Na3.88Mo15Se19: a novel ternary reduced molybdenum selenide containing Mo6 and Mo9 clusters

Salloum, D.; Gougeon, P.; Gall, P.

doi:10.1107/S1600536813025907

inorganic compounds

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Volume 69| Part 10| October 2013| Pages i67-i68

doi:10.1107/S1600536813025907

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

Diala Salloum,^a Patrick Gougeon ^b ^* and Philippe Gall ^b

^aFaculty of Science III, Lebanese University, PO Box 826, Kobbeh-Tripoli, Lebanon, and ^bUnité Sciences Chimiques de Rennes, UMR CNRS No. 6226, Université de Rennes I - INSA Rennes, Campus de Beaulieu, 35042 Rennes CEDEX, France
^*Correspondence e-mail: Patrick.Gougeon@univ-rennes1.fr

(Received 26 August 2013; accepted 19 September 2013; online 25 September 2013)

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).

CCDC reference: 962084

Related literature

For previous reports on the crystal structures of 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 isotypic 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 ).

Experimental

Crystal data

Na_3.88Mo₁₅Se₁₉
M_r = 3028.54
Hexagonal, P 6₃ /m
a = 9.8647 (1) Å
c = 19.5957 (3) Å
V = 1651.43 (3) Å³
Z = 2
Mo Kα radiation
μ = 26.47 mm⁻¹
T = 293 K
0.09 × 0.07 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: analytical (de Meulenaer & Tompa, 1965 ) T_min = 0.111, T_max = 0.215
25999 measured reflections
2487 independent reflections
2116 reflections with I > 2σ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.084
S = 1.06
2487 reflections
67 parameters
Δρ_max = 2.69 e Å⁻³
Δρ_min = −1.81 e Å⁻³

Table 1
Selected bond lengths (Å)

Mo1—Se4ⁱ	2.5287 (7)
Mo1—Se1ⁱⁱ	2.5600 (6)
Mo1—Se1	2.5810 (7)
Mo1—Se1ⁱⁱⁱ	2.6075 (7)
Mo1—Mo1ⁱⁱⁱ	2.6980 (7)
Mo1—Mo1ⁱⁱ	2.7152 (7)
Mo1—Se2^iv	2.7207 (7)
Mo2—Se5	2.5220 (7)
Mo2—Se2	2.6023 (8)
Mo2—Mo2^v	2.6311 (7)
Mo2—Se2^vi	2.6312 (8)
Mo2—Se3	2.6830 (6)
Mo2—Se1	2.7018 (7)
Mo2—Mo3^vi	2.7153 (6)
Mo2—Mo3	2.7537 (6)
Mo3—Se3	2.5586 (11)
Mo3—Se3^v	2.5675 (11)
Mo3—Se2	2.6153 (6)
Mo3—Se2^vii	2.6153 (6)
Mo3—Mo3^vi	2.6834 (11)
Se5—Na1	2.848 (6)
Na1—Se2^viii	3.2010 (11)
Na1—Se1^ix	3.462 (2)
Na2—Se3^v	2.657 (5)
Na2—Se4^vii	2.747 (4)
Na2—Se2^x	2.812 (4)
Na2—Se3^xi	3.096 (5)
Symmetry codes: (i) x+1, y, z; (ii) x-y, x-1, -z+1; (iii) -y+1, x-y-1, z; (iv) -x+y+1, -x, z; (v) -x+y+1, -x+1, z; (vi) -y+1, x-y, z; (vii) $[x, y, -z+{\script{3\over 2}}]$ ; (viii) -x+1, -y, -z+1; (ix) y+1, -x+y+1, -z+1; (x) $[-y, x-y, -z+{\script{3\over 2}}]$ ; (xi) x-1, y, z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: COLLECT; 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 and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 962084

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813025907/ru2054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813025907/ru2054Isup2.hkl

checkCIF report

Comment top

The reduced molybdenum compounds In_{3 +} _xMo₁₅X₁₉ (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 +} _xMo₁₅Se₁₉. 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 top

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).

