organic compounds
trans-1-{2-[4-(dimethylamino)phenyl]ethyl}-4-[2-(pyren-1-yl)ethyl]cyclohexane
ofaFS–SCS, Deutsches Elecktronen-Synchrotron (DESY), Notkestrasse 85, 22607 Hamburg, Germany, and bMax Planck Institute for Biophysical Chemistry, Am Fassberg 11, 37077 Göttingen, Germany
*Correspondence e-mail: sreevidya.thekku.veedu@desy.de, simone.techert@desy.de
The title compound, C34H37N, is a pyrene derivative in which the pyrene ring system is linked to an ethylcyclohexane unit which, in turn, carries a [4-(dimethylamino)phenyl]ethyl substituent in the para position. The central cyclohexane ring has a chair conformation, with the exocyclic C—C bonds in equatorial orientations. The benzene ring is inclined to the mean plane of the pyrene ring system [maximum deviation = 0.038 (4) Å] by 14.84 (15)°. In the crystal, molecules are linked by C—H⋯π interactions, forming chains propagating along [010]. The crystal was refined as a non-merohedral twin [domain ratio = 0.9989 (4):0.0011 (4)].
Keywords: crystal structure; pyrene; donor acceptor; electron transfer; C—H⋯π interactions.
CCDC reference: 1413890
1. Related literature
For charge transfer in donor–acceptor systems, see: Wasielewski (1992); Willemse et al. (2000); Thekku Veedu et al. (2014a). For related structures, see: Thekku Veedu et al. (2014b); Wang et al. (2010). For the synthesis of the title compound, see: Dewar & Mole (1956); Norman et al. (1958).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2012); cell SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).
Supporting information
CCDC reference: 1413890
https://doi.org/10.1107/S2056989015013729/su5171sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015013729/su5171Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015013729/su5171Isup3.cml
Electron-transfer reactions are fundamental processes in chemistry and also in biology. Going back to nature, photo-induced
(PI—ET) is the key step in photosynthesis where light harvesting complexes are functional centers in plants which converts solar energy into chemical energy. In the past decades, to gain more insight into processes extensive studies have been carried out on the optical behaviour of systems consisting of donor acceptor groups linked by different bridges (Thekku Veedu et al., 2014a; Wasielewski, 1992; Willemse et al., 2000). These molecules are also ideal systems for studying solvation dynamics and non-linear optical properties. In the title compound (PyDMAD), the N,N'-dimethylaniline (DMA) unit is covalently linked to the pyrene by an extended diethylcyclohexane bridge between the donor and acceptor.The molecular structure of the title pyrene derivative is illustrated in Fig. 1. Pyrene is linked to an ethylcyclohexane ring which in turn carries a 4-dimethylaminophenylethyl substituent in the para-position. The bond lengths and angles are within normal ranges and are comparable to those reported for similar structures (Thekku Veedu et al., 2014b; Wang et al., 2010). The cyclohexane ring (C9—C14) has a chair conformation. The benzene ring (C1—C6) is inclined to the mean plane of the pyrene ring system (maximum devation = 0.038 (4) Å for atom C29), by 14.84 (15) °. The various hetero atoms of the dimethylamino group are displaced from the benzene ring by 0.078 (4) Å for N1, 0.102 (4) Å for C33, but 0.549 (4) Å for atom C34.
In the crystal, molecules are linked via C—H···π interactions forming chains along the b axis direction (Table 1 and Fig. 2).
Commercially available 1-aminopyrene after diazotization reaction was coupled with N,N'-dimethylaniline according to the previously reported procedure (Dewar & Mole 1956; Norman et al., 1958). The crude product was then purified on an aluminium oxide column with a mixture of cyclohexane/toluene as
and applying HPLC. Plate-like colourless crystals of the title compound were obtained by slow evaporation of a solution in ethyl acetate.Crystal data, data collection and structure
details are summarized in Table 2. The C-bound H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 - 1.00 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. The crystal was refined as a non-merohedral twin [refined BASF ratio = 0.9989 (4):0.0011 (4)].Electron-transfer reactions are fundamental processes in chemistry and also in biology. Going back to nature, photo-induced
(PI—ET) is the key step in photosynthesis where light harvesting complexes are functional centers in plants which converts solar energy into chemical energy. In the past decades, to gain more insight into processes extensive studies have been carried out on the optical behaviour of systems consisting of donor acceptor groups linked by different bridges (Thekku Veedu et al., 2014a; Wasielewski, 1992; Willemse et al., 2000). These molecules are also ideal systems for studying solvation dynamics and non-linear optical properties. In the title compound (PyDMAD), the N,N'-dimethylaniline (DMA) unit is covalently linked to the pyrene by an extended diethylcyclohexane bridge between the donor and acceptor.The molecular structure of the title pyrene derivative is illustrated in Fig. 1. Pyrene is linked to an ethylcyclohexane ring which in turn carries a 4-dimethylaminophenylethyl substituent in the para-position. The bond lengths and angles are within normal ranges and are comparable to those reported for similar structures (Thekku Veedu et al., 2014b; Wang et al., 2010). The cyclohexane ring (C9—C14) has a chair conformation. The benzene ring (C1—C6) is inclined to the mean plane of the pyrene ring system (maximum devation = 0.038 (4) Å for atom C29), by 14.84 (15) °. The various hetero atoms of the dimethylamino group are displaced from the benzene ring by 0.078 (4) Å for N1, 0.102 (4) Å for C33, but 0.549 (4) Å for atom C34.
In the crystal, molecules are linked via C—H···π interactions forming chains along the b axis direction (Table 1 and Fig. 2).
For charge transfer in donor–acceptor systems, see: Wasielewski (1992); Willemse et al. (2000); Thekku Veedu et al. (2014a). For related structures, see: Thekku Veedu et al. (2014b); Wang et al. (2010). For the synthesis of the title compound, see: Dewar & Mole (1956); Norman et al. (1958).
Commercially available 1-aminopyrene after diazotization reaction was coupled with N,N'-dimethylaniline according to the previously reported procedure (Dewar & Mole 1956; Norman et al., 1958). The crude product was then purified on an aluminium oxide column with a mixture of cyclohexane/toluene as
and applying HPLC. Plate-like colourless crystals of the title compound were obtained by slow evaporation of a solution in ethyl acetate. detailsCrystal data, data collection and structure
details are summarized in Table 2. The C-bound H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 - 1.00 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. The crystal was refined as a non-merohedral twin [refined BASF ratio = 0.9989 (4):0.0011 (4)].Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).C34H37N | F(000) = 992 |
Mr = 459.64 | Dx = 1.221 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1927 (4) Å | Cell parameters from 2860 reflections |
b = 10.4082 (6) Å | θ = 2.5–26.8° |
c = 33.399 (2) Å | µ = 0.07 mm−1 |
β = 91.473 (4)° | T = 100 K |
V = 2499.5 (3) Å3 | Plate, colorless |
Z = 4 | 0.35 × 0.25 × 0.15 mm |
Bruker SMART APEXII DUO diffractometer | 23477 reflections with I > 2σ(I) |
Radiation source: Micro-focus | Rint = 0.087 |
φ and ω scan | θmax = 25.1°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −8→8 |
Tmin = 0.976, Tmax = 0.990 | k = −12→12 |
38082 measured reflections | l = −39→39 |
38082 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.069 | H-atom parameters constrained |
wR(F2) = 0.195 | w = 1/[σ2(Fo2) + (0.0001P)2 + 8.046P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
38082 reflections | Δρmax = 0.36 e Å−3 |
320 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0031 (4) |
C34H37N | V = 2499.5 (3) Å3 |
Mr = 459.64 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.1927 (4) Å | µ = 0.07 mm−1 |
b = 10.4082 (6) Å | T = 100 K |
c = 33.399 (2) Å | 0.35 × 0.25 × 0.15 mm |
β = 91.473 (4)° |
Bruker SMART APEXII DUO diffractometer | 38082 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | 23477 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.990 | Rint = 0.087 |
38082 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.195 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.36 e Å−3 |
38082 reflections | Δρmin = −0.32 e Å−3 |
320 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. Refined as a 2-component twin. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.7622 (6) | 0.4345 (4) | −0.13130 (13) | 0.0228 (11) | |
C2 | −0.6154 (6) | 0.3625 (4) | −0.14560 (13) | 0.0275 (12) | |
H2 | −0.6292 | 0.3197 | −0.1706 | 0.033* | |
C3 | −0.4497 (7) | 0.3522 (4) | −0.12399 (13) | 0.0293 (12) | |
H3 | −0.3522 | 0.3019 | −0.1346 | 0.035* | |
C4 | −0.4209 (6) | 0.4124 (4) | −0.08757 (13) | 0.0248 (12) | |
C5 | −0.5662 (6) | 0.4859 (4) | −0.07374 (13) | 0.0275 (12) | |
H5 | −0.5505 | 0.5298 | −0.0490 | 0.033* | |
