4-Amino-3,5-di­chloro­pyridinium 3-hy­droxy­pico­linate monohydrate

Ashokan, A.; Nehru, J.; Chakkarapani, N.; Khamrang, T.; Kavitha, S.J.; Rajakannan, V.; Hemamalini, M.

doi:10.1107/S2414314623008210

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 9| September 2023| x230821

https://doi.org/10.1107/S2414314623008210

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4-Amino-3,5-dichloropyridinium 3-hydroxypicolinate monohydrate

Agalya Ashokan,^a Jayasudha Nehru,^a Nandhini Chakkarapani,^b Themmila Khamrang,^c Savaridasan Jose Kavitha,^a Venkatachalam Rajakannan ^b and Madhukar Hemamalini ^a ^*

^aDepartment of Chemistry, Mother Teresa Women's University, Kodaikanal, Tamil Nadu, India, ^bDepartment of Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai-600 025, Tamil Nadu, India, and ^cAssistant Professor, Department of Chemistry, DM College of Science, Dhanamanjuri University, Imphal, Manipur-795 001, India
^*Correspondence e-mail: hemamalini2k3@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 15 September 2023; accepted 19 September 2023; online 22 September 2023)

In the title hydrated salt, C₅H₅Cl₂N₂⁺·C₆H₄NO₃⁻·H₂O, the pyridine N atom of the cation is protonated and an intramolecular O—H⋯O hydrogen bond is observed in the anion, which generates an S(6) ring. The crystal packing features N—H⋯N, O—H⋯O, N—H⋯O, C—H⋯Cl and C—H⋯O hydrogen bonds, which generate a three-dimensional network.

Keywords: crystal structure; hydrogen bonding; hydrated salt.

CCDC reference: 2294939

Structure description

4-Aminopyridine and its derivatives are used clinically to treat Lambert–Eaton myasthenic syndrome and multiple sclerosis because they block potassium channels, which prolongs action potentials and increases transmitter release at the neuromuscular junction (Judge & Bever, 2006 ). Picolinic acid, which contains N and O donors, has attracted much attention for the design and synthesis of self-assembling systems (e.g., Steiner, 2002 ). In this regard, 3-hydroxypicolinic acid is of interest because it can be used as a neutral ligand or, depending on the pH value, as an anionic or cationic ligand. In addition, due to the arrangement of its functional groups, it can act as a monodentate or bidentate ligand, which allows it to form five- or six-membered chelate rings. As part of our work in this area, we now report the synthesis and structure of the title hydrated molecular salt.

The asymmetric unit (Fig. 1) of the title salt contains a 4-amino-3,5-dichloropyridinium cation, a 3-hydroxy picolinate anion and a water molecule. The pyridinium cation is essentially planar, with a maximum deviation of 0.010 (2) Å for atom C2. A wider than normal angle [C5—N1—C1 = 120.41 (12)°] is subtended at the protonated N1 atom. In the anion, a typical intramolecular O—H⋯O hydrogen bond, which generates an S(6) ring, is seen. In the extended structure, the cations, anions and water molecules are connected by N—H⋯N, O—H⋯O, C—H⋯Cl, N—H⋯O and C—H⋯O hydrogen bonds (Table 1), forming a three-dimensional network (Figs. 2 and 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.82	1.79	2.5155 (17)	147
N1—H1⋯N3ⁱ	0.86	1.90	2.7546 (17)	171
N2—H2A⋯O1Wⁱⁱ	0.86	2.13	2.9414 (17)	157
N2—H2B⋯O1Wⁱⁱⁱ	0.86	2.05	2.8269 (17)	149
O1W—H1W⋯O2	0.85	1.90	2.7442 (17)	170
O1W—H2W⋯O1^iv	0.85	1.98	2.8181 (18)	170
C5—H5⋯O1ⁱ	0.93	2.31	2.9864 (18)	129
C5—H5⋯Cl2^v	0.93	2.97	3.7363 (16)	141
C7—H7⋯O3^vi	0.93	2.52	3.399 (2)	157
Symmetry codes: (i) x+1, y, z; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) .

Figure 1
The molecular structure of the title compound showing 50% displacement ellipsoids. The intramolecular hydrogen bond is shown with dashed lines.

Figure 2
One-dimensional supramolecular hydrogen-bonded chain mediated by water molecules in the title compound.

Figure 3
Crystal packing viewed down [100] in the title compound.

