Ag1.91Cs1.16Mo9S11: a novel quaternary reduced molybdenum sulfide containing Mo9 clusters

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

doi:10.1107/S1600536805028205

Ag_1.91Cs_1.16Mo₉S₁₁: a novel quaternary reduced molybdenum sulfide containing Mo₉ clusters

Ag_1.911 (6)Cs_1.16 (3)Mo₉S₁₁, silver caesium nonamolybdenum undecasulfide, is isostructural with the archetype h-Mo₉Se₁₁. Its crystal structure consists of Mo₉S₁₁S₆ cluster units centered on the Wyckhoff site 2d and interconnected through inter-unit Mo-S bonds. The Mo-S framework delimits channels in which the Cs⁺ cations are disordered. The Ag atoms are located on mirror planes around the threefold axes between two consecutive Mo₉S₁₁S₆ units.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028205/wm6090sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028205/wm6090Isup2.hkl Contains datablock I

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (o-S) = 0.001 Å
Disorder in main residue
R factor = 0.022
wR factor = 0.046
Data-to-parameter ratio = 39.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT214_ALERT_2_B Atom Cs2     (Anion/Solvent) ADP max/min Ratio         5.50 prolat

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT301_ALERT_3_C Main Residue  Disorder .........................       9.00 Perc.
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      41.00 Perc.
PLAT752_ALERT_4_C Angle   Calc       60.00, Rep    60.00(1) ......  Senseless su
              S2   -MO2  -MO1     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      36.70 Deg.
              CS2  -S1   -CS2     8.556   1.555   2.554
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      27.30 Deg.
              CS2  -S1   -CS1     8.556   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      32.07 Deg.
              MO1  -S1   -MO1     1.555   1.555   3.655
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      32.30 Deg.
              MO1  -S1   -MO1     4.665   1.555   3.655
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      26.60 Deg.
              CS1  -S2   -CS2     1.555   1.555   8.556
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      26.60 Deg.
              CS1  -S2   -CS2     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      32.69 Deg.
              MO2  -S2   -MO1     4.665   1.555  11.666
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      32.73 Deg.
              MO1  -S2   -MO1     8.556   1.555  11.666
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      32.69 Deg.
              MO2  -S2   -MO1     4.665   1.555   4.665
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      32.73 Deg.
              MO1  -S2   -MO1     1.555   1.555   4.665

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  19 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  11 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

In a previous paper, we reported the synthesis, crystal structures and physical properties of three isostructural selenide compounds, viz. Ag_2.6CsMo₉Se₁₁, Ag_4.1ClMo₉Se₁₁ and h-Mo₉Se₁₁, all of which crystallize in a new structure type containing Mo₉ clusters (Gougeon et al., 2004). We present here the crystal structure of the sulfide Ag_1.91Cs_1.16Mo₉S₁₁, which is isostructural with the three previously reported compounds.

The crystal structure of Ag_1.91Cs_1.16Mo₉S₁₁ (Fig. 1) contains Mo₉Sⁱ₁₁Sa₆ cluster units. The i-type ligands cap Mo triangular faces and the a-type ligands are in apical position for the external Mo1 atoms (Fig. 2); for details of the i- and a-type ligand notation, see Schäfer & von Schnering (1964). The Mo₉S₁₁ cluster unit is centered at a 2d position with 6 symmetry. The Mo—Mo distances within the Mo₉ cluster are 2.6376 (3) and 2.7232 (4) Å for Mo₃ triangles that are formed by Mo atoms related through the threefold axes, and 2.6867 (2) and 2.7232 (4) Å for the other Mo₃ triangles. The S atoms bridge either one (S1 and S3) or two (S2) Mo triangular faces of the cluster. Moreover, the S1 atoms are linked to a Mo atom of a neighboring cluster. The Mo—S bond distances range from 2.4172 (7) to 2.5788 (4) Å. Each Mo₉S₁₁ cluster is interconnected to six adjacent clusters via Mo1—S1 bonds to form the three-dimensional Mo–S framework, the connectivity formula of which is Mo₉Sⁱ₅S^i-a_6/2S^a-i_6/2. It results from this arrangement that the shortest intercluster Mo1···Mo1 distance is 3.4025 (3) Å, thus indicating only weak metal–metal interaction. The latter value is shorter than the value of 3.6614 (4) Å observed for the selenide Ag_2.6CsMo₉Se₁₁ (Gougeon et al., 2004), as expected from the smaller size of the S atoms.

The alkali metal cations occupy distorted tricapped trigonal prismatic cavities formed by S atoms. The Cs—S distances spread over the wide range 3.243 (3)–3.960 (10) Å. The Ag atoms are located on mirror planes around the threefold axes between two consecutive Mo₉S₁₁ units. They are surrounded by five S atoms forming a distorted square-based pyramid, with Ag—S distances in the range 2.5018 (8)–2.7754 (6) Å.

