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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o1998.
Published online 2010 July 14. doi:  10.1107/S160053681002684X
PMCID: PMC3007355

Pirimicarb: 2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethyl­carbamate

Abstract

In the title compound, C11H18N4O2 (systematic name: 2-dimethyl­amino-5,6-dimethyl­pyrimidin-4-yl N,N-dimethyl­carb­amate), the pyrimidine ring and dimethyl­amino group are almost in the same plane, making a dihedral angle of 1.6 (1)°. The dihedral angle between the mean plane of the pyrimidine ring and that of the dimethyl­carbamate group is 83.42 (5)°. In the crystal structure, inter­molecular C—H(...)O hydrogen bonds contribute to the stabilization of the packing.

Related literature

For the toxicity and insecticidal properties of the title compound, see: Pirisi et al. (1996 [triangle]). For related structures, see: Dalpozzo et al. (2001 [triangle]); Madre et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1998-scheme1.jpg

Experimental

Crystal data

  • C11H18N4O2
  • M r = 238.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1998-efi1.jpg
  • a = 13.5607 (7) Å
  • b = 7.7868 (4) Å
  • c = 13.1323 (7) Å
  • β = 114.907 (3)°
  • V = 1257.72 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 173 K
  • 0.29 × 0.25 × 0.11 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.975, T max = 0.990
  • 11979 measured reflections
  • 3093 independent reflections
  • 2390 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.146
  • S = 1.05
  • 3093 reflections
  • 160 parameters
  • H-atom parameters constrained
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681002684X/sj5033sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002684X/sj5033Isup2.hkl

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

Acknowledgments

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. 2010–0016386).

supplementary crystallographic information

Comment

Pirimicarb (systematic name: 2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate), is a well known insecticide used to control aphids on vegetable, cereal and orchard crops by inhibiting acetylcholinesterase activity (Pirisi et al., 1996). However it's crystal structure has not been reported yet.

In the title compound (Scheme 1, Fig.1), the pyrimidyl ring and dimethylamino group lie in the same plane with a dihedral angle of 1.6 (1)°. This coplanarity may be assisted by the conjugation of π-electrons between pyrimidyl group and nitrogen atom of dimethylamino group. The dihedral angle between the mean plane of the pyrimidyl ring(C1/N1/C2/N2/C3/C4) and the mean plane of the carbamate (O1/O2/C9/N4) is 83.42 (5)° (Fig.1). All bond lengths and bond angles are normal and comparable to those observed in similar structures (Dalpozzo et al., 2001; Madre et al., 2008).

In the crystal structure, weak C—H···O hydrogen bonds are observed [C5—H5C···O2; H5C···O2 = 2.60 Å; C5—H5C···O2 = 163°; C5···O2 = 3.549 (2) Å; -x + 1, -y + 1, -z + 1 and C10—H10C···O2; H10C···O2 = 2.51 Å; C10—H10C···O2 = 157°; C10···O2 = 3.431 (2) Å; x,-y + 3/2,z + 1/2] (Fig. 2).

Experimental

The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation of a solution in CH2Cl2 gave single crystals suitable for X-ray analysis.

Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.98 Å, Uiso = 1.5Ueq(C) for the H atoms of the methyl groups.

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
Crystal packing of the title compound with hydrogen bonds shown as dashed lines. H atoms not involved in intermolecular interactions have been omitted for clarity.

Crystal data

C11H18N4O2F(000) = 512
Mr = 238.29Dx = 1.258 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3964 reflections
a = 13.5607 (7) Åθ = 3.1–28.1°
b = 7.7868 (4) ŵ = 0.09 mm1
c = 13.1323 (7) ÅT = 173 K
β = 114.907 (3)°Block, colorless
V = 1257.72 (11) Å30.29 × 0.25 × 0.11 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer3093 independent reflections
Radiation source: fine-focus sealed tube2390 reflections with I > 2σ(I)
graphiteRint = 0.031
Detector resolution: 10.0 pixels mm-1θmax = 28.3°, θmin = 1.7°
[var phi] and ω scansh = −17→18
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)k = −10→10
Tmin = 0.975, Tmax = 0.990l = −15→17
11979 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0757P)2 + 0.3375P] where P = (Fo2 + 2Fc2)/3
3093 reflections(Δ/σ)max = 0.001
160 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = −0.26 e Å3

