research communications
Synthesis and structure of photodegradable 1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropyl N-butylcarbamate
aDepartment of Chemistry, Faculty of Science, Kanagawa University, Tsuchiya, Hiratsuka, Kanagawa 259-1293, Japan, and bRigaku Corporation 3-9-12 Matsubara-cho, Akishima, Tokyo 196-8666, Japan
*Correspondence e-mail: chikan01@kanagawa-u.ac.jp
The reaction of 1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropan-1-ol and butylisocyanate using dibutyltin dilaurate as a catalyst afforded 1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropyl N-butylcarbamate, C17H25N3O8, which released butylamine upon photoirradiation. Single crystals of the title compound were grown in a 1:1 mixed solution of hexane and ethyl acetate. Two nitro groups and one methoxy group are twisted out of the plane of the aromatic ring in the novel photo-protecting group. Intermolecular hydrogen bonds are observed between N-butylcarbamate moieties parallel to the a axis.
Keywords: photolabile carbamate; 2,3-dinitrobenzyl group; intermolecular hydrogen bonding; crystal structure.
CCDC reference: 2261578
1. Chemical context
Photodegradable protective groups (PPGs) are common tools in the field of organic, biochemical, and materials sciences (Cambie et al., 2016; Ellis-Davies, 2020; Hansen et al., 2015). 2-Nitrobenzyl groups are widely used as PPGs because several precursors are available, they react with various functional groups and the resulting protected compounds are soluble in common organic solvents. To increase the sensitivity of 2-nitrobenzyl-group-protected derivatives, several chemical modifications, such as the introduction of substituents at the α-position, have been performed (Kasuga et al., 2016; Zhao et al., 2012).
Herein, we report the synthesis and structure of the novel photolabile title compound 1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropyl N-butylcarbamate (1), which has an isopropyl group at the α-position and an additional nitro group at the 3-position. It was prepared from the corresponding alcohol and isocyanate using a tin catalyst based on a previously reported reaction with modifications (Stegmaier et al., 2008) and the amine was released upon photoirradiation, which indicated that the compound has high reactivity and the potential for application in various functional materials. Compound 1 exhibits a higher sensitivity to light than the corresponding compound with one nitro group at the ortho position (Kasuga et al., 2015).
2. Structural commentary
The 1 contains a single molecule in which four functional groups and a carbamate linkage site are connected to the aromatic ring. The substituents are positioned in a manner that prevents steric repulsion (Fig. 1).
ofThe aromatic ring (C1–C6) and five attached atoms (N1, N2, O5, O6, and C7) are almost planar, as indicated by the torsion angles N2—C3—C2—N1 = 4.4 (3)°, O5—C4—C5—O6 = −8.0 (3)°, and C7—C1—C2—N1 = −4.3 (3)°. However, the torsion angles involving the two nitro groups [O2—N1—C2—C1 = 56.9 (3)°, O1—N1—C2—C1 = −122.5 (2)°, O3—N2—C3—C2 = −125.9 (3)°, and O4—N2—C3—C2 = 53.9 (3)°] indicate that both NO2 groups are twisted relative to the plane of the aromatic ring. The torsion angles involving the two methoxy groups [C16—O5—C4—C3 and C17—O6—C5—C4) are −110.7 (2)° and 172.5 (2)°] indicate that one methoxy group (O5–C16) is twisted and the other (O6–C17) is located in the same plane as the aromatic ring.
In the related compound, 4,5-dimethoxy-2-nitrobenzyl acetate (shown in the scheme below), the nitro and dimethoxy groups are in the same plane as the aromatic ring and the whole molecule is flat in the absence of substituents at the α-position (Kasuga et al., 2015).
3. Supramolecular features
In the crystal, N3—H3⋯O8i hydrogen bonds link the molecules into chains parallel to the a axis (Fig. 2 and Table 1).
4. Synthesis and crystallization
The synthesis of compound 1 was based on the method reported by Stegmaier et al. (2008) with modifications. The synthesis and photocleavage is shown in the scheme below. This dinitrobenzyl protecting group photocleaved twice as fast as the corresponding 2-mononitrobenzyl group. Under an N2 atmosphere, a mixture of 1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropan-1-ol (150 mg, 0.5 mmol), n-butyl isocyanate (85 µL, 0.75 mmol), dibutyltin laurate (15 µL), and 1.5 ml of tetrahydrofuran were refluxed for 19 h. After removing the solvent, the crude solid was purified by silica gel Pale-yellow needle-shaped crystals were grown in a 1:1 mixed solution of hexane and ethyl acetate by slow evaporation. The crystals were washed with a small volume of ethyl acetate and dried in vacuo (50 mg).
