organic compounds
1,3-Bis(4-methylbenzoyl)-2,4-bis(2,4,5-trimethoxyphenyl)cyclobutane
aDepartment of Chemistry, SBRR Mahajana College, Mysuru 570 006, India, bInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, cDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysuru 570 005, India, and dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India
*Correspondence e-mail: naveen@ioe.uni-mysore.ac.in, ajaykumar@ycm.uni-mysore.ac.in
The title compound, C38H40O8, possess an inversion centre at the centroid of the four-membered ring. The dihedral angle between the methylbenzene and trimethoxybenzene rings is 46.19 (8)°. In the crystal, molecules are linked via weak C—H⋯π interactions, forming centrosymmetric supramolecular dimers.
Keywords: crystal structure; bis-chalcone; cyclobutane.
CCDC reference: 1529177
Structure description
Recently, a new route to polysubstituted cyclobutanes via K2S2O8-promoted [2 + 2]-cycloaddition was reported (Zhu et al., 2016). We carried out a reaction of 2,4,5-trimethoxybenzaldehyde and 4-methyl acetophenone in the presence of in 95% ethyl alcohol under reflux conditions. After completion, the reaction unexpectedly yielded the title compound via the intermolecular [2 + 2]-cycloaddition of the expected (E)-1-(p-tolyl)-3-(2,4,5-trimethoxyphenyl)prop-2-en-1-one.
The molecular structure of the title compound is shown in Fig. 1. The molecule is located about an inversion centre at the centroid of the four-membered ring. The dihedral angle between the aromatic rings is 46.19 (8)°. The methoxy groups at C4 and C6 lie close to the plane of theeir attached benzene ring, as indicated by the torsion angle values of −7.2 (2)° and 174.05 (14)° for C8—O3—C4—C5 and C7—O2—C6—C1 respectively whereas the methoxy group at C3 is twisted out of the plane of the benzene ring [C9—O4—C3—C2 = 119.22 (17)°] . In the crystal, the molecules are linked via weak C—H⋯π interactions (Table 1), forming centrosymmetric supramolecular dimers.
Synthesis and crystallization
A mixture of 2,4,5-trimethoxybenzaldehyde (5 mmol), 4-methyl acetophenone (5 mmol) and sodium hydroxide (5 mmol) in 95% ethyl alcohol (25 ml) was refluxed on a water bath conditions for 1 h. The progress of the reaction was monitored by TLC. After the completion of the reaction, the mixture was poured into ice-cold water and kept in the refrigerator overnight. The solid that formed was filtered, and washed with cold hydrochloric acid (5%). Recrystallization from methanol solution yielded yellow slabs of the title compound. Yield 78%, m.p. 108–110 °C.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1529177
