3-(p-Tol-yl)-4-{3-[(phenyl-amino)-meth-yl]-7H-[1,2,4]triazolo[3,4-b][1,3,4]thia-diazin-6-yl}sydnone.

In the title compound, C(20)H(17)N(7)O(2)S (systematic name: 3-(4-methyl-phen-yl)-4-{3-[(phenyl-amino)-meth-yl]-7H-1,2,4-triazolo[3,4-b][1,3,4]thia-diazin-6-yl}-1,2,3-oxadiazol-3-ium-5-olate), the 3,6-dihydro-2H-1,3,4-thia-diazine ring adopts a half-boat conformation. The oxadiazol-3-ium ring makes dihedral angles of 57.99 (6) and 54.48 (6)° with the phenyl and benzene rings, respectively, while the 1,2,4-triazole ring forms corresponding angles of 37.35 (6) and 73.89 (6)°. The dihedral angle between the oxadiazol-3-ium and 1,2,4-triazole rings is 21.12 (6)°. In the crystal, the mol-ecules are linked via inter-molecular N-H⋯O and C-H⋯N hydrogen bonds into a layer parallel to the (100) plane. The crystal structure is further consolidated by C-H⋯π inter-actions. An intra-molecular C-H⋯O hydrogen bond is also observed, which generates an S(6) ring motif.

Related literature

For general background to and the biological activity of sydnone derivatives, see: Rai et al. (2008 ▶); Kalluraya et al. (2002 ▶); Hedge et al. (2008 ▶). For general background to and the biological activity of triazolothia­diazine derivatives, see: Kalluraya & Rahiman (1997 ▶). For the synthesis of triazolothia­diazines, see: Kalluraya et al. (2003 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C20H17N7O2S

M = 419.47

Monoclinic,

a = 10.1210 (4) Å

b = 10.5065 (4) Å

c = 19.6370 (6) Å

β = 114.550 (2)°

V = 1899.36 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 100 K

0.35 × 0.28 × 0.27 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.932, T max = 0.947

22363 measured reflections

6845 independent reflections

5754 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.109

S = 1.06

6845 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.25 e Å−3

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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010786/is2692sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010786/is2692Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C20H17N7O2S	F(000) = 872
Mr = 419.47	Dx = 1.467 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8225 reflections
a = 10.1210 (4) Å	θ = 2.8–32.5°
b = 10.5065 (4) Å	µ = 0.21 mm−1
c = 19.6370 (6) Å	T = 100 K
β = 114.550 (2)°	Block, orange
V = 1899.36 (12) Å3	0.35 × 0.28 × 0.27 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	6845 independent reflections
Radiation source: fine-focus sealed tube	5754 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 32.6°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→15
Tmin = 0.932, Tmax = 0.947	k = −15→15
22363 measured reflections	l = −29→29

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0589P)2 + 0.4436P] where P = (Fo2 + 2Fc2)/3
6845 reflections	(Δ/σ)max = 0.002
272 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems 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.

