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R,2S,3R,4S,6S)-2,6-bis(furan-2-yl)-4-hydroxy-4-(thiophen-2-yl)cyclohexane-1,3-diyl]bis(thiophen-2-ylmethanone)
of racemic [(1aDepartment of Physics, Faculty of Sciences, Cumhuriyet University, 58140 Sivas, Turkey, bDepartment of Physics, Faculty of Arts and Sciences, Sinop University, 57010 Sinop, Turkey, cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and dDepartment of Chemistry, Faculty of Sciences, Cumhuriyet University, 58140 Sivas, Turkey
*Correspondence e-mail: akkurt@erciyes.edu.tr
In the title compound, C28H22O5S3, the central cyclohexane ring adopts a chair conformation. The atoms of the furan ring attached to the 6-position of the central cyclohexane ring are disordered over two sets of sites with occupancies of 0.832 (5) and 0.168 (5). The hydroxy group is disordered over two positions (at the 4- and 6-positions of the cyclohexane ring) in the ratio 0.832 (5):0.168 (5). In the crystal, molecules are linked by C—H⋯O hydrogen bonds and C—H⋯π interactions, forming layers parallel to (100).
CCDC reference: 1484675
1. Chemical context
Domino or cascade reactions have many applications in organic chemistry (Tietze et al., 2006). They are used for the synthesis of complex molecules that have polysubstituted and multiple stereocenters in a single step (Pellissier, 2012, 2013). Pentasubstituted cyclohexanol derivatives can be synthesized from aromatic and via domino reaction (Luo & Shan, 2006; Gezegen & Ceylan, 2015). In this paper we report the synthesis of [(1R,2S,3R,4S,6S)-2,6-bis(furan-2-yl)-4-hydroxy-4-(thiophen-2-yl)cyclohexane-1,3-diyl]bis(thiophen-2-ylmethanone) in a high yield starting from 2-acetylthiophene and furfural. The resulting product is a racemate crystallizing in a centrosymmetric space group.
2. Structural commentary
In the title compound, Fig. 1, the central cyclohexane ring adopts a chair conformation [the puckering parameters are QT = 0.586 (3) Å, θ = 0.0 (3)° and φ = 169 (17)°]. The mean plane of this ring makes dihedral angles of 80.42 (14), 59.57 (17), 85.65 (17), 66.82 (19), 84.88 (18) and 83.1 (8)°, respectively, with the five associated five-membered rings (S1/C8–C11, S2/C16–C19, S3/C21–C24, O2A/C12A–C15A, O5/C25–C28 and O2B/C12B–C15B).
3. Supramolecular features
The molecular conformation is stabilized by a weak intramolecular O—H⋯O interaction (Table 1). C—H⋯O hydrogen bonds together with C—H⋯π contacts, Table 1, form layers of molecules when viewed along both the a- and b-axis directions, Figs. and 3. Short S3⋯S3ii contacts [symmetry code: (ii) −x + 1, −y, −z + 1] at 3.5210 (12) Å may also contribute to the crystal packing (Figs. 2 and 3).
4. Semi-empirical quantum mechanical calculations
According to the results of theoretical calculations carried out using the semi-empirical quantum-mechanical CNDO/2 (Complete Neglect of Differential Overlap) method (Pople & Beveridge, 1970), the spatial view of the single molecule, with atomic labels, calculated as a closed-shell in a vacuum is shown in Fig. 4. The net charges on atoms O1, O2, O3, O4, O5, S1, S2 and S3 are −0.330, −0.113, −0.279, −0.341, −0.158, −0.014, −0.055 and −0.021 e−, respectively. This is useful as prediction of the electron-rich and electron-poor sites of a molecule provides a rough estimate of chemical and physical properties of the molecule. The of the title molecule is 3.626 Debye. The HOMO and LUMO energy levels are −10.31 and 1.72 eV, respectively. The values of the HOMO and LUMO energy levels determine the way in which the molecule interacts with other species and help to characterize the chemical reactivity and kinetics of the molecule.
The geometrical parameter values obtained by the X-ray ). Small differences between the theoretical and experimental results may result from the calculations assuming the molecule is in a vacuum.
of the title compound are consistent with those calculated by the CNDO/2 method within the error limits (Table 2
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5. Synthesis and crystallization
[(1R,2S,3R,4S,6S)-2,6-bis(furan-2-yl)-4-hydroxy-4-(thiophen-2-yl)cyclohexane-1,3-diyl]bis(thiophen-2-ylmethanone) was synthesized according to a literature method (Gezegen & Ceylan, 2015) in 87% yield. Colourless prisms were recrystallized from ethanol solution, m.p = 524–526 K.
