Diphenyl chloro­thio­phospho­nate

Abstract

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 ▶); Um et al. (2003 ▶).

Experimental

Crystal data

• C₁₂H₁₀ClO₂PS

• M _r = 284.68

• Orthorhombic,

• a = 14.9779 (18) Å

• b = 7.3709 (10) Å

• c = 5.8157 (10) Å

• V = 642.06 (16) ų

• Z = 2

• Mo Kα radiation

• μ = 0.57 mm⁻¹

• T = 113 K

• 0.26 × 0.20 × 0.16 mm

Data collection

• Rigaku Saturn724 CCD diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.866, T _max = 0.914

• 6462 measured reflections

• 1590 independent reflections

• 1422 reflections with I > 2σ(I)

• R _int = 0.046

Refinement

• R[F ² > 2σ(F ²)] = 0.026

• wR(F ²) = 0.059

• S = 1.01

• 1590 reflections

• 83 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.28 e Å⁻³

• Absolute structure: Flack (1983 ▶), 716 Friedel pairs

• Flack parameter: −0.25 (7)

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: 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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681104030X/hb6430Isup3.cml

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

supplementary crystallographic information

Experimental

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 column chromatography 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..

Refinement

All the H atoms were positioned geometrically (C—H = 0.95 Å) and refined as riding with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of (I) showing 50% displacement ellipsoids. Symmetry code: (i) –x, y, z.

Fig. 2.

The crystal packing for (I).

Crystal data

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

Data collection

Rigaku Saturn724 CCD diffractometer	1590 independent reflections
Radiation source: rotating anode	1422 reflections with I > 2σ(I)
multilayer	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

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	Flack parameter: −0.25 (7)

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, °)

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 codes: (i) −x, y, z.