2-(1-Benzo­thio­phen-2-yl)-4H-1,3,4-oxa­diazin-5(6H)-one

Sun, H.-S.; Li, Y.-L.; Xu, N.; Shen, L.-J.

doi:10.1107/S1600536813033291

organic compounds

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ISSN: 2056-9890

Volume 70| Part 1| January 2014| Page o41

https://doi.org/10.1107/S1600536813033291

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2-(1-Benzothiophen-2-yl)-4H-1,3,4-oxadiazin-5(6H)-one

Hong-Shun Sun,^a,^b ^* Yu-Long Li,^a Ning Xu ^a and Lin-Jiang Shen ^b

^aChemical Engineering Department, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China, and ^bCollege of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: njutshs@126.com

(Received 27 November 2013; accepted 9 December 2013; online 14 December 2013)

In the title compound, C₁₁H₈N₂O₂S, the oxadiazinone ring is nearly planar [maximum deviation = 0.016 (4) Å], and is approximately coplanar with the benzothiophene ring system [dihedral angle = 3.1 (5)°]. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains running along the b-axis direction.

CCDC reference: 975730

Related literature

For applications of oxadiazin derivatives, see: De Sarro et al. (2005 ); Shigeki et al. (2012 ).

Experimental

Crystal data

C₁₁H₈N₂O₂S
M_r = 232.25
Monoclinic, P 2₁ /n
a = 7.4950 (15) Å
b = 6.0350 (12) Å
c = 22.412 (5) Å
β = 93.08 (3)°
V = 1012.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.915, T_max = 0.970
1999 measured reflections
1848 independent reflections
1167 reflections with I > 2σ(I)
R_int = 0.064
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.192
S = 1.00
1848 reflections
145 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	2.03	2.848 (5)	158
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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.

Supporting information

CCDC reference: 975730

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S1600536813033291/xu5757sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813033291/xu5757Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813033291/xu5757Isup3.cml

checkCIF report

Comment top

Noncompetitive α-amino-3-hydroxy-5-methyl-4-isoxazolepropanoic acid (AMPA) receptor antagonists have actively been explored, driven by the belief that such drugs would exercise effectiveness independent of glutamatelevels and the synaptic membrane polarization state, with minor influence on normal glutamatergic activity compared with competitive antagonists (De Sarro et al., 2005). Commercially available 2,4-diphenyl-4H-1,3,4-oxadiazin-5-one was selected as a suitable starting compound with a novel structure versus other HTS (high throughput screening) hit compounds and known noncompetitive AMPA antagonists (Shigeki et al., 2012). The title compound is a new oxadiazin compound with a similar structure to it. We synthesized it and report here its crystal structure.

The molecular structure of the title compound is shown in Fig. 1. The benzothiophene ring makes a dihedral angle of 3.1 (5)° to oxadiazin ring.

As shown in Figure 2, the molecules are linked by N—H···O and weak S···S (Table 1) bonds into a three-dimensional network, which consolidate the crystal packing.

Related literature top

For applications of oxadiazin derivatives, see: De Sarro et al. (2005); Shigeki et al. (2012).

Experimental top

N'-(2-chloroacetyl)benzo[b]thiophene-2-carbohydrazide (0.27 g, 1 mmol) was dissolved in 10 ml acetonitrile, after which potassium carbonate (0.28 g, 2.0 mmol) was added and the mixture was refluxed for 3 h under heating. The reaction solution was left and cooled to room temperature, evaporated, diluted with EtOAc, washed with water and brine, and then dried over MgSO₄. After the drying agent was filtered off, the product was evaporated and the resulting crystalline residues were recrystallized from n-hexane and EtOAc to give the compound (0.19 g, 0.8 mmol, 80.0%) as a yellow crystal suitable for X-ray analysis.

Structure description top

The molecular structure of the title compound is shown in Fig. 1. The benzothiophene ring makes a dihedral angle of 3.1 (5)° to oxadiazin ring.

As shown in Figure 2, the molecules are linked by N—H···O and weak S···S (Table 1) bonds into a three-dimensional network, which consolidate the crystal packing.

For applications of oxadiazin derivatives, see: De Sarro et al. (2005); Shigeki et al. (2012).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level.
	Fig. 2. A packing diagram of (I). Intermolecular hydrogen bonds are shown as dashed lines.

