O,O-Bis(2-tert-butyl-4-methyl­phenyl) chloro­thio­phospho­nate

The title compound, C₂₂H₃₀ClO₂PS, displays distorted tetrahedral geometry around the P atom. The dihedral angle between the benzene rings is 43.7 (4)°. The aromatic rings have unusual endocyclic angles as a result of the steric effects of the tert-butyl groups. The mol­ecules are linked by weak C—H...π interactions.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.035
• wR factor = 0.090
• Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found





Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    Cl1    -   P1      ..       7.89 su
PLAT340_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ...         12

Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.390
           From the CIF: _refine_ls_abs_structure_Flack_su    0.160
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.39
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   P1      ..       6.32 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C27
PLAT732_ALERT_1_C Angle   Calc     96.8(3), Rep    96.81(8) ......       3.75 su-Rat
              O2   -P1   -O1      1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc  114.40(10), Rep   114.41(4) ......       2.50 su-Rat
              CL1  -P1   -S1      1.555   1.555   1.555

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           26.00
           From the CIF: _reflns_number_total               4235
           Count of symmetry unique reflns         2216
           Completeness (_total/calc)            191.11%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2019
           Fraction of Friedel pairs measured     0.911
           Are heavy atom types Z>Si present          yes

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

O,O-Bis(2-tert-butyl-4-methylphenyl) chlorothiophosphonate

Crystal data

C22H30ClO2PS	F(000) = 904
Mr = 424.94	Dx = 1.254 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 7293 reflections
a = 24.139 (2) Å	θ = 1.8–26.9°
b = 8.3588 (6) Å	µ = 0.35 mm^−1
c = 11.8747 (12) Å	T = 296 K
β = 110.014 (8)°	Prism, colorless
V = 2251.3 (4) Å^3	0.25 × 0.23 × 0.20 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	4235 independent reflections
Radiation source: fine-focus sealed tube	2583 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.8°
ω scans	h = −29→29
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −10→10
Tmin = 0.937, Tmax = 0.961	l = −14→14
14829 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)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0477P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.090	(Δ/σ)max < 0.001
S = 0.86	Δρmax = 0.14 e Å^−3
4235 reflections	Δρmin = −0.21 e Å^−3
251 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0048 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.39 (16)

