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Acta Cryst. (2008). E64, m1610-m1611    [ doi:10.1107/S1600536808038737 ]

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

M. Schutte, H. G. Visser and A. Roodt

Abstract top

The title complex, [Re(C7H2Br3O2)(CO)3(H2O)]·CH3OH, crystallized as a neutral ReI 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.

Comment top

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 ReI 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.

Related literature top

For a smiliar tribromotropolonato ReI 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 top

[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.

Refinement top

The aromatic H atoms were placed in geometrically idealized positions and constrained to ride on its parent atoms with Uiso(H) = 1.2Ueq(C). The highest electron density lies within 1.14 Å from Re. The hydrogen atoms of the coordinated water molecule were determined from a difference Fourier map and their positional parameters freely refined with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); 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: SHELXS97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Representation of the title compound, showing the numbering scheme and displacement ellipsoids (50% probability).
Aquatricarbonyl(3,5,7-tribromotropolonato)rhenium(I) methanol solvate top
Crystal data top
[Re(C7H2Br3O2)(CO)3(H2O)]·CH4OZ = 2
Mr = 678.1F(000) = 620
Triclinic, P1Dx = 2.901 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.090 (5) ÅCell parameters from 3145 reflections
b = 9.379 (5) Åθ = 2.2–28.2°
c = 10.010 (5) ŵ = 15.58 mm−1
α = 109.569 (5)°T = 100 K
β = 94.285 (5)°Plate, orange
γ = 102.133 (5)°0.19 × 0.06 × 0.03 mm
V = 776.3 (7) Å3
Data collection top
Bruker APEX
diffractometer		3018 reflections with I > 2σ(I)
φ and ω scansRint = 0.035
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		θmax = 28.3°, θmin = 2.2°
Tmin = 0.150, Tmax = 0.626h = −8→12
8673 measured reflectionsk = −11→12
3599 independent reflectionsl = −13→10
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.033 w = 1/[σ2(Fo2) + (0.0385P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.079(Δ/σ)max < 0.001
S = 1.05Δρmax = 2.40 e Å−3
3599 reflectionsΔρmin = −2.11 e Å−3
207 parameters
Crystal data top
[Re(C7H2Br3O2)(CO)3(H2O)]·CH4Oγ = 102.133 (5)°
Mr = 678.1V = 776.3 (7) Å3
Triclinic, P1Z = 2
a = 9.090 (5) ÅMo Kα radiation
b = 9.379 (5) ŵ = 15.58 mm−1
c = 10.010 (5) ÅT = 100 K
α = 109.569 (5)°0.19 × 0.06 × 0.03 mm
β = 94.285 (5)°
Data collection top
Bruker APEX
diffractometer		3018 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		Rint = 0.035
Tmin = 0.150, Tmax = 0.626θmax = 28.3°
8673 measured reflectionsStandard reflections: 0
3599 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079Δρmax = 2.40 e Å−3
S = 1.05Δρmin = −2.11 e Å−3
3599 reflectionsAbsolute structure: ?
207 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Re010.54228 (3)0.51098 (3)0.75340 (3)0.00853 (8)
Br10.46576 (7)0.05513 (7)0.28520 (6)0.01185 (14)
O40.3428 (5)0.3587 (5)0.7724 (4)0.0107 (9)
C110.3852 (7)0.1903 (7)0.5557 (7)0.0098 (13)
C20.7128 (8)0.6389 (7)0.7149 (7)0.0141 (8)
C150.1120 (7)−0.0432 (8)0.6174 (7)0.0130 (13)
H150.0347−0.0930.65430.016 (19)*
C30.5502 (8)0.6908 (8)0.9164 (7)0.0141 (8)
C170.2988 (7)0.2213 (7)0.6772 (6)0.0079 (12)
O50.4976 (5)0.3042 (5)0.5642 (4)0.0096 (9)
C160.1735 (7)0.1137 (7)0.6939 (6)0.0100 (13)
C120.3491 (7)0.0514 (7)0.4343 (6)0.0084 (12)
C130.2524 (7)−0.0921 (7)0.4077 (7)0.0101 (13)
H130.2554−0.16980.32170.012 (18)*
C140.1514 (7)−0.1368 (7)0.4909 (7)0.0135 (13)
Br20.04885 (8)−0.35228 (8)0.42285 (7)0.01741 (15)
Br30.08290 (7)0.19489 (8)0.85829 (7)0.01438 (15)
O20.8201 (5)0.7193 (5)0.6960 (5)0.0181 (11)
O30.5530 (6)0.8006 (6)1.0157 (5)0.0191 (11)
O10.7678 (6)0.4158 (6)0.9272 (5)0.0221 (11)
C10.6804 (8)0.4526 (8)0.8620 (7)0.0153 (14)
O70.1793 (6)0.6493 (6)0.8032 (5)0.0186 (11)
H70.14380.59130.84490.028*
C40.1962 (8)0.8155 (7)0.8974 (7)0.0141 (8)
H4C0.24480.8330.9920.021*
H4A0.09740.83650.90240.021*
H4B0.25720.88370.85830.021*
O60.3692 (6)0.5548 (6)0.6216 (5)0.0214 (11)
H6A0.295 (9)0.599 (9)0.681 (8)0.032*
H6B0.406 (9)0.640 (9)0.575 (8)0.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Re010.00886 (14)0.00633 (14)0.00918 (13)−0.00064 (10)0.00140 (9)0.00280 (10)
Br10.0139 (3)0.0099 (3)0.0110 (3)0.0015 (3)0.0039 (2)0.0033 (2)
O40.016 (3)0.006 (2)0.010 (2)0.001 (2)0.0039 (18)0.0042 (18)
C110.007 (3)0.012 (3)0.015 (3)0.005 (3)0.004 (2)0.008 (3)
C20.024 (2)0.0071 (19)0.0122 (17)0.0075 (18)0.0005 (15)0.0033 (15)
C150.010 (3)0.017 (4)0.014 (3)0.002 (3)−0.002 (2)0.009 (3)
C30.024 (2)0.0071 (19)0.0122 (17)0.0075 (18)0.0005 (15)0.0033 (15)
C170.010 (3)0.007 (3)0.010 (3)0.001 (3)0.000 (2)0.006 (2)
O50.010 (2)0.004 (2)0.011 (2)−0.0030 (19)0.0036 (17)−0.0002 (17)
C160.011 (3)0.012 (3)0.008 (3)0.002 (3)0.003 (2)0.005 (3)
C120.006 (3)0.013 (3)0.007 (3)0.001 (3)0.001 (2)0.005 (2)
C130.004 (3)0.010 (3)0.014 (3)0.000 (3)−0.002 (2)0.004 (3)
C140.010 (3)0.007 (3)0.019 (3)−0.004 (3)−0.004 (3)0.004 (3)
Br20.0181 (4)0.0091 (3)0.0225 (3)−0.0015 (3)0.0040 (3)0.0052 (3)
Br30.0123 (3)0.0144 (3)0.0140 (3)−0.0005 (3)0.0057 (3)0.0036 (3)
O20.016 (3)0.015 (3)0.025 (3)0.001 (2)0.010 (2)0.011 (2)
O30.017 (3)0.017 (3)0.018 (2)0.005 (2)0.003 (2)−0.001 (2)
O10.022 (3)0.025 (3)0.020 (3)0.008 (2)−0.001 (2)0.010 (2)
C10.020 (4)0.009 (3)0.012 (3)0.000 (3)0.003 (3)−0.001 (3)
O70.025 (3)0.021 (3)0.022 (3)0.013 (2)0.008 (2)0.018 (2)
C40.024 (2)0.0071 (19)0.0122 (17)0.0075 (18)0.0005 (15)0.0033 (15)
O60.025 (3)0.025 (3)0.025 (3)0.013 (3)0.008 (2)0.018 (2)
Geometric parameters (Å, °) top
Re01—C11.882 (7)C3—O31.162 (8)
Re01—C31.897 (6)C17—C161.415 (8)
Re01—C21.899 (7)C16—Br31.895 (6)
Re01—O42.123 (5)C12—C131.372 (9)
Re01—O52.146 (4)C13—C141.378 (9)
Re01—O62.170 (5)C13—H130.93
Br1—C121.899 (6)C14—Br21.900 (6)
O4—C171.278 (7)O1—C11.168 (8)
C11—O51.289 (7)O7—C41.495 (8)
C11—C121.408 (9)O7—H70.82
C11—C171.477 (8)C4—H4C0.96
C2—O21.171 (8)C4—H4A0.96
C15—C161.379 (9)C4—H4B0.96
C15—C141.398 (9)O6—H6A0.99 (8)
C15—H150.93O6—H6B1.06 (8)
C1—Re01—C389.5 (3)C16—C17—C11125.5 (6)
C1—Re01—C287.8 (3)C11—O5—Re01117.1 (4)
C3—Re01—C285.0 (3)C15—C16—C17131.3 (6)
C1—Re01—O496.2 (2)C15—C16—Br3113.9 (5)
C3—Re01—O499.6 (2)C17—C16—Br3114.6 (4)
C2—Re01—O4173.9 (2)C13—C12—C11131.5 (6)
C1—Re01—O596.7 (2)C13—C12—Br1113.1 (4)
C3—Re01—O5171.5 (2)C11—C12—Br1115.2 (5)
C2—Re01—O5100.9 (2)C12—C13—C14128.9 (6)
O4—Re01—O574.07 (16)C12—C13—H13115.6
C1—Re01—O6174.3 (3)C14—C13—H13115.6
C3—Re01—O694.2 (2)C13—C14—C15128.3 (6)
C2—Re01—O696.8 (2)C13—C14—Br2115.9 (5)
O4—Re01—O678.93 (19)C15—C14—Br2115.8 (5)
O5—Re01—O679.17 (18)O1—C1—Re01178.7 (6)
C17—O4—Re01118.0 (4)C4—O7—H7109.5
O5—C11—C12120.1 (5)O7—C4—H4C109.5
O5—C11—C17115.0 (5)O7—C4—H4A109.5
C12—C11—C17124.9 (6)H4C—C4—H4A109.5
O2—C2—Re01177.7 (6)O7—C4—H4B109.5
C16—C15—C14128.0 (6)H4C—C4—H4B109.5
C16—C15—H15116H4A—C4—H4B109.5
C14—C15—H15116Re01—O6—H6A110 (4)
O3—C3—Re01179.1 (6)Re01—O6—H6B117 (4)
O4—C17—C16119.0 (5)H6A—O6—H6B102 (6)
O4—C17—C11115.4 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H6B···Br1i1.06 (8)2.68 (8)3.421 (6)127 (5)
O6—H6B···O5i1.06 (8)1.86 (8)2.825 (7)149 (6)
C15—H15···O2ii0.932.53.409 (8)166
O7—H7···O1iii0.822.392.986 (7)130
O6—H6A···O70.99 (8)1.69 (8)2.665 (7)167 (7)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y−1, z; (iii) −x+1, −y+1, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Re01—C11.882 (7)Re01—O42.123 (5)
Re01—C31.897 (6)Re01—O52.146 (4)
Re01—C21.899 (7)Re01—O62.170 (5)
O4—Re01—O574.07 (16)O5—Re01—O679.17 (18)
O4—Re01—O678.93 (19)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H6B···Br1i1.06 (8)2.68 (8)3.421 (6)127 (5)
O6—H6B···O5i1.06 (8)1.86 (8)2.825 (7)149 (6)
C15—H15···O2ii0.932.53.409 (8)166
O7—H7···O1iii0.822.392.986 (7)130
O6—H6A···O70.99 (8)1.69 (8)2.665 (7)167 (7)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y−1, z; (iii) −x+1, −y+1, −z+2.
Acknowledgements top

