organic compounds
tert-butylsulfanyl)phenyl]ethynyl}azulene
of 1-iodo-3-{[4-(aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany
*Correspondence e-mail: edwin.weber@chemie.tu-freiberg.de
The title compound, C20H19IS, features a 1,3-disubstituted azulene involving an ethynylene elongated 4-(tert-butylsulfanyl)phenyl sidearm and an iodine atom as the substituents. The azulene ring system is almost planar (r.m.s. deviation = 0.012 Å) and subtends a dihedral angle of 35.7 (1)° with the benzene ring. As a result of the inherent dipole character of the azulene core, a supramolecular π–π dimer [separation between the centroids of the five- and seven-membered rings = 3.7632 (10) Å] with antiparallel orientated molecules can be observed in the crystal. The packing is consolidated by an unusual I⋯π(acetylene) contact [I⋯Cg = 3.34 Å, C—I⋯Cg = 173.3°], and a very weak C—H⋯π interaction is also found in the structure, with the azulene five-membered ring as the acceptor.
Keywords: crystal structure; azulene; 1,3-disubstitution; C—H⋯π interaction; I⋯π contact.
CCDC reference: 1409619
1. Related literature
For background to this work, see: Strachota et al. (2008); Xia et al. (2014). For related structures, see: Förster et al. (2012, 2014). For the synthesis of the starting compounds 1,3-diiodoazulene and 1-(tert-butylsulfanyl)-4-ethynylbenzene, see: Wakabayashi et al. (1998); Mayor et al. (2003). For the Sonogashira–Hagihara cross-coupling reaction, see: Sonogashira et al. (1975). For I⋯π contacts, see: Forni et al. (2012). For C—H⋯π interactions, see: Nishio et al. (2009).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2010); cell SAINT-NT (Sheldrick, 2008); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
CCDC reference: 1409619
https://doi.org/10.1107/S2056989015012542/hb7447sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015012542/hb7447Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015012542/hb7447Isup3.tif
Supporting information file. DOI: https://doi.org/10.1107/S2056989015012542/hb7447Isup4.cml
Owing to the remarkable electronic and optical properties of azulene and its derivatives, compounds of this type have recently received enormous interest for application in the field of molecular electronics (Strachota et al., 2008; Xia et al., 2014) Being connected to this, the title compound, C20H19IS, is a valuable intermediate in the preparation of corresponding azulenes having a characteristic 1,3-substitution pattern (Förster et al., 2012).
The π-stacking behavior (Förster et al., 2014). In the present case, supramolecular dimers with a head-to-tail fashioned orientation of the azulene cores are found (3.44 Å). On the side facing away from the azulene-contact, a benzene ring is located. However, considering the distance and geometry, the existence of a π···π-interaction can be excluded. Instead, the presence of a weak C—H···π-interaction [H17···Cg(C1, C10) 2.87 Å] is assumed (Nishio et al. 2009). In the crystal of the title compound, the packing is furthermore consolidated by a remarkable I···π-interaction (Forni et al. 2012) [I1···Cg(C11, C12) 3.34 Å, 173.3°].
