The Chevrel phase In_4.07Mo₁₅S_11.87Se_7.13 with mixed chalcogenide occupancy

The single-crystal of the title compound, indium pentadecamolybdenum nonadeca(sulfide/selenide), was obtained by solid state reaction with an S/Se mixture. It adopts the structure type of In₃Mo₁₅Se₁₉ and In_3.7Mo₁₅S₁₉, which are non-substituted Chevrel phases in the space group P6₃/m. The Mo, one S/Se and two In sites have point symmetry m.. and two S/Se and one In atoms are in 3.. sites. This compound contains isolated Mo₆ and Mo₉ clusters. The shapes of clusters are octa­hedral and confacial biocta­hedral, respectively, face-capped by chalcogen atoms over each triangle face. The Mo—X bonds (X = S, Se) play an important role for the constitution of the framework. The Mo—X distances of 2.479 (2)–2.6687 (9) Å are within the ranges of average values of Mo—S and Mo—Se distances. The In atoms located on sites with m.. symmetry are partially occupied.

Related literature

For discussion of the crystal structures of Chevrel phases, see: Grüttner et al. (1979). For applications, see: Suresh et al. (2008); Aurbach et al. (2007). For the syntheses and crystal structures of Chevrel phases with various cations, see: Salloum, Gautier et al. (2004); Salloum, Gougeon et al. (2004).

Experimental

Crystal data

• In_4.07Mo₁₅S_11.87Se_7.13

• M_r = 2847.4

• Hexagonal, P 6₃ /m

• a = 9.5974 (2) Å

• c = 19.1668 (5) Å

• V = 1528.93 (6) ų

• Z = 2

• Mo Kα radiation

• μ = 18.17 mm⁻¹

• T = 295 K

• 0.04 × 0.04 × 0.03 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2002) T_min = 0.431, T_max = 0.577

• 10366 measured reflections

• 1309 independent reflections

• 1047 reflections with I > 2σ(I)

• R_int = 0.048

Refinement

• R[F² > 2σ(F²)] = 0.039

• wR(F²) = 0.090

• S = 1.41

• 1309 reflections

• 77 parameters

• Δρ_max = 4.14 e Å⁻³

• Δρ_min = −4.12 e Å⁻³

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Supporting information

S1. Comment

The classical Chevrel phases, containing blocks of Mo₆X₈, have been in interest for both structural respects and application to rechargeable batteries (Suresh, et al., 2008; Aurbach, et al., 2007). The new Chevrel phases In_xMo₁₅Se₁₉ (x=2.9 and 3.3) also have been studied by X-ray single-crystal method (Grüttner et al., 1979). These were the first compound having a transition metal cluster with the isolated Mo₆ and Mo₉ clusters. The Mo₉ cluster has the shape of a confacial bioctahedron resulting from the condensation of two octahedral Mo₆ clusters. Both clusters are surrounded by face-capping Se atoms to form Mo₆Se₈ and Mo₉Se₁₁ cluster units, and they are interconnected through Mo—Se bonds to build the three dimensional framework (Fig. 1). On our continuous studies to develop new materials for rechargeable batteries, herein, we report the single-crystal structure of the mixed chalcogenide compound In_4.07Mo₁₅S_11.87Se_7.13 (1). We have investigated the effect of the partial substitution of Se by S atoms in the related Chevrel phase, hoping that the building blocks of Chevrel phase would not be changed.

