4-(1H-Tetra­zol-5-yl)benzene-1,3-diol

Kim, Y.

doi:10.1107/S160053681300411X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o380

doi:10.1107/S160053681300411X

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4-(1H-Tetrazol-5-yl)benzene-1,3-diol

Youngjo Kim ^a ^*

^aDepartment of Chemistry, Chungbuk National University, Cheongju, Chungbuk 361-763, Republic of Korea
^*Correspondence e-mail: ykim@chungbuk.ac.kr

(Received 24 January 2013; accepted 11 February 2013; online 16 February 2013)

In the title compound, C₇H₆N₄O₂, rings are almost coplanar, the dihedral angle between them being 8.45 (13)°. An intramolecular N—H⋯O hydrogen bond occurs. In the crystal, the molecules are linked by O—H⋯N and N—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For the structure of 4-(5-tetrazolyl)-1,3-benzenediol sesquihydrate, see: Gallardo et al. (1995 ). For the synthesis, see: Meyer et al. (1998 ).

Experimental

Crystal data

C₇H₆N₄O₂
M_r = 178.16
Orthorhombic, P c c n
a = 16.109 (2) Å
b = 7.2931 (11) Å
c = 12.8708 (17) Å
V = 1512.2 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.10 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.96, T_max = 0.98
20096 measured reflections
2452 independent reflections
1273 reflections with I > 2σ(I)
R_int = 0.110

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.168
S = 1.05
2452 reflections
124 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N4ⁱ	0.82	1.94	2.759 (3)	173
O2—H2⋯N3ⁱⁱ	0.82	2.00	2.817 (3)	173
N1—H101⋯O1	0.89 (3)	2.22 (3)	2.701 (3)	113 (2)
N1—H101⋯O2ⁱⁱⁱ	0.89 (3)	2.40 (3)	3.034 (3)	129 (2)
C3—H3⋯N2ⁱⁱ	0.93	2.57	3.439 (3)	155
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+2]$ ; (iii) $[x+{\script{1\over 2}}, -y+2, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); 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 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681300411X/ff2096sup1.cif

Supporting information file. DOI: 10.1107/S160053681300411X/ff2096Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S160053681300411X/ff2096Isup3.hkl

Supporting information file. DOI: 10.1107/S160053681300411X/ff2096Isup4.cml

checkCIF report

Comment top

The similar structure of the title compound with two tetrazolylbenzenediol molecules per asymmetric unit together with three water molecules was reported in the literature (Gallardo et al., 1995). In this compound, the two tetrazolylbenzendiol are linked through a hydrogen-bonded network to water molecules, forming layers extending along the face of the unit cell (Gallardo et al., 1995). Herein, we report the related X-ray structure of the title compound (I) with eight tetrazolylbenzenediol molecules in unit cell and only one molecule in the asymmetric unit without any solvents. The title compound (I) could be isolated in more than 80% yield via the previously reported method (Meyer et al., 1998). Like the structure of related compound (Gallardo et al., 1995), the phenyl ring and the tetrazole ring of each molecule in the asymmetric unit are coplanar (Fig. 1), with the dihedral angle between the benzene and tetrazole rings of 8.45 (13)°. They are connected by a network of intermolecular hydrogen bonds (Fig. 2).

Related literature top

For the structure of 4-(5-tetrazolyl)-1,3-benzenediol sesquihydrate, see: Gallardo et al. (1995). For the synthesis, see: Meyer et al. (1998).

Experimental top

The title compound could be synthesized by the previously reported method (Meyer et al., 1998). Crystal of the title compound suitable for X-ray analysis were grown in ethanol by slow evaporation.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Hydrogen bonding network viewed along the b-axis.

