[1-(4-Hydroxy­phen­yl)-1H-tetra­zol-5-ylsulfan­yl]acetic acid

Zhan, C.-H.; Zhang, S.-G.; Feng, Y.-L.

doi:10.1107/S1600536808037136

organic compounds

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Volume 64| Part 12| December 2008| Page o2451

doi:10.1107/S1600536808037136

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[1-(4-Hydroxyphenyl)-1H-tetrazol-5-ylsulfanyl]acetic acid

Cai-Hong Zhan,^a Shu-Guang Zhang ^a and Yun-Long Feng ^a ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
^*Correspondence e-mail: sky37@zjnu.edu.cn

(Received 7 November 2008; accepted 10 November 2008; online 26 November 2008)

The title compound, C₉H₈N₄O₃S, shows a layer structure constructed from intermolecular O—H⋯O and O—H⋯N hydrogen bonds. Interatomic distances suggest that extensive, but not uniform, π-electron delocalization is present in the tetrazole rings and extends over the exocyclic C—S bond.

Related literature

For related literature on tetrazol-5-thione and its derivatives, see: Cea-Olivares et al. (1997 ); Kim et al. (2003 ).

Experimental

Crystal data

C₉H₈N₄O₃S
M_r = 252.25
Orthorhombic, P b c a
a = 14.407 (3) Å
b = 7.3365 (16) Å
c = 21.107 (5) Å
V = 2231.0 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.28 × 0.16 × 0.10 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.95, T_max = 0.97
18595 measured reflections
2550 independent reflections
1834 reflections with I > 2σ(I)
R_int = 0.099

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.106
S = 1.06
2550 reflections
160 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 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
O1—H1⋯O3ⁱ	0.835 (17)	1.953 (17)	2.787 (3)	177 (3)
O2—H2⋯N4ⁱⁱ	0.834 (17)	1.866 (17)	2.699 (3)	176 (3)
O2—H2⋯N3ⁱⁱ	0.834 (17)	2.60 (2)	3.369 (3)	154 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808037136/at2673sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808037136/at2673Isup2.hkl

checkCIF report

Comment top

Tetrazol-5-thione and its derivatives are interesting ligands from a structural point of view since they can display a wide range of coordination patterns with metal ions. Due to a variety of potential coordination sites, they can act as monodentate (–S or –N) or bidentate (–N, N or –N, S) ligands, forming polymers or interacting with metal ions (Cea-Olivares et al., 1997; Kim et al., 2003).

As shown in Fig.1, the bond lengths within the tetrazole ring exhibit the expected pattern of four long bonds (C7—N1, C7—N4, N3—N4 and N1—N2) together with a short one (N2—N3). In detail, C7—N1 [1.340 (2) Å] and C7—N4 [1.324 (2) Å] are typical for carbon-nitrogen single bonds from 1.336 Å to 1.420 Å, while N3—N4 [1.365 (2) Å] and N1—N2 [1.358 (2) Å] are between the single and double bonds. And the bond distance N2—N3 of 1.283 (2) Å is similar to that of a double bond of 1.25 Å. The bond length of S1—C7 [1.723 (2) Å9 also falls between the double and single bonds. All these interatomic distances suggest that extensive but not uniform π electron delocalization is present in the tetrazole rings and extends over the exocyclic C—S bond.

Related literature top

For related literature on tetrazol-5-thione and its derivatives, see: Cea-Olivares et al. (1997); Kim et al. (2003).

