Crystal structure and Hirshfeld surface analysis of 2-amino­pyridinium hydrogen phthalate

Siva, V.; Suresh, M.; Athimoolam, S.; Asath Bahadur, S.

doi:10.1107/S2056989019012957

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1627-1631

https://doi.org/10.1107/S2056989019012957

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Crystal structure and Hirshfeld surface analysis of 2-aminopyridinium hydrogen phthalate

V. Siva,^a,^b M. Suresh,^c S. Athimoolam ^d ^* and S. Asath Bahadur ^a,^b

^aDepartment of Physics, School of Advanced Sciences, Kalasalingam Academy of Research and Education, Krishnankoil - 626 126, India, ^bCondensed Matter Physics Laboratory, International Research Centre, Kalasalingam Academy of Research and Education, Krishnankoil - 626 126, India, ^cDepartment of Physics, Er. Perumal Manimekalai College of Engineering, Hosur 635 117, India, and ^dDepartment of Physics, University College of Engineering, Anna University, Nagercoil 629 004, India
^*Correspondence e-mail: athi81s@yahoo.co.in

Edited by K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 27 August 2019; accepted 19 September 2019; online 8 October 2019)

Aminopyridine and phthalic acid are well known synthons for supramolecular architectures for the synthesis of new materials for optical applications. The 2-aminopyridinium hydrogen phthalate title salt, C₅H₇N₂⁺·C₈H₅O₄⁻, crystallizes in the non-centrosymmetric space group P2₁. The nitrogen atom of the –NH₂ group in the cation deviates from the fitted pyridine plane by 0.035 (7) Å. The plane of the pyridinium ring and phenyl ring of the anion are oriented at an angle of 80.5 (3)° to each other in the asymmetric unit. The anion features a strong intramolecular O—H⋯O hydrogen bond, forming a self-associated S(7) ring motif. The crystal packing is dominated by intermolecular N—H⋯O hydrogen bonds leading to the formation of 2₁ helices, with a C(11) chain motif. They propagate along the b axis and enclose R₂²(8) ring motifs. The helices are linked by C—H⋯O hydrogen bonds, forming layers parallel to the ab plane. Hirshfeld surface analysis and two-dimensional fingerprint plots were used to investigate and quantify the intermolecular interactions in the crystal.

Keywords: crystal structure; organic salt; hetero-synthon; NLO; hydrogen bonding; Hirshfeld surface analysis.

CCDC reference: 1954730

1. Chemical context

Crystal engineering and the design of supramolecular architectures are of significant interest owing to the technological applications of the resulting materials in the electronics and optical industries. Supramolecular interactions such as charge-assisted hydrogen bonds and π–π interactions play an important role in crystal engineering as they lead to directional molecular recognition events between molecules or ions, and therefore mediate self-assembly of well-defined supramolecular networks (Guelmami et al., 2007 ; Prakash et al., 2018 ; Siva et al., 2017 ). Amine-based materials are particularly important as they are synthesized by the condensation of the corresponding aldehydes and amines and exhibit strong intermolecular hydrogen bonds between the electronegative acceptor and the N atom of the imine moiety. Pyridinium families are now considered to be potential materials for optical applications because of their flexibility in molecular design, strength and thermal stability, which are derived from delocalized clouds of electrons. Another electronic field of research related to 2-aminopyridinium salts is focused on their optical limiting and frequency-conversion applications (Liu et al., 2015 ; Siva et al., 2019 ). The present work is a part of a structural study of new proton-transfer compounds of 2-aminopyridine with phthalic acid and the corresponding hydrogen-bonding interactions. The hydrogen bonding present in the crystal of the title salt was substantiated by Hirshfeld surface analysis.

