2-Amino-5-chloro­pyridinium 4-amino­benzoate

Kannan, V.; Sugumar, P.; Brahadeeswaran, S.; Ponnuswamy, M.N.

doi:10.1107/S1600536812043085

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3187

doi:10.1107/S1600536812043085

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2-Amino-5-chloropyridinium 4-aminobenzoate

V. Kannan,^a P. Sugumar,^b S. Brahadeeswaran ^c and M. N. Ponnuswamy ^b ^*

^aDepartment of Physics, M.A.M. School of Engineering, Siruganur, Tiruchirappalli 621 105, India, ^bCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^cDepartment of Physics, Anna University, BIT Campus, Tiruchirappalli 620 024, India
^*Correspondence e-mail: mnpsy2004@yahoo.com

(Received 1 October 2012; accepted 16 October 2012; online 20 October 2012)

In the title molecular salt, C₅H₆ClN₂⁺·C₇H₆NO₂⁻, the cations and anions are connected by cation-to-anion and anion-to-anion N—H⋯O hydrogen bonds into a three-dimensional network. The dihedral angle between the ring and the CO₂ group in the anion is 7.14 (7)°.

Related literature

For general background to chloropyridinium derivatives, see: Brahadeeswaran et al. (2006 ); Tomaru et al. (1991 ). For N—H⋯O hydrogen bonds, see: Blessing (1986 ); Brown (1976 ).

Experimental

Crystal data

C₅H₆ClN₂⁺·C₇H₆NO₂⁻
M_r = 265.70
Monoclinic, P 2₁ /n
a = 6.9879 (4) Å
b = 22.0074 (13) Å
c = 8.0554 (5) Å
β = 92.796 (1)°
V = 1237.33 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 293 K
0.20 × 0.19 × 0.18 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.941, T_max = 0.946
12108 measured reflections
3086 independent reflections
2642 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.112
S = 1.04
3086 reflections
179 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	1.76	2.6135 (15)	175
N2—H2A⋯O1ⁱ	0.89 (2)	1.94 (2)	2.8216 (18)	172.1 (19)
N2—H2B⋯O1ⁱⁱ	0.86 (2)	2.10 (2)	2.8776 (17)	150.3 (19)
N3—H3A⋯O1ⁱⁱⁱ	0.862 (19)	2.19 (2)	3.0357 (18)	167.4 (17)
N3—H3B⋯O2^iv	0.86 (2)	2.08 (2)	2.9291 (18)	171 (2)
Symmetry codes: (i) -x+1, -y, -z+2; (ii) x-1, y, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812043085/bt6844sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043085/bt6844Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812043085/bt6844Isup3.cml

checkCIF report

Comment top

Pyridine heterocycles and their derivatives are present in many large molecules having photo chemical, electro chemical and catalytic applications. Pyridine derivatives possess nonlinear optical (NLO) properties(Tomaru et al., 1991). 4-N,N-dimethylamino-4'-N'-methyl stilbazolium tosylate (DAST) is used in generating and detecting terahertz (THz) frequencies (Brahadeeswaran et al., 2006). An attempt is made to solve the pyridine based crystal structures to explore the NLO behaviour.

The ORTEP plot of the molecule is shown in Fig.1. The structure can be described as segregated (C₅H₆ClN₂)⁺.(C₇H₆NO₂)^- groups and connected via N—H···O hydrogen bonds (Blessing, 1986; Brown, 1976). The dihedral angle between the chloropyridinium ring and aminobenzoate group is 51.5 (7)°. The external bond angle [N1—C2—N2=] 118.1 (1)° at the attached amino group in pyridinium moiety is slightly widened due to the hydrogen bond formation between the ionic groups.

A dimer formation occurs through N—H···O hydrogen bonds between the symmetry related molecules(Fig.2). N—H···O type of hydrogen bonds stabilize the molecules in the unit cell.

Related literature top

For general background to chloropyridinium derivatives, see: Blessing (1986); Brahadeeswaran et al. (2006); Brown (1976); Tomaru et al. (1991).

Experimental top

Methanol solutions of 2-amino-5-chloropyridine (64.28 mg, Aldrich) and 4-aminobenzoic acid (68.57 mg, Merck) were mixed together and stirred for about 1 h to get a homogeneous mixture. The resulting solution was allowed to evaporate at 303 K slowly in a water bath which has a temperature accuracy of ± 0.01°C at ambient atmosphere. Brown colour crystals with developed morphology of title compound were obtained after 12 days.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The crystal packing of the molecules viewed down a axis.

2-Amino-5-chloropyridinium 4-aminobenzoate top

Crystal data top

C₅H₆ClN₂⁺·C₇H₆NO₂⁻	F(000) = 552
M_r = 265.70	D_x = 1.426 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2642 reflections
a = 6.9879 (4) Å	θ = 1.9–28.4°
b = 22.0074 (13) Å	µ = 0.31 mm⁻¹
c = 8.0554 (5) Å	T = 293 K
β = 92.796 (1)°	Block, white crystalline
V = 1237.33 (13) Å³	0.20 × 0.19 × 0.18 mm
Z = 4

Data collection top

Bruker APEXII area-detector diffractometer	3086 independent reflections
Radiation source: fine-focus sealed tube	2642 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scan	θ_max = 28.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
T_min = 0.941, T_max = 0.946	k = −29→29
12108 measured reflections	l = −10→10

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0572P)² + 0.3359P] where P = (F_o² + 2F_c²)/3
3086 reflections	(Δ/σ)_max = 0.001
179 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₅H₆ClN₂⁺·C₇H₆NO₂⁻	V = 1237.33 (13) Å³
M_r = 265.70	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.9879 (4) Å	µ = 0.31 mm⁻¹
b = 22.0074 (13) Å	T = 293 K
c = 8.0554 (5) Å	0.20 × 0.19 × 0.18 mm
β = 92.796 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	3086 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2642 reflections with I > 2σ(I)
T_min = 0.941, T_max = 0.946	R_int = 0.021
12108 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.20 e Å⁻³
3086 reflections	Δρ_min = −0.31 e Å⁻³
179 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
C2	0.3159 (2)	0.04218 (6)	0.77668 (17)	0.0407 (3)
C3	0.3355 (2)	0.09763 (7)	0.6908 (2)	0.0479 (3)
H3	0.2372	0.1261	0.6889	0.057*
C4	0.4987 (2)	0.10919 (7)	0.61093 (19)	0.0486 (4)
H4	0.5133	0.1460	0.5563	0.058*
C5	0.6448 (2)	0.06560 (7)	0.61107 (17)	0.0431 (3)
C6	0.6216 (2)	0.01208 (6)	0.69117 (17)	0.0406 (3)
H6	0.7173	−0.0173	0.6911	0.049*
C7	0.71327 (19)	0.12257 (6)	1.01810 (16)	0.0359 (3)
C8	0.71041 (18)	0.18462 (6)	0.94334 (16)	0.0346 (3)
C9	0.87870 (19)	0.21125 (6)	0.89231 (17)	0.0389 (3)
H9	0.9937	0.1902	0.9066	0.047*
C10	0.87784 (19)	0.26832 (6)	0.82089 (17)	0.0407 (3)
H10	0.9923	0.2854	0.7895	0.049*
C11	0.70654 (19)	0.30071 (6)	0.79533 (16)	0.0371 (3)
C12	0.5373 (2)	0.27406 (6)	0.84646 (18)	0.0412 (3)
H12	0.4219	0.2948	0.8311	0.049*
C13	0.54024 (19)	0.21735 (6)	0.91937 (17)	0.0390 (3)
H13	0.4264	0.2006	0.9533	0.047*
N1	0.45860 (17)	0.00142 (5)	0.77144 (14)	0.0385 (3)
H1	0.4461	−0.0329	0.8210	0.046*
N2	0.1643 (2)	0.02799 (7)	0.86228 (19)	0.0545 (4)
N3	0.7058 (2)	0.35808 (6)	0.72634 (18)	0.0477 (3)
O1	0.86491 (14)	0.09238 (5)	1.02101 (14)	0.0471 (3)
O2	0.55877 (14)	0.10303 (4)	1.07566 (14)	0.0483 (3)
Cl1	0.85224 (7)	0.07952 (2)	0.50832 (6)	0.06516 (16)
H3A	0.598 (3)	0.3696 (9)	0.680 (2)	0.049 (5)*
H2A	0.155 (3)	−0.0086 (11)	0.909 (2)	0.067 (6)*
H2B	0.078 (3)	0.0551 (10)	0.877 (3)	0.069 (6)*
H3B	0.808 (3)	0.3657 (9)	0.676 (3)	0.062 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0455 (7)	0.0342 (6)	0.0423 (7)	0.0007 (5)	0.0014 (5)	−0.0021 (5)
C3	0.0525 (8)	0.0348 (7)	0.0557 (8)	0.0043 (6)	−0.0035 (7)	0.0047 (6)
C4	0.0605 (9)	0.0358 (7)	0.0488 (8)	−0.0081 (6)	−0.0060 (7)	0.0091 (6)
C5	0.0458 (7)	0.0437 (7)	0.0395 (7)	−0.0108 (6)	−0.0008 (5)	0.0013 (6)
C6	0.0414 (7)	0.0371 (7)	0.0432 (7)	−0.0019 (5)	0.0007 (5)	−0.0009 (5)
C7	0.0370 (6)	0.0310 (6)	0.0397 (6)	0.0004 (5)	0.0026 (5)	−0.0017 (5)
C8	0.0366 (6)	0.0310 (6)	0.0364 (6)	−0.0006 (5)	0.0032 (5)	−0.0013 (5)
C9	0.0330 (6)	0.0389 (7)	0.0447 (7)	0.0017 (5)	0.0026 (5)	0.0013 (5)
C10	0.0349 (6)	0.0418 (7)	0.0457 (7)	−0.0061 (5)	0.0048 (5)	0.0027 (6)
C11	0.0417 (7)	0.0319 (6)	0.0377 (6)	−0.0027 (5)	0.0014 (5)	−0.0015 (5)
C12	0.0366 (7)	0.0360 (6)	0.0512 (8)	0.0044 (5)	0.0050 (6)	0.0026 (6)
C13	0.0346 (6)	0.0359 (6)	0.0470 (7)	−0.0019 (5)	0.0071 (5)	0.0008 (5)
N1	0.0444 (6)	0.0297 (5)	0.0414 (6)	−0.0003 (4)	0.0041 (5)	0.0025 (4)
N2	0.0529 (8)	0.0424 (7)	0.0698 (9)	0.0093 (6)	0.0199 (7)	0.0069 (6)
N3	0.0450 (7)	0.0381 (6)	0.0600 (8)	−0.0030 (5)	0.0026 (6)	0.0104 (6)
O1	0.0389 (5)	0.0374 (5)	0.0654 (7)	0.0055 (4)	0.0072 (5)	0.0045 (4)
O2	0.0403 (5)	0.0372 (5)	0.0686 (7)	0.0042 (4)	0.0144 (5)	0.0137 (5)
Cl1	0.0575 (3)	0.0704 (3)	0.0685 (3)	−0.0175 (2)	0.0128 (2)	0.0112 (2)

Geometric parameters (Å, º) top

C2—N2	1.329 (2)	C8—C13	1.3956 (18)
C2—N1	1.3433 (18)	C9—C10	1.3814 (19)
C2—C3	1.413 (2)	C9—H9	0.9300
C3—C4	1.360 (2)	C10—C11	1.3997 (19)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.401 (2)	C11—N3	1.3794 (18)
C4—H4	0.9300	C11—C12	1.3997 (19)
C5—C6	1.357 (2)	C12—C13	1.3791 (19)
C5—Cl1	1.7312 (15)	C12—H12	0.9300
C6—N1	1.3573 (17)	C13—H13	0.9300
C6—H6	0.9300	N1—H1	0.8600
C7—O1	1.2500 (16)	N2—H2A	0.89 (2)
C7—O2	1.2706 (16)	N2—H2B	0.86 (2)
C7—C8	1.4921 (18)	N3—H3A	0.862 (19)
C8—C9	1.3937 (18)	N3—H3B	0.86 (2)

N2—C2—N1	118.11 (13)	C8—C9—H9	119.4
N2—C2—C3	123.76 (14)	C9—C10—C11	120.70 (12)
N1—C2—C3	118.14 (13)	C9—C10—H10	119.6
C4—C3—C2	119.78 (14)	C11—C10—H10	119.6
C4—C3—H3	120.1	N3—C11—C10	120.77 (13)
C2—C3—H3	120.1	N3—C11—C12	121.04 (13)
C3—C4—C5	119.95 (13)	C10—C11—C12	118.16 (12)
C3—C4—H4	120.0	C13—C12—C11	120.62 (12)
C5—C4—H4	120.0	C13—C12—H12	119.7
C6—C5—C4	119.40 (14)	C11—C12—H12	119.7
C6—C5—Cl1	120.23 (12)	C12—C13—C8	121.38 (12)
C4—C5—Cl1	120.37 (11)	C12—C13—H13	119.3
C5—C6—N1	119.95 (13)	C8—C13—H13	119.3
C5—C6—H6	120.0	C2—N1—C6	122.74 (12)
N1—C6—H6	120.0	C2—N1—H1	118.6
O1—C7—O2	123.22 (12)	C6—N1—H1	118.6
O1—C7—C8	119.25 (12)	C2—N2—H2A	120.4 (13)
O2—C7—C8	117.53 (11)	C2—N2—H2B	119.4 (14)
C9—C8—C13	117.89 (12)	H2A—N2—H2B	120.1 (19)
C9—C8—C7	120.59 (12)	C11—N3—H3A	115.5 (12)
C13—C8—C7	121.51 (12)	C11—N3—H3B	112.7 (14)
C10—C9—C8	121.23 (12)	H3A—N3—H3B	117.8 (18)
C10—C9—H9	119.4

N2—C2—C3—C4	177.79 (15)	C7—C8—C9—C10	179.13 (12)
N1—C2—C3—C4	−2.3 (2)	C8—C9—C10—C11	−1.0 (2)
C2—C3—C4—C5	1.4 (2)	C9—C10—C11—N3	179.01 (13)
C3—C4—C5—C6	0.1 (2)	C9—C10—C11—C12	1.0 (2)
C3—C4—C5—Cl1	179.43 (12)	N3—C11—C12—C13	−178.26 (13)
C4—C5—C6—N1	−0.6 (2)	C10—C11—C12—C13	−0.2 (2)
Cl1—C5—C6—N1	−179.96 (10)	C11—C12—C13—C8	−0.5 (2)
O1—C7—C8—C9	−6.38 (19)	C9—C8—C13—C12	0.5 (2)
O2—C7—C8—C9	173.83 (12)	C7—C8—C13—C12	−178.37 (13)
O1—C7—C8—C13	172.44 (13)	N2—C2—N1—C6	−178.27 (13)
O2—C7—C8—C13	−7.35 (19)	C3—C2—N1—C6	1.8 (2)
C13—C8—C9—C10	0.3 (2)	C5—C6—N1—C2	−0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	1.76	2.6135 (15)	175
N2—H2A···O1ⁱ	0.89 (2)	1.94 (2)	2.8216 (18)	172.1 (19)
N2—H2B···O1ⁱⁱ	0.86 (2)	2.10 (2)	2.8776 (17)	150.3 (19)
N3—H3A···O1ⁱⁱⁱ	0.862 (19)	2.19 (2)	3.0357 (18)	167.4 (17)
N3—H3B···O2^iv	0.86 (2)	2.08 (2)	2.9291 (18)	171 (2)

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

Experimental details

Crystal data
Chemical formula	C₅H₆ClN₂⁺·C₇H₆NO₂⁻
M_r	265.70
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.9879 (4), 22.0074 (13), 8.0554 (5)
β (°)	92.796 (1)
V (Å³)	1237.33 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.20 × 0.19 × 0.18

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.941, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	12108, 3086, 2642
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.112, 1.04
No. of reflections	3086
No. of parameters	179
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.31

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	1.76	2.6135 (15)	175.3
N2—H2A···O1ⁱ	0.89 (2)	1.94 (2)	2.8216 (18)	172.1 (19)
N2—H2B···O1ⁱⁱ	0.86 (2)	2.10 (2)	2.8776 (17)	150.3 (19)
N3—H3A···O1ⁱⁱⁱ	0.862 (19)	2.19 (2)	3.0357 (18)	167.4 (17)
N3—H3B···O2^iv	0.86 (2)	2.08 (2)	2.9291 (18)	171 (2)

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

Acknowledgements

The authors thank the TBI Consultancy, University of Madras, India, for the data collection.

References

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