6-Amino-3,4-dimethyl-1,2,4-triazin-1-ium 2-anilino­benzoate–3-amino-5,6-dimethyl-1,2,4-triazine (1/1)

Sangeetha, R.; Balasubramani, K.; Thanigaimani, K.; Razak, I.A.

doi:10.1107/S241431461700829X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 6| June 2017| x170829

https://doi.org/10.1107/S241431461700829X

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6-Amino-3,4-dimethyl-1,2,4-triazin-1-ium 2-anilinobenzoate–3-amino-5,6-dimethyl-1,2,4-triazine (1/1)

Ramalingam Sangeetha,^a Kasthuri Balasubramani,^a ^* Kaliyaperumal Thanigaimani ^b and Ibrahim Abdul Razak ^c

^aDepartment of Chemistry, Government Arts College (Autonomous), Thanthonimalai, Karur 639 005, Tamil Nadu, India, ^bDepartment of Chemistry, Government Arts College, Thiruchirappalli 620 022, Tamilnadu, India, and ^cSchool of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: manavaibala@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 12 May 2017; accepted 5 June 2017; online 8 June 2017)

In the title molecular salt, C₅H₉N₄⁺·C₁₃H₁₀NO₂⁻·C₅H₈N₄, the asymmetric unit consists of a 6-amino-3,4-dimethyl-1,2,4-triazin-1-ium cation, a 2-anilinobenzoate anion and a neutral 3-amino-5,6-dimethyl-1,2,4-triazine molecule. The typical intramolecular N⋯H—O hydrogen bond is observed in the 2-anilinobenzoate anion. In the crystal, the protonated N atom and the 3-amino group are hydrogen bonded to the carboxylate oxygen atoms via a pair of N—H⋯O hydrogen bonds, forming an R²₂ (8) ring motif. These motifs are further linked with adjacent neutral 3-amino-5,6-dimethyl-1,2,4-triazine molecules by N—H⋯O and N—H⋯N hydrogen bonds to produce centrosymmetric six-membered units, enclosing R²₂(8) and R³₄(9) ring motifs. They are reinforced by a C—H⋯N hydrogen bond and stack up the b-axis direction.

Keywords: crystal structure; 1,2,4-triazine; 1,2,4-triazinium; benzoate; hydrogen bonding.

CCDC reference: 1554175

Structure description

Heterocyclic compounds play a role in the design of new drugs and materials (García-Valverde & Torroba, 2005 ; Kumar et al., 2014 ). 1,2,4-Triazines and their analogues occupy a important position in medicinal chemistry as a result of their pharmacological activities (Abdel-Monem, 2010 ). Drugs containing a 1,2,4-triazine ring are present in natural and many synthetic products, for example azaribine and lamotrigine, that have important biological activities. The crystal structure of 3-amino-5,6-dimethyl-1,2,4-triazine (Wu et al., 2012 ) and 3-amino-5,6-dimethyl-1,2,4-triazin-2-ium nitrate (Bel Haj Salah et al., 2013 ) have been reported. In order to study potential hydrogen-bonding interactions, the crystal structure determination of the title molecular salt was carried out.

The structure of the title molecular salt is illustrated in Fig. 1. It is composed of a 6-amino-3,4-dimethyl-1,2,4-triazinium cation, a 2-anilinobenzoate anion and one neutral 3-amino-5,6-dimethyl-1,2,4-triazine molecule. Proton transfer from one of the carboxylate oxygen atoms (O1) to atom N2A of the cation results in widening of the C1A—N2A—N1A angle of the triazinium ring to 123.40 (13)°, compared to the corresponding angle of 117.9 (3)° in neutral 3-amino-5,6-dimethyl-1,2,4-triazine (Wu et al., 2012), and that of the neutral 3-amino-5,6-dimethyl-1,2,4-triazine molecule present in the title molecular salt, where angle N1B—N2B—C1B is 117.46 (12) °. The dihedral angle between the rings in the anion is 44.55 (11)°. There is a typical intramolecular hydrogen bond N5—H1N5⋯O1 between the NH and carboxylate group of the 2-anilinobenzoate anion, forming an S(6) ring motif (Fig. 1).

