supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

cf2185 scheme

Acta Cryst. (2008). E64, o632    [ doi:10.1107/S1600536808005011 ]

Methyl 2-{[3-(4,6-dimethoxypyrimidin-2-yl)ureido]sulfonylmethyl}benzoate

J. Xia, F. Li, L. Yin, D. Yu and D. Wu

Abstract top

In the title compound, C16H18N4O7S, a synthetic sulfonylurea herbicide, there are intramolecular N-H...N and C-H...O hydrogen bonds. Intermolecular N-H...O and C-H...O hydrogen bonds form centrosymmetric dimers. The dihedral angle between the two rings is 50.00 (15)°.

Comment top

The title compound, bensulfuron-methyl, belongs to the class of systemic sulfonylurea herbicides inhibiting acetolactate synthase, a key enzyme in the biosynthesis of the branched-chain amino acids of target plants (Lee et al., 2002). It is widely used in transplanted and direct-seeded rice fields to control most annual and perennial broadleaved weeds selectively (Sabadie, 1996).

We report here the crystal structure of the title compound, (I). The molecular structure of (I) is shown in Fig. 1. The dihedral angle between the C3–C8 and C11/N3/C12/C13/C14/N4 rings is 50.00 (15)°. There are intramolecular N1—H1A···N3 and C9—H9B···O1 hydrogen bonds (Fig. 1), and intermolecular N—H···O and C—H···O hydrogen bonds form centrosymmetric dimers (Fig. 2).

Related literature top

For related literature, see: Kong et al. (1990); Lee et al. (2002); Sabadie (1996).

Experimental top

The title compound, (I), was prepared according to the literature method (Kong et al., 1990).

Crystals suitable for X-ray analysis were obtained by dissolving (I) (0.2 g) in ethyl acetate (25 ml) and evaporating the solvent slowly at room temperature for about 15 d.

Refinement top

All H atoms were positioned geometrically with C—H = 0.93–0.97 Å and N—H = 0.86 Å, and were and included in the refinement in a riding model approximation, with Uiso(H) = 1.2 or 1.5Ueq(N,C).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate intramolecular hydrogen bonds.
[Figure 2] Fig. 2. A hydrogen-bonded dimer. Dashed lines indicate hydrogen bonds.
Methyl 2-{[3-(4,6-dimethoxypyrimidin-2-yl)ureido]sulfonylmethyl}benzoate top
Crystal data top
C16H18N4O7SF000 = 1712
Mr = 410.41Dx = 1.505 Mg m−3
Monoclinic, C2/cMelting point = 450–451 K
Hall symbol: -C 2ycMo Kα radiation
λ = 0.71073 Å
a = 33.831 (7) ÅCell parameters from 25 reflections
b = 6.9020 (14) Åθ = 10–13º
c = 16.021 (3) ŵ = 0.23 mm−1
β = 104.48 (3)ºT = 298 (2) K
V = 3622.1 (13) Å3Needle, colorless
Z = 80.40 × 0.20 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.035
Radiation source: fine-focus sealed tubeθmax = 25.2º
Monochromator: graphiteθmin = 1.2º
T = 298(2) Kh = −40→38
ω/2θ scansk = 0→8
Absorption correction: ψ scan
(North et al., 1968)		l = 0→19
Tmin = 0.914, Tmax = 0.9783 standard reflections
3325 measured reflections every 200 reflections
3265 independent reflections intensity decay: none
2421 reflections with I > 2σ(I)
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)] = 0.056H-atom parameters constrained
wR(F2) = 0.156  w = 1/[σ2(Fo2) + (0.08P)2 + 5P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3265 reflectionsΔρmax = 0.26 e Å−3
253 parametersΔρmin = −0.31 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C16H18N4O7SV = 3622.1 (13) Å3
Mr = 410.41Z = 8
Monoclinic, C2/cMo Kα
a = 33.831 (7) ŵ = 0.23 mm−1
b = 6.9020 (14) ÅT = 298 (2) K
c = 16.021 (3) Å0.40 × 0.20 × 0.10 mm
β = 104.48 (3)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		2421 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.035
Tmin = 0.914, Tmax = 0.9783 standard reflections
3325 measured reflections every 200 reflections
3265 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.056253 parameters
wR(F2) = 0.156H-atom parameters constrained
S = 1.03Δρmax = 0.26 e Å−3
3265 reflectionsΔρmin = −0.31 e Å−3
Special details top

