Na_3.88Mo₁₅Se₁₉: a novel ternary reduced molybdenum selenide containing Mo₆ and Mo₉ clusters

The structure of tetrasodium penta­deca­molybdenum nona­deca­selenide, Na_3.88Mo₁₅Se₁₉, is isotypic with the In_3+xMo₁₅Se₁₉ compounds [Grüttner et al. (1979). Acta Cryst. B35, 285-292]. It is characterized by two cluster units, Mo₆Seⁱ₈Se^a₆ and Mo₉Seⁱ₁₁Se^a₆ (where i represents inner and a apical atoms), that are present in a 1:1 ratio. The cluster units are centered at Wyckoff positions 2b and 2c and have point-group symmetry -3 and -6, respectively. The clusters are inter­connected through additional Mo-Se bonds. In the title compound, the Na⁺ cations replace the trivalent as well as the monovalent indium atoms present in In_3.9Mo₁₅Se₁₉. One Mo, one Se and one Na atom are situated on mirror planes, and two other Se atoms and one Na atom [occupancy 0.628 (14)] are situated on threefold rotation axes. The crystal studied was twinned by merohedry with refined components of 0.4216 (12) and 0.5784 (12).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](Mo-Se) = 0.001 Å
• Disorder in solvent or counterion
• R factor = 0.033
• wR factor = 0.084
• Data-to-parameter ratio = 37.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ? Check
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given .....          ? Do !
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.2
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          2
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ? Do !
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ? Check
PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ...          2 Units
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo1    --  Se4_b   ..       13.7 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo1    --  Se1_d   ..        7.3 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo1    --  Se2_f   ..        6.7 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo2    --  Se3     ..       10.0 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo2    --  Se2_e   ..        5.7 su
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................         39 %
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   MO1    --  MO2     ..       3.52 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   MO1    --  MO1     ..       3.83 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   MO1    --  NA2     ..       3.86 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   MO2    --  MO1     ..       3.52 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA2    --  NA2     ..       3.60 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA2    --  NA2     ..       3.60 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA2    --  MO1     ..       3.86 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF:   NA2    --  MO1     ..       3.86 Ang.
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          ! Info
PLAT931_ALERT_5_G Check Twin Law ( 0 1  0)[       ] Estimated BASF       0.42

   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
  22 ALERT level G = General information/check it is not something unexpected

  13 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   4 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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S1. Comment

The reduced molybdenum compounds In_{3 + x}Mo₁₅X₁₉ (X = S, Se) (Grüttner et al., 1979; Salloum et al., 2004a) crystallize in an interesting structural type characterized by an equal mixture of Mo₆ and Mo₉ clusters and by In atoms that occupy two or three different crystallographically positions depending on their formal oxidation state of +1 or +3. Subsequently, isomorphous compounds such as Ho_0.76In_1.68Mo₁₅Se₁₉ (Salloum et al., 2006), In_0.87K₂Mo₁₅Se₁₉ (Salloum et al., 2007), V_1.42In_1.83Mo₁₅Se₁₉ (Gougeon et al., 2010), In_3.7Mo₁₅S₁₉ (Salloum et al., 2004a), In_1.6Rb₂Mo₁₅S₁₉, In_2.2CsMo₁₅S₁₉ and ScTl₂Mo₁₅S₁₉ (Salloum et al., 2004b) have been synthesized. In the latter compounds, the Ho, V and Sc atoms replace the trivalent indium and the K, Cs, and Tl atoms the monovalent one. We present here the crystal structure of Na_3.9Mo₁₅Se₁₉ in which the sodium replaces the monovalent as well as the trivalent indium for the first time.

