Ho0 76In1 68Mo15Se19

inorganic papers

Acta Cryst.(2006). E62, i83–i85 doi:10.1107/S1600536806007446 Salloumet al. _Ho

0.76In1.68Mo15Se19

i83

Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

Ho

In

Mo

Se

D. Salloum, P. Gougeon* and M. Potel

Laboratoire de Chimie du Solide et Inorganique Mole´culaire, URA CNRS No. 6511, Universite´ de Rennes I, Avenue du Ge´ne´ral Leclerc, 35042 Rennes Cedex, France

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(Mo–Se) = 0.007 A˚ Disorder in main residue

Rfactor = 0.040

wRfactor = 0.088

Data-to-parameter ratio = 36.9

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 14 February 2006 Accepted 1 March 2006

#2006 International Union of Crystallography All rights reserved

The structure of holmium indium molybdenum selenide, Ho0.76In1.68Mo15Se19, isotypic with In2.9Mo15Se19 [Gru¨ttner,

Yvon, Chevrel, Potel, Sergent & Seeber (1979). Acta Cryst.

B35, 285–292], is characterized by two cluster units Mo6Se

i

8Se

a

6

and Mo9Se

i

11Se

a

6 (where i = inner and a = apical) that are

present in a 1:1 ratio. The cluster units are centered at Wyckoff

positions 2band 2cand have point-group symmetry 3 and 6,

respectively. The clusters are interconnected through

addi-tional Mo—Se bonds. In the title compound, Ho3+ cations

replace the trivalent indium observed in In2.9Mo15Se19, and a

deficiency is observed on the monovalent indium site.

Comment

In 1979, Gru¨ttner et al. reported the crystal structures of

In2.9Mo15Se19 and In3.3Mo15Se19 as the first compounds

containing a transition metal cluster with a nuclearity higher

than 6, viz. the bioctahedral Mo9 cluster. The latter cluster,

which results from the face-sharing of two Mo6 octahedra,

coexists with the octahedral Mo6cluster in equal proportions.

Another interesting feature in these compounds concerns the In atoms that occupy two crystallographically different posi-tions depending on their formal oxidation state of +I or +III,

respectively. While the InIsite is fully occupied, the InIIIsite

Figure 1

presents a non-stoichiometry that leads to broad composition ranges from In2.9Mo15Se19 to In3.3Mo15Se19. We present here

the crystal structure of Ho0.76In1.68Mo15Se19 in which Ho

replaces the trivalent In site.

The Mo–Se framework of the title compound consists of the

cluster units Mo6Se

i

8Se

a

6and Mo9Se

i

11Se

a

6in a 1:1 ratio. These

units are interconnected through additional Mo—Se bonds

(Figs. 1 and 2); for details of thei- anda-type ligand notation,

see Scha¨fer & von Schnering (1964). The first unit can be

described as an Mo6 octahedron surrounded by eight

face-capping inner Seiand six apical Sealigands. The Mo9cluster is

surrounded by 11 Seiatoms capping the faces of the

biocta-hedron and six Sea ligands above the apical Mo atoms. The

Mo6Sei8Sea6 and Mo9Se11iSea6 units are centered at Wyckoff

positions 2band 2cand have point-group symmetry 3 and 6,

respectively. The Mo—Mo distances within the Mo6 cluster

are 2.7001 (7) A˚ for the distances of the Mo3triangles formed

by the Mo atoms related through the threefold axis, and

2.7104 (8) A˚ for the distances between these triangles. The

Mo—Mo distances within the Mo9clusters are 2.6470 (7) and

2.719 (1) A˚ for the intra-triangle distances between atoms

Mo2 and Mo3, respectively, and 2.7179 (5) and 2.7673 (6) A˚

for those between the Mo3 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 distances range from 2.5469 (9) to 2.6587 (7) A˚ within

the Mo6Se8iSea6unit, and from 2.5290 (8) to 2.6928 (6) A˚ within

the Mo9Se11i Sea6 unit. Each Mo9Se11iSea6 cluster is

inter-connected to six Mo6Se

i

8Se

a

6units (andvice versa)viaMo2—S1

bonds (and Mo1—S2 bonds, respectively), forming the three-dimensional Mo—S framework, the connective formula of

which is Mo9S

i

5S

i-a 6/2S

a-i

6/2, Mo6S

i

2S

i-a 6/2S

a-i

6/2. It results from this

arrangement that the shortest intercluster Mo1—Mo2

distance is 3.4666 (6) A˚ , 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

In2.9Mo15Se19. The Se5 and Se2 atoms forming the tetrahedron

are at 3.0647 (15) and 3.1591 (5) A˚ from the In atom, and the

capping Se1 atoms are at 3.5079 (7) A˚ . While in In2.9Mo15Se19

the latter site is fully occupied by monovalent In, in the title compound it is only 0.842 (3) occupied. This probably results from the higher temperature used during the crystal-growth process which led to a loss of InSe because of its high volatility

at 1773 K. The Ho3+ cations, as the In3+ cations in the

In3xMo15Se19 compounds, occupy partially [25.5 (2)%]

occupied distorted octahedral cavities around the threefold

axis, which are formed by two Mo6Se

i

8Se

a

6 and three

Mo9Se

i

11Se

a

6 units. The Ho—Se distances are in the range

2.5689 (13)–2.9690 (16) A˚ .

