Download citation
Download citation
link to html
The title compound, [Cr(C6H5Cl)(CO)3], is the first group 6 tri­carbonyl ­η6-monohaloarene compound to be structurally characterized. It adopts a classic piano-stool structure, with the Cr(CO)3 tripod assuming a syn-eclipsed conformation relative to the arene ring (φ = 2.0°). The extended structure is dominated by intermolecular π...H interactions (H...ring centroid = 2.94 Å) and non-classical hydrogen bonds between carbonyl and arene moieties (O...H = 2.50–2.58 Å).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103013787/fg1692sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103013787/fg1692Isup2.hkl
Contains datablock I

CCDC reference: 219551

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. (a) A molecular view and (b) the ring-plane projection of (I), showing the atomic numbering scheme and displacement ellipsoids at the 30% probability level.
[Figure 2] Fig. 2. A view of the intermolecular non-classical hydrogen bonds in the crystal structure of (I). The cell origin is at the lower front left corner. [Symmetry codes: (i) 3/2 − x, 1 − y, 1/2 + z; (ii) −1/2 + x, 3/2 − y, 1 − z; (iii) 3/2 − x, 1 − y, −1/2 + z.]
[Figure 3] Fig. 3. A view of the H···π interactions in the crystal structure of (I). The cell origin is at the lower rear right corner. [Symmetry codes: (i) 1/2 + x, 1/2 − y, 1 − z; (ii) −1/2 + x, 1/2 − y, 1 − z; (iii) 1 − x, 1/2 + y, 1/2 − z.]
(η6-Chlorobenzene)tricarbonylchromium top
Crystal data top
[Cr(C6H5Cl)(CO)3]F(000) = 496
Mr = 248.58Dx = 1.781 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5505 reflections
a = 7.1159 (6) Åθ = 1.0–27.5°
b = 10.7627 (11) ŵ = 1.49 mm1
c = 12.1055 (10) ÅT = 150 K
V = 927.12 (14) Å3Prism, yellow
Z = 40.2 × 0.15 × 0.15 mm
Data collection top
Nonius KappaCCD
diffractometer
2071 independent reflections
Radiation source: Enraf Nonius FR5901208 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.123
CCD rotation images, thick slices scansθmax = 27.4°, θmin = 3.3°
Absorption correction: multi-scan
R.H. Blessing, Acta Cryst. (1995), A51, 33-38
h = 97
Tmin = 0.754, Tmax = 0.807k = 1313
6363 measured reflectionsl = 1515
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H-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 reflectionsΔρmax = 0.50 e Å3
127 parametersΔρmin = 0.52 e Å3
0 restraintsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.06 (4)
Crystal data top
[Cr(C6H5Cl)(CO)3]V = 927.12 (14) Å3
Mr = 248.58Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.1159 (6) ŵ = 1.49 mm1
b = 10.7627 (11) ÅT = 150 K
c = 12.1055 (10) Å0.2 × 0.15 × 0.15 mm
Data collection top
