Diphenyl chloro­thio­phospho­nate

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.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.026
• wR factor = 0.059
• Data-to-parameter ratio = 19.2

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack parameter is too small
           From the CIF: _refine_ls_abs_structure_Flack   -0.250
           From the CIF: _refine_ls_abs_structure_Flack_su    0.070
PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given .....          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  P1      ..        6.0 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C4     --  C5      ..        5.2 su
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          2

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.94
           From the CIF: _reflns_number_total               1590
           Count of symmetry unique reflns          874
           Completeness (_total/calc)            181.92%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       716
           Fraction of Friedel pairs measured     0.819
           Are heavy atom types Z>Si present        yes
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT033_ALERT_4_G Flack x Parameter Value Deviates from Zero .....     -0.250
PLAT916_ALERT_2_G Hooft y and Flack x Parameter values differ by .       0.18
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level G
PUBL013_ALERT_1_G The _publ_section_comment (discussion of study) is
            missing. This is required for a full paper submission (but is
            optional for an electronic paper).

   0 ALERT level A = Data missing that is essential or data in wrong format
   1 ALERT level G = General alerts. Data that may be required is missing

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Related literature

For the application of related compounds as pesticides, see: Greenhalgh et al. (1980); Um et al. (2003).

S1. 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..

S2. 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).

Computing details

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

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).

Diphenyl chlorothiophosphonate

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) Å^3	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 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

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.026	w = 1/[σ^2(Fo^2) + (0.0202P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/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)

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)

	U^11	U^22	U^33	U^12	U^13	U^23
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, º)

P1—O1^i	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
O1^i—P1—O1	96.79 (9)	C2—C3—C4	119.77 (17)
O1^i—P1—S1	116.91 (6)	C2—C3—H3	120.1
O1—P1—S1	116.91 (6)	C4—C3—H3	120.1
O1^i—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
O1^i—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.