Experimental top

To an aqueous solution of 1-(4-hydroxyphenyl)-5-thiotetrazole (1.940 g, 10.0 mmol) and NaOH (0.80 g, 20.0 mmol) were sequentially added the aqueous solution of chloroactic acid (2.835 g, 30.0 mmol) and NaOH (1.400 g, 35.0 mmol). After stirring for 4 h at 353 K under nitrogen atmosphere, the mixture was cooled to room temperature slowly. Adjusted the pH to 2 by adding 1.0 mol/L HCl, the white deposit appeared rapidly. The solids were filtered and washed with water. The single crystals suitable for X-ray diffraction were obtained by the re-crystallization of sieved solid in the ethanol.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids

[1-(4-Hydroxyphenyl)-1H-tetrazol-5-ylsulfanyl]acetic acid top

Crystal data top

C₉H₈N₄O₃S	F(000) = 1040
M_r = 252.25	D_x = 1.502 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2531 reflections
a = 14.407 (3) Å	θ = 2.4–27.5°
b = 7.3365 (16) Å	µ = 0.29 mm⁻¹
c = 21.107 (5) Å	T = 293 K
V = 2231.0 (9) Å³	Block, colourless
Z = 8	0.28 × 0.16 × 0.10 mm

Data collection top

Bruker APEXII area-detector diffractometer	2550 independent reflections
Radiation source: fine-focus sealed tube	1834 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.099
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
T_min = 0.95, T_max = 0.97	k = −9→9
18595 measured reflections	l = −27→27

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0144P)² + 1.7635P] where P = (F_o² + 2F_c²)/3
2550 reflections	(Δ/σ)_max = 0.001
160 parameters	Δρ_max = 0.19 e Å⁻³
2 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₈N₄O₃S	V = 2231.0 (9) Å³
M_r = 252.25	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 14.407 (3) Å	µ = 0.29 mm⁻¹
b = 7.3365 (16) Å	T = 293 K
c = 21.107 (5) Å	0.28 × 0.16 × 0.10 mm