Analysis calculated for C17H25N3O8: C 51.12, H 6.31, N 10.52%. Found: C 51.07, H 6.20, N 10.42%. Prominent IR bands at 1800–400 cm−1 (KBr disc): 1693m, 1557m, 1359m. Melting point 379.9–381.1 K (uncorrected). 1H NMR (CDCl3, 292.2 K) 0.90 (3H, t), 0.91 (3H, d), 1.03 (3H, d), 1.32 (2H, m), 1.45 (2H, m), 2.18 (1H, m), 3.13 (2H, m), 3.93 (6H, s), 4.76 (1H, br), 5.61 (1H, d), 6.97 (1H, s). 13C NMR (CDCl3, 293.7 K) 13.69, 17.88, 19.21, 19.86, 31.88, 33.39, 40.85, 56.71, 62.58, 76.04, 111.29, 131.17, 134.82, 140.45, 141.14, 155.28, 155.84.
5. Refinement
Crystal data, data collection and structure . The C-bound H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined using a riding model with Uiso(H) = 1.2 or 1.5Ueq(C).
details are summarized in Table 2Supporting information
CCDC reference: 2261578
https://doi.org/10.1107/S2056989023004103/ex2069sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004103/ex2069Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989023004103/ex2069Isup4.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2056989023004103/ex2069Isup4.cml
Data collection: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); cell
CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); data reduction: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); program(s) used to solve structure: ShelXT (Sheldrick, 2015aa); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).C17H25N3O8 | Dx = 1.319 Mg m−3 |
Mr = 399.40 | Melting point = 380.1–274.2 K |
Monoclinic, Ia | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9490 (4) Å | Cell parameters from 10281 reflections |
b = 19.9223 (8) Å | θ = 3.4–31.2° |
c = 10.2378 (4) Å | µ = 0.11 mm−1 |
β = 97.616 (4)° | T = 120 K |
V = 2011.30 (14) Å3 | Block, clear light yellow |
Z = 4 | 0.25 × 0.21 × 0.18 mm |
F(000) = 848 |
Rigaku VariMax SaturnCCD724 diffractometer | 5927 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 4720 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 31.3°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018) | h = −14→14 |
Tmin = 0.906, Tmax = 1.000 | k = −27→28 |
18806 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.040P)2 + 0.1525P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
5927 reflections | Δρmax = 0.18 e Å−3 |
262 parameters | Δρmin = −0.18 e Å−3 |
2 restraints |
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 | ||
O1 | 0.13662 (19) | 0.40830 (14) | 0.6373 (2) | 0.0649 (7) | |
O2 | 0.18717 (19) | 0.32139 (11) | 0.5256 (2) | 0.0512 (5) | |
O3 | 0.2890 (2) | 0.41867 (10) | 0.9547 (2) | 0.0502 (5) | |
