Crystal structure, hydrogen bonding and Hirshfeld surface analysis of 2-amino-4-meth­oxy-6-methyl­pyrimidinium 4-chloro­benzoate

Jeevaraj, M.; Sivajeyanthi, P.; Edison, B.; Thanigaimani, K.; Balasubramani, K.

doi:10.1107/S2056989018005583

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ISSN: 2056-9890

Volume 74| Part 5| May 2018| Pages 656-659

https://doi.org/10.1107/S2056989018005583

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Crystal structure, hydrogen bonding and Hirshfeld surface analysis of 2-amino-4-methoxy-6-methylpyrimidinium 4-chlorobenzoate

Muthaiah Jeevaraj,^a Palaniyappan Sivajeyanthi,^a Bellarmin Edison,^a Kaliyaperumal Thanigaimani ^b and Kasthuri Balasubramani ^a ^*

^aDepartment of Chemistry, Government Arts College (Autonomous), Thanthonimalai, Karur 639 005, Tamil Nadu, India, and ^bDepartment of Chemistry, Government Arts College, Tiruchirappalli 620 022, Tamil Nadu, India
^*Correspondence e-mail: manavaibala@gmail.com

Edited by G. Smith, Queensland University of Technology, Australia (Received 21 February 2018; accepted 10 April 2018; online 12 April 2018)

In the crystal structure of the title salt, C₆H₁₀N₃O⁺·C₇H₄ClO₂⁻, the dihedral angle between the pyrimidine ring of the 2-amino-4-methoxy-6-methylpyrimidine cation and the the benzene ring of the 2-chlorobenzoate anion is 2.2 (1)°. In the anion, the benzene ring forms a dihedral angle of 8.5 (2)° with the carboxyl group. The pyrimidine N atom of the cation is protonated and the methoxy substituent is essentially coplanar with the parent ring. The protonated N atom and the N atom of the 2-amino group are hydrogen bonded to the 4-chlorobenzoate anion through a pair of N—H⋯O_carboxyl hydrogen bonds, forming an R²₂(8) ring motif linked through a centrosymmetric R²₄(8) ring motif, resulting in a pseudotetrameric DDAA array. These units are linked through intermolecular methoxy C—H⋯Cl hydrogen bonds into ribbon-like chains extending along the c-axis direction. The crystal structure also features π–π stacking interactions between the rings in the cation and anion [minimum ring centroid separation = 3.7707 (12) Å].

Keywords: crystal structure; pseudotetrameric; pyrimidine.

CCDC reference: 1835970

1. Chemical context

Pyrimidine and aminopyrimidine derivatives are biologically important compounds and they occur in nature as components of nucleic acids such as cytosine, uracil and thymine. Pyrimidine derivatives are also important molecules in biology and have many applications in the areas of pesticides and pharmaceutical agents (Condon et al., 1993 ). For example, imazosulfuron, ethirmol and mepanipyrim have been commercialized as agrochemicals (Maeno et al., 1990 ). Pyrimidine derivatives have also been developed as antiviral agents, such as AZT, which is the most widely used anti-AIDS drug (Gilchrist, 1997 ). In order to study the hydrogen-bonding interactions, the title compound, the 2-amino-4-methoxy-6-methylpyrimidinium salt of 4-chlorobenzoate, C₆H₁₀N₃O⁺·C₇H₄ClO₂⁻, was synthesized and its structure, hydrogen-bonding and Hirshfeld surface analysis are reported herein.

2. Structural commentary

The asymmetric unit of the title compound contains a 2-amino-4-methoxy-6-methylpyrimidinium cation and a 4-chlorobenzoate anion (Fig. 1), which are essentially coplanar, with a dihedral angle between the ring systems of the two species of 2.2 (1)°. In the cation, one of the pyrimidine nitrogen atoms (N1) is protonated and this is reflected in an increase in bond angle at N1 [C11—N1—C13 = 120.53 (17)°], when compared with that at the unprotonated atom (N3) [C9—N3—C13 = 116.32 (18)°] and the corresponding angle of 116.01 (18)° in neutral 2-amino-4-methoxy-6-methylpyrimidine (Glidewell et al., 2003 ). The methoxy substituent group at C9 of the cation is essentially coplanar with the ring, the N3—C9—O3—C8 torsion angle being −2.9 (3)°. The bond lengths and angles are normal for the carboxylate group of a 4-chlorobenzoate anion, and the benzene ring forms a dihedral angle of 8.5 (2)° with the carboxyl group.