6. details
Crystal data, data collection and structure . Atoms O2,C12-C15 atoms of the furan ring bound to the C1 atom of the central cyclohexane ring are disordered over two sets of sites with an occupancy ratio 0.832 (5):0.168 (5). The O3 hydroxy group is disordered over two positions (on the C1 and C3 atoms of the cyclohexane ring) in the same ratio. The positionally disordered H atoms (H1A on C1 and H1B on C3) were found from a difference Fourier map and their positions were constrained to the expected geometries [C—H = 0.95±0.02 Å] with a fixed U value of 0.05 Å2. All other H atoms were placed in calculated positions (C—H = 0.93–0.98, O—H = 0.82 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(carrier).
details are summarized in Table 3
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Supporting information
CCDC reference: 1484675
https://doi.org/10.1107/S2056989016009452/sj5500sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016009452/sj5500Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989016009452/sj5500Isup3.cml
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2003).C28H22O5S3 | F(000) = 1112 |
Mr = 534.64 | Dx = 1.410 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9982 reflections |
a = 14.0915 (11) Å | θ = 3.1–28.2° |
b = 15.8984 (12) Å | µ = 0.33 mm−1 |
c = 11.2964 (7) Å | T = 296 K |
β = 95.421 (2)° | Prism, colourless |
V = 2519.4 (3) Å3 | 0.19 × 0.17 × 0.13 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 3960 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.070 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | θmax = 28.4°, θmin = 3.1° |
Tmin = 0.597, Tmax = 0.746 | h = −18→18 |
52585 measured reflections | k = −21→21 |
6252 independent reflections | l = −15→13 |
Refinement on F2 | 6 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.204 | w = 1/[σ2(Fo2) + (0.101P)2 + 2.3401P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
6252 reflections | Δρmax = 0.75 e Å−3 |
338 parameters | Δρmin = −0.74 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 | Occ. (<1) | |
S1 | −0.10680 (6) | 0.34243 (6) | 0.32727 (9) | 0.0528 (3) | |
S2 | 0.57614 (7) | 0.33394 (7) | 0.55457 (10) | 0.0661 (4) | |
S3 | 0.38176 (6) | −0.03610 (5) | 0.49813 (8) | 0.0497 (3) | |
O1 | 0.06307 (16) | 0.33764 (15) | 0.50045 (19) | 0.0468 (7) | |
O2A | 0.1462 (2) | 0.51774 (19) | 0.4184 (3) | 0.0541 (10) | 0.832 (5) |
O2B | 0.2243 (12) | 0.4730 (9) | 0.2304 (15) | 0.0541 (10) | 0.168 (5) |
O3A | 0.3783 (2) | 0.30198 (19) | 0.6008 (2) | 0.0419 (8) | 0.832 (5) |
O3B | 0.2474 (13) | 0.4000 (12) | 0.5522 (11) | 0.050 (5) | 0.168 (5) |
O4 | 0.37016 (18) | 0.13400 (15) | 0.59929 (19) | 0.0516 (8) | |
O5 | 0.16291 (18) | 0.14210 (14) | 0.2732 (2) | 0.0522 (8) | |
