Crystal structure of 2,4-di­amino-6-oxo-3,6-di­hydro­pyrimidin-1-ium p-toluene­sulfonate

Mamallan, K.; Tagore, S.S.; Gomathi, S.; Sethuraman, V.

doi:10.1107/S2056989015006787

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages 476-478

https://doi.org/10.1107/S2056989015006787

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Crystal structure of 2,4-diamino-6-oxo-3,6-dihydropyrimidin-1-ium p-toluenesulfonate

Krishnasamy Mamallan,^a Sadasivam Sharmila Tagore,^a Sundaramoorthy Gomathi ^a and Velusamy Sethuraman ^a ^*

^aDepartment of Chemistry, Periyar Maniammai University, Thanjavur 613 403, Tamil Nadu, India
^*Correspondence e-mail: lvsethu13@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 1 April 2015; accepted 4 April 2015; online 11 April 2015)

In the title salt, C₄H₇N₄O⁺·C₇H₇O₃S⁻, the 2,6-diamino-4-oxo-1,3-dihydropyrimidin-1-ium cation interacts with the sulfonate group of the p-toluenesulfonate anion via a pair of N—H⋯O hydrogen bonds, forming a hetero-synthon R₂²(8) that mimics the role of a carboxylate. The self-assembled cations form a homo-synthon R₂¹(6) motif which is further linked with the sulfonate anion via N—H⋯O hydrogen bonds to generate an R₃²(10) ring motif. The three motifs are fused together and extended as supramolecular ribbons along the b-axis direction. Adjacent ribbons are further linked via N—H⋯O hydrogen bonds to form an annulus, with an R₄⁴(20) ring motif, resulting in a tunnel-like arrangement propagating along [010]. There are slipped parallel π–π stacking interactions [inter-centroid distance = 3.6539 (7) Å], between the tunnel-like polymer chains, forming slabs parallel to (100).

Keywords: crystal structure; diaminopyrimidines; triaminopyrimidines; p-toluenesulfonate; hydrogen bonding; N—H⋯O hydrogen bonds; π–π stacking interactions.

CCDC reference: 1057933

1. Chemical context

Di- and tri-aminopyrimidines show various biological and pharmacological properties like tyrosine kinase (Thomas, 1995a ,b ), dihydrofolate reductase inhibitors (Ayer, 1991 ) and are used as antiviral and antiprotozoan agents. 2,6-Diamino-4-hydroxy pyrimidine (DAHP), an inhibitor of guanosine triphosphate cyclohydrolase I, blocks the synthesis of tetrahydrobiopterin which is a known cofactor of inducible nitric oxide synthesis (iNOS) (Bogdan et al., 1995 ). The study of hydrogen-bonding patterns involving sulfonate groups in biological systems and metal complexes are of current interest (Gomathi & Muthiah, 2011 ; Wang, 2006 ). The present report deals with the supramolecular interactions exhibited by the title salt.

2. Structural commentary

The asymmetric unit of the title salt contains one 2,6-diamino-4-oxo-1,3-dihydropyrimidin-1-ium cation and one p-toluene sulfonate anion (Fig. 1). The cation is protonated at the N3 position, which is reflected by the slight increase in the C2—N3—C4 bond angle to 123.2 (1)°. The dihedral angle between the cation and anion ring mean planes is 54.04 (6)°.

Figure 1
A view of the molecular structure of the title molecular salt, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

The three C—S—O angles, C7—S1—O3 [106.83 (7)°], C7—S1—O2 [105.89 (7)°] and C7—S1—O4 [106.91 (7)°], and the O—S—O angles, O3—S1—O2 [110.84 (7)°], O2—S1—O4 [111.93 (7)°] and O3—S1—O4 [113.91 (8)°], indicate that the geometry of the sulfonate group is slightly distorted from an ideal tetrahedral geometry.