The crystal structure of the title compound in a unit cell is shown in Fig. 1. The framework is composed of Mo₆X₈ and Mo₉X₁₁ cluster units (X=Se/S) that are interconnected through Mo—X bonds. The Mo₆ cluster forms the octahedral geometry with Mo—Mo bonds between the six Mo atoms, and the eight faces on the octahedron share a chalcogen atom to create the Mo₆X₈ building block (Fig. 2). The Mo₉ cluster is formed by one dimensional trans-face sharing of two Mo₆ octahedron, and surrounded by eleven face-capping chalcogen atoms. The Mo—Mo bond distance related through the threefold axis in the Mo₆ clusters is 2.6728 (11) Å. And the Mo—Mo distances within the Mo₉ clusters are in the range of 2.6415 (10) - 2.7540 (8) Å which are within the normal range of the other Chevrel phases (Grüttner et al., 1979; Salloum, Gautier et al., 2004; Salloum, Gougeon et al., 2004). The amount of substitution of Se atoms by S atoms are dependent on the atomic positions with the range of 34% (for X3 atom) - 86% (for X1 atom). The higher the S atom occupation, the shorter Mo—X bond distances are.

Related literature

For discussion of the crystal structures of Chevrel phases, see: Grüttner et al. (1979). For applications, see: Suresh et al. (2008); Aurbach et al. (2007). For the syntheses and crystal structures of Chevrel phases with various cations, see: Salloum, Gautier et al. (2004); Salloum, Gougeon et al. (2004).

S2. Experimental

The title compound was prepared from powder elemental indium (99.999 at.%), molybdenum (99.999 at.%), sulfur (99.98 at.%), and selenium (99.99 at.%) from Aldrich products in the slightly off-stoichiometric 5:15:12:7 ratio. The reaction mixture was sealed under a nitrogen atmosphere in a silica tube and heated at 1343 K for 72 h and cooled to room temperature at the rate of 10 K/h to obtain black single crystals for X-ray studies.

S3. Refinement

The crystal structure of the title compound was solved and refined starting from the atomic coordinates reported for In_~3Mo₁₅Se₁₉ compound (Grüttner et al., 1979). In the first stage of the refinement, the positions of all atoms but In3 were obtained reasonably. The remaining In3 atom was located in subsequent difference Fourier syntheses. The maximum and minimum residual electron density peaks were located at 1.07 and 0.46 Å, respectively, from the In1 atom.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures

	Fig. 1. View of the crystal structure of the title compound along [110], with displacement ellipsoids at the 80% probability level.
	Fig. 2. Mo6X8 and Mo9X11 cluster units interconnected through Mo—X bonds (X=Se/S).

indium pentadecamolybdenum nonadeca(sulfide/selenide)

Crystal data

In4.07Mo15S11.87Se7.13	Dx = 6.185 Mg m^−3
Mr = 2847.4	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/m	Cell parameters from 1691 reflections
Hall symbol: -P 6c	θ = 2.5–28.3°
a = 9.5974 (2) Å	µ = 18.17 mm^−1
c = 19.1668 (5) Å	T = 295 K
V = 1528.93 (6) Å^3	Block, black
Z = 2	0.04 × 0.04 × 0.03 mm
F(000) = 2524.1

Data collection

Bruker SMART CCD area-detector diffractometer	1047 reflections with I > 2σ(I)
ϕ and ω scans	Rint = 0.048
Absorption correction: multi-scan (SADABS; Bruker, 2002)	θmax = 28.3°, θmin = 2.1°
Tmin = 0.431, Tmax = 0.577	h = −12→12
10366 measured reflections	k = −9→12
1309 independent reflections	l = −25→25

Refinement

Refinement on F^2	77 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0327P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.090	(Δ/σ)max < 0.001
S = 1.41	Δρmax = 4.14 e Å^−3
1309 reflections	Δρmin = −4.12 e Å^−3

