organic compounds
2-(1-Benzothiophen-2-yl)-4H-1,3,4-oxadiazin-5(6H)-one
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
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
|
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell 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
https://doi.org/10.1107/S1600536813033291/xu5757sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI: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
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
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.H atoms were positioned geometrically, with N— H = 0.86 Å and C—H = 0.93, and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms, Uiso(H) = 1.2Ueq(C,N).
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.
For applications of oxadiazin derivatives, see: De Sarro et al. (2005); Shigeki et al. (2012).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell
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).C11H8N2O2S | F(000) = 480 |
Mr = 232.25 | Dx = 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 |
Enraf–Nonius CAD-4 diffractometer | 1167 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.064 |
Graphite monochromator | θmax = 25.4°, θmin = 1.8° |
ω/2θ scans | h = 0→9 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→7 |
Tmin = 0.915, Tmax = 0.970 | l = −27→27 |
1999 measured reflections | 3 standard reflections every 200 reflections |
1848 independent reflections | intensity decay: 1% |
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(Fo2) + (0.1P)2 + 0.650P] where P = (Fo2 + 2Fc2)/3 |
1848 reflections | (Δ/σ)max < 0.001 |
145 parameters | Δρmax = 0.39 e Å−3 |
1 restraint | Δρmin = −0.39 e Å−3 |
C11H8N2O2S | V = 1012.3 (4) Å3 |
Mr = 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)° |
Enraf–Nonius CAD-4 diffractometer | 1167 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.064 |
Tmin = 0.915, Tmax = 0.970 | 3 standard reflections every 200 reflections |
1999 measured reflections | intensity decay: 1% |
1848 independent reflections |
R[F2 > 2σ(F2)] = 0.064 | 1 restraint |
wR(F2) = 0.192 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.39 e Å−3 |
1848 reflections | Δρmin = −0.39 e Å−3 |
145 parameters |
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 | ||
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) |
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) |
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) |
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. |
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
De Sarro, G., Gitto, R., Russo, E., Ibbadu, G. F., Barreca, M. L., De Luca, L. & Chimirri, A. (2005). Curr. Top. Med. Chem. 5, 31–42. Web of Science PubMed CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shigeki, H., Koshi, U., Satoshi, N., Koki, K., Koichi, I., Yoshikiko, N., Osamu, T., Takahisa, H. & Masahiro, Y. (2012). J. Med. Chem. 55, 10584–10600. Web of Science PubMed Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.