Figure 1
A view of the molecular structure of the title molecular salt, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

In the crystal, the protonated N atom, N2A, and the 3-amino group (N3A) are hydrogen bonded to the carboxylate oxygen atoms (O1 and O2) via a pair of N2A—H1N2⋯O1ⁱ and N3A—H1NA⋯O2ⁱ hydrogen bonds, forming an R₂² (8) ring motif (Table 1 and Fig. 2). These motifs are further linked with adjacent neutral 3-amino-5,6-dimethyl-1,2,4-triazine molecules by N3B—H2NB⋯O2, N3A—H2NA⋯N1Bⁱⁱ and N3B—H1NB⋯N2Bⁱⁱⁱ hydrogen bonds to produce a complementary DDAA (D = donor, A = acceptor) hydrogen-bonded array (Table 1 and Fig. 2). These centrosymmetric six-membered units enclose R₂²(8) and R₄³(9) ring motifs, are reinforced by a C—H⋯N hydrogen bond, and stack up the b-axis direction (Table 1, Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5N⋯O1	0.85 (2)	1.92 (2)	2.619 (2)	138 (2)
N2A—H2AA⋯O1ⁱ	1.02 (2)	1.58 (2)	2.593 (2)	179 (2)
N3A—H3AA⋯O2ⁱ	0.93 (2)	1.90 (2)	2.834 (2)	175 (2)
N3A—H3AB⋯N1Bⁱⁱ	0.92 (2)	2.07 (2)	2.986 (2)	172 (2)
N3B—H3BA⋯N2Bⁱⁱⁱ	0.89 (2)	2.20 (2)	3.089 (2)	179 (2)
N3B—H3BB⋯O2	0.97 (2)	1.98 (2)	2.915 (2)	163 (2)
C4B—H4BC⋯N4Aⁱⁱ	0.96	2.52	3.483 (2)	177
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y, -z; (iii) -x, -y, -z.

Figure 2
A view of the hydrogen bonded six-membered unit, involving the neutral triazine molecule, the triazinium cation and the benzoate anion. Hydrogen bonds are shown as dashed lines [symmetry codes for this figure are: (i) x + 1, y, z; (ii) −x + 1, −y, z; (iii) −x + 2, −y, −z], and H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 3
The crystal packing of the title molecular salt, viewed along the normal to (110). H atoms not involved in hydrogen bonding (dashed lines; see Table 1

) have been omitted for clarity.

Synthesis and crystallization

A hot methanol solution (20 ml) of 3-amino-5,6-dimethyl-1,2,4-triazine (62 mg, Aldrich) and 2-anilinobenzoic acid (100 mg, Merk) were mixed and warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and green plate-like 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	C₁₃H₁₀NO₂·C₅H₉N₄·C₅H₈N₄
M_r	461.53
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.5018 (3), 7.6661 (3), 21.4332 (9)
α, β, γ (°)	93.743 (1), 94.776 (1), 106.197 (1)
V (Å³)	1174.52 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.61 × 0.49 × 0.18

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.947, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	35176, 4622, 3468
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.133, 1.04
No. of reflections	4622
No. of parameters	335
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1554175

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461700829X/su4153sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700829X/su4153Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461700829X/su4153Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015) and PLATON (Spek, 2009).

6-Amino-3,4-dimethyl-1,2,4-triazin-1-ium 2-anilinobenzoate; 3-amino-5,6-dimethyl-1,2,4-triazine top

Crystal data top

C₅H₉N₄⁺·C₁₃H₁₀NO₂⁻·C₅H₈N₄	Z = 2
M_r = 461.53	F(000) = 488
Triclinic, P1	D_x = 1.305 Mg m⁻³
a = 7.5018 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6661 (3) Å	Cell parameters from 2760 reflections
c = 21.4332 (9) Å	θ = 1.0–29.0°
α = 93.743 (1)°	µ = 0.09 mm⁻¹
β = 94.776 (1)°	T = 293 K
γ = 106.197 (1)°	Plate, green
V = 1174.52 (8) Å³	0.61 × 0.49 × 0.18 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4622 independent reflections
Radiation source: fine-focus sealed tube	3468 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
φ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.947, T_max = 0.984	k = −9→9
35176 measured reflections	l = −26→26

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)] = 0.045	Hydrogen site location: mixed
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0628P)² + 0.222P] where P = (F_o² + 2F_c²)/3
4622 reflections	(Δ/σ)_max = 0.001
335 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.15 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.

