Home Crystal structure of bis(3-isopropylphenyl)-4,4′-bipyridinium dichloride dihydrate, C28H30N2⋅2Cl⋅2H2O
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Crystal structure of bis(3-isopropylphenyl)-4,4′-bipyridinium dichloride dihydrate, C28H30N2⋅2Cl⋅2H2O

  • Guangyi Li ORCID logo EMAIL logo
Published/Copyright: October 16, 2024

Abstract

C28H34Cl2N2O2, orthorhombic, Pbcn (no. 60), a = 30.5739(5) Å, b = 8.00310(10) Å, c = 10.5257(2) Å, V = 2575.49(7) Å3, Z = 4, R gt (F) = 0.0374, wR ref (F 2) = 0.1029, T = 100.01(10) K.

CCDC no.: 2387235

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 plate
Size: 0.20 × 0.20 × 0.10 mm
Wavelength:

μ:
Cu radiation (1.54184 Å)

2.48 mm−1
Diffractometer, scan mode:

θ max, completeness:
SuperNova, ω

66.6°, >99 %
N(hkl)measured, N(hkl)unique, R int: 5450, 2280, 0.025
Criterion for I obs, N(hkl)gt: I obs > 2σ(I obs), 1987
N(param)refined: 164
Programs: Olex2, 1 Bruker, 2 SHELX, 3 Diamond 4
Table 2:

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

Atom x y z U iso*/U eq
N1 0.41852 (4) 0.50900 (18) 0.48266 (14) 0.0143 (3)
C1 0.48299 (5) 0.5063 (2) 0.30046 (17) 0.0149 (4)
C2 0.45781 (6) 0.3634 (2) 0.32321 (17) 0.0158 (4)
H2 0.4632 0.2635 0.2771 0.019*
C3 0.42520 (5) 0.3689 (2) 0.41292 (17) 0.0162 (4)
H3 0.4072 0.2738 0.4262 0.019*
C4 0.44379 (5) 0.6469 (2) 0.46570 (17) 0.0152 (4)
H4 0.4395 0.7422 0.5181 0.018*
C5 0.47555 (5) 0.6495 (2) 0.37326 (17) 0.0159 (4)
H5 0.4923 0.7477 0.3590 0.019*
C6 0.38322 (5) 0.5128 (2) 0.57569 (17) 0.0152 (4)
C7 0.35568 (5) 0.6507 (2) 0.57738 (17) 0.0157 (4)
H7 0.3607 0.7422 0.5217 0.019*
C8 0.32052 (5) 0.6529 (2) 0.66214 (17) 0.0164 (4)
C9 0.31541 (6) 0.5194 (2) 0.74549 (17) 0.0180 (4)
H9 0.2922 0.5213 0.8054 0.022*
C10 0.34372 (6) 0.3827 (2) 0.74276 (18) 0.0184 (4)
H10 0.3396 0.2930 0.8006 0.022*
C11 0.37792 (6) 0.3771 (2) 0.65610 (17) 0.0170 (4)
H11 0.3970 0.2836 0.6520 0.020*
C12 0.28803 (5) 0.7966 (2) 0.65906 (17) 0.0181 (4)
H12 0.2652 0.7741 0.7249 0.022*
C13 0.30987 (6) 0.9629 (2) 0.6918 (2) 0.0275 (5)
H13A 0.3235 0.9549 0.7758 0.041*
H13B 0.2878 1.0517 0.6925 0.041*
H13C 0.3322 0.9886 0.6281 0.041*
C14 0.26508 (6) 0.8075 (2) 0.52974 (18) 0.0233 (4)
H14A 0.2862 0.8415 0.4648 0.035*
H14B 0.2414 0.8899 0.5342 0.035*
H14C 0.2529 0.6980 0.5076 0.035*
Cl1 0.44561 (2) 1.01245 (5) 0.64618 (4) 0.02029 (16)
O1 0.38844 (5) 0.98547 (18) 0.40139 (15) 0.0263 (3)
H1A 0.4046 (8) 0.983 (3) 0.338 (3) 0.029 (7)*
H1B 0.4066 (9) 0.998 (3) 0.464 (3) 0.041 (7)*

1 Source of materials

Bis(3-isopropylphenyl)-4,4′-bipyridinium dichloride was prepared by Zincke reaction according to the method described in ref. 5. A mixture of N,N-bis(2,4-dinitrophenyl) 4,4′-bipyridinium dichloride (56.0 mg, 0.1 mmol) and 3-isopropylaniline (41.0 mg, 0.3 mmol) was dissolved in ethanol (20 ml) in a round-bottomed flask. The solution was heated for 24 h at 80 °C and cooled to room temperature and the solvent was evaporated under reduced pressure. The crude product was washed by acetone (25 ml × 3). Yellow solids were obtained in vacuum in 73 % yield (34.0 mg).

2 Experimental details

Using Olex2, 1 the structure was solved using Charge Flipping and refined with the ShelXL 3 refinement. All hydrogen atoms were positioned geometrically, with the d(C–H) = 0.97–0.99 Å, U iso (H) = 1.2 times U eq (C) and U iso (H) = 1.5 times U eq(O).

3 Comment

Disubstituated bipyridinium ions, which also named viologen derivatives (RV2+), have been widely studied in electrochemistry, 6 conductivity and optoelectronic materials 7 , 8 , 9 attributed to their electron acceptor property. For example, the color change of viologens is mainly ascribed to the electron transfer from the electron-donating moieties to the viologen dication to form the corresponding radical cation ( V + ). However, the electron transfer process generally requires the presence of a reducing agent. Recent study revealed that the host-guest complexes of RV2+ with cucurbit[8]uril could be utilized as smart photochromism materials in the absence of reducing agent via the formation of through-space conjugated supramolecular polymer. In this case, the photoinduced electron transfer occurred between the π-conjugated electron donor and acceptor moieties of the guest in the assistance of the host encapsulation. 10 Here, we report the crystal structure of bis(3-isopropylphenyl)-4,4′-bipyridinium dichloride. The crystal structure shows that the V2+ moiety has reacted with 3-isopropylaniline to form a π-conjugated system with an electron donor-acceptor-donor structure (4,4′-bipyridinium was defined as the electron acceptor moiety and 3-isopropylphenyl was defined as the electron donor group). All the bond lengths and bond angles are within the normalscope. In particular, it was found that the distance between the nitrogen cations and the counter anion chloride ion is shorter than 4.5 Å. The color change of crystal sample indicated photoinduced electron transfer, which was processed in the compound of bis(3-isopropylphenyl)-4,4′-bipyridinium dichloride in the absence of a reducing agent.


Corresponding author: Guangyi Li, Department of General Surgery, Hunan Provincial People’s Hospital (The First-Affiliated Hospital of Hunan Normal University), Changsha, 410004, China, E-mail:

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

  2. Competing interests: The authors declare no conflicts of interest regarding this article.

References

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Received: 2024-07-16
Accepted: 2024-09-27
Published Online: 2024-10-16
Published in Print: 2024-12-17

© 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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