Crystal structure of Sc1.91In1.39Mo15Se19, containing Mo6 and Mo9 clusters

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

doi:10.1107/S2056989015010634

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Volume 71| Part 7| July 2015| Pages 760-762

doi:10.1107/S2056989015010634

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Crystal structure of Sc_1.91In_1.39Mo₁₅Se₁₉, containing Mo₆ and Mo₉ clusters

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

^aSciences Chimiques de Rennes, UMR CNRS No. 6226, Université de Rennes I - INSA Rennes, Avenue du Général Leclerc, 35042 Rennes CEDEX, France
^*Correspondence e-mail: Patrick.Gougeon@univ-rennes1.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 20 May 2015; accepted 2 June 2015; online 10 June 2015)

The structure of scandium indium pentadecamolybdenum nonadecaselenide, Sc_1.91In_1.39Mo₁₅Se₁₉, is isotypic with In_2.9Mo₁₅Se₁₉ [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. Sc—Se and In—Se bonds complete the structural set-up. In the title compound, the Sc³⁺ cations replace the trivalent indium atoms present in In_2.9Mo₁₅Se₁₉, and a deficiency is observed at the monovalent indium site. One Mo, one Se and the Sc atom are situated on mirror planes, whereas two other Se atoms and the In atom are situated on threefold rotation axes.

Keywords: crystal structure; Mo clusters; reduced molybdenum selenide; monovalent indium.

CCDC reference: 1404496

1. Chemical context

From a crystal–chemical point of view, reduced molybdenum selenides In₃Mo₁₅Se₁₉ (Grüttner et al., 1979) constitute an interesting family of compounds. Indeed, their crystal structures contain an equal mixture of Mo₆ and Mo₉ cluster units with the In atoms occupying two crystallographically different positions depending on their formal oxidation state of +1 or +3. Interest in these Mo cluster compounds also lies in their physical properties because they become superconductors with high critical magnetic fields at about 4 K (Seeber et al., 1979 ). Recently, we have shown that the In³⁺ cation can be replaced by other trivalent cations such as Ho³⁺ (resulting in a compound with composition Ho_0.76In_1.68Mo₁₅Se₁₉; Salloum et al., 2006 ) or V³⁺ (V_1.42In_1.83Mo₁₅Se₁₉; Gougeon et al., 2010 ), and the In⁺ cation by K⁺ (In_0.87K₂Mo₁₅Se₁₉; Salloum et al., 2007 ). We present here the crystal structure of Sc_1.91In_1.39Mo₁₅Se₁₉ in which scandium atoms replace the trivalent indium atoms.

2. Structural commentary

The Mo–Se framework of the title compound consists of the cluster units Mo₆Seⁱ₈Se^a₆ and Mo₉Seⁱ₁₁Se^a₆ in an 1:1 ratio (for details of the i- and a-type ligand notation, see: Schäfer & von Schnering, 1964 ). Both cluster units are interconnected through additional Mo—Se bonds (Table 1, 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 2b and 2c and have point-group symmetry $[\overline{3}]$ and $[\overline{6}]$ , respectively. The Mo—Mo distances within the Mo₆ cluster are 2.6995 (6) Å for the distances of the Mo triangles formed by the Mo1 atoms related through the threefold axis, and 2.7179 (5) Å for the distances between these triangles. The Mo—Mo distances within the Mo₉ clusters are 2.6460 (6) and 2.7127 (8) Å in the triangles formed by the atoms Mo2 and Mo3, respectively, and 2.7196 (4) and 2.7675 (4) 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 lengths range from 2.5480 (6) to 2.6531 (5) Å within the Mo₆Seⁱ₈Se^a₆ unit, and from 2.5290 (6) to 2.6966 (4) Å within the Mo₉Seⁱ₁₁Se^a₆ unit. Each Mo₉Seⁱ₁₁Se^a₆ cluster is interconnected by six Mo₆Seⁱ₈Se^a₆ units (and vice versa) via Mo2—Se1 bonds (and Mo1—Se2 bonds, respectively), forming the three-dimensional Mo–Se framework, the connectivity 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 3.4361 (5) Å, indicating only weak metal⋯metal interactions.

Table 1
Selected bond lengths (Å)

