V1.42In1.83Mo15Se19

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

doi:10.1107/S1600536810036834

inorganic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page i73

doi:10.1107/S1600536810036834

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V_1.42In_1.83Mo₁₅Se₁₉

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

(Received 6 September 2010; accepted 14 September 2010; online 18 September 2010)

The structure of the title compound, vanadium indium pentadecamolybdenum nonadecaselenide, V_1.42In_1.83Mo₁₅Se₁₉, 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 $[\overline{3}]$ and $[\overline{6}]$ , respectively. The clusters are interconnected through additional Mo—Se bonds. In the title compound, the V³⁺ cations replace the trivalent indium atoms present in In_2.9Mo₁₅Se₁₉, and a deficiency is observed on the monovalent indium site. One Mo, one Se and the V atom are situated on mirror planes, and two other Se atoms and the In atom are situated on threefold rotation axes.

Related literature

For previous reports on the crystal structure of In_∼3Mo₁₅Se₁₉ compounds, see: Grüttner et al. (1979). For physical properties of this type of compound, see: Seeber et al. (1979 ). The crystal structures of the substituted compounds Ho_0.76In_1.68Mo₁₅Se₁₉ and In_0.87K₂Mo₁₅Se₁₉ were reported by Salloum et al. (2006 ; 2007 ). For details of the i- and a-type ligand notation, see: Schäfer & von Schnering (1964 ).

Experimental

Crystal data

V_1.42In_1.83Mo₁₅Se₁₉
M_r = 3221.80
Hexagonal, P 6₃ /m
a = 9.7361 (1) Å
c = 19.3090 (4) Å
V = 1585.11 (4) Å³
Z = 2
Mo Kα radiation
μ = 29.21 mm⁻¹
T = 293 K
0.09 × 0.07 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: analytical (de Meulenaar & Tompa, 1965 ) T_min = 0.161, T_max = 0.329
27560 measured reflections
2390 independent reflections
1634 reflections with I > 2σ(I)
R_int = 0.093

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.087
S = 1.08
2390 reflections
67 parameters
Δρ_max = 3.22 e Å⁻³
Δρ_min = −2.57 e Å⁻³

Table 1
Selected bond lengths (Å)

Mo2—Se5	2.5259 (8)
Mo2—Se2	2.5974 (6)
Mo2—Se2ⁱ	2.6290 (6)
Mo2—Mo2ⁱ	2.6474 (7)
Mo2—Se1ⁱⁱ	2.6504 (6)
Mo2—Se3ⁱ	2.6966 (6)
Mo2—Mo3ⁱ	2.7136 (5)
Mo2—Mo3	2.7557 (5)
Mo1—Se1ⁱⁱⁱ	2.5467 (7)
Mo1—Se4	2.5481 (8)
Mo1—Se1	2.5717 (6)
Mo1—Se1^iv	2.6111 (6)
Mo1—Se2	2.6378 (7)
Mo1—Mo1^v	2.6992 (7)
Mo1—Mo1^vi	2.7223 (8)
Mo3—Se2	2.5631 (6)
Mo3—Se2^vii	2.5631 (6)
Mo3—Se3	2.5965 (9)
Mo3—Se3ⁱ	2.6095 (9)
Mo3—Mo3^viii	2.7056 (10)
Mo3—Mo2^ix	2.7136 (5)
In1—Se5	3.0759 (15)
In1—Se2^x	3.1221 (5)
In1—Se1^x	3.4904 (7)
V1—Se4	2.510 (2)
V1—Se3^iv	2.730 (3)
V1—Se2^v	2.7981 (18)
V1—Se3^v	2.831 (3)
V1—Mo3^v	2.865 (3)
Symmetry codes: (i) -y+1, x-y, z; (ii) -x+y+1, -x, z; (iii) x-y, x, -z+1; (iv) -y, x-y, z; (v) -x+y, -x, z; (vi) y, -x+y, -z+1; (vii) $[x, y, -z+{\script{3\over 2}}]$ ; (viii) -x+y+1, -x+1, z; (ix) $[-x+y+1, -x+1, -z+{\script{3\over 2}}]$ ; (x) -x+1, -y, -z+1.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: COLLECT; data reduction: EVALCCD (Duisenberg et al., 2003 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036834/wm2403sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810036834/wm2403Isup2.hkl

