Na_2.9KMo₁₂S₁₄: a novel quaternary reduced molybdenum sulfide containing Mo₁₂ clusters with a channel structure

The crystal structure of tris­odium potassium dodeca­molybdenum tetra­deca­sulfide, Na_2.9 (2)KMo₁₂S₁₄, consists of Mo₁₂S₁₄S₆ cluster units inter­connected through inter­unit Mo-S bonds and delimiting channels in which the Na⁺ cations are disordered. The cluster units are centered at Wyckoff positions 2d and have point-group symmetry 3.2. The K atom lies on sites with 3.2 symmetry (Wyckoff site 2c) between two consecutive Mo₁₂S₁₄S₆ units. One of the three independent S atoms and one Na atom lie on sites with 3.. symmetry (Wyckoff sites 4e and 4f). The other Na atom occupies a 2b position with -3.. symmetry. The crystal studied was a merohedral twin with refined components of 0.4951 (13) and 0.5049 (13).

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](Mo-S) = 0.001 Å
• Disorder in solvent or counterion
• R factor = 0.027
• wR factor = 0.073
• Data-to-parameter ratio = 48.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given .....          ?
PLAT214_ALERT_2_C Atom Na2     (Anion/Solvent) ADP max/min Ratio          5.0 prola
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
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    --  S2      ..       10.0 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo1    --  S3      ..        5.3 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo2    --  S2      ..        6.5 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo2    --  S2_a    ..        6.0 su
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................         68 %
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA1    --  S1      ..       3.86 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA1    --  S1      ..       3.86 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA1    --  S1      ..       3.86 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA1    --  S2      ..       3.90 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA1    --  S2      ..       3.90 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA1    --  S2      ..       3.90 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA2    --  S2      ..       3.56 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA2    --  S2      ..       3.56 Ang.
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3
              K
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          !
PLAT931_ALERT_5_G Check Twin Law ( 0 0  1)[       ] Estimated BASF       0.49

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

  11 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 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
   5 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

In a previous paper, we reported the synthesis, the crystal structures and, the physical properties of the compounds K_{1 + x}Mo₁₂S₁₄ (x= 0, 1.1, 1.3, and 1.6) which crystallize in a new structural type only based on the Mo₁₂ cluster (Picard et al., 2006). We present here the crystal structure of the sulfide Na_2.9KMo₁₂S₁₄ which is isomorphous with the latter compounds (Picard et al., 2006). Its crystal structure (Fig. 1) contains Mo₁₂Sⁱ₁₄S^a₆ cluster units (for details of the i- and a-type ligand notation, see Schäfer & von Schnering (1964)). The i-type ligands cap Mo triangular faces and the a-type ones are in apical position for the external Mo1 atoms (Fig. 2). The Mo₁₂S₁₄ cluster unit is centred at a 2 d (D₃ or 32 symmetry) position. The Mo—Mo distances within the Mo₁₂ clusters are 2.6296 (5) Å for the distances in the triangles formed by the Mo1 related through the threefold axis and 2.6764 (4) in the triangles formed by the Mo2 atoms. The distances between the triangles formed by the Mo1 and Mo2 atoms are 2.7155 (4) and 2.7803 (4) Å and those between the two Mo2₃ triangles, 2.6440 (5) and 2.6745 (5) Å. The sulfur atoms bridge either one [S1 and S3] or two [S2] Mo triangular faces of the clusters. Moreover the S1 atoms are linked to a Mo atom of a neighboring cluster. The Mo—S bond distances range from 2.3855 (10) to 2.5907 (7) Å. Each Mo₁₂S₁₄ unit is interconnected to 6 adjacent ones via Mo1—S1 bonds to form the three-dimensional Mo—S framework, the connective formula of which is Mo₁₂Sⁱ₈S^i-a_6/2S^a-i_6/2. It results from this arrangement that the shortest intercluster Mo1—Mo1 distance between the Mo₁₂ clusters is 3.4025 (3) Å, indicating only weak metal-metal interaction. The Na cations reside in large channels extending along the c axis (Fig. 3). The Na1 cations occupied distorted tri-capped trigonal prismatic cavities of sulfur atoms and the Na2 are in an octahedron compressed along the threefold axis. The Na—S distances spread over a wide range 3.210 (12) - 3.898 (11) Å. The K cation is eight-coordinated with six S2 atoms at 3.4188 (7), forming an octahedron compressed along the threefold axis, and the remaining two S3 atoms capping two opposite faces of the octahedron at 2.9460 (13).