3. Supramolecular features

The primary interaction between the cation and anion takes place via a pair of N—H⋯O hydrogen bonds, forming a robust six-membered hetero-synthon, R₂²(8), and here the sulfonate group mimics the role of a carboxylate. This motif links the protonated ring N atom, N3, and the 2-amino N atom, N2, of the cation with the sulfonate atoms O2 and O3 of the anion. Adjacent R₂²(8) ring motifs are connected via an N—H⋯O hydrogen bond by linking the 2-amino N atom, N2 with atom O3ⁱ [symmetry code: x, y + 1, z]. The cation undergoes self-association via a pair of bifurcated N—H⋯(O,O) hydrogen bonds, forming a homo-synthon, R₂¹(6). This motif involves ring N1 and the 6-amino N atoms and carbonyl atom O1ⁱ of the cation (Table 1). The self-assembled cations extend as a supramolecular chain propagating along [010]. The homo- and hetero-synthons [R₂²(8) and R₂¹(6)] are linked by an R₃²(10) ring motif. The three motifs are fused together continuously, forming supramolecular ribbons along [010]. Two such ribbons in adjacent planes are connected via N—H⋯O hydrogen bonds by linking the 6-amino N of the cation and the sulfonate atom O4ⁱⁱ [symmetry code: −x + 1, −y + 1, −z + 1] of the anion, generating an annulus (Su et al., 2007 ) with an R₄⁴(20) graph-set motif (Fig. 2). This motif extends in the direction of the supramolecular ribbons and generates a tunnel-like architecture along the b-axis direction (Figs. 2 and 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	1.86	2.6515 (14)	152
N2—H2A⋯O3	0.86	1.95	2.7935 (17)	166
N2—H2B⋯O2ⁱ	0.86	2.01	2.8669 (16)	175
N3—H3⋯O2	0.86	1.92	2.7689 (14)	169
N6—H6A⋯O4ⁱⁱ	0.86	2.25	2.9498 (18)	139
N6—H6B⋯O1ⁱ	0.86	2.08	2.8201 (15)	143
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z+1.

Figure 2
A view of the supramolecular tunnel-like architecture built by N—H⋯O hydrogen bonds [dashed lines; see Table 1

for details; symmetry codes: (i) x, y + 1, z; (ii) −x + 1, −y + 1, −z + 1], in the crystal structure of the title molecular salt.

Figure 3
A view along the b axis of the crystal packing of the title molecular salt. Hydrogen bonds (see Table 1

for details) and π–π interactions are shown as dashed lines.

Adjacent tunnels interact by off-set aromatic π–π stacking interactions which are observed between symmetry-related pyrimidine rings of the cations with a centroid–centroid distance Cg⋯Cgⁱⁱⁱ of 3.6539 (7) Å [Cg is the centroid of ring N1/C2/N3/C4–C6; the dihedral angle between the ring planes = 1.86 (6)°; perpendicular separation = 3.2501 (5) Å; symmetry code: (iii) −x + 1, y, −z + $[{3\over 2}]$ ]. These interactions result in the formation of slabs parallel to (100); as shown in Fig. 3.

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014 ) revealed the presence of over 700 compounds involving p-toluene sulfonate but only three hits for the 2,6-diamino-4-oxo-1,3-dihydropyrimidin-1-ium cation. These include the sulfate monohydrate (ACEYUD; Muthiah et al., 2004 ), the di(methanesulfanyl)amide (ESAQOE; Wijaya et al., 2004 ) and the chloride dihydrate (SUZFOJ; Suleiman Gwaram et al., 2010 ). In ACEYUD the cation is protonated at the N atom adjacent to the carbonyl group, as in the title compound, while in compounds ESAQOE and SUZFOJ it is the N atom para to the carbonyl group that is protonated. Otherwise, the bond distances in these three compounds are very similar and close to those observed for the title compound.