Experimental

Single crystals of Ho0.76In1.68Mo15Se19were prepared from a mixture of Ho2Se3, MoSe2, InSe and Mo with the nominal composition HoIn2Mo15Se19. Before use, Mo powder was reduced under flowing H2gas at 1273 K over a period 10 h in order to eliminate any trace of oxygen. The binaries Ho2Se3, MoSe2, InSe were obtained by heating stoichiometric mixtures of the elements in sealed evacuated silica tubes over a period of about 2 d. All handling of materials was carried out in an argon-filled glove-box. The initial mixture (ca5 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 h1up to 1773 K, the temperature which was held there for 48 h, then cooled at a rate of 100 K h1to 1373 K and finally allowed to cool in the switched-off furnace. On the basis of the X-ray powder diagram, the product was a single phase.

Crystal data

Ho0.76In1.68Mo15Se19 Mr= 3258.98

Hexagonal,P63=m a= 9.7969 (1) A˚

c= 19.3973 (4) A˚

V= 1612.31 (4) A˚3 Z= 2

Dx= 6.713 Mg m3

MoKradiation

Cell parameters from 31521 reflections

= 2.0–35.0

= 30.08 mm1

T= 293 (2) K Irregular block, black 0.080.050.03 mm

Data collection

Nonius KappaCCD diffractometer ’and!scans

Absorption correction: analytical (de Meulenaer & Tompa, 1965)

Tmin= 0.094,Tmax= 0.345

28264 measured reflections 2436 independent reflections

1625 reflections withI> 2(I)

Rint= 0.092

max= 35.1 h=11!15

k=15!15

l=31!31

Refinement

Refinement onF2 R[F2> 2(F2)] = 0.040

wR(F2_{) = 0.088} S= 1.07 2436 reflections 66 parameters

w= 1/[2_(F

o2) + (0.0398P)2

+ 0.2653P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 2.64 e A˚3

min=2.69 e A˚3

inorganic papers

i84

0.76In1.68Mo15Se19 Acta Cryst.(2006). E62, i83–i85

Figure 2

Plot showing the atom-numbering scheme and the inter-unit linkage of the Mo9Se11Se6and Mo6Se8Se6cluster units. Displacement ellipsoids are

Table 1

Selected bond lengths (A˚ ).

Mo1—Se4 2.5469 (9)

Mo1—Se1i

2.5526 (7)

Mo1—Se1 2.5765 (7)

Mo1—Se1ii

2.6163 (6)

Mo1—Se2 2.6587 (7)

Mo1—Mo1iii 2.7001 (7)

Mo1—Mo1iv

2.7104 (8)

Mo2—Se5 2.5290 (8)

Mo2—Se2 2.5862 (6)

Mo2—Se2v

2.6275 (7)

Mo2—Mo2v

2.6470 (7) Mo2—Se1vi

2.6675 (7)

Mo2—Se3v 2.6928 (6)

Mo2—Mo3v

2.7179 (5)

Mo2—Mo3 2.7673 (5)

Mo3—Se3v

2.5836 (9)

Mo3—Se2 2.5851 (6)

Mo3—Se2vii

2.5851 (6)

Mo3—Se3 2.5908 (9)

Mo3—Mo3viii 2.7193 (10)

In—Se5 3.0647 (15)

In—Se2ix

3.1591 (5) In—Se1ix

3.5079 (7) Ho—Se4vii

2.5689 (13) Ho—Se3ii

2.7270 (16) Ho—Se2iii

2.8314 (11)

Ho—Se2x 2.8314 (11)

Ho—Se3iii

2.9690 (16)

Symmetry codes: (i) xy;x;zþ1; (ii) y;xy;z; (iii) xþy;x;z; (iv)

y;xþy;zþ1; (v)yþ1;xy;z; (vi)xþyþ1;x;z; (vii)x;y;zþ3 2; (viii)

xþyþ1;xþ1;z; (ix)xþ1;y;zþ1; (x)xþy;x;zþ3 2.

The occupation factors for the Ho and In atoms were refined freely. The highest peak and the deepest hole in the final Fourier map are located 0.20 A˚ from In and 0.64 A˚ from Se4, respectively.

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, 1997); molecular graphics:DIAMOND(Brandenburg, 2001); software used to prepare material for publication:SHELXL97.

Intensity data were collected on the Nonius KappaCCD X-ray diffactometer system of the Centre de diffractome´trie de l’Universite´ de Rennes I (URL: www.cdifx.univ-rennes1. fr).

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999).J. Appl. Cryst.32, 115–119.

Brandenburg, K. (2001). DIAMOND. Version. 2.1e. Crystal Impact GbR, Bonn, Germany.

Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003).

J. Appl. Cryst.36, 220–229.

Gru¨ttner, A., Yvon, K., Chevrel R., Potel, M., Sergent, M. & Seeber, B. (1979).

Acta Cryst.B35, 285–292.