	x	y	z	Uiso*/Ueq
S1	0.76994 (3)	0.59534 (2)	1.086823 (13)	0.01634 (7)
O1	0.29144 (9)	0.96219 (7)	1.00427 (4)	0.01957 (15)
O2	0.51181 (10)	0.92364 (7)	1.10036 (4)	0.02034 (16)
N1	0.39442 (11)	0.30819 (8)	0.79980 (5)	0.01940 (18)
H1	0.4424	0.2500	0.8313	0.023*
N2	0.66867 (10)	0.35357 (8)	0.92354 (5)	0.01599 (16)
N3	0.76192 (10)	0.39417 (8)	0.99600 (5)	0.01605 (16)
N4	0.59144 (9)	0.53924 (8)	0.94311 (4)	0.01301 (15)
N5	0.49010 (9)	0.63271 (8)	0.93523 (4)	0.01330 (15)
N6	0.29928 (10)	0.84348 (8)	0.91836 (4)	0.01433 (15)
N7	0.21520 (11)	0.92571 (9)	0.93095 (5)	0.01882 (17)
C1	0.24653 (12)	0.35564 (10)	0.66818 (6)	0.01858 (19)
H1A	0.2696	0.4417	0.6759	0.022*
C2	0.15334 (12)	0.31226 (11)	0.59701 (6)	0.0203 (2)
H2A	0.1146	0.3701	0.5578	0.024*
C3	0.11761 (12)	0.18408 (11)	0.58390 (6)	0.0203 (2)
H3A	0.0557	0.1559	0.5364	0.024*
C4	0.17654 (12)	0.09824 (10)	0.64352 (6)	0.01943 (19)
H4A	0.1535	0.0123	0.6355	0.023*
C5	0.26881 (12)	0.13991 (10)	0.71441 (6)	0.01743 (18)
H5A	0.3070	0.0817	0.7534	0.021*
C6	0.30514 (11)	0.26966 (9)	0.72776 (5)	0.01523 (17)
C7	0.44975 (12)	0.43689 (9)	0.81634 (5)	0.01550 (17)
H7A	0.3723	0.4945	0.8128	0.019*
H7B	0.4872	0.4638	0.7805	0.019*
C8	0.56801 (11)	0.44026 (9)	0.89361 (5)	0.01385 (17)
C9	0.71259 (11)	0.50470 (9)	1.00598 (5)	0.01399 (16)
C10	0.68936 (11)	0.74328 (9)	1.03967 (6)	0.01621 (18)
H10A	0.6906	0.8051	1.0766	0.019*
H10B	0.7477	0.7769	1.0152	0.019*
C11	0.53525 (11)	0.72606 (9)	0.98234 (5)	0.01326 (16)
C12	0.42909 (11)	0.82264 (9)	0.97734 (5)	0.01385 (17)
C13	0.42779 (12)	0.90140 (9)	1.03598 (5)	0.01612 (18)
C14	0.24541 (11)	0.79366 (9)	0.84281 (5)	0.01405 (17)
C15	0.10991 (12)	0.73640 (11)	0.81278 (6)	0.0201 (2)
H15A	0.0557	0.7275	0.8409	0.024*
C16	0.05717 (12)	0.69250 (12)	0.73922 (6)	0.0215 (2)
H16A	−0.0334	0.6534	0.7180	0.026*
C17	0.13799 (12)	0.70619 (10)	0.69677 (5)	0.01611 (18)
C18	0.27547 (12)	0.76301 (10)	0.72997 (5)	0.01676 (18)
H18A	0.3308	0.7710	0.7024	0.020*
C19	0.33082 (12)	0.80769 (10)	0.80326 (5)	0.01638 (18)
H19A	0.4219	0.8457	0.8251	0.020*
C20	0.07796 (13)	0.66428 (11)	0.61610 (6)	0.0207 (2)
H20A	0.0210	0.5886	0.6099	0.031*
H20B	0.1567	0.6470	0.6022	0.031*
H20C	0.0180	0.7305	0.5848	0.031*

