Na2.9KMo12S14: a novel quaternary reduced molybdenum sulfide containing Mo12 clusters with a channel structure

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

doi:10.1107/S1600536813013603

inorganic compounds

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Volume 69| Part 6| June 2013| Page i38

doi:10.1107/S1600536813013603

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

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

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

(Received 15 April 2013; accepted 17 May 2013; online 25 May 2013)

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).

Related literature

For a previous report on the compounds K_1+xMo₁₂S₁₄ (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 in PLATON (Spek, 2009 ).

Experimental

Crystal data

Na_2.90KMo₁₂S₁₄
M_r = 1705.89
Trigonal, $[P \overline 3_1 c ]$
a = 9.3664 (1) Å
c = 16.2981 (2) Å
V = 1238.26 (2) Å³
Z = 2
Mo Kα radiation
μ = 7.24 mm⁻¹
T = 100 K
0.08 × 0.07 × 0.07 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: analytical (de Meulenaer & Tompa, 1965 ) T_min = 0.550, T_max = 0.572
37291 measured reflections
2536 independent reflections
2376 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.073
S = 1.13
2536 reflections
52 parameters
Δρ_max = 2.74 e Å⁻³
Δρ_min = −1.84 e Å⁻³

Table 1
Selected bond lengths (Å)

Mo1—S3	2.3855 (10)
Mo1—S1ⁱ	2.4620 (8)
Mo1—S1	2.4822 (8)
Mo1—S1ⁱⁱ	2.4944 (8)
Mo1—S2	2.5907 (7)
Mo1—Mo1ⁱⁱⁱ	2.6296 (5)
Mo1—Mo2	2.7155 (4)
Mo1—Mo2ⁱ	2.7803 (4)
Mo2—S1	2.4589 (7)
Mo2—S2	2.4655 (7)
Mo2—S2ⁱⁱⁱ	2.4904 (8)
Mo2—S2^iv	2.5866 (7)
Mo2—Mo2^v	2.6440 (5)
Mo2—Mo2^iv	2.6745 (5)
Mo2—Mo2ⁱ	2.6765 (4)
K1—S3	2.9460 (13)
K1—S2^vi	3.4188 (7)
K1—S2^vii	3.4188 (7)
K1—S2^viii	3.4188 (7)
Na1—S2^ix	3.3131 (17)
Na1—S1^x	3.856 (12)
Na1—S2^xi	3.898 (11)
Na2—S1^xii	3.210 (12)
Na2—S2^xiii	3.56 (2)
Symmetry codes: (i) -x+y+1, -x+1, z; (ii) -x+1, -y, -z; (iii) -y+1, x-y, z; (iv) $[-x+y+1, y, -z+{\script{1\over 2}}]$ ; (v) $[-y+1, -x+1, -z+{\script{1\over 2}}]$ ; (vi) y+1, -x+y+1, -z; (vii) $[-x+1, -x+y+1, z-{\script{1\over 2}}]$ ; (viii) x-y, x, -z; (ix) -x+y, -x, z; (x) -y, x-y-1, z; (xi) $[x, x-y, -z+{\script{1\over 2}}]$ ; (xii) x-1, y, z; (xiii) -y, x-y, z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: COLLECT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813013603/ru2051sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813013603/ru2051Isup2.hkl

checkCIF report

Comment top

In a previous paper, we reported the synthesis, the crystal structures and, the physical properties of the compounds K_{1 +} _xMo₁₂S₁₄ (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 top

For a previous report on the compounds K_{1 +} _xMo₁₂S₁₄ (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).

Experimental top

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.

Computing details top

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 top

	Fig. 1. : View of Na_2.9KMo₁₂S₁₄. 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 Na_2.9KMo₁₂S₁₄ along the c axis showing the channels. Displacement ellipsoids are drawn at the 50% probability level.

Trisodium potassium dodecamolybdenum tetradecasulfide top

Crystal data top

Na_2.90KMo₁₂S₁₄	D_x = 4.575 Mg m⁻³
M_r = 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) Å³	T = 100 K
Z = 2	Multi-faceted crystal, black
F(000) = 1558	0.08 × 0.07 × 0.07 mm

Data collection top

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

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)] = 0.027	w = 1/[σ²(F_o²) + (0.029P)² + 4.9317P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.073	(Δ/σ)_max = 0.001
S = 1.13	Δρ_max = 2.74 e Å⁻³
2536 reflections	Δρ_min = −1.84 e Å⁻³
52 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00032 (9)

Crystal data top

Na_2.90KMo₁₂S₁₄	Z = 2
M_r = 1705.89	Mo Kα radiation
Trigonal, P3₁c	µ = 7.24 mm⁻¹
a = 9.3664 (1) Å	T = 100 K
c = 16.2981 (2) Å	0.08 × 0.07 × 0.07 mm
V = 1238.26 (2) Å³

Data collection top

Nonius KappaCCD diffractometer	2536 independent reflections
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	2376 reflections with I > 2σ(I)
T_min = 0.550, T_max = 0.572	R_int = 0.056
37291 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	52 parameters
wR(F²) = 0.073	0 restraints
S = 1.13	Δρ_max = 2.74 e Å⁻³
2536 reflections	Δρ_min = −1.84 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	0.50983 (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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Mo1—S3	2.3855 (10)	S3—Mo1ⁱⁱⁱ	2.3855 (10)
Mo1—S1ⁱ	2.4620 (8)	S3—Mo1ⁱ	2.3855 (10)
Mo1—S1	2.4822 (8)	K1—S3	2.9460 (13)
Mo1—S1ⁱⁱ	2.4944 (8)	K1—S3^vii	2.9460 (13)
Mo1—S2	2.5907 (7)	K1—S2^viii	3.4188 (7)
Mo1—Mo1ⁱⁱⁱ	2.6296 (5)	K1—S2^ix	3.4188 (7)
Mo1—Mo1ⁱ	2.6296 (5)	K1—S2^x	3.4188 (7)
Mo1—Mo2	2.7155 (4)	K1—S2ⁱⁱ	3.4188 (7)
Mo1—Mo2ⁱ	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—S2ⁱⁱⁱ	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—Mo2ⁱⁱⁱ	2.6765 (4)	Na1—S1^xvii	3.856 (12)
Mo2—Mo2ⁱ	2.6765 (4)	Na1—S1ⁱ	3.856 (12)
Mo2—Mo1ⁱⁱⁱ	2.7803 (4)	Na1—S2^xviii	3.898 (11)
S1—Mo1ⁱⁱⁱ	2.4620 (8)	Na1—S2^xiii	3.898 (11)
S1—Mo1ⁱⁱ	2.4944 (8)	Na1—S2^xix	3.898 (11)
S1—Na2^vi	3.210 (12)	Na2—S1ⁱ	3.210 (12)
S2—Mo2ⁱ	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—K1ⁱⁱ	3.4188 (7)	Na2—S2^xv	3.56 (2)

