3-(4-Methyl-phen-yl)-4-[(thio-semi-carba-zono)meth-yl]-1,2,3-oxa-diazol-3-ium-5-olate 1,4-dioxane hemisolvate.

The asymmetric unit of the title compound, C11H11N5O2S·0.5C4H8O2, contains one 3-(p-tol-yl)sydnone 4-thio-semi-carba-zone mol-ecule and a half mol-ecule of 1,4-dioxane, which lies abount an inversion centre. The sydnone ring is almost planar, with a maximum deviation of 0.002 (1) Å, and forms a dihedral angle of 46.31 (5)° with the benzene ring. In the crystal, the two components are linked into a tape along [01-1] by N-H⋯O and N-H⋯S hydrogen bonds. The crystal structure is further stabilized by C-H⋯O and C-H⋯π inter-actions, forming a three-dimensional network.

Related literature

For the biological acitivity of sydnones, see: Rai et al. (2008 ▶); Jyothi et al. (2008 ▶); Nithinchandra et al. (2012 ▶); Kalluraya et al. (2001 ▶). For a related structure, see: Fun et al. (2011 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C11H11N5O2S·0.5C4H8O2

M = 321.36

Triclinic,

a = 7.7463 (1) Å

b = 9.3776 (1) Å

c = 10.4449 (2) Å

α = 79.689 (1)°

β = 87.168 (1)°

γ = 87.461 (1)°

V = 745.09 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.24 mm−1

T = 100 K

0.35 × 0.29 × 0.24 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.921, T max = 0.944

19865 measured reflections

5407 independent reflections

4782 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.090

S = 1.08

5407 reflections

212 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.24 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813008805/is5258sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008805/is5258Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813008805/is5258Isup3.cml

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

C11H11N5O2S·0.5C4H8O2	Z = 2
Mr = 321.36	F(000) = 336
Triclinic, P1	Dx = 1.432 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7463 (1) Å	Cell parameters from 9931 reflections
b = 9.3776 (1) Å	θ = 2.2–32.7°
c = 10.4449 (2) Å	µ = 0.24 mm−1
α = 79.689 (1)°	T = 100 K
β = 87.168 (1)°	Block, yellow
γ = 87.461 (1)°	0.35 × 0.29 × 0.24 mm
V = 745.09 (2) Å3

Bruker APEXII CCD area-detector diffractometer	5407 independent reflections
Radiation source: fine-focus sealed tube	4782 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 32.7°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.921, Tmax = 0.944	k = −14→14
19865 measured reflections	l = −15→15