The Mo—Se framework of the title compound consists of the cluster units Mo₆Seⁱ₈Se^a₆ and Mo₉Seⁱ₁₁Se^a₆ in a 1:1 ratio (for details of the i- and a-type ligand notation, see Schäfer & von Schnering (1964)). Both components are interconnected through additional Mo—Se bonds (Figs. 1 and 2). The first unit can be described as an Mo₆ octahedron surrounded by eight face-capping inner Seⁱ and six apical Se^a ligands. The Mo₉ cluster is surrounded by 11 Seⁱ atoms capping one or two faces of the bioctahedron and six Se^a ligands above the apical Mo atoms. The Mo₆Seⁱ₈Se^a₆ and Mo₉Seⁱ₁₁Se^a₆ units are centered at Wyckoff positions 2 b and 2c and have point-group symmetry 3 and 6, respectively. The Mo—Mo distances within the Mo₆ cluster are 2.6980 (7) Å for the distances of the Mo triangles formed by the Mo1 atoms related through the threefold axis, and 2.7152 (7) Å for the distances between these triangles. The Mo—Mo distances within the Mo₉ clusters are 2.6311 (7) and 2.6834 (11) Å in the triangles formed by the atoms Mo2 and Mo3, respectively, and 2.7153 (6) and 2.7537 (6) Å for those between the Mo2₃ and Mo3₃ triangles. The Se atoms bridge either one (Se1, Se2, Se4 and Se5) or two (Se3) triangular faces of the Mo clusters. Moreover, atoms Se1 and Se2 are linked to an Mo atom of a neighboring cluster. The Mo—Se bond distances range from 2.5287 (7) to 2.7207 (7) Å within the Mo₆Seⁱ₈Se^a₆ unit, and from 2.5220 (7) to 2.7018 (7) Å within the Mo₉Seⁱ₁₁Se^a₆ unit. In both cases, the shortest bonds involve the Se4 and Se5 terminal atoms and the longest ones correspond to the interunit Mo1—Se2 and Mo2—Se1 bonds. Each Mo₉Seⁱ₁₁Se^a₆ cluster is thus interconnected to six Mo₆Seⁱ₈Se^a₆ units (and vice versa) via Mo2—Se1 bonds (and Mo1—Se2 bonds, respectively), forming the three-dimensional Mo—Se framework, the connective formula of which is Mo₉Seⁱ₅Se^i-a_6/2Se^a-i_6/2, Mo₆Seⁱ₂Se^i-a_6/2Se^a-i_6/2. It results from this arrangement that the shortest intercluster Mo1—Mo2 distance is 3.5202 (6) Å, indicating only weak metal-metal interactions between the Mo clusters. The Na⁺ cations are surrounded by seven Se atoms forming a distorted tricapped tetrahedron, as is the case in In_{3 + x}Mo₁₅Se₁₉. The Se5 and Se2 atoms forming the tetrahedron are at 2.848 (6) and 3.2010 (11) Å from the Na1 atom, and the capping Se1 atoms are at 3.462 (2) Å. The Na2⁺ cations, as the In³⁺ cations in the In_3.9Mo₁₅Se₁₉ compounds, occupy partially at 62.7% a triangular group of distorted octahedral cavities around the threefold axis, which are formed by two Mo₆Seⁱ₈Se^a₆ and three Mo₉Seⁱ₁₁Se^a₆ units. The Na2—Se distances are in the 2.657 (5) - 3.096 (5) Å range.

Related literature

For previous reports on the crystal structure of the In₃Mo₁₅Se₁₉ compounds, see: Grüttner et al. (1979). For physical properties of this type of compounds, see: Seeber et al. (1979). The crystal structures of the substituted selenides Ho_0.76In_1.68Mo₁₅Se₁₉ and In_0.87K₂Mo₁₅Se₁₉ were reported by Salloum et al. (2006, 2007). For the isomorphous sulfides In_3.7Mo₁₅S₁₉, In_1.6Rb₂Mo₁₅S₁₉, In_2.2CsMo₁₅S₁₉ and ScTl₂Mo₁₅S₁₉, see: Salloum et al. (2004a,b); Gougeon et al. (2010). For details of the i- and a-type ligand notation, see: Schäfer & von Schnering (1964).

S2. Experimental

Single crystals of Na_3.9Mo₁₅Se₁₉ were prepared from an ion exchange reaction on single crystals of In_{3 + x}Mo₁₅Se₁₉ with an excess of NaI at 1073 K. The mixture was sealed under vacuum in a long silica tube. The end of tube containing the crystals of In_{3 + x}Mo₁₅Se₁₉ and InI was placed in a furnace with about 5 cm of the other end out from the furnace, at about the room temperature. The furnace was heated at 1073 K for 48 h. After reaction, crystals of InI were observed at the cool end of the tube. The black crystals of the title compound were subsequently washed with water to remove the excess of InI. Qualitative microanalyses using a Jeol JSM 6400 scanning electron microscope equipped with a Oxford INCA energy- dispersive-type X-ray spectrometer did not reveal the presence of indium in the crystals and indicated roughly stoichiometries comprised between 3.6 and 4.2 for the Na content.

