2-Amino-5-(4-carboxyl­atophen­yl)­pyridinium monohydrate

Wei, X.-H.; Yan, H.; Lin, W.-G.

doi:10.1107/S1600536812035854

organic compounds

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Volume 68| Part 9| September 2012| Page o2749

doi:10.1107/S1600536812035854

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2-Amino-5-(4-carboxylatophenyl)pyridinium monohydrate

Xiao-Hong Wei,^a ^* Hong Yan ^a and Wei-Gong Lin ^a

^aCollege of Mechanical and Materials Engineering, China Three Gorges University, Yichang 443002, People's Republic of China
^*Correspondence e-mail: wxhong1@126.com

(Received 11 August 2012; accepted 15 August 2012; online 23 August 2012)

The title compound, C₁₂H₁₀N₂O₂·H₂O, crystallizes as a zwitterion in which the pyridine N atom is protonated and the carboxy –OH group is deprotonated. The benzene and pyridinium rings are inclined with a dihedral angle of 6.63 (5)° between them. In the crystal, intermolecular O—H⋯O and N—H⋯O hydrogen-bonding interactions link adjacent molecules into a two-dimensional double layered supramolecular network.

Related literature

For the use of pyridinecarboxylate acid in coordination chemistry and for related structures, see: Jia et al. (2007 ); Zhang et al. (2011 ).

Experimental

Crystal data

C₁₂H₁₀N₂O₂·H₂O
M_r = 232.24
Monoclinic, P 2₁ /n
a = 7.796 (2) Å
b = 7.808 (2) Å
c = 18.480 (5) Å
β = 95.165 (14)°
V = 1120.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.23 × 0.16 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.977, T_max = 0.985
11449 measured reflections
2554 independent reflections
1505 reflections with I > 2σ(I)
R_int = 0.090

Refinement

R[F² > 2σ(F²)] = 0.080
wR(F²) = 0.208
S = 1.01
2554 reflections
160 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 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	1.82	2.648 (3)	160
N2—H2A⋯O2ⁱ	0.86	2.07	2.911 (4)	167
N2—H2B⋯O3	0.86	2.09	2.921 (4)	163
O3—H3C⋯O2ⁱⁱ	0.86 (2)	1.99 (2)	2.849 (4)	178 (4)
O3—H3D⋯O1ⁱⁱⁱ	0.86 (2)	1.91 (2)	2.768 (4)	176 (5)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536812035854/jj2150sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035854/jj2150Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812035854/jj2150Isup3.cml

checkCIF report

Comment top

Rigid pyridinecarboxylate ligands have been extensively employed to react with metal ions and generate coordination polymers with fascinating structures and properties(Jia et al., 2007; Zhang et al., 2011). We attempted to synthesize a Zn^IIcomplex with the ligand in hydrothermal synthesis conditions. However the title compound was obtained, its structure is reported here.

The asymmetric unit comprises one 2-amino-5-(4-carboxylatophenyl)pyridinium molecule and one lattice water. The dihedral angel between the benzene ring and pyridinium ring is 6.63 (5)°, while the deprotonated carboxylate COO(O1—C12—O2) group is slightly twisted with an angle of 13.74 (3) ^o (Fig. 1). Intermolecular O—H···O and N—H···O hydrogen- bonding interactions (Table 1)) link adjacent molecules into a two-dimensional double layered supramolecular network (Fig. 2).

Related literature top

For the use of pyridinecarboxylate acid in coordination chemistry and for related structures, see: Jia et al. (2007); Zhang et al. (2011).

Experimental top

A mixture of 4-(6-aminopyridin-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 two-dimensional supramolecular network formed by N—H···O and O—H···O (dashed lines) hydrogen-bonding interactions.

