(η4-s-cis-1,3-Butadiene)tetra­carbonyl­chromium(0)

Reiss, G.J.; Finze, M.

doi:10.1107/S1600536811004636

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page m333

doi:10.1107/S1600536811004636

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(η⁴-s-cis-1,3-Butadiene)tetracarbonylchromium(0)

Guido J. Reiss ^a ^* and Maik Finze ^a

^aInstitut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
^*Correspondence e-mail: reissg@uni-duesseldorf.de

(Received 31 January 2011; accepted 7 February 2011; online 12 February 2011)

In the title complex, [Cr(C₄H₆)(CO)₄], the Cr⁰ atom shows a distorted octahedral environment from four C atoms of the carbonyl ligands and the two π-bonds of the s-cis-1,3-butadiene ligand. The complex has an approximate non-crystallographic mirror symmetry m passing through the chromium atom, two carbonyl ligands and the mid-point of the central C—C bond of the s-cis-1,3-butadiene ligand. The C—C bond lengths in the s-cis-1,3-butadiene ligand alternate, the terminal distances being shorter than the central distance.

Related literature

For experimental and theoretical data for the title compound, see: Fischler et al. (1976 ); Kotzian et al. (1982 ); Kreiter & Özkar (1978 ); Okamoto et al. (1991 ); von Ragué Schleyer et al. (2000 ). For related chromium complexes, see: Pavkovic & Zaluzec (1989 ), Betz et al. (1993 ), Wang et al. (1990 ), Konietzny et al. (2010 ). For related s-cis-butadiene complexes, see: Reiss (2010 ), Reiss & Konietzny (2002 ).

Experimental

Crystal data

[Cr(C₄H₆)(CO)₄]
M_r = 218.13
Triclinic, $[P \overline 1]$
a = 6.4011 (8) Å
b = 6.7666 (8) Å
c = 11.0642 (10) Å
α = 84.728 (7)°
β = 81.840 (8)°
γ = 69.127 (8)°
V = 442.80 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 137 K
0.38 × 0.26 × 0.04 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: Gaussian (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.711, T_max = 0.946
2829 measured reflections
1735 independent reflections
1498 reflections with I > 2σ(I)
R_int = 0.020
3 standard reflections every 60 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.068
S = 1.05
1735 reflections
140 parameters
All H-atom parameters refined
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected bond lengths (Å)

Cr1—C5	1.852 (2)
Cr1—C6	1.887 (2)
Cr1—C7	1.873 (2)
Cr1—C8	1.914 (2)
Cr1—C1	2.312 (2)
Cr1—C2	2.184 (2)
Cr1—C3	2.190 (2)
Cr1—C4	2.325 (2)
C1—C2	1.379 (3)
C2—C3	1.436 (3)
C3—C4	1.371 (3)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811004636/si2332sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004636/si2332Isup2.hkl

checkCIF report

Comment top

Simple butadiene complexes of transition metals are of general interest because they are model systems that allow a deeper understanding of the bonding situation between transition metal centers and olefins that play an important role for example in catalysis. [Cr(C₄H₆)(CO)₄] that was first described in the 70s of the last century (Fischler et al. 1976) was subject to a number of spectroscopic (Kotzian et al. 1982) as well as theoretical studies (von Ragué Schleyer et al. 2000) and its chemistry was investigated (Kreiter & Özkar, 1978; Okamoto et al. 1991) with the focus on photochemical ligand exchange reactions (Fischler et al. 1976).

The coordination at Cr(0) in the title compound is best described as a distorted octahedron formed by four carbonyl ligands and one s-cis-1,3-butadiene ligand. The Cr–CO distances of the carbonyl ligands that are trans to the s-cis-1,3-butadiene ligand are slightly shorter than the two other Cr–CO distances (Table 1). This finding is in good agreement to Cr—CO distances in the structure of the related tetracarbonyl chromium(0) complex [Cr(C₁₉H₂₃NO₂)(CO)₄]: d(Cr–CO_trans) = 1.884 (4), 1.887 (6) Å and d(Cr–CO) = 1.847 (5), 1.837 (4) Å (Pavkovic & Zaluzec, 1989). In the structure of the title complex the Cr–C distances to the terminal carbon atoms of the s-cis-1,3-butadiene ligand are longer compared to the respective distances to the central carbon atoms of the diene ligand. A similar trend to longer Cr–C distances for the terminal carbon atoms was found for example for the s-cis-1,3-butadiene chromium(1) complex [CrCp*(C₄H₆)(CO)] (Betz et al. 1993). As known from a few other chromium(0) complexes of s-cis-1,3-butadiene and related coordination compounds (Pavkovic & Zaluzec, 1989; Betz et al. 1993; Wang et al. 1990; Konietzny et al. 2010) in [Cr(C₄H₆)(CO)₄] the terminal C–C distances are significantly shorter than the central d(C–C) Δ(d(C–C)) = 0.057–0.065 Å. In contrast, for comparable iron(0) and manganese(0) complexes almost equilibrated C–C distances have been reported (Reiss, 2010; Reiss & Konietzny 2002), e. g. in the structure of the s-cis-1,3-butadiene iron(0) complex [Fe(C₄H₆)(CO)₃] Δ(d(C–C)) = 0.005 Å [d(C–C)_central = 1.4142 (19) Å, d(C–C)_terminal = 1.4194 (14) Å] (Reiss, 2010).