2-(1-Benzothiophen-2-yl)-4H-1,3,4-oxadiazin-5(6H)-one top

Crystal data top

C₁₁H₈N₂O₂S	F(000) = 480
M_r = 232.25	D_x = 1.524 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.4950 (15) Å	θ = 9–12°
b = 6.0350 (12) Å	µ = 0.30 mm⁻¹
c = 22.412 (5) Å	T = 293 K
β = 93.08 (3)°	Block, colorless
V = 1012.3 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1167 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.064
Graphite monochromator	θ_max = 25.4°, θ_min = 1.8°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
T_min = 0.915, T_max = 0.970	l = −27→27
1999 measured reflections	3 standard reflections every 200 reflections
1848 independent reflections	intensity decay: 1%

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.192	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.650P] where P = (F_o² + 2F_c²)/3
1848 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.39 e Å⁻³
1 restraint	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₁₁H₈N₂O₂S	V = 1012.3 (4) Å³
M_r = 232.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4950 (15) Å	µ = 0.30 mm⁻¹
b = 6.0350 (12) Å	T = 293 K
c = 22.412 (5) Å	0.30 × 0.20 × 0.10 mm
β = 93.08 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1167 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.064
T_min = 0.915, T_max = 0.970	3 standard reflections every 200 reflections
1999 measured reflections	intensity decay: 1%
1848 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	1 restraint
wR(F²) = 0.192	H-atom parameters constrained
S = 1.00	Δρ_max = 0.39 e Å⁻³
1848 reflections	Δρ_min = −0.39 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
S	0.66885 (16)	0.2027 (2)	0.99910 (5)	0.0507 (4)
O2	0.8714 (5)	0.7881 (6)	1.23337 (14)	0.0632 (10)
O1	0.8545 (5)	0.7527 (5)	1.07326 (14)	0.0606 (10)
C1	0.6558 (5)	0.2443 (8)	0.92291 (17)	0.0391 (10)
N1	0.7891 (5)	0.5094 (6)	1.17093 (15)	0.0442 (9)
H1A	0.7685	0.4264	1.2010	0.053*
C2	0.5909 (6)	0.0894 (8)	0.8802 (2)	0.0491 (12)
H2B	0.5496	−0.0488	0.8917	0.059*
N2	0.7558 (5)	0.4203 (6)	1.11441 (15)	0.0430 (9)
C3	0.5905 (6)	0.1488 (9)	0.8209 (2)	0.0540 (13)
H3B	0.5454	0.0508	0.7918	0.065*
C4	0.6552 (6)	0.3490 (9)	0.8041 (2)	0.0555 (13)
H4A	0.6566	0.3817	0.7636	0.067*
C5	0.7186 (6)	0.5054 (8)	0.84494 (19)	0.0514 (12)
H5A	0.7590	0.6427	0.8325	0.062*
C6	0.7203 (6)	0.4501 (8)	0.90646 (18)	0.0429 (11)
C7	0.7809 (5)	0.5961 (8)	0.95690 (16)	0.0371 (10)
H7A	0.8256	0.7395	0.9550	0.044*
C8	0.7548 (5)	0.4656 (7)	1.00939 (17)	0.0379 (10)
C9	0.7923 (5)	0.5458 (7)	1.07104 (17)	0.0342 (9)
C10	0.8941 (6)	0.8522 (7)	1.13060 (19)	0.0461 (11)
H10A	0.8284	0.9903	1.1326	0.055*
H10B	1.0204	0.8878	1.1341	0.055*
C11	0.8500 (6)	0.7115 (8)	1.18252 (19)	0.0446 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0665 (8)	0.0529 (7)	0.0334 (7)	−0.0047 (6)	0.0096 (5)	0.0009 (6)
O2	0.076 (2)	0.082 (3)	0.0322 (18)	−0.002 (2)	0.0036 (15)	−0.0179 (18)
O1	0.104 (3)	0.049 (2)	0.0293 (18)	−0.0176 (18)	0.0092 (17)	−0.0028 (14)
C1	0.038 (2)	0.056 (3)	0.024 (2)	0.0058 (19)	0.0081 (17)	0.0047 (19)
N1	0.059 (2)	0.052 (2)	0.0225 (18)	−0.0017 (19)	0.0104 (16)	0.0012 (16)
C2	0.054 (3)	0.057 (3)	0.037 (3)	0.001 (2)	0.005 (2)	−0.006 (2)
N2	0.062 (2)	0.043 (2)	0.0248 (18)	0.0046 (18)	0.0097 (16)	−0.0007 (16)
C3	0.052 (3)	0.078 (4)	0.031 (2)	0.012 (3)	−0.002 (2)	−0.013 (3)
C4	0.064 (3)	0.079 (4)	0.024 (2)	0.019 (3)	0.007 (2)	0.003 (2)
C5	0.071 (3)	0.051 (3)	0.034 (3)	0.013 (2)	0.016 (2)	0.008 (2)
C6	0.046 (2)	0.053 (3)	0.031 (2)	0.009 (2)	0.0105 (18)	0.002 (2)
C7	0.0324 (19)	0.060 (3)	0.0186 (19)	0.013 (2)	0.0016 (15)	−0.0124 (19)
C8	0.049 (2)	0.041 (2)	0.024 (2)	0.007 (2)	0.0071 (17)	−0.0004 (18)
C9	0.042 (2)	0.036 (2)	0.026 (2)	0.0013 (18)	0.0036 (17)	−0.0014 (18)
C10	0.057 (3)	0.046 (3)	0.036 (2)	0.005 (2)	0.005 (2)	−0.007 (2)
C11	0.047 (2)	0.058 (3)	0.029 (2)	0.012 (2)	0.0056 (19)	−0.011 (2)