Experimental top

Single crystals of Ag_1.91Cs_1.16Mo₉S₁₁ were prepared from a mixture of Cs₂MoS₄, MoS₂, Ag and Mo with the nominal composition Ag₂CsMo₉S₁₁. 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 a rate of 300 K h⁻¹ to 1773 K, the temperature held for 48 h, then cooled at a rate of 100 K h⁻¹ to 1373 K and finally allowed to cool in the furnace to room temperature.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT; data reduction: EVALCCD (Duisenberg, 1998); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. View of the crystal structure of Ag_1.91Cs_1.16Mo₉S₁₁, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Plot showing the atom-numbering scheme of the Mo₉S₁₁S₆ cluster unit.

silver caesium nonamolybdenum undecasulfide top

Crystal data top

Ag_1.91Cs_1.16Mo₉S₁₁	D_x = 5.608 Mg m⁻³
M_r = 1576.99	Mo Kα radiation, λ = 0.71069 Å
Hexagonal, P6₃/m	Cell parameters from 13553 reflections
Hall symbol: -P 6c	θ = 1.7–39.1°
a = 9.6366 (1) Å	µ = 11.22 mm⁻¹
c = 11.6119 (3) Å	T = 293 K
V = 933.86 (3) Å³	Truncated octahedron, black
Z = 2	0.12 × 0.10 × 0.09 mm
F(000) = 1416

Data collection top

Nonius KappaCCD diffractometer	1982 independent reflections
Radiation source: fine-focus sealed tube	1752 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ scans and ω	θ_max = 39.8°, θ_min = 3.0°
Absorption correction: analytical (de Meulenaar & Tompa, 1965)	h = −17→17
T_min = 0.393, T_max = 0.513	k = −17→16
16326 measured reflections	l = −16→20

Refinement top

Refinement on F²	Primary atom site location: isomorphous structure methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²) + (0.0146P)² + 2.105P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.046	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 1.28 e Å⁻³
1982 reflections	Δρ_min = −1.32 e Å⁻³
50 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00338 (14)

Crystal data top

Ag_1.91Cs_1.16Mo₉S₁₁	Z = 2
M_r = 1576.99	Mo Kα radiation
Hexagonal, P6₃/m	µ = 11.22 mm⁻¹
a = 9.6366 (1) Å	T = 293 K
c = 11.6119 (3) Å	0.12 × 0.10 × 0.09 mm
V = 933.86 (3) Å³

Data collection top

Nonius KappaCCD diffractometer	1982 independent reflections
Absorption correction: analytical (de Meulenaar & Tompa, 1965)	1752 reflections with I > 2σ(I)
T_min = 0.393, T_max = 0.513	R_int = 0.039
16326 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	50 parameters
wR(F²) = 0.046	0 restraints
S = 1.08	Δρ_max = 1.28 e Å⁻³
1982 reflections	Δρ_min = −1.32 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	0.51582 (2)	0.16899 (2)	0.058863 (14)	0.00800 (4)
Mo2	0.67583 (3)	0.17495 (3)	0.2500	0.00711 (5)
S1	0.35745 (6)	0.30591 (6)	0.06805 (4)	0.01006 (9)
S2	0.38169 (9)	0.03069 (9)	0.2500	0.01058 (12)
S3	0.6667	0.3333	−0.10280 (8)	0.01318 (15)
Ag	0.57939 (6)	−0.16398 (5)	0.2500	0.02623 (15)	0.636 (2)
Cs1	0.0000	0.0000	0.2500	0.139 (5)	0.573 (15)
Cs2	0.0000	0.0000	0.4029 (18)	0.176 (8)	0.294 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.00863 (7)	0.00915 (7)	0.00700 (7)	0.00504 (6)	−0.00039 (5)	−0.00026 (5)
Mo2	0.00759 (9)	0.00727 (9)	0.00659 (9)	0.00382 (7)	0.000	0.000
S1	0.00986 (19)	0.01127 (19)	0.01034 (19)	0.00625 (16)	−0.00157 (14)	0.00042 (14)
S2	0.0088 (3)	0.0091 (3)	0.0114 (3)	0.0026 (2)	0.000	0.000
S3	0.0166 (2)	0.0166 (2)	0.0064 (3)	0.00829 (12)	0.000	0.000
Ag	0.0322 (3)	0.0139 (2)	0.0365 (3)	0.01437 (18)	0.000	0.000
Cs1	0.0359 (7)	0.0359 (7)	0.344 (17)	0.0179 (3)	0.000	0.000
Cs2	0.0165 (5)	0.0165 (5)	0.50 (2)	0.0083 (3)	0.000	0.000