4-(1H-Tetrazol-5-yl)benzene-1,3-diol top

Crystal data top

C₇H₆N₄O₂	D_x = 1.565 Mg m⁻³
M_r = 178.16	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn	Cell parameters from 3776 reflections
a = 16.109 (2) Å	θ = 3.1–27.9°
b = 7.2931 (11) Å	µ = 0.12 mm⁻¹
c = 12.8708 (17) Å	T = 296 K
V = 1512.2 (4) Å³	Block, white
Z = 8	0.10 × 0.10 × 0.08 mm
F(000) = 736

Data collection top

Bruker APEXII CCD diffractometer	2452 independent reflections
Radiation source: fine-focus sealed tube	1273 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.110
phi and ω scans	θ_max = 31.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −23→23
T_min = 0.96, T_max = 0.98	k = −10→9
20096 measured reflections	l = −18→18

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0419P)² + 1.9684P] where P = (F_o² + 2F_c²)/3
2452 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₇H₆N₄O₂	V = 1512.2 (4) Å³
M_r = 178.16	Z = 8
Orthorhombic, Pccn	Mo Kα radiation
a = 16.109 (2) Å	µ = 0.12 mm⁻¹
b = 7.2931 (11) Å	T = 296 K
c = 12.8708 (17) Å	0.10 × 0.10 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	2452 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	1273 reflections with I > 2σ(I)
T_min = 0.96, T_max = 0.98	R_int = 0.110
20096 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.35 e Å⁻³
2452 reflections	Δρ_min = −0.26 e Å⁻³
124 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
N1	0.86210 (12)	1.0811 (3)	0.86101 (16)	0.0332 (5)
H101	0.8653 (17)	1.079 (4)	0.792 (2)	0.047 (9)*
N2	0.92672 (12)	1.1375 (3)	0.91859 (16)	0.0387 (5)
N3	0.90167 (12)	1.1289 (3)	1.01390 (16)	0.0384 (5)
N4	0.82224 (11)	1.0674 (3)	1.01992 (15)	0.0322 (5)
O1	0.74465 (11)	1.0193 (3)	0.71535 (12)	0.0424 (5)
H1	0.7208	1.0311	0.6595	0.064*
O2	0.47535 (11)	0.8148 (3)	0.81787 (15)	0.0546 (6)
H2	0.4521	0.7686	0.8681	0.082*
C1	0.71543 (13)	0.9735 (3)	0.89292 (17)	0.0275 (5)
C2	0.66041 (14)	0.9179 (4)	0.97055 (18)	0.0329 (6)
H2A	0.6780	0.9178	1.0394	0.040*
C3	0.58072 (14)	0.8633 (4)	0.94770 (18)	0.0350 (6)
H3	0.5449	0.8270	1.0005	0.042*
C4	0.55424 (14)	0.8628 (4)	0.84451 (19)	0.0349 (6)
C5	0.60837 (15)	0.9128 (4)	0.76517 (19)	0.0355 (6)
H5	0.5909	0.9091	0.6963	0.043*
C6	0.68889 (14)	0.9686 (3)	0.78936 (17)	0.0292 (5)
C7	0.79789 (13)	1.0372 (3)	0.92276 (17)	0.0266 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0273 (9)	0.0474 (14)	0.0249 (10)	−0.0028 (9)	0.0009 (8)	0.0013 (9)
N2	0.0284 (10)	0.0561 (15)	0.0318 (11)	−0.0080 (10)	−0.0014 (8)	−0.0014 (10)
N3	0.0274 (10)	0.0547 (15)	0.0330 (11)	−0.0071 (10)	−0.0011 (8)	−0.0014 (10)
N4	0.0229 (9)	0.0453 (13)	0.0284 (10)	−0.0029 (9)	−0.0009 (7)	−0.0006 (9)
O1	0.0314 (8)	0.0715 (14)	0.0243 (8)	−0.0072 (9)	−0.0010 (7)	0.0069 (9)
O2	0.0359 (10)	0.0896 (18)	0.0382 (11)	−0.0275 (11)	−0.0102 (8)	0.0150 (11)
C1	0.0251 (10)	0.0299 (13)	0.0276 (11)	0.0006 (9)	−0.0018 (8)	0.0014 (10)
C2	0.0319 (11)	0.0427 (15)	0.0242 (11)	−0.0024 (11)	−0.0030 (9)	0.0018 (10)
C3	0.0280 (11)	0.0471 (16)	0.0300 (12)	−0.0090 (11)	0.0019 (9)	0.0032 (11)
C4	0.0279 (11)	0.0407 (16)	0.0359 (13)	−0.0057 (11)	−0.0046 (9)	0.0027 (11)
C5	0.0332 (11)	0.0466 (16)	0.0266 (12)	−0.0067 (11)	−0.0057 (9)	0.0038 (11)
C6	0.0270 (10)	0.0339 (13)	0.0268 (11)	0.0003 (10)	−0.0004 (9)	0.0031 (10)
C7	0.0254 (10)	0.0299 (13)	0.0245 (11)	0.0017 (9)	0.0006 (8)	0.0013 (9)