5. Synthesis and crystallization

A hot methanolic solution (20 ml) of 2,6-diamino-4-hydroxy pyrimidine (31.5 mg, Aldrich) and p-toluene sulfonic acid (43 mg, Loba chemie) was warmed at 323 K for 30 min over a water bath. The mixture was cooled slowly and kept at room temperature and after three weeks light-yellow needle-shaped crystals were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically and refined using a riding model: N—H = 0.86 Å, C—H = 0.93–0.96 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(N,C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₄H₇N₄O⁺·C₇H₇O₃S⁻
M_r	298.33
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	30.8628 (7), 6.5559 (2), 13.1565 (3)
β (°)	96.428 (1)
V (Å³)	2645.27 (12)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.27
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.925, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	14972, 3580, 2986
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.109, 1.06
No. of reflections	3580
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.25
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), PLATON (Spek, 2009 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1057933

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015006787/su5107sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015006787/su5107Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015006787/su5107Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

2,4-Diamino-6-oxo-3,6-dihydropyrimidin-1-ium p-toluenesulfonate top

Crystal data top

C₄H₇N₄O⁺·C₇H₇O₃S⁻	F(000) = 1248
M_r = 298.33	D_x = 1.498 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3580 reflections
a = 30.8628 (7) Å	θ = 2.7–29.3°
b = 6.5559 (2) Å	µ = 0.27 mm⁻¹
c = 13.1565 (3) Å	T = 296 K
β = 96.428 (1)°	Prism, colourless
V = 2645.27 (12) Å³	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	3580 independent reflections
Radiation source: fine-focus sealed tube	2986 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω and φ scan	θ_max = 29.2°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −40→42
T_min = 0.925, T_max = 0.949	k = −9→7
14972 measured reflections	l = −18→16

