5-Methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid

Lin, J.R.; Yao, J.Y.; Zhao, H.

doi:10.1107/S1600536808027311

organic compounds

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Volume 64| Part 9| September 2008| Page o1843

doi:10.1107/S1600536808027311

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5-Methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid

Jin Rui Lin,^a Ji Yuan Yao ^a and Hong Zhao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: zhaohong@seu.edu.cn

(Received 25 July 2008; accepted 25 August 2008; online 30 August 2008)

The title compound, C₁₀H₉N₃O₂, was synthesized from azidobenzene and ethyl acetylacetate. A pair of hydrogen bonds [2.617 (2) Å] interconnects a pair of the carboxyl groups, forming an R²₂(8) inversion dimer, a frequent motif in carboxylic acids. In the title structure, the bonding H atom in the aforementioned O—H⋯O hydrogen bond is significantly shifted towards the acceptor O atom [the donor and acceptor O—H distances are 1.25 (4) and 1.38 (4) Å, respectively]. A plot of the O⋯O versus O—H distances in compounds with paired carboxyl groups shows that the title structure belongs to the group of structures with abnormally long O—H distances with regard to the O⋯O contacts. The displacement of the bonding H atom towards the centre of the hydrogen bond is concomitant with more equal C—O bonding distances in the carboxyl group.

Related literature

For related literature, see: El Khadem et al. (1968 ); Olesen et al. (2003 ); Tian et al. (2005 ); Allen (2002 ); Etter et al. (1990 ); Radl et al. (2000 ).

Experimental

Crystal data

C₁₀H₉N₃O₂
M_r = 203.20
Monoclinic, C 2/c
a = 23.616 (3) Å
b = 7.7189 (15) Å
c = 12.606 (2) Å
β = 113.18 (3)°
V = 2112.5 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.20 × 0.18 × 0.15 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.965, T_max = 0.977
10370 measured reflections
2400 independent reflections
1583 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.148
S = 1.08
2400 reflections
141 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	1.25 (4)	1.38 (4)	2.617 (2)	173 (3)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808027311/fb2106sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027311/fb2106Isup2.hkl

checkCIF report

Comment top

Many triazole-related molecules have received much attention because of their biological activities (Olesen et al., 2003; Tian et al., 2005). We report herein the crystal structure of the title compound (Fig. 1).

The molecules are arranged into inversion dimers via carboxyl groups that are interconnected by pairs of the O-H···O hydrogen bonds (Fig. 2). The graph-set motif is R²₂(8) (Etter et al., 1990). The peculiarity of the title structure consists in the displacement of the bonding hydrogen towards the centre of the hydrogen bond (Tab. 1). Though not unprecedented, Fig. 3 shows that the title structure belongs among rather rare examples where in a relatively long O···O hydrogen bond the involved hydrogen is shifted towards the centre. The displacement of the bonding hydrogen towards the centre of the hydrogen bond is concomitant to more equal C-O bonding distances in the carboxyl group.

The dihedral angle between the triazole and phenyl ring planes is 41.85 (1)°.

Related literature top

For related literature, see: El Khadem et al. (1968); Olesen et al. (2003); Tian et al. (2005).

For related literature, see: Allen (2002); Etter et al. (1990); Radl et al. (2000).

Experimental top

The title compound was prepared from azidobenzene according to the reported method (El Khadem et al., 1968). The colourless prisms (average size: 0.5×0.8×1.0 mm) were obtained by slow evaporation from 95% ethanol/water solution at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. The title molecule, showing the atomic numbering scheme. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title molecules, showing the structure along the b axis.
	Fig. 3. The O-H vs. O···O distances (Å) for the structural motif of the pairs of the carboxyl groups that are interconnected by the hydrogen bonds. The structures were found in the Cambridge Structural Database (Allen, 2002; CSD version 5.29 including the updates from January 25, 2008). The query has been limited for the structures with the R factor <0.05; with no errors, no disorder. The polymers and the powder samples were excluded as well. 1028 hits were found. The title structure is symbolized by the large circle in the left upper corner of the plot.