2. Structural commentary

The molecular structure of the title salt is shown in Fig. 1. Protonation on the N-atom site of the pyridine ring, atom N11, is confirmed by the elongated C—N bond distances [C11—N11 = 1.341 (8) Å and C15—N11 = 1.357 (9) Å] and the enlarged C11—N11—C15 bond angle of 122.3 (6)°. The nitrogen atom of the –NH₂ group in the cation deviates from the pyridine ring plane (r.m.s. deviation = 0.0062 Å) by 0.035 (7) Å. The planes of the pyridinium ring of the cation and the phenyl ring of the anion are oriented at a dihedral angle of 80.5 (3)° in the asymmetric unit. In the anion the twisting of the carboxyl planes out of the benzene ring is negligible [planes O21/O22/C27 and O23/O24/C28 are inclined to the benzene ring (C21–C26) by 1.3 (8) and 0.7 (7)°, respectively], because of the strong O22—H22A⋯O23 intramolecular hydrogen bond (Fig. 1 and Table 1), which makes a self-associated S(7) ring motif.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O22—H22A⋯O23	1.08 (10)	1.32 (10)	2.402 (7)	173 (9)
N11—H1N⋯O24ⁱ	0.93 (7)	1.78 (7)	2.705 (7)	180 (7)
N12—H12A⋯O23ⁱ	0.86	2.11	2.965 (7)	174
N12—H12B⋯O22ⁱⁱ	0.86	2.31	3.003 (8)	138
C12—H12⋯O23ⁱⁱⁱ	0.93	2.53	3.374 (8)	151
C14—H14⋯O21^iv	0.93	2.50	3.203 (9)	132
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (ii) x, y, z+1; (iii) x+1, y, z+1; (iv) $[-x+2, y-{\script{1\over 2}}, -z+1]$ .

Figure 1
The asymmetric unit of the title salt, with atom labelling and 50% probability displacement ellipsoids.

3. Supramolecular features

2-Aminopyridine and phthalic acid are known materials for structure-extension properties, which connect the molecules in the supramolecular assembly. These supramolecular synthons are crystallized together not only to study the molecular structure but also the crystal packing via intermolecular interactions. This structure-extension property of the synthon molecules is generally exploited for possible non-centrosymmetric materials, which are desired as they possess many applications. The structure extension of the molecules is possible by linear (chain C motifs) and cyclic (ring R motifs) hydrogen-bonding associations. This was accomplished in the title compound, which exhibits non-linear optical (NLO) properties, because of the extensive intermolecular interactions.

The packing of the ions in the crystal is dominated by N—H⋯O and C—H⋯O hydrogen bonds (Table 1). A cation–anion hetero-synthon is formed via two N—H⋯O hydrogen bonds (N11—H1N⋯O24ⁱ and N12—H12A⋯O23ⁱ), that enclose an R₂²(8) ring motif (Fig. 2 and Table 1). These hetero-synthons are linked by a further N—H⋯O hydrogen bond (N12—H12B⋯O22ⁱⁱ), to form 2₁ helices, with a C(11) chain motif, that propagate along the b-axis direction. The helices are linked by C—H⋯O hydrogen bonds, forming layers lying parallel to the ab plane (Fig. 3 and Table 1). There are no significant C—H⋯π or π–π contacts present in the crystal (PLATON; Spek, 2009 ).

Figure 2
The crystal packing of the title salt viewed along the a axis. Hydrogen bonds are shown as dashed lines (Table 1

). For clarity, the C-bound H atoms have been omitted.

Figure 3
Packing of the title salt viewed along the c axis. Hydrogen bonds are shown as dashed lines (Table 1

). For clarity, H atoms not involved in hydrogen bonding have been omitted.

4. Hirshfeld surface analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were performed with CrystalExplorer17 (Turner et al., 2017 ). The Hirshfeld surface is colour-mapped with the normalized contact distance, d_norm, from red (distances shorter than the sum of the van der Waals radii) through white to blue (distances longer than the sum of the van der Waals radii).

The Hirshfeld surface (HS) of the title salt, mapped over d_norm in the colour range of −0.7098 to 1.1914 arbitrary units, is given in Fig. 4. The short interatomic contacts, i.e. the donors and acceptors of the hydrogen bonds (Table 1), are indicated by the red spots.

Figure 4
Hirshfeld surface for the title salt mapped over d_norm, in the colour range −0.7098 to 1.1914 au.

The two-dimensional fingerprint plots for the title salt, the cation and the anion are given in Fig. 5. The relative percentage contributions of close contacts to the Hirshfeld surfaces of the title salt (Fig. 5a), and the cation (Fig. 5b) and anion (Fig. 5c), are compared in Table 2.