Geometric parameters (Å, º) top

S—C8	1.723 (5)	C3—C4	1.363 (7)
S—C1	1.723 (4)	C3—H3B	0.9300
O2—C11	1.232 (5)	C4—C5	1.382 (7)
O1—C9	1.333 (5)	C4—H4A	0.9300
O1—C10	1.435 (5)	C5—C6	1.418 (6)
C1—C6	1.390 (6)	C5—H5A	0.9300
C1—C2	1.406 (6)	C6—C7	1.485 (6)
N1—C11	1.323 (6)	C7—C8	1.438 (6)
N1—N2	1.387 (5)	C7—H7A	0.9300
N1—H1A	0.8600	C8—C9	1.477 (5)
C2—C3	1.377 (6)	C10—C11	1.492 (6)
C2—H2B	0.9300	C10—H10A	0.9700
N2—C9	1.274 (5)	C10—H10B	0.9700

C8—S—C1	90.0 (2)	C1—C6—C5	118.9 (4)
C9—O1—C10	118.7 (3)	C1—C6—C7	115.1 (4)
C6—C1—C2	121.8 (4)	C5—C6—C7	125.9 (4)
C6—C1—S	113.0 (3)	C8—C7—C6	104.4 (4)
C2—C1—S	125.2 (4)	C8—C7—H7A	127.8
C11—N1—N2	125.5 (4)	C6—C7—H7A	127.8
C11—N1—H1A	117.3	C7—C8—C9	124.0 (4)
N2—N1—H1A	117.3	C7—C8—S	117.5 (3)
C3—C2—C1	117.8 (5)	C9—C8—S	118.6 (3)
C3—C2—H2B	121.1	N2—C9—O1	128.1 (4)
C1—C2—H2B	121.1	N2—C9—C8	118.8 (4)
C9—N2—N1	115.5 (4)	O1—C9—C8	113.0 (3)
C4—C3—C2	121.1 (5)	O1—C10—C11	114.6 (4)
C4—C3—H3B	119.5	O1—C10—H10A	108.6
C2—C3—H3B	119.5	C11—C10—H10A	108.6
C3—C4—C5	122.5 (4)	O1—C10—H10B	108.6
C3—C4—H4A	118.8	C11—C10—H10B	108.6
C5—C4—H4A	118.8	H10A—C10—H10B	107.6
C4—C5—C6	117.9 (5)	O2—C11—N1	123.6 (4)
C4—C5—H5A	121.0	O2—C11—C10	119.0 (4)
C6—C5—H5A	121.0	N1—C11—C10	117.4 (4)

C8—S—C1—C6	1.8 (3)	C6—C7—C8—S	0.0 (4)
C8—S—C1—C2	−179.4 (4)	C1—S—C8—C7	−1.0 (3)
C6—C1—C2—C3	−0.9 (6)	C1—S—C8—C9	177.3 (3)
S—C1—C2—C3	−179.7 (3)	N1—N2—C9—O1	−1.6 (6)
C11—N1—N2—C9	1.8 (6)	N1—N2—C9—C8	−178.0 (3)
C1—C2—C3—C4	1.7 (7)	C10—O1—C9—N2	2.6 (7)
C2—C3—C4—C5	−2.2 (7)	C10—O1—C9—C8	179.1 (4)
C3—C4—C5—C6	1.9 (7)	C7—C8—C9—N2	176.5 (4)
C2—C1—C6—C5	0.7 (6)	S—C8—C9—N2	−1.7 (5)
S—C1—C6—C5	179.5 (3)	C7—C8—C9—O1	−0.4 (6)
C2—C1—C6—C7	178.9 (4)	S—C8—C9—O1	−178.6 (3)
S—C1—C6—C7	−2.2 (4)	C9—O1—C10—C11	−3.3 (6)
C4—C5—C6—C1	−1.1 (6)	N2—N1—C11—O2	177.0 (4)
C4—C5—C6—C7	−179.1 (4)	N2—N1—C11—C10	−2.8 (6)
C1—C6—C7—C8	1.4 (4)	O1—C10—C11—O2	−176.5 (4)
C5—C6—C7—C8	179.5 (4)	O1—C10—C11—N1	3.4 (6)
C6—C7—C8—C9	−178.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.03	2.848 (5)	158

Symmetry code: (i) −x+3/2, y−1/2, −z+5/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.03	2.848 (5)	158

Symmetry code: (i) −x+3/2, y−1/2, −z+5/2.

Acknowledgements

The work was supported by Nanjing College of Chemical Technology, China (NHKY-2013–02).

References

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