Two organo­phospho­rus pesticides: methyl para­thion and dicapthon

Structural studies performed in this laboratory of organo­phospho­rus pesticides continue with these related compounds. The -NO₂ groups of methyl para­thion (systematic name: dimethyl 4-nitro­phenyl phospho­rothio­ate, C₈H₁₀NO₅PS) and dicapthon (systematic name: 2-chloro-4-nitro­phenyl dimethyl phospho­rothio­ate, C₈H₉ClNO₅PS) make dihedral angles of 10.67 (8) and 5.8 (1)°, respectively, with the planes of their attached rings, which accompanies angular distortion at the ring C atoms to which the -NO₂ groups are attached. Similar distortions are observed at the C atom to which the thio­phosphate groups are attached. Significant differences in distances and angles around the phenolic O, versus the -OMe groups, explain why it is the site of hydrolysis for these compounds. A comparison of a torsion angle involving the thio­phosphate group and phenolic O atom with similar pesticide structures is given and indicates steric influences on that angle.

S1. Introduction

Determinations of the structures of methyl para­thion, (I), and dicapthon, (I), were undertaken as part of an ongoing study of organo­phospho­rus insecticides. The structure of (I) has been determined previously (Bally, 1970) from room-temperature film work (R = 16%). However, the current determination has made it possible to make more precise geometric comparisons. An initial attempt in this laboratory to determine the structure of (I) at room temperature produced poor results since the melting point of (I) is \sim 20 K above room temperature. Data reported here for (I) were collected at 100 K to produce better results.

Dicapthon, (II), is the 2-chloro derivative of Methyl Para­thion and has noticable differences in toxicity, as determined by LD₅₀ values (0.018 versus 0.027 p.p.m. for mosquito larva and 15 versus 400 mg kg^-1 for rats for methyl para­thion and dicapthon, respectively; White-Stevens, 1971). So dicapthon is less toxic to mosquitos while being 27 times less toxic to mammals (rat). Structural differences, as noted below, between (I) and (II) presumably account for most of the notable differences in toxicity.

S2. Experimental

S2.1. Synthesis and crystallization

Methyl para­thion, (I), was commercially available (Sigma–Aldrich) and crystals were grown by slow evaporation of a solution in cyclo­hexane. Dicapthon, (II), was also commercially available (Chem Service) and crystals were grown by slow evaporation of a solution in ethanol.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The approximate positions of the H atoms were first obtained from a difference map, then placed in ideal positions. Bond lengths were constrained at 0.93 Å (AFIX 43) for aryl C—H groups and at 0.96 Å (AFIX 137) for methyl C—H groups; the U_iso(H) values were fixed at 1.5U_eq(C) for the methyl H atoms and at 1.2U_eq(C) for the aryl H atoms. For (II), the methyl H atoms were disordered and the occupancies were refined. In the final stages of refinement of (II), four reflections with very small or negative F_o values were deemed to be in high disagreement with their F_c values and were eliminated from the final refinement. No reflections were eliminated for (I).

S3. Results and discussion

For (I) (Fig. 1) and (II) (Fig. 2), the angles (Table 2) about atoms C3, C4, and C5 indicate distortions (from an ideal of 120°) that are likely due to the presence of the –NO₂ group at C4. Differences between (I) and (II) involving atom C1 are noted in Table 3; four angles have large (> 5) Δ/σ values. The pattern of increased C2—C1—C6 and C3—C4—C5 angles for p-nitro­thio­phosphates is comparable to similar compounds (cf. Table 4).

The plane defined by atoms C4/N1/O4/O5 in (I) makes a dihedral angle of 10.76 (8)° with that of the ring [the corresponding angle is 5.8 (1)° in (II)]. The tipped –NO₂ groups imply slightly diminished π-overlaps with the rings versus an ideal (coplanar) geometry.

