organic compounds
of metobromuron
aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea
*Correspondence e-mail: thkim@gnu.ac.kr, jekim@gnu.ac.kr
The title compound [systematic name: 3-(4-bromophenyl)-1-methoxy-1-methylurea], C9H11BrN2O2, is a phenylurea herbicide. The dihedral angle between the plane of the urea group and that of the bromophenyl ring is 39.13 (10)°. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds and weak C—H⋯π interactions link adjacent molecules, forming chains along the a-axis direction. In addition, short intermolecular Br⋯Br contacts [3.648 (4) Å] are present, resulting in a two-dimensional network extending parallel to (101).
CCDC reference: 1412609
1. Related literature
For information on the herbicidal properties of the title compound, see: Leila et al. (2011). For related crystal structures, see: Black et al. (2010); Kostyanovsky et al. (2010).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2013); cell SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
CCDC reference: 1412609
https://doi.org/10.1107/S205698901501347X/hg5451sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901501347X/hg5451Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S205698901501347X/hg5451Isup3.cml
The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation of a solution in ethyl acetate gave single crystals suitable for X-ray analysis.
All H-atoms were positioned geometrically and refined using a riding model with d(N—H) = 0.88 Å, Uiso = 1.2Ueq(C) for urea N—H, d(C—H) = 0.98 Å, Uiso = 1.5Ueq(C) for methyl group, d(C—H) = 0.95 Å, Uiso = 1.2Ueq(C) for aromatic C—H.
Metobromuron: 3-(4-bromophenyl)-1-methoxy-1-methylurea, is a phenylurea herbicide and has been used for the control of broadleaf weeds in cereal and vegetable crops, acting through the inhibition of photosynthesis (Leila et al., 2011). However, until now its
has not been reported. In the title compound (Fig. 1), the dihedral angle between the plane of the urea group and the bromophenyl ring is 39.13 (10) °. All bond lengths and bond angles are normal and comparable to those observed in similar crystal structures (Black et al., 2010; Kostyanovsky et al., 2010).In the π interactions link adjacent molecules (Table 1), forming one-dimensional chains along the a-axis direction. In addition, weak intermolecular short Br···Br contacts [3.648 (4) Å] are present, resulting in a two-dimensional network extending parallel to (101).
(Fig. 2), N–H···O and C–H···O hydrogen bonds and weak C–H···For information on the herbicidal properties of the title compound, see: Leila et al. (2011). For related crystal structures, see: Black et al. (2010); Kostyanovsky et al. (2010).
Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C9H11BrN2O2 | Dx = 1.632 Mg m−3 |
Mr = 259.11 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 3544 reflections |
a = 9.8184 (2) Å | θ = 3.0–24.1° |
b = 11.3286 (3) Å | µ = 3.88 mm−1 |
c = 18.9569 (5) Å | T = 173 K |
V = 2108.55 (9) Å3 | Plate, colourless |
Z = 8 | 0.30 × 0.16 × 0.02 mm |
F(000) = 1040 |
Bruker APEXII CCD diffractometer | 1857 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.048 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | θmax = 27.5°, θmin = 2.2° |
Tmin = 0.389, Tmax = 0.927 | h = −12→12 |
17922 measured reflections | k = −14→14 |
