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

Abstract

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 R ² ₂(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,

• a = 23.616 (3) Å

• b = 7.7189 (15) Å

• c = 12.606 (2) Å

• β = 113.18 (3)°

• V = 2112.5 (8) ų

• 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[F ² > 2σ(F ²)] = 0.062

• wR(F ²) = 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

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.

Supplementary Material

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
O2—H2⋯O1i	1.25 (4)	1.38 (4)	2.617 (2)	173 (3)

Symmetry code: (i) .

supplementary crystallographic information

Comment

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)°.

Experimental

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.

Refinement

All the hydrogen atoms could have been discerned in the difference electron density map, nevertheless, all the H atoms attached to the carbon atoms were constrained in a riding motion approximation. C_aryl—H=0.93 Å, with U_iso(H)=1.2U_eq(C). C_methyl—H=0.96 Å, with U_iso(H)=1.5U_eq(C). The hydroxyl hydrogen was refined freely.

Figures

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.

Crystal data

C10H9N3O2	F000 = 848
Mr = 203.20	Dx = 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 = 2.8–27.5º
b = 7.7189 (15) Å	µ = 0.09 mm−1
c = 12.606 (2) Å	T = 293 (2) K
β = 113.18 (3)º	Prism, colourless
V = 2112.5 (8) Å3	0.20 × 0.18 × 0.15 mm
Z = 8

Data collection

Rigaku SCXmini diffractometer	2400 independent reflections
Radiation source: fine-focus sealed tube	1583 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.053
T = 293(2) K	θmax = 27.5º
ω scans	θmin = 2.8º
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)	h = −30→30
Tmin = 0.965, Tmax = 0.977	k = −9→10
10370 measured reflections	l = −16→16

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.148	w = 1/[σ2(Fo2) + (0.0614P)2 + 0.4952P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
2400 reflections	Δρmax = 0.14 e Å−3
141 parameters	Δρmin = −0.18 e Å−3
31 constraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) −x+1, y, −z+3/2.