S3—Mo1—S1ⁱ	92.320 (19)	Mo1ⁱⁱⁱ—S1—Mo1ⁱⁱ	127.81 (3)
S3—Mo1—S1	91.819 (19)	Mo1—S1—Mo1ⁱⁱ	84.55 (3)
S1ⁱ—Mo1—S1	169.89 (3)	Mo2—S1—Na2^vi	99.6 (9)
S3—Mo1—S1ⁱⁱ	89.07 (3)	Mo1ⁱⁱⁱ—S1—Na2^vi	98.08 (6)
S1ⁱ—Mo1—S1ⁱⁱ	93.84 (4)	Mo1—S1—Na2^vi	160.3 (4)
S1—Mo1—S1ⁱⁱ	95.45 (3)	Mo1ⁱⁱ—S1—Na2^vi	114.5 (6)
S3—Mo1—S2	171.28 (3)	Mo2—S2—Mo2ⁱ	65.37 (2)
S1ⁱ—Mo1—S2	84.81 (3)	Mo2—S2—Mo2^iv	63.873 (19)
S1—Mo1—S2	89.74 (2)	Mo2ⁱ—S2—Mo2^iv	62.735 (18)
S1ⁱⁱ—Mo1—S2	99.32 (2)	Mo2—S2—Mo1	64.912 (19)
S3—Mo1—Mo1ⁱⁱⁱ	56.554 (16)	Mo2ⁱ—S2—Mo1	66.315 (19)
S1ⁱ—Mo1—Mo1ⁱⁱⁱ	118.03 (2)	Mo2^iv—S2—Mo1	118.36 (3)
S1—Mo1—Mo1ⁱⁱⁱ	57.50 (2)	Mo2—S2—Na1	154.66 (8)
S1ⁱⁱ—Mo1—Mo1ⁱⁱⁱ	131.58 (2)	Mo2ⁱ—S2—Na1	89.74 (2)
S2—Mo1—Mo1ⁱⁱⁱ	117.822 (17)	Mo2^iv—S2—Na1	101.5 (3)
S3—Mo1—Mo1ⁱ	56.554 (16)	Mo1—S2—Na1	110.7 (3)
S1ⁱ—Mo1—Mo1ⁱ	58.24 (2)	Mo2—S2—K1ⁱⁱ	92.19 (2)
S1—Mo1—Mo1ⁱ	117.29 (2)	Mo2ⁱ—S2—K1ⁱⁱ	150.01 (3)
S1ⁱⁱ—Mo1—Mo1ⁱ	130.870 (19)	Mo2^iv—S2—K1ⁱⁱ	90.10 (2)
S2—Mo1—Mo1ⁱ	115.293 (18)	Mo1—S2—K1ⁱⁱ	123.66 (3)
Mo1ⁱⁱⁱ—Mo1—Mo1ⁱ	60.0	Na1—S2—K1ⁱⁱ	109.13 (14)
S3—Mo1—Mo2	119.13 (2)	Mo1ⁱⁱⁱ—S3—Mo1	66.89 (3)
S1ⁱ—Mo1—Mo2	113.78 (2)	Mo1ⁱⁱⁱ—S3—Mo1ⁱ	66.89 (3)
S1—Mo1—Mo2	56.254 (17)	Mo1—S3—Mo1ⁱ	66.89 (3)
S1ⁱⁱ—Mo1—Mo2	137.91 (2)	Mo1ⁱⁱⁱ—S3—K1	140.47 (2)
S2—Mo1—Mo2	55.315 (17)	Mo1—S3—K1	140.47 (2)
Mo1ⁱⁱⁱ—Mo1—Mo2	62.662 (9)	Mo1ⁱ—S3—K1	140.47 (2)
Mo1ⁱ—Mo1—Mo2	91.183 (8)	S3—K1—S3^vii	180.0
S3—Mo1—Mo2ⁱ	116.65 (2)	S3—K1—S2^viii	70.407 (11)
S1ⁱ—Mo1—Mo2ⁱ	55.546 (18)	S3^vii—K1—S2^viii	109.593 (11)
S1—Mo1—Mo2ⁱ	114.41 (2)	S3—K1—S2^ix	109.593 (11)
S1ⁱⁱ—Mo1—Mo2ⁱ	138.42 (2)	S3^vii—K1—S2^ix	70.407 (11)
S2—Mo1—Mo2ⁱ	55.112 (17)	S2^viii—K1—S2^ix	171.43 (2)
Mo1ⁱⁱⁱ—Mo1—Mo2ⁱ	89.759 (7)	S3—K1—S2^x	109.593 (11)
Mo1ⁱ—Mo1—Mo2ⁱ	60.181 (8)	S3^vii—K1—S2^x	70.407 (11)
Mo2—Mo1—Mo2ⁱ	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—S2ⁱⁱⁱ	87.06 (3)	S3—K1—S2ⁱⁱ	70.407 (11)
S2—Mo2—S2ⁱⁱⁱ	173.83 (2)	S3^vii—K1—S2ⁱⁱ	109.593 (11)
S1—Mo2—S2^iv	117.76 (2)	S2^viii—K1—S2ⁱⁱ	109.349 (11)
S2—Mo2—S2^iv	90.68 (3)	S2^ix—K1—S2ⁱⁱ	63.43 (2)
S2ⁱⁱⁱ—Mo2—S2^iv	94.62 (3)	S2^x—K1—S2ⁱⁱ	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)
S2ⁱⁱⁱ—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)	S2ⁱⁱ—K1—S2^xi	171.43 (2)
S2ⁱⁱⁱ—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—Mo2ⁱⁱⁱ	115.260 (19)	S2^ix—K1—S2^xii	78.22 (2)
S2—Mo2—Mo2ⁱⁱⁱ	117.738 (19)	S2^x—K1—S2^xii	171.43 (2)
S2ⁱⁱⁱ—Mo2—Mo2ⁱⁱⁱ	56.865 (19)	S2ⁱⁱ—K1—S2^xii	109.349 (11)
S2^iv—Mo2—Mo2ⁱⁱⁱ	117.009 (17)	S2^xi—K1—S2^xii	63.43 (2)
Mo2^v—Mo2—Mo2ⁱⁱⁱ	60.350 (10)	Na2—Na1—Na1^xiii	180.000 (2)
Mo2^iv—Mo2—Mo2ⁱⁱⁱ	89.670 (5)	Na2—Na1—S2^xiv	86.1 (4)
S1—Mo2—Mo2ⁱ	119.02 (2)	Na1^xiii—Na1—S2^xiv	93.9 (4)
S2—Mo2—Mo2ⁱ	57.760 (19)	Na2—Na1—S2	86.1 (4)
S2ⁱⁱⁱ—Mo2—Mo2ⁱ	116.843 (19)	Na1^xiii—Na1—S2	93.9 (4)
S2^iv—Mo2—Mo2ⁱ	115.061 (17)	S2^xiv—Na1—S2	119.54 (9)
Mo2^v—Mo2—Mo2ⁱ	90.323 (5)	Na2—Na1—S2^xv	86.1 (4)
Mo2^iv—Mo2—Mo2ⁱ	59.222 (10)	Na1^xiii—Na1—S2^xv	93.9 (4)
Mo2ⁱⁱⁱ—Mo2—Mo2ⁱ	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)
S2ⁱⁱⁱ—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)
Mo2ⁱⁱⁱ—Mo2—Mo1	90.180 (8)	Na1—Na2—S1ⁱ	102.6 (9)
Mo2ⁱ—Mo2—Mo1	62.075 (8)	Na1—Na2—S1^xvii	102.6 (9)
S1—Mo2—Mo1ⁱⁱⁱ	55.650 (19)	S1ⁱ—Na2—S1^xvii	115.4 (7)
S2—Mo2—Mo1ⁱⁱⁱ	116.776 (19)	Na1—Na2—S1^xvi	102.6 (9)
S2ⁱⁱⁱ—Mo2—Mo1ⁱⁱⁱ	58.573 (17)	S1ⁱ—Na2—S1^xvi	115.4 (7)
S2^iv—Mo2—Mo1ⁱⁱⁱ	151.11 (2)	S1^xvii—Na2—S1^xvi	115.4 (7)
Mo2^v—Mo2—Mo1ⁱⁱⁱ	110.082 (13)	Na1—Na2—Na2^xx	180.000 (2)
Mo2^iv—Mo2—Mo1ⁱⁱⁱ	144.903 (10)	S1ⁱ—Na2—Na2^xx	77.4 (9)
Mo2ⁱⁱⁱ—Mo2—Mo1ⁱⁱⁱ	59.650 (8)	S1^xvii—Na2—Na2^xx	77.4 (9)
Mo2ⁱ—Mo2—Mo1ⁱⁱⁱ	88.804 (7)	S1^xvi—Na2—Na2^xx	77.4 (9)
Mo1—Mo2—Mo1ⁱⁱⁱ	57.157 (12)	Na1—Na2—Na1^xiii	0.000 (1)
Mo2—S1—Mo1ⁱⁱⁱ	68.80 (2)	S1ⁱ—Na2—Na1^xiii	102.6 (9)
Mo2—S1—Mo1	66.67 (2)	S1^xvii—Na2—Na1^xiii	102.6 (9)
Mo1ⁱⁱⁱ—S1—Mo1	64.26 (2)	S1^xvi—Na2—Na1^xiii	102.6 (9)
Mo2—S1—Mo1ⁱⁱ	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.

