organic compounds
2,2-Bis[3,5-bis(dimethylamino)phenyl]-1,1,1,3,3,3-hexamethyltrisilane
aInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
*Correspondence e-mail: mizu@boc.kuicr.kyoto-u.ac.jp
The title compound, C26H48N4Si3, was synthesized by the reaction of 2,2-dichlorotrisilane with 3,5-bis(dimethylamino)phenyllithium. In the molecule, the dihedral angle between the benzene rings is 57.57 (7)° and the Si—Si—Si bond angle is 110.08 (2)°. In the crystal, molecules are linked via an SiC–H⋯π(aryl) interaction, forming a chain along the c-axis direction.
Keywords: crystal structure; trisilane; 3,5-bis(dimethylamino)phenyl.
CCDC reference: 2033547
Structure description
Trisilane derivatives are often used as a precursor for divalent silicon compounds (silylenes) (Gaspar & West, 1998). Photoirradiation of a trisilane results in the elimination of a disilane derived from the silyl moieties of the both ends and the generation of a silylene from the central one. Silylenes are highly reactive and known to give the dimer, silicon–silicon double–bond compound (disilene) (West et al., 1981), or higher oligomers without trapping reagent. Herein, we describe the synthesis and structural characterization of a novel trisilane bearing two 3,5-bis(dimethylamino)phenyl substituents on the central silicon atom.
In the molecule (Fig. 1), the Si—Si bond lengths are 2.3488 (5) and 2.3465 (5) Å, which are close to the shortest bond lengths among those of the reported 2,2-diaryl-1,1,1,3,3,3-hexamethyltrisilanes (2.347–2.397 Å; Archibald et al., 1993; Lange et al., 1991; Millevolte et al., 1997; Pusztai et al., 2013). The sums of the angles around the nitrogen atoms (N1, N2, N3 and N4) are 353.8, 358.9, 344.6 and 350.5°, respectively, indicating that the geometries around the nitrogen atoms on one aryl substituent with N3/N4 are more pyramidalized than those on the other with N1/N2. In the crystal, molecules are linked by an SiC–H⋯π(aryl) interaction (Fig. 2 and Table 1).
Synthesis and crystallization
To a solution of 1-bromo-3,5-bis(dimethylamino)benzene (194.6 mg, 0.80 mmol) in Et2O (6.0 ml) was added t-BuLi (1.64 M in pentane, 1.07 ml, 1.76 mmol) at −78 °C, and the solution was stirred for 1 h at the same temperature. Then, 2,2-dichloro-1,1,1,3,3,3-hexamethyltrisilane (104.2 mg, 0.42 mmol) in Et2O (4 ml) was added dropwise, and the reaction mixture was gradually warmed up