Amicarbazone

Manpreet Kaur; Ray J Butcher; Jerry P Jasinski; H S Yathirajan; B P Siddaraju

doi:10.1107/S1600536813007782

. 2013 Mar 28;69(Pt 4):o603. doi: 10.1107/S1600536813007782

Amicarbazone

Manpreet Kaur ^a, Ray J Butcher ^b, Jerry P Jasinski ^c,^*, H S Yathirajan ^a, B P Siddaraju ^d

PMCID: PMC3629643 PMID: 23634130

Abstract

Three independent molecules comprise the asymmetric unit of the title compound, C₁₀H₁₉N₅O₂, (systematic name: 4-amino-N-tert-butyl-3-isopropyl-5-oxo-4,5-dihydro-1H-1,2,4-triazole-1-carboxamide) . In all three molecules, the triazole ring and the carboxamide group are almost coplanar [within 4.0–5.9 (9)°], particularly because of the formation of an intramolecular N—H⋯O hydrogen bond. On other hand, the orientation of the isopropyl group varies significantly from molecule to molecule. The crystal packing is dominated by N—H⋯O and N—H⋯N hydrogen bonds, which connect the molecules into infinite chains along [010].

Related literature

For herbicidal properties of amicarbazone and for its preparation, see: Dayan et al. (2009 ▶); Diehr (1998 ▶). For related structures, see: Crockett et al. (2004 ▶); Dupont et al. (1991 ▶); Heng et al. (2006 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₀H₁₉N₅O₂
M _r = 241.30
Triclinic,
a = 11.0298 (2) Å
b = 12.2135 (4) Å
c = 14.8542 (4) Å
α = 92.244 (2)°
β = 95.7020 (19)°
γ = 93.379 (2)°
V = 1985.65 (9) Å³
Z = 6
Cu Kα radiation
μ = 0.72 mm⁻¹
T = 123 K
0.35 × 0.25 × 0.15 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.791, T _max = 1.000
13380 measured reflections
7959 independent reflections
7592 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.115
S = 1.05
7959 reflections
499 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: SHELXTL.

Supplementary Material

Click here for additional data file.^{(43.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813007782/ld2097sup1.cif

e-69-0o603-sup1.cif^{(43.6KB, cif)}

Click here for additional data file.^{(389.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007782/ld2097Isup2.hkl

e-69-0o603-Isup2.hkl^{(389.3KB, hkl)}

Click here for additional data file.^{(4.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007782/ld2097Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H3N1⋯O1C	0.904 (19)	2.220 (19)	3.0832 (14)	159.6 (15)
N2A—H3N2⋯N3B	0.91 (2)	2.40 (2)	3.2251 (15)	150.9 (15)
N2A—H3N2⋯O2B	0.91 (2)	2.483 (19)	3.2492 (14)	141.7 (15)
N5A—H4AB⋯O1A	0.88	2.05	2.7770 (14)	140
N2B—H3B2⋯N3C ⁱ	0.929 (19)	2.233 (19)	3.1619 (15)	179.1 (15)
N2B—H3B1⋯O1B ⁱⁱ	0.89 (2)	2.27 (2)	3.1356 (15)	163.1 (16)
N5B—H4BB⋯O1B	0.88	2.04	2.7655 (14)	139
N2C—H3C2⋯O1A	0.906 (18)	2.171 (18)	2.9455 (15)	143.1 (15)
N2C—H3C1⋯O2B	0.88 (2)	2.41 (2)	3.0718 (14)	132.8 (16)
N5C—H4CB⋯O1C	0.88	2.05	2.7721 (13)	139

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

MK thanks the UOM for research facilities. RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

Amicarbazone (IUPAC name: 4-Amino-N-(tert-butyl)-4,5-dihydro-3- (iso-propyl)-5-oxo-1H-1,2,4-triazole-1-carboxamide) is a new triazolinone herbicide with a broad spectrum of weed control. The phenotypic responses of sensitive plants exposed to amicarbazone include chlorosis, stunted growth, tissue necrosis, and death. Its efficacy as both a foliar- and root-applied herbicide suggests that absorption and translocation of this compound is very rapid. This new herbicide is a potent inhibitor of photosynthetic electron transport, inducing chlorophyll fluorescence and interrupting oxygen evolution ostensibly via binding to the Qb domain of photosystem II (PSII) in a manner similar to the triazines and the triazinones classes of herbicides (Dayan et al., 2009). In view of the importance of amicarbazone derivatives, this paper reports the crystal and molecular structure of the title compound, (I), C₁₀H₁₉N₅O₂.

In (I), three independent molecules (A,B,C) crystallize in the asymmetric unit (Fig. 1). The dihedral angle between the mean planes of the triazole ring and carboxamide group (N4/C6/O2/N5) for each of the molecules lie between 4.0 (6)° and 5.9 (9)°. In each of the three molecules the torsion angles of the tert-butyl groups are quite similar [C6/N5/C7/C8 = -56.76 (17)° (A), 64.18 (17)° (B), -57.90 (17)° (C); C6/N5/C7/C9 = 66.03 (16)° (A), -57.99 (19)° (B), 64.87 (16)° (C); C6/N5/C7/C10 = -175.58 (12)° (A), -177.48 (19)° (B), -177.61 (13)° (C)] while those of the isopropyl group vary significantly [N3/C2/C3/C4 = 111.38(14° (A), 120.86 (14)° (B), 8.92 (17)° (C); N3/C2/C3/C5 = -11.65 (17)° (A), -113.15 (14)° (B), 88.83 (15)° (C)]. In the crystal molecular packing is dominated by N—H···O and N—H···N intermolecular interactions (Table 1) forming a network of infinite 1-D chains along [010] (Fig. 2).

Experimental

Amicarbazone was prepared according to the patent procedure (Diehr, 1998). The resulting compound was recrystallized from methyl t-butyl ether by slow evaporation (M.P.: 373–378 K).