of the compound contains one molecule in the asymmetric part of the The molecule deviates from planarity, which can be reflected by a twist angle of 35.7° with respect to the aromatic ring systems of benzene and azulene. The ability of azulene to shift electronic density from the seven-membered ring element toward the five-membered part of the ring system has already been shown to exercise a controlling effect on the supramolecular interactions in the crystal especially regardingThe title compound was prepared using a Sonogashira–Hagihara cross-coupling reaction (Sonogashira et al., 1975), starting with 1,3-diiodoazulene (Wakabayashi et al., 1998) and 1-(tert-butylsulfanyl)-4-ethynylbenzene (Mayor et al., 2003). The aryl iodide (8.0 g, 21.06 mmol) and the terminal alkyne (4.0 g, 21.06 mmol) were dissolved in 200 ml of diisopropylamine. After degassing of the solution and cooling to -30 °C, a mixture of bis(triphenylphosphane)palladium(II) chloride (110 mg, 0.16 mmol) and copper(I) iodide (60 mg, 0.32 mmol) was added. The mixture was stirred for 18 h at room temperature. After evaporation of the solvent, the residue was purified by δ/ppm = 1.32 (s, 9H CH3), 7.35 (t, 2H, ArH, 3JHH=9.8 Hz), 7.54 (m, 4H, ArH), 7.72 (d, 1H, ArH, 3JHH=9.9 Hz), 8.10 (s, 1H, ArH), 8.25 (d, 1H, ArH, 3JHH=9.7 Hz), 8.57 (d, 1H, ArH, 3JHH=9.5 Hz); 13CNMR: (CDCl3) δ/ppm = 31.01 (CH3), 46.50 (C-(CH3)3), 74.70 (ArC-I), 86.06 (C≡C), 94.34 (C≡C), 112.17 (ArC), 124.23 (ArC), 125.19 (ArC), 125.61 (ArC), 131.19 (ArC), 132.77 (ArC), 136.15 (ArC), 137.33 (ArC), 139.75 (ArC), 139.77 (ArC), 140.83 (ArC), 141.84 (ArC), 145.77 (ArC); GC/MS calc.: 442; found: 442 [M]+.; EA calc.: C: 59.73 %, H: 4.33 %, S: 7.25 %; found C: 60.03 %, H: 4.35 %, S: 7.21 %; Crystallization by slow solvent evaporation from acetone solution yielded suitable crystals.
on SiO2 [60 F254 Merck, hexane] to yield 4.11 g (44 %) of the title compound as a green solid. In addition to the product, 440 mg of 1,3-diiodoazulene and 80 mg of 1,3-bis{[4-(tert-butylsulfanyl)phenyl]ethynyl}azulene were isolated. Analytical data: mp = 120 °C; 1H-NMR: (CDCl3)Owing to the remarkable electronic and optical properties of azulene and its derivatives, compounds of this type have recently received enormous interest for application in the field of molecular electronics (Strachota et al., 2008; Xia et al., 2014) Being connected to this, the title compound, C20H19IS, is a valuable intermediate in the preparation of corresponding azulenes having a characteristic 1,3-substitution pattern (Förster et al., 2012).
The π-stacking behavior (Förster et al., 2014). In the present case, supramolecular dimers with a head-to-tail fashioned orientation of the azulene cores are found (3.44 Å). On the side facing away from the azulene-contact, a benzene ring is located. However, considering the distance and geometry, the existence of a π···π-interaction can be excluded. Instead, the presence of a weak C—H···π-interaction [H17···Cg(C1, C10) 2.87 Å] is assumed (Nishio et al. 2009). In the crystal of the title compound, the packing is furthermore consolidated by a remarkable I···π-interaction (Forni et al. 2012) [I1···Cg(C11, C12) 3.34 Å, 173.3°].
of the compound contains one molecule in the asymmetric part of the The molecule deviates from planarity, which can be reflected by a twist angle of 35.7° with respect to the aromatic ring systems of benzene and azulene. The ability of azulene to shift electronic density from the seven-membered ring element toward the five-membered part of the ring system has already been shown to exercise a controlling effect on the supramolecular interactions in the crystal especially regardingFor background to this work, see: Strachota et al. (2008); Xia et al. (2014). For related structures, see: Förster et al. (2012, 2014). For the synthesis of the starting compounds 1,3-diiodoazulene and 1-(tert-butylsulfanyl)-4-ethynylbenzene, see: Wakabayashi et al. (1998); Mayor et al. (2003). For the Sonogashira–Hagihara cross-coupling reaction, see: Sonogashira et al. (1975). For I···π contacts, see: Forni et al. (2012). For C—H···π interactions, see: Nishio et al. (2009).
