organic compounds
2,5-Dichloro-3,6-diisopropylcyclohexa-2,5-diene-1,4-dione
aFaculty of Chemistry and Chemical Engineering, TaiShan Medical University, Tai'an 271016, People's Republic of China
*Correspondence e-mail: Binboll@126.com
The molecule of the title compound, C12H14Cl2O2, lies about an inversion center. The six-membered ring is almost planar, with the largest deviation from the least-squares plane being 0.014 (4) Å. The molecular conformation is stabilized by a weak intramolecular C—H⋯O hydrogen bond. In the crystal, molecules are packed into stacks along the c-axis direction, with an intercentroid separation of 4.811 (2) Å. Neighboring molecules within the stack are related by the c-glide plane.
Related literature
Metal complexes of catechols, ). For standard bond lengths, see: Allen et al. (1987).
and are of general interest in the investigation of ligand centered redox reactions and as models for biochemical processes involving metal ions, see: Mostafa (1999Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536812032886/yk2064sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812032886/yk2064Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812032886/yk2064Isup3.cml
Potassium hydroxide (5.0 g) was added to a solution containing chloranil (5.0 g) in 2-propanol (100 ml). The resulting mixture was stirred under reflux for 1 h, and then the red reaction solution was cooled to 283 K. The precipitated yellow solid was collected and recrystallized in ethanol.
All H atoms were positioned geometrically and allowed to ride on their parent atoms with C—H = 0.98 Å and Uiso(H)= 1.2Ueq(C) for tertiary hydrogen and with C—H = 0.96 Å and Uiso(H)= 1.5Ueq(C) for methyl group.
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).Fig. 1. Molecular structure with atom labelling scheme and thermal ellipsoids drawn at the 30% probability level (symmetry code (i): 1 - x,1 - y,1 - z). |
C12H14Cl2O4 | F(000) = 608 |
Mr = 293.13 | Dx = 1.384 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 837 reflections |
a = 10.286 (2) Å | θ = 2.5–21.5° |
b = 15.034 (3) Å | µ = 0.46 mm−1 |
c = 9.621 (2) Å | T = 293 K |
β = 109.022 (4)° | Block, yellow |
V = 1406.5 (6) Å3 | 0.15 × 0.13 × 0.12 mm |
Z = 4 |
Brucker APEXII CCD diffractometer | 1248 independent reflections |
Radiation source: fine-focus sealed tube | 676 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −12→9 |
Tmin = 0.925, Tmax = 0.946 | k = −17→17 |
3544 measured reflections | l = −10→11 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.198 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.1P)2 + 0.P] where P = (Fo2 + 2Fc2)/3 |
1248 reflections | (Δ/σ)max = 0.001 |
84 parameters | Δρmax = 0.41 e Å−3 |
12 restraints | Δρmin = −0.24 e Å−3 |
C12H14Cl2O4 | V = 1406.5 (6) Å3 |
Mr = 293.13 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.286 (2) Å | µ = 0.46 mm−1 |
b = 15.034 (3) Å | T = 293 K |
c = 9.621 (2) Å | 0.15 × 0.13 × 0.12 mm |
β = 109.022 (4)° |
Brucker APEXII CCD diffractometer | 1248 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 676 reflections with I > 2σ(I) |
