2-(2-Pyridylsulfan­yl)acetic acid

Li, X.-F.; An, Y.; Chen, H.-G.; Dong, L.-H.; Yan, W.

doi:10.1107/S1600536809054373

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o234

doi:10.1107/S1600536809054373

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2-(2-Pyridylsulfanyl)acetic acid

Xiao-Feng Li,^a Yan An,^a ^* Hui-Guo Chen,^a Li-Hua Dong ^a and Wei Yan ^a

^aInstitute of Marine Materials Science and Engineering, Shanghai Maritime University, Shanghai 201306, People's Republic of China.
^*Correspondence e-mail: smuchem@yahoo.com.cn

(Received 14 December 2009; accepted 16 December 2009; online 24 December 2009)

All non-H atoms of the title compound, C₇H₇NO₂S, lie on a crystallographic mirror plane, with the two methylene H atoms bisected by this plane. The crystal packing is characterized by intermolecular C—H⋯O and O—H⋯N contacts, which link the molecules into infinite zigzag chains parallel to [010].

Related literature

For background to the design of similar ligands, see: Akrivos (2001 ); Ye et al. (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₇NO₂S
M_r = 169.20
Orthorhombic, P n m a
a = 14.5521 (19) Å
b = 6.6774 (13) Å
c = 7.7212 (19) Å
V = 750.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 293 K
0.37 × 0.35 × 0.27 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.875, T_max = 0.906
1160 measured reflections
805 independent reflections
473 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.140
S = 1.00
805 reflections
67 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯N1ⁱ	0.82	1.79	2.606 (5)	175
C2—H2A⋯O2ⁱⁱ	0.93	2.50	3.410 (6)	167
C3—H3A⋯O1ⁱⁱⁱ	0.93	2.46	3.229 (5)	140
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (iii) x, y, z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809054373/sj2712sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809054373/sj2712Isup2.hkl

checkCIF report

Comment top

Compounds involving heterocyclic thiolate groups are ambidentate ligands which can form various metal-organic coordination structures via coordination of the exocyclic sulfur or the endocyclic nitrogen atoms (Akrivos, 2001). Similarly, carboxylic acids also exhibit diverse coordination modes in different metal complexes (Ye et al., 2005). In attempts to develop novel coordination frameworks, we have designed and synthesized the title compound, 2-(pyridin-2-ylthio)acetic acid (I), as a potentially multidentate ligand. Its crystal structure is reported here.

The single-crystal X-ray analysis of I reveals that all the bond lengths in compound I are within normal ranges (Allen et al., 1987). All the non-hydrogen atoms in each molecule are coplanar with the methylene hydrogen atoms related by mirror symmetry (Fig. 1). In the crystal structure molecules are linked into infinite, one dimensional, zigzag chains due to intermolecular H-bonding (Fig. 2, Table 2).

Related literature top

For background to the design of similar ligands, see: Akrivos (2001); Ye et al. (2005). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by heating a mixture of 2-pyridinethione (0.335 g, 3 mmol), chloroacetic acid (0.292 g, 3.1 mmol) and sodium hydroxide (0.248 g, 6.2 mmol) in ethanol at 353 K with magnetic stirring for 8 h. The pH of the solution was adjusted to 6 with hydrochloric acid. Yellow crystals were obtained after being recrystrallized twice from the ethanol solution (yield 78%). Analysis, calculated for C₇H₇NO₂S: C 49.69, H 4.17, N 8.28%; Found: C 50.06, H 4.27, N 8.06%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. View of the structure of I. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Crystal packin of the title compound viewed down the b axis.

2-(2-Pyridylsulfanyl)acetic acid top

Crystal data top

C₇H₇NO₂S	F(000) = 352
M_r = 169.20	D_x = 1.498 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 343 reflections
a = 14.5521 (19) Å	θ = 2.8–28.0°
b = 6.6774 (13) Å	µ = 0.37 mm⁻¹
c = 7.7212 (19) Å	T = 293 K
V = 750.3 (3) Å³	Block, yellow
Z = 4	0.37 × 0.35 × 0.27 mm

Data collection top

Bruker APEXII CCD diffractometer	805 independent reflections
Radiation source: fine-focus sealed tube	473 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −17→1
T_min = 0.875, T_max = 0.906	k = −1→8
1160 measured reflections	l = −9→1

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0634P)²] where P = (F_o² + 2F_c²)/3
805 reflections	(Δ/σ)_max = 0.003
67 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₇H₇NO₂S	V = 750.3 (3) Å³
M_r = 169.20	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 14.5521 (19) Å	µ = 0.37 mm⁻¹
b = 6.6774 (13) Å	T = 293 K
c = 7.7212 (19) Å	0.37 × 0.35 × 0.27 mm

