Phosmet: O,O-dimethyl S-phthalimidomethyl phospho­rodithio­ate

Abstract

In the title compound, C₁₁H₁₂NO₄PS₂, the dihedral angle between the phthalimidyl ring plane and the PS₂ plane of the phospho­rodithio­ate group is 60.41 (3)°. In the crystal structure, weak inter­molecular C—H⋯O hydrogen bonds and S⋯S inter­actions [3.3825 (9) Å] contribute to the stabilization of the packing.

Related literature

For information on the toxicity and insecticidal properties of the title compound, see: Song et al. (2009 ▶). For related structures, see: Baughman & Allen (1995 ▶); Rohrbaugh et al. (1976 ▶). For the synthesis, see: Sinderhauf & Schwack (2004 ▶).

Experimental

Crystal data

• C₁₁H₁₂NO₄PS₂

• M _r = 317.31

• Triclinic,

• a = 8.3428 (18) Å

• b = 8.6014 (19) Å

• c = 10.218 (2) Å

• α = 85.253 (10)°

• β = 81.478 (10)°

• γ = 83.961 (9)°

• V = 719.4 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.49 mm⁻¹

• T = 173 K

• 0.29 × 0.25 × 0.15 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.871, T _max = 0.930

• 13076 measured reflections

• 3613 independent reflections

• 3404 reflections with I > 2σ(I)

• R _int = 0.025

Refinement

• R[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 0.095

• S = 1.04

• 3613 reflections

• 174 parameters

• H-atom parameters constrained

• Δρ_max = 0.34 e Å⁻³

• Δρ_min = −0.44 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O3i	0.98	2.57	3.272 (2)	128
C2—H2C⋯O4ii	0.98	2.70	3.420 (2)	130

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Phosmet (systematic name: O,O-dimethyl S-phthalimidomethyl phosphorodithioate), is a well known organothiophosphate acaricides and isoindole organothiophosphate insecticides used on plants and animals (Song et al., 2009). However, it's crystal structure has not been reported yet.

In the title compound (Scheme 1, Fig.1), the dihedral angle between the phthalimidyl ring plane and the S1/P1/S2 plane of phosphorodithioate group is 60.41 (3)°. All bond lengths and bond angles of phosphorodithioate group are are comparable to those observed in similar structures (Baughman & Allen, 1995; Rohrbaugh et al., 1976).

In the crystal structure, as shown in Fig. 2, weak C—H···O hydrogen bonds are observed [C2—H2B···O3; H2B···O3 = 2.57 Å; C2—H2B···O3 = 128°; C2···O3 = 3.272 (2) Å; -x + 1, -y + 1, -z and C2—H2C···O4; H2C···O4 = 2.70 Å; C2—H2C···O4 = 130°; C2···O4 = 3.420 (2) Å; -x + 1, -y + 1, -z + 1]. Weak intermolecular S···S interactions with 3.3825 (9) Å also exist. These intermolecular interactions may be contribute to the stabilization of the packing.

Experimental

The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation of a CH₂Cl₂ solution gave single crystals suitable for X-ray analysis.

Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.95 Å, U_iso = 1.2U_eq(C) for aromatic and 0.98 Å, U_iso = 1.5U_eq(C) for the d(C—H) = 0.98 Å, U_iso = 1.5U_eq(C) for CH₃ groups.

Figures

Fig. 1.

The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

Crystal packing of the title compound with intermolecular C—H···O and S···S interactions shown as dashed lines. H atoms not involved in intermolecular interactions have been omitted for clarity. (Symmetry codes: i) -x + 1, -y, -z + 1; ii) -x + 1, -y + 1, -z; iii) -x + 1, -y + 1, -z + 1)

Crystal data

C11H12NO4PS2	Z = 2
Mr = 317.31	F(000) = 328
Triclinic, P1	Dx = 1.465 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3428 (18) Å	Cell parameters from 9755 reflections
b = 8.6014 (19) Å	θ = 2.4–28.5°
c = 10.218 (2) Å	µ = 0.49 mm−1
α = 85.253 (10)°	T = 173 K
β = 81.478 (10)°	Block, colourless
γ = 83.961 (9)°	0.29 × 0.25 × 0.15 mm
V = 719.4 (3) Å3

Data collection

Bruker APEXII CCD diffractometer	3613 independent reflections
Radiation source: fine-focus sealed tube	3404 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 28.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.871, Tmax = 0.930	k = −11→11
13076 measured reflections	l = −13→13

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0575P)2 + 0.2633P] where P = (Fo2 + 2Fc2)/3
3613 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.44 e Å−3

