Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103013787/fg1692sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103013787/fg1692Isup2.hkl |
CCDC reference: 219551
The title compound was prepared according to the method of Alemagna et al. (1983). A mixture of chromium hexacarbonyl (1.77 g, 8.04 mmol), chlorobenzene (2.5 ml, 24.56 mmol) and catalytic THF (10 ml) were refluxed in di-n-butylether (80 ml) for 20 h. The mixture was subsequently cooled to 253 K and filtered through a No. 4 frit, to effect separation of residual Cr(CO)6. Concentration of the filtrate in vacuo led to the formation of a bright-yellow solid, which was purified by sublimation (2 m mH g, 333 K), yielding single crystals suitable for X-ray diffraction.
Molecule (1) crystallized in the orthorhombic system, and space group P212121 was uniquely determined from the systematic absences. H atoms were visible in difference maps and were treated as riding atoms, with C—H distances of 0.95 Å. Some 837 Friedel pairs were used in the refinement and the Flack value [−0.06 (4)] shows that the absolute structure has been correctly determined.
Data collection: Collect (Nonius, 1997–2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
[Cr(C6H5Cl)(CO)3] | F(000) = 496 |
Mr = 248.58 | Dx = 1.781 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5505 reflections |
a = 7.1159 (6) Å | θ = 1.0–27.5° |
b = 10.7627 (11) Å | µ = 1.49 mm−1 |
c = 12.1055 (10) Å | T = 150 K |
V = 927.12 (14) Å3 | Prism, yellow |
Z = 4 | 0.2 × 0.15 × 0.15 mm |
Nonius KappaCCD diffractometer | 2071 independent reflections |
Radiation source: Enraf Nonius FR590 | 1208 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.123 |
CCD rotation images, thick slices scans | θmax = 27.4°, θmin = 3.3° |
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38 | h = −9→7 |
Tmin = 0.754, Tmax = 0.807 | k = −13→13 |
6363 measured reflections | l = −15→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.031P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
2071 reflections | Δρmax = 0.50 e Å−3 |
127 parameters | Δρmin = −0.52 e Å−3 |
0 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.06 (4) |
[Cr(C6H5Cl)(CO)3] | V = 927.12 (14) Å3 |
Mr = 248.58 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.1159 (6) Å | µ = 1.49 mm−1 |
b = 10.7627 (11) Å | T = 150 K |
c = 12.1055 (10) Å | 0.2 × 0.15 × 0.15 mm |
Nonius KappaCCD diffractometer | 2071 independent reflections |
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38 | 1208 reflections with I > 2σ(I) |
Tmin = 0.754, Tmax = 0.807 | Rint = 0.123 |
6363 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.097 | Δρmax = 0.50 e Å−3 |
S = 0.99 | Δρmin = −0.52 e Å−3 |
2071 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
127 parameters | Absolute structure parameter: −0.06 (4) |
0 restraints |
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. |
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 > σ(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. |
x | y | z | Uiso*/Ueq | ||
Cr1 | 0.65225 (12) | 0.47479 (8) | 0.56678 (6) | 0.0175 (2) | |