The title compound was prepared using a Sonogashira–Hagihara cross-coupling reaction (Sonogashira et al., 1975), starting with 1,3-diiodoazulene (Wakabayashi et al., 1998) and 1-(tert-butylsulfanyl)-4-ethynylbenzene (Mayor et al., 2003). The aryl iodide (8.0 g, 21.06 mmol) and the terminal alkyne (4.0 g, 21.06 mmol) were dissolved in 200 ml of diisopropylamine. After degassing of the solution and cooling to -30 °C, a mixture of bis(triphenylphosphane)palladium(II) chloride (110 mg, 0.16 mmol) and copper(I) iodide (60 mg, 0.32 mmol) was added. The mixture was stirred for 18 h at room temperature. After evaporation of the solvent, the residue was purified by δ/ppm = 1.32 (s, 9H CH3), 7.35 (t, 2H, ArH, 3JHH=9.8 Hz), 7.54 (m, 4H, ArH), 7.72 (d, 1H, ArH, 3JHH=9.9 Hz), 8.10 (s, 1H, ArH), 8.25 (d, 1H, ArH, 3JHH=9.7 Hz), 8.57 (d, 1H, ArH, 3JHH=9.5 Hz); 13CNMR: (CDCl3) δ/ppm = 31.01 (CH3), 46.50 (C-(CH3)3), 74.70 (ArC-I), 86.06 (C≡C), 94.34 (C≡C), 112.17 (ArC), 124.23 (ArC), 125.19 (ArC), 125.61 (ArC), 131.19 (ArC), 132.77 (ArC), 136.15 (ArC), 137.33 (ArC), 139.75 (ArC), 139.77 (ArC), 140.83 (ArC), 141.84 (ArC), 145.77 (ArC); GC/MS calc.: 442; found: 442 [M]+.; EA calc.: C: 59.73 %, H: 4.33 %, S: 7.25 %; found C: 60.03 %, H: 4.35 %, S: 7.21 %; Crystallization by slow solvent evaporation from acetone solution yielded suitable crystals.
on SiO2 [60 F254 Merck, hexane] to yield 4.11 g (44 %) of the title compound as a green solid. In addition to the product, 440 mg of 1,3-diiodoazulene and 80 mg of 1,3-bis{[4-(tert-butylsulfanyl)phenyl]ethynyl}azulene were isolated. Analytical data: mp = 120 °C; 1H-NMR: (CDCl3) detailsCrystal data, data collection and structure
details are summarized in Table 1. The hydrogen atoms attached to C were fixed geometrically and treated as riding atoms, with d(C—H) = 0.93 and Uiso(H) = 1.2Ueq(C) for aromatic and Uiso(H) = 1.5Ueq(C) for methyl groups.Data collection: APEX2 (Bruker, 2010); cell
SAINT-NT (Sheldrick, 2008); data reduction: SAINT-NT (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C22H19IS | F(000) = 880 |
Mr = 442.33 | Dx = 1.527 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.7222 (2) Å | Cell parameters from 9945 reflections |
b = 11.9892 (2) Å | θ = 2.5–33.1° |
c = 13.7895 (3) Å | µ = 1.77 mm−1 |
β = 113.851 (1)° | T = 100 K |
V = 1923.68 (6) Å3 | Irregular, violet |
Z = 4 | 0.28 × 0.20 × 0.13 mm |
Bruker Kappa Apex CCD diffractometer | 4688 reflections with I > 2σ(I) |
phi and ω scans | Rint = 0.024 |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | θmax = 29.1°, θmin = 1.8° |
