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

The title compound, C(18)H(13)ClN(6)O(2)S, exists in trans and cis configurations with respect to the acyclic C=N bonds [C=N = 1.2837 (15) and 1.3000 (14) Å, respectively]. The 3,6-dihydro-2H-1,3,4-thia-diazine ring adopts a half-boat conformation. The sydnone ring is approximately planar [maximum deviation = 0.002 (1) Å] and forms dihedral angles of 50.45 (7) and 61.21 (6)° with the aromatic rings. In the crystal, inter-molecular N-H⋯N, C-H⋯Cl and C-H⋯S hydrogen bonds link the mol-ecules into layers parallel to ab plane. The crystal packing is stabilized by C-H⋯π inter-actions and further consolidated by π-π inter-actions involving the phenyl rings [centroid-centroid distance = 3.6306 (7) Å].

Related literature

For background to sydnones and their biological activity, see: Newton & Ramsden (1982 ▶); Wagner & Hill (1974 ▶); Kalluraya & Rahiman (1997 ▶); Kalluraya et al. (2003 ▶). For related structures, see: Fun et al. (2010 ▶); Fun, Loh et al. (2011 ▶); Fun, Quah et al. (2011 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). 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

C18H13ClN6O2S

M = 412.85

Triclinic,

a = 7.3180 (3) Å

b = 10.1567 (5) Å

c = 12.4721 (6) Å

α = 96.686 (1)°

β = 95.285 (1)°

γ = 95.229 (1)°

V = 911.92 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.35 mm−1

T = 100 K

0.51 × 0.23 × 0.07 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.842, T max = 0.976

18115 measured reflections

6480 independent reflections

5506 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.113

S = 1.05

6480 reflections

257 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.53 e Å−3

Δρmin = −0.27 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/S1600536811013912/bq2294sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013912/bq2294Isup2.hkl

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

C18H13ClN6O2S	Z = 2
Mr = 412.85	F(000) = 424
Triclinic, P1	Dx = 1.504 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3180 (3) Å	Cell parameters from 8568 reflections
b = 10.1567 (5) Å	θ = 2.8–35.0°
c = 12.4721 (6) Å	µ = 0.35 mm−1
α = 96.686 (1)°	T = 100 K
β = 95.285 (1)°	Plate, light purple
γ = 95.229 (1)°	0.51 × 0.23 × 0.07 mm
V = 911.92 (7) Å3

Bruker SMART APEXII DUO CCD area-detector diffractometer	6480 independent reflections
Radiation source: fine-focus sealed tube	5506 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 32.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.842, Tmax = 0.976	k = −15→15
18115 measured reflections	l = −18→18

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0611P)2 + 0.3032P] where P = (Fo2 + 2Fc2)/3
6480 reflections	(Δ/σ)max = 0.001
257 parameters	Δρmax = 0.53 e Å−3
0 restraints	Δρmin = −0.27 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	1.07800 (5)	0.08403 (3)	−0.18284 (3)	0.03779 (9)
S1	0.17791 (4)	0.27870 (3)	0.20939 (2)	0.02534 (8)
O1	−0.27472 (13)	0.52923 (9)	0.54724 (7)	0.02723 (18)
O2	−0.14178 (14)	0.66439 (9)	0.43584 (8)	0.02957 (19)
N1	0.32516 (14)	0.31817 (9)	0.01686 (8)	0.02134 (17)
N2	0.16931 (14)	0.38648 (10)	0.02374 (7)	0.02176 (17)
N3	−0.07075 (13)	0.42674 (10)	0.12269 (8)	0.02133 (17)
N4	−0.14591 (13)	0.45733 (9)	0.21809 (7)	0.01985 (17)
N5	−0.27251 (13)	0.33810 (9)	0.45894 (7)	0.01958 (16)
N6	−0.32110 (15)	0.39514 (10)	0.55021 (8)	0.02548 (19)
C1	0.63437 (17)	0.17276 (12)	−0.03615 (9)	0.0237 (2)
H1A	0.5690	0.1433	0.0185	0.028*
C2	0.78848 (17)	0.11197 (12)	−0.06418 (10)	0.0265 (2)
H2A	0.8263	0.0413	−0.0295	0.032*
C3	0.88538 (17)	0.15913 (12)	−0.14545 (10)	0.0264 (2)
C4	0.83211 (18)	0.26371 (12)	−0.19913 (10)	0.0275 (2)
H4A	0.8994	0.2941	−0.2527	0.033*
C5	0.67620 (18)	0.32191 (11)	−0.17115 (9)	0.0250 (2)
H5A	0.6374	0.3911	−0.2073	0.030*
C6	0.57626 (16)	0.27820 (11)	−0.08939 (9)	0.02146 (19)
C7	0.41298 (16)	0.34357 (11)	−0.06406 (9)	0.0225 (2)
H7A	0.3715	0.4053	−0.1077	0.027*
C8	0.08764 (15)	0.36783 (10)	0.10979 (8)	0.01926 (18)
C9	−0.02848 (18)	0.25579 (12)	0.27750 (11)	0.0272 (2)
H9A	−0.1132	0.1856	0.2353	0.033*
H9B	0.0039	0.2276	0.3479	0.033*
C10	−0.12334 (14)	0.38080 (10)	0.29279 (9)	0.01908 (18)
C11	−0.19794 (15)	0.42203 (10)	0.39393 (9)	0.01953 (18)
C12	−0.19652 (16)	0.55221 (11)	0.45021 (9)	0.0229 (2)
C13	−0.30832 (14)	0.19503 (10)	0.43535 (9)	0.01922 (18)
C14	−0.22133 (15)	0.11515 (11)	0.50272 (9)	0.02130 (19)
H14A	−0.1436	0.1523	0.5641	0.026*
C15	−0.25405 (16)	−0.02255 (11)	0.47558 (10)	0.0241 (2)
H15A	−0.1976	−0.0784	0.5194	0.029*
C16	−0.36970 (17)	−0.07694 (12)	0.38406 (11)	0.0257 (2)
H16A	−0.3901	−0.1690	0.3667	0.031*
C17	−0.45555 (17)	0.00539 (12)	0.31792 (10)	0.0261 (2)
H17A	−0.5334	−0.0318	0.2566	0.031*
C18	−0.42526 (15)	0.14293 (12)	0.34325 (10)	0.0235 (2)
H18A	−0.4820	0.1988	0.2995	0.028*
H1N3	−0.095 (3)	0.481 (2)	0.0777 (16)	0.040 (5)*

