Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028126/hg6241sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028126/hg6241Isup2.hkl |
CCDC reference: 287596
A mixture of 1,4-bis(bromomethyl)benzene (1.32 g, 5 mmol), ethyl malonate (1.53 ml, 10 mmol), potassium carbonate (1.38 g, 10 mmol) and acetone (25 ml) was stirred and refluxed for 8 h (Morenomanas et al., 1993). The solvent was evaporated on a rotary evaporator and the resulting oil was chromatographed on a silica-gel column, yielding the title compound (1.37 g, 65%). Crystals appropriate for data collection were obtained by slow evaporation from acetone solution at 283 K. M.p. 326–319 K. 1H NMR (CDCl3, 400 MHz, p.p.m.): δ 7.26 (s, 4H), 4.15 (q, 2H, J = 7.2 Hz), 3.60 (t, 1H, J = 7.6 Hz), 3.17 (d, 2H, J = 7.6 Hz), 1.23 (t, 3H, J = 7.2 Hz). MS: 423 (M+1,100), 348 (80.99), 274 (90.56), 262 (62.24), 189 (67.31).
One pair of symmetrically related ethyl groups are found to be disordered over two orientations. The occupancies of the disordered positions C10/C10' and C11/C11' were refined to 0.736 (18)/0.264 (18); C10a/C10a' and C11a/C11a' were also refined to 0.736 (18)/0.264 (18). All H atoms were refined as riding; C—H (methyl H) = 0.96 Å, C—H (methylene H) = 0.97 Å, C—H (methene H) = 0.98 Å and C—H (aromatic H) = 0.93 Å. The constraint Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C) was applied.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
C22H30O8 | F(000) = 452 |
Mr = 422.46 | Dx = 1.213 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1926 reflections |
a = 9.461 (2) Å | θ = 2.4–21.4° |
b = 8.3944 (17) Å | µ = 0.09 mm−1 |
c = 14.601 (3) Å | T = 292 K |
β = 94.069 (4)° | Block, colorless |
V = 1156.8 (4) Å3 | 0.20 × 0.20 × 0.20 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1518 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ϕ and ω scans | h = −10→11 |
5515 measured reflections | k = −9→9 |
1991 independent reflections | l = −13→17 |
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)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.197 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1046P)2 + 0.3206P] where P = (Fo2 + 2Fc2)/3 |
1991 reflections | (Δ/σ)max < 0.001 |
146 parameters | Δρmax = 0.42 e Å−3 |
3 restraints | Δρmin = −0.22 e Å−3 |
C22H30O8 | V = 1156.8 (4) Å3 |
Mr = 422.46 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.461 (2) Å | µ = 0.09 mm−1 |
b = 8.3944 (17) Å | T = 292 K |
c = 14.601 (3) Å | 0.20 × 0.20 × 0.20 mm |
β = 94.069 (4)° |
Bruker SMART CCD area-detector diffractometer | 1518 reflections with I > 2σ(I) |
5515 measured reflections | Rint = 0.025 |
1991 independent reflections |
R[F2 > 2σ(F2)] = 0.066 | 3 restraints |
wR(F2) = 0.197 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.42 e Å−3 |
1991 reflections | Δρmin = −0.22 e Å−3 |
146 parameters |
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 | Occ. (<1) | |
C1 | 0.6168 (3) | 0.0600 (3) | 0.46213 (18) | 0.0754 (8) | |
H1 | 0.6965 | 0.1022 | 0.4373 | 0.090* | |
C2 | 0.5309 (3) | −0.0454 (3) | 0.41066 (15) | 0.0612 (6) | |
C3 | 0.4140 (3) | −0.1034 (3) | 0.45040 (17) | 0.0707 (7) | |
H3 | 0.3540 | −0.1738 | 0.4174 | 0.085* | |
C4 | 0.5649 (3) | −0.1023 (3) | 0.31665 (17) | 0.0707 (7) | |
H4A | 0.4816 | −0.1543 | 0.2879 | 0.085* | |
H4B | 0.6395 | −0.1814 | 0.3239 | 0.085* | |
C6 | 0.4968 (3) | 0.1520 (3) | 0.23399 (16) | 0.0652 (6) | |
C7 | 0.4511 (5) | 0.4295 (5) | 0.2205 (3) | 0.1228 (14) | |
H7A | 0.3546 | 0.4001 | 0.2315 | 0.147* | |
H7B | 0.4765 | 0.5227 | 0.2574 | 0.147* | |
C8 | 0.4606 (5) | 0.4662 (6) | 0.1240 (4) | 0.148 (2) | |
H8A | 0.5569 | 0.4918 | 0.1131 | 0.223* | |
H8B | 0.4007 | 0.5555 | 0.1075 | 0.223* | |
H8C | 0.4305 | 0.3756 | 0.0875 | 0.223* | |
C9 | 0.6466 (3) | −0.0445 (3) | 0.16142 (17) | 0.0682 (7) | |
C10' | 0.780 (3) | 0.022 (3) | 0.0280 (14) | 0.108 (2) | 0.264 (18) |
H10C | 0.7635 | −0.0853 | 0.0045 | 0.129* | 0.264 (18) |
H10D | 0.8804 | 0.0411 | 0.0414 | 0.129* | 0.264 (18) |
C11' | 0.704 (4) | 0.1531 (19) | −0.032 (2) | 0.169 (5) | 0.264 (18) |
H11D | 0.7030 | 0.1234 | −0.0955 | 0.254* | 0.264 (18) |
H11E | 0.7537 | 0.2522 | −0.0227 | 0.254* | 0.264 (18) |
H11F | 0.6085 | 0.1650 | −0.0149 | 0.254* | 0.264 (18) |
C10 | 0.7133 (13) | 0.0081 (9) | 0.0115 (4) | 0.108 (2) | 0.736 (18) |
H10A | 0.7744 | −0.0848 | 0.0148 | 0.129* | 0.736 (18) |
H10B | 0.6231 | −0.0228 | −0.0192 | 0.129* | 0.736 (18) |
C11 | 0.7742 (16) | 0.1262 (12) | −0.0386 (5) | 0.169 (5) | 0.736 (18) |
H11A | 0.7271 | 0.2256 | −0.0293 | 0.254* | 0.736 (18) |
H11B | 0.7650 | 0.0991 | −0.1026 | 0.254* | 0.736 (18) |
H11C | 0.8727 | 0.1360 | −0.0187 | 0.254* | 0.736 (18) |
C5 | 0.6115 (3) | 0.0279 (3) | 0.25239 (15) | 0.0618 (6) | |
H5 | 0.6964 | 0.0800 | 0.2807 | 0.074* | |
O1 | 0.3770 (2) | 0.1213 (3) | 0.21006 (16) | 0.0949 (7) | |
O2 | 0.5466 (2) | 0.2984 (2) | 0.24678 (14) | 0.0871 (7) | |
O3 | 0.6350 (2) | −0.1816 (2) | 0.14195 (14) | 0.0923 (7) | |
O4 | 0.6906 (3) | 0.0642 (3) | 0.10625 (14) | 0.1075 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0767 (17) | 0.0800 (17) | 0.0717 (16) | −0.0140 (13) | 0.0215 (12) | 0.0021 (13) |
C2 | 0.0760 (15) | 0.0508 (12) | 0.0576 (13) | 0.0035 (11) | 0.0096 (11) | 0.0099 (10) |
C3 | 0.0783 (17) | 0.0673 (15) | 0.0670 (15) | −0.0116 (12) | 0.0080 (12) | −0.0009 (12) |
C4 | 0.0907 (18) | 0.0579 (13) | 0.0653 (15) | 0.0008 (12) | 0.0171 (12) | 0.0030 (11) |
C6 | 0.0723 (16) | 0.0686 (15) | 0.0552 (13) | −0.0015 (12) | 0.0079 (11) | −0.0012 (11) |
C7 | 0.136 (3) | 0.078 (2) | 0.149 (4) | 0.026 (2) | −0.024 (3) | −0.002 (2) |
C8 | 0.131 (4) | 0.123 (3) | 0.185 (5) | −0.014 (3) | −0.036 (3) | 0.072 (3) |
C9 | 0.0760 (16) | 0.0683 (16) | 0.0619 (14) | −0.0024 (12) | 0.0146 (11) | −0.0046 (12) |
