1,4-Bis[4-(meth­oxy­carbon­yl)benz­yl]-1H-1,2,4-triazol-4-ium bromide

Wen-Jiao Guo; Hua-Rong Huang; Zhi-Yun Du; Yan-Xiong Fang; Kun Zhang

doi:10.1107/S1600536812016728

. 2012 Apr 28;68(Pt 5):o1553. doi: 10.1107/S1600536812016728

1,4-Bis[4-(methoxycarbonyl)benzyl]-1H-1,2,4-triazol-4-ium bromide

Wen-Jiao Guo ^a, Hua-Rong Huang ^a,^*, Zhi-Yun Du ^a, Yan-Xiong Fang ^a, Kun Zhang ^a

PMCID: PMC3344652 PMID: 22590414

Abstract

In the title salt, C₂₀H₂₀N₃O₄ ⁺·Br⁻, the dihedral angle between the benzene rings is 8.69 (16)°, and those between the benzene rings and the triazole ring are 69.98 (18) and 72.17 (18)°. In the crystal, C—H⋯Br hydrogen bonds link the cations and anions into chains along the c axis.

Related literature

For general background to triazole derivatives, see: Zanardi et al. (2011) ▶. For a related structure, see: Huang et al. (2010 ▶).

Experimental

Crystal data

C₂₀H₂₀N₃O₄ ⁺·Br⁻
M _r = 446.30
Orthorhombic,
a = 33.6880 (15) Å
b = 4.7962 (3) Å
c = 12.3337 (6) Å
V = 1992.81 (18) Å³
Z = 4
Cu Kα radiation
μ = 3.08 mm⁻¹
T = 173 K
0.40 × 0.32 × 0.31 mm

Data collection

Oxford Diffraction Xcalibur Atlas Gemini Ultra diffractometer
Absorption correction: multi-scan (ABSPACK in CrysAlis PRO; Oxford Diffraction, 2006 ▶) T _min = 0.372, T _max = 0.449
6375 measured reflections
2709 independent reflections
2541 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.069
S = 1.05
2709 reflections
255 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ▶), 840 Friedel pairs
Flack parameter: 0.021 (18)

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999) ▶ and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812016728/ng5263sup1.cif

e-68-o1553-sup1.cif^{(21.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016728/ng5263Isup2.hkl

e-68-o1553-Isup2.hkl^{(133KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812016728/ng5263Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Br1	0.95	2.61	3.461 (3)	149
C3—H3A⋯Br1	0.99	2.91	3.795 (4)	149
C2—H2⋯Br1ⁱ	0.95	2.75	3.657 (3)	161

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was funded by the 211 Project of Guangdong Province.

supplementary crystallographic information

Comment

1H-1,2,4-Triazole, like imidazole and benzimidazole, can be N-alkylated to form N-heterocyclic carbine (Zanardi et al., 2011).

In an earlier report, we presented a N-heterocyclic benzimidazole derivative. The crystal structure consists of infinite chains connected via C—H···Br and C—H···O hydrogen bonds; it also shows π···π stacking interactions (Huang et al., 2010).

In this work, we report the structure of a triazole-based N-heterocyclic carbene, 1,4-bis[4-(methoxycarbonyl)benzyl]-1H-1,2,4-triazolium bromide (Fig. 1).

In the crystal structure, the dihedral angles between the triazole ring system and the two (C4–C9) and (C13–C18) benzene rings are 69.98 (18) ° and 72.17 (18) °, respectively; the dihedral angle between the two benzene rings is 8.69 (16) °.

The bromide anions and cations form infinite hydrogen bonding chains along the c-axis via C—H···Br hydrogen bonds between the bromide anions and carbineen atoms of triazole ring and ethylene linkage (Fig. 2, Table 1).

Experimental

4-(Methoxycarbonyl)benzyl bromide (2.28 g, 10.0 mmol) was slowly added to a solution of 1H-1,2,4-triazole (0.35 g, 5.0 mmol) in acetonitrile (25 ml) and the resulting mixture was stirred under reflux for 8 h.

The solvent was evaporated under reduced pressure. The solid residue was recrystallized in methanol, and colorless block crystals were obtained after few days, yield 1.42 g, 63.5%.

Elemental analysis, calcd (%) for C₂₀H₂₀N₃BrO₄: C 53.82, H 4.52, N 9.42; found(%): C 53.80, H 4.60, N 9.41.

The FAB mass spectrum showed tje ions at 447.