• No results found

O,O Di­ethyl phthalimido­phosphono­thio­ate (Ditalimphos)

N/A
N/A
Protected

Academic year: 2020

Share "O,O Di­ethyl phthalimido­phosphono­thio­ate (Ditalimphos)"

Copied!
9
0
0

Loading.... (view fulltext now)

Full text

(1)

organic papers

o2352

Baughman and Paulos C

12H14NO4PS doi:10.1107/S1600536805019872 Acta Cryst.(2005). E61, o2352–o2353 Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

O

,

O

-Diethyl phthalimidophosphonothioate

(Ditalimphos)

Russell G. Baughman* and Chrystal M. Paulos

Division of Science, Truman State University, Kirksville, MO 63501-4221, USA

Correspondence e-mail: baughman@truman.edu

Key indicators

Single-crystal X-ray study

T= 298 K

Mean(C–C) = 0.008 A˚

Rfactor = 0.064

wRfactor = 0.200

Data-to-parameter ratio = 15.0

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography

Printed in Great Britain – all rights reserved

The crystal structure ofO,O-diethyl phthalimidophosphono-thioate (also known as Ditalimphos, Laptran1 and Plon-drel1), C12H14NO4PS, contains two molecules per asymmetric

unit. The ring systems of the two molecules are at a van der Waals distance from each other, are nearly parallel, and are twisted by21with respect to each other.

Comment

As part of an ongoing study of organophophorus (OP) pesticides (Baughman & Allen, 1995; Baker & Baughman, 1995; Baughman, 1997, and references therein), a determina-tion of the structure of the title antifungal compound (Dita-limphos), (I), was undertaken and the results are presented here. Accurate three-dimensional structure determinations of a series of OP compounds should shed light on any structure– activity relationships.

[image:1.610.275.391.382.466.2]

The systems of the two molecules present in the asym-metric unit of (I) are in close contact, as the least-squares planes of the approximately parallel ring skeletons (C1/N1/ C2–C8) are separated by a distance of about 3.5 A˚ . As seen in Fig. 1, the thiophosphate groups point in opposite directions, leaving the more electron-deficient N-containing rings stacked with respect to the benzene rings. The distances and angles noted in Table 1 show structural similarities between the two molecules. The P S, P—ORand C O bond lengths are in general agreement with corresponding bond lengths observed in similar compounds (Baughman & Allen, 1995; Baker & Baughman, 1995; Baughman, 1997). Only one weak inter-molecular hydrogen bond involving atoms H4band O2b(via

an inversion) is noted (Table 2).

The C1/N1/C2–C8 skeletons of the phthalimide rings are planar (r.m.s. deviations of 0.017 A˚ for both a andbrings). The planes are at a dihedral angle of 4.8 (2)and are slightly

twisted with respect to each other [C8a—C3a C3b—C8b= 20.9 (4)]. While the four S1—P1—O—C—C groups are

nearly planar (see Table 3), the dihedral angles of the S1— P1—N1 planes to the ring skeletons are similar, but are

(2)

significantly (14) different [82.9 (1) and 81.45 (9) for

moleculesaandb, respectively].

Experimental

Crystals of (I) were purchased from Chem Service and were grown by slow evaporation of a solution in ethanol at 298 K. In order to rule out the possibility that the slight disorder in moleculeawas a result of crystallization conditions, an attempt to minimize the effect was conducted by slow recrystallization from MeOH at 253 K. Of the three crystals analyzed by this procedure, none produced results as good as those reported here (the best of the three crystals obtained from EtOH at 298 K).

Crystal data

C12H14NO4PS Mr= 299.27

Triclinic,P1 a= 8.1696 (6) A˚ b= 12.4578 (8) A˚ c= 14.8541 (9) A˚

= 101.277 (4) = 90.134 (5) = 96.332 (5)

V= 1473.10 (17) A˚3

Z= 4

Dx= 1.349 Mg m 3 MoKradiation Cell parameters from 100

reflections

= 10.4–18.3 = 0.34 mm1 T= 298 (2) K

Parallelepiped, colorless 0.480.480.29 mm

Data collection

Bruker P4 diffractometer

!/2scans

Absorption correction: integration (XSHELL; Bruker, 1999) Tmin= 0.851,Tmax= 0.916 6338 measured reflections 5158 independent reflections 3394 reflections withI> 2(I)

Rint= 0.020

max= 25.0 h=9!1 k=14!14 l=17!17 3 standard reflections

every 100 reflections intensity decay: 1.2%

Refinement

Refinement onF2 R[F2> 2(F2)] = 0.064 wR(F2) = 0.200 S= 1.02 5158 reflections 343 parameters

H-atom parameters constrained

w= 1/[2(F

o2) + (0.1005P)2 + 0.8864P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.37 e A˚

3

min=0.32 e A˚

[image:2.610.47.296.71.195.2]

3

Table 1

Selected geometric parameters (A˚ ,).

