organic papers
o2352
Baughman and Paulos C12H14NO4PS 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
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]supporting information
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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 Kα 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
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
supporting information
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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
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)
supporting information
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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
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
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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