catena-Poly[tetra­sodium [[cis-dioxido-trans-bis­(sulfato-κO)molybdate(VI)]-μ-sulfato-κ2O:O′]]

Schäffer, S.J.C.; Berg, R.W.

doi:10.1107/S1600536808030328

inorganic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page i73

doi:10.1107/S1600536808030328

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catena-Poly[tetrasodium [[cis-dioxido-trans-bis(sulfato-κO)molybdate(VI)]-μ-sulfato-κ²O:O′]]

Susan J. Cline Schäffer ^a ^* and Rolf W. Berg ^b

^aTårnby Gymnasium & HF, Tejn Allé 5, DK-2770 Kastrup, Denmark, and ^bThe Technical University of Denmark, The Department of Chemistry, Building 207, DK-2800 Lyngby, Denmark
^*Correspondence e-mail: su@tgy.dk

(Received 15 July 2008; accepted 21 September 2008; online 15 October 2008)

Single crystals of the title compound, {Na₄[Mo^VIO₂(SO₄)₃]}_n, were grown from a melt of MoO₃ and Na₂SO₄ in Na₂S₂O₇. In contrast to the structure of the isoformular K compound, K₄[Mo^VIO₂(SO₄)₃], with its monomeric anion, this sodium analogue contains a polymeric anion of the type {[Mo^VIO₂(SO₄)₂-μ-(SO₄)]⁴⁻}_n. The Mo^VI cations, surrounded by two tightly bonded O atoms and four O atoms of one bridging and two terminal sulfato ligands, form zigzag chains parallel to [100]. All four Na⁺ cations are situated between the anionic chains and have distorted octahedral coordination spheres.

Related literature

The structure of the title isoformular potassium compound, K₄[Mo^VIO₂(SO₄)₃], was determined by Schäffer & Berg (2008 ). For related Mo-containing compounds, see Salles et al. (1996 ) and Nørbygaard et al. (1998 ). Related compounds with Mo replaced by W were discussed by Schäffer & Berg (2005 ) and Berg et al. (2006 ). Other sulfato complexes coordinated to late transition metal centers were reported by Berg & Thorup (2005 ), Borup et al. (1990 ), Nielsen et al. (1993 ) and Rasmussen et al. (2003 ).

Experimental

Crystal data

Na₄[MoO₂(SO₄)₃]
M_r = 508.08
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.4739 (6) Å
b = 9.2892 (7) Å
c = 15.1046 (11) Å
V = 1188.97 (15) Å³
Z = 4
Mo Kα radiation
μ = 1.85 mm⁻¹
T = 120 (2) K
0.24 × 0.18 × 0.02 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: gaussian (SHELXTL; Sheldrick, 2008 ) T_min = 0.665, T_max = 0.964
14125 measured reflections
2861 independent reflections
2817 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.042
S = 1.10
2861 reflections
199 parameters
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Absolute structure: Flack (1983 ), 1205 Friedel pairs
Flack parameter: 0.01 (2)

Table 1
Selected bond lengths (Å)

Mo1—O2	1.6905 (16)
Mo1—O1	1.7108 (16)
Mo1—O5	1.9925 (16)
Mo1—O4	2.0102 (16)
Mo1—O6ⁱ	2.1661 (15)
Mo1—O3	2.1907 (15)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030328/wm2186sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030328/wm2186Isup2.hkl

checkCIF report

Comment top

Considerable amounts of molybdenum(VI) oxide, a solid well known for its insolubility in many acids, can be dissolved in sulfate melts at high temperatures, as was previously found for the chemically related tungsten(VI) oxide (Schäffer & Berg, 2005, Berg et al., 2006). When varying molar amounts of MoO₃, Na₂SO₄, and hygroscopic Na₂S₂O₇ are placed in ampoules in a dry box, sealed, and heated to equilibration in a rocking furnace at 773 K for ca. 1 h, the resulting clear melts contain [MoO₂]²⁺ moieties that are bonded to SO₄^2- units. The compositions of the reaction products have been determined to be in the stoichiometric ratio 1:1:1, or MoO₃ + M₂SO₄ + M₂S₂O₇ → M₄[Mo(SO₄)₃O₂]. In the case where M = K, a monomeric anion is formed (Schäffer & Berg, 2008), while for M = Na the anion is in a polymeric form.

