2-(4-Isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)-5-methyl­nicotinic acid

Liu, L.-P.; Wang, X.-D.; Zhang, S.; Gao, J.-S.

doi:10.1107/S1600536812020478

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1692

doi:10.1107/S1600536812020478

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2-(4-Isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)-5-methylnicotinic acid

Li-Ping Liu,^a Xiao-Dan Wang,^a Shuang Zhang ^a and Jin-Sheng Gao ^a ^*

^aEngineering Research Center of Pesticides of Heilongjiang University, Heilongjiang University, Harbin 150050, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 28 April 2012; accepted 7 May 2012; online 12 May 2012)

In the title herbicideh/phytocide, known as imazapic, C₁₄H₁₇N₃O₃, the pyridine and imidazole rings are almost coplanar [dihedral angle = 3.08 (5)°]. An intramolecular O—H⋯N hydrogen bond occurs. In the crystal, an N—H⋯O hydrogen bond links molecules into a chain parallel to [010].

Related literature

For the synthesis, see: Szezepanski et al. (1988 ).

Experimental

Crystal data

C₁₄H₁₇N₃O₃
M_r = 275.31
Monoclinic, P 2₁ /c
a = 12.102 (2) Å
b = 16.035 (3) Å
c = 7.2883 (15) Å
β = 94.17 (3)°
V = 1410.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.60 × 0.30 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.946, T_max = 0.984
13471 measured reflections
3202 independent reflections
2234 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.145
S = 1.00
3202 reflections
192 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.82 (1)	1.68 (1)	2.4972 (16)	173 (2)
N3—H3⋯O2ⁱ	0.90 (1)	2.06 (1)	2.9387 (18)	165 (2)
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812020478/ng5267sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020478/ng5267Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020478/ng5267Isup3.cml

checkCIF report

Comment top

Imazapic is an effective and widely used herbicide. Imazapic for the control of annual broadleaf and gramineae weeds has important achievements in agriculture. Herein, we report the crystal structure of this herbicide (Scheme I).

The pyridine and imidazole ring are almost coplanar with small dihedral angle of 3.08 (5) ° (Figure 1). There is an intramolecular O—H···N hydrogen bond; an intermolecular N—H···O hydrogen bond links isolated molecules into chain structure along [010] (Figure 2, Table 1).

Related literature top

For the synthesis, see: Szezepanski et al. (1988).

Experimental top

The title compound was prepared by the reaction of diethyl 5-methylpyridine-2,3-dicarboxylate and 2-amino-2,3-dimethylbutanehydrazide according to a method reported in the patent literature. A white powder was obtained in 78% yield (Szezepanski et al., 1988). Colorless crystals were obtained by the recrystallization of title compound from acetonitrile.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); 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

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms.
	Fig. 2. A partial packing view, showing the hydrogen-bonding chain structure along [010].

2-(4-Isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)- 5-methylnicotinic acid top

Crystal data top

C₁₄H₁₇N₃O₃	F(000) = 584
M_r = 275.31	D_x = 1.296 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10539 reflections
a = 12.102 (2) Å	θ = 3.1–27.4°
b = 16.035 (3) Å	µ = 0.09 mm⁻¹
c = 7.2883 (15) Å	T = 293 K
β = 94.17 (3)°	Block, colorless
V = 1410.6 (5) Å³	0.60 × 0.30 × 0.18 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3202 independent reflections
Radiation source: fine-focus sealed tube	2234 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scan	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −15→15
T_min = 0.946, T_max = 0.984	k = −20→20
13471 measured reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0979P)²] where P = (F_o² + 2F_c²)/3
3202 reflections	(Δ/σ)_max = 0.001
192 parameters	Δρ_max = 0.28 e Å⁻³
2 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₁₇N₃O₃	V = 1410.6 (5) Å³
M_r = 275.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.102 (2) Å	µ = 0.09 mm⁻¹
b = 16.035 (3) Å	T = 293 K
c = 7.2883 (15) Å	0.60 × 0.30 × 0.18 mm
β = 94.17 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3202 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2234 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.984	R_int = 0.033
13471 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	2 restraints
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.28 e Å⁻³
3202 reflections	Δρ_min = −0.17 e Å⁻³
192 parameters

Special details top

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 > 2sigma(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

