4-[3-(Phen­oxy­meth­yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thia­diazin-6-yl]-3-(p-tol­yl)sydnone

Goh, J.H.; Fun, H.-K.; Nithinchandra; Kalluraya, B.

doi:10.1107/S1600536810029910

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages o2178-o2179

https://doi.org/10.1107/S1600536810029910

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4-[3-(Phenoxymethyl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazin-6-yl]-3-(p-tolyl)sydnone

Jia Hao Goh,^a ‡ Hoong-Kun Fun,^a ^*§ Nithinchandra ^b and B. Kalluraya ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 21 July 2010; accepted 27 July 2010; online 31 July 2010)

In the title triazolothiadiazine derivative, C₂₀H₁₆N₆O₃S {systematic name: 3-(4-methylphenyl)-4-[3-(phenoxymethyl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazin-6-yl]-1,2,3-oxadiazol-3-ium-5-olate}, an S(6) ring motif is generated by an intramolecular C—H⋯O hydrogen bond. The 3,6-dihydro-1,3,4-thiadiazine ring adopts a twist-boat conformation. The dihedral angle between the 1,2,3-oxadiazole and 1,2,4-triazole rings is 46.45 (14)°. The 1,2,3-oxadiazole ring is inclined at dihedral angle of 59.49 (13)° with respect to the benzene ring attached to it. In the crystal structure, intermolecular C—H⋯O and C—H⋯N hydrogen bonds link neighbouring molecules into two-molecule-thick arrays parallel to the bc plane. A short S⋯O interaction [2.9565 (19) Å] also occurs.

Related literature

For general background to and applications of materials related to the title compound, see: Kalluraya & Rahiman (1997 ); Newton & Ramsden (1982 ); Wagner & Hill (1974 ). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ). For closely related structures, see: Goh et al. (2010a ,b ,c ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₀H₁₆N₆O₃S
M_r = 420.45
Monoclinic, P 2₁ /c
a = 20.6555 (7) Å
b = 8.1918 (3) Å
c = 11.1979 (4) Å
β = 96.127 (2)°
V = 1883.93 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.26 × 0.13 × 0.07 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.947, T_max = 0.985
17653 measured reflections
4318 independent reflections
2829 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.133
S = 1.03
4318 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O3	0.97	2.26	3.026 (3)	135
C10—H10A⋯O3ⁱ	0.97	2.55	3.165 (3)	122
C10—H10B⋯O3ⁱⁱ	0.97	2.44	3.279 (3)	145
C19—H19A⋯N5ⁱⁱⁱ	0.93	2.61	3.491 (3)	158
Symmetry codes: (i) -x, -y, -z+1; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810029910/hb5566sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029910/hb5566Isup2.hkl

checkCIF report

Comment top

Sydnones are a novel class of mesoionic compounds consisting of 1,2,3-oxadiazole ring system. A number of sydnone derivatives have shown diverse biological activities such as anti-inflammatory, analgesic and anti-arthritic (Newton & Ramsden, 1982; Wagner & Hill, 1974) properties. Sydnones possessing heterocyclic moieties at the 4-position are also known for a wide range of biological properties (Kalluraya & Rahiman, 1997). Encouraged by these reports and in continuation of our research for biologically active nitrogen containing heterocycles, a triazolothiadiazine moiety at the 4-position of the phenylsydnone was introduced.

In the title triazolothiadiazine derivative, an intramolecular C10—H10A···O3 hydrogen bond (Table 1) generates a six-membered ring, producing an S(6) hydrogen bond ring motif (Fig. 1, Bernstein et al., 1995). The 3,6-dihydro-1,3,4-thiadiazine ring (C9-C11/N3/N4/S1) adopts twist-boat conformation, with puckering parameters of Q = 0.634 (2) Å, θ = 67.08 (18)° and φ = 322.1 (2)° (Cremer & Pople, 1975). The dihedral angle formed between these essentially planar 1,2,3-oxadiazole (C12/C13/O2/N5/N6) and 1,2,4-triazole (C8/N1/N2/C9/N3) rings is 46.45 (14)°. The C1-C6 and C14-C19 phenyl rings are inclined at dihedral angles of 77.56 (14) and 59.49 (13)°, respectively, with respect to 1,2,3-oxadiazole and 1,2,4-triazole rings. The geometric parameters are consistent to those observed in closely related structures (Goh et al., 2010a,b,c).