checkCIF report

Comment top

From the point of view of crystal chemistry and physical properties, the reduced molybdenum selenides In_~3Mo₁₅Se₁₉ (Grüttner et al., 1979) constitute an interesting family of compounds. Indeed, their crystal structure contains an equal mixture of Mo₆ and Mo₉ cluster units and the In atoms occupy two crystallographically different positions depending on their formal oxidation state of +1 or +3. Recently, we have shown that the In³⁺ cation can be replaced by other trivalent cations such as Ho³⁺ (Salloum et al., 2006) and the In⁺ cation by K⁺ (Salloum et al., 2007). 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). We present here the crystal structure of V_1.42In_1.83Mo₁₅Se₁₉ in which a 3d element replaces the trivalent indium atom.

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 cluster units 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 2b and 2c and have point-group symmetry 3 and 6, respectively. The Mo—Mo distances within the Mo₆ cluster are 2.6992 (7) Å for the distances of the Mo triangles formed by the Mo1 atoms related through the threefold axis, and 2.7223 (8) Å for the distances between these triangles. The Mo—Mo distances within the Mo₉ clusters are 2.6474 (7) and 2.7056 (10) Å in the triangles formed by the atoms Mo2 and Mo3, respectively, and 2.7136 (5) and 2.7557 (5) 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 2.5467 (7) to 2.6378 (7) Å within the Mo₆Seⁱ₈Se^a₆ unit, and from 2.5259 (8) to 2.6966 (6) 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 3.4216 (6) Å, indicating only weak metal—metal interaction. The In⁺ cations are surrounded by seven Se atoms forming a distorted tricapped tetrahedron, as is the case in In_2.9Mo₁₅Se₁₉. The Se5 and Se2 atoms forming the tetrahedron are at 3.0759 (15) and 3.1221 (5) Å from the In atom, and the capping Se1 atoms are at 3.4904 (7) Å. The V³⁺ cations, as the In³⁺ cations in the In₃Mo₁₅Se₁₉ compounds, occupy partially at 47.4 (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 V—Se distances are in the 2.510 (2) - 2.831 (3) Å range.

Related literature top

For previous reports on the crystal structure of In_~3Mo₁₅Se₁₉ compounds, see: Grüttner et al. (1979). For physical properties of this type of compound, see: Seeber et al. (1979). The crystal structures of the substituted compounds Ho_0.76In_1.68Mo₁₅Se₁₉ and In_0.87K₂Mo₁₅Se₁₉ were reported by Salloum et al. (2006; 2007). For details of the i- and a-type ligand notation, see: Schäfer & von Schnering (1964).

Experimental top

Single crystals of V_1.42In_1.83Mo₁₅Se₁₉ were prepared from a mixture of V₂Se₃, MoSe₂, InSe and Mo with a nominal composition V_1.5In₂Mo₁₅Se₁₉. Before use, Mo powder was reduced under H₂ flowing gas at 1273 K during ten hours in order to eliminate any trace of oxygen. The binaries V₂Se₃, MoSe₂, InSe were obtained by heating stoichioetric mixtures of the elements in sealed evacuated silica tubes during about 2 days. All handlings of materials were done 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 up to 1773 K, the temperature which was held for 48 hours, then cooled at 100 K/h down to 1373 K and finally furnace cooled.