https://doi.org/10.1107/S2414314617001134/xu4021sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001134/xu4021Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617001134/xu4021Isup3.cml
Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C38H40O8 | Z = 1 |
Mr = 624.70 | F(000) = 332 |
Triclinic, P1 | Dx = 1.332 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 8.1155 (4) Å | Cell parameters from 2458 reflections |
b = 9.9316 (5) Å | θ = 5.9–64.3° |
c = 11.0656 (6) Å | µ = 0.76 mm−1 |
α = 70.471 (1)° | T = 296 K |
β = 81.955 (1)° | Rectangle, yellow |
γ = 67.854 (1)° | 0.28 × 0.25 × 0.22 mm |
V = 778.47 (7) Å3 |
Bruker X8 Proteum diffractometer | 2539 independent reflections |
Radiation source: Bruker MicroStar microfocus rotating anode | 2458 reflections with I > 2σ(I) |
Helios multilayer optics monochromator | Rint = 0.042 |
Detector resolution: 18.4 pixels mm-1 | θmax = 64.3°, θmin = 5.9° |
φ and ω scans | h = −8→9 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −11→11 |
Tmin = 0.817, Tmax = 0.852 | l = −12→12 |
8126 measured reflections |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.1056P)2 + 0.2971P] where P = (Fo2 + 2Fc2)/3 |
2539 reflections | (Δ/σ)max < 0.001 |
212 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2sigma(F2) is used only for calculating -R-factor-obs 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 | ||
O1 | 0.44259 (16) | 0.19813 (15) | 0.23209 (11) | 0.0295 (4) | |
O2 | 0.01550 (14) | 0.26130 (12) | 0.51807 (11) | 0.0198 (3) | |
O3 | 0.11060 (15) | 0.46294 (13) | 0.83588 (11) | 0.0230 (3) | |
O4 | 0.47051 (15) | 0.31512 (13) | 0.81383 (11) | 0.0223 (3) | |
C1 | 0.3046 (2) | 0.20001 (17) | 0.58511 (14) | 0.0162 (4) | |
C2 | 0.4151 (2) | 0.21892 (17) | 0.65963 (15) | 0.0175 (5) | |
C3 | 0.3506 (2) | 0.30910 (17) | 0.74005 (15) | 0.0175 (5) | |
C4 | 0.1670 (2) | 0.38172 (17) | 0.75073 (15) | 0.0179 (5) | |
C5 | 0.0533 (2) | 0.36687 (17) | 0.67677 (15) | 0.0180 (5) | |
C6 | 0.1219 (2) | 0.27751 (17) | 0.59445 (14) | 0.0162 (5) | |
C7 | −0.1718 (2) | 0.32646 (19) | 0.53436 (16) | 0.0220 (5) | |
C8 | −0.0744 (2) | 0.55118 (19) | 0.83837 (17) | 0.0248 (5) | |
C9 | 0.4770 (2) | 0.4642 (2) | 0.78940 (19) | 0.0297 (6) | |
C10 | 0.3761 (2) | 0.10060 (17) | 0.49825 (15) | 0.0164 (5) | |
C11 | 0.5654 (2) | 0.07947 (17) | 0.44097 (15) | 0.0165 (5) | |
C12 | 0.5760 (2) | 0.14150 (17) | 0.29597 (15) | 0.0184 (5) | |
C13 | 0.7536 (2) | 0.13001 (17) | 0.23417 (15) | 0.0186 (5) | |
C14 | 0.9074 (2) | 0.07966 (18) | 0.30416 (15) | 0.0199 (5) | |
C15 | 1.0701 (2) | 0.06841 (18) | 0.24225 (16) | 0.0222 (5) | |
C16 | 1.0864 (2) | 0.10438 (18) | 0.10918 (16) | 0.0215 (5) | |
