5-Methyl-1-(3-nitro­benz­yl)-1H-1,2,3-triazole-4-carboxylic acid monohydrate

Xiao, J.; Wang, W.X.; Zhao, H.

doi:10.1107/S1600536808030584

organic compounds

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Volume 64| Part 11| November 2008| Page o2085

doi:10.1107/S1600536808030584

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5-Methyl-1-(3-nitrobenzyl)-1H-1,2,3-triazole-4-carboxylic acid monohydrate

Jie Xiao,^a Wen Xiang Wang ^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 29 August 2008; accepted 23 September 2008; online 9 October 2008)

The title compound, C₁₁H₁₀N₄O₄·H₂O, was synthesized from 1-azidomethyl-3-nitrobenzene and ethyl acetylacetate. Single-crystal X-ray analysis reveals that the dihedral angle between the triazole and benzene ring planes is 84.80 (2)°. The packing of the molecules is stabilized by strong O—H⋯O hydrogen bonds involving the solvent water molecules as donors and acceptors. The resulting layers are arranged into a three-dimensional framework via weak C—H⋯O interactions.

Related literature

For the synthesis of the title compound, see: El Khadem et al. (1968 ). For related literature about biological activity of triazole-based compounds, see: Olesen et al. (2003 ); Tian et al. (2005 ).

Experimental

Crystal data

C₁₁H₁₀N₄O₄·H₂O
M_r = 280.25
Triclinic, $[P \overline 1]$
a = 7.1649 (14) Å
b = 8.2064 (16) Å
c = 11.281 (2) Å
α = 84.88 (3)°
β = 77.70 (2)°
γ = 89.38 (3)°
V = 645.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293.1 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
6749 measured reflections
2959 independent reflections
1824 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.181
S = 1.02
2959 reflections
186 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O4ⁱ	0.96	2.52	3.267 (3)	135
O1W—H1A⋯O1ⁱⁱ	0.85	1.94	2.755 (3)	161
O1W—H1B⋯N1ⁱⁱⁱ	0.93	1.95	2.846 (3)	160
C11—H11⋯O3^iv	0.93	2.57	3.423 (4)	153
O2—H2⋯O1W^iv	0.77 (5)	1.88 (5)	2.592 (3)	153 (6)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y, -z; (iii) x-1, y+1, z; (iv) x, y-1, z.

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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030584/bh2192sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030584/bh2192Isup2.hkl

checkCIF report

Comment top

It is well known that many triazole-related molecules have received much attention due to their biological activities (Olesen et al., 2003; Tian et al., 2005). We report herein the crystal structure of the title compound, (I, Fig. 1). The bond lengths and angles have normal values. The dihedral angle between the triazole and phenyl planes is 84.80 (2)°. The packing of the molecules is stabilized by strong hydrogen bonds (Table 1) between the triazole molecules and lattice water molecules. Meanwhile, the 0D discrete molecules are arranged into a three-dimensional framework via hydrogen bond interactions and weak contacts (Fig. 2).

Related literature top

For the synthesis of the title compound, see: EI Khadem et al. (1968). For related literature about biological activity of triazole-based compounds, see: Olesen et al. (2003); Tian et al. (2005).

Experimental top

The title compound was prepared from 1-(azidomethyl)-3-nitrobenzene, according to the reported method (EI Khadem et al., 1968), in 70% yield. Colourless prisms of (I) were obtained by slow evaporation of a 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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title compound, showing the crystal structure along the b axis.