Geometric parameters (Å, º) top

Mo1—S3	2.4172 (7)	S3—Mo1^xii	4.2747 (2)
Mo1—S1	2.4688 (5)	S3—Mo1^iv	4.2747 (2)
Mo1—S1ⁱ	2.4877 (5)	S3—Mo1^ix	4.2747 (2)
Mo1—S1ⁱⁱ	2.5458 (5)	Ag—S2^xiii	2.5018 (8)
Mo1—S2	2.5788 (4)	Ag—S3^iv	2.7088 (7)
Mo1—Mo1ⁱⁱⁱ	2.6376 (3)	Ag—S3^xi	2.7088 (7)
Mo1—Mo1ⁱ	2.6376 (3)	Ag—S1^vi	2.7754 (6)
Mo1—Mo2	2.6867 (2)	Ag—S1ⁱ	2.7754 (6)
Mo1—Mo2ⁱⁱⁱ	2.7255 (2)	Ag—Cs1^xiv	3.5385 (5)
Mo1—Mo1^iv	3.4025 (3)	Ag—Mo1^xi	3.6963 (2)
Mo1—Ag^iv	3.6963 (2)	Ag—Mo1^iv	3.6963 (2)
Mo1—Mo2ⁱ	3.8084 (2)	Ag—Cs2^xiv	3.959 (10)
Mo1—Ag	4.1908 (4)	Ag—Cs2^xv	3.959 (10)
Mo1—S3^iv	4.2747 (2)	Ag—Mo1^vii	4.1908 (4)
Mo1—S1ⁱⁱⁱ	4.3810 (5)	Cs1—Cs2	1.78 (2)
Mo1—Ag^v	4.3975 (4)	Cs1—Cs2^vii	1.78 (2)
Mo2—S2	2.4549 (8)	Cs1—Agⁱⁱⁱ	3.5385 (5)
Mo2—S2ⁱ	2.4654 (8)	Cs1—Ag^xvi	3.5385 (5)
Mo2—S1^vi	2.4736 (5)	Cs1—Ag^v	3.5385 (5)
Mo2—S1ⁱ	2.4736 (5)	Cs1—S2^xvii	3.5396 (7)
Mo2—Mo1^vii	2.6867 (2)	Cs1—S2^xviii	3.5396 (7)
Mo2—Mo2ⁱ	2.7232 (4)	Cs1—S1^vii	3.8555 (5)
Mo2—Mo2ⁱⁱⁱ	2.7232 (4)	Cs1—S1^xviii	3.8555 (5)
Mo2—Mo1^vi	2.7255 (2)	Cs1—S1^xix	3.8555 (5)
Mo2—Mo1ⁱ	2.7255 (2)	Cs1—S1^xvii	3.8555 (5)
Mo2—Ag	2.9148 (5)	Cs1—S1^xx	3.8555 (5)
Mo2—Mo1^viii	3.8084 (2)	Cs1—Cs2^x	4.03 (2)
S1—Mo2ⁱⁱⁱ	2.4736 (5)	Cs1—Cs2^xxi	4.03 (2)
S1—Mo1ⁱⁱⁱ	2.4877 (5)	Cs1—Mo2ⁱⁱⁱ	4.2270 (2)
S1—Mo1^ix	2.5458 (5)	Cs1—Mo2^v	4.2270 (2)
S1—Agⁱⁱⁱ	2.7754 (6)	Cs1—Mo2^xvi	4.2270 (2)
S1—Cs2^vii	3.243 (2)	Cs1—S1^xxii	4.9031 (5)
S1—Cs2^x	3.752 (11)	Cs2—Cs2^xxi	2.26 (4)
S1—Cs1	3.8555 (5)	Cs2—S1^vii	3.243 (2)
S1—Mo1ⁱ	4.3810 (5)	Cs2—S1^xix	3.243 (2)
S2—Mo2ⁱⁱⁱ	2.4654 (8)	Cs2—S1^xx	3.243 (2)
S2—Ag^v	2.5018 (8)	Cs2—Cs2^vii	3.55 (4)
S2—Mo1^vii	2.5788 (4)	Cs2—S1^xxii	3.752 (11)
S2—Cs1	3.5396 (7)	Cs2—S1^xxiii	3.752 (11)
S2—Cs2^vii	3.960 (10)	Cs2—S1^xxiv	3.752 (11)
S2—Cs2	3.960 (10)	Cs2—Ag^xvi	3.959 (10)
S2—Mo1^viii	4.4085 (7)	Cs2—Agⁱⁱⁱ	3.959 (10)
S2—Mo1ⁱⁱⁱ	4.4085 (7)	Cs2—Ag^v	3.959 (10)
S2—Mo1^xi	4.4093 (5)	Cs2—S2^xvii	3.960 (10)
S2—Mo1^iv	4.4093 (5)	Cs2—S2^xviii	3.960 (10)
S3—Mo1ⁱ	2.4172 (7)	Cs2—Cs1^xxi	4.03 (2)
S3—Mo1ⁱⁱⁱ	2.4172 (7)	Cs2—Mo1^xix	4.412 (2)
S3—Ag^xii	2.7088 (7)	Cs2—Mo1^xx	4.412 (2)
S3—Ag^iv	2.7088 (7)	Cs2—Mo1^vii	4.412 (2)
S3—Ag^ix	2.7088 (7)	Cs2—Mo2^v	4.585 (8)