For (I) and (II), the P1—O1 distances are significantly (52σ and 32σ, respectively) greater than the averages of the P1—O2 and P1—O3 distances (Table 2). In addition, the O1—C1 distances are ~41σ and 23σ, respectively, shorter than the corresponding average meth­oxy O—C distance, thus indicating some double-bond character with atoms O1 and C1. Both effects likely contribute to O1 being the site of known hydrolysis of organo­phospho­rus pesticides.

When atom P1 is bonded to two meth­oxy groups, the C2—C1—O1—P1 torsion angles (per the numbering used here) for some similar thio­phosphate pesticides (Table 3) are in the range ~90–117°; the range for the other substituents is ~100–165° (most of which are greater than the –OMe range). For those containing the smaller –OMe angles, it is likely that the torsion angles are more influenced by intra­molecular rather than inter­molecular forces.

The C2—C1—O1—P1 torsion angles [90.42 (12) and 113.28 (19)° for (I) and (II), respectively] indicate that P1 leans away from Cl1 in (II), while S1 is tipped towards Cl1 [C1—O1—P1—S1 = -37.32 (18)°, versus -42.48 (10)° for (I)]. This `scorpion-like' appearance (Figs. 1 and 2) has been noted in previous structures; see citations in Table 3. No intra- or inter­molecular hydrogen bonding is observed in the title compounds.

Related literature

For related literature, see: Bally (1970); White-Stevens (1971).

Computing details

Data collection: APEX2 (Bruker, 2008) for MeParatI; XSCANS (Bruker, 1996) for DicapthonII. Cell refinement: APEX2 (Bruker, 2008) for MeParatI; XSCANS (Bruker, 1996) for DicapthonII. Data reduction: SADABS and SAINT (Bruker, 2008) for MeParatI; XSCANS (Bruker, 1996) for DicapthonII. For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008) and SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit of (I), showing the labeling of the non-H atoms. Displacement ellipsoids are drawn at the 50% probability levels and H atoms have been omitted for clarity.
	Fig. 2. The asymmetric unit of (II) showing the labeling of the non-H atoms. Displacement ellipsoids are drawn at the 50% probability levels and H atoms have been omitted for clarity.

(MeParatI) Dimethyl 4-nitrophenyl phosphorothioate

Crystal data

C8H10NO5PS	F(000) = 544
Mr = 263.20	Dx = 1.525 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9098 reflections
a = 7.0232 (3) Å	θ = 2.6–27.5°
b = 21.1563 (8) Å	µ = 0.43 mm^−1
c = 7.9679 (3) Å	T = 100 K
β = 104.4284 (4)°	Parallelepiped, colorless
V = 1146.57 (8) Å^3	0.53 × 0.45 × 0.31 mm
Z = 4