Data collection top

Bruker APEXII area-detector diffractometer	2550 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1834 reflections with I > 2σ(I)
T_min = 0.95, T_max = 0.97	R_int = 0.099
18595 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	2 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.19 e Å⁻³
2550 reflections	Δρ_min = −0.21 e Å⁻³
160 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
S1	0.51454 (4)	0.15070 (9)	0.09961 (3)	0.05074 (19)
O1	0.15861 (13)	0.3256 (3)	0.28120 (9)	0.0610 (5)
H1	0.177 (2)	0.270 (4)	0.3133 (11)	0.073*
O2	0.75012 (12)	0.0102 (3)	0.01914 (8)	0.0551 (5)
H2	0.8048 (13)	0.010 (4)	0.0322 (13)	0.066*
O3	0.72494 (12)	0.1471 (3)	0.11139 (8)	0.0645 (5)
N1	0.45507 (13)	0.4915 (3)	0.12461 (10)	0.0468 (5)
N2	0.47350 (16)	0.6679 (3)	0.10961 (12)	0.0637 (6)
N3	0.54403 (16)	0.6653 (3)	0.07237 (12)	0.0619 (6)
N4	0.57366 (13)	0.4912 (3)	0.06208 (10)	0.0480 (5)
C1	0.23393 (16)	0.3617 (3)	0.24421 (11)	0.0441 (5)
C2	0.21686 (16)	0.4284 (3)	0.18436 (12)	0.0470 (6)
H2A	0.1561	0.4457	0.1708	0.056*
C3	0.28941 (16)	0.4695 (3)	0.14462 (12)	0.0478 (6)
H3A	0.2783	0.5152	0.1042	0.057*
C4	0.37920 (15)	0.4418 (3)	0.16560 (11)	0.0436 (5)
C5	0.39734 (17)	0.3749 (4)	0.22511 (12)	0.0509 (6)
H5A	0.4582	0.3576	0.2386	0.061*
C6	0.32408 (17)	0.3336 (4)	0.26463 (12)	0.0509 (6)
H6A	0.3352	0.2870	0.3049	0.061*
C7	0.51693 (14)	0.3855 (3)	0.09473 (11)	0.0402 (5)
C8	0.59818 (15)	0.0925 (3)	0.03998 (12)	0.0465 (6)
H8A	0.5826	−0.0265	0.0231	0.056*
H8B	0.5931	0.1797	0.0056	0.056*
C9	0.69718 (16)	0.0887 (3)	0.06206 (11)	0.0429 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0418 (3)	0.0418 (3)	0.0686 (4)	−0.0030 (3)	0.0098 (3)	−0.0001 (3)
O1	0.0472 (10)	0.0753 (14)	0.0607 (11)	0.0032 (9)	0.0128 (9)	0.0151 (10)
O2	0.0389 (8)	0.0757 (13)	0.0508 (10)	0.0116 (9)	−0.0034 (8)	−0.0121 (9)
O3	0.0490 (11)	0.0903 (15)	0.0542 (11)	0.0078 (10)	−0.0099 (8)	−0.0217 (11)
N1	0.0421 (11)	0.0421 (12)	0.0563 (12)	0.0009 (9)	0.0080 (9)	0.0042 (10)
N2	0.0611 (14)	0.0407 (12)	0.0894 (17)	0.0025 (11)	0.0171 (13)	0.0099 (12)
N3	0.0520 (13)	0.0486 (13)	0.0850 (16)	−0.0031 (11)	0.0140 (12)	0.0113 (12)
N4	0.0375 (10)	0.0481 (12)	0.0584 (12)	−0.0027 (9)	0.0030 (9)	0.0048 (10)
C1	0.0426 (13)	0.0412 (13)	0.0484 (13)	0.0017 (10)	0.0062 (10)	−0.0012 (11)
C2	0.0389 (12)	0.0491 (14)	0.0529 (14)	0.0016 (11)	−0.0015 (11)	0.0025 (12)
C3	0.0486 (14)	0.0487 (15)	0.0460 (13)	0.0035 (11)	−0.0012 (11)	0.0050 (11)
C4	0.0414 (12)	0.0392 (12)	0.0502 (14)	0.0007 (10)	0.0080 (11)	0.0005 (11)
C5	0.0391 (12)	0.0588 (16)	0.0547 (15)	0.0029 (11)	−0.0014 (11)	0.0016 (12)
C6	0.0515 (14)	0.0555 (15)	0.0456 (14)	0.0018 (12)	0.0002 (11)	0.0041 (12)
C7	0.0319 (11)	0.0428 (13)	0.0458 (12)	−0.0020 (9)	0.0000 (10)	0.0000 (10)
C8	0.0394 (12)	0.0443 (14)	0.0558 (14)	0.0005 (10)	−0.0043 (11)	−0.0080 (11)
C9	0.0408 (12)	0.0445 (13)	0.0435 (13)	0.0040 (10)	−0.0030 (11)	0.0003 (11)

Geometric parameters (Å, º) top

S1—C7	1.726 (2)	C1—C2	1.377 (3)
S1—C8	1.794 (2)	C1—C6	1.384 (3)
O1—C1	1.363 (3)	C2—C3	1.374 (3)
O1—H1	0.835 (17)	C2—H2A	0.9300
O2—C9	1.317 (3)	C3—C4	1.382 (3)
O2—H2	0.834 (17)	C3—H3A	0.9300
O3—C9	1.195 (3)	C4—C5	1.374 (3)
N1—C7	1.341 (3)	C5—C6	1.379 (3)
N1—N2	1.359 (3)	C5—H5A	0.9300
N1—C4	1.441 (3)	C6—H6A	0.9300
N2—N3	1.285 (3)	C8—C9	1.501 (3)
N3—N4	1.364 (3)	C8—H8A	0.9700
N4—C7	1.321 (3)	C8—H8B	0.9700

