Na1.67Mn2.17(MoO4)3.

The title compound, disodium dimanganese(II) tris-[ortho-molybdate(VI)], was prepared by solid-state reactions. The structure can be described as being composed of Mn2Mo2O14 double-chains that are inter-connected by corner-sharing with MoO4 tetra-hedra, leading to a three-dimensional framework with channels propagating in [100] and [001] in which the Na(+) counter-cations are located. One of these Na sites is located on an inversion centre, one is partially occupied [occupancy 0.341 (9)], and one is statistically occupied by Na and Mn in a ratio of 0.829 (5):0.171 (5). Na1.67Mn2.17(MoO4)3 is isotypic with structures of the Ag2 M 2(MoO4)3 (M = Zn, Mg, Co, Mn) family. A comparative structural description is provided between the structure of the title compound and those of related phases containing (MXO8) n chains (M = Mo, Mn and X = As) or M 2O10 (M = Mo, Mn, Nb, V) dimers.

Related literature

For isotypic compounds, see: Tsyrenova et al. (2004 ▶); Gicquel-Mayer et al. (1981 ▶); Balsanova et al. (2009 ▶). For background to the physico-chemical properties of related compounds, see: Gueho et al. (1993 ▶); Piffard et al. (1985 ▶); Solodovnikov et al. (1986 ▶, 1997 ▶, 1998 ▶); Prabaharan et al. (1997 ▶). For details of structurally related compounds, see: Frigui et al. (2011 ▶, 2012 ▶); Guesmi & Driss (2012 ▶); Belkhiri et al. (2009 ▶); Chérif et al. (2011 ▶); Ledain et al. (1996 ▶); Ezzine Yahmed et al. (2013 ▶). For bond lengths and bond-valence sums, see: Souilem et al. (2014 ▶); Ennajeh et al. (2013 ▶); Brown & Altermatt (1985 ▶).

Experimental

Crystal data

Na1.67Mn2.17(MoO4)3

M = 637.43

Triclinic,

a = 7.1072 (7) Å

b = 8.8120 (8) Å

c = 10.4330 (9) Å

α = 106.501 (9)°

β = 105.361 (9)°

γ = 102.756 (8)°

V = 572.31 (11) Å3

Z = 2

Mo Kα radiation

μ = 5.64 mm−1

T = 298 K

0.28 × 0.15 × 0.11 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.371, T max = 0.540

3079 measured reflections

2474 independent reflections

2206 reflections with I > 2σ(I)

R int = 0.017

2 standard reflections every 120 min intensity decay: 1.3%

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.083

S = 1.09

2474 reflections

180 parameters

Δρmax = 1.52 e Å−3

Δρmin = −1.24 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, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681400614X/wm5009sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400614X/wm5009Isup2.hkl

CCDC reference: 992636

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

Na1.67Mn2.17(MoO4)3	Z = 2
Mr = 637.43	F(000) = 589
Triclinic, P1	Dx = 3.699 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1072 (7) Å	Cell parameters from 25 reflections
b = 8.8120 (8) Å	θ = 10–15°
c = 10.4330 (9) Å	µ = 5.64 mm−1
α = 106.501 (9)°	T = 298 K
β = 105.361 (9)°	Prism, yellow
γ = 102.756 (8)°	0.28 × 0.15 × 0.11 mm
V = 572.31 (11) Å3

Enraf–Nonius CAD-4 diffractometer	2206 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 27.0°, θmin = 2.2°
ω/2θ scans	h = −1→9
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
Tmin = 0.371, Tmax = 0.540	l = −13→13
3079 measured reflections	2 standard reflections every 120 min
2474 independent reflections	intensity decay: 1.3%

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)] = 0.030	w = 1/[σ2(Fo2) + (0.0429P)2 + 1.7705P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.083	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 1.52 e Å−3
2474 reflections	Δρmin = −1.24 e Å−3
180 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0295 (11)

