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Acta Cryst. (2008). E64, m1314    [ doi:10.1107/S1600536808029966 ]

fac-Bis(acetonitrile-[kappa]N)tricarbonyl(trifluoroacetato-[kappa]O)rhenium(I)

R. Kia and H.-K. Fun

Abstract top

In the title compound, [Re(CF3COO)(CH3CN)2(CO)3], the Re atom has a distorted octahedral configuration. The two acetonitrile molecules and two of the three carbonyl groups occupy the equatorial plane of the complex, with the third carbonyl ligand and the trifluoroacetato ligand in the axial positions. The three carbonyl ligands are arranged in a fac configuration around the Re atom. The CF3 segment of the trifluoroacetato ligand shows rotational disorder and the refined site-occupancy factors of the disordered parts are ca 0.5/0.5. The crystal structure is stabilized by C-H...O and C-H...F hydrogen bonds.

Comment top

The synthesis of solvent-coordinated complexes is a matter of considerable interest since they are useful sources for synthesis of new species resulting from the substitution of the coordinated solvent by a more basic ligand (Davies & Hartely, 1981). The lability of the solvent ligand easily gives rise to a highly reactive 16e- electrophilic fragment able to activate small molecules thus providing an important step in many chemical processes. On the other hand, Rhenium tricarbonyl complexes have been the subject of much attention, mainly because of their photophysical (Meyer 1989) and photochemical properties (Collin & Sauvage 1989) and in supramolecular chemistry (Balzani et al., 1996).

In the title compound (I) (Fig. 1), the Re atom adopts a distorted octahedral geometry. The bond lengths (Allen et al., 1987) and angles are within the normal ranges and are comparable to the related structures (Chan et al., 1977; Lazarova et al., 2004). The two acetonitriles and two carbonyl groups occupy the equatorial plane of the complex, with the third carbonyl ligands and the trifluoroacetate in the axial positions. The three carbonyl ligands at Re atom are arranged in a fac configuration. The cis-equatorial angle of N1–Re1–N2 is 81.88 (13) °. The deviation of the Re atom from the C1/C2/N1/N2 plane is -0.048 (1) Å.

The crystal structure is stabilized by C—H···O and C—H···F hydrogen bonds (Table 1, Fig. 2).

Related literature top

For values of standard bond lengths, see: Allen et al. (1987). For related structures, see, for example: Chan et al. (1977); Lazarova et al. (2004). For background on the applications, see, for example: Davies & Hartely (1981); Collin & Sauvage (1989, 1989); Balzani et al. (1996); Meyer (1989).

Experimental top

The synthetic method has been described earlier (Chan et al., 1977). Single crystals suitable for X-ray diffraction were obtained by evaporation of an acetonitrile solution at room temperature.

