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Acta Cryst. (2007). E63, o3667    [ doi:10.1107/S1600536807036690 ]

1-(2,2-Dimethylcyclopropylcarbonyl)-3-(2-pyridyl)thiourea

J. Wang, L. Tian and S.-Y. Liu

Abstract top

In the molecule of the title compound, C12H15N3OS, an intramolecular N-H...O hydrogen bond causes the formation of a planar six-membered ring (A). Dihedral angles between this and the cyclopropane (B) and pyridine (C) rings are: A/B = 79.14 (3)°, A/C = 14.60 (2)° and B/C = 83.45 (3)°. In the crystal structure, intermolecular N-H...N hydrogen bonds link the molecules.

Comment top

Cyclopropane derivatives have several biological activities. 2,2-Dichloro-3,3 -dimethylcyclopropanecarboxylic acid is an effective inducer against the rice blast fungus (Langcake et al., 1983). 1-Aminocyclopropane-1-carboxylic acid (ACC) is an intermediate in the biosynthesis of the ripening hormone ethylene (Adams & Yang, 1979), a component of bacterial phytotoxines, and azetidine-2 -carboxylic acid (Nadler et al., 1988). Thus, it is very important to synthesize other new compounds containing cyclopropane, and study their biological activities. Acyl thiourea derivatives have many biological activities, for example, they have been used as bactericides, fungicides and insecticides in many plants (Kamala & Rao, 1989). A pyridine ring is often used as an active component in pesticide discovery (Elbert et al., 2000). The title compound, (I), contains all these three active parts and may show some insecticidal activity. It was characterized by 1H NMR and elemental analysis, and we report herein its crystal structure.

In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular N—H···O hydrogen bond (Table 1) causes to the formation of a six-membered planar ring A (H2A/N2/C6/N3/C7/O1). Rings B (C8—C10) and C (N1/C1—C5) are, of course, planar and the dihedral angles between them are A/B = 79.14 (3)°, A/C = 14.60 (2)° and B/C = 83.45 (3)°.

In the crystal structure, intermolecular N—H····N hydrogen bonds (Table 1) link the molecules (Fig. 2). The intra- and intermolecular hydrogen bonds seem to be effective in the stabilization of the crystal structure.

Related literature top

For general background, see: Langcake et al. (1983); Adams & Yang (1979); Nadler et al. (1988); Kamala & Rao (1989); Elbert et al. (2000). For bond-length data, see: Allen et al. (1987).

Experimental top

To a solution of NaSCN (0.49 g, 6 mmol) in anhydrous acetonitrile (10 ml) was added dropwise a solution of 2,2-dimethylcycloprpopanecarbonyl chloride (0.60 g, 4.5 mmol) in anhyrous acetonitrile (3 ml) at room temperature. The reaction mixture was kept at room temperature for half an hour and then at 333 K for 3 h. The solution was cooled, filtered and concentrated to about 4 ml. The residue was added dropwise to a solution of 2-aminopyridine (0.42 g, 4.5 mmol) in anhydrous acetonitrile (8 ml) at room temperature. The rection mixture refluxed for 5 h, and then was concentrated. The residue was separated by silica gel chromatography to afford the title compound, (I). Yellow single crystals were grown from a solution of AcOEt-cyclohexane (1:4).

Refinement top

H atoms were positioned geometrically with N—H = 0.86 Å (for NH), C—H = 0.93, 0.98, 0.97 and 0.96 Å for aromatic, methine, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. The formation of the title compound.
1-(2,2-Dimethylcyclopropylcarbonyl)-3-(2-pyridyl)thiourea top
Crystal data top
C12H15N3OSDx = 1.236 Mg m−3
Mr = 249.33Melting point: 365 K
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3793 reflections
a = 13.785 (5) Åθ = 2.2–23.3º
b = 10.664 (4) ŵ = 0.23 mm−1
c = 18.233 (6) ÅT = 294 (2) K
V = 2680.2 (16) Å3Block, colorless
Z = 80.24 × 0.22 × 0.20 mm
F000 = 1056
Data collection top
Bruker SMART CCD area-detector
diffractometer		2371 independent reflections
Radiation source: fine-focus sealed tube1825 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 294(2) Kθmax = 25.0º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −16→15
Tmin = 0.737, Tmax = 0.950k = −12→10
13556 measured reflectionsl = −21→21
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.042  w = 1/[σ2(Fo2) + (0.0509P)2 + 1.1474P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.121(Δ/σ)max < 0.001
S = 1.06Δρmax = 0.49 e Å−3
2371 reflectionsΔρmin = −0.50 e Å−3
156 parametersExtinction correction: SHELXL97
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0045 (6)
Secondary atom site location: difference Fourier map
Crystal data top
C12H15N3OSV = 2680.2 (16) Å3
Mr = 249.33Z = 8
Orthorhombic, PbcaMo Kα
a = 13.785 (5) ŵ = 0.23 mm−1
b = 10.664 (4) ÅT = 294 (2) K
c = 18.233 (6) Å0.24 × 0.22 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2371 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		1825 reflections with I > 2σ(I)
Tmin = 0.737, Tmax = 0.950Rint = 0.024
13556 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042156 parameters
wR(F2) = 0.121H-atom parameters constrained
S = 1.06Δρmax = 0.49 e Å−3
2371 reflectionsΔρmin = −0.50 e Å−3
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.