Cl1 | 0.2363 (2) | 0.64927 (15) | 0.62762 (12) | 0.0389 (4) | |
O7 | 0.9372 (6) | 0.3805 (4) | 0.7280 (3) | 0.0346 (11) | |
O8 | 0.9625 (6) | 0.5119 (4) | 0.4036 (3) | 0.0369 (11) | |
O9 | 0.7319 (6) | 0.7279 (4) | 0.6588 (3) | 0.0405 (12) | |
C1 | 0.3494 (7) | 0.5166 (5) | 0.5780 (4) | 0.0209 (11) | |
C2 | 0.3893 (7) | 0.4208 (5) | 0.6518 (4) | 0.0211 (14) | |
H2 | 0.3557 | 0.4279 | 0.7275 | 0.025* | |
C3 | 0.4794 (8) | 0.3141 (5) | 0.6130 (4) | 0.0217 (14) | |
H3 | 0.5097 | 0.2493 | 0.6632 | 0.026* | |
C4 | 0.5259 (8) | 0.3008 (6) | 0.5008 (5) | 0.0265 (15) | |
H4 | 0.5820 | 0.2266 | 0.4739 | 0.032* | |
C5 | 0.4869 (8) | 0.4008 (5) | 0.4293 (5) | 0.0258 (14) | |
H5 | 0.5229 | 0.3943 | 0.3539 | 0.031* | |
C6 | 0.3971 (7) | 0.5093 (6) | 0.4649 (4) | 0.0264 (15) | |
H6 | 0.3694 | 0.5752 | 0.4153 | 0.032* | |
C7 | 0.8260 (9) | 0.4172 (5) | 0.6658 (4) | 0.0213 (13) | |
C8 | 0.8423 (8) | 0.4992 (5) | 0.4669 (4) | 0.0251 (13) | |
C9 | 0.6989 (8) | 0.6304 (5) | 0.6222 (4) | 0.0255 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr1 | 0.0179 (5) | 0.0183 (4) | 0.0163 (4) | −0.0010 (4) | 0.0006 (4) | −0.0013 (4) |
Cl1 | 0.0321 (10) | 0.0370 (10) | 0.0476 (10) | 0.0092 (8) | 0.0055 (7) | −0.0088 (8) |
O7 | 0.034 (3) | 0.035 (3) | 0.034 (2) | 0.006 (2) | −0.012 (2) | 0.0058 (19) |
O8 | 0.031 (3) | 0.056 (3) | 0.024 (2) | −0.007 (2) | 0.0044 (17) | 0.002 (2) |
O9 | 0.044 (3) | 0.025 (3) | 0.053 (3) | −0.010 (2) | 0.011 (2) | −0.015 (2) |
C1 | 0.013 (3) | 0.021 (3) | 0.028 (3) | 0.001 (3) | 0.001 (2) | −0.005 (2) |
C2 | 0.015 (4) | 0.031 (4) | 0.017 (3) | −0.006 (3) | 0.001 (2) | −0.002 (2) |
C3 | 0.017 (3) | 0.021 (4) | 0.026 (3) | −0.001 (3) | 0.001 (2) | 0.003 (2) |
C4 | 0.021 (4) | 0.023 (4) | 0.036 (3) | −0.005 (3) | 0.001 (3) | −0.010 (3) |
C5 | 0.023 (3) | 0.031 (4) | 0.023 (3) | 0.000 (3) | −0.007 (3) | −0.004 (3) |
C6 | 0.027 (4) | 0.030 (4) | 0.023 (3) | −0.003 (3) | −0.011 (2) | 0.005 (2) |
C7 | 0.027 (4) | 0.019 (3) | 0.018 (3) | −0.001 (3) | 0.005 (3) | 0.000 (2) |
C8 | 0.028 (3) | 0.026 (4) | 0.021 (3) | −0.001 (3) | −0.003 (3) | −0.002 (2) |
C9 | 0.024 (4) | 0.028 (4) | 0.024 (3) | 0.002 (3) | −0.002 (2) | 0.001 (3) |
Cr1—C1 | 2.206 (5) | O9—C9 | 1.163 (6) |
Cr1—C2 | 2.214 (5) | C1—C2 | 1.394 (7) |
Cr1—C3 | 2.195 (5) | C1—C6 | 1.413 (6) |
Cr1—C4 | 2.226 (6) | C2—C3 | 1.397 (7) |
Cr1—C5 | 2.189 (5) | C2—H2 | 0.95 |
Cr1—C6 | 2.226 (5) | C3—C4 | 1.405 (7) |
Cr1—C7 | 1.830 (6) | C3—H3 | 0.95 |
Cr1—C8 | 1.833 (6) | C4—C5 | 1.408 (8) |
Cr1—C9 | 1.834 (6) | C4—H4 | 0.95 |
Cl1—C1 | 1.745 (5) | C5—C6 | 1.400 (7) |
O7—C7 | 1.161 (6) | C5—H5 | 0.95 |
O8—C8 | 1.157 (6) | C6—H6 | 0.95 |
C7—Cr1—C8 | 89.0 (2) | C6—C1—Cl1 | 119.3 (4) |
C7—Cr1—C9 | 87.0 (2) | C2—C1—Cr1 | 71.9 (3) |
C8—Cr1—C9 | 88.7 (2) | C6—C1—Cr1 | 72.2 (3) |
C7—Cr1—C5 | 137.6 (2) | Cl1—C1—Cr1 | 129.7 (3) |
C8—Cr1—C5 | 87.0 (2) | C1—C2—C3 | 119.1 (5) |
C9—Cr1—C5 | 135.0 (2) | C1—C2—Cr1 | 71.3 (3) |
C7—Cr1—C3 | 86.9 (2) | C3—C2—Cr1 | 70.8 (3) |
C8—Cr1—C3 | 134.0 (2) | C1—C2—H2 | 120.5 |
C9—Cr1—C3 | 136.7 (2) | C3—C2—H2 | 120.5 |
C5—Cr1—C3 | 66.8 (2) | Cr1—C2—H2 | 129.8 |
C7—Cr1—C1 | 133.5 (2) | C2—C3—C4 | 121.2 (5) |