The distorted octahedral coordination sphere of the Mo^VI cation contains two oxido ligands (cis), two terminally bound sulfato ligands (trans), and two O atoms of symmetry-related (x + 1/2, -y + 1/2, -z + 1) bridging sulfato ligands (cis), with O–Mo–O angles between any two cis oxygen atoms deviating as much as 15° from ideal values. The Mo–O bond distances to the tightly- bonded oxido ligands are similar (1.6905 (16) Å, 1.7108 (16) Å), which is expected as both bonds are trans to oxygen atoms in the bridging sulfato ligands. The Mo–O distances to the terminal sulfato ligands (Mo1–O4 and Mo1–O5) are slightly shorter than those to the brigding sulfato ligands, Mo1–03 and Mo1–O6A. The Mo–O distances compare well with previously reported values for related structures (Salles et al., 1996; Nørbygaard et al., 1998; Schäffer & Berg, 2008).

The coordination geometry of the sulfato ligands can be described as slightly distorted from tetrahedral, with angles ranging from 103.55 (9) to 113.77 (10)°. From the shortest to the longest, the S–O bond distances vary by type: S to terminal O atoms, 1.4516 (17)–1.4681 (17) Å; S to briding O atoms, 1.4941 (16) Å and 1.4953 (16) Å; S in the terminal sulfato ligands to the coordinating O atoms, 1.5589 (17) Å and 1.5346 (16) Å. This variation is typical for sulfato complexes of many different transition metal centers (Borup et al., 1990; Nielsen et al., 1993; Rasmussen et al., 2003, and Berg & Thorup, 2005).

All four sodium cations are situated between the anionic chains and are six-coordinate with Na–O bond distances ranging from 2.2713 (18) to 2.7652 (18) Å.

Related literature top

The structure of the title isoformular potassium compound, K₄[Mo^VI(SO₄)₃O₂], was determined by Schäffer & Berg (2008). For related Mo-containing compounds, see: Salles et al. (1996) and Nørbygaard et al. (1998). Related compounds with Mo replaced by W were discussed by Schäffer & Berg (2005) and Berg et al. (2006). Other sulfato complexes coordinated to late transition metal centers were reported by Berg & Thorup (2005), Borup et al. (1990), Nielsen et al. (1993) and Rasmussen et al. (2003).

Experimental top

Crystals were grown from a melt of equimolar amounts of MoO₃, Na₂SO₄, and Na₂S₂O₇, using a method described previously (Nørbygaard et al., 1998).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Plot of the asymmetric unit of Na₄[Mo^VI(SO₄)₃O₂], showing atoms as ellipsoids at the 50% probability level. [Symmetry code A) x+0.5, -y+0.5, -z+1.]
	Fig. 2. The crystal packing of Na₄[Mo^VI(SO₄)₃O₂], viewed along the b axis, showing the chains (thick black lines). Ellipsoids are displayed at the 50% probability level.

catena-Poly[tetrasodium [[cis-dioxido-trans- bis(sulfato-κO)molybdate(VI)]-µ-sulfato-κ²O:O']] top

Crystal data top

Na₄[Mo(SO₄)₃O₂]	F(000) = 984
M_r = 508.08	D_x = 2.838 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5457 reflections
a = 8.4739 (6) Å	θ = 2.6–27.9°
b = 9.2892 (7) Å	µ = 1.86 mm⁻¹
c = 15.1046 (11) Å	T = 120 K
V = 1188.97 (15) Å³	Tabular, colorless
Z = 4	0.24 × 0.18 × 0.02 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2861 independent reflections
Radiation source: normal-focus sealed tube	2817 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 28.0°, θ_min = 2.6°
Absorption correction: gaussian (SHELXTL; Sheldrick, 2008)	h = −11→11
T_min = 0.665, T_max = 0.964	k = −12→12
14125 measured reflections	l = −19→19

Refinement top

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)] = 0.017	w = 1/[σ²(F_o²) + (0.0214P)² + 0.3747P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.042	(Δ/σ)_max = 0.001
S = 1.10	Δρ_max = 0.51 e Å⁻³
2861 reflections	Δρ_min = −0.26 e Å⁻³
199 parameters	Absolute structure: Flack (1983), 1205 Friedel pairs
0 restraints	Absolute structure parameter: 0.01 (2)

