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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o707.
Published online 2010 February 27. doi:  10.1107/S160053681000663X
PMCID: PMC2983541

Ethyl N-[3-(N,N-dimethyl­carbamo­yl)pyridin-2-ylsulfon­yl]carbamate

Abstract

In the mol­ecular structure of the title compound, C11H15N3O5S, the amide group is nearly perpendicular to the pyridine ring, making a dihedral angle of 86.30 (13)°. The terminal ethyl group is disordered over two sites of equal occupancy. Inter­molecular N—H(...)O hydrogen bonding is present in the crystal structure.

Related literature

The title compound is used in the preparation of nicosulfuron, a member of the sulfonyl­urea family of herbicides, see: Green & Ulrich (1993 [triangle]). For the synthesis, see: Murai et al. (1992 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o707-scheme1.jpg

Experimental

Crystal data

  • C11H15N3O5S
  • M r = 301.32
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o707-efi1.jpg
  • a = 8.4370 (11) Å
  • b = 11.1141 (15) Å
  • c = 15.074 (2) Å
  • β = 100.594 (2)°
  • V = 1389.4 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.26 mm−1
  • T = 296 K
  • 0.17 × 0.16 × 0.15 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.958, T max = 0.963
  • 7979 measured reflections
  • 3036 independent reflections
  • 2384 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.129
  • S = 1.04
  • 3036 reflections
  • 195 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.47 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681000663X/xu2723sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681000663X/xu2723Isup2.hkl

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

Acknowledgments

We thank the National Natural Science Foundation of China (No. 20872030) and Heilongjiang University of China for supporting this study.

supplementary crystallographic information

Comment

The ethyl 3-(dimethylcarbamoyl)pyridin-2-ylsulfonylcarbamate is used for preparation of nicosulfuron, which is a member of the sulfonylurea family of herbicides (Green et al., 1993).

The molecular structure is shown in Fig. 1. In the molecular structure the amide group is nearly perpendicular to the pyridine ring, the dihedral angle being 86.30 (13)°. Intermolecular N—H···O hydrogen bonding (Table 1) helps to stabilize the crystal structure.

Experimental

To a solution of N,N-dimethyl-2-sulfamoylnicotinamide (10 mmol) and NaOH (12 mmol) in anhydrous toluene (50 ml) was added ethyl carbonochloridate (12 mmol). After stirring the mixture for 10 h at room temperature, the solvent was removed and 100 ml water was added. The oil after separation was concentrated under reduced pressure and the residue was recrystallized from methanol to give the title compound in a yield of 90% (Murai et al. 1992). Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallization from ethanol at room temperature in a yield of 60%. Analysis found: C 43.9, H 4.9, N 13.9%; C11H15N3O5S requires: C 43.9, H 5.0, N 14.0%.

Refinement

The ethyl group is disordered over two positions with 0.5 occupancy for each component. In the refinement. Imino H atom was located in a difference Fourier map and was refined isotropically. Other H atoms were placed in idealized positions with C—H = 0.96 (methyl), 0.97 (methylene) and 0.93 Å (aromatic), and refined in the riding-model approximation with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the others.

Figures

Fig. 1.
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. The disorder is shown.
Fig. 2.
A part of packing of the crystal structure of the title compound, viewed down the a direction. Dashed lines indicate hydrogen bonds.

Crystal data

C11H15N3O5SF(000) = 632
Mr = 301.32Dx = 1.441 Mg m3
Monoclinic, P21/nMelting point = 436–437 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 8.4370 (11) ÅCell parameters from 2785 reflections
b = 11.1141 (15) Åθ = 2.3–26.9°
c = 15.074 (2) ŵ = 0.26 mm1
β = 100.594 (2)°T = 296 K
V = 1389.4 (3) Å3Prism, colorless
Z = 40.17 × 0.16 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer3036 independent reflections
Radiation source: fine-focus sealed tube2384 reflections with I > 2σ(I)
graphiteRint = 0.026
[var phi] and ω scansθmax = 27.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.958, Tmax = 0.963k = −13→14
7979 measured reflectionsl = −19→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0732P)2 + 0.3548P] where P = (Fo2 + 2Fc2)/3
3036 reflections(Δ/σ)max = 0.001
195 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = −0.47 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/UeqOcc. (<1)
S10.81078 (6)0.56615 (4)0.24067 (3)0.03700 (17)
O11.05540 (17)0.28321 (14)0.28830 (10)0.0475 (4)
O20.97802 (19)0.58254 (14)0.27370 (11)0.0526 (4)
O30.7045 (2)0.54186 (15)0.30175 (11)0.0554 (4)
O40.90004 (19)0.68423 (15)0.08036 (11)0.0539 (4)
O50.6813 (2)0.80460 (14)0.06652 (12)0.0552 (4)
N10.6502 (2)0.45464 (16)0.10014 (12)0.0432 (4)
N21.19984 (19)0.39369 (16)0.20603 (12)0.0407 (4)
N30.7342 (2)0.68519 (15)0.18467 (12)0.0379 (4)
H30.641 (3)0.709 (2)0.1945 (16)0.045 (6)*
C10.6257 (3)0.37404 (19)0.03341 (15)0.0480 (5)
H1A0.52890.3764−0.00760.058*
C20.7368 (3)0.28809 (19)0.02256 (15)0.0490 (5)
H2A0.71620.2340−0.02530.059*
C30.8789 (3)0.28309 (19)0.08340 (15)0.0434 (5)
H3A0.95430.22390.07780.052*
C40.9110 (2)0.36615 (16)0.15349 (12)0.0315 (4)
C50.7912 (2)0.45025 (16)0.15719 (12)0.0313 (4)
C61.0625 (2)0.34801 (17)0.22302 (13)0.0341 (4)
C71.2086 (3)0.4806 (2)0.13467 (18)0.0538 (6)
H7A1.10290.49290.09950.081*
H7B1.27900.45050.09650.081*
H7C1.24980.55550.16100.081*
C81.3496 (3)0.3661 (3)0.26777 (18)0.0624 (7)
H8A1.32930.30650.31050.094*
H8B1.39070.43780.29930.094*
H8C1.42730.33570.23420.094*
C90.7842 (2)0.72299 (17)0.10698 (14)0.0381 (4)
C10A0.698 (2)0.8377 (11)−0.0234 (15)0.068 (3)0.50
H10A0.59430.8591−0.05910.082*0.50
H10B0.74280.7715−0.05280.082*0.50
C11A0.8134 (12)0.9468 (6)−0.0135 (5)0.0974 (19)0.50
H11A0.81500.9806−0.07200.146*0.50
H11B0.92010.92120.01330.146*0.50
H11C0.77681.00630.02420.146*0.50
C10B0.734 (2)0.8705 (11)−0.0110 (16)0.068 (3)0.50
H10C0.84570.89530.00460.082*0.50
H10D0.72030.8205−0.06460.082*0.50
C11B0.6287 (12)0.9729 (6)−0.0249 (5)0.0974 (19)0.50
H11D0.66251.0259−0.06820.146*0.50
H11E0.63301.01470.03120.146*0.50
H11F0.52030.9466−0.04710.146*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0368 (3)0.0411 (3)0.0317 (3)0.0050 (2)0.00264 (19)−0.00259 (19)
O10.0327 (8)0.0603 (9)0.0480 (9)−0.0012 (7)0.0035 (6)0.0214 (7)
O20.0417 (9)0.0563 (9)0.0520 (10)0.0039 (7)−0.0116 (7)−0.0142 (7)
O30.0664 (11)0.0635 (10)0.0407 (9)0.0091 (8)0.0214 (8)0.0056 (7)
O40.0500 (10)0.0582 (10)0.0589 (10)0.0103 (8)0.0243 (8)0.0051 (8)
O50.0601 (11)0.0493 (9)0.0592 (10)0.0162 (8)0.0191 (8)0.0155 (8)
N10.0331 (9)0.0446 (10)0.0461 (10)0.0040 (7)−0.0076 (7)−0.0011 (8)
N20.0248 (8)0.0466 (9)0.0516 (10)0.0009 (7)0.0094 (7)0.0087 (8)
N30.0364 (9)0.0384 (9)0.0401 (9)0.0081 (7)0.0098 (7)−0.0021 (7)
C10.0455 (12)0.0434 (12)0.0472 (12)−0.0058 (10)−0.0125 (10)−0.0005 (10)
C20.0632 (15)0.0402 (11)0.0406 (12)−0.0055 (10)0.0010 (10)−0.0050 (9)
C30.0483 (12)0.0385 (10)0.0444 (11)0.0060 (9)0.0115 (10)−0.0015 (9)
C40.0283 (9)0.0337 (9)0.0334 (9)0.0000 (7)0.0079 (7)0.0058 (7)
C50.0280 (9)0.0332 (9)0.0316 (9)−0.0002 (7)0.0025 (7)0.0013 (7)
C60.0274 (9)0.0363 (9)0.0390 (10)0.0040 (7)0.0071 (8)0.0045 (8)
C70.0412 (13)0.0582 (14)0.0667 (16)−0.0022 (10)0.0219 (11)0.0172 (12)
C80.0280 (11)0.0805 (18)0.0759 (17)0.0020 (11)0.0024 (11)0.0118 (14)
C90.0383 (11)0.0310 (9)0.0453 (11)−0.0002 (8)0.0087 (9)−0.0025 (8)
C10A0.083 (7)0.044 (6)0.083 (6)0.002 (4)0.030 (5)0.026 (6)
C11A0.170 (6)0.059 (2)0.069 (3)0.005 (3)0.036 (4)0.007 (2)
C10B0.083 (7)0.044 (6)0.083 (6)0.002 (4)0.030 (5)0.026 (6)
C11B0.170 (6)0.059 (2)0.069 (3)0.005 (3)0.036 (4)0.007 (2)