to room temperature over 14 h. After quenching with a saturated aqueous solution of NH4Cl (10 ml), the water phase was extracted with Et2O (10 ml × 2). The combined organic phase was dried over Na2SO4 and evaporated in vacuo. Finally, recrystallization from the mixed solvents of hexane/dichloromethane gave the title compound (101.3 mg, 0.21 mmol, 50%) as colorless crystals. 1H NMR (300 Hz, CDCl3) δ 6.40 (d, J = 1.2 Hz, 4H), 6.11 (t, J = 1.2 Hz, 2H), 2.90 (s, 24H), 0.19 (s, 18H); 13C NMR (75.5 Hz, CDCl3) δ 151.1 (CH), 136.7 (C), 110.9 (CH), 98.6 (C), 41.1 (NCH3), −0.012 (SiCH3).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 2033547
https://doi.org/10.1107/S2414314620012997/is4044sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620012997/is4044Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314620012997/is4044Isup3.cml
Data collection: CrystalClear (Rigaku, 1999); cell
CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: Yadokari-XG (Kabuto et al., 2009) Mercury (Macrae et al., 2020); software used to prepare material for publication: Yadokari-XG.C26H48N4Si3 | F(000) = 1096 |
Mr = 500.95 | Dx = 1.108 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.6543 (3) Å | Cell parameters from 24488 reflections |
b = 8.3650 (1) Å | θ = 1.8–30.3° |
c = 17.5215 (3) Å | µ = 0.18 mm−1 |
β = 97.371 (2)° | T = 103 K |
V = 3002.23 (8) Å3 | Prism, colorless |
Z = 4 | 0.20 × 0.20 × 0.20 mm |
Rigaku Saturn diffractometer | 5581 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 4877 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 25.5°, θmin = 2.0° |
ω scans | h = −25→25 |
Absorption correction: multi-scan (CrysAlisPro (Rigaku OD, 2018) | k = −10→10 |
Tmin = 0.977, Tmax = 1.000 | l = −21→21 |
33409 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0427P)2 + 1.4907P] where P = (Fo2 + 2Fc2)/3 |
5581 reflections | (Δ/σ)max = 0.001 |
312 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.30425 (2) | 0.26359 (5) | 0.40578 (2) | 0.01776 (11) | |
Si2 | 0.25081 (2) | 0.23923 (4) | 0.27966 (2) | 0.01378 (10) | |
Si3 | 0.20713 (2) | −0.01864 (5) | 0.26001 (2) | 0.01934 (11) | |
C1 | 0.32187 (9) | 0.4774 (2) | 0.43281 (10) | 0.0326 (4) | |
H1 | 0.342782 | 0.529781 | 0.392332 | 0.049* | |
H2 | 0.351105 | 0.481717 | 0.481460 | 0.049* | |
H3 | 0.280943 | 0.532430 | 0.438785 | 0.049* | |
C2 | 0.25745 (8) | 0.1727 (2) | 0.47983 (9) | 0.0338 (4) | |
