2-(1H-Tetra­zol-1-yl)acetic acid monohydrate

Wang, W.-X.

doi:10.1107/S1600536812033090

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2561

https://doi.org/10.1107/S1600536812033090

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2-(1H-Tetrazol-1-yl)acetic acid monohydrate

Wen-Xiang Wang ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: wxwang@seu.edu.cn

(Received 20 May 2012; accepted 21 July 2012; online 28 July 2012)

The crystal structure of the title compound, C₃H₄N₄O₂·H₂O, exhibits O—H⋯O and O—H⋯N hydrogen bonds, which lead to the formation of a two-dimensional network parallel to the bc plane. The dihedral angle between the ring and the carboxylic acid group is 84.6 (14)°.

Related literature

For the use of 2-(1H-tetrazol-1-yl) acetic acid as a pharmaceutical intermediate, see: Gunnlaugsson & Stomeo (2007 ). For its coordination properties, see: Ghosh & Bharadwaj (2004 ). For the synthesis, see: Jústiz et al. (1997 ).

Experimental

Crystal data

C₃H₄N₄O₂·H₂O
M_r = 146.12
Orthorhombic, P n a 2₁
a = 12.618 (3) Å
b = 5.1871 (10) Å
c = 9.874 (2) Å
V = 646.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.26 × 0.23 × 0.19 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.965, T_max = 0.983
6216 measured reflections
786 independent reflections
715 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.069
S = 1.17
786 reflections
103 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯N2	0.83 (4)	2.11 (4)	2.864 (3)	150 (3)
O1—H1A⋯O3ⁱ	0.89 (4)	1.72 (4)	2.603 (3)	175 (4)
O3—H3A⋯O2ⁱⁱ	0.76 (3)	2.00 (3)	2.752 (3)	168 (3)
Symmetry codes: (i) x, y, z+1; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812033090/fy2060sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812033090/fy2060Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812033090/fy2060Isup3.cml

checkCIF report

Comment top

2-(1H-tetrazol-1-yl) acetic acid is an important raw material to prepare a variety of antibiotic drugs, and is widely used as an important pharmaceutical intermediate (Gunnlaugsson & Stomeo, 2007). In recent years, researchers found that tetrazole acetic acid has excellent coordination properties (Ghosh & Bharadwaj, 2004). We report here the crystal structure of the title compound (Fig. 1).

In the title compound the carboxyl functional group is almost perpendicular to the tetrazole heterocycle with a dihedral angle of 87.3 (2)°. The O3—H3B···N2 hydrogen bond anchors the water molecule to the tetrazole heterocycle. Two intermolecular hydrogen bonds (O1—H1A···O3 and O3—H3A···O2) connect the water molecule and two carboxyl groups from the neighboring asymmetric unit, forming layers with louver-like network (Fig. 2).

Related literature top

For the use of 2-(1H-tetrazol-1-yl) acetic acid as a pharmaceutical intermediate, see: Gunnlaugsson & Stomeo (2007). For its coordination properties, see: Ghosh & Bharadwaj (2004). For the synthesis, see: Jústiz et al. (1997).

Experimental top

A procedure similar to the previously published method of Jústiz et al. (1997) was applied. To a solution of 2-aminoacetic acid (7.5 g, 0.1 mol) in 50 ml acetic acid was added triethoxymethane (32.4 g, 0.22 mol) and sodium azide (7.15 g, 0.11 mol). The mixture was refluxed for 3.0 h at 80°C. Active carbon was used to discolor the mixture, which was then refluxed for another 10 minutes. Heating was stopped and cooled to room temperature, the mixture was filtered to remove the active carbon and concentrated hydrochloric acid was trickled into the filtrate and a white solid product precipitated out. The precipitate was extracted by ethyl acetate and washed with saturated solution of sodium bicarbonate, brine, and then dried over MgSO₄. Evaporation of the solvent in vacuum afforded the 2-(1H-tetrazol-1-yl) acetic acid compound. The pale yellow single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of a solution in the 3:7 (v/v) mixture of petroleum ether and ethyl acetate.