	U11	U22	U33	U12	U13	U23
Cl1	0.02970 (16)	0.03100 (16)	0.0513 (2)	0.00136 (11)	0.01490 (14)	−0.00771 (13)
S1	0.02671 (14)	0.02899 (15)	0.02507 (14)	0.01210 (10)	0.00651 (10)	0.01304 (10)
O1	0.0348 (5)	0.0217 (4)	0.0254 (4)	0.0064 (3)	0.0034 (3)	0.0011 (3)
O2	0.0342 (5)	0.0175 (4)	0.0367 (5)	0.0035 (3)	0.0001 (4)	0.0044 (3)
N1	0.0247 (4)	0.0201 (4)	0.0196 (4)	0.0045 (3)	0.0019 (3)	0.0024 (3)
N2	0.0257 (4)	0.0222 (4)	0.0183 (4)	0.0059 (3)	0.0016 (3)	0.0039 (3)
N3	0.0241 (4)	0.0227 (4)	0.0187 (4)	0.0064 (3)	0.0012 (3)	0.0067 (3)
N4	0.0212 (4)	0.0194 (4)	0.0196 (4)	0.0031 (3)	0.0011 (3)	0.0054 (3)
N5	0.0213 (4)	0.0185 (4)	0.0200 (4)	0.0044 (3)	0.0019 (3)	0.0051 (3)
N6	0.0314 (5)	0.0235 (4)	0.0228 (4)	0.0057 (4)	0.0055 (4)	0.0042 (3)
C1	0.0275 (5)	0.0233 (5)	0.0211 (5)	0.0033 (4)	0.0040 (4)	0.0037 (4)
C2	0.0280 (5)	0.0254 (5)	0.0262 (5)	0.0047 (4)	0.0037 (4)	0.0021 (4)
C3	0.0251 (5)	0.0236 (5)	0.0285 (5)	−0.0011 (4)	0.0061 (4)	−0.0051 (4)
C4	0.0320 (6)	0.0228 (5)	0.0259 (5)	−0.0057 (4)	0.0093 (4)	−0.0023 (4)
C5	0.0336 (6)	0.0194 (5)	0.0213 (5)	−0.0027 (4)	0.0054 (4)	0.0014 (4)
C6	0.0261 (5)	0.0193 (4)	0.0184 (4)	0.0010 (4)	0.0027 (4)	0.0007 (3)
C7	0.0286 (5)	0.0199 (5)	0.0192 (4)	0.0036 (4)	0.0022 (4)	0.0028 (3)
C8	0.0220 (4)	0.0168 (4)	0.0187 (4)	0.0023 (3)	−0.0007 (3)	0.0032 (3)
C9	0.0342 (6)	0.0197 (5)	0.0329 (6)	0.0097 (4)	0.0137 (5)	0.0118 (4)
C10	0.0200 (4)	0.0160 (4)	0.0223 (4)	0.0030 (3)	0.0022 (3)	0.0058 (3)
C11	0.0214 (4)	0.0167 (4)	0.0216 (4)	0.0038 (3)	0.0014 (3)	0.0059 (3)
C12	0.0240 (5)	0.0197 (5)	0.0251 (5)	0.0053 (4)	−0.0007 (4)	0.0040 (4)
C13	0.0198 (4)	0.0168 (4)	0.0222 (4)	0.0021 (3)	0.0038 (3)	0.0057 (3)
C14	0.0233 (5)	0.0209 (5)	0.0213 (5)	0.0043 (4)	0.0035 (4)	0.0070 (3)
C15	0.0247 (5)	0.0205 (5)	0.0301 (5)	0.0059 (4)	0.0074 (4)	0.0091 (4)
C16	0.0247 (5)	0.0189 (5)	0.0347 (6)	0.0008 (4)	0.0099 (4)	0.0039 (4)
C17	0.0227 (5)	0.0252 (5)	0.0290 (5)	−0.0025 (4)	0.0019 (4)	0.0018 (4)
C18	0.0205 (5)	0.0242 (5)	0.0259 (5)	0.0004 (4)	−0.0005 (4)	0.0074 (4)