S3—Mo1—S1	90.767 (13)	Ag—Mo2—Mo1^viii	139.984 (7)
S3—Mo1—S1ⁱ	90.316 (13)	Mo1—S1—Mo2ⁱⁱⁱ	66.934 (14)
S1—Mo1—S1ⁱ	173.41 (2)	Mo1—S1—Mo1ⁱⁱⁱ	64.301 (15)
S3—Mo1—S1ⁱⁱ	93.662 (19)	Mo2ⁱⁱⁱ—S1—Mo1ⁱⁱⁱ	65.577 (14)
S1—Mo1—S1ⁱⁱ	91.47 (2)	Mo1—S1—Mo1^ix	132.91 (2)
S1ⁱ—Mo1—S1ⁱⁱ	94.947 (17)	Mo2ⁱⁱⁱ—S1—Mo1^ix	132.69 (2)
S3—Mo1—S2	171.42 (2)	Mo1ⁱⁱⁱ—S1—Mo1^ix	85.053 (17)
S1—Mo1—S2	87.42 (2)	Mo1—S1—Agⁱⁱⁱ	132.75 (2)
S1ⁱ—Mo1—S2	90.55 (2)	Mo2ⁱⁱⁱ—S1—Agⁱⁱⁱ	67.178 (15)
S1ⁱⁱ—Mo1—S2	94.766 (19)	Mo1ⁱⁱⁱ—S1—Agⁱⁱⁱ	105.42 (2)
S3—Mo1—Mo1ⁱⁱⁱ	56.935 (11)	Mo1^ix—S1—Agⁱⁱⁱ	87.886 (18)
S1—Mo1—Mo1ⁱⁱⁱ	58.196 (14)	Mo1—S1—Cs2^vii	100.262 (19)
S1ⁱ—Mo1—Mo1ⁱⁱⁱ	117.442 (14)	Mo2ⁱⁱⁱ—S1—Cs2^vii	105.9 (3)
S1ⁱⁱ—Mo1—Mo1ⁱⁱⁱ	133.873 (14)	Mo1ⁱⁱⁱ—S1—Cs2^vii	164.08 (8)
S2—Mo1—Mo1ⁱⁱⁱ	115.366 (16)	Mo1^ix—S1—Cs2^vii	109.6 (2)
S3—Mo1—Mo1ⁱ	56.935 (11)	Agⁱⁱⁱ—S1—Cs2^vii	81.9 (3)
S1—Mo1—Mo1ⁱ	118.134 (14)	Mo1—S1—Cs2^x	97.35 (4)
S1ⁱ—Mo1—Mo1ⁱ	57.503 (14)	Mo2ⁱⁱⁱ—S1—Cs2^x	138.6 (2)
S1ⁱⁱ—Mo1—Mo1ⁱ	135.936 (13)	Mo1ⁱⁱⁱ—S1—Cs2^x	143.6 (3)
S2—Mo1—Mo1ⁱ	116.908 (15)	Mo1^ix—S1—Cs2^x	86.70 (18)
Mo1ⁱⁱⁱ—Mo1—Mo1ⁱ	60.0	Agⁱⁱⁱ—S1—Cs2^x	109.6 (2)
S3—Mo1—Mo2	118.478 (13)	Cs2^vii—S1—Cs2^x	36.7 (7)
S1—Mo1—Mo2	117.028 (14)	Mo1—S1—Cs1	99.773 (16)
S1ⁱ—Mo1—Mo2	56.959 (13)	Mo2ⁱⁱⁱ—S1—Cs1	80.599 (14)
S1ⁱⁱ—Mo1—Mo2	134.752 (14)	Mo1ⁱⁱⁱ—S1—Cs1	145.951 (19)
S2—Mo1—Mo2	55.533 (16)	Mo1^ix—S1—Cs1	123.317 (17)
Mo1ⁱⁱⁱ—Mo1—Mo2	91.328 (6)	Agⁱⁱⁱ—S1—Cs1	62.002 (15)
Mo1ⁱ—Mo1—Mo2	61.573 (7)	Cs2^vii—S1—Cs1	27.3 (4)
S3—Mo1—Mo2ⁱⁱⁱ	117.007 (14)	Cs2^x—S1—Cs1	64.0 (3)
S1—Mo1—Mo2ⁱⁱⁱ	56.616 (13)	Mo1—S1—Mo1ⁱ	32.068 (8)
S1ⁱ—Mo1—Mo2ⁱⁱⁱ	117.281 (14)	Mo2ⁱⁱⁱ—S1—Mo1ⁱ	60.088 (11)
S1ⁱⁱ—Mo1—Mo2ⁱⁱⁱ	133.564 (15)	Mo1ⁱⁱⁱ—S1—Mo1ⁱ	32.297 (8)
S2—Mo1—Mo2ⁱⁱⁱ	55.311 (16)	Mo1^ix—S1—Mo1ⁱ	111.611 (16)
Mo1ⁱⁱⁱ—Mo1—Mo2ⁱⁱⁱ	60.100 (6)	Agⁱⁱⁱ—S1—Mo1ⁱ	122.614 (18)
Mo1ⁱ—Mo1—Mo2ⁱⁱⁱ	90.472 (6)	Cs2^vii—S1—Mo1ⁱ	132.03 (3)
Mo2—Mo1—Mo2ⁱⁱⁱ	60.413 (9)	Cs2^x—S1—Mo1ⁱ	124.33 (12)
S3—Mo1—Mo1^iv	92.971 (12)	Cs1—S1—Mo1ⁱ	125.054 (13)
S1—Mo1—Mo1^iv	138.201 (15)	Mo2—S2—Mo2ⁱⁱⁱ	67.21 (2)
S1ⁱ—Mo1—Mo1^iv	48.195 (12)	Mo2—S2—Ag^v	135.94 (4)
S1ⁱⁱ—Mo1—Mo1^iv	46.752 (12)	Mo2ⁱⁱⁱ—S2—Ag^v	156.85 (4)
S2—Mo1—Mo1^iv	93.968 (17)	Mo2—S2—Mo1^vii	64.462 (15)
Mo1ⁱⁱⁱ—Mo1—Mo1^iv	148.814 (8)	Mo2ⁱⁱⁱ—S2—Mo1^vii	65.366 (16)
Mo1ⁱ—Mo1—Mo1^iv	98.328 (11)	Ag^v—S2—Mo1^vii	119.883 (15)
Mo2—Mo1—Mo1^iv	97.361 (8)	Mo2—S2—Mo1	64.462 (15)
Mo2ⁱⁱⁱ—Mo1—Mo1^iv	148.292 (10)	Mo2ⁱⁱⁱ—S2—Mo1	65.366 (16)
S3—Mo1—Ag^iv	47.083 (15)	Ag^v—S2—Mo1	119.883 (15)
S1—Mo1—Ag^iv	80.398 (15)	Mo1^vii—S2—Mo1	118.78 (3)
S1ⁱ—Mo1—Ag^iv	105.012 (15)	Mo2—S2—Cs1	154.78 (3)