Data collection

Bruker APEXII diffractometer	2619 independent reflections
Radiation source: normal-focus sealed tube	2489 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans; a full Eward sphere was collected.	θmax = 27.5°, θmin = 1.9°
Absorption correction: part of the refinement model (ΔF) (SADABS; Bruker, 2008)	h = −9→9
Tmin = 0.80, Tmax = 0.88	k = −27→27
13180 measured reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: difference Fourier map
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.035P)^2 + 0.601P] where P = (Fo^2 + 2Fc^2)/3
2619 reflections	(Δ/σ)max = 0.001
147 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
S1	0.71351 (4)	0.650889 (14)	0.95845 (4)	0.01876 (9)
P1	0.49957 (4)	0.604017 (14)	0.81734 (4)	0.01366 (9)
O1	0.34735 (13)	0.64565 (4)	0.67538 (11)	0.01658 (18)
O2	0.54622 (13)	0.55080 (4)	0.69687 (11)	0.01832 (19)
O3	0.37555 (13)	0.56917 (4)	0.92679 (11)	0.01931 (19)
O4	0.15843 (16)	0.93043 (4)	0.77112 (14)	0.0293 (2)
O5	−0.05299 (15)	0.88617 (5)	0.89039 (13)	0.0276 (2)
N1	0.08003 (16)	0.88373 (5)	0.81565 (14)	0.0203 (2)
C1	0.28390 (17)	0.70508 (5)	0.71516 (14)	0.0150 (2)
C2	0.38926 (18)	0.75822 (6)	0.68980 (15)	0.0167 (2)
H2	0.5076	0.7540	0.6510	0.020*
C3	0.32064 (18)	0.81738 (6)	0.72072 (15)	0.0172 (2)
H3	0.3900	0.8550	0.7039	0.021*
C4	0.14957 (18)	0.82104 (6)	0.77789 (15)	0.0165 (2)
C5	0.04286 (18)	0.76823 (6)	0.80226 (15)	0.0178 (2)
H5	−0.0750	0.7726	0.8417	0.021*
C6	0.11124 (17)	0.70906 (6)	0.76944 (15)	0.0170 (2)
H6	0.0400	0.6715	0.7836	0.020*
C7	0.6579 (2)	0.56617 (6)	0.57091 (17)	0.0216 (3)
H7A	0.6944	0.5279	0.5223	0.032*	0.645 (18)
H7B	0.7742	0.5891	0.6271	0.032*	0.645 (18)
H7C	0.5787	0.5916	0.4803	0.032*	0.645 (18)
H7D	0.6705	0.6112	0.5642	0.032*	0.355 (18)
H7E	0.5906	0.5500	0.4593	0.032*	0.355 (18)
H7F	0.7862	0.5475	0.6062	0.032*	0.355 (18)
C8	0.2118 (2)	0.52777 (7)	0.8468 (2)	0.0271 (3)
H8A	0.1201	0.5263	0.9182	0.041*	0.92 (2)
H8B	0.2605	0.4860	0.8354	0.041*	0.92 (2)
H8C	0.1472	0.5438	0.7344	0.041*	0.92 (2)
H8D	0.2318	0.5111	0.7404	0.041*	0.08 (2)
H8E	0.0914	0.5514	0.8232	0.041*	0.08 (2)
H8F	0.2047	0.4936	0.9242	0.041*	0.08 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01532 (15)	0.01926 (16)	0.01971 (16)	−0.00199 (10)	0.00065 (11)	−0.00190 (11)
P1	0.01408 (15)	0.01236 (15)	0.01455 (15)	−0.00054 (10)	0.00356 (11)	−0.00027 (10)
O1	0.0186 (4)	0.0142 (4)	0.0151 (4)	0.0018 (3)	0.0007 (3)	−0.0018 (3)
O2	0.0220 (4)	0.0136 (4)	0.0217 (4)	−0.0009 (3)	0.0099 (3)	−0.0024 (3)
O3	0.0211 (4)	0.0187 (4)	0.0194 (4)	−0.0049 (3)	0.0074 (3)	0.0001 (3)
O4	0.0351 (6)	0.0155 (4)	0.0379 (6)	0.0015 (4)	0.0100 (5)	−0.0010 (4)
O5	0.0306 (5)	0.0291 (5)	0.0252 (5)	0.0104 (4)	0.0110 (4)	−0.0013 (4)
N1	0.0226 (5)	0.0190 (5)	0.0171 (5)	0.0050 (4)	0.0006 (4)	−0.0016 (4)
C1	0.0167 (5)	0.0148 (5)	0.0117 (5)	0.0019 (4)	0.0002 (4)	−0.0005 (4)
C2	0.0165 (5)	0.0186 (6)	0.0151 (5)	0.0001 (4)	0.0041 (4)	0.0010 (4)
C3	0.0195 (6)	0.0164 (5)	0.0147 (5)	−0.0015 (4)	0.0025 (4)	0.0011 (4)
C4	0.0190 (6)	0.0157 (6)	0.0130 (5)	0.0036 (4)	0.0006 (4)	−0.0003 (4)
C5	0.0158 (5)	0.0221 (6)	0.0150 (5)	0.0016 (4)	0.0029 (4)	0.0009 (4)
C6	0.0159 (5)	0.0179 (6)	0.0161 (5)	−0.0017 (4)	0.0019 (4)	0.0011 (4)
C7	0.0243 (6)	0.0213 (6)	0.0225 (6)	0.0003 (5)	0.0121 (5)	−0.0023 (5)
C8	0.0256 (7)	0.0242 (7)	0.0327 (7)	−0.0112 (5)	0.0095 (6)	−0.0013 (6)

