Crystal structure of metobromuron

Kang, G.; Kim, J.; Kwon, E.; Kim, T.H.

doi:10.1107/S205698901501347X

organic compounds

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Volume 71| Part 8| August 2015| Page o589

https://doi.org/10.1107/S205698901501347X

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Crystal structure of metobromuron

Gihaeng Kang,^a Jineun Kim,^a ^* Eunjin Kwon ^a and Tae Ho Kim ^a ^*

^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

Edited by P. C. Healy, Griffith University, Australia (Received 6 July 2015; accepted 14 July 2015; online 22 July 2015)

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).

Keywords: crystal structure; metobromuron; phenylurea herbicide; hydrogen bonding; Br⋯Br contacts.

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

C₉H₁₁BrN₂O₂
M_r = 259.11
Orthorhombic, P b c a
a = 9.8184 (2) Å
b = 11.3286 (3) Å
c = 18.9569 (5) Å
V = 2108.55 (9) Å³
Z = 8
Mo Kα radiation
μ = 3.88 mm⁻¹
T = 173 K
0.30 × 0.16 × 0.02 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.389, T_max = 0.927
17922 measured reflections
2424 independent reflections
1857 reflections with I > 2σ(I)
R_int = 0.048

2.3. Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.066
S = 1.03
2424 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2013); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S205698901501347X/hg5451sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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).

Experimental top

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.

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: 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).

Figures top

	Fig. 1. The asymmetric unit of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. Crystal packing viewed along the b axis. The intermolecular interactions are shown as dashed lines.

3-(4-Bromophenyl)-1-methoxy-1-methylurea top

Crystal data top

C₉H₁₁BrN₂O₂	D_x = 1.632 Mg m⁻³
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	1857 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.048
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θ_max = 27.5°, θ_min = 2.2°
T_min = 0.389, T_max = 0.927	h = −12→12
17922 measured reflections	k = −14→14
2424 independent reflections	l = −23→24

Refinement top

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(F_o²) + (0.0255P)² + 1.105P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2424 reflections	Δρ_max = 0.41 e Å⁻³
129 parameters	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₉H₁₁BrN₂O₂	V = 2108.55 (9) Å³
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	2424 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1857 reflections with I > 2σ(I)
T_min = 0.389, T_max = 0.927	R_int = 0.048
17922 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.03	Δρ_max = 0.41 e Å⁻³
2424 reflections	Δρ_min = −0.42 e Å⁻³
129 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 8| August 2015| Page o589

https://doi.org/10.1107/S205698901501347X

Open

access