Related literature

For a previous report on the compounds K_{1 + x}Mo₁₂S₁₄ (x = 0, 1.1, 1.3, and 1.6), see: Picard et al. (2006). For details of the i- and a-type ligand notation, see: Schäfer & von Schnering (1964). For the program JANA2000, see: Petříček & Dušek (2000). The twinning was identified using the TwinRotMat routine of PLATON (Spek, 2009).

S2. Experimental

Single crystals of Na_2.9KMo₁₂S₁₄ were obtained by treating crystals of KMo₁₂S₁₄ in a basic reducing solution of Na₂S₂O₃/NaOH at 333 K for 3 days. The KMo₁₂S₁₄ compound was prepared by oxidation of single crystals of K_2.3Mo₁₂S₁₄ in an aqueous solution of iodine at 363 K for 48 h. Single crystals of K_2.3Mo₁₂S₁₄ were prepared from a mixture of K₂MoS₄, MoS₂, and Mo with the nominal composition K₂Mo₃S₄. The initial mixture (ca 5 g) was cold pressed and loaded into a molybdenum crucible, which was sealed under a low argon pressure using an arc welding system. The charge was heated at the rate of 300 K/h up to 1773 K, temperature which was held for 6 h, then cooled at 100 K/h down to 1373 K and finally furnace cooled. All handlings of materials were done in an argon-filled glove box.

S3. Refinement

In the first stage of the refinement, the atomic positions of the Mo and S atoms were deduced from those in KMo₁₂S₁₄ (Picard et al., 2006). A subsequent difference-Fourier synthesis reveals the potassium atom and a quasi-continuous electron density along the c axis due to the sodium atoms. The latter was modelled with two partly occupied sodium sites (4 e and 2 b positions) using second-order tensors for the anisotropic displacement parameters. Anharmonic treatment of the Na1 and Na2 atoms using the program JANA2000 (Petříček & Dušek, 2000) was unsuccessful. The final occupation factors for the Na atoms were refined freely. The highest peak and the deepest hole in the final Fourier map are located 1.07 Å from Na2 and 0.58 Å from Mo2, respectively. Analysis of the intensity data using the TwinRotMat routine of PLATON (Spek, 2009) revealed the studied crystal was twinned by merohedry with [100, 010, 001]as the twin matrix. The ratio of the twin components was refined to 0.4951 (13):0.5049 (13). The Na content found seems reliable since the cationic electron transfer towards the Mo₁₂ cluster deduced from our refinement is +3.9 and is in agreement with the maximal limit of +4 that the Mo₁₂ cluster can accept to be well bonded and with the semi-conductor behavior observed on a single-crystal. Indeed, a lower stoichiometry in Na would lead to a metallic behavior. This is also confirmed by semi-quantitative analyses by energy dispersive spectroscopy (eds) which indicated roughly stoichiometries comprised between 2.6 and 3.2 for the Na content.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT (Nonius, 1998); data reduction: EVALCCD (Duisenberg, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. : View of Na2.9KMo12S14. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. : Plot showing the atom-numbering scheme of the Mo12S14S6 cluster units. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. : View of Na2.9KMo12S14 along the c axis showing the channels. Displacement ellipsoids are drawn at the 50% probability level.