C8—Cr1—C1 | 137.1 (2) | C2—C3—Cr1 | 72.2 (3) |
C9—Cr1—C1 | 88.2 (2) | C4—C3—Cr1 | 72.7 (3) |
C5—Cr1—C1 | 66.18 (19) | C2—C3—H3 | 119.4 |
C3—Cr1—C1 | 66.27 (19) | C4—C3—H3 | 119.4 |
C7—Cr1—C2 | 100.2 (2) | Cr1—C3—H3 | 127.9 |
C8—Cr1—C2 | 165.5 (2) | C3—C4—C5 | 118.0 (6) |
C9—Cr1—C2 | 102.9 (2) | C3—C4—Cr1 | 70.3 (3) |
C5—Cr1—C2 | 78.7 (2) | C5—C4—Cr1 | 70.0 (3) |
C3—Cr1—C2 | 36.95 (18) | C3—C4—H4 | 121.0 |
C1—Cr1—C2 | 36.77 (18) | C5—C4—H4 | 121.0 |
C7—Cr1—C4 | 102.9 (2) | Cr1—C4—H4 | 131.3 |
C8—Cr1—C4 | 100.5 (2) | C6—C5—C4 | 122.6 (5) |
C9—Cr1—C4 | 166.5 (2) | C6—C5—Cr1 | 73.0 (3) |
C5—Cr1—C4 | 37.2 (2) | C4—C5—Cr1 | 72.8 (3) |
C3—Cr1—C4 | 37.06 (19) | C6—C5—H5 | 118.7 |
C1—Cr1—C4 | 78.4 (2) | C4—C5—H5 | 118.7 |
C2—Cr1—C4 | 66.7 (2) | Cr1—C5—H5 | 127.7 |
C7—Cr1—C6 | 166.0 (2) | C5—C6—C1 | 117.0 (5) |
C8—Cr1—C6 | 102.3 (2) | C5—C6—Cr1 | 70.1 (3) |
C9—Cr1—C6 | 101.4 (2) | C1—C6—Cr1 | 70.6 (3) |
C5—Cr1—C6 | 36.97 (19) | C5—C6—H6 | 121.5 |
C3—Cr1—C6 | 79.4 (2) | C1—C6—H6 | 121.5 |
C1—Cr1—C6 | 37.17 (17) | Cr1—C6—H6 | 130.1 |
C2—Cr1—C6 | 67.17 (19) | O7—C7—Cr1 | 179.5 (5) |
C4—Cr1—C6 | 67.2 (2) | O8—C8—Cr1 | 178.6 (5) |
C2—C1—C6 | 122.1 (5) | O9—C9—Cr1 | 178.4 (5) |
C2—C1—Cl1 | 118.6 (4) | ||
C6—C1—C2—C3 | 0.1 (8) | C3—C4—C5—C6 | −2.8 (8) |
Cl1—C1—C2—C3 | 179.8 (4) | C4—C5—C6—C1 | 1.4 (8) |
C1—C2—C3—C4 | −1.6 (8) | C2—C1—C6—C5 | 0.1 (8) |
C2—C3—C4—C5 | 2.9 (8) | Cl1—C1—C6—C5 | −179.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O8i | 0.96 | 2.58 | 3.306 (6) | 134 |
C6—H6···O9ii | 0.96 | 2.50 | 3.409 (6) | 160 |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x−1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cr(C6H5Cl)(CO)3] |
Mr | 248.58 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 7.1159 (6), 10.7627 (11), 12.1055 (10) |
V (Å3) | 927.12 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.49 |
Crystal size (mm) | 0.2 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38 |
Tmin, Tmax | 0.754, 0.807 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6363, 2071, 1208 |
Rint | 0.123 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.097, 0.99 |
No. of reflections | 2071 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.52 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | −0.06 (4) |
Computer programs: Collect (Nonius, 1997–2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
Cr1—C1 | 2.206 (5) | Cr1—C8 | 1.833 (6) |
Cr1—C2 | 2.214 (5) | Cr1—C9 | 1.834 (6) |
Cr1—C3 | 2.195 (5) | Cl1—C1 | 1.745 (5) |
Cr1—C4 | 2.226 (6) | O7—C7 | 1.161 (6) |
Cr1—C5 | 2.189 (5) | O8—C8 | 1.157 (6) |
Cr1—C6 | 2.226 (5) | O9—C9 | 1.163 (6) |
Cr1—C7 | 1.830 (6) | ||
C7—Cr1—C8 | 89.0 (2) | O7—C7—Cr1 | 179.5 (5) |
C7—Cr1—C9 | 87.0 (2) | O8—C8—Cr1 | 178.6 (5) |
C8—Cr1—C9 | 88.7 (2) | O9—C9—Cr1 | 178.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O8i | 0.96 | 2.58 | 3.306 (6) | 134 |
C6—H6···O9ii | 0.96 | 2.50 | 3.409 (6) | 160 |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x−1/2, −y+3/2, −z+1. |