C10' | 0.147 (7) | 0.112 (3) | 0.069 (3) | −0.050 (4) | 0.040 (4) | −0.029 (2) |
C11' | 0.231 (13) | 0.190 (6) | 0.097 (3) | −0.098 (7) | 0.089 (5) | −0.054 (4) |
C10 | 0.147 (7) | 0.112 (3) | 0.069 (3) | −0.050 (4) | 0.040 (4) | −0.029 (2) |
C11 | 0.231 (13) | 0.190 (6) | 0.097 (3) | −0.098 (7) | 0.089 (5) | −0.054 (4) |
C5 | 0.0717 (15) | 0.0589 (13) | 0.0554 (13) | 0.0002 (11) | 0.0085 (10) | −0.0017 (10) |
O1 | 0.0750 (14) | 0.0930 (15) | 0.1155 (17) | 0.0003 (11) | −0.0013 (11) | −0.0012 (12) |
O2 | 0.0980 (15) | 0.0606 (11) | 0.1008 (15) | 0.0076 (9) | −0.0068 (11) | 0.0003 (9) |
O3 | 0.1199 (17) | 0.0748 (13) | 0.0849 (13) | 0.0007 (11) | 0.0250 (11) | −0.0181 (10) |
O4 | 0.172 (2) | 0.0874 (14) | 0.0686 (12) | −0.0267 (14) | 0.0473 (13) | −0.0132 (10) |
C1—C3i | 1.379 (4) | C8—H8C | 0.9600 |
C1—C2 | 1.386 (4) | C9—O3 | 1.189 (3) |
C1—H1 | 0.9300 | C9—O4 | 1.304 (3) |
C2—C3 | 1.374 (4) | C9—C5 | 1.519 (3) |
C2—C4 | 1.509 (3) | C10'—O4 | 1.512 (9) |
C3—C1i | 1.379 (4) | C10'—C11' | 1.55 (4) |
C3—H3 | 0.9300 | C10'—H10C | 0.9700 |
C4—C5 | 1.526 (3) | C10'—H10D | 0.9700 |
C4—H4A | 0.9700 | C11'—H11D | 0.9600 |
C4—H4B | 0.9700 | C11'—H11E | 0.9600 |
C6—O1 | 1.190 (3) | C11'—H11F | 0.9600 |
C6—O2 | 1.325 (3) | C10—C11 | 1.383 (10) |
C6—C5 | 1.514 (4) | C10—O4 | 1.491 (4) |
C7—C8 | 1.452 (6) | C10—H10A | 0.9700 |
C7—O2 | 1.458 (4) | C10—H10B | 0.9700 |
C7—H7A | 0.9700 | C11—H11A | 0.9600 |
C7—H7B | 0.9700 | C11—H11B | 0.9600 |
C8—H8A | 0.9600 | C11—H11C | 0.9600 |
C8—H8B | 0.9600 | C5—H5 | 0.9800 |
C3i—C1—C2 | 121.1 (2) | O3—C9—O4 | 123.9 (2) |
C3i—C1—H1 | 119.5 | O3—C9—C5 | 125.1 (2) |
C2—C1—H1 | 119.5 | O4—C9—C5 | 111.1 (2) |
C3—C2—C1 | 117.1 (2) | O4—C10'—C11' | 89.9 (17) |
C3—C2—C4 | 120.1 (2) | O4—C10'—H10C | 113.7 |
C1—C2—C4 | 122.7 (2) | C11'—C10'—H10C | 113.7 |
C2—C3—C1i | 121.8 (2) | O4—C10'—H10D | 113.7 |
C2—C3—H3 | 119.1 | C11'—C10'—H10D | 113.7 |
C1i—C3—H3 | 119.1 | H10C—C10'—H10D | 110.9 |
C2—C4—C5 | 115.0 (2) | C10'—C11'—H11D | 109.5 |
C2—C4—H4A | 108.5 | C10'—C11'—H11E | 109.5 |
C5—C4—H4A | 108.5 | H11D—C11'—H11E | 109.5 |
C2—C4—H4B | 108.5 | C10'—C11'—H11F | 109.5 |
C5—C4—H4B | 108.5 | H11D—C11'—H11F | 109.5 |
H4A—C4—H4B | 107.5 | H11E—C11'—H11F | 109.5 |
O1—C6—O2 | 124.3 (3) | C11—C10—O4 | 110.9 (5) |
O1—C6—C5 | 124.0 (2) | C11—C10—H10A | 109.4 |
O2—C6—C5 | 111.7 (2) | O4—C10—H10A | 109.4 |
C8—C7—O2 | 109.6 (4) | C11—C10—H10B | 109.4 |
C8—C7—H7A | 109.8 | O4—C10—H10B | 109.4 |
O2—C7—H7A | 109.8 | H10A—C10—H10B | 108.0 |
C8—C7—H7B | 109.8 | C6—C5—C9 | 108.56 (19) |
O2—C7—H7B | 109.8 | C6—C5—C4 | 111.5 (2) |
H7A—C7—H7B | 108.2 | C9—C5—C4 | 110.0 (2) |
C7—C8—H8A | 109.5 | C6—C5—H5 | 108.9 |
C7—C8—H8B | 109.5 | C9—C5—H5 | 108.9 |
H8A—C8—H8B | 109.5 | C4—C5—H5 | 108.9 |
C7—C8—H8C | 109.5 | C6—O2—C7 | 117.1 (3) |
H8A—C8—H8C | 109.5 | C9—O4—C10 | 115.2 (4) |