C1 | 0.2479 (2) | 0.38831 (18) | 0.4265 (3) | 0.0354 (9) | |
C2 | 0.3529 (2) | 0.37285 (18) | 0.4141 (3) | 0.0360 (9) | |
C3 | 0.3902 (2) | 0.29228 (18) | 0.4759 (2) | 0.0339 (8) | |
C4 | 0.33066 (19) | 0.21646 (17) | 0.4248 (2) | 0.0302 (8) | |
C5 | 0.22355 (19) | 0.23054 (17) | 0.4381 (2) | 0.0317 (8) | |
C6 | 0.18765 (19) | 0.31239 (16) | 0.3769 (2) | 0.0304 (8) | |
C7 | 0.0835 (2) | 0.32507 (17) | 0.3991 (3) | 0.0335 (8) | |
C8 | 0.0088 (2) | 0.32100 (18) | 0.3002 (3) | 0.0354 (9) | |
C9 | 0.0139 (2) | 0.3006 (2) | 0.1833 (3) | 0.0433 (10) | |
C10 | −0.0750 (3) | 0.3032 (2) | 0.1164 (3) | 0.0578 (12) | |
C11 | −0.1458 (3) | 0.3250 (2) | 0.1826 (4) | 0.0592 (14) | |
C12A | 0.2159 (3) | 0.46624 (16) | 0.3713 (3) | 0.0372 (10) | 0.832 (5) |
C12B | 0.2063 (16) | 0.4706 (10) | 0.3519 (15) | 0.0372 (10) | 0.168 (5) |
C13A | 0.2394 (3) | 0.5031 (3) | 0.2634 (3) | 0.0602 (17) | 0.832 (5) |
C13B | 0.1550 (17) | 0.5444 (12) | 0.3766 (17) | 0.0602 (17) | 0.168 (5) |
C14A | 0.1842 (3) | 0.5774 (2) | 0.2437 (4) | 0.089 (3) | 0.832 (5) |
C14B | 0.1413 (19) | 0.5924 (11) | 0.270 (2) | 0.089 (3) | 0.168 (5) |
C15A | 0.1266 (3) | 0.58644 (17) | 0.3395 (4) | 0.095 (3) | 0.832 (5) |
C15B | 0.1841 (17) | 0.5483 (12) | 0.1800 (16) | 0.095 (3) | 0.168 (5) |
C16 | 0.4946 (2) | 0.28136 (19) | 0.4597 (3) | 0.0368 (9) | |
C17 | 0.5386 (2) | 0.2391 (2) | 0.3737 (3) | 0.0446 (10) | |
C18 | 0.6395 (3) | 0.2524 (3) | 0.3902 (4) | 0.0607 (14) | |
C19 | 0.6665 (3) | 0.3005 (3) | 0.4807 (4) | 0.0648 (15) | |
C20 | 0.3597 (2) | 0.13466 (19) | 0.4899 (3) | 0.0349 (9) | |
C21 | 0.3687 (2) | 0.05818 (18) | 0.4227 (3) | 0.0364 (9) | |
C22 | 0.3728 (3) | 0.0465 (2) | 0.3024 (3) | 0.0470 (11) | |
C23 | 0.3884 (3) | −0.0380 (2) | 0.2741 (4) | 0.0588 (14) | |
C24 | 0.3939 (3) | −0.0894 (2) | 0.3709 (4) | 0.0564 (13) | |
C25 | 0.1672 (2) | 0.15642 (18) | 0.3943 (3) | 0.0364 (9) | |
C26 | 0.1219 (3) | 0.0946 (2) | 0.4462 (4) | 0.0583 (14) | |
C27 | 0.0863 (3) | 0.0390 (2) | 0.3511 (4) | 0.0651 (14) | |
C28 | 0.1138 (3) | 0.0694 (3) | 0.2513 (4) | 0.0681 (16) | |
H1A | 0.237 (5) | 0.395 (4) | 0.511 (2) | 0.0500* | 0.832 (5) |
H1B | 0.38 (2) | 0.310 (18) | 0.557 (10) | 0.0500* | 0.168 (5) |
H2A | 0.38950 | 0.42030 | 0.44750 | 0.0430* | |
H2B | 0.36240 | 0.36950 | 0.33030 | 0.0430* | |
H3A | 0.39870 | 0.26000 | 0.63700 | 0.0630* | 0.832 (5) |
H3B | 0.26770 | 0.35740 | 0.58690 | 0.0750* | 0.168 (5) |
H4 | 0.33970 | 0.21010 | 0.34030 | 0.0360* | |
H5 | 0.21640 | 0.23630 | 0.52310 | 0.0380* | |
H6 | 0.19240 | 0.30770 | 0.29120 | 0.0370* | |
H9 | 0.07030 | 0.28640 | 0.15160 | 0.0520* | |
H10 | −0.08410 | 0.29140 | 0.03550 | 0.0690* | |
H11 | −0.20920 | 0.32990 | 0.15220 | 0.0710* | |