Table 2
Relative percentage contributions of close contacts to the Hirshfeld surface for the title salt, the cation and the anion

Contact	cation+anion	cation	anion
H⋯H	32.0	40.4	30.6
O⋯H/H⋯O	31.0	26.3	31.6
C⋯H/H⋯C	22.0	18.2	24.0
C⋯O	7.3	4.6	8.8
N⋯H/H⋯N	2.5	5.1	0.4
C⋯C	2.5	2.2	2.6

Figure 5
(a) The full two-dimensional fingerprint plot and the fingerprint plots delineated into H⋯H, O⋯H/H⋯O, C⋯H/H⋯C and C⋯O contacts for the title salt, (b) the full two-dimensional fingerprint plot and fingerprint plots delineated into H⋯H, O⋯H/H⋯O, C⋯H/H⋯C and C⋯O contacts for the cation, and (c) the full two-dimensional fingerprint plot and fingerprint plots delineated into H⋯H, O⋯H/H⋯O, C⋯H/H⋯C and C⋯O contacts for the anion (see Table 2

for further details).

For the title salt (Fig. 5a), the most significant contributions to the HS are from H⋯H (32.0%), O⋯H/H⋯O (31.0%), C⋯H/H⋯C (22.0%) and C⋯O (7.3%) contacts. On examination of the contributions to the HS of the cation (Fig. 5b) and anion (Fig. 5c) individually, it can be seen that the cation makes the largest contribution to the H⋯H contacts (40.4%), while the anion makes the largest contributions to the O⋯H/H⋯O (31.6%), C⋯H/H⋯C(24.0%) and C⋯O (8.8%) contacts (see also Table 2).

5. Database survey

A search of the Cambridge Structural Database (Version 5.40, last update May 2019; Groom et al., 2016 ) for 2-aminopyridinium salts indicated that the crystal structures of more than 220 structures have been reported. A search for 2-aminopyridinium benzoate salts gave 45 hits for 35 structures. The most significant in relation to the title salt are: 2-aminopyridinium benzoate (LUPZOL; Odabaşoğlu et al., 2003 ), 2-aminopyridinium 2′-carboxybiphenyl-4-carboxylate (DEZCOC; Wang et al., 2013 ), bis(2-aminopyridine) terephthalate (LAPMUL; Bis & Zaworotko), 2-aminopyridinium isophthalate (Bis & Zaworotko, 2005 ) and bis(2-aminopyridinium) 2,5-dicarboxybenzene-1,4-dicarboxylate (Rodrigues et al., 2012 ). In the crystals, the same hetero-synthon is formed via N—H⋯O hydrogen bonds. The CO₂⁻ groups in general lie close to the plane of the benzene ring in LUPZOL, LAQGOA and ZARHOR; the dihedral angle varies from 1.85–6.09°. However, the corresponding dihedral angles in DEZCOC and LAPMUL are considerably lager; ca 47.92 and 23.97° in DEZCOC and 17.37° in LAPMUK. While DEZCOC crystallizes in a chiral space group, P3₂, the other four compounds, LUPZOL, LAPMUL, LAQGOA and ZARHOR, crystallize in a centrosymmetric monoclinic space group (P2₁/c or P2₁/n) and hence do not exhibit NLO properties.

6. Synthesis and crystallization

A 1:1 mixture of 2-aminopyridine and phthalic acid was heated to 313 K and stirred for 1 h before being poured into a petri dish and kept undisturbed for 25 days. Colourless block-shaped single crystals were obtained by the slow evaporation of a methanol and water (v:v = 20:80%) solution.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The OH and NH H atoms were located in a difference-Fourier map and refined freely. The NH₂ and C-bound H atoms were included in calculated positions and treated as riding atoms: N—H = 0.86 Å, C—H = 0.93 Å with U_iso(H) = 1.2U_eq(N, C).