2424 independent reflections | l = −23→24 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0255P)2 + 1.105P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2424 reflections | Δρmax = 0.41 e Å−3 |
129 parameters | Δρmin = −0.42 e Å−3 |
C9H11BrN2O2 | V = 2108.55 (9) Å3 |
Mr = 259.11 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.8184 (2) Å | µ = 3.88 mm−1 |
b = 11.3286 (3) Å | T = 173 K |
c = 18.9569 (5) Å | 0.30 × 0.16 × 0.02 mm |
Bruker APEXII CCD diffractometer | 2424 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | 1857 reflections with I > 2σ(I) |
Tmin = 0.389, Tmax = 0.927 | Rint = 0.048 |
17922 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.41 e Å−3 |
2424 reflections | Δρmin = −0.42 e Å−3 |
129 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.86464 (3) | 0.10694 (2) | 0.51608 (2) | 0.03673 (10) | |
O1 | 0.88255 (14) | 0.47320 (14) | 0.80131 (9) | 0.0337 (4) | |
O2 | 0.55297 (15) | 0.56454 (15) | 0.83862 (9) | 0.0338 (4) | |
N1 | 0.67399 (18) | 0.41832 (16) | 0.75709 (10) | 0.0259 (4) | |
H1N | 0.5855 | 0.4269 | 0.7624 | 0.031* | |
N2 | 0.69171 (18) | 0.54270 (17) | 0.85274 (10) | 0.0297 (5) | |
C1 | 0.7206 (2) | 0.34339 (18) | 0.70276 (12) | 0.0224 (5) | |
C2 | 0.6508 (2) | 0.34425 (19) | 0.63907 (12) | 0.0249 (5) | |
H2 | 0.5732 | 0.3934 | 0.6335 | 0.030* | |
C3 | 0.6936 (2) | 0.2741 (2) | 0.58381 (12) | 0.0276 (5) | |
H3 | 0.6467 | 0.2756 | 0.5400 | 0.033* | |
C4 | 0.8053 (2) | 0.20197 (19) | 0.59297 (12) | 0.0265 (5) | |
C5 | 0.8734 (2) | 0.19632 (19) | 0.65655 (12) | 0.0278 (5) | |
H5 | 0.9485 | 0.1444 | 0.6625 | 0.033* | |
C6 | 0.8306 (2) | 0.26736 (19) | 0.71147 (12) | 0.0264 (5) | |
H6 | 0.8766 | 0.2643 | 0.7555 | 0.032* | |
C7 | 0.7577 (2) | 0.47817 (19) | 0.80181 (12) | 0.0248 (5) | |
C8 | 0.7580 (3) | 0.6412 (2) | 0.88719 (14) | 0.0378 (6) | |
H8A | 0.8452 | 0.6152 | 0.9069 | 0.057* | |
H8B | 0.6996 | 0.6709 | 0.9252 | 0.057* | |
H8C | 0.7740 | 0.7042 | 0.8528 | 0.057* | |
C9 | 0.4734 (3) | 0.5087 (3) | 0.89159 (16) | 0.0525 (8) | |
H9A | 0.4974 | 0.4249 | 0.8941 | 0.079* | |
H9B | 0.3766 | 0.5168 | 0.8800 | 0.079* | |
H9C | 0.4914 | 0.5461 | 0.9373 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.04164 (16) | 0.03414 (14) | 0.03440 (17) | 0.00799 (11) | 0.01142 (11) | −0.00470 (11) |
O1 | 0.0172 (9) | 0.0434 (10) | 0.0404 (10) | 0.0032 (7) | −0.0014 (7) | −0.0051 (8) |
O2 | 0.0191 (8) | 0.0430 (10) | 0.0395 (10) | 0.0057 (7) | −0.0011 (7) | −0.0108 (8) |
N1 | 0.0157 (9) | 0.0335 (11) | 0.0285 (11) | 0.0028 (7) | 0.0012 (8) | −0.0047 (9) |
N2 | 0.0195 (10) | 0.0382 (12) | 0.0314 (12) | 0.0014 (8) | −0.0023 (8) | −0.0082 (9) |
C1 | 0.0194 (11) | 0.0238 (11) | 0.0241 (12) | 0.0008 (8) | 0.0040 (9) | 0.0012 (9) |
C2 | 0.0203 (12) | 0.0278 (11) | 0.0267 (13) | 0.0060 (9) | 0.0009 (9) | 0.0021 (10) |
C3 | 0.0275 (12) | 0.0311 (12) | 0.0241 (13) | 0.0037 (9) | −0.0005 (10) | 0.0014 (10) |
C4 | 0.0282 (12) | 0.0256 (11) | 0.0255 (13) | 0.0023 (9) | 0.0092 (10) | 0.0001 (10) |
C5 | 0.0229 (12) | 0.0254 (11) | 0.0350 (14) | 0.0057 (9) | 0.0063 (10) | 0.0046 (10) |
C6 | 0.0235 (12) | 0.0301 (12) | 0.0254 (12) | 0.0034 (9) | 0.0009 (9) | 0.0033 (10) |
C7 | 0.0223 (12) | 0.0273 (11) | 0.0249 (12) | 0.0011 (9) | 0.0003 (9) | 0.0032 (9) |
C8 | 0.0338 (14) | 0.0426 (15) | 0.0371 (15) | −0.0010 (11) | −0.0087 (12) | −0.0110 (12) |
C9 | 0.0383 (16) | 0.0555 (18) | 0.064 (2) | −0.0075 (13) | 0.0224 (15) | −0.0177 (16) |