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	0.89052 (6)	0.41054 (5)	0.66707 (4)	0.01200 (14)
Mo2	0.21772 (6)	0.16273 (5)	0.26393 (4)	0.01185 (14)
Mo3	0.59566 (6)	0.76438 (5)	0.12859 (4)	0.01514 (14)
Mn1	0.37898 (12)	0.45559 (10)	0.60871 (8)	0.01386 (18)
Mn2	0.04434 (12)	0.70486 (9)	0.01860 (8)	0.01258 (18)
Na3	0.2869 (3)	0.7921 (2)	0.80026 (18)	0.0198 (5)	0.829 (5)
Mn3	0.2869 (3)	0.7921 (2)	0.80026 (18)	0.0198 (5)	0.171 (5)
Na1	0.0000	0.0000	0.5000	0.0534 (13)
Na2	0.5195 (17)	0.9729 (14)	0.4581 (10)	0.054 (4)	0.341 (9)
O1	0.7228 (9)	0.9722 (6)	0.2412 (6)	0.0554 (16)
O2	0.8393 (8)	0.1999 (5)	0.5790 (5)	0.0320 (10)
O3	0.7536 (7)	0.6998 (6)	0.0365 (5)	0.0320 (10)
O4	0.2232 (6)	0.2013 (5)	0.4419 (4)	0.0205 (8)
O5	0.1747 (7)	0.9506 (5)	0.1815 (5)	0.0282 (9)
O6	0.1209 (6)	0.5181 (5)	0.6519 (4)	0.0206 (8)
O7	0.0200 (6)	0.2252 (5)	0.1661 (4)	0.0213 (8)
O8	0.3534 (6)	0.7437 (6)	0.0055 (4)	0.0247 (9)
O9	0.6776 (5)	0.4713 (5)	0.5818 (4)	0.0169 (7)
O10	0.9224 (6)	0.4447 (5)	0.8498 (4)	0.0169 (7)
O11	0.4624 (6)	0.2725 (5)	0.2679 (4)	0.0197 (8)
O12	0.5617 (8)	0.6484 (7)	0.2375 (5)	0.0443 (13)

	U11	U22	U33	U12	U13	U23
Mo1	0.0137 (2)	0.0142 (2)	0.0126 (2)	0.00713 (17)	0.00657 (16)	0.00746 (17)
Mo2	0.0132 (2)	0.0107 (2)	0.0131 (2)	0.00356 (16)	0.00512 (16)	0.00613 (16)
Mo3	0.0143 (2)	0.0171 (2)	0.0151 (2)	0.00401 (17)	0.00602 (17)	0.00724 (17)
Mn1	0.0142 (4)	0.0157 (4)	0.0155 (4)	0.0055 (3)	0.0078 (3)	0.0083 (3)
Mn2	0.0154 (4)	0.0126 (4)	0.0138 (4)	0.0062 (3)	0.0072 (3)	0.0073 (3)
Na3	0.0175 (9)	0.0210 (9)	0.0236 (9)	0.0081 (7)	0.0113 (7)	0.0070 (7)
Mn3	0.0175 (9)	0.0210 (9)	0.0236 (9)	0.0081 (7)	0.0113 (7)	0.0070 (7)
Na1	0.100 (4)	0.0235 (18)	0.080 (3)	0.031 (2)	0.076 (3)	0.031 (2)
Na2	0.032 (5)	0.046 (7)	0.061 (8)	−0.012 (4)	−0.015 (5)	0.032 (6)
O1	0.049 (3)	0.028 (3)	0.055 (3)	−0.010 (2)	0.016 (3)	−0.013 (2)
O2	0.050 (3)	0.018 (2)	0.031 (2)	0.016 (2)	0.017 (2)	0.0072 (18)
O3	0.021 (2)	0.046 (3)	0.034 (2)	0.016 (2)	0.0123 (18)	0.014 (2)
O4	0.026 (2)	0.0176 (18)	0.0165 (17)	0.0023 (16)	0.0092 (16)	0.0071 (15)
O5	0.037 (2)	0.0133 (18)	0.031 (2)	0.0050 (17)	0.0146 (19)	0.0034 (16)
O6	0.0193 (19)	0.027 (2)	0.0203 (19)	0.0108 (16)	0.0111 (16)	0.0099 (16)
O7	0.0162 (18)	0.030 (2)	0.024 (2)	0.0058 (16)	0.0070 (16)	0.0189 (17)
O8	0.020 (2)	0.037 (2)	0.030 (2)	0.0175 (18)	0.0116 (17)	0.0197 (19)
O9	0.0131 (17)	0.0257 (19)	0.0167 (17)	0.0078 (15)	0.0070 (14)	0.0116 (15)
O10	0.0221 (19)	0.0181 (18)	0.0162 (17)	0.0076 (15)	0.0091 (15)	0.0116 (15)
O11	0.0185 (18)	0.0196 (18)	0.0232 (19)	0.0075 (15)	0.0088 (16)	0.0086 (15)
O12	0.037 (3)	0.067 (4)	0.036 (3)	0.010 (3)	0.006 (2)	0.040 (3)