5-Methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid top

Crystal data top

C₁₀H₉N₃O₂	F(000) = 848
M_r = 203.20	D_x = 1.278 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2025 reflections
a = 23.616 (3) Å	θ = 2.8–27.5°
b = 7.7189 (15) Å	µ = 0.09 mm⁻¹
c = 12.606 (2) Å	T = 293 K
β = 113.18 (3)°	Prism, colourless
V = 2112.5 (8) Å³	0.20 × 0.18 × 0.15 mm
Z = 8

Data collection top

Rigaku SCXmini diffractometer	2400 independent reflections
Radiation source: fine-focus sealed tube	1583 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −30→30
T_min = 0.965, T_max = 0.977	k = −9→10
10370 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.062	Hydrogen site location: difference Fourier map
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0614P)² + 0.4952P] where P = (F_o² + 2F_c²)/3
2400 reflections	(Δ/σ)_max < 0.001
141 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³
31 constraints

Crystal data top

C₁₀H₉N₃O₂	V = 2112.5 (8) Å³
M_r = 203.20	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 23.616 (3) Å	µ = 0.09 mm⁻¹
b = 7.7189 (15) Å	T = 293 K
c = 12.606 (2) Å	0.20 × 0.18 × 0.15 mm
β = 113.18 (3)°

Data collection top

Rigaku SCXmini diffractometer	2400 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1583 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.977	R_int = 0.053
10370 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.14 e Å⁻³
2400 reflections	Δρ_min = −0.18 e Å⁻³
141 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.41473 (10)	0.1278 (3)	0.72134 (18)	0.0555 (5)
C2	0.34886 (9)	0.1172 (3)	0.69727 (16)	0.0491 (5)
C3	0.31868 (9)	0.1493 (2)	0.76949 (15)	0.0461 (5)
C4	0.20319 (9)	0.1379 (2)	0.72119 (16)	0.0466 (5)
C5	0.20037 (10)	0.0713 (3)	0.82132 (17)	0.0538 (5)
H5	0.2350	0.0218	0.8780	0.065*
C6	0.14517 (11)	0.0799 (3)	0.8352 (2)	0.0655 (6)
H6	0.1426	0.0364	0.9020	0.079*
C7	0.09414 (11)	0.1525 (3)	0.7506 (2)	0.0761 (7)
H7	0.0571	0.1574	0.7603	0.091*
C8	0.09745 (10)	0.2184 (3)	0.6509 (2)	0.0734 (7)
H8	0.0626	0.2666	0.5940	0.088*
C9	0.15210 (9)	0.2129 (3)	0.63569 (18)	0.0578 (5)
H9	0.1547	0.2585	0.5695	0.069*
C10	0.34155 (10)	0.2068 (3)	0.89199 (16)	0.0579 (6)
H10A	0.3099	0.2716	0.9041	0.087*
H10B	0.3773	0.2786	0.9091	0.087*
H10C	0.3522	0.1073	0.9417	0.087*
N1	0.30730 (8)	0.0743 (2)	0.58988 (14)	0.0577 (5)
N2	0.25230 (8)	0.0763 (2)	0.59058 (13)	0.0571 (5)
N3	0.25867 (7)	0.1228 (2)	0.70044 (13)	0.0475 (4)
O1	0.45271 (7)	0.1465 (2)	0.82345 (13)	0.0733 (5)
O2	0.43008 (7)	0.1161 (3)	0.63484 (13)	0.0799 (6)
H2	0.4867 (19)	0.125 (5)	0.661 (3)	0.193 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0557 (12)	0.0670 (14)	0.0444 (12)	0.0033 (10)	0.0201 (10)	0.0024 (10)
C2	0.0508 (11)	0.0572 (12)	0.0404 (11)	0.0029 (9)	0.0190 (9)	0.0016 (8)
C3	0.0505 (11)	0.0472 (11)	0.0407 (10)	0.0013 (8)	0.0182 (9)	0.0020 (8)
C4	0.0488 (10)	0.0506 (11)	0.0416 (11)	−0.0023 (9)	0.0190 (9)	−0.0050 (8)
C5	0.0562 (12)	0.0617 (13)	0.0443 (11)	−0.0008 (9)	0.0206 (10)	−0.0031 (9)
C6	0.0660 (14)	0.0826 (16)	0.0573 (14)	−0.0081 (12)	0.0343 (12)	−0.0071 (11)
C7	0.0548 (14)	0.102 (2)	0.0797 (17)	−0.0006 (13)	0.0350 (14)	−0.0096 (15)
C8	0.0528 (13)	0.0884 (18)	0.0717 (16)	0.0117 (12)	0.0165 (12)	0.0013 (13)
C9	0.0566 (13)	0.0654 (14)	0.0481 (12)	0.0046 (10)	0.0169 (10)	0.0026 (10)
C10	0.0580 (12)	0.0714 (15)	0.0429 (11)	−0.0024 (10)	0.0184 (10)	−0.0071 (10)
N1	0.0544 (10)	0.0770 (12)	0.0430 (10)	0.0019 (9)	0.0208 (8)	−0.0018 (8)
N2	0.0567 (11)	0.0774 (13)	0.0381 (9)	−0.0015 (8)	0.0196 (8)	−0.0064 (8)
N3	0.0505 (9)	0.0554 (10)	0.0372 (8)	0.0005 (7)	0.0178 (7)	−0.0002 (7)
O1	0.0532 (9)	0.1133 (14)	0.0506 (9)	−0.0020 (8)	0.0176 (8)	−0.0084 (8)
O2	0.0585 (10)	0.1372 (16)	0.0504 (9)	0.0041 (9)	0.0282 (8)	0.0032 (9)