H13A | 0.28330 | 0.48230 | 0.21420 | 0.0720* | 0.832 (5) |
H13B | 0.13400 | 0.55880 | 0.44960 | 0.0720* | 0.168 (5) |
H14A | 0.18560 | 0.61380 | 0.17940 | 0.1060* | 0.832 (5) |
H14B | 0.10970 | 0.64380 | 0.26150 | 0.1060* | 0.168 (5) |
H15A | 0.08360 | 0.62980 | 0.34890 | 0.1140* | 0.832 (5) |
H15B | 0.18560 | 0.56560 | 0.10150 | 0.1140* | 0.168 (5) |
H17 | 0.50730 | 0.20670 | 0.31360 | 0.0540* | |
H18 | 0.68180 | 0.22900 | 0.34100 | 0.0730* | |
H19 | 0.72980 | 0.31490 | 0.50210 | 0.0780* | |
H22 | 0.36600 | 0.08960 | 0.24650 | 0.0560* | |
H23 | 0.39440 | −0.05700 | 0.19730 | 0.0710* | |
H24 | 0.40330 | −0.14720 | 0.36740 | 0.0670* | |
H26 | 0.11480 | 0.08860 | 0.52680 | 0.0700* | |
H27 | 0.05050 | −0.00950 | 0.35890 | 0.0780* | |
H28 | 0.10130 | 0.04470 | 0.17690 | 0.0820* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0311 (4) | 0.0639 (6) | 0.0647 (6) | 0.0092 (4) | 0.0107 (4) | 0.0048 (4) |
S2 | 0.0504 (6) | 0.0790 (7) | 0.0673 (7) | −0.0109 (5) | −0.0031 (5) | 0.0003 (5) |
S3 | 0.0463 (5) | 0.0395 (4) | 0.0629 (6) | 0.0047 (3) | 0.0033 (4) | 0.0151 (4) |
O1 | 0.0406 (12) | 0.0624 (14) | 0.0392 (12) | 0.0037 (11) | 0.0140 (10) | −0.0035 (10) |
O2A | 0.0456 (16) | 0.0549 (18) | 0.064 (2) | 0.0046 (14) | 0.0166 (14) | −0.0075 (15) |
O2B | 0.0456 (16) | 0.0549 (18) | 0.064 (2) | 0.0046 (14) | 0.0166 (14) | −0.0075 (15) |
O3A | 0.0450 (15) | 0.0512 (16) | 0.0295 (13) | 0.0019 (12) | 0.0033 (13) | −0.0089 (13) |
O3B | 0.055 (9) | 0.060 (9) | 0.035 (7) | 0.003 (7) | 0.007 (7) | −0.011 (8) |
O4 | 0.0655 (16) | 0.0536 (14) | 0.0353 (12) | 0.0054 (12) | 0.0029 (11) | 0.0087 (10) |
O5 | 0.0627 (16) | 0.0415 (12) | 0.0497 (13) | −0.0028 (11) | −0.0083 (11) | −0.0046 (10) |
C1 | 0.0337 (15) | 0.0335 (14) | 0.0395 (16) | −0.0014 (12) | 0.0065 (13) | −0.0067 (12) |
C2 | 0.0298 (14) | 0.0328 (14) | 0.0454 (17) | −0.0019 (11) | 0.0034 (12) | −0.0019 (12) |
C3 | 0.0315 (14) | 0.0365 (15) | 0.0335 (15) | −0.0007 (11) | 0.0028 (12) | −0.0015 (12) |
C4 | 0.0284 (14) | 0.0320 (14) | 0.0303 (14) | 0.0006 (11) | 0.0032 (11) | −0.0003 (11) |
C5 | 0.0306 (14) | 0.0325 (14) | 0.0322 (14) | 0.0012 (11) | 0.0044 (11) | 0.0010 (11) |
C6 | 0.0282 (14) | 0.0313 (13) | 0.0325 (14) | 0.0007 (11) | 0.0067 (11) | −0.0026 (11) |
C7 | 0.0309 (14) | 0.0301 (14) | 0.0403 (16) | 0.0012 (11) | 0.0084 (12) | 0.0005 (11) |
C8 | 0.0278 (14) | 0.0330 (14) | 0.0458 (17) | 0.0023 (11) | 0.0061 (12) | 0.0022 (12) |
C9 | 0.0369 (16) | 0.0456 (18) | 0.0470 (18) | 0.0050 (14) | 0.0026 (14) | −0.0055 (14) |
C10 | 0.056 (2) | 0.059 (2) | 0.055 (2) | 0.0027 (18) | −0.0126 (18) | −0.0101 (17) |
C11 | 0.0371 (19) | 0.059 (2) | 0.078 (3) | 0.0043 (16) | −0.0125 (18) | 0.0010 (19) |