S3. Refinement

Analysis of the intensity data using the TwinRotMat routine of PLATON (Spek, 2009) revealed the studied crystal was twinned by merohedry with [110, 010, 001] as the twin matrix. The ratio of the twin components was refined to 0.4216 (12):0.5784 (12). No significant deviation from full occupancy was observed for Na1. The site occupation factor of Na2 was refined freely leading to the final stoichiometry Na_3.88 (4)Mo₁₅Se₁₉.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT (Nonius, 1998); data reduction: EVALCCD (Duisenberg, 1998); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. : View of Na3.9Mo15Se19 along [110]. Displacement ellipsoids are drawn at the 97% probability level.
	Fig. 2. Plot showing the atom-numbering scheme and the interunit linkage of the Mo9Se11Se6 and Mo6Se8Se6 cluster units. Displacement ellipsoids are drawn at the 97% probability level.

Tetrasodium pentadecamolybdenum nonadecaselenide

Crystal data

Na3.88Mo15Se19	Dx = 6.091 Mg m^−3
Mr = 3028.54	Mo Kα radiation, λ = 0.71069 Å
Hexagonal, P63/m	Cell parameters from 26001 reflections
a = 9.8647 (1) Å	θ = 1.7–35.0°
c = 19.5957 (3) Å	µ = 26.47 mm^−1
V = 1651.43 (3) Å^3	T = 293 K
Z = 2	Multi-faceted crystal, black
F(000) = 2637	0.09 × 0.07 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer	2487 independent reflections
Radiation source: fine-focus sealed tube	2116 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
ϕ scans (κ = 0) + additional ω scans	θmax = 35.0°, θmin = 2.4°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = −15→15
Tmin = 0.111, Tmax = 0.215	k = −15→15
25999 measured reflections	l = −19→31

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)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0435P)^2 + 3.7236P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.084	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 2.69 e Å^−3
2487 reflections	Δρmin = −1.81 e Å^−3
67 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00058 (8)

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	0.84973 (5)	−0.16457 (5)	0.556745 (19)	0.01378 (9)
Mo2	0.68549 (6)	0.18962 (5)	0.63450 (2)	0.01510 (9)
Mo3	0.51739 (7)	0.16952 (8)	0.7500	0.01574 (11)
Se1	0.68259 (6)	−0.03045 (6)	0.55145 (2)	0.01653 (11)
Se2	0.38303 (7)	0.00893 (7)	0.63968 (2)	0.01760 (11)
Se3	0.69343 (10)	0.04771 (10)	0.7500	0.01993 (16)
Se4	0.0000	0.0000	0.65840 (4)	0.0222 (2)
Se5	0.6667	0.3333	0.53176 (4)	0.01851 (18)
Na1	0.6667	0.3333	0.3864 (3)	0.0618 (18)
Na2	0.0558 (6)	0.2330 (7)	0.7500	0.0214 (16)	0.628 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01667 (19)	0.01711 (19)	0.00794 (16)	0.00872 (17)	0.00032 (12)	0.00005 (13)
Mo2	0.0186 (2)	0.0185 (2)	0.00811 (15)	0.00916 (17)	−0.00004 (14)	−0.00039 (13)
Mo3	0.0195 (3)	0.0198 (3)	0.0079 (2)	0.0097 (2)	0.000	0.000
Se1	0.0181 (2)	0.0198 (3)	0.01279 (19)	0.0103 (2)	0.00148 (17)	−0.00079 (17)
Se2	0.0198 (2)	0.0200 (2)	0.01247 (19)	0.0095 (2)	−0.00268 (17)	−0.00173 (17)
Se3	0.0252 (4)	0.0232 (4)	0.0131 (3)	0.0134 (3)	0.000	0.000
Se4	0.0297 (3)	0.0297 (3)	0.0071 (3)	0.01486 (15)	0.000	0.000
Se5	0.0239 (3)	0.0239 (3)	0.0078 (3)	0.01194 (14)	0.000	0.000
Na1	0.079 (3)	0.079 (3)	0.028 (3)	0.0393 (15)	0.000	0.000
Na2	0.017 (3)	0.035 (3)	0.019 (2)	0.018 (2)	0.000	0.000

Geometric parameters (Å, º)