In the crystal structure, intermolecular C10—H10A···O3, C10—H10B···O3 and C19—H19A···N5 hydrogen bonds (Table 1) interconnect neighbouring molecules into two-molecule-thick arrays parallel to the bc plane (Fig. 2). The interesting feature of the crystal structure is the intermolecular short S1···O3 interaction [2.9565 (19) Å; symmetry code: -x, -y, -z+1], which is significantly shorter than the sum of Van der Waals radii of the relevant atoms, further stabilizing the crystal structure.

Related literature top

For general background to and applications of materials related to the title compound, see: Kalluraya & Rahiman (1997); Newton & Ramsden (1982); Wagner & Hill (1974). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995). For closely related structures, see: Goh et al. (2010a,b,c). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

A solution of triazole (0.01 mol) and 4-bromoacetyl-3-tolylsydnone (0.01 mol) in absolute ethanol (20 ml) was heated under reflux for 10–12 h. The solution was concentrated, cooled to room temperature and neutrallized with 10 % sodium bicarbonate solution. The solid separated was filtered, washed with water, dried and recrystallized from ethanol. Colourless blocks of (I) were obtained from a 1:2 mixture of DMF and ethanol by slow evaporation.

Structure description top

For general background to and applications of materials related to the title compound, see: Kalluraya & Rahiman (1997); Newton & Ramsden (1982); Wagner & Hill (1974). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995). For closely related structures, see: Goh et al. (2010a,b,c). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For puckering parameters, see: Cremer & Pople (1975).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids for non-H atoms. An intramolecular hydrogen bond is shown as dashed line.
	Fig. 2. The crystal structure of (I), viewed along the b axis, showing two-molecule-thick arrays parallel to the bc plane. Hydrogen atoms not involved in intermolecular interactions (dashed lines) have been omitted for clarity.

3-(4-methylphenyl)-4-[3-(phenoxymethyl)-7H-1,2,4- triazolo[3,4-b][1,3,4]thiadiazin-6-yl]-1,2,3-oxadiazol-3-ium-5-olate top

Crystal data top

C₂₀H₁₆N₆O₃S	F(000) = 872
M_r = 420.45	D_x = 1.482 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4257 reflections
a = 20.6555 (7) Å	θ = 2.7–30.6°
b = 8.1918 (3) Å	µ = 0.21 mm⁻¹
c = 11.1979 (4) Å	T = 100 K
β = 96.127 (2)°	Block, colourless
V = 1883.93 (12) Å³	0.26 × 0.13 × 0.07 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	4318 independent reflections
Radiation source: fine-focus sealed tube	2829 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
φ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −26→26
T_min = 0.947, T_max = 0.985	k = −10→10
17653 measured reflections	l = −14→14

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.060P)² + 0.4167P] where P = (F_o² + 2F_c²)/3
4318 reflections	(Δ/σ)_max = 0.003
272 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

C₂₀H₁₆N₆O₃S	V = 1883.93 (12) Å³
M_r = 420.45	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 20.6555 (7) Å	µ = 0.21 mm⁻¹
b = 8.1918 (3) Å	T = 100 K
c = 11.1979 (4) Å	0.26 × 0.13 × 0.07 mm
β = 96.127 (2)°

Data collection top

Bruker SMART APEXII CCD diffractometer	4318 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2829 reflections with I > 2σ(I)
T_min = 0.947, T_max = 0.985	R_int = 0.065
17653 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.03	Δρ_max = 0.67 e Å⁻³
4318 reflections	Δρ_min = −0.53 e Å⁻³
272 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

