organic compounds
Dimethyl 1-(4-methylphenyl)-8-(thiophen-2-yl)-11-oxatricyclo[6.2.1.02,7]undeca-2,4,6,9-tetraene-9,10-dicarboxylate
aDepartment of Physics, P.T. Lee Chengalvaraya Naicker College of Engineering & Technology, Kancheepuram 631 502, India, bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India, and cPostGraduate & Research Department of Physics, Agurchand Manmull Jain College, Chennai 600 114, India
*Correspondence e-mail: seshadri_pr@yahoo.com
The title compound, C25H20O5S, is the product of a Diels–Alder reaction. The molecule consists of a fused tricyclic system containing two five-membered rings and one six-membered ring. The five-membered rings both show an with the O atom at the flap, whereas the six-membered ring adopts a boat conformation. The thiophene ring is disordered over two sets of sites with an occupancy ratio of 0.53 (1):0.47 (1). The dihedral angles between the 4-methylphenyl ring and the major and minor components of the thiophene ring are 66.3 (1) and 67.9 (1)°, respectively, while the dihedral angle between the disordered thiophenyl components is 3.1 (1)°. The mean plane of the tricyclic ring system makes dihedral angles of 35.8 (1), 30.8 (1) and 32.8 (1)°, respectively, with the 4-methylphenyl ring and the major and minor components of the thiophenyl ring. In the crystal, inversion dimers are formed through pairs of C—H⋯π interactions. In addition, C—H⋯O interactions are observed.
Related literature
For background to Diels–Alder reactions, see: Denmark & Thorarensen (1996). For related structures, see: Ohwada et al. (2001); Takahashi et al. (2003); Fun et al. (2011); Gurbanov et al. (2009); Balakrishnan et al. (2013). For puckering and asymmetry parameters, see: Cremer & Pople (1975); Nardelli (1983).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536813005308/im2420sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813005308/im2420Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813005308/im2420Isup3.cml
To a stirred solution of 1-(thiophen-2-yl)-3-p-tolylisobenzofuran (2 g, 6.897 mmol) in dry DCM was added DMAD (1.08 g, 7.59 mmol) and the reaction mixture was stirred for 0.5 h at room temperature under nitrogen atmosphere. The solvent was removed and the resulting solid was washed with methanol to give the title compound as a colourless solid. This adduct was crystallized from CHCl3/CH3OH (3:1) by slow evaporation method.
All H atoms were positioned geometrically and allowed to ride on their parent atoms, with (C—H= 0.93–0.96 Å), and Uiso(H) = 1.5 Ueq(C) for methyl H atoms and 1.2 Ueq(C) for other H atoms.The thiophene ring is disordered over two sites with occupancy ratio of 0.53 (3): 0.47 (3).