H4 | 0.282593 | 0.183946 | 0.530913 | 0.051* | |
H5 | 0.249861 | 0.059114 | 0.468290 | 0.051* | |
H6 | 0.215449 | 0.227615 | 0.478973 | 0.051* | |
C3 | 0.38414 (7) | 0.1570 (2) | 0.40627 (9) | 0.0278 (4) | |
H7 | 0.409142 | 0.164627 | 0.457597 | 0.042* | |
H8 | 0.408976 | 0.206399 | 0.368441 | 0.042* | |
H9 | 0.376058 | 0.044327 | 0.393031 | 0.042* | |
C4 | 0.17831 (7) | 0.37787 (16) | 0.26124 (8) | 0.0157 (3) | |
C5 | 0.15255 (7) | 0.42232 (16) | 0.18664 (8) | 0.0166 (3) | |
H10 | 0.174097 | 0.391031 | 0.144264 | 0.020* | |
C6 | 0.09489 (7) | 0.51314 (16) | 0.17395 (8) | 0.0164 (3) | |
C7 | 0.06416 (7) | 0.55949 (17) | 0.23737 (8) | 0.0175 (3) | |
H11 | 0.025674 | 0.622675 | 0.229263 | 0.021* | |
C8 | 0.08913 (7) | 0.51440 (17) | 0.31244 (8) | 0.0189 (3) | |
C9 | 0.14687 (7) | 0.42416 (17) | 0.32341 (8) | 0.0181 (3) | |
H12 | 0.164780 | 0.394190 | 0.374040 | 0.022* | |
N1 | 0.06746 (6) | 0.55413 (15) | 0.09955 (7) | 0.0211 (3) | |
C10 | 0.10803 (8) | 0.5412 (2) | 0.03772 (8) | 0.0247 (3) | |
H13 | 0.120610 | 0.429339 | 0.031923 | 0.037* | |
H14 | 0.147335 | 0.606661 | 0.050088 | 0.037* | |
H15 | 0.083461 | 0.578969 | −0.010478 | 0.037* | |
C11 | 0.01575 (7) | 0.6719 (2) | 0.08958 (9) | 0.0252 (3) | |
H16 | 0.032046 | 0.773793 | 0.112060 | 0.038* | |
H17 | −0.020940 | 0.635214 | 0.115365 | 0.038* | |
H18 | 0.001115 | 0.686560 | 0.034579 | 0.038* | |
N2 | 0.05745 (7) | 0.55862 (18) | 0.37463 (7) | 0.0305 (3) | |
C12 | 0.00044 (7) | 0.65851 (19) | 0.36342 (9) | 0.0235 (3) | |
H19 | −0.032513 | 0.609127 | 0.325453 | 0.035* | |
H20 | 0.012242 | 0.763704 | 0.344817 | 0.035* | |
H21 | −0.017287 | 0.670837 | 0.412357 | 0.035* | |
C13 | 0.08889 (8) | 0.5299 (2) | 0.45176 (8) | 0.0253 (3) | |
H22 | 0.131207 | 0.584552 | 0.459169 | 0.038* | |
H23 | 0.095511 | 0.414821 | 0.459639 | 0.038* | |
H24 | 0.061305 | 0.570997 | 0.488874 | 0.038* | |
C14 | 0.31425 (7) | 0.28489 (17) | 0.21410 (8) | 0.0151 (3) | |
C15 | 0.35872 (7) | 0.16651 (17) | 0.19910 (8) | 0.0170 (3) | |
H25 | 0.353827 | 0.060958 | 0.217532 | 0.020* | |
C16 | 0.41035 (7) | 0.20138 (17) | 0.15730 (8) | 0.0169 (3) | |
C17 | 0.41619 (7) | 0.35685 (17) | 0.12925 (8) | 0.0167 (3) | |
H26 | 0.450754 | 0.381126 | 0.100236 | 0.020* | |
C18 | 0.37191 (7) | 0.47750 (17) | 0.14323 (8) | 0.0162 (3) | |
C19 | 0.32122 (7) | 0.43937 (17) | 0.18636 (8) | 0.0160 (3) | |
H27 | 0.291203 | 0.520064 | 0.196795 | 0.019* | |