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
S1	0.06014 (3)	0.33229 (8)	0.37690 (6)	0.01451 (18)
O1	0.28045 (8)	0.2544 (2)	0.08679 (15)	0.0183 (5)
O2	0.10735 (9)	−0.3314 (2)	0.48621 (15)	0.0174 (4)
O3	0.01271 (9)	−0.1961 (2)	0.43267 (15)	0.0168 (4)
N1	0.16326 (10)	0.4933 (3)	0.13016 (18)	0.0159 (5)
N2	0.12096 (10)	0.5222 (3)	0.21876 (19)	0.0159 (5)
N3	0.14032 (10)	0.2588 (3)	0.20962 (18)	0.0119 (5)
N4	0.15133 (10)	0.0982 (3)	0.24765 (18)	0.0134 (5)
N5	0.17122 (11)	−0.3211 (3)	0.46629 (19)	0.0167 (5)
N6	0.17491 (10)	−0.1933 (3)	0.39705 (18)	0.0130 (5)
C1	0.38786 (14)	0.2084 (4)	0.0490 (2)	0.0226 (7)
H1A	0.4012	0.2624	0.1204	0.027*
C2	0.43384 (14)	0.1464 (4)	−0.0207 (3)	0.0282 (8)
H2A	0.4779	0.1602	0.0040	0.034*
C3	0.41449 (14)	0.0641 (4)	−0.1269 (3)	0.0263 (7)
H3A	0.4453	0.0212	−0.1730	0.032*
C4	0.34920 (14)	0.0469 (4)	−0.1629 (3)	0.0235 (7)
H4A	0.3361	−0.0070	−0.2345	0.028*
C5	0.30230 (14)	0.1081 (4)	−0.0949 (2)	0.0194 (7)
H5A	0.2583	0.0949	−0.1202	0.023*
C6	0.32231 (13)	0.1897 (3)	0.0121 (2)	0.0168 (6)
C7	0.21295 (12)	0.2477 (3)	0.0432 (2)	0.0149 (6)
H7A	0.1988	0.1348	0.0363	0.018*
H7B	0.2060	0.2974	−0.0357	0.018*
C8	0.17459 (12)	0.3361 (3)	0.1279 (2)	0.0142 (6)
C9	0.10811 (12)	0.3793 (3)	0.2631 (2)	0.0123 (6)
C10	0.04330 (12)	0.1268 (3)	0.3200 (2)	0.0148 (6)
H10A	0.0185	0.0674	0.3746	0.018*
H10B	0.0175	0.1323	0.2424	0.018*
C11	0.10610 (12)	0.0393 (3)	0.3078 (2)	0.0125 (6)
C12	0.11699 (12)	−0.1155 (3)	0.3677 (2)	0.0123 (6)
C13	0.07074 (14)	−0.2057 (3)	0.4260 (2)	0.0143 (6)
C14	0.24014 (12)	−0.1537 (3)	0.3708 (2)	0.0137 (6)
C15	0.28634 (13)	−0.1262 (3)	0.4668 (2)	0.0182 (6)
H15A	0.2749	−0.1266	0.5449	0.022*
C16	0.35008 (14)	−0.0980 (4)	0.4450 (3)	0.0228 (7)
H16A	0.3817	−0.0798	0.5092	0.027*
C17	0.36760 (14)	−0.0964 (4)	0.3281 (3)	0.0213 (7)
C18	0.31939 (13)	−0.1232 (3)	0.2334 (2)	0.0206 (7)
H18A	0.3305	−0.1209	0.1551	0.025*
C19	0.25567 (13)	−0.1529 (3)	0.2528 (2)	0.0178 (6)
H19A	0.2240	−0.1718	0.1889	0.021*
C20	0.43702 (14)	−0.0674 (4)	0.3043 (3)	0.0351 (8)
H20D	0.4422	−0.0966	0.2229	0.053*
H20A	0.4655	−0.1330	0.3581	0.053*
H20B	0.4476	0.0458	0.3169	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0213 (4)	0.0098 (4)	0.0135 (3)	0.0003 (3)	0.0064 (2)	0.0003 (3)
O1	0.0180 (10)	0.0225 (12)	0.0146 (9)	0.0027 (9)	0.0028 (7)	−0.0026 (9)
O2	0.0265 (11)	0.0118 (11)	0.0144 (9)	0.0002 (9)	0.0041 (8)	0.0034 (9)
O3	0.0196 (10)	0.0162 (11)	0.0150 (9)	−0.0027 (9)	0.0040 (7)	0.0016 (9)
N1	0.0233 (13)	0.0158 (14)	0.0094 (10)	−0.0014 (11)	0.0052 (9)	0.0023 (11)
N2	0.0229 (13)	0.0122 (13)	0.0130 (11)	0.0001 (11)	0.0039 (9)	0.0019 (11)
N3	0.0174 (12)	0.0089 (12)	0.0105 (10)	−0.0002 (10)	0.0059 (9)	0.0032 (10)
N4	0.0242 (13)	0.0075 (12)	0.0084 (10)	0.0003 (10)	0.0017 (9)	0.0002 (10)
N5	0.0247 (13)	0.0109 (13)	0.0148 (11)	−0.0014 (11)	0.0039 (9)	−0.0016 (11)
N6	0.0238 (12)	0.0072 (12)	0.0079 (10)	−0.0003 (10)	0.0015 (9)	−0.0003 (10)
C1	0.0280 (16)	0.0200 (17)	0.0193 (14)	0.0012 (14)	0.0003 (12)	−0.0037 (14)
C2	0.0205 (16)	0.030 (2)	0.0342 (17)	0.0029 (14)	0.0025 (13)	0.0007 (17)
C3	0.0305 (18)	0.0229 (18)	0.0278 (16)	0.0045 (15)	0.0143 (13)	0.0008 (15)
C4	0.0322 (17)	0.0199 (17)	0.0193 (14)	0.0023 (15)	0.0079 (12)	−0.0012 (14)
C5	0.0237 (15)	0.0181 (17)	0.0169 (14)	−0.0030 (13)	0.0040 (11)	0.0005 (14)
C6	0.0217 (15)	0.0133 (16)	0.0161 (13)	0.0035 (13)	0.0058 (11)	0.0055 (13)
C7	0.0207 (14)	0.0135 (16)	0.0109 (12)	0.0000 (12)	0.0039 (10)	0.0030 (12)
C8	0.0195 (14)	0.0126 (15)	0.0107 (12)	−0.0032 (13)	0.0015 (10)	0.0031 (13)
C9	0.0167 (14)	0.0087 (15)	0.0117 (12)	−0.0004 (12)	0.0020 (10)	−0.0001 (12)
C10	0.0205 (14)	0.0086 (15)	0.0156 (13)	−0.0019 (12)	0.0025 (11)	0.0021 (12)
C11	0.0177 (14)	0.0122 (15)	0.0074 (12)	−0.0003 (12)	0.0009 (10)	−0.0039 (12)
C12	0.0164 (14)	0.0105 (15)	0.0103 (12)	0.0006 (12)	0.0028 (10)	−0.0036 (12)
C13	0.0304 (16)	0.0058 (15)	0.0070 (12)	0.0004 (13)	0.0035 (11)	−0.0005 (12)
C14	0.0172 (14)	0.0087 (15)	0.0154 (13)	0.0023 (12)	0.0023 (10)	−0.0015 (13)
C15	0.0287 (16)	0.0152 (16)	0.0111 (12)	0.0022 (13)	0.0040 (11)	0.0014 (13)
C16	0.0243 (16)	0.0198 (17)	0.0236 (15)	0.0013 (14)	−0.0002 (12)	−0.0005 (15)
C17	0.0239 (16)	0.0148 (16)	0.0265 (16)	0.0010 (13)	0.0083 (12)	0.0040 (14)
C18	0.0293 (16)	0.0177 (17)	0.0164 (13)	0.0048 (14)	0.0097 (12)	0.0033 (13)
C19	0.0291 (16)	0.0108 (16)	0.0134 (13)	0.0039 (13)	0.0023 (11)	0.0005 (13)
C20	0.0268 (17)	0.043 (2)	0.0368 (19)	−0.0018 (17)	0.0080 (14)	0.0098 (18)