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
C1	0.1508 (3)	0.3442 (10)	0.5114 (7)	0.0485 (19)
C2	0.1273 (4)	0.2028 (9)	0.5417 (7)	0.0535 (19)
H2	0.1510	0.1195	0.5836	0.064*
C3	0.0663 (4)	0.1970 (12)	0.5045 (7)	0.068 (2)
H3	0.0494	0.1024	0.5184	0.081*
C4	0.0303 (3)	0.3136 (12)	0.4513 (7)	0.053 (2)
C5	0.0566 (3)	0.4515 (11)	0.4304 (7)	0.053 (2)
H5	0.0321	0.5365	0.3943	0.064*
C6	0.1190 (3)	0.4743 (9)	0.4601 (7)	0.0449 (18)
C7	0.1450 (4)	0.6314 (9)	0.4289 (8)	0.052 (2)
C8	0.1783 (4)	0.5971 (10)	0.3447 (8)	0.067 (2)
H8A	0.1930	0.6955	0.3240	0.100*
H8B	0.1523	0.5472	0.2733	0.100*
H8C	0.2107	0.5268	0.3831	0.100*
C9	0.1839 (3)	0.7139 (9)	0.5417 (6)	0.0528 (19)
H9A	0.1986	0.8122	0.5208	0.079*
H9B	0.2164	0.6455	0.5832	0.079*
H9C	0.1613	0.7364	0.5925	0.079*
C10	0.0979 (3)	0.7560 (10)	0.3633 (8)	0.069 (2)
H10A	0.0745	0.7820	0.4119	0.104*
H10B	0.0730	0.7127	0.2882	0.104*
H10C	0.1168	0.8510	0.3490	0.104*
C11	−0.0354 (3)	0.3021 (12)	0.4223 (8)	0.072 (3)
H11A	−0.0446	0.3189	0.4939	0.109*
H11B	−0.0488	0.1980	0.3905	0.109*
H11C	−0.0547	0.3822	0.3641	0.109*
C21	0.3712 (3)	0.3456 (8)	0.5866 (6)	0.0426 (18)
C22	0.3945 (3)	0.2089 (11)	0.5655 (8)	0.062 (2)
H22	0.3695	0.1239	0.5317	0.074*
C23	0.4555 (3)	0.1887 (10)	0.5923 (7)	0.0541 (19)
H23	0.4711	0.0949	0.5733	0.065*
C24	0.4924 (3)	0.3191 (11)	0.6501 (7)	0.052 (2)
C25	0.4667 (3)	0.4563 (9)	0.6764 (7)	0.0483 (18)
H25	0.4912	0.5403	0.7146	0.058*
C26	0.4077 (3)	0.4741 (8)	0.6491 (6)	0.0431 (18)
C27	0.3812 (3)	0.6268 (9)	0.6779 (8)	0.051 (2)
C28	0.3444 (4)	0.5893 (11)	0.7594 (7)	0.068 (2)
H28A	0.3123	0.5197	0.7176	0.102*
H28B	0.3292	0.6870	0.7795	0.102*
H28C	0.3691	0.5378	0.8313	0.102*
C29	0.3412 (3)	0.7053 (10)	0.5586 (8)	0.073 (3)
H29A	0.3104	0.6322	0.5165	0.109*
H29B	0.3645	0.7304	0.5096	0.109*
H29C	0.3241	0.8016	0.5762	0.109*
C30	0.4305 (4)	0.7436 (10)	0.7451 (10)	0.088 (3)
H30A	0.4134	0.8398	0.7629	0.132*
H30B	0.4537	0.7688	0.6959	0.132*
H30C	0.4552	0.6952	0.8184	0.132*
C31	0.5586 (3)	0.3017 (11)	0.6893 (8)	0.066 (2)
H31A	0.5747	0.2945	0.7751	0.099*
H31B	0.5750	0.3930	0.6630	0.099*
H31C	0.5682	0.2065	0.6547	0.099*
O1	0.2141 (2)	0.3630 (6)	0.5535 (5)	0.0508 (14)
O2	0.3106 (2)	0.3636 (6)	0.5522 (5)	0.0528 (15)
P1	0.26315 (15)	0.23937 (7)	0.5520 (3)	0.05266 (19)
S1	0.23776 (8)	0.1118 (3)	0.40487 (18)	0.0701 (7)
Cl1	0.28846 (8)	0.1143 (3)	0.69852 (17)	0.0763 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.038 (4)	0.053 (4)	0.055 (4)	−0.012 (3)	0.016 (3)	−0.015 (3)
C2	0.070 (5)	0.037 (3)	0.059 (4)	0.000 (3)	0.029 (4)	0.012 (3)
C3	0.067 (5)	0.076 (6)	0.066 (5)	−0.031 (4)	0.032 (4)	−0.011 (4)
C4	0.055 (4)	0.061 (5)	0.052 (5)	−0.018 (4)	0.029 (4)	−0.011 (4)
C5	0.035 (3)	0.069 (5)	0.053 (5)	0.000 (4)	0.010 (3)	−0.005 (4)
C6	0.038 (4)	0.045 (4)	0.055 (4)	−0.007 (3)	0.020 (3)	−0.013 (3)
C7	0.047 (4)	0.044 (4)	0.061 (5)	−0.007 (3)	0.013 (4)	0.008 (4)
C8	0.063 (5)	0.050 (4)	0.087 (6)	0.005 (3)	0.024 (4)	0.021 (4)
C9	0.041 (4)	0.050 (4)	0.061 (4)	0.008 (3)	0.011 (3)	0.001 (3)
C10	0.045 (3)	0.061 (4)	0.090 (5)	0.012 (3)	0.007 (3)	0.006 (3)
C11	0.042 (4)	0.088 (6)	0.085 (5)	−0.023 (4)	0.019 (4)	−0.010 (5)
C21	0.039 (4)	0.040 (4)	0.042 (4)	0.000 (3)	0.005 (3)	−0.007 (3)
C22	0.045 (4)	0.062 (5)	0.069 (5)	0.011 (3)	0.008 (3)	−0.003 (4)
C23	0.057 (4)	0.039 (3)	0.067 (5)	0.004 (3)	0.022 (3)	−0.011 (3)
C24	0.040 (4)	0.059 (5)	0.059 (5)	0.008 (3)	0.017 (3)	0.011 (4)
C25	0.049 (4)	0.039 (4)	0.060 (5)	0.005 (3)	0.022 (4)	0.001 (3)
C26	0.044 (4)	0.045 (4)	0.037 (3)	−0.003 (3)	0.008 (3)	−0.010 (3)
C27	0.035 (4)	0.048 (4)	0.070 (5)	−0.007 (3)	0.019 (4)	−0.014 (4)
C28	0.065 (5)	0.095 (6)	0.053 (4)	0.006 (4)	0.032 (4)	−0.009 (4)
C29	0.063 (5)	0.045 (4)	0.120 (7)	0.020 (3)	0.043 (5)	0.012 (4)
C30	0.066 (5)	0.062 (4)	0.132 (8)	0.001 (3)	0.027 (5)	−0.054 (4)
C31	0.061 (5)	0.073 (5)	0.081 (5)	0.019 (4)	0.047 (4)	0.027 (4)
O1	0.036 (3)	0.043 (3)	0.070 (4)	−0.002 (2)	0.013 (2)	0.000 (3)
O2	0.041 (3)	0.041 (3)	0.067 (4)	−0.006 (2)	0.006 (3)	0.003 (3)
P1	0.0500 (4)	0.0378 (3)	0.0720 (4)	0.0012 (13)	0.0232 (3)	−0.0003 (14)
S1	0.0741 (15)	0.0654 (14)	0.0722 (15)	−0.0112 (12)	0.0269 (12)	−0.0198 (13)
Cl1	0.0813 (16)	0.0753 (15)	0.0717 (15)	0.0201 (13)	0.0254 (12)	0.0253 (13)

