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ISSN: 2056-9890

O,O-Di­methyl O-(4-sulfamoylphen­yl) phospho­ro­thio­ate (cythio­ate)

aDepartment of Chemistry, Truman State University, Kirksville, MO 63501-4221, USA
*Correspondence e-mail: baughman@truman.edu

(Received 30 April 2013; accepted 28 May 2013; online 8 June 2013)

The title mol­ecule, C8H12NO5PS2, exhibits a crystallographic mirror plane that is perpendicular to the ring and bis­ects the sulfamoyl and thio­phosphate ester groups. In the crystal, mol­ecules are linked by N—H⋯O hydrogen-bonding inter­actions reminiscent of carb­oxy­lic acid hydrogen bonding pairs, forming chains parallel to the b-axis direction.

Related literature

The structure of a very similar compound {Famphur; systematic name O,O-dimethyl O-[p-[(N,N-dimethylsulfamoyl)phenyl] phosphorothioate} was published by Baughman (1997[Baughman, R. G. (1997). Acta Cryst. C53, 1928-1929.]).

[Scheme 1]

Experimental

Crystal data
  • C8H12NO5PS2

  • Mr = 297.28

  • Monoclinic, P 21 /m

  • a = 6.6634 (2) Å

  • b = 8.5514 (3) Å

  • c = 11.8716 (5) Å

  • β = 105.067 (3)°

  • V = 653.21 (4) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.54 mm−1

  • T = 295 K

  • 0.50 × 0.38 × 0.26 mm

Data collection
  • Bruker P4 diffractometer

  • Absorption correction: integration (XSHELL; Bruker, 1999[Bruker (1999). XSHELL. Bruker AXS, Inc., Madison, Wisconsin, USA.]) Tmin = 0.745, Tmax = 0.890

  • 2229 measured reflections

  • 1591 independent reflections

  • 1421 reflections with I > 2σ(I)

  • Rint = 0.031

  • 3 standard reflections every 100 reflections intensity decay: 1.2%

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.112

  • S = 1.21

  • 1591 reflections

  • 89 parameters

  • 5 restraints

  • H-atom parameters constrained

  • Δρmax = 0.38 e Å−3

  • Δρmin = −0.30 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O3i 0.86 2.36 3.134 (3) 150
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: XSCANS (Bruker, 1996[Bruker (1996). XSCANS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL/PC (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL/PC and SHELXL97.

Supporting information


Comment top

Cythioate (Fig. 1) is an organophosphorous insecticide and anthelmintic that has also been sold as Cyflea or Proban. It can be taken orally by pets against fleas, and functions as an acetylcholinesterase inhibitor which interferes with neuromuscular transmission in ectoparastites.

Existence of intermolecular carboxylic acid-like hydrogen bonding is observed between inversion-related H1 and O3 pairs (Fig. 2, Table 1) resulting in the formation of chains parallel to the b axis. This hydrogen bonding may also contribute to the observed pyramidal shape on the nitrogen.

Though Cythioate has a structure similar to that of Famphur (O,O-dimethyl O-[p-[(N,N-dimethylsulfamoyl)phenyl] phosphorothioate; Baughman, 1997), the differences cannot be ignored as they may be the cause of differences in toxicity/activity. The Cythioate molecule exhibits a mirror plane that is perpendicular to the ring and bisects the sulfamoyl and thiophosphate groups. The presence of this mirror and the absence of one in Famphur result from most of the differences in overall molecular shape as well as specific differences.

Between Cythioate and Famphur a 70 σ difference in the O2—P—S1 bond angles, a 60 σ difference in the O2—P—O2a angles, and a 65 σ difference in O1—P—S1 bond angles are observed. This may be due to the distortion of the phosphorothioate group caused by the hydrogen bonding in Famphur. Interestingly, the P1—O1, P1—O2, and P1—S1 bond lengths are within 3 σ of each other.

Related literature top

The structure of a very similar compound (Famphur) was published by Baughman (1997).

Experimental top

Crystals were grown by slow evaporation of a solution in EtOH.

Refinement top

Approximate positions of the six symmetry-independent H's were first obtained from a difference map, then placed into "ideal" positions and refined as a rotational group. Bond lengths were constrained at 0.93 Å (AFIX 43) for aryl C—H's at 0.96 Å (AFIX 137) for methyl C—H's; and at 0.86 Å (DFIX s: N1—H1 = 0.86 Å; H1···H1A = 1.404 Å ; S2···H1 = 2.092 Å to insure that H1–N1–H1A = 109.5°) for N—H's. Uiso(H) were fixed at 1.5Ueq(parent) for NH and methyl H's, and 1.2 Ueq(parent) for all other H's.

In the final stages of refinement, two reflections with very small or negative Fo's were deemed to be in high disagreement with their Fc's and were eliminated from final refinement.

