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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o673.
Published online 2009 March 6. doi:  10.1107/S160053680900693X
PMCID: PMC2969034

O,O′-Diethyl {(Z)-[(2-chloro­phen­yl)(cyano)methyl­ene]amino­oxy}thio­phospho­nate

Abstract

The title mol­ecule, C12H14ClN2O3PS, has a cis configuration with respect to the C=N bond. Inter­molecular C—H(...)O inter­actions inter­connect the mol­ecules into chains along the c axis. The chains are further connected into a two-dimensional network parallel to the bc plane by weak π–π inter­actions between adjacent aromatic rings (centroid–centroid distance = 3.772Å).

Related literature

For the insectidal activity of the title compound, see: Hudson & Obudho (1972 [triangle]); Le Berre et al. (1972 [triangle]). For its preparation and reactivity, see: Walter & Clifton (1973 [triangle]); Wang et al. (1996 [triangle]).

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Object name is e-65-0o673-scheme1.jpg

Experimental

Crystal data

  • C12H14ClN2O3PS
  • M r = 332.73
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o673-efi1.jpg
  • a = 10.518 (2) Å
  • b = 20.215 (4) Å
  • c = 7.9650 (16) Å
  • β = 110.11 (3)°
  • V = 1590.3 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.48 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 [triangle]) T min = 0.870, T max = 0.954
  • 2889 measured reflections
  • 2889 independent reflections
  • 1981 reflections with I > 2σ(I)
  • 3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.061
  • wR(F 2) = 0.192
  • S = 1.09
  • 2889 reflections
  • 183 parameters
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.39 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900693X/fb2135sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900693X/fb2135Isup2.hkl

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

Acknowledgments

This work was supported by the Social Development Foundation of Jiangsu Province, China (No. BS2007060).

supplementary crystallographic information

Comment

O,O-diethyl-O-(2-chlorophenylglyoxylonitrile oximino)thiophosphate (Chlorphoxim) was shown to be efficient against adult mosquitoes as well as agricultural insects (Hudson et al., 1972). It was also successfully tested against the larvae of the blackfly (Simulium damnosum), the insect vector of human onchocerciasis in West Africa (Le Berre et al., 1972). The title substance combined with niclosamide exhibited significant molluscicidal synergism against snails (Oncomelania hupensis) (Wang et al., 1996). The synthesis of the title compound has been described by Walter et al. (1973). As a part of our own studies in this area, we report here its crystal structure.

The title molecule shows a cis configuration (Fig. 1) on the C═N bond. The molecules are linked into chains along the axis c via weak intermolecular C—H···O interactions (Fig. 2, Tab. 1). The chains are further connected into a two-dimensional network via weak π-π electron interactions between the adjacent phenyl rings: The centroid-centroid distance is 3.772 Å.

Experimental

Sodium, 2.30 g (0.1 mol), reacted with 50 ml of absolute ethanol in order to get sodium ethoxide solution. 15.20 g (0.1 mol) of 2-chlorophenylacetonitrile, was added dropwise to the cooled sodium ethoxide (about 278 K) and then 10.30 g (0.1 mol) of butyl nitrite was added dropwise. The mixture was stirred at room temperature for 1 h under reduced pressure until the volume was reduced to 30 ml. Then 50 ml of ethyl ether was added, and the precipitated solid was filtered off and washed with ethyl ether to afford sodium 2-chlorophenylglyoxylonitrile oxime (11.3 g, 56%). Diethyl phosphorochloridothionate, 5.70 g (0.03 mol), was added dropwise to 6.00 g (0.03 mol) of sodium 2-chlorophenylglyoxylonitrile oxime, which was suspended in 20 ml of dry acetone. The mixture was stirred for 1 h. Thin layered chromatography using petroleum ether and ethyl acetate as expanding solvent indicated just one point. The mixture was then concentrated under reduced pressure and 50 ml of water was added to the residue. The precipitated solid that had appeared was filtered off, washed thoroughly with absolute ethanol, dried and recrystallized from petroleum ether to afford the title compound (8.9 g, yield 89%) as a white crystalline solid. The title crystals suitable for X-ray diffraction were obtained by slow evaporation of the acetone solution. The average size of the block-like crystals is 0.2 × 0.2 × 0.2 mm.