Experimental top

Single crystals of Na_3.9Mo₁₅Se₁₉ were prepared from an ion exchange reaction on single crystals of In_{3 +} _xMo₁₅Se₁₉ 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 +} _xMo₁₅Se₁₉ 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.

Computing details top

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 top

	Fig. 1. : View of Na_3.9Mo₁₅Se₁₉ 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 top

Crystal data top

Na_3.88Mo₁₅Se₁₉	D_x = 6.091 Mg m⁻³
M_r = 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) Å³	T = 293 K
Z = 2	Multi-faceted crystal, black
F(000) = 2637	0.09 × 0.07 × 0.06 mm

Data collection top

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

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)] = 0.033	w = 1/[σ²(F_o²) + (0.0435P)² + 3.7236P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.084	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 2.69 e Å⁻³
2487 reflections	Δρ_min = −1.81 e Å⁻³
67 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00058 (8)

Crystal data top

Na_3.88Mo₁₅Se₁₉	Z = 2
M_r = 3028.54	Mo Kα radiation
Hexagonal, P6₃/m	µ = 26.47 mm⁻¹
a = 9.8647 (1) Å	T = 293 K
c = 19.5957 (3) Å	0.09 × 0.07 × 0.06 mm
V = 1651.43 (3) Å³

Data collection top

Nonius KappaCCD diffractometer	2487 independent reflections
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	2116 reflections with I > 2σ(I)
T_min = 0.111, T_max = 0.215	R_int = 0.075
25999 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	67 parameters
wR(F²) = 0.084	0 restraints
S = 1.06	Δρ_max = 2.69 e Å⁻³
2487 reflections	Δρ_min = −1.81 e Å⁻³

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. 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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Mo1—Se4ⁱ	2.5287 (7)	Se1—Na1^xiii	3.462 (2)
Mo1—Se1ⁱⁱ	2.5600 (6)	Se2—Mo2^ix	2.6312 (8)
Mo1—Se1	2.5810 (7)	Se2—Mo1^xiv	2.7207 (7)
Mo1—Se1ⁱⁱⁱ	2.6075 (7)	Se2—Na2^xii	2.812 (4)
Mo1—Mo1ⁱⁱⁱ	2.6980 (7)	Se2—Na1^xiii	3.2010 (11)
Mo1—Mo1^iv	2.6980 (7)	Se3—Mo3^viii	2.5675 (11)
Mo1—Mo1ⁱⁱ	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—Na2ⁱ	3.096 (5)
Mo1—Mo2ⁱⁱⁱ	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)