Table 3
Experimental details

Crystal data
Chemical formula	C₅H₇N₂⁺·C₈H₅O₄⁻
M_r	260.25
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	5.1593 (6), 8.6124 (9), 13.5745 (19)
β (°)	97.087 (4)
V (Å³)	598.56 (13)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.26 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
No. of measured, independent and observed [I > 2σ(I)] reflections	6704, 2099, 1972
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.186, 1.24
No. of reflections	2099
No. of parameters	180
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.24
Absolute structure	Flack x determined using 880 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.1 (4)
Computer programs: SMART and SAINT (Bruker, 2001 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009).

Supporting information

CCDC reference: 1954730

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2056989019012957/ff2163sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019012957/ff2163Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019012957/ff2163Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2009).

2-Aminopyridinium hydrogen phthalate top

Crystal data top

C₅H₇N₂⁺·C₈H₅O₄⁻	F(000) = 272
M_r = 260.25	D_x = 1.444 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 5.1593 (6) Å	Cell parameters from 2425 reflections
b = 8.6124 (9) Å	θ = 2.2–24.7°
c = 13.5745 (19) Å	µ = 0.11 mm⁻¹
β = 97.087 (4)°	T = 293 K
V = 598.56 (13) Å³	Block, colourless
Z = 2	0.26 × 0.24 × 0.20 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	R_int = 0.023
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 1.5°
ω scans	h = −6→6
6704 measured reflections	k = −10→10
2099 independent reflections	l = −16→14
1972 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.186	w = 1/[σ²(F_o²) + (0.0796P)² + 0.5949P] where P = (F_o² + 2F_c²)/3
S = 1.24	(Δ/σ)_max < 0.001
2099 reflections	Δρ_max = 0.35 e Å⁻³
180 parameters	Δρ_min = −0.24 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 880 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.1 (4)

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.