Refinement top

The hydrogen atoms of the methyl groups were first located from the difference Fourier map and then constrained to refine using a rotating-group model. The CF3 segment of the trifluoroacete ligand has rotational disorder and the refined site-occupancy factores of the disorder parts are 0.501 (2)/0.499 (2). The highest peak (2.80 eÅ-3) is located 0.61 Å from Re1 and the deepest hole (-1.27 eÅ-3) is located 1.01 Å from Re1.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering scheme. The open bonds indicate the disordered parts.
[Figure 2] Fig. 2. The crystal packing of the major component of (I), viewed down the c-axis. Intermolecular interactions are shown as dashed lines.
fac-Bis(acetonitrile-κN)tricarbonyl(trifluoroacetato-κO)rhenium(I) top
Crystal data top
[Re(C2F3O2)(C2H3N)2(CO)3]F(000) = 864
Mr = 465.36Dx = 2.316 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9896 reflections
a = 10.8243 (2) Åθ = 2.6–40.1°
b = 10.4745 (2) ŵ = 9.16 mm−1
c = 14.4772 (3) ÅT = 100 K
β = 125.584 (1)°Block, colourless
V = 1334.90 (4) Å30.32 × 0.23 × 0.19 mm
Z = 4
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		5819 independent reflections
Radiation source: fine-focus sealed tube5087 reflections with I > 2σ(I)
graphiteRint = 0.037
φ and ω scansθmax = 35.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −17→14
Tmin = 0.098, Tmax = 0.175k = −10→16
24096 measured reflectionsl = −23→23
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0375P)2 + 1.8212P]
where P = (Fo2 + 2Fc2)/3
5819 reflections(Δ/σ)max = 0.002
211 parametersΔρmax = 2.80 e Å−3
0 restraintsΔρmin = −1.27 e Å−3
Crystal data top
[Re(C2F3O2)(C2H3N)2(CO)3]V = 1334.90 (4) Å3
Mr = 465.36Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.8243 (2) ŵ = 9.16 mm−1
b = 10.4745 (2) ÅT = 100 K
c = 14.4772 (3) Å0.32 × 0.23 × 0.19 mm
β = 125.584 (1)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		5819 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		5087 reflections with I > 2σ(I)
Tmin = 0.098, Tmax = 0.175Rint = 0.037
24096 measured reflectionsθmax = 35.0°
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.078Δρmax = 2.80 e Å−3
S = 1.06Δρmin = −1.27 e Å−3
5819 reflectionsAbsolute structure: ?
211 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Re10.681282 (13)−0.021815 (12)0.800806 (9)0.02552 (4)
F1A0.9350 (14)0.2534 (7)1.1194 (5)0.073 (4)0.501 (19)
F2A0.7397 (8)0.3650 (13)1.0179 (9)0.075 (4)0.501 (19)
F3A0.938 (2)0.4097 (12)1.0310 (12)0.101 (6)0.501 (19)
F1B0.818 (2)0.2830 (10)1.0906 (11)0.096 (7)0.499 (19)
F2B0.7687 (18)0.4304 (11)0.9808 (9)0.104 (6)0.499 (19)
F3B0.9837 (11)0.358 (2)1.0782 (13)0.121 (8)0.499 (19)
O10.9541 (3)0.0126 (3)0.7902 (3)0.0368 (5)
O20.5020 (4)0.1538 (3)0.5934 (2)0.0477 (7)
O30.5809 (4)−0.2505 (3)0.6407 (3)0.0461 (6)
O40.7533 (3)0.1237 (2)0.9276 (2)0.0308 (4)
O50.8149 (4)0.2725 (3)0.8489 (2)0.0425 (6)
N10.7910 (3)−0.1433 (3)0.9467 (2)0.0307 (5)
N20.4997 (4)−0.0360 (3)0.8190 (3)0.0338 (6)
C10.8537 (4)−0.0010 (3)0.7956 (3)0.0284 (5)
C20.5700 (4)0.0891 (4)0.6720 (3)0.0353 (7)
C30.6165 (4)−0.1638 (4)0.7004 (3)0.0339 (6)
C40.2941 (6)−0.0491 (6)0.8572 (5)0.0620 (15)
H4A0.3436−0.06240.93860.093*
H4B0.2247−0.12010.81440.093*
H4C0.23680.03110.83360.093*
C50.4088 (5)−0.0429 (4)0.8350 (3)0.0401 (8)
C60.8744 (5)−0.3017 (4)1.1107 (3)0.0398 (7)
H6A0.9143−0.25421.18110.060*
H6B0.9531−0.35911.12110.060*
H6C0.7859−0.35171.09150.060*
C70.8301 (4)−0.2132 (3)1.0199 (3)0.0327 (6)
C80.8016 (4)0.2303 (3)0.9217 (3)0.0322 (6)
C90.8499 (5)0.3206 (4)1.0215 (3)0.0405 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Re10.02296 (6)0.02704 (7)0.02680 (6)−0.00061 (4)0.01461 (5)0.00002 (4)
F1A0.093 (8)0.062 (4)0.035 (3)0.002 (4)0.020 (3)−0.009 (2)
F2A0.045 (3)0.095 (8)0.076 (6)0.009 (4)0.030 (4)−0.042 (6)
F3A0.165 (15)0.083 (7)0.109 (9)−0.093 (9)0.110 (11)−0.062 (6)
F1B0.173 (17)0.072 (6)0.102 (8)−0.060 (9)0.113 (11)−0.049 (6)
