5-({[(E)-Benzyl­idene­amino]­oxy}meth­yl)-1,3,4-thia­diazol-2-amine

Yin, W.; Wang, Z.; Yang, Z.-W.

doi:10.1107/S1600536812003893

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o769

doi:10.1107/S1600536812003893

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5-({[(E)-Benzylideneamino]oxy}methyl)-1,3,4-thiadiazol-2-amine

Weiyan Yin,^a ^* Zhi Wang ^a and Zi-Wen Yang ^a

^aHubei Biopesticide Engineering Research Center, Hubei Academy of Agricultural Science, Wuhan 430064, People's Republic of China
^*Correspondence e-mail: hpywy2006@163.com

(Received 15 December 2011; accepted 30 January 2012; online 17 February 2012)

In the molecule of the title compound, C₁₀H₁₀N₄OS, the configuration about the C=N double bond is E. The dihedral angle between the thiadiazole and benzene rings is 81.1 (1)°. In the crystal, molecules are linked by N—H⋯N and C—H⋯O hydrogen bonds to form a two-dimensional network parallel with the bc plane.

Related literature

For the biological activity of thiadiazol compounds, see: Cressier et al. (2009 ); Ferrari et al. (2011 ). For a related structure, see: Boechat et al. (2006 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₁₀N₄OS
M_r = 234.28
Monoclinic, P 2₁ /c
a = 14.504 (4) Å
b = 9.272 (3) Å
c = 8.361 (3) Å
β = 106.75 (1)°
V = 1076.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 K
0.16 × 0.12 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.956, T_max = 0.967
5840 measured reflections
1808 independent reflections
1707 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.110
S = 1.09
1808 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N2ⁱ	0.88	2.24	3.077 (3)	159
N4—H4B⋯N3ⁱⁱ	0.88	2.07	2.929 (3)	164
C8—H8A⋯O1ⁱⁱⁱ	0.99	2.51	3.468 (3)	163
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812003893/fy2038sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003893/fy2038Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003893/fy2038Isup3.cml

checkCIF report

Comment top

The thiadiazol moiety is the constituent of many biologically significant compounds. Thiadiazol derivatives showed diverse biological properties, such as antiparasitic activity (Ferrari et al., 2011), antioxidant properties and radioprotective effects (Cressier et al., 2009). As a part of our study on the synthesis of novel thiadiazol-containing compounds with good biological activities, we report here the crystal structure of the title compound, (I)(Fig. 1).

In the molecule, all bond lengths and angles are normal(Allen et al., 1987). The conformation of the N—H and the C=N bonds in the thiadiazol segment is similar to that observed in other thiadiazol compounds (Boechat et al., 2006). The dihedral angle between the thiadiazol and the benzene rings is 81.1 (1)°. The molecular structure is linked by intermolecular N—H···N and C—H···O hydrogen-bonds to form a two-dimensional network (Table 1, Fig. 2).

Related literature top

For the biological activity of thiadiazol compounds, see: Cressier et al. (2009); Ferrari et al. (2011). For a related structure, see: Boechat et al. (2006). For reference structural data, see: Allen et al. (1987).

Experimental top

To a mixture of aminothiourea (0.43 g, 4.7 mmol) and benzylideneaminooxyacetic acid (0.75 g, 4.3 mmol) phosphorus oxychloride (16.3 mmol) was added dropwise. The reaction mixture was heated at 353 K for 15 min, then cooled to room temperature and water (4.8 mL) was added slowly. After the addtion of water, the reaction mixture was first heated at 383 K for 4 h then cooled to room temperature. The pH of the reaction mixture was then adjusted to 8–9 by addition of 40% aqueous NaOH solution. The crude product was collected by filtration. Single crystals were obtained by evaporation of an ether solution of (I) at room temperature over a period of several days.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. Crystal packing diagram of (I). Hydrogen bonds are shown as dashed lines.

5-({[(E)-Benzylideneamino]oxy}methyl)-1,3,4-thiadiazol-2-amine top

Crystal data top

C₁₀H₁₀N₄OS	F(000) = 488
M_r = 234.28	D_x = 1.445 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7867 reflections
a = 14.504 (4) Å	θ = 2.2–31.8°
b = 9.272 (3) Å	µ = 0.28 mm⁻¹
c = 8.361 (3) Å	T = 100 K
β = 106.75 (1)°	Block, colorless
V = 1076.7 (6) Å³	0.16 × 0.12 × 0.12 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	1808 independent reflections
Radiation source: fine-focus sealed tube	1707 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→15
T_min = 0.956, T_max = 0.967	k = −11→10
5840 measured reflections	l = −9→9

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0274P)² + 2.2787P] where P = (F_o² + 2F_c²)/3
1808 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

C₁₀H₁₀N₄OS	V = 1076.7 (6) Å³
M_r = 234.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.504 (4) Å	µ = 0.28 mm⁻¹
b = 9.272 (3) Å	T = 100 K
c = 8.361 (3) Å	0.16 × 0.12 × 0.12 mm
β = 106.75 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	1808 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1707 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.967	R_int = 0.034
5840 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.09	Δρ_max = 0.31 e Å⁻³
1808 reflections	Δρ_min = −0.61 e Å⁻³
145 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.01298 (17)	0.3905 (3)	0.3290 (3)	0.0184 (5)
C2	−0.03790 (18)	0.4774 (3)	0.1867 (3)	0.0215 (6)
H2	0.0110	0.5234	0.1502	0.026*
C3	−0.13385 (19)	0.4967 (3)	0.0985 (4)	0.0252 (6)
H3	−0.1507	0.5548	0.0007	0.030*
C4	−0.20545 (19)	0.4310 (3)	0.1531 (4)	0.0264 (6)
H4	−0.2712	0.4441	0.0925	0.032*
C5	−0.18121 (18)	0.3468 (3)	0.2954 (4)	0.0253 (6)
H5	−0.2304	0.3018	0.3320	0.030*
C6	−0.08548 (18)	0.3276 (3)	0.3849 (3)	0.0215 (6)
H6	−0.0692	0.2716	0.4843	0.026*
C7	0.08712 (17)	0.3580 (3)	0.4188 (3)	0.0196 (5)
H7	0.1040	0.3320	0.5335	0.024*
C8	0.30958 (17)	0.3047 (3)	0.3626 (3)	0.0209 (6)
H8A	0.2771	0.2631	0.2517	0.025*
H8B	0.3607	0.2370	0.4222	0.025*
C9	0.35421 (16)	0.4469 (3)	0.3404 (3)	0.0178 (5)
C12	0.42588 (16)	0.6806 (3)	0.3667 (3)	0.0171 (5)
N1	0.15225 (14)	0.3645 (2)	0.3424 (3)	0.0208 (5)
N2	0.39251 (14)	0.4743 (2)	0.2222 (3)	0.0196 (5)
N3	0.43442 (15)	0.6105 (2)	0.2357 (3)	0.0201 (5)
N4	0.45809 (15)	0.8148 (2)	0.4095 (3)	0.0213 (5)
H4A	0.4876	0.8624	0.3475	0.026*
H4B	0.4498	0.8552	0.4995	0.026*
O1	0.24135 (12)	0.3211 (2)	0.4548 (2)	0.0230 (4)
S1	0.36427 (4)	0.58523 (7)	0.48329 (8)	0.0189 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0195 (12)	0.0160 (12)	0.0206 (14)	−0.0003 (9)	0.0072 (10)	−0.0032 (10)
C2	0.0232 (13)	0.0183 (13)	0.0249 (14)	−0.0024 (10)	0.0100 (11)	−0.0010 (10)
C3	0.0291 (14)	0.0167 (13)	0.0267 (15)	0.0039 (10)	0.0029 (11)	0.0012 (11)
C4	0.0184 (12)	0.0258 (14)	0.0328 (16)	0.0029 (10)	0.0040 (11)	−0.0073 (12)
C5	0.0193 (12)	0.0270 (14)	0.0325 (16)	−0.0021 (11)	0.0122 (11)	−0.0026 (12)
C6	0.0224 (12)	0.0194 (13)	0.0243 (14)	0.0006 (10)	0.0095 (11)	0.0000 (10)
C7	0.0206 (12)	0.0162 (12)	0.0222 (14)	−0.0008 (10)	0.0064 (10)	0.0007 (10)
C8	0.0168 (11)	0.0216 (13)	0.0260 (15)	0.0008 (10)	0.0090 (10)	−0.0007 (10)
C9	0.0144 (11)	0.0186 (12)	0.0202 (13)	0.0033 (9)	0.0049 (10)	0.0010 (10)
C12	0.0119 (10)	0.0237 (13)	0.0163 (13)	0.0037 (9)	0.0051 (9)	0.0027 (10)
N1	0.0165 (10)	0.0211 (11)	0.0218 (12)	−0.0007 (8)	0.0007 (9)	0.0007 (9)
N2	0.0180 (10)	0.0227 (11)	0.0190 (11)	0.0005 (8)	0.0067 (8)	−0.0010 (9)
N3	0.0200 (10)	0.0203 (11)	0.0212 (12)	0.0026 (8)	0.0079 (9)	0.0001 (9)
N4	0.0257 (11)	0.0207 (11)	0.0210 (12)	−0.0044 (9)	0.0122 (9)	−0.0029 (9)
O1	0.0157 (8)	0.0283 (10)	0.0239 (10)	0.0009 (7)	0.0038 (7)	0.0023 (8)
S1	0.0204 (3)	0.0219 (3)	0.0177 (4)	−0.0020 (2)	0.0106 (2)	−0.0010 (2)

Geometric parameters (Å, º) top

C1—C2	1.396 (4)	C8—O1	1.426 (3)
C1—C6	1.396 (4)	C8—C9	1.503 (3)
C1—C7	1.461 (3)	C8—H8A	0.9900
C2—C3	1.386 (4)	C8—H8B	0.9900
C2—H2	0.9500	C9—N2	1.291 (3)
C3—C4	1.390 (4)	C9—S1	1.730 (3)
C3—H3	0.9500	C12—N3	1.309 (3)
C4—C5	1.381 (4)	C12—N4	1.341 (3)
C4—H4	0.9500	C12—S1	1.742 (2)
C5—C6	1.386 (4)	N1—O1	1.419 (3)
C5—H5	0.9500	N2—N3	1.392 (3)
C6—H6	0.9500	N4—H4A	0.8800
C7—N1	1.285 (3)	N4—H4B	0.8800
C7—H7	0.9500

C2—C1—C6	119.5 (2)	O1—C8—C9	111.4 (2)
C2—C1—C7	122.2 (2)	O1—C8—H8A	109.4
C6—C1—C7	118.3 (2)	C9—C8—H8A	109.4
C3—C2—C1	120.1 (2)	O1—C8—H8B	109.4
C3—C2—H2	119.9	C9—C8—H8B	109.4
C1—C2—H2	119.9	H8A—C8—H8B	108.0
C2—C3—C4	120.0 (3)	N2—C9—C8	124.3 (2)
C2—C3—H3	120.0	N2—C9—S1	114.39 (19)
C4—C3—H3	120.0	C8—C9—S1	121.23 (19)
C5—C4—C3	120.1 (2)	N3—C12—N4	125.0 (2)
C5—C4—H4	119.9	N3—C12—S1	113.79 (19)
C3—C4—H4	119.9	N4—C12—S1	121.15 (19)
C4—C5—C6	120.3 (2)	C7—N1—O1	108.5 (2)
C4—C5—H5	119.9	C9—N2—N3	113.0 (2)
C6—C5—H5	119.9	C12—N3—N2	112.0 (2)
C5—C6—C1	120.0 (3)	C12—N4—H4A	120.0
C5—C6—H6	120.0	C12—N4—H4B	120.0
C1—C6—H6	120.0	H4A—N4—H4B	120.0
N1—C7—C1	119.9 (2)	N1—O1—C8	108.28 (19)
N1—C7—H7	120.0	C9—S1—C12	86.84 (12)
C1—C7—H7	120.0

C6—C1—C2—C3	−2.3 (4)	C1—C7—N1—O1	−177.0 (2)
C7—C1—C2—C3	175.2 (2)	C8—C9—N2—N3	−176.0 (2)
C1—C2—C3—C4	0.9 (4)	S1—C9—N2—N3	0.3 (3)
C2—C3—C4—C5	0.1 (4)	N4—C12—N3—N2	−178.9 (2)
C3—C4—C5—C6	0.2 (4)	S1—C12—N3—N2	−0.6 (3)
C4—C5—C6—C1	−1.6 (4)	C9—N2—N3—C12	0.2 (3)
C2—C1—C6—C5	2.6 (4)	C7—N1—O1—C8	170.3 (2)
C7—C1—C6—C5	−175.0 (2)	C9—C8—O1—N1	83.4 (2)
C2—C1—C7—N1	−24.1 (4)	N2—C9—S1—C12	−0.50 (19)
C6—C1—C7—N1	153.4 (2)	C8—C9—S1—C12	175.9 (2)
O1—C8—C9—N2	−156.5 (2)	N3—C12—S1—C9	0.63 (19)
O1—C8—C9—S1	27.5 (3)	N4—C12—S1—C9	179.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2ⁱ	0.88	2.24	3.077 (3)	159
N4—H4B···N3ⁱⁱ	0.88	2.07	2.929 (3)	164
C8—H8A···O1ⁱⁱⁱ	0.99	2.51	3.468 (3)	163

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+3/2, z+1/2; (iii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₄OS
M_r	234.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.504 (4), 9.272 (3), 8.361 (3)
β (°)	106.75 (1)
V (Å³)	1076.7 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.16 × 0.12 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.956, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	5840, 1808, 1707
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.110, 1.09
No. of reflections	1808
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.61

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2ⁱ	0.88	2.24	3.077 (3)	159
N4—H4B···N3ⁱⁱ	0.88	2.07	2.929 (3)	164
C8—H8A···O1ⁱⁱⁱ	0.99	2.51	3.468 (3)	163

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+3/2, z+1/2; (iii) x, −y+1/2, z−1/2.

Acknowledgements

We gratefully acknowledge the financial support of this work by the Foundation of Hubei Agricultural Scientific and Technological Innovation.

References

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