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0552P)² + 1.4509P] where P = (F_o² + 2F_c²)/3
3580 reflections	(Δ/σ)_max = 0.001
182 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
S1	0.37258 (1)	0.33503 (6)	0.60709 (3)	0.0395 (1)
O2	0.41787 (3)	0.26937 (17)	0.63677 (10)	0.0469 (4)
O3	0.36871 (4)	0.55423 (17)	0.61453 (11)	0.0559 (4)
O4	0.35526 (4)	0.2530 (2)	0.50899 (10)	0.0594 (4)
C7	0.34167 (4)	0.2292 (2)	0.69886 (12)	0.0379 (4)
C8	0.33328 (5)	0.3414 (3)	0.78333 (14)	0.0508 (5)
C9	0.30882 (6)	0.2558 (4)	0.85489 (15)	0.0631 (7)
C10	0.29210 (5)	0.0608 (4)	0.84233 (15)	0.0611 (7)
C11	0.30171 (6)	−0.0499 (3)	0.75883 (16)	0.0595 (6)
C12	0.32634 (5)	0.0315 (3)	0.68668 (14)	0.0477 (5)
C13	0.26346 (7)	−0.0295 (5)	0.9167 (2)	0.0946 (12)
O1	0.52384 (3)	0.28686 (15)	0.61202 (10)	0.0461 (4)
N1	0.50945 (3)	0.88937 (16)	0.62432 (8)	0.0306 (3)
N2	0.43613 (4)	0.84071 (18)	0.63472 (10)	0.0382 (3)
N3	0.48173 (3)	0.56345 (16)	0.62787 (9)	0.0314 (3)
N6	0.58157 (4)	0.95420 (18)	0.60830 (11)	0.0424 (4)
C2	0.47500 (4)	0.76549 (19)	0.62867 (9)	0.0289 (3)
C4	0.52230 (4)	0.4758 (2)	0.61702 (10)	0.0321 (3)
C5	0.55713 (4)	0.6088 (2)	0.61103 (11)	0.0343 (4)
C6	0.55075 (4)	0.8158 (2)	0.61406 (10)	0.0308 (3)
H8	0.34390	0.47360	0.79230	0.0610*
H9	0.30360	0.33110	0.91220	0.0760*
H11	0.29140	−0.18290	0.75060	0.0710*
H12	0.33250	−0.04600	0.63080	0.0570*
H13A	0.23360	0.00590	0.89590	0.1420*
H13B	0.27210	0.02330	0.98400	0.1420*
H13C	0.26650	−0.17530	0.91740	0.1420*
H1	0.50570	1.01900	0.62810	0.0370*
H2A	0.41430	0.76020	0.63830	0.0460*
H2B	0.43230	0.97070	0.63510	0.0460*
H3	0.46010	0.48390	0.63430	0.0380*
H5	0.58480	0.55720	0.60500	0.0410*
H6A	0.60780	0.91650	0.60220	0.0510*
H6B	0.57530	1.08180	0.61070	0.0510*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0285 (2)	0.0340 (2)	0.0570 (2)	−0.0021 (1)	0.0095 (1)	−0.0001 (2)
O2	0.0284 (5)	0.0346 (5)	0.0788 (8)	−0.0014 (4)	0.0105 (5)	0.0016 (5)
O3	0.0434 (6)	0.0332 (6)	0.0928 (10)	0.0018 (5)	0.0154 (6)	0.0087 (6)
O4	0.0459 (6)	0.0783 (9)	0.0554 (7)	−0.0116 (6)	0.0117 (5)	−0.0091 (6)
C7	0.0265 (6)	0.0356 (7)	0.0519 (8)	−0.0021 (5)	0.0053 (5)	0.0004 (6)
C8	0.0409 (8)	0.0524 (10)	0.0600 (10)	−0.0048 (7)	0.0094 (7)	−0.0104 (8)
C9	0.0469 (9)	0.0889 (15)	0.0554 (10)	−0.0014 (10)	0.0140 (8)	−0.0057 (10)
C10	0.0336 (7)	0.0877 (15)	0.0618 (11)	−0.0043 (8)	0.0039 (7)	0.0239 (10)
C11	0.0458 (9)	0.0518 (11)	0.0791 (13)	−0.0138 (8)	−0.0004 (8)	0.0191 (9)
C12	0.0411 (7)	0.0379 (8)	0.0638 (10)	−0.0056 (6)	0.0047 (7)	−0.0005 (7)
C13	0.0533 (11)	0.149 (3)	0.0824 (15)	−0.0176 (14)	0.0114 (10)	0.0509 (16)
O1	0.0415 (5)	0.0209 (5)	0.0767 (8)	0.0010 (4)	0.0104 (5)	0.0001 (5)
N1	0.0338 (5)	0.0190 (5)	0.0395 (6)	−0.0006 (4)	0.0066 (4)	0.0008 (4)
N2	0.0333 (5)	0.0271 (6)	0.0552 (7)	0.0018 (4)	0.0092 (5)	0.0027 (5)
N3	0.0307 (5)	0.0221 (5)	0.0417 (6)	−0.0022 (4)	0.0061 (4)	0.0018 (4)
N6	0.0353 (6)	0.0269 (6)	0.0665 (8)	−0.0041 (5)	0.0126 (6)	−0.0005 (5)
C2	0.0332 (6)	0.0244 (6)	0.0293 (6)	−0.0003 (5)	0.0042 (4)	0.0014 (4)
C4	0.0346 (6)	0.0230 (6)	0.0388 (6)	0.0009 (5)	0.0040 (5)	0.0010 (5)
C5	0.0316 (6)	0.0256 (6)	0.0462 (7)	0.0008 (5)	0.0068 (5)	0.0001 (5)
C6	0.0328 (6)	0.0261 (6)	0.0338 (6)	−0.0020 (5)	0.0055 (5)	0.0008 (5)

Geometric parameters (Å, º) top

S1—O2	1.4728 (10)	C7—C12	1.383 (2)
S1—O3	1.4462 (12)	C7—C8	1.381 (2)
S1—O4	1.4444 (14)	C8—C9	1.389 (3)
S1—C7	1.7628 (15)	C9—C10	1.382 (4)
O1—C4	1.2416 (16)	C10—C13	1.511 (3)
N1—C6	1.3835 (16)	C10—C11	1.376 (3)
N1—C2	1.3442 (16)	C11—C12	1.388 (3)
N2—C2	1.3077 (18)	C8—H8	0.9300
N3—C2	1.3410 (16)	C9—H9	0.9300
N3—C4	1.3994 (16)	C11—H11	0.9300
N6—C6	1.3228 (18)	C12—H12	0.9300
N1—H1	0.8600	C13—H13C	0.9600
N2—H2A	0.8600	C13—H13A	0.9600
N2—H2B	0.8600	C13—H13B	0.9600
N3—H3	0.8600	C4—C5	1.3932 (18)
N6—H6B	0.8600	C5—C6	1.3725 (19)
N6—H6A	0.8600	C5—H5	0.9300