	x	y	z	U_iso*/U_eq
C1	1.01695 (11)	0.78025 (8)	0.26937 (16)	0.0326 (3)
C2	1.12083 (12)	0.76017 (9)	0.35266 (18)	0.0377 (3)
H2	1.1400	0.7043	0.3680	0.045*
C3	1.19647 (12)	0.82072 (10)	0.41336 (19)	0.0414 (3)
C4	1.16383 (14)	0.90226 (10)	0.3862 (2)	0.0502 (4)
H4	1.2136	0.9439	0.4251	0.060*
C5	0.99292 (11)	0.86611 (8)	0.25086 (18)	0.0343 (3)
C6	0.94567 (12)	0.70446 (8)	0.2115 (2)	0.0380 (3)
C7	1.30826 (14)	0.79919 (12)	0.5050 (2)	0.0574 (5)
H7A	1.3650	0.8150	0.4264	0.086*
H7B	1.3122	0.7402	0.5275	0.086*
H7C	1.3189	0.8286	0.6197	0.086*
C8	0.88794 (12)	0.90408 (8)	0.17407 (18)	0.0364 (3)
C9	0.77171 (13)	1.00954 (9)	0.1004 (2)	0.0463 (4)
C10	0.71625 (13)	0.92605 (9)	0.0469 (2)	0.0403 (3)
C11	0.60962 (13)	0.91307 (11)	0.1470 (2)	0.0502 (4)
H11	0.5570	0.9565	0.1037	0.060*
C12	0.69487 (16)	0.92380 (12)	−0.1627 (2)	0.0565 (5)
H12A	0.7637	0.9304	−0.2187	0.085*
H12B	0.6455	0.9683	−0.2015	0.085*
H12C	0.6620	0.8713	−0.1991	0.085*
C13	0.62931 (18)	0.92271 (16)	0.3541 (2)	0.0755 (6)
H13A	0.6825	0.8821	0.4004	0.113*
H13B	0.5609	0.9145	0.4104	0.113*
H13C	0.6570	0.9777	0.3823	0.113*
C14	0.5557 (2)	0.82921 (17)	0.1010 (4)	0.0935 (8)
H14A	0.6040	0.7852	0.1465	0.140*
H14B	0.5424	0.8240	−0.0299	0.140*
H14C	0.4866	0.8255	0.1576	0.140*
N1	1.06558 (11)	0.92563 (7)	0.30766 (19)	0.0475 (3)
N2	0.80181 (10)	0.86483 (7)	0.10681 (16)	0.0382 (3)
N3	0.87614 (11)	0.98947 (8)	0.17332 (19)	0.0459 (3)
H3	0.9282 (14)	1.0274 (10)	0.208 (3)	0.066 (5)*
O1	0.85037 (10)	0.71349 (6)	0.12055 (16)	0.0499 (3)
H1	0.8310 (18)	0.7624 (4)	0.109 (3)	0.075*
O2	0.98114 (10)	0.63550 (7)	0.25044 (19)	0.0606 (4)
O3	0.73227 (11)	1.07853 (7)	0.0816 (2)	0.0687 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0366 (7)	0.0277 (6)	0.0341 (6)	0.0013 (5)	0.0064 (5)	0.0019 (5)
C2	0.0377 (8)	0.0335 (7)	0.0422 (7)	0.0061 (6)	0.0051 (6)	0.0037 (5)
C3	0.0362 (8)	0.0468 (8)	0.0412 (7)	0.0022 (6)	0.0021 (6)	0.0027 (6)
C4	0.0417 (9)	0.0429 (9)	0.0641 (9)	−0.0103 (7)	−0.0101 (7)	0.0015 (7)
C5	0.0353 (7)	0.0283 (6)	0.0392 (7)	−0.0019 (5)	0.0021 (5)	0.0023 (5)
C6	0.0399 (8)	0.0271 (7)	0.0474 (7)	0.0013 (6)	0.0054 (6)	−0.0007 (5)
C7	0.0376 (9)	0.0683 (12)	0.0649 (10)	0.0034 (8)	−0.0059 (7)	0.0029 (8)
C8	0.0389 (8)	0.0257 (7)	0.0444 (7)	−0.0004 (5)	0.0019 (6)	0.0017 (5)
C9	0.0439 (9)	0.0318 (8)	0.0625 (9)	0.0029 (6)	−0.0005 (7)	0.0021 (6)
C10	0.0389 (8)	0.0338 (7)	0.0470 (8)	0.0030 (6)	−0.0049 (6)	0.0013 (6)
C11	0.0362 (8)	0.0590 (10)	0.0543 (9)	−0.0013 (7)	−0.0032 (6)	−0.0023 (7)
C12	0.0643 (11)	0.0590 (11)	0.0454 (8)	0.0105 (8)	−0.0020 (7)	0.0053 (7)
C13	0.0623 (13)	0.1113 (19)	0.0536 (10)	−0.0148 (11)	0.0090 (9)	−0.0095 (10)
C14	0.0753 (16)	0.1046 (18)	0.1019 (17)	−0.0496 (14)	0.0153 (13)	−0.0230 (14)
N1	0.0431 (8)	0.0325 (7)	0.0652 (8)	−0.0056 (5)	−0.0082 (6)	0.0031 (6)
N2	0.0370 (7)	0.0290 (6)	0.0478 (6)	−0.0004 (5)	−0.0033 (5)	0.0015 (5)
N3	0.0406 (7)	0.0266 (6)	0.0689 (8)	−0.0005 (5)	−0.0075 (6)	−0.0002 (5)
O1	0.0463 (6)	0.0279 (5)	0.0737 (7)	−0.0019 (5)	−0.0094 (5)	−0.0031 (5)
O2	0.0548 (7)	0.0265 (5)	0.0989 (9)	0.0039 (5)	−0.0055 (6)	0.0038 (5)
O3	0.0566 (8)	0.0315 (6)	0.1157 (11)	0.0103 (5)	−0.0100 (7)	0.0003 (6)