Tmin = 0.637, Tmax = 0.802 | h = −17→17 |
23474 measured reflections | k = −16→16 |
5163 independent reflections | l = −18→18 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0333P)2 + 0.9341P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
5163 reflections | Δρmax = 1.37 e Å−3 |
220 parameters | Δρmin = −0.39 e Å−3 |
C22H19IS | V = 1923.68 (6) Å3 |
Mr = 442.33 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.7222 (2) Å | µ = 1.77 mm−1 |
b = 11.9892 (2) Å | T = 100 K |
c = 13.7895 (3) Å | 0.28 × 0.20 × 0.13 mm |
β = 113.851 (1)° |
Bruker Kappa Apex CCD diffractometer | 5163 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 4688 reflections with I > 2σ(I) |
Tmin = 0.637, Tmax = 0.802 | Rint = 0.024 |
23474 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.37 e Å−3 |
5163 reflections | Δρmin = −0.39 e Å−3 |
220 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. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.84013 (2) | 0.46782 (2) | 0.23899 (2) | 0.02206 (5) | |
S2 | 0.11506 (4) | −0.30969 (4) | 0.07255 (4) | 0.02563 (10) | |
C1 | 0.69313 (13) | 0.37992 (13) | 0.14949 (13) | 0.0173 (3) | |
C2 | 0.64454 (13) | 0.29623 (13) | 0.18826 (13) | 0.0179 (3) | |
H2 | 0.6733 | 0.2710 | 0.2596 | 0.022* | |
C3 | 0.54571 (13) | 0.25519 (13) | 0.10422 (13) | 0.0173 (3) | |
C4 | 0.53172 (13) | 0.31415 (13) | 0.01096 (13) | 0.0163 (3) | |
C5 | 0.44468 (14) | 0.29644 (14) | −0.08807 (14) | 0.0204 (3) | |
H5 | 0.3916 | 0.2391 | −0.0919 | 0.024* | |
C6 | 0.42455 (15) | 0.35115 (15) | −0.18259 (14) | 0.0236 (3) | |
H6 | 0.3600 | 0.3256 | −0.2426 | 0.028* | |
C7 | 0.48585 (16) | 0.43818 (16) | −0.20148 (14) | 0.0238 (3) | |
H7 | 0.4551 | 0.4657 | −0.2721 | 0.029* | |
C8 | 0.58518 (16) | 0.49110 (16) | −0.13288 (16) | 0.0249 (4) | |
H8 | 0.6140 | 0.5480 | −0.1634 | 0.030* | |
C9 | 0.64791 (15) | 0.47161 (13) | −0.02540 (15) | 0.0207 (3) | |
H9 | 0.7142 | 0.5168 | 0.0076 | 0.025* | |
C10 | 0.62711 (13) | 0.39541 (13) | 0.04023 (13) | 0.0160 (3) | |
C11 | 0.47274 (14) | 0.16724 (14) | 0.10849 (14) | 0.0197 (3) | |
C12 | 0.41110 (14) | 0.09113 (14) | 0.10767 (14) | 0.0214 (3) | |
C13 | 0.34086 (13) | −0.00436 (14) | 0.10156 (14) | 0.0183 (3) | |
C14 | 0.31147 (16) | −0.03408 (14) | 0.18573 (15) | 0.0230 (4) | |
H14 | 0.3377 | 0.0096 | 0.2486 | 0.028* | |
C15 | 0.24401 (15) | −0.12745 (15) | 0.17689 (14) | 0.0219 (3) | |
H15 | 0.2249 | −0.1478 | 0.2343 | 0.026* | |
C16 | 0.20377 (14) | −0.19206 (13) | 0.08477 (14) | 0.0188 (3) | |