Cl1—C3	1.7379 (13)	C4—C5	1.3861 (18)
S1—C8	1.7374 (10)	C4—H4A	0.9300
S1—C9	1.8097 (12)	C5—C6	1.3984 (16)
O1—N6	1.3788 (13)	C5—H5A	0.9300
O1—C12	1.4197 (15)	C6—C7	1.4607 (16)
O2—C12	1.2117 (14)	C7—H7A	0.9300
N1—C7	1.2837 (15)	C9—C10	1.5030 (15)
N1—N2	1.3921 (13)	C9—H9A	0.9700
N2—C8	1.3000 (14)	C9—H9B	0.9700
N3—C8	1.3659 (14)	C10—C11	1.4526 (15)
N3—N4	1.3712 (13)	C11—C12	1.4217 (15)
N3—H1N3	0.85 (2)	C13—C14	1.3870 (14)
N4—C10	1.2896 (13)	C13—C18	1.3881 (16)
N5—N6	1.3101 (14)	C14—C15	1.3935 (16)
N5—C11	1.3563 (13)	C14—H14A	0.9300
N5—C13	1.4434 (14)	C15—C16	1.3836 (18)
C1—C2	1.3874 (17)	C15—H15A	0.9300
C1—C6	1.4018 (16)	C16—C17	1.3912 (18)
C1—H1A	0.9300	C16—H16A	0.9300
C2—C3	1.3940 (17)	C17—C18	1.3886 (17)
C2—H2A	0.9300	C17—H17A	0.9300
C3—C4	1.3861 (19)	C18—H18A	0.9300
C8—S1—C9	97.34 (5)	N3—C8—S1	119.98 (8)
N6—O1—C12	111.31 (8)	C10—C9—S1	112.38 (8)
C7—N1—N2	112.59 (9)	C10—C9—H9A	109.1
C8—N2—N1	112.52 (9)	S1—C9—H9A	109.1
C8—N3—N4	126.88 (9)	C10—C9—H9B	109.1
C8—N3—H1N3	114.7 (14)	S1—C9—H9B	109.1
N4—N3—H1N3	111.8 (14)	H9A—C9—H9B	107.9
C10—N4—N3	118.20 (9)	N4—C10—C11	115.66 (9)
N6—N5—C11	115.55 (9)	N4—C10—C9	123.01 (10)
N6—N5—C13	117.95 (9)	C11—C10—C9	121.33 (9)
C11—N5—C13	126.46 (9)	N5—C11—C12	105.58 (9)
N5—N6—O1	104.02 (9)	N5—C11—C10	125.07 (9)
C2—C1—C6	120.65 (11)	C12—C11—C10	129.17 (10)
C2—C1—H1A	119.7	O2—C12—O1	120.14 (11)
C6—C1—H1A	119.7	O2—C12—C11	136.24 (12)
C1—C2—C3	118.54 (11)	O1—C12—C11	103.54 (9)
C1—C2—H2A	120.7	C14—C13—C18	122.57 (10)
C3—C2—H2A	120.7	C14—C13—N5	119.37 (10)
C4—C3—C2	122.18 (11)	C18—C13—N5	118.04 (9)
C4—C3—Cl1	118.32 (10)	C13—C14—C15	117.91 (10)
C2—C3—Cl1	119.49 (10)	C13—C14—H14A	121.0
C5—C4—C3	118.46 (11)	C15—C14—H14A	121.0
C5—C4—H4A	120.8	C16—C15—C14	120.63 (10)
C3—C4—H4A	120.8	C16—C15—H15A	119.7
C4—C5—C6	121.04 (11)	C14—C15—H15A	119.7
C4—C5—H5A	119.5	C15—C16—C17	120.33 (11)
C6—C5—H5A	119.5	C15—C16—H16A	119.8
C5—C6—C1	119.11 (11)	C17—C16—H16A	119.8
C5—C6—C7	118.29 (10)	C18—C17—C16	120.13 (11)
C1—C6—C7	122.59 (10)	C18—C17—H17A	119.9
N1—C7—C6	121.78 (10)	C16—C17—H17A	119.9