Meulenaer, J. de & Tompa, H. (1965).Acta Cryst.19, 1014–1018. Nonius (1998).COLLECT. Nonius BV, Delft, The Netherlands. Scha¨fer, H. & von Schnering, H. G. (1964).Angew. Chem.76, 833–845. Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany.

inorganic papers

Acta Cryst.(2006). E62, i83–i85 Salloumet al. _Ho

supporting information

sup-1

Acta Cryst. (2006). E62, i83–i85

supporting information

Acta Cryst. (2006). E62, i83–i85 [https://doi.org/10.1107/S1600536806007446]

Ho

In

Mo

Se

D. Salloum, P. Gougeon and M. Potel

holmium indium molybdenum selenide

Crystal data Ho0.76In1.68Mo15Se19

Mr = 3258.98 Hexagonal, P63/m

Hall symbol: -P 6c a = 9.7969 (1) Å c = 19.3973 (4) Å V = 1612.31 (4) Å3

Z = 2

F(000) = 2820

Dx = 6.713 Mg m−3

Mo Kα radiation, λ = 0.71069 Å Cell parameters from 31521 reflections θ = 2.0–35.0°

µ = 30.08 mm−1

T = 293 K

Irregular block, black 0.08 × 0.05 × 0.03 mm

Data collection Nonius Kappa CCD

diffractometer

Radiation source: fine-focus sealed tube Horizontally mounted graphite crystal

monochromator

Detector resolution: 9 pixels mm-1

φ and ω scans

Absorption correction: analytical (de Meulenaar & Tompa, 1965)

Tmin = 0.094, Tmax = 0.345

28264 measured reflections 2436 independent reflections 1625 reflections with I > 2σ(I) Rint = 0.092

θmax = 35.1°, θmin = 3.2°

h = −11→15 k = −15→15 l = −31→31

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.040}

wR(F2_{) = 0.088}

S = 1.07 2436 reflections 66 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

w = 1/[σ2_(F

o2) + (0.0398P)2 + 0.2653P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 2.64 e Å−3

Δρmin = −2.69 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

supporting information

sup-2

Acta Cryst. (2006). E62, i83–i85

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq Occ. (<1)

Mo1 0.16651 (5) 0.01597 (5) 0.55715 (2) 0.00634 (10) Mo2 0.68338 (5) 0.18637 (5) 0.63335 (2) 0.00570 (10) Mo3 0.51229 (7) 0.16779 (7) 0.7500 0.00581 (12) Se1 0.03516 (6) −0.28658 (6) 0.55165 (3) 0.00840 (11) Se2 0.38029 (6) 0.00931 (6) 0.63934 (3) 0.00904 (12) Se3 0.35216 (8) 0.31290 (9) 0.7500 0.00907 (15) Se4 0.0000 0.0000 0.66099 (5) 0.0201 (2) Se5 0.6667 0.3333 0.52947 (5) 0.00926 (18)

In 0.6667 0.3333 0.37147 (6) 0.0356 (4) 0.842 (3) Ho −0.20999 (18) −0.17299 (16) 0.7500 0.0135 (4) 0.2553 (16)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Mo1 0.0079 (2) 0.00649 (19) 0.0046 (2) 0.00365 (16) 0.00012 (15) 0.00014 (14) Mo2 0.00623 (19) 0.00645 (19) 0.00453 (19) 0.00325 (16) −0.00007 (15) −0.00021 (14) Mo3 0.0071 (3) 0.0067 (3) 0.0044 (2) 0.0040 (2) 0.000 0.000

Se1 0.0092 (2) 0.0081 (2) 0.0082 (2) 0.0046 (2) 0.00081 (18) 0.00175 (18) Se2 0.0073 (2) 0.0080 (2) 0.0107 (3) 0.00297 (19) −0.00287 (18) −0.00156 (18) Se3 0.0070 (3) 0.0119 (4) 0.0094 (3) 0.0055 (3) 0.000 0.000

Se4 0.0280 (4) 0.0280 (4) 0.0043 (4) 0.01399 (18) 0.000 0.000 Se5 0.0115 (3) 0.0115 (3) 0.0047 (4) 0.00577 (13) 0.000 0.000 In 0.0373 (5) 0.0373 (5) 0.0324 (7) 0.0186 (2) 0.000 0.000 Ho 0.0151 (8) 0.0096 (7) 0.0147 (7) 0.0053 (6) 0.000 0.000

Geometric parameters (Å, º)

