Crystal structure of a mixed-valence μ-oxide Sn12 cluster

Marina M Kireenko; Kirill V Zaitsev; Sergey S Karlov; Mikhail P Egorov; Andrei V Churakov

doi:10.1107/S1600536814023460

. 2014 Oct 29;70(Pt 11):m378–m379. doi: 10.1107/S1600536814023460

Crystal structure of a mixed-valence μ-oxide Sn₁₂ cluster

Marina M Kireenko ^a, Kirill V Zaitsev ^a, Sergey S Karlov ^a, Mikhail P Egorov ^b, Andrei V Churakov ^c,^*

PMCID: PMC4257312 PMID: 25484784

Abstract

The mixed-valence μ-oxide Sn₁₂ cluster, decacarbonyltetra-μ₄-oxido-hexa-μ₃-oxido-tetrakis[μ-2,2′-(pyridine-2,6-diyl)bis(1,1-diphenylethanolato)]decatin(II)ditin(IV)dimolybdenum(O)(2 Mo—Sn) toluene heptasolvate, [Mo₂Sn₁₂(C₃₃H₂₇NO₂)₄O₁₀(CO)₁₀]·7C₇H₈, has a crystallographically imposed inversion centre. The asymmetric unit also contains three and a half toluene solvent molecules, one of which is disordered about a centre of symmetry. The complex molecule comprises six distinct Sn atom species with four different coordination numbers, namely 3, 4, 5, and 6. The Sn^II atoms forming the central Sn₁₀O₁₀ core adopt distorted trigonal–pyramidal, square-pyramidal and octahedral coordination geometries provided by the μ-oxide atoms and by the O- and N-donor atoms of two pyridinediethanolate ligands. The terminal Sn^IV atoms have distorted trigonal–bipyramidal coordination geometries, with a μ₄-oxide atom and the N atom of a pyridinediethanolate ligand occupying the axial positions, and the Mo atom of a Mo(CO)₅ group and the alkoxy O atoms of a ligand forming the equatorial plane. In the crystal, weak intra- and intermolecular C—H⋯O hydrogen bonds are observed.

Keywords: crystal structure, stannylenes, S₁₂ cluster, carbonyls

Related literature

For general background to the chemistry of stannylene complexes with transition metals, see: Baumgartner & Marschner (2014 ▶); Lee & Sekiguchi (2010 ▶). For our previous work on heavy carbene analogs, see: Kireenko et al. (2012 ▶, 2013 ▶); Huang et al. (2012 ▶, 2013 ▶).

Experimental

Crystal data

[Mo₂Sn₁₂(C₃₃H₂₇NO₂)₄O₁₀(CO)₁₀]·7C₇H₈
M _r = 4579.42
Triclinic,
a = 15.8218 (17) Å
b = 15.9933 (17) Å
c = 18.806 (2) Å
α = 94.833 (2)°
β = 95.014 (2)°
γ = 110.605 (2)°
V = 4403.5 (8) Å³
Z = 1
Mo Kα radiation
μ = 1.88 mm⁻¹
T = 173 K
0.25 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.651, T _max = 0.864
32165 measured reflections
15393 independent reflections
12647 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.081
S = 1.02
15393 reflections
939 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814023460/rz5135sup1.cif

e-70-0m378-sup1.cif^{(69.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023460/rz5135Isup2.hkl

e-70-0m378-Isup2.hkl^{(752.3KB, hkl)}

Click here for additional data file.^{(1.7MB, tif)}

x y z . DOI: 10.1107/S1600536814023460/rz5135fig1.tif

The molecular structure of the title compound, with displacement ellipsoids shown at the 50% probability level. Toluene solvent molecules, hydrogen atoms and labels for carbon atoms are omitted for clarity. Suffix A indicates the symmetry operator 2-x, 2-y, −z.

CCDC reference: 1030879

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C22H22AO9	0.99	2.28	3.052(5)	134
C28H28AO7	0.99	2.48	3.378(5)	151
C33H33O1ⁱ	0.95	2.53	3.205(6)	128

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by a grant from the Russian Scientific Fund (14–13-01456).

supplementary crystallographic information

S1. Comment

Nowadays, carbenes and their heavy analogues (germylenes and stannylenes) are regarded as a new perspective ligands for homogeneous catalysis which coordinate to late transition metals (Baumgartner & Marschner, 2014; Lee & Sekiguchi, 2010). Recently we described the synthesis and structures of some Pd, Mo and W complexes bearing Ge(II) and Sn(II) containing ligands (Kireenko et al., 2012, 2013; Huang et al., 2012, 2013).

The structure of the mixed-valence µ-oxo Sn₁₂ title compound is shown in Fig. 1. The molecule comprises six distinct tin atom species with four different coordination numbers, namely 3, 4, 5, and 6. The three-coordinated Sn4, Sn5, Sn6 tin(II) atoms adopt a distorted trigonal pyramidal coordination geometry, with Sn—O bond lengths ranging from 2.064 (3) to 2.240 (3) Å and O—Sn—O angles narrower than 93.2 (1) °. The four-coordinated tin(II) atom Sn3 exhibits a distorted square pyramidal geometry with Sn—O distances lying within 2.109 (3)–2.475 (3) Å and cis O—Sn—O angles varying within 70.3 (1)–76.3 (1) °. The coordination polyhedron about the six-coordinated Sn2 tin(II) atom is a distorted octahedron; the apical positions are occupied by the N2 and O8 atoms, the best equatorial plane is provided by the O7, O8ⁱ, O9, O21 atoms (maximum displacement: 0.232 (3) Å for O7; symmetry code: (i) 2 - x, 2 - y, -z), with the metal atom displaced by 0.1462 (3) Å toward N7. The terminal Sn1 tin(IV) atom shows a trigonal bipyramidal coordination geometry, with the N1 nitrogen atom and the O6 µ₄-oxygen atom occupying the axial positions, and the equatorial positions engaged by the Mo atoms of a Mo(CO)₅ group and by the O atoms of an alkoxy ligand (). The Sn—Mo bond length is 2.7879 (5) Å. Among five Mo—C bonds, the Mo—C1 bond lengths (opposite to the Sn1 atom) is the shortest (1.986 (5) Å). Both µ₄-oxygen atoms O6 and O8 have a significantly distorted tetrahedral tin environment with Sn—O—Sn angles ranging from 94.9 (1) to 130.1 (1)°. Two intramolecular C—H···O hydrogen bonds (Table 1) involving methylene carbon atoms are present. In the crystal, pairs of weak intermolecular C—H···O hydrogen bonds (Table 1) link centrosymmetrically related complex molecules into dimers.

S2. Experimental

The title compound was obtained in 10% yield by the reaction of equimolar mixture of [C₅H₃N(CH₂CPh₂O)₂]₂Sn and Mo(CO)₅*THF (generated at room temperature in THF in situ under UV irradiation of Mo(CO)₆ in THF) in toluene solution. The crystals suitable for X-Ray analysis were obtained after recrystallization from toluene at room temperature.