Data collection top

Bruker APEXII CCD diffractometer	805 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	473 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.906	R_int = 0.066
1160 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.00	Δρ_max = 0.27 e Å⁻³
805 reflections	Δρ_min = −0.35 e Å⁻³
67 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	Occ. (<1)
S1	0.34558 (7)	0.2500	0.33858 (14)	0.0562 (6)
C1	0.5342 (3)	0.2500	0.6916 (6)	0.0583 (19)
H1A	0.5981	0.2500	0.6879	0.070*
C2	0.4919 (3)	0.2500	0.8503 (6)	0.0560 (17)
H2A	0.5262	0.2500	0.9520	0.067*
C3	0.3973 (3)	0.2500	0.8547 (6)	0.0545 (17)
H3A	0.3668	0.2500	0.9605	0.065*
C4	0.3481 (3)	0.2500	0.7029 (5)	0.0484 (15)
H4A	0.2842	0.2500	0.7050	0.058*
C5	0.3950 (3)	0.2500	0.5463 (5)	0.0452 (15)
C6	0.2251 (2)	0.2500	0.3861 (5)	0.0459 (15)
H6A	0.2093	0.1322	0.4533	0.055*	0.50
H6B	0.2093	0.3678	0.4533	0.055*	0.50
C7	0.1723 (3)	0.2500	0.2160 (6)	0.0454 (15)
N1	0.4877 (2)	0.2500	0.5405 (5)	0.0474 (13)
O1	0.2095 (2)	0.2500	0.0775 (4)	0.0638 (13)
O2	0.08419 (18)	0.2500	0.2437 (4)	0.0557 (12)
H2B	0.0569	0.2500	0.1508	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0240 (6)	0.1177 (15)	0.0269 (6)	0.000	−0.0001 (5)	0.000
C1	0.025 (2)	0.109 (6)	0.041 (3)	0.000	−0.0074 (19)	0.000
C2	0.042 (3)	0.095 (5)	0.031 (2)	0.000	−0.007 (2)	0.000
C3	0.041 (3)	0.099 (5)	0.023 (2)	0.000	0.006 (2)	0.000
C4	0.028 (2)	0.086 (5)	0.031 (2)	0.000	0.0029 (18)	0.000
C5	0.023 (2)	0.083 (5)	0.030 (2)	0.000	−0.0021 (17)	0.000
C6	0.0196 (19)	0.088 (5)	0.030 (2)	0.000	−0.0003 (17)	0.000
C7	0.027 (2)	0.080 (5)	0.029 (2)	0.000	0.0009 (18)	0.000
N1	0.0240 (17)	0.088 (4)	0.0304 (18)	0.000	−0.0001 (15)	0.000
O1	0.0268 (15)	0.134 (4)	0.0310 (16)	0.000	−0.0006 (13)	0.000
O2	0.0211 (16)	0.112 (4)	0.0345 (16)	0.000	−0.0018 (13)	0.000

Geometric parameters (Å, º) top

S1—C5	1.757 (4)	C4—C5	1.389 (6)
S1—C6	1.791 (4)	C4—H4A	0.9300
C1—N1	1.348 (5)	C5—N1	1.350 (5)
C1—C2	1.372 (6)	C6—C7	1.522 (6)
C1—H1A	0.9300	C6—H6A	0.9700
C2—C3	1.377 (6)	C6—H6B	0.9700
C2—H2A	0.9300	C7—O1	1.198 (5)
C3—C4	1.374 (6)	C7—O2	1.301 (5)
C3—H3A	0.9300	O2—H2B	0.8200

C5—S1—C6	102.31 (19)	N1—C5—S1	112.3 (3)
N1—C1—C2	123.2 (4)	C4—C5—S1	126.4 (3)
N1—C1—H1A	118.4	C7—C6—S1	108.5 (3)
C2—C1—H1A	118.4	C7—C6—H6A	110.0
C1—C2—C3	118.1 (4)	S1—C6—H6A	110.0
C1—C2—H2A	121.0	C7—C6—H6B	110.0
C3—C2—H2A	121.0	S1—C6—H6B	110.0
C4—C3—C2	120.0 (4)	H6A—C6—H6B	108.4
C4—C3—H3A	120.0	O1—C7—O2	126.3 (4)
C2—C3—H3A	120.0	O1—C7—C6	122.9 (4)
C3—C4—C5	119.1 (4)	O2—C7—C6	110.8 (4)
C3—C4—H4A	120.4	C1—N1—C5	118.3 (4)
C5—C4—H4A	120.4	C7—O2—H2B	109.5
N1—C5—C4	121.3 (4)

N1—C1—C2—C3	0.000 (1)	C5—S1—C6—C7	180.0
C1—C2—C3—C4	0.000 (1)	S1—C6—C7—O1	0.0
C2—C3—C4—C5	0.000 (1)	S1—C6—C7—O2	180.0
C3—C4—C5—N1	0.0	C2—C1—N1—C5	0.0
C3—C4—C5—S1	180.0	C4—C5—N1—C1	0.0
C6—S1—C5—N1	180.0	S1—C5—N1—C1	180.0
C6—S1—C5—C4	0.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···N1ⁱ	0.82	1.79	2.606 (5)	175
C2—H2A···O2ⁱⁱ	0.93	2.50	3.410 (6)	167
C3—H3A···O1ⁱⁱⁱ	0.93	2.46	3.229 (5)	140

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

Experimental details

Crystal data
Chemical formula	C₇H₇NO₂S
M_r	169.20
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	14.5521 (19), 6.6774 (13), 7.7212 (19)
V (Å³)	750.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.37 × 0.35 × 0.27

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.875, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	1160, 805, 473
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.140, 1.00
No. of reflections	805
No. of parameters	67
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.35

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), 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
O2—H2B···N1ⁱ	0.82	1.79	2.606 (5)	174.7
C2—H2A···O2ⁱⁱ	0.931	2.496	3.410 (6)	167.4
C3—H3A···O1ⁱⁱⁱ	0.930	2.461	3.229 (5)	140.0

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

Acknowledgements

The authors thank the Project of the Shanghai Municipal Education Commission (2008080, 2008068, 09YZ245, 10YZ111, 10ZZ98), the `Chen Guang' project supported by the Shanghai Municipal Education Commission and the Shanghai Education Development Foundation (09 C G52), the Innovative Activities of University Students in Shanghai Maritime University Project (090503) and the State Key Laboratory of Pollution Control and Resource Re-use Foundation (PCRRF09001) for financial support.

References

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