Figure 1
The asymmetric unit of the the title compound with atom labels, showing non-hydrogen atoms as 30% probability displacement ellipsoids. Inter-species hydrogen bonds are shown as dashed lines.

3. Supramolecular features

In the crystal, the protonated nitrogen atom (N1) and the amino nitrogen atom (N2) of the cation interact with the carboxyl oxygen atoms O2 and O1, respectively, of the anion through N—H⋯O hydrogen bonds (Table 1), forming an eight-membered $[R_{2}^{2}]$ (8) ring motif. This is extended into a DDAA array (where D represents a hydrogen-bond donor and A represents a hydrogen-bond acceptor) by N2—H1N⋯O1ⁱ hydrogen bonds in a centrosymmetric $[R_{4}^{2}]$ (8) association [symmetry code: (i) −x + 1, −y + 2, −z + 1], the corresponding graph-set notations for the heterotetramer being $[R_{2}^{2}]$ (8), $[R_{4}^{2}]$ (8), $[R_{2}^{2}]$ (8). The heterotetrameric units are linked through methoxy C8—H8A⋯Clⁱⁱ hydrogen bonds, forming one-dimensional ribbon-like structures (Fig. 2) [symmetry code: (ii) x + 2, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ]. Only very weak methyl C12—H⋯O2 interactions [C⋯O = 3.442 (3) Å; H⋯O2 = 2.76 Å] exist between ribbons. The crystal structure also features π–π stacking interactions between the aromatic pyrimidine ring of the cation (Fig. 3) and the benzene ring of the anion, with minimum centroid–centroid and perpendicular interplanar distances of 3.7780 (12) and 3.7075 (8) Å, respectively, and a slip angle of 19.44° (Hunter et al., 1994 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	1.04 (3)	1.60 (3)	2.636 (3)	176 (2)
N2—H1N⋯O1ⁱ	0.86	2.12	2.846 (2)	142
N2—H2N⋯O1	0.86	1.97	2.824 (3)	169
C8—H8A⋯Cl1ⁱⁱ	0.96	2.82	3.770 (3)	171
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x+2, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Hydrogen bonding in the structure of the title compound showing the $[R_{2}^{2}]$ (8) and centrosymmetric $[R_{4}^{2}]$ (8) ring motifs and C—H⋯Cl extensions. Dashed lines indicate the hydrogen bonds.

Figure 3
The overall view of the packing and stacking interactions in the title compound.

4. Hirshfeld surface analysis

Three-dimensional (3D) d_norm surface analyis is a useful tool for analysing and visualizing the intermolecular interactions. d_norm takes negative or positive values depending on whether the intermolecular contact is shorter or longer, respectively, than the van der Waals radii (Spackman & Jayatilaka, 2009 ; McKinnon et al., 2007 ). The 3D d_norm surface of the title compound was shown in Fig. 4. The red points represent closer contacts and negative d_norm values on the surface corresponding to the N—H⋯O interactions, while C—H⋯O interactions are light red in colour. Two-dimensional fingerprint plots from the Hirshfeld surface analysis are shown in Fig. 5, revealing the intermolecular contacts and their percentage distributions on the Hirshfeld surface. H⋯H interactions (44.8%) are present as a major contributor while O⋯H/H⋯O (14.6%), H⋯Cl/Cl⋯H (13.3%), C⋯H/H⋯C (7.5%), C⋯C (6.6%), N⋯H/H⋯N (3.4%), C⋯N/N⋯C (3.3%), Cl⋯N/N⋯Cl (1.8%), C⋯Cl/Cl⋯C (1.0%) and Cl⋯O/O⋯Cl (0.7%) contacts also make significant contributions to the Hirshfeld surface. Two `wingtips' in the fingerprint plot are related to H⋯O and O⋯H interactions and are shown in Fig. 5.

Figure 4
The three-dimensional d_norm surface of the title compound.

Figure 5
Two-dimensional fingerprint plots with the relative contributions to the Hirshfeld surface.

5. Database survey

A search of the Cambridge Structural Database (Version 5.37, update February 2017; Groom et al., 2016 ) for 2-amino-4-methoxy-6-methylpyrimidine yielded only seven structures of proton-transfer salts with carboxylic acids: VAQSOW [with 3-(N,N-dimethylamino)benzoic acid]; VAQSUC [with methylene hydrogen succinic acid (a monohydrate)]; VAQSEM (with 3-nitrobenzoic acid); VAQSIQ (with benzoic acid); VAQRUB (with 2-fluorobenzoic acid) and VAQSAI (with 3-chlorobenzoic acid) (all from Aakeröy et al., 2003 ) and NUQTOJ (with picric acid; Jasinski et al., 2010 ).