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 = 0.807Rint = 0.123
6363 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.097Δρmax = 0.50 e Å3
S = 0.99Δρmin = 0.52 e Å3
2071 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
127 parametersAbsolute structure parameter: 0.06 (4)
0 restraints
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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cr10.65225 (12)0.47479 (8)0.56678 (6)0.0175 (2)
Cl10.2363 (2)0.64927 (15)0.62762 (12)0.0389 (4)
O70.9372 (6)0.3805 (4)0.7280 (3)0.0346 (11)
O80.9625 (6)0.5119 (4)0.4036 (3)0.0369 (11)
O90.7319 (6)0.7279 (4)0.6588 (3)0.0405 (12)
C10.3494 (7)0.5166 (5)0.5780 (4)0.0209 (11)
C20.3893 (7)0.4208 (5)0.6518 (4)0.0211 (14)
H20.35570.42790.72750.025*
C30.4794 (8)0.3141 (5)0.6130 (4)0.0217 (14)
H30.50970.24930.66320.026*
C40.5259 (8)0.3008 (6)0.5008 (5)0.0265 (15)
H40.58200.22660.47390.032*
C50.4869 (8)0.4008 (5)0.4293 (5)0.0258 (14)
H50.52290.39430.35390.031*
C60.3971 (7)0.5093 (6)0.4649 (4)0.0264 (15)
H60.36940.57520.41530.032*
C70.8260 (9)0.4172 (5)0.6658 (4)0.0213 (13)
C80.8423 (8)0.4992 (5)0.4669 (4)0.0251 (13)
C90.6989 (8)0.6304 (5)0.6222 (4)0.0255 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.0179 (5)0.0183 (4)0.0163 (4)0.0010 (4)0.0006 (4)0.0013 (4)
Cl10.0321 (10)0.0370 (10)0.0476 (10)0.0092 (8)0.0055 (7)0.0088 (8)
O70.034 (3)0.035 (3)0.034 (2)0.006 (2)0.012 (2)0.0058 (19)
O80.031 (3)0.056 (3)0.024 (2)0.007 (2)0.0044 (17)0.002 (2)
O90.044 (3)0.025 (3)0.053 (3)0.010 (2)0.011 (2)0.015 (2)
C10.013 (3)0.021 (3)0.028 (3)0.001 (3)0.001 (2)0.005 (2)
C20.015 (4)0.031 (4)0.017 (3)0.006 (3)0.001 (2)0.002 (2)
C30.017 (3)0.021 (4)0.026 (3)0.001 (3)0.001 (2)0.003 (2)
C40.021 (4)0.023 (4)0.036 (3)0.005 (3)0.001 (3)0.010 (3)
C50.023 (3)0.031 (4)0.023 (3)0.000 (3)0.007 (3)0.004 (3)
C60.027 (4)0.030 (4)0.023 (3)0.003 (3)0.011 (2)0.005 (2)
C70.027 (4)0.019 (3)0.018 (3)0.001 (3)0.005 (3)0.000 (2)
C80.028 (3)0.026 (4)0.021 (3)0.001 (3)0.003 (3)0.002 (2)
C90.024 (4)0.028 (4)0.024 (3)0.002 (3)0.002 (2)0.001 (3)
Geometric parameters (Å, º) top
Cr1—C12.206 (5)O9—C91.163 (6)
Cr1—C22.214 (5)C1—C21.394 (7)
Cr1—C32.195 (5)C1—C61.413 (6)
Cr1—C42.226 (6)C2—C31.397 (7)
Cr1—C52.189 (5)C2—H20.95
Cr1—C62.226 (5)C3—C41.405 (7)
Cr1—C71.830 (6)C3—H30.95
Cr1—C81.833 (6)C4—C51.408 (8)
Cr1—C91.834 (6)C4—H40.95
Cl1—C11.745 (5)C5—C61.400 (7)
O7—C71.161 (6)C5—H50.95
O8—C81.157 (6)C6—H60.95
C7—Cr1—C889.0 (2)C6—C1—Cl1119.3 (4)
C7—Cr1—C987.0 (2)C2—C1—Cr171.9 (3)
C8—Cr1—C988.7 (2)C6—C1—Cr172.2 (3)
C7—Cr1—C5137.6 (2)Cl1—C1—Cr1129.7 (3)
C8—Cr1—C587.0 (2)C1—C2—C3119.1 (5)
C9—Cr1—C5135.0 (2)C1—C2—Cr171.3 (3)
C7—Cr1—C386.9 (2)C3—C2—Cr170.8 (3)
C8—Cr1—C3134.0 (2)C1—C2—H2120.5