S1ⁱⁱ—Mo1—Ag^iv	48.621 (14)	Mo2ⁱⁱⁱ—S2—Cs1	87.57 (2)
S2—Mo1—Ag^iv	140.474 (17)	Ag^v—S2—Cs1	69.28 (2)
Mo1ⁱⁱⁱ—Mo1—Ag^iv	89.624 (8)	Mo1^vii—S2—Cs1	105.936 (18)
Mo1ⁱ—Mo1—Ag^iv	101.897 (8)	Mo1—S2—Cs1	105.936 (18)
Mo2—Mo1—Ag^iv	159.697 (11)	Mo2—S2—Cs2^vii	143.97 (19)
Mo2ⁱⁱⁱ—Mo1—Ag^iv	135.639 (10)	Mo2ⁱⁱⁱ—S2—Cs2^vii	87.83 (2)
Mo1^iv—Mo1—Ag^iv	72.229 (9)	Ag^v—S2—Cs2^vii	71.56 (5)
S3—Mo1—Mo2ⁱ	86.599 (14)	Mo1^vii—S2—Cs2^vii	129.1 (2)
S1—Mo1—Mo2ⁱ	87.663 (13)	Mo1—S2—Cs2^vii	81.9 (2)
S1ⁱ—Mo1—Mo2ⁱ	85.913 (13)	Cs1—S2—Cs2^vii	26.6 (3)
S1ⁱⁱ—Mo1—Mo2ⁱ	179.099 (14)	Mo2—S2—Cs2	143.97 (19)
S2—Mo1—Mo2ⁱ	84.950 (15)	Mo2ⁱⁱⁱ—S2—Cs2	87.83 (2)
Mo1ⁱⁱⁱ—Mo1—Mo2ⁱ	45.695 (4)	Ag^v—S2—Cs2	71.56 (5)
Mo1ⁱ—Mo1—Mo2ⁱ	44.852 (4)	Mo1^vii—S2—Cs2	81.9 (2)
Mo2—Mo1—Mo2ⁱ	45.645 (6)	Mo1—S2—Cs2	129.1 (2)
Mo2ⁱⁱⁱ—Mo1—Mo2ⁱ	45.632 (6)	Cs1—S2—Cs2	26.6 (3)
Mo1^iv—Mo1—Mo2ⁱ	134.107 (9)	Cs2^vii—S2—Cs2	53.3 (6)
Ag^iv—Mo1—Mo2ⁱ	131.401 (9)	Mo2—S2—Mo1^viii	59.586 (13)
S3—Mo1—Ag	129.991 (9)	Mo2ⁱⁱⁱ—S2—Mo1^viii	32.688 (7)
S1—Mo1—Ag	138.797 (14)	Ag^v—S2—Mo1^viii	148.289 (10)
S1ⁱ—Mo1—Ag	39.675 (14)	Mo1^vii—S2—Mo1^viii	32.726 (11)
S1ⁱⁱ—Mo1—Ag	91.533 (14)	Mo1—S2—Mo1^viii	91.451 (19)
S2—Mo1—Ag	51.381 (18)	Cs1—S2—Mo1^viii	99.188 (16)
Mo1ⁱⁱⁱ—Mo1—Ag	134.457 (8)	Cs2^vii—S2—Mo1^viii	111.62 (11)
Mo1ⁱ—Mo1—Ag	86.317 (10)	Cs2—S2—Mo1^viii	85.24 (15)
Mo2—Mo1—Ag	43.682 (7)	Mo2—S2—Mo1ⁱⁱⁱ	59.586 (13)
Mo2ⁱⁱⁱ—Mo1—Ag	93.447 (7)	Mo2ⁱⁱⁱ—S2—Mo1ⁱⁱⁱ	32.688 (7)
Mo1^iv—Mo1—Ag	57.132 (6)	Ag^v—S2—Mo1ⁱⁱⁱ	148.289 (9)
Ag^iv—Mo1—Ag	129.361 (6)	Mo1^vii—S2—Mo1ⁱⁱⁱ	91.451 (19)
Mo2ⁱ—Mo1—Ag	88.957 (7)	Mo1—S2—Mo1ⁱⁱⁱ	32.726 (11)
S3—Mo1—S3^iv	127.354 (6)	Cs1—S2—Mo1ⁱⁱⁱ	99.188 (16)
S1—Mo1—S3^iv	125.862 (13)	Cs2^vii—S2—Mo1ⁱⁱⁱ	85.24 (14)
S1ⁱ—Mo1—S3^iv	57.743 (12)	Cs2—S2—Mo1ⁱⁱⁱ	111.62 (11)
S1ⁱⁱ—Mo1—S3^iv	54.445 (15)	Mo1^viii—S2—Mo1ⁱⁱⁱ	60.456 (11)
S2—Mo1—S3^iv	59.730 (19)	Mo2—S2—Mo1^xi	78.462 (13)
Mo1ⁱⁱⁱ—Mo1—S3^iv	171.677 (11)	Mo2ⁱⁱⁱ—S2—Mo1^xi	115.221 (13)
Mo1ⁱ—Mo1—S3^iv	115.075 (8)	Ag^v—S2—Mo1^xi	76.342 (14)
Mo2—Mo1—S3^iv	80.349 (12)	Mo1^vii—S2—Mo1^xi	50.338 (10)
Mo2ⁱⁱⁱ—Mo1—S3^iv	114.859 (13)	Mo1—S2—Mo1^xi	139.63 (2)
Mo1^iv—Mo1—S3^iv	34.383 (11)	Cs1—S2—Mo1^xi	114.437 (11)
Ag^iv—Mo1—S3^iv	98.170 (14)	Cs2^vii—S2—Mo1^xi	137.3 (2)
Mo2ⁱ—Mo1—S3^iv	125.983 (11)	Cs2—S2—Mo1^xi	90.3 (3)
Ag—Mo1—S3^iv	37.307 (10)	Mo1^viii—S2—Mo1^xi	82.629 (6)
S3—Mo1—S1ⁱⁱⁱ	52.347 (15)	Mo1ⁱⁱⁱ—S2—Mo1^xi	133.686 (16)
S1—Mo1—S1ⁱⁱⁱ	87.873 (8)	Mo2—S2—Mo1^iv	78.462 (13)
S1ⁱ—Mo1—S1ⁱⁱⁱ	87.644 (8)	Mo2ⁱⁱⁱ—S2—Mo1^iv	115.221 (13)
S1ⁱⁱ—Mo1—S1ⁱⁱⁱ	145.971 (9)	Ag^v—S2—Mo1^iv	76.342 (14)