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0369P)2 + 0.310P] where P = (Fo2 + 2Fc2)/3
5407 reflections	(Δ/σ)max = 0.002
212 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.24 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
S1	1.09153 (3)	0.32862 (3)	−0.33706 (2)	0.01659 (6)
O1	0.47671 (10)	0.67385 (8)	0.20795 (7)	0.01898 (15)
O2	0.57636 (11)	0.75787 (8)	0.00058 (8)	0.02035 (15)
N1	0.59090 (11)	0.46077 (9)	0.24338 (8)	0.01427 (15)
N2	0.48951 (12)	0.54926 (10)	0.29962 (9)	0.01841 (17)
N3	0.79973 (11)	0.49150 (9)	−0.07807 (8)	0.01443 (15)
N4	0.91376 (11)	0.40423 (9)	−0.13781 (8)	0.01460 (15)
N5	0.90336 (13)	0.57238 (10)	−0.32586 (9)	0.01962 (17)
C1	0.68059 (14)	0.31717 (11)	0.44782 (10)	0.01739 (18)
H1A	0.6855	0.4040	0.4823	0.021*
C2	0.72069 (14)	0.18334 (11)	0.52322 (10)	0.01834 (18)
H2A	0.7512	0.1787	0.6109	0.022*
C3	0.71703 (13)	0.05535 (11)	0.47262 (10)	0.01713 (18)
C4	0.66732 (14)	0.06363 (11)	0.34462 (10)	0.01855 (18)
H4A	0.6633	−0.0228	0.3095	0.022*
C5	0.62369 (14)	0.19592 (11)	0.26773 (10)	0.01751 (18)
H5A	0.5883	0.2008	0.1812	0.021*
C6	0.63314 (13)	0.32100 (10)	0.32082 (9)	0.01490 (17)
C7	0.57264 (13)	0.65882 (11)	0.09278 (10)	0.01562 (17)
C8	0.64729 (12)	0.51563 (10)	0.11978 (9)	0.01360 (16)
C9	0.76555 (12)	0.44016 (10)	0.04353 (9)	0.01363 (16)
H9A	0.8197	0.3512	0.0827	0.016*
C10	0.96088 (12)	0.44310 (10)	−0.26539 (9)	0.01415 (16)
C11	0.76728 (15)	−0.08866 (12)	0.55341 (11)	0.0222 (2)
H11A	0.6967	−0.1643	0.5313	0.033*
H11B	0.7480	−0.0838	0.6460	0.033*
H11C	0.8898	−0.1117	0.5356	0.033*
O3	−0.07175 (11)	0.12953 (8)	1.03347 (8)	0.02138 (16)
C12	0.07792 (15)	0.05932 (12)	1.09562 (11)	0.0217 (2)
H12A	0.0419	−0.0077	1.1759	0.026*
H12B	0.1517	0.1328	1.1203	0.026*
C13	−0.17918 (15)	0.02410 (13)	0.99557 (12)	0.0237 (2)
H13A	−0.2815	0.0737	0.9518	0.028*
H13B	−0.2203	−0.0436	1.0739	0.028*
H1N4	0.947 (2)	0.3189 (18)	−0.0967 (16)	0.028 (4)*
H1N5	0.919 (2)	0.5963 (19)	−0.4101 (18)	0.036 (4)*
H2N5	0.826 (2)	0.6209 (18)	−0.2864 (16)	0.030 (4)*

	U11	U22	U33	U12	U13	U23
S1	0.02010 (12)	0.01732 (11)	0.01242 (10)	0.00041 (8)	0.00249 (8)	−0.00394 (8)
O1	0.0199 (3)	0.0181 (3)	0.0193 (3)	0.0032 (3)	0.0007 (3)	−0.0054 (3)
O2	0.0241 (4)	0.0157 (3)	0.0206 (4)	0.0000 (3)	−0.0040 (3)	−0.0009 (3)
N1	0.0148 (3)	0.0160 (3)	0.0123 (3)	−0.0012 (3)	0.0019 (3)	−0.0038 (3)
N2	0.0190 (4)	0.0195 (4)	0.0168 (4)	0.0016 (3)	0.0036 (3)	−0.0054 (3)
N3	0.0155 (3)	0.0152 (3)	0.0129 (3)	−0.0005 (3)	0.0013 (3)	−0.0036 (3)
N4	0.0182 (4)	0.0145 (3)	0.0107 (3)	0.0008 (3)	0.0022 (3)	−0.0021 (3)
N5	0.0247 (4)	0.0181 (4)	0.0139 (4)	0.0032 (3)	0.0046 (3)	0.0006 (3)
C1	0.0214 (4)	0.0179 (4)	0.0133 (4)	−0.0031 (4)	0.0020 (3)	−0.0042 (3)
C2	0.0215 (5)	0.0214 (4)	0.0123 (4)	−0.0021 (4)	−0.0009 (3)	−0.0031 (3)
C3	0.0170 (4)	0.0184 (4)	0.0149 (4)	−0.0002 (3)	0.0018 (3)	−0.0007 (3)
C4	0.0240 (5)	0.0168 (4)	0.0153 (4)	−0.0014 (4)	0.0013 (3)	−0.0042 (3)
C5	0.0224 (5)	0.0180 (4)	0.0125 (4)	−0.0027 (4)	0.0012 (3)	−0.0037 (3)
C6	0.0166 (4)	0.0155 (4)	0.0121 (4)	−0.0018 (3)	0.0025 (3)	−0.0015 (3)
C7	0.0158 (4)	0.0161 (4)	0.0160 (4)	−0.0012 (3)	−0.0012 (3)	−0.0056 (3)
C8	0.0149 (4)	0.0138 (4)	0.0120 (4)	−0.0007 (3)	0.0013 (3)	−0.0026 (3)
C9	0.0148 (4)	0.0139 (4)	0.0124 (4)	−0.0012 (3)	0.0007 (3)	−0.0032 (3)
C10	0.0149 (4)	0.0155 (4)	0.0122 (4)	−0.0027 (3)	0.0012 (3)	−0.0026 (3)
C11	0.0242 (5)	0.0199 (5)	0.0206 (5)	0.0029 (4)	−0.0003 (4)	0.0004 (4)
O3	0.0263 (4)	0.0143 (3)	0.0233 (4)	0.0020 (3)	0.0021 (3)	−0.0041 (3)
C12	0.0271 (5)	0.0205 (5)	0.0178 (5)	−0.0019 (4)	−0.0015 (4)	−0.0036 (4)
C13	0.0207 (5)	0.0227 (5)	0.0281 (5)	0.0016 (4)	−0.0007 (4)	−0.0060 (4)