O4 | 0.2377 (2) | 0.32211 (10) | 0.8644 (2) | 0.0483 (5) | |
O5 | 0.57340 (17) | 0.39172 (8) | 0.96576 (16) | 0.0313 (4) | |
O6 | 0.75485 (16) | 0.42284 (9) | 0.80062 (16) | 0.0341 (4) | |
O7 | 0.48515 (15) | 0.43395 (7) | 0.34698 (15) | 0.0246 (3) | |
O8 | 0.30610 (16) | 0.50552 (8) | 0.34710 (17) | 0.0349 (4) | |
N1 | 0.2168 (2) | 0.36864 (14) | 0.5995 (2) | 0.0403 (6) | |
N2 | 0.3014 (2) | 0.37462 (11) | 0.8748 (2) | 0.0346 (5) | |
N3 | 0.5126 (2) | 0.54139 (9) | 0.30272 (19) | 0.0248 (4) | |
C1 | 0.4522 (2) | 0.38928 (11) | 0.5581 (2) | 0.0242 (5) | |
C2 | 0.3608 (2) | 0.38015 (11) | 0.6472 (2) | 0.0266 (5) | |
C3 | 0.4010 (2) | 0.38545 (11) | 0.7824 (2) | 0.0270 (5) | |
C4 | 0.5334 (2) | 0.39790 (11) | 0.8338 (2) | 0.0260 (5) | |
C5 | 0.6271 (2) | 0.40978 (11) | 0.7437 (2) | 0.0255 (5) | |
C6 | 0.5857 (2) | 0.40607 (11) | 0.6096 (2) | 0.0249 (5) | |
C7 | 0.4121 (2) | 0.38328 (11) | 0.4104 (2) | 0.0262 (5) | |
C8 | 0.4431 (3) | 0.31488 (12) | 0.3535 (2) | 0.0309 (5) | |
C9 | 0.5937 (3) | 0.29733 (13) | 0.3712 (3) | 0.0413 (6) | |
C10 | 0.3836 (3) | 0.31118 (14) | 0.2093 (3) | 0.0426 (7) | |
C11 | 0.4244 (2) | 0.49560 (11) | 0.3336 (2) | 0.0233 (4) | |
C12 | 0.4751 (2) | 0.61096 (11) | 0.2740 (2) | 0.0288 (5) | |
C13 | 0.4652 (2) | 0.62909 (11) | 0.1295 (2) | 0.0289 (5) | |
C14 | 0.4296 (3) | 0.70286 (12) | 0.1055 (3) | 0.0374 (6) | |
C15 | 0.4166 (3) | 0.72204 (14) | −0.0381 (3) | 0.0421 (7) | |
C16 | 0.6073 (3) | 0.45403 (14) | 1.0351 (3) | 0.0446 (7) | |
C17 | 0.8593 (2) | 0.42724 (15) | 0.7164 (3) | 0.0412 (7) | |
H3 | 0.588 (3) | 0.5291 (12) | 0.310 (3) | 0.026 (7)* | |
H6 | 0.648082 | 0.414974 | 0.551752 | 0.030* | |
H7 | 0.314682 | 0.392050 | 0.389922 | 0.031* | |
H8 | 0.397129 | 0.280852 | 0.400680 | 0.037* | |
H9A | 0.642527 | 0.331190 | 0.330187 | 0.062* | |
H9B | 0.606179 | 0.254638 | 0.331034 | 0.062* | |
H9C | 0.627043 | 0.295128 | 0.463472 | 0.062* | |
H10A | 0.288238 | 0.320714 | 0.200686 | 0.064* | |
H10B | 0.397234 | 0.266968 | 0.176167 | 0.064* | |
H10C | 0.427650 | 0.343506 | 0.159920 | 0.064* | |
H12A | 0.541687 | 0.639913 | 0.323654 | 0.035* | |
H12B | 0.388247 | 0.619657 | 0.303969 | 0.035* | |
H13A | 0.396452 | 0.601434 | 0.079559 | 0.035* | |
H13B | 0.551210 | 0.619674 | 0.098363 | 0.035* | |
H14A | 0.344649 | 0.712310 | 0.138677 | 0.045* | |
H14B | 0.499305 | 0.730341 | 0.154638 | 0.045* | |
H15A | 0.500225 | 0.712690 | −0.071672 | 0.063* | |
H15B | 0.396447 | 0.769065 | −0.047350 | 0.063* | |
H15C | 0.344706 | 0.696579 | −0.086689 | 0.063* | |
H16A | 0.675426 | 0.477282 | 0.994558 | 0.067* | |
H16B | 0.641171 | 0.444566 | 1.125445 | 0.067* | |
H16C | 0.527663 | 0.481566 | 1.031391 | 0.067* | |
H17A | 0.839687 | 0.463759 | 0.655666 | 0.062* | |
H17B | 0.862726 | 0.386057 | 0.668233 | 0.062* | |
H17C | 0.945213 | 0.434835 | 0.768997 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0257 (10) | 0.1028 (19) | 0.0698 (16) | 0.0228 (11) | 0.0194 (10) | 0.0230 (14) |
O2 | 0.0328 (10) | 0.0666 (14) | 0.0513 (13) | −0.0210 (10) | −0.0052 (9) | 0.0176 (11) |
O3 | 0.0577 (13) | 0.0498 (12) | 0.0502 (13) | 0.0163 (10) | 0.0334 (10) | 0.0051 (9) |
O4 | 0.0390 (11) | 0.0518 (13) | 0.0586 (14) | −0.0083 (9) | 0.0227 (9) | 0.0144 (10) |
O5 | 0.0398 (10) | 0.0322 (9) | 0.0233 (8) | −0.0001 (7) | 0.0097 (7) | −0.0013 (7) |
O6 | 0.0253 (8) | 0.0503 (11) | 0.0274 (9) | −0.0058 (7) | 0.0067 (7) | −0.0059 (7) |
O7 | 0.0201 (7) | 0.0261 (8) | 0.0288 (8) | 0.0013 (6) | 0.0069 (6) | 0.0082 (6) |
O8 | 0.0193 (8) | 0.0366 (9) | 0.0498 (11) | 0.0031 (7) | 0.0078 (7) | 0.0056 (8) |
N1 | 0.0195 (10) | 0.0607 (15) | 0.0417 (13) | 0.0005 (10) | 0.0079 (9) | 0.0249 (11) |
N2 | 0.0297 (11) | 0.0389 (12) | 0.0384 (12) | 0.0114 (10) | 0.0170 (9) | 0.0152 (10) |
N3 | 0.0199 (9) | 0.0250 (10) | 0.0301 (10) | 0.0015 (8) | 0.0051 (8) | 0.0023 (7) |
C1 | 0.0215 (11) | 0.0249 (11) | 0.0269 (12) | 0.0025 (8) | 0.0059 (9) | 0.0063 (9) |
C2 | 0.0197 (10) | 0.0296 (12) | 0.0316 (13) | 0.0027 (9) | 0.0073 (9) | 0.0087 (9) |
C3 | 0.0256 (11) | 0.0253 (11) | 0.0333 (12) | 0.0052 (9) | 0.0157 (9) | 0.0087 (9) |
C4 | 0.0298 (12) | 0.0239 (11) | 0.0259 (12) | 0.0032 (9) | 0.0105 (9) | 0.0008 (8) |
C5 | 0.0234 (11) | 0.0259 (11) | 0.0280 (12) | 0.0006 (9) | 0.0067 (9) | −0.0016 (9) |
C6 | 0.0208 (10) | 0.0283 (12) | 0.0278 (12) | −0.0005 (9) | 0.0114 (9) | 0.0032 (9) |
C7 | 0.0206 (10) | 0.0303 (12) | 0.0278 (12) | −0.0034 (9) | 0.0034 (9) | 0.0104 (9) |
C8 | 0.0343 (13) | 0.0287 (12) | 0.0293 (12) | −0.0065 (10) | 0.0021 (10) | 0.0062 (9) |
C9 | 0.0410 (15) | 0.0332 (14) | 0.0485 (17) | 0.0066 (12) | 0.0019 (12) | −0.0069 (12) |
C10 | 0.0525 (16) | 0.0427 (15) | 0.0310 (14) | −0.0119 (13) | −0.0006 (12) | 0.0028 (11) |
C11 | 0.0228 (11) | 0.0278 (11) | 0.0189 (10) | 0.0037 (9) | 0.0008 (8) | 0.0024 (8) |
C12 | 0.0302 (12) | 0.0232 (11) | 0.0332 (13) | 0.0023 (9) | 0.0050 (10) | 0.0002 (9) |
C13 | 0.0252 (11) | 0.0268 (12) | 0.0351 (13) | 0.0001 (9) | 0.0052 (9) | 0.0028 (10) |
C14 | 0.0370 (14) | 0.0301 (13) | 0.0459 (16) | 0.0013 (11) | 0.0087 (12) | 0.0065 (11) |
C15 | 0.0353 (14) | 0.0404 (16) | 0.0510 (17) | 0.0019 (12) | 0.0071 (12) | 0.0169 (13) |