2-Amino-5-(4-carboxylatophenyl)pyridinium monohydrate top

Crystal data top

C₁₂H₁₀N₂O₂·H₂O	F(000) = 488
M_r = 232.24	D_x = 1.377 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yn	Cell parameters from 1672 reflections
a = 7.796 (2) Å	θ = 2.8–27.5°
b = 7.808 (2) Å	µ = 0.10 mm⁻¹
c = 18.480 (5) Å	T = 296 K
β = 95.165 (14)°	Prism, colorless
V = 1120.4 (6) Å³	0.23 × 0.16 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2554 independent reflections
Radiation source: fine-focus sealed tube	1505 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.090
phi and ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.977, T_max = 0.985	k = −10→10
11449 measured reflections	l = −23→24

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.208	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0766P)² + 0.595P] where P = (F_o² + 2F_c²)/3
2554 reflections	(Δ/σ)_max < 0.001
160 parameters	Δρ_max = 0.17 e Å⁻³
3 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₂H₁₀N₂O₂·H₂O	V = 1120.4 (6) Å³
M_r = 232.24	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.796 (2) Å	µ = 0.10 mm⁻¹
b = 7.808 (2) Å	T = 296 K
c = 18.480 (5) Å	0.23 × 0.16 × 0.15 mm
β = 95.165 (14)°

Data collection top

Bruker SMART CCD diffractometer	2554 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1505 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.985	R_int = 0.090
11449 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.080	3 restraints
wR(F²) = 0.208	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.17 e Å⁻³
2554 reflections	Δρ_min = −0.16 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
C1	0.5962 (4)	0.7159 (4)	0.15326 (17)	0.0568 (8)
C2	0.6222 (4)	0.7885 (4)	0.08526 (18)	0.0669 (9)
H2C	0.6003	0.9042	0.0767	0.080*
C3	0.6796 (4)	0.6884 (4)	0.03225 (17)	0.0647 (9)
H3A	0.6927	0.7373	−0.0128	0.078*
C4	0.7203 (4)	0.5123 (4)	0.04277 (15)	0.0522 (7)
C5	0.6949 (4)	0.4505 (4)	0.11010 (16)	0.0600 (8)
H5A	0.7200	0.3362	0.1205	0.072*
C6	0.7823 (4)	0.4004 (4)	−0.01377 (15)	0.0528 (7)
C7	0.8241 (4)	0.4649 (4)	−0.08022 (16)	0.0642 (9)
H7B	0.8121	0.5815	−0.0895	0.077*
