4-[2-(2-Benzyl-idene-hydrazin-ylidene)-3,6-dihydro-2H-1,3,4-thia-diazin-5-yl]-3-(4-meth-oxy-phen-yl)-sydnone.

In the title compound, C(19)H(16)N(6)O(3)S, the 3,6-dihydro-1,3,4-thia-diazine ring adopts a twist-boat conformation. The dihedral angle between the meth-oxy-substituted benzene ring and the oxadiazole ring is 71.91 (7)°. In the crystal structure, centrosymmetrically related mol-ecules are linked into dimers via pairs of inter-molecular N-H⋯N hydrogen bonds, generating R(2) (2)(8) ring motifs. There is an intra-molecular C-H⋯O hydrogen bond which generates an S(6) ring motif.

Related literature

For applications of sydnones, see: Baker et al. (1949 ▶); Hedge et al. (2008 ▶); Rai et al. (2008 ▶); Kalluraya et al. (2003 ▶). For the definition of ring-puckering parameters, see: Cremer & Pople (1975 ▶). For the definition of graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C19H16N6O3S

M = 408.44

Monoclinic,

a = 14.9236 (15) Å

b = 5.9331 (7) Å

c = 21.425 (2) Å

β = 99.338 (2)°

V = 1871.9 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 296 K

0.77 × 0.07 × 0.04 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.856, T max = 0.992

15668 measured reflections

4269 independent reflections

2889 reflections with I > 2σ(I)

R int = 0.062

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.106

S = 1.03

4269 reflections

267 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.37 e Å−3

Δρmin = −0.29 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/S1600536811009329/rz2567sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009329/rz2567Isup2.hkl

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

C19H16N6O3S	F(000) = 848
Mr = 408.44	Dx = 1.449 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1908 reflections
a = 14.9236 (15) Å	θ = 3.0–27.3°
b = 5.9331 (7) Å	µ = 0.21 mm−1
c = 21.425 (2) Å	T = 296 K
β = 99.338 (2)°	Needle, orange
V = 1871.9 (4) Å3	0.77 × 0.07 × 0.04 mm
Z = 4

Bruker APEXII DUO CCD area-detector diffractometer	4269 independent reflections
Radiation source: fine-focus sealed tube	2889 reflections with I > 2σ(I)
graphite	Rint = 0.062
φ and ω scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −19→19
Tmin = 0.856, Tmax = 0.992	k = −7→7
15668 measured reflections	l = −27→27

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0401P)2 + 0.4767P] where P = (Fo2 + 2Fc2)/3
4269 reflections	(Δ/σ)max = 0.001
267 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 > 2σ(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	0.51196 (3)	0.06066 (11)	0.18109 (2)	0.02408 (16)
O1	0.29051 (9)	−0.7158 (3)	0.24009 (6)	0.0274 (4)
O2	0.43051 (9)	−0.5875 (3)	0.28329 (6)	0.0261 (4)
O3	0.03886 (9)	−0.2449 (3)	−0.06332 (6)	0.0302 (4)
N1	0.58722 (11)	0.3462 (3)	0.10107 (7)	0.0197 (4)
N2	0.53281 (10)	0.1897 (3)	0.06401 (7)	0.0203 (4)
N3	0.45763 (11)	−0.1430 (3)	0.06974 (7)	0.0189 (4)
N4	0.39709 (10)	−0.2843 (3)	0.09276 (7)	0.0185 (4)
N5	0.26615 (11)	−0.5345 (3)	0.15329 (7)	0.0202 (4)
N6	0.22703 (11)	−0.6811 (4)	0.18620 (7)	0.0264 (5)
C1	0.73234 (13)	0.6171 (4)	0.16329 (9)	0.0242 (5)
H1A	0.7205	0.4846	0.1837	0.029*
C2	0.79578 (14)	0.7681 (5)	0.19293 (10)	0.0320 (6)
H2A	0.8264	0.7369	0.2334	0.038*
C3	0.81414 (15)	0.9647 (5)	0.16313 (11)	0.0339 (6)
H3A	0.8574	1.0645	0.1833	0.041*
C4	0.76819 (14)	1.0137 (5)	0.10314 (10)	0.0287 (6)
H4A	0.7796	1.1476	0.0833	0.034*
C5	0.70513 (13)	0.8620 (4)	0.07295 (9)	0.0230 (5)
H5A	0.6753	0.8936	0.0323	0.028*
C6	0.68565 (13)	0.6638 (4)	0.10230 (8)	0.0199 (5)
C7	0.62003 (13)	0.5032 (4)	0.06982 (8)	0.0204 (5)
H7A	0.6018	0.5142	0.0263	0.025*
C8	0.50177 (12)	0.0383 (4)	0.09904 (8)	0.0181 (5)
C9	0.49414 (13)	−0.2359 (4)	0.19578 (8)	0.0221 (5)
H9A	0.5470	−0.3213	0.1886	0.026*
H9B	0.4866	−0.2566	0.2395	0.026*
C10	0.41158 (12)	−0.3220 (4)	0.15311 (8)	0.0191 (5)
C11	0.34998 (13)	−0.4661 (4)	0.18046 (8)	0.0189 (5)
C12	0.36813 (13)	−0.5822 (4)	0.23935 (8)	0.0220 (5)
C13	0.21053 (12)	−0.4579 (4)	0.09497 (8)	0.0199 (5)
C14	0.17263 (14)	−0.2452 (4)	0.09297 (9)	0.0240 (5)
H14A	0.1857	−0.1480	0.1273	0.029*
C15	0.11479 (14)	−0.1796 (5)	0.03878 (9)	0.0266 (5)
H15A	0.0881	−0.0376	0.0365	0.032*
C16	0.09668 (13)	−0.3280 (5)	−0.01245 (8)	0.0227 (5)
C17	0.13592 (13)	−0.5395 (5)	−0.00988 (9)	0.0247 (5)
H17A	0.1242	−0.6363	−0.0444	0.030*
C18	0.19321 (13)	−0.6064 (4)	0.04498 (9)	0.0234 (5)
H18A	0.2194	−0.7490	0.0478	0.028*
C19	0.01814 (14)	−0.3879 (5)	−0.11771 (9)	0.0340 (7)
H19A	−0.0240	−0.3128	−0.1496	0.051*
H19B	−0.0084	−0.5258	−0.1059	0.051*
H19C	0.0729	−0.4210	−0.1340	0.051*
H1N3	0.4553 (16)	−0.161 (5)	0.0291 (12)	0.041 (7)*