Trisodium potassium dodecamolybdenum tetradecasulfide

Crystal data

Na2.90KMo12S14	Dx = 4.575 Mg m^−3
Mr = 1705.89	Mo Kα radiation, λ = 0.71069 Å
Trigonal, P31c	Cell parameters from 5780 reflections
a = 9.3664 (1) Å	θ = 3.5–39.8°
c = 16.2981 (2) Å	µ = 7.24 mm^−1
V = 1238.26 (2) Å^3	T = 100 K
Z = 2	Multi-faceted crystal, black
F(000) = 1558	0.08 × 0.07 × 0.07 mm

Data collection

Nonius KappaCCD diffractometer	2536 independent reflections
Radiation source: fine-focus sealed tube	2376 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ϕ scans (κ = 0) + additional ω scans	θmax = 39.8°, θmin = 3.5°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = −16→16
Tmin = 0.550, Tmax = 0.572	k = −16→16
37291 measured reflections	l = −29→27

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)] = 0.027	w = 1/[σ^2(Fo^2) + (0.029P)^2 + 4.9317P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.073	(Δ/σ)max = 0.001
S = 1.13	Δρmax = 2.74 e Å^−3
2536 reflections	Δρmin = −1.84 e Å^−3
52 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00032 (9)

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	0.50983 (3)	0.16646 (3)	0.043656 (15)	0.00973 (6)
Mo2	0.66853 (3)	0.16929 (3)	0.183610 (15)	0.00826 (5)
S1	0.68780 (10)	0.04088 (9)	0.05564 (4)	0.01069 (11)
S2	0.36482 (9)	0.02520 (9)	0.17966 (4)	0.01064 (11)
S3	0.6667	0.3333	−0.06924 (8)	0.0129 (2)
K1	0.6667	0.3333	−0.2500	0.0195 (3)
Na1	0.0000	0.0000	0.1936 (13)	0.36 (4)	0.71 (5)
Na2	0.0000	0.0000	0.099 (3)	0.40 (4)	0.74 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01224 (10)	0.01354 (11)	0.00434 (9)	0.00714 (8)	−0.00045 (7)	0.00041 (7)
Mo2	0.01081 (9)	0.01033 (10)	0.00371 (9)	0.00535 (8)	−0.00034 (6)	−0.00060 (7)
S1	0.0143 (3)	0.0125 (3)	0.0063 (2)	0.0074 (2)	−0.0003 (2)	−0.00134 (19)
S2	0.0121 (2)	0.0118 (2)	0.0064 (2)	0.0047 (2)	−0.0014 (2)	−0.0007 (2)
S3	0.0172 (3)	0.0172 (3)	0.0044 (4)	0.00859 (16)	0.000	0.000
K1	0.0264 (5)	0.0264 (5)	0.0058 (6)	0.0132 (3)	0.000	0.000
Na1	0.47 (6)	0.47 (6)	0.12 (2)	0.24 (3)	0.000	0.000
Na2	0.045 (4)	0.045 (4)	1.12 (12)	0.023 (2)	0.000	0.000

Geometric parameters (Å, º)