C12A | 0.0323 (18) | 0.0281 (14) | 0.051 (2) | 0.0009 (12) | 0.0032 (16) | −0.0054 (14) |
C12B | 0.0323 (18) | 0.0281 (14) | 0.051 (2) | 0.0009 (12) | 0.0032 (16) | −0.0054 (14) |
C13A | 0.060 (3) | 0.052 (3) | 0.070 (3) | 0.014 (2) | 0.014 (2) | 0.022 (2) |
C13B | 0.060 (3) | 0.052 (3) | 0.070 (3) | 0.014 (2) | 0.014 (2) | 0.022 (2) |
C14A | 0.069 (4) | 0.054 (3) | 0.137 (6) | −0.006 (3) | −0.020 (4) | 0.041 (3) |
C14B | 0.069 (4) | 0.054 (3) | 0.137 (6) | −0.006 (3) | −0.020 (4) | 0.041 (3) |
C15A | 0.063 (4) | 0.047 (3) | 0.167 (7) | 0.011 (3) | −0.032 (4) | −0.013 (4) |
C15B | 0.063 (4) | 0.047 (3) | 0.167 (7) | 0.011 (3) | −0.032 (4) | −0.013 (4) |
C16 | 0.0291 (14) | 0.0404 (16) | 0.0402 (16) | −0.0010 (12) | 0.0001 (12) | 0.0064 (12) |
C17 | 0.0301 (16) | 0.0478 (18) | 0.057 (2) | 0.0030 (13) | 0.0097 (14) | 0.0030 (15) |
C18 | 0.0379 (19) | 0.067 (2) | 0.080 (3) | 0.0084 (17) | 0.0205 (18) | 0.017 (2) |
C19 | 0.0372 (19) | 0.078 (3) | 0.077 (3) | −0.0060 (18) | −0.0054 (18) | 0.025 (2) |
C20 | 0.0290 (14) | 0.0395 (15) | 0.0360 (16) | −0.0002 (12) | 0.0028 (12) | 0.0034 (12) |
C21 | 0.0291 (14) | 0.0351 (15) | 0.0446 (17) | 0.0043 (12) | 0.0015 (12) | 0.0058 (12) |
C22 | 0.057 (2) | 0.0389 (17) | 0.0451 (18) | 0.0042 (15) | 0.0043 (15) | 0.0027 (14) |
C23 | 0.069 (3) | 0.046 (2) | 0.062 (2) | 0.0062 (18) | 0.0095 (19) | −0.0109 (17) |
C24 | 0.049 (2) | 0.0344 (17) | 0.085 (3) | 0.0054 (15) | 0.0028 (18) | 0.0012 (17) |
C25 | 0.0279 (14) | 0.0341 (14) | 0.0469 (17) | 0.0036 (12) | 0.0027 (12) | 0.0012 (12) |
C26 | 0.053 (2) | 0.0427 (19) | 0.083 (3) | −0.0021 (16) | 0.0257 (19) | 0.0041 (18) |
C27 | 0.057 (2) | 0.0389 (19) | 0.099 (3) | −0.0146 (17) | 0.005 (2) | −0.007 (2) |
C28 | 0.070 (3) | 0.049 (2) | 0.081 (3) | −0.0066 (19) | −0.016 (2) | −0.010 (2) |
S1—C8 | 1.720 (3) | C14A—C15A | 1.420 (6) |
S1—C11 | 1.697 (5) | C14B—C15B | 1.42 (3) |
S2—C16 | 1.713 (3) | C16—C17 | 1.376 (4) |
S2—C19 | 1.674 (4) | C17—C18 | 1.432 (5) |
S3—C21 | 1.725 (3) | C18—C19 | 1.304 (6) |
S3—C24 | 1.691 (4) | C20—C21 | 1.445 (4) |
O1—C7 | 1.223 (4) | C21—C22 | 1.378 (5) |
O2A—C12A | 1.420 (5) | C22—C23 | 1.403 (5) |
O2A—C15A | 1.420 (5) | C23—C24 | 1.361 (6) |
O2B—C12B | 1.42 (2) | C25—C26 | 1.337 (5) |
O2B—C15B | 1.42 (2) | C26—C27 | 1.444 (6) |
O3A—C3 | 1.445 (3) | C27—C28 | 1.318 (6) |
O3B—C1 | 1.433 (13) | C1—H1A | 0.99 (3) |
O4—C20 | 1.231 (4) | C2—H2A | 0.9700 |
O5—C25 | 1.383 (4) | C2—H2B | 0.9700 |
O5—C28 | 1.358 (5) | C3—H1B | 0.98 (16) |
O3A—H3A | 0.8200 | C4—H4 | 0.9800 |
O3B—H3B | 0.8200 | C5—H5 | 0.9800 |
C1—C2 | 1.519 (4) | C6—H6 | 0.9800 |
C1—C12B | 1.635 (17) | C9—H9 | 0.9300 |
C1—C12A | 1.440 (4) | C10—H10 | 0.9300 |
C1—C6 | 1.550 (4) | C11—H11 | 0.9300 |