Structure description top

For the use of 2-(1H-tetrazol-1-yl) acetic acid as a pharmaceutical intermediate, see: Gunnlaugsson & Stomeo (2007). For its coordination properties, see: Ghosh & Bharadwaj (2004). For the synthesis, see: Jústiz et al. (1997).

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: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit with anisotropic ellipsoid representation, shown with the atom labeling scheme. Ellispoids are shown at the 50% probability level.
	Fig. 2. Packing diagram for the title compound. Hydrogen bonds are denoted by dashed lines.

2-(1H-Tetrazol-1-yl)acetic acid monohydrate top

Crystal data top

C₃H₄N₄O₂·H₂O	F(000) = 304
M_r = 146.12	D_x = 1.502 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 6216 reflections
a = 12.618 (3) Å	θ = 3.2–27.5°
b = 5.1871 (10) Å	µ = 0.13 mm⁻¹
c = 9.874 (2) Å	T = 293 K
V = 646.2 (2) Å³	Needle, pale yellow
Z = 4	0.26 × 0.23 × 0.19 mm

Data collection top

Rigaku SCXmini diffractometer	786 independent reflections
Radiation source: fine-focus sealed tube	715 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −16→16
T_min = 0.965, T_max = 0.983	k = −6→6
6216 measured reflections	l = −12→12

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.029P)² + 0.0792P] where P = (F_o² + 2F_c²)/3
786 reflections	(Δ/σ)_max < 0.001
103 parameters	Δρ_max = 0.11 e Å⁻³
1 restraint	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₃H₄N₄O₂·H₂O	V = 646.2 (2) Å³
M_r = 146.12	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 12.618 (3) Å	µ = 0.13 mm⁻¹
b = 5.1871 (10) Å	T = 293 K
c = 9.874 (2) Å	0.26 × 0.23 × 0.19 mm

Data collection top

Rigaku SCXmini diffractometer	786 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	715 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.983	R_int = 0.031
6216 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.11 e Å⁻³
786 reflections	Δρ_min = −0.12 e Å⁻³
103 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
O1	0.38513 (14)	0.5364 (3)	1.01953 (17)	0.0450 (4)
O2	0.30421 (14)	0.8326 (3)	0.89450 (17)	0.0525 (5)
N2	0.37640 (16)	0.8301 (4)	0.4743 (2)	0.0436 (5)
C5	0.36860 (19)	0.6540 (4)	0.5678 (2)	0.0381 (5)
H5A	0.3281	0.5047	0.5614	0.046*
N4	0.47431 (18)	0.9471 (4)	0.6448 (2)	0.0497 (5)
C7	0.37025 (18)	0.6679 (4)	0.9087 (2)	0.0358 (5)
N1	0.44272 (18)	1.0105 (4)	0.5252 (2)	0.0527 (6)
N3	0.42748 (14)	0.7205 (3)	0.67377 (18)	0.0334 (4)
C6	0.44751 (19)	0.5888 (4)	0.8003 (2)	0.0379 (5)
H6A	0.5190	0.6270	0.8302	0.046*
H6B	0.4424	0.4042	0.7860	0.046*
O3	0.27445 (17)	0.7053 (4)	0.22354 (17)	0.0509 (5)
H1A	0.344 (3)	0.595 (6)	1.086 (4)	0.079 (11)*
H3A	0.246 (2)	0.600 (6)	0.263 (4)	0.062 (10)*
H3B	0.310 (3)	0.789 (6)	0.279 (4)	0.062 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0495 (9)	0.0525 (10)	0.0330 (9)	0.0046 (8)	−0.0002 (8)	0.0146 (8)
O2	0.0605 (10)	0.0645 (11)	0.0327 (9)	0.0259 (9)	0.0079 (8)	0.0131 (9)
N2	0.0554 (12)	0.0453 (11)	0.0303 (9)	−0.0005 (9)	0.0026 (9)	0.0036 (9)
C5	0.0438 (14)	0.0403 (12)	0.0303 (11)	−0.0033 (9)	0.0011 (9)	−0.0052 (9)
N4	0.0678 (14)	0.0421 (11)	0.0393 (11)	−0.0149 (10)	0.0003 (11)	−0.0023 (9)
C7	0.0409 (12)	0.0368 (11)	0.0298 (11)	−0.0010 (10)	−0.0039 (9)	0.0036 (10)
N1	0.0729 (14)	0.0454 (11)	0.0396 (12)	−0.0118 (10)	0.0050 (12)	0.0042 (10)
N3	0.0402 (9)	0.0325 (9)	0.0276 (8)	0.0000 (8)	0.0031 (8)	−0.0036 (7)
C6	0.0446 (12)	0.0366 (11)	0.0326 (11)	0.0070 (11)	−0.0046 (10)	−0.0011 (9)
O3	0.0612 (11)	0.0625 (12)	0.0289 (9)	−0.0116 (10)	−0.0018 (8)	0.0107 (9)

Geometric parameters (Å, º) top

O1—C7	1.303 (3)	N4—N3	1.346 (3)
O1—H1A	0.89 (4)	C7—C6	1.505 (3)
O2—C7	1.202 (3)	N3—C6	1.446 (3)
N2—C5	1.303 (3)	C6—H6A	0.9700
N2—N1	1.352 (3)	C6—H6B	0.9700
C5—N3	1.329 (3)	O3—H3A	0.76 (3)
C5—H5A	0.9300	O3—H3B	0.83 (4)
N4—N1	1.289 (3)

C7—O1—H1A	111 (2)	C5—N3—N4	107.74 (19)
C5—N2—N1	105.6 (2)	C5—N3—C6	130.92 (19)
N2—C5—N3	109.49 (19)	N4—N3—C6	121.31 (19)
N2—C5—H5A	125.3	N3—C6—C7	111.87 (17)
N3—C5—H5A	125.3	N3—C6—H6A	109.2
N1—N4—N3	106.37 (19)	C7—C6—H6A	109.2
O2—C7—O1	124.8 (2)	N3—C6—H6B	109.2
O2—C7—C6	124.0 (2)	C7—C6—H6B	109.2
O1—C7—C6	111.19 (19)	H6A—C6—H6B	107.9
N4—N1—N2	110.82 (19)	H3A—O3—H3B	107 (3)

N1—N2—C5—N3	0.1 (3)	N1—N4—N3—C6	178.50 (19)
N3—N4—N1—N2	−0.3 (3)	C5—N3—C6—C7	−92.1 (3)
C5—N2—N1—N4	0.1 (3)	N4—N3—C6—C7	90.3 (3)
N2—C5—N3—N4	−0.3 (3)	O2—C7—C6—N3	−4.4 (3)
N2—C5—N3—C6	−178.2 (2)	O1—C7—C6—N3	176.12 (18)
N1—N4—N3—C5	0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···N2	0.83 (4)	2.11 (4)	2.864 (3)	150 (3)
O1—H1A···O3ⁱ	0.89 (4)	1.72 (4)	2.603 (3)	175 (4)
O3—H3A···O2ⁱⁱ	0.76 (3)	2.00 (3)	2.752 (3)	168 (3)

Symmetry codes: (i) x, y, z+1; (ii) −x+1/2, y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₃H₄N₄O₂·H₂O
M_r	146.12
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	12.618 (3), 5.1871 (10), 9.874 (2)
V (Å³)	646.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.26 × 0.23 × 0.19

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.965, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	6216, 786, 715
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.069, 1.17
No. of reflections	786
No. of parameters	103
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.12

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···N2	0.83 (4)	2.11 (4)	2.864 (3)	150 (3)
O1—H1A···O3ⁱ	0.89 (4)	1.72 (4)	2.603 (3)	175 (4)
O3—H3A···O2ⁱⁱ	0.76 (3)	2.00 (3)	2.752 (3)	168 (3)

Symmetry codes: (i) x, y, z+1; (ii) −x+1/2, y−1/2, z−1/2.

Acknowledgements

This work was supported by Southeast University.

References

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