Mo1—Se4	2.5480 (6)	Mo3—Se2	2.5780 (5)
Mo1—Se1ⁱ	2.5488 (5)	Mo3—Se3ⁱⁱⁱ	2.5884 (7)
Mo1—Se1	2.5749 (5)	Mo3—Se3	2.5900 (7)
Mo1—Se1ⁱⁱ	2.6145 (5)	Mo3—Mo3ⁱⁱⁱ	2.7127 (8)
Mo1—Se2	2.6531 (5)	In—Se5	3.0662 (13)
Mo1—Mo1ⁱⁱ	2.6995 (6)	In—Se2^vii	3.1273 (4)
Mo1—Mo1ⁱ	2.7179 (5)	In—Se2^viii	3.1273 (4)
Mo2—Se5	2.5290 (6)	In—Se2ⁱ	3.1273 (4)
Mo2—Se2	2.5931 (5)	In—Se1^vii	3.4912 (6)
Mo2—Se2ⁱⁱⁱ	2.6275 (5)	In—Se1ⁱ	3.4912 (6)
Mo2—Mo2^iv	2.6460 (6)	In—Se1^viii	3.4912 (6)
Mo2—Se1^v	2.6581 (5)	Sc—Se4^vi	2.5691 (15)
Mo2—Se3ⁱⁱⁱ	2.6965 (4)	Sc—Se3ⁱⁱ	2.696 (2)
Mo2—Mo3ⁱⁱⁱ	2.7196 (4)	Sc—Se2^ix	2.8056 (12)
Mo2—Mo3	2.7675 (4)	Sc—Se2^x	2.8056 (12)
Mo3—Se2^vi	2.5780 (5)	Sc—Se3^ix	2.931 (2)
Symmetry codes: (i) x-y, x, -z+1; (ii) -y, x-y, z; (iii) -y+1, x-y, z; (iv) -x+y+1, -x+1, z; (v) -x+y+1, -x, z; (vi) $[x, y, -z+{\script{3\over 2}}]$ ; (vii) -x+1, -y, -z+1; (viii) y+1, -x+y+1, -z+1; (ix) -x+y, -x, z; (x) $[-x+y, -x, -z+{\script{3\over 2}}]$ .

Figure 1
View of the crystal structure of Sc_1.91In_1.39Mo₁₅Se₁₉ along [110]. Displacement ellipsoids are drawn at the 97% probability level.

Figure 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.

Comparison of the Mo—Mo and Mo—Se distances with those of the other substituted compounds Ho_0.76In_1.68Mo₁₅Se₁₉, In_0.87K₂Mo₁₅Se₁₉ and V_1.42In_1.83Mo₁₅Se₁₉ does not reveal great differences although the cationic charges are different in the four compounds. The In⁺ cations are surrounded by seven Se atoms, forming a distorted tricapped tetrahedron as in In_2.9Mo₁₅Se₁₉. The Se5 and Se2 atoms forming the tetrahedron are at 3.0662 (13) and 3.1273 (4) Å from the In⁺ cation, and the capping Se1 atoms are at 3.4912 (6) Å. While in In_2.9Mo₁₅Se₁₉ the monovalent In site is fully occupied, in the title compound it is only has 69.5 (3)% occupancy. This deficiency probably results from the higher temperature used during the crystal-growth process, which led to a loss of indium and selenium because of the high volatility of these elements at 1773 K. The Sc³⁺ cations, as the In³⁺ cations in the In₃Mo₁₅Se₁₉ compounds, occupy partially at 63.8 (6)% a triangular group of distorted octahedral cavities, which are formed by two Mo₆Seⁱ₈Se^a₆ and three Mo₉Seⁱ₁₁Se^a₆ units, around the threefold rotation axis. The Sc—Se distances are in the 2.5691 (15)–2.931 (2) Å range.

3. Synthesis and crystallization

Single crystals of Sc_1.91In_1.39Mo₁₅Se₁₉ were obtained from a mixture of Sc₂Se₃, MoSe₂, InSe and Mo with a nominal composition Sc₂In₂Mo₁₅Se₁₉. Before use, Mo powder was reduced under H₂ flowing gas at 1273 K for ten h in order to eliminate any trace of oxygen. The binaries Sc₂Se₃, MoSe₂, InSe were obtained by heating stoichiometric mixtures of the elements in sealed evacuated silica tubes for about two days. All handling of materials was performed in an argon-filled glove box. 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⁻¹ up to 1773 K, the temperature which was held for 48 h, then cooled at 100 K h⁻¹ down to 1373 K and finally furnace cooled.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The highest and lowest remaining electron densities are located 0.66 and 0.62 Å from the In site, respectively. Refinement of the occupancy factors of the Sc and In atoms led to the final composition Sc_1.914 (12)In_1.390 (6)Mo₁₅Se₁₉.

Table 2
Experimental details

Crystal data
Chemical formula	Sc_1.91In_1.39Mo₁₅Se₁₉
M_r	3185.04
Crystal system, space group	Hexagonal, P6₃/m
Temperature (K)	293
a, c (Å)	9.7530 (2), 19.3977 (2)
V (Å³)	1597.93 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	28.65
Crystal size (mm)	0.06 × 0.05 × 0.04

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Analytical (de Meulenaar & Tompa, 1965 )
T_min, T_max	0.279, 0.424
No. of measured, independent and observed [I > 2σ(I)] reflections	31413, 2414, 1847
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.063, 1.08
No. of reflections	2414
No. of parameters	67
Δρ_max, Δρ_min (e Å⁻³)	2.22, −1.97
Computer programs: COLLECT (Nonius, 1998 ), EVALCCD (Duisenberg et al., 2003 ), SIR97 (Altomare et al., 1999 ), SHELXL2014/6 (Sheldrick, 2015 ) and DIAMOND (Bergerhoff, 1996 ).