Geometric parameters (Å, º)

S1—P1	1.9139 (4)	C4—C5	1.3857 (17)
P1—O3	1.5624 (9)	C5—C6	1.3889 (17)
P1—O2	1.5663 (9)	C5—H5	0.9599
P1—O1	1.6110 (9)	C6—H6	0.9596
O1—C1	1.3966 (14)	C7—H7A	0.9600
O2—C7	1.4562 (15)	C7—H7B	0.9600
O3—C8	1.4594 (15)	C7—H7C	0.9599
O4—N1	1.2257 (15)	C7—H7D	0.9601
O5—N1	1.2277 (15)	C7—H7E	0.9600
N1—C4	1.4701 (15)	C7—H7F	0.9600
C1—C6	1.3877 (17)	C8—H8A	0.9600
C1—C2	1.3880 (17)	C8—H8B	0.9601
C2—C3	1.3852 (17)	C8—H8C	0.9600
C2—H2	0.9601	C8—H8D	0.9600
C3—C4	1.3891 (17)	C8—H8E	0.9600
C3—H3	0.9600	C8—H8F	0.9600
O3—P1—O2	103.51 (5)	O2—C7—H7D	109.5
O3—P1—O1	106.57 (5)	H7A—C7—H7D	141.1
O2—P1—O1	99.57 (5)	H7B—C7—H7D	56.3
O3—P1—S1	112.45 (4)	H7C—C7—H7D	56.3
O2—P1—S1	118.62 (4)	O2—C7—H7E	109.5
O1—P1—S1	114.56 (4)	H7A—C7—H7E	56.3
C1—O1—P1	121.75 (7)	H7B—C7—H7E	141.1
C7—O2—P1	119.52 (8)	H7C—C7—H7E	56.2
C8—O3—P1	121.85 (8)	H7D—C7—H7E	109.5
O4—N1—O5	123.89 (11)	O2—C7—H7F	109.5
O4—N1—C4	118.15 (11)	H7A—C7—H7F	56.3
O5—N1—C4	117.96 (11)	H7B—C7—H7F	56.2
C6—C1—C2	122.36 (11)	H7C—C7—H7F	141.1
C6—C1—O1	118.57 (11)	H7D—C7—H7F	109.5
C2—C1—O1	118.97 (10)	H7E—C7—H7F	109.5
C3—C2—C1	118.95 (11)	O3—C8—H8A	109.5
C3—C2—H2	120.5	O3—C8—H8B	109.5
C1—C2—H2	120.5	H8A—C8—H8B	109.5
C2—C3—C4	118.45 (11)	O3—C8—H8C	109.5
C2—C3—H3	120.9	H8A—C8—H8C	109.5
C4—C3—H3	120.7	H8B—C8—H8C	109.5
C5—C4—C3	122.90 (11)	O3—C8—H8D	109.5
C5—C4—N1	118.67 (11)	H8A—C8—H8D	141.1
C3—C4—N1	118.42 (11)	H8B—C8—H8D	56.3
C4—C5—C6	118.42 (11)	H8C—C8—H8D	56.2
C4—C5—H5	120.6	O3—C8—H8E	109.5
C6—C5—H5	120.9	H8A—C8—H8E	56.3
C1—C6—C5	118.90 (11)	H8B—C8—H8E	141.1
C1—C6—H6	120.5	H8C—C8—H8E	56.3
C5—C6—H6	120.6	H8D—C8—H8E	109.5
O2—C7—H7A	109.5	O3—C8—H8F	109.5
O2—C7—H7B	109.5	H8A—C8—H8F	56.3
H7A—C7—H7B	109.5	H8B—C8—H8F	56.2
O2—C7—H7C	109.5	H8C—C8—H8F	141.1
H7A—C7—H7C	109.5	H8D—C8—H8F	109.5
H7B—C7—H7C	109.5	H8E—C8—H8F	109.5
O3—P1—O1—C1	82.55 (9)	C1—C2—C3—C4	0.69 (17)
O2—P1—O1—C1	−170.15 (9)	C2—C3—C4—C5	−1.21 (18)
S1—P1—O1—C1	−42.48 (10)	C2—C3—C4—N1	178.21 (10)
O3—P1—O2—C7	178.51 (9)	O4—N1—C4—C5	−169.94 (11)
O1—P1—O2—C7	68.76 (9)	O5—N1—C4—C5	10.23 (16)
S1—P1—O2—C7	−56.14 (10)	O4—N1—C4—C3	10.62 (16)
O2—P1—O3—C8	−47.32 (11)	O5—N1—C4—C3	−169.21 (11)
O1—P1—O3—C8	57.15 (10)	C3—C4—C5—C6	0.59 (18)
S1—P1—O3—C8	−176.54 (9)	N1—C4—C5—C6	−178.83 (10)
P1—O1—C1—C6	−93.16 (12)	C2—C1—C6—C5	−1.05 (18)
P1—O1—C1—C2	90.42 (12)	O1—C1—C6—C5	−177.34 (10)
C6—C1—C2—C3	0.42 (18)	C4—C5—C6—C1	0.54 (17)
O1—C1—C2—C3	176.69 (10)

(DicapthonII) 2-Chloro-4-nitrophenyl dimethyl phosphorothioate

Crystal data

C8H9ClNO5PS	F(000) = 608
Mr = 297.66	Dx = 1.570 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 100 reflections
a = 10.9108 (14) Å	θ = 9.5–16.2°
b = 17.0968 (19) Å	µ = 0.60 mm^−1
c = 6.8940 (6) Å	T = 295 K
β = 101.65 (5)°	Block cut from larger crystal, colorless
V = 1259.5 (2) Å^3	0.49 × 0.48 × 0.43 mm
Z = 4

Data collection

Bruker P4 diffractometer	1841 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
θ/2θ; a little over one quadrant of data was collected. scans	h = −12→12
Absorption correction: integration (XSHELL; Bruker, 1999)	k = −1→20
Tmin = 0.706, Tmax = 0.791	l = −1→8
2989 measured reflections	3 standard reflections every 100 reflections
2206 independent reflections	intensity decay: 2.1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0494P)^2 + 0.3678P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2206 reflections	Δρmax = 0.35 e Å^−3
155 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.097 (4)

Special details

Experimental. A little over one quadrant of data was collected.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cl1	0.37550 (7)	0.53209 (4)	0.66806 (11)	0.0716 (3)
S1	0.26547 (6)	0.41051 (4)	0.11872 (10)	0.0601 (2)
P1	0.14382 (5)	0.39892 (3)	0.27916 (8)	0.0475 (2)
O1	0.19664 (14)	0.40801 (9)	0.5140 (2)	0.0512 (4)
O2	0.03273 (15)	0.45803 (11)	0.2539 (3)	0.0628 (5)
O3	0.07694 (16)	0.31815 (10)	0.2504 (2)	0.0624 (5)
O4	0.7479 (2)	0.34501 (16)	0.9468 (4)	0.1053 (8)
O5	0.67985 (19)	0.22736 (14)	0.9190 (4)	0.0898 (7)
N1	0.6654 (2)	0.29774 (16)	0.8946 (3)	0.0685 (6)
C1	0.31313 (19)	0.38014 (13)	0.6058 (3)	0.0449 (5)
C2	0.4053 (2)	0.43300 (13)	0.6867 (3)	0.0483 (5)
C3	0.5212 (2)	0.40649 (14)	0.7826 (3)	0.0549 (6)
H3	0.5863	0.4425	0.8385	0.066*
C4	0.5407 (2)	0.32679 (14)	0.7954 (3)	0.0512 (5)
C5	0.4499 (2)	0.27324 (14)	0.7199 (3)	0.0541 (6)
H5	0.4662	0.2181	0.7340	0.065*
C6	0.3350 (2)	0.30057 (14)	0.6240 (3)	0.0531 (6)
H6	0.2698	0.2644	0.5697	0.064*
C7	0.0557 (3)	0.54154 (17)	0.2618 (5)	0.0766 (8)
H7A	−0.0224	0.5691	0.2440	0.115*
H7B	0.1063	0.5547	0.3883	0.115*
H7C	0.0987	0.5560	0.1588	0.115*
C8	−0.0247 (3)	0.2976 (2)	0.3494 (4)	0.0788 (8)
H8A	−0.0528	0.2455	0.3122	0.118*
H8B	0.0049	0.2999	0.4902	0.118*
H8C	−0.0928	0.3336	0.3113	0.118*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0773 (5)	0.0498 (4)	0.0818 (5)	−0.0019 (3)	0.0020 (4)	−0.0046 (3)
S1	0.0642 (4)	0.0630 (4)	0.0583 (4)	0.0049 (3)	0.0248 (3)	0.0039 (3)
P1	0.0456 (3)	0.0517 (4)	0.0448 (3)	0.0014 (2)	0.0084 (2)	−0.0007 (2)
O1	0.0464 (8)	0.0614 (10)	0.0451 (8)	0.0036 (7)	0.0078 (7)	−0.0047 (7)
O2	0.0514 (9)	0.0741 (12)	0.0621 (10)	0.0137 (8)	0.0094 (8)	0.0043 (9)
O3	0.0616 (10)	0.0664 (11)	0.0586 (10)	−0.0159 (8)	0.0110 (8)	−0.0082 (8)
O4	0.0631 (13)	0.1064 (18)	0.129 (2)	−0.0085 (12)	−0.0220 (13)	0.0148 (15)
O5	0.0699 (13)	0.0825 (15)	0.1140 (17)	0.0187 (11)	0.0117 (12)	0.0253 (13)
N1	0.0543 (13)	0.0875 (17)	0.0624 (13)	0.0041 (12)	0.0089 (10)	0.0145 (12)
C1	0.0446 (11)	0.0546 (12)	0.0364 (10)	−0.0005 (9)	0.0104 (9)	−0.0003 (9)
C2	0.0559 (13)	0.0492 (12)	0.0404 (11)	−0.0033 (10)	0.0109 (9)	−0.0010 (9)
C3	0.0531 (13)	0.0621 (14)	0.0473 (12)	−0.0101 (11)	0.0052 (10)	0.0005 (11)
C4	0.0486 (12)	0.0641 (14)	0.0412 (11)	0.0003 (10)	0.0096 (9)	0.0081 (10)
C5	0.0597 (14)	0.0505 (12)	0.0535 (13)	0.0005 (11)	0.0147 (11)	0.0051 (10)
C6	0.0528 (13)	0.0536 (13)	0.0525 (13)	−0.0082 (11)	0.0098 (10)	−0.0017 (11)
C7	0.086 (2)	0.0673 (17)	0.0775 (18)	0.0270 (15)	0.0189 (16)	0.0038 (14)
C8	0.0736 (18)	0.093 (2)	0.0707 (17)	−0.0266 (16)	0.0158 (14)	0.0066 (16)

Geometric parameters (Å, º)