S1···H2A	3.0800	C5···O4ⁱⁱ	3.4031 (18)
S1···H2Bⁱ	3.0100	C6···N2^v	3.2886 (19)
S1···H3	2.8600	C6···O1^iv	3.1973 (16)
O1···C6ⁱ	3.1973 (16)	C6···C2^v	3.5776 (18)
O1···N1ⁱ	2.6515 (14)	C13···O4^vi	3.298 (3)
O1···N6ⁱ	2.8201 (15)	C4···H1ⁱ	3.0400
O1···C2ⁱⁱ	3.1894 (18)	C4···H6Bⁱ	3.0600
O2···N3	2.7689 (14)	C7···H13A^vii	3.1000
O2···N2ⁱ	2.8669 (16)	C12···H13Bⁱⁱⁱ	3.0100
O3···N2	2.7935 (17)	H1···H2B	2.3000
O4···C5ⁱⁱ	3.4031 (18)	H1···H6B	2.2200
O4···N6ⁱⁱ	2.9498 (18)	H1···C4^iv	3.0400
O4···C13ⁱⁱⁱ	3.298 (3)	H1···O1^iv	1.8600
O1···H6Bⁱ	2.0800	H2A···H3	2.3000
O1···H1ⁱ	1.8600	H2A···S1	3.0800
O2···H3	1.9200	H2A···O3	1.9500
O2···H2Bⁱ	2.0100	H2B···H1	2.3000
O3···H12^iv	2.8700	H2B···S1^iv	3.0100
O3···H3	2.8400	H2B···O2^iv	2.0100
O3···H8	2.6000	H3···S1	2.8600
O3···H2A	1.9500	H3···H2A	2.3000
O4···H5ⁱⁱ	2.8000	H3···O2	1.9200
O4···H13Cⁱⁱⁱ	2.9100	H3···O3	2.8400
O4···H6Aⁱⁱ	2.2500	H5···O4ⁱⁱ	2.8000
O4···H12	2.6800	H5···H8^v	2.5100
N1···O1^iv	2.6515 (14)	H5···H6A	2.4600
N1···C2^v	3.3319 (16)	H6A···O4ⁱⁱ	2.2500
N2···O3	2.7935 (17)	H6A···H5	2.4600
N2···O2^iv	2.8669 (16)	H6B···C4^iv	3.0600
N2···C6^v	3.2886 (19)	H6B···H1	2.2200
N3···C5ⁱⁱ	3.4276 (18)	H6B···O1^iv	2.0800
N3···O2	2.7689 (14)	H8···H5^v	2.5100
N3···N3^v	3.2844 (17)	H8···O3	2.6000
N3···C4^v	3.4212 (18)	H9···H13B	2.4700
N3···C4ⁱⁱ	3.2207 (18)	H11···H13C	2.4100
N6···O1^iv	2.8201 (15)	H12···O4	2.6800
N6···O4ⁱⁱ	2.9498 (18)	H12···H13Bⁱⁱⁱ	2.5300
C2···N1^v	3.3319 (16)	H12···O3ⁱ	2.8700
C2···C2^v	3.3868 (17)	H13A···C7^viii	3.1000
C2···C6^v	3.5776 (18)	H13B···H9	2.4700
C2···O1ⁱⁱ	3.1894 (18)	H13B···C12^vi	3.0100
C4···N3ⁱⁱ	3.2207 (18)	H13B···H12^vi	2.5300
C4···C4ⁱⁱ	3.2446 (18)	H13C···H11	2.4100
C4···N3^v	3.4212 (18)	H13C···O4^vi	2.9100
C5···N3ⁱⁱ	3.4276 (18)