Geometric parameters (Å, º) top

S1—C9	1.739 (3)	C4—H4A	0.9300
S1—C10	1.820 (3)	C5—C6	1.395 (4)
O1—C6	1.372 (3)	C5—H5A	0.9300
O1—C7	1.428 (3)	C7—C8	1.487 (4)
O2—N5	1.364 (3)	C7—H7A	0.9700
O2—C13	1.406 (3)	C7—H7B	0.9700
O3—C13	1.212 (3)	C10—C11	1.501 (4)
N1—C8	1.310 (3)	C10—H10A	0.9700
N1—N2	1.410 (3)	C10—H10B	0.9700
N2—C9	1.310 (3)	C11—C12	1.441 (4)
N3—C9	1.364 (3)	C12—C13	1.420 (4)
N3—C8	1.371 (3)	C14—C15	1.378 (4)
N3—N4	1.395 (3)	C14—C19	1.393 (3)
N4—C11	1.301 (3)	C15—C16	1.384 (4)
N5—N6	1.310 (3)	C15—H15A	0.9300
N6—C12	1.364 (3)	C16—C17	1.395 (4)
N6—C14	1.446 (3)	C16—H16A	0.9300
C1—C6	1.381 (4)	C17—C18	1.392 (4)
C1—C2	1.388 (4)	C17—C20	1.505 (4)
C1—H1A	0.9300	C18—C19	1.378 (4)
C2—C3	1.389 (4)	C18—H18A	0.9300
C2—H2A	0.9300	C19—H19A	0.9300
C3—C4	1.373 (4)	C20—H20D	0.9600
C3—H3A	0.9300	C20—H20A	0.9600
C4—C5	1.389 (4)	C20—H20B	0.9600