C17 | 0.23511 (15) | −0.16333 (14) | 0.00239 (15) | 0.0217 (3) | |
H17 | 0.2099 | −0.2079 | −0.0599 | 0.026* | |
C18 | 0.30281 (15) | −0.07036 (15) | 0.01021 (14) | 0.0218 (3) | |
H18 | 0.3234 | −0.0514 | −0.0467 | 0.026* | |
C19 | −0.03091 (15) | −0.24833 (16) | 0.01235 (15) | 0.0258 (4) | |
C20 | −0.05345 (17) | −0.19664 (19) | −0.09463 (17) | 0.0337 (4) | |
H20A | −0.1330 | −0.1700 | −0.1272 | 0.051* | |
H20B | −0.0411 | −0.2527 | −0.1407 | 0.051* | |
H20C | −0.0008 | −0.1339 | −0.0851 | 0.051* | |
C21 | −0.04654 (19) | −0.1617 (2) | 0.0863 (2) | 0.0435 (6) | |
H21A | 0.0031 | −0.0974 | 0.0917 | 0.065* | |
H21B | −0.0259 | −0.1946 | 0.1567 | 0.065* | |
H21C | −0.1269 | −0.1374 | 0.0579 | 0.065* | |
C22 | −0.1104 (2) | −0.3474 (2) | −0.0007 (2) | 0.0454 (6) | |
H22A | −0.1904 | −0.3218 | −0.0299 | 0.068* | |
H22B | −0.0920 | −0.3824 | 0.0684 | 0.068* | |
H22C | −0.0999 | −0.4018 | −0.0491 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.01979 (7) | 0.02162 (7) | 0.02101 (7) | −0.00596 (4) | 0.00437 (5) | −0.00162 (4) |
S2 | 0.0270 (2) | 0.01496 (19) | 0.0329 (2) | −0.00596 (16) | 0.01011 (19) | 0.00387 (16) |
C1 | 0.0149 (7) | 0.0151 (7) | 0.0203 (8) | −0.0020 (6) | 0.0054 (6) | −0.0022 (6) |
C2 | 0.0170 (7) | 0.0161 (7) | 0.0202 (8) | 0.0007 (6) | 0.0070 (6) | 0.0020 (6) |
C3 | 0.0165 (7) | 0.0136 (7) | 0.0214 (8) | −0.0004 (6) | 0.0071 (6) | 0.0008 (6) |
C4 | 0.0162 (7) | 0.0121 (7) | 0.0212 (8) | 0.0000 (5) | 0.0081 (6) | −0.0007 (6) |
C5 | 0.0202 (7) | 0.0167 (7) | 0.0229 (8) | −0.0031 (6) | 0.0073 (7) | −0.0020 (6) |
C6 | 0.0238 (8) | 0.0243 (9) | 0.0183 (8) | −0.0017 (7) | 0.0040 (7) | −0.0010 (6) |
C7 | 0.0294 (9) | 0.0243 (8) | 0.0176 (8) | 0.0005 (7) | 0.0094 (7) | 0.0021 (6) |
C8 | 0.0269 (9) | 0.0213 (8) | 0.0295 (10) | −0.0012 (7) | 0.0146 (8) | 0.0059 (7) |
C9 | 0.0208 (8) | 0.0174 (8) | 0.0251 (9) | −0.0047 (6) | 0.0106 (7) | −0.0014 (6) |
C10 | 0.0157 (7) | 0.0135 (7) | 0.0193 (7) | −0.0006 (5) | 0.0076 (6) | −0.0016 (6) |
C11 | 0.0178 (7) | 0.0171 (7) | 0.0225 (8) | 0.0009 (6) | 0.0064 (6) | 0.0035 (6) |
C12 | 0.0168 (7) | 0.0203 (8) | 0.0244 (8) | 0.0003 (6) | 0.0057 (6) | 0.0055 (6) |
C13 | 0.0141 (7) | 0.0153 (7) | 0.0239 (8) | −0.0005 (6) | 0.0060 (6) | 0.0037 (6) |
C14 | 0.0229 (8) | 0.0243 (9) | 0.0195 (8) | −0.0065 (6) | 0.0063 (7) | −0.0008 (6) |
C15 | 0.0231 (8) | 0.0238 (8) | 0.0190 (8) | −0.0051 (6) | 0.0087 (7) | 0.0018 (6) |
C16 | 0.0181 (7) | 0.0140 (7) | 0.0240 (8) | −0.0013 (6) | 0.0080 (6) | 0.0026 (6) |