C6 | −0.7332 (6) | 0.4975 (4) | −0.09472 (13) | 0.0267 (12) | |
H6 | −0.8295 | 0.5488 | −0.0842 | 0.032* | |
C7 | −0.2415 (6) | 0.3977 (4) | −0.06387 (13) | 0.0285 (12) | |
H7A | −0.2037 | 0.4827 | −0.0532 | 0.034* | |
H7B | −0.1436 | 0.3684 | −0.0821 | 0.034* | |
C8 | −0.2532 (6) | 0.3027 (4) | −0.02897 (12) | 0.0242 (12) | |
H8A | −0.3531 | 0.3312 | −0.0112 | 0.029* | |
H8B | −0.2891 | 0.2175 | −0.0398 | 0.029* | |
C9 | −0.0743 (6) | 0.2881 (4) | −0.00411 (12) | 0.0214 (11) | |
H9 | −0.0325 | 0.3758 | 0.0043 | 0.026* | |
C10 | 0.0814 (6) | 0.2270 (4) | −0.02735 (12) | 0.0229 (11) | |
H10A | 0.1087 | 0.2814 | −0.0508 | 0.027* | |
H10B | 0.0401 | 0.1419 | −0.0374 | 0.027* | |
C11 | 0.2574 (6) | 0.2107 (4) | −0.00179 (12) | 0.0253 (12) | |
H11A | 0.3071 | 0.2967 | 0.0053 | 0.030* | |
H11B | 0.3518 | 0.1660 | −0.0177 | 0.030* | |
C12 | 0.2274 (6) | 0.1351 (4) | 0.03662 (12) | 0.0209 (11) | |
H12 | 0.1892 | 0.0459 | 0.0290 | 0.025* | |
C13 | 0.0694 (6) | 0.1953 (4) | 0.05960 (12) | 0.0245 (12) | |
H13A | 0.0425 | 0.1411 | 0.0831 | 0.029* | |
H13B | 0.1087 | 0.2809 | 0.0695 | 0.029* | |
C14 | −0.1066 (6) | 0.2095 (4) | 0.03377 (12) | 0.0230 (11) | |
H14A | −0.2035 | 0.2519 | 0.0496 | 0.028* | |
H14B | −0.1528 | 0.1232 | 0.0261 | 0.028* | |
C15 | 0.4070 (6) | 0.1263 (4) | 0.06140 (12) | 0.0243 (12) | |
H15A | 0.4422 | 0.2138 | 0.0704 | 0.029* | |
H15B | 0.5065 | 0.0948 | 0.0440 | 0.029* | |
C16 | 0.3996 (6) | 0.0392 (4) | 0.09817 (12) | 0.0260 (12) | |
H16A | 0.3020 | 0.0710 | 0.1160 | 0.031* | |
H16B | 0.3644 | −0.0487 | 0.0895 | 0.031* | |
C17 | 0.5821 (6) | 0.0335 (4) | 0.12126 (12) | 0.0217 (11) | |
C18 | 0.7102 (6) | −0.0601 (4) | 0.11161 (13) | 0.0251 (12) | |
H18 | 0.6801 | −0.1189 | 0.0907 | 0.030* | |
C19 | 0.8802 (6) | −0.0707 (4) | 0.13140 (12) | 0.0237 (12) | |
H19 | 0.9652 | −0.1355 | 0.1237 | 0.028* | |
C20 | 0.9282 (6) | 0.0124 (4) | 0.16246 (12) | 0.0196 (11) | |
C21 | 1.1005 (6) | 0.0024 (4) | 0.18479 (12) | 0.0233 (11) | |
H21 | 1.1862 | −0.0630 | 0.1780 | 0.028* | |
C22 | 1.1442 (6) | 0.0829 (4) | 0.21503 (12) | 0.0232 (11) | |
H22 | 1.2603 | 0.0736 | 0.2290 | 0.028* | |
C23 | 1.0191 (6) | 0.1825 (4) | 0.22666 (12) | 0.0195 (11) | |
C24 | 1.0607 (6) | 0.2681 (4) | 0.25782 (13) | 0.0262 (12) | |
H24 | 1.1770 | 0.2618 | 0.2718 | 0.031* | |
C25 | 0.9356 (7) | 0.3615 (4) | 0.26856 (13) | 0.0271 (12) | |
H25 | 0.9661 | 0.4183 | 0.2900 | 0.033* | |
C26 | 0.7664 (6) | 0.3732 (4) | 0.24839 (13) | 0.0254 (12) | |
H26 | 0.6808 | 0.4373 | 0.2563 | 0.031* | |
C27 | 0.7201 (6) | 0.2921 (4) | 0.21650 (12) | 0.0204 (11) | |
C28 | 0.5495 (6) | 0.3042 (4) | 0.19410 (13) | 0.0254 (12) | |
H28 | 0.4646 | 0.3701 | 0.2009 | 0.030* | |
C29 | 0.5058 (6) | 0.2241 (4) | 0.16343 (13) | 0.0236 (11) | |
H29 | 0.3916 | 0.2359 | 0.1490 | 0.028* | |