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

	x	y	z	U_iso*/U_eq
C11	0.5973 (12)	0.4659 (7)	0.8983 (5)	0.0401 (14)
C12	0.7974 (14)	0.3719 (9)	0.9463 (6)	0.0545 (19)
H12	0.8233	0.3657	1.0152	0.065*
C13	0.9516 (13)	0.2908 (8)	0.8913 (7)	0.056 (2)
H13	1.0809	0.2268	0.9232	0.067*
C14	0.9221 (15)	0.3005 (8)	0.7882 (7)	0.057 (2)
H14	1.0323	0.2466	0.7510	0.069*
C15	0.7263 (13)	0.3915 (8)	0.7440 (5)	0.0489 (16)
H15	0.7002	0.3992	0.6751	0.059*
N11	0.5683 (10)	0.4714 (6)	0.7988 (4)	0.0370 (12)
N12	0.4392 (12)	0.5509 (8)	0.9461 (4)	0.0532 (16)
H12A	0.3216	0.6079	0.9134	0.064*
H12B	0.4542	0.5492	1.0099	0.064*
H1N	0.448 (13)	0.538 (8)	0.764 (5)	0.031 (15)*
C21	0.1288 (10)	0.3445 (6)	0.3331 (4)	0.0302 (12)
C22	0.0707 (13)	0.3464 (8)	0.4303 (4)	0.0421 (15)
H22	−0.0615	0.2820	0.4472	0.050*
C23	0.1998 (15)	0.4394 (9)	0.5026 (5)	0.0534 (18)
H23	0.1531	0.4385	0.5666	0.064*
C24	0.3968 (15)	0.5326 (9)	0.4797 (5)	0.0514 (17)
H24	0.4850	0.5969	0.5278	0.062*
C25	0.4648 (13)	0.5309 (8)	0.3840 (5)	0.0465 (15)
H25	0.6035	0.5925	0.3697	0.056*
C26	0.3347 (10)	0.4413 (7)	0.3089 (4)	0.0333 (13)
C27	0.4332 (12)	0.4634 (9)	0.2093 (5)	0.0431 (15)
C28	−0.0455 (11)	0.2378 (7)	0.2648 (4)	0.0335 (13)
O21	0.6142 (12)	0.5515 (7)	0.2021 (4)	0.0696 (16)
O22	0.3306 (11)	0.3890 (8)	0.1326 (4)	0.0627 (15)
O23	−0.0154 (9)	0.2241 (6)	0.1742 (3)	0.0469 (11)
O24	−0.2148 (10)	0.1635 (6)	0.3020 (3)	0.0488 (12)
H22A	0.17 (2)	0.320 (11)	0.149 (7)	0.08 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C11	0.039 (3)	0.039 (3)	0.043 (3)	−0.011 (3)	0.004 (3)	0.009 (3)
C12	0.052 (4)	0.052 (4)	0.055 (4)	−0.006 (3)	−0.014 (3)	0.020 (3)
C13	0.034 (3)	0.046 (4)	0.083 (6)	0.000 (3)	−0.008 (4)	0.016 (4)
C14	0.046 (4)	0.044 (4)	0.084 (6)	0.009 (3)	0.014 (4)	−0.003 (4)
C15	0.046 (3)	0.048 (4)	0.052 (4)	0.001 (3)	0.002 (3)	−0.007 (3)
N11	0.034 (2)	0.038 (3)	0.038 (3)	−0.002 (2)	0.002 (2)	0.006 (2)
N12	0.059 (4)	0.066 (4)	0.036 (3)	0.016 (3)	0.010 (3)	0.011 (3)
C21	0.029 (3)	0.031 (3)	0.030 (3)	0.004 (2)	0.003 (2)	0.001 (2)
C22	0.046 (3)	0.048 (4)	0.032 (3)	−0.006 (3)	0.006 (3)	−0.003 (3)
C23	0.068 (4)	0.058 (4)	0.033 (3)	0.000 (4)	0.001 (3)	−0.009 (3)
C24	0.056 (4)	0.053 (4)	0.042 (4)	−0.003 (3)	−0.006 (3)	−0.016 (3)
C25	0.039 (3)	0.047 (4)	0.051 (4)	−0.006 (3)	−0.001 (3)	−0.001 (3)
C26	0.031 (3)	0.032 (3)	0.036 (3)	0.004 (2)	0.003 (2)	0.002 (2)
C27	0.040 (3)	0.046 (3)	0.044 (4)	−0.001 (3)	0.007 (3)	0.011 (3)
C28	0.038 (3)	0.031 (3)	0.031 (3)	0.003 (3)	0.001 (2)	0.003 (2)
O21	0.067 (3)	0.073 (4)	0.075 (4)	−0.023 (3)	0.033 (3)	−0.001 (3)
O22	0.065 (3)	0.093 (4)	0.033 (2)	−0.016 (3)	0.015 (2)	0.001 (3)
O23	0.056 (3)	0.056 (3)	0.028 (2)	−0.009 (2)	0.0030 (19)	−0.006 (2)
O24	0.056 (3)	0.055 (3)	0.035 (2)	−0.021 (2)	0.002 (2)	−0.004 (2)

Geometric parameters (Å, º) top

C11—N12	1.325 (9)	C21—C28	1.519 (8)
C11—N11	1.341 (8)	C22—C23	1.374 (10)
C11—C12	1.407 (9)	C22—H22	0.9300
C12—C13	1.351 (11)	C23—C24	1.361 (11)
C12—H12	0.9300	C23—H23	0.9300
C13—C14	1.391 (12)	C24—C25	1.387 (10)
C13—H13	0.9300	C24—H24	0.9300
C14—C15	1.359 (10)	C25—C26	1.385 (9)
C14—H14	0.9300	C25—H25	0.9300
C15—N11	1.357 (9)	C26—C27	1.514 (9)
C15—H15	0.9300	C27—O21	1.216 (9)
N11—H1N	0.93 (7)	C27—O22	1.280 (9)
N12—H12A	0.8600	C28—O24	1.239 (7)
N12—H12B	0.8600	C28—O23	1.264 (7)
C21—C22	1.389 (8)	O22—H22A	1.08 (10)
C21—C26	1.421 (8)	O23—H22A	1.32 (11)

