Experimental. Crystal data. C 20 H 23 N 4 O 6 PS M r = Monoclinic, P2 1 =n a = (2) Å b = (4) Å c = (2) Å = 117.

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1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Diethyl {(4-methoxyphenyl)[5-(4-nitro- phenyl)-1,3,4-thiadiazol-2-ylamino]- methyl}phosphonate Li-He Yin, Rong Wan,* Feng Han, Bin Wang and Jin-Tang Wang Department of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing , People s Republic of China Correspondence rwan@njut.edu.cn Received 6 March 2008; accepted 9 June 2008 Key indicators: single-crystal X-ray study; T = 298 K; mean (C C) = Å; R factor = 0.069; wr factor = 0.146; data-to-parameter ratio = Experimental Crystal data C 20 H 23 N 4 O 6 PS M r = Monoclinic, P2 1 =n a = (2) Å b = (4) Å c = (2) Å = (3) Data collection Enraf Nonius CAD-4 diffractometer Absorption correction: scan (North et al., 1968) T min = 0.930, T max = measured reflections Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections V = (10) Å 3 Z =4 Mo K radiation = 0.25 mm 1 T = 298 (2) K mm 4276 independent reflections 2330 reflections with I > 2(I) R int = standard reflections every 200 reflections intensity decay: none 289 parameters H-atom parameters constrained max = 0.30 e Å 3 min = 0.21 e Å 3 The title compound, C 20 H 23 N 4 O 6 PS, was synthesized by the reaction of N-(4-methoxybenzylidene)-5-(4-nitrophenyl)- 1,3,4-thiadiazol-2-amine and diethyl phosphite. The thiadiazole and nitro-substituted phenyl rings in the molecule are approximately coplanar, the dihedral angle being 5.3 (2). The dihedral angle formed by the mean plane through all non- H atoms of both the thiadiazole and the nitro-substituted phenyl ring with the plane of the methoxy-substituted phenyl ring is 48.9 (2). In the crystal structure, molecules form centrosymmetric dimers as a result of N HO bonds involving amine H and phosphine oxide O atoms. Related literature For related literature, see: Nakagawa et al. (1996); Wang et al. (1999). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA N1 H1AO5 i (6) 165 Symmetry code: (i) x; y; z. Data collection: CAD-4 Software (Enraf Nonius,1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995); 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: SHELXL97. The authors are grateful to Professor Hua-Qin Wang of Nanjing University, for providing the Enraf Nonius CAD-4 diffractometer for this research project. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: YA2071). References Enraf Nonius (1989). CAD-4 Software. Enraf Nonius, Delft, The Netherlands. Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Nakagawa, Y., Nishimura, K., Izumi, K., Kinoshita, K., Kimura, T. & Kurihara, N. (1996). J. Pesticide Sci. 21, North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, Sheldrick, G. M. (2008). Acta Cryst. A64, Wang, Y. G., Cao, L., Yan, J., Ye, W. F., Zhou, Q. C. & Lu, B. X. (1999). Chem. J. Chin. Univ. 20, o1376 Yin et al. doi: /s

2 supporting information [doi: /s ] Diethyl {(4-methoxyphenyl)[5-(4-nitrophenyl)-1,3,4-thiadiazol-2-ylamino]- methyl}phosphonate Li-He Yin, Rong Wan, Feng Han, Bin Wang and Jin-Tang Wang S1. Comment 1,3,4-Thiadiazole derivatives represent an interesting class of biologically important compounds, which often exhibit insecticidal, fungicidal and other biological activities (Nakagawa et al., 1996; Wang et al., 1999). We report here the X-ray structure of the title compound,(i)(fig. 1). The thiadiazole and nitro-substituted phenyl rings in the molecule of (I) are approximately coplanar: the dihedral angle between the C11 C16 and S/C10/N2/N3/C9 planes being 5.3 (2), the maximum deviation from the mean plane N1/C9/C10/N2/N3/S/C11/C12/C13/C14/C15/C16 does not exceed 0.11 Å. The dihedral angle formed by the latter plane with the plane of the methoxy- substituted phenyl ring C2 C7 is equal to 48.9 (2). In the crystal structure, molecules of (I) form centrosymmetric dimers due to N H O bonds involving amine hydrogen and phosphineoxide oxygen [N1 O5 i (6) Å; symmetry code (i): -x, -y, -z]. S2. Experimental N-(4-methoxybenzylidene)-5-(4-nitrophenyl)-1,3,4-thiadiazol-2-amine (2 mmol) and diethyl phosphite (5 mmol) were mixed in a 25 ml flask (without any solvent),and kept in the oil bath at 90 C for 6 h. After cooling, the crude product (I) precipitated and was filtered. Pure compound (I) was obtained by recrystallization from ethanol(20 ml). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution. S3. Refinement All H atoms were positioned geometrically, with N H=0.86 Å and C H=0.98, 0.97, 0.96 and 0.93 Å for methine, methylene, methyl and aromatic H atoms, respectively, and constrained to ride on their parent atoms, with U iso (H)=xU eq (C, N), where x=1.5 for methyl H atoms and x=1.2 for all other H atoms. sup-1