Mo1—O2	1.726 (4)	Mn2—O7v	2.153 (4)
Mo1—O6i	1.772 (4)	Mn2—O10iii	2.161 (4)
Mo1—O10	1.787 (4)	Mn2—O8	2.194 (4)
Mo1—O9	1.812 (4)	Mn2—O10vi	2.264 (4)
Mo2—O5ii	1.739 (4)	Na3—O11iii	2.212 (4)
Mo2—O11	1.777 (4)	Na3—O1vii	2.250 (7)
Mo2—O4	1.778 (4)	Na3—O8viii	2.250 (4)
Mo2—O7	1.795 (4)	Na3—O7ix	2.279 (4)
Mo3—O1	1.742 (5)	Na3—O6	2.296 (4)
Mo3—O3	1.747 (4)	Na1—O2iv	2.376 (4)
Mo3—O12	1.757 (5)	Na1—O2x	2.376 (4)
Mo3—O8	1.790 (4)	Na1—O4xi	2.430 (4)
Mn1—O12iii	2.060 (4)	Na1—O4	2.430 (4)
Mn1—O6	2.148 (4)	Na1—O1iii	2.797 (6)
Mn1—O9	2.193 (4)	Na1—O1xii	2.797 (6)
Mn1—O9iii	2.224 (4)	Na2—O2xiii	2.408 (11)
Mn1—O4	2.224 (4)	Na2—O2iii	2.529 (12)
Mn1—O11iii	2.226 (4)	Na2—O4iii	2.815 (13)
Mn2—O3iv	2.115 (4)	Na2—O1	2.990 (12)
Mn2—O5	2.151 (4)
O2—Mo1—O6i	107.4 (2)	O7v—Mn2—O8	83.66 (15)
O2—Mo1—O10	108.02 (19)	O10iii—Mn2—O8	95.72 (15)
O6i—Mo1—O10	110.69 (18)	O3iv—Mn2—O10vi	93.72 (16)
O2—Mo1—O9	108.4 (2)	O5—Mn2—O10vi	177.23 (16)
O6i—Mo1—O9	110.42 (17)	O7v—Mn2—O10vi	82.20 (14)
O10—Mo1—O9	111.77 (17)	O10iii—Mn2—O10vi	79.09 (14)
O5ii—Mo2—O11	107.62 (19)	O8—Mn2—O10vi	92.25 (15)
O5ii—Mo2—O4	108.4 (2)	O11iii—Na3—O1vii	104.9 (2)
O11—Mo2—O4	109.13 (18)	O11iii—Na3—O8viii	100.10 (15)
O5ii—Mo2—O7	110.2 (2)	O1vii—Na3—O8viii	130.52 (19)
O11—Mo2—O7	110.29 (17)	O11iii—Na3—O7ix	162.72 (17)
O4—Mo2—O7	111.16 (19)	O1vii—Na3—O7ix	87.64 (19)
O1—Mo3—O3	107.7 (3)	O8viii—Na3—O7ix	79.60 (15)
O1—Mo3—O12	107.1 (3)	O11iii—Na3—O6	79.28 (15)
O3—Mo3—O12	110.1 (3)	O1vii—Na3—O6	129.81 (19)
O1—Mo3—O8	110.5 (3)	O8viii—Na3—O6	96.19 (16)
O3—Mo3—O8	110.2 (2)	O7ix—Na3—O6	83.56 (15)
O12—Mo3—O8	111.1 (2)	O2iv—Na1—O2x	180.000 (1)
O12iii—Mn1—O6	94.94 (19)	O2iv—Na1—O4xi	90.01 (15)
O12iii—Mn1—O9	93.48 (18)	O2x—Na1—O4xi	89.99 (15)
O6—Mn1—O9	163.16 (15)	O2iv—Na1—O4	89.99 (15)
O12iii—Mn1—O9iii	169.9 (2)	O2x—Na1—O4	90.01 (15)
O6—Mn1—O9iii	92.19 (14)	O4xi—Na1—O4	180.0
O9—Mn1—O9iii	81.49 (14)	O2iv—Na1—O1iii	101.44 (16)
O12iii—Mn1—O4	89.8 (2)	O2x—Na1—O1iii	78.56 (16)
O6—Mn1—O4	101.04 (16)	O4xi—Na1—O1iii	80.94 (15)
O9—Mn1—O4	93.54 (15)	O4—Na1—O1iii	99.06 (15)
O9iii—Mn1—O4	81.83 (14)	O2iv—Na1—O1xii	78.56 (16)
O12iii—Mn1—O11iii	103.0 (2)	O2x—Na1—O1xii	101.44 (16)
O6—Mn1—O11iii	82.21 (15)	O4xi—Na1—O1xii	99.06 (15)
O9—Mn1—O11iii	81.69 (14)	O4—Na1—O1xii	80.94 (15)
O9iii—Mn1—O11iii	84.99 (14)	O1iii—Na1—O1xii	180.0
O4—Mn1—O11iii	166.52 (14)	O2xiii—Na2—O2iii	156.6 (5)
O3iv—Mn2—O5	88.82 (18)	Na2vii—Na2—O4iii	104.7 (13)
O3iv—Mn2—O7v	93.21 (17)	O2xiii—Na2—O4iii	80.8 (3)
O5—Mn2—O7v	98.77 (16)	O2iii—Na2—O4iii	104.7 (4)
O3iv—Mn2—O10iii	89.32 (17)	Na2vii—Na2—O1	154.6 (14)
O5—Mn2—O10iii	99.87 (16)	O2xiii—Na2—O1	74.3 (3)
O7v—Mn2—O10iii	161.24 (15)	O2iii—Na2—O1	128.2 (4)
O3iv—Mn2—O8	172.82 (18)	O4iii—Na2—O1	86.6 (4)
O5—Mn2—O8	85.29 (17)