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: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of V_1.42In_1.83Mo₁₅Se₁₉ 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.

vanadium indium pentadecamolybdenum nonadecaselenide top

Crystal data top

V_1.42In_1.83Mo₁₅Se₁₉	D_x = 6.750 Mg m⁻³
M_r = 3221.80	Mo Kα radiation, λ = 0.71069 Å
Hexagonal, P6₃/m	Cell parameters from 26495 reflections
Hall symbol: -P 6c	θ = 2.6–35.0°
a = 9.7361 (1) Å	µ = 29.21 mm⁻¹
c = 19.3090 (4) Å	T = 293 K
V = 1585.11 (4) Å³	Irregular block, black
Z = 2	0.09 × 0.07 × 0.05 mm
F(000) = 2797

Data collection top

Nonius KappaCCD diffractometer	2390 independent reflections
Radiation source: fine-focus sealed tube	1634 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.093
ϕ scans (κ = 0) + additional ω scans	θ_max = 35.0°, θ_min = 2.6°
Absorption correction: analytical (de Meulenaar & Tompa, 1965)	h = −15→15
T_min = 0.161, T_max = 0.329	k = −15→12
27560 measured reflections	l = −30→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)] = 0.037	w = 1/[σ²(F_o²) + (0.0413P)² + 0.9587P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.087	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 3.22 e Å⁻³
2390 reflections	Δρ_min = −2.57 e Å⁻³
67 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00025 (5)

Crystal data top

V_1.42In_1.83Mo₁₅Se₁₉	Z = 2
M_r = 3221.80	Mo Kα radiation
Hexagonal, P6₃/m	µ = 29.21 mm⁻¹
a = 9.7361 (1) Å	T = 293 K
c = 19.3090 (4) Å	0.09 × 0.07 × 0.05 mm
V = 1585.11 (4) Å³

Data collection top

Nonius KappaCCD diffractometer	2390 independent reflections
Absorption correction: analytical (de Meulenaar & Tompa, 1965)	1634 reflections with I > 2σ(I)
T_min = 0.161, T_max = 0.329	R_int = 0.093
27560 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	67 parameters
wR(F²) = 0.087	0 restraints
S = 1.08	Δρ_max = 3.22 e Å⁻³
2390 reflections	Δρ_min = −2.57 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.

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 > 2sigma(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	0.16776 (5)	0.01669 (5)	0.55780 (2)	0.00914 (10)
Mo2	0.68407 (5)	0.18577 (5)	0.63317 (2)	0.00965 (10)
Mo3	0.51292 (7)	0.16694 (7)	0.7500	0.00868 (11)
Se1	0.03647 (6)	−0.28702 (6)	0.55134 (3)	0.01070 (11)
Se2	0.37798 (6)	0.00665 (6)	0.64065 (3)	0.01233 (12)
Se3	0.34594 (8)	0.30753 (9)	0.7500	0.01280 (15)
Se4	0.0000	0.0000	0.66221 (5)	0.01643 (19)
Se5	0.6667	0.3333	0.52902 (5)	0.01225 (17)
In1	0.6667	0.3333	0.36972 (6)	0.0374 (4)	0.916 (4)
V1	−0.2026 (4)	−0.1744 (3)	0.7500	0.0177 (9)	0.474 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.00996 (18)	0.00853 (18)	0.0089 (2)	0.00456 (15)	0.00070 (14)	−0.00012 (14)
Mo2	0.00995 (18)	0.00993 (18)	0.0089 (2)	0.00488 (15)	0.00013 (14)	−0.00037 (14)
Mo3	0.0096 (2)	0.0099 (3)	0.0071 (3)	0.0053 (2)	0.000	0.000
Se1	0.0110 (2)	0.0097 (2)	0.0116 (2)	0.00543 (19)	0.00107 (17)	0.00229 (17)
Se2	0.0115 (2)	0.0119 (2)	0.0138 (3)	0.00598 (18)	−0.00305 (18)	−0.00208 (18)
Se3	0.0121 (3)	0.0158 (3)	0.0117 (3)	0.0079 (3)	0.000	0.000
Se4	0.0203 (3)	0.0203 (3)	0.0086 (4)	0.01016 (14)	0.000	0.000
Se5	0.0142 (2)	0.0142 (2)	0.0083 (4)	0.00712 (12)	0.000	0.000
In1	0.0345 (4)	0.0345 (4)	0.0431 (7)	0.0172 (2)	0.000	0.000
V1	0.0216 (16)	0.0095 (13)	0.0165 (16)	0.0038 (11)	0.000	0.000