Mo1—S3	2.3855 (10)	S3—Mo1^iii	2.3855 (10)
Mo1—S1^i	2.4620 (8)	S3—Mo1^i	2.3855 (10)
Mo1—S1	2.4822 (8)	K1—S3	2.9460 (13)
Mo1—S1^ii	2.4944 (8)	K1—S3^vii	2.9460 (13)
Mo1—S2	2.5907 (7)	K1—S2^viii	3.4188 (7)
Mo1—Mo1^iii	2.6296 (5)	K1—S2^ix	3.4188 (7)
Mo1—Mo1^i	2.6296 (5)	K1—S2^x	3.4188 (7)
Mo1—Mo2	2.7155 (4)	K1—S2^ii	3.4188 (7)
Mo1—Mo2^i	2.7803 (4)	K1—S2^xi	3.4188 (7)
Mo2—S1	2.4589 (7)	K1—S2^xii	3.4188 (7)
Mo2—S2	2.4655 (7)	Na1—Na2	1.55 (5)
Mo2—S2^iii	2.4904 (8)	Na1—Na1^xiii	1.84 (4)
Mo2—S2^iv	2.5866 (7)	Na1—S2^xiv	3.3131 (17)
Mo2—Mo2^v	2.6440 (5)	Na1—S2^xv	3.3131 (17)
Mo2—Mo2^iv	2.6745 (5)	Na1—S1^xvi	3.856 (12)
Mo2—Mo2^iii	2.6765 (4)	Na1—S1^xvii	3.856 (12)
Mo2—Mo2^i	2.6765 (4)	Na1—S1^i	3.856 (12)
Mo2—Mo1^iii	2.7803 (4)	Na1—S2^xviii	3.898 (11)
S1—Mo1^iii	2.4620 (8)	Na1—S2^xiii	3.898 (11)
S1—Mo1^ii	2.4944 (8)	Na1—S2^xix	3.898 (11)
S1—Na2^vi	3.210 (12)	Na2—S1^i	3.210 (12)
S2—Mo2^i	2.4904 (8)	Na2—S1^xvi	3.210 (12)
S2—Mo2^iv	2.5866 (7)	Na2—S1^xvii	3.210 (12)
S2—Na1	3.3131 (17)	Na2—S2^xiv	3.56 (2)
S2—K1^ii	3.4188 (7)	Na2—S2^xv	3.56 (2)
S3—Mo1—S1^i	92.320 (19)	Mo1^iii—S1—Mo1^ii	127.81 (3)
S3—Mo1—S1	91.819 (19)	Mo1—S1—Mo1^ii	84.55 (3)
S1^i—Mo1—S1	169.89 (3)	Mo2—S1—Na2^vi	99.6 (9)
S3—Mo1—S1^ii	89.07 (3)	Mo1^iii—S1—Na2^vi	98.08 (6)
S1^i—Mo1—S1^ii	93.84 (4)	Mo1—S1—Na2^vi	160.3 (4)
S1—Mo1—S1^ii	95.45 (3)	Mo1^ii—S1—Na2^vi	114.5 (6)
S3—Mo1—S2	171.28 (3)	Mo2—S2—Mo2^i	65.37 (2)
S1^i—Mo1—S2	84.81 (3)	Mo2—S2—Mo2^iv	63.873 (19)
S1—Mo1—S2	89.74 (2)	Mo2^i—S2—Mo2^iv	62.735 (18)
S1^ii—Mo1—S2	99.32 (2)	Mo2—S2—Mo1	64.912 (19)
S3—Mo1—Mo1^iii	56.554 (16)	Mo2^i—S2—Mo1	66.315 (19)
S1^i—Mo1—Mo1^iii	118.03 (2)	Mo2^iv—S2—Mo1	118.36 (3)
S1—Mo1—Mo1^iii	57.50 (2)	Mo2—S2—Na1	154.66 (8)
S1^ii—Mo1—Mo1^iii	131.58 (2)	Mo2^i—S2—Na1	89.74 (2)
S2—Mo1—Mo1^iii	117.822 (17)	Mo2^iv—S2—Na1	101.5 (3)
S3—Mo1—Mo1^i	56.554 (16)	Mo1—S2—Na1	110.7 (3)
S1^i—Mo1—Mo1^i	58.24 (2)	Mo2—S2—K1^ii	92.19 (2)
S1—Mo1—Mo1^i	117.29 (2)	Mo2^i—S2—K1^ii	150.01 (3)
S1^ii—Mo1—Mo1^i	130.870 (19)	Mo2^iv—S2—K1^ii	90.10 (2)