Crystal data top

Na₄[Mo(SO₄)₃O₂]	V = 1188.97 (15) Å³
M_r = 508.08	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.4739 (6) Å	µ = 1.86 mm⁻¹
b = 9.2892 (7) Å	T = 120 K
c = 15.1046 (11) Å	0.24 × 0.18 × 0.02 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2861 independent reflections
Absorption correction: gaussian (SHELXTL; Sheldrick, 2008)	2817 reflections with I > 2σ(I)
T_min = 0.665, T_max = 0.964	R_int = 0.031
14125 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	0 restraints
wR(F²) = 0.042	Δρ_max = 0.51 e Å⁻³
S = 1.10	Δρ_min = −0.26 e Å⁻³
2861 reflections	Absolute structure: Flack (1983), 1205 Friedel pairs
199 parameters	Absolute structure parameter: 0.01 (2)

Special details top

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. Five frame series were filtered for statistical outliers then corrected for absorption by integration using SHELXTL/XPREP (Bruker, 2001) before using SAINT/SADABS (Bruker, 2002) to sort, merge, and scale the combined data. A series of identical frames was collected twice during the experiment to monitor decay. No decay correction was applied. The systematic conditions suggested the uambiguous space group. The structure was solved by direct methods (Sheldrick, 2001). The final space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F². An extinction correction was not applied. The two highest peaks in the final difference Fourier map were, repectively, 0.78Å and 0.79Å from Mo1; the deepest hole was 1.31Å from S2. The final map had no other significant features. A final analysis of variance between observed and calculated structure factors showed no dependence on amplitude or resolution.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mo1	0.77389 (2)	0.108886 (19)	0.426923 (11)	0.00683 (5)
S1	0.42167 (6)	0.29669 (6)	0.38157 (3)	0.00770 (11)
S2	0.52730 (7)	−0.14389 (6)	0.48393 (3)	0.00870 (11)
S3	0.87553 (6)	0.37753 (6)	0.29746 (3)	0.00819 (10)
Na1	0.20072 (11)	0.58268 (10)	0.34042 (6)	0.01293 (19)
Na2	0.80653 (11)	0.75841 (10)	0.31656 (6)	0.01239 (19)
Na3	0.67303 (11)	0.51270 (10)	0.46834 (6)	0.0144 (2)
Na4	0.57005 (11)	0.46216 (10)	0.21305 (6)	0.01274 (19)
O1	0.70335 (19)	0.03236 (17)	0.33180 (10)	0.0107 (3)
O2	0.94651 (19)	0.02131 (17)	0.44263 (11)	0.0119 (3)
O3	0.57359 (18)	0.25797 (17)	0.42577 (11)	0.0107 (3)
O4	0.6456 (2)	−0.02040 (17)	0.50576 (10)	0.0116 (3)
O5	0.88450 (19)	0.28237 (18)	0.38036 (10)	0.0120 (3)
O6	0.29354 (19)	0.27689 (17)	0.44854 (9)	0.0096 (3)
O7	0.3902 (2)	0.20606 (18)	0.30489 (10)	0.0123 (3)
O8	0.4313 (2)	0.44896 (18)	0.35609 (11)	0.0124 (3)
O9	0.49519 (19)	−0.20813 (17)	0.56967 (11)	0.0130 (3)
O10	0.60611 (19)	−0.24259 (18)	0.42327 (12)	0.0147 (3)
O11	0.38958 (19)	−0.07781 (18)	0.44282 (11)	0.0139 (3)
O12	0.7888 (2)	0.29908 (17)	0.22934 (10)	0.0124 (3)
O13	0.7899 (2)	0.50790 (17)	0.32281 (10)	0.0126 (3)
O14	1.03833 (19)	0.40786 (18)	0.27218 (10)	0.0133 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.00576 (8)	0.00737 (9)	0.00738 (8)	0.00034 (7)	−0.00028 (6)	−0.00021 (7)
S1	0.0056 (2)	0.0096 (3)	0.0078 (2)	0.0014 (2)	−0.00017 (19)	−0.0001 (2)
S2	0.0073 (2)	0.0093 (2)	0.0095 (2)	−0.0009 (2)	0.0006 (2)	−0.00087 (19)
S3	0.0073 (2)	0.0087 (2)	0.0086 (2)	−0.0001 (2)	0.00067 (18)	0.0004 (2)
Na1	0.0125 (5)	0.0130 (5)	0.0133 (4)	0.0022 (4)	0.0012 (3)	0.0019 (3)
Na2	0.0111 (5)	0.0126 (4)	0.0135 (4)	0.0012 (4)	0.0018 (4)	0.0017 (3)
Na3	0.0123 (4)	0.0166 (5)	0.0145 (5)	−0.0034 (4)	0.0023 (4)	−0.0024 (4)
Na4	0.0107 (4)	0.0156 (5)	0.0120 (4)	0.0010 (4)	−0.0008 (4)	0.0020 (4)
O1	0.0097 (8)	0.0119 (8)	0.0104 (7)	0.0002 (6)	−0.0002 (6)	−0.0008 (6)
O2	0.0113 (8)	0.0112 (8)	0.0130 (8)	0.0020 (6)	−0.0021 (6)	−0.0007 (6)
O3	0.0086 (7)	0.0128 (7)	0.0107 (7)	0.0044 (6)	−0.0029 (7)	−0.0008 (7)
O4	0.0138 (8)	0.0116 (8)	0.0095 (7)	−0.0053 (7)	−0.0018 (6)	0.0001 (6)
O5	0.0116 (8)	0.0121 (8)	0.0122 (8)	−0.0036 (6)	−0.0020 (6)	0.0042 (6)
O6	0.0080 (7)	0.0110 (7)	0.0098 (7)	−0.0010 (6)	0.0006 (6)	−0.0012 (6)
O7	0.0116 (8)	0.0162 (9)	0.0092 (7)	0.0016 (7)	−0.0016 (6)	−0.0028 (6)
O8	0.0121 (8)	0.0111 (8)	0.0140 (8)	0.0018 (7)	0.0023 (7)	0.0023 (6)
O9	0.0141 (8)	0.0131 (8)	0.0119 (7)	−0.0042 (6)	−0.0001 (7)	0.0028 (7)
O10	0.0151 (8)	0.0119 (8)	0.0171 (8)	−0.0010 (7)	0.0051 (7)	−0.0045 (7)
O11	0.0093 (8)	0.0190 (9)	0.0133 (8)	0.0021 (7)	−0.0016 (6)	0.0017 (6)
O12	0.0141 (8)	0.0120 (8)	0.0109 (7)	−0.0002 (7)	−0.0015 (6)	−0.0011 (6)
O13	0.0106 (8)	0.0108 (8)	0.0163 (8)	0.0025 (7)	−0.0008 (7)	−0.0015 (6)
O14	0.0095 (8)	0.0167 (9)	0.0136 (7)	−0.0012 (7)	0.0042 (6)	0.0008 (7)