	U11	U22	U33	U12	U13	U23
S1	0.0287 (3)	0.0285 (4)	0.0149 (2)	−0.0068 (3)	0.00304 (18)	−0.0044 (2)
O1	0.0302 (8)	0.0318 (12)	0.0200 (6)	−0.0042 (8)	0.0033 (6)	0.0077 (7)
O2	0.0281 (7)	0.0319 (12)	0.0177 (6)	0.0013 (8)	0.0016 (5)	0.0023 (7)
O3	0.0242 (7)	0.0414 (13)	0.0238 (7)	0.0037 (8)	0.0003 (6)	0.0051 (7)
N1	0.0198 (8)	0.0190 (12)	0.0199 (7)	−0.0040 (9)	0.0022 (6)	−0.0060 (8)
N2	0.0207 (8)	0.0229 (13)	0.0170 (7)	−0.0048 (9)	0.0018 (6)	−0.0034 (8)
N3	0.0239 (8)	0.0198 (12)	0.0134 (7)	−0.0055 (9)	0.0043 (6)	−0.0014 (7)
N4	0.0185 (8)	0.0200 (12)	0.0176 (7)	−0.0032 (8)	0.0046 (6)	−0.0006 (7)
N5	0.0213 (8)	0.0217 (12)	0.0186 (7)	−0.0008 (9)	0.0059 (6)	0.0017 (8)
N6	0.0282 (9)	0.0287 (14)	0.0218 (8)	−0.0087 (10)	0.0021 (7)	0.0045 (8)
C1	0.0245 (10)	0.0246 (16)	0.0233 (9)	0.0005 (11)	0.0030 (8)	0.0008 (10)
C2	0.0273 (11)	0.0363 (19)	0.0287 (10)	−0.0002 (13)	−0.0061 (9)	−0.0048 (11)
C3	0.0263 (11)	0.0294 (18)	0.0441 (12)	−0.0085 (12)	0.0003 (10)	−0.0118 (12)
C4	0.0258 (10)	0.0220 (16)	0.0404 (11)	−0.0015 (11)	0.0113 (9)	−0.0006 (11)
C5	0.0225 (10)	0.0235 (15)	0.0237 (9)	0.0006 (11)	0.0063 (8)	0.0005 (10)
C6	0.0188 (9)	0.0213 (15)	0.0203 (9)	−0.0011 (10)	0.0052 (7)	−0.0033 (9)
C7	0.0216 (9)	0.0217 (15)	0.0175 (8)	0.0005 (10)	0.0021 (7)	−0.0023 (9)
C8	0.0156 (8)	0.0227 (14)	0.0156 (8)	0.0003 (10)	0.0011 (7)	−0.0040 (9)
C9	0.0215 (9)	0.0277 (16)	0.0166 (8)	−0.0040 (11)	0.0018 (7)	0.0024 (9)
C10	0.0187 (9)	0.0217 (15)	0.0173 (8)	0.0001 (10)	0.0042 (7)	−0.0026 (9)
C11	0.0191 (9)	0.0207 (14)	0.0172 (8)	0.0008 (10)	0.0039 (7)	−0.0004 (9)
C12	0.0259 (10)	0.0223 (15)	0.0196 (9)	0.0026 (11)	0.0093 (8)	−0.0001 (9)
C13	0.0165 (9)	0.0244 (15)	0.0187 (8)	−0.0056 (10)	0.0026 (7)	−0.0009 (9)
C14	0.0274 (10)	0.0234 (15)	0.0219 (9)	−0.0004 (12)	0.0059 (8)	−0.0014 (10)
C15	0.0297 (11)	0.0238 (16)	0.0271 (10)	0.0012 (12)	0.0069 (8)	0.0014 (10)
C16	0.0161 (9)	0.0309 (17)	0.0215 (9)	−0.0018 (11)	0.0047 (7)	0.0035 (10)
C17	0.0235 (10)	0.0282 (16)	0.0226 (9)	−0.0046 (12)	0.0041 (8)	−0.0049 (10)
C18	0.0211 (9)	0.0241 (16)	0.0251 (9)	−0.0014 (11)	0.0039 (8)	−0.0023 (10)
C19	0.0268 (11)	0.051 (2)	0.0227 (10)	−0.0061 (13)	−0.0011 (8)	0.0030 (11)

