co(MoO4)3. Les éllipsoïdes ont été définis avec 50% de probabilité. [Code de symétrie]: (i) −x,y,-z + ; (ii) x,y + 1,z; (iii) x,-y + 1,z − 1/2; (iv) −x + ,-y + ,-z + 1; (v) x,-y + 1,z + 1/2; (vi) −x + ,y − 1/2,-z + .

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a 8 b 2 2 14 . DOI: 10.1107/S1600536814016729/br2240fig2.tif

Représentation: (a) des chaînes classiques CoMoO8, (b) des rubans de type Co2Mo2O14.

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. DOI: 10.1107/S1600536814016729/br2240fig3.tif

Représentation des couches disposées parallèlement au plan (100).

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4 4 3 c . DOI: 10.1107/S1600536814016729/br2240fig4.tif

Projection de la structure de Na4Co(MoO4)3 selon c.

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2 3 4 3 c 3+ 6 . DOI: 10.1107/S1600536814016729/br2240fig5.tif

Projection de la structure de K2Mn3(AsO4)3, selon c, montrant la disposition des octa­èdres Mn3+O6.

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1,09 3,46 4 3 a . DOI: 10.1107/S1600536814016729/br2240fig6.tif

Projection de la structure de Ag1,09Mn3,46(AsO4)3, selon a, montrant la jonction des octa­èdes par arêtes.

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4 4 3 b . DOI: 10.1107/S1600536814016729/br2240fig7.tif

Projection de la structure de Cs4Fe(MoO4)3, selon b, mettant en évidence les espaces inter-couches.

CCDC reference: 1015075

Additional supporting information: crystallographic information; 3D view; checkCIF report

Na4Co(MoO4)3	F(000) = 1172
Mr = 630.71	Dx = 3.664 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 12.8770 (8) Å	θ = 10–15°
b = 13.4384 (9) Å	µ = 4.85 mm−1
c = 7.1292 (7) Å	T = 298 K
β = 112.072 (6)°	Prism, blue
V = 1143.27 (15) Å3	0.84 × 0.28 × 0.22 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	1156 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
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 = 0.214, Tmax = 0.344	l = −9→9
2898 measured reflections	2 standard reflections every 120 min
1242 independent reflections	intensity decay: 1.4%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025	w = 1/[σ2(Fo2) + (0.0303P)2 + 3.9296P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.065	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 1.14 e Å−3
1242 reflections	Δρmin = −0.81 e Å−3
95 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0136 (5)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mo1	0.0000	0.21721 (3)	0.2500	0.01688 (16)
Mo2	0.26106 (3)	0.89054 (2)	0.37349 (4)	0.01710 (15)
Co1	0.28417 (6)	0.16208 (6)	0.37580 (10)	0.01443 (19)	0.503 (5)
Na1	0.28417 (6)	0.16208 (6)	0.37580 (10)	0.01443 (19)	0.497 (6)
Na2	0.0000	0.23993 (19)	0.7500	0.0245 (5)
Na3	0.0000	0.0000	0.0000	0.0372 (6)
Na4	0.5000	0.0060 (3)	0.7500	0.0454 (7)
O1	0.2761 (3)	0.8197 (2)	0.1715 (4)	0.0283 (7)
O2	0.3244 (3)	0.8298 (2)	0.6100 (4)	0.0264 (6)
O3	0.1067 (3)	0.1352 (2)	0.2466 (5)	0.0324 (7)
O4	0.3248 (3)	0.0080 (3)	0.3900 (5)	0.0345 (7)
O5	0.1179 (3)	0.9099 (2)	0.3156 (5)	0.0290 (7)
O6	0.0439 (2)	0.2916 (2)	0.4718 (4)	0.0238 (6)

