2-Amino-6-chloro­pyridine–glutaric acid (1/1)

Manickam, R.; Prabhaharan, M.; Jagadeesan, G.; Rajakannan, V.; Srinivasan, G.

doi:10.1107/S2414314619007818

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 6| June 2019| x190781

https://doi.org/10.1107/S2414314619007818

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2-Amino-6-chloropyridine–glutaric acid (1/1)

R. Manickam,^a M. Prabhaharan,^b G. Jagadeesan,^c V. Rajakannan ^d and G. Srinivasan ^a ^*

^aPG and Research Department of Physics, Government Arts College for Men (Autonomous), Nandanam, Chennai 600 035, India, ^bDepartment of Physics, Annai Violet Arts and Science College, Chennai 600 053, India, ^cDepartment of Physics, Jeppiaar Engineering College, Jeppiaar Nagar, OMR, Chennai 600 119, India, and ^dCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: agsv71@yahoo.com

Edited by H. Ishida, Okayama University, Japan (Received 6 May 2019; accepted 30 May 2019; online 14 June 2019)

In the title 1:1 co-crystal [systematic name: 6-chloropyridin-2-amine–pentanedioic acid (1/1)], C₅H₅ClN₂·C₅H₈O₄, the pyridine ring is essentially planar, with a maximum deviation of 0.003 (1) Å. The base and acid molecules are linked via N—H⋯O and O—H⋯N hydrogen bonds, while inversion-related acid molecules are linked via pairs of O—H⋯O hydrogen bonds. These interactions together with a C—H⋯O hydrogen bond connect the two components, forming (001) sheets.

Keywords: crystal structure; pentanedioic acid; chloropyridinium; amine.

CCDC reference: 1913526

Structure description

In order to study hydrogen-bonding interactions in pyridine–carboxy acid systems, the crystal structure determination of the title compound was carried out. Some related crystal structures have previously been reported, viz. 2-amino-5-methylpyridinium 4-carboxybutanoate (Hemamalini & Fun, 2010 ), 2,6-diamino-4-chloropyrimidinium 4-carboxybutanoate (Edison et al., 2014 ), pyrimidin-2-amine–glutaric acid (1/1) and bis(2-aminopyrimidinium)glutarate–glutaric acid (1/2) (Odiase et al., 2015 ).

As expected, the pyridine ring of the title compound is essentially planar, with a maximum deviation of 0.004 (1) Å for atom C1. The backbone conformation of the acid molecule can be described by the torsion angles C6—C7—C8—C9 [−174.76 (9)°] and C7—C8—C9—C10 [171.92 (9)°], which indicates a fully extended conformation of the molecule. The dihedral angle between the CO₂H groups is 13.8 (10)°.. As evident from the torsion angles, the backbone exhibits a fully extended conformation of the two carboxyl groups (Fig. 1). In the crystal, the N1 atom and the 2-amino group (N2) are linked to the carboxyl oxygen atoms (O3 and O4) via O—H⋯N and N—H⋯O hydrogen bonds with an R₂²(8) ring motif. The acid and base molecules are further linked by O—H⋯O and C—H⋯O hydrogen bonds (Table 1), forming (001) sheets (Fig. 2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2ⁱ	0.93	2.55	3.3711 (13)	147
N2—H2A⋯O3ⁱⁱ	0.87 (1)	2.08 (1)	2.9443 (13)	171 (2)
N2—H2B⋯O3ⁱ	0.87 (1)	2.18 (1)	2.9525 (13)	147 (1)
O1—H1A⋯O2ⁱⁱⁱ	0.83 (1)	1.82 (1)	2.6433 (12)	173 (2)
O4—H4A⋯N1^iv	0.83 (1)	1.93 (1)	2.7545 (12)	171 (2)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) ; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The asymmetric unit of the title compound. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Figure 2
A packing view of the title compound, showing the sheet structure formed by O—H⋯O, O—H⋯N, N—H⋯O and C—H⋯O hydrogen bonds (dashed lines).

Synthesis and crystallization

Hot methanol solutions (20 ml) of 2-amino-6-chloropyridine (34 mg, Aldrich) and glutaric acid (34 mg, Merck) were mixed. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound appeared after a few days.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₅ClN₂·C₅H₈O₄
M_r	260.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.7115 (16), 4.9598 (6), 17.3105 (19)
β (°)	112.960 (2)
V (Å³)	1163.0 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.33
Crystal size (mm)	0.80 × 0.30 × 0.04

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.774, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	14500, 3966, 3264
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.742

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.094, 0.93
No. of reflections	3966
No. of parameters	170
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.29
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS2016 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1913526

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314619007818/is4033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619007818/is4033Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619007818/is4033Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

6-Chloropyridin-2-amine–pentanedioic acid (1/1) top

Crystal data top

C₅H₅ClN₂·C₅H₈O₄	F(000) = 544
M_r = 260.67	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.7115 (16) Å	Cell parameters from 3966 reflections
b = 4.9598 (6) Å	θ = 3.1–31.8°
c = 17.3105 (19) Å	µ = 0.33 mm⁻¹
β = 112.960 (2)°	T = 296 K
V = 1163.0 (2) Å³	Plate, yellow
Z = 4	0.80 × 0.30 × 0.04 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	3264 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2012)	θ_max = 31.8°, θ_min = 3.1°
T_min = 0.774, T_max = 0.987	h = −21→21
14500 measured reflections	k = −7→6
3966 independent reflections	l = −25→25