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

	x	y	z	U_iso*/U_eq
O1	−0.06951 (14)	0.41109 (18)	0.27879 (6)	0.0645 (4)
O2	0.04258 (14)	0.29631 (16)	0.19905 (5)	0.0577 (3)
N5	0.1635 (2)	0.6138 (2)	0.37067 (7)	0.0626 (4)
H5N	0.052 (3)	0.560 (3)	0.3544 (9)	0.067 (6)*
C6	0.06398 (19)	0.4021 (2)	0.24742 (7)	0.0426 (3)
C7	0.25436 (19)	0.52475 (19)	0.27027 (7)	0.0406 (3)
C8	0.3935 (2)	0.5411 (2)	0.23022 (8)	0.0484 (4)
H8	0.3652	0.4748	0.1910	0.058*
C9	0.5720 (2)	0.6525 (2)	0.24700 (9)	0.0596 (5)
H9	0.6636	0.6598	0.2198	0.071*
C10	0.6127 (2)	0.7530 (3)	0.30453 (10)	0.0638 (5)
H10	0.7325	0.8299	0.3160	0.077*
C11	0.4795 (2)	0.7416 (2)	0.34506 (9)	0.0602 (5)
H11	0.5100	0.8125	0.3834	0.072*
C12	0.2980 (2)	0.6253 (2)	0.33008 (7)	0.0472 (4)
C13	0.1844 (3)	0.6725 (2)	0.43498 (8)	0.0601 (5)
C14	0.3339 (3)	0.6662 (4)	0.47597 (10)	0.0913 (7)
H14	0.4305	0.6270	0.4610	0.110*
C15	0.3400 (4)	0.7182 (5)	0.53918 (12)	0.1181 (10)
H15	0.4412	0.7134	0.5665	0.142*
C16	0.2015 (5)	0.7762 (4)	0.56239 (12)	0.1152 (10)
H16	0.2079	0.8122	0.6050	0.138*
C17	0.0526 (5)	0.7806 (4)	0.52206 (13)	0.1038 (9)
H17	−0.0440	0.8187	0.5375	0.125*
C18	0.0435 (3)	0.7293 (3)	0.45877 (10)	0.0760 (6)
H18	−0.0590	0.7332	0.4319	0.091*
N1A	0.48051 (18)	0.19326 (19)	0.29896 (6)	0.0516 (3)
N2A	0.59717 (17)	0.18820 (18)	0.25468 (6)	0.0474 (3)
H2AA	0.727 (3)	0.276 (3)	0.2642 (9)	0.072 (5)*
N3A	0.67322 (19)	0.0737 (2)	0.16252 (7)	0.0519 (4)
H3AA	0.796 (3)	0.147 (2)	0.1719 (8)	0.059 (5)*
H3AB	0.633 (3)	0.001 (3)	0.1252 (9)	0.063 (5)*
N4A	0.36953 (16)	−0.02836 (18)	0.18697 (6)	0.0479 (3)
C1A	0.54793 (19)	0.0788 (2)	0.20174 (7)	0.0425 (3)
C2A	0.2532 (2)	−0.0255 (2)	0.22879 (8)	0.0478 (4)
C3A	0.3111 (2)	0.0859 (2)	0.28723 (8)	0.0500 (4)
C4A	0.1833 (3)	0.0886 (3)	0.33697 (10)	0.0702 (5)
H4AA	0.1544	−0.0262	0.3550	0.105*
H4AC	0.0703	0.1087	0.3187	0.105*
H4AB	0.2433	0.1850	0.3692	0.105*
C5A	0.0571 (2)	−0.1422 (3)	0.21318 (10)	0.0635 (5)
H5AB	0.0453	−0.2096	0.1730	0.095*
H5AA	−0.0256	−0.0666	0.2118	0.095*
H5AC	0.0253	−0.2257	0.2447	0.095*
N1B	0.41507 (18)	0.15155 (19)	−0.03886 (6)	0.0511 (3)
N2B	0.25699 (17)	0.11190 (18)	−0.01023 (6)	0.0485 (3)
N3B	0.1073 (2)	0.1583 (2)	0.07556 (7)	0.0583 (4)
H3BA	0.003 (3)	0.080 (3)	0.0562 (9)	0.063 (5)*
H3BB	0.112 (3)	0.218 (3)	0.1170 (10)	0.067 (5)*
N4B	0.41980 (17)	0.30830 (18)	0.07997 (6)	0.0496 (3)
C1B	0.2648 (2)	0.1919 (2)	0.04733 (7)	0.0442 (4)
C2B	0.5721 (2)	0.3445 (2)	0.05112 (7)	0.0458 (4)
C3B	0.5703 (2)	0.2650 (2)	−0.01015 (8)	0.0462 (4)
C4B	0.7392 (2)	0.3046 (3)	−0.04550 (9)	0.0610 (5)
H4BC	0.7099	0.2325	−0.0853	0.092*
H4BB	0.8390	0.2750	−0.0216	0.092*
H4BA	0.7769	0.4317	−0.0523	0.092*
