The crystal structure of bis(2-picolinium) hexachlorostannate dichloromethane monosolvate, C13H18Cl8N2Sn
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Dharmveer Bhedi
Abstract
C12H16Cl6N2Sn·CH2Cl2, monoclinic, P2/n (no. 13), a = 9.2218(10) Å, b = 9.9617(10) Å, c = 12.3674(13) Å, β = 107.243(3)°, V = 1085.1(2) Å3, Z = 2, Rgt(F) = 0.0295, wRref(F2) = 0.0548, T = 100(2) K.
Table 1 contains crystallographic data. The list of the atoms including atomic coordinates and displacement parameters can be found in the cif-file attached to this article.
Data collection and handling.
| Crystal: | Yellow block |
| Size: | 0.21 × 0.16 × 0.15 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 2.16 mm−1 |
| Diffractometer, scan mode: | Bruker APEX-II, φ and ω scans |
| θmax, completeness: | 27.0°, 100 % |
| N(hkl)measured, N(hkl)unique, Rint: | 20342, 2373, 0.049 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 2,157 |
| N(param)refined: | 114 |
| Programs: | Bruker, 1 SHELX, 2 , 3 WinGX 4 |
1 Source of materials
2-(Chloromethyl)pyridine hydrochloride and toluene were received from Spectrochem Pvt. Ltd., India. Tin powder was obtained from Central Drug House (CDH), India and used after activation by washing with a 10 % aqueous solution of NaOH. Dichloromethane (DCM) was received from Central Drug House (CDH) and distilled before use. 1H & 13C NMR were recorded on a Bruker 500 MHz spectrometer. NMR spectra were recorded using CDCl3 [1H (δ) = 7.26, 13C (δ) = 77.0]. We have recorded the melting point on a digital Buchi M−560 device. SCXRD was done at IIT–Kanpur using Bruker 1 Smart Apex Single Crystal XRD. We moistened the activated elemental tin powder (0.361 g, 3 mmol) with three drops of distilled water. We stirred this mixture for 10 min to make a paste, then distilled toluene (20 mL) was added, and the solution was further heated at 110 °C under reflux for 30 min then 2-(chloromethyl)pyridine hydrochloride (0.500 g, 3 mmol) was added to hot toluene, and the solution was heated for 16 h at 110 °C under reflux. The mixture was then cooled in the refrigerator. After 2 h, the dark yellow solid deposited on the wall of the round-bottom flask. The reaction mixture was filtered, and the filtrate was evaporated using a rotary evaporator to obtain the solid. Block-shaped crystals suitable for single-crystal XRD were obtained from the slow evaporation of a DCM solution of the solid, [2-(CH3)C5H4NH]2[SnCl6]·CH2Cl2 (0.085 g, 9 %). M.pt.: 106 °C. 1 H NMR (CDCl3, 500 MHz, ppm): δ 3.02 (s, 3H), 7.74 (d, J = 8 Hz, 1H,), 7.82 (m, 1H), 8.36 (m, 1H), 9.18 (d, J = 6 Hz, 1H). 13 C{ 1 H} NMR (CDCl3, 125 MHz, ppm): δ 20.8, 124.1, 127.5, 142.6, 145.5, 154.2.
2 Experimental details
We have determined and refined the crystal structure using the SHELXT 2 and SHELXL 3 programs in the WinGx 4 program. The data for absorption was corrected using the SADABS 5 program. Hydrogen atoms were positioned based on idealized geometry and refined using a riding model. The N-bound H atom was located on a difference Fourier map.
3 Comment
Bis(arylmethyl)tin dichloride is a necessary starting precursor for the easy formation of the Sn–O motif by hydrolysis or treatment with carboxylic/phosphonic/phosphinic/sulfonic acid. 6 Sisido and his coworkers first reported the synthesis of bis(arylmethyl)tin dichloride by the direct reaction of arylmethyl chloride with tin powder in toluene. 7 There are no reports for synthesizing bis(2-pyridylmethyl)tin dichlorides using this approach. We have recently shown the importance of bis(arylmethyl)tin dichlorides in preparing various simple organic molecules. 8 Hence, we attempted to explore the reaction of 2-(chloromethyl)pyridine hydrochloride with tin powder.