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) top
xyzUiso*/Ueq
S0.12664 (2)0.14338 (13)0.69392 (5)0.0401 (2)
N10.07804 (7)0.1705 (4)0.64572 (16)0.0424 (7)
H1A0.07190.18360.59060.051*
O10.15578 (7)0.0798 (4)0.92720 (16)0.0557 (7)
C10.19376 (12)−0.2563 (5)0.9629 (3)0.0570 (10)
H1B0.2121−0.36460.97040.085*
H1C0.1676−0.29460.92780.085*
H1D0.1909−0.21391.01820.085*
O20.20987 (7)−0.0991 (3)0.92109 (16)0.0484 (6)
N20.00822 (7)0.1970 (4)0.63164 (16)0.0388 (6)
H2A−0.01140.18570.65650.047*
C20.18727 (9)0.0615 (5)0.90655 (19)0.0379 (7)
N30.02372 (7)0.2300 (4)0.49733 (16)0.0363 (6)
O30.13329 (8)−0.0390 (4)0.73670 (16)0.0576 (7)
C30.20669 (9)0.2172 (5)0.86550 (18)0.0356 (7)
O40.14650 (7)0.1838 (4)0.62677 (15)0.0542 (7)
N4−0.04352 (7)0.2765 (4)0.51521 (16)0.0375 (6)
C40.24906 (9)0.2405 (5)0.8922 (2)0.0432 (8)
H4C0.26470.15130.93000.052*
O50.05149 (7)0.1570 (4)0.76305 (14)0.0509 (6)
C50.26803 (10)0.3949 (5)0.8631 (2)0.0470 (8)
H5A0.29620.41010.88190.056*
O60.03580 (7)0.2645 (4)0.36258 (15)0.0531 (6)
C60.24518 (11)0.5258 (6)0.8063 (2)0.0505 (9)
H6A0.25780.63020.78700.061*
O7−0.09468 (7)0.3699 (4)0.39861 (15)0.0508 (6)
C70.20337 (10)0.5023 (5)0.7779 (2)0.0468 (8)
H7A0.18830.58960.73820.056*
C80.18338 (9)0.3511 (5)0.80731 (19)0.0363 (7)
C90.13757 (9)0.3323 (5)0.7722 (2)0.0406 (8)
H9A0.12640.45370.74600.049*
H9B0.12490.30340.81880.049*
C100.04638 (9)0.1743 (5)0.6850 (2)0.0369 (7)
C11−0.00401 (9)0.2356 (4)0.54321 (19)0.0341 (7)
C120.00998 (10)0.2704 (5)0.4133 (2)0.0388 (7)
C13−0.03018 (10)0.3179 (5)0.3764 (2)0.0438 (8)
H13A−0.03950.34690.31810.053*
C14−0.05548 (9)0.3198 (5)0.4314 (2)0.0391 (7)
C15−0.12294 (10)0.3408 (6)0.4504 (2)0.0573 (10)
H15A−0.14960.38340.41930.086*
H15B−0.11430.41380.50280.086*
H15C−0.12390.20560.46390.086*
C160.07680 (10)0.1963 (6)0.3980 (2)0.0597 (10)
H16A0.09180.20130.35450.090*
H16B0.07600.06520.41750.090*
H16C0.08990.27700.44570.090*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0287 (4)0.0485 (5)0.0398 (4)0.0025 (3)0.0022 (3)−0.0034 (4)
N10.0293 (13)0.0636 (19)0.0332 (14)−0.0023 (13)0.0057 (11)0.0033 (13)
O10.0422 (14)0.0684 (17)0.0634 (15)0.0099 (12)0.0260 (12)0.0167 (13)
C10.067 (2)0.041 (2)0.065 (2)−0.0069 (18)0.0199 (19)0.0080 (19)
O20.0434 (13)0.0434 (14)0.0610 (15)0.0055 (10)0.0178 (11)0.0100 (11)
N20.0292 (13)0.0450 (16)0.0394 (14)0.0004 (11)0.0035 (11)0.0083 (12)
C20.0350 (17)0.0447 (18)0.0313 (15)0.0025 (14)0.0032 (13)−0.0006 (14)
N30.0344 (14)0.0381 (15)0.0353 (14)−0.0032 (11)0.0069 (11)−0.0003 (11)
O30.0556 (16)0.0440 (15)0.0620 (16)0.0068 (12)−0.0061 (12)0.0009 (12)
C30.0359 (16)0.0420 (18)0.0281 (14)−0.0003 (14)0.0067 (12)−0.0035 (13)
O40.0377 (13)0.0835 (19)0.0434 (13)−0.0003 (12)0.0140 (10)−0.0076 (12)
N40.0319 (13)0.0339 (14)0.0419 (15)−0.0018 (11)0.0001 (11)0.0019 (12)
C40.0339 (16)0.055 (2)0.0373 (17)0.0008 (15)0.0018 (13)−0.0002 (16)
O50.0351 (12)0.0769 (18)0.0383 (13)0.0013 (12)0.0046 (10)0.0061 (12)
C50.0336 (17)0.062 (2)0.0423 (18)−0.0094 (16)0.0041 (14)−0.0014 (17)
O60.0460 (14)0.0707 (17)0.0428 (13)0.0023 (12)0.0117 (11)0.0010 (12)
C60.049 (2)0.057 (2)0.0463 (19)−0.0161 (17)0.0120 (16)0.0005 (17)
O70.0359 (12)0.0585 (15)0.0513 (14)0.0048 (11)−0.0016 (10)0.0134 (12)
C70.0469 (19)0.050 (2)0.0393 (17)0.0003 (16)0.0035 (15)0.0036 (16)
C80.0306 (15)0.0397 (17)0.0360 (16)−0.0009 (13)0.0035 (12)−0.0060 (14)
C90.0344 (16)0.0445 (19)0.0406 (17)0.0049 (14)0.0050 (13)−0.0014 (15)
C100.0304 (15)0.0371 (17)0.0412 (18)−0.0007 (13)0.0052 (13)0.0015 (14)
C110.0312 (15)0.0291 (16)0.0389 (16)−0.0024 (12)0.0028 (13)0.0013 (13)
C120.0439 (18)0.0330 (17)0.0385 (17)−0.0033 (14)0.0083 (14)−0.0030 (14)
C130.0460 (19)0.045 (2)0.0340 (16)−0.0047 (15)−0.0020 (14)0.0006 (14)
C140.0363 (17)0.0323 (17)0.0433 (18)−0.0011 (13)−0.0001 (14)0.0054 (14)
C150.0384 (19)0.068 (3)0.062 (2)0.0021 (18)0.0057 (17)0.011 (2)
C160.0396 (19)0.081 (3)0.057 (2)−0.0040 (19)0.0105 (16)−0.009 (2)
Geometric parameters (Å, °) top
S—O31.424 (3)O5—C101.224 (4)
S—O41.431 (2)C5—C61.374 (5)
S—N11.643 (3)C5—H5A0.930
S—C91.782 (3)O6—C121.334 (4)
N1—C101.372 (4)O6—C161.440 (4)
N1—H1A0.860C6—C71.383 (5)
O1—C21.199 (4)C6—H6A0.930
C1—O21.451 (4)O7—C141.344 (4)
C1—H1B0.960O7—C151.428 (4)
C1—H1C0.960C7—C81.388 (5)
C1—H1D0.960C7—H7A0.930
O2—C21.333 (4)C8—C91.516 (4)
N2—C101.368 (4)C9—H9A0.970
N2—C111.399 (4)C9—H9B0.970
N2—H2A0.860C12—C131.379 (4)
C2—C31.495 (5)C13—C141.373 (5)
N3—C111.329 (4)C13—H13A0.930
N3—C121.339 (4)C15—H15A0.960
C3—C41.399 (4)C15—H15B0.960
C3—C81.406 (4)C15—H15C0.960
N4—C111.330 (4)C16—H16A0.960
N4—C141.336 (4)C16—H16B0.960
C4—C51.384 (5)C16—H16C0.960
C4—H4C0.930
O3—S—O4119.13 (17)C6—C7—H7A119.3
O3—S—N1110.25 (15)C8—C7—H7A119.3
O4—S—N1103.13 (14)C7—C8—C3118.6 (3)
O3—S—C9109.17 (16)C7—C8—C9118.5 (3)
O4—S—C9109.40 (16)C3—C8—C9122.8 (3)
N1—S—C9104.73 (15)C8—C9—S109.7 (2)
C10—N1—S126.2 (2)C8—C9—H9A109.7
C10—N1—H1A116.9S—C9—H9A109.7
S—N1—H1A116.9C8—C9—H9B109.7
O2—C1—H1B109.5S—C9—H9B109.7
O2—C1—H1C109.5H9A—C9—H9B108.2
H1B—C1—H1C109.5O5—C10—N2121.3 (3)
O2—C1—H1D109.5O5—C10—N1122.7 (3)
H1B—C1—H1D109.5N2—C10—N1116.0 (3)
H1C—C1—H1D109.5N3—C11—N4127.5 (3)
C2—O2—C1115.9 (3)N3—C11—N2118.9 (3)
C10—N2—C11130.5 (3)N4—C11—N2113.6 (3)