Experimental details

Crystal data
Chemical formula	Na_2.90KMo₁₂S₁₄
M_r	1705.89
Crystal system, space group	Trigonal, P3₁c
Temperature (K)	100
a, c (Å)	9.3664 (1), 16.2981 (2)
V (Å³)	1238.26 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	7.24
Crystal size (mm)	0.08 × 0.07 × 0.07

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Analytical (de Meulenaer & Tompa, 1965)
T_min, T_max	0.550, 0.572
No. of measured, independent and observed [I > 2σ(I)] reflections	37291, 2536, 2376
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.900

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.13
No. of reflections	2536
No. of parameters	52
Δρ_max, Δρ_min (e Å⁻³)	2.74, −1.84

Computer programs: COLLECT (Nonius, 1998), EVALCCD (Duisenberg, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Bergerhoff, 1996).

Selected bond lengths (Å) top

Mo1—S3	2.3855 (10)	Mo2—Mo2^v	2.6440 (5)
Mo1—S1ⁱ	2.4620 (8)	Mo2—Mo2^iv	2.6745 (5)
Mo1—S1	2.4822 (8)	Mo2—Mo2ⁱ	2.6765 (4)
Mo1—S1ⁱⁱ	2.4944 (8)	K1—S3	2.9460 (13)
Mo1—S2	2.5907 (7)	K1—S2^vi	3.4188 (7)
Mo1—Mo1ⁱⁱⁱ	2.6296 (5)	K1—S2^vii	3.4188 (7)
Mo1—Mo2	2.7155 (4)	K1—S2^viii	3.4188 (7)
Mo1—Mo2ⁱ	2.7803 (4)	Na1—S2^ix	3.3131 (17)
Mo2—S1	2.4589 (7)	Na1—S1^x	3.856 (12)
Mo2—S2	2.4655 (7)	Na1—S2^xi	3.898 (11)
Mo2—S2ⁱⁱⁱ	2.4904 (8)	Na2—S1^xii	3.210 (12)
Mo2—S2^iv	2.5866 (7)	Na2—S2^xiii	3.56 (2)

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) y+1, −x+y+1, −z; (vii) −x+1, −x+y+1, z−1/2; (viii) x−y, x, −z; (ix) −x+y, −x, z; (x) −y, x−y−1, z; (xi) x, x−y, −z+1/2; (xii) x−1, y, z; (xiii) −y, x−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).

References

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