S1a—P1a 1.9135 (17) P1a—O3a 1.559 (3) P1a—O4a 1.545 (4) P1a—N1a 1.707 (3) O1a—C1a 1.194 (6) O2a—C2a 1.189 (6)

S1b—P1b 1.9116 (16) P1b—O3b 1.557 (3) P1b—O4b 1.553 (3) P1b—N1b 1.705 (3) O1b—C1b 1.199 (5) O2b—C2b 1.193 (5)

S1a—P1a—O3a 118.19 (14) S1a—P1a—O4a 118.08 (14) S1a—P1a—N1a 114.73 (13) O3a—P1a—O4a 100.82 (18) O3a—P1a—N1a 99.79 (17) O4a—P1a—N1a 102.35 (18)

S1b—P1b—O3b 118.71 (13) S1b—P1b—O4b 117.75 (13) S1b—P1b—N1b 114.52 (12) O3b—P1b—O4b 100.51 (18) O3b—P1b—N1b 99.70 (15) O4b—P1b—N1b 102.80 (16)

Table 2

Hydrogen-bond geometry (A˚ ,).

D—H A D—H H A D A D—H A

C4b—H4b O2bi

0.93 2.48 3.408 (6) 176

[image:2.610.312.568.93.213.2]

Symmetry code: (i)xþ1;yþ1;zþ1.

Table 3

R.m.s. deviations (A˚ ) for (I).

Plane Moleculea Moleculeb

S1/P1/O3/C11/C12 0.091 0.054

S1/P1/O4/C9/C10 0.213 0.268

Although a number of H atoms were observed in a difference map, methyl H atoms (on C10 and C12) and methylene H atoms (on C9 and C11) were placed in ideal positions and refined as riding. Bond lengths were constrained to 0.93 A˚ for aromatic C—H, 0.96 A˚ for methyl C—H and 0.97 A˚ for methylene C—H, andUiso(H) were fixed at 1.5Ueq(parent) for methyl H atoms and 1.2Ueq(parent) for all other H atoms. In the final stages of refinement, nine very small or negative

Fovalues were deemed to be in severe disagreement with their Fc values and were eliminated from the final refinement.

Data collection: XSCANS (Bruker, 1996); cell refinement:

XSCANS; data reduction: XSCANS; program(s) used to solve structure:SHELXS86(Sheldrick, 1990a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL/PC(Sheldrick, 1990b); software used to prepare material for publication:SHELXTL/PCandSHELXL97.

References

Baughman, R. G. & Allen, J. L. (1995).Acta Cryst.C51, 521–523.

Baker, S. M. & Baughman, R. G. (1995).J. Agric. Food. Chem.43, 503–506. Baughman, R. G. (1997).Acta Cryst.C53, 1928–1929.

Bruker (1996).XSCANS(Version 2.2). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1999).XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA. Sheldrick, G. M. (1990a).Acta Cryst.A46, 467–473.

Sheldrick, G. M. (1990b).SHELXTL/PC. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Figure 1

[image:2.610.313.565.351.390.2]
(3)

supporting information

sup-1

Acta Cryst. (2005). E61, o2352–o2353

supporting information

Acta Cryst. (2005). E61, o2352–o2353 [https://doi.org/10.1107/S1600536805019872]

O

,

O

-Diethyl phthalimidophosphonothioate (Ditalimphos)

Russell G. Baughman and Chrystal M. Paulos

O,O-Diethyl phthalimidophosphonothioate

Crystal data

C12H14NO4PS

Mr = 299.27

Triclinic, P1 Hall symbol: -P 1

a = 8.1696 (6) Å

b = 12.4578 (8) Å

c = 14.8541 (9) Å

α = 101.277 (4)°

β = 90.134 (5)°

γ = 96.332 (5)°

V = 1473.10 (17) Å3

Z = 4

F(000) = 624

Dx = 1.349 Mg m−3

Mo radiation, λ = 0.71073 Å Cell parameters from 100 reflections

θ = 10.4–18.3°

µ = 0.34 mm−1

T = 298 K

Parallelpiped, colorless 0.48 × 0.48 × 0.29 mm

Data collection

Bruker P4 diffractometer

Radiation source: normal-focus sealed tube Graphite monochromator

θ/2θ scans

Absorption correction: integration (XSHELL; Bruker, 1999)