Refinement

The aryl and methylene H atoms were situated into idealized positions though the aryl H atoms were clearly discernible in the difference electron density map. After the refinement with these H atoms whose parameters were fully constrained had converged the electron density map revealed that the methyl H atoms were not disordered. They were also situated into the idealized positions and constrained. C—Hmethyl, C—Hmethylene, C—Haryl = 0.96, 0.97, 0.93 Å, UisoHmethyl=1.5UeqCmethyl, UisoHmethylene=1.2UeqCmethylene, UisoHaryl=1.2UeqCaryl.

Figures

Fig. 1.
The molecular structure of the title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A packing diagram of the title structure. The dashed lines represent weak C—H···O interactions.

Crystal data

C12H14ClN2O3PSF(000) = 688
Mr = 332.73Dx = 1.390 Mg m3
Monoclinic, P21/cMelting point: 341.5 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 10.518 (2) ÅCell parameters from 25 reflections
b = 20.215 (4) Åθ = 9.0–13.0°
c = 7.9650 (16) ŵ = 0.48 mm1
β = 110.11 (3)°T = 293 K
V = 1590.3 (6) Å3Block, colourless
Z = 40.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer1981 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.0000
graphiteθmax = 25.3°, θmin = 2.0°
ω/2θ scansh = −12→11
Absorption correction: ψ scan (North et al., 1968)k = 0→24
Tmin = 0.870, Tmax = 0.954l = 0→9
2889 measured reflections3 standard reflections every 120 min
2889 independent reflections intensity decay: 1.0%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: difference Fourier map
wR(F2) = 0.192H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0957P)2 + 1.1623P] where P = (Fo2 + 2Fc2)/3
2889 reflections(Δ/σ)max < 0.001
183 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = −0.38 e Å3

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 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)

