Crystal structure of a second polymorph of 2-cyclo­penta­dienyl-1,7-dicarba-2-cobalta-closo-dodeca­borane(11)

Wing Y Man; Georgina M Rosair; Alan J Welch

doi:10.1107/S2056989015011445

. 2015 Jun 17;71(Pt 7):m141–m142. doi: 10.1107/S2056989015011445

Crystal structure of a second polymorph of 2-cyclopentadienyl-1,7-dicarba-2-cobalta-closo-dodecaborane(11)

Wing Y Man ^a, Georgina M Rosair ^a, Alan J Welch ^a,^*

PMCID: PMC4518921 PMID: 26279892

Abstract

A new polymorph of the title compound 2-(η-C₅H₅)-2,1,7-closo-CoC₂B₉H₁₁, [Co(C₅H₅)(C₂H₁₁B₉)], in the space group P2₁/n has been characterized, including the unambiguous location of both cage C atoms. The precision of this study is an order of magnitude greater than that of the first polymorph [C2/c; Lopez et al. (2010). Collect. Czech. Chem. Commun. 75, 853–869].

Keywords: metallacarborane, polymorph, crystal structure

Related literature

For the structure of the C2/c polymorph, see: Lopez et al. (2010 ▸). For structures of other (η-C₅H₅)CoC₂B₉H₁₁ isomers, see: Smith & Welch (1986 ▸), Lopez et al. (2010 ▸) and Man et al. (2014 ▸). Methods used to identify cage C atoms: Vertex-to-Centroid Distance (McAnaw et al., 2013 ▸) and Boron-Hydrogen Distance (McAnaw et al., 2014 ▸). graphic file with name e-71-0m141-scheme1.jpg

Experimental

Crystal data

[Co(C₅H₅)(C₂H₁₁B₉)]
M _r = 256.42
Monoclinic,
a = 12.4903 (11) Å
b = 8.7207 (7) Å
c = 12.7392 (12) Å
β = 116.123 (4)°
V = 1245.86 (19) Å³
Z = 4
Mo Kα radiation
μ = 1.34 mm⁻¹
T = 100 K
0.46 × 0.44 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker,2008 ▸) T _min = 0.649, T _max = 0.747
37238 measured reflections
5019 independent reflections
4268 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.058
S = 1.03
5019 reflections
218 parameters
All H-atom parameters refined
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▸); cell refinement: SAINT (Bruker, 2011 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015011445/pj2020sup1.cif

e-71-0m141-sup1.cif^{(1.1MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011445/pj2020Isup2.hkl

e-71-0m141-Isup2.hkl^{(399.5KB, hkl)}

Click here for additional data file.^{(2KB, mol)}

Supporting information file. DOI: 10.1107/S2056989015011445/pj2020Isup3.mol

Click here for additional data file.^{(3.6MB, tif)}

. DOI: 10.1107/S2056989015011445/pj2020fig1.tif

Perspective view of the title compound with atom numbering and displacement ellipsoids drawn at the 50% probability level except for H atoms.

Click here for additional data file.^{(2.8MB, tif)}

. DOI: 10.1107/S2056989015011445/pj2020fig2.tif

Packing diagram of the title compound.

CCDC reference: 1406489

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

Table 1. Selected bond lengths ().

C1Co2	2.0556(8)
Co2B3	2.0471(9)
Co2B6	2.0762(9)
Co2C7	2.0539(8)
Co2B11	2.0746(10)
Co2C21	2.0574(9)
Co2C22	2.0536(9)
Co2C23	2.0759(9)
Co2C24	2.0823(9)
Co2C25	2.0548(9)

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Acknowledgments

The authors thank the EPSRC for support of WYM (grant EP/I031545/1).

supplementary crystallographic information

S1. Synthesis and crystallization

The compound was prepared as previously reported (Lopez et al. 2010) and purity established by NMR spectroscopy: ¹H NMR (CDCl₃); 5.64 (s, 5 H, C₅H₅), 2.65 (br s, 2 H, CH_cage). ¹¹B{¹H} NMR (CDCl₃): 2.9 (1 B), -2.4 (2 B), -9.0 (1 B), -10.8 (1 B), -11.8 (2 B), -17.0 (2 B). Single crystals were grown by diffusion of a solution of the compound in CH₂Cl₂ and petroleum ether at 4 °C.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The carbon atoms in the metallaccarborane were located using the Vertex-to-Centroid Distance (VCD) (McAnaw et al., 2013) and Boron-Hydrogen Distance (BHD) (McAnaw et al., 2014) methods that we have developed for C/B discrimination. In this case the methods afford unequivocal assignment of the carbon location.