5-Methyl-1-(3-nitrobenzyl)-1H-1,2,3-triazole-4-carboxylic acid monohydrate top

Crystal data top

C₁₁H₁₀N₄O₄·H₂O	Z = 2
M_r = 280.25	F(000) = 292
Triclinic, P1	D_x = 1.442 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1649 (14) Å	Cell parameters from 5670 reflections
b = 8.2064 (16) Å	θ = 3.1–27.5°
c = 11.281 (2) Å	µ = 0.12 mm⁻¹
α = 84.88 (3)°	T = 293 K
β = 77.70 (2)°	Prism, colourless
γ = 89.38 (3)°	0.20 × 0.18 × 0.15 mm
V = 645.5 (2) Å³

Data collection top

Rigaku SCXmini diffractometer	2959 independent reflections
Radiation source: fine-focus sealed tube	1824 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.965, T_max = 0.977	l = −14→14
6749 measured reflections

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0847P)² + 0.0594P] where P = (F_o² + 2F_c²)/3
2959 reflections	(Δ/σ)_max < 0.001
186 parameters	Δρ_max = 0.27 e Å⁻³
3 restraints	Δρ_min = −0.21 e Å⁻³
0 constraints

Crystal data top

C₁₁H₁₀N₄O₄·H₂O	γ = 89.38 (3)°
M_r = 280.25	V = 645.5 (2) Å³
Triclinic, P1	Z = 2
a = 7.1649 (14) Å	Mo Kα radiation
b = 8.2064 (16) Å	µ = 0.12 mm⁻¹
c = 11.281 (2) Å	T = 293 K
α = 84.88 (3)°	0.20 × 0.18 × 0.15 mm
β = 77.70 (2)°