Cl1—C2	1.725 (2)	C2—C3	1.379 (3)
S1—P1	1.9019 (11)	C3—C4	1.379 (3)
P1—O3	1.5558 (17)	C3—H3	0.9600
P1—O2	1.5606 (17)	C4—C5	1.372 (3)
P1—O1	1.6123 (16)	C5—C6	1.375 (3)
O1—C1	1.385 (3)	C5—H5	0.9602
O2—C7	1.449 (3)	C6—H6	0.9601
O3—C8	1.458 (3)	C7—H7A	0.9600
O4—N1	1.210 (3)	C7—H7B	0.9600
O5—N1	1.221 (3)	C7—H7C	0.9599
N1—C4	1.479 (3)	C8—H8A	0.9600
C1—C6	1.382 (3)	C8—H8B	0.9600
C1—C2	1.383 (3)	C8—H8C	0.9599
O3—P1—O2	103.11 (10)	C5—C4—C3	123.0 (2)
O3—P1—O1	106.09 (9)	C5—C4—N1	118.5 (2)
O2—P1—O1	99.31 (10)	C3—C4—N1	118.5 (2)
O3—P1—S1	112.50 (7)	C4—C5—C6	118.3 (2)
O2—P1—S1	119.02 (8)	C4—C5—H5	120.7
O1—P1—S1	115.08 (7)	C6—C5—H5	121.0
C1—O1—P1	122.32 (14)	C5—C6—C1	120.1 (2)
C7—O2—P1	120.63 (17)	C5—C6—H6	120.1
C8—O3—P1	122.41 (18)	C1—C6—H6	119.8
O4—N1—O5	123.3 (2)	O2—C7—H7A	109.7
O4—N1—C4	118.2 (3)	O2—C7—H7B	109.2
O5—N1—C4	118.4 (2)	H7A—C7—H7B	109.5
C6—C1—C2	120.5 (2)	O2—C7—H7C	109.5
C6—C1—O1	120.39 (19)	H7A—C7—H7C	109.5
C2—C1—O1	119.0 (2)	H7B—C7—H7C	109.5
C3—C2—C1	120.0 (2)	O3—C8—H8A	109.4
C3—C2—Cl1	119.95 (18)	O3—C8—H8B	109.3
C1—C2—Cl1	120.05 (18)	H8A—C8—H8B	109.5
C4—C3—C2	118.1 (2)	O3—C8—H8C	109.7
C4—C3—H3	121.0	H8A—C8—H8C	109.5
C2—C3—H3	120.9	H8B—C8—H8C	109.5
O3—P1—O1—C1	87.76 (18)	O1—C1—C2—Cl1	−1.3 (3)
O2—P1—O1—C1	−165.59 (17)	C1—C2—C3—C4	−0.4 (3)
S1—P1—O1—C1	−37.32 (18)	Cl1—C2—C3—C4	179.52 (18)
O3—P1—O2—C7	−177.31 (19)	C2—C3—C4—C5	−1.0 (4)
O1—P1—O2—C7	73.6 (2)	C2—C3—C4—N1	178.9 (2)
S1—P1—O2—C7	−52.0 (2)	O4—N1—C4—C5	174.2 (3)
O2—P1—O3—C8	−47.1 (2)	O5—N1—C4—C5	−5.6 (3)
O1—P1—O3—C8	56.8 (2)	O4—N1—C4—C3	−5.6 (4)
S1—P1—O3—C8	−176.54 (18)	O5—N1—C4—C3	174.6 (3)
P1—O1—C1—C6	−69.6 (2)	C3—C4—C5—C6	1.3 (3)
P1—O1—C1—C2	113.28 (19)	N1—C4—C5—C6	−178.6 (2)
C6—C1—C2—C3	1.5 (3)	C4—C5—C6—C1	−0.1 (3)
O1—C1—C2—C3	178.6 (2)	C2—C1—C6—C5	−1.2 (3)
C6—C1—C2—Cl1	−178.44 (17)	O1—C1—C6—C5	−178.3 (2)