Computing details top

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS (Bruker, 1996); data reduction: XSCANS (Bruker, 1996); program(s) used to solve structure: SHELXS86 (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 top
[Figure 1] Fig. 1. One molecule (2 asymmetric units) of the title compound showing the labeling of all atoms. For clarity methyl and aryl H's have been omitted. Displacement ellipsoids are drawn at the 50% probability level; H's are drawn as small spheres of arbitrary radius. Atoms labeled with the suffix a are generated by the symmetry operation (x, 1/2-y, z).
[Figure 2] Fig. 2. Four molecules (8 asymmetric units) illustrating packing in the b direction. Spheres of arbitrary size are shown. The upper right molecule contains the original asymmetric unit (x,y,z); lower right = (1+x, y, z); upper left = (1-x, -y, 1-z); lower left = (1-x, + y, 1-z). Hydrogen atoms not involved in hydrogen bonding are omitted.
O,O-Dimethyl O-(4-sulfamoylphenyl) phosphorothioate top
Crystal data top
C8H12NO5PS2F(000) = 308
Mr = 297.28Dx = 1.511 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 100 reflections
a = 6.6634 (2) Åθ = 11.3–20.7°
b = 8.5514 (3) ŵ = 0.54 mm1
c = 11.8716 (5) ÅT = 295 K
β = 105.067 (3)°Parallelepiped, colorless
V = 653.21 (4) Å30.50 × 0.38 × 0.26 mm
Z = 2
Data collection top
Bruker P4
diffractometer
1421 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.031
Graphite monochromatorθmax = 27.5°, θmin = 1.8°
θ/2θ scansh = 18
Absorption correction: integration
(XSHELL; Bruker, 1999)
k = 111
Tmin = 0.745, Tmax = 0.890l = 1515
2229 measured reflections3 standard reflections every 100 reflections
1591 independent reflections intensity decay: 1.2%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.112 w = 1/[σ2(Fo2) + (0.0241P)2 + 0.6341P]
where P = (Fo2 + 2Fc2)/3
S = 1.21(Δ/σ)max < 0.001
1591 reflectionsΔρmax = 0.38 e Å3
89 parametersΔρmin = 0.30 e Å3
5 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.024 (3)
Crystal data top
C8H12NO5PS2V = 653.21 (4) Å3
Mr = 297.28Z = 2
Monoclinic, P21/mMo Kα radiation
a = 6.6634 (2) ŵ = 0.54 mm1
b = 8.5514 (3) ÅT = 295 K
c = 11.8716 (5) Å0.50 × 0.38 × 0.26 mm
β = 105.067 (3)°
Data collection top
Bruker P4
diffractometer
1421 reflections with I > 2σ(I)
Absorption correction: integration
(XSHELL; Bruker, 1999)
Rint = 0.031
Tmin = 0.745, Tmax = 0.8903 standard reflections every 100 reflections
2229 measured reflections intensity decay: 1.2%
1591 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0415 restraints
wR(F2) = 0.112H-atom parameters constrained
S = 1.21Δρmax = 0.38 e Å3
1591 reflectionsΔρmin = 0.30 e Å3
89 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
S10.23323 (18)0.25001.05126 (9)0.0538 (3)
S20.35491 (5)0.25000.47670 (7)0.0436 (3)
P10.21467 (14)0.25000.89334 (8)0.0369 (3)
O10.0232 (4)0.25000.8914 (2)0.0492 (7)
O20.3172 (3)0.1128 (2)0.81215 (17)0.0516 (5)
O30.3035 (3)0.1053 (3)0.41556 (17)0.0604 (6)
N10.60337 (16)0.25000.5300 (2)0.0517 (8)
H10.64580.16790.57110.078*
C10.0859 (5)0.25000.7865 (3)0.0394 (8)
C20.1203 (5)0.1098 (4)0.7397 (3)0.0521 (7)
H20.09290.01630.77270.063*
C30.1974 (4)0.1100 (4)0.6413 (3)0.0498 (7)
H30.22220.01600.60780.060*
C40.2367 (5)0.25000.5937 (3)0.0376 (7)
C50.3293 (6)0.0430 (4)0.8543 (3)0.0646 (9)
H5A0.39810.10950.79080.097*
H5B0.19160.08170.88810.097*
H5C0.40610.04230.91250.097*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0682 (7)0.0611 (7)0.0411 (5)0.0000.0304 (5)0.000
S20.0563 (6)0.0460 (5)0.0327 (4)0.0000.0191 (4)0.000
P10.0415 (5)0.0381 (5)0.0349 (4)0.0000.0167 (4)0.000
O10.0391 (13)0.077 (2)0.0339 (13)0.0000.0138 (10)0.000
O20.0653 (12)0.0450 (11)0.0449 (10)0.0096 (9)0.0150 (9)0.0015 (9)
O30.0803 (14)0.0615 (14)0.0433 (10)0.0078 (12)0.0233 (10)0.0151 (10)
N10.056 (2)0.055 (2)0.0513 (19)0.0000.0257 (16)0.000
C10.0340 (17)0.053 (2)0.0332 (16)0.0000.0125 (13)0.000
C20.0647 (17)0.0463 (16)0.0550 (16)0.0077 (14)0.0330 (14)0.0131 (13)
C30.0656 (17)0.0399 (15)0.0527 (15)0.0062 (13)0.0313 (13)0.0026 (12)
C40.0394 (17)0.0416 (19)0.0329 (16)0.0000.0118 (13)0.000
C50.091 (2)0.0439 (17)0.0617 (19)0.0109 (17)0.0243 (17)0.0017 (15)
Geometric parameters (Å, º) top
S1—P11.9107 (13)C1—C21.366 (3)
S2—O3i1.431 (2)C1—C2i1.366 (3)
S2—O31.431 (2)C2—C31.393 (4)
S2—N11.6114 (6)C2—H20.9300
S2—C41.766 (3)C3—C41.377 (3)
P1—O2i1.559 (2)C3—H30.9300
P1—O21.559 (2)C4—C3i1.377 (3)
P1—O11.591 (3)C5—H5A0.9604
O1—C11.413 (4)C5—H5B0.9599
O2—C51.433 (4)C5—H5C0.9606
N1—H10.8600
O3i—S2—O3119.80 (19)C2i—C1—O1118.57 (16)
O3i—S2—N1106.56 (11)C1—C2—C3118.5 (3)
O3—S2—N1106.56 (11)C1—C2—H2120.7
O3i—S2—C4107.59 (10)C3—C2—H2120.7
O3—S2—C4107.59 (10)C4—C3—C2119.7 (3)
N1—S2—C4108.30 (16)C4—C3—H3120.1
O2i—P1—O297.65 (16)C2—C3—H3120.1
O2i—P1—O1105.61 (10)C3—C4—C3i120.7 (3)
O2—P1—O1105.61 (10)C3—C4—S2119.57 (16)
O2i—P1—S1118.48 (8)C3i—C4—S2119.57 (16)
O2—P1—S1118.48 (8)O2—C5—H5A109.5
O1—P1—S1109.46 (11)O2—C5—H5B109.4
C1—O1—P1122.5 (2)H5A—C5—H5B109.5
C5—O2—P1122.63 (19)O2—C5—H5C109.5
S2—N1—H1112.0H5A—C5—H5C109.5
C2—C1—C2i122.8 (3)H5B—C5—H5C109.4
C2—C1—O1118.57 (16)
O2i—P1—O1—C151.40 (8)C1—C2—C3—C40.1 (5)
O2—P1—O1—C151.40 (8)C2—C3—C4—C3i1.1 (6)
S1—P1—O1—C1180.000 (1)C2—C3—C4—S2174.7 (2)
O2i—P1—O2—C5160.9 (2)O3i—S2—C4—C3157.3 (3)
O1—P1—O2—C590.5 (3)O3—S2—C4—C326.9 (3)
S1—P1—O2—C532.6 (3)N1—S2—C4—C387.9 (3)
P1—O1—C1—C291.7 (3)O3i—S2—C4—C3i26.9 (3)
P1—O1—C1—C2i91.7 (3)O3—S2—C4—C3i157.3 (3)
C2i—C1—C2—C31.2 (6)N1—S2—C4—C3i87.9 (3)
O1—C1—C2—C3175.2 (3)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3ii0.862.363.134 (3)150
Symmetry code: (ii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC8H12NO5PS2
Mr297.28
Crystal system, space groupMonoclinic, P21/m
Temperature (K)295
a, b, c (Å)6.6634 (2), 8.5514 (3), 11.8716 (5)
β (°) 105.067 (3)
V3)653.21 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.54
Crystal size (mm)0.50 × 0.38 × 0.26
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionIntegration
(XSHELL; Bruker, 1999)
Tmin, Tmax0.745, 0.890
No. of measured, independent and
observed [I > 2σ(I)] reflections
2229, 1591, 1421
Rint0.031
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.112, 1.21
No. of reflections1591
No. of parameters89
No. of restraints5
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.30

Computer programs: XSCANS (Bruker, 1996), SHELXS86 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008) and SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.862.363.134 (3)150
Symmetry code: (i) x+1, y, z+1.
 

References

First citationBaughman, R. G. (1997). Acta Cryst. C53, 1928–1929.  Web of Science CSD CrossRef CAS IUCr Journals
First citationBruker (1996). XSCANS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationBruker (1999). XSHELL. Bruker AXS, Inc., Madison, Wisconsin, USA.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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ISSN: 2056-9890
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