Mo1—Se4^i	2.5287 (7)	Se1—Na1^xiii	3.462 (2)
Mo1—Se1^ii	2.5600 (6)	Se2—Mo2^ix	2.6312 (8)
Mo1—Se1	2.5810 (7)	Se2—Mo1^xiv	2.7207 (7)
Mo1—Se1^iii	2.6075 (7)	Se2—Na2^xii	2.812 (4)
Mo1—Mo1^iii	2.6980 (7)	Se2—Na1^xiii	3.2010 (11)
Mo1—Mo1^iv	2.6980 (7)	Se3—Mo3^viii	2.5675 (11)
Mo1—Mo1^ii	2.7152 (7)	Se3—Na2^viii	2.657 (5)
Mo1—Mo1^v	2.7152 (7)	Se3—Mo2^x	2.6830 (6)
Mo1—Se2^vi	2.7207 (7)	Se3—Na2^i	3.096 (5)
Mo1—Mo2^iii	3.5202 (6)	Se4—Mo1^xv	2.5287 (7)
Mo1—Mo1^vii	3.8278 (8)	Se4—Mo1^xiv	2.5287 (7)
Mo1—Na2^viii	3.8628 (12)	Se4—Mo1^ix	2.5287 (7)
Mo2—Se5	2.5220 (7)	Se4—Na2^xii	2.747 (4)
Mo2—Se2	2.6023 (8)	Se4—Na2	2.747 (4)
Mo2—Mo2^ix	2.6311 (7)	Se4—Na2^xvi	2.747 (5)
Mo2—Mo2^viii	2.6311 (7)	Se5—Mo2^viii	2.5220 (7)
Mo2—Se2^viii	2.6312 (8)	Se5—Mo2^ix	2.5220 (7)
Mo2—Se3	2.6830 (6)	Se5—Na1	2.848 (6)
Mo2—Se1	2.7018 (7)	Na1—Se2^xiii	3.2010 (11)
Mo2—Mo3^viii	2.7153 (6)	Na1—Se2^v	3.2010 (11)
Mo2—Mo3	2.7537 (6)	Na1—Se2^xvii	3.2010 (11)
Mo2—Mo1^iv	3.5202 (6)	Na1—Se1^v	3.462 (2)
Mo3—Se3	2.5586 (11)	Na1—Se1^xiii	3.462 (2)
Mo3—Se3^ix	2.5675 (11)	Na1—Se1^xvii	3.462 (2)
Mo3—Se2	2.6153 (6)	Na2—Se3^ix	2.657 (5)
Mo3—Se2^x	2.6153 (6)	Na2—Se4^x	2.747 (4)
Mo3—Mo3^viii	2.6834 (11)	Na2—Se2^xviii	2.812 (4)
Mo3—Mo3^ix	2.6834 (11)	Na2—Se2^xvi	2.812 (4)
Mo3—Mo2^xi	2.7153 (6)	Na2—Mo3^xvi	2.956 (5)
Mo3—Mo2^ix	2.7153 (6)	Na2—Se3^xv	3.096 (5)
Mo3—Mo2^x	2.7537 (6)	Na2—Na2^xvi	3.601 (10)
Mo3—Na2^xii	2.956 (5)	Na2—Na2^xii	3.601 (10)
Se1—Mo1^v	2.5600 (6)	Na2—Mo1^xi	3.8628 (12)
Se1—Mo1^iv	2.6075 (7)	Na2—Mo1^ix	3.8628 (12)
Se4^i—Mo1—Se1^ii	176.02 (2)	Mo3^ix—Mo3—Mo2	89.039 (15)
Se4^i—Mo1—Se1	91.274 (18)	Mo2^xi—Mo3—Mo2	146.42 (3)
Se1^ii—Mo1—Se1	89.153 (17)	Mo2^ix—Mo3—Mo2	57.508 (17)
Se4^i—Mo1—Se1^iii	90.664 (18)	Mo2^x—Mo3—Mo2	110.55 (3)
Se1^ii—Mo1—Se1^iii	88.572 (18)	Se3—Mo3—Na2^xii	115.38 (12)
Se1—Mo1—Se1^iii	174.67 (3)	Se3^ix—Mo3—Na2^xii	67.75 (12)
Se4^i—Mo1—Mo1^iii	57.759 (12)	Se2—Mo3—Na2^xii	60.24 (4)
Se1^ii—Mo1—Mo1^iii	118.706 (18)	Se2^x—Mo3—Na2^xii	60.24 (4)
Se1—Mo1—Mo1^iii	119.10 (2)	Mo3^viii—Mo3—Na2^xii	173.98 (12)