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
xyzUiso*/Ueq
S10.20197 (6)0.31298 (7)0.39880 (4)0.0880 (3)
N10.06932 (13)0.68893 (15)0.47218 (10)0.0573 (5)
N20.17241 (13)0.52421 (15)0.47711 (9)0.0540 (4)
H2A0.19720.56950.51130.065*
N30.29367 (13)0.39256 (16)0.51506 (10)0.0562 (4)
H3A0.32870.32790.50560.067*
O10.28019 (13)0.55553 (14)0.59591 (9)0.0729 (5)
C10.03215 (16)0.5184 (2)0.39285 (12)0.0603 (6)
H10.04840.44010.37410.072*
C2−0.04982 (17)0.5802 (2)0.36940 (14)0.0669 (6)
H2−0.08980.54350.33430.080*
C3−0.07274 (17)0.6952 (2)0.39747 (13)0.0639 (6)
H3−0.12820.73780.38260.077*
C4−0.01104 (17)0.7452 (2)0.44817 (13)0.0637 (6)
H4−0.02600.82370.46720.076*
C50.08957 (14)0.57576 (17)0.44482 (11)0.0483 (5)
C60.22019 (15)0.41698 (19)0.46441 (11)0.0533 (5)
C70.31854 (17)0.45635 (19)0.57795 (13)0.0580 (5)
C80.39334 (18)0.3926 (2)0.62153 (13)0.0682 (6)
H80.43170.33020.59480.082*
C90.37782 (19)0.3640 (2)0.70296 (13)0.0662 (6)
C100.4473 (2)0.4617 (3)0.68099 (15)0.0853 (8)
H10A0.51580.44350.68690.102*
H10B0.42950.54830.69010.102*
C110.4160 (3)0.2389 (2)0.72840 (16)0.0987 (10)
H11A0.47920.22510.70800.148*
H11B0.37290.17360.71250.148*
H11C0.42000.23840.78100.148*
C120.2849 (2)0.4015 (3)0.73987 (16)0.0930 (9)
H12A0.29510.40650.79190.139*
H12B0.23580.34020.72960.139*
H12C0.26450.48180.72180.139*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.1028 (6)0.0876 (5)0.0736 (4)0.0359 (4)−0.0289 (4)−0.0302 (4)
N10.0604 (11)0.0481 (10)0.0633 (11)0.0035 (8)−0.0025 (9)0.0014 (8)
N20.0589 (11)0.0453 (9)0.0578 (10)0.0006 (8)−0.0089 (8)−0.0005 (8)
N30.0603 (11)0.0498 (9)0.0585 (10)0.0080 (8)−0.0079 (8)−0.0016 (8)
O10.0922 (12)0.0477 (9)0.0788 (11)0.0052 (8)−0.0285 (9)−0.0096 (8)
C10.0607 (13)0.0535 (12)0.0666 (14)0.0020 (10)−0.0064 (11)−0.0032 (10)
C20.0616 (14)0.0668 (14)0.0723 (15)0.0002 (11)−0.0125 (12)0.0005 (12)
C30.0530 (13)0.0641 (14)0.0746 (15)0.0041 (10)−0.0014 (11)0.0110 (12)
C40.0662 (14)0.0500 (12)0.0750 (14)0.0073 (11)0.0027 (12)0.0020 (11)
C50.0507 (11)0.0443 (10)0.0500 (11)−0.0022 (9)0.0036 (9)0.0079 (9)
C60.0575 (13)0.0521 (12)0.0503 (11)0.0018 (10)−0.0005 (9)0.0045 (9)
C70.0634 (13)0.0463 (12)0.0642 (13)−0.0039 (10)−0.0111 (10)0.0014 (10)
C80.0709 (15)0.0659 (14)0.0680 (14)0.0114 (12)−0.0183 (12)−0.0063 (11)
C90.0790 (17)0.0526 (12)0.0671 (14)0.0036 (11)−0.0261 (12)−0.0049 (11)
C100.0817 (18)0.0794 (17)0.0947 (19)−0.0100 (14)−0.0385 (15)0.0026 (15)
C110.140 (3)0.0620 (15)0.094 (2)0.0146 (17)−0.0489 (19)0.0006 (14)
C120.098 (2)0.108 (2)0.0722 (18)0.0091 (18)−0.0160 (15)0.0025 (16)
