Aqua­tricarbon­yl(3,5,7-tribromo­tropolonato)rhenium(I) methanol solvate

Marietjie Schutte; Hendrik G Visser; Andreas Roodt

doi:10.1107/S1600536808038737

. 2008 Nov 22;64(Pt 12):m1610–m1611. doi: 10.1107/S1600536808038737

Aquatricarbonyl(3,5,7-tribromotropolonato)rhenium(I) methanol solvate

Marietjie Schutte ^a,^*, Hendrik G Visser ^a, Andreas Roodt ^a

PMCID: PMC2960052 PMID: 21581205

Abstract

The title complex, [Re(C₇H₂Br₃O₂)(CO)₃(H₂O)]·CH₃OH, crystallized as a neutral Re^I compound and one methanol solvent molecule in the asymmetric unit. The metal centre is coordinated facially by three carbonyl groups. The bidentate tribromotropolanate ligand and a water molecule complete the distorted octahedral coordination around the central metal. Intermolecular Br⋯O [3.226 (5) Å] and Br⋯Br [3.590 (2) Å] contacts are observed between adjacent molecules. These contacts, together with an array of O—H⋯O, O—H⋯Br and C—H⋯O hydrogen bonds, complete a three-dimensional polymeric network formed between the methanol solvent and the complex.

Related literature

For a smiliar tribromotropolonato Re^I structure, see: Schutte et al. (2007 ▶). For other related structures, see: Kemp (2006 ▶); Roodt et al. (2003 ▶); Wang et al. (2003 ▶); Alvarez et al. (2007 ▶); Brasey et al. (2004 ▶); Gibson et al. (1999 ▶); Bochkova et al. (1987 ▶); Cheng et al. (1988 ▶); Mundwiler et al. (2004 ▶). For the synthesis of the precursor, see: Alberto et al. (1996 ▶). For synthesis of the tribromotropolone ligand, see: Steyl & Roodt (2006 ▶).

Experimental

Crystal data

[Re(C₇H₂Br₃O₂)(CO)₃(H₂O)]·CH₄O
M _r = 678.1
Triclinic,
a = 9.090 (5) Å
b = 9.379 (5) Å
c = 10.010 (5) Å
α = 109.569 (5)°
β = 94.285 (5)°
γ = 102.133 (5)°
V = 776.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 15.58 mm⁻¹
T = 100 (2) K
0.19 × 0.06 × 0.03 mm

Data collection

Bruker APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.150, T _max = 0.626
8673 measured reflections
3599 independent reflections
3018 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.079
S = 1.05
3599 reflections
207 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.40 e Å⁻³
Δρ_min = −2.11 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenberg & Putz, 2005 ▶) and ORTEP-3 (Farrugia, 1999 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038737/kj2103sup1.cif

e-64-m1610-sup1.cif^{(14.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038737/kj2103Isup2.hkl

e-64-m1610-Isup2.hkl^{(172.9KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Re01—C1	1.882 (7)
Re01—C3	1.897 (6)
Re01—C2	1.899 (7)
Re01—O4	2.123 (5)
Re01—O5	2.146 (4)
Re01—O6	2.170 (5)

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O4—Re01—O5	74.07 (16)
O4—Re01—O6	78.93 (19)
O5—Re01—O6	79.17 (18)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6B⋯Br1ⁱ	1.06 (8)	2.68 (8)	3.421 (6)	127 (5)
O6—H6B⋯O5ⁱ	1.06 (8)	1.86 (8)	2.825 (7)	149 (6)
C15—H15⋯O2ⁱⁱ	0.93	2.5	3.409 (8)	166
O7—H7⋯O1ⁱⁱⁱ	0.82	2.39	2.986 (7)	130
O6—H6A⋯O7	0.99 (8)	1.69 (8)	2.665 (7)	167 (7)

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

Acknowledgments

The University of the Free State is gratefully acknowledged for financial support, Dr A.J. Muller for the data collection and Dr G. Steyl for providing the ligand.

supplementary crystallographic information

Comment

This structure forms part of an ongoing investigation of the structural and kinetic behaviour of fac-Re(CO)₃ compounds (Schutte et al., 2007; Roodt et al., 2003). The title complex crystallized as a neutral Re^I compound and one methanol solvate molecule in the assymetric unit. The Re—CO bond distances are well within the normal range. The Re—O bond distances compare well with the analogous bromido complex (Schutte et al., 2007) and other related structures (Alvarez et al., 2007; Brasey et al., 2004; Gibson et al., 1999; Bochkova et al., 1987; Cheng et al., 1988; Wang et al., 2003). The Re—OH₂ distance is also comparable to that of related structures (Mundwiler et al., 2004; Kemp, 2006). The small bite angle O4—Re01—O5 might be the reason for the slightly distorted octahedral geometry around the Re¹ metal centre.

Interesting intermolecular Br···O and Br···Br contacts are observed between adjacent molecules with distances of 3.226 (5) Å between Br1 and O3 and 3.590 (2) Å between Br2 and Br2 of the next molecule. These contacts together with an array of O—H···O, O—H···Br and C—H···O hydrogen bonds (see Table 2), complete a complex three-dimensional polymeric network.

Experimental

[NEt₄]₂[Re(CO)₃Br₃] was prepared as described by Alberto et al. (1996). 300 mg (0.3894 mmole) of [NEt₄]₂[Re(CO)₃Br₃] was dissolved in 10 ml of H₂O at pH 2.2 and stirred for 30 minutes (until dissolved). AgNO₃ (198 mg, 1.167 mmol) was added to the solution and stirred for 24 h at room temperature. AgBr was formed as a grey precipitate and was filtered off and weighed (0.220 g). Tribromotroplone [151 mg, 0.4514 mmol for synthesis see Steyl & Roodt (2006)] in 2 ml of methanol was added the solution and stirred for 40 h at room temperature. The filtrate was left to stand for a few days and orange plate-like crystals suitable for X-ray diffraction were collected.