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).Fig. 1. Molecular structure of the title compound, showing 30% probability displacement ellipsoids. | |
Fig. 2. A view of the C—H···π interactions in the crystal structure of the title compound. |
C25H20O5S | V = 1096.6 (4) Å3 |
Mr = 432.47 | Z = 2 |
Triclinic, P1 | F(000) = 452 |
Hall symbol: -P 1 | Dx = 1.310 Mg m−3 |
a = 7.5966 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.877 (2) Å | θ = 1.5–28.5° |
c = 13.515 (3) Å | µ = 0.18 mm−1 |
α = 91.339 (5)° | T = 293 K |
β = 93.456 (4)° | Block, colourless |
γ = 100.129 (5)° | 0.35 × 0.30 × 0.25 mm |
Bruker Kappa APEXII CCD diffractometer | 4142 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 28.5°, θmin = 1.5° |
ω and ϕ scans | h = −10→10 |
19981 measured reflections | k = −14→14 |
5464 independent reflections | l = −18→18 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0648P)2 + 0.1968P] where P = (Fo2 + 2Fc2)/3 |
5464 reflections | (Δ/σ)max < 0.001 |
321 parameters | Δρmax = 0.25 e Å−3 |
52 restraints | Δρmin = −0.16 e Å−3 |
C25H20O5S | γ = 100.129 (5)° |
Mr = 432.47 | V = 1096.6 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5966 (15) Å | Mo Kα radiation |
b = 10.877 (2) Å | µ = 0.18 mm−1 |
c = 13.515 (3) Å | T = 293 K |
α = 91.339 (5)° | 0.35 × 0.30 × 0.25 mm |
β = 93.456 (4)° |
Bruker Kappa APEXII CCD diffractometer | 4142 reflections with I > 2σ(I) |
19981 measured reflections | Rint = 0.024 |
5464 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 52 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.25 e Å−3 |
5464 reflections | Δρmin = −0.16 e Å−3 |
321 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) | |
C17 | −0.3508 (4) | −0.3528 (2) | 0.05041 (17) | 0.1061 (10) | |
H17A | −0.2958 | −0.4245 | 0.0396 | 0.159* | |
H17B | −0.3950 | −0.3260 | −0.0121 | 0.159* | |
H17C | −0.4485 | −0.3742 | 0.0923 | 0.159* | |
C16 | −0.2140 (3) | −0.24828 (15) | 0.09987 (12) | 0.0618 (5) | |
C18 | −0.2271 (2) | −0.21039 (15) | 0.19687 (12) | 0.0577 (4) | |
H18 | −0.3214 | −0.2500 | 0.2319 | 0.069* | |
C19 | −0.1036 (2) | −0.11537 (14) | 0.24304 (11) | 0.0484 (3) | |
H19 | −0.1157 | −0.0918 | 0.3085 | 0.058* | |
C13 | 0.03822 (19) | −0.05453 (11) | 0.19297 (9) | 0.0391 (3) | |
C14 | 0.0529 (2) | −0.09272 (14) | 0.09555 (10) | 0.0520 (4) | |
H14 | 0.1476 | −0.0537 | 0.0605 | 0.062* | |
C15 | −0.0721 (3) | −0.18817 (16) | 0.05039 (11) | 0.0647 (5) | |
H15 | −0.0601 | −0.2125 | −0.0149 | 0.078* | |
C1 | 0.15925 (18) | 0.05759 (11) | 0.24036 (9) | 0.0365 (3) | |
C2 | 0.34514 (18) | 0.10769 (12) | 0.20407 (9) | 0.0394 (3) | |
C3 | 0.4745 (2) | 0.05272 (16) | 0.16187 (11) | 0.0510 (4) | |
H3 | 0.4534 | −0.0321 | 0.1446 | 0.061* | |
C4 | 0.6378 (2) | 0.12840 (19) | 0.14586 (12) | 0.0622 (5) | |