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.

references
References top

Alberto, R., Schibli, R. & Schubiger, P. A. (1996). Polyhedron, 15, 1079–1083.

Alvarez, C. M., Garcia-Rodriguez, R. & Miguel, D. (2007). Dalton Trans. pp. 3546–3554.

Bochkova, R. I., Zakharov, L. N., Patrikeeva, N. V., Shal?nova, K. G., Abakumov, G. A. & Cherkasov, V. K. (1987). Koord. Khim. 13, 702–705.

Brandenberg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Brasey, T., Buryak, A., Scopelliti, R. & Severin, K. (2004). Eur. J. Inorg. Chem. pp. 964–967.

Bruker (2004). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Cheng, C. P., Wang, S. R., Lin, J. C. & Wang, S.-L. (1988). J. Organomet. Chem. 349, 375–382.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Gibson, D. H., Ding, Y., Miller, R. L., Sleadd, B. A., Mashuta, M. S. & Richardson, J. F. (1999). Polyhedron, 18, 1189–1200.

Kemp, G. (2006). PhD thesis, University of Johannesburg, South Africa.

Mundwiler, S., Kundig, M., Ortner, K. & Alberto, R. (2004). Dalton Trans., pp. 1320–1328.

Roodt, A., Otto, S. & Steyl, G. (2003). Coord. Chem. Rev. 245, 121–129.

Schutte, M., Visser, H. G. & Steyl, G. (2007). Acta Cryst. E63, m3195–m3196.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Steyl, G. & Roodt, A. (2006). S. Afr. J. Chem. 49, 21–22.

Wang, W., Spingler, B. & Alberto, R. (2003). Inorg. Chim. Acta, 355, 386–391.