4-{2-[2-(4-Chloro-benzyl-idene)hydrazinyl-idene]-3,6-dihydro-2H-1,3,4-thia-diazin-5-yl}-3-(4-meth-oxy-phen-yl)sydnone.

The title compound, C(19)H(15)ClN(6)O(3)S, exists in trans and cis configurations with respect to the acyclic C=N bonds. The 3,6-dihydro-2H-1,3,4-thia-diazine ring adopts a half-boat conformation. The sydnone ring is approximately planar [maximum deviation = 0.013 (1) Å] and forms dihedral angles of 34.76 (4) and 48.67 (4)° with the benzene rings. An intra-molecular C-H⋯O hydrogen bond stabilizes the mol-ecular structure and forms an S(6) ring motif. In the crystal packing, inter-molecular N-H⋯N hydrogen bonds link centrosymmetrically related mol-ecules into dimers, generating R(2) (2)(8) ring motifs. The dimers are then linked into a three-dimensional network by inter-molecular C-H⋯O and C-H⋯Cl hydrogen bonds, and by C-H⋯π inter-actions. Further stabilization is provided by π-π inter-actions involving the sydnone rings, with centroid-centroid separations of 3.4198 (5) Å.

Related literature

For background to and the biological activity of sydnones, see: Baker et al. (1949 ▶); Hedge et al. (2008 ▶); Rai et al. (2008 ▶); Kalluraya et al. (2003 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For related structures, see: Fun et al. (2010 ▶, 2011 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C19H15ClN6O3S

M = 442.88

Monoclinic,

a = 7.2322 (2) Å

b = 22.7311 (6) Å

c = 12.9299 (3) Å

β = 114.426 (1)°

V = 1935.37 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.34 mm−1

T = 100 K

0.56 × 0.33 × 0.19 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T min = 0.832, T max = 0.937

38523 measured reflections

10172 independent reflections

8764 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.088

S = 1.03

10172 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −0.31 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/S1600536811013900/rz2581sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013900/rz2581Isup2.hkl

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

C19H15ClN6O3S	F(000) = 912
Mr = 442.88	Dx = 1.520 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9060 reflections
a = 7.2322 (2) Å	θ = 3.5–37.6°
b = 22.7311 (6) Å	µ = 0.34 mm−1
c = 12.9299 (3) Å	T = 100 K
β = 114.426 (1)°	Block, red
V = 1935.37 (9) Å3	0.56 × 0.33 × 0.19 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	10172 independent reflections
Radiation source: fine-focus sealed tube	8764 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 37.6°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
Tmin = 0.832, Tmax = 0.937	k = −37→38
38523 measured reflections	l = −22→22

