3-(6-Amino­pyridinium-3-yl)benzoate monohydrate

Yuan, Z.-Y.; Zhao, J.; Peng, Z.

doi:10.1107/S1600536812041943

organic compounds

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Volume 68| Part 11| November 2012| Page o3119

doi:10.1107/S1600536812041943

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3-(6-Aminopyridinium-3-yl)benzoate monohydrate

Zong-Yong Yuan,^a Jun Zhao ^a ^* and Zhao Peng ^a

^aCollege of Mechanical and Material Engineering, China Three Gorges University, Yichang 443002, People's Republic of China
^*Correspondence e-mail: junzhao08@126.com

(Received 9 September 2012; accepted 7 October 2012; online 13 October 2012)

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

C₁₂H₁₀N₂O₂·H₂O
M_r = 232.24
Monoclinic, P 2₁ /c
a = 7.1956 (18) Å
b = 13.091 (9) Å
c = 11.987 (10) Å
β = 101.44 (3)°
V = 1106.8 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.17 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.980, T_max = 0.983
9294 measured reflections
1942 independent reflections
1344 reflections with I > 2σ(I)
R_int = 0.095

Refinement

R[F² > 2σ(F²)] = 0.084
wR(F²) = 0.215
S = 1.09
1942 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.30 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
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) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z.

Data collection: SMART (Bruker, 1999 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812041943/jj2152sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812041943/jj2152Isup2.hkl

checkCIF report

Comment top

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 Zn^II 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).

Related literature top

For the use of pyridinecarboxylic acid in coordination chemistry and for related structures, see: Tang et al. (2011); Zhong et al. (2008).

Experimental top

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.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: 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).

Figures top

	Fig. 1. The structure of the title compound with the atom-numbering scheme showing displacement ellipsoids at the 30% probability level for non-H atoms.
	Fig. 2. The three-dimensional supramolecular network formed by N—H···O and O—H···O hydrogen-bonding interactions. H atoms not involved in hydrogen bonding have been removed for clarity.

3-(6-Aminopyridinium-3-yl)benzoate monohydrate top

Crystal data top

C₁₂H₁₀N₂O₂·H₂O	F(000) = 488
M_r = 232.24	D_x = 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

Data collection top

Bruker SMART CCD diffractometer	1942 independent reflections
Radiation source: fine-focus sealed tube	1344 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.095
ϕ and ω scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.980, T_max = 0.983	k = −15→15
9294 measured reflections	l = −14→14

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)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.215	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0884P)² + 0.8024P] where P = (F_o² + 2F_c²)/3
1942 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₂H₁₀N₂O₂·H₂O	V = 1106.8 (12) Å³
M_r = 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)°

Data collection top

Bruker SMART CCD diffractometer	1942 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1344 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.983	R_int = 0.095
9294 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.084	0 restraints
wR(F²) = 0.215	H-atom parameters constrained
S = 1.09	Δρ_max = 0.30 e Å⁻³
1942 reflections	Δρ_min = −0.21 e Å⁻³
154 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
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.980, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	9294, 1942, 1344
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.21

Computer programs: SMART (Bruker, 1999), SAINT (Bruker,1999), 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
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

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