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
S1	0.09888 (5)	0.15933 (5)	0.28102 (5)	0.03924 (12)
S2	0.43827 (4)	0.15124 (4)	0.39691 (3)	0.02668 (10)
P1	0.32713 (4)	0.16877 (4)	0.22735 (3)	0.02349 (10)
O1	0.41933 (14)	0.04388 (11)	0.13285 (10)	0.0328 (2)
O2	0.38169 (14)	0.31782 (11)	0.13866 (10)	0.0306 (2)
O3	0.75419 (15)	0.31462 (15)	0.07640 (10)	0.0384 (3)
O4	0.72161 (16)	0.33782 (15)	0.52567 (10)	0.0419 (3)
N1	0.71376 (14)	0.29623 (13)	0.30631 (11)	0.0258 (2)
C1	0.4028 (2)	−0.12177 (17)	0.16526 (19)	0.0450 (4)
H1A	0.4367	−0.1523	0.2523	0.067*
H1B	0.4716	−0.1830	0.0979	0.067*
H1C	0.2889	−0.1418	0.1674	0.067*
C2	0.3344 (2)	0.47159 (17)	0.18799 (18)	0.0412 (4)
H2A	0.2154	0.4890	0.2049	0.062*
H2B	0.3767	0.5518	0.1218	0.062*
H2C	0.3791	0.4780	0.2706	0.062*
C3	0.65366 (16)	0.14476 (16)	0.32840 (14)	0.0273 (3)
H3A	0.7178	0.0791	0.3900	0.033*
H3B	0.6704	0.0942	0.2432	0.033*
C4	0.76056 (16)	0.36963 (16)	0.18021 (13)	0.0271 (3)
C5	0.82125 (17)	0.51897 (16)	0.20613 (14)	0.0286 (3)
C6	0.8801 (2)	0.63735 (19)	0.11828 (17)	0.0377 (3)
H6	0.8815	0.6351	0.0253	0.045*
C7	0.9376 (2)	0.76105 (19)	0.1734 (2)	0.0453 (4)
H7	0.9779	0.8456	0.1165	0.054*
C8	0.9370 (2)	0.76272 (19)	0.3089 (2)	0.0446 (4)
H8	0.9788	0.8474	0.3428	0.053*
C9	0.8763 (2)	0.64295 (19)	0.39698 (17)	0.0380 (3)
H9	0.8758	0.6442	0.4899	0.046*
C10	0.81732 (17)	0.52298 (17)	0.34284 (14)	0.0290 (3)
C11	0.74723 (17)	0.38001 (17)	0.40935 (13)	0.0286 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.02281 (18)	0.0388 (2)	0.0582 (3)	−0.00383 (14)	−0.00798 (16)	−0.01070 (17)
S2	0.02212 (17)	0.03314 (18)	0.02380 (16)	−0.00471 (12)	−0.00268 (11)	0.00543 (12)
P1	0.02404 (18)	0.01980 (16)	0.02735 (17)	−0.00243 (12)	−0.00559 (12)	−0.00190 (12)
O1	0.0399 (6)	0.0230 (5)	0.0348 (5)	−0.0046 (4)	0.0011 (4)	−0.0068 (4)
O2	0.0425 (6)	0.0219 (4)	0.0278 (5)	−0.0033 (4)	−0.0083 (4)	0.0022 (3)
O3	0.0422 (6)	0.0503 (6)	0.0252 (5)	−0.0161 (5)	−0.0042 (4)	−0.0026 (4)
O4	0.0488 (7)	0.0529 (7)	0.0246 (5)	−0.0133 (5)	−0.0027 (4)	−0.0001 (5)
N1	0.0242 (5)	0.0295 (5)	0.0237 (5)	−0.0068 (4)	−0.0021 (4)	0.0008 (4)
C1	0.0568 (11)	0.0217 (6)	0.0540 (10)	−0.0065 (7)	0.0052 (8)	−0.0085 (6)
C2	0.0593 (11)	0.0198 (6)	0.0460 (9)	−0.0006 (6)	−0.0155 (7)	−0.0001 (6)
C3	0.0209 (6)	0.0269 (6)	0.0331 (7)	−0.0025 (5)	−0.0031 (5)	0.0027 (5)
C4	0.0217 (6)	0.0339 (6)	0.0255 (6)	−0.0062 (5)	−0.0031 (5)	0.0026 (5)
C5	0.0233 (6)	0.0297 (6)	0.0321 (7)	−0.0039 (5)	−0.0022 (5)	0.0014 (5)
C6	0.0334 (8)	0.0370 (7)	0.0407 (8)	−0.0067 (6)	−0.0020 (6)	0.0080 (6)
C7	0.0356 (8)	0.0301 (7)	0.0672 (11)	−0.0081 (6)	0.0004 (8)	0.0072 (7)
C8	0.0343 (8)	0.0304 (7)	0.0693 (12)	−0.0063 (6)	−0.0008 (7)	−0.0130 (7)
C9	0.0327 (8)	0.0365 (7)	0.0456 (8)	−0.0039 (6)	−0.0010 (6)	−0.0141 (6)
C10	0.0236 (6)	0.0296 (6)	0.0334 (7)	−0.0033 (5)	−0.0006 (5)	−0.0042 (5)
C11	0.0249 (6)	0.0336 (7)	0.0270 (6)	−0.0039 (5)	−0.0016 (5)	−0.0023 (5)

Geometric parameters (Å, °)