Supporting information

CCDC reference: 1404496

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015010634/wm5164sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015010634/wm5164Isup2.hkl

checkCIF report

Chemical context top

From a crystal–chemical point of view, reduced molybdenum selenides In_~3Mo₁₅Se₁₉ (Grüttner et al., 1979) constitute an interesting family of compounds. Indeed, their crystal structures contain an equal mixture of Mo₆ and Mo₉ cluster units with the In atoms occupying two crystallographically different positions depending on their formal oxidation state of +1 or +3. Interest in these Mo cluster compounds also lies in their physical properties because they become superconductors with high critical magnetic fields at about 4 K (Seeber et al., 1979). Recently, we have shown that the In³⁺ cation can be replaced by other trivalent cations such as Ho³⁺ (resulting in a compound with composition Ho_0.76In_1.68Mo₁₅Se₁₉; Salloum et al., 2006) or V³⁺ (V_1.42In_1.83Mo₁₅Se₁₉; Gougeon et al., 2010), and the In⁺ cation by K⁺ (In_0.87K₂Mo₁₅Se₁₉; Salloum et al., 2007). We present here the crystal structure of Sc_1.91In_1.39Mo₁₅Se₁₉ in which scandium atoms replace the trivalent indium atoms.

Structural commentary top

The Mo–Se framework of the title compound consists of the cluster units Mo₆Seⁱ₈Se^a₆ and Mo₉Seⁱ₁₁Se^a₆ in an 1:1 ratio (for details of the i- and a-type ligand notation, see: Schäfer & von Schnering, 1964). Both cluster units are interconnected through additional Mo—Se bonds (Table 1, 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 2b and 2c and have point-group symmetry 3 and 6, respectively. The Mo—Mo distances within the Mo₆ cluster are 2.6995 (6) Å for the distances of the Mo triangles formed by the Mo1 atoms related through the threefold axis, and 2.7179 (5) Å for the distances between these triangles. The Mo—Mo distances within the Mo₉ clusters are 2.6460 (6) and 2.7127 (8) Å in the triangles formed by the atoms Mo2 and Mo3, respectively, and 2.7196 (4) and 2.7675 (4) 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 lengths range from 2.5480 (6) to 2.6531 (5) Å within the Mo₆Seⁱ₈Se^a₆ unit, and from 2.5290 (6) to 2.6966 (4) Å within the Mo₉Seⁱ₁₁Se^a₆ unit. Each Mo₉Seⁱ₁₁Se^a₆ cluster is interconnected by six Mo₆Seⁱ₈Se^a₆ units (and vice versa) via Mo2—Se1 bonds (and Mo1—Se2 bonds, respectively), forming the three-dimensional Mo–Se framework, the connectivity formula of which is Mo₉Seⁱ₅Se^i-a_6/2Se^-ai_6/2, Mo₆Seⁱ₂Se^i-a_6/2Se^a-i_6/2. It results from this arrangement that the shortest intercluster Mo1—Mo2 distance is 3.4361 (5) Å, indicating only weak metal···metal interactions.

Synthesis and crystallization top

Single crystals of Sc_1.91In_1.39Mo₁₅Se₁₉ were prepared from a mixture of Sc₂Se₃, MoSe₂, InSe and Mo with a nominal composition Sc₂In₂Mo₁₅Se₁₉. Before use, Mo powder was reduced under H₂ flowing gas at 1273 K for ten hours in order to eliminate any trace of oxygen. The binaries Sc₂Se₃, MoSe₂, InSe were obtained by heating stoichiometric mixtures of the elements in sealed evacuated silica tubes for about two days. All handling of materials was performed in an argon-filled glove box. 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^-1 up to 1773 K, the temperature which was held for 48 hours, then cooled at 100 K h^-1 down to 1373 K and finally furnace cooled.

Refinement top

Related literature top

For related literature, see: Gougeon et al. (2010); Grüttner et al. (1979); Salloum et al. (2006, 2007); Schäfer & von Schnering (1964); Seeber et al. (1979).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT (Nonius, 1998); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL2014/6 (Sheldrick, 2015).

Figures top

	Fig. 1. View of the crystal structure of Sc_1.91In_1.39Mo₁₅Se₁₉ 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.

Scandium indium pentadecamolybdenum nonadecaselenide top

Crystal data top

Sc_1.91In_1.39Mo₁₅Se₁₉	F(000) = 2769
M_r = 3185.04	D_x = 6.620 Mg m⁻³
Hexagonal, P6₃/m	Mo Kα radiation, λ = 0.71069 Å
a = 9.7530 (2) Å	µ = 28.65 mm⁻¹
c = 19.3977 (2) Å	T = 293 K
V = 1597.93 (7) Å³	Irregular block, black
Z = 2	0.06 × 0.05 × 0.04 mm

Data collection top

Nonius KappaCCD diffractometer	2414 independent reflections
Radiation source: fine-focus sealed tube	1847 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
ϕ scans (κ = 0) + additional ω scans	θ_max = 35.0°, θ_min = 2.4°
Absorption correction: analytical (de Meulenaar & Tompa, 1965)	h = −13→15
T_min = 0.279, T_max = 0.424	k = −15→13
31413 measured reflections	l = −31→26