xyzUiso*/Ueq
Cl0.9833 (2)0.10567 (10)1.4318 (2)0.1103 (7)
S0.44401 (12)0.05415 (6)0.77933 (17)0.0620 (4)
P0.49482 (11)0.14026 (6)0.73194 (14)0.0468 (3)
O10.3963 (3)0.19852 (15)0.7185 (4)0.0562 (8)
O20.5248 (4)0.15378 (16)0.5556 (4)0.0687 (9)
O30.6273 (3)0.16956 (14)0.8892 (4)0.0518 (7)
N10.7388 (3)0.12634 (16)0.9243 (4)0.0477 (8)
N20.8474 (5)0.2615 (3)1.2012 (8)0.0939 (16)
C10.2127 (6)0.2550 (3)0.7678 (8)0.0898 (18)
H1B0.16640.26240.85110.135*
H1C0.15010.23760.65830.135*
H1D0.24930.29600.74410.135*
C20.3231 (5)0.2074 (3)0.8440 (7)0.0690 (13)
H2A0.38430.22360.95750.083*
H2B0.28640.16530.86450.083*
C30.5814 (7)0.1315 (3)0.2996 (7)0.0884 (18)
H3A0.62150.09960.24370.133*
H3B0.62900.17270.31180.133*
H3C0.48810.13790.22730.133*
C40.5897 (7)0.1079 (3)0.4736 (8)0.0847 (17)
H4A0.54600.06500.46230.102*
H4B0.68390.10270.54820.102*
C50.8423 (4)0.2119 (2)1.1322 (6)0.0599 (12)
C60.8431 (4)0.14942 (19)1.0451 (5)0.0436 (9)
C70.9702 (4)0.1113 (2)1.0871 (6)0.0475 (9)
C81.0192 (5)0.0965 (2)0.9514 (7)0.0590 (11)
H8A0.97150.11050.83560.071*
C91.1372 (5)0.0612 (3)0.9845 (9)0.0759 (15)
H9A1.16860.05120.89170.091*
C101.2084 (5)0.0411 (3)1.1563 (10)0.0865 (19)
H10A1.28850.01741.17970.104*
C111.1627 (6)0.0554 (3)1.2906 (9)0.0836 (17)
H11A1.21180.04201.40650.100*
C121.0435 (5)0.0899 (2)1.2575 (6)0.0642 (12)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.1224 (14)0.1444 (17)0.0590 (8)0.0170 (12)0.0247 (9)0.0086 (9)
S0.0607 (7)0.0481 (6)0.0785 (8)−0.0014 (5)0.0256 (6)−0.0008 (6)
P0.0463 (6)0.0495 (6)0.0467 (6)0.0072 (5)0.0187 (5)0.0010 (5)
O10.0543 (16)0.0572 (18)0.0650 (18)0.0168 (14)0.0309 (14)0.0129 (14)
O20.084 (2)0.070 (2)0.063 (2)0.0186 (18)0.0395 (18)0.0105 (16)
O30.0433 (14)0.0463 (16)0.0648 (18)0.0068 (12)0.0173 (13)−0.0028 (14)
N10.0452 (18)0.0482 (19)0.0533 (19)0.0053 (15)0.0216 (16)0.0008 (15)
N20.077 (3)0.080 (3)0.124 (4)−0.006 (3)0.035 (3)−0.046 (3)
C10.081 (4)0.111 (5)0.081 (4)0.041 (4)0.033 (3)0.001 (3)
C20.079 (3)0.072 (3)0.065 (3)0.020 (3)0.036 (3)0.005 (2)
C30.120 (5)0.096 (4)0.070 (3)−0.002 (4)0.060 (4)0.004 (3)
C40.106 (4)0.081 (4)0.078 (4)0.016 (3)0.045 (3)−0.001 (3)
C50.044 (2)0.068 (3)0.067 (3)−0.004 (2)0.018 (2)−0.014 (2)
C60.048 (2)0.041 (2)0.042 (2)−0.0015 (16)0.0155 (17)−0.0039 (16)
C70.041 (2)0.043 (2)0.058 (2)−0.0001 (17)0.0169 (18)0.0001 (19)
C80.056 (3)0.052 (3)0.075 (3)−0.002 (2)0.031 (2)−0.004 (2)
C90.063 (3)0.059 (3)0.121 (5)0.001 (2)0.051 (3)−0.010 (3)
C100.053 (3)0.055 (3)0.142 (6)0.008 (2)0.020 (3)−0.001 (3)
C110.065 (3)0.070 (3)0.093 (4)0.005 (3)−0.002 (3)0.009 (3)
C120.062 (3)0.060 (3)0.062 (3)0.001 (2)0.010 (2)−0.006 (2)

Geometric parameters (Å, °)