C5B	0.7458 (2)	0.4714 (3)	0.08573 (9)	0.0647 (5)
H5BA	0.7891	0.5753	0.0625	0.097*
H5BC	0.8403	0.4093	0.0904	0.097*
H5BB	0.7197	0.5111	0.1265	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0336 (6)	0.0799 (8)	0.0667 (7)	−0.0027 (5)	0.0164 (5)	−0.0197 (6)
O2	0.0390 (6)	0.0671 (7)	0.0558 (7)	−0.0016 (5)	0.0124 (5)	−0.0122 (6)
N5	0.0453 (8)	0.0807 (11)	0.0498 (8)	0.0014 (7)	0.0105 (7)	−0.0138 (7)
C6	0.0343 (7)	0.0445 (8)	0.0463 (8)	0.0055 (6)	0.0089 (6)	0.0049 (7)
C7	0.0318 (7)	0.0410 (8)	0.0479 (8)	0.0072 (6)	0.0080 (6)	0.0061 (6)
C8	0.0389 (8)	0.0501 (9)	0.0542 (9)	0.0073 (7)	0.0124 (7)	0.0035 (7)
C9	0.0355 (8)	0.0656 (11)	0.0727 (12)	0.0035 (7)	0.0179 (8)	0.0042 (9)
C10	0.0344 (8)	0.0642 (11)	0.0804 (13)	−0.0047 (7)	0.0055 (8)	0.0002 (9)
C11	0.0458 (9)	0.0623 (11)	0.0613 (10)	0.0005 (8)	0.0029 (8)	−0.0065 (8)
C12	0.0391 (8)	0.0489 (9)	0.0502 (9)	0.0073 (6)	0.0071 (7)	0.0014 (7)
C13	0.0631 (11)	0.0580 (10)	0.0490 (9)	0.0003 (8)	0.0144 (8)	−0.0030 (8)
C14	0.0760 (14)	0.127 (2)	0.0610 (13)	0.0152 (13)	0.0033 (11)	−0.0005 (13)
C15	0.106 (2)	0.161 (3)	0.0582 (14)	−0.0041 (19)	−0.0043 (14)	0.0025 (16)
C16	0.148 (3)	0.118 (2)	0.0536 (14)	−0.005 (2)	0.0274 (17)	−0.0105 (14)
C17	0.146 (3)	0.0996 (19)	0.0746 (16)	0.0367 (18)	0.0564 (18)	0.0055 (14)
C18	0.0891 (15)	0.0833 (14)	0.0600 (11)	0.0244 (12)	0.0320 (11)	0.0092 (10)
N1A	0.0436 (7)	0.0580 (8)	0.0523 (8)	0.0101 (6)	0.0131 (6)	0.0076 (6)
N2A	0.0345 (7)	0.0522 (7)	0.0510 (8)	0.0033 (6)	0.0099 (6)	0.0052 (6)
N3A	0.0349 (7)	0.0623 (9)	0.0525 (8)	0.0031 (6)	0.0103 (6)	0.0020 (7)
N4A	0.0324 (6)	0.0512 (8)	0.0563 (8)	0.0050 (5)	0.0059 (6)	0.0062 (6)
C1A	0.0316 (7)	0.0459 (8)	0.0485 (8)	0.0065 (6)	0.0072 (6)	0.0107 (7)
C2A	0.0339 (8)	0.0473 (9)	0.0637 (10)	0.0092 (6)	0.0119 (7)	0.0174 (8)
C3A	0.0405 (8)	0.0532 (9)	0.0587 (10)	0.0121 (7)	0.0151 (7)	0.0166 (8)
C4A	0.0587 (11)	0.0821 (13)	0.0730 (12)	0.0164 (10)	0.0305 (10)	0.0170 (10)
C5A	0.0335 (8)	0.0637 (11)	0.0876 (13)	0.0016 (7)	0.0115 (8)	0.0130 (10)
N1B	0.0418 (7)	0.0583 (8)	0.0508 (8)	0.0079 (6)	0.0137 (6)	0.0046 (6)
N2B	0.0366 (7)	0.0562 (8)	0.0480 (7)	0.0047 (6)	0.0097 (6)	0.0033 (6)
N3B	0.0374 (8)	0.0774 (10)	0.0518 (9)	0.0030 (7)	0.0126 (6)	−0.0048 (8)
N4B	0.0406 (7)	0.0559 (8)	0.0493 (7)	0.0082 (6)	0.0069 (6)	0.0039 (6)
C1B	0.0363 (8)	0.0500 (8)	0.0460 (8)	0.0103 (6)	0.0073 (6)	0.0080 (7)
C2B	0.0378 (8)	0.0454 (8)	0.0524 (9)	0.0076 (6)	0.0062 (7)	0.0088 (7)
C3B	0.0371 (8)	0.0460 (8)	0.0554 (9)	0.0089 (6)	0.0111 (7)	0.0090 (7)
C4B	0.0455 (9)	0.0643 (11)	0.0695 (11)	0.0064 (8)	0.0199 (8)	0.0037 (9)
C5B	0.0454 (9)	0.0691 (11)	0.0681 (11)	−0.0008 (8)	0.0042 (8)	0.0018 (9)

Geometric parameters (Å, º) top

O1—C6	1.2665 (17)	N3A—C1A	1.3189 (19)
O2—C6	1.2445 (18)	N3A—H3AA	0.933 (19)
N5—C12	1.375 (2)	N3A—H3AB	0.92 (2)
N5—C13	1.404 (2)	N4A—C2A	1.3056 (19)
N5—H5N	0.85 (2)	N4A—C1A	1.3595 (18)
C6—C7	1.496 (2)	C2A—C3A	1.431 (2)
C7—C8	1.390 (2)	C2A—C5A	1.490 (2)
C7—C12	1.416 (2)	C3A—C4A	1.494 (2)
C8—C9	1.376 (2)	C4A—H4AA	0.9600
C8—H8	0.9300	C4A—H4AC	0.9600
C9—C10	1.375 (3)	C4A—H4AB	0.9600
C9—H9	0.9300	C5A—H5AB	0.9600
C10—C11	1.366 (2)	C5A—H5AA	0.9600
C10—H10	0.9300	C5A—H5AC	0.9600
C11—C12	1.402 (2)	N1B—C3B	1.318 (2)
C11—H11	0.9300	N1B—N2B	1.3490 (17)
C13—C18	1.373 (3)	N2B—C1B	1.331 (2)
C13—C14	1.380 (3)	N3B—C1B	1.3412 (19)
C14—C15	1.380 (3)	N3B—H3BA	0.89 (2)
C14—H14	0.9300	N3B—H3BB	0.97 (2)
C15—C16	1.356 (4)	N4B—C2B	1.3142 (19)
C15—H15	0.9300	N4B—C1B	1.3572 (19)
C16—C17	1.364 (4)	C2B—C3B	1.409 (2)
C16—H16	0.9300	C2B—C5B	1.494 (2)
C17—C18	1.378 (3)	C3B—C4B	1.499 (2)
C17—H17	0.9300	C4B—H4BC	0.9600
C18—H18	0.9300	C4B—H4BB	0.9600
N1A—C3A	1.301 (2)	C4B—H4BA	0.9600
N1A—N2A	1.3493 (17)	C5B—H5BA	0.9600
N2A—C1A	1.327 (2)	C5B—H5BC	0.9600
N2A—H2AA	1.02 (2)	C5B—H5BB	0.9600

C12—N5—C13	129.15 (16)	C2A—N4A—C1A	116.78 (14)
C12—N5—H5N	114.8 (13)	N3A—C1A—N2A	119.79 (13)
C13—N5—H5N	116.0 (13)	N3A—C1A—N4A	119.16 (14)
O2—C6—O1	122.75 (13)	N2A—C1A—N4A	121.05 (13)
O2—C6—C7	119.44 (12)	N4A—C2A—C3A	121.44 (13)
O1—C6—C7	117.81 (13)	N4A—C2A—C5A	117.34 (15)
C8—C7—C12	118.97 (14)	C3A—C2A—C5A	121.22 (14)
C8—C7—C6	117.89 (13)	N1A—C3A—C2A	120.46 (14)
C12—C7—C6	123.13 (13)	N1A—C3A—C4A	116.60 (16)
C9—C8—C7	121.86 (16)	C2A—C3A—C4A	122.94 (15)
C9—C8—H8	119.1	C3A—C4A—H4AA	109.5
C7—C8—H8	119.1	C3A—C4A—H4AC	109.5
C10—C9—C8	118.98 (15)	H4AA—C4A—H4AC	109.5
C10—C9—H9	120.5	C3A—C4A—H4AB	109.5
C8—C9—H9	120.5	H4AA—C4A—H4AB	109.5
C11—C10—C9	120.92 (15)	H4AC—C4A—H4AB	109.5
C11—C10—H10	119.5	C2A—C5A—H5AB	109.5
C9—C10—H10	119.5	C2A—C5A—H5AA	109.5
C10—C11—C12	121.42 (16)	H5AB—C5A—H5AA	109.5
C10—C11—H11	119.3	C2A—C5A—H5AC	109.5
C12—C11—H11	119.3	H5AB—C5A—H5AC	109.5
N5—C12—C11	121.59 (15)	H5AA—C5A—H5AC	109.5
N5—C12—C7	120.56 (14)	C3B—N1B—N2B	120.50 (13)
C11—C12—C7	117.79 (14)	C1B—N2B—N1B	117.46 (12)
C18—C13—C14	118.46 (18)	C1B—N3B—H3BA	119.5 (11)
C18—C13—N5	118.06 (18)	C1B—N3B—H3BB	118.4 (11)
C14—C13—N5	123.37 (18)	H3BA—N3B—H3BB	122.0 (16)
C15—C14—C13	119.9 (3)	C2B—N4B—C1B	116.13 (13)
C15—C14—H14	120.0	N2B—C1B—N3B	118.09 (14)
C13—C14—H14	120.0	N2B—C1B—N4B	125.25 (13)
C16—C15—C14	121.5 (3)	N3B—C1B—N4B	116.65 (14)
C16—C15—H15	119.3	N4B—C2B—C3B	120.74 (14)
C14—C15—H15	119.3	N4B—C2B—C5B	117.67 (14)
C15—C16—C17	118.7 (2)	C3B—C2B—C5B	121.59 (14)
C15—C16—H16	120.6	N1B—C3B—C2B	119.91 (13)
C17—C16—H16	120.6	N1B—C3B—C4B	117.31 (15)
C16—C17—C18	120.8 (3)	C2B—C3B—C4B	122.79 (14)
C16—C17—H17	119.6	C3B—C4B—H4BC	109.5
C18—C17—H17	119.6	C3B—C4B—H4BB	109.5
C13—C18—C17	120.6 (2)	H4BC—C4B—H4BB	109.5
C13—C18—H18	119.7	C3B—C4B—H4BA	109.5
C17—C18—H18	119.7	H4BC—C4B—H4BA	109.5
C3A—N1A—N2A	116.69 (14)	H4BB—C4B—H4BA	109.5
C1A—N2A—N1A	123.40 (13)	C2B—C5B—H5BA	109.5
C1A—N2A—H2AA	121.3 (11)	C2B—C5B—H5BC	109.5
N1A—N2A—H2AA	115.3 (11)	H5BA—C5B—H5BC	109.5
C1A—N3A—H3AA	120.2 (11)	C2B—C5B—H5BB	109.5
C1A—N3A—H3AB	117.7 (11)	H5BA—C5B—H5BB	109.5
H3AA—N3A—H3AB	122.0 (16)	H5BC—C5B—H5BB	109.5