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0228P)² + 7.5263P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.031	(Δ/σ)_max = 0.002
wR(F²) = 0.063	Δρ_max = 2.22 e Å⁻³
S = 1.08	Δρ_min = −1.96 e Å⁻³
2414 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
67 parameters	Extinction coefficient: 0.00065 (4)

Crystal data top

Sc_1.91In_1.39Mo₁₅Se₁₉	Z = 2
M_r = 3185.04	Mo Kα radiation
Hexagonal, P6₃/m	µ = 28.65 mm⁻¹
a = 9.7530 (2) Å	T = 293 K
c = 19.3977 (2) Å	0.06 × 0.05 × 0.04 mm
V = 1597.93 (7) Å³

Data collection top

Nonius KappaCCD diffractometer	2414 independent reflections
Absorption correction: analytical (de Meulenaar & Tompa, 1965)	1847 reflections with I > 2σ(I)
T_min = 0.279, T_max = 0.424	R_int = 0.073
31413 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	67 parameters
wR(F²) = 0.063	0 restraints
S = 1.08	Δρ_max = 2.22 e Å⁻³
2414 reflections	Δρ_min = −1.96 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	0.16732 (4)	0.01628 (4)	0.55740 (2)	0.00813 (7)
Mo2	0.68442 (4)	0.18633 (4)	0.63321 (2)	0.00769 (7)
Mo3	0.51261 (5)	0.16694 (5)	0.7500	0.00748 (8)
Se1	0.03573 (5)	−0.28735 (5)	0.55124 (2)	0.01007 (8)
Se2	0.37937 (5)	0.00705 (5)	0.64001 (2)	0.01114 (9)
Se3	0.34923 (7)	0.30997 (7)	0.7500	0.01107 (11)
Se4	0.0000	0.0000	0.66131 (3)	0.01933 (16)
Se5	0.6667	0.3333	0.52931 (3)	0.01116 (13)
In	0.6667	0.3333	0.37124 (6)	0.0358 (4)	0.695 (3)
Sc	−0.2115 (2)	−0.1745 (2)	0.7500	0.0143 (5)	0.638 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01005 (15)	0.00828 (15)	0.00598 (13)	0.00453 (12)	0.00026 (9)	0.00006 (9)
Mo2	0.00846 (14)	0.00829 (14)	0.00626 (12)	0.00415 (12)	−0.00015 (9)	−0.00030 (9)
Mo3	0.0087 (2)	0.0085 (2)	0.00563 (16)	0.00458 (16)	0.000	0.000
Se1	0.01139 (18)	0.00980 (18)	0.00960 (15)	0.00572 (15)	0.00112 (12)	0.00197 (12)
Se2	0.00992 (18)	0.01101 (19)	0.01187 (16)	0.00477 (14)	−0.00272 (12)	−0.00153 (12)
Se3	0.0098 (3)	0.0142 (3)	0.0104 (2)	0.0069 (2)	0.000	0.000
Se4	0.0264 (3)	0.0264 (3)	0.0053 (3)	0.01318 (13)	0.000	0.000
Se5	0.0136 (2)	0.0136 (2)	0.0063 (2)	0.00679 (10)	0.000	0.000
In	0.0355 (5)	0.0355 (5)	0.0363 (6)	0.0178 (2)	0.000	0.000
Sc	0.0176 (10)	0.0064 (8)	0.0159 (8)	0.0038 (7)	0.000	0.000