S1—C10	1.6893 (10)	C3—C11	1.5051 (14)
O1—N2	1.3749 (12)	C4—C5	1.3897 (14)
O1—C7	1.4079 (12)	C4—H4A	0.9500
O2—C7	1.2126 (12)	C5—C6	1.3903 (14)
N1—N2	1.3122 (11)	C5—H5A	0.9500
N1—C8	1.3597 (12)	C7—C8	1.4244 (13)
N1—C6	1.4449 (13)	C8—C9	1.4306 (13)
N3—C9	1.2939 (12)	C9—H9A	0.9500
N3—N4	1.3797 (11)	C11—H11A	0.9800
N4—C10	1.3534 (12)	C11—H11B	0.9800
N4—H1N4	0.871 (16)	C11—H11C	0.9800
N5—C10	1.3316 (13)	O3—C12	1.4329 (14)
N5—H1N5	0.872 (18)	O3—C13	1.4395 (14)
N5—H2N5	0.868 (17)	C12—C13i	1.5076 (16)
C1—C6	1.3878 (14)	C12—H12A	0.9900
C1—C2	1.3884 (14)	C12—H12B	0.9900
C1—H1A	0.9500	C13—C12i	1.5076 (16)
C2—C3	1.3972 (14)	C13—H13A	0.9900
C2—H2A	0.9500	C13—H13B	0.9900
C3—C4	1.3974 (14)
N2—O1—C7	111.07 (7)	O2—C7—C8	135.35 (10)
N2—N1—C8	114.90 (8)	O1—C7—C8	104.14 (8)
N2—N1—C6	116.69 (8)	N1—C8—C7	105.26 (8)
C8—N1—C6	128.37 (8)	N1—C8—C9	123.94 (9)
N1—N2—O1	104.63 (7)	C7—C8—C9	130.70 (9)
C9—N3—N4	113.44 (8)	N3—C9—C8	120.84 (9)
C10—N4—N3	120.28 (8)	N3—C9—H9A	119.6
C10—N4—H1N4	118.9 (11)	C8—C9—H9A	119.6
N3—N4—H1N4	120.4 (11)	N5—C10—N4	117.10 (9)
C10—N5—H1N5	119.6 (12)	N5—C10—S1	124.08 (7)
C10—N5—H2N5	119.2 (11)	N4—C10—S1	118.81 (7)
H1N5—N5—H2N5	118.8 (15)	C3—C11—H11A	109.5
C6—C1—C2	118.34 (9)	C3—C11—H11B	109.5
C6—C1—H1A	120.8	H11A—C11—H11B	109.5
C2—C1—H1A	120.8	C3—C11—H11C	109.5
C1—C2—C3	121.26 (9)	H11A—C11—H11C	109.5
C1—C2—H2A	119.4	H11B—C11—H11C	109.5
C3—C2—H2A	119.4	C12—O3—C13	110.28 (8)
C2—C3—C4	118.66 (9)	O3—C12—C13i	109.89 (9)
C2—C3—C11	120.90 (9)	O3—C12—H12A	109.7
C4—C3—C11	120.44 (9)	C13i—C12—H12A	109.7
C5—C4—C3	121.25 (9)	O3—C12—H12B	109.7
C5—C4—H4A	119.4	C13i—C12—H12B	109.7
C3—C4—H4A	119.4	H12A—C12—H12B	108.2
C4—C5—C6	118.22 (9)	O3—C13—C12i	109.94 (9)
C4—C5—H5A	120.9	O3—C13—H13A	109.7
C6—C5—H5A	120.9	C12i—C13—H13A	109.7
C1—C6—C5	122.23 (9)	O3—C13—H13B	109.7
C1—C6—N1	117.89 (9)	C12i—C13—H13B	109.7
C5—C6—N1	119.87 (9)	H13A—C13—H13B	108.2
O2—C7—O1	120.50 (9)
C8—N1—N2—O1	−0.38 (11)	N2—O1—C7—O2	179.80 (9)
C6—N1—N2—O1	177.55 (8)	N2—O1—C7—C8	−0.36 (10)
C7—O1—N2—N1	0.46 (10)	N2—N1—C8—C7	0.17 (11)
C9—N3—N4—C10	179.48 (9)	C6—N1—C8—C7	−177.48 (9)
C6—C1—C2—C3	1.24 (16)	N2—N1—C8—C9	176.73 (9)
C1—C2—C3—C4	−1.73 (16)	C6—N1—C8—C9	−0.92 (16)
C1—C2—C3—C11	177.64 (10)	O2—C7—C8—N1	179.92 (12)
C2—C3—C4—C5	0.61 (16)	O1—C7—C8—N1	0.12 (10)
C11—C3—C4—C5	−178.75 (10)	O2—C7—C8—C9	3.7 (2)
C3—C4—C5—C6	0.93 (16)	O1—C7—C8—C9	−176.11 (10)
C2—C1—C6—C5	0.39 (15)	N4—N3—C9—C8	−178.91 (8)
C2—C1—C6—N1	179.72 (9)	N1—C8—C9—N3	172.48 (9)
C4—C5—C6—C1	−1.46 (15)	C7—C8—C9—N3	−11.90 (16)
C4—C5—C6—N1	179.22 (9)	N3—N4—C10—N5	5.06 (14)
N2—N1—C6—C1	−45.36 (13)	N3—N4—C10—S1	−176.46 (7)
C8—N1—C6—C1	132.25 (11)	C13—O3—C12—C13i	58.64 (12)
N2—N1—C6—C5	133.99 (10)	C12—O3—C13—C12i	−58.67 (12)
C8—N1—C6—C5	−48.40 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···O3ii	0.872 (17)	2.040 (17)	2.8624 (12)	156.8 (14)
N5—H1N5···S1iii	0.872 (18)	2.613 (18)	3.4754 (9)	170.2 (14)
C5—H5A···O2iv	0.95	2.31	3.2215 (13)	162
C9—H9A···O3ii	0.95	2.34	3.1394 (12)	141
C12—H12B···O2v	0.99	2.56	3.2626 (14)	128
C11—H11A···Cg1vi	0.98	2.94	3.5736 (12)	123

Table 1

Hydrogen-bond geometry (Å, °)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯O3i	0.872 (17)	2.040 (17)	2.8624 (12)	156.8 (14)
N5—H1N5⋯S1ii	0.872 (18)	2.613 (18)	3.4754 (9)	170.2 (14)
C5—H5A⋯O2iii	0.95	2.31	3.2215 (13)	162
C9—H9A⋯O3i	0.95	2.34	3.1394 (12)	141
C12—H12B⋯O2iv	0.99	2.56	3.2626 (14)	128
C11—H11A⋯Cg1v	0.98	2.94	3.5736 (12)	123

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