Tmin = 0.851, Tmax = 0.916

6338 measured reflections

5158 independent reflections 3394 reflections with I > 2σ(I)

Rint = 0.020

θmax = 25.0°, θmin = 2.0°

h = −9→1

k = −14→14

l = −17→17

3 standard reflections every 100 reflections intensity decay: average in σ(I) of 1.2%

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.064

wR(F2) = 0.200

S = 1.02 5158 reflections 343 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2(F

o2) + (0.1005P)2 + 0.8864P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.37 e Å−3

(4)

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 (Å2)

x y z Uiso*/Ueq

(5)

supporting information

sup-3

Acta Cryst. (2005). E61, o2352–o2353

O1B −0.0689 (4) 0.6381 (3) 0.3085 (2) 0.0982 (10) O2B 0.3957 (4) 0.4977 (3) 0.3837 (2) 0.1001 (11) O3B 0.1895 (4) 0.6413 (2) 0.17456 (19) 0.0836 (9) O4B 0.4122 (4) 0.5428 (2) 0.2045 (2) 0.0864 (9) N1B 0.1811 (4) 0.5672 (2) 0.31908 (19) 0.0611 (7) C1B 0.0389 (5) 0.6175 (3) 0.3551 (3) 0.0685 (10) C2B 0.2773 (5) 0.5467 (3) 0.3927 (3) 0.0660 (10) C3B 0.1971 (5) 0.5944 (3) 0.4783 (3) 0.0616 (9) C4B 0.2467 (6) 0.5997 (4) 0.5687 (3) 0.0765 (11) H4B 0.3416 0.5711 0.5833 0.080* C5B 0.1475 (7) 0.6497 (4) 0.6356 (3) 0.0890 (14) H5B 0.1774 0.6564 0.6970 0.080* C6B 0.0075 (7) 0.6893 (4) 0.6138 (3) 0.0916 (14) H6B −0.0570 0.7211 0.6609 0.080* C7B −0.0423 (6) 0.6839 (4) 0.5242 (3) 0.0851 (13) H7B −0.1382 0.7116 0.5101 0.080* C8B 0.0571 (5) 0.6353 (3) 0.4559 (3) 0.0637 (9) C9B 0.5149 (8) 0.4526 (5) 0.1873 (5) 0.125 (2) H9BA 0.5682 0.4480 0.2447 0.080* H9BB 0.4448 0.3841 0.1666 0.080* C10B 0.6303 (9) 0.4631 (6) 0.1252 (6) 0.161 (3) H10D 0.7094 0.4123 0.1283 0.080* H10E 0.6846 0.5370 0.1377 0.080* H10F 0.5798 0.4475 0.0650 0.080* C11B 0.0991 (8) 0.6497 (4) 0.0956 (3) 0.1025 (16) H11C −0.0169 0.6281 0.1035 0.080* H11D 0.1355 0.5999 0.0427 0.080* C12B 0.1211 (8) 0.7604 (4) 0.0797 (4) 0.1146 (19) H12D 0.0539 0.7653 0.0279 0.080* H12E 0.2347 0.7799 0.0675 0.080* H12F 0.0894 0.8100 0.1331 0.080*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

(6)