C7—S1—C8	100.49 (11)	C3—C4—N1	118.7 (2)
C1—O1—H1	108 (2)	C4—C5—C6	119.1 (2)
C9—O2—H2	109 (2)	C4—C5—H5A	120.5
C7—N1—N2	108.24 (19)	C6—C5—H5A	120.5
C7—N1—C4	129.8 (2)	C5—C6—C1	119.8 (2)
N2—N1—C4	121.94 (19)	C5—C6—H6A	120.1
N3—N2—N1	106.4 (2)	C1—C6—H6A	120.1
N2—N3—N4	111.0 (2)	N4—C7—N1	108.4 (2)
C7—N4—N3	105.86 (19)	N4—C7—S1	129.03 (18)
O1—C1—C2	116.9 (2)	N1—C7—S1	122.53 (17)
O1—C1—C6	122.7 (2)	C9—C8—S1	115.16 (17)
C2—C1—C6	120.4 (2)	C9—C8—H8A	108.5
C3—C2—C1	120.2 (2)	S1—C8—H8A	108.5
C3—C2—H2A	119.9	C9—C8—H8B	108.5
C1—C2—H2A	119.9	S1—C8—H8B	108.5
C2—C3—C4	119.0 (2)	H8A—C8—H8B	107.5
C2—C3—H3A	120.5	O3—C9—O2	124.2 (2)
C4—C3—H3A	120.5	O3—C9—C8	125.6 (2)
C5—C4—C3	121.6 (2)	O2—C9—C8	110.2 (2)
C5—C4—N1	119.7 (2)

C7—N1—N2—N3	−0.2 (3)	C4—C5—C6—C1	−0.7 (4)
C4—N1—N2—N3	−179.5 (2)	O1—C1—C6—C5	−179.3 (2)
N1—N2—N3—N4	−0.2 (3)	C2—C1—C6—C5	0.9 (4)
N2—N3—N4—C7	0.5 (3)	N3—N4—C7—N1	−0.6 (3)
O1—C1—C2—C3	179.4 (2)	N3—N4—C7—S1	177.64 (19)
C6—C1—C2—C3	−0.7 (4)	N2—N1—C7—N4	0.5 (3)
C1—C2—C3—C4	0.4 (4)	C4—N1—C7—N4	179.7 (2)
C2—C3—C4—C5	−0.2 (4)	N2—N1—C7—S1	−177.85 (18)
C2—C3—C4—N1	−177.7 (2)	C4—N1—C7—S1	1.3 (3)
C7—N1—C4—C5	70.7 (3)	C8—S1—C7—N4	−7.9 (2)
N2—N1—C4—C5	−110.2 (3)	C8—S1—C7—N1	170.13 (19)
C7—N1—C4—C3	−111.7 (3)	C7—S1—C8—C9	86.2 (2)
N2—N1—C4—C3	67.4 (3)	S1—C8—C9—O3	−12.3 (4)
C3—C4—C5—C6	0.3 (4)	S1—C8—C9—O2	167.39 (17)
N1—C4—C5—C6	177.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.84 (2)	1.95 (2)	2.787 (3)	177 (3)
O2—H2···N4ⁱⁱ	0.83 (2)	1.87 (2)	2.699 (3)	176 (3)
O2—H2···N3ⁱⁱ	0.83 (2)	2.60 (2)	3.369 (3)	154 (3)

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

Experimental details

Crystal data
Chemical formula	C₉H₈N₄O₃S
M_r	252.25
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	14.407 (3), 7.3365 (16), 21.107 (5)
V (Å³)	2231.0 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.28 × 0.16 × 0.10

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.95, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	18595, 2550, 1834
R_int	0.099
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.106, 1.06
No. of reflections	2550
No. of parameters	160
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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
O1—H1···O3ⁱ	0.835 (17)	1.953 (17)	2.787 (3)	177 (3)
O2—H2···N4ⁱⁱ	0.834 (17)	1.866 (17)	2.699 (3)	176 (3)
O2—H2···N3ⁱⁱ	0.834 (17)	2.60 (2)	3.369 (3)	154 (3)

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

References

Bruker (2002). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cea-Olivares, R., Ebert, K. E., Silaghi-Dumitrescu, L. & Haiduc, I. (1997). Heteroatom. Chem. 8, 317–321. CSD CrossRef CAS Web of Science Google Scholar
Kim, Y.-J., Han, J.-T., Kang, S., Han, W. S. & Lee, S. W. (2003). Dalton Trans. pp. 3357–3364. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536808037136

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