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0455P)2 + 0.4618P] where P = (Fo2 + 2Fc2)/3
10172 reflections	(Δ/σ)max = 0.003
272 parameters	Δρmax = 0.61 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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 e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
Cl1	−0.20673 (3)	0.599009 (8)	−0.296760 (19)	0.02044 (4)
S1	0.27993 (3)	0.865504 (7)	0.177439 (15)	0.01416 (4)
O1	0.86209 (8)	0.99555 (2)	0.58612 (4)	0.01533 (9)
O2	0.69250 (10)	0.90827 (3)	0.56018 (5)	0.01973 (10)
O3	0.62847 (10)	1.19710 (2)	0.08415 (5)	0.01920 (10)
N1	−0.02123 (10)	0.86024 (3)	−0.03458 (5)	0.01436 (10)
N2	0.00267 (10)	0.91926 (3)	−0.00409 (5)	0.01412 (10)
N3	0.16911 (9)	0.98004 (3)	0.14755 (5)	0.01379 (9)
H1	0.1098	1.0093	0.1006	0.017*
N4	0.34093 (9)	0.99876 (3)	0.23756 (5)	0.01274 (9)
N5	0.72206 (9)	1.03311 (3)	0.42028 (5)	0.01207 (9)
N6	0.86571 (10)	1.04359 (3)	0.52215 (5)	0.01467 (10)
C1	−0.20026 (12)	0.77461 (3)	−0.29399 (6)	0.01656 (12)
H1A	−0.2271	0.8050	−0.3464	0.020*
C2	−0.22174 (12)	0.71639 (3)	−0.33105 (6)	0.01765 (12)
H2A	−0.2614	0.7077	−0.4075	0.021*
C3	−0.18281 (11)	0.67161 (3)	−0.25156 (6)	0.01502 (11)
C4	−0.12243 (11)	0.68343 (3)	−0.13639 (6)	0.01594 (11)
H4A	−0.0979	0.6529	−0.0845	0.019*
C5	−0.09958 (11)	0.74165 (3)	−0.10043 (6)	0.01524 (11)
H5A	−0.0579	0.7501	−0.0237	0.018*
C6	−0.13877 (11)	0.78790 (3)	−0.17873 (6)	0.01341 (10)
C7	−0.11200 (11)	0.84940 (3)	−0.14139 (6)	0.01443 (11)
H7A	−0.1597	0.8799	−0.1938	0.017*
C8	0.13666 (10)	0.92500 (3)	0.10070 (6)	0.01224 (10)
C9	0.37326 (12)	0.89915 (3)	0.31690 (6)	0.01527 (11)
H9A	0.2663	0.8990	0.3437	0.018*
H9B	0.4857	0.8761	0.3696	0.018*
C10	0.44244 (10)	0.96112 (3)	0.31486 (6)	0.01225 (10)
C11	0.62297 (10)	0.98132 (3)	0.41035 (6)	0.01216 (10)
C12	0.71662 (11)	0.95431 (3)	0.51973 (6)	0.01398 (11)
C13	0.69885 (10)	1.07654 (3)	0.33459 (6)	0.01235 (10)
C14	0.68466 (12)	1.13502 (3)	0.35876 (6)	0.01581 (11)
H14A	0.6883	1.1460	0.4289	0.019*
C15	0.66483 (12)	1.17767 (3)	0.27707 (7)	0.01669 (12)
H15A	0.6581	1.2173	0.2928	0.020*
C16	0.65519 (11)	1.16009 (3)	0.17168 (6)	0.01458 (11)
C17	0.67298 (12)	1.10052 (3)	0.14935 (6)	0.01655 (12)
H17A	0.6690	1.0892	0.0793	0.020*
C18	0.69642 (12)	1.05866 (3)	0.23103 (6)	0.01542 (11)
H18A	0.7104	1.0191	0.2172	0.019*
C19	0.61977 (13)	1.25837 (3)	0.10431 (8)	0.02065 (13)
H19A	0.5968	1.2798	0.0361	0.031*
H19B	0.7459	1.2707	0.1638	0.031*
H19C	0.5108	1.2659	0.1266	0.031*

	U11	U22	U33	U12	U13	U23
Cl1	0.02240 (8)	0.01084 (7)	0.03075 (9)	−0.00245 (5)	0.01366 (7)	−0.00500 (6)
S1	0.01632 (7)	0.00916 (6)	0.01430 (7)	0.00094 (5)	0.00364 (6)	−0.00035 (5)
O1	0.0158 (2)	0.0165 (2)	0.01175 (19)	0.00025 (17)	0.00369 (17)	0.00065 (16)
O2	0.0252 (3)	0.0156 (2)	0.0162 (2)	−0.00022 (19)	0.0064 (2)	0.00420 (18)
O3	0.0257 (3)	0.0128 (2)	0.0186 (2)	−0.00033 (19)	0.0087 (2)	0.00338 (18)
N1	0.0161 (2)	0.0102 (2)	0.0146 (2)	−0.00112 (18)	0.00425 (19)	−0.00205 (17)
N2	0.0163 (2)	0.0099 (2)	0.0132 (2)	−0.00053 (18)	0.00306 (19)	−0.00127 (17)
N3	0.0150 (2)	0.0094 (2)	0.0127 (2)	0.00004 (17)	0.00144 (18)	−0.00074 (17)
N4	0.0135 (2)	0.0108 (2)	0.0118 (2)	−0.00057 (17)	0.00305 (18)	−0.00070 (17)
N5	0.0124 (2)	0.0115 (2)	0.0114 (2)	−0.00024 (17)	0.00396 (17)	−0.00076 (17)
N6	0.0152 (2)	0.0152 (2)	0.0117 (2)	−0.00103 (19)	0.00366 (19)	−0.00106 (18)
C1	0.0208 (3)	0.0119 (3)	0.0134 (3)	−0.0007 (2)	0.0035 (2)	−0.0005 (2)
C2	0.0218 (3)	0.0133 (3)	0.0156 (3)	−0.0015 (2)	0.0056 (2)	−0.0025 (2)
C3	0.0144 (3)	0.0103 (2)	0.0202 (3)	−0.0011 (2)	0.0071 (2)	−0.0021 (2)
C4	0.0176 (3)	0.0116 (2)	0.0188 (3)	0.0002 (2)	0.0077 (2)	0.0014 (2)
C5	0.0175 (3)	0.0125 (2)	0.0146 (3)	0.0001 (2)	0.0056 (2)	0.0005 (2)
C6	0.0137 (3)	0.0105 (2)	0.0137 (2)	−0.00017 (19)	0.0034 (2)	−0.00092 (19)
C7	0.0159 (3)	0.0108 (2)	0.0137 (2)	−0.0004 (2)	0.0032 (2)	−0.00090 (19)
C8	0.0131 (2)	0.0100 (2)	0.0127 (2)	−0.00038 (19)	0.0044 (2)	−0.00029 (18)
C9	0.0185 (3)	0.0112 (2)	0.0134 (2)	−0.0021 (2)	0.0039 (2)	0.0007 (2)
C10	0.0132 (2)	0.0105 (2)	0.0120 (2)	−0.00038 (19)	0.0041 (2)	−0.00019 (18)
C11	0.0130 (2)	0.0108 (2)	0.0116 (2)	0.00004 (19)	0.00400 (19)	0.00039 (18)
C12	0.0148 (3)	0.0137 (3)	0.0122 (2)	0.0012 (2)	0.0045 (2)	0.00047 (19)
C13	0.0139 (2)	0.0103 (2)	0.0126 (2)	−0.00055 (19)	0.0052 (2)	−0.00006 (19)
C14	0.0207 (3)	0.0117 (2)	0.0157 (3)	−0.0002 (2)	0.0082 (2)	−0.0019 (2)
C15	0.0216 (3)	0.0106 (2)	0.0184 (3)	0.0005 (2)	0.0088 (2)	−0.0007 (2)
C16	0.0156 (3)	0.0116 (2)	0.0162 (3)	−0.0006 (2)	0.0061 (2)	0.0010 (2)
C17	0.0238 (3)	0.0123 (3)	0.0157 (3)	−0.0014 (2)	0.0103 (2)	−0.0010 (2)
C18	0.0219 (3)	0.0107 (2)	0.0153 (3)	−0.0008 (2)	0.0094 (2)	−0.0013 (2)
C19	0.0221 (3)	0.0127 (3)	0.0274 (4)	−0.0001 (2)	0.0105 (3)	0.0042 (2)

