Crystal structure of 1-mesityl-3-methyl-4-phenyl-1H-1,2,3-triazol-3-ium iodide

Daniel Canseco-González; Juventino J García; Marcos Flores-Alamo

doi:10.1107/S2056989015023403

. 2015 Dec 12;71(Pt 12):o1041–o1042. doi: 10.1107/S2056989015023403

Crystal structure of 1-mesityl-3-methyl-4-phenyl-1H-1,2,3-triazol-3-ium iodide

Daniel Canseco-González ^a, Juventino J García ^a,^*, Marcos Flores-Alamo ^a

PMCID: PMC4719969 PMID: 26870488

Abstract

In the cation of the title salt, C₁₈H₂₀N₃ ⁺·I⁻, the mesityl and phenyl rings are inclined to the central triazolium ring by 61.39 (16) and 30.99 (16)°, respectively, and to one another by 37.75 (15)°. In the crystal, molecules are linked via C—H⋯I hydrogen bonds, forming slabs parallel to the ab plane. Within the slabs there are weak π–π interactions present involving the mesityl and phenyl rings [inter-centroid distances are 3.8663 (18) and 3.8141 (18) Å].

Keywords: crystal structure, triazolium salt, mesityl group, C—H⋯I hydrogen bonds

Related literature

For classical Arduengo-type imidazol-2-ylidene N-heterocyclic carbenes (NHCs), see: Arduengo et al. (1995 ▸); Mathew et al. (2008 ▸). For similar 1-mesityl-3-methyl-4-phenyl-1H-1,2,3-triazol-3-ium structures and some complexes, see: Saravanakumar et al. (2011 ▸); Hohloch et al. (2011 ▸, 2013 ▸); Shaik et al. (2013 ▸).

Experimental

Crystal data

C₁₈H₂₀N₃ ⁺·I⁻
M _r = 405.27
Monoclinic,
a = 7.6704 (3) Å
b = 9.9341 (3) Å
c = 22.8541 (10) Å
β = 98.982 (4)°
V = 1720.09 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.86 mm⁻¹
T = 130 K
0.14 × 0.08 × 0.02 mm

Data collection

Agilent Xcalibur Atlas Gemini diffractometer
Absorption correction: analytical (CrysAlis RED; Agilent, 2013 ▸) T _min = 0.864, T _max = 0.963
8948 measured reflections
4073 independent reflections
3374 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.084
S = 1.16
4073 reflections
203 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: (CrysAlis PRO; Agilent, 2013 ▸); cell refinement: (CrysAlis RED; Agilent, 2013 ▸); data reduction: (CrysAlis RED; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015023403/su5254sup1.cif

e-71-o1041-sup1.cif^{(324.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023403/su5254Isup2.hkl

e-71-o1041-Isup2.hkl^{(324.7KB, hkl)}

Click here for additional data file.^{(6.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015023403/su5254Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015023403/su5254fig1.tif

The molecular structure of the title salt, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(2.5MB, tif)}

a . DOI: 10.1107/S2056989015023403/su5254fig2.tif

A view along the a axis of the crystal packing of the title compound. The C—H⋯I hydrogen bonds are shown as dashed lines (see Table 1). H atoms not involved in these interactions have been omitted for clarity.

CCDC reference: 1440705

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯I1ⁱ	0.95	3.12	4.049 (3)	168
C12—H12A⋯I1ⁱⁱ	0.98	3.20	3.916 (3)	131
C12—H12B⋯I1	0.98	3.22	4.172 (3)	163

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

DCG would like to thank DGAPA–UNAM for a postdoctoral fellowship. The authors thank Dr Alma Arévalo for her technical assistance. This work was supported financially by CONACYT (178265) and DGAPA-PAPIIT-IN-210613, which is gratefully acknowledged

supplementary crystallographic information

S1. Commentary

Mesoionic 1,2,3-triazol-5-ylidenes bear only one nitrogen adjacent to the carbene bonding site and are more basic than the classical Arduengo-type imidazol-2-ylidene NHCs (Arduengo et al., 1995; Mathew et al., 2008). This type of triazolylidene has recently been applied for the development of a variety of organometallic complexes, specially directed towards catalytic purposes (Saravanakumar et al., 2011; Hohloch et al., 2011,2013); Shaik et al., 2013).