H4 | 0.7257 | 0.0938 | 0.1160 | 0.075* | |
C5 | 0.6713 (2) | 0.25310 (19) | 0.17340 (13) | 0.0608 (4) | |
H5 | 0.7816 | 0.3014 | 0.1622 | 0.073* | |
C6 | 0.5419 (2) | 0.30857 (15) | 0.21812 (11) | 0.0494 (3) | |
H6 | 0.5653 | 0.3926 | 0.2381 | 0.059* | |
C7 | 0.37929 (18) | 0.23483 (12) | 0.23151 (9) | 0.0391 (3) | |
C8 | 0.21057 (17) | 0.25712 (11) | 0.28215 (9) | 0.0359 (3) | |
C23 | 0.21701 (17) | 0.18743 (11) | 0.38086 (9) | 0.0358 (3) | |
C20 | 0.18841 (18) | 0.06611 (12) | 0.35510 (9) | 0.0364 (3) | |
C21 | 0.23243 (19) | −0.03877 (12) | 0.41371 (10) | 0.0409 (3) | |
C22 | 0.2710 (3) | −0.11567 (19) | 0.57314 (13) | 0.0660 (5) | |
H22A | 0.2071 | −0.1960 | 0.5492 | 0.099* | |
H22B | 0.2407 | −0.1000 | 0.6397 | 0.099* | |
H22C | 0.3975 | −0.1145 | 0.5725 | 0.099* | |
C24 | 0.2738 (2) | 0.25025 (12) | 0.47907 (10) | 0.0413 (3) | |
C25 | 0.5151 (3) | 0.3704 (2) | 0.57359 (15) | 0.0837 (7) | |
H25A | 0.4399 | 0.4267 | 0.5952 | 0.126* | |
H25B | 0.6332 | 0.4162 | 0.5656 | 0.126* | |
H21C | 0.5214 | 0.3081 | 0.6222 | 0.126* | |
C9 | 0.16129 (19) | 0.38335 (12) | 0.28373 (10) | 0.0409 (3) | |
O2 | 0.2780 (2) | −0.12775 (11) | 0.37594 (9) | 0.0698 (4) | |
O3 | 0.22201 (16) | −0.01996 (10) | 0.50989 (7) | 0.0536 (3) | |
O4 | 0.17981 (19) | 0.24950 (13) | 0.54677 (9) | 0.0712 (4) | |
O5 | 0.44061 (16) | 0.31032 (11) | 0.47947 (8) | 0.0606 (3) | |
O1 | 0.07523 (12) | 0.16735 (8) | 0.22614 (6) | 0.0360 (2) | |
S1 | 0.2161 (5) | 0.4865 (3) | 0.1956 (3) | 0.0697 (7) | 0.531 (3) |
C12 | 0.0495 (16) | 0.4293 (11) | 0.3505 (9) | 0.093 (5) | 0.531 (3) |
H12 | 0.0023 | 0.3858 | 0.4041 | 0.112* | 0.531 (3) |
C11 | 0.019 (3) | 0.5478 (14) | 0.3260 (14) | 0.066 (2) | 0.531 (3) |
H11 | −0.0536 | 0.5916 | 0.3607 | 0.079* | 0.531 (3) |
C10 | 0.1054 (17) | 0.5919 (11) | 0.2473 (9) | 0.063 (2) | 0.531 (3) |
H10 | 0.1048 | 0.6714 | 0.2235 | 0.076* | 0.531 (3) |
S1' | 0.0250 (4) | 0.4286 (3) | 0.3645 (2) | 0.0532 (4) | 0.466 (3) |
C12' | 0.214 (2) | 0.4812 (10) | 0.2173 (8) | 0.071 (4) | 0.466 (3) |
H12' | 0.2990 | 0.4796 | 0.1708 | 0.085* | 0.466 (3) |
C11' | 0.122 (2) | 0.5793 (14) | 0.2312 (12) | 0.082 (3) | 0.466 (3) |
H11' | 0.1272 | 0.6462 | 0.1892 | 0.098* | 0.466 (3) |
C10' | 0.024 (4) | 0.5679 (16) | 0.3107 (17) | 0.063 (3) | 0.466 (3) |
H10' | −0.0362 | 0.6289 | 0.3338 | 0.076* | 0.466 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C17 | 0.132 (2) | 0.0921 (16) | 0.0677 (12) | −0.0455 (15) | −0.0117 (13) | −0.0130 (11) |
C16 | 0.0819 (12) | 0.0487 (8) | 0.0460 (8) | −0.0072 (8) | −0.0117 (8) | 0.0001 (6) |
C18 | 0.0628 (10) | 0.0538 (9) | 0.0509 (8) | −0.0046 (7) | 0.0019 (7) | 0.0017 (7) |
C19 | 0.0553 (9) | 0.0477 (8) | 0.0410 (7) | 0.0068 (6) | 0.0034 (6) | −0.0043 (6) |