C2—C3 | 1.528 (4) | C13A—H13A | 0.9300 |
C3—C16 | 1.510 (4) | C13B—H13B | 0.9300 |
C3—C4 | 1.549 (4) | C14A—H14A | 0.9300 |
C4—C5 | 1.547 (4) | C14B—H14B | 0.9300 |
C4—C20 | 1.531 (4) | C15A—H15A | 0.9300 |
C5—C6 | 1.537 (4) | C15B—H15B | 0.9300 |
C5—C25 | 1.480 (4) | C17—H17 | 0.9300 |
C6—C7 | 1.526 (4) | C18—H18 | 0.9300 |
C7—C8 | 1.462 (4) | C19—H19 | 0.9300 |
C8—C9 | 1.368 (5) | C22—H22 | 0.9300 |
C9—C10 | 1.401 (5) | C23—H23 | 0.9300 |
C10—C11 | 1.348 (6) | C24—H24 | 0.9300 |
C12A—C13A | 1.420 (5) | C26—H26 | 0.9300 |
C12B—C13B | 1.42 (3) | C27—H27 | 0.9300 |
C13A—C14A | 1.420 (6) | C28—H28 | 0.9300 |
C13B—C14B | 1.42 (3) | ||
C8—S1—C11 | 91.29 (19) | C21—C22—C23 | 112.1 (3) |
C16—S2—C19 | 91.72 (19) | C22—C23—C24 | 113.0 (4) |
C21—S3—C24 | 91.73 (17) | S3—C24—C23 | 112.3 (3) |
C12A—O2A—C15A | 108.0 (3) | O5—C25—C26 | 109.6 (3) |
C12B—O2B—C15B | 108.0 (15) | C5—C25—C26 | 134.6 (3) |
C25—O5—C28 | 107.1 (3) | O5—C25—C5 | 115.7 (2) |
C3—O3A—H3A | 109.00 | C25—C26—C27 | 105.7 (4) |
C1—O3B—H3B | 109.00 | C26—C27—C28 | 107.6 (3) |
O3B—C1—C12B | 111.8 (10) | O5—C28—C27 | 110.0 (4) |
O3B—C1—C2 | 102.0 (8) | C2—C1—H1A | 110 (4) |
O3B—C1—C6 | 113.9 (8) | C6—C1—H1A | 108 (4) |
C2—C1—C12B | 112.8 (8) | C12A—C1—H1A | 105 (4) |
C6—C1—C12A | 112.0 (3) | C1—C2—H2A | 109.00 |
C6—C1—C12B | 106.2 (7) | C1—C2—H2B | 109.00 |
C2—C1—C12A | 111.5 (3) | C3—C2—H2A | 109.00 |
C2—C1—C6 | 110.2 (2) | C3—C2—H2B | 109.00 |
C1—C2—C3 | 112.9 (2) | H2A—C2—H2B | 108.00 |
O3A—C3—C2 | 106.9 (2) | C2—C3—H1B | 96 (14) |
C2—C3—C4 | 109.4 (2) | C4—C3—H1B | 117 (15) |
O3A—C3—C4 | 109.8 (2) | C16—C3—H1B | 112 (17) |
O3A—C3—C16 | 109.6 (2) | C3—C4—H4 | 109.00 |
C4—C3—C16 | 111.4 (2) | C5—C4—H4 | 109.00 |
C2—C3—C16 | 109.8 (2) | C20—C4—H4 | 109.00 |
C3—C4—C20 | 111.8 (2) | C4—C5—H5 | 107.00 |
C3—C4—C5 | 110.5 (2) | C6—C5—H5 | 108.00 |
C5—C4—C20 | 107.2 (2) | C25—C5—H5 | 107.00 |
C4—C5—C25 | 110.5 (2) | C1—C6—H6 | 109.00 |
C4—C5—C6 | 111.2 (2) | C5—C6—H6 | 109.00 |
C6—C5—C25 | 112.4 (2) | C7—C6—H6 | 109.00 |
C5—C6—C7 | 108.6 (2) | C8—C9—H9 | 124.00 |
C1—C6—C7 | 109.9 (2) | C10—C9—H9 | 124.00 |
C1—C6—C5 | 110.6 (2) | C9—C10—H10 | 124.00 |
O1—C7—C6 | 119.4 (3) | C11—C10—H10 | 124.00 |
O1—C7—C8 | 120.4 (3) | S1—C11—H11 | 124.00 |
C6—C7—C8 | 120.2 (3) | C10—C11—H11 | 124.00 |
S1—C8—C7 | 118.8 (2) | C12A—C13A—H13A | 126.00 |
C7—C8—C9 | 130.4 (3) | C14A—C13A—H13A | 126.00 |
S1—C8—C9 | 110.8 (2) | C12B—C13B—H13B | 126.00 |
C8—C9—C10 | 112.8 (3) | C14B—C13B—H13B | 126.00 |
C9—C10—C11 | 112.3 (3) | C15A—C14A—H14A | 126.00 |
S1—C11—C10 | 112.8 (3) | C13A—C14A—H14A | 126.00 |
O2A—C12A—C13A | 108.0 (3) | C15B—C14B—H14B | 126.00 |
O2A—C12A—C1 | 122.2 (3) | C13B—C14B—H14B | 126.00 |
C1—C12A—C13A | 129.7 (3) | O2A—C15A—H15A | 126.00 |