O2—C6—C7—C8	12.1 (2)	C3A—N1A—N2A—C1A	−1.2 (2)
O1—C6—C7—C8	−168.01 (14)	N1A—N2A—C1A—N3A	−175.83 (13)
O2—C6—C7—C12	−168.55 (15)	N1A—N2A—C1A—N4A	4.4 (2)
O1—C6—C7—C12	11.4 (2)	C2A—N4A—C1A—N3A	176.54 (14)
C12—C7—C8—C9	−0.2 (2)	C2A—N4A—C1A—N2A	−3.7 (2)
C6—C7—C8—C9	179.15 (15)	C1A—N4A—C2A—C3A	0.2 (2)
C7—C8—C9—C10	−1.2 (3)	C1A—N4A—C2A—C5A	179.96 (14)
C8—C9—C10—C11	0.8 (3)	N2A—N1A—C3A—C2A	−2.3 (2)
C9—C10—C11—C12	1.1 (3)	N2A—N1A—C3A—C4A	178.65 (14)
C13—N5—C12—C11	−16.2 (3)	N4A—C2A—C3A—N1A	2.9 (2)
C13—N5—C12—C7	166.56 (17)	C5A—C2A—C3A—N1A	−176.87 (15)
C10—C11—C12—N5	−179.81 (17)	N4A—C2A—C3A—C4A	−178.16 (15)
C10—C11—C12—C7	−2.5 (3)	C5A—C2A—C3A—C4A	2.1 (2)
C8—C7—C12—N5	179.39 (15)	C3B—N1B—N2B—C1B	0.2 (2)
C6—C7—C12—N5	0.0 (2)	N1B—N2B—C1B—N3B	177.90 (14)
C8—C7—C12—C11	2.0 (2)	N1B—N2B—C1B—N4B	−1.0 (2)
C6—C7—C12—C11	−177.32 (14)	C2B—N4B—C1B—N2B	0.9 (2)
C12—N5—C13—C18	148.89 (19)	C2B—N4B—C1B—N3B	−178.02 (14)
C12—N5—C13—C14	−34.9 (3)	C1B—N4B—C2B—C3B	0.0 (2)
C18—C13—C14—C15	−0.7 (4)	C1B—N4B—C2B—C5B	−179.67 (15)
N5—C13—C14—C15	−176.9 (2)	N2B—N1B—C3B—C2B	0.6 (2)
C13—C14—C15—C16	−0.1 (5)	N2B—N1B—C3B—C4B	−178.99 (13)
C14—C15—C16—C17	0.8 (5)	N4B—C2B—C3B—N1B	−0.7 (2)
C15—C16—C17—C18	−0.8 (5)	C5B—C2B—C3B—N1B	178.95 (15)
C14—C13—C18—C17	0.7 (3)	N4B—C2B—C3B—C4B	178.86 (15)
N5—C13—C18—C17	177.1 (2)	C5B—C2B—C3B—C4B	−1.5 (2)
C16—C17—C18—C13	0.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O1	0.85 (2)	1.92 (2)	2.619 (2)	138 (2)
N2A—H2AA···O1ⁱ	1.02 (2)	1.58 (2)	2.593 (2)	179 (2)
N3A—H3AA···O2ⁱ	0.93 (2)	1.90 (2)	2.834 (2)	175 (2)
N3A—H3AB···N1Bⁱⁱ	0.92 (2)	2.07 (2)	2.986 (2)	172 (2)
N3B—H3BA···N2Bⁱⁱⁱ	0.89 (2)	2.20 (2)	3.089 (2)	179 (2)
N3B—H3BB···O2	0.97 (2)	1.98 (2)	2.915 (2)	163 (2)
C4B—H4BC···N4Aⁱⁱ	0.96	2.52	3.483 (2)	177

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

Acknowledgements

KB thanks the Department of Science and Technology (DST-SERB), New Delhi, India, for financial support (grant No. SB/ FT/CS-058/2013), RS thanks the Department of Science and Technology (DST), New Delhi, India, for financial support in the form of an INSPIRE fellowship (INSPIRE code No. IF131050).

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