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mo1	0.16177 (10)	0.50528 (10)	0.25	0.0084 (2)
Mo2	0.01379 (7)	0.16724 (7)	0.05730 (3)	0.00754 (18)
Mo3	0.31869 (7)	0.50095 (7)	0.13306 (3)	0.00801 (18)
Se1	0	0	0.15855 (13)	0.0164 (9)	0.140 (9)
S1	0	0	0.15855 (13)	0.0164 (9)	0.860 (9)
Se2	0.3333	0.6667	0.03438 (13)	0.0137 (9)	0.142 (9)
S2	0.3333	0.6667	0.03438 (13)	0.0137 (9)	0.858 (9)
Se3	0.31626 (16)	0.34882 (16)	0.25	0.0139 (5)	0.658 (8)
S3	0.31626 (16)	0.34882 (16)	0.25	0.0139 (5)	0.342 (8)
Se4	0.71167 (14)	0.03659 (14)	0.05076 (5)	0.0122 (4)	0.437 (6)
S4	0.71167 (14)	0.03659 (14)	0.05076 (5)	0.0122 (4)	0.563 (6)
Se5	0.01082 (16)	0.38207 (15)	0.13790 (6)	0.0149 (5)	0.328 (6)
S5	0.01082 (16)	0.38207 (15)	0.13790 (6)	0.0149 (5)	0.672 (6)
In1	0.6667	0.3333	0.10758 (9)	0.0837 (6)
In2	0.2155 (3)	0.0510 (3)	0.25	0.0331 (8)	0.468 (4)
In3	0.5545 (8)	0.2420 (7)	0.25	0.055 (2)	0.224 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0086 (4)	0.0086 (4)	0.0080 (4)	0.0043 (4)	0	0
Mo2	0.0079 (3)	0.0083 (3)	0.0066 (3)	0.0041 (3)	−0.0002 (2)	−0.0006 (2)
Mo3	0.0083 (3)	0.0085 (3)	0.0072 (3)	0.0042 (3)	−0.0002 (2)	−0.0005 (2)
Se1	0.0198 (11)	0.0198 (11)	0.0098 (13)	0.0099 (6)	0	0
S1	0.0198 (11)	0.0198 (11)	0.0098 (13)	0.0099 (6)	0	0
Se2	0.0132 (10)	0.0132 (10)	0.0146 (14)	0.0066 (5)	0	0
S2	0.0132 (10)	0.0132 (10)	0.0146 (14)	0.0066 (5)	0	0
Se3	0.0143 (8)	0.0136 (8)	0.0129 (7)	0.0064 (6)	0	0
S3	0.0143 (8)	0.0136 (8)	0.0129 (7)	0.0064 (6)	0	0
Se4	0.0108 (6)	0.0127 (6)	0.0107 (6)	0.0041 (5)	0.0031 (4)	0.0006 (4)
S4	0.0108 (6)	0.0127 (6)	0.0107 (6)	0.0041 (5)	0.0031 (4)	0.0006 (4)
Se5	0.0197 (8)	0.0110 (7)	0.0136 (7)	0.0073 (6)	−0.0028 (5)	−0.0045 (5)
S5	0.0197 (8)	0.0110 (7)	0.0136 (7)	0.0073 (6)	−0.0028 (5)	−0.0045 (5)
In1	0.0967 (10)	0.0967 (10)	0.0579 (10)	0.0483 (5)	0	0
In2	0.0608 (17)	0.0434 (14)	0.0201 (10)	0.0446 (13)	0	0
In3	0.072 (4)	0.043 (4)	0.060 (4)	0.037 (3)	0	0

Geometric parameters (Å, º)