C9—S1—C10	92.89 (12)	N2—C9—S1	129.0 (2)
C6—O1—C7	115.64 (19)	N3—C9—S1	120.3 (2)
N5—O2—C13	110.89 (19)	C11—C10—S1	109.82 (18)
C8—N1—N2	107.7 (2)	C11—C10—H10A	109.7
C9—N2—N1	106.4 (2)	S1—C10—H10A	109.7
C9—N3—C8	105.7 (2)	C11—C10—H10B	109.7
C9—N3—N4	128.3 (2)	S1—C10—H10B	109.7
C8—N3—N4	124.1 (2)	H10A—C10—H10B	108.2
C11—N4—N3	113.9 (2)	N4—C11—C12	118.8 (2)
N6—N5—O2	105.33 (19)	N4—C11—C10	123.0 (2)
N5—N6—C12	114.3 (2)	C12—C11—C10	118.1 (2)
N5—N6—C14	114.4 (2)	N6—C12—C13	105.2 (2)
C12—N6—C14	131.2 (2)	N6—C12—C11	127.8 (2)
C6—C1—C2	120.0 (3)	C13—C12—C11	126.3 (2)
C6—C1—H1A	120.0	O3—C13—O2	120.2 (2)
C2—C1—H1A	120.0	O3—C13—C12	135.5 (3)
C1—C2—C3	120.5 (3)	O2—C13—C12	104.3 (2)
C1—C2—H2A	119.8	C15—C14—C19	121.9 (2)
C3—C2—H2A	119.8	C15—C14—N6	117.5 (2)
C4—C3—C2	119.0 (3)	C19—C14—N6	120.5 (2)
C4—C3—H3A	120.5	C14—C15—C16	118.8 (2)
C2—C3—H3A	120.5	C14—C15—H15A	120.6
C3—C4—C5	121.5 (3)	C16—C15—H15A	120.6
C3—C4—H4A	119.2	C15—C16—C17	120.9 (3)
C5—C4—H4A	119.2	C15—C16—H16A	119.5
C4—C5—C6	119.0 (3)	C17—C16—H16A	119.5
C4—C5—H5A	120.5	C18—C17—C16	118.5 (3)
C6—C5—H5A	120.5	C18—C17—C20	120.6 (3)
O1—C6—C1	115.9 (2)	C16—C17—C20	121.0 (3)
O1—C6—C5	124.1 (2)	C19—C18—C17	121.7 (2)
C1—C6—C5	120.0 (3)	C19—C18—H18A	119.1
O1—C7—C8	109.3 (2)	C17—C18—H18A	119.1
O1—C7—H7A	109.8	C18—C19—C14	118.1 (2)
C8—C7—H7A	109.8	C18—C19—H19A	121.0
O1—C7—H7B	109.8	C14—C19—H19A	121.0
C8—C7—H7B	109.8	C17—C20—H20D	109.5
H7A—C7—H7B	108.3	C17—C20—H20A	109.5
N1—C8—N3	109.6 (2)	H20D—C20—H20A	109.5
N1—C8—C7	126.9 (2)	C17—C20—H20B	109.5
N3—C8—C7	123.3 (2)	H20D—C20—H20B	109.5
N2—C9—N3	110.6 (2)	H20A—C20—H20B	109.5