C13 | 0.0477 (8) | 0.0339 (6) | 0.0363 (6) | 0.0110 (5) | −0.0027 (5) | −0.0017 (5) |
C14 | 0.0696 (10) | 0.0478 (8) | 0.0349 (7) | 0.0001 (7) | 0.0030 (6) | −0.0001 (6) |
C15 | 0.0943 (14) | 0.0575 (9) | 0.0345 (7) | −0.0049 (9) | −0.0011 (8) | −0.0058 (6) |
C1 | 0.0425 (7) | 0.0344 (6) | 0.0345 (6) | 0.0132 (5) | −0.0005 (5) | −0.0023 (5) |
C2 | 0.0411 (7) | 0.0453 (7) | 0.0339 (6) | 0.0142 (6) | 0.0007 (5) | −0.0009 (5) |
C3 | 0.0522 (9) | 0.0610 (9) | 0.0448 (7) | 0.0249 (7) | 0.0025 (6) | −0.0059 (6) |
C4 | 0.0465 (9) | 0.0950 (14) | 0.0521 (9) | 0.0301 (9) | 0.0098 (7) | 0.0011 (9) |
C5 | 0.0393 (8) | 0.0861 (12) | 0.0565 (9) | 0.0080 (8) | 0.0061 (7) | 0.0083 (8) |
C6 | 0.0434 (8) | 0.0558 (8) | 0.0473 (8) | 0.0050 (6) | −0.0004 (6) | 0.0041 (6) |
C7 | 0.0390 (7) | 0.0450 (7) | 0.0345 (6) | 0.0117 (5) | 0.0005 (5) | 0.0011 (5) |
C8 | 0.0375 (7) | 0.0338 (6) | 0.0368 (6) | 0.0085 (5) | 0.0003 (5) | −0.0019 (5) |
C23 | 0.0365 (6) | 0.0374 (6) | 0.0351 (6) | 0.0113 (5) | 0.0026 (5) | −0.0010 (5) |
C20 | 0.0383 (7) | 0.0374 (6) | 0.0344 (6) | 0.0100 (5) | 0.0016 (5) | −0.0015 (5) |
C21 | 0.0447 (7) | 0.0383 (6) | 0.0401 (7) | 0.0097 (6) | −0.0012 (5) | 0.0004 (5) |
C22 | 0.0725 (12) | 0.0807 (12) | 0.0532 (9) | 0.0335 (10) | 0.0043 (8) | 0.0249 (8) |
C24 | 0.0514 (8) | 0.0363 (6) | 0.0380 (7) | 0.0142 (6) | −0.0005 (6) | −0.0036 (5) |
C25 | 0.0901 (15) | 0.0779 (13) | 0.0740 (12) | 0.0069 (11) | −0.0338 (11) | −0.0254 (10) |
C9 | 0.0450 (8) | 0.0343 (6) | 0.0446 (7) | 0.0122 (6) | −0.0013 (6) | −0.0020 (5) |
O2 | 0.1124 (11) | 0.0517 (6) | 0.0545 (7) | 0.0423 (7) | −0.0019 (7) | −0.0020 (5) |
O3 | 0.0697 (7) | 0.0588 (6) | 0.0388 (5) | 0.0287 (5) | 0.0024 (5) | 0.0074 (4) |
O4 | 0.0834 (9) | 0.0810 (8) | 0.0479 (6) | 0.0093 (7) | 0.0176 (6) | −0.0169 (6) |
O5 | 0.0544 (7) | 0.0663 (7) | 0.0561 (6) | 0.0035 (5) | −0.0083 (5) | −0.0156 (5) |
O1 | 0.0372 (5) | 0.0334 (4) | 0.0382 (5) | 0.0104 (4) | −0.0025 (4) | −0.0017 (3) |
S1 | 0.0928 (13) | 0.0521 (9) | 0.0734 (13) | 0.0312 (9) | 0.0184 (10) | 0.0206 (9) |
C12 | 0.100 (8) | 0.061 (5) | 0.118 (8) | 0.014 (4) | −0.009 (5) | 0.016 (4) |
C11 | 0.068 (4) | 0.059 (6) | 0.076 (6) | 0.031 (5) | −0.001 (4) | −0.012 (4) |
C10 | 0.087 (4) | 0.035 (2) | 0.072 (5) | 0.027 (2) | −0.012 (4) | −0.001 (3) |
S1' | 0.0557 (7) | 0.0439 (8) | 0.0641 (7) | 0.0204 (6) | 0.0050 (6) | −0.0040 (6) |
C12' | 0.088 (6) | 0.059 (6) | 0.064 (6) | 0.019 (4) | −0.011 (4) | −0.027 (4) |
C11' | 0.129 (7) | 0.050 (5) | 0.071 (5) | 0.025 (4) | 0.018 (4) | 0.013 (4) |
C10' | 0.078 (5) | 0.044 (4) | 0.075 (6) | 0.035 (4) | −0.005 (4) | −0.002 (3) |
C17—C16 | 1.511 (2) | C23—C20 | 1.3335 (17) |
C17—H17A | 0.9600 | C23—C24 | 1.4831 (17) |