Related literature top

For experimental and theoretical data for the title compound, see: Fischler et al. (1976); Kotzian et al. (1982); Kreiter & Özkar (1978); Okamoto et al. (1991); von Ragué Schleyer et al. (2000). For related chromium complexes, see: Pavkovic & Zaluzec (1989), Betz et al. (1993), Wang et al. (1990), Konietzny et al. (2010). For related s-cis-butadiene complexes, see: Reiss (2010), Reiss & Konietzny (2002).

Experimental top

Synthesis

[Cr(C₄H₆)(CO)₄] was synthesized according to a published procedure (Fischler, 1976). The crystal was obtained by slow evaporation of a solution of pentane.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Hydrogen atoms are drawn with an arbitrary radius and the displacement ellipsoids are shown at the 50% probability level.

(η⁴-s-cis-1,3-Butadiene)tetracarbonylchromium(0) top

Crystal data top

[Cr(C₄H₆)(CO)₄]	Z = 2
M_r = 218.13	F(000) = 220
Triclinic, P1	D_x = 1.636 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4011 (8) Å	Cell parameters from 2257 reflections
b = 6.7666 (8) Å	θ = 3.4–28.7°
c = 11.0642 (10) Å	µ = 1.27 mm⁻¹
α = 84.728 (7)°	T = 137 K
β = 81.840 (8)°	Platelet, yellow
γ = 69.127 (8)°	0.38 × 0.26 × 0.04 mm
V = 442.80 (8) Å³

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1498 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 26.0°, θ_min = 4.1°
ω scans	h = −7→7
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2009)	k = −8→8
T_min = 0.711, T_max = 0.946	l = −13→13
2829 measured reflections	3 standard reflections every 60 min
1735 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	All H-atom parameters refined
S = 1.05	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
1735 reflections	(Δ/σ)_max = 0.001
140 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Cr(C₄H₆)(CO)₄]	γ = 69.127 (8)°
M_r = 218.13	V = 442.80 (8) Å³
Triclinic, P1	Z = 2
a = 6.4011 (8) Å	Mo Kα radiation
b = 6.7666 (8) Å	µ = 1.27 mm⁻¹
c = 11.0642 (10) Å	T = 137 K
α = 84.728 (7)°	0.38 × 0.26 × 0.04 mm
β = 81.840 (8)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1498 reflections with I > 2σ(I)
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2009)	R_int = 0.020
T_min = 0.711, T_max = 0.946	3 standard reflections every 60 min
2829 measured reflections	intensity decay: none
1735 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.068	All H-atom parameters refined
S = 1.05	Δρ_max = 0.29 e Å⁻³
1735 reflections	Δρ_min = −0.38 e Å⁻³
140 parameters

Special details top

Experimental. A single-crystal suitable for structure determination was harvested under a dry nitrogen atmosphere and was directly transferred into the cooling stream of an Oxford-Xcalibur diffractometer equipped with an EOS-CCD detector. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.33.52 (release 06–11-2009). Numerical absorption correction based on Gaussian integration over a multifaceted crystal model.

