Tri­carbonyl­chlorido­(6′,7′-di­hydro-5′H-spiro­[cyclo­hexane-1,6′-dipyrido[3,2-d:2′,3′-f][1,3]diazepine]-κ2 N 1,N 11)rhenium(I)

Oliver R Clegg; Lindsay P Harding; John W Miller; Craig R Rice

doi:10.1107/S1600536813024288

. 2013 Sep 4;69(Pt 10):m527. doi: 10.1107/S1600536813024288

Tricarbonylchlorido(6′,7′-dihydro-5′H-spiro[cyclohexane-1,6′-dipyrido[3,2-d:2′,3′-f][1,3]diazepine]-κ² N ¹,N ¹¹)rhenium(I)

Oliver R Clegg ^a, Lindsay P Harding ^a,^*, John W Miller ^a, Craig R Rice ^a

PMCID: PMC3790342 PMID: 24098164

Abstract

In the title compound, [ReCl(C₁₆H₁₈N₄)(CO)₃], the Re^I ion is coordinated in a distorted octahedral geometry by one Cl atom, two N atoms of the bidentate ligand and three carbonyl groups. The cyclohexane group is orientated in a transoid fashion with respect to the chloride ligand. In the crystal, N—H⋯Cl hydrogen bonds link complex molecules, forming a two-dimensional network parallel to (100).

Related literature

For a review of the photophysical properties of Re–polypyridyl complexes, see: Coleman et al. (2008 ▶). For the synthesis of [Re(3,3′-diamino-2,2′-bipyridine)(CO)₃Cl] and for the preparation of oxo-steroid derivatives of [Re(3,3′-diamino-2,2′-bipyridine)(CO)₃Cl], see: Bullock et al. (2012 ▶). For the reaction of [Re(3,3′-diamino-2,2′-bipyridine)(CO)₃Cl] with ketones, see: Clayton et al. (2008 ▶). For the structure of the cyclopentane analogue of the title compound, see: Clegg et al. (2013 ▶).

Experimental

Crystal data

[ReCl(C₁₆H₁₈N₄)(CO)₃]
M _r = 572.02
Monoclinic,
a = 12.6794 (6) Å
b = 11.9040 (6) Å
c = 12.7732 (6) Å
β = 97.066 (1)°
V = 1913.29 (16) Å³
Z = 4
Mo Kα radiation
μ = 6.52 mm⁻¹
T = 150 K
0.10 × 0.10 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.562, T _max = 0.828
22579 measured reflections
5590 independent reflections
4543 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.051
S = 1.04
5590 reflections
259 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.08 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813024288/lh5645sup1.cif

e-69-0m527-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024288/lh5645Isup2.hkl

e-69-0m527-Isup2.hkl^{(273.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Cl1ⁱ	0.89 (3)	2.64 (2)	3.417 (3)	146 (3)
N4—H4⋯Cl1ⁱⁱ	0.89 (3)	2.46 (3)	3.334 (3)	171 (3)

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

Acknowledgments

The authors wish to thank the University of Huddersfield for financial support.

supplementary crystallographic information

1. Comment

The title complex was prepared as part of a larger study into conjugation of [Re(3,3'-diamino-2,2'-bipyridine)(CO)₃Cl] with oxo-steroids to form luminescent derivatives (Bullock et al. 2012). These steroids contain a cyclohexyl ring (ring A) with a ketone group in the 3-position; therefore, cyclohexanone was used as a model compound to examine the potential reactivity of such steroids with the rhenium complex.

Single-crystal X-ray analysis of the title complex gave the structure shown in Fig. 1. The rhenium centre adopts a distorted octahedral geometry which is coordinated by two nitrogen atoms from a 3,3'-diamino-2,2'-bipyridyl ligand and two carbonyl ligands in the equatorial sites and by a carbonyl ligand and a chloride ion in the axial sites. The cyclohexyl ring adopts a chair conformation and is orientated in a trans-oid fashion relative to the chloride ion on the rhenium centre. In the crystal, N—H···Cl hydrogen bonds (Table 1 & Fig. 2) link complex molecules to form a two-dimensional network parallel (100).

A similar compound has been prepared using cyclopentanone instead of cyclohexanone. The title compound compound is essentially isostructural with that compound (Clegg et al. 2013).

2. Experimental

To a solution of [Re(3,3'-diamino-2,2'-bipyridine)(CO)₃Cl] in dichloromethane was added cyclohexanone (10 µL, ca. 2 eq.) and a few grains of camphorsulfonic acid. The solution was stirred at room temperature for 2 h. The resulting precipitate was filtered in vacuo, washed with dichloromethane and dried, giving the product as a yellow solid. Crystals suitable for X-ray analysis were prepared by slow evaporation of an acetonitrile solution of the complex.