N12—C11—N11	118.4 (6)	C23—C22—C21	122.9 (6)
N12—C11—C12	123.5 (6)	C23—C22—H22	118.5
N11—C11—C12	118.1 (7)	C21—C22—H22	118.5
C13—C12—C11	119.3 (7)	C24—C23—C22	119.4 (7)
C13—C12—H12	120.3	C24—C23—H23	120.3
C11—C12—H12	120.3	C22—C23—H23	120.3
C12—C13—C14	121.8 (7)	C23—C24—C25	119.3 (6)
C12—C13—H13	119.1	C23—C24—H24	120.3
C14—C13—H13	119.1	C25—C24—H24	120.3
C15—C14—C13	117.5 (7)	C26—C25—C24	122.7 (7)
C15—C14—H14	121.2	C26—C25—H25	118.7
C13—C14—H14	121.2	C24—C25—H25	118.7
N11—C15—C14	120.9 (7)	C25—C26—C21	117.8 (6)
N11—C15—H15	119.5	C25—C26—C27	113.7 (6)
C14—C15—H15	119.5	C21—C26—C27	128.5 (5)
C11—N11—C15	122.3 (6)	O21—C27—O22	119.4 (6)
C11—N11—H1N	121 (4)	O21—C27—C26	119.7 (6)
C15—N11—H1N	117 (4)	O22—C27—C26	120.8 (6)
C11—N12—H12A	120.0	O24—C28—O23	121.7 (5)
C11—N12—H12B	120.0	O24—C28—C21	117.2 (5)
H12A—N12—H12B	120.0	O23—C28—C21	121.1 (5)
C22—C21—C26	117.9 (5)	C27—O22—H22A	112 (5)
C22—C21—C28	114.0 (5)	C28—O23—H22A	112 (4)
C26—C21—C28	128.1 (5)

N12—C11—C12—C13	−179.0 (6)	C24—C25—C26—C27	177.2 (7)
N11—C11—C12—C13	−0.2 (9)	C22—C21—C26—C25	0.2 (8)
C11—C12—C13—C14	1.6 (11)	C28—C21—C26—C25	179.0 (6)
C12—C13—C14—C15	−1.9 (11)	C22—C21—C26—C27	−178.7 (6)
C13—C14—C15—N11	0.9 (10)	C28—C21—C26—C27	0.1 (9)
N12—C11—N11—C15	178.1 (6)	C25—C26—C27—O21	1.4 (9)
C12—C11—N11—C15	−0.8 (9)	C21—C26—C27—O21	−179.7 (6)
C14—C15—N11—C11	0.5 (10)	C25—C26—C27—O22	−179.5 (7)
C26—C21—C22—C23	1.2 (10)	C21—C26—C27—O22	−0.6 (10)
C28—C21—C22—C23	−177.7 (6)	C22—C21—C28—O24	−1.0 (7)
C21—C22—C23—C24	−1.1 (11)	C26—C21—C28—O24	−179.9 (6)
C22—C23—C24—C25	−0.6 (11)	C22—C21—C28—O23	−179.9 (6)
C23—C24—C25—C26	2.1 (11)	C26—C21—C28—O23	1.2 (8)
C24—C25—C26—C21	−1.9 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O22—H22A···O23	1.08 (10)	1.32 (10)	2.402 (7)	173 (9)
N11—H1N···O24ⁱ	0.93 (7)	1.78 (7)	2.705 (7)	180 (7)
N12—H12A···O23ⁱ	0.86	2.11	2.965 (7)	174
N12—H12B···O22ⁱⁱ	0.86	2.31	3.003 (8)	138
C12—H12···O23ⁱⁱⁱ	0.93	2.53	3.374 (8)	151
C14—H14···O21^iv	0.93	2.50	3.203 (9)	132

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

Relative percentage contributions of close contacts to the Hirshfeld surface for the title salt, the cation and the anion top

Contact	cation+anion	cation	anion
H···H	32.0	40.4	30.6
O···H/H···O	31.0	26.3	31.6
C···H/H···C	22.0	18.2	24.0
C···O	7.3	4.6	8.8
N···H/H···N	2.5	5.1	0.4
C···C	2.5	2.2	2.6

Acknowledgements

SAB and VS are thankful to the management, Kalasalingam Academy of Research and Education, Krishnankoil, for their support.

Funding information

Funding for this research was provided by: Council of Scientific and Industrial Research.

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