C30 | 0.6270 (6) | 0.1218 (4) | 0.15210 (12) | 0.0197 (11) | |
C31 | 0.8004 (6) | 0.1096 (4) | 0.17320 (12) | 0.0182 (11) | |
C32 | 0.8462 (6) | 0.1942 (4) | 0.20562 (12) | 0.0183 (11) | |
C33 | −0.9569 (7) | 0.3722 (4) | −0.18918 (13) | 0.0396 (14) | |
H33A | −0.8768 | 0.4107 | −0.2092 | 0.059* | |
H33B | −1.0870 | 0.3778 | −0.1984 | 0.059* | |
H33C | −0.9228 | 0.2818 | −0.1853 | 0.059* | |
C34 | −1.0444 (6) | 0.5568 (4) | −0.14819 (14) | 0.0340 (13) | |
H34A | −1.1253 | 0.5494 | −0.1251 | 0.051* | |
H34B | −1.1207 | 0.5681 | −0.1727 | 0.051* | |
H34C | −0.9619 | 0.6310 | −0.1445 | 0.051* | |
N1 | −0.9334 (5) | 0.4406 (4) | −0.15151 (11) | 0.0309 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.025 (3) | 0.019 (3) | 0.025 (3) | −0.002 (2) | 0.003 (2) | 0.002 (2) |
C2 | 0.031 (3) | 0.031 (3) | 0.021 (3) | 0.000 (3) | 0.003 (2) | −0.003 (2) |
C3 | 0.025 (3) | 0.030 (3) | 0.033 (3) | 0.003 (2) | 0.011 (2) | 0.000 (2) |
C4 | 0.023 (3) | 0.025 (3) | 0.028 (3) | −0.004 (2) | 0.005 (2) | 0.003 (2) |
C5 | 0.030 (3) | 0.029 (3) | 0.024 (3) | −0.005 (3) | 0.001 (2) | −0.006 (2) |
C6 | 0.026 (3) | 0.025 (3) | 0.030 (3) | 0.004 (2) | 0.005 (2) | −0.004 (2) |
C7 | 0.026 (3) | 0.029 (3) | 0.031 (3) | −0.005 (2) | 0.002 (2) | 0.005 (2) |
C8 | 0.021 (3) | 0.027 (3) | 0.024 (3) | −0.001 (2) | 0.003 (2) | −0.003 (2) |
C9 | 0.023 (3) | 0.018 (3) | 0.024 (3) | −0.006 (2) | 0.002 (2) | −0.001 (2) |
C10 | 0.022 (3) | 0.029 (3) | 0.018 (2) | −0.004 (2) | 0.003 (2) | 0.001 (2) |
C11 | 0.021 (3) | 0.032 (3) | 0.023 (3) | 0.000 (2) | 0.005 (2) | −0.002 (2) |
C12 | 0.020 (3) | 0.024 (3) | 0.020 (3) | −0.005 (2) | 0.003 (2) | 0.001 (2) |
C13 | 0.025 (3) | 0.026 (3) | 0.022 (3) | −0.005 (2) | 0.004 (2) | 0.001 (2) |
C14 | 0.018 (3) | 0.028 (3) | 0.023 (3) | −0.002 (2) | 0.006 (2) | −0.003 (2) |
C15 | 0.022 (3) | 0.028 (3) | 0.023 (3) | −0.002 (2) | 0.003 (2) | −0.002 (2) |
C16 | 0.026 (3) | 0.029 (3) | 0.023 (3) | −0.004 (2) | 0.000 (2) | 0.000 (2) |
C17 | 0.025 (3) | 0.023 (3) | 0.017 (3) | −0.004 (2) | 0.002 (2) | 0.003 (2) |
C18 | 0.036 (3) | 0.022 (3) | 0.017 (3) | −0.004 (2) | 0.002 (2) | −0.002 (2) |
C19 | 0.030 (3) | 0.020 (3) | 0.021 (3) | 0.003 (2) | 0.007 (2) | 0.001 (2) |
C20 | 0.022 (3) | 0.019 (3) | 0.018 (2) | −0.002 (2) | 0.005 (2) | 0.004 (2) |
C21 | 0.026 (3) | 0.021 (3) | 0.024 (3) | 0.003 (2) | 0.006 (2) | 0.007 (2) |
C22 | 0.023 (3) | 0.024 (3) | 0.023 (3) | 0.001 (2) | 0.000 (2) | 0.006 (2) |
C23 | 0.023 (3) | 0.018 (3) | 0.017 (3) | −0.002 (2) | 0.004 (2) | 0.004 (2) |
C24 | 0.027 (3) | 0.030 (3) | 0.022 (3) | −0.004 (2) | −0.002 (2) | 0.001 (2) |
C25 | 0.035 (3) | 0.025 (3) | 0.022 (3) | −0.005 (3) | 0.003 (2) | −0.004 (2) |
C26 | 0.029 (3) | 0.021 (3) | 0.026 (3) | 0.000 (2) | 0.007 (2) | −0.003 (2) |
C27 | 0.020 (3) | 0.019 (3) | 0.022 (3) | −0.001 (2) | 0.006 (2) | 0.003 (2) |
C28 | 0.024 (3) | 0.023 (3) | 0.029 (3) | 0.002 (2) | 0.005 (2) | 0.002 (2) |
C29 | 0.022 (3) | 0.024 (3) | 0.025 (3) | −0.002 (2) | 0.002 (2) | 0.003 (2) |
C30 | 0.021 (3) | 0.021 (3) | 0.018 (2) | −0.004 (2) | 0.005 (2) | 0.004 (2) |
C31 | 0.023 (3) | 0.016 (2) | 0.015 (2) | −0.003 (2) | 0.004 (2) | 0.004 (2) |
C32 | 0.020 (3) | 0.017 (3) | 0.017 (2) | −0.004 (2) | 0.004 (2) | 0.005 (2) |
C33 | 0.051 (4) | 0.035 (3) | 0.031 (3) | −0.005 (3) | −0.010 (3) | 0.001 (3) |
C34 | 0.029 (3) | 0.038 (3) | 0.036 (3) | 0.001 (3) | 0.000 (2) | 0.009 (2) |
N1 | 0.030 (2) | 0.034 (3) | 0.029 (2) | 0.003 (2) | −0.005 (2) | −0.0074 (19) |
C1—C2 | 1.389 (6) | C16—H16A | 0.9900 |
C1—N1 | 1.390 (5) | C16—H16B | 0.9900 |
C1—C6 | 1.397 (6) | C17—C18 | 1.385 (6) |
C2—C3 | 1.382 (6) | C17—C30 | 1.412 (6) |
C2—H2 | 0.9500 | C18—C19 | 1.379 (6) |
C3—C4 | 1.380 (6) | C18—H18 | 0.9500 |
C3—H3 | 0.9500 | C19—C20 | 1.387 (5) |
C4—C5 | 1.384 (6) | C19—H19 | 0.9500 |
C4—C7 | 1.504 (6) | C20—C31 | 1.419 (6) |
C5—C6 | 1.380 (6) | C20—C21 | 1.433 (6) |
C5—H5 | 0.9500 | C21—C22 | 1.343 (6) |
C6—H6 | 0.9500 | C21—H21 | 0.9500 |
C7—C8 | 1.532 (6) | C22—C23 | 1.433 (6) |
C7—H7A | 0.9900 | C22—H22 | 0.9500 |
C7—H7B | 0.9900 | C23—C24 | 1.396 (6) |
C8—C9 | 1.521 (5) | C23—C32 | 1.418 (6) |
C8—H8A | 0.9900 | C24—C25 | 1.378 (6) |
C8—H8B | 0.9900 | C24—H24 | 0.9500 |
C9—C10 | 1.518 (6) | C25—C26 | 1.381 (6) |
C9—C14 | 1.529 (5) | C25—H25 | 0.9500 |
C9—H9 | 1.0000 | C26—C27 | 1.393 (6) |
C10—C11 | 1.518 (5) | C26—H26 | 0.9500 |
C10—H10A | 0.9900 | C27—C32 | 1.417 (6) |
C10—H10B | 0.9900 | C27—C28 | 1.426 (6) |
C11—C12 | 1.525 (5) | C28—C29 | 1.351 (6) |
C11—H11A | 0.9900 | C28—H28 | 0.9500 |
C11—H11B | 0.9900 | C29—C30 | 1.433 (6) |
C12—C15 | 1.519 (5) | C29—H29 | 0.9500 |
C12—C13 | 1.522 (6) | C30—C31 | 1.422 (6) |
C12—H12 | 1.0000 | C31—C32 | 1.428 (5) |
C13—C14 | 1.520 (5) | C33—N1 | 1.452 (5) |
C13—H13A | 0.9900 | C33—H33A | 0.9800 |
C13—H13B | 0.9900 | C33—H33B | 0.9800 |
C14—H14A | 0.9900 | C33—H33C | 0.9800 |
C14—H14B | 0.9900 | C34—N1 | 1.454 (5) |
C15—C16 | 1.529 (5) | C34—H34A | 0.9800 |
C15—H15A | 0.9900 | C34—H34B | 0.9800 |
C15—H15B | 0.9900 | C34—H34C | 0.9800 |
C16—C17 | 1.507 (6) | ||
C2—C1—N1 | 122.0 (4) | H15A—C15—H15B | 107.5 |
C2—C1—C6 | 117.1 (4) | C17—C16—C15 | 112.7 (4) |
N1—C1—C6 | 120.9 (4) | C17—C16—H16A | 109.0 |
C3—C2—C1 | 121.0 (4) | C15—C16—H16A | 109.0 |
C3—C2—H2 | 119.5 | C17—C16—H16B | 109.0 |
C1—C2—H2 | 119.5 | C15—C16—H16B | 109.0 |
C4—C3—C2 | 122.2 (5) | H16A—C16—H16B | 107.8 |
C4—C3—H3 | 118.9 | C18—C17—C30 | 119.1 (4) |
C2—C3—H3 | 118.9 | C18—C17—C16 | 119.0 (4) |
C3—C4—C5 | 116.6 (4) | C30—C17—C16 | 121.9 (4) |
C3—C4—C7 | 121.6 (4) | C19—C18—C17 | 122.1 (4) |
C5—C4—C7 | 121.7 (4) | C19—C18—H18 | 118.9 |
C6—C5—C4 | 122.3 (4) | C17—C18—H18 | 118.9 |