Geometric parameters (Å, º)

C1—C6	1.350 (10)	C21—C26	1.426 (9)
C1—C2	1.410 (11)	C22—C23	1.406 (11)
C1—O1	1.444 (9)	C22—H22	0.9300
C2—C3	1.385 (11)	C23—C24	1.425 (11)
C2—H2	0.9300	C23—H23	0.9300
C3—C4	1.315 (12)	C24—C25	1.390 (11)
C3—H3	0.9300	C24—C31	1.511 (10)
C4—C5	1.379 (12)	C25—C26	1.357 (10)
C4—C11	1.506 (10)	C25—H25	0.9300
C5—C6	1.437 (10)	C26—C27	1.518 (10)
C5—H5	0.9300	C27—C30	1.534 (10)
C6—C7	1.555 (11)	C27—C28	1.552 (11)
C7—C8	1.509 (13)	C27—C29	1.560 (11)
C7—C9	1.513 (10)	C28—H28A	0.9600
C7—C10	1.543 (10)	C28—H28B	0.9600
C8—H8A	0.9600	C28—H28C	0.9600
C8—H8B	0.9600	C29—H29A	0.9600
C8—H8C	0.9600	C29—H29B	0.9600
C9—H9A	0.9600	C29—H29C	0.9600
C9—H9B	0.9600	C30—H30A	0.9600
C9—H9C	0.9600	C30—H30B	0.9600
C10—H10A	0.9600	C30—H30C	0.9600
C10—H10B	0.9600	C31—H31A	0.9600
C10—H10C	0.9600	C31—H31B	0.9600
C11—H11A	0.9600	C31—H31C	0.9600
C11—H11B	0.9600	O1—P1	1.576 (6)
C11—H11C	0.9600	O2—P1	1.545 (6)
C21—C22	1.336 (11)	P1—Cl1	1.941 (4)
C21—O2	1.385 (9)	P1—S1	1.957 (4)
C6—C1—C2	125.0 (7)	C21—C22—H22	118.8
C6—C1—O1	116.0 (7)	C23—C22—H22	118.8
C2—C1—O1	118.3 (7)	C22—C23—C24	116.7 (7)
C3—C2—C1	115.1 (7)	C22—C23—H23	121.6
C3—C2—H2	122.4	C24—C23—H23	121.6
C1—C2—H2	122.4	C25—C24—C23	119.1 (7)
C4—C3—C2	125.7 (8)	C25—C24—C31	121.1 (8)
C4—C3—H3	117.2	C23—C24—C31	119.7 (8)
C2—C3—H3	117.2	C26—C25—C24	123.4 (7)
C3—C4—C5	115.8 (8)	C26—C25—H25	118.3
C3—C4—C11	122.3 (8)	C24—C25—H25	118.3
C5—C4—C11	121.8 (8)	C25—C26—C21	116.9 (7)
C4—C5—C6	125.1 (8)	C25—C26—C27	121.8 (6)
C4—C5—H5	117.4	C21—C26—C27	121.2 (6)
C6—C5—H5	117.4	C26—C27—C30	109.9 (6)
C1—C6—C5	113.0 (7)	C26—C27—C28	110.2 (7)
C1—C6—C7	125.1 (7)	C30—C27—C28	108.2 (8)
C5—C6—C7	121.9 (7)	C26—C27—C29	109.0 (7)
C8—C7—C9	111.4 (7)	C30—C27—C29	109.5 (7)
C8—C7—C10	105.1 (7)	C28—C27—C29	110.0 (7)
C9—C7—C10	105.4 (6)	C27—C28—H28A	109.5
C8—C7—C6	110.3 (7)	C27—C28—H28B	109.5
C9—C7—C6	110.7 (7)	H28A—C28—H28B	109.5
C10—C7—C6	113.7 (7)	C27—C28—H28C	109.5
C7—C8—H8A	109.5	H28A—C28—H28C	109.5
C7—C8—H8B	109.5	H28B—C28—H28C	109.5
H8A—C8—H8B	109.5	C27—C29—H29A	109.5
C7—C8—H8C	109.5	C27—C29—H29B	109.5