Cl1—C3	1.7353 (7)	C4—C5	1.3897 (10)
S1—C8	1.7426 (7)	C4—H4A	0.9300
S1—C9	1.8125 (7)	C5—C6	1.4047 (10)
O1—N6	1.3767 (8)	C5—H5A	0.9300
O1—C12	1.4055 (9)	C6—C7	1.4653 (9)
O2—C12	1.2145 (9)	C7—H7A	0.9300
O3—C16	1.3582 (9)	C9—C10	1.4988 (9)
O3—C19	1.4231 (10)	C9—H9A	0.9700
N1—C7	1.2842 (9)	C9—H9B	0.9700
N1—N2	1.3887 (8)	C10—C11	1.4514 (10)
N2—C8	1.3061 (9)	C11—C12	1.4295 (9)
N3—C8	1.3675 (9)	C13—C14	1.3790 (9)
N3—N4	1.3724 (8)	C13—C18	1.3924 (9)
N3—H1	0.8830	C14—C15	1.3968 (10)
N4—C10	1.2896 (9)	C14—H14A	0.9300
N5—N6	1.3188 (8)	C15—C16	1.3939 (10)
N5—C11	1.3564 (9)	C15—H15A	0.9300
N5—C13	1.4411 (9)	C16—C17	1.4017 (10)
C1—C2	1.3942 (10)	C17—C18	1.3788 (10)
C1—C6	1.4007 (10)	C17—H17A	0.9300
C1—H1A	0.9300	C18—H18A	0.9300
C2—C3	1.3902 (11)	C19—H19A	0.9600
C2—H2A	0.9300	C19—H19B	0.9600
C3—C4	1.3938 (11)	C19—H19C	0.9600
C8—S1—C9	97.36 (3)	C10—C9—H9A	109.3
N6—O1—C12	110.94 (5)	S1—C9—H9A	109.3
C16—O3—C19	117.09 (6)	C10—C9—H9B	109.3
C7—N1—N2	116.04 (6)	S1—C9—H9B	109.3
C8—N2—N1	110.05 (6)	H9A—C9—H9B	108.0
C8—N3—N4	126.06 (6)	N4—C10—C11	118.23 (6)
C8—N3—H1	116.0	N4—C10—C9	123.36 (6)
N4—N3—H1	111.2	C11—C10—C9	118.15 (6)
C10—N4—N3	118.51 (6)	N5—C11—C12	105.27 (6)
N6—N5—C11	114.74 (6)	N5—C11—C10	127.54 (6)
N6—N5—C13	115.93 (6)	C12—C11—C10	126.68 (6)
C11—N5—C13	129.25 (6)	O2—C12—O1	121.08 (6)
N5—N6—O1	104.71 (5)	O2—C12—C11	134.63 (7)
C2—C1—C6	120.77 (7)	O1—C12—C11	104.28 (6)
C2—C1—H1A	119.6	C14—C13—C18	121.78 (6)
C6—C1—H1A	119.6	C14—C13—N5	118.81 (6)
C3—C2—C1	118.77 (7)	C18—C13—N5	119.38 (6)
C3—C2—H2A	120.6	C13—C14—C15	119.45 (6)
C1—C2—H2A	120.6	C13—C14—H14A	120.3
C2—C3—C4	121.79 (6)	C15—C14—H14A	120.3
C2—C3—Cl1	119.07 (6)	C16—C15—C14	119.24 (6)
C4—C3—Cl1	119.13 (5)	C16—C15—H15A	120.4
C5—C4—C3	118.85 (6)	C14—C15—H15A	120.4
C5—C4—H4A	120.6	O3—C16—C15	124.71 (6)
C3—C4—H4A	120.6	O3—C16—C17	114.86 (6)
C4—C5—C6	120.73 (7)	C15—C16—C17	120.43 (6)
C4—C5—H5A	119.6	C18—C17—C16	120.11 (6)
C6—C5—H5A	119.6	C18—C17—H17A	119.9
C1—C6—C5	119.08 (6)	C16—C17—H17A	119.9
C1—C6—C7	119.79 (6)	C17—C18—C13	118.94 (6)
C5—C6—C7	121.11 (6)	C17—C18—H18A	120.5
N1—C7—C6	118.46 (6)	C13—C18—H18A	120.5
N1—C7—H7A	120.8	O3—C19—H19A	109.5
C6—C7—H7A	120.8	O3—C19—H19B	109.5
N2—C8—N3	117.95 (6)	H19A—C19—H19B	109.5
N2—C8—S1	121.64 (5)	O3—C19—H19C	109.5
