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organic compounds
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accessDiphenyl chlorothiophosphonate
aResearch Center for Engineering Technology of Polymeric Composites of Shanxi Province, School of Materials Science and Engineering, North University of China, Taiyuan 030051, People's Republic of China
*Correspondence e-mail: zph2004@yahoo.com.cn
The complete molecule of the title compound, C12H10ClO2PS, is generated by crystallographic mirror symmetry, with the P, S and Cl atoms lying on the mirror plane. The resulting PO2SCl tetrahedron is significantly distorted [O—P—O = 96.79 (9)°]. The crystal packing exhibits no directional interactions.
Related literature
For the application of related compounds as pesticides, see: Greenhalgh et al. (1980![[Greenhalgh, R., Dhawson, K. L. & Weinberg, P. (1980). J. Agric. Food Chem. 28, 102-105.]](../../../../../../logos/arrows/e_arr.gif "Greenhalgh, R., Dhawson, K. L. & Weinberg, P. (1980). J. Agric. Food Chem. 28, 102-105.")
); Um et al. (2003).
![[Scheme 1]](hb6430scheme1.gif)
Experimental
Crystal data
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Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear; data reduction: CrystalClear; 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: CrystalStructure (Rigaku/MSC, 2005).
Supporting information
contains datablocks global, I. DOI: 10.1107/S160053681104030X/hb6430sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S160053681104030X/hb6430Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681104030X/hb6430Isup3.cml
Triethylamine (127.0 mmol) were added to the dichloromethane solution (80.0 ml) of phenol (120.0 mmol) while stirring. Thiophosphory chloride (60.0 mmol) was slowly dropwise added to the above solution, and then the rection mixture was refluxed. After the reaction was completed, it is cooled to room temperature. The reaction mixture was washed with water and brine, respectively. The separated organic phase was dried with anhydrous sodium sulfate, and then the solvents were evporated thoroughly in vacuo. The obtained crude was separated through on silica gel to give the white product. Colourless prisms of the title compound were obtained by slow evaporation of the dichloromethane/n-hexane solutions at room temperature. 31P NMR(161.9 MHz, CDCl3, TMS): 58.73 (s) p.p.m..
All the H atoms were positioned geometrically (C—H = 0.95 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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: CrystalStructure (Rigaku/MSC, 2005).
![[Figure 1]](./hb6430fig1thm.gif) | Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids. Symmetry code: (i) –x, y, z. |
![[Figure 2]](./hb6430fig2thm.gif) | Fig. 2. The crystal packing for (I). |
| C12H10ClO2PS | Dx = 1.473 Mg m−3 |
| Mr = 284.68 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, Pmn21 | Cell parameters from 2338 reflections |
| a = 14.9779 (18) Å | θ = 2.7–28.0° |
| b = 7.3709 (10) Å | µ = 0.57 mm−1 |
| c = 5.8157 (10) Å | T = 113 K |
| V = 642.06 (16) Å3 | Prism, colorless |
| Z = 2 | 0.26 × 0.20 × 0.16 mm |
| F(000) = 292 |