Special details

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)

xyzUiso*/Ueq
O10.24024 (9)0.53521 (13)0.53519 (9)0.0354 (3)
O20.32335 (9)0.74531 (13)0.48118 (9)0.0370 (3)
N10.14628 (10)0.43992 (15)0.35622 (10)0.0312 (3)
N20.22281 (10)0.23436 (15)0.27478 (10)0.0294 (3)
N30.05012 (11)0.34353 (18)0.17468 (11)0.0402 (3)
N40.27470 (12)0.78741 (17)0.62525 (11)0.0385 (3)
C10.23902 (12)0.43542 (17)0.44613 (12)0.0293 (3)
C20.14204 (11)0.33785 (18)0.27129 (12)0.0296 (3)
C30.31494 (11)0.23573 (17)0.36835 (12)0.0287 (3)
C40.32953 (12)0.33878 (18)0.46103 (12)0.0302 (3)
C50.40316 (13)0.1190 (2)0.36877 (15)0.0417 (4)
H5A0.38720.08460.29160.063*
H5B0.40680.01660.41370.063*
H5C0.47300.17940.40130.063*
C60.43355 (14)0.3450 (2)0.56746 (13)0.0416 (4)
H6A0.42650.27070.62430.062*
H6B0.44740.46320.59550.062*
H6C0.49420.30490.55160.062*
C70.03605 (14)0.2330 (2)0.08023 (14)0.0444 (4)
H7A−0.00650.13160.08110.067*
H7B0.10740.19670.08610.067*
H7C−0.00230.29610.00990.067*
C8−0.04504 (14)0.4381 (3)0.16659 (16)0.0493 (4)
H8A−0.02340.52480.22620.074*
H8B−0.09720.35870.17490.074*
H8C−0.07880.49480.09320.074*
C90.28291 (11)0.69672 (18)0.54274 (11)0.0292 (3)
C100.22081 (15)0.7283 (2)0.69413 (14)0.0451 (4)
H10A0.20930.60390.68510.068*
H10B0.15050.78630.67050.068*
H10C0.26640.75480.77310.068*
C110.31354 (17)0.9642 (2)0.64121 (17)0.0536 (5)
H11A0.35350.98570.59530.080*
H11B0.36180.98300.72050.080*
H11C0.25141.04270.61850.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0517 (7)0.0303 (5)0.0323 (6)−0.0064 (4)0.0258 (5)−0.0063 (4)
O20.0458 (6)0.0318 (5)0.0394 (6)−0.0063 (4)0.0236 (5)−0.0044 (4)
N10.0350 (6)0.0273 (6)0.0343 (7)−0.0024 (5)0.0174 (5)−0.0023 (5)
N20.0350 (6)0.0252 (6)0.0289 (6)−0.0022 (5)0.0145 (5)−0.0024 (5)
N30.0341 (7)0.0422 (7)0.0370 (7)−0.0009 (6)0.0078 (6)−0.0073 (6)
N40.0487 (8)0.0343 (7)0.0350 (7)0.0003 (6)0.0200 (6)−0.0089 (5)
C10.0415 (8)0.0230 (6)0.0286 (7)−0.0063 (5)0.0199 (6)−0.0022 (5)
C20.0327 (7)0.0258 (6)0.0315 (7)−0.0052 (5)0.0148 (6)−0.0007 (5)
C30.0348 (7)0.0228 (6)0.0301 (7)−0.0024 (5)0.0151 (6)0.0010 (5)
C40.0371 (7)0.0259 (7)0.0275 (7)−0.0026 (5)0.0135 (6)−0.0004 (5)
C50.0403 (8)0.0411 (9)0.0411 (9)0.0074 (7)0.0146 (7)−0.0054 (7)
C60.0461 (9)0.0405 (8)0.0305 (8)0.0011 (7)0.0088 (7)−0.0018 (7)
C70.0426 (9)0.0520 (10)0.0332 (8)−0.0093 (8)0.0107 (7)−0.0084 (7)
C80.0358 (9)0.0564 (11)0.0496 (10)0.0051 (7)0.0120 (8)0.0006 (8)
C90.0311 (7)0.0275 (7)0.0259 (7)0.0024 (5)0.0090 (6)−0.0015 (5)
C100.0606 (11)0.0501 (10)0.0299 (8)0.0136 (8)0.0242 (8)−0.0006 (7)
C110.0651 (12)0.0372 (9)0.0581 (11)−0.0025 (8)0.0257 (10)−0.0191 (8)

Geometric parameters (Å, °)