S2—Mo1—S1ⁱⁱⁱ	119.170 (16)	Mo1^vii—S2—Mo1^iv	139.63 (2)
Mo1ⁱⁱⁱ—Mo1—S1ⁱⁱⁱ	29.798 (8)	Mo1—S2—Mo1^iv	50.338 (10)
Mo1ⁱ—Mo1—S1ⁱⁱⁱ	30.261 (8)	Cs1—S2—Mo1^iv	114.437 (11)
Mo2—Mo1—S1ⁱⁱⁱ	73.770 (9)	Cs2^vii—S2—Mo1^iv	90.3 (3)
Mo2ⁱⁱⁱ—Mo1—S1ⁱⁱⁱ	72.252 (9)	Cs2—S2—Mo1^iv	137.3 (2)
Mo1^iv—Mo1—S1ⁱⁱⁱ	126.158 (10)	Mo1^viii—S2—Mo1^iv	133.686 (16)
Ag^iv—Mo1—S1ⁱⁱⁱ	97.930 (11)	Mo1ⁱⁱⁱ—S2—Mo1^iv	82.629 (6)
Mo2ⁱ—Mo1—S1ⁱⁱⁱ	34.262 (7)	Mo1^xi—S2—Mo1^iv	108.857 (17)
Ag—Mo1—S1ⁱⁱⁱ	110.937 (10)	Mo1ⁱ—S3—Mo1	66.13 (2)
S3^iv—Mo1—S1ⁱⁱⁱ	144.595 (8)	Mo1ⁱ—S3—Mo1ⁱⁱⁱ	66.13 (2)
S3—Mo1—Ag^v	159.014 (15)	Mo1—S3—Mo1ⁱⁱⁱ	66.13 (2)
S1—Mo1—Ag^v	94.721 (15)	Mo1ⁱ—S3—Ag^xii	92.109 (8)
S1ⁱ—Mo1—Ag^v	86.546 (14)	Mo1—S3—Ag^xii	123.937 (11)
S1ⁱⁱ—Mo1—Ag^v	66.003 (13)	Mo1ⁱⁱⁱ—S3—Ag^xii	151.048 (14)
S2—Mo1—Ag^v	29.556 (14)	Mo1ⁱ—S3—Ag^iv	151.048 (14)
Mo1ⁱⁱⁱ—Mo1—Ag^v	141.538 (8)	Mo1—S3—Ag^iv	92.109 (8)
Mo1ⁱ—Mo1—Ag^v	134.938 (9)	Mo1ⁱⁱⁱ—S3—Ag^iv	123.937 (11)
Mo2—Mo1—Ag^v	76.681 (7)	Ag^xii—S3—Ag^iv	84.42 (2)
Mo2ⁱⁱⁱ—Mo1—Ag^v	82.602 (8)	Mo1ⁱ—S3—Ag^ix	123.937 (11)
Mo1^iv—Mo1—Ag^v	69.615 (8)	Mo1—S3—Ag^ix	151.048 (14)
Ag^iv—Mo1—Ag^v	114.012 (11)	Mo1ⁱⁱⁱ—S3—Ag^ix	92.109 (8)
Mo2ⁱ—Mo1—Ag^v	113.814 (5)	Ag^xii—S3—Ag^ix	84.42 (2)
Ag—Mo1—Ag^v	50.079 (14)	Ag^iv—S3—Ag^ix	84.42 (2)
S3^iv—Mo1—Ag^v	36.367 (10)	Mo1ⁱ—S3—Mo1^xii	52.646 (6)
S1ⁱⁱⁱ—Mo1—Ag^v	147.955 (8)	Mo1—S3—Mo1^xii	118.23 (2)
S2—Mo2—S2ⁱ	172.79 (2)	Mo1ⁱⁱⁱ—S3—Mo1^xii	81.704 (11)
S2—Mo2—S1^vi	93.858 (16)	Ag^xii—S3—Mo1^xii	69.665 (9)
S2ⁱ—Mo2—S1^vi	89.883 (16)	Ag^iv—S3—Mo1^xii	147.59 (3)
S2—Mo2—S1ⁱ	93.858 (16)	Ag^ix—S3—Mo1^xii	74.286 (10)
S2ⁱ—Mo2—S1ⁱ	89.883 (16)	Mo1ⁱ—S3—Mo1^iv	81.704 (11)
S1^vi—Mo2—S1ⁱ	117.33 (3)	Mo1—S3—Mo1^iv	52.646 (6)
S2—Mo2—Mo1	60.004 (8)	Mo1ⁱⁱⁱ—S3—Mo1^iv	118.23 (2)
S2ⁱ—Mo2—Mo1	117.603 (9)	Ag^xii—S3—Mo1^iv	74.286 (10)
S1^vi—Mo2—Mo1	150.850 (16)	Ag^iv—S3—Mo1^iv	69.665 (9)
S1ⁱ—Mo2—Mo1	57.464 (13)	Ag^ix—S3—Mo1^iv	147.59 (3)
S2—Mo2—Mo1^vii	60.004 (8)	Mo1^xii—S3—Mo1^iv	118.596 (5)
S2ⁱ—Mo2—Mo1^vii	117.603 (9)	Mo1ⁱ—S3—Mo1^ix	118.23 (2)
S1^vi—Mo2—Mo1^vii	57.464 (13)	Mo1—S3—Mo1^ix	81.704 (11)
S1ⁱ—Mo2—Mo1^vii	150.850 (16)	Mo1ⁱⁱⁱ—S3—Mo1^ix	52.646 (6)
Mo1—Mo2—Mo1^vii	111.397 (11)	Ag^xii—S3—Mo1^ix	147.59 (3)
S2—Mo2—Mo2ⁱ	116.58 (2)	Ag^iv—S3—Mo1^ix	74.286 (10)
S2ⁱ—Mo2—Mo2ⁱ	56.21 (2)	Ag^ix—S3—Mo1^ix	69.665 (9)
S1^vi—Mo2—Mo2ⁱ	115.536 (14)	Mo1^xii—S3—Mo1^ix	118.596 (5)
S1ⁱ—Mo2—Mo2ⁱ	115.536 (14)	Mo1^iv—S3—Mo1^ix	118.596 (5)
Mo1—Mo2—Mo2ⁱ	89.490 (6)	S2^xiii—Ag—S3^iv	90.901 (18)
Mo1^vii—Mo2—Mo2ⁱ	89.490 (6)	S2^xiii—Ag—S3^xi	90.901 (18)