C6—C5—H5 | 118.9 | C18—C19—C20 | 120.6 (4) |
C4—C5—H5 | 118.9 | C18—C19—H19 | 119.7 |
C5—C6—C1 | 120.8 (4) | C20—C19—H19 | 119.7 |
C5—C6—H6 | 119.6 | C19—C20—C31 | 118.9 (4) |
C1—C6—H6 | 119.6 | C19—C20—C21 | 122.6 (4) |
C4—C7—C8 | 113.8 (4) | C31—C20—C21 | 118.5 (4) |
C4—C7—H7A | 108.8 | C22—C21—C20 | 122.0 (4) |
C8—C7—H7A | 108.8 | C22—C21—H21 | 119.0 |
C4—C7—H7B | 108.8 | C20—C21—H21 | 119.0 |
C8—C7—H7B | 108.8 | C21—C22—C23 | 121.2 (4) |
H7A—C7—H7B | 107.7 | C21—C22—H22 | 119.4 |
C9—C8—C7 | 114.7 (4) | C23—C22—H22 | 119.4 |
C9—C8—H8A | 108.6 | C24—C23—C32 | 118.9 (4) |
C7—C8—H8A | 108.6 | C24—C23—C22 | 122.7 (4) |
C9—C8—H8B | 108.6 | C32—C23—C22 | 118.5 (4) |
C7—C8—H8B | 108.6 | C25—C24—C23 | 121.0 (4) |
H8A—C8—H8B | 107.6 | C25—C24—H24 | 119.5 |
C10—C9—C8 | 112.8 (3) | C23—C24—H24 | 119.5 |
C10—C9—C14 | 109.2 (4) | C24—C25—C26 | 120.5 (4) |
C8—C9—C14 | 111.2 (4) | C24—C25—H25 | 119.7 |
C10—C9—H9 | 107.8 | C26—C25—H25 | 119.7 |
C8—C9—H9 | 107.8 | C25—C26—C27 | 120.6 (4) |
C14—C9—H9 | 107.8 | C25—C26—H26 | 119.7 |
C9—C10—C11 | 112.0 (3) | C27—C26—H26 | 119.7 |
C9—C10—H10A | 109.2 | C26—C27—C32 | 119.3 (4) |
C11—C10—H10A | 109.2 | C26—C27—C28 | 122.2 (4) |
C9—C10—H10B | 109.2 | C32—C27—C28 | 118.5 (4) |
C11—C10—H10B | 109.2 | C29—C28—C27 | 121.6 (4) |
H10A—C10—H10B | 107.9 | C29—C28—H28 | 119.2 |
C10—C11—C12 | 113.4 (4) | C27—C28—H28 | 119.2 |
C10—C11—H11A | 108.9 | C28—C29—C30 | 121.8 (4) |
C12—C11—H11A | 108.9 | C28—C29—H29 | 119.1 |
C10—C11—H11B | 108.9 | C30—C29—H29 | 119.1 |
C12—C11—H11B | 108.9 | C17—C30—C31 | 119.0 (4) |
H11A—C11—H11B | 107.7 | C17—C30—C29 | 123.2 (4) |
C15—C12—C13 | 112.7 (4) | C31—C30—C29 | 117.9 (4) |
C15—C12—C11 | 110.6 (4) | C20—C31—C30 | 120.3 (4) |
C13—C12—C11 | 109.6 (4) | C20—C31—C32 | 119.5 (4) |
C15—C12—H12 | 107.9 | C30—C31—C32 | 120.2 (4) |
C13—C12—H12 | 107.9 | C27—C32—C23 | 119.6 (4) |
C11—C12—H12 | 107.9 | C27—C32—C31 | 120.0 (4) |
C14—C13—C12 | 112.0 (3) | C23—C32—C31 | 120.4 (4) |
C14—C13—H13A | 109.2 | N1—C33—H33A | 109.5 |
C12—C13—H13A | 109.2 | N1—C33—H33B | 109.5 |
C14—C13—H13B | 109.2 | H33A—C33—H33B | 109.5 |
C12—C13—H13B | 109.2 | N1—C33—H33C | 109.5 |
H13A—C13—H13B | 107.9 | H33A—C33—H33C | 109.5 |
C13—C14—C9 | 112.3 (4) | H33B—C33—H33C | 109.5 |
C13—C14—H14A | 109.1 | N1—C34—H34A | 109.5 |
C9—C14—H14A | 109.1 | N1—C34—H34B | 109.5 |
C13—C14—H14B | 109.1 | H34A—C34—H34B | 109.5 |
C9—C14—H14B | 109.1 | N1—C34—H34C | 109.5 |
H14A—C14—H14B | 107.9 | H34A—C34—H34C | 109.5 |
C12—C15—C16 | 115.2 (4) | H34B—C34—H34C | 109.5 |
C12—C15—H15A | 108.5 | C1—N1—C33 | 118.7 (4) |
C16—C15—H15A | 108.5 | C1—N1—C34 | 118.8 (4) |
C12—C15—H15B | 108.5 | C33—N1—C34 | 115.0 (4) |
C16—C15—H15B | 108.5 | ||
N1—C1—C2—C3 | −176.5 (4) | C32—C23—C24—C25 | 0.9 (7) |
C6—C1—C2—C3 | 1.2 (7) | C22—C23—C24—C25 | −179.0 (4) |