Geometric parameters (Å, °)

S1—O21.4191 (16)C3—H3A0.9300
S1—O31.4241 (16)C4—C51.385 (3)
S1—N31.6369 (18)C4—C61.510 (3)
S1—C51.7871 (19)C7—H7A0.9600
O1—C61.230 (2)C7—H7B0.9600
O4—C91.202 (2)C7—H7C0.9600
O5—C91.324 (2)C8—H8A0.9600
O5—C10A1.44 (2)C8—H8B0.9600
O5—C10B1.51 (2)C8—H8C0.9600
N1—C11.334 (3)C10A—C11A1.544 (11)
N1—C51.335 (2)C10A—H10A0.9700
N2—C61.332 (2)C10A—H10B0.9700
N2—C71.458 (3)C11A—H11A0.9600
N2—C81.457 (3)C11A—H11B0.9600
N3—C91.381 (3)C11A—H11C0.9600
N3—H30.87 (2)C10B—C11B1.434 (19)
C1—C21.369 (3)C10B—H10C0.9700
C1—H1A0.9300C10B—H10D0.9700
C2—C31.370 (3)C11B—H11D0.9600
C2—H2A0.9300C11B—H11E0.9600
C3—C41.392 (3)C11B—H11F0.9600
O2—S1—O3120.07 (11)N2—C7—H7A109.5
O2—S1—N3110.48 (10)N2—C7—H7B109.5
O3—S1—N3104.54 (9)H7A—C7—H7B109.5
O2—S1—C5107.25 (9)N2—C7—H7C109.5
O3—S1—C5109.34 (10)H7A—C7—H7C109.5
N3—S1—C5104.06 (9)H7B—C7—H7C109.5
C9—O5—C10A116.1 (8)N2—C8—H8A109.5
C9—O5—C10B115.3 (7)N2—C8—H8B109.5
C10A—O5—C10B18.8 (10)H8A—C8—H8B109.5
C1—N1—C5117.19 (18)N2—C8—H8C109.5
C6—N2—C7123.95 (18)H8A—C8—H8C109.5
C6—N2—C8118.64 (18)H8B—C8—H8C109.5
C7—N2—C8117.07 (18)O4—C9—O5126.6 (2)
C9—N3—S1122.01 (14)O4—C9—N3124.59 (19)
C9—N3—H3118.8 (16)O5—C9—N3108.80 (17)
S1—N3—H3116.1 (16)O5—C10A—C11A106.2 (12)
N1—C1—C2123.0 (2)O5—C10A—H10A110.5
N1—C1—H1A118.5C11A—C10A—H10A110.5
C2—C1—H1A118.5O5—C10A—H10B110.5
C1—C2—C3118.8 (2)C11A—C10A—H10B110.5
C1—C2—H2A120.6H10A—C10A—H10B108.7
C3—C2—H2A120.6C11B—C10B—O5103.6 (13)
C2—C3—C4120.37 (19)C11B—C10B—H10C111.0
C2—C3—H3A119.8O5—C10B—H10C111.0
C4—C3—H3A119.8C11B—C10B—H10D111.0
C5—C4—C3115.90 (18)O5—C10B—H10D111.0
C5—C4—C6126.36 (17)H10C—C10B—H10D109.0
C3—C4—C6117.39 (17)C10B—C11B—H11D109.5
N1—C5—C4124.70 (17)C10B—C11B—H11E109.5
N1—C5—S1112.53 (14)H11D—C11B—H11E109.5
C4—C5—S1122.77 (14)C10B—C11B—H11F109.5
O1—C6—N2123.32 (18)H11D—C11B—H11F109.5
O1—C6—C4118.27 (16)H11E—C11B—H11F109.5
N2—C6—C4118.10 (17)
O2—S1—N3—C962.57 (18)N3—S1—C5—C4138.92 (16)
O3—S1—N3—C9−166.94 (17)C7—N2—C6—O1−173.2 (2)
C5—S1—N3—C9−52.26 (18)C8—N2—C6—O1−0.1 (3)
C5—N1—C1—C20.9 (3)C7—N2—C6—C413.3 (3)
N1—C1—C2—C30.9 (4)C8—N2—C6—C4−173.57 (19)
C1—C2—C3—C4−1.7 (3)C5—C4—C6—O185.0 (3)
C2—C3—C4—C50.7 (3)C3—C4—C6—O1−87.8 (2)
C2—C3—C4—C6174.29 (19)C5—C4—C6—N2−101.2 (2)
C1—N1—C5—C4−2.0 (3)C3—C4—C6—N286.0 (2)
C1—N1—C5—S1177.97 (16)C10A—O5—C9—O48.8 (6)
C3—C4—C5—N11.2 (3)C10B—O5—C9—O4−12.0 (7)
C6—C4—C5—N1−171.70 (18)C10A—O5—C9—N3−169.1 (6)
C3—C4—C5—S1−178.77 (14)C10B—O5—C9—N3170.0 (7)
C6—C4—C5—S18.3 (3)S1—N3—C9—O4−10.6 (3)
O2—S1—C5—N1−158.18 (15)S1—N3—C9—O5167.38 (14)
O3—S1—C5—N170.14 (16)C9—O5—C10A—C11A−91.5 (10)
N3—S1—C5—N1−41.09 (16)C10B—O5—C10A—C11A1(4)
O2—S1—C5—C421.83 (18)C9—O5—C10B—C11B−164.2 (7)
O3—S1—C5—C4−109.86 (17)C10A—O5—C10B—C11B99 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3···O1i0.87 (2)1.91 (3)2.773 (2)172 (2)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2723).

References

  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Green, J. M. & Ulrich, J. F. (1993). Weed Sci. 41, 508-516.
  • Murai, S., Nakamura, Y., Akagi, T., Sakashita, T. & Haga, T. (1992). Synthesis and Chemistry of Agrochemicals III, ACS Symposium Series, Vol. 504, edited by D. R., Baker, J. G. Fenyes & J. J. Steffens, pp. 43–55. Washington: American Chemical Society.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). publCIF In preparation.

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