Geometric parameters (Å, º) top

Mo2—Se5	2.5259 (8)	Mo3—Mo3ⁱⁱ	2.7056 (10)
Mo2—Se2	2.5974 (6)	Mo3—Mo3ⁱ	2.7056 (10)
Mo2—Se2ⁱ	2.6290 (6)	Mo3—Mo2^ix	2.7136 (5)
Mo2—Mo2ⁱ	2.6474 (7)	Mo3—Mo2ⁱⁱ	2.7136 (5)
Mo2—Mo2ⁱⁱ	2.6474 (7)	Mo3—Mo2^viii	2.7557 (5)
Mo2—Se1ⁱⁱⁱ	2.6504 (6)	In1—Se5	3.0759 (15)
Mo2—Se3ⁱ	2.6966 (6)	In1—Se2^x	3.1221 (5)
Mo2—Mo3ⁱ	2.7136 (5)	In1—Se2^xi	3.1221 (5)
Mo2—Mo3	2.7557 (5)	In1—Se2^iv	3.1221 (5)
Mo1—Se1^iv	2.5467 (7)	In1—Se1^x	3.4904 (7)
Mo1—Se4	2.5481 (8)	In1—Se1^xi	3.4904 (7)
Mo1—Se1	2.5717 (6)	In1—Se1^iv	3.4904 (7)
Mo1—Se1^v	2.6111 (6)	In1—Se3^vii	4.2444 (9)
Mo1—Se2	2.6378 (7)	In1—Se3^xii	4.2444 (9)
Mo1—Mo1^vi	2.6992 (7)	In1—Se3^xiii	4.2444 (9)
Mo1—Mo1^v	2.6992 (7)	V1—Se4	2.510 (2)
Mo1—Mo1^vii	2.7223 (8)	V1—Se4^viii	2.510 (2)
Mo1—Mo1^iv	2.7223 (8)	V1—Se3^v	2.730 (3)
Mo3—Se2	2.5631 (6)	V1—Se2^vi	2.7981 (18)
Mo3—Se2^viii	2.5631 (6)	V1—Se2^xiv	2.7981 (18)
Mo3—Se3	2.5965 (9)	V1—Se3^vi	2.831 (3)
Mo3—Se3ⁱ	2.6095 (9)	V1—Mo3^vi	2.865 (3)

