Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013034/cv6050sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013034/cv6050Isup2.hkl |
CCDC reference: 157877
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.053
- wR factor = 0.150
- Data-to-parameter ratio = 18.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound, (I), was synthesized from commercially available diphenyl sulfide (Aldrich) by Friedel–Crafts acylation with excess of acetyl chloride and anhydrous aluminium chloride followed by the formation of bis-chloroaldehyde (phosphorustrichloride and dimethylformamide) and its condensation with two equivalents of methyl thioglycolate/triethylamine, and concomitant ring closure with 50% potasium hydroxide. Single crystals suitable for X-ray structure determination were obtained by slow evaporation from a benzene solution.
After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their attached atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids with the atom-numbering scheme. |
C24H18O4S3 | F(000) = 968 |
Mr = 466.56 | Dx = 1.459 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.8692 (3) Å | Cell parameters from 4461 reflections |
b = 6.0255 (2) Å | θ = 1.4–28.5° |
c = 29.7783 (6) Å | µ = 0.38 mm−1 |
β = 94.221 (1)° | T = 293 K |
V = 2123.9 (1) Å3 | Prism, yellow |
Z = 4 | 0.48 × 0.44 × 0.18 mm |
Siemens SMART CCD area-detector diffractometer | 2620 independent reflections |
Radiation source: fine-focus sealed tube | 1895 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.6°, θmin = 1.4° |
ω scans | h = −13→15 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −7→8 |
Tmin = 0.839, Tmax = 0.935 | l = −36→39 |
7327 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0803P)2] where P = (Fo2 + 2Fc2)/3 |
2620 reflections | (Δ/σ)max < 0.001 |
142 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C24H18O4S3 | V = 2123.9 (1) Å3 |
Mr = 466.56 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.8692 (3) Å | µ = 0.38 mm−1 |
b = 6.0255 (2) Å | T = 293 K |
c = 29.7783 (6) Å | 0.48 × 0.44 × 0.18 mm |
β = 94.221 (1)° |
Siemens SMART CCD area-detector diffractometer | 2620 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1895 reflections with I > 2σ(I) |
Tmin = 0.839, Tmax = 0.935 | Rint = 0.062 |
7327 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.27 e Å−3 |
2620 reflections | Δρmin = −0.32 e Å−3 |
142 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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 | ||
S1 | 0.0000 | −0.16957 (14) | 0.7500 | 0.0505 (3) | |
S2 | 0.40061 (5) | 0.32091 (10) | 0.61642 (2) | 0.0497 (2) | |
O1 | 0.52659 (15) | 0.7968 (3) | 0.54722 (6) | 0.0589 (5) | |
O2 | 0.58680 (18) | 0.4490 (4) | 0.55765 (8) | 0.0805 (7) | |
C1 | 0.08103 (18) | 0.0117 (4) | 0.71879 (7) | 0.0416 (5) | |
C2 | 0.0359 (2) | 0.2012 (4) | 0.69829 (10) | 0.0587 (7) | |
H2A | −0.0382 | 0.2417 | 0.7025 | 0.070* | |
C3 | 0.0995 (2) | 0.3296 (4) | 0.67184 (9) | 0.0569 (7) | |
H3A | 0.0683 | 0.4585 | 0.6590 | 0.068* | |
C4 | 0.20864 (18) | 0.2725 (3) | 0.66372 (7) | 0.0385 (5) | |
C5 | 0.25295 (19) | 0.0836 (4) | 0.68444 (8) | 0.0461 (5) | |
H5A | 0.3268 | 0.0425 | 0.6800 | 0.055* | |
C6 | 0.19001 (19) | −0.0460 (4) | 0.71161 (8) | 0.0458 (5) | |
H6A | 0.2217 | −0.1729 | 0.7251 | 0.055* | |
C7 | 0.27439 (18) | 0.4104 (4) | 0.63471 (7) | 0.0405 (5) | |
C8 | 0.2482 (2) | 0.6151 (4) | 0.61736 (8) | 0.0493 (6) | |
H8A | 0.1823 | 0.6903 | 0.6229 | 0.059* | |
C9 | 0.3288 (2) | 0.7012 (4) | 0.59064 (9) | 0.0497 (6) | |
H9A | 0.3227 | 0.8393 | 0.5767 | 0.060* | |
C10 | 0.4173 (2) | 0.5621 (4) | 0.58709 (7) | 0.0442 (5) | |
C11 | 0.51936 (19) | 0.5915 (4) | 0.56306 (8) | 0.0489 (6) | |
C12 | 0.6210 (2) | 0.8446 (5) | 0.52157 (10) | 0.0701 (8) | |
H12C | 0.6315 | 1.0023 | 0.5201 | 0.105* | |
H12A | 0.6070 | 0.7863 | 0.4917 | 0.105* | |
H12B | 0.6877 | 0.7772 | 0.5357 | 0.105* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0509 (5) | 0.0421 (5) | 0.0608 (5) | 0.000 | 0.0193 (4) | 0.000 |
S2 | 0.0499 (4) | 0.0426 (3) | 0.0583 (4) | 0.0110 (3) | 0.0151 (3) | 0.0122 (3) |
O1 | 0.0563 (10) | 0.0586 (11) | 0.0640 (11) | 0.0020 (8) | 0.0192 (8) | 0.0193 (9) |
O2 | 0.0664 (12) | 0.0698 (14) | 0.1097 (17) | 0.0223 (11) | 0.0358 (11) | 0.0218 (12) |
C1 | 0.0420 (11) | 0.0423 (12) | 0.0410 (11) | 0.0004 (9) | 0.0064 (8) | −0.0026 (9) |
C2 | 0.0395 (12) | 0.0599 (16) | 0.0779 (18) | 0.0120 (11) | 0.0118 (11) | 0.0180 (13) |
C3 | 0.0496 (14) | 0.0512 (14) | 0.0712 (17) | 0.0138 (11) | 0.0126 (12) | 0.0208 (12) |
C4 | 0.0438 (11) | 0.0354 (11) | 0.0367 (11) | 0.0024 (9) | 0.0052 (8) | −0.0023 (8) |
C5 | 0.0439 (12) | 0.0444 (13) | 0.0515 (13) | 0.0097 (10) | 0.0130 (9) | 0.0036 (10) |
C6 | 0.0492 (13) | 0.0390 (12) | 0.0504 (13) | 0.0085 (10) | 0.0114 (10) | 0.0058 (10) |
C7 | 0.0454 (11) | 0.0378 (11) | 0.0389 (11) | 0.0034 (9) | 0.0063 (8) | −0.0023 (9) |
C8 | 0.0509 (13) | 0.0409 (12) | 0.0570 (14) | 0.0106 (10) | 0.0111 (10) | 0.0042 (10) |
C9 | 0.0564 (14) | 0.0365 (12) | 0.0567 (14) | 0.0056 (10) | 0.0084 (11) | 0.0055 (10) |
C10 | 0.0514 (13) | 0.0377 (12) | 0.0441 (12) | 0.0022 (10) | 0.0074 (9) | 0.0035 (9) |
C11 | 0.0475 (13) | 0.0513 (14) | 0.0485 (13) | 0.0027 (11) | 0.0079 (10) | 0.0073 (11) |
C12 | 0.0578 (16) | 0.089 (2) | 0.0649 (18) | −0.0105 (15) | 0.0165 (13) | 0.0180 (15) |
S1—C1 | 1.765 (2) | C4—C7 | 1.464 (3) |
S1—C1i | 1.765 (2) | C5—C6 | 1.382 (3) |
S2—C10 | 1.715 (2) | C5—H5A | 0.9300 |
S2—C7 | 1.718 (2) | C6—H6A | 0.9300 |
O1—C11 | 1.329 (3) | C7—C8 | 1.364 (3) |
O1—C12 | 1.431 (3) | C8—C9 | 1.389 (3) |
O2—C11 | 1.193 (3) | C8—H8A | 0.9300 |
C1—C6 | 1.371 (3) | C9—C10 | 1.354 (3) |
C1—C2 | 1.384 (3) | C9—H9A | 0.9300 |
C2—C3 | 1.370 (3) | C10—C11 | 1.462 (3) |
C2—H2A | 0.9300 | C12—H12C | 0.9600 |
C3—C4 | 1.379 (3) | C12—H12A | 0.9600 |
C3—H3A | 0.9300 | C12—H12B | 0.9600 |
C4—C5 | 1.380 (3) | ||
C1—S1—C1i | 103.51 (14) | C8—C7—C4 | 128.3 (2) |
C10—S2—C7 | 91.82 (11) | C8—C7—S2 | 110.07 (17) |
C11—O1—C12 | 116.8 (2) | C4—C7—S2 | 121.60 (16) |
C6—C1—C2 | 118.7 (2) | C7—C8—C9 | 114.1 (2) |
C6—C1—S1 | 118.83 (17) | C7—C8—H8A | 123.0 |
C2—C1—S1 | 122.31 (17) | C9—C8—H8A | 123.0 |
C3—C2—C1 | 120.5 (2) | C10—C9—C8 | 112.6 (2) |
C3—C2—H2A | 119.8 | C10—C9—H9A | 123.7 |
C1—C2—H2A | 119.8 | C8—C9—H9A | 123.7 |
C2—C3—C4 | 121.6 (2) | C9—C10—C11 | 129.7 (2) |
C2—C3—H3A | 119.2 | C9—C10—S2 | 111.44 (18) |
C4—C3—H3A | 119.2 | C11—C10—S2 | 118.88 (18) |
C3—C4—C5 | 117.4 (2) | O2—C11—O1 | 124.1 (2) |
C3—C4—C7 | 120.7 (2) | O2—C11—C10 | 124.5 (2) |
C5—C4—C7 | 121.96 (19) | O1—C11—C10 | 111.4 (2) |
C4—C5—C6 | 121.5 (2) | O1—C12—H12C | 109.5 |
C4—C5—H5A | 119.2 | O1—C12—H12A | 109.5 |
C6—C5—H5A | 119.2 | H12C—C12—H12A | 109.5 |
C1—C6—C5 | 120.3 (2) | O1—C12—H12B | 109.5 |
C1—C6—H6A | 119.8 | H12C—C12—H12B | 109.5 |
C5—C6—H6A | 119.8 | H12A—C12—H12B | 109.5 |
C1i—S1—C1—C6 | 143.3 (2) | C10—S2—C7—C8 | 1.38 (19) |
C1i—S1—C1—C2 | −41.89 (19) | C10—S2—C7—C4 | 179.85 (19) |
C6—C1—C2—C3 | −0.8 (4) | C4—C7—C8—C9 | −179.6 (2) |
S1—C1—C2—C3 | −175.6 (2) | S2—C7—C8—C9 | −1.3 (3) |
C1—C2—C3—C4 | 1.8 (4) | C7—C8—C9—C10 | 0.4 (3) |
C2—C3—C4—C5 | −1.9 (4) | C8—C9—C10—C11 | −178.8 (2) |
C2—C3—C4—C7 | 178.9 (2) | C8—C9—C10—S2 | 0.7 (3) |
C3—C4—C5—C6 | 1.2 (4) | C7—S2—C10—C9 | −1.2 (2) |
C7—C4—C5—C6 | −179.7 (2) | C7—S2—C10—C11 | 178.4 (2) |
C2—C1—C6—C5 | 0.1 (4) | C12—O1—C11—O2 | 1.0 (4) |
S1—C1—C6—C5 | 175.03 (18) | C12—O1—C11—C10 | −177.8 (2) |
C4—C5—C6—C1 | −0.3 (4) | C9—C10—C11—O2 | −171.0 (3) |
C3—C4—C7—C8 | 9.2 (4) | S2—C10—C11—O2 | 9.5 (4) |
C5—C4—C7—C8 | −169.9 (2) | C9—C10—C11—O1 | 7.8 (4) |
C3—C4—C7—S2 | −169.0 (2) | S2—C10—C11—O1 | −171.65 (17) |
C5—C4—C7—S2 | 11.9 (3) |
Symmetry code: (i) −x, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C24H18O4S3 |
Mr | 466.56 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.8692 (3), 6.0255 (2), 29.7783 (6) |
β (°) | 94.221 (1) |
V (Å3) | 2123.9 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.48 × 0.44 × 0.18 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.839, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7327, 2620, 1895 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.673 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.151, 1.03 |
No. of reflections | 2620 |
No. of parameters | 142 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.32 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
S1—C1 | 1.765 (2) | C4—C7 | 1.464 (3) |
S2—C10 | 1.715 (2) | C7—C8 | 1.364 (3) |
S2—C7 | 1.718 (2) | C8—C9 | 1.389 (3) |
O1—C12 | 1.431 (3) | C9—C10 | 1.354 (3) |
C1—C2 | 1.384 (3) | C10—C11 | 1.462 (3) |
C1—S1—C1i | 103.51 (14) | C9—C10—S2 | 111.44 (18) |
C10—S2—C7 | 91.82 (11) | O2—C11—C10 | 124.5 (2) |
C6—C1—S1 | 118.83 (17) | O1—C11—C10 | 111.4 (2) |
C8—C7—S2 | 110.07 (17) | ||
C1i—S1—C1—C6 | 143.3 (2) | S2—C10—C11—O2 | 9.5 (4) |
C1i—S1—C1—C2 | −41.89 (19) | C9—C10—C11—O1 | 7.8 (4) |
C5—C4—C7—S2 | 11.9 (3) |
Symmetry code: (i) −x, y, −z+3/2. |
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Supramolecular chemistry based on molecular recognition has added a new dimension to chemistry and stereochemistry and is a fast growing subject. Considered efforts generally directed towards modeling for biological non-covalent binding in chemical systems resulted not only in the synthesis of numerous artificial receptors but also in the development of innovative approaches to the generation of selective non-covalent binders (Haldar et al., 1997). Ray et al. (2001) have prepared the title compound, (I), by a very recently method developed for the synthesis of sulfur pivoted cavity-shaped polycyclic thiophene derivatives in three steps from diphenyl sulfide. We have undertaken an X-ray structure determination of (I) in order to establish its chemical structure and conformation.
In the compound (I), the bond lengths and angles show normal values. The values of the phenylthiophene moiety agree with those observed in the related structure previuously studied (Joseph et al., 1991). The C1—S1—C1' angle is 103.5 (1)°.
In the structure (I), there is only one half of the molecule in the asymmetric unit, and the unit-cell volume contains four molecules. One half of the molecule is related to the other by a twofold axis passing through the S1 atom. One half of the molecule is nearly planar. Both the phenyl and thienyl rings are planar, with maximum deviations of 0.009 (3) Å at C3 and 0.009 (2) Å at C7. The mean planes through the phenyl and thienyl rings form a dihedral angle of 10.9 (1)°. The carbomethoxy group is also planar and is twisted by 8.4 (1)° from the plane of the thienyl ring.