C1—C2—C3—C4 | −0.2 (7) | C23—C24—C25—C26 | −0.6 (7) |
C2—C3—C4—C5 | −0.8 (7) | C24—C25—C26—C27 | −0.9 (7) |
C2—C3—C4—C7 | 178.4 (4) | C25—C26—C27—C32 | 1.9 (6) |
C3—C4—C5—C6 | 1.0 (7) | C25—C26—C27—C28 | −177.8 (4) |
C7—C4—C5—C6 | −178.3 (4) | C26—C27—C28—C29 | −179.5 (4) |
C4—C5—C6—C1 | 0.0 (7) | C32—C27—C28—C29 | 0.8 (7) |
C2—C1—C6—C5 | −1.1 (7) | C27—C28—C29—C30 | 0.8 (7) |
N1—C1—C6—C5 | 176.7 (4) | C18—C17—C30—C31 | −1.9 (6) |
C3—C4—C7—C8 | −101.6 (5) | C16—C17—C30—C31 | 178.9 (4) |
C5—C4—C7—C8 | 77.7 (6) | C18—C17—C30—C29 | 178.2 (4) |
C4—C7—C8—C9 | −178.9 (4) | C16—C17—C30—C29 | −1.0 (6) |
C7—C8—C9—C10 | −66.3 (5) | C28—C29—C30—C17 | 177.4 (4) |
C7—C8—C9—C14 | 170.6 (4) | C28—C29—C30—C31 | −2.5 (6) |
C8—C9—C10—C11 | −178.8 (4) | C19—C20—C31—C30 | −0.6 (6) |
C14—C9—C10—C11 | −54.7 (5) | C21—C20—C31—C30 | −179.3 (4) |
C9—C10—C11—C12 | 55.3 (5) | C19—C20—C31—C32 | 178.8 (4) |
C10—C11—C12—C15 | −178.0 (4) | C21—C20—C31—C32 | 0.0 (6) |
C10—C11—C12—C13 | −53.2 (5) | C17—C30—C31—C20 | 1.9 (6) |
C15—C12—C13—C14 | 177.1 (4) | C29—C30—C31—C20 | −178.2 (4) |
C11—C12—C13—C14 | 53.5 (5) | C17—C30—C31—C32 | −177.4 (4) |
C12—C13—C14—C9 | −56.7 (5) | C29—C30—C31—C32 | 2.5 (6) |
C10—C9—C14—C13 | 55.9 (5) | C26—C27—C32—C23 | −1.6 (6) |
C8—C9—C14—C13 | −179.0 (4) | C28—C27—C32—C23 | 178.2 (4) |
C13—C12—C15—C16 | 63.9 (5) | C26—C27—C32—C31 | 179.6 (4) |
C11—C12—C15—C16 | −173.0 (4) | C28—C27—C32—C31 | −0.7 (6) |
C12—C15—C16—C17 | 179.5 (4) | C24—C23—C32—C27 | 0.2 (6) |
C15—C16—C17—C18 | −90.4 (5) | C22—C23—C32—C27 | −179.9 (4) |
C15—C16—C17—C30 | 88.8 (5) | C24—C23—C32—C31 | 179.0 (4) |
C30—C17—C18—C19 | 0.6 (7) | C22—C23—C32—C31 | −1.0 (6) |
C16—C17—C18—C19 | 179.8 (4) | C20—C31—C32—C27 | 179.7 (4) |
C17—C18—C19—C20 | 0.8 (7) | C30—C31—C32—C27 | −1.0 (6) |
C18—C19—C20—C31 | −0.8 (6) | C20—C31—C32—C23 | 0.8 (6) |
C18—C19—C20—C21 | 177.9 (4) | C30—C31—C32—C23 | −179.8 (4) |
C19—C20—C21—C22 | −179.4 (4) | C2—C1—N1—C33 | −1.6 (7) |
C31—C20—C21—C22 | −0.7 (7) | C6—C1—N1—C33 | −179.2 (4) |
C20—C21—C22—C23 | 0.5 (7) | C2—C1—N1—C34 | −149.8 (4) |
C21—C22—C23—C24 | −179.7 (4) | C6—C1—N1—C34 | 32.5 (6) |
C21—C22—C23—C32 | 0.4 (6) |
Cg1 is the centroid of the C20–C23/C32/C31 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C26—H26···Cg1i | 0.95 | 2.60 | 3.4927 (15) | 156 |
Symmetry code: (i) −x+3/2, y+1/2, −z+1/2. |
Cg1 is the centroid of the C20–C23/C32/C31 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C26—H26···Cg1i | 0.95 | 2.603 | 3.4927 (15) | 156 |
Symmetry code: (i) −x+3/2, y+1/2, −z+1/2. |
Acknowledgements
ST thanks DFG, SFB 755 and SFB 1073 for financial support. STV thanks G. and L. Busse for technical help, and the synthesis group at Max Planck Institute for Biophysical Chemistry, Göttingen.
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