C17 | 0.9319 (2) | 0.15728 (18) | 0.03947 (16) | 0.0228 (5) | |
C18 | 0.7680 (2) | 0.17084 (18) | 0.10031 (16) | 0.0208 (5) | |
C19 | 1.2655 (2) | 0.0854 (2) | 0.04421 (17) | 0.0269 (5) | |
H2 | 0.53720 | 0.16870 | 0.65500 | 0.0210* | |
H5 | −0.06890 | 0.41670 | 0.68220 | 0.0220* | |
H7A | −0.20530 | 0.28090 | 0.62070 | 0.0330* | |
H7B | −0.23080 | 0.30790 | 0.47550 | 0.0330* | |
H7C | −0.20570 | 0.43450 | 0.51790 | 0.0330* | |
H8A | −0.11030 | 0.62020 | 0.75420 | 0.0370* | |
H8B | −0.09580 | 0.60840 | 0.89740 | 0.0370* | |
H8C | −0.14150 | 0.48430 | 0.86520 | 0.0370* | |
H9A | 0.50480 | 0.50400 | 0.70040 | 0.0450* | |
H9B | 0.56710 | 0.45760 | 0.84120 | 0.0450* | |
H9C | 0.36360 | 0.53080 | 0.81030 | 0.0450* | |
H10 | 0.29200 | 0.13580 | 0.42910 | 0.0200* | |
H11 | 0.62770 | 0.12040 | 0.48140 | 0.0200* | |
H14 | 0.90040 | 0.05350 | 0.39320 | 0.0240* | |
H15 | 1.17070 | 0.03610 | 0.29040 | 0.0270* | |
H17 | 0.93920 | 0.18390 | −0.04950 | 0.0270* | |
H18 | 0.66660 | 0.20740 | 0.05180 | 0.0250* | |
H19A | 1.30410 | 0.16480 | 0.04640 | 0.0400* | |
H19B | 1.25710 | 0.09150 | −0.04330 | 0.0400* | |
H19C | 1.34970 | −0.01230 | 0.08800 | 0.0400* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0193 (6) | 0.0386 (8) | 0.0237 (7) | −0.0057 (5) | −0.0007 (5) | −0.0061 (5) |
O2 | 0.0152 (6) | 0.0226 (6) | 0.0242 (6) | −0.0059 (5) | −0.0006 (4) | −0.0114 (5) |
O3 | 0.0209 (6) | 0.0233 (6) | 0.0253 (6) | −0.0018 (5) | −0.0009 (5) | −0.0149 (5) |
O4 | 0.0221 (6) | 0.0211 (6) | 0.0260 (6) | −0.0057 (5) | −0.0059 (5) | −0.0101 (5) |
C1 | 0.0171 (8) | 0.0130 (7) | 0.0174 (8) | −0.0050 (6) | 0.0013 (6) | −0.0044 (6) |
C2 | 0.0148 (8) | 0.0156 (8) | 0.0203 (8) | −0.0042 (6) | 0.0006 (6) | −0.0050 (6) |
C3 | 0.0183 (8) | 0.0150 (8) | 0.0187 (8) | −0.0058 (6) | −0.0024 (6) | −0.0039 (6) |
C4 | 0.0212 (8) | 0.0149 (8) | 0.0166 (8) | −0.0048 (6) | 0.0018 (6) | −0.0063 (6) |
C5 | 0.0152 (8) | 0.0154 (8) | 0.0210 (8) | −0.0037 (6) | 0.0022 (6) | −0.0054 (6) |
C6 | 0.0168 (8) | 0.0149 (8) | 0.0171 (8) | −0.0070 (6) | 0.0002 (6) | −0.0038 (6) |
C7 | 0.0160 (8) | 0.0233 (9) | 0.0282 (9) | −0.0074 (7) | −0.0006 (6) | −0.0091 (7) |
C8 | 0.0212 (9) | 0.0236 (9) | 0.0293 (9) | −0.0026 (7) | 0.0020 (7) | −0.0148 (7) |
C9 | 0.0263 (9) | 0.0270 (10) | 0.0428 (11) | −0.0105 (8) | −0.0044 (8) | −0.0166 (8) |
C10 | 0.0147 (8) | 0.0157 (8) | 0.0186 (8) | −0.0041 (6) | −0.0002 (6) | −0.0065 (6) |
C11 | 0.0149 (8) | 0.0158 (8) | 0.0212 (8) | −0.0053 (6) | 0.0013 (6) | −0.0093 (6) |
C12 | 0.0202 (9) | 0.0132 (7) | 0.0223 (8) | −0.0048 (6) | −0.0008 (7) | −0.0070 (6) |