Lemon yellow solids were obtained after evaporation of DCM extraction from the evaporated filtrate in the reaction of 2-(chloromethyl)pyridine hydrochloride with tin powder in refluxing toluene. The chemical shift of the methylene proton for 2-(chloromethyl)pyridine hydrochloride occurs at 5.22 ppm, which was upfield shifted to 3.02 ppm in lemon yellow solid, and proton integration changes from two to three, which indicates the –CH2Cl, converting it to –CH3. Peak at 20.8 ppm in 13C{1H} NMR further confirms the presence of a –CH3 group attached to the 2-methylpyridinium moiety.
The asymmetric unit of the title compound consists of one full 2-methylpyridinium cation, one-half of the [SnCl6] dianionic unit, and one-half of the dichloromethane molecule. The molecular structure is shown in the figure. Four 2-methylpyridinium monocations nicely surround the [SnCl6] dianionic species, and two cations provide six hydrogen donors interacting with six chloride ions from two neighboring dianionic units. We have seen three different Sn–Cl bond lengths in our synthesized compound: Sn1–Cl1 2.4347(7) Å; Sn1–Cl3 2.4371(7) Å; Sn1–Cl2 2.4143(7) Å. The first two distances (2.4313(6) and 2.4330(9) Å) are almost similar, but the disparity has been seen in the last distance (2.4420(6) Å) in comparison to the report made by Horiuchi and his coworkers. 9 They have reported the crystal structure of [2-(CH3)C5H4NH]2[SnCl6] without any solvent molecule. 9 Nevertheless, three crystallographically inequivalent Sn–Cl bonds in [SnCl6] dianionic unit are within the range to the recently reported examples: bis(theophyllinium) hexachloridostannate (2.4182(5)–2.4482(6) Å); 10 [bis(2-amino-4-methylpyridinium)][SnCl6] (2.4097(8)–2.4369(7) Å); 11 [P(C4H9)4]2[SnCl6] (2.4203(1)–2.4478(1) Å); 12 [C7H10NO)]2[SnCl6]·2H2O (2.4235(4)–2.4470(5) Å); 13 3,7-diaminohexahydro-8,5-(epiminomethano)pyrido[3,4-b]pyrazin-10-ol in its tetraprotonated hydrochloric salt form with [SnCl6]2− (2.3962(9)–2.4494(10) Å). 14 The most probable reason these values of Sn–Cl bond get slightly different is that the nature of countercations varies; consequently, the packing may be changed. The metric parameters for the 2-methylpyridium ion in the title compound are closely related to [tris(2-methylpyridinium)][RhCl6]. 15 Because of the dichloromethane molecule (space-filling model) present in our compound, the packing structure shows a minimum number of hydrogen bonding interactions between cations and anions (C5–H5⋯·Cl1 2.8557(8) Å; C5–H5⋯Cl1 131.3(2)°; C4–H4⋯Cl2 2.6944(8) Å; C4–H4⋯Cl2 175.3(2)°; N1–H1⋯Cl3 2.751(30) Å; N1–H1⋯Cl3 158.7(28)°) with respect to Horiuchi structure. This may be the probable reason that the Sn1–Cl2 bond differs concerning to Horiuchi structure. 9
Funding source: Science and Engineering Research Board
Award Identifier / Grant number: CRG/2023/003075
Acknowledgements
DB is thankful to UGC for the Senior Research Fellowship. AS gratefully acknowledges CURAJ for the University Fellowship. RT thanks the Science and Engineering Research Board (SERB), Core Research Grant (No. CRG/2023/003075) for financial support and the University of Delhi for seed money grant.
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Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
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Conflict of interest: The authors declare no conflicts of interest regarding this article.
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