C17—H17B | 0.9600 | C20—C21 | 1.4782 (18) |
C17—H17C | 0.9600 | C21—O2 | 1.1969 (17) |
C16—C15 | 1.377 (3) | C21—O3 | 1.3204 (17) |
C16—C18 | 1.379 (2) | C22—O3 | 1.4465 (18) |
C18—C19 | 1.377 (2) | C22—H22A | 0.9600 |
C18—H18 | 0.9300 | C22—H22B | 0.9600 |
C19—C13 | 1.384 (2) | C22—H22C | 0.9600 |
C19—H19 | 0.9300 | C24—O4 | 1.1932 (18) |
C13—C14 | 1.3881 (19) | C24—O5 | 1.3195 (19) |
C13—C1 | 1.4970 (17) | C25—O5 | 1.453 (2) |
C14—C15 | 1.380 (2) | C25—H25A | 0.9600 |
C14—H14 | 0.9300 | C25—H25B | 0.9600 |
C15—H15 | 0.9300 | C25—H21C | 0.9600 |
C1—O1 | 1.4606 (14) | C9—C12 | 1.417 (9) |
C1—C2 | 1.5353 (19) | C9—C12' | 1.428 (10) |
C1—C20 | 1.5515 (17) | C9—S1' | 1.673 (3) |
C2—C3 | 1.381 (2) | C9—S1 | 1.676 (3) |
C2—C7 | 1.3984 (19) | S1—C10 | 1.697 (11) |
C3—C4 | 1.395 (3) | C12—C11 | 1.392 (14) |
C3—H3 | 0.9300 | C12—H12 | 0.9300 |
C4—C5 | 1.374 (3) | C11—C10 | 1.338 (7) |
C4—H4 | 0.9300 | C11—H11 | 0.9300 |
C5—C6 | 1.399 (2) | C10—H10 | 0.9300 |
C5—H5 | 0.9300 | S1'—C10' | 1.696 (12) |
C6—C7 | 1.374 (2) | C12'—C11' | 1.390 (14) |
C6—H6 | 0.9300 | C12'—H12' | 0.9300 |
C7—C8 | 1.5419 (19) | C11'—C10' | 1.337 (7) |
C8—O1 | 1.4498 (15) | C11'—H11' | 0.9300 |
C8—C9 | 1.4853 (18) | C10'—H10' | 0.9300 |
C8—C23 | 1.5521 (17) | ||
C16—C17—H17A | 109.5 | C24—C23—C8 | 124.05 (11) |
C16—C17—H17B | 109.5 | C23—C20—C21 | 128.37 (11) |
H17A—C17—H17B | 109.5 | C23—C20—C1 | 106.33 (11) |
C16—C17—H17C | 109.5 | C21—C20—C1 | 122.53 (10) |
H17A—C17—H17C | 109.5 | O2—C21—O3 | 125.26 (13) |
H17B—C17—H17C | 109.5 | O2—C21—C20 | 122.09 (13) |
C15—C16—C18 | 117.71 (14) | O3—C21—C20 | 112.60 (11) |
C15—C16—C17 | 121.50 (17) | O3—C22—H22A | 109.5 |
C18—C16—C17 | 120.79 (18) | O3—C22—H22B | 109.5 |
C19—C18—C16 | 121.53 (16) | H22A—C22—H22B | 109.5 |
C19—C18—H18 | 119.2 | O3—C22—H22C | 109.5 |
C16—C18—H18 | 119.2 | H22A—C22—H22C | 109.5 |
C18—C19—C13 | 120.66 (14) | H22B—C22—H22C | 109.5 |
C18—C19—H19 | 119.7 | O4—C24—O5 | 125.08 (13) |
C13—C19—H19 | 119.7 | O4—C24—C23 | 124.66 (14) |
C19—C13—C14 | 118.14 (13) | O5—C24—C23 | 110.22 (12) |
C19—C13—C1 | 119.86 (12) | O5—C25—H25A | 109.5 |
C14—C13—C1 | 121.69 (13) | O5—C25—H25B | 109.5 |
C15—C14—C13 | 120.44 (15) | H25A—C25—H25B | 109.5 |
C15—C14—H14 | 119.8 | O5—C25—H21C | 109.5 |
C13—C14—H14 | 119.8 | H25A—C25—H21C | 109.5 |
C16—C15—C14 | 121.52 (15) | H25B—C25—H21C | 109.5 |
C16—C15—H15 | 119.2 | C12—C9—C12' | 106.5 (9) |
C14—C15—H15 | 119.2 | C12—C9—C8 | 126.6 (5) |
O1—C1—C13 | 109.03 (10) | C12'—C9—C8 | 126.9 (6) |
O1—C1—C2 | 99.71 (10) | C12—C9—S1' | 3.5 (6) |
C13—C1—C2 | 122.54 (11) | C12'—C9—S1' | 109.8 (6) |
O1—C1—C20 | 98.77 (9) | C8—C9—S1' | 123.20 (15) |
C13—C1—C20 | 118.47 (11) | C12—C9—S1 | 110.4 (5) |
C2—C1—C20 | 104.23 (10) | C12'—C9—S1 | 6.3 (6) |