	U11	U22	U33	U12	U13	U23
S1	0.01723 (12)	0.01541 (11)	0.01298 (10)	−0.00007 (8)	0.00287 (9)	−0.00047 (7)
O1	0.0246 (4)	0.0170 (3)	0.0176 (3)	0.0046 (3)	0.0092 (3)	−0.0020 (3)
O2	0.0298 (4)	0.0152 (3)	0.0137 (3)	0.0000 (3)	0.0068 (3)	−0.0018 (2)
N1	0.0258 (5)	0.0125 (3)	0.0133 (3)	−0.0004 (3)	0.0017 (3)	−0.0003 (3)
N2	0.0175 (4)	0.0158 (4)	0.0149 (3)	0.0018 (3)	0.0069 (3)	−0.0007 (3)
N3	0.0152 (4)	0.0168 (4)	0.0154 (3)	0.0015 (3)	0.0056 (3)	−0.0002 (3)
N4	0.0135 (4)	0.0120 (3)	0.0127 (3)	0.0014 (3)	0.0046 (3)	−0.0004 (3)
N5	0.0151 (4)	0.0114 (3)	0.0135 (3)	0.0021 (3)	0.0061 (3)	0.0004 (3)
N6	0.0169 (4)	0.0128 (3)	0.0136 (3)	0.0011 (3)	0.0066 (3)	0.0006 (3)
N7	0.0214 (4)	0.0178 (4)	0.0173 (4)	0.0049 (3)	0.0081 (3)	−0.0010 (3)
C1	0.0210 (5)	0.0182 (4)	0.0146 (4)	0.0002 (4)	0.0055 (4)	0.0007 (3)
C2	0.0192 (5)	0.0264 (5)	0.0143 (4)	0.0004 (4)	0.0058 (4)	0.0013 (4)
C3	0.0178 (5)	0.0278 (5)	0.0152 (4)	−0.0025 (4)	0.0067 (4)	−0.0050 (4)
C4	0.0186 (5)	0.0200 (4)	0.0203 (4)	−0.0017 (4)	0.0087 (4)	−0.0059 (3)
C5	0.0186 (5)	0.0156 (4)	0.0175 (4)	0.0009 (4)	0.0069 (4)	−0.0016 (3)
C6	0.0164 (4)	0.0157 (4)	0.0136 (4)	0.0008 (3)	0.0062 (3)	−0.0016 (3)
C7	0.0191 (5)	0.0137 (4)	0.0126 (4)	0.0004 (3)	0.0055 (3)	−0.0002 (3)
C8	0.0166 (4)	0.0128 (4)	0.0134 (4)	−0.0003 (3)	0.0074 (3)	−0.0010 (3)
C9	0.0123 (4)	0.0153 (4)	0.0136 (4)	0.0001 (3)	0.0046 (3)	0.0007 (3)
C10	0.0157 (4)	0.0137 (4)	0.0168 (4)	−0.0010 (3)	0.0043 (3)	−0.0010 (3)
C11	0.0157 (4)	0.0122 (4)	0.0124 (3)	0.0000 (3)	0.0064 (3)	0.0008 (3)
C12	0.0167 (4)	0.0118 (4)	0.0126 (3)	0.0008 (3)	0.0056 (3)	0.0001 (3)
C13	0.0225 (5)	0.0114 (4)	0.0153 (4)	0.0014 (3)	0.0087 (4)	0.0010 (3)
C14	0.0157 (4)	0.0140 (4)	0.0120 (3)	0.0011 (3)	0.0053 (3)	0.0008 (3)
C15	0.0167 (5)	0.0283 (5)	0.0175 (4)	−0.0025 (4)	0.0091 (4)	−0.0018 (4)
C16	0.0155 (5)	0.0306 (5)	0.0176 (4)	−0.0047 (4)	0.0061 (4)	−0.0026 (4)
C17	0.0161 (4)	0.0175 (4)	0.0132 (4)	0.0011 (3)	0.0046 (3)	0.0015 (3)
C18	0.0184 (5)	0.0190 (4)	0.0139 (4)	−0.0026 (4)	0.0078 (3)	0.0013 (3)
C19	0.0170 (4)	0.0177 (4)	0.0144 (4)	−0.0033 (3)	0.0066 (3)	0.0008 (3)
C20	0.0203 (5)	0.0254 (5)	0.0134 (4)	−0.0004 (4)	0.0040 (4)	−0.0004 (3)