S1—C8	1.7448 (17)	C4—C5	1.384 (3)
S1—C9	1.814 (3)	C4—H4A	0.9300
O1—N6	1.385 (2)	C5—C6	1.387 (3)
O1—C12	1.406 (3)	C5—H5A	0.9300
O2—C12	1.212 (2)	C6—C7	1.459 (3)
O3—C16	1.368 (2)	C7—H7A	0.9300
O3—C19	1.434 (3)	C9—C10	1.500 (3)
N1—C7	1.289 (3)	C9—H9A	0.9700
N1—N2	1.394 (2)	C9—H9B	0.9700
N2—C8	1.303 (3)	C10—C11	1.447 (3)
N3—C8	1.360 (3)	C11—C12	1.425 (3)
N3—N4	1.381 (2)	C13—C18	1.379 (3)
N3—H1N3	0.87 (2)	C13—C14	1.381 (3)
N4—C10	1.295 (2)	C14—C15	1.385 (3)
N5—N6	1.314 (2)	C14—H14A	0.9300
N5—C11	1.354 (2)	C15—C16	1.399 (3)
N5—C13	1.456 (2)	C15—H15A	0.9300
C1—C2	1.381 (3)	C16—C17	1.382 (3)
C1—C6	1.405 (3)	C17—C18	1.394 (3)
C1—H1A	0.9300	C17—H17A	0.9300
C2—C3	1.378 (4)	C18—H18A	0.9300
C2—H2A	0.9300	C19—H19A	0.9600
C3—C4	1.386 (3)	C19—H19B	0.9600
C3—H3A	0.9300	C19—H19C	0.9600
C8—S1—C9	96.30 (10)	C10—C9—H9A	109.5
N6—O1—C12	111.11 (15)	S1—C9—H9A	109.5
C16—O3—C19	117.3 (2)	C10—C9—H9B	109.5
C7—N1—N2	114.88 (15)	S1—C9—H9B	109.5
C8—N2—N1	111.09 (15)	H9A—C9—H9B	108.1
C8—N3—N4	127.66 (15)	N4—C10—C11	119.49 (18)
C8—N3—H1N3	119.9 (18)	N4—C10—C9	122.47 (18)
N4—N3—H1N3	111.0 (17)	C11—C10—C9	117.88 (16)
C10—N4—N3	116.66 (16)	N5—C11—C12	105.40 (18)
N6—N5—C11	115.31 (16)	N5—C11—C10	127.34 (17)
N6—N5—C13	115.21 (16)	C12—C11—C10	127.04 (17)
C11—N5—C13	129.33 (17)	O2—C12—O1	120.48 (19)
N5—N6—O1	104.03 (15)	O2—C12—C11	135.4 (2)
C2—C1—C6	119.9 (2)	O1—C12—C11	104.12 (16)
C2—C1—H1A	120.0	C18—C13—C14	122.39 (19)
C6—C1—H1A	120.0	C18—C13—N5	118.4 (2)
C3—C2—C1	120.6 (2)	C14—C13—N5	119.06 (18)
C3—C2—H2A	119.7	C13—C14—C15	118.6 (2)
C1—C2—H2A	119.7	C13—C14—H14A	120.7
C2—C3—C4	120.1 (2)	C15—C14—H14A	120.7
C2—C3—H3A	120.0	C14—C15—C16	119.7 (2)
C4—C3—H3A	120.0	C14—C15—H15A	120.1
C5—C4—C3	119.6 (2)	C16—C15—H15A	120.1
C5—C4—H4A	120.2	O3—C16—C17	124.6 (2)
C3—C4—H4A	120.2	O3—C16—C15	114.5 (2)
C4—C5—C6	121.07 (19)	C17—C16—C15	120.89 (19)
C4—C5—H5A	119.5	C16—C17—C18	119.3 (2)
C6—C5—H5A	119.5	C16—C17—H17A	120.3
C5—C6—C1	118.7 (2)	C18—C17—H17A	120.3
C5—C6—C7	120.74 (18)	C13—C18—C17	119.0 (2)
