organic compounds
3-(6-Aminopyridinium-3-yl)benzoate monohydrate
aCollege of Mechanical and Material Engineering, China Three Gorges University, Yichang 443002, People's Republic of China
*Correspondence e-mail: junzhao08@126.com
The title compound, C12H10N2O2·H2O, crystallizes as a zwitterion in which the pyridine N atom is protonated and the carboxyl OH group is deprotonated. The benzene and pyridinium rings are inclined at a dihedral angle of 54.93 (1)°. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular network.
Related literature
For the use of pyridinecarboxylic acid in coordination chemistry and for related structures, see: Tang et al. (2011); Zhong et al. (2008).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1999); cell SAINT (Bruker,1999); 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
10.1107/S1600536812041943/jj2152sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041943/jj2152Isup2.hkl
A mixture of 3-(6-Amino-pyridin-3-yl)-benzoic acid (0.0214 g, 0.1 mmol), Zn(CH3COO)2.2H2O (0.0219 g, 0.1 mmol) and water (8 ml) was stired vigorously for 30 min and then sealed in a Teflon-lined stainless-steel autoclave. The autoclave was heated and maintained at 393 K for 2 days, and then cooled to room temperature at 5 K h-1 to obtain colorless prism crystals suitable for X-ray analysis.
The H atoms bonded to C and N atoms were positioned geometrically (C—H = 0.93 Å, N—H = 0.86 Å) and allowed to ride on their parent atoms, with Uiso(H) value equal to 1.2Ueq(C or N). The H atoms bonded to water O atoms were included in calculated positions and refined with Uiso(H) = 1.5Ueq(O).
Data collection: SMART (Bruker, 1999); cell
SAINT (Bruker,1999); data reduction: SAINT (Bruker,1999); 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).C12H10N2O2·H2O | F(000) = 488 |
Mr = 232.24 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1519 reflections |
a = 7.1956 (18) Å | θ = 3.1–25.0° |
b = 13.091 (9) Å | µ = 0.10 mm−1 |
c = 11.987 (10) Å | T = 296 K |
β = 101.44 (3)° | Prism, colourless |
V = 1106.8 (12) Å3 | 0.20 × 0.18 × 0.17 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 1942 independent reflections |
Radiation source: fine-focus sealed tube | 1344 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.095 |
ϕ and ω scans | θmax = 25.0°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.980, Tmax = 0.983 | k = −15→15 |
9294 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)] = 0.084 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.215 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0884P)2 + 0.8024P] where P = (Fo2 + 2Fc2)/3 |
1942 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C12H10N2O2·H2O | V = 1106.8 (12) Å3 |
Mr = 232.24 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.1956 (18) Å | µ = 0.10 mm−1 |
b = 13.091 (9) Å | T = 296 K |