S1—C9	1.7315 (10)	C4—H4A	0.9300
S1—C10	1.8196 (10)	C5—C6	1.4079 (14)
O1—N7	1.3756 (12)	C5—H5A	0.9300
O1—C13	1.4093 (13)	C7—C8	1.4924 (14)
O2—C13	1.2177 (12)	C7—H7A	0.9700
N1—C6	1.3855 (12)	C7—H7B	0.9700
N1—C7	1.4479 (13)	C10—C11	1.5079 (14)
N1—H1	0.8621	C10—H10A	0.9700
N2—C8	1.3097 (13)	C10—H10B	0.9700
N2—N3	1.4075 (12)	C11—C12	1.4511 (14)
N3—C9	1.3106 (13)	C12—C13	1.4226 (13)
N4—C8	1.3751 (12)	C14—C15	1.3851 (15)
N4—C9	1.3790 (12)	C14—C19	1.3893 (14)
N4—N5	1.3814 (11)	C15—C16	1.3941 (15)
N5—C11	1.2943 (12)	C15—H15A	0.9300
N6—N7	1.3063 (12)	C16—C17	1.3968 (15)
N6—C12	1.3605 (13)	C16—H16A	0.9300
N6—C14	1.4491 (12)	C17—C18	1.4013 (15)
C1—C2	1.3983 (14)	C17—C20	1.5075 (14)
C1—C6	1.3999 (14)	C18—C19	1.3914 (13)
C1—H1A	0.9300	C18—H18A	0.9300
C2—C3	1.3904 (16)	C19—H19A	0.9300
C2—H2A	0.9300	C20—H20A	0.9600
C3—C4	1.3998 (16)	C20—H20B	0.9600
C3—H3A	0.9300	C20—H20C	0.9600
C4—C5	1.3861 (14)
C9—S1—C10	95.43 (5)	N3—C9—N4	110.58 (8)
N7—O1—C13	110.89 (8)	N3—C9—S1	128.39 (8)
C6—N1—C7	121.96 (8)	N4—C9—S1	120.71 (7)
C6—N1—H1	117.3	C11—C10—S1	112.54 (7)
C7—N1—H1	116.9	C11—C10—H10A	109.1
C8—N2—N3	108.22 (8)	S1—C10—H10A	109.1
C9—N3—N2	106.42 (8)	C11—C10—H10B	109.1
C8—N4—C9	105.18 (8)	S1—C10—H10B	109.1
C8—N4—N5	123.82 (8)	H10A—C10—H10B	107.8
C9—N4—N5	129.05 (8)	N5—C11—C12	116.74 (9)
C11—N5—N4	115.69 (8)	N5—C11—C10	124.96 (9)
N7—N6—C12	114.83 (8)	C12—C11—C10	118.28 (8)
N7—N6—C14	115.79 (8)	N6—C12—C13	105.37 (9)
C12—N6—C14	129.26 (8)	N6—C12—C11	126.59 (8)
N6—N7—O1	104.84 (8)	C13—C12—C11	127.41 (9)
C2—C1—C6	120.04 (10)	O2—C13—O1	120.33 (9)
C2—C1—H1A	120.0	O2—C13—C12	135.62 (10)
C6—C1—H1A	120.0	O1—C13—C12	104.05 (8)
C3—C2—C1	121.08 (10)	C15—C14—C19	122.95 (9)
C3—C2—H2A	119.5	C15—C14—N6	118.54 (9)
C1—C2—H2A	119.5	C19—C14—N6	118.50 (9)
C2—C3—C4	118.79 (10)	C14—C15—C16	118.04 (10)
C2—C3—H3A	120.6	C14—C15—H15A	121.0
C4—C3—H3A	120.6	C16—C15—H15A	121.0
C5—C4—C3	120.77 (10)	C15—C16—C17	121.14 (10)
C5—C4—H4A	119.6	C15—C16—H16A	119.4
C3—C4—H4A	119.6	C17—C16—H16A	119.4
C4—C5—C6	120.51 (9)	C16—C17—C18	118.74 (9)
C4—C5—H5A	119.7	C16—C17—C20	121.11 (10)
C6—C5—H5A	119.7	C18—C17—C20	120.13 (9)
N1—C6—C1	122.34 (9)	C19—C18—C17	121.34 (9)
N1—C6—C5	118.82 (9)	C19—C18—H18A	119.3
C1—C6—C5	118.81 (9)	C17—C18—H18A	119.3
N1—C7—C8	108.80 (8)	C14—C19—C18	117.77 (10)
N1—C7—H7A	109.9	C14—C19—H19A	121.1
C8—C7—H7A	109.9	C18—C19—H19A	121.1
N1—C7—H7B	109.9	C17—C20—H20A	109.5
C8—C7—H7B	109.9	C17—C20—H20B	109.5
H7A—C7—H7B	108.3	H20A—C20—H20B	109.5
N2—C8—N4	109.59 (8)	C17—C20—H20C	109.5
N2—C8—C7	125.84 (9)	H20A—C20—H20C	109.5
N4—C8—C7	124.51 (9)	H20B—C20—H20C	109.5
C8—N2—N3—C9	−0.32 (11)	C9—S1—C10—C11	46.28 (8)
C8—N4—N5—C11	−172.93 (9)	N4—N5—C11—C12	−177.38 (8)
C9—N4—N5—C11	25.42 (14)	N4—N5—C11—C10	4.59 (14)
C12—N6—N7—O1	−1.21 (12)	S1—C10—C11—N5	−43.10 (12)
C14—N6—N7—O1	−177.58 (8)	S1—C10—C11—C12	138.89 (8)
C13—O1—N7—N6	1.44 (11)	N7—N6—C12—C13	0.52 (12)
C6—C1—C2—C3	−0.22 (17)	C14—N6—C12—C13	176.30 (9)
C1—C2—C3—C4	0.11 (17)	N7—N6—C12—C11	171.94 (9)
C2—C3—C4—C5	0.03 (17)	C14—N6—C12—C11	−12.28 (16)
C3—C4—C5—C6	−0.06 (17)	N5—C11—C12—N6	−17.48 (15)
C7—N1—C6—C1	−8.93 (16)	C10—C11—C12—N6	160.69 (9)
C7—N1—C6—C5	172.89 (10)	N5—C11—C12—C13	152.08 (10)
C2—C1—C6—N1	−177.99 (11)	C10—C11—C12—C13	−29.75 (15)
C2—C1—C6—C5	0.19 (16)	N7—O1—C13—O2	178.77 (9)
C4—C5—C6—N1	178.20 (10)	N7—O1—C13—C12	−1.14 (11)
C4—C5—C6—C1	−0.05 (16)	N6—C12—C13—O2	−179.49 (12)
C6—N1—C7—C8	−166.77 (10)	C11—C12—C13—O2	9.2 (2)
N3—N2—C8—N4	0.91 (11)	N6—C12—C13—O1	0.39 (10)
N3—N2—C8—C7	178.01 (9)	C11—C12—C13—O1	−170.93 (9)
C9—N4—C8—N2	−1.12 (11)	N7—N6—C14—C15	−55.54 (13)
N5—N4—C8—N2	−166.45 (9)	C12—N6—C14—C15	128.71 (11)
C9—N4—C8—C7	−178.27 (9)	N7—N6—C14—C19	123.23 (10)
N5—N4—C8—C7	16.41 (15)	C12—N6—C14—C19	−52.52 (14)
N1—C7—C8—N2	40.77 (14)	C19—C14—C15—C16	−0.75 (16)
N1—C7—C8—N4	−142.55 (10)	N6—C14—C15—C16	177.97 (10)
N2—N3—C9—N4	−0.40 (11)	C14—C15—C16—C17	−0.28 (17)
N2—N3—C9—S1	173.15 (8)	C15—C16—C17—C18	1.25 (17)
C8—N4—C9—N3	0.92 (11)	C15—C16—C17—C20	−177.10 (11)
N5—N4—C9—N3	165.20 (9)	C16—C17—C18—C19	−1.25 (16)
C8—N4—C9—S1	−173.20 (7)	C20—C17—C18—C19	177.12 (10)
N5—N4—C9—S1	−8.92 (14)	C15—C14—C19—C18	0.75 (15)
C10—S1—C9—N3	161.54 (10)	N6—C14—C19—C18	−177.96 (9)
C10—S1—C9—N4	−25.49 (9)	C17—C18—C19—C14	0.28 (15)

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O2	0.97	2.40	3.1654 (14)	136
N1—H1···O2i	0.86	2.20	3.0218 (11)	160
C18—H18A···N2ii	0.93	2.62	3.4246 (14)	145
C15—H15A···Cg1iii	0.93	2.73	3.5537 (14)	148

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O2	0.97	2.40	3.1654 (14)	136
N1—H1⋯O2i	0.86	2.20	3.0218 (11)	160
C18—H18A⋯N2ii	0.93	2.62	3.4246 (14)	145
C15—H15A⋯Cg1iii	0.93	2.73	3.5537 (14)	148

Symmetry codes: (i) ; (ii) ; (iii) .