C16 | 0.0603 (19) | 0.0421 (16) | 0.0335 (15) | −0.0066 (13) | 0.0147 (13) | −0.0108 (11) |
C17 | 0.0259 (13) | 0.0651 (19) | 0.0339 (15) | −0.0097 (12) | 0.0085 (11) | −0.0077 (13) |
O2—N1 | 1.219 (3) | C8—C9 | 1.525 (4) |
O3—N2 | 1.217 (3) | C8—C10 | 1.518 (4) |
O5—C4 | 1.363 (3) | C9—H9A | 0.9600 |
O5—C16 | 1.448 (3) | C9—H9B | 0.9600 |
O8—C11 | 1.220 (3) | C9—H9C | 0.9600 |
O6—C5 | 1.351 (3) | C10—H10A | 0.9600 |
O6—C17 | 1.438 (3) | C10—H10B | 0.9600 |
O7—C11 | 1.367 (3) | C10—H10C | 0.9600 |
O7—C7 | 1.447 (2) | C12—H12A | 0.9700 |
N1—O1 | 1.222 (3) | C12—H12B | 0.9700 |
N1—C2 | 1.469 (3) | C12—C13 | 1.513 (3) |
N2—O4 | 1.220 (3) | C13—H13A | 0.9700 |
N2—C3 | 1.473 (3) | C13—H13B | 0.9700 |
N3—C11 | 1.332 (3) | C13—C14 | 1.524 (3) |
N3—C12 | 1.455 (3) | C14—H14A | 0.9700 |
N3—H3 | 0.78 (3) | C14—H14B | 0.9700 |
C1—C6 | 1.402 (3) | C14—C15 | 1.508 (4) |
C1—C2 | 1.383 (3) | C15—H15A | 0.9600 |
C1—C7 | 1.517 (3) | C15—H15B | 0.9600 |
C3—C2 | 1.394 (3) | C15—H15C | 0.9600 |
C4—C3 | 1.374 (3) | C16—H16A | 0.9600 |
C4—C5 | 1.416 (3) | C16—H16B | 0.9600 |
C6—H6 | 0.9300 | C16—H16C | 0.9600 |
C6—C5 | 1.382 (3) | C17—H17A | 0.9600 |
C7—H7 | 0.9800 | C17—H17B | 0.9600 |
C8—H8 | 0.9800 | C17—H17C | 0.9600 |
C8—C7 | 1.529 (3) | ||
O1—N1—C2 | 116.3 (3) | C8—C9—H9C | 109.5 |
O2—N1—O1 | 125.6 (2) | C8—C10—H10A | 109.5 |
O2—N1—C2 | 118.1 (2) | C8—C10—H10B | 109.5 |
O3—N2—O4 | 125.4 (2) | C8—C10—H10C | 109.5 |
O3—N2—C3 | 117.5 (2) | C9—C8—H8 | 107.3 |
O4—N2—C3 | 117.1 (2) | C9—C8—C7 | 113.8 (2) |
O5—C4—C3 | 120.13 (19) | C10—C8—H8 | 107.3 |
O5—C4—C5 | 122.0 (2) | C10—C8—C7 | 110.0 (2) |
O5—C16—H16A | 109.5 | C10—C8—C9 | 110.8 (2) |
O5—C16—H16B | 109.5 | C11—O7—C7 | 115.47 (17) |
O5—C16—H16C | 109.5 | C11—N3—C12 | 122.75 (19) |
O6—C5—C4 | 114.47 (19) | C11—N3—H3 | 114.4 (19) |
O6—C5—C6 | 125.36 (19) | C12—N3—H3 | 122.3 (19) |
O6—C17—H17A | 109.5 | C12—C13—H13A | 109.3 |
O6—C17—H17B | 109.5 | C12—C13—H13B | 109.3 |
O6—C17—H17C | 109.5 | C12—C13—C14 | 111.8 (2) |
O7—C7—C1 | 108.12 (17) | C13—C12—H12A | 108.8 |
O7—C7—C8 | 108.20 (18) | C13—C12—H12B | 108.8 |
O7—C7—H7 | 108.7 | C13—C14—H14A | 109.0 |
O8—C11—O7 | 123.68 (19) | C13—C14—H14B | 109.0 |
O8—C11—N3 | 126.3 (2) | C14—C13—H13A | 109.3 |
N3—C12—H12A | 108.8 | C14—C13—H13B | 109.3 |
N3—C12—H12B | 108.8 | C14—C15—H15A | 109.5 |
N3—C12—C13 | 113.99 (19) | C14—C15—H15B | 109.5 |
N3—C11—O7 | 110.05 (18) | C14—C15—H15C | 109.5 |
C1—C6—H6 | 119.0 | C15—C14—C13 | 112.9 (2) |
C1—C2—N1 | 120.0 (2) | C15—C14—H14A | 109.0 |
C1—C2—C3 | 121.2 (2) | C15—C14—H14B | 109.0 |
C1—C7—C8 | 114.22 (18) | H9A—C9—H9B | 109.5 |
