4-(4-Hy­droxy­methyl-1H-1,2,3-triazol-1-yl)benzoic acid

Dayang Hazwani Abang Ishak; Hairul Anuar Tajuddin; Zanariah Abdullah; Siti Nadiah Abd Halim; Edward R T Tiekink

doi:10.1107/S1600536811022409

. 2011 Jun 18;67(Pt 7):o1658. doi: 10.1107/S1600536811022409

4-(4-Hydroxymethyl-1H-1,2,3-triazol-1-yl)benzoic acid

Dayang Hazwani Abang Ishak ^a, Hairul Anuar Tajuddin ^a,^‡, Zanariah Abdullah ^a, Siti Nadiah Abd Halim ^a, Edward R T Tiekink ^a,^*

PMCID: PMC3151797 PMID: 21837058

Abstract

In the title compound, C₁₀H₉N₃O₃, there is a small twist between the benzene and triazole rings [dihedral angle = 6.32 (7)°]; the carboxylic acid residue is almost coplanar with the benzene ring to which it is attached [O—C—C—C torsion angle = 1.49 (19)°]. The main deviation from coplanarity of the non-H atoms is found for the hydroxy group which is almost perpendicular to the remaining atoms [N—C—C—O torsion angle = −75.46 (16)°]. In the crystal, the presence of O—H⋯O (between carboxyl groups) and O—H⋯N (between the hydroxy group and the triazole ring) hydrogen bonds leads to supramolecular chains along [03 Inline graphic ]. The chains are connected into sheets via C—H⋯O(hydroxy) interactions.

Related literature

For background to the fluorescence potential, see: McCaroll & Wandruzska (1997 ▶). For synthetic protocols, see: Rostovtsev et al. (2002 ▶); Ryu & Zhao (2005 ▶); Himo et al. (2005 ▶). For additional geometric analysis, see: Spek (2009 ▶).

Experimental

Crystal data

C₁₀H₉N₃O₃
M _r = 219.20
Triclinic,
a = 5.4641 (7) Å
b = 6.6596 (8) Å
c = 13.1898 (16) Å
α = 88.828 (2)°
β = 83.577 (2)°
γ = 75.828 (2)°
V = 462.42 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.684, T _max = 0.746
5837 measured reflections
2099 independent reflections
1852 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.130
S = 1.08
2099 reflections
151 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811022409/hb5906sup1.cif

e-67-o1658-sup1.cif^{(16KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022409/hb5906Isup2.hkl

e-67-o1658-Isup2.hkl^{(101.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811022409/hb5906Isup3.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
O1—H1o⋯O2ⁱ	0.85 (1)	1.77 (2)	2.6119 (14)	173 (2)
O3—H3o⋯N3ⁱⁱ	0.85 (1)	1.96 (1)	2.7995 (16)	169 (2)
C6—H6⋯O3ⁱⁱⁱ	0.95	2.60	3.5309 (19)	167
C8—H8⋯O3ⁱⁱⁱ	0.95	2.23	3.1262 (18)	158

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

Acknowledgments

The University of Malaya is thanked for a University of Malaya Research Grant (No. RG080/09AFR) and for support of the crystallographic facility.

supplementary crystallographic information

Comment

The title compound, (I), is a precursor for the synthesis of fluorescent surfactants (McCaroll & Wandruzska, 1997). With the exception of the hydroxy substituent, the molecule of (I), Fig. 1, is essentially planar. The triazole ring is slightly twisted out of the plane of the benzene ring as seen in the value of the N2—N1—C5—C4 torsion angle of -6.43 (19) °; the dihedral angle between the rings is 6.32 (7) °. The carboxylic acid group is co-planar with the benzene ring to which it is attached: the O1—C1—C2—C3 torsion angle is 1.49 (19) °. The hydroxy group occupies a position almost perpendicular to the rest of the molecule with the N3—C9—C10—O3 torsion angle being -75.46 (16) °. Within the triazole ring, the sequence of N1—N2 [1.3562 (15) Å], N2—N3 [1.3141 (16) Å], N1—C8 [1.3579 (17) Å], N3—C9 [1.3627 (17) Å] and C8—C9 [1.3624 (19) Å] bond distances indicates considerable delocalization of π-electron density within the ring.

The crystal packing is dominated by O—H···O,N hydrogen bonding, Table 1. The carboxylic acid residues self-associate via the familiar eight-membered {··· HOC(═O)}₂ synthon, and the hydroxy groups forms a hydrogen bond with the triazole-N3 atom via centrosymmetric 10-membered {···HOC₂N}₂ synthons. The result is the formation of a linear supramolecular chain with base vector [0 3 1], Fig. 2. Chains are connected into flat arrays via C—H···O hydrogen bonds and centrosymmetric ten-membered {···HC₃O}₂ synthons, Table 1 and Fig. 2. The closest interactions between layers are weak π···π contacts occurring between translationally related benzene and triazole rings [3.9433 (9) Å for symmetry operation x, 1 + y, z].

Experimental

The title compound was synthesized via a Cu(I)-catalyzed cycloaddition between 4-azidobenzoic acid and propargyl alcohol after literature procedures (Rostovtsev et al., 2002; Ryu & Zhao, 2005). 4-Azidobenzoic acid (1.0 g, 6.1 mmol) and propargyl alcohol (1.03 g, 18.4 mmol) were dissolved in methanol (20 ml) while stirring in the dark. Freshly prepared catalyst was prepared from the reduction of copper(II) sulfate (0.2 g, 0.08 mmol) with sodium ascorbate (0.4 g, 2 mmol) in about 2 ml of water (Himo et al., 2005). The catalyst was then added into the mixture followed by stirring for 3 h. The crude product was dissolved in diethyl ether and washed with cold distilled water (50 ml). The organic layer was dried over magnesium sulfate, and the solvent was removed under vacuum to obtain 0.12 g (21%) of pure product. Yellow blocks were grown from its solution of THF (with a drop of ethyl acetate); M.pt. 529 - 532 K.