O2B—C12B—C1 | 115.6 (13) | C14A—C15A—H15A | 126.00 |
O2B—C12B—C13B | 108.0 (15) | C14B—C15B—H15B | 126.00 |
C1—C12B—C13B | 136.4 (15) | O2B—C15B—H15B | 126.00 |
C12A—C13A—C14A | 108.0 (3) | C18—C17—H17 | 125.00 |
C12B—C13B—C14B | 107.9 (17) | C16—C17—H17 | 125.00 |
C13A—C14A—C15A | 108.0 (3) | C17—C18—H18 | 123.00 |
C13B—C14B—C15B | 108.0 (17) | C19—C18—H18 | 123.00 |
O2A—C15A—C14A | 108.0 (3) | S2—C19—H19 | 123.00 |
O2B—C15B—C14B | 108.1 (16) | C18—C19—H19 | 123.00 |
S2—C16—C17 | 111.1 (2) | C23—C22—H22 | 124.00 |
C3—C16—C17 | 130.6 (3) | C21—C22—H22 | 124.00 |
S2—C16—C3 | 118.2 (2) | C22—C23—H23 | 124.00 |
C16—C17—C18 | 110.1 (3) | C24—C23—H23 | 123.00 |
C17—C18—C19 | 113.7 (4) | S3—C24—H24 | 124.00 |
S2—C19—C18 | 113.4 (3) | C23—C24—H24 | 124.00 |
O4—C20—C4 | 119.4 (3) | C27—C26—H26 | 127.00 |
O4—C20—C21 | 120.8 (3) | C25—C26—H26 | 127.00 |
C4—C20—C21 | 119.7 (3) | C26—C27—H27 | 126.00 |
S3—C21—C20 | 118.8 (3) | C28—C27—H27 | 126.00 |
S3—C21—C22 | 110.9 (2) | C27—C28—H28 | 125.00 |
C20—C21—C22 | 130.2 (3) | O5—C28—H28 | 125.00 |
C11—S1—C8—C7 | −179.5 (2) | C3—C4—C20—O4 | 46.3 (3) |
C11—S1—C8—C9 | −0.6 (3) | C3—C4—C5—C6 | 57.1 (2) |
C8—S1—C11—C10 | 0.5 (3) | C5—C4—C20—O4 | −75.0 (3) |
C19—S2—C16—C3 | −175.7 (3) | C20—C4—C5—C25 | −55.4 (3) |
C19—S2—C16—C17 | 0.2 (3) | C4—C5—C6—C7 | −176.9 (2) |
C16—S2—C19—C18 | −0.3 (4) | C6—C5—C25—O5 | 57.1 (3) |
C24—S3—C21—C22 | 0.7 (3) | C6—C5—C25—C26 | −127.6 (4) |
C24—S3—C21—C20 | −176.8 (3) | C25—C5—C6—C7 | 58.7 (3) |
C21—S3—C24—C23 | 0.0 (3) | C25—C5—C6—C1 | 179.3 (2) |
C15A—O2A—C12A—C1 | −176.4 (3) | C4—C5—C25—O5 | −67.7 (3) |
C12A—O2A—C15A—C14A | 0.0 (4) | C4—C5—C6—C1 | −56.2 (3) |
C15A—O2A—C12A—C13A | 0.0 (4) | C4—C5—C25—C26 | 107.5 (4) |
C28—O5—C25—C5 | 176.3 (3) | C1—C6—C7—O1 | −55.6 (3) |
C28—O5—C25—C26 | −0.2 (4) | C5—C6—C7—O1 | 65.5 (3) |
C25—O5—C28—C27 | 1.1 (4) | C5—C6—C7—C8 | −113.6 (3) |
C6—C1—C12A—O2A | 90.7 (4) | C1—C6—C7—C8 | 125.3 (3) |
C2—C1—C12A—C13A | 39.2 (5) | C6—C7—C8—C9 | 5.6 (5) |
C2—C1—C6—C5 | 55.4 (3) | O1—C7—C8—C9 | −173.5 (3) |
C6—C1—C12A—C13A | −84.9 (5) | O1—C7—C8—S1 | 5.1 (4) |
C12A—C1—C6—C7 | −59.9 (3) | C6—C7—C8—S1 | −175.8 (2) |
C12A—C1—C6—C5 | −179.8 (3) | S1—C8—C9—C10 | 0.6 (4) |
C12A—C1—C2—C3 | 177.8 (3) | C7—C8—C9—C10 | 179.3 (3) |
C2—C1—C6—C7 | 175.3 (2) | C8—C9—C10—C11 | −0.2 (4) |
C2—C1—C12A—O2A | −145.2 (3) | C9—C10—C11—S1 | −0.3 (4) |
C6—C1—C2—C3 | −57.1 (3) | C1—C12A—C13A—C14A | 176.0 (4) |
C1—C2—C3—C16 | −180.0 (3) | O2A—C12A—C13A—C14A | 0.0 (4) |
C1—C2—C3—O3A | −61.2 (3) | C12A—C13A—C14A—C15A | 0.0 (5) |
C1—C2—C3—C4 | 57.5 (3) | C13A—C14A—C15A—O2A | 0.0 (4) |
C2—C3—C4—C5 | −56.4 (3) | S2—C16—C17—C18 | −0.1 (4) |
C2—C3—C16—C17 | −92.0 (4) | C3—C16—C17—C18 | 175.2 (3) |