| Rigaku Saturn724 CCD diffractometer | 1590 independent reflections |
| Radiation source: rotating anode | 1422 reflections with I > 2σ(I) |
| Multilayer monochromator | Rint = 0.046 |
| Detector resolution: 14.22 pixels mm-1 | θmax = 27.9°, θmin = 2.7° |
| ω and ϕ scans | h = −18→19 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −9→9 |
| Tmin = 0.866, Tmax = 0.914 | l = −7→7 |
| 6462 measured reflections |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.0202P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.059 | (Δ/σ)max = 0.002 |
| S = 1.01 | Δρmax = 0.33 e Å−3 |
| 1590 reflections | Δρmin = −0.28 e Å−3 |
| 83 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 1 restraint | Extinction coefficient: 0.034 (2) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 716 Friedel pairs |
| Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.25 (7) |
| C12H10ClO2PS | V = 642.06 (16) Å3 |
| Mr = 284.68 | Z = 2 |
| Orthorhombic, Pmn21 | Mo Kα radiation |
| a = 14.9779 (18) Å | µ = 0.57 mm−1 |
| b = 7.3709 (10) Å | T = 113 K |
| c = 5.8157 (10) Å | 0.26 × 0.20 × 0.16 mm |
| Rigaku Saturn724 CCD diffractometer | 1590 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1422 reflections with I > 2σ(I) |
| Tmin = 0.866, Tmax = 0.914 | Rint = 0.046 |
| 6462 measured reflections |
| R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
| wR(F2) = 0.059 | Δρmax = 0.33 e Å−3 |
| S = 1.01 | Δρmin = −0.28 e Å−3 |
| 1590 reflections | Absolute structure: Flack (1983), 716 Friedel pairs |
| 83 parameters | Absolute structure parameter: −0.25 (7) |
| 1 restraint |
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 | ||
| P1 | 0.0000 | 0.74395 (10) | 0.33956 (11) | 0.01650 (17) | |
| Cl1 | 0.0000 | 0.78689 (13) | 0.00139 (10) | 0.0391 (3) | |
| S1 | 0.0000 | 0.49265 (10) | 0.42063 (18) | 0.0294 (2) | |
| O1 | 0.07867 (7) | 0.86334 (15) | 0.4369 (2) | 0.0162 (3) | |
| C1 | 0.16873 (10) | 0.8018 (2) | 0.4313 (4) | 0.0137 (4) | |
| C2 | 0.20060 (11) | 0.7047 (2) | 0.6162 (3) | 0.0166 (4) | |
| H2 | 0.1623 | 0.6729 | 0.7400 | 0.020* | |
| C3 | 0.29001 (12) | 0.6542 (3) | 0.6177 (3) | 0.0196 (4) | |
| H3 | 0.3137 | 0.5884 | 0.7442 | 0.024* | |
| C4 | 0.34463 (11) | 0.7004 (2) | 0.4335 (4) | 0.0191 (4) | |
| H4 | 0.4056 | 0.6646 | 0.4337 | 0.023* | |
| C5 | 0.31099 (12) | 0.7976 (3) | 0.2507 (3) | 0.0203 (5) | |
| H5 | 0.3491 | 0.8291 | 0.1264 | 0.024* | |
| C6 | 0.22133 (11) | 0.8504 (2) | 0.2460 (3) | 0.0166 (4) | |
| H6 | 0.1975 | 0.9170 | 0.1204 | 0.020* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| P1 | 0.0102 (3) | 0.0226 (4) | 0.0167 (4) | 0.000 | 0.000 | −0.0060 (3) |
| Cl1 | 0.0210 (4) | 0.0820 (7) | 0.0144 (4) | 0.000 | 0.000 | −0.0040 (4) |
| S1 | 0.0152 (3) | 0.0179 (3) | 0.0549 (5) | 0.000 | 0.000 | −0.0040 (4) |
| O1 | 0.0084 (6) | 0.0174 (7) | 0.0228 (7) | −0.0005 (5) | −0.0024 (5) | −0.0040 (6) |
| C1 | 0.0078 (8) | 0.0143 (9) | 0.0188 (9) | −0.0010 (7) | −0.0003 (8) | −0.0051 (8) |
| C2 | 0.0150 (9) | 0.0197 (12) | 0.0151 (11) | −0.0015 (8) | 0.0002 (7) | 0.0007 (8) |
| C3 | 0.0181 (9) | 0.0188 (11) | 0.0219 (11) | 0.0012 (8) | −0.0054 (8) | 0.0023 (9) |
| C4 | 0.0125 (9) | 0.0180 (9) | 0.0267 (11) | 0.0020 (7) | −0.0026 (8) | −0.0029 (9) |