Metal–arene π-complexes continue to be the subject of extensive study in respect of their utility as intermediaries for key synthetic transformations. In particular, the tricarbonylchromium moiety has long been employed as a means of activating aromatic hydrocarbons towards nucleophilic reaction pathways, because of its strongly electrophilic nature. Consequently, complexes containing this moiety continue to be investigated, and numerous examples have been structurally characterized. However, while the structural facets of η6-benzene-tricarbonylchromium (Rees & Coppens, 1973) and a range of polysubstituted analogues are well documented, no such investigation of the monohalo derivatives has previously been undertaken. We report here the first structural study of (η6-C6H5Cl)Cr(CO)3.
The asymmetric unit (Fig. 1) of the title compound, (I), comprises a single molecule that exhibits the classic 'piano-stool' structure, with the Cr(CO)3 tripod adopting a syn eclipsed conformation relative to the aromatic ring (ϕ 2.0°), which is typical of the presence of a π-donor substituent (Muetterties et al., 1982). The σ-acceptor character of chlorine is manifest in a relatively short [1.707 (2) Å] Cr···Cg distance (Cg is the ring centroid), which is characteristic of an electron-poor complex and is confirmed by high carbonyl stretching frequencies (νmax 1988, 1923 cm−1) similar to those reported previously (Gassman & Deck, 1994). The metal–centroid distance agrees with those of 1.700 Å reported for (η6-C6H5Cl)Cr(CO)2PPh3 (Eglin & Smith, 2001) and 1.680 (5) Å observed in the fully substituted (η6-C6Cl6)Cr(CO)3 (Gassman & Deck, 1994). The latter is the current limiting case for halosubstituted (η6-arene)Cr(CO)3 complexes. It is, however, interesting to note that the distance found here for the monochloro arene is comparable to that determined in (η6-p-C6H4F2)Cr(CO)3 (Cr···Cg = 1.719 Å), which is counter-intuitive. Further internal distances are largely as expected, with Cr—CO distances falling in the typical range for related materials, as are the C—O and ring C—C distances.
The extended structure is dominated by an extensive network of non-classical hydrogen bonds involving the arene H atoms and carbonyl fragments of adjacent molecules. The two o-H atoms (H2 and H4) of each arene interact with the O atom of one of the carbonyl groups from each of two different neighbouring molecules (Fig. 2), thus generating an extended three-dimensional network. A search of the Cambridge Structural Database (Allen, 2002) shows that the C—H···O bond distances (Table 2) are unexceptional. Indeed, analogous bonding is observed in (η6-C6H5Cl)Cr(CO)2PPh3, with an H···O bonding distance of 2.50 Å. The interaction angles observed in the present case (134 and 160 °) are also similar. In addition, a significant H···π interaction is apparent (Fig. 3) between the p-H atom (H4) and the arene ring of an adjacent molecule (at 1/2 + x,1/2 − y,1 − z) with an H···Cg distance of 2.94 Å. The H···Cg vector is at 10 ° to the ring normal, while the C4—H4···Cg angle at the H atom is 143 °. These interactions result in stacks of molecules through the crystal, with molecules alternately aligned by 54° with respect to one another in each stack.