Data collection top

Rigaku SCXmini diffractometer	2959 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1824 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.977	R_int = 0.040
6749 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	3 restraints
wR(F²) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.27 e Å⁻³
2959 reflections	Δρ_min = −0.21 e Å⁻³
186 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.7354 (3)	−0.2576 (3)	0.1023 (2)	0.0489 (6)
C2	0.8477 (3)	−0.1276 (3)	0.13603 (19)	0.0445 (5)
C3	0.7947 (3)	0.0281 (3)	0.16613 (19)	0.0453 (5)
C4	0.6141 (4)	0.1200 (3)	0.1754 (3)	0.0662 (7)
H4A	0.5476	0.1149	0.2591	0.099*
H4B	0.5357	0.0725	0.1281	0.099*
H4C	0.6419	0.2321	0.1451	0.099*
C5	0.9906 (4)	0.2546 (3)	0.2222 (2)	0.0552 (6)
H5A	0.9527	0.3352	0.1637	0.066*
H5B	1.1266	0.2683	0.2166	0.066*
C6	0.8858 (3)	0.2880 (3)	0.3486 (2)	0.0481 (6)
C7	0.8471 (3)	0.4501 (3)	0.3709 (2)	0.0490 (6)
H7	0.8787	0.5334	0.3083	0.059*
C8	0.7616 (3)	0.4858 (3)	0.4866 (2)	0.0525 (6)
C9	0.7117 (4)	0.3678 (4)	0.5813 (2)	0.0673 (7)
H9	0.6549	0.3952	0.6589	0.081*
C10	0.7481 (5)	0.2061 (4)	0.5582 (2)	0.0755 (8)
H10	0.7139	0.1233	0.6209	0.091*
C11	0.8352 (4)	0.1670 (3)	0.4426 (2)	0.0634 (7)
H11	0.8597	0.0582	0.4282	0.076*
N1	1.0337 (3)	−0.1508 (2)	0.14233 (18)	0.0543 (5)
N2	1.0999 (3)	−0.0190 (2)	0.17513 (19)	0.0584 (6)
N3	0.9557 (3)	0.0908 (2)	0.18882 (17)	0.0487 (5)
N4	0.7247 (3)	0.6596 (3)	0.5081 (3)	0.0710 (7)
O1	0.8110 (3)	−0.3876 (2)	0.07308 (19)	0.0758 (6)
O2	0.5593 (3)	−0.2220 (3)	0.1079 (2)	0.0867 (7)
H2	0.506 (8)	−0.295 (6)	0.091 (5)	0.18 (2)*
O3	0.7575 (4)	0.7611 (3)	0.4204 (3)	0.1067 (9)
O4	0.6635 (3)	0.6915 (3)	0.6118 (2)	0.1040 (8)
O1W	0.2862 (2)	0.5822 (2)	0.09151 (18)	0.0707 (6)
H1A	0.2667	0.5412	0.0287	0.106*
H1B	0.1813	0.6510	0.1111	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0516 (14)	0.0470 (13)	0.0509 (14)	−0.0009 (11)	−0.0142 (10)	−0.0120 (10)
C2	0.0458 (13)	0.0474 (12)	0.0410 (12)	0.0008 (10)	−0.0070 (9)	−0.0130 (9)
C3	0.0468 (13)	0.0465 (12)	0.0426 (12)	−0.0009 (10)	−0.0066 (9)	−0.0113 (9)
C4	0.0578 (16)	0.0592 (16)	0.085 (2)	0.0136 (13)	−0.0185 (13)	−0.0156 (14)
C5	0.0648 (16)	0.0449 (13)	0.0547 (14)	−0.0102 (11)	−0.0053 (11)	−0.0150 (11)
C6	0.0523 (14)	0.0444 (13)	0.0492 (13)	−0.0073 (10)	−0.0112 (10)	−0.0122 (10)
C7	0.0528 (14)	0.0455 (13)	0.0500 (13)	−0.0056 (11)	−0.0120 (10)	−0.0087 (10)
C8	0.0467 (13)	0.0567 (14)	0.0573 (15)	−0.0022 (11)	−0.0113 (11)	−0.0218 (12)
C9	0.0653 (17)	0.086 (2)	0.0511 (15)	−0.0053 (15)	−0.0088 (12)	−0.0182 (14)
C10	0.093 (2)	0.077 (2)	0.0520 (17)	−0.0084 (17)	−0.0088 (14)	0.0071 (14)
C11	0.0809 (19)	0.0481 (14)	0.0610 (17)	−0.0022 (13)	−0.0148 (13)	−0.0049 (12)
N1	0.0478 (12)	0.0561 (12)	0.0629 (13)	0.0029 (9)	−0.0125 (9)	−0.0257 (10)
N2	0.0509 (12)	0.0593 (13)	0.0689 (14)	0.0023 (10)	−0.0136 (10)	−0.0255 (11)
N3	0.0495 (11)	0.0448 (11)	0.0521 (11)	−0.0024 (9)	−0.0068 (8)	−0.0163 (9)
N4	0.0608 (14)	0.0758 (17)	0.0824 (18)	0.0047 (12)	−0.0141 (12)	−0.0429 (15)
O1	0.0991 (15)	0.0526 (11)	0.0874 (14)	0.0051 (10)	−0.0357 (11)	−0.0311 (10)
O2	0.0653 (14)	0.0731 (14)	0.132 (2)	−0.0111 (11)	−0.0395 (13)	−0.0188 (13)
O3	0.144 (2)	0.0529 (13)	0.115 (2)	−0.0030 (14)	−0.0029 (17)	−0.0215 (13)
O4	0.1111 (19)	0.1131 (19)	0.0943 (17)	0.0254 (15)	−0.0156 (14)	−0.0625 (15)
O1W	0.0632 (12)	0.0561 (11)	0.0935 (14)	−0.0015 (9)	−0.0099 (10)	−0.0259 (10)

Geometric parameters (Å, º) top

C1—O1	1.230 (3)	C7—C8	1.374 (3)
C1—O2	1.282 (3)	C7—H7	0.9300
C1—C2	1.467 (3)	C8—C9	1.366 (4)
C2—N1	1.360 (3)	C8—N4	1.479 (3)
C2—C3	1.380 (3)	C9—C10	1.386 (4)
C3—N3	1.350 (3)	C9—H9	0.9300
C3—C4	1.479 (3)	C10—C11	1.385 (4)
C4—H4A	0.9600	C10—H10	0.9300
C4—H4B	0.9600	C11—H11	0.9300
C4—H4C	0.9600	N1—N2	1.300 (3)
C5—N3	1.466 (3)	N2—N3	1.356 (3)
C5—C6	1.510 (3)	N4—O4	1.210 (3)
C5—H5A	0.9700	N4—O3	1.219 (3)
C5—H5B	0.9700	O2—H2	0.77 (5)
C6—C11	1.377 (3)	O1W—H1B	0.9349
C6—C7	1.391 (3)	O1W—H1A	0.8483

O1—C1—O2	125.6 (2)	C8—C7—H7	120.4
O1—C1—C2	120.3 (2)	C6—C7—H7	120.4
O2—C1—C2	114.1 (2)	C9—C8—C7	122.6 (2)
N1—C2—C3	109.06 (19)	C9—C8—N4	119.4 (2)
N1—C2—C1	121.1 (2)	C7—C8—N4	118.0 (2)
C3—C2—C1	129.8 (2)	C8—C9—C10	118.1 (2)
N3—C3—C2	103.26 (19)	C8—C9—H9	121.0
N3—C3—C4	123.4 (2)	C10—C9—H9	121.0
C2—C3—C4	133.4 (2)	C11—C10—C9	120.4 (2)
C3—C4—H4A	109.5	C11—C10—H10	119.8
C3—C4—H4B	109.5	C9—C10—H10	119.8
H4A—C4—H4B	109.5	C6—C11—C10	120.6 (2)
C3—C4—H4C	109.5	C6—C11—H11	119.7
H4A—C4—H4C	109.5	C10—C11—H11	119.7
H4B—C4—H4C	109.5	N2—N1—C2	109.17 (19)
N3—C5—C6	114.05 (19)	N1—N2—N3	106.90 (18)
N3—C5—H5A	108.7	C3—N3—N2	111.60 (18)
C6—C5—H5A	108.7	C3—N3—C5	129.1 (2)
N3—C5—H5B	108.7	N2—N3—C5	119.26 (18)
C6—C5—H5B	108.7	O4—N4—O3	124.3 (3)
H5A—C5—H5B	107.6	O4—N4—C8	117.7 (3)
C11—C6—C7	119.2 (2)	O3—N4—C8	118.0 (2)
C11—C6—C5	123.2 (2)	C1—O2—H2	110 (4)
C7—C6—C5	117.5 (2)	H1B—O1W—H1A	102.8
C8—C7—C6	119.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O4ⁱ	0.96	2.52	3.267 (3)	135
O1W—H1A···O1ⁱⁱ	0.85	1.94	2.755 (3)	161
O1W—H1B···N1ⁱⁱⁱ	0.93	1.95	2.846 (3)	160
C11—H11···O3^iv	0.93	2.57	3.423 (4)	153
O2—H2···O1W^iv	0.77 (5)	1.88 (5)	2.592 (3)	153 (6)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z; (iii) x−1, y+1, z; (iv) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₄O₄·H₂O
M_r	280.25
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.1649 (14), 8.2064 (16), 11.281 (2)
α, β, γ (°)	84.88 (3), 77.70 (2), 89.38 (3)
V (Å³)	645.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
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	6749, 2959, 1824
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.181, 1.03
No. of reflections	2959
No. of parameters	186
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.21

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O4ⁱ	0.96	2.52	3.267 (3)	135
O1W—H1A···O1ⁱⁱ	0.85	1.94	2.755 (3)	160.5
O1W—H1B···N1ⁱⁱⁱ	0.93	1.95	2.846 (3)	160.3
C11—H11···O3^iv	0.93	2.57	3.423 (4)	153
O2—H2···O1W^iv	0.77 (5)	1.88 (5)	2.592 (3)	153 (6)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z; (iii) x−1, y+1, z; (iv) x, y−1, z.

Acknowledgements

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

References

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