6. Synthesis and crystallization

The title compound was synthesized by the reaction of a 1:1 stoichiometric mixture of 2-amino-4-methoxy-6-methylpyrimidine [0.139 mg (Aldrich)] and 4-chlorobenzoic acid [0.156 mg (Merck)] in 20 ml of a hot methanolic solution. After warming for a few minutes over a water bath, the solution was cooled and kept at room temperature. Within a few days, colourless block-shaped crystals suitable for the X-ray analysis were obtained (yield: 65%).

7. refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. N-bound pyrimidinium H atoms were located in a difference-Fourier map and refined freely [N—H = 1.03 (3) Å]. The remaining H atoms were positioned geometrically and refined using a riding model with (N—H = 0.86 Å and C—H = 0.93 or 0.96 Å) and U_iso(H) = 1.2 U_eq(C,N) or 1.5U_eq(methyl C). A rotating-group model was used for the methyl groups.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₁₀N₃O⁺·C₇H₄ClO₂⁻
M_r	295.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.1148 (8), 11.2236 (8), 14.579 (1)
β (°)	120.940 (5)
V (Å³)	1419.57 (19)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.28
Crystal size (mm)	0.35 × 0.30 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.909, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	10962, 3423, 2125
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.152, 0.99
No. of reflections	3423
No. of parameters	188
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.35
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1999 ), SHELXL2017 (Sheldrick, 2015 ), ORTEP-3 (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1835970

Crystal structure: contains datablocks global, I, 81R. DOI: https://doi.org/10.1107/S2056989018005583/zs2399sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018005583/zs2399Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018005583/zs2399Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2017 (Sheldrick, 2015).