C17 | 0.0248 (8) | 0.0175 (8) | 0.0269 (9) | −0.0028 (6) | 0.0147 (7) | −0.0041 (6) |
C18 | 0.0240 (8) | 0.0207 (8) | 0.0261 (9) | −0.0010 (6) | 0.0157 (7) | 0.0022 (7) |
C19 | 0.0210 (8) | 0.0274 (9) | 0.0279 (9) | −0.0097 (7) | 0.0087 (7) | 0.0018 (7) |
C20 | 0.0284 (9) | 0.0367 (11) | 0.0314 (10) | −0.0069 (8) | 0.0072 (8) | 0.0088 (8) |
C21 | 0.0270 (10) | 0.0586 (15) | 0.0486 (14) | −0.0018 (10) | 0.0191 (10) | −0.0132 (11) |
C22 | 0.0338 (11) | 0.0454 (13) | 0.0482 (14) | −0.0219 (10) | 0.0073 (10) | 0.0110 (11) |
I1—C1 | 2.0651 (15) | C13—C18 | 1.398 (3) |
S2—C16 | 1.7712 (16) | C13—C14 | 1.402 (2) |
S2—C19 | 1.8526 (19) | C14—C15 | 1.386 (2) |
C1—C2 | 1.394 (2) | C14—H14 | 0.9500 |
C1—C10 | 1.409 (2) | C15—C16 | 1.396 (2) |
C2—C3 | 1.410 (2) | C15—H15 | 0.9500 |
C2—H2 | 0.9500 | C16—C17 | 1.391 (2) |
C3—C4 | 1.414 (2) | C17—C18 | 1.386 (2) |
C3—C11 | 1.422 (2) | C17—H17 | 0.9500 |
C4—C5 | 1.383 (2) | C18—H18 | 0.9500 |
C4—C10 | 1.479 (2) | C19—C20 | 1.517 (3) |
C5—C6 | 1.387 (2) | C19—C22 | 1.523 (3) |
C5—H5 | 0.9500 | C19—C21 | 1.523 (3) |
C6—C7 | 1.389 (3) | C20—H20A | 0.9800 |
C6—H6 | 0.9500 | C20—H20B | 0.9800 |
C7—C8 | 1.388 (3) | C20—H20C | 0.9800 |
C7—H7 | 0.9500 | C21—H21A | 0.9800 |
C8—C9 | 1.390 (3) | C21—H21B | 0.9800 |
C8—H8 | 0.9500 | C21—H21C | 0.9800 |
C9—C10 | 1.385 (2) | C22—H22A | 0.9800 |
C9—H9 | 0.9500 | C22—H22B | 0.9800 |
C11—C12 | 1.200 (2) | C22—H22C | 0.9800 |
C12—C13 | 1.434 (2) | ||
C16—S2—C19 | 102.19 (8) | C13—C14—H14 | 120.1 |
C2—C1—C10 | 109.87 (14) | C14—C15—C16 | 120.96 (16) |
C2—C1—I1 | 124.97 (12) | C14—C15—H15 | 119.5 |
C10—C1—I1 | 125.15 (12) | C16—C15—H15 | 119.5 |
C1—C2—C3 | 108.81 (14) | C17—C16—C15 | 119.00 (15) |
C1—C2—H2 | 125.6 | C17—C16—S2 | 120.11 (13) |
C3—C2—H2 | 125.6 | C15—C16—S2 | 120.89 (13) |
C2—C3—C4 | 108.39 (14) | C18—C17—C16 | 120.67 (16) |
C2—C3—C11 | 127.23 (15) | C18—C17—H17 | 119.7 |
C4—C3—C11 | 124.35 (15) | C16—C17—H17 | 119.7 |
C5—C4—C3 | 125.25 (15) | C17—C18—C13 | 120.22 (16) |
C5—C4—C10 | 127.69 (15) | C17—C18—H18 | 119.9 |
C3—C4—C10 | 107.06 (14) | C13—C18—H18 | 119.9 |
C4—C5—C6 | 128.67 (16) | C20—C19—C22 | 110.38 (17) |
C4—C5—H5 | 115.7 | C20—C19—C21 | 110.34 (19) |
C6—C5—H5 | 115.7 | C22—C19—C21 | 110.54 (18) |
C5—C6—C7 | 128.83 (17) | C20—C19—S2 | 111.05 (13) |
C5—C6—H6 | 115.6 | C22—C19—S2 | 103.93 (14) |
C7—C6—H6 | 115.6 | C21—C19—S2 | 110.44 (14) |
C8—C7—C6 | 129.86 (17) | C19—C20—H20A | 109.5 |
C8—C7—H7 | 115.1 | C19—C20—H20B | 109.5 |
C6—C7—H7 | 115.1 | H20A—C20—H20B | 109.5 |
C7—C8—C9 | 128.44 (17) | C19—C20—H20C | 109.5 |