Se5—Mo2—Se2	92.603 (17)	Se2^viii—Mo3—Mo3ⁱ	117.84 (2)
Se5—Mo2—Se2ⁱ	91.858 (17)	Se3—Mo3—Mo3ⁱ	118.92 (3)
Se2—Mo2—Se2ⁱ	173.59 (3)	Se3ⁱ—Mo3—Mo3ⁱ	58.45 (3)
Se5—Mo2—Mo2ⁱ	58.396 (13)	Mo3ⁱⁱ—Mo3—Mo3ⁱ	60.0
Se2—Mo2—Mo2ⁱ	120.06 (2)	Se2—Mo3—Mo2^ix	149.88 (3)
Se2ⁱ—Mo2—Mo2ⁱ	58.978 (19)	Se2^viii—Mo3—Mo2^ix	59.685 (15)
Se5—Mo2—Mo2ⁱⁱ	58.396 (13)	Se3—Mo3—Mo2^ix	60.991 (14)
Se2—Mo2—Mo2ⁱⁱ	60.16 (2)	Se3ⁱ—Mo3—Mo2^ix	118.165 (16)
Se2ⁱ—Mo2—Mo2ⁱⁱ	118.878 (19)	Mo3ⁱⁱ—Mo3—Mo2^ix	61.129 (16)
Mo2ⁱ—Mo2—Mo2ⁱⁱ	60.0	Mo3ⁱ—Mo3—Mo2^ix	89.824 (14)
Se5—Mo2—Se1ⁱⁱⁱ	90.42 (2)	Se2—Mo3—Mo2ⁱⁱ	59.685 (15)
Se2—Mo2—Se1ⁱⁱⁱ	86.03 (2)	Se2^viii—Mo3—Mo2ⁱⁱ	149.88 (3)
Se2ⁱ—Mo2—Se1ⁱⁱⁱ	98.54 (2)	Se3—Mo3—Mo2ⁱⁱ	60.991 (14)
Mo2ⁱ—Mo2—Se1ⁱⁱⁱ	137.757 (18)	Se3ⁱ—Mo3—Mo2ⁱⁱ	118.165 (16)
Mo2ⁱⁱ—Mo2—Se1ⁱⁱⁱ	129.74 (2)	Mo3ⁱⁱ—Mo3—Mo2ⁱⁱ	61.129 (16)
Se5—Mo2—Se3ⁱ	175.68 (2)	Mo3ⁱ—Mo3—Mo2ⁱⁱ	89.824 (14)
Se2—Mo2—Se3ⁱ	85.76 (2)	Mo2^ix—Mo3—Mo2ⁱⁱ	112.47 (3)
Se2ⁱ—Mo2—Se3ⁱ	89.46 (2)	Se2—Mo3—Mo2^viii	145.46 (3)
Mo2ⁱ—Mo2—Se3ⁱ	119.150 (18)	Se2^viii—Mo3—Mo2^viii	58.328 (15)
Mo2ⁱⁱ—Mo2—Se3ⁱ	117.432 (18)	Se3—Mo3—Mo2^viii	118.823 (15)
Se1ⁱⁱⁱ—Mo2—Se3ⁱ	93.45 (2)	Se3ⁱ—Mo3—Mo2^viii	60.271 (14)
Se5—Mo2—Mo3ⁱ	120.23 (2)	Mo3ⁱⁱ—Mo3—Mo2^viii	88.941 (14)
Se2—Mo2—Mo3ⁱ	116.35 (2)	Mo3ⁱ—Mo3—Mo2^viii	59.578 (16)
Se2ⁱ—Mo2—Mo3ⁱ	57.311 (17)	Mo2^ix—Mo3—Mo2^viii	57.893 (17)
Mo2ⁱ—Mo2—Mo3ⁱ	61.851 (15)	Mo2ⁱⁱ—Mo3—Mo2^viii	146.06 (3)
Mo2ⁱⁱ—Mo2—Mo3ⁱ	91.063 (14)	Se2—Mo3—Mo2	58.328 (15)
Se1ⁱⁱⁱ—Mo2—Mo3ⁱ	138.90 (2)	Se2^viii—Mo3—Mo2	145.46 (3)
Se3ⁱ—Mo2—Mo3ⁱ	57.36 (2)	Se3—Mo3—Mo2	118.823 (15)
Se5—Mo2—Mo3	118.64 (2)	Se3ⁱ—Mo3—Mo2	60.271 (14)
Se2—Mo2—Mo3	57.123 (17)	Mo3ⁱⁱ—Mo3—Mo2	88.941 (14)
Se2ⁱ—Mo2—Mo3	116.58 (2)	Mo3ⁱ—Mo3—Mo2	59.578 (16)
Mo2ⁱ—Mo2—Mo3	90.142 (14)	Mo2^ix—Mo3—Mo2	146.06 (3)
Mo2ⁱⁱ—Mo2—Mo3	60.255 (15)	Mo2ⁱⁱ—Mo3—Mo2	57.893 (17)
Se1ⁱⁱⁱ—Mo2—Mo3	131.66 (2)	Mo2^viii—Mo3—Mo2	109.90 (3)
Se3ⁱ—Mo2—Mo3	57.177 (19)	Mo1^vii—Se1—Mo1	64.26 (2)
Mo3ⁱ—Mo2—Mo3	59.29 (2)	Mo1^vii—Se1—Mo1^vi	63.70 (2)
Se1^iv—Mo1—Se4	176.34 (2)	Mo1—Se1—Mo1^vi	62.77 (2)
Se1^iv—Mo1—Se1	88.948 (17)	Mo1^vii—Se1—Mo2^xv	131.23 (2)
Se4—Mo1—Se1	91.765 (17)	Mo1—Se1—Mo2^xv	128.19 (2)
Se1^iv—Mo1—Se1^v	88.084 (17)	Mo1^vi—Se1—Mo2^xv	81.114 (19)
Se4—Mo1—Se1^v	90.859 (17)	Mo3—Se2—Mo2	64.549 (18)