C13 | 0.0215 (9) | 0.0135 (8) | 0.0218 (8) | −0.0068 (6) | 0.0031 (7) | −0.0073 (6) |
C14 | 0.0239 (9) | 0.0175 (8) | 0.0175 (8) | −0.0079 (7) | 0.0015 (6) | −0.0045 (6) |
C15 | 0.0208 (8) | 0.0194 (8) | 0.0259 (9) | −0.0071 (7) | −0.0014 (7) | −0.0061 (7) |
C16 | 0.0240 (9) | 0.0145 (8) | 0.0264 (9) | −0.0081 (6) | 0.0039 (7) | −0.0072 (6) |
C17 | 0.0289 (9) | 0.0204 (8) | 0.0180 (8) | −0.0096 (7) | 0.0039 (7) | −0.0051 (6) |
C18 | 0.0223 (9) | 0.0183 (8) | 0.0212 (8) | −0.0062 (7) | −0.0014 (6) | −0.0060 (6) |
C19 | 0.0269 (9) | 0.0259 (9) | 0.0271 (9) | −0.0110 (7) | 0.0058 (7) | −0.0076 (7) |
O1—C12 | 1.216 (2) | C16—C19 | 1.502 (3) |
O2—C6 | 1.373 (2) | C17—C18 | 1.384 (2) |
O2—C7 | 1.422 (2) | C2—H2 | 0.9300 |
O3—C4 | 1.363 (2) | C5—H5 | 0.9300 |
O3—C8 | 1.427 (2) | C7—H7A | 0.9600 |
O4—C3 | 1.384 (2) | C7—H7B | 0.9600 |
O4—C9 | 1.434 (2) | C7—H7C | 0.9600 |
C1—C2 | 1.399 (2) | C8—H8A | 0.9600 |
C1—C6 | 1.397 (2) | C8—H8B | 0.9600 |
C1—C10 | 1.511 (2) | C8—H8C | 0.9600 |
C2—C3 | 1.385 (2) | C9—H9A | 0.9600 |
C3—C4 | 1.397 (2) | C9—H9B | 0.9600 |
C4—C5 | 1.392 (2) | C9—H9C | 0.9600 |
C5—C6 | 1.398 (2) | C10—H10 | 0.9800 |
C10—C11 | 1.543 (2) | C11—H11 | 0.9800 |
C10—C11i | 1.588 (2) | C14—H14 | 0.9300 |
C11—C12 | 1.517 (2) | C15—H15 | 0.9300 |
C12—C13 | 1.487 (2) | C17—H17 | 0.9300 |
C13—C14 | 1.396 (2) | C18—H18 | 0.9300 |
C13—C18 | 1.399 (2) | C19—H19A | 0.9600 |
C14—C15 | 1.383 (2) | C19—H19B | 0.9600 |
C15—C16 | 1.394 (2) | C19—H19C | 0.9600 |
C16—C17 | 1.395 (2) | ||
C6—O2—C7 | 117.55 (13) | C6—C5—H5 | 120.00 |
C4—O3—C8 | 117.44 (14) | O2—C7—H7A | 109.00 |
C3—O4—C9 | 114.77 (13) | O2—C7—H7B | 109.00 |
C2—C1—C6 | 116.90 (14) | O2—C7—H7C | 109.00 |
C2—C1—C10 | 122.54 (15) | H7A—C7—H7B | 109.00 |
C6—C1—C10 | 120.56 (15) | H7A—C7—H7C | 109.00 |
C1—C2—C3 | 122.91 (16) | H7B—C7—H7C | 109.00 |
O4—C3—C2 | 118.38 (15) | O3—C8—H8A | 109.00 |
O4—C3—C4 | 122.34 (14) | O3—C8—H8B | 109.00 |
C2—C3—C4 | 119.12 (16) | O3—C8—H8C | 109.00 |
O3—C4—C3 | 116.61 (15) | H8A—C8—H8B | 109.00 |
O3—C4—C5 | 123.95 (15) | H8A—C8—H8C | 109.00 |
C3—C4—C5 | 119.45 (15) | H8B—C8—H8C | 110.00 |
C4—C5—C6 | 120.32 (16) | O4—C9—H9A | 109.00 |
O2—C6—C1 | 116.25 (14) | O4—C9—H9B | 109.00 |
O2—C6—C5 | 122.50 (15) | O4—C9—H9C | 109.00 |
C1—C6—C5 | 121.26 (15) | H9A—C9—H9B | 109.00 |
C1—C10—C11 | 118.41 (14) | H9A—C9—H9C | 110.00 |
C1—C10—C11i | 119.20 (13) | H9B—C9—H9C | 109.00 |
C11—C10—C11i | 89.08 (12) | C1—C10—H10 | 110.00 |
C10—C11—C12 | 115.28 (14) | C11—C10—H10 | 110.00 |
C10—C11—C10i | 90.92 (12) | C11i—C10—H10 | 110.00 |
C10i—C11—C12 | 116.86 (13) | C10—C11—H11 | 111.00 |
O1—C12—C11 | 120.71 (15) | C12—C11—H11 | 111.00 |