F2B0.127 (11)0.060 (6)0.068 (5)0.036 (6)0.025 (5)−0.015 (4)
F3B0.037 (4)0.202 (19)0.112 (10)−0.039 (7)0.037 (5)−0.108 (12)
O10.0305 (13)0.0433 (14)0.0409 (13)−0.0065 (10)0.0232 (11)−0.0090 (10)
O20.0454 (16)0.0530 (17)0.0389 (13)0.0121 (14)0.0212 (12)0.0132 (12)
O30.0558 (18)0.0402 (14)0.0468 (14)−0.0161 (13)0.0324 (14)−0.0126 (12)
O40.0333 (12)0.0281 (10)0.0346 (10)−0.0033 (9)0.0218 (10)−0.0029 (8)
O50.0503 (16)0.0378 (13)0.0446 (13)−0.0049 (12)0.0306 (13)0.0024 (11)
N10.0304 (13)0.0288 (12)0.0331 (12)−0.0023 (10)0.0187 (11)−0.0003 (10)
N20.0314 (14)0.0352 (14)0.0377 (13)−0.0035 (11)0.0218 (12)−0.0036 (11)
C10.0280 (14)0.0268 (12)0.0309 (13)−0.0012 (11)0.0175 (12)−0.0028 (10)
C20.0330 (16)0.0398 (18)0.0342 (14)0.0019 (13)0.0202 (13)0.0022 (13)
C30.0306 (15)0.0362 (16)0.0339 (14)−0.0062 (13)0.0182 (13)−0.0017 (12)
C40.050 (3)0.086 (4)0.073 (3)−0.026 (3)0.049 (3)−0.037 (3)
C50.0329 (17)0.051 (2)0.0396 (17)−0.0085 (15)0.0229 (15)−0.0123 (15)
C60.0372 (18)0.0422 (19)0.0367 (15)0.0006 (15)0.0196 (14)0.0103 (14)
C70.0289 (15)0.0321 (15)0.0351 (14)−0.0015 (12)0.0175 (12)0.0000 (12)
C80.0299 (15)0.0305 (14)0.0344 (13)0.0002 (12)0.0178 (12)−0.0008 (11)
C90.044 (2)0.0376 (17)0.0414 (17)−0.0063 (15)0.0254 (16)−0.0054 (14)
Geometric parameters (Å, °) top
Re1—C31.905 (4)O3—C31.155 (4)
Re1—C21.914 (4)O4—C81.257 (4)
Re1—C11.924 (3)O5—C81.227 (4)
Re1—N22.135 (3)N1—C71.147 (4)
Re1—N12.138 (3)N2—C51.136 (5)
Re1—O42.153 (2)C4—C51.454 (6)
F1A—C91.354 (8)C4—H4A0.9800
F2A—C91.253 (7)C4—H4B0.9800
F3A—C91.285 (9)C4—H4C0.9800
F1B—C91.296 (8)C6—C71.444 (5)
F2B—C91.356 (9)C6—H6A0.9800
F3B—C91.241 (10)C6—H6B0.9800
O1—C11.143 (4)C6—H6C0.9800
O2—C21.149 (4)C8—C91.541 (5)
C3—Re1—C289.26 (15)H6A—C6—H6B109.5
C3—Re1—C189.64 (14)C7—C6—H6C109.5
C2—Re1—C188.16 (15)H6A—C6—H6C109.5
C3—Re1—N294.75 (13)H6B—C6—H6C109.5
C2—Re1—N293.44 (14)N1—C7—C6178.2 (4)
C1—Re1—N2175.34 (12)O5—C8—O4129.8 (3)
C3—Re1—N192.03 (13)O5—C8—C9116.0 (3)
C2—Re1—N1175.23 (12)O4—C8—C9114.2 (3)
C1—Re1—N196.43 (13)F3B—C9—F2A128.8 (8)
N2—Re1—N181.88 (12)F3B—C9—F3A36.0 (9)
C3—Re1—O4173.21 (12)F2A—C9—F3A111.5 (9)
C2—Re1—O496.39 (13)F3B—C9—F1B108.5 (9)
C1—Re1—O494.28 (11)F2A—C9—F1B57.9 (7)
N2—Re1—O481.20 (10)F3A—C9—F1B130.9 (7)
N1—Re1—O482.04 (10)F3B—C9—F1A69.5 (10)
C8—O4—Re1122.0 (2)F2A—C9—F1A106.7 (7)
C7—N1—Re1170.6 (3)F3A—C9—F1A104.8 (8)
C5—N2—Re1176.2 (3)F1B—C9—F1A50.1 (7)
O1—C1—Re1178.5 (3)F3B—C9—F2B103.4 (10)
O2—C2—Re1178.7 (4)F2A—C9—F2B46.1 (7)
O3—C3—Re1178.3 (3)F3A—C9—F2B71.6 (10)
C5—C4—H4A109.5F1B—C9—F2B101.3 (9)
C5—C4—H4B109.5F1A—C9—F2B140.3 (6)
H4A—C4—H4B109.5F3B—C9—C8116.3 (6)
C5—C4—H4C109.5F2A—C9—C8113.1 (5)
H4A—C4—H4C109.5F3A—C9—C8111.8 (6)
H4B—C4—H4C109.5F1B—C9—C8116.1 (4)
N2—C5—C4178.6 (5)F1A—C9—C8108.4 (4)
C7—C6—H6A109.5F2B—C9—C8109.4 (5)
C7—C6—H6B109.5
C2—Re1—O4—C8−43.2 (3)O4—C8—C9—F2A−72.6 (9)
C1—Re1—O4—C845.4 (3)O5—C8—C9—F3A−19.7 (11)
N2—Re1—O4—C8−135.7 (3)O4—C8—C9—F3A160.5 (10)
N1—Re1—O4—C8141.3 (3)O5—C8—C9—F1B171.4 (10)
Re1—O4—C8—O51.2 (5)O4—C8—C9—F1B−8.3 (11)
Re1—O4—C8—C9−179.1 (2)O5—C8—C9—F1A−134.7 (7)
O5—C8—C9—F3B−59.0 (13)O4—C8—C9—F1A45.5 (8)
O4—C8—C9—F3B121.3 (13)O5—C8—C9—F2B57.6 (11)
O5—C8—C9—F2A107.1 (9)O4—C8—C9—F2B−122.1 (10)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4B···O5i0.982.423.113 (5)127.
C6—H6A···F1Aii0.982.353.237 (8)150.
C6—H6B···O5iii0.982.463.075 (5)121.
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, y−1/2, −z+5/2; (iii) −x+2, −y, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4B···O5i0.982.423.113 (5)127.
C6—H6A···F1Aii0.982.353.237 (8)150.
C6—H6B···O5iii0.982.463.075 (5)121.
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, y−1/2, −z+5/2; (iii) −x+2, −y, −z+2.
Acknowledgements top

H-KF and RK thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a postdoctoral research fellowship.

references
References top

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