Mo1—Se4 2.5469 (9) Se3—Mo2x _{2.6928 (6)}

Mo1—Se1i _{2.5526 (7) Se3—Mo2}v _{2.6928 (6)}

Mo1—Se1 2.5765 (7) Se3—Hoiii _{2.7270 (16)}

Mo1—Se1ii _{2.6163 (6) Se3—Ho}ii _{2.9690 (16)}

Mo1—Se2 2.6587 (7) Se3—Inxii _{4.2704 (9)}

Mo1—Mo1iii _{2.7001 (7) Se3—In}xiii _{4.2704 (9)}

Mo1—Mo1ii _{2.7001 (7) Se4—Mo1}iii _{2.5469 (9)}

Mo1—Mo1iv _{2.7104 (8) Se4—Mo1}ii _{2.5469 (9)}

Mo1—Mo1i _{2.7104 (8) Se4—Ho}iii _{2.5689 (13)}

Mo1—Mo2v _{3.4666 (6) Se4—Ho}ii _{2.5689 (13)}

Mo1—Invi _{4.6789 (5) Se4—Ho 2.5689 (13)}

Mo2—Se5 2.5290 (8) Se5—Mo2vii _{2.5290 (8)}

supporting information

sup-3

Acta Cryst. (2006). E62, i83–i85

Mo2—Se2vii _{2.6275 (7) In—Se5 3.0647 (15)}

Mo2—Mo2vii _{2.6470 (7) In—Se2}vi _{3.1591 (5)}

Mo2—Mo2v _{2.6470 (7) In—Se2}xiv _{3.1591 (5)}

Mo2—Se1viii _{2.6675 (7) In—Se2}i _{3.1591 (5)}

Mo2—Se3vii _{2.6928 (6) In—Se1}vi _{3.5079 (7)}

Mo2—Mo3vii _{2.7179 (5) In—Se1}i _{3.5079 (7)}

Mo2—Mo3 2.7673 (5) In—Se1xiv _{3.5079 (7)}

Mo2—Invi _{4.4980 (4) In—Se3}iv _{4.2704 (9)}

Mo3—Se3vii _{2.5836 (9) In—Se3}xv _{4.2704 (9)}

Mo3—Se2 2.5851 (6) In—Se3xiii _{4.2704 (9)}

Mo3—Se2ix _{2.5851 (6) In—Mo2}xiv _{4.4980 (4)}

Mo3—Se3 2.5908 (9) In—Mo2vi _{4.4980 (4)}

Mo3—Mo2x _{2.7179 (5) In—Mo2}i _{4.4980 (4)}

Mo3—Mo2v _{2.7179 (5) In—Ho}xvi _{4.5834 (15)}

Mo3—Mo3v _{2.7193 (10) In—Ho}xvii _{4.5834 (15)}

Mo3—Mo3vii _{2.7193 (10) In—Ho}xviii _{4.5834 (15)}

Mo3—Mo2ix _{2.7673 (5) Ho—Se4}ix _{2.5689 (13)}

Mo3—Hoii _{2.8993 (15) Ho—Se3}ii _{2.7270 (16)}

Se1—Mo1iv _{2.5526 (7) Ho—Se2}iii _{2.8314 (11)}

Se1—Mo1iii _{2.6163 (6) Ho—Se2}xix _{2.8314 (11)}

Se1—Mo2xi _{2.6675 (7) Ho—Mo3}iii _{2.8993 (15)}

Se1—Invi _{3.5079 (7) Ho—Se3}iii _{2.9690 (16)}

Se2—Mo2v _{2.6275 (6) Ho—Ho}iii _{3.295 (3)}

Se2—Hoii _{2.8314 (11) Ho—Ho}ii _{3.295 (3)}

Se2—Invi _{3.1591 (5) Ho—In}xvii _{4.5834 (15)}

Se3—Mo3v _{2.5836 (9) Ho—In}xx _{4.5834 (15)}

Se4—Mo1—Se1i _{176.38 (3) In}xii_—Se3—Inxiii _{66.97 (3)}

Se4—Mo1—Se1 91.489 (17) Mo1iii_—Se4—Mo1ii _{64.02 (3)}

Se1i_{—Mo1—Se1 89.250 (17) Mo1}iii_{—Se4—Mo1 64.02 (3)}

Se4—Mo1—Se1ii _{90.580 (17) Mo1}ii_{—Se4—Mo1 64.02 (3)}

Se1i_—Mo1—Se1ii _{88.377 (17) Mo1}iii_—Se4—Hoiii _{148.11 (3)}

Se1—Mo1—Se1ii _{174.56 (3) Mo1}ii_—Se4—Hoiii _{95.32 (2)}

Se4—Mo1—Se2 90.72 (2) Mo1—Se4—Hoiii _{130.75 (3)}

Se1i_{—Mo1—Se2 92.86 (2) Mo1}iii_—Se4—Hoii _{130.75 (3)}

Se1—Mo1—Se2 86.74 (2) Mo1ii_—Se4—Hoii _{148.11 (3)}

Se1ii_{—Mo1—Se2 98.27 (2) Mo1—Se4—Ho}ii _{95.32 (2)}

Se4—Mo1—Mo1iii _{57.990 (13) Ho}iii_—Se4—Hoii _{79.77 (4)}

Se1i_—Mo1—Mo1iii _{119.638 (17) Mo1}iii_{—Se4—Ho 95.32 (2)}

Se1—Mo1—Mo1iii _{59.39 (2) Mo1}ii_{—Se4—Ho 130.75 (3)}

Se1ii_—Mo1—Mo1iii _{117.90 (2) Mo1—Se4—Ho 148.11 (3)}

Se2—Mo1—Mo1iii _{130.04 (2) Ho}iii_{—Se4—Ho 79.77 (4)}