Geometric parameters (Å, º) top

Mo1—O2	1.6905 (16)	Na1—O9^iv	2.4972 (19)
Mo1—O1	1.7108 (16)	Na1—O1ⁱⁱ	2.7652 (18)
Mo1—O5	1.9925 (16)	Na2—O13	2.3333 (18)
Mo1—O4	2.0102 (16)	Na2—O14^v	2.3350 (19)
Mo1—O6ⁱ	2.1661 (15)	Na2—O10^vi	2.3415 (19)
Mo1—O3	2.1907 (15)	Na2—O9ⁱ	2.3932 (19)
S1—O7	1.4564 (16)	Na2—O7ⁱⁱ	2.5262 (18)
S1—O8	1.4681 (17)	Na2—O1^vi	2.7006 (19)
S1—O3	1.4941 (16)	Na2—S3^v	3.3837 (11)
S1—O6	1.4953 (16)	Na3—O11ⁱ	2.3524 (19)
S2—O9	1.4516 (17)	Na3—O2^iv	2.3649 (19)
S2—O11	1.4575 (17)	Na3—O13	2.4115 (18)
S2—O10	1.4581 (17)	Na3—O10^vi	2.4398 (19)
S2—O4	1.5589 (17)	Na3—O3	2.5928 (19)
S3—O14	1.4590 (17)	Na3—O8	2.724 (2)
S3—O12	1.4595 (16)	Na4—O7ⁱⁱ	2.3065 (19)
S3—O13	1.4627 (16)	Na4—O12	2.407 (2)
S3—O5	1.5346 (16)	Na4—O11ⁱⁱ	2.4078 (19)
Na1—O12ⁱⁱ	2.2713 (18)	Na4—O8	2.4629 (19)
Na1—O8	2.3273 (19)	Na4—O1ⁱⁱ	2.5003 (19)
Na1—O14ⁱⁱⁱ	2.3649 (19)	Na4—O13	2.5297 (19)
Na1—O4^iv	2.4394 (18)

O2—Mo1—O1	102.72 (8)	O11ⁱ—Na3—O3	129.03 (7)
O2—Mo1—O5	91.81 (7)	O2^iv—Na3—O3	75.84 (6)
O1—Mo1—O5	101.77 (7)	O13—Na3—O3	83.71 (6)
O2—Mo1—O4	95.58 (7)	O10^vi—Na3—O3	134.87 (6)
O1—Mo1—O4	93.46 (7)	O11ⁱ—Na3—O8	175.92 (7)
O5—Mo1—O4	161.18 (7)	O2^iv—Na3—O8	73.41 (6)
O2—Mo1—O6ⁱ	92.71 (7)	O13—Na3—O8	74.78 (6)
O1—Mo1—O6ⁱ	163.68 (7)	O10^vi—Na3—O8	81.61 (6)
O5—Mo1—O6ⁱ	82.77 (6)	O3—Na3—O8	53.34 (5)
O4—Mo1—O6ⁱ	79.62 (6)	O7ⁱⁱ—Na4—O12	121.20 (7)
O2—Mo1—O3	167.36 (7)	O7ⁱⁱ—Na4—O11ⁱⁱ	90.91 (6)
O1—Mo1—O3	89.16 (7)	O12—Na4—O11ⁱⁱ	83.88 (6)
O5—Mo1—O3	81.39 (6)	O7ⁱⁱ—Na4—O8	102.80 (7)
O4—Mo1—O3	87.91 (6)	O12—Na4—O8	104.28 (6)
O6ⁱ—Mo1—O3	75.92 (6)	O11ⁱⁱ—Na4—O8	156.62 (7)
O7—S1—O8	111.01 (10)	O7ⁱⁱ—Na4—O1ⁱⁱ	81.21 (6)
O7—S1—O3	111.95 (9)	O12—Na4—O1ⁱⁱ	154.90 (7)
O8—S1—O3	107.53 (10)	O11ⁱⁱ—Na4—O1ⁱⁱ	84.66 (6)
O7—S1—O6	109.52 (9)	O8—Na4—O1ⁱⁱ	78.95 (6)
O8—S1—O6	109.65 (10)	O7ⁱⁱ—Na4—O13	78.73 (6)
O3—S1—O6	107.08 (9)	O12—Na4—O13	58.10 (6)
O9—S2—O11	113.77 (10)	O11ⁱⁱ—Na4—O13	124.20 (7)
O9—S2—O10	112.83 (10)	O8—Na4—O13	77.59 (6)
O11—S2—O10	111.33 (10)	O1ⁱⁱ—Na4—O13	144.70 (7)
O9—S2—O4	103.55 (9)	Mo1—O1—Na4^vii	131.27 (9)
O11—S2—O4	107.18 (10)	Mo1—O1—Na2^viii	110.49 (7)
O10—S2—O4	107.52 (10)	Na4^vii—O1—Na2^viii	91.78 (6)
O14—S3—O12	112.83 (10)	Mo1—O1—Na1^vii	128.10 (8)
O14—S3—O13	112.19 (10)	Na4^vii—O1—Na1^vii	93.53 (5)
O12—S3—O13	110.37 (10)	Na2^viii—O1—Na1^vii	89.08 (5)
O14—S3—O5	106.14 (9)	Mo1—O2—Na3ⁱ	147.82 (9)
O12—S3—O5	108.22 (9)	S1—O3—Mo1	145.42 (10)
O13—S3—O5	106.73 (10)	S1—O3—Na3	99.86 (8)
O12ⁱⁱ—Na1—O8	119.12 (7)	Mo1—O3—Na3	108.85 (6)
O12ⁱⁱ—Na1—O14ⁱⁱⁱ	115.36 (7)	S2—O4—Mo1	131.46 (9)
O8—Na1—O14ⁱⁱⁱ	99.58 (7)	S2—O4—Na1ⁱ	98.63 (8)
O12ⁱⁱ—Na1—O4^iv	131.24 (7)	Mo1—O4—Na1ⁱ	127.05 (8)
O8—Na1—O4^iv	86.40 (6)	S3—O5—Mo1	136.93 (10)
O14ⁱⁱⁱ—Na1—O4^iv	98.10 (6)	S1—O6—Mo1^iv	125.67 (9)
O12ⁱⁱ—Na1—O9^iv	82.33 (6)	S1—O7—Na4^vii	129.39 (10)
O8—Na1—O9^iv	141.19 (7)	S1—O7—Na2^vii	125.94 (10)
O14ⁱⁱⁱ—Na1—O9^iv	98.72 (7)	Na4^vii—O7—Na2^vii	101.54 (7)
O4^iv—Na1—O9^iv	57.26 (6)	S1—O8—Na1	119.62 (10)
O12ⁱⁱ—Na1—O1ⁱⁱ	72.64 (6)	S1—O8—Na4	107.73 (9)
O8—Na1—O1ⁱⁱ	76.04 (6)	Na1—O8—Na4	106.56 (7)
O14ⁱⁱⁱ—Na1—O1ⁱⁱ	69.21 (5)	S1—O8—Na3	95.05 (8)
O4^iv—Na1—O1ⁱⁱ	155.81 (6)	Na1—O8—Na3	125.35 (7)
O9^iv—Na1—O1ⁱⁱ	142.71 (6)	Na4—O8—Na3	100.15 (7)