S2—Mo1—Mo1^i	115.293 (18)	Mo1—S2—K1^ii	123.66 (3)
Mo1^iii—Mo1—Mo1^i	60.0	Na1—S2—K1^ii	109.13 (14)
S3—Mo1—Mo2	119.13 (2)	Mo1^iii—S3—Mo1	66.89 (3)
S1^i—Mo1—Mo2	113.78 (2)	Mo1^iii—S3—Mo1^i	66.89 (3)
S1—Mo1—Mo2	56.254 (17)	Mo1—S3—Mo1^i	66.89 (3)
S1^ii—Mo1—Mo2	137.91 (2)	Mo1^iii—S3—K1	140.47 (2)
S2—Mo1—Mo2	55.315 (17)	Mo1—S3—K1	140.47 (2)
Mo1^iii—Mo1—Mo2	62.662 (9)	Mo1^i—S3—K1	140.47 (2)
Mo1^i—Mo1—Mo2	91.183 (8)	S3—K1—S3^vii	180.0
S3—Mo1—Mo2^i	116.65 (2)	S3—K1—S2^viii	70.407 (11)
S1^i—Mo1—Mo2^i	55.546 (18)	S3^vii—K1—S2^viii	109.593 (11)
S1—Mo1—Mo2^i	114.41 (2)	S3—K1—S2^ix	109.593 (11)
S1^ii—Mo1—Mo2^i	138.42 (2)	S3^vii—K1—S2^ix	70.407 (11)
S2—Mo1—Mo2^i	55.112 (17)	S2^viii—K1—S2^ix	171.43 (2)
Mo1^iii—Mo1—Mo2^i	89.759 (7)	S3—K1—S2^x	109.593 (11)
Mo1^i—Mo1—Mo2^i	60.181 (8)	S3^vii—K1—S2^x	70.407 (11)
Mo2—Mo1—Mo2^i	58.275 (11)	S2^viii—K1—S2^x	63.43 (2)
S1—Mo2—S2	93.26 (3)	S2^ix—K1—S2^x	109.349 (11)
S1—Mo2—S2^iii	87.06 (3)	S3—K1—S2^ii	70.407 (11)
S2—Mo2—S2^iii	173.83 (2)	S3^vii—K1—S2^ii	109.593 (11)
S1—Mo2—S2^iv	117.76 (2)	S2^viii—K1—S2^ii	109.349 (11)
S2—Mo2—S2^iv	90.68 (3)	S2^ix—K1—S2^ii	63.43 (2)
S2^iii—Mo2—S2^iv	94.62 (3)	S2^x—K1—S2^ii	78.22 (2)
S1—Mo2—Mo2^v	144.46 (2)	S3—K1—S2^xi	109.593 (11)
S2—Mo2—Mo2^v	120.668 (19)	S3^vii—K1—S2^xi	70.407 (11)
S2^iii—Mo2—Mo2^v	60.414 (17)	S2^viii—K1—S2^xi	78.22 (2)
S2^iv—Mo2—Mo2^v	56.852 (18)	S2^ix—K1—S2^xi	109.349 (11)
S1—Mo2—Mo2^iv	150.83 (2)	S2^x—K1—S2^xi	109.349 (12)
S2—Mo2—Mo2^iv	60.265 (17)	S2^ii—K1—S2^xi	171.43 (2)
S2^iii—Mo2—Mo2^iv	120.634 (19)	S3—K1—S2^xii	70.407 (11)
S2^iv—Mo2—Mo2^iv	55.862 (18)	S3^vii—K1—S2^xii	109.593 (11)
Mo2^v—Mo2—Mo2^iv	60.428 (12)	S2^viii—K1—S2^xii	109.349 (11)
S1—Mo2—Mo2^iii	115.260 (19)	S2^ix—K1—S2^xii	78.22 (2)
S2—Mo2—Mo2^iii	117.738 (19)	S2^x—K1—S2^xii	171.43 (2)
S2^iii—Mo2—Mo2^iii	56.865 (19)	S2^ii—K1—S2^xii	109.349 (11)
S2^iv—Mo2—Mo2^iii	117.009 (17)	S2^xi—K1—S2^xii	63.43 (2)
Mo2^v—Mo2—Mo2^iii	60.350 (10)	Na2—Na1—Na1^xiii	180.000 (2)
Mo2^iv—Mo2—Mo2^iii	89.670 (5)	Na2—Na1—S2^xiv	86.1 (4)
S1—Mo2—Mo2^i	119.02 (2)	Na1^xiii—Na1—S2^xiv	93.9 (4)
S2—Mo2—Mo2^i	57.760 (19)	Na2—Na1—S2	86.1 (4)
S2^iii—Mo2—Mo2^i	116.843 (19)	Na1^xiii—Na1—S2	93.9 (4)
S2^iv—Mo2—Mo2^i	115.061 (17)	S2^xiv—Na1—S2	119.54 (9)
Mo2^v—Mo2—Mo2^i	90.323 (5)	Na2—Na1—S2^xv	86.1 (4)
Mo2^iv—Mo2—Mo2^i	59.222 (10)	Na1^xiii—Na1—S2^xv	93.9 (4)
Mo2^iii—Mo2—Mo2^i	60.0	S2^xiv—Na1—S2^xv	119.54 (9)
S1—Mo2—Mo1	57.07 (2)	S2—Na1—S2^xv	119.54 (9)
S2—Mo2—Mo1	59.773 (17)	Na2—Na1—Na2^xiii	180.000 (2)
S2^iii—Mo2—Mo1	115.73 (2)	Na1^xiii—Na1—Na2^xiii	0.000 (2)
S2^iv—Mo2—Mo1	147.71 (2)	S2^xiv—Na1—Na2^xiii	93.9 (4)
Mo2^v—Mo2—Mo1	147.951 (10)	S2—Na1—Na2^xiii	93.9 (4)
Mo2^iv—Mo2—Mo1	111.157 (13)	S2^xv—Na1—Na2^xiii	93.9 (4)
Mo2^iii—Mo2—Mo1	90.180 (8)	Na1—Na2—S1^i	102.6 (9)
Mo2^i—Mo2—Mo1	62.075 (8)	Na1—Na2—S1^xvii	102.6 (9)
S1—Mo2—Mo1^iii	55.650 (19)	S1^i—Na2—S1^xvii	115.4 (7)
S2—Mo2—Mo1^iii	116.776 (19)	Na1—Na2—S1^xvi	102.6 (9)
S2^iii—Mo2—Mo1^iii	58.573 (17)	S1^i—Na2—S1^xvi	115.4 (7)
S2^iv—Mo2—Mo1^iii	151.11 (2)	S1^xvii—Na2—S1^xvi	115.4 (7)
Mo2^v—Mo2—Mo1^iii	110.082 (13)	Na1—Na2—Na2^xx	180.000 (2)
Mo2^iv—Mo2—Mo1^iii	144.903 (10)	S1^i—Na2—Na2^xx	77.4 (9)
Mo2^iii—Mo2—Mo1^iii	59.650 (8)	S1^xvii—Na2—Na2^xx	77.4 (9)
Mo2^i—Mo2—Mo1^iii	88.804 (7)	S1^xvi—Na2—Na2^xx	77.4 (9)
Mo1—Mo2—Mo1^iii	57.157 (12)	Na1—Na2—Na1^xiii	0.000 (1)
Mo2—S1—Mo1^iii	68.80 (2)	S1^i—Na2—Na1^xiii	102.6 (9)
Mo2—S1—Mo1	66.67 (2)	S1^xvii—Na2—Na1^xiii	102.6 (9)
Mo1^iii—S1—Mo1	64.26 (2)	S1^xvi—Na2—Na1^xiii	102.6 (9)
Mo2—S1—Mo1^ii	136.36 (4)	Na2^xx—Na2—Na1^xiii	180.000 (1)

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −x+1, −y, −z; (iii) −y+1, x−y, z; (iv) −x+y+1, y, −z+1/2; (v) −y+1, −x+1, −z+1/2; (vi) x+1, y, z; (vii) −y+1, −x+1, −z−1/2; (viii) y+1, −x+y+1, −z; (ix) x−y, −y, z−1/2; (x) y+1, x, z−1/2; (xi) −x+1, −x+y+1, z−1/2; (xii) x−y, x, −z; (xiii) −y, −x, −z+1/2; (xiv) −x+y, −x, z; (xv) −y, x−y, z; (xvi) −y, x−y−1, z; (xvii) x−1, y, z; (xviii) x, x−y, −z+1/2; (xix) −x+y, y, −z+1/2; (xx) −x, −y, −z.