3 Figure 1 Molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms are shown as small circles of arbitrary radius. Diethyl {(4-methoxyphenyl)[5-(4-nitrophenyl)-1,3,4-thiadiazol-2- ylamino]methyl}phosphonate Crystal data C 20 H 23 N 4 O 6 PS M r = Monoclinic, P2 1 /n Hall symbol: -P 2yn a = (2) Å b = (4) Å c = (2) Å β = (3) V = (10) Å 3 Z = 4 Data collection Enraf Nonius CAD-4 diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω/2θ scans Absorption correction: ψ scan (North et al., 1968) T min = 0.930, T max = measured reflections F(000) = 1000 D x = Mg m 3 Melting point: 476 K Mo Kα radiation, λ = Å Cell parameters from 25 reflections θ = 9 13 µ = 0.25 mm 1 T = 298 K Block, light yellow mm 4276 independent reflections 2330 reflections with I > 2σ(I) R int = θ max = 25.2, θ min = 2.0 h = k = 0 23 l = standard reflections every 200 reflections intensity decay: none sup-2

4 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 289 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.03P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.30 e Å 3 Δρ min = 0.21 e Å 3 Special details 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq S (9) (5) (11) (4) P (11) (6) (12) (4) N (3) (17) (3) (10) H1A * O (4) (2) (4) (12) C (7) (3) (6) (2) H1B * H1C * H1D * N (3) (16) (3) (9) O (4) (19) (4) (2) C (7) (3) (7) (2) N (3) (16) (3) (10) O (4) (17) (4) (17) C (6) (3) (6) (19) H3B * N (5) (2) (4) (14) C (4) (2) (5) (16) H4A * O (4) (19) (4) (13) O (3) (17) (3) (10) C (4) (2) (4) (11) O (3) (2) (3) (12) C (5) (3) (5) (16) H6A * sup-3

5 C (6) (3) (6) (17) H7A * C (4) (2) (4) (12) H8A * C (3) (2) (4) (10) C (3) (18) (4) (10) C (3) (19) (3) (10) C (3) (19) (4) (12) H12A * C (4) (2) (4) (14) H13A * C (4) (2) (4) (13) C (4) (2) (4) (13) H15A * C (3) (2) (4) (12) H16A * C (7) (4) (7) (3) H17A * H17B * H17C * C (7) (3) (7) (2) H18A * H18B * C (6) (3) (6) (2) H19A * H19B * H19C * C (6) (3) (6) (18) H20A * H20B * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 S (5) (6) (8) (5) (5) (6) P (7) (8) (8) (6) (6) (7) N (18) (2) (2) (16) (17) (18) O (3) (3) (3) (3) (3) (2) C (5) (6) (5) (5) (5) (4) N (17) (2) (2) (15) (15) (17) O (4) (2) (4) (2) (3) (2) C (6) (3) (6) (3) (5) (3) N (18) (2) (2) (15) (17) (18) O (3) (2) (4) (2) (3) (2) C (4) (4) (5) (3) (4) (4) N (3) (3) (3) (2) (3) (2) C (3) (3) (4) (2) (3) (3) O (3) (3) (3) (2) (3) (2) sup-4

6 O (19) (2) (2) (17) (17) (19) C (2) (2) (3) (2) (2) (2) O (2) (3) (3) (2) (19) (2) C (3) (4) (5) (3) (3) (3) C (5) (3) (5) (3) (4) (3) C (2) (3) (3) (18) (2) (2) C (2) (2) (3) (17) (18) (2) C (19) (2) (3) (16) (18) (19) C (2) (2) (2) (17) (17) (19) C (2) (2) (3) (17) (19) (2) C (3) (2) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (2) (2) (3) (18) (19) (2) C (7) (7) (6) (6) (5) (6) C (6) (5) (6) (4) (5) (4) C (5) (5) (5) (4) (4) (4) C (4) (5) (5) (4) (4) (4) Geometric parameters (Å, º) S C (3) O6 C (6) S C (4) C6 C (7) P O (3) C6 H6A P O (3) C7 H7A P O (3) C8 H8A P C (5) C10 C (5) N1 C (5) C11 C (5) N1 C (5) C11 C (5) N1 H1A C12 C (5) O1 C (6) C12 H12A O1 C (6) C13 C (5) C1 H1B C13 H13A C1 H1C C14 C (5) C1 H1D C15 C (5) N2 C (4) C15 H15A N2 N (4) C16 H16A O2 N (5) C17 C (8) C2 C (7) C17 H17A C2 C (7) C17 H17B N3 C (4) C17 H17C O3 N (5) C18 H18A C3 C (6) C18 H18B C3 H3B C19 C (7) N4 C (6) C19 H19A C4 C (5) C19 H19B C4 H4A C19 H19C O4 C (7) C20 H20A sup-5

7 C5 C (6) C20 H20B C5 C (5) C10 S C (18) N3 C9 N (3) O5 P O (2) N3 C9 S (3) O5 P O (2) N1 C9 S (3) O6 P O (2) N2 C10 C (3) O5 P C (19) N2 C10 S (3) O6 P C (2) C11 C10 S (3) O4 P C (2) C12 C11 C (4) C9 N1 C (3) C12 C11 C (3) C9 N1 H1A C16 C11 C (3) C8 N1 H1A C11 C12 C (4) C1 O1 C (5) C11 C12 H12A O1 C1 H1B C13 C12 H12A O1 C1 H1C C14 C13 C (4) H1B C1 H1C C14 C13 H13A O1 C1 H1D C12 C13 H13A H1B C1 H1D C13 C14 N (4) H1C C1 H1D C13 C14 C (4) C10 N2 N (3) N4 C14 C (4) C3 C2 C (5) C16 C15 C (4) C3 C2 O (6) C16 C15 H15A C7 C2 O (6) C14 C15 H15A C9 N3 N (3) C15 C16 C (3) C2 C3 C (5) C15 C16 H16A C2 C3 H3B C11 C16 H16A C4 C3 H3B C18 C17 H17A O2 N4 O (4) C18 C17 H17B O2 N4 C (4) H17A C17 H17B O3 N4 C (4) C18 C17 H17C C5 C4 C (5) H17A C17 H17C C5 C4 H4A H17B C17 H17C C3 C4 H4A O4 C18 C (6) C18 O4 P (4) O4 C18 H18A C4 C5 C (4) C17 C18 H18A C4 C5 C (4) O4 C18 H18B C6 C5 C (4) C17 C18 H18B C20 O6 P (3) H18A C18 H18B C7 C6 C (5) C20 C19 H19A C7 C6 H6A C20 C19 H19B C5 C6 H6A H19A C19 H19B C2 C7 C (5) C20 C19 H19C C2 C7 H7A H19A C19 H19C C6 C7 H7A H19B C19 H19C N1 C8 C (3) O6 C20 C (5) N1 C8 P (3) O6 C20 H20A C5 C8 P (3) C19 C20 H20A sup-6

8 N1 C8 H8A O6 C20 H20B C5 C8 H8A C19 C20 H20B P C8 H8A H20A C20 H20B C1 O1 C2 C3 6.7 (9) N2 N3 C9 N (4) C1 O1 C2 C (5) N2 N3 C9 S 0.5 (5) C10 N2 N3 C9 1.4 (5) C8 N1 C9 N3 0.6 (7) C7 C2 C3 C4 2.2 (10) C8 N1 C9 S (3) O1 C2 C3 C (6) C10 S C9 N3 0.3 (3) C2 C3 C4 C5 0.9 (9) C10 S C9 N (4) O5 P O4 C (5) N3 N2 C10 C (4) O6 P O4 C (5) N3 N2 C10 S 1.6 (5) C8 P O4 C (5) C9 S C10 N2 1.0 (3) C3 C4 C5 C6 0.3 (8) C9 S C10 C (4) C3 C4 C5 C (5) N2 C10 C11 C (4) O5 P O6 C (5) S C10 C11 C (6) O4 P O6 C (5) N2 C10 C11 C (6) C8 P O6 C (4) S C10 C11 C (3) C4 C5 C6 C7 1.1 (7) C16 C11 C12 C (6) C8 C5 C6 C (5) C10 C11 C12 C (4) C3 C2 C7 C6 3.0 (9) C11 C12 C13 C (7) O1 C2 C7 C (5) C12 C13 C14 N (4) C5 C6 C7 C2 2.5 (9) C12 C13 C14 C (7) C9 N1 C8 C (4) O2 N4 C14 C (5) C9 N1 C8 P (4) O3 N4 C14 C (8) C4 C5 C8 N (6) O2 N4 C14 C (8) C6 C5 C8 N (4) O3 N4 C14 C (5) C4 C5 C8 P 74.1 (5) C13 C14 C15 C (7) C6 C5 C8 P (4) N4 C14 C15 C (5) O5 P C8 N (3) C14 C15 C16 C (7) O6 P C8 N (3) C12 C11 C16 C (7) O4 P C8 N (3) C10 C11 C16 C (4) O5 P C8 C (3) P O4 C18 C (5) O6 P C8 C (3) P O6 C20 C (5) O4 P C8 C (3) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A N1 H1A O5 i (6) 165 Symmetry code: (i) x, y, z. sup-7