C1—C7—H7 | 108.7 | H9A—C9—H9C | 109.5 |
C2—C3—N2 | 119.8 (2) | H9B—C9—H9C | 109.5 |
C2—C1—C6 | 117.2 (2) | H10A—C10—H10B | 109.5 |
C2—C1—C7 | 122.5 (2) | H10A—C10—H10C | 109.5 |
C3—C4—C5 | 117.5 (2) | H10B—C10—H10C | 109.5 |
C3—C2—N1 | 118.75 (19) | H12A—C12—H12B | 107.7 |
C4—O5—C16 | 115.31 (19) | H13A—C13—H13B | 107.9 |
C4—C3—N2 | 118.2 (2) | H14A—C14—H14B | 107.8 |
C4—C3—C2 | 121.9 (2) | H15A—C15—H15B | 109.5 |
C5—O6—C17 | 117.76 (18) | H15A—C15—H15C | 109.5 |
C5—C6—C1 | 121.93 (19) | H15B—C15—H15C | 109.5 |
C5—C6—H6 | 119.0 | H16A—C16—H16B | 109.5 |
C6—C1—C7 | 120.26 (19) | H16A—C16—H16C | 109.5 |
C6—C5—C4 | 120.2 (2) | H16B—C16—H16C | 109.5 |
C7—C8—H8 | 107.3 | H17A—C17—H17B | 109.5 |
C8—C7—H7 | 108.7 | H17A—C17—H17C | 109.5 |
C8—C9—H9A | 109.5 | H17B—C17—H17C | 109.5 |
C8—C9—H9B | 109.5 | ||
O1—N1—C2—C1 | −122.5 (2) | C5—C4—C3—C2 | 4.2 (3) |
O1—N1—C2—C3 | 53.9 (3) | C6—C1—C2—N1 | 174.4 (2) |
O2—N1—C2—C1 | 56.9 (3) | C6—C1—C2—C3 | −1.9 (3) |
O2—N1—C2—C3 | −126.7 (2) | C6—C1—C7—O7 | −36.3 (3) |
O3—N2—C3—C4 | 56.7 (3) | C6—C1—C7—C8 | 84.2 (2) |
O3—N2—C3—C2 | −125.9 (3) | C7—O7—C11—O8 | −15.0 (3) |
O4—N2—C3—C4 | −123.5 (2) | C7—O7—C11—N3 | 165.85 (18) |
O4—N2—C3—C2 | 53.9 (3) | C7—C1—C6—C5 | −177.8 (2) |
O5—C4—C3—N2 | 8.2 (3) | C7—C1—C2—N1 | −4.3 (3) |
O5—C4—C3—C2 | −169.1 (2) | C7—C1—C2—C3 | 179.4 (2) |
O5—C4—C5—O6 | −8.0 (3) | C9—C8—C7—O7 | 58.3 (3) |
O5—C4—C5—C6 | 170.6 (2) | C9—C8—C7—C1 | −62.1 (3) |
N2—C3—C2—N1 | 4.4 (3) | C10—C8—C7—O7 | −66.6 (2) |
N2—C3—C2—C1 | −179.3 (2) | C10—C8—C7—C1 | 172.9 (2) |
N3—C12—C13—C14 | −178.41 (19) | C11—O7—C7—C1 | −86.6 (2) |
C1—C6—C5—O6 | 177.1 (2) | C11—O7—C7—C8 | 149.19 (18) |
C1—C6—C5—C4 | −1.4 (3) | C11—N3—C12—C13 | −106.4 (2) |
C2—C1—C7—O7 | 142.3 (2) | C12—N3—C11—O7 | 176.03 (19) |
C2—C1—C7—C8 | −97.2 (3) | C12—N3—C11—O8 | −3.1 (4) |
C2—C1—C6—C5 | 3.6 (3) | C12—C13—C14—C15 | −178.9 (2) |
C3—C4—C5—O6 | 178.9 (2) | C16—O5—C4—C3 | −110.7 (2) |
C3—C4—C5—C6 | −2.5 (3) | C16—O5—C4—C5 | 76.3 (3) |
C4—C3—C2—N1 | −178.3 (2) | C17—O6—C5—C4 | 172.5 (2) |
C4—C3—C2—C1 | −2.0 (3) | C17—O6—C5—C6 | −6.0 (3) |
C5—C4—C3—N2 | −178.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O8i | 0.78 (3) | 2.26 (3) | 3.042 (3) | 176 (3) |
Symmetry code: (i) x+1/2, −y+1, z. |
Acknowledgements
The support of Kanagawa University, including the use of the diffractometer, is gratefully acknowledged. Author contributions: conceptualization, MI, NCK, and KY; synthesis and analysis, HT, MI, and NCK; writing, NCK and KY; validation, NCK and HS.
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