Geometric parameters (Å, º) top

Mo1—Se4	2.5480 (6)	Se3—Scⁱⁱ	2.931 (2)
Mo1—Se1ⁱ	2.5488 (5)	Se4—Mo1ⁱⁱⁱ	2.5479 (6)
Mo1—Se1	2.5749 (5)	Se4—Mo1ⁱⁱ	2.5479 (6)
Mo1—Se1ⁱⁱ	2.6145 (5)	Se4—Scⁱⁱⁱ	2.5691 (15)
Mo1—Se2	2.6531 (5)	Se4—Scⁱⁱ	2.5691 (15)
Mo1—Mo1ⁱⁱ	2.6995 (6)	Se4—Sc	2.5691 (15)
Mo1—Mo1ⁱⁱⁱ	2.6995 (6)	Se5—Mo2^v	2.5290 (6)
Mo1—Mo1ⁱ	2.7179 (5)	Se5—Mo2^vi	2.5290 (6)
Mo1—Mo1^iv	2.7179 (5)	In—Se5	3.0662 (13)
Mo2—Se5	2.5290 (6)	In—Se2^xi	3.1273 (4)
Mo2—Se2	2.5931 (5)	In—Se2^xii	3.1273 (4)
Mo2—Se2^v	2.6275 (5)	In—Se2ⁱ	3.1273 (4)
Mo2—Mo2^vi	2.6460 (6)	In—Se1^xi	3.4912 (6)
Mo2—Mo2^v	2.6460 (6)	In—Se1ⁱ	3.4912 (6)
Mo2—Se1^vii	2.6581 (5)	In—Se1^xii	3.4912 (6)
Mo2—Se3^v	2.6965 (4)	In—Se3^iv	4.2657 (8)
Mo2—Mo3^v	2.7196 (4)	In—Se3^xiii	4.2657 (8)
Mo2—Mo3	2.7675 (4)	In—Se3^xiv	4.2657 (8)
Mo3—Se2^viii	2.5780 (5)	In—Sc^xv	4.5565 (18)
Mo3—Se2	2.5780 (5)	In—Sc^xvi	4.5565 (18)
Mo3—Se3^v	2.5884 (7)	In—Sc^xvii	4.5565 (18)
Mo3—Se3	2.5900 (7)	Sc—Se4^viii	2.5691 (15)
Mo3—Mo3^v	2.7127 (8)	Sc—Se3ⁱⁱ	2.696 (2)
Mo3—Mo3^vi	2.7127 (8)	Sc—Se2ⁱⁱⁱ	2.8056 (12)
Mo3—Mo2^ix	2.7196 (4)	Sc—Se2^xviii	2.8056 (12)
Mo3—Mo2^vi	2.7196 (4)	Sc—Mo3ⁱⁱⁱ	2.8760 (18)
Mo3—Mo2^viii	2.7675 (4)	Sc—Se3ⁱⁱⁱ	2.931 (2)
Mo3—Scⁱⁱ	2.8760 (18)	Sc—Scⁱⁱⁱ	3.305 (3)
Se1—Mo1^iv	2.5488 (5)	Sc—Scⁱⁱ	3.305 (3)
Se1—Mo1ⁱⁱⁱ	2.6145 (5)	Sc—Mo1^xviii	3.7775 (4)
Se1—Mo2^x	2.6581 (5)	Sc—Mo1ⁱⁱⁱ	3.7775 (4)
Se2—Mo2^vi	2.6275 (5)	Sc—Mo2^x	4.0216 (15)
Se2—Scⁱⁱ	2.8056 (12)	Sc—Mo2^xix	4.0216 (15)
Se3—Mo3^vi	2.5884 (7)	Sc—Se1^xviii	4.3993 (10)
Se3—Mo2^ix	2.6966 (4)	Sc—Se1ⁱⁱⁱ	4.3993 (10)
Se3—Mo2^vi	2.6966 (4)	Sc—In^xvi	4.5564 (18)
Se3—Scⁱⁱⁱ	2.696 (2)