C9—Cr1—C3136.7 (2)C3—C2—H2120.5
C5—Cr1—C366.8 (2)Cr1—C2—H2129.8
C7—Cr1—C1133.5 (2)C2—C3—C4121.2 (5)
C8—Cr1—C1137.1 (2)C2—C3—Cr172.2 (3)
C9—Cr1—C188.2 (2)C4—C3—Cr172.7 (3)
C5—Cr1—C166.18 (19)C2—C3—H3119.4
C3—Cr1—C166.27 (19)C4—C3—H3119.4
C7—Cr1—C2100.2 (2)Cr1—C3—H3127.9
C8—Cr1—C2165.5 (2)C3—C4—C5118.0 (6)
C9—Cr1—C2102.9 (2)C3—C4—Cr170.3 (3)
C5—Cr1—C278.7 (2)C5—C4—Cr170.0 (3)
C3—Cr1—C236.95 (18)C3—C4—H4121.0
C1—Cr1—C236.77 (18)C5—C4—H4121.0
C7—Cr1—C4102.9 (2)Cr1—C4—H4131.3
C8—Cr1—C4100.5 (2)C6—C5—C4122.6 (5)
C9—Cr1—C4166.5 (2)C6—C5—Cr173.0 (3)
C5—Cr1—C437.2 (2)C4—C5—Cr172.8 (3)
C3—Cr1—C437.06 (19)C6—C5—H5118.7
C1—Cr1—C478.4 (2)C4—C5—H5118.7
C2—Cr1—C466.7 (2)Cr1—C5—H5127.7
C7—Cr1—C6166.0 (2)C5—C6—C1117.0 (5)
C8—Cr1—C6102.3 (2)C5—C6—Cr170.1 (3)
C9—Cr1—C6101.4 (2)C1—C6—Cr170.6 (3)
C5—Cr1—C636.97 (19)C5—C6—H6121.5
C3—Cr1—C679.4 (2)C1—C6—H6121.5
C1—Cr1—C637.17 (17)Cr1—C6—H6130.1
C2—Cr1—C667.17 (19)O7—C7—Cr1179.5 (5)
C4—Cr1—C667.2 (2)O8—C8—Cr1178.6 (5)
C2—C1—C6122.1 (5)O9—C9—Cr1178.4 (5)
C2—C1—Cl1118.6 (4)
C6—C1—C2—C30.1 (8)C3—C4—C5—C62.8 (8)
Cl1—C1—C2—C3179.8 (4)C4—C5—C6—C11.4 (8)
C1—C2—C3—C41.6 (8)C2—C1—C6—C50.1 (8)
C2—C3—C4—C52.9 (8)Cl1—C1—C6—C5179.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O8i0.962.583.306 (6)134
C6—H6···O9ii0.962.503.409 (6)160
Symmetry codes: (i) x+3/2, y+1, z+1/2; (ii) x1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formula[Cr(C6H5Cl)(CO)3]
Mr248.58
Crystal system, space groupOrthorhombic, P212121
Temperature (K)150
a, b, c (Å)7.1159 (6), 10.7627 (11), 12.1055 (10)
V3)927.12 (14)
Z4
Radiation typeMo Kα
µ (mm1)1.49
Crystal size (mm)0.2 × 0.15 × 0.15
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
R.H. Blessing, Acta Cryst. (1995), A51, 33-38
Tmin, Tmax0.754, 0.807
No. of measured, independent and
observed [I > 2σ(I)] reflections
6363, 2071, 1208
Rint0.123
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.097, 0.99
No. of reflections2071
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.52
Absolute structureFlack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter0.06 (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).

Selected geometric parameters (Å, º) top
Cr1—C12.206 (5)Cr1—C81.833 (6)
Cr1—C22.214 (5)Cr1—C91.834 (6)
Cr1—C32.195 (5)Cl1—C11.745 (5)
Cr1—C42.226 (6)O7—C71.161 (6)
Cr1—C52.189 (5)O8—C81.157 (6)
Cr1—C62.226 (5)O9—C91.163 (6)
Cr1—C71.830 (6)
C7—Cr1—C889.0 (2)O7—C7—Cr1179.5 (5)
C7—Cr1—C987.0 (2)O8—C8—Cr1178.6 (5)
C8—Cr1—C988.7 (2)O9—C9—Cr1178.4 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O8i0.962.583.306 (6)134
C6—H6···O9ii0.962.503.409 (6)160
Symmetry codes: (i) x+3/2, y+1, z+1/2; (ii) x1/2, y+3/2, z+1.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds