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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): m1610–m1611.
Published online 2008 November 22. doi:  10.1107/S1600536808038737
PMCID: PMC2960052

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

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-m1610-scheme1.jpg

Experimental

Crystal data

  • [Re(C7H2Br3O2)(CO)3(H2O)]·CH4O
  • M r = 678.1
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1610-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 2.40 e Å−3
  • Δρmin = −2.11 e Å−3

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

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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 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.

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.

Refinement

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).

Figures

Fig. 1.
Representation of the title compound, showing the numbering scheme and displacement ellipsoids (50% probability).

Crystal data

[Re(C7H2Br3O2)(CO)3(H2O)]·CH4OZ = 2
Mr = 678.1F000 = 620
Triclinic, P1Dx = 2.901 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 9.090 (5) ÅCell parameters from 3145 reflections
b = 9.379 (5) Åθ = 2.2–28.2º
c = 10.010 (5) ŵ = 15.58 mm1
α = 109.569 (5)ºT = 100 (2) K
β = 94.285 (5)ºPlate, orange
γ = 102.133 (5)º0.19 × 0.06 × 0.03 mm
V = 776.3 (7) Å3

Data collection

Bruker APEX diffractometerRint = 0.035
[var phi] and ω scansθmax = 28.3º
Absorption correction: multi-scan(SADABS; Bruker, 2004)θmin = 2.2º
Tmin = 0.150, Tmax = 0.626h = −8→12
8673 measured reflectionsk = −11→12
3599 independent reflectionsl = −13→10
3018 reflections with I > 2σ(I)

Refinement

Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0385P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.033(Δ/σ)max < 0.001
wR(F2) = 0.079Δρmax = 2.41 e Å3
S = 1.05Δρmin = −2.11 e Å3
3599 reflectionsExtinction correction: none
207 parameters

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KJ2103).

References

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