S2—Mo2—Mo2ⁱⁱⁱ	56.58 (2)	S3^iv—Ag—S3^xi	78.25 (3)
S2ⁱ—Mo2—Mo2ⁱⁱⁱ	116.21 (2)	S2^xiii—Ag—S1^vi	117.004 (19)
S1^vi—Mo2—Mo2ⁱⁱⁱ	117.870 (14)	S3^iv—Ag—S1^vi	146.34 (2)
S1ⁱ—Mo2—Mo2ⁱⁱⁱ	117.870 (14)	S3^xi—Ag—S1^vi	82.624 (17)
Mo1—Mo2—Mo2ⁱⁱⁱ	60.499 (7)	S2^xiii—Ag—S1ⁱ	117.004 (19)
Mo1^vii—Mo2—Mo2ⁱⁱⁱ	60.499 (7)	S3^iv—Ag—S1ⁱ	82.624 (17)
Mo2ⁱ—Mo2—Mo2ⁱⁱⁱ	60.0	S3^xi—Ag—S1ⁱ	146.34 (2)
S2—Mo2—Mo1^vi	118.128 (9)	S1^vi—Ag—S1ⁱ	99.15 (2)
S2ⁱ—Mo2—Mo1^vi	59.323 (8)	S2^xvii—Cs1—S2	120.0
S1^vi—Mo2—Mo1^vi	56.450 (13)	S2^xvii—Cs1—S2^xviii	120.0
S1ⁱ—Mo2—Mo1^vi	146.973 (16)	S2—Cs1—S2^xviii	120.0
Mo1—Mo2—Mo1^vi	145.118 (10)	S2^xvii—Cs1—S1^vii	144.962 (8)
Mo1^vii—Mo2—Mo1^vi	58.327 (7)	S2—Cs1—S1^vii	56.104 (12)
Mo2ⁱ—Mo2—Mo1^vi	59.088 (7)	S2^xviii—Cs1—S1^vii	74.866 (12)
Mo2ⁱⁱⁱ—Mo2—Mo1^vi	88.686 (6)	S2^xvii—Cs1—S1^xviii	74.866 (12)
S2—Mo2—Mo1ⁱ	118.128 (9)	S2—Cs1—S1^xviii	144.962 (8)
S2ⁱ—Mo2—Mo1ⁱ	59.323 (8)	S2^xviii—Cs1—S1^xviii	56.104 (12)
S1^vi—Mo2—Mo1ⁱ	146.973 (16)	S1^vii—Cs1—S1^xviii	130.553 (5)
S1ⁱ—Mo2—Mo1ⁱ	56.450 (13)	S2^xvii—Cs1—S1^xix	74.866 (12)
Mo1—Mo2—Mo1ⁱ	58.327 (7)	S2—Cs1—S1^xix	144.962 (8)
Mo1^vii—Mo2—Mo1ⁱ	145.118 (10)	S2^xviii—Cs1—S1^xix	56.104 (12)
Mo2ⁱ—Mo2—Mo1ⁱ	59.088 (7)	S1^vii—Cs1—S1^xix	92.841 (11)
Mo2ⁱⁱⁱ—Mo2—Mo1ⁱ	88.686 (6)	S1^xviii—Cs1—S1^xix	66.458 (15)
Mo1^vi—Mo2—Mo1ⁱ	109.041 (11)	S2^xvii—Cs1—S1^xvii	56.104 (12)
S2—Mo2—Ag	74.60 (2)	S2—Cs1—S1^xvii	74.866 (12)
S2ⁱ—Mo2—Ag	112.61 (2)	S2^xviii—Cs1—S1^xvii	144.962 (8)
S1^vi—Mo2—Ag	61.360 (13)	S1^vii—Cs1—S1^xvii	130.553 (5)
S1ⁱ—Mo2—Ag	61.360 (13)	S1^xviii—Cs1—S1^xvii	92.841 (11)
Mo1—Mo2—Ag	96.777 (9)	S1^xix—Cs1—S1^xvii	130.553 (5)
Mo1^vii—Mo2—Ag	96.777 (9)	S1^vii—Cs2—S1^xix	118.93 (13)
Mo2ⁱ—Mo2—Ag	168.818 (17)	S1^vii—Cs2—S1^xx	118.93 (13)
Mo2ⁱⁱⁱ—Mo2—Ag	131.182 (17)	S1^xix—Cs2—S1^xx	118.93 (13)
Mo1^vi—Mo2—Ag	116.846 (8)	S1^vii—Cs2—S1^xxii	61.27 (15)
Mo1ⁱ—Mo2—Ag	116.846 (8)	S1^xix—Cs2—S1^xxii	61.27 (15)
S2—Mo2—Mo1^viii	86.642 (16)	S1^xx—Cs2—S1^xxii	143.3 (7)
S2ⁱ—Mo2—Mo1^viii	87.502 (15)	S1^vii—Cs2—S1^xxiii	61.27 (15)
S1^vi—Mo2—Mo1^viii	85.649 (13)	S1^xix—Cs2—S1^xxiii	143.3 (7)
S1ⁱ—Mo2—Mo1^viii	156.879 (14)	S1^xx—Cs2—S1^xxiii	61.27 (15)
Mo1—Mo2—Mo1^viii	103.965 (8)	S1^xxii—Cs2—S1^xxiii	96.2 (4)
Mo1^vii—Mo2—Mo1^viii	43.820 (5)	S1^vii—Cs2—S1^xxiv	143.3 (7)
Mo2ⁱ—Mo2—Mo1^viii	45.682 (4)	S1^xix—Cs2—S1^xxiv	61.27 (15)
Mo2ⁱⁱⁱ—Mo2—Mo1^viii	44.865 (4)	S1^xx—Cs2—S1^xxiv	61.27 (15)
Mo1^vi—Mo2—Mo1^viii	43.833 (5)	S1^xxii—Cs2—S1^xxiv	96.2 (4)
Mo1ⁱ—Mo2—Mo1^viii	103.166 (7)	S1^xxiii—Cs2—S1^xxiv	96.2 (4)