O1—C91.3704 (18)C5—H5B0.9800
O1—C11.3985 (16)C5—H5C0.9800
O2—C91.2128 (18)C6—H6A0.9800
N1—C11.3138 (19)C6—H6B0.9800
N1—C21.3510 (18)C6—H6C0.9800
N2—C31.3333 (19)C7—H7A0.9800
N2—C21.3449 (19)C7—H7B0.9800
N3—C21.3540 (19)C7—H7C0.9800
N3—C81.450 (2)C8—H8A0.9800
N3—C71.455 (2)C8—H8B0.9800
N4—C91.3367 (19)C8—H8C0.9800
N4—C101.456 (2)C10—H10A0.9800
N4—C111.457 (2)C10—H10B0.9800
C1—C41.381 (2)C10—H10C0.9800
C3—C41.401 (2)C11—H11A0.9800
C3—C51.501 (2)C11—H11B0.9800
C4—C61.512 (2)C11—H11C0.9800
C5—H5A0.9800
C9—O1—C1115.24 (11)C4—C6—H6C109.5
C1—N1—C2114.71 (12)H6A—C6—H6C109.5
C3—N2—C2117.40 (12)H6B—C6—H6C109.5
C2—N3—C8121.66 (14)N3—C7—H7A109.5
C2—N3—C7121.19 (13)N3—C7—H7B109.5
C8—N3—C7116.42 (13)H7A—C7—H7B109.5
C9—N4—C10124.84 (14)N3—C7—H7C109.5
C9—N4—C11117.86 (14)H7A—C7—H7C109.5
C10—N4—C11117.05 (14)H7B—C7—H7C109.5
N1—C1—C4126.79 (13)N3—C8—H8A109.5
N1—C1—O1113.98 (13)N3—C8—H8B109.5
C4—C1—O1119.16 (13)H8A—C8—H8B109.5
N2—C2—N1124.99 (13)N3—C8—H8C109.5
N2—C2—N3117.82 (13)H8A—C8—H8C109.5
N1—C2—N3117.17 (13)H8B—C8—H8C109.5
N2—C3—C4122.69 (13)O2—C9—N4126.22 (14)
N2—C3—C5115.77 (13)O2—C9—O1122.26 (12)
C4—C3—C5121.55 (13)N4—C9—O1111.52 (13)
C1—C4—C3113.39 (13)N4—C10—H10A109.5
C1—C4—C6122.76 (13)N4—C10—H10B109.5
C3—C4—C6123.85 (14)H10A—C10—H10B109.5
C3—C5—H5A109.5N4—C10—H10C109.5
C3—C5—H5B109.5H10A—C10—H10C109.5
H5A—C5—H5B109.5H10B—C10—H10C109.5
C3—C5—H5C109.5N4—C11—H11A109.5
H5A—C5—H5C109.5N4—C11—H11B109.5
H5B—C5—H5C109.5H11A—C11—H11B109.5
C4—C6—H6A109.5N4—C11—H11C109.5
C4—C6—H6B109.5H11A—C11—H11C109.5
H6A—C6—H6B109.5H11B—C11—H11C109.5
C2—N1—C1—C40.0 (2)N1—C1—C4—C3−1.1 (2)
C2—N1—C1—O1−177.02 (11)O1—C1—C4—C3175.74 (11)
C9—O1—C1—N1−95.73 (15)N1—C1—C4—C6178.91 (14)
C9—O1—C1—C487.02 (16)O1—C1—C4—C6−4.2 (2)
C3—N2—C2—N1−1.6 (2)N2—C3—C4—C11.0 (2)
C3—N2—C2—N3176.89 (13)C5—C3—C4—C1−178.95 (13)
C1—N1—C2—N21.5 (2)N2—C3—C4—C6−179.06 (14)
C1—N1—C2—N3−177.02 (13)C5—C3—C4—C61.0 (2)
C8—N3—C2—N2173.88 (15)C10—N4—C9—O2176.80 (15)
C7—N3—C2—N24.0 (2)C11—N4—C9—O22.7 (2)
C8—N3—C2—N1−7.5 (2)C10—N4—C9—O1−3.9 (2)
C7—N3—C2—N1−177.33 (13)C11—N4—C9—O1−178.05 (14)
C2—N2—C3—C40.3 (2)C1—O1—C9—O2−4.7 (2)
C2—N2—C3—C5−179.80 (13)C1—O1—C9—N4175.97 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C5—H5C···O2i0.982.603.549 (2)163
C10—H10C···O2ii0.982.513.431 (2)157

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ5033).

References

  • Brandenburg, K. (1998). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2006). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Dalpozzo, R., Nino, A. D., Maiuolo, L., Procopio, A., Munno, G. D. & Sindona, G. (2001). Tetrahedron, 57, 4035–4038.
  • Madre, M., Petrova, M. & Belyakov, S. (2008). Synthesis, 19, 3053–3060.
  • Pirisi, F. M., Cabras, P., Garau, V. L., Melis, M. & Secchi, E. (1996). J. Agric. Food Chem.44, 2417–2422.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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