Se4—Mo1—Mo1ii _{57.990 (13) Ho}ii_{—Se4—Ho 79.77 (4)}

Se1i_—Mo1—Mo1ii _{118.656 (17) Mo2}vii_{—Se5—Mo2 63.11 (2)}

Se1—Mo1—Mo1ii _{119.34 (2) Mo2}vii_—Se5—Mo2v _{63.11 (2)}

Se1ii_—Mo1—Mo1ii _{57.95 (2) Mo2—Se5—Mo2}v _{63.11 (2)}

Se2—Mo1—Mo1ii _{137.221 (19) Mo2}vii_{—Se5—In 142.822 (15)}

supporting information

sup-4

Acta Cryst. (2006). E62, i83–i85

Se4—Mo1—Mo1iv _{118.092 (16) Mo2}v_{—Se5—In 142.822 (15)}

Se1i_—Mo1—Mo1iv _{59.53 (2) Se5—In—Se2}vi _{93.80 (2)}

Se1—Mo1—Mo1iv _{57.673 (15) Se5—In—Se2}xiv _{93.80 (2)}

Se1ii_—Mo1—Mo1iv _{116.97 (2) Se2}vi_—In—Se2xiv _{119.564 (5)}

Se2—Mo1—Mo1iv _{132.37 (2) Se5—In—Se2}i _{93.80 (2)}

Mo1iii_—Mo1—Mo1iv _{60.125 (11) Se2}vi_—In—Se2i _{119.564 (5)}

Mo1ii_—Mo1—Mo1iv _{90.0 Se2}xiv_—In—Se2i _{119.564 (5)}

Se4—Mo1—Mo1i _{118.092 (16) Se5—In—Se1}vi _{64.840 (19)}

Se1i_—Mo1—Mo1i _{58.53 (2) Se2}vi_—In—Se1vi _{65.026 (13)}

Se1—Mo1—Mo1i _{117.42 (2) Se2}xiv_—In—Se1vi _{64.880 (14)}

Se1ii_—Mo1—Mo1i _{57.236 (15) Se2}i_—In—Se1vi _{158.64 (4)}

Se2—Mo1—Mo1i _{139.85 (2) Se5—In—Se1}i _{64.840 (19)}

Mo1iii_—Mo1—Mo1i _{90.0 Se2}vi_—In—Se1i _{64.880 (14)}

Mo1ii_—Mo1—Mo1i _{60.125 (11) Se2}xiv_—In—Se1i _{158.64 (4)}

Mo1iv_—Mo1—Mo1i _{59.75 (2) Se2}i_—In—Se1i _{65.026 (13)}

Se4—Mo1—Invi _{99.688 (19) Se1}vi_—In—Se1i _{103.23 (2)}

Se1i_—Mo1—Invi _{83.419 (19) Se5—In—Se1}xiv _{64.840 (19)}

Se1—Mo1—Invi _{47.705 (14) Se2}vi_—In—Se1xiv _{158.64 (4)}

Se1ii_—Mo1—Invi _{136.719 (18) Se2}xiv_—In—Se1xiv _{65.026 (13)}

Se2—Mo1—Invi _{40.278 (15) Se2}i_—In—Se1xiv _{64.880 (14)}

Mo1iii_—Mo1—Invi _{102.863 (18) Se1}vi_—In—Se1xiv _{103.23 (2)}

Mo1ii_—Mo1—Invi _{156.315 (16) Se1}i_—In—Se1xiv _{103.23 (2)}

Mo1iv_—Mo1—Invi _{94.923 (17) Se5—In—Se3}iv _{123.487 (14)}

Mo1i_—Mo1—Invi _{140.93 (2) Se2}vi_—In—Se3iv _{55.274 (16)}

Se5—Mo2—Se2 92.189 (17) Se2xiv_—In—Se3iv _{141.57 (4)}

Se5—Mo2—Se2vii _{91.227 (17) Se2}i_—In—Se3iv _{71.125 (17)}

Se2—Mo2—Se2vii _{174.78 (3) Se1}vi_—In—Se3iv _{119.728 (14)}

Se5—Mo2—Mo2vii _{58.444 (12) Se1}i_—In—Se3iv _{59.375 (11)}

Se2—Mo2—Mo2vii _{120.20 (2) Se1}xiv_—In—Se3iv _{135.828 (14)}

Se2vii_—Mo2—Mo2vii _{58.72 (2) Se5—In—Se3}xv _{123.487 (14)}

Se5—Mo2—Mo2v _{58.444 (12) Se2}vi_—In—Se3xv _{71.125 (17)}

Se2—Mo2—Mo2v _{60.26 (2) Se2}xiv_—In—Se3xv _{55.274 (16)}

Se2vii_—Mo2—Mo2v _{118.66 (2) Se2}i_—In—Se3xv _{141.57 (4)}

Mo2vii_—Mo2—Mo2v _{60.0 Se1}vi_—In—Se3xv _{59.375 (11)}

Se5—Mo2—Se1viii _{90.55 (2) Se1}i_—In—Se3xv _{135.828 (14)}

Se2—Mo2—Se1viii _{86.15 (2) Se1}xiv_—In—Se3xv _{119.728 (14)}

Se2vii_—Mo2—Se1viii _{97.77 (2) Se3}iv_—In—Se3xv _{92.49 (2)}

Mo2vii_—Mo2—Se1viii _{137.526 (19) Se5—In—Se3}xiii _{123.487 (14)}

Mo2v_—Mo2—Se1viii _{130.30 (2) Se2}vi_—In—Se3xiii _{141.57 (4)}

Se5—Mo2—Se3vii _{175.06 (3) Se2}xiv_—In—Se3xiii _{71.125 (17)}