Se1—Mo1—Se1^v	173.79 (3)	Mo3—Se2—Mo2ⁱⁱ	63.004 (18)
Se1^iv—Mo1—Se2	93.50 (2)	Mo2—Se2—Mo2ⁱⁱ	60.86 (2)
Se4—Mo1—Se2	90.13 (2)	Mo3—Se2—Mo1	130.39 (2)
Se1—Mo1—Se2	86.306 (19)	Mo2—Se2—Mo1	126.33 (2)
Se1^v—Mo1—Se2	99.32 (2)	Mo2ⁱⁱ—Se2—Mo1	81.018 (19)
Se1^iv—Mo1—Mo1^vi	119.568 (17)	Mo3—Se3—Mo3ⁱⁱ	62.62 (3)
Se4—Mo1—Mo1^vi	58.018 (12)	Mo3—Se3—Mo2^ix	61.649 (16)
Se1—Mo1—Mo1^vi	59.33 (2)	Mo3ⁱⁱ—Se3—Mo2^ix	62.551 (16)
Se1^v—Mo1—Mo1^vi	117.827 (19)	Mo3—Se3—Mo2ⁱⁱ	61.649 (16)
Se2—Mo1—Mo1^vi	129.11 (2)	Mo3ⁱⁱ—Se3—Mo2ⁱⁱ	62.551 (16)
Se1^iv—Mo1—Mo1^v	118.595 (17)	Mo2^ix—Se3—Mo2ⁱⁱ	113.56 (3)
Se4—Mo1—Mo1^v	58.018 (12)	Mo1^vi—Se4—Mo1	63.96 (2)
Se1—Mo1—Mo1^v	119.25 (2)	Mo1^vi—Se4—Mo1^v	63.96 (2)
Se1^v—Mo1—Mo1^v	57.903 (19)	Mo1—Se4—Mo1^v	63.96 (2)
Se2—Mo1—Mo1^v	137.270 (18)	Mo2ⁱ—Se5—Mo2	63.21 (3)
Mo1^vi—Mo1—Mo1^v	60.0	Mo2ⁱ—Se5—Mo2ⁱⁱ	63.21 (3)
Se1^iv—Mo1—Mo1^vii	59.30 (2)	Mo2—Se5—Mo2ⁱⁱ	63.21 (3)
Se4—Mo1—Mo1^vii	118.273 (15)	Mo2ⁱ—Se5—In1	142.763 (16)
Se1—Mo1—Mo1^vii	57.423 (15)	Mo2—Se5—In1	142.763 (16)
Se1^v—Mo1—Mo1^vii	116.42 (2)	Mo2ⁱⁱ—Se5—In1	142.763 (16)
Se2—Mo1—Mo1^vii	132.182 (19)	Se4^viii—V1—Se4	84.98 (9)
Mo1^vi—Mo1—Mo1^vii	60.281 (10)	Se4^viii—V1—Se3^v	87.27 (7)
Mo1^v—Mo1—Mo1^vii	90.0	Se4—V1—Se3^v	87.27 (7)
Se1^iv—Mo1—Mo1^iv	58.31 (2)	Se4^viii—V1—Se2^vi	166.76 (13)
Se4—Mo1—Mo1^iv	118.273 (15)	Se4—V1—Se2^vi	87.36 (2)
Se1—Mo1—Mo1^iv	116.86 (2)	Se3^v—V1—Se2^vi	103.16 (8)
Se1^v—Mo1—Mo1^iv	56.998 (14)	Se4^viii—V1—Se2^xiv	87.36 (2)
Se2—Mo1—Mo1^iv	140.74 (2)	Se4—V1—Se2^xiv	166.76 (13)
Mo1^vi—Mo1—Mo1^iv	90.0	Se3^v—V1—Se2^xiv	103.16 (8)
Mo1^v—Mo1—Mo1^iv	60.281 (10)	Se2^vi—V1—Se2^xiv	97.98 (8)
Mo1^vii—Mo1—Mo1^iv	59.44 (2)	Se4^viii—V1—Se3^vi	85.09 (8)
Se2—Mo3—Se2^viii	110.93 (3)	Se4—V1—Se3^vi	85.09 (8)
Se2—Mo3—Se3	93.18 (2)	Se3^v—V1—Se3^vi	169.63 (12)
Se2^viii—Mo3—Se3	93.18 (2)	Se2^vi—V1—Se3^vi	83.50 (6)
Se2—Mo3—Se3ⁱ	88.30 (2)	Se2^xiv—V1—Se3^vi	83.50 (6)
Se2^viii—Mo3—Se3ⁱ	88.30 (2)	Se4^viii—V1—Mo3^vi	122.97 (8)
Se3—Mo3—Se3ⁱ	177.38 (3)	Se4—V1—Mo3^vi	122.97 (8)
Se2—Mo3—Mo3ⁱⁱ	120.789 (19)	Se3^v—V1—Mo3^vi	136.14 (12)
Se2^viii—Mo3—Mo3ⁱⁱ	120.789 (19)	Se2^vi—V1—Mo3^vi	53.80 (4)
Se3—Mo3—Mo3ⁱⁱ	58.92 (3)	Se2^xiv—V1—Mo3^vi	53.80 (4)
Se3ⁱ—Mo3—Mo3ⁱⁱ	118.45 (3)	Se3^vi—V1—Mo3^vi	54.23 (5)
Se2—Mo3—Mo3ⁱ	117.84 (2)