Geometric parameters (Å, º) top

N1—N2	1.342 (3)	C1—C2	1.396 (3)
N1—C7	1.343 (3)	C1—C6	1.400 (3)
N1—H101	0.89 (3)	C1—C7	1.459 (3)
N2—N3	1.293 (3)	C2—C3	1.376 (3)
N3—N4	1.358 (3)	C2—H2A	0.9300
N4—C7	1.329 (3)	C3—C4	1.395 (3)
O1—C6	1.360 (3)	C3—H3	0.9300
O1—H1	0.8200	C4—C5	1.391 (3)
O2—C4	1.362 (3)	C5—C6	1.395 (3)
O2—H2	0.8200	C5—H5	0.9300

N2—N1—C7	110.1 (2)	C2—C3—H3	120.4
N2—N1—H101	120.8 (18)	C4—C3—H3	120.4
C7—N1—H101	129.1 (18)	O2—C4—C5	117.9 (2)
N3—N2—N1	105.49 (19)	O2—C4—C3	121.7 (2)
N2—N3—N4	111.35 (19)	C5—C4—C3	120.4 (2)
C7—N4—N3	106.20 (18)	C4—C5—C6	119.7 (2)
C6—O1—H1	109.5	C4—C5—H5	120.2
C4—O2—H2	109.5	C6—C5—H5	120.2
C2—C1—C6	118.7 (2)	O1—C6—C5	122.5 (2)
C2—C1—C7	118.8 (2)	O1—C6—C1	117.3 (2)
C6—C1—C7	122.5 (2)	C5—C6—C1	120.3 (2)
C3—C2—C1	121.6 (2)	N4—C7—N1	106.87 (19)
C3—C2—H2A	119.2	N4—C7—C1	124.7 (2)
C1—C2—H2A	119.2	N1—C7—C1	128.4 (2)
C2—C3—C4	119.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N4ⁱ	0.82	1.94	2.759 (3)	173
O2—H2···N3ⁱⁱ	0.82	2.00	2.817 (3)	173
N1—H101···O1	0.89 (3)	2.22 (3)	2.701 (3)	113 (2)
N1—H101···O2ⁱⁱⁱ	0.89 (3)	2.40 (3)	3.034 (3)	129 (2)
C3—H3···N2ⁱⁱ	0.93	2.57	3.439 (3)	155

Symmetry codes: (i) −x+3/2, y, z−1/2; (ii) x−1/2, y−1/2, −z+2; (iii) x+1/2, −y+2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₇H₆N₄O₂
M_r	178.16
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	296
a, b, c (Å)	16.109 (2), 7.2931 (11), 12.8708 (17)
V (Å³)	1512.2 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.96, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	20096, 2452, 1273
R_int	0.110
(sin θ/λ)_max (Å⁻¹)	0.730

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.168, 1.05
No. of reflections	2452
No. of parameters	124
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.26

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N4ⁱ	0.8196	1.9438	2.759 (3)	172.80
O2—H2···N3ⁱⁱ	0.8196	2.0012	2.817 (3)	173.44
N1—H101···O1	0.89 (3)	2.22 (3)	2.701 (3)	113 (2)
N1—H101···O2ⁱⁱⁱ	0.89 (3)	2.40 (3)	3.034 (3)	129 (2)
C3—H3···N2ⁱⁱ	0.9300	2.5727	3.439 (3)	155.21

Symmetry codes: (i) −x+3/2, y, z−1/2; (ii) x−1/2, y−1/2, −z+2; (iii) x+1/2, −y+2, −z+3/2.

Acknowledgements

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2010–0007092).

References

Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gallardo, H., Meyer, E. & Vencato, I. (1995). Acta Cryst. C51, 2430–2432. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Meyer, E., Zucco, C. & Gallardo, H. (1998). J. Mater. Chem., 8, 1351–1354. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar