organic compounds
2-Amino-5-chloropyridinium 4-aminobenzoate
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
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
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell 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
10.1107/S1600536812043085/bt6844sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043085/bt6844Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812043085/bt6844Isup3.cml
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.
H atoms bonded to aromatic C and N atoms were positioned geometrically (N—H = 0.86 Å and C—H = 0.93 Å) and allowed to ride on their parent atoms,with Uiso(H) = 1.2Ueq(C,N). The H atoms of the two NH2 groups were freely refined.
Data collection: APEX2 (Bruker, 2008); cell
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).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. |
C5H6ClN2+·C7H6NO2− | F(000) = 552 |
Mr = 265.70 | Dx = 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 |
Bruker APEXII area-detector diffractometer | 3086 independent reflections |
Radiation source: fine-focus sealed tube | 2642 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scan | θmax = 28.4°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −9→9 |
Tmin = 0.941, Tmax = 0.946 | k = −29→29 |
12108 measured reflections | l = −10→10 |
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(Fo2) + (0.0572P)2 + 0.3359P] where P = (Fo2 + 2Fc2)/3 |
3086 reflections | (Δ/σ)max = 0.001 |
179 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C5H6ClN2+·C7H6NO2− | V = 1237.33 (13) Å3 |
Mr = 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)° |
Bruker APEXII area-detector diffractometer | 3086 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2642 reflections with I > 2σ(I) |
Tmin = 0.941, Tmax = 0.946 | Rint = 0.021 |
12108 measured reflections |
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 | Δρmax = 0.20 e Å−3 |
3086 reflections | Δρmin = −0.31 e Å−3 |
179 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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···O2iv | 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− |
Mr | 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) |
Tmin, Tmax | 0.941, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12108, 3086, 2642 |
Rint | 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 |
Δρmax, Δρmin (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).
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···O2iv | 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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Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.