Se2—Mo2—Se3vii _{85.50 (2) Se2}i_—In—Se3xiii _{55.274 (15)}

Se2vii_—Mo2—Se3vii _{90.79 (2) Se1}vi_—In—Se3xiii _{135.829 (14)}

Mo2vii_—Mo2—Se3vii _{119.183 (18) Se1}i_—In—Se3xiii _{119.727 (14)}

Mo2v_—Mo2—Se3vii _{116.678 (19) Se1}xiv_—In—Se3xiii _{59.375 (11)}

Se1viii_—Mo2—Se3vii _{93.64 (2) Se3}iv_—In—Se3xiii _{92.49 (2)}

Se5—Mo2—Mo3vii _{120.52 (2) Se3}xv_—In—Se3xiii _{92.49 (2)}

Se2—Mo2—Mo3vii _{116.98 (2) Se5—In—Mo2}xiv _{91.190 (16)}

supporting information

sup-5

Acta Cryst. (2006). E62, i83–i85

Mo2vii_—Mo2—Mo3vii _{62.086 (16) Se2}xiv_—In—Mo2xiv _{34.134 (11)}

Mo2v_—Mo2—Mo3vii _{91.285 (15) Se2}i_—In—Mo2xiv _{153.608 (13)}

Se1viii_—Mo2—Mo3vii _{138.15 (2) Se1}vi_—In—Mo2xiv _{36.333 (10)}

Se3vii_—Mo2—Mo3vii _{57.21 (2) Se1}i_—In—Mo2xiv _{139.26 (2)}

Se5—Mo2—Mo3 118.65 (2) Se1xiv_—In—Mo2xiv _{94.266 (12)}

Se2—Mo2—Mo3 57.630 (18) Se3iv_—In—Mo2xiv _{126.11 (2)}

Se2vii_{—Mo2—Mo3 117.19 (2) Se3}xv_—In—Mo2xiv _{35.650 (9)}

Mo2vii_{—Mo2—Mo3 90.204 (15) Se3}xiii_—In—Mo2xiv _{100.888 (15)}

Mo2v_{—Mo2—Mo3 60.216 (15) Se5—In—Mo2}vi _{91.190 (16)}

Se1viii_{—Mo2—Mo3 131.91 (2) Se2}vi_—In—Mo2vi _{34.134 (11)}

Se3vii_{—Mo2—Mo3 56.463 (19) Se2}xiv_—In—Mo2vi _{153.608 (13)}

Mo3vii_{—Mo2—Mo3 59.43 (2) Se2}i_—In—Mo2vi _{85.861 (11)}

Se5—Mo2—Invi _{113.462 (19) Se1}vi_—In—Mo2vi _{94.266 (12)}

Se2—Mo2—Invi _{43.269 (13) Se1}i_—In—Mo2vi _{36.333 (10)}

Se2vii_—Mo2—Invi _{137.970 (17) Se1}xiv_—In—Mo2vi _{139.26 (2)}

Mo2vii_—Mo2—Invi _{163.303 (19) Se3}iv_—In—Mo2vi _{35.649 (9)}

Mo2v_—Mo2—Invi _{103.341 (19) Se3}xv_—In—Mo2vi _{100.888 (15)}

Se1viii_—Mo2—Invi _{51.183 (17) Se3}xiii_—In—Mo2vi _{126.11 (2)}

Se3vii_—Mo2—Invi _{67.56 (2) Mo2}xiv_—In—Mo2vi _{119.957 (1)}

Mo3vii_—Mo2—Invi _{123.41 (2) Se5—In—Mo2}i _{91.190 (16)}

Mo3—Mo2—Invi _{81.293 (19) Se2}vi_—In—Mo2i _{153.608 (13)}

Se3vii_{—Mo3—Se2 87.80 (2) Se2}xiv_—In—Mo2i _{85.861 (11)}

Se3vii_—Mo3—Se2ix _{87.80 (2) Se2}i_—In—Mo2i _{34.134 (11)}

Se2—Mo3—Se2ix _{112.27 (3) Se1}vi_—In—Mo2i _{139.26 (2)}

Se3vii_{—Mo3—Se3 176.59 (3) Se1}i_—In—Mo2i _{94.266 (12)}

Se2—Mo3—Se3 94.09 (2) Se1xiv_—In—Mo2i _{36.333 (10)}

Se2ix_{—Mo3—Se3 94.09 (2) Se3}iv_—In—Mo2i _{100.888 (15)}

Se3vii_—Mo3—Mo2x _{118.011 (16) Se3}xv_—In—Mo2i _{126.11 (2)}

Se2—Mo3—Mo2x _{150.76 (3) Se3}xiii_—In—Mo2i _{35.650 (9)}

Se2ix_—Mo3—Mo2x _{59.337 (15) Mo2}xiv_—In—Mo2i _{119.957 (1)}

Se3—Mo3—Mo2x _{60.904 (15) Mo2}vi_—In—Mo2i _{119.957 (1)}

Se3vii_—Mo3—Mo2v _{118.011 (16) Se5—In—Ho}xvi _{120.935 (16)}

Se2—Mo3—Mo2v _{59.337 (15) Se2}vi_—In—Hoxvi _{37.513 (19)}

Se2ix_—Mo3—Mo2v _{150.76 (3) Se2}xiv_—In—Hoxvi _{90.18 (2)}

Se3—Mo3—Mo2v _{60.904 (15) Se2}i_—In—Hoxvi _{133.45 (3)}

Mo2x_—Mo3—Mo2v _{112.72 (3) Se1}vi_—In—Hoxvi _{64.173 (16)}

Se3vii_—Mo3—Mo3v _{118.43 (3) Se1}i_—In—Hoxvi _{100.582 (19)}

Se2—Mo3—Mo3v _{120.47 (2) Se1}xiv_—In—Hoxvi _{155.19 (2)}

Se2ix_—Mo3—Mo3v _{120.47 (2) Se3}iv_—In—Hoxvi _{64.13 (2)}

Se3—Mo3—Mo3v _{58.17 (3) Se3}xv_—In—Hoxvi _{35.66 (2)}

Mo2x_—Mo3—Mo3v _{61.188 (17) Se3}xiii_—In—Hoxvi _{113.45 (3)}

Mo2v_—Mo3—Mo3v _{61.188 (17) Mo2}xiv_—In—Hoxvi _{62.630 (18)}

Se3vii_—Mo3—Mo3vii _{58.43 (3) Mo2}vi_—In—Hoxvi _{65.238 (19)}

Se2—Mo3—Mo3vii _{116.97 (2) Mo2}i_—In—Hoxvi _{147.84 (3)}

Se2ix_—Mo3—Mo3vii _{116.97 (2) Se5—In—Ho}xvii _{120.935 (16)}

Se3—Mo3—Mo3vii _{118.17 (3) Se2}vi_—In—Hoxvii _{90.18 (2)}

Mo2x_—Mo3—Mo3vii _{89.748 (15) Se2}xiv_—In—Hoxvii _{133.45 (3)}

supporting information

sup-6

Acta Cryst. (2006). E62, i83–i85

Mo3v_—Mo3—Mo3vii _{60.0 Se1}vi_—In—Hoxvii _{155.19 (2)}

Se3vii_—Mo3—Mo2ix _{60.314 (14) Se1}i_—In—Hoxvii _{64.172 (16)}

Se2—Mo3—Mo2ix _{145.40 (3) Se1}xiv_—In—Hoxvii _{100.582 (19)}

Se2ix_—Mo3—Mo2ix _{57.667 (15) Se3}iv_—In—Hoxvii _{35.66 (2)}

Se3—Mo3—Mo2ix _{118.486 (16) Se3}xv_—In—Hoxvii _{113.45 (3)}

Mo2x_—Mo3—Mo2ix _{57.698 (17) Se3}xiii_—In—Hoxvii _{64.13 (2)}

Mo2v_—Mo3—Mo2ix _{145.81 (3) Mo2}xiv_—In—Hoxvii _{147.84 (3)}

Mo3v_—Mo3—Mo2ix _{88.722 (14) Mo2}vi_—In—Hoxvii _{62.630 (18)}

Mo3vii_—Mo3—Mo2ix _{59.383 (16) Mo2}i_—In—Hoxvii _{65.238 (18)}

Se3vii_{—Mo3—Mo2 60.314 (14) Ho}xvi_—In—Hoxvii _{95.95 (2)}

Se2—Mo3—Mo2 57.667 (15) Se5—In—Hoxviii _{120.935 (16)}

Se2ix_{—Mo3—Mo2 145.40 (3) Se2}vi_—In—Hoxviii _{133.45 (3)}

Se3—Mo3—Mo2 118.486 (16) Se2xiv_—In—Hoxviii _{37.513 (19)}

Mo2x_{—Mo3—Mo2 145.81 (3) Se2}i_—In—Hoxviii _{90.18 (2)}

Mo2v_{—Mo3—Mo2 57.698 (17) Se1}vi_—In—Hoxviii _{100.582 (19)}

Mo3v_{—Mo3—Mo2 88.722 (14) Se1}i_—In—Hoxviii _{155.19 (2)}

Mo3vii_{—Mo3—Mo2 59.383 (16) Se1}xiv_—In—Hoxviii _{64.173 (16)}

Mo2ix_{—Mo3—Mo2 109.71 (3) Se3}iv_—In—Hoxviii _{113.45 (3)}

Se3vii_—Mo3—Hoii _{118.21 (4) Se3}xv_—In—Hoxviii _{64.13 (2)}

Se2—Mo3—Hoii _{61.851 (19) Se3}xiii_—In—Hoxviii _{35.66 (2)}

Se2ix_—Mo3—Hoii _{61.851 (19) Mo2}xiv_—In—Hoxviii _{65.238 (19)}

Se3—Mo3—Hoii _{65.19 (4) Mo2}vi_—In—Hoxviii _{147.84 (3)}

Mo2x_—Mo3—Hoii _{92.11 (2) Mo2}i_—In—Hoxviii _{62.630 (18)}

Mo2v_—Mo3—Hoii _{92.11 (2) Ho}xvi_—In—Hoxviii _{95.95 (2)}

Mo3v_—Mo3—Hoii _{123.36 (4) Ho}xvii_—In—Hoxviii _{95.95 (2)}

Mo3vii_—Mo3—Hoii _{176.64 (4) Se4}ix_{—Ho—Se4 84.46 (5)}

Mo2ix_—Mo3—Hoii _{119.517 (18) Se4}ix_—Ho—Se3ii _{88.65 (4)}

Mo2—Mo3—Hoii _{119.517 (18) Se4—Ho—Se3}ii _{88.65 (4)}

Mo1iv_{—Se1—Mo1 63.80 (2) Se4}ix_—Ho—Se2iii _{163.32 (6)}

Mo1iv_—Se1—Mo1iii _{63.24 (2) Se4—Ho—Se2}iii _{86.49 (2)}

Mo1—Se1—Mo1iii _{62.66 (2) Se3}ii_—Ho—Se2iii _{105.14 (4)}

Mo1iv_—Se1—Mo2xi _{131.54 (2) Se4}ix_—Ho—Se2xix _{86.49 (2)}

Mo1—Se1—Mo2xi _{129.02 (2) Se4—Ho—Se2}xix _{163.32 (6)}

Mo1iii_—Se1—Mo2xi _{82.00 (2) Se3}ii_—Ho—Se2xix _{105.14 (4)}

Mo1iv_—Se1—Invi _{134.69 (2) Se2}iii_—Ho—Se2xix _{98.60 (5)}

Mo1—Se1—Invi _{99.386 (18) Se4}ix_—Ho—Mo3iii _{120.75 (4)}

Mo1iii_—Se1—Invi _{148.54 (3) Se4—Ho—Mo3}iii _{120.75 (4)}

Mo2xi_—Se1—Invi _{92.48 (2) Se3}ii_—Ho—Mo3iii _{138.15 (6)}

Mo3—Se2—Mo2 64.703 (19) Se2iii_—Ho—Mo3iii _{53.61 (3)}

Mo3—Se2—Mo2v _{62.848 (18) Se2}xix_—Ho—Mo3iii _{53.61 (3)}

Mo2—Se2—Mo2v _{61.02 (2) Se4}ix_—Ho—Se3iii _{83.57 (4)}

Mo3—Se2—Mo1 130.30 (3) Se4—Ho—Se3iii _{83.57 (4)}

Mo2—Se2—Mo1 127.66 (2) Se3ii_—Ho—Se3iii _{169.47 (6)}

Mo2v_{—Se2—Mo1 81.96 (2) Se2}iii_—Ho—Se3iii _{81.51 (3)}

Mo3—Se2—Hoii _{64.54 (3) Se2}xix_—Ho—Se3iii _{81.51 (3)}

Mo2—Se2—Hoii _{129.24 (3) Mo3}iii_—Ho—Se3iii _{52.38 (3)}

Mo2v_—Se2—Hoii _{95.61 (4) Se4}ix_—Ho—Hoiii _{50.12 (2)}

supporting information

sup-7

Acta Cryst. (2006). E62, i83–i85

Mo3—Se2—Invi _{117.17 (3) Se3}ii_—Ho—Hoiii _{58.17 (5)}

Mo2—Se2—Invi _{102.597 (19) Se2}iii_—Ho—Hoiii _{130.20 (3)}

Mo2v_—Se2—Invi _{162.70 (2) Se2}xix_—Ho—Hoiii _{130.20 (3)}

Mo1—Se2—Invi _{106.76 (2) Mo3}iii_—Ho—Hoiii _{163.68 (7)}

Hoii_—Se2—Invi _{99.69 (4) Se3}iii_—Ho—Hoiii _{111.30 (5)}

Mo3v_{—Se3—Mo3 63.41 (3) Se4}ix_—Ho—Hoii _{50.12 (2)}

Mo3v_—Se3—Mo2x _{63.224 (17) Se4—Ho—Ho}ii _{50.12 (2)}

Mo3—Se3—Mo2x _{61.881 (17) Se3}ii_—Ho—Hoii _{118.17 (5)}

Mo3v_—Se3—Mo2v _{63.224 (17) Se2}iii_—Ho—Hoii _{113.79 (5)}

Mo3—Se3—Mo2v _{61.881 (17) Se2}xix_—Ho—Hoii _{113.79 (5)}

Mo2x_—Se3—Mo2v _{114.35 (3) Mo3}iii_—Ho—Hoii _{103.68 (7)}

Mo3v_—Se3—Hoiii _{163.64 (5) Se3}iii_—Ho—Hoii _{51.30 (5)}

Mo3—Se3—Hoiii _{132.95 (5) Ho}iii_—Ho—Hoii _60.0

Mo2x_—Se3—Hoiii _{121.145 (17) Se4}ix_—Ho—Inxvii _{153.40 (5)}

Mo2v_—Se3—Hoiii _{121.145 (17) Se4—Ho—In}xvii _{101.72 (3)}

Mo3v_—Se3—Hoii _{125.83 (4) Se3}ii_—Ho—Inxvii _{65.90 (3)}

Mo3—Se3—Hoii _{62.42 (3) Se2}iii_—Ho—Inxvii _{42.80 (2)}

Mo2x_—Se3—Hoii _{91.10 (2) Se2}xix_—Ho—Inxvii _{92.62 (4)}

Mo2v_—Se3—Hoii _{91.10 (2) Mo3}iii_—Ho—Inxvii _{78.51 (3)}

Hoiii_—Se3—Hoii _{70.53 (6) Se3}iii_—Ho—Inxvii _{122.64 (3)}

Mo3v_—Se3—Inxii _{87.95 (2) Ho}iii_—Ho—Inxvii _{115.19 (5)}

Mo3—Se3—Inxii _{136.807 (19) Ho}ii_—Ho—Inxvii _{149.064 (16)}

Mo2x_—Se3—Inxii _{76.790 (18) Se4}ix_—Ho—Inxx _{101.72 (3)}

Mo2v_—Se3—Inxii _{134.33 (3) Se4—Ho—In}xx _{153.40 (5)}

Hoiii_—Se3—Inxii _{78.44 (3) Se3}ii_—Ho—Inxx _{65.90 (3)}

Hoii_—Se3—Inxii _{134.15 (2) Se2}iii_—Ho—Inxx _{92.62 (4)}

Mo3v_—Se3—Inxiii _{87.95 (2) Se2}xix_—Ho—Inxx _{42.80 (2)}

Mo3—Se3—Inxiii _{136.807 (19) Mo3}iii_—Ho—Inxx _{78.51 (3)}

Mo2x_—Se3—Inxiii _{134.33 (3) Se3}iii_—Ho—Inxx _{122.64 (3)}

Mo2v_—Se3—Inxiii _{76.790 (18) Ho}iii_—Ho—Inxx _{115.19 (5)}

Hoiii_—Se3—Inxiii _{78.44 (3) Ho}ii_—Ho—Inxx _{149.064 (16)}

Hoii_—Se3—Inxiii _{134.15 (2) In}xvii_—Ho—Inxx _{61.87 (3)}