Se4—Mo1—Se1ⁱ	176.406 (19)	Mo2^ix—Mo3—Mo2	145.97 (2)
Se4—Mo1—Se1	91.698 (13)	Mo2^vi—Mo3—Mo2	57.653 (13)
Se1ⁱ—Mo1—Se1	89.030 (13)	Se2^viii—Mo3—Mo2^viii	57.907 (12)
Se4—Mo1—Se1ⁱⁱ	90.788 (13)	Se2—Mo3—Mo2^viii	145.46 (2)
Se1ⁱ—Mo1—Se1ⁱⁱ	88.161 (13)	Se3^v—Mo3—Mo2^viii	60.349 (12)
Se1—Mo1—Se1ⁱⁱ	174.05 (2)	Se3—Mo3—Mo2^viii	118.538 (13)
Se4—Mo1—Se2	90.338 (16)	Mo3^v—Mo3—Mo2^viii	59.495 (13)
Se1ⁱ—Mo1—Se2	93.220 (16)	Mo3^vi—Mo3—Mo2^viii	88.794 (12)
Se1—Mo1—Se2	86.430 (16)	Mo2^ix—Mo3—Mo2^viii	57.654 (13)
Se1ⁱⁱ—Mo1—Se2	98.964 (16)	Mo2^vi—Mo3—Mo2^viii	145.97 (2)
Se4—Mo1—Mo1ⁱⁱ	58.012 (9)	Mo2—Mo3—Mo2^viii	109.89 (2)
Se1ⁱ—Mo1—Mo1ⁱⁱ	118.654 (14)	Se2^viii—Mo3—Scⁱⁱ	61.629 (19)
Se1—Mo1—Mo1ⁱⁱ	119.304 (17)	Se2—Mo3—Scⁱⁱ	61.629 (19)
Se1ⁱⁱ—Mo1—Mo1ⁱⁱ	57.940 (16)	Se3^v—Mo3—Scⁱⁱ	118.59 (5)
Se2—Mo1—Mo1ⁱⁱ	137.271 (14)	Se3—Mo3—Scⁱⁱ	64.60 (4)
Se4—Mo1—Mo1ⁱⁱⁱ	58.012 (9)	Mo3^v—Mo3—Scⁱⁱ	177.02 (5)
Se1ⁱ—Mo1—Mo1ⁱⁱⁱ	119.634 (13)	Mo3^vi—Mo3—Scⁱⁱ	122.98 (5)
Se1—Mo1—Mo1ⁱⁱⁱ	59.376 (17)	Mo2^ix—Mo3—Scⁱⁱ	91.85 (3)
Se1ⁱⁱ—Mo1—Mo1ⁱⁱⁱ	117.870 (16)	Mo2^vi—Mo3—Scⁱⁱ	91.85 (3)
Se2—Mo1—Mo1ⁱⁱⁱ	129.426 (16)	Mo2—Mo3—Scⁱⁱ	119.536 (18)
Mo1ⁱⁱ—Mo1—Mo1ⁱⁱⁱ	60.0	Mo2^viii—Mo3—Scⁱⁱ	119.536 (18)
Se4—Mo1—Mo1ⁱ	118.212 (12)	Mo1^iv—Se1—Mo1	64.071 (16)
Se1ⁱ—Mo1—Mo1ⁱ	58.430 (15)	Mo1^iv—Se1—Mo1ⁱⁱⁱ	63.509 (16)
Se1—Mo1—Mo1ⁱ	117.048 (15)	Mo1—Se1—Mo1ⁱⁱⁱ	62.685 (17)
Se1ⁱⁱ—Mo1—Mo1ⁱ	57.068 (11)	Mo1^iv—Se1—Mo2^x	131.401 (19)
Se2—Mo1—Mo1ⁱ	140.439 (16)	Mo1—Se1—Mo2^x	128.246 (18)
Mo1ⁱⁱ—Mo1—Mo1ⁱ	60.224 (8)	Mo1ⁱⁱⁱ—Se1—Mo2^x	81.335 (15)
Mo1ⁱⁱⁱ—Mo1—Mo1ⁱ	90.0	Mo3—Se2—Mo2	64.712 (15)
Se4—Mo1—Mo1^iv	118.212 (12)	Mo3—Se2—Mo2^vi	62.984 (14)
Se1ⁱ—Mo1—Mo1^iv	59.423 (15)	Mo2—Se2—Mo2^vi	60.903 (17)
Se1—Mo1—Mo1^iv	57.499 (11)	Mo3—Se2—Mo1	130.17 (2)
Se1ⁱⁱ—Mo1—Mo1^iv	116.606 (15)	Mo2—Se2—Mo1	126.687 (18)
Se2—Mo1—Mo1^iv	132.232 (15)	Mo2^vi—Se2—Mo1	81.187 (15)
Mo1ⁱⁱ—Mo1—Mo1^iv	90.0	Mo3—Se2—Scⁱⁱ	64.42 (3)
Mo1ⁱⁱⁱ—Mo1—Mo1^iv	60.224 (8)	Mo2—Se2—Scⁱⁱ	129.13 (3)
Mo1ⁱ—Mo1—Mo1^iv	59.550 (15)	Mo2^vi—Se2—Scⁱⁱ	95.44 (4)
Se5—Mo2—Se2	92.412 (13)	Mo1—Se2—Scⁱⁱ	87.53 (3)
Se5—Mo2—Se2^v	91.604 (13)	Mo3^vi—Se3—Mo3	63.18 (2)
Se2—Mo2—Se2^v	174.13 (2)	Mo3^vi—Se3—Mo2^ix	63.118 (13)
Se5—Mo2—Mo2^vi	58.457 (9)	Mo3—Se3—Mo2^ix	61.881 (13)
Se2—Mo2—Mo2^vi	60.191 (17)	Mo3^vi—Se3—Mo2^vi	63.118 (13)
Se2^v—Mo2—Mo2^vi	118.823 (16)	Mo3—Se3—Mo2^vi	61.881 (14)
Se5—Mo2—Mo2^v	58.457 (9)	Mo2^ix—Se3—Mo2^vi	114.31 (2)
Se2—Mo2—Mo2^v	120.106 (17)	Mo3^vi—Se3—Scⁱⁱⁱ	162.59 (5)
Se2^v—Mo2—Mo2^v	58.906 (16)	Mo3—Se3—Scⁱⁱⁱ	134.23 (5)
Mo2^vi—Mo2—Mo2^v	60.0	Mo2^ix—Se3—Scⁱⁱⁱ	121.404 (15)
Se5—Mo2—Se1^vii	90.196 (15)	Mo2^vi—Se3—Scⁱⁱⁱ	121.404 (15)
Se2—Mo2—Se1^vii	85.764 (16)	Mo3^vi—Se3—Scⁱⁱ	125.62 (4)
Se2^v—Mo2—Se1^vii	98.510 (16)	Mo3—Se3—Scⁱⁱ	62.43 (4)
Mo2^vi—Mo2—Se1^vii	129.579 (16)	Mo2^ix—Se3—Scⁱⁱ	91.14 (2)
Mo2^v—Mo2—Se1^vii	137.688 (14)	Mo2^vi—Se3—Scⁱⁱ	91.14 (2)
Se5—Mo2—Se3^v	175.172 (19)	Scⁱⁱⁱ—Se3—Scⁱⁱ	71.79 (8)
Se2—Mo2—Se3^v	85.424 (18)	Mo1ⁱⁱⁱ—Se4—Mo1ⁱⁱ	63.974 (19)