O2—S1—O3	110.84 (7)	C7—C12—C11	119.19 (17)
O2—S1—O4	111.93 (7)	C9—C8—H8	120.00
O2—S1—C7	105.89 (7)	C7—C8—H8	120.00
O3—S1—O4	113.91 (8)	C10—C9—H9	119.00
O3—S1—C7	106.83 (7)	C8—C9—H9	119.00
O4—S1—C7	106.91 (7)	C10—C11—H11	119.00
C2—N1—C6	122.36 (11)	C12—C11—H11	119.00
C2—N3—C4	123.20 (10)	C11—C12—H12	120.00
C6—N1—H1	119.00	C7—C12—H12	120.00
C2—N1—H1	119.00	C10—C13—H13C	109.00
C2—N2—H2B	120.00	H13B—C13—H13C	109.00
H2A—N2—H2B	120.00	C10—C13—H13A	109.00
C2—N2—H2A	120.00	C10—C13—H13B	109.00
C4—N3—H3	118.00	H13A—C13—H13C	109.00
C2—N3—H3	118.00	H13A—C13—H13B	110.00
C6—N6—H6A	120.00	N1—C2—N3	118.20 (11)
H6A—N6—H6B	120.00	N1—C2—N2	120.67 (12)
C6—N6—H6B	120.00	N2—C2—N3	121.13 (11)
S1—C7—C12	119.60 (12)	N3—C4—C5	116.98 (11)
C8—C7—C12	119.99 (15)	O1—C4—C5	125.95 (12)
S1—C7—C8	120.41 (11)	O1—C4—N3	117.07 (11)
C7—C8—C9	119.68 (18)	C4—C5—C6	120.20 (12)
C8—C9—C10	121.11 (19)	N1—C6—N6	116.28 (12)
C11—C10—C13	120.3 (2)	N1—C6—C5	118.97 (11)
C9—C10—C13	121.5 (2)	N6—C6—C5	124.76 (12)
C9—C10—C11	118.19 (18)	C4—C5—H5	120.00
C10—C11—C12	121.79 (19)	C6—C5—H5	120.00

O2—S1—C7—C8	94.26 (13)	S1—C7—C12—C11	−179.44 (13)
O2—S1—C7—C12	−84.77 (13)	S1—C7—C8—C9	179.93 (13)
O3—S1—C7—C8	−23.93 (14)	C12—C7—C8—C9	−1.0 (2)
O3—S1—C7—C12	157.04 (12)	C8—C7—C12—C11	1.5 (2)
O4—S1—C7—C8	−146.24 (13)	C7—C8—C9—C10	−1.0 (3)
O4—S1—C7—C12	34.72 (14)	C8—C9—C10—C13	−176.68 (19)
C6—N1—C2—N2	−177.54 (12)	C8—C9—C10—C11	2.4 (3)
C6—N1—C2—N3	3.24 (18)	C13—C10—C11—C12	177.18 (19)
C2—N1—C6—N6	178.45 (12)	C9—C10—C11—C12	−2.0 (3)
C2—N1—C6—C5	−1.84 (19)	C10—C11—C12—C7	0.0 (3)
C2—N3—C4—O1	−176.29 (13)	O1—C4—C5—C6	177.72 (14)
C2—N3—C4—C5	2.62 (19)	N3—C4—C5—C6	−1.1 (2)
C4—N3—C2—N2	177.12 (12)	C4—C5—C6—N6	−179.57 (14)
C4—N3—C2—N1	−3.67 (18)	C4—C5—C6—N1	0.8 (2)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) x, −y, z−1/2; (iv) x, y+1, z; (v) −x+1, y, −z+3/2; (vi) x, −y, z+1/2; (vii) −x+1/2, y+1/2, −z+3/2; (viii) −x+1/2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^iv	0.86	1.86	2.6515 (14)	152
N2—H2A···O3	0.86	1.95	2.7935 (17)	166
N2—H2B···O2^iv	0.86	2.01	2.8669 (16)	175
N3—H3···O2	0.86	1.92	2.7689 (14)	169
N6—H6A···O4ⁱⁱ	0.86	2.25	2.9498 (18)	139
N6—H6B···O1^iv	0.86	2.08	2.8201 (15)	143

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

Acknowledgements

The authors thank Dr Babu Varghese and the Sophisticated Analytical Instrument Facility (SAIF), Indian Institute of Technology, Chennai, Tamil Nadu, India, for the data collection.

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