O3A—C3—C4—C20 | −58.7 (3) | C16—C17—C18—C19 | −0.1 (5) |
C2—C3—C16—S2 | 83.0 (3) | C17—C18—C19—S2 | 0.2 (5) |
O3A—C3—C4—C5 | 60.6 (3) | O4—C20—C21—C22 | −170.1 (4) |
C16—C3—C4—C20 | 62.9 (3) | O4—C20—C21—S3 | 6.8 (4) |
C2—C3—C4—C20 | −175.6 (2) | C4—C20—C21—C22 | 13.8 (5) |
O3A—C3—C16—C17 | 150.9 (3) | C4—C20—C21—S3 | −169.3 (2) |
O3A—C3—C16—S2 | −34.1 (3) | S3—C21—C22—C23 | −1.3 (4) |
C4—C3—C16—C17 | 29.3 (4) | C20—C21—C22—C23 | 175.8 (3) |
C4—C3—C16—S2 | −155.75 (19) | C21—C22—C23—C24 | 1.3 (5) |
C16—C3—C4—C5 | −177.9 (2) | C22—C23—C24—S3 | −0.8 (5) |
C3—C4—C5—C25 | −177.4 (2) | O5—C25—C26—C27 | −0.7 (4) |
C20—C4—C5—C6 | 179.2 (2) | C5—C25—C26—C27 | −176.2 (3) |
C5—C4—C20—C21 | 101.2 (3) | C25—C26—C27—C28 | 1.4 (5) |
C3—C4—C20—C21 | −137.6 (3) | C26—C27—C28—O5 | −1.5 (5) |
Cg1 and Cg2 are the centroids of the S1/C8–C11 and S2/C16–C19 thiophene rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3A—H3A···O4 | 0.82 | 2.08 | 2.673 (4) | 129 |
C5—H5···O3A | 0.98 | 2.59 | 2.944 (4) | 102 |
C22—H22···O3Ai | 0.93 | 2.40 | 3.321 (4) | 170 |
C24—H24···Cg2ii | 0.93 | 2.95 | 3.650 (4) | 133 |
C27—H27···Cg1iii | 0.93 | 2.89 | 3.612 (4) | 135 |
C14B—H14B···Cg1iv | 0.93 | 2.87 | 3.772 (19) | 163 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y, −z+1; (iii) −x, y−1/2, −z+1/2; (iv) −x, y+1/2, −z+1/2. |
Bond | X-ray | CNDO/2 |
S1—C8 | 1.720 (3) | 1.7707 |
S1—C11 | 1.698 (4) | 1.7665 |
S2—C16 | 1.713 (3) | 1.7781 |
S2—C19 | 1.673 (5) | 1.7628 |
S3—C21 | 1.726 (3) | 1.7689 |
S3—C24 | 1.691 (4) | 1.7653 |
O1—C7 | 1.223 (4) | 1.2131 |
O2A—C12A | 1.420 (5) | 1.3602 |
O2A—C15A | 1.420 (5) | 1.3577 |
O3A—C3 | 1.445 (3) | 1.4203 |
O4—C20 | 1.231 (4) | 1.2136 |
O5—C28 | 1.358 (5) | 1.3559 |
O5—C25 | 1.383 (4) | 1.3600 |
C2—C1—C12A | 112.8 (8) | 112.15 |
C2—C1—C6 | 110.2 (2) | 113.29 |
C6—C1—C12A | 112.0 (3) | 111.15 |
C2—C3—C16 | 109.8 (2) | 113.64 |
C2—C3—C4 | 109.4 (2) | 110.56 |
C4—C3—C16 | 111.4 (2) | 110.66 |
O3A—C3—C16 | 109.6 (2) | 106.60 |
C3—C4—C20 | 111.8 (2) | 111.33 |
C5—C4—C20 | 107.2 (2) | 109.38 |
C3—C4—C5 | 110.5 (2) | 112.83 |
C6—C5—C25 | 112.4 (2) | 111.32 |
C4—C5—C25 | 110.5 (2) | 111.87 |
C4—C5—C6 | 111.2 (2) | 112.50 |
C5—C6—C7 | 108.6 (2) | 113.14 |
C1—C6—C7 | 109.9 (2) | 109.87 |
C1—C6—C5 | 110.6 (2) | 107.85 |
O1—C7—C8 | 120.4 (3) | 121.83 |
C6—C7—C8 | 120.2 (3) | 118.24 |
O1—C7—C6 | 119.4 (3) | 119.93 |
O4—C20—C4 | 119.4 (3) | 119.14 |
C4—C20—C21 | 119.7 (3) | 119.62 |
O4—C20—C21 | 120.8 (3) | 121.24 |
Acknowledgements
The authors are indebted to the X-ray laboratory of Sinop University Scientific and Technological Applied and Research Center, Sinop, Turkey, for use of the X-ray diffractometer.
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