Se2^v—Mo2—Se3^v	90.244 (18)	Mo1ⁱⁱⁱ—Se4—Mo1	63.975 (19)
Mo2^vi—Mo2—Se3^v	116.797 (15)	Mo1ⁱⁱ—Se4—Mo1	63.974 (19)
Mo2^v—Mo2—Se3^v	119.114 (14)	Mo1ⁱⁱⁱ—Se4—Scⁱⁱⁱ	148.00 (4)
Se1^vii—Mo2—Se3^v	93.942 (17)	Mo1ⁱⁱ—Se4—Scⁱⁱⁱ	95.16 (3)
Se5—Mo2—Mo3^v	120.527 (17)	Mo1—Se4—Scⁱⁱⁱ	130.64 (4)
Se2—Mo2—Mo3^v	116.554 (16)	Mo1ⁱⁱⁱ—Se4—Scⁱⁱ	130.64 (4)
Se2^v—Mo2—Mo3^v	57.619 (13)	Mo1ⁱⁱ—Se4—Scⁱⁱ	148.00 (4)
Mo2^vi—Mo2—Mo3^v	91.213 (12)	Mo1—Se4—Scⁱⁱ	95.16 (3)
Mo2^v—Mo2—Mo3^v	62.083 (12)	Scⁱⁱⁱ—Se4—Scⁱⁱ	80.06 (5)
Se1^vii—Mo2—Mo3^v	138.895 (18)	Mo1ⁱⁱⁱ—Se4—Sc	95.16 (3)
Se3^v—Mo2—Mo3^v	57.133 (16)	Mo1ⁱⁱ—Se4—Sc	130.64 (4)
Se5—Mo2—Mo3	118.709 (16)	Mo1—Se4—Sc	148.00 (4)
Se2—Mo2—Mo3	57.381 (13)	Scⁱⁱⁱ—Se4—Sc	80.06 (5)
Se2^v—Mo2—Mo3	116.832 (16)	Scⁱⁱ—Se4—Sc	80.06 (5)
Mo2^vi—Mo2—Mo3	60.264 (12)	Mo2^v—Se5—Mo2	63.086 (18)
Mo2^v—Mo2—Mo3	90.162 (12)	Mo2^v—Se5—Mo2^vi	63.086 (18)
Se1^vii—Mo2—Mo3	131.676 (18)	Mo2—Se5—Mo2^vi	63.086 (18)
Se3^v—Mo2—Mo3	56.533 (15)	Se4^viii—Sc—Se4	84.08 (6)
Mo3^v—Mo2—Mo3	59.250 (17)	Se4^viii—Sc—Se3ⁱⁱ	88.06 (5)
Se2^viii—Mo3—Se2	111.71 (3)	Se4—Sc—Se3ⁱⁱ	88.06 (5)
Se2^viii—Mo3—Se3^v	87.997 (16)	Se4^viii—Sc—Se2ⁱⁱⁱ	163.50 (8)
Se2—Mo3—Se3^v	87.997 (16)	Se4—Sc—Se2ⁱⁱⁱ	86.578 (17)
Se2^viii—Mo3—Se3	93.784 (17)	Se3ⁱⁱ—Sc—Se2ⁱⁱⁱ	105.20 (5)
Se2—Mo3—Se3	93.784 (17)	Se4^viii—Sc—Se2^xviii	86.579 (17)
Se3^v—Mo3—Se3	176.82 (2)	Se4—Sc—Se2^xviii	163.51 (8)
Se2^viii—Mo3—Mo3^v	117.324 (17)	Se3ⁱⁱ—Sc—Se2^xviii	105.20 (5)
Se2—Mo3—Mo3^v	117.324 (17)	Se2ⁱⁱⁱ—Sc—Se2^xviii	99.02 (6)
Se3^v—Mo3—Mo3^v	58.44 (2)	Se4^viii—Sc—Mo3ⁱⁱⁱ	120.92 (5)
Se3—Mo3—Mo3^v	118.38 (2)	Se4—Sc—Mo3ⁱⁱⁱ	120.92 (5)
Se2^viii—Mo3—Mo3^vi	120.613 (15)	Se3ⁱⁱ—Sc—Mo3ⁱⁱⁱ	138.83 (8)
Se2—Mo3—Mo3^vi	120.614 (15)	Se2ⁱⁱⁱ—Sc—Mo3ⁱⁱⁱ	53.95 (3)
Se3^v—Mo3—Mo3^vi	118.44 (2)	Se2^xviii—Sc—Mo3ⁱⁱⁱ	53.95 (3)
Se3—Mo3—Mo3^vi	58.38 (2)	Se4^viii—Sc—Se3ⁱⁱⁱ	83.19 (5)
Mo3^v—Mo3—Mo3^vi	60.0	Se4—Sc—Se3ⁱⁱⁱ	83.19 (5)
Se2^viii—Mo3—Mo2^ix	59.397 (12)	Se3ⁱⁱ—Sc—Se3ⁱⁱⁱ	168.21 (8)
Se2—Mo3—Mo2^ix	150.43 (2)	Se2ⁱⁱⁱ—Sc—Se3ⁱⁱⁱ	82.23 (4)
Se3^v—Mo3—Mo2^ix	118.002 (13)	Se2^xviii—Sc—Se3ⁱⁱⁱ	82.23 (4)
Se3—Mo3—Mo2^ix	60.986 (12)	Mo3ⁱⁱⁱ—Sc—Se3ⁱⁱⁱ	52.97 (3)
Mo3^v—Mo3—Mo2^ix	89.795 (12)	Se4^viii—Sc—Scⁱⁱⁱ	49.97 (2)
Mo3^vi—Mo3—Mo2^ix	61.256 (13)	Se4—Sc—Scⁱⁱⁱ	49.97 (2)
Se2^viii—Mo3—Mo2^vi	150.43 (2)	Se3ⁱⁱ—Sc—Scⁱⁱⁱ	57.39 (6)
Se2—Mo3—Mo2^vi	59.397 (12)	Se2ⁱⁱⁱ—Sc—Scⁱⁱⁱ	129.92 (3)
Se3^v—Mo3—Mo2^vi	118.002 (13)	Se2^xviii—Sc—Scⁱⁱⁱ	129.92 (3)
Se3—Mo3—Mo2^vi	60.986 (12)	Mo3ⁱⁱⁱ—Sc—Scⁱⁱⁱ	163.78 (9)
Mo3^v—Mo3—Mo2^vi	89.795 (12)	Se3ⁱⁱⁱ—Sc—Scⁱⁱⁱ	110.81 (7)
Mo3^vi—Mo3—Mo2^vi	61.256 (13)	Se4^viii—Sc—Scⁱⁱ	49.97 (2)
Mo2^ix—Mo3—Mo2^vi	112.82 (2)	Se4—Sc—Scⁱⁱ	49.97 (2)
Se2^viii—Mo3—Mo2	145.46 (2)	Se3ⁱⁱ—Sc—Scⁱⁱ	117.39 (6)
Se2—Mo3—Mo2	57.907 (12)	Se2ⁱⁱⁱ—Sc—Scⁱⁱ	114.00 (7)
Se3^v—Mo3—Mo2	60.350 (12)	Se2^xviii—Sc—Scⁱⁱ	114.00 (7)
Se3—Mo3—Mo2	118.538 (13)	Mo3ⁱⁱⁱ—Sc—Scⁱⁱ	103.78 (9)
Mo3^v—Mo3—Mo2	59.495 (13)	Se3ⁱⁱⁱ—Sc—Scⁱⁱ	50.81 (7)
Mo3^vi—Mo3—Mo2	88.794 (12)	Scⁱⁱⁱ—Sc—Scⁱⁱ	60.0

