Home Physical Sciences Crystal structure of 4,8a-bis(4-chlorophenyl)-1,5,6-tris(4-fluorobenzyl)-1,4,4a,4b,5,6,8a,8b-octahydrocyclobuta[1,2-b:3,4-c′]dipyridine-3,8-dicarbonitrile, C45H33Cl2F3N4
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Crystal structure of 4,8a-bis(4-chlorophenyl)-1,5,6-tris(4-fluorobenzyl)-1,4,4a,4b,5,6,8a,8b-octahydrocyclobuta[1,2-b:3,4-c′]dipyridine-3,8-dicarbonitrile, C45H33Cl2F3N4

  • Zhuo-Jun Li , Lu-Yao Xiao , Wei-Kang Shi and Kai-Yin Yang EMAIL logo
Published/Copyright: May 31, 2024

Abstract

C45H33Cl2F3N4, monoclinic, P21/c (no. 14), a = 11.7076(13) Å, b = 11.8186(13) Å, c = 27.473(3) Å, β = 91.188(2)°, V = 3800.6(7) Å3, Z = 4, Rgt (F) = 0.0591, wRref (F 2) = 0.1856, T = 293 K.

CCDC no.: 2351879

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: Colourless block
Size: 0.25 × 0.23 × 0.20 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 0.22 mm−1
Diffractometer, scan mode: Bruker APEX-II, φ and ω
θ max, completeness: 25.0°, >99 %
N(hkl)measured, N(hkl)unique, R int: 21,414, 6690, 0.040
Criterion for I obs, N(hkl)gt: I obs > 2 σ(I obs), 4678
N(param)refined: 487
Programs: CrysAlisPRO, 1 Olex2, 2 SHELX 3 , 4
Table 2:

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

Atom x y z U iso*/U eq
C1 0.4336 (3) −0.1335 (3) 0.19940 (11) 0.0543 (8)
C2 0.3534 (3) −0.1818 (3) 0.16860 (11) 0.0561 (8)
H2 0.352422 −0.259669 0.163693 0.067*
C3 0.2740 (2) −0.1132 (2) 0.14499 (10) 0.0448 (7)
H3 0.221259 −0.145823 0.123464 0.054*
C4 0.2711 (2) 0.0034 (2) 0.15260 (9) 0.0352 (6)
C5 0.3510 (2) 0.0482 (2) 0.18563 (9) 0.0440 (6)
H5 0.349153 0.125179 0.192489 0.053*
C6 0.4332 (2) −0.0189 (3) 0.20857 (10) 0.0507 (7)
H6 0.487039 0.012953 0.229798 0.061*
C7 0.1820 (2) 0.0782 (2) 0.12780 (9) 0.0335 (6)
C8 0.1013 (2) 0.0163 (2) 0.09319 (9) 0.0392 (6)
C9 −0.0127 (2) 0.0128 (2) 0.09944 (10) 0.0443 (7)
H9 −0.056936 −0.022038 0.075265 0.053*
C10 −0.0045 (2) 0.1110 (2) 0.17791 (9) 0.0407 (6)
H10 −0.049631 0.176762 0.187624 0.049*
C11 0.1099 (2) 0.1548 (2) 0.16143 (9) 0.0336 (6)
H11 0.156426 0.174653 0.190250 0.040*
C12 0.1465 (2) −0.0221 (3) 0.04857 (11) 0.0492 (7)
C13 −0.1921 (2) 0.0523 (3) 0.14028 (13) 0.0580 (8)
H13A −0.213740 0.020516 0.171312 0.070*
H13B −0.222400 0.003545 0.114709 0.070*
C14 −0.2432 (2) 0.1681 (3) 0.13482 (10) 0.0454 (7)
C15 −0.2439 (3) 0.2224 (3) 0.09003 (11) 0.0564 (8)
H15 −0.212246 0.186038 0.063478 0.068*
C16 −0.2896 (3) 0.3275 (3) 0.08394 (13) 0.0650 (9)
H16 −0.291071 0.362247 0.053560 0.078*
C17 −0.3329 (3) 0.3803 (3) 0.12344 (14) 0.0642 (9)
C18 −0.3343 (3) 0.3331 (3) 0.16828 (12) 0.0616 (9)
H18 −0.364211 0.371911 0.194564 0.074*
C19 −0.2893 (2) 0.2238 (3) 0.17391 (11) 0.0554 (8)
H19 −0.290464 0.188759 0.204200 0.066*
C20 0.0192 (3) 0.6293 (3) 0.04401 (11) 0.0585 (8)
C21 −0.0568 (3) 0.5566 (3) 0.06428 (12) 0.0611 (9)
H21 −0.134290 0.562065 0.056409 0.073*
C22 −0.0182 (2) 0.4746 (2) 0.09661 (11) 0.0505 (7)
H22 −0.070512 0.425866 0.110636 0.061*
C23 0.0965 (2) 0.4637 (2) 0.10846 (9) 0.0391 (6)
C24 0.1720 (3) 0.5383 (3) 0.08713 (11) 0.0521 (7)
H24 0.249730 0.532666 0.094386 0.063*
C25 0.1331 (3) 0.6214 (3) 0.05504 (11) 0.0620 (9)
H25 0.184425 0.671412 0.041161 0.074*
C26 0.1334 (2) 0.3720 (2) 0.14466 (9) 0.0354 (6)
H26 0.084109 0.378801 0.172892 0.042*
C27 0.2547 (2) 0.3855 (2) 0.16302 (9) 0.0390 (6)
C28 0.3411 (2) 0.3238 (2) 0.14486 (9) 0.0406 (6)
H28 0.414996 0.342914 0.154844 0.049*
C29 0.2180 (2) 0.1920 (2) 0.10023 (9) 0.0349 (6)
H29 0.207281 0.185771 0.064865 0.042*
C30 0.1169 (2) 0.2520 (2) 0.12424 (9) 0.0337 (6)
H30 0.049899 0.250191 0.102273 0.040*
C31 0.2799 (2) 0.4727 (3) 0.19732 (11) 0.0502 (7)
C32 0.4272 (2) 0.1854 (3) 0.09027 (10) 0.0464 (7)
H32A 0.416776 0.103989 0.089704 0.056*
H32B 0.495201 0.201331 0.109852 0.056*
C33 0.4460 (3) 0.2256 (3) 0.03943 (11) 0.0530 (8)
C34 0.4087 (4) 0.3248 (4) 0.02276 (16) 0.1144 (19)
H34 0.363473 0.369590 0.042450 0.137*
C35 0.4356 (6) 0.3631 (5) −0.0233 (2) 0.169 (3)
H35 0.410683 0.433680 −0.034029 0.203*
C36 0.4967 (6) 0.2984 (6) −0.05162 (19) 0.165 (3)
C37 0.5441 (5) 0.2027 (5) −0.03561 (18) 0.132 (2)
H37 0.594231 0.162343 −0.054884 0.159*
C38 0.5171 (4) 0.1644 (4) 0.01042 (15) 0.0909 (13)
H38 0.547531 0.096413 0.021747 0.109*
C39 0.0067 (3) 0.0326 (2) 0.22278 (11) 0.0511 (7)
H39A −0.067218 −0.000136 0.229557 0.061*
H39B 0.058876 −0.028684 0.215671 0.061*
C40 0.0497 (3) 0.0954 (2) 0.26663 (10) 0.0466 (7)
C41 −0.0195 (3) 0.1724 (3) 0.29054 (11) 0.0561 (8)
H41 −0.095036 0.181624 0.280156 0.067*
C42 0.0217 (4) 0.2352 (3) 0.32922 (13) 0.0680 (10)
H42 −0.025466 0.285944 0.345059 0.082*
C43 0.1321 (4) 0.2220 (3) 0.34392 (12) 0.0676 (10)
C44 0.2040 (3) 0.1471 (3) 0.32211 (13) 0.0703 (10)
H44 0.279409 0.139389 0.332839 0.084*
C45 0.1612 (3) 0.0830 (3) 0.28352 (11) 0.0600 (8)
H45 0.208464 0.030529 0.268705 0.072*
Cl1 0.53555 (9) −0.21899 (9) 0.22787 (4) 0.0900 (4)
Cl3 −0.02984 (11) 0.73577 (8) 0.00502 (4) 0.0911 (4)
F1 −0.3816 (2) 0.48454 (19) 0.11768 (10) 0.1061 (8)
F2 0.5236 (5) 0.3383 (5) −0.09634 (15) 0.286 (4)
F3 0.1730 (3) 0.2834 (2) 0.38219 (9) 0.1050 (8)
N1 −0.06710 (18) 0.0556 (2) 0.13773 (9) 0.0476 (6)
N2 0.1891 (3) −0.0498 (3) 0.01330 (11) 0.0788 (9)
N3 0.32899 (17) 0.23697 (18) 0.11352 (8) 0.0383 (5)
N4 0.2968 (3) 0.5439 (3) 0.22499 (11) 0.0748 (9)