C8	0.8830 (4)	0.3594 (4)	−0.13264 (16)	0.0648 (9)
H8C	0.9119	0.4067	−0.1761	0.078*
C9	0.8999 (4)	0.1853 (4)	−0.12169 (15)	0.0555 (7)
C10	0.8584 (5)	0.1196 (4)	−0.05641 (17)	0.0728 (10)
H10A	0.8683	0.0025	−0.0478	0.087*
C11	0.8022 (5)	0.2251 (4)	−0.00347 (18)	0.0770 (11)
H11A	0.7770	0.1774	0.0404	0.092*
C12	0.9664 (4)	0.0670 (4)	−0.17777 (17)	0.0634 (8)
N1	0.6345 (3)	0.5496 (3)	0.16235 (13)	0.0606 (7)
H1A	0.6200	0.5033	0.2036	0.073*
N2	0.5351 (3)	0.8023 (4)	0.20782 (15)	0.0693 (8)
H2A	0.5210	0.7511	0.2481	0.083*
H2B	0.5100	0.9091	0.2027	0.083*
O1	1.0359 (3)	0.1364 (3)	−0.22902 (12)	0.0757 (7)
O2	0.9515 (4)	−0.0921 (3)	−0.17007 (13)	0.0853 (8)
O3	0.4085 (4)	1.1412 (3)	0.16247 (15)	0.0866 (8)
H3C	0.300 (3)	1.128 (6)	0.165 (2)	0.130*
H3D	0.447 (5)	1.207 (5)	0.1977 (19)	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0564 (17)	0.0549 (18)	0.0606 (19)	−0.0067 (14)	0.0137 (14)	−0.0057 (14)
C2	0.085 (2)	0.0504 (17)	0.068 (2)	−0.0074 (16)	0.0206 (17)	0.0030 (16)
C3	0.082 (2)	0.0570 (18)	0.0581 (19)	−0.0106 (16)	0.0216 (16)	0.0042 (15)
C4	0.0583 (17)	0.0535 (17)	0.0454 (16)	−0.0112 (14)	0.0088 (13)	0.0015 (12)
C5	0.075 (2)	0.0542 (17)	0.0516 (17)	0.0010 (16)	0.0116 (15)	0.0009 (14)
C6	0.0579 (17)	0.0570 (17)	0.0441 (16)	−0.0110 (14)	0.0079 (13)	−0.0008 (13)
C7	0.091 (2)	0.0542 (17)	0.0480 (17)	−0.0022 (17)	0.0119 (16)	0.0042 (14)
C8	0.091 (2)	0.065 (2)	0.0397 (16)	−0.0048 (18)	0.0144 (15)	0.0046 (14)
C9	0.0617 (17)	0.0595 (18)	0.0452 (16)	−0.0059 (14)	0.0042 (13)	−0.0028 (13)
C10	0.109 (3)	0.058 (2)	0.0543 (19)	0.0010 (19)	0.0242 (18)	0.0045 (15)
C11	0.124 (3)	0.058 (2)	0.0527 (18)	−0.003 (2)	0.0330 (19)	0.0092 (15)
C12	0.072 (2)	0.069 (2)	0.0497 (18)	−0.0034 (17)	0.0087 (15)	−0.0035 (16)
N1	0.0786 (17)	0.0604 (16)	0.0444 (14)	−0.0014 (13)	0.0153 (12)	0.0001 (12)
N2	0.0809 (18)	0.0634 (16)	0.0668 (17)	−0.0017 (14)	0.0254 (15)	−0.0080 (13)
O1	0.1006 (18)	0.0747 (15)	0.0557 (13)	−0.0044 (13)	0.0287 (13)	−0.0042 (11)
O2	0.130 (2)	0.0615 (15)	0.0686 (16)	−0.0009 (15)	0.0326 (15)	−0.0012 (12)
O3	0.117 (2)	0.0677 (16)	0.0786 (18)	−0.0107 (16)	0.0272 (16)	−0.0095 (13)