(I) top

Crystal data top

C₆H₁₀N₃O⁺·C₇H₄ClO₂⁻	F(000) = 616
M_r = 295.72	D_x = 1.384 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.1148 (8) Å	Cell parameters from 3319 reflections
b = 11.2236 (8) Å	θ = 4.7–53.1°
c = 14.579 (1) Å	µ = 0.28 mm⁻¹
β = 120.940 (5)°	T = 296 K
V = 1419.57 (19) Å³	Block, colorless
Z = 4	0.35 × 0.30 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2125 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
ω and φ scan	θ_max = 28.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→12
T_min = 0.909, T_max = 0.946	k = −14→14
10962 measured reflections	l = −15→18
3423 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.0728P)² + 0.324P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.003
3423 reflections	Δρ_max = 0.26 e Å⁻³
188 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Extinction correction: SHELXL2017 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (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. 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 > 2sigma(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
O3	1.08061 (18)	0.73298 (18)	0.57812 (14)	0.0840 (5)
N1	0.62562 (18)	0.71035 (13)	0.45066 (13)	0.0513 (4)
N2	0.61625 (18)	0.91121 (14)	0.47011 (15)	0.0649 (5)
H1N	0.659761	0.979882	0.489408	0.078*
H2N	0.518251	0.904882	0.442578	0.078*
N3	0.85256 (18)	0.82711 (15)	0.52563 (13)	0.0555 (4)
C8	1.1555 (3)	0.8473 (3)	0.6048 (2)	0.0926 (9)
H8A	1.258389	0.838988	0.618161	0.139*
H8B	1.159254	0.877851	0.667577	0.139*
H8C	1.098704	0.901435	0.546305	0.139*
C9	0.9288 (2)	0.7287 (2)	0.53678 (16)	0.0616 (6)
C10	0.8601 (3)	0.6168 (2)	0.50699 (19)	0.0703 (6)
H10	0.919348	0.548952	0.518504	0.084*
C11	0.7049 (3)	0.60891 (17)	0.46085 (17)	0.0595 (5)
C12	0.6128 (3)	0.49752 (19)	0.4188 (2)	0.0872 (8)
H12A	0.531726	0.509732	0.346014	0.131*
H12B	0.568913	0.477063	0.461457	0.131*
H12C	0.678410	0.433995	0.421663	0.131*
C13	0.6995 (2)	0.81598 (16)	0.48261 (15)	0.0489 (4)
Cl1	−0.42873 (6)	0.70123 (7)	0.18780 (6)	0.0859 (3)
O1	0.30336 (15)	0.87707 (12)	0.40502 (13)	0.0710 (5)
O2	0.32766 (15)	0.68727 (12)	0.37489 (12)	0.0648 (4)
C1	0.2501 (2)	0.77506 (16)	0.37387 (15)	0.0506 (5)
C2	0.0808 (2)	0.75559 (16)	0.33048 (14)	0.0455 (4)
C3	0.0178 (2)	0.64290 (17)	0.30515 (16)	0.0532 (5)
H3	0.081505	0.577740	0.317181	0.064*
C4	−0.1384 (2)	0.62496 (19)	0.26221 (16)	0.0591 (5)
H4	−0.179743	0.548535	0.245653	0.071*
C5	−0.2314 (2)	0.72173 (19)	0.24443 (16)	0.0552 (5)
C6	−0.1725 (2)	0.83473 (19)	0.26959 (17)	0.0615 (5)
H6	−0.237007	0.899426	0.257249	0.074*
C7	−0.0160 (2)	0.85154 (17)	0.31355 (16)	0.0559 (5)
H7	0.025012	0.927932	0.332014	0.067*
H1N1	0.508 (3)	0.700 (2)	0.418 (2)	0.089 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0495 (9)	0.1165 (14)	0.0927 (12)	0.0275 (9)	0.0414 (9)	0.0152 (11)
N1	0.0479 (9)	0.0476 (9)	0.0551 (9)	0.0080 (7)	0.0242 (8)	−0.0032 (7)
N2	0.0389 (8)	0.0483 (9)	0.0946 (13)	0.0010 (7)	0.0251 (8)	−0.0125 (8)
N3	0.0411 (9)	0.0722 (11)	0.0533 (10)	0.0081 (7)	0.0243 (7)	−0.0019 (8)
C8	0.0457 (13)	0.140 (3)	0.0899 (19)	0.0033 (14)	0.0337 (13)	0.0031 (17)
C9	0.0507 (12)	0.0858 (15)	0.0564 (13)	0.0194 (10)	0.0333 (10)	0.0100 (11)
C10	0.0728 (15)	0.0697 (14)	0.0839 (16)	0.0340 (12)	0.0514 (13)	0.0182 (12)
C11	0.0738 (14)	0.0508 (11)	0.0653 (13)	0.0173 (9)	0.0439 (11)	0.0081 (9)
C12	0.112 (2)	0.0478 (12)	0.121 (2)	0.0116 (12)	0.0732 (18)	0.0017 (13)
C13	0.0406 (9)	0.0533 (10)	0.0497 (11)	0.0050 (8)	0.0210 (8)	−0.0029 (8)
Cl1	0.0454 (3)	0.1120 (6)	0.0929 (5)	−0.0142 (3)	0.0302 (3)	−0.0069 (4)
O1	0.0424 (7)	0.0458 (8)	0.1021 (12)	−0.0028 (6)	0.0210 (7)	−0.0149 (7)
O2	0.0454 (8)	0.0481 (7)	0.0872 (11)	0.0023 (6)	0.0242 (7)	−0.0098 (7)
C1	0.0404 (9)	0.0449 (10)	0.0527 (11)	0.0003 (7)	0.0141 (8)	−0.0010 (8)
C2	0.0406 (9)	0.0447 (9)	0.0424 (10)	0.0005 (7)	0.0149 (8)	0.0012 (7)
C3	0.0495 (11)	0.0465 (10)	0.0573 (11)	−0.0031 (8)	0.0230 (9)	−0.0053 (8)
C4	0.0549 (12)	0.0578 (12)	0.0623 (13)	−0.0144 (9)	0.0285 (10)	−0.0095 (10)
C5	0.0416 (10)	0.0722 (13)	0.0468 (11)	−0.0074 (9)	0.0191 (8)	−0.0020 (9)
C6	0.0429 (10)	0.0607 (12)	0.0702 (14)	0.0087 (9)	0.0215 (10)	0.0076 (10)
C7	0.0442 (10)	0.0459 (10)	0.0643 (12)	0.0007 (8)	0.0184 (9)	0.0034 (9)

Geometric parameters (Å, º) top

O3—C9	1.331 (2)	C12—H12A	0.9600
O3—C8	1.438 (4)	C12—H12B	0.9600
N1—C13	1.350 (2)	C12—H12C	0.9600
N1—C11	1.356 (2)	Cl1—C5	1.7385 (19)
N1—H1N1	1.03 (3)	O1—C1	1.247 (2)
N2—C13	1.314 (2)	O2—C1	1.255 (2)
N2—H1N	0.8600	C1—C2	1.506 (2)
N2—H2N	0.8600	C2—C3	1.379 (3)
N3—C9	1.308 (3)	C2—C7	1.389 (3)
N3—C13	1.344 (2)	C3—C4	1.383 (3)
C8—H8A	0.9600	C3—H3	0.9300
C8—H8B	0.9600	C4—C5	1.372 (3)
C8—H8C	0.9600	C4—H4	0.9300
C9—C10	1.392 (3)	C5—C6	1.369 (3)
C10—C11	1.356 (3)	C6—C7	1.381 (3)
C10—H10	0.9300	C6—H6	0.9300
C11—C12	1.490 (3)	C7—H7	0.9300