| C5 | 0.0137 (10) | 0.0216 (11) | 0.0255 (11) | −0.0039 (8) | 0.0076 (7) | −0.0015 (8) |
| C6 | 0.0162 (10) | 0.0163 (10) | 0.0174 (10) | −0.0016 (8) | −0.0050 (7) | 0.0021 (8) |
| P1—O1i | 1.5758 (12) | C2—H2 | 0.9500 |
| P1—O1 | 1.5758 (12) | C3—C4 | 1.390 (3) |
| P1—S1 | 1.9114 (11) | C3—H3 | 0.9500 |
| P1—Cl1 | 1.9920 (9) | C4—C5 | 1.378 (3) |
| O1—C1 | 1.4234 (17) | C4—H4 | 0.9500 |
| C1—C2 | 1.377 (3) | C5—C6 | 1.398 (2) |
| C1—C6 | 1.382 (3) | C5—H5 | 0.9500 |
| C2—C3 | 1.390 (2) | C6—H6 | 0.9500 |
| O1i—P1—O1 | 96.79 (9) | C2—C3—C4 | 119.77 (17) |
| O1i—P1—S1 | 116.91 (6) | C2—C3—H3 | 120.1 |
| O1—P1—S1 | 116.91 (6) | C4—C3—H3 | 120.1 |
| O1i—P1—Cl1 | 105.42 (6) | C5—C4—C3 | 120.46 (16) |
| O1—P1—Cl1 | 105.42 (6) | C5—C4—H4 | 119.8 |
| S1—P1—Cl1 | 113.42 (6) | C3—C4—H4 | 119.8 |
| C1—O1—P1 | 121.50 (11) | C4—C5—C6 | 120.71 (18) |
| C2—C1—C6 | 123.07 (15) | C4—C5—H5 | 119.6 |
| C2—C1—O1 | 118.43 (16) | C6—C5—H5 | 119.6 |
| C6—C1—O1 | 118.41 (17) | C1—C6—C5 | 117.43 (17) |
| C1—C2—C3 | 118.56 (16) | C1—C6—H6 | 121.3 |
| C1—C2—H2 | 120.7 | C5—C6—H6 | 121.3 |
| C3—C2—H2 | 120.7 | ||
| O1i—P1—O1—C1 | 169.66 (11) | C1—C2—C3—C4 | −0.7 (3) |
| S1—P1—O1—C1 | 44.80 (16) | C2—C3—C4—C5 | 0.7 (3) |
| Cl1—P1—O1—C1 | −82.25 (14) | C3—C4—C5—C6 | −0.5 (3) |
| P1—O1—C1—C2 | −90.03 (19) | C2—C1—C6—C5 | −0.3 (3) |
| P1—O1—C1—C6 | 93.23 (17) | O1—C1—C6—C5 | 176.31 (15) |
| C6—C1—C2—C3 | 0.5 (3) | C4—C5—C6—C1 | 0.2 (3) |
| O1—C1—C2—C3 | −176.05 (16) |
| Symmetry code: (i) −x, y, z. |
Experimental details
| Crystal data | |
| Chemical formula | C12H10ClO2PS |
| Mr | 284.68 |
| Crystal system, space group | Orthorhombic, Pmn21 |
| Temperature (K) | 113 |
| a, b, c (Å) | 14.9779 (18), 7.3709 (10), 5.8157 (10) |
| V (Å3) | 642.06 (16) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.57 |
| Crystal size (mm) | 0.26 × 0.20 × 0.16 |
| Data collection | |
| Diffractometer | Rigaku Saturn724 CCD diffractometer |
| Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
| Tmin, Tmax | 0.866, 0.914 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6462, 1590, 1422 |
| Rint | 0.046 |
| (sin θ/λ)max (Å−1) | 0.659 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.059, 1.01 |
| No. of reflections | 1590 |
| No. of parameters | 83 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.33, −0.28 |
| Absolute structure | Flack (1983), 716 Friedel pairs |
| Absolute structure parameter | −0.25 (7) |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku/MSC, 2005).
Acknowledgements
This work was supported financially by the Start-up Foundation of the North University of China and the Youth Foundation of the North University of China.
References
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Greenhalgh, R., Dhawson, K. L. & Weinberg, P. (1980). J. Agric. Food Chem. 28, 102–105. CrossRef CAS Web of Science Google Scholar
Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC Inc. The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Um, I. H., Jeom, S. E., Baek, M. H. & Dark, H. R. (2003). Chem. Commun. 24, 3016–3017. Web of Science CrossRef Google Scholar
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