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

Experimental details

Crystal data
Chemical formula	Ag_1.91Cs_1.16Mo₉S₁₁
M_r	1576.99
Crystal system, space group	Hexagonal, P6₃/m
Temperature (K)	293
a, c (Å)	9.6366 (1), 11.6119 (3)
V (Å³)	933.86 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	11.22
Crystal size (mm)	0.12 × 0.10 × 0.09

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Analytical (de Meulenaar & Tompa, 1965)
T_min, T_max	0.393, 0.513
No. of measured, independent and observed [I > 2σ(I)] reflections	16326, 1982, 1752
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.900

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.046, 1.08
No. of reflections	1982
No. of parameters	50
Δρ_max, Δρ_min (e Å⁻³)	1.28, −1.32

Computer programs: COLLECT (Nonius, 1998), COLLECT, EVALCCD (Duisenberg, 1998), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996), SHELXL97.

Selected bond lengths (Å) top

Mo1—S3	2.4172 (7)	Mo2—Mo2ⁱ	2.7232 (4)
Mo1—S1	2.4688 (5)	Ag—S2^v	2.5018 (8)
Mo1—S1ⁱ	2.4877 (5)	Ag—S3^vi	2.7088 (7)
Mo1—S1ⁱⁱ	2.5458 (5)	Ag—S3^vii	2.7088 (7)
Mo1—S2	2.5788 (4)	Ag—S1^iv	2.7754 (6)
Mo1—Mo1ⁱⁱⁱ	2.6376 (3)	Ag—S1ⁱ	2.7754 (6)
Mo1—Mo2	2.6867 (2)	Cs1—S2^viii	3.5396 (7)
Mo1—Mo2ⁱⁱⁱ	2.7255 (2)	Cs1—S1^ix	3.8555 (5)
Mo2—S2	2.4549 (8)	Cs2—S1^ix	3.243 (2)
Mo2—S2ⁱ	2.4654 (8)	Cs2—S1^x	3.752 (11)
Mo2—S1^iv	2.4736 (5)	Cs2—S2^viii	3.960 (10)
Mo2—S1ⁱ	2.4736 (5)

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

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