A search of the Cambridge Structural Database (Version 5.43, update November 2022; Groom et al., 2016 ) for the 3,5-dichloro-4-amino pyridine fragment with additional substituents yielded hexaaquamagnesium(II) bis(4-amino-3,5,6-trichloro-picolinate) tetrahydrate (CSD refcode BAWGOV; Smith et al., 1981 ), [(4-amino-3,5-dichloro-6-fluoropyridin-2-yl)oxy]acetic acid (EZONOY; Park et al., 2016 ), sodium picloramate hexahydrate (CURLIM; Smith et al., 2015 ), guanidinium 4-amino-3,5,6-trichloropicolinate (GUPICL10; Parthasarathi et al., 1982 ), and 6-chloro-3-(trifluoromethoxy)pyridine-2-carboxylic acid (MAFTEU; Manteau et al., 2010 ).

Synthesis and crystallization

A hot methanol solution of 3-hydroxy picolinic acid (40 mg) was mixed with a hot aqueous solution of 4-amino 3,5-dichloro pyridine (34 mg). The mixture was cooled slowly and kept at room temperature. After a few days, colourless block shaped crystals were obtained.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₅Cl₂N₂⁺·C₆H₄NO₃⁻·H₂O
M_r	320.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.4267 (19), 14.084 (3), 10.900 (2)
β (°)	91.953 (8)
V (Å³)	1292.9 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.52
Crystal size (mm)	0.46 × 0.32 × 0.13

Data collection
Diffractometer	Agilent Xcalibur, Atlas, Gemini
Absorption correction	Multi-scan
T_min, T_max	0.819, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	45801, 3296, 2853
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.091, 1.03
No. of reflections	3296
No. of parameters	185
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.35
Computer programs: CrysAlis PRO (Agilent, 2012 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and PLATON (Spek, 2020 ).

Structural data

CCDC reference: 2294939

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314623008210/hb4452sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623008210/hb4452Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: PLATON (Spek, 2020).

4-Amino-3,5-dichloropyridinium 3-hydroxypyridine-2-carboxylate monohydrate top

Crystal data top

C₅H₅Cl₂N₂⁺·C₆H₄NO₃⁻·H₂O	F(000) = 656
M_r = 320.13	D_x = 1.645 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.4267 (19) Å	Cell parameters from 3676 reflections
b = 14.084 (3) Å	θ = 2.5–28.8°
c = 10.900 (2) Å	µ = 0.52 mm⁻¹
β = 91.953 (8)°	T = 296 K
V = 1292.9 (5) Å³	Plate, colourless
Z = 4	0.46 × 0.32 × 0.13 mm

Data collection top

Agilent Xcalibur, Atlas, Gemini diffractometer	2853 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
ω scans	θ_max = 28.7°, θ_min = 2.4°
Absorption correction: multi-scan	h = −11→11
T_min = 0.819, T_max = 0.937	k = −18→18
45801 measured reflections	l = −14→14
3296 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0465P)² + 0.3959P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3296 reflections	Δρ_max = 0.24 e Å⁻³
185 parameters	Δρ_min = −0.35 e Å⁻³

Special details top

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. The water H atoms were located in a difference Fourier map and allowed to refine freely. The remaining H atoms were positioned geometrically (C—H = 0.93 and N—H = 0.86 Å) and were refined using a riding model, with U_iso(H) = 1.2 U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.85851 (4)	0.68420 (3)	0.15096 (4)	0.04683 (12)
Cl2	0.89478 (5)	0.30311 (2)	0.10521 (4)	0.04737 (12)
O1	0.42463 (12)	0.67099 (7)	0.27823 (11)	0.0439 (3)
O2	0.61861 (13)	0.71788 (7)	0.40818 (11)	0.0459 (3)
O3	0.82471 (14)	0.60173 (8)	0.48694 (13)	0.0535 (3)
H3	0.780642	0.653220	0.477230	0.080*
N3	0.50360 (13)	0.48436 (8)	0.31752 (10)	0.0321 (2)
N1	1.19792 (14)	0.49866 (8)	0.22147 (11)	0.0371 (3)
H1	1.294531	0.500301	0.249479	0.045*
N2	0.73770 (13)	0.49223 (8)	0.08094 (11)	0.0355 (3)
H2A	0.685153	0.544264	0.072057	0.043*
H2B	0.694906	0.439155	0.059109	0.043*
C10	0.59379 (14)	0.55395 (9)	0.36845 (11)	0.0288 (3)
C11	0.53872 (15)	0.65512 (9)	0.34965 (13)	0.0326 (3)
C3	0.88438 (14)	0.49383 (9)	0.12820 (11)	0.0291 (3)
C4	0.96128 (15)	0.57881 (9)	0.16585 (12)	0.0321 (3)
C6	0.73510 (16)	0.53325 (10)	0.43364 (13)	0.0353 (3)
C2	0.97853 (16)	0.41096 (9)	0.14404 (12)	0.0325 (3)
C5	1.11412 (16)	0.57934 (10)	0.21103 (13)	0.0362 (3)
H5	1.160941	0.636508	0.234961	0.043*
C1	1.13192 (17)	0.41529 (10)	0.18845 (13)	0.0373 (3)
H1A	1.191375	0.359836	0.195919	0.045*
C9	0.55198 (17)	0.39478 (10)	0.32671 (14)	0.0388 (3)
H9	0.488901	0.347163	0.291583	0.047*
C8	0.69351 (18)	0.37002 (10)	0.38699 (15)	0.0428 (3)
H8	0.725723	0.306886	0.390273	0.051*
C7	0.78549 (17)	0.43927 (11)	0.44166 (15)	0.0431 (3)
H7	0.880028	0.423758	0.483433	0.052*
O1W	0.48614 (13)	0.86692 (8)	0.53048 (11)	0.0441 (3)
H1W	0.518086	0.816660	0.495934	0.066*
H2W	0.462944	0.849278	0.602250	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0388 (2)	0.03527 (19)	0.0658 (3)	0.00513 (13)	−0.00686 (17)	−0.01076 (16)
Cl2	0.0497 (2)	0.03070 (18)	0.0608 (3)	−0.00776 (14)	−0.01108 (18)	0.00405 (15)
O1	0.0385 (5)	0.0339 (5)	0.0585 (7)	0.0032 (4)	−0.0120 (5)	0.0042 (5)
O2	0.0429 (6)	0.0320 (5)	0.0621 (7)	−0.0008 (4)	−0.0073 (5)	−0.0116 (5)
O3	0.0416 (6)	0.0449 (6)	0.0723 (8)	−0.0023 (5)	−0.0249 (6)	−0.0072 (6)
N3	0.0294 (5)	0.0297 (5)	0.0371 (6)	0.0000 (4)	−0.0023 (4)	−0.0008 (4)
N1	0.0295 (5)	0.0419 (6)	0.0393 (6)	−0.0021 (5)	−0.0075 (5)	0.0026 (5)
N2	0.0278 (5)	0.0345 (6)	0.0438 (6)	−0.0027 (4)	−0.0051 (5)	−0.0019 (5)
C10	0.0268 (6)	0.0282 (6)	0.0313 (6)	−0.0006 (5)	0.0004 (5)	−0.0009 (5)
C11	0.0294 (6)	0.0290 (6)	0.0397 (7)	0.0010 (5)	0.0023 (5)	−0.0010 (5)
C3	0.0273 (6)	0.0342 (6)	0.0258 (6)	−0.0031 (5)	0.0007 (5)	0.0009 (5)
C4	0.0299 (6)	0.0327 (6)	0.0335 (6)	−0.0009 (5)	−0.0010 (5)	−0.0027 (5)
C6	0.0290 (6)	0.0371 (7)	0.0396 (7)	−0.0004 (5)	−0.0039 (5)	0.0003 (6)
C2	0.0340 (6)	0.0304 (6)	0.0329 (6)	−0.0047 (5)	−0.0028 (5)	0.0039 (5)
C5	0.0323 (6)	0.0387 (7)	0.0374 (7)	−0.0054 (5)	−0.0035 (5)	−0.0036 (6)
C1	0.0357 (7)	0.0363 (7)	0.0396 (7)	0.0008 (5)	−0.0048 (6)	0.0065 (6)
C9	0.0387 (7)	0.0292 (6)	0.0483 (8)	−0.0009 (5)	−0.0021 (6)	−0.0018 (6)
C8	0.0413 (8)	0.0320 (7)	0.0549 (9)	0.0084 (6)	0.0016 (7)	0.0068 (6)
C7	0.0327 (7)	0.0436 (8)	0.0526 (9)	0.0074 (6)	−0.0066 (6)	0.0075 (7)
O1W	0.0418 (6)	0.0358 (5)	0.0542 (7)	0.0069 (4)	−0.0077 (5)	−0.0016 (5)

Geometric parameters (Å, º) top

Cl1—C4	1.7233 (14)	C10—C11	1.5103 (18)
Cl2—C2	1.7217 (14)	C3—C4	1.4151 (17)
O1—C11	1.2366 (17)	C3—C2	1.4184 (18)
O2—C11	1.2697 (17)	C4—C5	1.3631 (18)
O3—C6	1.3446 (17)	C6—C7	1.392 (2)
O3—H3	0.8200	C2—C1	1.3661 (19)
N3—C9	1.3287 (18)	C5—H5	0.9300
N3—C10	1.3481 (16)	C1—H1A	0.9300
N1—C5	1.3406 (18)	C9—C8	1.386 (2)
N1—C1	1.3430 (18)	C9—H9	0.9300
N1—H1	0.8600	C8—C7	1.370 (2)
N2—C3	1.3229 (16)	C8—H8	0.9300
N2—H2A	0.8600	C7—H7	0.9300
N2—H2B	0.8600	O1W—H1W	0.8499
C10—C6	1.3965 (18)	O1W—H2W	0.8500