C3—C2—C7 | 120.66 (14) | C8—C9—S1 | 122.68 (15) |
C3—C2—C1 | 134.05 (13) | S1'—C9—S1 | 113.69 (18) |
C7—C2—C1 | 105.03 (11) | C21—O3—C22 | 116.20 (12) |
C2—C3—C4 | 117.93 (15) | C24—O5—C25 | 115.45 (14) |
C2—C3—H3 | 121.0 | C8—O1—C1 | 97.66 (9) |
C4—C3—H3 | 121.0 | C9—S1—C10 | 92.5 (5) |
C5—C4—C3 | 121.26 (15) | C11—C12—C9 | 111.6 (11) |
C5—C4—H4 | 119.4 | C11—C12—H12 | 124.2 |
C3—C4—H4 | 119.4 | C9—C12—H12 | 124.2 |
C4—C5—C6 | 120.97 (16) | C10—C11—C12 | 112.9 (12) |
C4—C5—H5 | 119.5 | C10—C11—H11 | 123.6 |
C6—C5—H5 | 119.5 | C12—C11—H11 | 123.6 |
C7—C6—C5 | 117.80 (15) | C11—C10—S1 | 112.4 (11) |
C7—C6—H6 | 121.1 | C11—C10—H10 | 123.8 |
C5—C6—H6 | 121.1 | S1—C10—H10 | 123.8 |
C6—C7—C2 | 121.35 (13) | C9—S1'—C10' | 93.2 (6) |
C6—C7—C8 | 133.63 (13) | C11'—C12'—C9 | 111.2 (12) |
C2—C7—C8 | 104.81 (11) | C11'—C12'—H12' | 124.4 |
O1—C8—C9 | 111.21 (10) | C9—C12'—H12' | 124.4 |
O1—C8—C7 | 100.06 (9) | C10'—C11'—C12' | 113.4 (14) |
C9—C8—C7 | 120.07 (11) | C10'—C11'—H11' | 123.3 |
O1—C8—C23 | 98.86 (9) | C12'—C11'—H11' | 123.3 |
C9—C8—C23 | 118.64 (11) | C11'—C10'—S1' | 111.8 (13) |
C7—C8—C23 | 104.50 (10) | C11'—C10'—H10' | 124.1 |
C20—C23—C24 | 129.51 (12) | S1'—C10'—H10' | 124.1 |
C20—C23—C8 | 105.73 (10) | ||
C15—C16—C18—C19 | 0.4 (3) | C2—C1—C20—C21 | −92.07 (14) |
C17—C16—C18—C19 | 180.0 (2) | C23—C20—C21—O2 | −145.48 (17) |
C16—C18—C19—C13 | 0.1 (3) | C1—C20—C21—O2 | 13.0 (2) |
C18—C19—C13—C14 | −0.5 (2) | C23—C20—C21—O3 | 32.2 (2) |
C18—C19—C13—C1 | 173.23 (14) | C1—C20—C21—O3 | −169.33 (12) |
C19—C13—C14—C15 | 0.5 (2) | C20—C23—C24—O4 | −73.8 (2) |
C1—C13—C14—C15 | −173.11 (15) | C8—C23—C24—O4 | 117.26 (17) |
C18—C16—C15—C14 | −0.4 (3) | C20—C23—C24—O5 | 108.36 (17) |
C17—C16—C15—C14 | −180.0 (2) | C8—C23—C24—O5 | −60.61 (16) |
C13—C14—C15—C16 | −0.1 (3) | O1—C8—C9—C12 | 84.9 (7) |
C19—C13—C1—O1 | −81.69 (15) | C7—C8—C9—C12 | −158.9 (7) |
C14—C13—C1—O1 | 91.80 (15) | C23—C8—C9—C12 | −28.6 (7) |
C19—C13—C1—C2 | 162.74 (13) | O1—C8—C9—C12' | −93.7 (7) |
C14—C13—C1—C2 | −23.77 (19) | C7—C8—C9—C12' | 22.5 (7) |
C19—C13—C1—C20 | 30.06 (18) | C23—C8—C9—C12' | 152.7 (7) |
C14—C13—C1—C20 | −156.45 (13) | O1—C8—C9—S1' | 83.85 (18) |
O1—C1—C2—C3 | −152.34 (15) | C7—C8—C9—S1' | −159.97 (15) |
C13—C1—C2—C3 | −32.2 (2) | C23—C8—C9—S1' | −29.7 (2) |
C20—C1—C2—C3 | 105.94 (16) | O1—C8—C9—S1 | −88.1 (2) |
O1—C1—C2—C7 | 33.71 (12) | C7—C8—C9—S1 | 28.1 (2) |
C13—C1—C2—C7 | 153.82 (11) | C23—C8—C9—S1 | 158.34 (19) |
C20—C1—C2—C7 | −68.00 (12) | O2—C21—O3—C22 | 0.3 (2) |
C7—C2—C3—C4 | −1.3 (2) | C20—C21—O3—C22 | −177.29 (13) |
C1—C2—C3—C4 | −174.46 (14) | O4—C24—O5—C25 | 5.3 (2) |
C2—C3—C4—C5 | 1.6 (2) | C23—C24—O5—C25 | −176.88 (14) |
C3—C4—C5—C6 | −0.3 (3) | C9—C8—O1—C1 | −178.92 (11) |
