Crystal structure of tricarbon­yltris(pyri­dine-κN)rhenium(I) tetra­fluorido­borate

Adebomi A Ikotun; Micheal P Coogan; Abimbola A Owoseni; Nattamai Bhuvanesh; Gabriel O Egharevba

doi:10.1107/S2056989015006180

. 2015 Apr 11;71(Pt 5):m106–m107. doi: 10.1107/S2056989015006180

Crystal structure of tricarbonyltris(pyridine-κN)rhenium(I) tetrafluoridoborate

Adebomi A Ikotun ^a, Micheal P Coogan ^b,^c, Abimbola A Owoseni ^d, Nattamai Bhuvanesh ^e, Gabriel O Egharevba ^f,^*

PMCID: PMC4420038 PMID: 25995887

Abstract

In the title compound, [Re(C₆H₅N)₃(CO)₃]BF₄, the Re^I ion is six-coordinated by three pyridine N atoms and three carbonyl C atoms. In each case, the carbonyl C atom lies trans to a pyridine N atom. In the crystal, the ions are linked via C—H⋯F hydrogen bonds and C—H⋯π interactions, forming a three-dimensional framework. The F atoms of the BF₄ anion are disordered over two positions and gave a final refined occupancy ratio of 0.705 (11):0.295 (11).

Keywords: crystal structure, rhenium(I) tricarbonyl complexes, tricarbonyl tris-pyridyl rhenium(I) cation, luminescent agent.

Related literature

For background to rhenium tricarbonyl complexes, see: Amoroso et al. (2008 ▸); Coogan et al. (2009 ▸). For the structure of tricarbonyl tris-pyridyl rhenium(I) hexafluorophosphate, see: Franklin et al. (2008 ▸). For the preparation of [Re(C₁₄H₁₀N₂O)(CO)₃Br] used in the synthesis, see: Al Subari et al. (2010 ▸); Coogan et al. (2009 ▸). graphic file with name e-71-0m106-scheme1.jpg

Experimental

Crystal data

[Re(C₆H₅N)₃(CO)₃]BF₄
M _r = 594.34
Monoclinic,
a = 8.1272 (12) Å
b = 18.718 (3) Å
c = 13.046 (2) Å
β = 97.317 (9)°
V = 1968.5 (5) Å³
Z = 4
Cu Kα radiation
μ = 12.66 mm⁻¹
T = 110 K
0.08 × 0.06 × 0.02 mm

Data collection

Bruker GADDS D8 Discover diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2006 ▸) T _min = 0.431, T _max = 0.786
39315 measured reflections
2891 independent reflections
2589 reflections with I > 2σ(I)
R _int = 0.052
θ_max = 60.0°
Standard reflections: 0

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.048
S = 1.11
2891 reflections
308 parameters
172 restraints
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.98 e Å⁻³

Data collection: APEX2 and FRAMBO (Bruker, 2004 ▸); cell refinement: SAINT (Bruker, 2004 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: X-SEED (Barbour, 2001 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸) and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015006180/su5093sup1.cif

e-71-0m106-sup1.cif^{(19KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015006180/su5093Isup2.hkl

e-71-0m106-Isup2.hkl^{(141.9KB, hkl)}

Click here for additional data file.^{(1.8MB, tif)}

. DOI: 10.1107/S2056989015006180/su5093fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(989.3KB, tif)}

. DOI: 10.1107/S2056989015006180/su5093fig2.tif

Preparation of the title compound.

CCDC reference: 1022851

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

Table 1. Selected bond lengths ().

Re1C3	1.916(5)
Re1C1	1.924(5)
Re1C2	1.926(5)
Re1N1	2.215(3)
Re1N2	2.229(4)
Re1N3	2.240(4)

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Table 2. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the N1/C4C8 pyrdine ring.

DHA	DH	HA	D A	DHA
C4H4AF3ⁱ	0.95	2.31	3.240(7)	165
C13H13AF4ⁱⁱ	0.95	2.31	3.219(12)	160
C17H17AF3ⁱⁱⁱ	0.95	2.32	3.123(7)	142
C10H10A Cg1^iv	0.95	2.61	3.302(5)	130

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

We thank Professor John A. Gladysz for providing facilities for a portion of these studies, and helpful discussions. The US National Science Foundation (NSF, CHE1153085) is thanked for the portion of the research carried out at Texas A & M University.

supplementary crystallographic information

S1. Comment

Amoroso and coworkers (Amoroso et al., 2008) prepared a novel 3-chloromethylpyridyl bipyridine tricarbonyl rhenium complex and demonstrated the suitability of this complex in Mitochondria. That report represents the first application of a luminescent agent for specific targeting of a biological entity in imaging. Recently, Coogan and co-workers (Coogan et al., 2009) have also directed their research focus towards such complexes, thus preparing more novel rhenium tricarbonyl compounds to prove that heavy metals are not only erroneously termed as poisons, but can also be useful towards preparing drugs of great biological significance to man. Thus the design, syntheses and characterization of rhenium(I) tricarbonyl complexes has being of great interest due to their biological significance. The first report of the tricarbonyl tris-pyridyl rhenium(I) cation was published by Franklin et al. (2008), viz. tricarbonyl tris-pyridyl rhenium(I) hexafluorophosphate, which is quite similar to the title compound with some slight differences.

The molecular structure of the title complex is illustrated in Fig. 1. The Re^I ion is six-coordinated by three pyridine N atoms and three carbonyl C atoms.

In the crystal, the ions are linked via C-H···F hydrogen bonds and C-H···π interactions forming a three-dimensional framework (Table 1).

S2. Experimental

The preparation of the title compound is illustrated in Fig. 2. [Re(C₁₄H₁₀N₂O)(CO)₃Br] (0.16 g, 0.28 mmol), prepared according to literature procedures (Al Subari et al., 2010; Coogan et al., 2009), was reacted with AgBF₄ (0.05 g, 0.28 mmol) in 11 ml diethyl ether under nitrogen with refluxing for 35 min. The solution was then filtered through celite and to the clear filtrate pyridine (0.023 ml, 0.28 mmol) was added. The mixture was stirred for ca. 24 h. After it was poured into a vial and petroleum ether was added drop wise in excess to precipitate out the complex. This was covered with perforated foil and left overnight in the hood. Colourless block-like crystals grew on the sides of the vial.