C8—N1—N2—C9	−1.4 (3)	C9—S1—C10—C11	54.65 (19)
C9—N3—N4—C11	30.0 (3)	N3—N4—C11—C12	−170.4 (2)
C8—N3—N4—C11	−167.9 (2)	N3—N4—C11—C10	8.3 (3)
C13—O2—N5—N6	0.5 (2)	S1—C10—C11—N4	−53.7 (3)
O2—N5—N6—C12	−0.3 (3)	S1—C10—C11—C12	125.0 (2)
O2—N5—N6—C14	176.24 (18)	N5—N6—C12—C13	0.1 (3)
C6—C1—C2—C3	−0.6 (5)	C14—N6—C12—C13	−175.8 (2)
C1—C2—C3—C4	0.9 (5)	N5—N6—C12—C11	170.7 (2)
C2—C3—C4—C5	−0.8 (4)	C14—N6—C12—C11	−5.2 (4)
C3—C4—C5—C6	0.4 (4)	N4—C11—C12—N6	18.5 (4)
C7—O1—C6—C1	174.7 (2)	C10—C11—C12—N6	−160.3 (2)
C7—O1—C6—C5	−5.8 (4)	N4—C11—C12—C13	−172.8 (2)
C2—C1—C6—O1	179.8 (3)	C10—C11—C12—C13	8.4 (4)
C2—C1—C6—C5	0.2 (4)	N5—O2—C13—O3	179.4 (2)
C4—C5—C6—O1	−179.7 (3)	N5—O2—C13—C12	−0.4 (2)
C4—C5—C6—C1	−0.1 (4)	N6—C12—C13—O3	−179.6 (3)
C6—O1—C7—C8	−174.6 (2)	C11—C12—C13—O3	9.6 (5)
N2—N1—C8—N3	1.3 (3)	N6—C12—C13—O2	0.2 (3)
N2—N1—C8—C7	175.7 (2)	C11—C12—C13—O2	−170.6 (2)
C9—N3—C8—N1	−0.8 (3)	N5—N6—C14—C15	−56.8 (3)
N4—N3—C8—N1	−166.3 (2)	C12—N6—C14—C15	119.1 (3)
C9—N3—C8—C7	−175.4 (2)	N5—N6—C14—C19	119.8 (3)
N4—N3—C8—C7	19.1 (4)	C12—N6—C14—C19	−64.4 (4)
O1—C7—C8—N1	84.4 (3)	C19—C14—C15—C16	−0.4 (4)
O1—C7—C8—N3	−101.9 (3)	N6—C14—C15—C16	176.1 (2)
N1—N2—C9—N3	0.8 (3)	C14—C15—C16—C17	0.3 (4)
N1—N2—C9—S1	178.78 (18)	C15—C16—C17—C18	0.3 (4)
C8—N3—C9—N2	−0.1 (3)	C15—C16—C17—C20	−179.4 (3)
N4—N3—C9—N2	164.6 (2)	C16—C17—C18—C19	−0.9 (4)
C8—N3—C9—S1	−178.20 (18)	C20—C17—C18—C19	178.8 (3)
N4—N3—C9—S1	−13.6 (3)	C17—C18—C19—C14	0.8 (4)
C10—S1—C9—N2	154.7 (2)	C15—C14—C19—C18	−0.1 (4)
C10—S1—C9—N3	−27.6 (2)	N6—C14—C19—C18	−176.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O3	0.97	2.26	3.026 (3)	135
C10—H10A···O3ⁱ	0.97	2.55	3.165 (3)	122
C10—H10B···O3ⁱⁱ	0.97	2.44	3.279 (3)	145
C19—H19A···N5ⁱⁱⁱ	0.93	2.61	3.491 (3)	158

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

Experimental details

Crystal data
Chemical formula	C₂₀H₁₆N₆O₃S
M_r	420.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	20.6555 (7), 8.1918 (3), 11.1979 (4)
β (°)	96.127 (2)
V (Å³)	1883.93 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.26 × 0.13 × 0.07

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.947, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	17653, 4318, 2829
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.133, 1.03
No. of reflections	4318
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.53

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O3	0.97	2.26	3.026 (3)	135
C10—H10A···O3ⁱ	0.97	2.55	3.165 (3)	122
C10—H10B···O3ⁱⁱ	0.97	2.44	3.279 (3)	145
C19—H19A···N5ⁱⁱⁱ	0.93	2.61	3.491 (3)	158

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

Footnotes

‡Thomson Reuters ResearcherID: C-7576-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors thank Universiti Sains Malaysia (USM) for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

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