N3 | 0.45454 (6) | 0.07908 (15) | 0.14290 (7) | 0.0215 (3) | |
N4 | 0.37992 (6) | 0.63483 (15) | 0.11844 (7) | 0.0219 (3) | |
C20 | 0.47693 (9) | −0.0230 (2) | 0.20856 (10) | 0.0358 (4) | |
H28 | 0.439219 | −0.073086 | 0.227626 | 0.054* | |
H29 | 0.500814 | 0.041608 | 0.249542 | 0.054* | |
H30 | 0.505801 | −0.106202 | 0.192602 | 0.054* | |
C21 | 0.50722 (8) | 0.1230 (2) | 0.09949 (11) | 0.0366 (4) | |
H31 | 0.536208 | 0.199436 | 0.129305 | 0.055* | |
H32 | 0.488974 | 0.171889 | 0.050608 | 0.055* | |
H33 | 0.532024 | 0.027143 | 0.089272 | 0.055* | |
C22 | 0.43019 (8) | 0.6685 (2) | 0.07004 (10) | 0.0313 (4) | |
H34 | 0.419445 | 0.614702 | 0.020332 | 0.047* | |
H35 | 0.472326 | 0.629362 | 0.095198 | 0.047* | |
H36 | 0.432763 | 0.784068 | 0.061867 | 0.047* | |
C23 | 0.32265 (9) | 0.7339 (2) | 0.10043 (12) | 0.0361 (4) | |
H37 | 0.294343 | 0.722489 | 0.140908 | 0.054* | |
H38 | 0.298835 | 0.700536 | 0.051007 | 0.054* | |
H39 | 0.335941 | 0.845920 | 0.097152 | 0.054* | |
C24 | 0.18019 (8) | −0.0508 (2) | 0.15471 (10) | 0.0310 (4) | |
H40 | 0.146709 | 0.028127 | 0.136380 | 0.047* | |
H41 | 0.162104 | −0.158697 | 0.146642 | 0.047* | |
H42 | 0.217687 | −0.038664 | 0.126137 | 0.047* | |
C25 | 0.13399 (8) | −0.0289 (2) | 0.31312 (10) | 0.0332 (4) | |
H43 | 0.148027 | −0.019567 | 0.368531 | 0.050* | |
H44 | 0.111634 | −0.131258 | 0.302292 | 0.050* | |
H45 | 0.104091 | 0.058891 | 0.296305 | 0.050* | |
C26 | 0.26437 (9) | −0.18132 (19) | 0.29957 (11) | 0.0340 (4) | |
H46 | 0.242957 | −0.285333 | 0.290345 | 0.051* | |
H47 | 0.276191 | −0.165481 | 0.355026 | 0.051* | |
H48 | 0.303862 | −0.178120 | 0.274009 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.0165 (2) | 0.0216 (2) | 0.0150 (2) | −0.00027 (16) | 0.00150 (15) | 0.00142 (15) |
Si2 | 0.01451 (19) | 0.01279 (19) | 0.0143 (2) | 0.00137 (14) | 0.00278 (15) | 0.00109 (14) |
Si3 | 0.0186 (2) | 0.0153 (2) | 0.0246 (2) | −0.00180 (15) | 0.00459 (16) | −0.00247 (16) |
C1 | 0.0323 (9) | 0.0292 (9) | 0.0344 (9) | −0.0007 (7) | −0.0026 (7) | −0.0108 (7) |
C2 | 0.0262 (9) | 0.0523 (11) | 0.0230 (8) | 0.0001 (8) | 0.0038 (7) | 0.0145 (8) |
C3 | 0.0216 (8) | 0.0364 (9) | 0.0241 (8) | 0.0064 (7) | −0.0022 (6) | 0.0008 (7) |
C4 | 0.0161 (7) | 0.0121 (7) | 0.0191 (7) | −0.0007 (5) | 0.0024 (5) | 0.0003 (5) |
C5 | 0.0185 (7) | 0.0161 (7) | 0.0161 (7) | 0.0002 (6) | 0.0055 (5) | −0.0011 (5) |
C6 | 0.0174 (7) | 0.0141 (7) | 0.0174 (7) | −0.0013 (5) | 0.0017 (5) | 0.0016 (5) |