Geometric parameters (Å, º) top

C1—N2	1.336 (4)	C8—C9	1.379 (4)
C1—N1	1.339 (4)	C8—H8C	0.9300
C1—C2	1.410 (4)	C9—C10	1.376 (4)
C2—C3	1.360 (4)	C9—C12	1.514 (4)
C2—H2C	0.9300	C10—C11	1.380 (4)
C3—C4	1.421 (4)	C10—H10A	0.9300
C3—H3A	0.9300	C11—H11A	0.9300
C4—C5	1.365 (4)	C12—O1	1.256 (4)
C4—C6	1.477 (4)	C12—O2	1.257 (4)
C5—N1	1.355 (4)	N1—H1A	0.8600
C5—H5A	0.9300	N2—H2A	0.8600
C6—C11	1.389 (4)	N2—H2B	0.8600
C6—C7	1.393 (4)	O3—H3C	0.860 (18)
C7—C8	1.381 (4)	O3—H3D	0.861 (18)
C7—H7B	0.9300

N2—C1—N1	119.0 (3)	C9—C8—H8C	119.4
N2—C1—C2	124.0 (3)	C7—C8—H8C	119.4
N1—C1—C2	117.0 (3)	C10—C9—C8	118.0 (3)
C3—C2—C1	119.6 (3)	C10—C9—C12	119.6 (3)
C3—C2—H2C	120.2	C8—C9—C12	122.3 (3)
C1—C2—H2C	120.2	C9—C10—C11	120.9 (3)
C2—C3—C4	122.8 (3)	C9—C10—H10A	119.6
C2—C3—H3A	118.6	C11—C10—H10A	119.6
C4—C3—H3A	118.6	C10—C11—C6	122.0 (3)
C5—C4—C3	114.7 (3)	C10—C11—H11A	119.0
C5—C4—C6	121.3 (3)	C6—C11—H11A	119.0
C3—C4—C6	124.0 (3)	O1—C12—O2	124.3 (3)
N1—C5—C4	122.4 (3)	O1—C12—C9	116.8 (3)
N1—C5—H5A	118.8	O2—C12—C9	119.0 (3)
C4—C5—H5A	118.8	C1—N1—C5	123.5 (3)
C11—C6—C7	116.4 (3)	C1—N1—H1A	118.2
C11—C6—C4	121.7 (3)	C5—N1—H1A	118.2
C7—C6—C4	121.8 (3)	C1—N2—H2A	120.0
C8—C7—C6	121.4 (3)	C1—N2—H2B	120.0
C8—C7—H7B	119.3	H2A—N2—H2B	120.0
C6—C7—H7B	119.3	H3C—O3—H3D	108 (3)
C9—C8—C7	121.2 (3)

N2—C1—C2—C3	−177.8 (3)	C7—C8—C9—C10	−0.8 (5)
N1—C1—C2—C3	1.7 (5)	C7—C8—C9—C12	−179.2 (3)
C1—C2—C3—C4	−2.0 (5)	C8—C9—C10—C11	−0.3 (5)
C2—C3—C4—C5	0.9 (5)	C12—C9—C10—C11	178.1 (3)
C2—C3—C4—C6	179.8 (3)	C9—C10—C11—C6	1.1 (6)
C3—C4—C5—N1	0.4 (4)	C7—C6—C11—C10	−0.8 (5)
C6—C4—C5—N1	−178.5 (3)	C4—C6—C11—C10	179.3 (3)
C5—C4—C6—C11	6.1 (5)	C10—C9—C12—O1	−165.4 (3)
C3—C4—C6—C11	−172.8 (3)	C8—C9—C12—O1	12.9 (5)
C5—C4—C6—C7	−173.9 (3)	C10—C9—C12—O2	13.6 (5)
C3—C4—C6—C7	7.3 (5)	C8—C9—C12—O2	−168.1 (3)
C11—C6—C7—C8	−0.3 (5)	N2—C1—N1—C5	179.1 (3)
C4—C6—C7—C8	179.6 (3)	C2—C1—N1—C5	−0.4 (5)
C6—C7—C8—C9	1.2 (5)	C4—C5—N1—C1	−0.7 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	1.82	2.648 (3)	160
N2—H2A···O2ⁱ	0.86	2.07	2.911 (4)	167
N2—H2B···O3	0.86	2.09	2.921 (4)	163
O3—H3C···O2ⁱⁱ	0.86 (2)	1.99 (2)	2.849 (4)	178 (4)
O3—H3D···O1ⁱⁱⁱ	0.86 (2)	1.91 (2)	2.768 (4)	176 (5)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₂O₂·H₂O
M_r	232.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.796 (2), 7.808 (2), 18.480 (5)
β (°)	95.165 (14)
V (Å³)	1120.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.23 × 0.16 × 0.15

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.977, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	11449, 2554, 1505
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.080, 0.208, 1.01
No. of reflections	2554
No. of parameters	160
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16

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	1.82	2.648 (3)	160.3
N2—H2A···O2ⁱ	0.86	2.07	2.911 (4)	167.1
N2—H2B···O3	0.86	2.09	2.921 (4)	163.0
O3—H3C···O2ⁱⁱ	0.860 (18)	1.990 (18)	2.849 (4)	178 (4)
O3—H3D···O1ⁱⁱⁱ	0.861 (18)	1.909 (18)	2.768 (4)	176 (5)

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

References

Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jia, J. H., Lin, X., Wilson, C., Blake, A. J., Champness, N. R., Hubberstey, P., Walker, G., Cussen, E. J. & Schröder, M. (2007). Chem. Commun. 8, 840–842. Web of Science CSD CrossRef 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
Zhang, X. M., Wang, Y. Q., Song, Y. & Gao, E. Q. (2011). Inorg. Chem. 50, 7284–7294. Web of Science CSD CrossRef CAS PubMed Google Scholar

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