C7A 0.145 (5) 0.114 (5) 0.119 (5) −0.024 (4) −0.039 (4) 0.044 (4) C8A 0.107 (4) 0.079 (3) 0.079 (3) −0.025 (3) −0.014 (3) 0.025 (2) C9A 0.146 (6) 0.108 (4) 0.125 (5) 0.034 (4) −0.031 (4) 0.013 (4) C10A 0.149 (7) 0.115 (5) 0.309 (13) 0.005 (5) −0.069 (8) 0.082 (7) C11A 0.187 (7) 0.096 (4) 0.195 (8) −0.005 (4) 0.117 (6) −0.021 (4) C12A 0.151 (6) 0.097 (4) 0.214 (8) 0.019 (4) 0.074 (6) −0.027 (5) S1B 0.1471 (12) 0.0654 (7) 0.0729 (7) 0.0025 (7) 0.0024 (7) 0.0001 (5) P1B 0.0958 (8) 0.0585 (6) 0.0553 (6) 0.0140 (5) 0.0073 (5) 0.0103 (4) O1B 0.087 (2) 0.123 (3) 0.090 (2) 0.040 (2) −0.0110 (18) 0.0201 (19) O2B 0.100 (2) 0.133 (3) 0.080 (2) 0.058 (2) 0.0123 (17) 0.0286 (19) O3B 0.121 (2) 0.0660 (16) 0.0655 (16) 0.0124 (16) −0.0114 (16) 0.0166 (13) O4B 0.093 (2) 0.0847 (19) 0.087 (2) 0.0253 (16) 0.0289 (16) 0.0229 (16) N1B 0.073 (2) 0.0584 (17) 0.0522 (16) 0.0140 (14) 0.0037 (14) 0.0078 (13) C1B 0.072 (3) 0.061 (2) 0.072 (2) 0.0086 (19) 0.000 (2) 0.0101 (18) C2B 0.073 (3) 0.066 (2) 0.060 (2) 0.012 (2) 0.0068 (19) 0.0151 (17) C3B 0.068 (2) 0.0559 (19) 0.060 (2) −0.0008 (17) 0.0046 (18) 0.0137 (16) C4B 0.085 (3) 0.081 (3) 0.062 (2) −0.001 (2) 0.000 (2) 0.016 (2) C5B 0.118 (4) 0.083 (3) 0.058 (2) −0.008 (3) 0.012 (3) 0.006 (2) C6B 0.118 (4) 0.078 (3) 0.071 (3) 0.003 (3) 0.035 (3) 0.000 (2) C7B 0.081 (3) 0.080 (3) 0.091 (3) 0.016 (2) 0.023 (2) 0.005 (2) C8B 0.067 (2) 0.056 (2) 0.065 (2) 0.0018 (17) 0.0085 (18) 0.0063 (17) C9B 0.144 (5) 0.128 (5) 0.131 (5) 0.072 (4) 0.066 (4) 0.058 (4) C10B 0.164 (7) 0.139 (6) 0.203 (8) 0.064 (5) 0.088 (6) 0.065 (5) C11B 0.137 (5) 0.089 (3) 0.084 (3) 0.006 (3) −0.027 (3) 0.027 (3) C12B 0.135 (5) 0.097 (4) 0.120 (4) −0.003 (3) −0.035 (4) 0.050 (3)

Geometric parameters (Å, º)

(7)

supporting information

sup-5

Acta Cryst. (2005). E61, o2352–o2353

C7A—C8A 1.386 (8) C7B—C8B 1.388 (6) C7A—H7A 0.9300 C7B—H7B 0.9300 C9A—C10A 1.324 (8) C9B—C10B 1.334 (7) C9A—H9AA 0.9700 C9B—H9BA 0.9700 C9A—H9AB 0.9700 C9B—H9BB 0.9700 C10A—H10A 0.9600 C10B—H10D 0.9600 C10A—H10B 0.9600 C10B—H10E 0.9600 C10A—H10C 0.9600 C10B—H10F 0.9600 C11A—C12A 1.305 (8) C11B—C12B 1.437 (6) C11A—H11A 0.9700 C11B—H11C 0.9700 C11A—H11B 0.9700 C11B—H11D 0.9700 C12A—H12A 0.9600 C12B—H12D 0.9600 C12A—H12B 0.9600 C12B—H12E 0.9600 C12A—H12C 0.9600 C12B—H12F 0.9600

(8)

C3A—C8A—C1A 109.1 (4) C3B—C8B—C1B 109.3 (3) C7A—C8A—C1A 132.1 (7) C7B—C8B—C1B 130.3 (4) C10A—C9A—O4A 112.5 (6) C10B—C9B—O4B 114.0 (5) C10A—C9A—H9AA 109.1 C10B—C9B—H9BA 108.8 O4A—C9A—H9AA 109.1 O4B—C9B—H9BA 108.8 C10A—C9A—H9AB 109.1 C10B—C9B—H9BB 108.8 O4A—C9A—H9AB 109.1 O4B—C9B—H9BB 108.8 H9AA—C9A—H9AB 107.8 H9BA—C9B—H9BB 107.7 C9A—C10A—H10A 109.5 C9B—C10B—H10D 109.5 C9A—C10A—H10B 109.5 C9B—C10B—H10E 109.5 H10A—C10A—H10B 109.5 H10D—C10B—H10E 109.5 C9A—C10A—H10C 109.5 C9B—C10B—H10F 109.5 H10A—C10A—H10C 109.5 H10D—C10B—H10F 109.5 H10B—C10A—H10C 109.5 H10E—C10B—H10F 109.5 C12A—C11A—O3A 119.4 (6) O3B—C11B—C12B 110.8 (4) C12A—C11A—H11A 107.5 O3B—C11B—H11C 109.5 O3A—C11A—H11A 107.5 C12B—C11B—H11C 109.5 C12A—C11A—H11B 107.5 O3B—C11B—H11D 109.5 O3A—C11A—H11B 107.5 C12B—C11B—H11D 109.5 H11A—C11A—H11B 107.0 H11C—C11B—H11D 108.1 C11A—C12A—H12A 109.5 C11B—C12B—H12D 109.5 C11A—C12A—H12B 109.5 C11B—C12B—H12E 109.5 H12A—C12A—H12B 109.5 H12D—C12B—H12E 109.5 C11A—C12A—H12C 109.5 C11B—C12B—H12F 109.5 H12A—C12A—H12C 109.5 H12D—C12B—H12F 109.5 H12B—C12A—H12C 109.5 H12E—C12B—H12F 109.5