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0538P)² + 0.4259P] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max < 0.001
3966 reflections	Δρ_max = 0.49 e Å⁻³
170 parameters	Δρ_min = −0.29 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 C-bound H atoms were positioned geometrically (C—H = 0.93 or 0.97 Å) and were refined using a riding model, with U_iso(H) = 1.2U_eq(C). Other H atoms were located in a difference map and refined with bond length restraints [O—H = 0.83 (1) Å and N—H = 0.88 (1) Å].

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

	x	y	z	U_iso*/U_eq
C1	0.32219 (7)	0.5358 (2)	0.18568 (6)	0.01383 (18)
C2	0.40778 (8)	0.6161 (2)	0.17751 (7)	0.0171 (2)
H2	0.468418	0.536117	0.208091	0.021*
C3	0.39787 (8)	0.8254 (2)	0.12033 (7)	0.0183 (2)
H3	0.453167	0.888572	0.112474	0.022*
C4	0.30710 (8)	0.9376 (2)	0.07589 (6)	0.0171 (2)
H4	0.300439	1.076883	0.038085	0.021*
C5	0.22388 (8)	0.8382 (2)	0.08852 (6)	0.01566 (19)
C6	0.36785 (8)	−0.0963 (2)	0.42745 (7)	0.0158 (2)
C7	0.26506 (7)	−0.1901 (2)	0.37424 (7)	0.01589 (19)
H7A	0.257736	−0.376398	0.387846	0.019*
H7B	0.255794	−0.182763	0.315646	0.019*
C8	0.18569 (7)	−0.0211 (2)	0.38679 (7)	0.01630 (19)
H8A	0.198131	−0.014805	0.446066	0.020*
H8B	0.188724	0.161843	0.368117	0.020*
C9	0.08316 (8)	−0.1353 (2)	0.33855 (7)	0.0173 (2)
H9A	0.067398	−0.118190	0.278884	0.021*
H9B	0.083179	−0.325822	0.351259	0.021*
C10	0.00447 (7)	0.0044 (2)	0.35926 (6)	0.0161 (2)
N1	0.23222 (6)	0.6371 (2)	0.14376 (5)	0.01474 (17)
N2	0.13245 (7)	0.9357 (2)	0.04534 (7)	0.0232 (2)
H2A	0.0834 (10)	0.882 (4)	0.0580 (11)	0.039 (5)*
H2B	0.1237 (11)	1.074 (2)	0.0120 (9)	0.026 (4)*
O1	0.43745 (6)	−0.2565 (2)	0.42360 (6)	0.0258 (2)
H1A	0.4925 (9)	−0.197 (4)	0.4543 (10)	0.039 (5)*
O2	0.38508 (6)	0.10702 (17)	0.47067 (5)	0.01919 (17)
O3	0.02085 (6)	0.19918 (19)	0.40576 (6)	0.0255 (2)
O4	−0.08387 (6)	−0.10152 (19)	0.32075 (5)	0.02091 (18)
H4A	−0.1240 (12)	−0.019 (4)	0.3347 (12)	0.052 (6)*
Cl1	0.32782 (2)	0.28122 (6)	0.25664 (2)	0.01679 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0167 (4)	0.0121 (5)	0.0126 (4)	−0.0002 (4)	0.0056 (3)	0.0002 (3)
C2	0.0156 (4)	0.0188 (5)	0.0165 (4)	−0.0003 (4)	0.0057 (4)	0.0007 (4)
C3	0.0196 (5)	0.0193 (6)	0.0169 (4)	−0.0036 (4)	0.0082 (4)	−0.0008 (4)
C4	0.0215 (5)	0.0160 (5)	0.0148 (4)	−0.0023 (4)	0.0081 (4)	0.0007 (4)
C5	0.0184 (4)	0.0149 (5)	0.0135 (4)	−0.0001 (4)	0.0061 (4)	0.0012 (4)
C6	0.0168 (4)	0.0154 (5)	0.0167 (4)	−0.0001 (4)	0.0081 (4)	0.0004 (4)
C7	0.0153 (4)	0.0155 (5)	0.0170 (4)	−0.0010 (4)	0.0064 (4)	−0.0019 (4)
C8	0.0158 (4)	0.0149 (5)	0.0181 (4)	−0.0003 (4)	0.0065 (4)	−0.0021 (4)
C9	0.0155 (4)	0.0174 (5)	0.0186 (5)	−0.0002 (4)	0.0061 (4)	−0.0038 (4)
C10	0.0150 (4)	0.0164 (5)	0.0155 (4)	−0.0005 (4)	0.0042 (3)	−0.0005 (4)
N1	0.0153 (4)	0.0147 (4)	0.0139 (4)	0.0001 (3)	0.0054 (3)	0.0017 (3)
N2	0.0187 (4)	0.0256 (6)	0.0246 (5)	0.0033 (4)	0.0075 (4)	0.0126 (4)
O1	0.0141 (4)	0.0260 (5)	0.0345 (5)	0.0004 (3)	0.0063 (3)	−0.0149 (4)
O2	0.0169 (3)	0.0168 (4)	0.0231 (4)	−0.0004 (3)	0.0070 (3)	−0.0051 (3)
O3	0.0173 (4)	0.0266 (5)	0.0316 (5)	−0.0025 (3)	0.0083 (3)	−0.0143 (4)
O4	0.0148 (3)	0.0227 (5)	0.0254 (4)	−0.0033 (3)	0.0081 (3)	−0.0081 (3)
Cl1	0.01809 (12)	0.01660 (13)	0.01572 (12)	0.00172 (9)	0.00664 (9)	0.00420 (9)

Geometric parameters (Å, º) top

C1—N1	1.3346 (13)	C7—H7A	0.9700
C1—C2	1.3794 (14)	C7—H7B	0.9700
C1—Cl1	1.7409 (11)	C8—C9	1.5202 (15)
C2—C3	1.4022 (16)	C8—H8A	0.9700
C2—H2	0.9300	C8—H8B	0.9700
C3—C4	1.3724 (16)	C9—C10	1.5076 (15)
C3—H3	0.9300	C9—H9A	0.9700
C4—C5	1.4137 (14)	C9—H9B	0.9700
C4—H4	0.9300	C10—O3	1.2199 (14)
C5—N2	1.3481 (14)	C10—O4	1.3165 (13)
C5—N1	1.3540 (14)	N2—H2A	0.873 (9)
C6—O2	1.2217 (14)	N2—H2B	0.873 (9)
C6—O1	1.3181 (13)	O1—H1A	0.830 (9)
C6—C7	1.5049 (15)	O4—H4A	0.828 (9)
C7—C8	1.5202 (15)

N1—C1—C2	125.94 (10)	H7A—C7—H7B	107.8
N1—C1—Cl1	114.88 (7)	C9—C8—C7	111.65 (9)
C2—C1—Cl1	119.18 (8)	C9—C8—H8A	109.3
C1—C2—C3	116.00 (10)	C7—C8—H8A	109.3
C1—C2—H2	122.0	C9—C8—H8B	109.3
C3—C2—H2	122.0	C7—C8—H8B	109.3
C4—C3—C2	120.43 (10)	H8A—C8—H8B	108.0
C4—C3—H3	119.8	C10—C9—C8	112.80 (9)
C2—C3—H3	119.8	C10—C9—H9A	109.0
C3—C4—C5	118.93 (10)	C8—C9—H9A	109.0
C3—C4—H4	120.5	C10—C9—H9B	109.0
C5—C4—H4	120.5	C8—C9—H9B	109.0
N2—C5—N1	116.87 (9)	H9A—C9—H9B	107.8
N2—C5—C4	121.74 (10)	O3—C10—O4	123.51 (10)
N1—C5—C4	121.39 (10)	O3—C10—C9	123.27 (10)
O2—C6—O1	123.27 (10)	O4—C10—C9	113.20 (9)
O2—C6—C7	123.29 (10)	C1—N1—C5	117.31 (9)
O1—C6—C7	113.43 (9)	C5—N2—H2A	119.6 (13)
C6—C7—C8	112.74 (9)	C5—N2—H2B	120.4 (10)
C6—C7—H7A	109.0	H2A—N2—H2B	119.0 (16)
C8—C7—H7A	109.0	C6—O1—H1A	109.8 (13)
C6—C7—H7B	109.0	C10—O4—H4A	109.2 (14)
C8—C7—H7B	109.0

N1—C1—C2—C3	0.78 (17)	C6—C7—C8—C9	−174.76 (9)
Cl1—C1—C2—C3	−178.87 (8)	C7—C8—C9—C10	171.92 (9)
C1—C2—C3—C4	−0.39 (16)	C8—C9—C10—O3	4.34 (16)
C2—C3—C4—C5	−0.21 (16)	C8—C9—C10—O4	−176.99 (9)
C3—C4—C5—N2	−178.41 (11)	C2—C1—N1—C5	−0.50 (16)
C3—C4—C5—N1	0.52 (16)	Cl1—C1—N1—C5	179.16 (8)
O2—C6—C7—C8	−5.66 (15)	N2—C5—N1—C1	178.80 (10)
O1—C6—C7—C8	173.62 (10)	C4—C5—N1—C1	−0.18 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱ	0.93	2.55	3.3711 (13)	147
N2—H2A···O3ⁱⁱ	0.87 (1)	2.08 (1)	2.9443 (13)	171 (2)
N2—H2B···O3ⁱ	0.87 (1)	2.18 (1)	2.9525 (13)	147 (1)
O1—H1A···O2ⁱⁱⁱ	0.83 (1)	1.82 (1)	2.6433 (12)	173 (2)
O4—H4A···N1^iv	0.83 (1)	1.93 (1)	2.7545 (12)	171 (2)

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

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