Table 1

Selected bond lengths (Å)

Mo1—O2	1.726 (4)
Mo1—O6i	1.772 (4)
Mo1—O10	1.787 (4)
Mo1—O9	1.812 (4)
Mo2—O5ii	1.739 (4)
Mo2—O11	1.777 (4)
Mo2—O4	1.778 (4)
Mo2—O7	1.795 (4)
Mo3—O1	1.742 (5)
Mo3—O3	1.747 (4)
Mo3—O12	1.757 (5)
Mo3—O8	1.790 (4)
Mn1—O12iii	2.060 (4)
Mn1—O6	2.148 (4)
Mn1—O9	2.193 (4)
Mn1—O9iii	2.224 (4)
Mn1—O4	2.224 (4)
Mn1—O11iii	2.226 (4)
Mn2—O3iv	2.115 (4)
Mn2—O5	2.151 (4)
Mn2—O7v	2.153 (4)
Mn2—O10iii	2.161 (4)
Mn2—O8	2.194 (4)
Mn2—O10vi	2.264 (4)
Na3—O11iii	2.212 (4)
Na3—O1vii	2.250 (7)
Na3—O8viii	2.250 (4)
Na3—O7ix	2.279 (4)
Na1—O2iv	2.376 (4)
Na1—O2x	2.376 (4)
Na1—O4xi	2.430 (4)
Na1—O4	2.430 (4)
Na1—O1iii	2.797 (6)
Na1—O1xii	2.797 (6)
Na2—O2xiii	2.408 (11)
Na2—O2iii	2.529 (12)
Na2—O4iii	2.815 (13)
Na2—O1	2.990 (12)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) ; (xii) ; (xiii) .