C7—C8—H8 | 115.8 | H20A—C20—H20C | 109.5 |
C9—C8—H8 | 115.8 | H20B—C20—H20C | 109.5 |
C10—C9—C8 | 128.97 (16) | C19—C21—H21A | 109.5 |
C10—C9—H9 | 115.5 | C19—C21—H21B | 109.5 |
C8—C9—H9 | 115.5 | H21A—C21—H21B | 109.5 |
C9—C10—C1 | 126.65 (15) | C19—C21—H21C | 109.5 |
C9—C10—C4 | 127.49 (15) | H21A—C21—H21C | 109.5 |
C1—C10—C4 | 105.87 (13) | H21B—C21—H21C | 109.5 |
C12—C11—C3 | 176.91 (19) | C19—C22—H22A | 109.5 |
C11—C12—C13 | 175.55 (19) | C19—C22—H22B | 109.5 |
C18—C13—C14 | 119.41 (15) | H22A—C22—H22B | 109.5 |
C18—C13—C12 | 119.05 (16) | C19—C22—H22C | 109.5 |
C14—C13—C12 | 121.53 (16) | H22A—C22—H22C | 109.5 |
C15—C14—C13 | 119.71 (16) | H22B—C22—H22C | 109.5 |
C15—C14—H14 | 120.1 | ||
C10—C1—C2—C3 | 0.28 (19) | C5—C4—C10—C9 | 1.0 (3) |
I1—C1—C2—C3 | −179.64 (11) | C3—C4—C10—C9 | −179.53 (16) |
C1—C2—C3—C4 | −0.09 (18) | C5—C4—C10—C1 | −179.21 (16) |
C1—C2—C3—C11 | 177.91 (16) | C3—C4—C10—C1 | 0.28 (17) |
C2—C3—C4—C5 | 179.39 (15) | C18—C13—C14—C15 | −0.8 (3) |
C11—C3—C4—C5 | 1.3 (3) | C12—C13—C14—C15 | −179.58 (16) |
C2—C3—C4—C10 | −0.12 (17) | C13—C14—C15—C16 | −0.6 (3) |
C11—C3—C4—C10 | −178.19 (15) | C14—C15—C16—C17 | 1.8 (3) |
C3—C4—C5—C6 | 179.33 (17) | C14—C15—C16—S2 | −178.67 (14) |
C10—C4—C5—C6 | −1.3 (3) | C19—S2—C16—C17 | −89.74 (15) |
C4—C5—C6—C7 | −0.8 (3) | C19—S2—C16—C15 | 90.77 (15) |
C5—C6—C7—C8 | 2.6 (3) | C15—C16—C17—C18 | −1.6 (3) |
C6—C7—C8—C9 | −1.7 (3) | S2—C16—C17—C18 | 178.85 (14) |
C7—C8—C9—C10 | −0.4 (3) | C16—C17—C18—C13 | 0.2 (3) |
C8—C9—C10—C1 | −179.23 (18) | C14—C13—C18—C17 | 1.0 (3) |
C8—C9—C10—C4 | 0.5 (3) | C12—C13—C18—C17 | 179.80 (16) |
C2—C1—C10—C9 | 179.47 (16) | C16—S2—C19—C20 | 60.73 (15) |
I1—C1—C10—C9 | −0.6 (2) | C16—S2—C19—C22 | 179.40 (14) |
C2—C1—C10—C4 | −0.35 (18) | C16—S2—C19—C21 | −62.02 (16) |
I1—C1—C10—C4 | 179.57 (11) |
Cg1 is the centroid of the C1–C4/C10 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17···Cg1i | 0.95 | 2.95 | 3.471 (2) | 116 |
Symmetry code: (i) −x+1, −y, −z. |
Cg1 is the centroid of the C1–C4/C10 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17···Cg1i | 0.95 | 2.95 | 3.471 (2) | 116 |
Symmetry code: (i) −x+1, −y, −z. |
Acknowledgements
This work has been performed within the Cluster of Excellence: `Structure Design of Novel High-Performance Materials via Atomic Design and Defect Engineering' (ADDE), which was supported financially by the European Union (European Regional Development Fund) and by the Ministry of Science and Art of Saxony (SMWK).
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