(9)

supporting information

sup-7

Acta Cryst. (2005). E61, o2352–o2353

N1A—C2A—C3A—C8A −2.9 (5) N1B—C2B—C3B—C8B 3.0 (4) O2A—C2A—C3A—C4A −3.9 (8) O2B—C2B—C3B—C4B 4.6 (7) N1A—C2A—C3A—C4A 177.2 (4) N1B—C2B—C3B—C4B −177.3 (4) C8A—C3A—C4A—C5A −0.4 (7) C8B—C3B—C4B—C5B −0.6 (6) C2A—C3A—C4A—C5A 179.5 (5) C2B—C3B—C4B—C5B 179.8 (4) C3A—C4A—C5A—C6A 0.8 (11) C3B—C4B—C5B—C6B 1.3 (7) C4A—C5A—C6A—C7A −0.5 (13) C4B—C5B—C6B—C7B −1.2 (7) C5A—C6A—C7A—C8A −0.2 (11) C5B—C6B—C7B—C8B 0.3 (7) C4A—C3A—C8A—C7A −0.3 (7) C4B—C3B—C8B—C7B −0.3 (6) C2A—C3A—C8A—C7A 179.8 (4) C2B—C3B—C8B—C7B 179.4 (4) C4A—C3A—C8A—C1A −179.8 (4) C4B—C3B—C8B—C1B 179.8 (3) C2A—C3A—C8A—C1A 0.3 (5) C2B—C3B—C8B—C1B −0.5 (4) C6A—C7A—C8A—C3A 0.6 (8) C6B—C7B—C8B—C3B 0.4 (6) C6A—C7A—C8A—C1A 179.9 (5) C6B—C7B—C8B—C1B −179.7 (4) O1A—C1A—C8A—C3A −176.5 (5) O1B—C1B—C8B—C3B 177.4 (4) N1A—C1A—C8A—C3A 2.4 (5) N1B—C1B—C8B—C3B −2.2 (4) O1A—C1A—C8A—C7A 4.1 (9) O1B—C1B—C8B—C7B −2.5 (7) N1A—C1A—C8A—C7A −177.0 (5) N1B—C1B—C8B—C7B 177.9 (4) P1A—O4A—C9A—C10A −146.7 (7) P1B—O4B—C9B—C10B 130.4 (6) P1A—O3A—C11A—C12A 161.0 (7) P1B—O3B—C11B—C12B −169.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C4B—H4B···O2Bi 0.93 2.48 3.408 (6) 176

Figure

Fig. 1, the thiophosphate groups point in opposite directions,
Figure 1O3aO4—P1a—N1aa—P1a—N1a

References

Related documents

In this study, we identified 9 protein markers for predicting time to recurrence using the protein expression data on 222 TCGA pri- marily high-grade serous ovarian cancers

For the purpose of analyzing the impurities in the water samples coming from different roofs, four building within the KCAET campus viz location 1(library -

To overcome the problems and weakness, this project need to do some research and studying to develop better technology. There are list of the objectives to be conduct

The above block diagram shows the SPV fed to Dc/Dc Converter for different dc applications, To analysis the performance of dc-dc converters(Buck, Boost,

22 subjects showing low or undetectable activities of BAT were randomly divided into 2 groups: one was exposed to cold at 17°C for 2 hours every day for 6 weeks (cold group; n

Foxo deletion on osteoblast differentiation in both bone marrow and calvaria cells suggests that the increases in ALP activity and mineralization observed in the bone

Histologically, the lesion is composed of fibrous connective tissue trabeculae (top quarter of image) and adipose connective tissue (bottom three quarters of image); within

• Data shows credit using and rationing of risk averts, risk neutrals and risk lovers respectively. As to risk averts, the credit is mainly used to pay children’s tuition, medical