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

Experimental details

Crystal data
Chemical formula	V_1.42In_1.83Mo₁₅Se₁₉
M_r	3221.80
Crystal system, space group	Hexagonal, P6₃/m
Temperature (K)	293
a, c (Å)	9.7361 (1), 19.3090 (4)
V (Å³)	1585.11 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	29.21
Crystal size (mm)	0.09 × 0.07 × 0.05

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Analytical (de Meulenaar & Tompa, 1965)
T_min, T_max	0.161, 0.329
No. of measured, independent and observed [I > 2σ(I)] reflections	27560, 2390, 1634
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.806

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.087, 1.08
No. of reflections	2390
No. of parameters	67
Δρ_max, Δρ_min (e Å⁻³)	3.22, −2.57

Computer programs: COLLECT (Nonius, 1998), EVALCCD (Duisenberg et al., 2003), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Bergerhoff, 1996).

Selected bond lengths (Å) top

Mo2—Se5	2.5259 (8)	Mo3—Se2	2.5631 (6)
Mo2—Se2	2.5974 (6)	Mo3—Se2^vii	2.5631 (6)
Mo2—Se2ⁱ	2.6290 (6)	Mo3—Se3	2.5965 (9)
Mo2—Mo2ⁱ	2.6474 (7)	Mo3—Se3ⁱ	2.6095 (9)
Mo2—Se1ⁱⁱ	2.6504 (6)	Mo3—Mo3^viii	2.7056 (10)
Mo2—Se3ⁱ	2.6966 (6)	Mo3—Mo2^ix	2.7136 (5)
Mo2—Mo3ⁱ	2.7136 (5)	In1—Se5	3.0759 (15)
Mo2—Mo3	2.7557 (5)	In1—Se2^x	3.1221 (5)
Mo1—Se1ⁱⁱⁱ	2.5467 (7)	In1—Se1^x	3.4904 (7)
Mo1—Se4	2.5481 (8)	V1—Se4	2.510 (2)
Mo1—Se1	2.5717 (6)	V1—Se3^iv	2.730 (3)
Mo1—Se1^iv	2.6111 (6)	V1—Se2^v	2.7981 (18)
Mo1—Se2	2.6378 (7)	V1—Se3^v	2.831 (3)
Mo1—Mo1^v	2.6992 (7)	V1—Mo3^v	2.865 (3)
Mo1—Mo1^vi	2.7223 (8)

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

References

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