O13—Na2—O14^v	130.56 (7)	S2—O9—Na2^iv	147.79 (11)
O13—Na2—O10^vi	85.66 (6)	S2—O9—Na1ⁱ	99.36 (8)
O14^v—Na2—O10^vi	143.70 (7)	Na2^iv—O9—Na1ⁱ	99.58 (7)
O13—Na2—O9ⁱ	79.43 (6)	S2—O10—Na2^viii	139.66 (10)
O14^v—Na2—O9ⁱ	98.75 (7)	S2—O10—Na3^viii	121.13 (10)
O10^vi—Na2—O9ⁱ	89.40 (7)	Na2^viii—O10—Na3^viii	91.56 (6)
O13—Na2—O7ⁱⁱ	78.32 (6)	S2—O11—Na3^iv	119.33 (9)
O14^v—Na2—O7ⁱⁱ	93.97 (6)	S2—O11—Na4^vii	111.58 (9)
O10^vi—Na2—O7ⁱⁱ	91.17 (7)	Na3^iv—O11—Na4^vii	128.97 (8)
O9ⁱ—Na2—O7ⁱⁱ	157.64 (7)	S3—O12—Na1^vii	138.53 (11)
O13—Na2—O1^vi	156.46 (7)	S3—O12—Na4	98.37 (8)
O14^v—Na2—O1^vi	70.79 (6)	Na1^vii—O12—Na4	122.67 (8)
O10^vi—Na2—O1^vi	73.15 (6)	S3—O13—Na2	141.74 (10)
O9ⁱ—Na2—O1^vi	109.81 (6)	S3—O13—Na3	117.23 (9)
O7ⁱⁱ—Na2—O1^vi	91.70 (6)	Na2—O13—Na3	92.48 (6)
O11ⁱ—Na3—O2^iv	110.07 (7)	S3—O13—Na4	93.14 (8)
O11ⁱ—Na3—O13	101.80 (6)	Na2—O13—Na4	100.69 (7)
O2^iv—Na3—O13	148.13 (7)	Na3—O13—Na4	107.34 (7)
O11ⁱ—Na3—O10^vi	95.79 (7)	S3—O14—Na2^ix	124.60 (10)
O2^iv—Na3—O10^vi	95.42 (7)	S3—O14—Na1^x	124.66 (10)
O13—Na3—O10^vi	81.85 (6)	Na2^ix—O14—Na1^x	109.32 (7)

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

Experimental details

Crystal data
Chemical formula	Na₄[Mo(SO₄)₃O₂]
M_r	508.08
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	120
a, b, c (Å)	8.4739 (6), 9.2892 (7), 15.1046 (11)
V (Å³)	1188.97 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.86
Crystal size (mm)	0.24 × 0.18 × 0.02

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Gaussian (SHELXTL; Sheldrick, 2008)
T_min, T_max	0.665, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	14125, 2861, 2817
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.042, 1.10
No. of reflections	2861
No. of parameters	199
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.26
Absolute structure	Flack (1983), 1205 Friedel pairs
Absolute structure parameter	0.01 (2)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mo1—O2	1.6905 (16)	Mo1—O4	2.0102 (16)
Mo1—O1	1.7108 (16)	Mo1—O6ⁱ	2.1661 (15)
Mo1—O5	1.9925 (16)	Mo1—O3	2.1907 (15)

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

Acknowledgements

The authors thank Astrid Schøneberg and Bodil Holten for their help and advice.

References

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