Se1^iii—Mo1—Mo1^iii	58.19 (2)	Mo3^ix—Mo3—Na2^xii	126.02 (12)
Se4^i—Mo1—Mo1^iv	57.759 (12)	Mo2^xi—Mo3—Na2^xii	93.47 (6)
Se1^ii—Mo1—Mo1^iv	119.357 (19)	Mo2^ix—Mo3—Na2^xii	93.47 (6)
Se1—Mo1—Mo1^iv	59.15 (2)	Mo2^x—Mo3—Na2^xii	118.06 (4)
Se1^iii—Mo1—Mo1^iv	118.14 (2)	Mo2—Mo3—Na2^xii	118.06 (4)
Mo1^iii—Mo1—Mo1^iv	60.0	Mo1^v—Se1—Mo1	63.76 (2)
Se4^i—Mo1—Mo1^ii	117.937 (16)	Mo1^v—Se1—Mo1^iv	63.39 (2)
Se1^ii—Mo1—Mo1^ii	58.50 (2)	Mo1—Se1—Mo1^iv	62.66 (2)
Se1—Mo1—Mo1^ii	117.326 (19)	Mo1^v—Se1—Mo2	132.81 (3)
Se1^iii—Mo1—Mo1^ii	57.453 (14)	Mo1—Se1—Mo2	129.41 (2)
Mo1^iii—Mo1—Mo1^ii	60.209 (10)	Mo1^iv—Se1—Mo2	83.04 (2)
Mo1^iv—Mo1—Mo1^ii	90.0	Mo1^v—Se1—Na1^xiii	130.23 (8)
Se4^i—Mo1—Mo1^v	117.937 (16)	Mo1—Se1—Na1^xiii	99.13 (2)
Se1^ii—Mo1—Mo1^v	59.16 (2)	Mo1^iv—Se1—Na1^xiii	151.91 (7)
Se1—Mo1—Mo1^v	57.743 (15)	Mo2—Se1—Na1^xiii	95.04 (6)
Se1^iii—Mo1—Mo1^v	117.026 (19)	Mo2—Se2—Mo3	63.71 (2)
Mo1^iii—Mo1—Mo1^v	90.0	Mo2—Se2—Mo2^ix	60.36 (2)
Mo1^iv—Mo1—Mo1^v	60.209 (9)	Mo3—Se2—Mo2^ix	62.333 (19)
Mo1^ii—Mo1—Mo1^v	59.583 (19)	Mo2—Se2—Mo1^xiv	127.69 (2)
Se4^i—Mo1—Se2^vi	91.21 (2)	Mo3—Se2—Mo1^xiv	130.42 (3)
Se1^ii—Mo1—Se2^vi	92.77 (2)	Mo2^ix—Se2—Mo1^xiv	82.24 (2)
Se1—Mo1—Se2^vi	87.51 (2)	Mo2—Se2—Na2^xii	129.48 (9)
Se1^iii—Mo1—Se2^vi	97.41 (2)	Mo3—Se2—Na2^xii	65.90 (8)
Mo1^iii—Mo1—Se2^vi	136.97 (2)	Mo2^ix—Se2—Na2^xii	98.77 (11)
Mo1^iv—Mo1—Se2^vi	130.63 (2)	Mo1^xiv—Se2—Na2^xii	88.56 (10)
Mo1^ii—Mo1—Se2^vi	139.27 (2)	Mo2—Se2—Na1^xiii	103.57 (2)
Mo1^v—Mo1—Se2^vi	132.73 (2)	Mo3—Se2—Na1^xiii	122.35 (10)
Se4^i—Mo1—Mo2^iii	91.163 (16)	Mo2^ix—Se2—Na1^xiii	160.83 (7)
Se1^ii—Mo1—Mo2^iii	91.320 (19)	Mo1^xiv—Se2—Na1^xiii	102.71 (7)
Se1—Mo1—Mo2^iii	135.27 (2)	Na2^xii—Se2—Na1^xiii	99.85 (14)
Se1^iii—Mo1—Mo2^iii	49.629 (15)	Mo3—Se3—Mo3^viii	63.13 (3)
Mo1^iii—Mo1—Mo2^iii	99.53 (2)	Mo3—Se3—Na2^viii	157.67 (13)
Mo1^iv—Mo1—Mo2^iii	148.233 (15)	Mo3^viii—Se3—Na2^viii	139.20 (13)
Mo1^ii—Mo1—Mo2^iii	100.519 (16)	Mo3—Se3—Mo2^x	63.33 (2)
Mo1^v—Mo1—Mo2^iii	149.644 (19)	Mo3^viii—Se3—Mo2^x	62.236 (19)
Se2^vi—Mo1—Mo2^iii	47.784 (15)	Na2^viii—Se3—Mo2^x	121.81 (2)
Se4^i—Mo1—Mo1^vii	87.495 (19)	Mo3—Se3—Mo2	63.33 (2)
Se1^ii—Mo1—Mo1^vii	88.562 (18)	Mo3^viii—Se3—Mo2	62.236 (19)
Se1—Mo1—Mo1^vii	87.95 (2)	Na2^viii—Se3—Mo2	121.81 (2)
Se1^iii—Mo1—Mo1^vii	87.18 (2)	Mo2^x—Se3—Mo2	115.04 (3)
Mo1^iii—Mo1—Mo1^vii	45.181 (8)	Mo3—Se3—Na2^i	125.24 (11)
Mo1^iv—Mo1—Mo1^vii	45.181 (8)	Mo3^viii—Se3—Na2^i	62.11 (11)
Mo1^ii—Mo1—Mo1^vii	44.819 (8)	Na2^viii—Se3—Na2^i	77.1 (2)
Mo1^v—Mo1—Mo1^vii	44.819 (8)	Mo2^x—Se3—Na2^i	91.04 (6)
Se2^vi—Mo1—Mo1^vii	175.25 (3)	Mo2—Se3—Na2^i	91.04 (6)
Mo2^iii—Mo1—Mo1^vii	136.78 (2)	Mo1^xv—Se4—Mo1^xiv	64.48 (2)
Se4^i—Mo1—Na2^viii	45.18 (9)	Mo1^xv—Se4—Mo1^ix	64.48 (2)
Se1^ii—Mo1—Na2^viii	138.79 (9)	Mo1^xiv—Se4—Mo1^ix	64.48 (2)
Se1—Mo1—Na2^viii	82.95 (8)	Mo1^xv—Se4—Na2^xii	127.86 (10)
Se1^iii—Mo1—Na2^viii	101.91 (8)	Mo1^xiv—Se4—Na2^xii	94.05 (8)
Mo1^iii—Mo1—Na2^viii	100.18 (9)	Mo1^ix—Se4—Na2^xii	149.31 (10)
Mo1^iv—Mo1—Na2^viii	90.73 (8)	Mo1^xv—Se4—Na2	149.31 (9)
Mo1^ii—Mo1—Na2^viii	156.33 (8)	Mo1^xiv—Se4—Na2	127.86 (10)
Mo1^v—Mo1—Na2^viii	138.84 (7)	Mo1^ix—Se4—Na2	94.05 (8)
Se2^vi—Mo1—Na2^viii	46.69 (8)	Na2^xii—Se4—Na2	81.92 (12)
Mo2^iii—Mo1—Na2^viii	67.91 (7)	Mo1^xv—Se4—Na2^xvi	94.05 (8)
Mo1^vii—Mo1—Na2^viii	131.19 (9)	Mo1^xiv—Se4—Na2^xvi	149.31 (9)
Se5—Mo2—Se2	91.991 (19)	Mo1^ix—Se4—Na2^xvi	127.86 (10)
Se5—Mo2—Mo2^ix	58.558 (12)	Na2^xii—Se4—Na2^xvi	81.92 (12)
Se2—Mo2—Mo2^ix	60.37 (3)	Na2—Se4—Na2^xvi	81.92 (12)
Se5—Mo2—Mo2^viii	58.558 (12)	Mo2^viii—Se5—Mo2	62.88 (2)
Se2—Mo2—Mo2^viii	120.31 (3)	Mo2^viii—Se5—Mo2^ix	62.88 (2)
Mo2^ix—Mo2—Mo2^viii	60.0	Mo2—Se5—Mo2^ix	62.88 (2)
Se5—Mo2—Se2^viii	91.314 (18)	Mo2^viii—Se5—Na1	142.963 (15)
Se2—Mo2—Se2^viii	175.53 (3)	Mo2—Se5—Na1	142.963 (15)
Mo2^ix—Mo2—Se2^viii	119.22 (2)	Mo2^ix—Se5—Na1	142.963 (15)
Mo2^viii—Mo2—Se2^viii	59.27 (2)	Se5—Na1—Se2^xiii	99.20 (10)
Se5—Mo2—Se3	175.05 (3)	Se5—Na1—Se2^v	99.20 (10)
Se2—Mo2—Se3	86.12 (2)	Se2^xiii—Na1—Se2^v	117.49 (6)
Mo2^ix—Mo2—Se3	116.64 (2)	Se5—Na1—Se2^xvii	99.20 (10)
Mo2^viii—Mo2—Se3	118.69 (2)	Se2^xiii—Na1—Se2^xvii	117.49 (6)
Se2^viii—Mo2—Se3	90.35 (3)	Se2^v—Na1—Se2^xvii	117.49 (6)
Se5—Mo2—Se1	89.81 (2)	Se5—Na1—Se1^v	69.42 (9)
Se2—Mo2—Se1	85.71 (2)	Se2^xiii—Na1—Se1^v	66.67 (2)
Mo2^ix—Mo2—Se1	129.77 (2)	Se2^v—Na1—Se1^v	65.44 (2)
Mo2^viii—Mo2—Se1	137.17 (2)	Se2^xvii—Na1—Se1^v	168.60 (19)
Se2^viii—Mo2—Se1	97.31 (2)	Se5—Na1—Se1^xiii	69.42 (9)
Se3—Mo2—Se1	94.60 (2)	Se2^xiii—Na1—Se1^xiii	65.44 (2)
Se5—Mo2—Mo3^viii	120.52 (2)	Se2^v—Na1—Se1^xiii	168.60 (19)
Se2—Mo2—Mo3^viii	117.08 (2)	Se2^xvii—Na1—Se1^xiii	66.67 (2)
Mo2^ix—Mo2—Mo3^viii	90.964 (15)	Se1^v—Na1—Se1^xiii	108.34 (9)
Mo2^viii—Mo2—Mo3^viii	61.980 (17)	Se5—Na1—Se1^xvii	69.42 (9)
Se2^viii—Mo2—Mo3^viii	58.547 (18)	Se2^xiii—Na1—Se1^xvii	168.60 (19)
Se3—Mo2—Mo3^viii	56.80 (2)	Se2^v—Na1—Se1^xvii	66.67 (2)
Se1—Mo2—Mo3^viii	139.02 (2)	Se2^xvii—Na1—Se1^xvii	65.44 (2)
Se5—Mo2—Mo3	119.05 (2)	Se1^v—Na1—Se1^xvii	108.34 (9)
Se2—Mo2—Mo3	58.376 (18)	Se1^xiii—Na1—Se1^xvii	108.34 (9)
Mo2^ix—Mo2—Mo3	60.511 (18)	Se3^ix—Na2—Se4	87.67 (13)
Mo2^viii—Mo2—Mo3	90.119 (16)	Se3^ix—Na2—Se4^x	87.67 (13)
Se2^viii—Mo2—Mo3	117.29 (2)	Se4—Na2—Se4^x	81.61 (16)
Se3—Mo2—Mo3	56.13 (2)	Se3^ix—Na2—Se2^xviii	111.08 (14)
Se1—Mo2—Mo3	132.31 (2)	Se4—Na2—Se2^xviii	156.4 (2)
Mo3^viii—Mo2—Mo3	58.76 (2)	Se4^x—Na2—Se2^xviii	84.93 (4)
Se5—Mo2—Mo1^iv	91.085 (16)	Se3^ix—Na2—Se2^xvi	111.08 (14)
Se2—Mo2—Mo1^iv	132.93 (2)	Se4—Na2—Se2^xvi	84.93 (4)
Mo2^ix—Mo2—Mo1^iv	149.106 (14)	Se4^x—Na2—Se2^xvi	156.4 (2)
Mo2^viii—Mo2—Mo1^iv	100.94 (2)	Se2^xviii—Na2—Se2^xvi	100.51 (17)
Se2^viii—Mo2—Mo1^iv	49.978 (15)	Se3^ix—Na2—Mo3^xvi	146.9 (2)
Se3—Mo2—Mo1^iv	93.55 (2)	Se4—Na2—Mo3^xvi	116.51 (14)
Se1—Mo2—Mo1^iv	47.329 (15)	Se4^x—Na2—Mo3^xvi	116.51 (14)
Mo3^viii—Mo2—Mo1^iv	101.18 (2)	Se2^xviii—Na2—Mo3^xvi	53.86 (9)
Mo3—Mo2—Mo1^iv	149.02 (2)	Se2^xvi—Na2—Mo3^xvi	53.86 (9)
Se3—Mo3—Se3^ix	176.87 (3)	Se3^ix—Na2—Se3^xv	162.9 (2)
Se3—Mo3—Se2	88.45 (2)	Se4—Na2—Se3^xv	79.44 (13)
Se3^ix—Mo3—Se2	93.31 (2)	Se4^x—Na2—Se3^xv	79.44 (13)
Se3—Mo3—Se2^x	88.45 (2)	Se2^xviii—Na2—Se3^xv	79.14 (11)
Se3^ix—Mo3—Se2^x	93.31 (2)	Se2^xvi—Na2—Se3^xv	79.14 (11)
Se2—Mo3—Se2^x	111.50 (3)	Mo3^xvi—Na2—Se3^xv	50.14 (8)
Se3—Mo3—Mo3^viii	58.60 (4)	Se3^ix—Na2—Na2^xvi	116.92 (17)
Se3^ix—Mo3—Mo3^viii	118.27 (4)	Se4—Na2—Na2^xvi	49.04 (6)
Se2—Mo3—Mo3^viii	117.76 (2)	Se4^x—Na2—Na2^xvi	49.04 (6)
Se2^x—Mo3—Mo3^viii	117.76 (2)	Se2^xviii—Na2—Na2^xvi	107.97 (17)
Se3—Mo3—Mo3^ix	118.60 (3)	Se2^xvi—Na2—Na2^xvi	107.97 (17)
Se3^ix—Mo3—Mo3^ix	58.27 (4)	Mo3^xvi—Na2—Na2^xvi	96.1 (2)
Se2—Mo3—Mo3^ix	120.43 (2)	Se3^xv—Na2—Na2^xvi	45.99 (16)
Se2^x—Mo3—Mo3^ix	120.43 (2)	Se3^ix—Na2—Na2^xii	56.92 (17)
Mo3^viii—Mo3—Mo3^ix	60.0	Se4—Na2—Na2^xii	49.04 (6)
Se3—Mo3—Mo2^xi	118.045 (18)	Se4^x—Na2—Na2^xii	49.04 (6)
Se3^ix—Mo3—Mo2^xi	60.968 (17)	Se2^xviii—Na2—Na2^xii	129.74 (9)
Se2—Mo3—Mo2^xi	149.86 (3)	Se2^xvi—Na2—Na2^xii	129.74 (9)
Se2^x—Mo3—Mo2^xi	59.121 (17)	Mo3^xvi—Na2—Na2^xii	156.1 (2)
Mo3^viii—Mo3—Mo2^xi	89.853 (16)	Se3^xv—Na2—Na2^xii	105.99 (16)
Mo3^ix—Mo3—Mo2^xi	61.335 (19)	Na2^xvi—Na2—Na2^xii	60.000 (1)
Se3—Mo3—Mo2^ix	118.045 (18)	Se3^ix—Na2—Mo1^xi	96.57 (7)
Se3^ix—Mo3—Mo2^ix	60.968 (17)	Se4—Na2—Mo1^xi	121.60 (17)
Se2—Mo3—Mo2^ix	59.121 (17)	Se4^x—Na2—Mo1^xi	40.767 (18)
Se2^x—Mo3—Mo2^ix	149.86 (3)	Se2^xviii—Na2—Mo1^xi	44.758 (19)
Mo3^viii—Mo3—Mo2^ix	89.853 (16)	Se2^xvi—Na2—Mo1^xi	142.89 (16)
Mo3^ix—Mo3—Mo2^ix	61.335 (19)	Mo3^xvi—Na2—Mo1^xi	89.52 (8)
Mo2^xi—Mo3—Mo2^ix	112.93 (3)	Se3^xv—Na2—Mo1^xi	80.99 (8)
Se3—Mo3—Mo2^x	60.536 (17)	Na2^xvi—Na2—Mo1^xi	78.76 (9)
Se3^ix—Mo3—Mo2^x	118.389 (19)	Na2^xii—Na2—Mo1^xi	85.87 (7)
Se2—Mo3—Mo2^x	145.85 (3)	Se3^ix—Na2—Mo1^ix	96.57 (7)
Se2^x—Mo3—Mo2^x	57.914 (17)	Se4—Na2—Mo1^ix	40.767 (18)
Mo3^viii—Mo3—Mo2^x	59.903 (18)	Se4^x—Na2—Mo1^ix	121.60 (17)
Mo3^ix—Mo3—Mo2^x	89.039 (15)	Se2^xviii—Na2—Mo1^ix	142.89 (16)
Mo2^xi—Mo3—Mo2^x	57.509 (17)	Se2^xvi—Na2—Mo1^ix	44.758 (19)
Mo2^ix—Mo3—Mo2^x	146.42 (3)	Mo3^xvi—Na2—Mo1^ix	89.52 (8)
Se3—Mo3—Mo2	60.536 (17)	Se3^xv—Na2—Mo1^ix	80.99 (8)
Se3^ix—Mo3—Mo2	118.388 (19)	Na2^xvi—Na2—Mo1^ix	78.76 (9)
Se2—Mo3—Mo2	57.913 (17)	Na2^xii—Na2—Mo1^ix	85.87 (7)
Se2^x—Mo3—Mo2	145.85 (3)	Mo1^xi—Na2—Mo1^ix	157.26 (17)
Mo3^viii—Mo3—Mo2	59.903 (18)

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