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

	x	y	z	U_iso*/U_eq
Cr1	0.66351 (5)	0.59871 (5)	0.74506 (3)	0.01600 (12)
O6	0.8591 (3)	0.2852 (3)	0.94893 (13)	0.0342 (4)
C6	0.7852 (3)	0.4125 (3)	0.87540 (17)	0.0212 (4)
O5	0.3023 (3)	0.4055 (2)	0.79702 (16)	0.0342 (4)
O8	0.4722 (3)	0.7542 (3)	0.50255 (13)	0.0329 (4)
C8	0.5444 (3)	0.7032 (3)	0.59328 (18)	0.0222 (4)
C5	0.4434 (3)	0.4763 (3)	0.77460 (18)	0.0216 (4)
O7	1.0248 (3)	0.2629 (3)	0.59598 (14)	0.0329 (4)
C7	0.8870 (3)	0.3908 (3)	0.65151 (18)	0.0222 (4)
C3	0.8024 (4)	0.8098 (3)	0.81772 (19)	0.0258 (5)
H3	0.921 (4)	0.746 (4)	0.864 (2)	0.027 (6)*
C2	0.5762 (4)	0.8487 (3)	0.8746 (2)	0.0269 (5)
H2	0.556 (3)	0.811 (3)	0.955 (2)	0.019 (5)*
C1	0.3978 (4)	0.9184 (4)	0.8059 (2)	0.0287 (5)
H12	0.403 (4)	1.009 (4)	0.732 (2)	0.031 (4)*
H11	0.261 (4)	0.918 (4)	0.846 (2)	0.031 (4)*
C4	0.8493 (4)	0.8394 (4)	0.6940 (2)	0.0282 (5)
H41	0.748 (4)	0.940 (4)	0.647 (2)	0.027 (4)*
H42	0.995 (4)	0.789 (4)	0.655 (2)	0.027 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr1	0.01916 (18)	0.01729 (18)	0.01228 (17)	−0.00607 (13)	−0.00425 (11)	−0.00170 (12)
O6	0.0401 (9)	0.0363 (10)	0.0225 (8)	−0.0080 (8)	−0.0115 (7)	0.0083 (7)
C6	0.0233 (10)	0.0242 (11)	0.0161 (10)	−0.0078 (9)	−0.0006 (8)	−0.0052 (9)
O5	0.0282 (8)	0.0266 (9)	0.0510 (10)	−0.0139 (7)	−0.0031 (7)	−0.0027 (8)
O8	0.0432 (9)	0.0350 (9)	0.0230 (8)	−0.0128 (8)	−0.0179 (7)	0.0042 (7)
C8	0.0234 (10)	0.0225 (11)	0.0223 (11)	−0.0089 (9)	−0.0038 (8)	−0.0034 (9)
C5	0.0233 (10)	0.0165 (10)	0.0222 (10)	−0.0017 (9)	−0.0065 (8)	−0.0023 (8)
O7	0.0317 (9)	0.0334 (9)	0.0260 (8)	−0.0027 (7)	0.0040 (7)	−0.0098 (7)
C7	0.0258 (11)	0.0263 (11)	0.0171 (10)	−0.0113 (9)	−0.0066 (8)	0.0025 (9)
C3	0.0335 (12)	0.0233 (11)	0.0266 (11)	−0.0133 (10)	−0.0142 (9)	−0.0010 (9)
C2	0.0429 (13)	0.0194 (11)	0.0200 (11)	−0.0111 (10)	−0.0045 (9)	−0.0073 (9)
C1	0.0309 (12)	0.0188 (11)	0.0339 (13)	−0.0047 (9)	−0.0013 (10)	−0.0080 (10)
C4	0.0312 (13)	0.0305 (13)	0.0302 (12)	−0.0189 (11)	−0.0080 (10)	0.0021 (10)

Geometric parameters (Å, º) top

Cr1—C5	1.852 (2)	O8—C8	1.138 (2)
Cr1—C6	1.887 (2)	C1—C2	1.379 (3)
Cr1—C7	1.873 (2)	C2—C3	1.436 (3)
Cr1—C8	1.914 (2)	C3—C4	1.371 (3)
Cr1—C1	2.312 (2)	C1—H11	0.92 (2)
Cr1—C2	2.184 (2)	C1—H12	0.98 (3)
Cr1—C3	2.190 (2)	C2—H2	0.90 (2)
Cr1—C4	2.325 (2)	C3—H3	0.92 (2)
O5—C5	1.153 (3)	C4—H41	0.93 (3)
O6—C6	1.148 (3)	C4—H42	0.93 (3)
O7—C7	1.142 (3)

C5—Cr1—C6	83.10 (9)	C2—C3—C4	121.6 (2)
C5—Cr1—C7	99.88 (9)	C2—C1—H11	116.0 (15)
C7—Cr1—C6	82.30 (8)	C2—C1—H12	120.2 (14)
C5—Cr1—C8	85.80 (9)	C1—C2—H2	120.7 (14)
C7—Cr1—C8	84.94 (9)	C3—C2—H2	118.0 (14)
C6—Cr1—C8	161.38 (9)	C4—C3—H3	118.6 (15)
O6—C6—Cr1	174.03 (18)	C2—C3—H3	119.2 (15)
O8—C8—Cr1	176.01 (19)	C3—C4—H41	122.7 (15)
O5—C5—Cr1	177.16 (18)	C3—C4—H42	121.8 (15)
O7—C7—Cr1	178.99 (18)	H12—C1—H11	120 (2)
C1—C2—C3	120.8 (2)	H41—C4—H42	114 (2)

C4—C3—C2—C1	−0.3 (3)

Experimental details

Crystal data
Chemical formula	[Cr(C₄H₆)(CO)₄]
M_r	218.13
Crystal system, space group	Triclinic, P1
Temperature (K)	137
a, b, c (Å)	6.4011 (8), 6.7666 (8), 11.0642 (10)
α, β, γ (°)	84.728 (7), 81.840 (8), 69.127 (8)
V (Å³)	442.80 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.27
Crystal size (mm)	0.38 × 0.26 × 0.04

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	Gaussian (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.711, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	2829, 1735, 1498
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.068, 1.05
No. of reflections	1735
No. of parameters	140
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.38

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010).

Selected bond lengths (Å) top

Cr1—C5	1.852 (2)	Cr1—C3	2.190 (2)
Cr1—C6	1.887 (2)	Cr1—C4	2.325 (2)
Cr1—C7	1.873 (2)	C1—C2	1.379 (3)
Cr1—C8	1.914 (2)	C2—C3	1.436 (3)
Cr1—C1	2.312 (2)	C3—C4	1.371 (3)
Cr1—C2	2.184 (2)

References

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