H8B—C8—H8C | 109.5 | C9—O4—C10' | 121.5 (10) |
C3i—C1—C2—C3 | 0.4 (4) | C2—C4—C5—C6 | −61.1 (3) |
C3i—C1—C2—C4 | −176.8 (2) | C2—C4—C5—C9 | 178.4 (2) |
C1—C2—C3—C1i | −0.4 (4) | O1—C6—O2—C7 | −6.6 (4) |
C4—C2—C3—C1i | 176.9 (2) | C5—C6—O2—C7 | 172.7 (3) |
C3—C2—C4—C5 | 137.5 (2) | C8—C7—O2—C6 | −86.8 (4) |
C1—C2—C4—C5 | −45.3 (3) | O3—C9—O4—C10 | 5.7 (7) |
O1—C6—C5—C9 | 70.8 (3) | C5—C9—O4—C10 | −173.8 (6) |
O2—C6—C5—C9 | −108.5 (2) | O3—C9—O4—C10' | −22.8 (14) |
O1—C6—C5—C4 | −50.5 (3) | C5—C9—O4—C10' | 157.7 (14) |
O2—C6—C5—C4 | 130.2 (2) | C11—C10—O4—C9 | −173.5 (11) |
O3—C9—C5—C6 | −120.0 (3) | C11—C10—O4—C10' | −63 (3) |
O4—C9—C5—C6 | 59.5 (3) | C11'—C10'—O4—C9 | 144.1 (15) |
O3—C9—C5—C4 | 2.3 (4) | C11'—C10'—O4—C10 | 61 (3) |
O4—C9—C5—C4 | −178.2 (2) |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C22H30O8 |
Mr | 422.46 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 292 |
a, b, c (Å) | 9.461 (2), 8.3944 (17), 14.601 (3) |
β (°) | 94.069 (4) |
V (Å3) | 1156.8 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5515, 1991, 1518 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.197, 1.04 |
No. of reflections | 1991 |
No. of parameters | 146 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.22 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
C2—C4 | 1.509 (3) | C9—O3 | 1.189 (3) |
C4—C5 | 1.526 (3) | C9—O4 | 1.304 (3) |
C6—O1 | 1.190 (3) | C9—C5 | 1.519 (3) |
C6—O2 | 1.325 (3) | C10'—O4 | 1.512 (9) |
C6—C5 | 1.514 (4) | C10'—C11' | 1.55 (4) |
C7—C8 | 1.452 (6) | C10—C11 | 1.383 (10) |
C7—O2 | 1.458 (4) | C10—O4 | 1.491 (4) |
C3—C2—C4 | 120.1 (2) | O4—C9—C5 | 111.1 (2) |
C1—C2—C4 | 122.7 (2) | O4—C10'—C11' | 89.9 (17) |
C2—C4—C5 | 115.0 (2) | C11—C10—O4 | 110.9 (5) |
O1—C6—O2 | 124.3 (3) | C6—C5—C9 | 108.56 (19) |
O1—C6—C5 | 124.0 (2) | C6—C5—C4 | 111.5 (2) |
O2—C6—C5 | 111.7 (2) | C9—C5—C4 | 110.0 (2) |
C8—C7—O2 | 109.6 (4) | C6—O2—C7 | 117.1 (3) |
O3—C9—O4 | 123.9 (2) | C9—O4—C10 | 115.2 (4) |
O3—C9—C5 | 125.1 (2) | C9—O4—C10' | 121.5 (10) |
β-keto esters are multicoupling reagents with electrophilic and nucleophilic sites that have proven to be valuable tools in the synthesis of a wide variety of molecular systems (Benetti et al., 1995). In the present paper, we report the crystal structure of the title compound, (I). The molecule of (I) lies on a crystallographic inversion center located in the middle of the central benzene ring. Selected bond distances and angles are given in Table 1. One pair of symmetrically related ethyl groups are found to be disordered over two orientations (Fig. 1). The occupancies of the disordered positions C10/C10' and C11/C11' were refined to 0.736 (18)/0.264 (18); C10a/C10a' and C11a/C11a' were also refined to 0.736 (18)/0.264 (18). The molecular structure is stabilized by C—H···π intermolecular interactions (Fig. 2).