In the cation of the title salt, Fig. 1, the central triazolium ring (N1—N3/C10/C11) is inclined to the mesityl (C1—C6) and phenyl (C13—C18) rings by 61.39 (16) and 30.99 (16) °, respectively, while the two six-membered aromatic rings are inclined to one another by 37.75 (15) °.

In the crystal, molecules are linked via C—H···I hydrogen bonds forming slabs parallel to the ab plane (Table 1 and Fig. 2). Within the slabs there are slipped parallel π-π interactions present involving the mesityl and phenyl rings: Cg2···Cg3ⁱ = 3.8663 (18) Å [where Cg2 and Cg3 are the centroids of rings C1—C6 and C13—C18, interplanar distance = 3.6798 (13) Å, slippage = 1.595 Å; symmetry ocde: (i) − x + 3/2, y + 1/2, − z + 1/3], and Cg2···Cg3ⁱⁱ = 3.8141 (18) Å [interplanar distance = 3.5739 (13) Å, slippage = 1.797 Å; symmetry ocde: (ii) − x + 5/2, y + 1/2, −z + 1/2]; see Fig. 2.

S2. Synthesis and crystallization

Synthesis of 1-mesityl-4-phenyl-1,2,3-triazole

2-azido-1,3,5-trimethylbenzene (868 mg, 5.4 mmol), and phenylacetylene (1000 mg, 4.9 mmol) were suspended in a mixture of water (16.0 ml) and ^tBuOH (16.0 ml). To the previous mixture CuSO₄ (10.6 mg, 0.05 mmol), and sodium ascorbate (97 mg, 0.50 mmol) were added and stirred for 24 h at 100 °C. The reaction mixture was allowed to cool and ^tBuOH was evaporated off. The resulted mixture was extracted with CH₂Cl₂ (2 × 100 ml). The combined organic phases were washed with water (2 × 60 ml), brine (2 × 50 ml), dried over MgSO₄ and evaporated to dryness. The residue was washed with pentane (50 ml) to afford the crude triazole as an off brown solid. The crude product was recrystallized from hot acetone to give the corresponding pure triazole (yield: 1100 mg, 85%). ¹H NMR (CDCl₃, 300 MHz): δ 7.93 (d, ³J_HH = 7.8 Hz, 2H, H_ar), 7.84 (s, 1H, H_trz), 7.47 (t, ³J_HH = 7.8 Hz, 2H, H_ar), 7.36 (t, ³J_HH = 7.5 Hz, 1H, H_ar), 7.01 (s, 2H, H_mes), 2.37 (s, 3H, ArCH₃), 2.02 (s, 6H, ArCH₃). ¹³C{¹H} NMR (CDCl₃, 75 MHz): δ 147.5 (C_trz–Mes), 140.0, 135.1, 133.5, 130.4, 129.1 (5 × C_ar), 128.9 (C_trz-H), 130.4, 128.8, 128.2 (3 × C_ar), 21.1 (Ar—CH₃), 17.3 (Ar—CH₃).

Synthesis of 1-mesityl-3-methyl-4-phenyl-1H-1,2,3-triazol-3-ium iodide

A solution of 1-mesityl-4-phenyl-1,2,3-triazole (500 mg, 1.3 mmol) in MeCN (12 ml) was added CH₃I (1.7 g, 12 mmol) and the mixture was stirred at 373 K for 48 h. The workup and purification were carried out according to the general method. The title compound was obtained as a white solid (yield: 612 mg, 80%). Colourless plate-like crystals were obtained by ???? - please complete.¹H NMR (CDCl₃, 300 MHz): δ 8.86 (s, 1H, H_trz), 8.04 (m, 2H, Har), 7.58 (m, 3H, Har), 7.05 (s, 2H, Hmes), 4.58 (s, 3H, NCH3), 2.37 (s, 3H, ArCH3), 2.22 (s, 6H, ArCH3). ¹³C{¹H} NMR (CDCl3, 75 MHz): δ 144.2 (Ctrz–Mes), 142.5, 134.4, 132.2, 130.4, 130.1, 129.9, 129.7, 121.2, (8 × Car), 40.7 (NCH3), 21.2 (Ar—CH3), 18.5 (Ar—CH3). Anal. Calcd. for C18H20IN3 x 1 H2O (423.28): C 51.44, H 5.24, N 9.93. Found: C 51.44, H 4.34, N 10.17.

S3. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were placed in geometrically idealized positions and refined as riding on their parent atoms: C—H = 0.95–0.98 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms.