Home Physical Sciences Crystal structure of bis(((3a,7a-dihydro-1H-benzo[d][1,2,3]triazol-1-yl)methyl) triphenylphosphonium) tetrachloridomanganate(II), C50H42Cl4MnN6P2
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Crystal structure of bis(((3a,7a-dihydro-1H-benzo[d][1,2,3]triazol-1-yl)methyl) triphenylphosphonium) tetrachloridomanganate(II), C50H42Cl4MnN6P2

  • Chanchan Liu , Dandan Cui , Jingyin Yu , Mengjia Yang and Wenqiang Tang ORCID logo EMAIL logo
Published/Copyright: September 16, 2025

Abstract

C50H42Cl4MnN6P2, monoclinic, C2/c (no. 15), a = 26.2608(7) Å, b = 9.7828(2) Å, c = 18.5648(5) Å, β = 94.103(2)°, V = 4757(2) Å3, Z = 4, R gt (F) = 0.0479 wR ref (F 2) = 0.1046, T = 293 K.

CCDC no.: 2484879

The molecular structure is shown in the figure. Table 1 contains the crystallographic data and the list of the atoms including atomic coordinates and displacement parameters can be found in the cif-file attached to this article.

Table 1:

Data collection and handling.

Crystal: Clear greenish green block
Size: 0.38 × 0.23 × 0.21 mm
Wavelength:

μ:
Mo radiation (0.71073 Å)

0.61 mm−1
Diffractometer, scan mode:

θ max, completeness:
Rigaku, ω scans

29.2°, 100 %
N(hkl)measured, N(hkl)unique, R int: 11698, 5498, 0.023
Criterion for I obs, N(hkl)gt: I obs > 2 σ(I obs), 4,069
N(param)refined: 285
Programs: Rigaku, 1 SHELX, 2 , 3 Olex2 4

1 Source of materials

The crystalline material was prepared by dissolving ((3a,7a-dihydro-1H-benzo [d][1,2,3]triazol-1-yl)methyl)triphenylphosphonium chloride (0.05 mmol) and manganese dichloride (0.05 mmol) in anhydrous ethanol (4.0 mL) within a 10 mL Schlenk tube. Concentrated hydrochloric acid (37 %, 0.50 mL) was added dropwise with stirring. The homogeneous solution was filtered through a 0.45 μm PTFE syringe filter into a clean 5 mL glass vial, which was subsequently placed inside a larger vessel containing 10 mL of diethyl ether as a reservoir for vapor diffusion. Crystallization occurred over 7 days at room temperature. Crystal dimensions were optimized by adjusting the evaporative flux through controlled needle aperture occlusion.

2 Experimental details

The structure was solved using intrinsic phasing methods within SHELXT. 2 Subsequent anisotropic full-matrix least-squares refinement on all non-hydrogen atoms was conducted using SHELXL 3 within the Olex2 platform. 4 Hydrogen atoms were incorporated at idealized positions employing riding models, with fixed isotropic displacement parameters.

3 Comment

Triphenylphosphonium (TPP) cations constitute a privileged class of supramolecular building blocks in crystal engineering, renowned for their capacity to direct hierarchical assembly through synergistic cation-π interactions, C–H⋯π contacts, and van der Waals forces. 5 , 6 , 7 , 8 The steric bulk and electronic anisotropy of TPP systems have been leveraged to construct functional materials with engineered void spaces, tunable luminescence, and proton-conducting behavior, as evidenced by structural studies of tetrafluoroborate and hexafluorophosphate analogues. Our elucidation of the single-crystal structure of ((3a,7a-dihydro-1H-benzo[d][1, 2,3]triazol-1-yl)methyl)triphenylphosphonium manganese tetrachloride represents the first systematic integration of benzotriazole-functionalized TPP cations with paramagnetic [MnCl4]2− moieties. The crystalline hybrid material exhibits prospects as a prototype for designing stimuli-responsive magnetic systems.

As illustrated in the Figure, the crystal structure of the title compound reveals a phosphorus atom bonded to four substituents: three phenyl groups and one 3a,7a-dihydro-1H-benzo[d][1,2,3]triazolyl group. The observed P–C bond lengths are approximately 1.80 Å, consistent with values reported in the literature for similar systems. 9 , 10 , 11 , 12 The interplanar angles between the three phenyl groups are 89.7°, 67.9°, and 87.9°, respectively. The dihedral angles formed between the 3a,7a-dihydro-1H-benzo[d][1,2,3] triazolyl group and each of the phenyl rings are 70.9°, 19.1°, and 83.6°.

Within the title compound, the [MnCl4]2− anion interacts with the triphenylphosphonium moiety, forming an organic-inorganic hybrid architecture (right side of the figure). The [MnCl4]2− anion exhibits a tetrahedral geometry, with Mn–Cl bond lengths averaging approximately 2.38 Å, in agreement with literature precedents. 13 , 14 , 15 , 16 The crystal structure features an alternating arrangement of these organic cations and inorganic anions.


Corresponding author: Wenqiang Tang, Xianyang Key Laboratory of Molecular Imaging and Drug Synthesis, School of Pharmacy, Shaanxi Institute of International Trade & Commerce, Xianyang, Shaanxi, China, E-mail:

Acknowledgments

This work was financially supported by the projects of Social Development in Shaanxi Province Science and Technology Department (2025JC-YBMS-1076), the 2024 Scientific Research Program Projects of the Shaanxi Provincial Department of Education (24JK0334), the 2023 research and development project of the Xianyang Science and Technology Bureau (L2023-ZDYF-SF-030), Key Laboratory of Molecular Imaging and Drug Synthesis of Xianyang city (2021QXNL-PT-0008), School-level Scientific and Technological Innovation Team for Design, Synthesis and Structural Modification of Drug Molecules (2024KCTD04).

References

1. Rigaku, O. D. CrysAlisPRO; Rigaku Oxford Diffraction Ltd: Yarnton, Oxfordshire, England, 2017.Search in Google Scholar

2. Sheldrick, G. M. SHELXT – Integrated Space-Group and Crystal-Structure Determination. Acta Crystallogr., Sect. A: Found. Adv. 2015, 71, 3–8; https://doi.org/10.1107/s2053273314026370.Search in Google Scholar PubMed PubMed Central

3. Sheldrick, G. M. Crystal Structure Refinement with Shelxl. Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 3–8; https://doi.org/10.1107/s2053229614024218.Search in Google Scholar PubMed PubMed Central

4. Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A.; Puschmann, H. OLEX2: a Complete Structure Solution, Refinement and Analysis Program. J. Appl. Crystallogr. 2009, 42, 339–341; https://doi.org/10.1107/s0021889808042726.Search in Google Scholar

5. Giese, M.; Albrecht, M.; Valkonen, A.; Rissanen, K. Anion-π Interaction: an Influential Force in Solid State Molecular Microstructures. Eur. J. Org Chem. 2013, 2013, 3247–3253; https://doi.org/10.1002/ejoc.201201704.Search in Google Scholar

6. Morita, K.; Ohta, R.; Aoyama, H.; Yahata, K.; Arisawa, M.; Fujioka, H. Concise Synthesis of Oxacyclic Compounds Using Highly Discriminative two-way Transformations of α,β-unsaturated Esters in the Presence of Enones. Chem. Commun. 2017, 53, 6605–6608; https://doi.org/10.1039/c7cc03287k.Search in Google Scholar PubMed

7. Wood, J. S.; Wikholm, R. J.; McEwen, W. E. The Crystal and Molecular Structure of Benzyl (2-methoxyphenyl)-diphenylphosphonium bromide. Phosphorus Sulfur Relat. Elem. 1977, 3, 163–169; https://doi.org/10.1080/03086647708077706.Search in Google Scholar