C6—O3—H3	109.5	O3—C6—C10	121.79 (13)
C9—N3—C10	119.47 (12)	C7—C6—C10	118.91 (13)
C5—N1—C1	120.41 (12)	C1—C2—C3	121.66 (12)
C5—N1—H1	119.8	C1—C2—Cl2	120.10 (11)
C1—N1—H1	119.8	C3—C2—Cl2	118.24 (10)
C3—N2—H2A	120.0	N1—C5—C4	120.96 (13)
C3—N2—H2B	120.0	N1—C5—H5	119.5
H2A—N2—H2B	120.0	C4—C5—H5	119.5
N3—C10—C6	121.12 (12)	N1—C1—C2	120.81 (13)
N3—C10—C11	117.62 (11)	N1—C1—H1A	119.6
C6—C10—C11	121.24 (11)	C2—C1—H1A	119.6
O1—C11—O2	125.31 (13)	N3—C9—C8	122.09 (13)
O1—C11—C10	118.99 (12)	N3—C9—H9	119.0
O2—C11—C10	115.68 (12)	C8—C9—H9	119.0
N2—C3—C4	122.67 (12)	C7—C8—C9	119.48 (13)
N2—C3—C2	123.00 (12)	C7—C8—H8	120.3
C4—C3—C2	114.33 (11)	C9—C8—H8	120.3
C5—C4—C3	121.81 (12)	C8—C7—C6	118.88 (13)
C5—C4—Cl1	119.66 (11)	C8—C7—H7	120.6
C3—C4—Cl1	118.52 (10)	C6—C7—H7	120.6
O3—C6—C7	119.29 (12)	H1W—O1W—H2W	104.5

C9—N3—C10—C6	−1.8 (2)	C4—C3—C2—C1	−1.97 (19)
C9—N3—C10—C11	176.65 (12)	N2—C3—C2—Cl2	−2.54 (18)
N3—C10—C11—O1	−7.84 (19)	C4—C3—C2—Cl2	178.22 (10)
C6—C10—C11—O1	170.60 (13)	C1—N1—C5—C4	−0.6 (2)
N3—C10—C11—O2	173.80 (12)	C3—C4—C5—N1	0.0 (2)
C6—C10—C11—O2	−7.76 (19)	Cl1—C4—C5—N1	−178.74 (11)
N2—C3—C4—C5	−178.05 (13)	C5—N1—C1—C2	−0.2 (2)
C2—C3—C4—C5	1.20 (19)	C3—C2—C1—N1	1.5 (2)
N2—C3—C4—Cl1	0.74 (18)	Cl2—C2—C1—N1	−178.65 (11)
C2—C3—C4—Cl1	179.99 (10)	C10—N3—C9—C8	−0.2 (2)
N3—C10—C6—O3	−178.70 (13)	N3—C9—C8—C7	1.6 (2)
C11—C10—C6—O3	2.9 (2)	C9—C8—C7—C6	−0.9 (2)
N3—C10—C6—C7	2.4 (2)	O3—C6—C7—C8	−179.94 (15)
C11—C10—C6—C7	−175.97 (13)	C10—C6—C7—C8	−1.0 (2)
N2—C3—C2—C1	177.27 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.79	2.5155 (17)	147
N1—H1···N3ⁱ	0.86	1.90	2.7546 (17)	171
N2—H2A···O1Wⁱⁱ	0.86	2.13	2.9414 (17)	157
N2—H2B···O1Wⁱⁱⁱ	0.86	2.05	2.8269 (17)	149
O1W—H1W···O2	0.85	1.90	2.7442 (17)	170
O1W—H2W···O1^iv	0.85	1.98	2.8181 (18)	170
C5—H5···O1ⁱ	0.93	2.31	2.9864 (18)	129
C5—H5···Cl2^v	0.93	2.97	3.7363 (16)	141
C7—H7···O3^vi	0.93	2.52	3.399 (2)	157

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

Funding information

MH thanks SERB-IRE for financial support (Ref. No. SIR/2022/000011). SJK thanks TANSCHE for financial support (File No. RGP/2019–20/MTWU/HECP-0080).

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