	U11	U22	U33	U12	U13	U23
Mo1	0.0256 (3)	0.0134 (2)	0.0097 (2)	0.000	0.00436 (17)	0.000
Mo2	0.0212 (2)	0.0184 (2)	0.0106 (2)	−0.00135 (12)	0.00467 (13)	0.00017 (11)
Co1	0.0183 (4)	0.0159 (4)	0.0092 (3)	0.0006 (3)	0.0054 (3)	−0.0009 (3)
Na1	0.0183 (4)	0.0159 (4)	0.0092 (3)	0.0006 (3)	0.0054 (3)	−0.0009 (3)
Na2	0.0248 (11)	0.0317 (12)	0.0208 (11)	0.000	0.0131 (9)	0.000
Na3	0.0506 (16)	0.0234 (12)	0.0239 (13)	0.0014 (12)	−0.0018 (11)	−0.0011 (11)
Na4	0.0233 (12)	0.0505 (18)	0.0527 (19)	0.000	0.0031 (12)	0.000
O1	0.0368 (16)	0.0338 (17)	0.0165 (13)	−0.0011 (14)	0.0124 (12)	−0.0011 (12)
O2	0.0339 (15)	0.0267 (15)	0.0142 (13)	0.0072 (13)	0.0041 (11)	0.0009 (11)
O3	0.0363 (16)	0.0248 (15)	0.0289 (16)	0.0052 (13)	0.0042 (13)	−0.0075 (13)
O4	0.0416 (18)	0.0309 (17)	0.0294 (16)	−0.0123 (15)	0.0114 (14)	0.0030 (14)
O5	0.0266 (15)	0.0268 (15)	0.0329 (16)	0.0042 (12)	0.0104 (13)	0.0043 (13)
O6	0.0306 (15)	0.0293 (15)	0.0127 (12)	−0.0020 (12)	0.0094 (11)	−0.0047 (11)

Mo1—O3i	1.769 (3)	Na2—O6	2.361 (3)
Mo1—O3	1.769 (3)	Na2—O2viii	2.424 (3)
Mo1—O6	1.774 (3)	Na2—O2ix	2.424 (3)
Mo1—O6i	1.774 (3)	Na2—O5x	2.458 (4)
Mo2—O5	1.750 (3)	Na2—O5v	2.458 (4)
Mo2—O4ii	1.762 (3)	Na3—O5xi	2.503 (3)
Mo2—O2	1.772 (3)	Na3—O5xii	2.503 (3)
Mo2—O1	1.796 (3)	Na3—O3xiii	2.543 (3)
Co1—O4	2.129 (4)	Na3—O3	2.543 (3)
Co1—O2iii	2.146 (3)	Na3—O5iii	2.646 (3)
Co1—O3	2.149 (3)	Na3—O5xiv	2.646 (3)
Co1—O6iv	2.159 (3)	Na4—O4xv	2.706 (3)
Co1—O1v	2.164 (3)	Na4—O4	2.706 (3)
Co1—O1vi	2.237 (3)	Na4—O4xvi	2.795 (4)
Na2—O6vii	2.361 (3)	Na4—O4xvii	2.795 (4)
O3i—Mo1—O3	102.9 (2)	O2iii—Co1—O3	101.57 (12)
O3i—Mo1—O6	109.14 (14)	O4—Co1—O6iv	93.97 (13)
O3—Mo1—O6	111.98 (14)	O2iii—Co1—O6iv	83.55 (11)
O3i—Mo1—O6i	111.98 (14)	O3—Co1—O6iv	171.19 (12)
O3—Mo1—O6i	109.14 (14)	O4—Co1—O1v	99.48 (13)
O6—Mo1—O6i	111.42 (19)	O2iii—Co1—O1v	166.02 (13)
O5—Mo2—O4ii	107.81 (16)	O3—Co1—O1v	90.22 (12)
O5—Mo2—O2	111.10 (15)	O6iv—Co1—O1v	83.85 (11)
O4ii—Mo2—O2	108.20 (15)	O4—Co1—O1vi	173.29 (12)
O5—Mo2—O1	108.10 (15)	O2iii—Co1—O1vi	90.23 (11)
O4ii—Mo2—O1	109.90 (15)	O3—Co1—O1vi	80.90 (12)
O2—Mo2—O1	111.66 (14)	O6iv—Co1—O1vi	92.00 (12)
O4—Co1—O2iii	87.41 (13)	O1v—Co1—O1vi	84.19 (12)
O4—Co1—O3	93.43 (13)