C9—O3—C8	118.61 (18)	H12A—C12—H12C	109.5
C13—N1—C11	120.53 (17)	H12B—C12—H12C	109.5
C13—N1—H1N1	124.1 (13)	N2—C13—N3	119.43 (17)
C11—N1—H1N1	115.4 (13)	N2—C13—N1	117.68 (16)
C13—N2—H1N	120.0	N3—C13—N1	122.89 (16)
C13—N2—H2N	120.0	O1—C1—O2	124.51 (17)
H1N—N2—H2N	120.0	O1—C1—C2	118.10 (16)
C9—N3—C13	116.32 (18)	O2—C1—C2	117.39 (16)
O3—C8—H8A	109.5	C3—C2—C7	118.48 (17)
O3—C8—H8B	109.5	C3—C2—C1	121.00 (16)
H8A—C8—H8B	109.5	C7—C2—C1	120.51 (16)
O3—C8—H8C	109.5	C2—C3—C4	121.22 (18)
H8A—C8—H8C	109.5	C2—C3—H3	119.4
H8B—C8—H8C	109.5	C4—C3—H3	119.4
N3—C9—O3	119.7 (2)	C5—C4—C3	118.90 (18)
N3—C9—C10	123.68 (19)	C5—C4—H4	120.5
O3—C9—C10	116.64 (19)	C3—C4—H4	120.5
C11—C10—C9	118.62 (18)	C6—C5—C4	121.40 (18)
C11—C10—H10	120.7	C6—C5—Cl1	119.04 (16)
C9—C10—H10	120.7	C4—C5—Cl1	119.55 (16)
C10—C11—N1	117.9 (2)	C5—C6—C7	119.23 (18)
C10—C11—C12	125.36 (19)	C5—C6—H6	120.4
N1—C11—C12	116.74 (19)	C7—C6—H6	120.4
C11—C12—H12A	109.5	C6—C7—C2	120.74 (18)
C11—C12—H12B	109.5	C6—C7—H7	119.6
H12A—C12—H12B	109.5	C2—C7—H7	119.6
C11—C12—H12C	109.5

O1—C1—C2—C3	−173.20 (19)	C4—C5—C6—C7	0.2 (3)
O1—C1—C2—C7	7.8 (3)	C5—C6—C7—C2	1.2 (3)
O2—C1—C2—C3	7.7 (3)	C13—N1—C11—C10	2.1 (3)
O2—C1—C2—C7	−171.35 (18)	C13—N1—C11—C12	−177.2 (2)
C1—C2—C3—C4	−177.99 (18)	C11—N1—C13—N2	179.63 (19)
C7—C2—C3—C4	1.0 (3)	C11—N1—C13—N3	−0.1 (3)
C1—C2—C7—C6	177.29 (19)	C13—N3—C9—O3	179.53 (18)
C3—C2—C7—C6	−1.8 (3)	C13—N3—C9—C10	−0.1 (3)
C2—C3—C4—C5	0.3 (3)	C9—N3—C13—N1	−0.9 (3)
C8—O3—C9—C10	176.7 (2)	C9—N3—C13—N2	179.37 (19)
C8—O3—C9—N3	−2.9 (3)	O3—C9—C10—C11	−177.6 (2)
C3—C4—C5—C6	−0.9 (3)	N3—C9—C10—C11	2.0 (4)
C3—C4—C5—Cl1	178.62 (16)	C9—C10—C11—N1	−2.9 (3)
Cl1—C5—C6—C7	−179.32 (16)	C9—C10—C11—C12	176.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	1.04 (3)	1.60 (3)	2.636 (3)	176 (2)
N2—H1N···O1ⁱ	0.86	2.12	2.846 (2)	142
N2—H2N···O1	0.86	1.97	2.824 (3)	169
C8—H8A···Cl1ⁱⁱ	0.96	2.82	3.770 (3)	171

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

Acknowledgements

The authors thank the Sophisticated Analytical Instrumentation Facility (SAIF) at STIC, Cochin University of Science and Technology, Cochin, for X-ray data collection.

Funding information

PS and KB thank the Department of Science and Technology (DST–SERB), grant No. SB/FT/CS-058/2013, New Delhi, India, for financial support.

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