Geometric parameters (Å, º) top

C1—C2	1.393 (2)	C9—N3	1.373 (2)
C1—C5	1.4116 (18)	C9—C10	1.535 (2)
C1—C6	1.5317 (19)	C10—N2	1.4699 (17)
C2—C3	1.385 (2)	C10—C12	1.531 (2)
C2—H2	0.9300	C10—C11	1.542 (2)
C3—C4	1.376 (2)	C11—C13	1.519 (2)
C3—C7	1.505 (2)	C11—C14	1.521 (3)
C4—N1	1.335 (2)	C11—H11	0.9800
C4—H4	0.9300	C12—H12A	0.9600
C5—N1	1.3426 (18)	C12—H12B	0.9600
C5—C8	1.4813 (19)	C12—H12C	0.9600
C6—O2	1.2124 (17)	C13—H13A	0.9600
C6—O1	1.2959 (19)	C13—H13B	0.9600
C7—H7A	0.9600	C13—H13C	0.9600
C7—H7B	0.9600	C14—H14A	0.9600
C7—H7C	0.9600	C14—H14B	0.9600
C8—N2	1.2840 (18)	C14—H14C	0.9600
C8—N3	1.3767 (18)	N3—H3	0.898 (9)
C9—O3	1.2087 (18)	O1—H1	0.8203 (10)

C2—C1—C5	116.11 (12)	N2—C10—C11	111.41 (12)
C2—C1—C6	114.13 (12)	C12—C10—C11	112.47 (13)
C5—C1—C6	129.76 (12)	C9—C10—C11	111.28 (13)
C3—C2—C1	122.12 (13)	C13—C11—C14	110.02 (17)
C3—C2—H2	118.9	C13—C11—C10	112.34 (14)
C1—C2—H2	118.9	C14—C11—C10	112.06 (15)
C4—C3—C2	116.36 (13)	C13—C11—H11	107.4
C4—C3—C7	121.43 (15)	C14—C11—H11	107.4
C2—C3—C7	122.21 (15)	C10—C11—H11	107.4
N1—C4—C3	124.46 (14)	C10—C12—H12A	109.5
N1—C4—H4	117.8	C10—C12—H12B	109.5
C3—C4—H4	117.8	H12A—C12—H12B	109.5
N1—C5—C1	122.55 (13)	C10—C12—H12C	109.5
N1—C5—C8	110.42 (12)	H12A—C12—H12C	109.5
C1—C5—C8	127.01 (12)	H12B—C12—H12C	109.5
O2—C6—O1	120.56 (13)	C11—C13—H13A	109.5
O2—C6—C1	118.47 (13)	C11—C13—H13B	109.5
O1—C6—C1	120.97 (11)	H13A—C13—H13B	109.5
C3—C7—H7A	109.5	C11—C13—H13C	109.5
C3—C7—H7B	109.5	H13A—C13—H13C	109.5
H7A—C7—H7B	109.5	H13B—C13—H13C	109.5
C3—C7—H7C	109.5	C11—C14—H14A	109.5
H7A—C7—H7C	109.5	C11—C14—H14B	109.5
H7B—C7—H7C	109.5	H14A—C14—H14B	109.5
N2—C8—N3	113.88 (12)	C11—C14—H14C	109.5
N2—C8—C5	126.36 (12)	H14A—C14—H14C	109.5
N3—C8—C5	119.75 (12)	H14B—C14—H14C	109.5
O3—C9—N3	127.10 (15)	C4—N1—C5	118.40 (13)
O3—C9—C10	127.42 (15)	C8—N2—C10	108.71 (11)
N3—C9—C10	105.48 (12)	C9—N3—C8	109.09 (12)
N2—C10—C12	110.19 (13)	C9—N3—H3	123.8 (13)
N2—C10—C9	102.79 (11)	C8—N3—H3	127.1 (14)
C12—C10—C9	108.25 (13)	C6—O1—H1	113.3 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.82 (1)	1.68 (1)	2.4972 (16)	173 (2)
N3—H3···O2ⁱ	0.90 (1)	2.06 (1)	2.9387 (18)	165 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₇N₃O₃
M_r	275.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.102 (2), 16.035 (3), 7.2883 (15)
β (°)	94.17 (3)
V (Å³)	1410.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.60 × 0.30 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.946, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	13471, 3202, 2234
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.145, 1.00
No. of reflections	3202
No. of parameters	192
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.17

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.8203 (10)	1.681 (3)	2.4972 (16)	173 (2)
N3—H3···O2ⁱ	0.898 (9)	2.062 (11)	2.9387 (18)	165.0 (19)

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

Acknowledgements

The authors thank the project of the Innovation Service Platform of Heilongjiang Province (PG09J001) and Heilongjiang University for supporting this work.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Szezepanski, H., Dieter, W. & Bottmingen, D. (1988). US Patent No. US4758667. Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-(4-Iso­propyl-4-methyl-5-oxo-4,5-di­hydro-1H-imidazol-2-yl)-5-methyl­nicotinic acid

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-(4-Isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)-5-methylnicotinic acid