organic compounds
2-(Carboxymethylsulfanyl)pyridine-3-carboxylic acid monohydrate
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
The title compound, C8H7NO4S·H2O, was obtained by reaction of 2-mercaptopyridine-3-carboxylic acid with chloroacetic acid. In the molecular structure, the dihedral angle between the two least-squares planes defined by the pyridine ring and the carboxy group is 8.32 (9)°. The carboxymethylsulfanyl group makes a torsion angle of 82.64 (12)° with the pyridine ring. An intramolecular O—H⋯N hydrogen bond between the acidic function of the carboxymethylsulfanyl group and the pyridine N atom stabilizes the conformation, whereas intermolecular O—H⋯O hydrogen bonding with the uncoordinated water molecules is responsible for packing of the structure, leading to chains propagating in [001].
Related literature
For derivatives of 2-mercaptopyridine-3-carboxylic acid and compounds with 2-mercaptopyridine-3-carboxylate ligands, see: Panagiotis et al. (2003); Smith & Sagatys (2003); Humphrey et al. (2006); Ma et al. (2004); Quintal et al. (2002).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2006); cell 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: DIAMOND (Crystal Impact, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
https://doi.org/10.1107/S1600536810016120/wm2333sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016120/wm2333Isup2.hkl
The mixture of 2-mercaptopyridine-3-carboxylic acid (1.552 g, 10.0 mmol) and chloroacetic acid (2.835 g, 30.0 mmol) was stirred and refluxed under basic condition in which sodium hydroxide solution was needed to keep the pH around 11. After reaction for 4 h at 328 K, the mixture was cooled to room temperature. By adjusting the pH around 3 with concentrated hydrochloric acid, a white precipitate appeared rapidly. The solid was filtered off and washed with water. Single crystals suitable for X-ray diffraction were obtained in the mother liquid after evaporation within a few days.
The carbon-bound H-atoms were positioned geometrically and included in the
using a riding model [C—H 0.93, 0.97 Å Uiso(H) = 1.2Ueq(C)]. The oxygen-bound H-atoms were located in a difference Fourier maps and refined with an O—H distance restraint of 0.83 Å [Uiso(H) = 1.2Ueq(O)].2-Mercaptopyridine-3-carboxylic acid is an interesting ligand because of its potential versatile coordinate behavior. It may act as a deprotonated ligand through either the carboxylate or the thiolate group, such as 2-mercaptopyridine-3-carboxylate hydrate (Smith et al., 2003) or 2-mercapto-nicotinic acid (Panagiotis et al., 2003). Thus it can act as a monodentate (O or N), bidentate (O, O or O, N) or chelating (O, O or O, N) ligand interacting with metal ions, and a variety of coordination polymers have been characterised (Humphrey et al., 2006; Ma et al., 2004; Quintal et al., 2002). In this work, we report a new derivative, 2-(carboxymethylsulfanyl)pyridine-3-carboxylic acid, (I), which was obtained by reaction of 2-mercaptopyridine-3-carboxylic acid with chloroacetic acid.
The molecular structure of (I) is presented in Fig. 1. The carboxylate group is almost parallel to the pyridine group with a dihedral angle of 8.32 (9)°, while the carboxymethylsulfanyl group makes a torsion angle of 82.64 (12)° with the pyridine ring. The carboxylic O atoms, pyridine N atom together with lattice water molecules are involved in hydrogen-bonding interactions (Fig. 2). In detail, the structure is stabilized by an intramolecular O—H···N hydrogen bond between the carboxy function of the carboxymethylsulfanyl group and the pyridine N atom. The other carboxy function acts as a donor and acceptor group for intermolecular O—H···O hydrogen bonds with the adjacent lattice water molecules which results in the formation of a chain structure running along the c direction.
For derivatives of 2-mercaptopyridine-3-carboxylic acid and compounds with 2-mercaptopyridine-3-carboxylate ligands, see: Panagiotis et al. (2003); Smith et al. (2003); Humphrey et al. (2006); Ma et al. (2004); Quintal et al. (2002).
