Home The crystal structure of bis(μ2-iodido)-bis(η6-benzene)-bis(iodido)-diosmium(II), C12H12I4Os2
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The crystal structure of bis(μ2-iodido)-bis(η6-benzene)-bis(iodido)-diosmium(II), C12H12I4Os2

  • Kgaugelo C. Tapala ORCID logo and Hadley S. Clayton ORCID logo EMAIL logo
Published/Copyright: November 12, 2021

Abstract

C12H12I4Os2, orthorhombic, Pbca (no. 61), a = 11.9720(5) Å, b = 10.4991(4) Å, c = 13.2810(6) Å, V = 1669.36(12) Å3, Z = 4, R gt (F) = 0.0349, wR ref (F 2) = 0.0848, T = 173(2) K.

CCDC no.: 2114617

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal: Red plate
Size: 0.45 × 0.23 × 0.04 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 22.6 mm−1
Diffractometer, scan mode: Bruker D8 Venture Photon, ω
θ max, completeness: 28.0°, >99%
N(hkl)measuredN(hkl)uniqueR int: 26,320, 2011, 0.062
Criterion for I obs, N(hkl)gt: I obs > 2 σ(I obs), 1934
N(param)refined: 70
Programs: Bruker [1], SHELX [2], WinGX [3], PLATON [4]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

Atom x y z U iso*/U eq
C1 0.6057 (5) 0.8142 (6) 0.6068 (5) 0.0304 (18)
H1 0.665895 0.800638 0.652153 0.036*
C2 0.5024 (6) 0.8536 (6) 0.6431 (4) 0.0307 (17)
H2 0.492051 0.866963 0.71328 0.037*
C3 0.4143 (5) 0.8735 (6) 0.5768 (6) 0.0337 (18)
H3 0.343693 0.900424 0.601663 0.04*
C4 0.4294 (5) 0.8540 (6) 0.4742 (5) 0.0293 (17)
H4 0.369178 0.86756 0.428918 0.035*
C5 0.5327 (6) 0.8146 (6) 0.4379 (4) 0.0284 (18)
H5 0.54302 0.801235 0.36779 0.034*
C6 0.6208 (4) 0.7947 (6) 0.5042 (5) 0.0274 (17)
H6 0.691379 0.767774 0.479406 0.033*
I1 0.33304 (5) 0.58731 (6) 0.69308 (4) 0.01803 (15)
I2 0.38608 (4) 0.52380 (5) 0.41369 (4) 0.01314 (14)
Os1 0.47884 (3) 0.68286 (3) 0.55414 (2) 0.00830 (11)

Source of material

All reagents are commercially available and were used without further purification. Potassium osmate K2[OsO2(OH)4] (1.020 g, 2.77 mmol) was refluxed in hydroiodic acid/ethanol (50 mL 3:2 v/v) at 150 °C for 8 h to generate the [OsI6]2− intermediate. To the cooled reaction mixture was added 1,3-cyclohexadiene (3 mL, 31 mmol). The reaction mixture was then heated under microwave irradiation (140 °C, 400 W) for 20 min. A red crystalline product was obtained upon cooling, which was collected by filtration and washed with hexane (10 mL). Yield 67% (0.974 g, 0.933 mmol). Crystals were obtained as red plates directly upon cooling the reaction solution to room temperature.

Experimental details

Intensity data was determined on a Bruker Venture D8 Photon CMOS diffractometer with graphite-monochromated Mo K α1 (λ = 0.71073 Å) radiation at 173 K using an Oxford Cryostream 600 cooler. Data reduction was carried out using the program SAINT-Plus, version 6.02 [1] and empirical absorption corrections were made using SADABS [1]. The structure was solved in the WinGX [2] Suite of programs, using intrinsic phasing through SHELXT [3] and refined using SHELXL-2018-3 [3]. All C bound hydrogen atoms were placed at idealized positions and refined as riding atoms with isotropic parameters 1.2 times those of their parent atoms. SIMU and DELU commands were used to constraint the anisotropic displacement parameters for all the C atoms and AFIX66 to idealize the phenyl ring. Diagrams and publication material were generated using ORTEP-3 [2], and PLATON [4].

Comment

Metal-arenes are a well established subclass of organometallic compounds since the synthesis of the archetypal complex [Cr(η6-C6H6)2] by Fischer and Hafner in 1955 [5]. Dinuclear metal-arene compounds of the heavier transition metals such as ruthenium and osmium are extensively employed in organometallic chemistry as precursors [6, 7], providing synthetic pathways for various organometallic compounds with applications in catalysis [8] and bioorganometallic chemistry [9, 10].

The title compound crystallizes in the space group Pbca, with a centrosymmetric molecular unit. The dinuclear complex adopts a pseudo-octahedral geometry at each Os2+ ion, with the hexahaptic benzene ring occupying three coordination sites together with two bridging iodido ligands and one terminal iodido ligand occupying a further three coordination sites.

For the terminal iodido ligand the Os–I bond length is measured as 2.7310(6) Å while for the two bridging iodido ligands Os–I bond lengths of 2.7388(6) and 2.7396(6) Å are measured. The distance from the benzene ring centroid to the Os center is calculated to be 1.664 Å. The benzene ligand is symmetrically coordinated to the metal with the six Os–C bond lengths in the narrow range of 2.165–2.171 Å with no evidence of ring puckering. The distance between the two Os2+ ions is 4.131 Å which confirms the absence of a direct metal-metal bond.

The crystal growth of the title compound is supported by C–H⃛I interactions. There are also strong intermolecular ππ-interactions observed between benzene rings to adjacent complexes with a plane-to-plane distance of 3.324 Å.


Corresponding author: Hadley S. Clayton, Chemistry Department, Unisa Science Campus, University of South Africa, Johannesburg, South Africa, E-mail:

Acknowledgments

The authors would like to thank Professor A. Lemmerer (University of the Witwatersrand) for his assistance with crystallographic data collection. The authors gratefully acknowledge Anglo American Technical Solutions Research for generous donations of potassium osmate.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2021-10-14
Accepted: 2021-10-29
Published Online: 2021-11-12
Published in Print: 2022-02-23

© 2021 Kgaugelo C. Tapala and Hadley S. Clayton, published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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