C1—C6—C7	120.5 (2)	C13—C18—H18A	120.5
N1—C7—C6	120.39 (17)	C17—C18—H18A	120.5
N1—C7—H7A	119.8	O3—C19—H19A	109.5
C6—C7—H7A	119.8	O3—C19—H19B	109.5
N2—C8—N3	118.03 (16)	H19A—C19—H19B	109.5
N2—C8—S1	123.16 (17)	O3—C19—H19C	109.5
N3—C8—S1	118.79 (15)	H19A—C19—H19C	109.5
C10—C9—S1	110.72 (15)	H19B—C19—H19C	109.5
C7—N1—N2—C8	−179.44 (19)	N6—N5—C11—C10	174.4 (2)
C8—N3—N4—C10	−33.8 (3)	C13—N5—C11—C10	−10.3 (4)
C11—N5—N6—O1	−0.5 (2)	N4—C10—C11—N5	−14.9 (4)
C13—N5—N6—O1	−176.51 (17)	C9—C10—C11—N5	169.6 (2)
C12—O1—N6—N5	1.3 (2)	N4—C10—C11—C12	158.9 (2)
C6—C1—C2—C3	−0.2 (3)	C9—C10—C11—C12	−16.6 (3)
C1—C2—C3—C4	0.7 (4)	N6—O1—C12—O2	178.8 (2)
C2—C3—C4—C5	−1.3 (3)	N6—O1—C12—C11	−1.6 (2)
C3—C4—C5—C6	1.4 (3)	N5—C11—C12—O2	−179.3 (3)
C4—C5—C6—C1	−1.0 (3)	C10—C11—C12—O2	5.8 (4)
C4—C5—C6—C7	−179.12 (19)	N5—C11—C12—O1	1.2 (2)
C2—C1—C6—C5	0.4 (3)	C10—C11—C12—O1	−173.7 (2)
C2—C1—C6—C7	178.52 (19)	N6—N5—C13—C18	−71.5 (2)
N2—N1—C7—C6	−173.51 (17)	C11—N5—C13—C18	113.2 (3)
C5—C6—C7—N1	−164.7 (2)	N6—N5—C13—C14	104.6 (2)
C1—C6—C7—N1	17.2 (3)	C11—N5—C13—C14	−70.7 (3)
N1—N2—C8—N3	−171.36 (17)	C18—C13—C14—C15	0.3 (3)
N1—N2—C8—S1	10.1 (2)	N5—C13—C14—C15	−175.62 (17)
N4—N3—C8—N2	−158.81 (19)	C13—C14—C15—C16	−0.5 (3)
N4—N3—C8—S1	19.8 (3)	C19—O3—C16—C17	−0.3 (3)
C9—S1—C8—N2	−160.46 (18)	C19—O3—C16—C15	179.43 (17)
C9—S1—C8—N3	21.05 (18)	C14—C15—C16—O3	−179.88 (18)
C8—S1—C9—C10	−49.20 (14)	C14—C15—C16—C17	−0.1 (3)
N3—N4—C10—C11	179.15 (19)	O3—C16—C17—C18	−179.35 (17)
N3—N4—C10—C9	−5.5 (3)	C15—C16—C17—C18	1.0 (3)
S1—C9—C10—N4	48.2 (3)	C14—C13—C18—C17	0.5 (3)
S1—C9—C10—C11	−136.34 (18)	N5—C13—C18—C17	176.44 (17)
N6—N5—C11—C12	−0.4 (3)	C16—C17—C18—C13	−1.1 (3)
C13—N5—C11—C12	174.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···N2i	0.87 (3)	2.04 (3)	2.905 (2)	173 (2)
C9—H9B···O2	0.97	2.39	3.057 (3)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯N2i	0.87 (3)	2.04 (3)	2.905 (2)	173 (2)
C9—H9B⋯O2	0.97	2.39	3.057 (3)	126

Symmetry code: (i) .