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

Selected bond lengths (Å) top

Mo1—Se4	2.5480 (6)	Mo3—Se2	2.5780 (5)
Mo1—Se1ⁱ	2.5488 (5)	Mo3—Se3ⁱⁱⁱ	2.5884 (7)
Mo1—Se1	2.5749 (5)	Mo3—Se3	2.5900 (7)
Mo1—Se1ⁱⁱ	2.6145 (5)	Mo3—Mo3ⁱⁱⁱ	2.7127 (8)
Mo1—Se2	2.6531 (5)	In—Se5	3.0662 (13)
Mo1—Mo1ⁱⁱ	2.6995 (6)	In—Se2^vii	3.1273 (4)
Mo1—Mo1ⁱ	2.7179 (5)	In—Se2^viii	3.1273 (4)
Mo2—Se5	2.5290 (6)	In—Se2ⁱ	3.1273 (4)
Mo2—Se2	2.5931 (5)	In—Se1^vii	3.4912 (6)
Mo2—Se2ⁱⁱⁱ	2.6275 (5)	In—Se1ⁱ	3.4912 (6)
Mo2—Mo2^iv	2.6460 (6)	In—Se1^viii	3.4912 (6)
Mo2—Se1^v	2.6581 (5)	Sc—Se4^vi	2.5691 (15)
Mo2—Se3ⁱⁱⁱ	2.6965 (4)	Sc—Se3ⁱⁱ	2.696 (2)
Mo2—Mo3ⁱⁱⁱ	2.7196 (4)	Sc—Se2^ix	2.8056 (12)
Mo2—Mo3	2.7675 (4)	Sc—Se2^x	2.8056 (12)
Mo3—Se2^vi	2.5780 (5)	Sc—Se3^ix	2.931 (2)

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

Experimental details

Crystal data
Chemical formula	Sc_1.91In_1.39Mo₁₅Se₁₉
M_r	3185.04
Crystal system, space group	Hexagonal, P6₃/m
Temperature (K)	293
a, c (Å)	9.7530 (2), 19.3977 (2)
V (Å³)	1597.93 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	28.65
Crystal size (mm)	0.06 × 0.05 × 0.04

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Analytical (de Meulenaar & Tompa, 1965)
T_min, T_max	0.279, 0.424
No. of measured, independent and observed [I > 2σ(I)] reflections	31413, 2414, 1847
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.063, 1.08
No. of reflections	2414
No. of parameters	67
Δρ_max, Δρ_min (e Å⁻³)	2.22, −1.96

Computer programs: COLLECT (Nonius, 1998), EVALCCD (Duisenberg et al., 2003), SIR97 (Altomare et al., 1999), SHELXL2014/6 (Sheldrick, 2015), DIAMOND (Bergerhoff, 1996).

Acknowledgements

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

References

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Volume 71| Part 7| July 2015| Pages 760-762

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