Br1—C4 | 1.904 (2) | C3—C4 | 1.378 (3) |
O1—C7 | 1.228 (3) | C3—H3 | 0.9500 |
O2—N2 | 1.410 (2) | C4—C5 | 1.380 (3) |
O2—C9 | 1.421 (3) | C5—C6 | 1.381 (3) |
N1—C7 | 1.361 (3) | C5—H5 | 0.9500 |
N1—C1 | 1.411 (3) | C6—H6 | 0.9500 |
N1—H1N | 0.8800 | C8—H8A | 0.9800 |
N2—C7 | 1.373 (3) | C8—H8B | 0.9800 |
N2—C8 | 1.448 (3) | C8—H8C | 0.9800 |
C1—C2 | 1.388 (3) | C9—H9A | 0.9800 |
C1—C6 | 1.391 (3) | C9—H9B | 0.9800 |
C2—C3 | 1.380 (3) | C9—H9C | 0.9800 |
C2—H2 | 0.9500 | ||
N2—O2—C9 | 108.60 (19) | C4—C5—H5 | 120.5 |
C7—N1—C1 | 123.95 (18) | C6—C5—H5 | 120.5 |
C7—N1—H1N | 118.0 | C5—C6—C1 | 120.5 (2) |
C1—N1—H1N | 118.0 | C5—C6—H6 | 119.8 |
C7—N2—O2 | 114.55 (17) | C1—C6—H6 | 119.8 |
C7—N2—C8 | 121.04 (19) | O1—C7—N1 | 125.1 (2) |
O2—N2—C8 | 112.62 (18) | O1—C7—N2 | 120.1 (2) |
C2—C1—C6 | 119.4 (2) | N1—C7—N2 | 114.73 (19) |
C2—C1—N1 | 118.07 (19) | N2—C8—H8A | 109.5 |
C6—C1—N1 | 122.5 (2) | N2—C8—H8B | 109.5 |
C3—C2—C1 | 120.4 (2) | H8A—C8—H8B | 109.5 |
C3—C2—H2 | 119.8 | N2—C8—H8C | 109.5 |
C1—C2—H2 | 119.8 | H8A—C8—H8C | 109.5 |
C4—C3—C2 | 119.2 (2) | H8B—C8—H8C | 109.5 |
C4—C3—H3 | 120.4 | O2—C9—H9A | 109.5 |
C2—C3—H3 | 120.4 | O2—C9—H9B | 109.5 |
C3—C4—C5 | 121.5 (2) | H9A—C9—H9B | 109.5 |
C3—C4—Br1 | 118.85 (18) | O2—C9—H9C | 109.5 |
C5—C4—Br1 | 119.62 (16) | H9A—C9—H9C | 109.5 |
C4—C5—C6 | 119.0 (2) | H9B—C9—H9C | 109.5 |
C9—O2—N2—C7 | 116.7 (2) | Br1—C4—C5—C6 | 178.85 (16) |
C9—O2—N2—C8 | −99.8 (2) | C4—C5—C6—C1 | 0.0 (3) |
C7—N1—C1—C2 | −141.5 (2) | C2—C1—C6—C5 | 2.3 (3) |
C7—N1—C1—C6 | 40.2 (3) | N1—C1—C6—C5 | −179.4 (2) |
C6—C1—C2—C3 | −2.8 (3) | C1—N1—C7—O1 | −1.2 (4) |
N1—C1—C2—C3 | 178.9 (2) | C1—N1—C7—N2 | −177.6 (2) |
C1—C2—C3—C4 | 0.9 (3) | O2—N2—C7—O1 | 165.9 (2) |
C2—C3—C4—C5 | 1.4 (3) | C8—N2—C7—O1 | 25.7 (3) |
C2—C3—C4—Br1 | −179.30 (17) | O2—N2—C7—N1 | −17.6 (3) |
C3—C4—C5—C6 | −1.9 (3) | C8—N2—C7—N1 | −157.8 (2) |
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.88 | 2.39 | 3.130 (2) | 142 |
C2—H2···O1i | 0.95 | 2.42 | 3.217 (3) | 142 |
C9—H9A···Cg1i | 0.98 | 2.99 | 3.477 (3) | 112 |
Symmetry code: (i) x−1/2, y, −z+3/2. |
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.88 | 2.39 | 3.130 (2) | 142.2 |
C2—H2···O1i | 0.95 | 2.42 | 3.217 (3) | 141.6 |
C9—H9A···Cg1i | 0.98 | 2.99 | 3.477 (3) | 112 |
Symmetry code: (i) x−1/2, y, −z+3/2. |
Acknowledgements
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2014R1A1A4A01009105).
References
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Metobromuron: 3-(4-bromophenyl)-1-methoxy-1-methylurea, is a phenylurea herbicide and has been used for the control of broadleaf weeds in cereal and vegetable crops, acting through the inhibition of photosynthesis (Leila et al., 2011). However, until now its crystal structure has not been reported. In the title compound (Fig. 1), the dihedral angle between the plane of the urea group and the bromophenyl ring is 39.13 (10) °. All bond lengths and bond angles are normal and comparable to those observed in similar crystal structures (Black et al., 2010; Kostyanovsky et al., 2010).
In the crystal structure (Fig. 2), N–H···O and C–H···O hydrogen bonds and weak C–H···π interactions link adjacent molecules (Table 1), forming one-dimensional chains along the a-axis direction. In addition, weak intermolecular short Br···Br contacts [3.648 (4) Å] are present, resulting in a two-dimensional network extending parallel to (101).