Geometric parameters (Å, º) top

C1—O1	1.254 (2)	C6—H6	0.9300
C1—O2	1.281 (2)	C7—C8	1.386 (3)
C1—C2	1.465 (3)	C7—H7	0.9300
C2—N1	1.364 (3)	C8—C9	1.378 (3)
C2—C3	1.382 (3)	C8—H8	0.9300
C3—N3	1.356 (2)	C9—H9	0.9300
C3—C10	1.489 (3)	C10—H10A	0.9600
C4—C5	1.389 (3)	C10—H10B	0.9600
C4—C9	1.389 (3)	C10—H10C	0.9600
C4—N3	1.438 (2)	N1—N2	1.302 (2)
C5—C6	1.384 (3)	N2—N3	1.380 (2)
C5—H5	0.9300	O2—H2	1.25 (4)
C6—C7	1.376 (3)

O1—C1—O2	123.66 (19)	C8—C7—H7	119.7
O1—C1—C2	119.41 (19)	C9—C8—C7	120.3 (2)
O2—C1—C2	116.94 (19)	C9—C8—H8	119.8
N1—C2—C3	109.96 (17)	C7—C8—H8	119.8
N1—C2—C1	120.64 (17)	C8—C9—C4	118.7 (2)
C3—C2—C1	129.38 (19)	C8—C9—H9	120.7
N3—C3—C2	103.29 (16)	C4—C9—H9	120.7
N3—C3—C10	124.88 (17)	C3—C10—H10A	109.5
C2—C3—C10	131.79 (18)	C3—C10—H10B	109.5
C5—C4—C9	121.47 (19)	H10A—C10—H10B	109.5
C5—C4—N3	120.56 (18)	C3—C10—H10C	109.5
C9—C4—N3	117.90 (17)	H10A—C10—H10C	109.5
C6—C5—C4	118.8 (2)	H10B—C10—H10C	109.5
C6—C5—H5	120.6	N2—N1—C2	108.68 (15)
C4—C5—H5	120.6	N1—N2—N3	107.15 (15)
C7—C6—C5	120.2 (2)	C3—N3—N2	110.92 (15)
C7—C6—H6	119.9	C3—N3—C4	131.92 (16)
C5—C6—H6	119.9	N2—N3—C4	117.15 (15)
C6—C7—C8	120.5 (2)	C1—O2—H2	113.8 (15)
C6—C7—H7	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	1.25 (4)	1.38 (4)	2.617 (2)	173 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₉N₃O₂
M_r	203.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	23.616 (3), 7.7189 (15), 12.606 (2)
β (°)	113.18 (3)
V (Å³)	2112.5 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.965, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	10370, 2400, 1583
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.148, 1.08
No. of reflections	2400
No. of parameters	141
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.18

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	1.25 (4)	1.38 (4)	2.617 (2)	173 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Acknowledgements

This work was supported by a start-up grant from Southeast University to HZ.

References

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