Abstract
C45H48N2O5, monoclinic, P21/c (no. 14), a = 21.3971(8) Å, b = 15.2249(6) Å, c = 11.2610(5) Å, β = 92.125(4)°, V = 3666.0(3) Å3, Z = 4, Rgt(F) = 0.0519, wRref(F2) = 0.1308, T = 128.15 K.
The title crystal structure has been shown in the figure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Colourless monoclinic |
| Size: | 0.36 × 0.26 × 0.14 mm |
| Wavelength: | Mo K α radiation (0.71073 Å) |
| μ: | 0.82 cm−1 |
| Diffractometer, scan mode: | Rigaku XtaLAB P200, φ and ω |
| θmax, completeness: | 52.7°, >99% |
| N(hkl)measured, N(hkl)unique, Rint: | 38645, 7481, 0.0840 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 5642 |
| N(param)refined: | 476 |
| Programs: | Rigaku [1], Olex2 [2], SHELX [3], [4] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | Uiso*/U(eq) |
|---|---|---|---|---|
| O1 | 3572.3(6) | 5027.7(9) | 9236.9(11) | 28.1(3) |
| O2 | 611.2(6) | 4540.5(9) | 7973.4(12) | 33.7(3) |
| O3 | 642.3(6) | 8319.1(9) | 4190.9(12) | 32.0(3) |
| O4 | 4134.7(6) | 563.9(8) | 7695.5(12) | 31.3(3) |
| N1 | 2193.4(6) | 5805.6(9) | 7380.5(13) | 19.2(3) |
| N2 | 2201.0(6) | 3491.3(9) | 7862.7(12) | 19.0(3) |
| C1 | 1881.5(8) | 5029.8(11) | 7834.7(15) | 19.0(4) |
| C2 | 2416.7(8) | 4360.6(11) | 8231.4(15) | 18.9(4) |
| C3 | 2980.2(8) | 4636.3(11) | 7461.3(15) | 19.0(4) |
| C4 | 2678.6(8) | 5409.4(11) | 6680.4(15) | 19.4(4) |
| C5 | 1919.2(8) | 3677.1(11) | 6689.8(15) | 19.2(4) |
| C6 | 1523.1(8) | 4550.0(11) | 6793.4(15) | 19.2(4) |
| C7 | 1637.5(8) | 5000.8(11) | 5596.7(15) | 19.6(4) |
| C8 | 2355.8(8) | 4920.0(11) | 5594.9(15) | 19.7(4) |
| C9 | 2461.9(8) | 3939.4(11) | 5852.5(15) | 19.7(4) |
| C10 | 3097.9(8) | 3919.0(11) | 6523.5(15) | 20.0(4) |
| C11 | 3562.2(8) | 4932.1(11) | 8164.3(17) | 22.4(4) |
| C12 | 4143.4(9) | 5108.7(15) | 7481.9(19) | 35.1(5) |
| C13 | 834.7(8) | 4377.5(12) | 7023.1(17) | 23.0(4) |
| C14 | 434.3(9) | 3986.7(15) | 6040.9(19) | 37.5(5) |
| C15 | 2409.8(8) | 6390.3(11) | 8339.1(16) | 21.8(4) |
| C16 | 2655.9(8) | 7265.8(12) | 7926.7(16) | 22.0(4) |
| C17 | 2443.3(9) | 7658.2(12) | 6880.4(17) | 27.0(4) |
| C18 | 2633.3(10) | 8506.6(13) | 6604.7(19) | 33.6(5) |
| C19 | 3041.2(10) | 8958.4(14) | 7364(2) | 37.3(5) |
| C20 | 3255.5(9) | 8567.6(14) | 8406(2) | 36.7(5) |
| C21 | 3063.8(9) | 7726.4(13) | 8686.2(19) | 30.3(4) |
| C22 | 1784.6(8) | 3069.6(11) | 8701.2(16) | 22.0(4) |
| C23 | 1559.3(8) | 2198.4(12) | 8214.9(16) | 22.7(4) |
| C24 | 927.5(9) | 1989.8(14) | 8171.5(19) | 33.8(5) |
| C25 | 715.7(11) | 1199.6(15) | 7703(2) | 43.7(6) |
| C26 | 1135.9(12) | 611.8(15) | 7263(2) | 46.3(6) |
| C27 | 1769.5(11) | 809.1(14) | 7293.5(19) | 38.7(5) |
| C28 | 1980.9(9) | 1595.4(12) | 7771.9(17) | 28.3(4) |
| C29 | 1355.2(7) | 5892.1(11) | 5303.2(15) | 19.3(4) |
| C30 | 986.4(8) | 6369.4(12) | 6056.2(16) | 21.6(4) |
| C31 | 735.2(8) | 7181.5(12) | 5724.5(16) | 23.2(4) |
| C32 | 853.3(8) | 7524.1(12) | 4615.7(16) | 22.3(4) |