N3—C8—S1	120.34 (5)	H19A—C19—H19C	109.5
C10—C9—S1	111.64 (5)	H19B—C19—H19C	109.5
C7—N1—N2—C8	−164.75 (7)	C13—N5—C11—C12	175.91 (6)
C8—N3—N4—C10	−31.43 (10)	N6—N5—C11—C10	171.22 (6)
C11—N5—N6—O1	−0.60 (8)	C13—N5—C11—C10	−11.96 (11)
C13—N5—N6—O1	−177.86 (5)	N4—C10—C11—N5	−12.74 (10)
C12—O1—N6—N5	1.94 (7)	C9—C10—C11—N5	172.88 (6)
C6—C1—C2—C3	0.59 (12)	N4—C10—C11—C12	157.77 (7)
C1—C2—C3—C4	−0.26 (11)	C9—C10—C11—C12	−16.60 (10)
C1—C2—C3—Cl1	−179.36 (6)	N6—O1—C12—O2	178.68 (7)
C2—C3—C4—C5	−0.40 (11)	N6—O1—C12—C11	−2.46 (7)
Cl1—C3—C4—C5	178.71 (6)	N5—C11—C12—O2	−179.41 (8)
C3—C4—C5—C6	0.72 (11)	C10—C11—C12—O2	8.38 (13)
C2—C1—C6—C5	−0.27 (11)	N5—C11—C12—O1	1.97 (7)
C2—C1—C6—C7	178.37 (7)	C10—C11—C12—O1	−170.25 (6)
C4—C5—C6—C1	−0.40 (11)	N6—N5—C13—C14	−49.70 (9)
C4—C5—C6—C7	−179.03 (7)	C11—N5—C13—C14	133.51 (8)
N2—N1—C7—C6	179.07 (6)	N6—N5—C13—C18	128.71 (7)
C1—C6—C7—N1	−167.55 (7)	C11—N5—C13—C18	−48.07 (10)
C5—C6—C7—N1	11.07 (11)	C18—C13—C14—C15	0.78 (11)
N1—N2—C8—N3	−175.58 (6)	N5—C13—C14—C15	179.15 (7)
N1—N2—C8—S1	7.51 (8)	C13—C14—C15—C16	1.44 (11)
N4—N3—C8—N2	−157.12 (7)	C19—O3—C16—C15	3.20 (11)
N4—N3—C8—S1	19.84 (9)	C19—O3—C16—C17	−176.93 (7)
C9—S1—C8—N2	−165.71 (6)	C14—C15—C16—O3	177.44 (7)
C9—S1—C8—N3	17.44 (6)	C14—C15—C16—C17	−2.43 (11)
C8—S1—C9—C10	−44.06 (6)	O3—C16—C17—C18	−178.67 (7)
N3—N4—C10—C11	−179.45 (6)	C15—C16—C17—C18	1.21 (12)
N3—N4—C10—C9	−5.39 (10)	C16—C17—C18—C13	0.99 (12)
S1—C9—C10—N4	44.63 (9)	C14—C13—C18—C17	−2.00 (11)
S1—C9—C10—C11	−141.30 (5)	N5—C13—C18—C17	179.63 (7)
N6—N5—C11—C12	−0.91 (8)

Cg2 is the centroid of the N3/N4/C10/C9/S1 thiadiazine ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···N2i	0.88	2.00	2.8841 (9)	174
C1—H1A···O2ii	0.93	2.59	3.4898 (10)	162
C9—H9B···O2	0.97	2.41	3.0433 (10)	123
C18—H18A···Cl1iii	0.93	2.77	3.6978 (7)	173
C19—H19B···Cg2iv	0.96	2.79	3.5792 (11)	140

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the N3/N4/C10/C9/S1 thia­diazine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯N2i	0.88	2.00	2.8841 (9)	174
C1—H1A⋯O2ii	0.93	2.59	3.4898 (10)	162
C9—H9B⋯O2	0.97	2.41	3.0433 (10)	123
C18—H18A⋯Cl1iii	0.93	2.77	3.6978 (7)	173
C19—H19B⋯Cg2iv	0.96	2.79	3.5792 (11)	140

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