C10—N2—H2A114.8O6—C12—N3119.4 (3)
C11—N2—H2A114.8O6—C12—C13118.1 (3)
O1—C2—O2123.4 (3)N3—C12—C13122.5 (3)
O1—C2—C3124.3 (3)C14—C13—C12115.6 (3)
O2—C2—C3112.2 (3)C14—C13—H13A122.2
C11—N3—C12115.7 (3)C12—C13—H13A122.2
C4—C3—C8119.3 (3)N4—C14—O7118.1 (3)
C4—C3—C2118.5 (3)N4—C14—C13124.2 (3)
C8—C3—C2121.9 (3)O7—C14—C13117.7 (3)
C11—N4—C14114.4 (3)O7—C15—H15A109.5
C5—C4—C3120.8 (3)O7—C15—H15B109.5
C5—C4—H4C119.6H15A—C15—H15B109.5
C3—C4—H4C119.6O7—C15—H15C109.5
C6—C5—C4119.8 (3)H15A—C15—H15C109.5
C6—C5—H5A120.1H15B—C15—H15C109.5
C4—C5—H5A120.1O6—C16—H16A109.5
C12—O6—C16118.8 (3)O6—C16—H16B109.5
C5—C6—C7120.1 (3)H16A—C16—H16B109.5
C5—C6—H6A120.0O6—C16—H16C109.5
C7—C6—H6A120.0H16A—C16—H16C109.5
C14—O7—C15118.4 (3)H16B—C16—H16C109.5
C6—C7—C8121.4 (3)
O3—S—N1—C1061.5 (3)N1—S—C9—C8−167.4 (2)
O4—S—N1—C10−170.2 (3)C11—N2—C10—O5173.7 (3)
C9—S—N1—C10−55.8 (3)C11—N2—C10—N1−6.9 (5)
C1—O2—C2—O11.1 (5)S—N1—C10—O5−0.1 (5)
C1—O2—C2—C3178.5 (3)S—N1—C10—N2−179.5 (2)
O1—C2—C3—C4139.0 (3)C12—N3—C11—N40.0 (5)
O2—C2—C3—C4−38.4 (4)C12—N3—C11—N2−179.3 (3)
O1—C2—C3—C8−34.9 (5)C14—N4—C11—N3−1.4 (5)
O2—C2—C3—C8147.7 (3)C14—N4—C11—N2178.0 (3)
C8—C3—C4—C51.0 (5)C10—N2—C11—N38.8 (5)
C2—C3—C4—C5−173.1 (3)C10—N2—C11—N4−170.6 (3)
C3—C4—C5—C6−0.9 (5)C16—O6—C12—N36.0 (5)
C4—C5—C6—C7−0.5 (5)C16—O6—C12—C13−173.8 (3)
C5—C6—C7—C81.9 (5)C11—N3—C12—O6−178.8 (3)
C6—C7—C8—C3−1.7 (5)C11—N3—C12—C131.0 (5)
C6—C7—C8—C9−179.0 (3)O6—C12—C13—C14179.3 (3)
C4—C3—C8—C70.3 (4)N3—C12—C13—C14−0.5 (5)
C2—C3—C8—C7174.2 (3)C11—N4—C14—O7−177.5 (3)
C4—C3—C8—C9177.5 (3)C11—N4—C14—C131.9 (5)
C2—C3—C8—C9−8.7 (5)C15—O7—C14—N4−11.2 (4)
C7—C8—C9—S102.8 (3)C15—O7—C14—C13169.4 (3)
C3—C8—C9—S−74.3 (3)C12—C13—C14—N4−1.0 (5)
O3—S—C9—C874.5 (3)C12—C13—C14—O7178.4 (3)
O4—S—C9—C8−57.5 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N30.861.942.648 (4)138
N2—H2A···O5i0.862.102.951 (3)170
C9—H9B···O10.972.362.970 (4)120
C15—H15C···O1i0.962.433.068 (4)124
Symmetry codes: (i) −x, y, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N30.861.942.648 (4)138
N2—H2A···O5i0.862.102.951 (3)170
C9—H9B···O10.972.362.970 (4)120
C15—H15C···O1i0.962.433.068 (4)124
Symmetry codes: (i) −x, y, −z+3/2.
references
References top

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

Kong, F., Hu, X., Wang, L., Tao, Z., Wang, X. & Cao, W. (1990). Huaxue Shijie, 31, 211–213.

Lee, J. K., Ahn, K. C., Park, O. S., Ko, Y. K. & Kim, D.-W. (2002). J. Agric. Food Chem. 50, 1791–1803.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Sabadie, J. (1996). Weed Res. 36, 441–448.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.