Tmin = 0.925, Tmax = 0.946 | Rint = 0.079 |
3544 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 12 restraints |
wR(F2) = 0.198 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.41 e Å−3 |
1248 reflections | Δρmin = −0.24 e Å−3 |
84 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'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 s.u.'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 | ||
C1 | 0.4914 (5) | 0.5935 (3) | 0.5241 (4) | 0.0672 (11) | |
C2 | 0.5842 (4) | 0.5580 (3) | 0.4504 (4) | 0.0686 (12) | |
C3 | 0.5968 (4) | 0.4704 (3) | 0.4308 (4) | 0.0632 (11) | |
C4 | 0.7787 (5) | 0.3702 (3) | 0.4212 (5) | 0.0903 (13) | |
H4 | 0.7285 | 0.3149 | 0.4223 | 0.108* | |
C5 | 0.8654 (6) | 0.3916 (4) | 0.5744 (6) | 0.1146 (16) | |
H5A | 0.9196 | 0.4436 | 0.5740 | 0.172* | |
H5B | 0.9252 | 0.3424 | 0.6150 | 0.172* | |
H5C | 0.8075 | 0.4027 | 0.6331 | 0.172* | |
C6 | 0.8576 (7) | 0.3595 (4) | 0.3175 (6) | 0.1114 (16) | |
H6A | 0.7949 | 0.3508 | 0.2198 | 0.167* | |
H6B | 0.9173 | 0.3089 | 0.3459 | 0.167* | |
H6C | 0.9115 | 0.4120 | 0.3198 | 0.167* | |
Cl1 | 0.68016 (14) | 0.63397 (8) | 0.39265 (14) | 0.0914 (7) | |
O1 | 0.4891 (4) | 0.6728 (2) | 0.5509 (4) | 0.0948 (11) | |
O2 | 0.6789 (3) | 0.4409 (2) | 0.3567 (3) | 0.0789 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.085 (3) | 0.052 (3) | 0.065 (3) | 0.012 (2) | 0.025 (2) | 0.007 (2) |
C2 | 0.086 (3) | 0.061 (3) | 0.058 (2) | −0.001 (2) | 0.022 (2) | 0.007 (2) |
C3 | 0.075 (3) | 0.059 (3) | 0.057 (2) | 0.010 (2) | 0.023 (2) | 0.0061 (19) |
C4 | 0.095 (3) | 0.100 (3) | 0.079 (3) | 0.027 (2) | 0.033 (2) | 0.006 (2) |
C5 | 0.114 (3) | 0.124 (3) | 0.094 (3) | 0.026 (3) | 0.018 (3) | −0.006 (3) |
C6 | 0.124 (3) | 0.121 (3) | 0.092 (3) | 0.044 (3) | 0.040 (3) | 0.004 (3) |
Cl1 | 0.1161 (12) | 0.0720 (9) | 0.0961 (10) | −0.0080 (6) | 0.0484 (8) | 0.0120 (6) |
O1 | 0.125 (3) | 0.055 (2) | 0.119 (3) | 0.0052 (18) | 0.059 (2) | −0.0032 (18) |
O2 | 0.102 (2) | 0.0689 (19) | 0.075 (2) | 0.0238 (16) | 0.0414 (18) | 0.0111 (14) |
C1—O1 | 1.221 (4) | C4—C5 | 1.489 (7) |
C1—C2 | 1.463 (5) | C4—H4 | 0.9800 |
C1—C3i | 1.480 (6) | C5—H5A | 0.9600 |
C2—C3 | 1.343 (5) | C5—H5B | 0.9600 |
C2—Cl1 | 1.715 (4) | C5—H5C | 0.9600 |
C3—O2 | 1.346 (5) | C6—H6A | 0.9600 |
C4—O2 | 1.468 (5) | C6—H6B | 0.9600 |
C4—C6 | 1.486 (7) | C6—H6C | 0.9600 |
O1—C1—C2 | 121.2 (4) | C5—C4—H4 | 108.7 |
O1—C1—C3i | 121.0 (4) | C4—C5—H5A | 109.5 |
C2—C1—C3i | 117.7 (4) | C4—C5—H5B | 109.5 |
C3—C2—C1 | 122.2 (4) | H5A—C5—H5B | 109.5 |
C3—C2—Cl1 | 121.1 (3) | C4—C5—H5C | 109.5 |
C1—C2—Cl1 | 116.7 (3) | H5A—C5—H5C | 109.5 |
C2—C3—O2 | 120.2 (4) | H5B—C5—H5C | 109.5 |
C2—C3—C1i | 120.0 (4) | C4—C6—H6A | 109.5 |
O2—C3—C1i | 119.5 (4) | C4—C6—H6B | 109.5 |
O2—C4—C6 | 104.7 (4) | H6A—C6—H6B | 109.5 |
O2—C4—C5 | 111.9 (4) | C4—C6—H6C | 109.5 |
C6—C4—C5 | 114.0 (5) | H6A—C6—H6C | 109.5 |
O2—C4—H4 | 108.7 | H6B—C6—H6C | 109.5 |
C6—C4—H4 | 108.7 | C3—O2—C4 | 119.2 (3) |
O1—C1—C2—C3 | 174.3 (4) | C1—C2—C3—C1i | 4.0 (6) |
C3i—C1—C2—C3 | −3.9 (6) | Cl1—C2—C3—C1i | −177.4 (3) |
O1—C1—C2—Cl1 | −4.3 (5) | C2—C3—O2—C4 | 130.7 (4) |
C3i—C1—C2—Cl1 | 177.4 (3) | C1i—C3—O2—C4 | −56.2 (5) |
C1—C2—C3—O2 | 177.1 (3) | C6—C4—O2—C3 | −175.7 (4) |
Cl1—C2—C3—O2 | −4.4 (5) | C5—C4—O2—C3 | −51.8 (6) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O1i | 0.98 | 2.34 | 2.926 (7) | 117 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H14Cl2O4 |
Mr | 293.13 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.286 (2), 15.034 (3), 9.621 (2) |
β (°) | 109.022 (4) |
V (Å3) | 1406.5 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.46 |
Crystal size (mm) | 0.15 × 0.13 × 0.12 |
Data collection | |
Diffractometer | Brucker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.925, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3544, 1248, 676 |
Rint | 0.079 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.198, 1.08 |
No. of reflections | 1248 |
No. of parameters | 84 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.24 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O1i | 0.98 | 2.34 | 2.926 (7) | 117 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
This work was supported by the Shandong College research program (J11LB15) and the Young and Middle-aged Scientist Research Awards Foundation of Shandong Province (BS2010CL045)
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Mostafa, S. I. (1999). Transition Met. Chem. 24, 306–310. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Metal complexes of catechols, semiquinones and quinones are of general interest in the investigation of ligand centered redox reactions and as models for biochemical processes involving metal ions (Mostafa, 1999). The title compound is the synthetic precusor for chloranilic acid, which is a simple, readily available ligand combining chelating and bridging capabilities.
In the title molecule, the six-membered ring and attached oxygen and clorine atoms bound to every vertex of this carbon hexagon, share a same plane with the largest deviation being 0.053 (4) Å for C3. The two isopropyl groups extend from the plane, one above and one below the plane, as shown in Fig. 1. The C1═O1 bond has a lengths of 1.221 (4) Å, typical of Csp2═ O double bonds (Allen et al., 1987). The C3—O2 bond, however, is a Csp2—O single bond with the lengths of 1.346 (5) Å, which is slightly shorter than the value expected for enol ester systems [1.354 (16) Å (Allen et al.,1987). The carbon-carbon bonds in the six-membered ring can also be divided into two groups: the C2═C3 bond is a typical double bond with the length of 1.343 (5) Å, whereas the C1—C2 and C1—C3i bonds with the lengths of 1.463 (5) Å and 1.480 (6) Å, reaspectively, are obviously the Csp2—Csp2 single bonds.
There are weak intramolecular interactions C2—H2A···O2 (1 - x,1 - y,1 - z) [H···O = 2.34 Å, C···O = 2.926 (7) Å, and C—H···O = 117°], which stabilize the molecule conformation.
In the crystal, the molecules of the title compound are packed into stacks along the c direction with intercentroid separation of 4.811 (2) Å. Neighboring molecules within the stack are related by the c glide plane.