Se4ⁱ—Mo1—Se1ⁱⁱ	176.02 (2)	Mo3^ix—Mo3—Mo2	89.039 (15)
Se4ⁱ—Mo1—Se1	91.274 (18)	Mo2^xi—Mo3—Mo2	146.42 (3)
Se1ⁱⁱ—Mo1—Se1	89.153 (17)	Mo2^ix—Mo3—Mo2	57.508 (17)
Se4ⁱ—Mo1—Se1ⁱⁱⁱ	90.664 (18)	Mo2^x—Mo3—Mo2	110.55 (3)
Se1ⁱⁱ—Mo1—Se1ⁱⁱⁱ	88.572 (18)	Se3—Mo3—Na2^xii	115.38 (12)
Se1—Mo1—Se1ⁱⁱⁱ	174.67 (3)	Se3^ix—Mo3—Na2^xii	67.75 (12)
Se4ⁱ—Mo1—Mo1ⁱⁱⁱ	57.759 (12)	Se2—Mo3—Na2^xii	60.24 (4)
Se1ⁱⁱ—Mo1—Mo1ⁱⁱⁱ	118.706 (18)	Se2^x—Mo3—Na2^xii	60.24 (4)
Se1—Mo1—Mo1ⁱⁱⁱ	119.10 (2)	Mo3^viii—Mo3—Na2^xii	173.98 (12)
Se1ⁱⁱⁱ—Mo1—Mo1ⁱⁱⁱ	58.19 (2)	Mo3^ix—Mo3—Na2^xii	126.02 (12)
Se4ⁱ—Mo1—Mo1^iv	57.759 (12)	Mo2^xi—Mo3—Na2^xii	93.47 (6)
Se1ⁱⁱ—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)
Se1ⁱⁱⁱ—Mo1—Mo1^iv	118.14 (2)	Mo2—Mo3—Na2^xii	118.06 (4)
Mo1ⁱⁱⁱ—Mo1—Mo1^iv	60.0	Mo1^v—Se1—Mo1	63.76 (2)
Se4ⁱ—Mo1—Mo1ⁱⁱ	117.937 (16)	Mo1^v—Se1—Mo1^iv	63.39 (2)
Se1ⁱⁱ—Mo1—Mo1ⁱⁱ	58.50 (2)	Mo1—Se1—Mo1^iv	62.66 (2)
Se1—Mo1—Mo1ⁱⁱ	117.326 (19)	Mo1^v—Se1—Mo2	132.81 (3)
Se1ⁱⁱⁱ—Mo1—Mo1ⁱⁱ	57.453 (14)	Mo1—Se1—Mo2	129.41 (2)
Mo1ⁱⁱⁱ—Mo1—Mo1ⁱⁱ	60.209 (10)	Mo1^iv—Se1—Mo2	83.04 (2)
Mo1^iv—Mo1—Mo1ⁱⁱ	90.0	Mo1^v—Se1—Na1^xiii	130.23 (8)
Se4ⁱ—Mo1—Mo1^v	117.937 (16)	Mo1—Se1—Na1^xiii	99.13 (2)
Se1ⁱⁱ—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)
Se1ⁱⁱⁱ—Mo1—Mo1^v	117.026 (19)	Mo2—Se2—Mo3	63.71 (2)
Mo1ⁱⁱⁱ—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)
Mo1ⁱⁱ—Mo1—Mo1^v	59.583 (19)	Mo2—Se2—Mo1^xiv	127.69 (2)
Se4ⁱ—Mo1—Se2^vi	91.21 (2)	Mo3—Se2—Mo1^xiv	130.42 (3)
Se1ⁱⁱ—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)
Se1ⁱⁱⁱ—Mo1—Se2^vi	97.41 (2)	Mo3—Se2—Na2^xii	65.90 (8)
Mo1ⁱⁱⁱ—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)
Mo1ⁱⁱ—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)
Se4ⁱ—Mo1—Mo2ⁱⁱⁱ	91.163 (16)	Mo2^ix—Se2—Na1^xiii	160.83 (7)
Se1ⁱⁱ—Mo1—Mo2ⁱⁱⁱ	91.320 (19)	Mo1^xiv—Se2—Na1^xiii	102.71 (7)
Se1—Mo1—Mo2ⁱⁱⁱ	135.27 (2)	Na2^xii—Se2—Na1^xiii	99.85 (14)
Se1ⁱⁱⁱ—Mo1—Mo2ⁱⁱⁱ	49.629 (15)	Mo3—Se3—Mo3^viii	63.13 (3)
Mo1ⁱⁱⁱ—Mo1—Mo2ⁱⁱⁱ	99.53 (2)	Mo3—Se3—Na2^viii	157.67 (13)
Mo1^iv—Mo1—Mo2ⁱⁱⁱ	148.233 (15)	Mo3^viii—Se3—Na2^viii	139.20 (13)
Mo1ⁱⁱ—Mo1—Mo2ⁱⁱⁱ	100.519 (16)	Mo3—Se3—Mo2^x	63.33 (2)
Mo1^v—Mo1—Mo2ⁱⁱⁱ	149.644 (19)	Mo3^viii—Se3—Mo2^x	62.236 (19)
Se2^vi—Mo1—Mo2ⁱⁱⁱ	47.784 (15)	Na2^viii—Se3—Mo2^x	121.81 (2)
Se4ⁱ—Mo1—Mo1^vii	87.495 (19)	Mo3—Se3—Mo2	63.33 (2)
Se1ⁱⁱ—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)
Se1ⁱⁱⁱ—Mo1—Mo1^vii	87.18 (2)	Mo2^x—Se3—Mo2	115.04 (3)
Mo1ⁱⁱⁱ—Mo1—Mo1^vii	45.181 (8)	Mo3—Se3—Na2ⁱ	125.24 (11)
Mo1^iv—Mo1—Mo1^vii	45.181 (8)	Mo3^viii—Se3—Na2ⁱ	62.11 (11)
Mo1ⁱⁱ—Mo1—Mo1^vii	44.819 (8)	Na2^viii—Se3—Na2ⁱ	77.1 (2)
Mo1^v—Mo1—Mo1^vii	44.819 (8)	Mo2^x—Se3—Na2ⁱ	91.04 (6)
Se2^vi—Mo1—Mo1^vii	175.25 (3)	Mo2—Se3—Na2ⁱ	91.04 (6)
Mo2ⁱⁱⁱ—Mo1—Mo1^vii	136.78 (2)	Mo1^xv—Se4—Mo1^xiv	64.48 (2)
Se4ⁱ—Mo1—Na2^viii	45.18 (9)	Mo1^xv—Se4—Mo1^ix	64.48 (2)
Se1ⁱⁱ—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)
Se1ⁱⁱⁱ—Mo1—Na2^viii	101.91 (8)	Mo1^xiv—Se4—Na2^xii	94.05 (8)
Mo1ⁱⁱⁱ—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)
Mo1ⁱⁱ—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)
Mo2ⁱⁱⁱ—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.

Selected bond lengths (Å) top

Mo1—Se4ⁱ	2.5287 (7)	Mo2—Mo3	2.7537 (6)
Mo1—Se1ⁱⁱ	2.5600 (6)	Mo3—Se3	2.5586 (11)
Mo1—Se1	2.5810 (7)	Mo3—Se3^v	2.5675 (11)
Mo1—Se1ⁱⁱⁱ	2.6075 (7)	Mo3—Se2	2.6153 (6)
Mo1—Mo1ⁱⁱⁱ	2.6980 (7)	Mo3—Se2^vii	2.6153 (6)
Mo1—Mo1ⁱⁱ	2.7152 (7)	Mo3—Mo3^vi	2.6834 (11)
Mo1—Se2^iv	2.7207 (7)	Se5—Na1	2.848 (6)
Mo2—Se5	2.5220 (7)	Na1—Se2^viii	3.2010 (11)
Mo2—Se2	2.6023 (8)	Na1—Se1^ix	3.462 (2)
Mo2—Mo2^v	2.6311 (7)	Na2—Se3^v	2.657 (5)
Mo2—Se2^vi	2.6312 (8)	Na2—Se4^vii	2.747 (4)
Mo2—Se3	2.6830 (6)	Na2—Se2^x	2.812 (4)
Mo2—Se1	2.7018 (7)	Na2—Se3^xi	3.096 (5)
Mo2—Mo3^vi	2.7153 (6)

Symmetry codes: (i) x+1, y, z; (ii) x−y, x−1, −z+1; (iii) −y+1, x−y−1, z; (iv) −x+y+1, −x, z; (v) −x+y+1, −x+1, z; (vi) −y+1, x−y, z; (vii) x, y, −z+3/2; (viii) −x+1, −y, −z+1; (ix) y+1, −x+y+1, −z+1; (x) −y, x−y, −z+3/2; (xi) x−1, y, z.

Acknowledgements

Intensity data were collected on the Nonius KappaCCD X-ray diffactometer system of the Centre de diffractométrie de l'Université de Rennes I (www.cdifx.univ-rennes1.fr).

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