S1—P1	1.9103 (6)	C2—H2B	0.9800
S2—C3	1.8261 (14)	C2—H2C	0.9800
S2—P1	2.0706 (6)	C3—H3A	0.9900
P1—O1	1.5671 (10)	C3—H3B	0.9900
P1—O2	1.5749 (10)	C4—C5	1.4864 (19)
O1—C1	1.4520 (18)	C5—C6	1.381 (2)
O2—C2	1.4494 (17)	C5—C10	1.396 (2)
O3—C4	1.2070 (18)	C6—C7	1.402 (2)
O4—C11	1.2081 (18)	C6—H6	0.9500
N1—C11	1.4003 (18)	C7—C8	1.386 (3)
N1—C4	1.4069 (17)	C7—H7	0.9500
N1—C3	1.4335 (17)	C8—C9	1.396 (2)
C1—H1A	0.9800	C8—H8	0.9500
C1—H1B	0.9800	C9—C10	1.377 (2)
C1—H1C	0.9800	C9—H9	0.9500
C2—H2A	0.9800	C10—C11	1.4870 (19)
C3—S2—P1	102.12 (5)	N1—C3—H3B	108.9
O1—P1—O2	96.75 (6)	S2—C3—H3B	108.9
O1—P1—S1	118.01 (5)	H3A—C3—H3B	107.7
O2—P1—S1	117.12 (5)	O3—C4—N1	124.76 (13)
O1—P1—S2	107.80 (5)	O3—C4—C5	129.98 (13)
O2—P1—S2	108.52 (4)	N1—C4—C5	105.23 (11)
S1—P1—S2	107.86 (3)	C6—C5—C10	121.80 (14)
C1—O1—P1	120.26 (10)	C6—C5—C4	129.95 (14)
C2—O2—P1	119.12 (10)	C10—C5—C4	108.20 (12)
C11—N1—C4	112.65 (11)	C5—C6—C7	116.55 (16)
C11—N1—C3	122.77 (11)	C5—C6—H6	121.7
C4—N1—C3	124.30 (12)	C7—C6—H6	121.7
O1—C1—H1A	109.5	C8—C7—C6	121.44 (15)
O1—C1—H1B	109.5	C8—C7—H7	119.3
H1A—C1—H1B	109.5	C6—C7—H7	119.3
O1—C1—H1C	109.5	C7—C8—C9	121.56 (15)
H1A—C1—H1C	109.5	C7—C8—H8	119.2
H1B—C1—H1C	109.5	C9—C8—H8	119.2
O2—C2—H2A	109.5	C10—C9—C8	116.89 (16)
O2—C2—H2B	109.5	C10—C9—H9	121.6
H2A—C2—H2B	109.5	C8—C9—H9	121.6
O2—C2—H2C	109.5	C9—C10—C5	121.73 (14)
H2A—C2—H2C	109.5	C9—C10—C11	129.60 (14)
H2B—C2—H2C	109.5	C5—C10—C11	108.65 (12)
N1—C3—S2	113.49 (9)	O4—C11—N1	124.50 (14)
N1—C3—H3A	108.9	O4—C11—C10	130.34 (14)
S2—C3—H3A	108.9	N1—C11—C10	105.15 (11)
C3—S2—P1—O1	46.79 (6)	C10—C5—C6—C7	0.8 (2)
C3—S2—P1—O2	−56.96 (6)	C4—C5—C6—C7	−176.42 (15)
C3—S2—P1—S1	175.23 (5)	C5—C6—C7—C8	0.8 (3)
O2—P1—O1—C1	−176.64 (13)	C6—C7—C8—C9	−1.2 (3)
S1—P1—O1—C1	−50.98 (14)	C7—C8—C9—C10	0.1 (2)
S2—P1—O1—C1	71.40 (13)	C8—C9—C10—C5	1.5 (2)
O1—P1—O2—C2	−176.16 (12)	C8—C9—C10—C11	179.35 (15)
S1—P1—O2—C2	57.54 (12)	C6—C5—C10—C9	−2.0 (2)
S2—P1—O2—C2	−64.80 (12)	C4—C5—C10—C9	175.78 (14)
C11—N1—C3—S2	75.68 (15)	C6—C5—C10—C11	179.78 (13)
C4—N1—C3—S2	−110.89 (13)	C4—C5—C10—C11	−2.49 (16)
P1—S2—C3—N1	90.77 (10)	C4—N1—C11—O4	−178.01 (14)
C11—N1—C4—O3	174.74 (14)	C3—N1—C11—O4	−3.9 (2)
C3—N1—C4—O3	0.7 (2)	C4—N1—C11—C10	1.89 (15)
C11—N1—C4—C5	−3.36 (15)	C3—N1—C11—C10	176.00 (12)
C3—N1—C4—C5	−177.37 (12)	C9—C10—C11—O4	2.3 (3)
O3—C4—C5—C6	3.1 (3)	C5—C10—C11—O4	−179.63 (16)
N1—C4—C5—C6	−178.98 (15)	C9—C10—C11—N1	−177.61 (15)
O3—C4—C5—C10	−174.42 (15)	C5—C10—C11—N1	0.48 (15)
N1—C4—C5—C10	3.54 (15)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O3i	0.98	2.57	3.272 (2)	128
C2—H2C···O4ii	0.98	2.70	3.420 (2)	130

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1.