[Bis(pyridin-2-ylmeth­yl)amine-κ3 N,N′,N′′]tricarbonyl­rhenium(I) bromide hemihydrate

Marietjie Schutte; Theunis J Muller; Hendrik G Visser; Andreas Roodt

doi:10.1107/S1600536812019654

. 2012 May 5;68(Pt 6):m741–m742. doi: 10.1107/S1600536812019654

[Bis(pyridin-2-ylmethyl)amine-κ³ N,N′,N′′]tricarbonylrhenium(I) bromide hemihydrate

Marietjie Schutte ^a,^*, Theunis J Muller ^a, Hendrik G Visser ^a, Andreas Roodt ^a

PMCID: PMC3379082 PMID: 22719303

Abstract

The title compound, fac-[Re(C₁₂H₁₂N₃)(CO)₃]Br·0.5H₂O, crystallizes with a cationic rhenium(I) unit, a bromide ion and half a water molecule, situated on a twofold rotation axis, in the asymmetric unit. The Re^I atom is facially surrounded by three carbonyl ligands and a tridentate bis(pyridin-2-ylmethyl)amine ligand in a distorted octahedral environment. N—H⋯Br, O—H⋯Br, C—H⋯O and C—H⋯Br hydrogen bonds are present in the crystal structure and π–π stacking is also observed [centroid–centroid distances = 3.669 (1) Å and 4.054 (1) Å], giving rise to a three-dimentional network. The molecules pack in a head-to-head fashion along the ac plane.

Related literature

For the synthesis of the fac-Re^I-tricarbonyl synthon, see: Alberto et al. (1996 ▶). For a similar structure, see: Banerjee et al. (2002 ▶). For related structures, see: Raszeja et al. (2011 ▶); Banerjee & Zubieta (2005 ▶); Banerjee et al. (2004 ▶, 2006 ▶); Kunz et al. (2007 ▶); Wei et al. (2006 ▶); Moore et al. (2010 ▶). graphic file with name e-68-0m741-scheme1.jpg

Experimental

Crystal data

[Re(C₁₂H₁₂N₃)(CO)₃]Br·0.5H₂O
M _r = 558.4
Monoclinic,
a = 21.542 (5) Å
b = 11.684 (5) Å
c = 15.126 (5) Å
β = 118.172 (5)°
V = 3356 (2) Å³
Z = 8
Mo Kα radiation
μ = 9.64 mm⁻¹
T = 100 K
0.34 × 0.12 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.265, T _max = 0.432
28139 measured reflections
4032 independent reflections
3688 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.014
wR(F ²) = 0.031
S = 1.05
4032 reflections
220 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.14 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812019654/ru2033sup1.cif

e-68-0m741-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019654/ru2033Isup2.hkl

e-68-0m741-Isup2.hkl^{(193.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Re1—C1	1.918 (2)
Re1—C2	1.921 (2)
Re1—C3	1.928 (2)
Re1—N1	2.1819 (19)
Re1—N2	2.1906 (18)
Re1—N3	2.2104 (19)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Br1	0.85 (2)	2.50 (2)	3.340 (2)	170 (3)
O4—H4A⋯Br1	0.94 (2)	2.31 (2)	3.2429 (18)	171 (3)
C11—H11⋯O2ⁱ	0.93	2.57	3.023 (3)	111
C12—H12⋯O1ⁱⁱ	0.93	2.57	3.285 (3)	134
C21—H21⋯O2ⁱ	0.93	2.56	3.193 (3)	125
C26—H26A⋯Br1ⁱⁱⁱ	0.97	2.88	3.767 (3)	153
C26—H26B⋯O4	0.97	2.31	3.221 (3)	156

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

Acknowledgments

We would like to thank the University of the Free State, the Chemistry Department, the NRF and Sasol Ltd for financial support.

supplementary crystallographic information

Comment

N,N-Bis(2-pyridylmethyl)₂aminetricarbonylrhenium(I)bromidehydrate crystallized in the monoclinc spacegroup with the cationic fac- [Re(CO)₃({2-pyridyl-CH₂}₂NH)], bromide anion and half a water molecule in the assymetric unit. The tridentate ligand, N,N-(2-pyridylmethyl)₂amine, coordinate facially to the Re^I core and the other three positions are occupied by carbonyl ligands. The oxygen atom in the water molecule occupies a special position on a mirror plane (Wyckoff position 4e, site symmetry 2). Seven hydrogen bonds (N—H···Br, O—H···Br, C—H···O, C—H···Br) are observed in the crystal structure. Some weak π–π stacking, with a centroid-to-centroid distance of 3.669 (1) Å and 4.054 (1) Å, is also observed between the different pyridine rings of the ligand system. These interactions complete a three dimensional polymericnetwork formed between the Re^I units. Overall, the bond distances and angles compare well with the similar structure reported by Banerjee et al. (2002), N,N-bis(2-pyridylmethyl)₂aminetricarbonylrhenium(I)bromide, that crystallized in the tetragonal P4₁ spacegroup. The three Rhenium to carbonyl distances ranging from 1.918 (2) Å to 1.928 (2) Å compare well to similar structures (Raszeja et al. (2011), Banerjee et al. (2004), Kunz et al. (2007), Wei et al. (2006), Banerjee et al. (2005), Banerjee et al. (2006), Moore et al. (2010)) and also to the N,N-Bis(2-pyridylmethyl)₂aminetricarbonylrhenium(I)bromide structure reported by Banerjee et al. (2002) of 1.901 (6) Å to 1.926 (7) Å. The Re-amine distance of 2.210 (2) Å and the Re-pyridine distances of 2.182 (2) Å and 2.191 (2) Å are slightly longer than the Re-Amine distance of 2.187 (4) Å and the Re-pyridine distances of 2.177 (5) Å and 2.183 (5) Å reported by Banerjee et al. (2002).

Experimental

[NEt₄]₂[Re(CO)₃Br₃] (75 mg, 0.097 mmol), as prepared by Alberto et al. (1996), was dissolved in 20 ml of water, acidified with HNO₃ to pH 2.2. Silver nitrate (50 mg, 0.291 mmol) was added to the solution and stirred for 24 h at room temperature. The grey silver bromide precipitate was filtered off, N,N-bis(2-pyridylmethyl)amine (19.4 mg, 0.100 mmol) was added to the filtrate and stirred overnight at room temperature. The colourless crystals were grown from the filtrate by slow evaporation.