C4—C5—C6—C7 | −1.4 (2) | C7—C8—O1—C1 | 53.14 (10) |
C5—C6—C7—C2 | 1.8 (2) | C23—C8—O1—C1 | −53.42 (10) |
C5—C6—C7—C8 | 175.54 (14) | C13—C1—O1—C8 | 176.84 (10) |
C3—C2—C7—C6 | −0.4 (2) | C2—C1—O1—C8 | −53.64 (10) |
C1—C2—C7—C6 | 174.50 (12) | C20—C1—O1—C8 | 52.55 (11) |
C3—C2—C7—C8 | −175.79 (12) | C12—C9—S1—C10 | 2.8 (7) |
C1—C2—C7—C8 | −0.84 (13) | C12'—C9—S1—C10 | −49 (7) |
C6—C7—C8—O1 | 152.90 (14) | C8—C9—S1—C10 | 176.8 (4) |
C2—C7—C8—O1 | −32.60 (12) | S1'—C9—S1—C10 | 4.2 (5) |
C6—C7—C8—C9 | 31.1 (2) | C12'—C9—C12—C11 | 3.9 (16) |
C2—C7—C8—C9 | −154.42 (11) | C8—C9—C12—C11 | −174.9 (13) |
C6—C7—C8—C23 | −105.12 (16) | S1'—C9—C12—C11 | −160 (11) |
C2—C7—C8—C23 | 69.38 (12) | S1—C9—C12—C11 | −1.2 (16) |
O1—C8—C23—C20 | 34.38 (12) | C9—C12—C11—C10 | −2 (2) |
C9—C8—C23—C20 | 154.53 (12) | C12—C11—C10—S1 | 4 (2) |
C7—C8—C23—C20 | −68.50 (13) | C9—S1—C10—C11 | −3.8 (15) |
O1—C8—C23—C24 | −154.44 (12) | C12—C9—S1'—C10' | 20 (10) |
C9—C8—C23—C24 | −34.28 (18) | C12'—C9—S1'—C10' | 3.0 (13) |
C7—C8—C23—C24 | 102.68 (14) | C8—C9—S1'—C10' | −174.9 (11) |
C24—C23—C20—C21 | −10.6 (2) | S1—C9—S1'—C10' | −2.3 (12) |
C8—C23—C20—C21 | 159.93 (13) | C12—C9—C12'—C11' | −7.9 (14) |
C24—C23—C20—C1 | −171.81 (13) | C8—C9—C12'—C11' | 170.9 (9) |
C8—C23—C20—C1 | −1.28 (13) | S1'—C9—C12'—C11' | −6.9 (13) |
O1—C1—C20—C23 | −31.92 (13) | S1—C9—C12'—C11' | 122 (7) |
C13—C1—C20—C23 | −149.24 (12) | C9—C12'—C11'—C10' | 8 (2) |
C2—C1—C20—C23 | 70.50 (13) | C12'—C11'—C10'—S1' | −6 (3) |
O1—C1—C20—C21 | 165.50 (12) | C9—S1'—C10'—C11' | 2 (2) |
C13—C1—C20—C21 | 48.18 (18) |
Cg is the centroid of the C2–C7 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O4i | 0.93 | 2.47 | 3.378 (1) | 165 |
C17—H17B···Cgii | 0.96 | 3.26 | 3.99 (2) | 136 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C25H20O5S |
Mr | 432.47 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.5966 (15), 10.877 (2), 13.515 (3) |
α, β, γ (°) | 91.339 (5), 93.456 (4), 100.129 (5) |
V (Å3) | 1096.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19981, 5464, 4142 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.670 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.129, 1.03 |
No. of reflections | 5464 |
No. of parameters | 321 |
No. of restraints | 52 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.16 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Cg is the centroid of the C2–C7 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O4i | 0.93 | 2.47 | 3.378 (1) | 165 |
C17—H17B···Cgii | 0.96 | 3.26 | 3.99 (2) | 136 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1, y, z. |
Acknowledgements
The authors acknowledge the Technology Business Incubator (TBI), CAS in Crystallography, University of Madras, Chennai 600 025, India, for the data collection.
References
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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.
The Diels-Alder reaction involves [4 + 2] cycloaddition of a conjucated diene and a dienophile (an alkene or alkyne). The Diels-Alder reaction is among the most powerful C—C bond forming process and one of most widely used and studied transformation in organic chemistry (Denmark & Thorarensen, 1996). The title compound, C25H20O5S, comprises a fused tricyclic system with one 4-methylphenyl and one thiophenyl group attached to it. The tricyclic system consists of two 5-membered rings and one aromatic ring. In addition, two carboxylate units are attached to the tricyclic system. Geometrical parameters agree well with reported structures (Fun et al., 2011; Gurbanov et al., 2009; Ohwada et al. 2001; Takahashi et al. 2003). The five membered ring C1\C2\C7\C8\O1 adopts an envelope conformation with atom O1 displaced by 0.787 Å from the mean plane of the other ring atoms C1\C2\C7\C8.The puckering parameters (Cremer & Pople, 1975) and asymmetry parameters (Nardelli, 1983) are q2 = 0.539 (1) Å, ϕ = 144.8 (1)°, ΔS(O1) = 0.006 (1)° and Δ2(O1) = 0.325 (1)°.The second five membered ring C1\ C20\C23\C8\O1 also adopts an envelope conformation with O1 displaced by -0.787 Å from the mean plane of the other ring atoms C1\ C20\C23\C8.The puckering parameters (Cremer & Pople, 1975) and asymmetry parameters (Nardelli, 1983) are q2 = 0.542 (1) Å, ϕ = -37.3 (1)°, ΔS(O1) = 0.011 (1)° and Δ2(O1) = 0.327 (1)°.The six membered ring C1/C2/C7/C8/C23/C20 adopts boat conformation with puckering parameter q2 = 0.9849 (1) Å, θ= 89.9 (8)° and ϕ = 359.2 (8)°.
The thiophene ring is disordered over two sites with occupancy ratio of 0.53 (3): 0.47 (3).The dihedral angle between the rings C1/C2/C7/C8/O1 and C1/C20/C23/C8/O1 is 82.15 (1)°. The dihedral angle between the terminal 4-methylphenyl and major and minor components of the thiophene rings are 66.3 (1)° and 67.9 (1)° respectively. The mean plane of the tricyclic system makes dihedral angles of 35.8 (1)°, 30.8 (1)° and 32.8 (1)°, respectively, with the 4-methylphenyl ring and the major and minor components of the thiophenyl group. The carboxylate ligand at the C20 carbon atom is turned out the plane in the positive direction of the five membered ring C20/ C1/ O1/ C8/ C23 (the torsion angle C23—C20—C21—O3= 32.2 (2)°, while that at the C23 carbon atom is turned out of this plane in the negative direction (the torsion angle is C20—C23—C24=O4 = -73.8 (2)°). In the crystal structure centrosymmetric dimers are realised by C—H···π interactions. In addition, intermolecular C—H···O interactions are observed (Table 1).