Data collection: APEX2 (Bruker, 2006); cell
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: DIAMOND (Crystal Impact, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. View of the molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. A view of the one-dimensional chain structure of (I). Intermolecular hydrogen bonds interactions are depicted by dashed lines. |
C8H7NO4S·H2O | Z = 2 |
Mr = 231.22 | F(000) = 240 |
Triclinic, P1 | Dx = 1.572 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2824 (2) Å | Cell parameters from 3676 reflections |
b = 7.3132 (2) Å | θ = 2.0–27.6° |
c = 10.9090 (4) Å | µ = 0.33 mm−1 |
α = 77.901 (2)° | T = 296 K |
β = 71.787 (2)° | Sheet, colourless |
γ = 62.590 (2)° | 0.48 × 0.43 × 0.04 mm |
V = 488.43 (3) Å3 |
Bruker APEXII CCD diffractometer | 2217 independent reflections |
Radiation source: fine-focus sealed tube | 1910 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 27.6°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.853, Tmax = 0.987 | k = −9→9 |
7375 measured reflections | l = −14→14 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0509P)2 + 0.088P] where P = (Fo2 + 2Fc2)/3 |
2217 reflections | (Δ/σ)max = 0.001 |
148 parameters | Δρmax = 0.24 e Å−3 |
5 restraints | Δρmin = −0.24 e Å−3 |
C8H7NO4S·H2O | γ = 62.590 (2)° |
Mr = 231.22 | V = 488.43 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2824 (2) Å | Mo Kα radiation |
b = 7.3132 (2) Å | µ = 0.33 mm−1 |
c = 10.9090 (4) Å | T = 296 K |
α = 77.901 (2)° | 0.48 × 0.43 × 0.04 mm |
β = 71.787 (2)° |
Bruker APEXII CCD diffractometer | 2217 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1910 reflections with I > 2σ(I) |
Tmin = 0.853, Tmax = 0.987 | Rint = 0.024 |
7375 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 5 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.24 e Å−3 |
2217 reflections | Δρmin = −0.24 e Å−3 |
148 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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. |
x | y | z | Uiso*/Ueq | ||
S1 | −0.82738 (6) | 0.36814 (5) | 1.36087 (3) | 0.04015 (13) | |
N1 | −0.5286 (2) | 0.09443 (18) | 1.19465 (11) | 0.0391 (3) | |
O2 | −0.92675 (19) | 0.12020 (17) | 1.57117 (11) | 0.0515 (3) | |
O4 | −0.6871 (2) | 0.41454 (18) | 1.04260 (11) | 0.0545 (3) | |
C5 | −0.6485 (2) | 0.1157 (2) | 1.31717 (13) | 0.0336 (3) | |
O1 | −0.7165 (2) | −0.20956 (19) | 1.61482 (11) | 0.0523 (3) | |
C4 | −0.6261 (2) | −0.0580 (2) | 1.40665 (13) | 0.0344 (3) | |
O3 | −0.8462 (2) | 0.74565 (18) | 1.07003 (11) | 0.0612 (4) | |
C6 | −0.7717 (2) | −0.0376 (2) | 1.53873 (14) | 0.0381 (3) | |
C3 | −0.3782 (3) | −0.0926 (2) | 1.15876 (15) | 0.0446 (4) | |
H3A | −0.2974 | −0.1047 | 1.0734 | 0.054* | |
C8 | −0.7529 (2) | 0.5679 (2) | 1.11102 (15) | 0.0431 (3) | |
C7 | −0.7046 (3) | 0.5195 (2) | 1.24178 (14) | 0.0408 (3) | |
H7A | −0.7496 | 0.6490 | 1.2771 | 0.049* | |
H7B | −0.5511 | 0.4459 | 1.2295 | 0.049* | |
C2 | −0.4654 (2) | −0.2483 (2) | 1.36726 (15) | 0.0412 (3) | |
H2A | −0.4430 | −0.3646 | 1.4256 | 0.049* | |
C1 | −0.3389 (3) | −0.2664 (2) | 1.24242 (16) | 0.0461 (4) | |
H1A | −0.2298 | −0.3931 | 1.2158 | 0.055* | |
O1W | −0.0210 (2) | 0.1439 (2) | 1.15804 (12) | 0.0589 (3) | |
H1WA | 0.034 (3) | 0.020 (2) | 1.145 (2) | 0.071* | |
H1WB | −0.081 (3) | 0.200 (3) | 1.0980 (19) | 0.071* | |
H4 | −0.626 (3) | 0.302 (3) | 1.087 (2) | 0.071* | |
H1 | −0.809 (3) | −0.177 (3) | 1.6845 (18) | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0438 (2) | 0.0341 (2) | 0.0296 (2) | −0.00903 (16) | −0.00324 (15) | −0.00379 (14) |
N1 | 0.0419 (7) | 0.0382 (6) | 0.0309 (6) | −0.0151 (5) | −0.0021 (5) | −0.0057 (5) |
O2 | 0.0511 (7) | 0.0457 (6) | 0.0380 (6) | −0.0125 (5) | 0.0027 (5) | −0.0045 (5) |
O4 | 0.0775 (9) | 0.0477 (7) | 0.0319 (6) | −0.0222 (6) | −0.0154 (6) | 0.0017 (5) |
C5 | 0.0334 (7) | 0.0354 (7) | 0.0301 (7) | −0.0134 (6) | −0.0065 (5) | −0.0043 (5) |
O1 | 0.0528 (7) | 0.0501 (6) | 0.0378 (6) | −0.0165 (6) | −0.0070 (5) | 0.0093 (5) |
C4 | 0.0351 (7) | 0.0357 (7) | 0.0326 (7) | −0.0158 (6) | −0.0080 (6) | −0.0020 (5) |
O3 | 0.0693 (8) | 0.0445 (7) | 0.0426 (6) | −0.0061 (6) | −0.0137 (6) | 0.0073 (5) |
C6 | 0.0417 (8) | 0.0420 (8) | 0.0328 (7) | −0.0206 (7) | −0.0102 (6) | 0.0008 (6) |
C3 | 0.0426 (8) | 0.0450 (8) | 0.0376 (8) | −0.0160 (7) | 0.0029 (6) | −0.0121 (6) |
C8 | 0.0408 (8) | 0.0432 (8) | 0.0352 (8) | −0.0148 (7) | −0.0052 (6) | 0.0031 (6) |
C7 | 0.0482 (9) | 0.0333 (7) | 0.0376 (7) | −0.0147 (6) | −0.0123 (7) | −0.0001 (6) |
C2 | 0.0428 (8) | 0.0345 (7) | 0.0437 (8) | −0.0154 (6) | −0.0103 (7) | −0.0011 (6) |
C1 | 0.0414 (8) | 0.0369 (8) | 0.0504 (9) | −0.0107 (6) | −0.0025 (7) | −0.0124 (7) |
O1W | 0.0736 (9) | 0.0588 (8) | 0.0365 (6) | −0.0272 (7) | −0.0108 (6) | 0.0050 (6) |
S1—C5 | 1.7606 (14) | O3—C8 | 1.2184 (18) |
S1—C7 | 1.8151 (15) | C3—C1 | 1.368 (2) |
N1—C3 | 1.3421 (19) | C3—H3A | 0.9300 |
N1—C5 | 1.3438 (18) | C8—C7 | 1.507 (2) |
O2—C6 | 1.2057 (18) | C7—H7A | 0.9700 |
O4—C8 | 1.2949 (19) | C7—H7B | 0.9700 |
O4—H4 | 0.861 (15) | C2—C1 | 1.379 (2) |
C5—C4 | 1.4078 (19) | C2—H2A | 0.9300 |
O1—C6 | 1.3180 (18) | C1—H1A | 0.9300 |
O1—H1 | 0.834 (16) | O1W—H1WA | 0.831 (15) |
C4—C2 | 1.388 (2) | O1W—H1WB | 0.830 (15) |
C4—C6 | 1.487 (2) | ||
C5—S1—C7 | 101.30 (7) | O3—C8—O4 | 121.27 (15) |
C3—N1—C5 | 119.77 (13) | O3—C8—C7 | 121.00 (15) |
C8—O4—H4 | 108.4 (15) | O4—C8—C7 | 117.70 (13) |
N1—C5—C4 | 120.67 (13) | C8—C7—S1 | 116.34 (11) |
N1—C5—S1 | 117.29 (10) | C8—C7—H7A | 108.2 |
C4—C5—S1 | 122.02 (11) | S1—C7—H7A | 108.2 |
C6—O1—H1 | 103.5 (16) | C8—C7—H7B | 108.2 |
C2—C4—C5 | 117.92 (13) | S1—C7—H7B | 108.2 |
C2—C4—C6 | 121.27 (13) | H7A—C7—H7B | 107.4 |
C5—C4—C6 | 120.81 (13) | C1—C2—C4 | 120.56 (14) |
O2—C6—O1 | 123.86 (14) | C1—C2—H2A | 119.7 |
O2—C6—C4 | 122.82 (13) | C4—C2—H2A | 119.7 |
O1—C6—C4 | 113.31 (13) | C3—C1—C2 | 118.13 (14) |
N1—C3—C1 | 122.77 (14) | C3—C1—H1A | 120.9 |
N1—C3—H3A | 118.6 | C2—C1—H1A | 120.9 |
C1—C3—H3A | 118.6 | H1WA—O1W—H1WB | 101.9 (18) |
C3—N1—C5—C4 | −3.5 (2) | C2—C4—C6—O1 | 7.13 (19) |
C3—N1—C5—S1 | 174.95 (11) | C5—C4—C6—O1 | −173.44 (13) |
C7—S1—C5—N1 | −23.50 (12) | C5—N1—C3—C1 | −0.4 (2) |
C7—S1—C5—C4 | 154.90 (12) | O3—C8—C7—S1 | 117.68 (15) |
N1—C5—C4—C2 | 5.0 (2) | O4—C8—C7—S1 | −64.05 (18) |
S1—C5—C4—C2 | −173.31 (11) | C5—S1—C7—C8 | 82.64 (12) |
N1—C5—C4—C6 | −174.42 (12) | C5—C4—C2—C1 | −2.8 (2) |
S1—C5—C4—C6 | 7.24 (18) | C6—C4—C2—C1 | 176.64 (13) |
C2—C4—C6—O2 | −171.59 (14) | N1—C3—C1—C2 | 2.6 (2) |
C5—C4—C6—O2 | 7.8 (2) | C4—C2—C1—C3 | −0.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3i | 0.83 (2) | 2.02 (2) | 2.8319 (18) | 166 (2) |
O1W—H1WB···O3ii | 0.83 (2) | 1.98 (2) | 2.7784 (18) | 162 (2) |
O1—H1···O1Wiii | 0.83 (2) | 1.76 (2) | 2.5917 (17) | 171 (2) |
O4—H4···N1 | 0.86 (2) | 1.72 (2) | 2.5778 (17) | 172 (2) |
Symmetry codes: (i) x+1, y−1, z; (ii) −x−1, −y+1, −z+2; (iii) −x−1, −y, −z+3. |
Experimental details
Crystal data | |
Chemical formula | C8H7NO4S·H2O |
Mr | 231.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.2824 (2), 7.3132 (2), 10.9090 (4) |
α, β, γ (°) | 77.901 (2), 71.787 (2), 62.590 (2) |
V (Å3) | 488.43 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.48 × 0.43 × 0.04 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.853, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7375, 2217, 1910 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.090, 1.02 |
No. of reflections | 2217 |
No. of parameters | 148 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.24 |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Crystal Impact, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3i | 0.831 (15) | 2.018 (16) | 2.8319 (18) | 166 (2) |
O1W—H1WB···O3ii | 0.830 (15) | 1.976 (17) | 2.7784 (18) | 162 (2) |
O1—H1···O1Wiii | 0.834 (16) | 1.764 (16) | 2.5917 (17) | 171 (2) |
O4—H4···N1 | 0.861 (15) | 1.722 (16) | 2.5778 (17) | 172 (2) |
Symmetry codes: (i) x+1, y−1, z; (ii) −x−1, −y+1, −z+2; (iii) −x−1, −y, −z+3. |
References
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Crystal Impact (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
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2-Mercaptopyridine-3-carboxylic acid is an interesting ligand because of its potential versatile coordinate behavior. It may act as a deprotonated ligand through either the carboxylate or the thiolate group, such as 2-mercaptopyridine-3-carboxylate hydrate (Smith et al., 2003) or 2-mercapto-nicotinic acid (Panagiotis et al., 2003). Thus it can act as a monodentate (O or N), bidentate (O, O or O, N) or chelating (O, O or O, N) ligand interacting with metal ions, and a variety of coordination polymers have been characterised (Humphrey et al., 2006; Ma et al., 2004; Quintal et al., 2002). In this work, we report a new derivative, 2-(carboxymethylsulfanyl)pyridine-3-carboxylic acid, (I), which was obtained by reaction of 2-mercaptopyridine-3-carboxylic acid with chloroacetic acid.
The molecular structure of (I) is presented in Fig. 1. The carboxylate group is almost parallel to the pyridine group with a dihedral angle of 8.32 (9)°, while the carboxymethylsulfanyl group makes a torsion angle of 82.64 (12)° with the pyridine ring. The carboxylic O atoms, pyridine N atom together with lattice water molecules are involved in hydrogen-bonding interactions (Fig. 2). In detail, the structure is stabilized by an intramolecular O—H···N hydrogen bond between the carboxy function of the carboxymethylsulfanyl group and the pyridine N atom. The other carboxy function acts as a donor and acceptor group for intermolecular O—H···O hydrogen bonds with the adjacent lattice water molecules which results in the formation of a chain structure running along the c direction.