| C33 | 1216.6(8) | 7050.2(12) | 3844.3(16) | 23.6(4) |
| C34 | 1463.1(8) | 6249.0(12) | 4190.4(16) | 22.1(4) |
| C35 | 268.5(11) | 8829.6(14) | 4950(2) | 42.7(6) |
| C36 | 3354.8(8) | 3031.1(11) | 6912.0(16) | 19.8(4) |
| C37 | 3331.1(8) | 2327.9(12) | 6112.2(17) | 24.3(4) |
| C38 | 3584.8(8) | 1517.1(12) | 6395.8(17) | 26.0(4) |
| C39 | 3881.3(8) | 1385.7(12) | 7499.6(17) | 23.8(4) |
| C40 | 3907.5(8) | 2064.8(12) | 8316.3(17) | 25.1(4) |
| C41 | 3646.2(8) | 2875.6(12) | 8010.5(16) | 23.4(4) |
| C42 | 4401.2(9) | 388.8(13) | 8844.2(18) | 32.0(5) |
| O5 | 4397.0(9) | 6885.9(14) | 5636(2) | 78.7(7) |
| C43 | 4811.9(13) | 7562(2) | 3981(3) | 66.0(8) |
| C44 | 4556.9(10) | 7560.4(18) | 5177(2) | 47.4(6) |
| C45 | 4515.7(19) | 8419(2) | 5783(3) | 93.1(12) |
Source of materials
The title compound was synthesizd by [2 + 2] photocycloaddition reaction. 3-Acetyl-N-benzyl-4-methoxyphenyl-1,4-dihydropyridin was selected as the substrate under irradiation of 410 nm UV-light in methanol/THF sovent. After 7 days, the product was purified by silica gel (P:E = 50:1, V/V). After concentration in vacuum, freeze-drying, a colorless powder was obtained. The powder was recrystallized from acetone. Two days later the crystals of the title compound were harvested.
Experimental details
All hydrogens were placed in idealized positions and added using the riding models implemented in the SHELX system. Using Olex2 [2], the structure was solved with the ShelXT [3] structure solution program using intrinsic phasing and refined with the ShelXL [4] refinement package using least squares minimisation.
Discussion
Organic photochemical reactions have advantages of easy operation methods, high efficiency and more environmental-friendly conditions, controllable cost and so on. The products of the photochemical reaction found may have many kinds of pharmacological activities [5], [6]. Despite all efforts, accessibility of cage compounds analogous to cubane is limited [7]. Only a small number of 6,12-diazatetrakishomocubanes have been reported so far [8].
The structure of title compound was determined by X-ray diffraction analysis. The crystal structure revealed that the two piperidine rings are in boat conformation, the apexes (prows) being the N1, C7 and N2, C10 atoms, and the five-membered rings adopt an envelope form conformation in the compound (see the figure). The compound is a cage structure, which belongs to the class of 6,12-diazatetrakishomocubanes [7], [8], [9]. The feature of torsion angel are C1—N1—C15—C16: −171.85°, C4—N1—C15—C16: 72.46°, C2—N2—C22—C23: 176.94°, C5—N2—C22—C23: 60.29°.
Acknowledgements
We gratefully acknowledge support by the Natural Science Foundation of Hebei Province (H2019209496, H2019209571, H2015209094).
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©2020 Xiaoxia Wang et al., published by De Gruyter, Berlin/Boston
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