Mo1—Mo3	2.7123 (7)	Mo3—S3	2.6687 (9)
Mo1—Mo3^i	2.7540 (8)	Mo3—S4^vii	2.6034 (12)
Mo2—Mo2^ii	2.6728 (11)	Mo3—S5^iii	2.4976 (14)
Mo3—Mo3^iii	2.6415 (10)	Mo3—S5	2.5827 (15)
Mo1—S3	2.5844 (16)	In1—In3	2.904 (3)
Mo1—S3^i	2.5681 (16)	In2—In3	2.825 (7)
Mo1—S5^iv	2.5299 (13)	In2—Mo1^viii	2.862 (2)
Mo2—S1	2.479 (2)	In1—S2^ix	2.721 (3)
Mo2—S4^v	2.5093 (12)	In2—S1^iv	2.564 (2)
Mo2—S4^vi	2.5219 (13)	In2—S3	2.518 (3)
Mo2—S4^vii	2.6101 (13)	In2—S5^viii	2.8445 (18)
Mo2—S5	2.5880 (13)	In3—S3	2.937 (6)
Mo3—S2	2.430 (2)	In3—S5^viii	3.055 (4)
Mo2^ii—Mo2—Mo2^viii	60.0	S1—Mo2—Mo2^ii	57.39 (3)
Mo3^iii—Mo3—Mo3^i	60.0	S4^v—Mo2—Mo2^ii	120.33 (3)
Mo3—Mo1—Mo3^iv	111.46 (4)	S4^vi—Mo2—Mo2^ii	60.24 (4)
Mo3—Mo1—Mo3^i	57.79 (2)	S4^vii—Mo2—Mo2^ii	116.94 (3)
Mo3^x—Mo1—Mo3^i	108.95 (4)	S4^v—Mo2—Mo2^viii	118.11 (3)
Mo3—Mo1—Mo3^x	144.30 (4)	S4^vi—Mo2—Mo2^viii	120.16 (4)
S5—Mo1—S5^iv	116.27 (7)	S4^vii—Mo2—Mo2^viii	57.01 (3)
S5—Mo1—S3^i	87.54 (4)	S5—Mo2—Mo2^ii	131.12 (4)
S5—Mo1—S3	95.12 (4)	S5—Mo2—Mo2^viii	136.62 (4)
S3^i—Mo1—S3	174.93 (5)	S2—Mo3—S3	173.60 (5)
S5—Mo1—Mo3	58.91 (3)	S2—Mo3—S5^iii	91.81 (3)
S5^iv—Mo1—Mo3	152.53 (5)	S5^iii—Mo3—S5	175.03 (5)
S3^i—Mo1—Mo3	117.85 (3)	S5^iii—Mo3—S3	86.03 (4)
S3—Mo1—Mo3	60.45 (2)	S5^iii—Mo3—S4^vii	86.33 (4)
S5—Mo1—Mo3^x	145.74 (5)	S5—Mo3—S4^vii	98.34 (4)
S5^iv—Mo1—Mo3^x	56.23 (3)	S2—Mo3—Mo3^iii	57.07 (3)
S3^i—Mo1—Mo3^x	60.07 (2)	S3^iii—Mo3—Mo3	116.82 (3)
S3—Mo1—Mo3^x	118.08 (2)	S3^i—Mo3—Mo3	119.14 (3)
S5^iv—Mo1—Mo3^i	145.74 (5)	S4^vii—Mo3—Mo3^i	136.62 (3)
S3^i—Mo1—Mo3^i	60.07 (2)	S4^vii—Mo3—Mo3^iii	130.06 (4)
S1—Mo2—S4^v	175.41 (5)	S5^iii—Mo3—Mo3^iii	60.26 (4)
S1—Mo2—S4^vi	92.35 (3)	S5^iii—Mo3—Mo3^i	120.21 (4)
S1—Mo2—S4^vii	90.27 (3)	Mo1^iii—S3—Mo1	65.07 (5)
S1—Mo2—S5	91.73 (5)	Mo1^iii—S3—Mo3^iv	63.42 (3)
S4^v—Mo2—S5	92.56 (4)	Mo1—S5—Mo3	64.07 (4)
S4^vi—Mo2—S5	87.58 (4)	Mo2^ii—S1—Mo2^viii	65.23 (6)
S4^v—Mo2—S4^vii	87.51 (3)	Mo2^xi—S4—Mo2^xii	64.49 (4)
S4^vi—Mo2—S4^vii	173.73 (5)	Mo2^xi—S4—Mo3^xiii	131.31 (5)
S4^v—Mo2—S4^vi	89.47 (3)	Mo2^xii—S4—Mo3^xiii	127.85 (5)
S5—Mo2—S4^vii	98.04 (4)

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