Cl—C121.743 (5)C3—H3A0.9600
S—P1.8966 (16)C3—H3B0.9600
P—O11.548 (3)C3—H3C0.9600
P—O21.566 (3)C4—H4A0.9700
P—O31.631 (3)C4—H4B0.9700
O1—C21.467 (5)C5—C61.442 (6)
O2—C41.435 (6)C6—C71.478 (5)
O3—N11.412 (4)C7—C121.380 (6)
N1—C61.273 (5)C7—C81.381 (6)
N2—C51.136 (6)C8—C91.376 (7)
C1—C21.469 (7)C8—H8A0.9300
C1—H1B0.9600C9—C101.377 (9)
C1—H1C0.9600C9—H9A0.9300
C1—H1D0.9600C10—C111.347 (9)
C2—H2A0.9700C10—H10A0.9300
C2—H2B0.9700C11—C121.378 (7)
C3—C41.440 (7)C11—H11A0.9300
O1—P—O298.17 (17)O2—C4—C3110.1 (5)
O1—P—O398.71 (16)O2—C4—H4A109.6
O2—P—O3104.07 (18)C3—C4—H4A109.6
O1—P—S118.96 (13)O2—C4—H4B109.6
O2—P—S119.75 (15)C3—C4—H4B109.6
O3—P—S113.90 (12)H4A—C4—H4B108.2
C2—O1—P122.8 (3)N2—C5—C6177.0 (5)
C4—O2—P124.7 (3)N1—C6—C5122.6 (4)
N1—O3—P111.1 (2)N1—C6—C7117.2 (3)
C6—N1—O3111.4 (3)C5—C6—C7120.1 (4)
C2—C1—H1B109.5C12—C7—C8118.0 (4)
C2—C1—H1C109.5C12—C7—C6122.8 (4)
H1B—C1—H1C109.5C8—C7—C6119.2 (4)
C2—C1—H1D109.5C9—C8—C7121.1 (5)
H1B—C1—H1D109.5C9—C8—H8A119.4
H1C—C1—H1D109.5C7—C8—H8A119.4
O1—C2—C1108.9 (4)C8—C9—C10119.4 (5)
O1—C2—H2A109.9C8—C9—H9A120.3
C1—C2—H2A109.9C10—C9—H9A120.3
O1—C2—H2B109.9C11—C10—C9120.3 (5)
C1—C2—H2B109.9C11—C10—H10A119.8
H2A—C2—H2B108.3C9—C10—H10A119.8
C4—C3—H3A109.5C10—C11—C12120.4 (5)
C4—C3—H3B109.5C10—C11—H11A119.8
H3A—C3—H3B109.5C12—C11—H11A119.8
C4—C3—H3C109.5C11—C12—C7120.7 (5)
H3A—C3—H3C109.5C11—C12—Cl119.7 (4)
H3B—C3—H3C109.5C7—C12—Cl119.6 (4)
O2—P—O1—C2174.0 (4)C5—C6—C7—C1258.7 (6)
O3—P—O1—C2−80.3 (4)N1—C6—C7—C855.6 (5)
S—P—O1—C243.2 (4)C5—C6—C7—C8−120.9 (5)
O1—P—O2—C4−166.5 (4)C12—C7—C8—C90.2 (7)
O3—P—O2—C492.3 (5)C6—C7—C8—C9179.9 (4)
S—P—O2—C4−36.3 (5)C7—C8—C9—C10−0.7 (7)
O1—P—O3—N1−177.2 (2)C8—C9—C10—C110.2 (8)
O2—P—O3—N1−76.5 (3)C9—C10—C11—C120.6 (9)
S—P—O3—N155.7 (3)C10—C11—C12—C7−1.1 (8)
P—O3—N1—C6179.0 (3)C10—C11—C12—Cl177.9 (5)
P—O1—C2—C1−164.6 (4)C8—C7—C12—C110.7 (7)
P—O2—C4—C3170.6 (4)C6—C7—C12—C11−179.0 (4)
O3—N1—C6—C50.4 (5)C8—C7—C12—Cl−178.3 (3)
O3—N1—C6—C7−176.0 (3)C6—C7—C12—Cl2.0 (6)
N1—C6—C7—C12−124.7 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2A···O1i0.972.583.396 (6)142

Symmetry codes: (i) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2135).

References

  • Enraf–Nonius (1994). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Hudson, J. E. & Obudho, W. O. (1972). Mosq. News, 32, 37-46.
  • Le Berre, R., Escaffre, H., Pendriez, B., Grebaut, S. & Pengalet, P. (1972). Control of Simulium damnosum, the Vector of Human Onchocerciasis in West Africa. II. Test by Classic Application of New Insecticides and New Formulations. Bobo-Dioulasso, Upper Volta:
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Walter, A. M. & Clifton, E. M. (1973). J. Agric. Food Chem.21, 762-763. [PubMed]
  • Wang, P. H., Wang, R., Dai, J. R., Wu, X. Q. & Xu, J. (1996). Acta Pharm. Sin.31, 918-924.

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