N1—C7—H7A	119.1	C13—C18—C17	118.43 (10)
C6—C7—H7A	119.1	C13—C18—H18A	120.8
N2—C8—N3	117.39 (9)	C17—C18—H18A	120.8
N2—C8—S1	122.56 (8)
C7—N1—N2—C8	−175.59 (10)	S1—C9—C10—C11	−137.68 (9)
C8—N3—N4—C10	−32.21 (16)	N6—N5—C11—C12	0.24 (13)
C11—N5—N6—O1	−0.32 (13)	C13—N5—C11—C12	177.95 (10)
C13—N5—N6—O1	−178.24 (9)	N6—N5—C11—C10	175.72 (10)
C12—O1—N6—N5	0.28 (12)	C13—N5—C11—C10	−6.57 (17)
C6—C1—C2—C3	0.77 (18)	N4—C10—C11—N5	145.80 (11)
C1—C2—C3—C4	−0.37 (19)	C9—C10—C11—N5	−33.52 (17)
C1—C2—C3—Cl1	−179.55 (9)	N4—C10—C11—C12	−39.82 (16)
C2—C3—C4—C5	−0.58 (18)	C9—C10—C11—C12	140.87 (12)
Cl1—C3—C4—C5	178.61 (9)	N6—O1—C12—O2	−177.42 (10)
C3—C4—C5—C6	1.14 (18)	N6—O1—C12—C11	−0.15 (12)
C4—C5—C6—C1	−0.75 (17)	N5—C11—C12—O2	176.55 (13)
C4—C5—C6—C7	−179.85 (11)	C10—C11—C12—O2	1.3 (2)
C2—C1—C6—C5	−0.23 (17)	N5—C11—C12—O1	−0.04 (11)
C2—C1—C6—C7	178.83 (11)	C10—C11—C12—O1	−175.28 (10)
N2—N1—C7—C6	−177.30 (10)	N6—N5—C13—C14	−63.26 (14)
C5—C6—C7—N1	−172.94 (11)	C11—N5—C13—C14	119.08 (12)
C1—C6—C7—N1	8.00 (18)	N6—N5—C13—C18	118.73 (11)
N1—N2—C8—N3	−177.81 (9)	C11—N5—C13—C18	−58.93 (15)
N1—N2—C8—S1	5.18 (14)	C18—C13—C14—C15	0.06 (16)
N4—N3—C8—N2	−157.47 (11)	N5—C13—C14—C15	−177.86 (10)
N4—N3—C8—S1	19.62 (15)	C13—C14—C15—C16	0.09 (16)
C9—S1—C8—N2	−165.26 (10)	C14—C15—C16—C17	−0.21 (17)
C9—S1—C8—N3	17.80 (10)	C15—C16—C17—C18	0.17 (18)
C8—S1—C9—C10	−43.84 (10)	C14—C13—C18—C17	−0.10 (17)
N3—N4—C10—C11	177.00 (9)	N5—C13—C18—C17	177.85 (10)
N3—N4—C10—C9	−3.70 (16)	C16—C17—C18—C13	−0.01 (17)
S1—C9—C10—N4	43.07 (15)

Cg2 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···N2i	0.84 (2)	2.03 (2)	2.8752 (14)	178 (2)
C9—H9A···Cl1ii	0.97	2.78	3.4904 (13)	130
C18—H18A···S1iii	0.93	2.86	3.6729 (12)	147
C17—H17A···Cg2iv	0.93	2.64	3.5208 (15)	158

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯N2i	0.84 (2)	2.03 (2)	2.8752 (14)	178 (2)
C9—H9A⋯Cl1ii	0.97	2.78	3.4904 (13)	130
C18—H18A⋯S1iii	0.93	2.86	3.6729 (12)	147
C17—H17A⋯Cg2iv	0.93	2.64	3.5208 (15)	158

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