C7 | 0.0161 (7) | 0.0160 (7) | 0.0205 (7) | 0.0026 (5) | 0.0031 (6) | 0.0010 (6) |
C8 | 0.0213 (7) | 0.0179 (7) | 0.0184 (7) | 0.0018 (6) | 0.0058 (6) | −0.0005 (6) |
C9 | 0.0215 (7) | 0.0187 (7) | 0.0142 (7) | 0.0025 (6) | 0.0022 (6) | 0.0020 (6) |
N1 | 0.0211 (6) | 0.0263 (7) | 0.0160 (6) | 0.0063 (5) | 0.0023 (5) | 0.0031 (5) |
C10 | 0.0269 (8) | 0.0313 (9) | 0.0160 (7) | 0.0049 (7) | 0.0036 (6) | 0.0021 (6) |
C11 | 0.0208 (8) | 0.0324 (9) | 0.0221 (8) | 0.0058 (7) | 0.0017 (6) | 0.0082 (7) |
N2 | 0.0318 (8) | 0.0440 (9) | 0.0167 (7) | 0.0209 (7) | 0.0063 (6) | 0.0012 (6) |
C12 | 0.0197 (7) | 0.0287 (8) | 0.0234 (8) | 0.0037 (6) | 0.0076 (6) | −0.0035 (6) |
C13 | 0.0286 (8) | 0.0308 (9) | 0.0174 (7) | 0.0046 (7) | 0.0065 (6) | −0.0015 (6) |
C14 | 0.0162 (7) | 0.0170 (7) | 0.0120 (6) | −0.0003 (5) | 0.0009 (5) | −0.0009 (5) |
C15 | 0.0205 (7) | 0.0139 (7) | 0.0168 (7) | 0.0003 (6) | 0.0029 (6) | 0.0012 (5) |
C16 | 0.0165 (7) | 0.0186 (7) | 0.0151 (7) | 0.0019 (6) | −0.0001 (5) | −0.0027 (6) |
C17 | 0.0147 (7) | 0.0210 (7) | 0.0145 (7) | −0.0017 (6) | 0.0026 (5) | −0.0009 (6) |
C18 | 0.0179 (7) | 0.0160 (7) | 0.0143 (7) | −0.0020 (6) | 0.0000 (5) | −0.0009 (5) |
C19 | 0.0167 (7) | 0.0150 (7) | 0.0162 (7) | 0.0017 (5) | 0.0020 (5) | −0.0013 (5) |
N3 | 0.0209 (6) | 0.0216 (6) | 0.0235 (7) | 0.0063 (5) | 0.0081 (5) | 0.0010 (5) |
N4 | 0.0241 (7) | 0.0167 (6) | 0.0263 (7) | −0.0010 (5) | 0.0091 (5) | 0.0041 (5) |
C20 | 0.0400 (10) | 0.0374 (10) | 0.0298 (9) | 0.0231 (8) | 0.0042 (7) | 0.0039 (8) |
C21 | 0.0317 (9) | 0.0311 (9) | 0.0515 (11) | 0.0105 (8) | 0.0228 (8) | 0.0035 (8) |
C22 | 0.0336 (9) | 0.0212 (8) | 0.0424 (10) | −0.0047 (7) | 0.0176 (8) | 0.0052 (7) |
C23 | 0.0356 (10) | 0.0219 (8) | 0.0543 (12) | 0.0070 (7) | 0.0190 (9) | 0.0157 (8) |
C24 | 0.0274 (9) | 0.0335 (9) | 0.0315 (9) | 0.0003 (7) | 0.0012 (7) | −0.0130 (7) |
C25 | 0.0278 (9) | 0.0335 (9) | 0.0405 (10) | −0.0119 (7) | 0.0129 (7) | −0.0069 (8) |
C26 | 0.0376 (10) | 0.0169 (8) | 0.0474 (11) | 0.0013 (7) | 0.0056 (8) | 0.0039 (7) |
Si1—C1 | 1.8737 (17) | C12—H20 | 0.9800 |
Si1—C3 | 1.8744 (16) | C12—H21 | 0.9800 |
Si1—C2 | 1.8755 (16) | C13—H22 | 0.9800 |
Si1—Si2 | 2.3488 (5) | C13—H23 | 0.9800 |
Si2—C4 | 1.8887 (14) | C13—H24 | 0.9800 |
Si2—C14 | 1.8890 (14) | C14—C19 | 1.395 (2) |
Si2—Si3 | 2.3465 (5) | C14—C15 | 1.398 (2) |
Si3—C25 | 1.8751 (17) | C15—C16 | 1.400 (2) |
Si3—C26 | 1.8762 (17) | C15—H25 | 0.9500 |
Si3—C24 | 1.8767 (17) | C16—C17 | 1.401 (2) |
C1—H1 | 0.9800 | C16—N3 | 1.4151 (18) |
C1—H2 | 0.9800 | C17—C18 | 1.404 (2) |
C1—H3 | 0.9800 | C17—H26 | 0.9500 |
C2—H4 | 0.9800 | C18—N4 | 1.4023 (18) |
C2—H5 | 0.9800 | C18—C19 | 1.404 (2) |
C2—H6 | 0.9800 | C19—H27 | 0.9500 |
C3—H7 | 0.9800 | N3—C21 | 1.452 (2) |
C3—H8 | 0.9800 | N3—C20 | 1.460 (2) |
C3—H9 | 0.9800 | N4—C23 | 1.446 (2) |
C4—C9 | 1.393 (2) | N4—C22 | 1.4499 (19) |
C4—C5 | 1.3971 (19) | C20—H28 | 0.9800 |
C5—C6 | 1.406 (2) | C20—H29 | 0.9800 |
C5—H10 | 0.9500 | C20—H30 | 0.9800 |
C6—N1 | 1.3959 (18) | C21—H31 | 0.9800 |
C6—C7 | 1.403 (2) | C21—H32 | 0.9800 |
C7—C8 | 1.402 (2) | C21—H33 | 0.9800 |
C7—H11 | 0.9500 | C22—H34 | 0.9800 |
C8—N2 | 1.3911 (19) | C22—H35 | 0.9800 |
C8—C9 | 1.404 (2) | C22—H36 | 0.9800 |
C9—H12 | 0.9500 | C23—H37 | 0.9800 |
N1—C11 | 1.4473 (19) | C23—H38 | 0.9800 |
N1—C10 | 1.4562 (19) | C23—H39 | 0.9800 |
C10—H13 | 0.9800 | C24—H40 | 0.9800 |
C10—H14 | 0.9800 | C24—H41 | 0.9800 |
C10—H15 | 0.9800 | C24—H42 | 0.9800 |
C11—H16 | 0.9800 | C25—H43 | 0.9800 |
C11—H17 | 0.9800 | C25—H44 | 0.9800 |
C11—H18 | 0.9800 | C25—H45 | 0.9800 |
N2—C12 | 1.4365 (19) | C26—H46 | 0.9800 |
N2—C13 | 1.4423 (19) | C26—H47 | 0.9800 |
C12—H19 | 0.9800 | C26—H48 | 0.9800 |
C1—Si1—C3 | 108.08 (8) | N2—C12—H21 | 109.5 |
C1—Si1—C2 | 108.21 (9) | H19—C12—H21 | 109.5 |
C3—Si1—C2 | 109.61 (8) | H20—C12—H21 | 109.5 |
C1—Si1—Si2 | 111.92 (6) | N2—C13—H22 | 109.5 |
C3—Si1—Si2 | 105.68 (5) | N2—C13—H23 | 109.5 |
C2—Si1—Si2 | 113.20 (6) | H22—C13—H23 | 109.5 |
C4—Si2—C14 | 111.62 (6) | N2—C13—H24 | 109.5 |
C4—Si2—Si3 | 104.95 (4) | H22—C13—H24 | 109.5 |
C14—Si2—Si3 | 112.35 (5) | H23—C13—H24 | 109.5 |
C4—Si2—Si1 | 111.97 (5) | C19—C14—C15 | 119.40 (13) |
C14—Si2—Si1 | 106.00 (4) | C19—C14—Si2 | 120.66 (10) |
Si3—Si2—Si1 | 110.08 (2) | C15—C14—Si2 | 119.65 (10) |
C25—Si3—C26 | 107.05 (8) | C14—C15—C16 | 120.91 (13) |
C25—Si3—C24 | 108.98 (8) | C14—C15—H25 | 119.5 |
C26—Si3—C24 | 110.64 (8) | C16—C15—H25 | 119.5 |
C25—Si3—Si2 | 106.75 (6) | C15—C16—C17 | 118.86 (13) |
C26—Si3—Si2 | 113.60 (6) | C15—C16—N3 | 119.66 (13) |
C24—Si3—Si2 | 109.63 (6) | C17—C16—N3 | 121.47 (13) |
Si1—C1—H1 | 109.5 | C16—C17—C18 | 121.24 (13) |
Si1—C1—H2 | 109.5 | C16—C17—H26 | 119.4 |
H1—C1—H2 | 109.5 | C18—C17—H26 | 119.4 |
Si1—C1—H3 | 109.5 | N4—C18—C19 | 120.37 (13) |
H1—C1—H3 | 109.5 | N4—C18—C17 | 121.00 (13) |
H2—C1—H3 | 109.5 | C19—C18—C17 | 118.54 (13) |
Si1—C2—H4 | 109.5 | C14—C19—C18 | 121.03 (13) |
Si1—C2—H5 | 109.5 | C14—C19—H27 | 119.5 |
H4—C2—H5 | 109.5 | C18—C19—H27 | 119.5 |
Si1—C2—H6 | 109.5 | C16—N3—C21 | 117.02 (12) |
H4—C2—H6 | 109.5 | C16—N3—C20 | 115.40 (12) |
H5—C2—H6 | 109.5 | C21—N3—C20 | 112.20 (13) |
Si1—C3—H7 | 109.5 | C18—N4—C23 | 118.68 (12) |
Si1—C3—H8 | 109.5 | C18—N4—C22 | 119.02 (12) |
H7—C3—H8 | 109.5 | C23—N4—C22 | 112.84 (13) |
Si1—C3—H9 | 109.5 | N3—C20—H28 | 109.5 |
H7—C3—H9 | 109.5 | N3—C20—H29 | 109.5 |
H8—C3—H9 | 109.5 | H28—C20—H29 | 109.5 |
C9—C4—C5 | 119.86 (13) | N3—C20—H30 | 109.5 |
C9—C4—Si2 | 118.43 (10) | H28—C20—H30 | 109.5 |
C5—C4—Si2 | 121.45 (11) | H29—C20—H30 | 109.5 |
C4—C5—C6 | 120.33 (13) | N3—C21—H31 | 109.5 |
C4—C5—H10 | 119.8 | N3—C21—H32 | 109.5 |
C6—C5—H10 | 119.8 | H31—C21—H32 | 109.5 |
N1—C6—C7 | 120.08 (13) | N3—C21—H33 | 109.5 |
N1—C6—C5 | 120.96 (13) | H31—C21—H33 | 109.5 |
C7—C6—C5 | 118.95 (13) | H32—C21—H33 | 109.5 |
C8—C7—C6 | 121.30 (13) | N4—C22—H34 | 109.5 |
C8—C7—H11 | 119.4 | N4—C22—H35 | 109.5 |
C6—C7—H11 | 119.4 | H34—C22—H35 | 109.5 |
N2—C8—C7 | 120.67 (13) | N4—C22—H36 | 109.5 |
N2—C8—C9 | 120.83 (13) | H34—C22—H36 | 109.5 |
C7—C8—C9 | 118.50 (13) | H35—C22—H36 | 109.5 |
C4—C9—C8 | 121.05 (13) | N4—C23—H37 | 109.5 |
C4—C9—H12 | 119.5 | N4—C23—H38 | 109.5 |
C8—C9—H12 | 119.5 | H37—C23—H38 | 109.5 |
C6—N1—C11 | 118.99 (12) | N4—C23—H39 | 109.5 |
C6—N1—C10 | 118.25 (12) | H37—C23—H39 | 109.5 |
C11—N1—C10 | 116.55 (12) | H38—C23—H39 | 109.5 |
N1—C10—H13 | 109.5 | Si3—C24—H40 | 109.5 |
N1—C10—H14 | 109.5 | Si3—C24—H41 | 109.5 |
H13—C10—H14 | 109.5 | H40—C24—H41 | 109.5 |
N1—C10—H15 | 109.5 | Si3—C24—H42 | 109.5 |
H13—C10—H15 | 109.5 | H40—C24—H42 | 109.5 |
H14—C10—H15 | 109.5 | H41—C24—H42 | 109.5 |
N1—C11—H16 | 109.5 | Si3—C25—H43 | 109.5 |
N1—C11—H17 | 109.5 | Si3—C25—H44 | 109.5 |
H16—C11—H17 | 109.5 | H43—C25—H44 | 109.5 |
N1—C11—H18 | 109.5 | Si3—C25—H45 | 109.5 |
H16—C11—H18 | 109.5 | H43—C25—H45 | 109.5 |
H17—C11—H18 | 109.5 | H44—C25—H45 | 109.5 |
C8—N2—C12 | 120.48 (12) | Si3—C26—H46 | 109.5 |
C8—N2—C13 | 119.29 (12) | Si3—C26—H47 | 109.5 |
C12—N2—C13 | 119.17 (12) | H46—C26—H47 | 109.5 |
N2—C12—H19 | 109.5 | Si3—C26—H48 | 109.5 |
N2—C12—H20 | 109.5 | H46—C26—H48 | 109.5 |
H19—C12—H20 | 109.5 | H47—C26—H48 | 109.5 |
C14—Si2—C4—C9 | −145.45 (11) | C4—Si2—C14—C19 | 28.69 (13) |
Si3—Si2—C4—C9 | 92.60 (11) | Si3—Si2—C14—C19 | 146.27 (10) |
Si1—Si2—C4—C9 | −26.80 (12) | Si1—Si2—C14—C19 | −93.46 (11) |
C14—Si2—C4—C5 | 40.35 (13) | C4—Si2—C14—C15 | −157.41 (11) |
Si3—Si2—C4—C5 | −81.60 (12) | Si3—Si2—C14—C15 | −39.83 (12) |
Si1—Si2—C4—C5 | 159.00 (10) | Si1—Si2—C14—C15 | 80.44 (11) |
C9—C4—C5—C6 | −0.2 (2) | C19—C14—C15—C16 | 0.6 (2) |
Si2—C4—C5—C6 | 173.90 (10) | Si2—C14—C15—C16 | −173.39 (10) |
C4—C5—C6—N1 | −177.96 (13) | C14—C15—C16—C17 | −1.2 (2) |
C4—C5—C6—C7 | 0.6 (2) | C14—C15—C16—N3 | −179.91 (12) |
N1—C6—C7—C8 | 177.34 (13) | C15—C16—C17—C18 | 0.8 (2) |
C5—C6—C7—C8 | −1.3 (2) | N3—C16—C17—C18 | 179.53 (12) |
C6—C7—C8—N2 | −178.75 (14) | C16—C17—C18—N4 | 176.69 (13) |
C6—C7—C8—C9 | 1.4 (2) | C16—C17—C18—C19 | 0.1 (2) |
C5—C4—C9—C8 | 0.4 (2) | C15—C14—C19—C18 | 0.4 (2) |
Si2—C4—C9—C8 | −173.87 (11) | Si2—C14—C19—C18 | 174.32 (10) |
N2—C8—C9—C4 | 179.17 (14) | N4—C18—C19—C14 | −177.34 (13) |
C7—C8—C9—C4 | −1.0 (2) | C17—C18—C19—C14 | −0.7 (2) |
C7—C6—N1—C11 | 13.1 (2) | C15—C16—N3—C21 | −179.75 (14) |
C5—C6—N1—C11 | −168.37 (13) | C17—C16—N3—C21 | 1.6 (2) |
C7—C6—N1—C10 | 164.45 (13) | C15—C16—N3—C20 | −44.38 (19) |
C5—C6—N1—C10 | −17.0 (2) | C17—C16—N3—C20 | 136.94 (15) |
C7—C8—N2—C12 | −3.3 (2) | C19—C18—N4—C23 | −32.2 (2) |
C9—C8—N2—C12 | 176.48 (14) | C17—C18—N4—C23 | 151.30 (15) |
C7—C8—N2—C13 | −171.42 (14) | C19—C18—N4—C22 | −176.24 (13) |
C9—C8—N2—C13 | 8.4 (2) | C17—C18—N4—C22 | 7.3 (2) |
Cg is the centroid of the C14–C19 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H4···Cgi | 0.98 | 2.81 | 3.7869 (17) | 172 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Funding information
This work was supported by KAKENHI (JP16H04110, JP18H01963, JP19H05528, JP19H05635, JP24109013, and JP25288021) and the Integrated Research Consortium on Chemical Science (IRCCS). KI gratefully acknowledges a Research Fellowship for Young Scientists (JP20J12946) from the Japan Society for the Promotion of Science (JSPS). This study was supported by the Joint Usage/Research Center [JURC, Institute for Chemical Research (ICR), Kyoto University] by providing access to a Bruker Avance III 600 NMR spectrometer. The authors are furthermore grateful for computation time, which was provided by the Super Computer System (ICR, Kyoto University).
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