Home The crystal structure of 1,2-bis(pyridinium-4-yl)ethane diperchlorate, C12H14N2·2ClO4 – a second polymorph
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The crystal structure of 1,2-bis(pyridinium-4-yl)ethane diperchlorate, C12H14N2·2ClO4 – a second polymorph

  • Qi-Ming Qiu ORCID logo EMAIL logo , Jian-Biao Song , Li Yan , Ai-Guo Dong , Chuan-Tao Li and Zhi-Yuan Zheng EMAIL logo
Published/Copyright: May 25, 2022

Abstract

C12H14N2·2ClO4, monoclinic, P21/c (no. 14), a = 5.3170(4) Å, b = 12.8711(8) Å, c = 11.6788(7) Å, β = 100.888(2)°, V = 784.86(9) Å3, Z = 2, R gt (F) = 0.0434, wR ref (F2) = 0.1211, T = 298 K.

CCDC no.: 2164314

The asymmetric unit (labeled atoms) of the title crystal 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: Colorless block
Size: 0.10 × 0.05 × 0.04 mm
Wavelength: Cu Kα radiation (1.54178 Å)
μ: 4.17 mm−1
Diffractometer, scan mode: Bruker Apex-II, φ and ω
θmax, completeness: 71.5°, >99%
N(hkl)measured, N(hkl)unique, Rint: 2587, 1500, 0.025
Criterion for Iobs, N(hkl)gt: Iobs > 2σ(Iobs), 1338
N(param)refined: 110
Programs: Bruker [1], SHELX [2, 3]
Table 2:

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

Atom x y z Uiso*/Ueq
C1 0.3463 (5) 0.9660 (3) 0.8381 (2) 0.0552 (8)
H1A 0.230091 0.985707 0.884468 0.066*
C2 0.3460 (5) 1.0154 (2) 0.7338 (2) 0.0513 (7)
H2 0.229471 1.068425 0.709045 0.062*
C3 0.5219 (5) 0.98538 (19) 0.6653 (2) 0.0408 (6)
C4 0.6890 (5) 0.9061 (2) 0.7074 (2) 0.0441 (6)
H4 0.809190 0.884236 0.664155 0.053*
C5 0.6805 (6) 0.8597 (2) 0.8108 (2) 0.0504 (7)
H5 0.793518 0.806186 0.838106 0.060*
C6 0.5286 (7) 1.0364 (2) 0.5505 (2) 0.0648 (9)
H6A 0.404808 1.092604 0.538650 0.078*
H6B 0.696914 1.066438 0.553110 0.078*
O1 0.4271 (4) 0.70887 (16) 0.57945 (18) 0.0599 (6)
O2 0.0654 (4) 0.60474 (17) 0.5571 (2) 0.0681 (7)
O3 0.1610 (4) 0.71803 (19) 0.71709 (17) 0.0668 (7)
O4 0.0215 (5) 0.78368 (17) 0.5288 (2) 0.0690 (6)
N1 0.5111 (5) 0.89091 (19) 0.87248 (18) 0.0523 (6)
H1 0.508191 0.860886 0.937997 0.063*
Cl1 0.16707 (11) 0.70393 (4) 0.59677 (5) 0.0399 (3)

Source of material

An aqueous solution (5 mL) of 2′-deoxycytidine-5′-monophosphate (dCMP, 30 mg, 0.10 mmol) was added into an aqueous solution (5 mL) of Co(ClO4)2⋯6H2O (18 mg, 0.05 mmol). After stirring for 10 min, 1,2-bis(4-pyridyl)ethane (bpa, 9 mg, 0.05 mmol) in distilled water (5 mL) was added to this mixture. Perchloric acid was also dropped in it and the resulting solution (pH = 3) was stirred at room temperature for 30 min. The colorless block crystals of the perchlorate salt of the starting material 1,2-bis(4-pyridyl) ethane were obtained by evaporation at room temperature after two weeks by accident.

Experimental details

The structure was solved by direct methods and refined using the Shelxl programs [2, 3]. The hydrogen atoms were restrained. Their Uiso values were set to 1.2Ueq of the parent atoms.

Comment

1,2-bis(4-pyridyl)ethane (bpa) is a perfect ligand to form supramolecular structures [4], [5], [6]. In our previous work [7], we used auxiliary ligands, namely bpa, to competitively coordinate a metal ion to a mononucleotide to restrain the nonenzymatic hydrolysis of the phosphate group catalyzed by metal ions, and we got complex Co-dCMP-bpa (dCMP = 2′-deoxycytidine-5′-monophosphate) below pH = 6. Due to the different charged states of dCMP in aqueous solution, it is meaningful to study nucleotide complex in other different pH values. Single crystals of thetitle compound has been obtained under a more acidic environment (pH = 3).

Polymorphism in crystals is defined as a compound has identical chemical compositions while adopting more than one arrangement [8]. Widely used drugs such as aspirin and acetaminophen are all known to be polymorphic, and the crystal packing of them have a significant impact on their properties [9]. There is a recently reported example of organic polymorphs: 3-ammonio4-aminobenzoate is found to form two polymorphs [10, 11]. The title compound consists of bpa molecules located around a two-fold axes and perchlorate anions in general positions with a ratio of 1:2 (monoclinic space group P21/c, Z = 2). In contrast the reported polymorph (space group P21, Z = 4) [6] consists of two crystallographically independent bpa molecules. In the previous polymorph, the distance between two adjacent six membered rings is 4.007(2) and 3.945(3) Å, which shows very weak π–π-stacking interactions [6]. However, in title compound, this value is expanded to 5.613(1) Å, indicating that there is no π–π-stacking interactions in the compound. In addition, neighboring bpa molecules are linked by the N1–H1·N2/N3–H3A·N4 to form a one-dimensional chain expanded along the b-axis in the previous polymorph [6], while, the hydrogen bonds in the title structure are weaker.


Corresponding authors: Qi-Ming Qiu and Zhi-Yuan Zheng, School of Science, China University of Geosciences, Beijing 100083, P. R. China, E-mail: ,

Funding source: New Teachers’ Basic Scientific Research Ability Improvement Project http://dx.doi.org/10.13039/501100002366

Award Identifier / Grant number: 2-9-2021-008

Acknowledgements

We gratefully acknowledge support by Analytical and Testing Centre in Beijing Institute of Technology and the New Teachers’ Basic Scientific Research Ability Improvement Project (grant no. 2-9-2021-008) in China University of Geosciences.

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

  2. Research funding: New Teachers’ Basic Scientific Research Ability Improvement Project (grant no. 2-9-2021-008) in China University of Geosciences.

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

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Received: 2022-04-11
Accepted: 2022-05-12
Published Online: 2022-05-25
Published in Print: 2022-08-26

© 2022 Qi-Ming Qiu et al., published by De Gruyter, Berlin/Boston

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

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