8. Yunker, L. P. E.; Ahmadi, Z.; Logan, J. R.; Wu, W.; Li, T.; Martindale, A.; Oliver, A. G.; McIndoe, J. S. Real–Time Mass Spectrometric Investigations into the Mechanism of the Suzuki–Miyaura Reaction. Organometallics 2018, 37, 4297–4308; https://doi.org/10.1021/acs.organomet.8b00705.Search in Google Scholar

9. Babu, K. N.; Massarwe, F.; Shioukhi, I.; Masarwa, A. Sequential Selective C–H and C(sp3)-+P Bond Functionalizations: An Entry to Bioactive Arylated Scaffolds. Angew. Chem., Int. Ed. 2021, 60, 26199–26209; https://doi.org/10.1002/anie.202111164.Search in Google Scholar PubMed

10. Sharutin, V. V.; Sharutina, O. K.; Senchurin, V. S. Synthesis and Structure of Gold Complexes [Ph3P(4–FC6H4CH2)]+[AuCl4]– and [Ph3PCH2CH=CHMe]+[AuCl4]–. Russ. J. Gen. Chem. 2016, 86, 2356–2360; https://doi.org/10.1134/s1070363216100182.Search in Google Scholar

11. Davis, M. C.; Parrish, D. A. Synthesis of 4-(N,N-Dialkylamino) Benzyltriphenylphosphonium Iodides from Hydroxymethyltriphenylphosphonium Iodide and N,N-Dialkylaniline. Synth. Commun. 2008, 38, 3909–3918; https://doi.org/10.1080/00397910802238783.Search in Google Scholar

12. Imanieh, H.; Ghammamy, S.; Nikje, M. M. A.; Hosseini, F.; Aghbolagh, Z. S.; Fun, H.-K.; Khavasi, H. R.; Kia, R. Synthesis, Characterization, X–Ray Structural Analysis, and Iodination Ability of Benzyl(triphenyl)Phosphonium Dichloroiodate. Helv. Chim. Acta 2011, 94, 2248–2255; https://doi.org/10.1002/hlca.201100198.Search in Google Scholar

13. Pan, H.-M.; Yang, Q.-L.; Xing, X.-X.; Li, J.-P.; Meng, F.-L.; Zhang, X.; Xiao, P.-C.; Yue, C.-Y.; Lei, X.-W. Enhancement of the Photoluminescence Efficiency of Hybrid Manganese Halides Through Rational Structural Design. Chem. Commun. 2021, 57, 6907–6910; https://doi.org/10.1039/d1cc02353e.Search in Google Scholar PubMed

14. Reiss, G. J. The Crystal Structure of 3-((1R,2S)-1-methylpyrrolidin-1-ium-2-yl)pyridin-1-ium tetrachloridomanganate(II), C10H16Cl4MnN2. Z. Kristallogr. N. Cryst. Struct. 2020, 235 (2), 415–417. https://doi.org/10.1515/ncrs-2019–0717.10.1515/ncrs-2019-0717Search in Google Scholar

15. He, Z.-L.; Wei, J.-H.; Zhang, Z.-Z.; Luo, J.-B.; Kuang, D.-B. Manganese–Halide Single–Crystal Scintillator Toward High–Performance X–Ray Detection and Imaging: Influences of Halogen and Thickness. Adv. Opt. Mater. 2023, 11, 2300449; https://doi.org/10.1002/adom.202300449.Search in Google Scholar

16. Zhou, G.; Liu, Z.; Molokeev, M. S.; Xiao, Z.; Xia, Z.; Zhang, X.-M. Manipulation of Cl/Br Transmutation in Zero-dimensional Mn2+ -based Metal Halides Toward Tunable Photoluminescence and Thermal Quenching Behaviors. J. Mater. Chem. C 2021, 9, 2047–2053; https://doi.org/10.1039/d0tc05137c.Search in Google Scholar

Received: 2025-07-01
Accepted: 2025-09-04
Published Online: 2025-09-16
Published in Print: 2025-12-17

© 2025 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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