Crystal structure of diethyl 6,12-dimethyl-3,9-di-p-tolyl-3,9-diazapentacyclo[6.4.0.02,7.04,11.05,10]dodecane-1,5-dicarboxylate, C32H38N2O4

Shuai Yang; Jin-Ling Dong; Jin-Ming Chen

doi:10.1515/ncrs-2021-0358

Open Access Published by De Gruyter (O) October 22, 2021

Crystal structure of diethyl 6,12-dimethyl-3,9-di-p-tolyl-3,9-diazapentacyclo[6.4.0.0^2,7.0^4,11.0^5,10]dodecane-1,5-dicarboxylate, C₃₂H₃₈N₂O₄

Shuai Yang , Jin-Ling Dong and Jin-Ming Chen

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2021-0358

Abstract

C₁₅H₁₄N₂O, triclinic, P 1 ‾ (no. 2), a = 6.983(5) Å, b = 8.472(6) Å, c = 12.113(7) Å, β = 73.45°, V = 679.29(8) Å³, Z = 1, R _gt(F) = 0.0566, wR _ref(F ²) = 0.1875, T = 296 K.

CCDC no.: 2109607

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:	Red block
Size:	0.18 × 0.16 × 0.15 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	0.08 mm⁻¹
Diffractometer, scan mode:	Bruker APEX-II, φ and ω
θ _max, completeness:	27.6°, 99%
N(hkl)_measured, N(hkl)_unique, R _int:	4252, 3054, 0.026
Criterion for I _obs, N(hkl)_gt:	I _obs > 2 σ(I _obs), 2416
N(param)_refined:	175
Programs:	Bruker [1], SHELX [2, 3]

Table 2:

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

Atom	x	y	z	U _iso*/U _eq
O1	0.02312 (17)	0.28526 (16)	0.46273 (11)	0.0514 (4)
O2	0.29314 (16)	0.35214 (14)	0.33028 (9)	0.0426 (3)
N1	0.30503 (18)	0.00094 (15)	0.64789 (10)	0.0319 (3)
C1	0.2940 (4)	0.5395 (3)	0.18096 (18)	0.0720 (7)
H1A	0.213974	0.622278	0.151057	0.108*
H1B	0.354800	0.458629	0.123087	0.108*
H1C	0.397681	0.583680	0.202300	0.108*
C2	0.1630 (3)	0.4678 (2)	0.28415 (15)	0.0496 (5)
H2A	0.093260	0.549674	0.341189	0.060*
H2B	0.063264	0.416255	0.262729	0.060*
C3	0.2016 (2)	0.26758 (18)	0.42067 (12)	0.0331 (4)
C4	0.3522 (2)	0.15220 (17)	0.46035 (12)	0.0301 (3)
C5	0.4799 (2)	0.02059 (17)	0.36868 (12)	0.0301 (3)
H5	0.445168	0.032310	0.295651	0.036*
C6	0.3727 (2)	−0.10906 (17)	0.44699 (11)	0.0308 (3)
H6	0.282916	−0.155574	0.412076	0.037*
C7	0.2545 (2)	0.01883 (17)	0.53912 (11)	0.0299 (3)
H7	0.108634	0.029251	0.550152	0.036*
C8	0.4892 (2)	0.23705 (17)	0.51030 (12)	0.0324 (4)
H8	0.574127	0.293154	0.447073	0.039*
C9	0.3729 (3)	0.3600 (2)	0.60231 (15)	0.0441 (4)
H9A	0.465995	0.411599	0.628355	0.066*
H9B	0.289547	0.307984	0.666011	0.066*
H9C	0.289531	0.437944	0.570672	0.066*
C10	0.1737 (2)	−0.06464 (17)	0.74303 (11)	0.0317 (3)
C11	0.2414 (3)	−0.1815 (2)	0.81168 (14)	0.0447 (4)
H11	0.377096	−0.224097	0.792268	0.054*
C12	0.1075 (3)	−0.2351 (2)	0.90925 (15)	0.0525 (5)
H12	0.157013	−0.312215	0.954479	0.063*
C13	−0.0947 (3)	−0.1789 (2)	0.94147 (14)	0.0496 (5)
C14	−0.1624 (3)	−0.0653 (3)	0.87170 (15)	0.0527 (5)
H14	−0.299115	−0.026280	0.890073	0.063*
C15	−0.0313 (2)	−0.0079 (2)	0.77470 (14)	0.0438 (4)
H15	−0.081587	0.069837	0.730201	0.053*
C16	−0.2368 (4)	−0.2359 (3)	1.05037 (17)	0.0748 (7)
H16A	−0.372670	−0.215889	1.045017	0.112*
H16B	−0.227379	−0.179727	1.115682	0.112*
H16C	−0.200175	−0.348247	1.059279	0.112*

Source of material

Dissolve 1,4-diphenyl-1,4-dihydropyridine-3-carboxylic acid ethyl ester (10 mmol) in 50 mL of methanol: tetrahydrofuran = 1:1 mixed solution, and add to a 100 mL Quartz flask. Place the reaction solution in an LED photoreactor with a wavelength of 365 nm, put it in a freezer, and irradiate it under the protection of nitrogen. After reacting for one week, the product precipitates out and is filtered to obtain the title compound.

Experimental details

All hydrogen atoms were placed in the calculated positions and all the non-hydrogen atoms were refined anisotropically.

Comment

The [2+2] -photocyclization reaction is an important type of organic photocyclization reaction. Under the induction of visible light or ultraviolet light, an addition reaction occurs between the unsaturated double bonds of two molecules, turning the double bonds into single bonds. There are two unsaturated double bonds in the molecular structure of 1,4-dihydropyridine compounds. Under light induction [2+2] photocyclization reaction can occur to generate 3,9-diazatetrastarane with inversion symmetry. Some cis/trans tetrahydrocyclobutane dipyridine compounds show pharmacological activities in the field of anti-HIV and anti-tumor [4, 6], [7], [8]. The title structure is shown in the figure. The asymmetric unit is defined as one half of the title molecule. The bond lengths and angles are in the expected ranges [5, 9].

Corresponding author: Jin-Ming Chen, School of Pharmacy, North China University of Science and Technology, Caofeidian District, 063210 Tangshan, P. R. China, E-mail: ming19821205@163.com

Funding source: Hebei Provincial Universities

Award Identifier / Grant number: JQN2020007

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: This study was financially supported by Hebei Provincial Universities (JQN2020007).
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2021-09-14

Accepted: 2021-10-07

Published Online: 2021-10-22

Published in Print: 2021-12-20

This work is licensed under the Creative Commons Attribution 4.0 International License.