O1—C12—C13 | 120.96 (14) | C10i—C11—H11 | 111.00 |
C11—C12—C13 | 118.33 (14) | C13—C14—H14 | 120.00 |
C12—C13—C14 | 122.74 (14) | C15—C14—H14 | 120.00 |
C12—C13—C18 | 118.87 (15) | C14—C15—H15 | 119.00 |
C14—C13—C18 | 118.39 (16) | C16—C15—H15 | 119.00 |
C13—C14—C15 | 120.54 (15) | C16—C17—H17 | 119.00 |
C14—C15—C16 | 121.40 (16) | C18—C17—H17 | 119.00 |
C15—C16—C17 | 117.85 (16) | C13—C18—H18 | 120.00 |
C15—C16—C19 | 120.54 (16) | C17—C18—H18 | 120.00 |
C17—C16—C19 | 121.61 (15) | C16—C19—H19A | 110.00 |
C16—C17—C18 | 121.23 (16) | C16—C19—H19B | 109.00 |
C13—C18—C17 | 120.54 (16) | C16—C19—H19C | 109.00 |
C1—C2—H2 | 119.00 | H19A—C19—H19B | 109.00 |
C3—C2—H2 | 119.00 | H19A—C19—H19C | 109.00 |
C4—C5—H5 | 120.00 | H19B—C19—H19C | 109.00 |
C7—O2—C6—C1 | 174.05 (14) | C1—C10—C11—C12 | −116.41 (16) |
C7—O2—C6—C5 | −6.3 (2) | C1—C10—C11—C10i | 123.10 (14) |
C8—O3—C4—C3 | 173.45 (14) | C11i—C10—C11—C12 | 120.49 (14) |
C8—O3—C4—C5 | −7.2 (2) | C11i—C10—C11—C10i | 0.00 (11) |
C9—O4—C3—C2 | 119.22 (17) | C1—C10—C11i—C10i | −122.43 (16) |
C9—O4—C3—C4 | −65.4 (2) | C1—C10—C11i—C12i | −3.3 (2) |
C6—C1—C2—C3 | 0.2 (2) | C11—C10—C11i—C10i | 0.00 (10) |
C10—C1—C2—C3 | −179.61 (15) | C11—C10—C11i—C12i | 119.13 (15) |
C2—C1—C6—O2 | 178.24 (14) | C10—C11—C12—O1 | −2.6 (2) |
C2—C1—C6—C5 | −1.4 (2) | C10—C11—C12—C13 | 177.95 (14) |
C10—C1—C6—O2 | −2.0 (2) | C10i—C11—C12—O1 | 102.45 (19) |
C10—C1—C6—C5 | 178.38 (15) | C10i—C11—C12—C13 | −77.0 (2) |
C2—C1—C10—C11 | −28.5 (2) | O1—C12—C13—C14 | 173.58 (17) |
C2—C1—C10—C11i | 77.8 (2) | O1—C12—C13—C18 | −6.6 (2) |
C6—C1—C10—C11 | 151.72 (15) | C11—C12—C13—C14 | −6.9 (2) |
C6—C1—C10—C11i | −101.93 (18) | C11—C12—C13—C18 | 172.89 (15) |
C1—C2—C3—O4 | 177.31 (15) | C12—C13—C14—C15 | 178.84 (16) |
C1—C2—C3—C4 | 1.8 (2) | C18—C13—C14—C15 | −1.0 (3) |
O4—C3—C4—O3 | 1.6 (2) | C12—C13—C18—C17 | −178.03 (16) |
O4—C3—C4—C5 | −177.83 (15) | C14—C13—C18—C17 | 1.8 (3) |
C2—C3—C4—O3 | 176.91 (14) | C13—C14—C15—C16 | −1.0 (3) |
C2—C3—C4—C5 | −2.5 (2) | C14—C15—C16—C17 | 2.1 (3) |
O3—C4—C5—C6 | −178.04 (15) | C14—C15—C16—C19 | −177.55 (17) |
C3—C4—C5—C6 | 1.3 (2) | C15—C16—C17—C18 | −1.3 (3) |
C4—C5—C6—O2 | −178.93 (14) | C19—C16—C17—C18 | 178.38 (17) |
C4—C5—C6—C1 | 0.7 (2) | C16—C17—C18—C13 | −0.7 (3) |
Symmetry code: (i) −x+1, −y, −z+1. |
Cg2 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7C···Cg2ii | 0.96 | 2.75 | 3.5764 (19) | 145 |
Symmetry code: (ii) −x, −y+1, −z+1. |
Acknowledgements
The authors are grateful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, India, for providing the single-crystal X-ray diffractometer facility.
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