Synthesis and structure of photodegradable 1-(4,5-dimeth­oxy-2,3-di­nitro­phen­yl)-2-methyl­propyl N-butyl­carbamate

Honda, T.; Ito, M.; Yamaguchi, K.; Kasuga, N.C.; Sato, H.

doi:10.1107/S2056989023004103

research communications

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ISSN: 2056-9890

Volume 79| Part 6| June 2023| Pages 549-551

https://doi.org/10.1107/S2056989023004103

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Synthesis and structure of photodegradable 1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropyl N-butylcarbamate

Takafumi Honda,^a Michiko Ito,^a Kazuo Yamaguchi,^a Noriko Chikaraishi Kasuga ^a ^* and Hiroyasu Sato ^b

^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

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 23 February 2023; accepted 9 May 2023; online 16 May 2023)

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 asymmetric unit of 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).

Figure 1
Molecular structure of photocleavable 1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropyl butylcarbamate. Displacement ellipsoids are drawn at the 50% probability level. The intermolecular hydrogen bonds (Table 1

) are drawn as dotted lines.

The 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).

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x+{\script{1\over 2}}, -y+1, z]$ .

Figure 2
Intermolecular hydrogen bonds (Table 1

) between the carbamate moieties, shown as dotted lines, link the molecules into chains parallel to the a axis.

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 column chromatography. 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 refinement details are summarized in Table 2. The C-bound H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined using a riding model with U_iso(H) = 1.2 or 1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₂₅N₃O₈
M_r	399.40
Crystal system, space group	Monoclinic, Ia
Temperature (K)	120
a, b, c (Å)	9.9490 (4), 19.9223 (8), 10.2378 (4)
β (°)	97.616 (4)
V (Å³)	2011.30 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.21 × 0.18

Data collection
Diffractometer	Rigaku VariMax SaturnCCD724
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.906, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18806, 5927, 4720
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.730

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.094, 1.04
No. of reflections	5927
No. of parameters	262
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2261578

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989023004103/ex2069sup1.cif

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

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); cell refinement: 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).

1-(4,5-Dimethoxy-2,3-dinitrophenyl)-2-methylpropyl N-butylcarbamate top

Crystal data top

C₁₇H₂₅N₃O₈	D_x = 1.319 Mg m⁻³
M_r = 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

Data collection top

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	R_int = 0.039
ω scans	θ_max = 31.3°, θ_min = 3.4°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	h = −14→14
T_min = 0.906, T_max = 1.000	k = −27→28
18806 measured reflections	l = −14→14

Refinement top

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(F_o²) + (0.040P)² + 0.1525P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
5927 reflections	Δρ_max = 0.18 e Å⁻³
262 parameters	Δρ_min = −0.18 e Å⁻³
2 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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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