c = 11.987 (10) Å | 0.20 × 0.18 × 0.17 mm |
β = 101.44 (3)° |
Bruker SMART CCD diffractometer | 1942 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1344 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.983 | Rint = 0.095 |
9294 measured reflections |
R[F2 > 2σ(F2)] = 0.084 | 0 restraints |
wR(F2) = 0.215 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.30 e Å−3 |
1942 reflections | Δρmin = −0.21 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6726 (5) | 0.2413 (3) | −0.2146 (3) | 0.0454 (10) | |
C2 | 0.4946 (5) | 0.1869 (3) | −0.1993 (3) | 0.0408 (9) | |
C3 | 0.4506 (5) | 0.1783 (3) | −0.0921 (3) | 0.0418 (9) | |
H3A | 0.5360 | 0.2026 | −0.0291 | 0.050* | |
C4 | 0.2823 (5) | 0.1342 (3) | −0.0766 (3) | 0.0422 (9) | |
C5 | 0.1555 (6) | 0.0988 (3) | −0.1711 (4) | 0.0518 (11) | |
H5A | 0.0407 | 0.0704 | −0.1626 | 0.062* | |
C6 | 0.1995 (6) | 0.1055 (3) | −0.2783 (4) | 0.0546 (11) | |
H6A | 0.1146 | 0.0805 | −0.3410 | 0.066* | |
C7 | 0.3682 (5) | 0.1489 (3) | −0.2930 (3) | 0.0475 (10) | |
H7A | 0.3969 | 0.1526 | −0.3652 | 0.057* | |
C8 | 0.2383 (5) | 0.1250 (3) | 0.0394 (3) | 0.0414 (9) | |
C9 | 0.0750 (5) | 0.1644 (3) | 0.0640 (3) | 0.0461 (10) | |
H9A | −0.0115 | 0.1964 | 0.0067 | 0.055* | |
C10 | 0.1542 (5) | 0.1128 (3) | 0.2573 (3) | 0.0442 (10) | |
C11 | 0.3236 (5) | 0.0713 (3) | 0.2355 (3) | 0.0482 (10) | |
H11A | 0.4080 | 0.0389 | 0.2936 | 0.058* | |
C12 | 0.3642 (5) | 0.0783 (3) | 0.1300 (3) | 0.0478 (10) | |
H12A | 0.4779 | 0.0517 | 0.1172 | 0.057* | |
N1 | 0.0361 (4) | 0.1579 (2) | 0.1700 (3) | 0.0454 (8) | |
H1A | −0.0681 | 0.1837 | 0.1819 | 0.054* | |
N2 | 0.1056 (5) | 0.1100 (3) | 0.3583 (3) | 0.0558 (10) | |
H2A | 0.0003 | 0.1366 | 0.3671 | 0.067* | |
H2B | 0.1795 | 0.0814 | 0.4149 | 0.067* | |
O1 | 0.7197 (4) | 0.2360 (2) | −0.3109 (2) | 0.0626 (9) | |
O1W | 0.2996 (5) | −0.0676 (3) | 0.4736 (3) | 0.0984 (13) | |
H1WA | 0.3198 | −0.0995 | 0.5372 | 0.148* | |
H1WB | 0.2433 | −0.1120 | 0.4237 | 0.148* | |
O2 | 0.7649 (4) | 0.2900 (2) | −0.1316 (2) | 0.0611 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.040 (2) | 0.050 (2) | 0.048 (2) | 0.0020 (18) | 0.0135 (18) | 0.007 (2) |
C2 | 0.0366 (19) | 0.038 (2) | 0.052 (2) | 0.0037 (16) | 0.0172 (17) | 0.0019 (17) |
C3 | 0.039 (2) | 0.043 (2) | 0.046 (2) | 0.0025 (17) | 0.0136 (17) | −0.0019 (17) |
C4 | 0.043 (2) | 0.034 (2) | 0.055 (2) | −0.0038 (16) | 0.0223 (18) | −0.0001 (17) |
C5 | 0.045 (2) | 0.046 (2) | 0.068 (3) | −0.0120 (19) | 0.019 (2) | −0.007 (2) |
C6 | 0.051 (3) | 0.055 (3) | 0.055 (3) | −0.008 (2) | 0.004 (2) | −0.007 (2) |
C7 | 0.047 (2) | 0.045 (2) | 0.053 (2) | 0.0009 (19) | 0.0162 (19) | −0.0021 (19) |
C8 | 0.043 (2) | 0.0304 (19) | 0.055 (2) | 0.0031 (16) | 0.0192 (18) | 0.0039 (17) |
C9 | 0.046 (2) | 0.043 (2) | 0.053 (2) | −0.0009 (18) | 0.0183 (19) | 0.0058 (18) |
C10 | 0.047 (2) | 0.035 (2) | 0.056 (2) | −0.0028 (17) | 0.0215 (19) | 0.0021 (18) |
C11 | 0.046 (2) | 0.043 (2) | 0.060 (3) | 0.0058 (18) | 0.0190 (19) | 0.0039 (19) |
C12 | 0.044 (2) | 0.039 (2) | 0.065 (3) | 0.0067 (18) | 0.023 (2) | −0.0010 (19) |
N1 | 0.0381 (17) | 0.0437 (18) | 0.060 (2) | 0.0043 (15) | 0.0242 (16) | 0.0041 (16) |
N2 | 0.053 (2) | 0.062 (2) | 0.058 (2) | 0.0078 (17) | 0.0229 (17) | 0.0039 (17) |
O1 | 0.0569 (18) | 0.089 (2) | 0.0477 (17) | −0.0125 (16) | 0.0258 (14) | −0.0030 (15) |
O1W | 0.120 (3) | 0.107 (3) | 0.070 (2) | 0.030 (3) | 0.024 (2) | 0.032 (2) |
O2 | 0.0484 (16) | 0.083 (2) | 0.0543 (18) | −0.0193 (16) | 0.0175 (14) | −0.0085 (16) |
C1—O2 | 1.256 (4) | C8—C12 | 1.408 (5) |
C1—O1 | 1.267 (5) | C9—N1 | 1.357 (5) |
C1—C2 | 1.508 (5) | C9—H9A | 0.9300 |
C2—C3 | 1.387 (5) | C10—N2 | 1.326 (5) |
C2—C7 | 1.390 (5) | C10—N1 | 1.346 (5) |
C3—C4 | 1.387 (5) | C10—C11 | 1.406 (5) |
C3—H3A | 0.9300 | C11—C12 | 1.357 (5) |
C4—C5 | 1.386 (5) | C11—H11A | 0.9300 |
C4—C8 | 1.491 (5) | C12—H12A | 0.9300 |
C5—C6 | 1.385 (5) | N1—H1A | 0.8600 |
C5—H5A | 0.9300 | N2—H2A | 0.8600 |
C6—C7 | 1.383 (5) | N2—H2B | 0.8600 |
C6—H6A | 0.9300 | O1W—H1WA | 0.8554 |
C7—H7A | 0.9300 | O1W—H1WB | 0.8736 |
C8—C9 | 1.368 (5) | ||
O2—C1—O1 | 123.7 (4) | C9—C8—C4 | 121.4 (4) |
O2—C1—C2 | 118.1 (3) | C12—C8—C4 | 122.1 (3) |
O1—C1—C2 | 118.2 (4) | N1—C9—C8 | 121.6 (4) |
C3—C2—C7 | 119.1 (3) | N1—C9—H9A | 119.2 |
C3—C2—C1 | 120.5 (3) | C8—C9—H9A | 119.2 |
C7—C2—C1 | 120.3 (3) | N2—C10—N1 | 118.8 (3) |
C4—C3—C2 | 121.5 (4) | N2—C10—C11 | 123.6 (4) |
C4—C3—H3A | 119.2 | N1—C10—C11 | 117.6 (3) |
C2—C3—H3A | 119.2 | C12—C11—C10 | 120.1 (4) |
C5—C4—C3 | 118.7 (4) | C12—C11—H11A | 120.0 |
C5—C4—C8 | 120.6 (3) | C10—C11—H11A | 120.0 |
C3—C4—C8 | 120.7 (4) | C11—C12—C8 | 121.6 (4) |
C6—C5—C4 | 120.2 (4) | C11—C12—H12A | 119.2 |
C6—C5—H5A | 119.9 | C8—C12—H12A | 119.2 |
C4—C5—H5A | 119.9 | C10—N1—C9 | 122.7 (3) |
C7—C6—C5 | 120.8 (4) | C10—N1—H1A | 118.7 |
C7—C6—H6A | 119.6 | C9—N1—H1A | 118.7 |
C5—C6—H6A | 119.6 | C10—N2—H2A | 120.0 |
C6—C7—C2 | 119.6 (4) | C10—N2—H2B | 120.0 |
C6—C7—H7A | 120.2 | H2A—N2—H2B | 120.0 |
C2—C7—H7A | 120.2 | H1WA—O1W—H1WB | 105.1 |
C9—C8—C12 | 116.5 (3) | ||
O2—C1—C2—C3 | −9.5 (5) | C5—C4—C8—C9 | −55.5 (5) |
O1—C1—C2—C3 | 171.0 (4) | C3—C4—C8—C9 | 124.6 (4) |
O2—C1—C2—C7 | 167.5 (4) | C5—C4—C8—C12 | 126.5 (4) |
O1—C1—C2—C7 | −11.9 (5) | C3—C4—C8—C12 | −53.5 (5) |
C7—C2—C3—C4 | −1.1 (5) | C12—C8—C9—N1 | −0.6 (6) |
C1—C2—C3—C4 | 176.0 (3) | C4—C8—C9—N1 | −178.7 (3) |
C2—C3—C4—C5 | −0.4 (5) | N2—C10—C11—C12 | −179.2 (4) |
C2—C3—C4—C8 | 179.6 (3) | N1—C10—C11—C12 | 0.7 (6) |
C3—C4—C5—C6 | 1.5 (6) | C10—C11—C12—C8 | −1.3 (6) |
C8—C4—C5—C6 | −178.5 (4) | C9—C8—C12—C11 | 1.2 (6) |
C4—C5—C6—C7 | −1.1 (6) | C4—C8—C12—C11 | 179.3 (4) |
C5—C6—C7—C2 | −0.5 (6) | N2—C10—N1—C9 | 179.9 (4) |
C3—C2—C7—C6 | 1.5 (5) | C11—C10—N1—C9 | −0.1 (5) |
C1—C2—C7—C6 | −175.6 (3) | C8—C9—N1—C10 | 0.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 1.87 | 2.715 (4) | 167 |
N2—H2A···O2i | 0.86 | 1.95 | 2.803 (4) | 172 |
N2—H2B···O1W | 0.86 | 2.19 | 2.915 (5) | 142 |
O1W—H1WA···O2ii | 0.86 | 2.00 | 2.761 (5) | 147 |
O1W—H1WB···O1iii | 0.87 | 2.16 | 2.928 (5) | 146 |
Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C12H10N2O2·H2O |
Mr | 232.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 7.1956 (18), 13.091 (9), 11.987 (10) |
β (°) | 101.44 (3) |
V (Å3) | 1106.8 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.20 × 0.18 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.980, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9294, 1942, 1344 |
Rint | 0.095 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.084, 0.215, 1.09 |
No. of reflections | 1942 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.21 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker,1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 1.87 | 2.715 (4) | 167.2 |
N2—H2A···O2i | 0.86 | 1.95 | 2.803 (4) | 171.6 |
N2—H2B···O1W | 0.86 | 2.19 | 2.915 (5) | 141.5 |
O1W—H1WA···O2ii | 0.86 | 2.00 | 2.761 (5) | 146.9 |
O1W—H1WB···O1iii | 0.87 | 2.16 | 2.928 (5) | 146.0 |
Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y, −z. |
References
Bruker (1999). SMART and SAINT. Bruker AXS Inc., Wisconsin, USA. 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
Tang, L., Fu, F., Wu, Y. P., Hou, X. Y. & Gao, L. J. (2011). J. Coord. Chem. 64, 3146–3157. Web of Science CSD CrossRef Google Scholar
Zhong, R. Q., Zou, R. Q., Du, M., Jiang, L., Yamada, T., Maruta, G., Takeda, S. & Xu, Q. (2008). CrystEngComm, 10, 605–613. Web of Science CSD CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Multidentate bridging ligands containing functional groups such as the familiar pyridyl and/or carboxylate groups have proven to be among the most important types of organic ligands for the design and construction of coordination polymers exhibiting remarkable polymeric structural motifs due to their rich coordination modes (Tang et al., 2011; Zhong et al., 2008). We attempted to synthesize a ZnII complex with the ligand in hydrothermal synthesis conditions. However the title compound was obtained, its structure is reported here.
The asymmetric unit of the title compound, C12H10N2O2. H2O is composed of one 3-(6-Amino-pyridinium-3-yl)-benzoate acid molecule and one lattice water molecule. The dihedral angle between the mean planes of the benzene and pyridinium rings is 54.93 (1)°. The deprotonated carboxylate COO(O1—C1—O2) group is slightly twisted from the benzene ring by an angle of 11.61 (7)° between their mean planes (Fig. 1). Intermolecular O—H···O and N—H···O hydrogen-bonding interactions (Table 1) link adjacent molecules into a three-dimensional supramolecular network (Fig. 2).