1 Source of material

N-(4-fluoro-benzyl)-3-cyano-4-(4-chlorophenyl)-1,4-dihydrop-yridine (0.5 g, 1.63 mmol) and 4-fluorobenzyl bromide (0.15 g, 0.82 mmol) were dissolved in 30 mL of the organic solvent methanol:tetrahydrofuran = 1:1, placed in a quartz photo reactor at room temperature, and irradiated with a high-pressure mercury lamp with the wavelength of 365 nm was selected for 1 day. The reaction was complete. The solvent was removed by distillation under reduced pressure. The product was separated and purified by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate (5:1), and 0.35 g of white solid product was obtained in 56 % yield.

2 Experimental details

Using Olex2, 2 the structure was solved with the ShelXT 3 structure solution program and refined with the ShelXL 4 refinement package.

3 Comment

The dimeric form of pyridine has attracted extensive interest in recent research, with important developments in its synthesis and medical applications. It has been shown that certain pyridine dimer compounds have significant inhibitory effects on cancer cells, possibly by interfering with cell cycle regulation or inducing apoptosis to achieve anti-tumor effects. In addition, pyridine dimers have been investigated for use as drug precursors in antibiotics, anti-inflammatory drugs and antiviral agents. 5 , 6

Researchers have developed various methods for the synthesis of pyridine dimers, and in this paper, UV light was used to induce the dihydropyridine backbone to generate structurally novel pyridine dimers. The key lengths and angles obtained from the title structure are within the normal range. 7 , 8


Corresponding author: Kai-Yin Yang, School of Pharmacy, North China University of Science and Technology, 063210 Caofeidian District, Tangshan, P.R. China, E-mail:

  1. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

  2. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  3. Research funding: None declared.

References

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Received: 2024-03-22
Accepted: 2024-04-29
Published Online: 2024-05-31
Published in Print: 2024-08-27

© 2024 the author(s), published by De Gruyter, Berlin/Boston

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

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