H8A—C8—H8C	109.5	H29A—C29—H29B	109.5
H8B—C8—H8C	109.5	C27—C29—H29C	109.5
C7—C9—H9A	109.5	H29A—C29—H29C	109.5
C7—C9—H9B	109.5	H29B—C29—H29C	109.5
H9A—C9—H9B	109.5	C27—C30—H30A	109.5
C7—C9—H9C	109.5	C27—C30—H30B	109.5
H9A—C9—H9C	109.5	H30A—C30—H30B	109.5
H9B—C9—H9C	109.5	C27—C30—H30C	109.5
C7—C10—H10A	109.5	H30A—C30—H30C	109.5
C7—C10—H10B	109.5	H30B—C30—H30C	109.5
H10A—C10—H10B	109.5	C24—C31—H31A	109.5
C7—C10—H10C	109.5	C24—C31—H31B	109.5
H10A—C10—H10C	109.5	H31A—C31—H31B	109.5
H10B—C10—H10C	109.5	C24—C31—H31C	109.5
C4—C11—H11A	109.5	H31A—C31—H31C	109.5
C4—C11—H11B	109.5	H31B—C31—H31C	109.5
H11A—C11—H11B	109.5	C1—O1—P1	129.4 (5)
C4—C11—H11C	109.5	C21—O2—P1	129.4 (5)
H11A—C11—H11C	109.5	O2—P1—O1	96.81 (8)
H11B—C11—H11C	109.5	O2—P1—Cl1	110.8 (3)
C22—C21—O2	120.6 (6)	O1—P1—Cl1	110.5 (3)
C22—C21—C26	121.1 (7)	O2—P1—S1	111.9 (3)
O2—C21—C26	118.3 (6)	O1—P1—S1	111.1 (3)
C21—C22—C23	122.5 (8)	Cl1—P1—S1	114.41 (4)
C6—C1—C2—C3	6.0 (13)	C23—C24—C25—C26	−0.5 (12)
O1—C1—C2—C3	176.3 (7)	C31—C24—C25—C26	−176.2 (7)
C1—C2—C3—C4	−4.2 (13)	C24—C25—C26—C21	−2.2 (11)
C2—C3—C4—C5	0.9 (13)	C24—C25—C26—C27	−179.3 (8)
C2—C3—C4—C11	−175.1 (8)	C22—C21—C26—C25	5.6 (12)
C3—C4—C5—C6	1.2 (12)	O2—C21—C26—C25	−176.8 (7)
C11—C4—C5—C6	177.3 (7)	C22—C21—C26—C27	−177.3 (8)
C2—C1—C6—C5	−4.1 (12)	O2—C21—C26—C27	0.3 (11)
O1—C1—C6—C5	−174.7 (6)	C25—C26—C27—C30	−3.0 (11)
C2—C1—C6—C7	178.8 (8)	C21—C26—C27—C30	180.0 (8)
O1—C1—C6—C7	8.3 (12)	C25—C26—C27—C28	−122.2 (8)
C4—C5—C6—C1	0.4 (11)	C21—C26—C27—C28	60.9 (10)
C4—C5—C6—C7	177.5 (8)	C25—C26—C27—C29	117.0 (8)
C1—C6—C7—C8	58.4 (11)	C21—C26—C27—C29	−60.0 (10)
C5—C6—C7—C8	−118.4 (8)	C6—C1—O1—P1	−143.4 (6)
C1—C6—C7—C9	−65.3 (10)	C2—C1—O1—P1	45.4 (10)
C5—C6—C7—C9	117.8 (8)	C22—C21—O2—P1	36.2 (11)
C1—C6—C7—C10	176.2 (8)	C26—C21—O2—P1	−141.5 (7)
C5—C6—C7—C10	−0.6 (11)	C21—O2—P1—O1	158.4 (5)
O2—C21—C22—C23	176.1 (7)	C21—O2—P1—Cl1	43.4 (7)
C26—C21—C22—C23	−6.3 (13)	C21—O2—P1—S1	−85.5 (7)
C21—C22—C23—C24	3.4 (13)	C1—O1—P1—O2	154.8 (5)
C22—C23—C24—C25	0.0 (12)	C1—O1—P1—Cl1	−90.0 (6)
C22—C23—C24—C31	175.8 (7)	C1—O1—P1—S1	38.1 (7)