Geometric parameters (Å, °) top
S1—C61.651 (2)C4—H40.9300
N1—C41.334 (3)C7—C81.469 (3)
N1—C51.335 (2)C8—C101.507 (3)
N2—C61.340 (3)C8—H80.9800
N2—C51.397 (3)C9—C81.531 (3)
N2—H2A0.8600C9—C101.471 (4)
N3—C71.377 (3)C9—C111.507 (3)
N3—C61.395 (3)C9—C121.501 (4)
N3—H3A0.8600C10—H10A0.9700
O1—C71.227 (3)C10—H10B0.9700
C1—C21.376 (3)C11—H11A0.9600
C1—C51.378 (3)C11—H11B0.9600
C1—H10.9300C11—H11C0.9600
C2—H20.9300C12—H12A0.9600
C3—C41.365 (3)C12—H12B0.9600
C3—C21.366 (3)C12—H12C0.9600
C3—H30.9300
C4—N1—C5117.24 (19)C7—C8—C9121.3 (2)
C6—N2—C5131.66 (18)C10—C8—C957.90 (16)
C6—N2—H2A114.2C7—C8—H8115.1
C5—N2—H2A114.2C10—C8—H8115.1
C7—N3—C6129.78 (18)C9—C8—H8115.1
C7—N3—H3A115.1C10—C9—C12119.3 (2)
C6—N3—H3A115.1C10—C9—C11118.9 (2)
C2—C1—C5118.2 (2)C12—C9—C11113.3 (3)
C2—C1—H1120.9C10—C9—C860.25 (17)
C5—C1—H1120.9C12—C9—C8120.1 (2)
C3—C2—C1120.2 (2)C11—C9—C8115.2 (2)
C3—C2—H2119.9C9—C10—C861.85 (17)
C1—C2—H2119.9C9—C10—H10A117.6
C4—C3—C2117.4 (2)C8—C10—H10A117.6
C4—C3—H3121.3C9—C10—H10B117.6
C2—C3—H3121.3C8—C10—H10B117.6
N1—C4—C3124.4 (2)H10A—C10—H10B114.7
N1—C4—H4117.8C9—C11—H11A109.5
C3—C4—H4117.8C9—C11—H11B109.5
N1—C5—C1122.53 (19)H11A—C11—H11B109.5
N1—C5—N2111.65 (18)C9—C11—H11C109.5
C1—C5—N2125.78 (19)H11A—C11—H11C109.5
N2—C6—N3113.69 (17)H11B—C11—H11C109.5
N2—C6—S1128.60 (16)C9—C12—H12A109.5
N3—C6—S1117.70 (15)C9—C12—H12B109.5
O1—C7—N3122.8 (2)H12A—C12—H12B109.5
O1—C7—C8123.8 (2)C9—C12—H12C109.5
N3—C7—C8113.38 (19)H12A—C12—H12C109.5
C7—C8—C10120.7 (2)H12B—C12—H12C109.5
C5—N1—C4—C3−0.6 (3)C4—C3—C2—C10.7 (4)
C4—N1—C5—C11.3 (3)C2—C3—C4—N1−0.4 (4)
C4—N1—C5—N2−176.82 (18)O1—C7—C8—C10−16.7 (4)
C6—N2—C5—N1−176.9 (2)N3—C7—C8—C10164.6 (2)
C6—N2—C5—C15.1 (3)O1—C7—C8—C952.1 (3)
C5—N2—C6—N3−172.60 (19)N3—C7—C8—C9−126.7 (2)
C5—N2—C6—S16.5 (3)C7—C8—C10—C9109.9 (3)
C7—N3—C6—N25.6 (3)C10—C9—C8—C7−108.9 (3)
C7—N3—C6—S1−173.64 (18)C12—C9—C8—C7−0.2 (3)
C6—N3—C7—O1−5.6 (4)C11—C9—C8—C7140.9 (2)
C6—N3—C7—C8173.2 (2)C12—C9—C8—C10108.7 (3)
C5—C1—C2—C30.0 (3)C11—C9—C8—C10−110.3 (3)
C2—C1—C5—N1−1.0 (3)C12—C9—C10—C8−109.9 (2)
C2—C1—C5—N2176.8 (2)C11—C9—C10—C8104.2 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.861.932.648 (2)141
N3—H3A···N1i0.862.132.982 (3)170
Symmetry codes: (i) −x+1/2, y−1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.861.932.648 (2)141
N3—H3A···N1i0.862.132.982 (3)170
Symmetry codes: (i) −x+1/2, y−1/2, z.
Acknowledgements top

LT acknowledges financial support from the Doctor's Foundation of Tianjin Normal University (grant No. 5RL029).

references
References top

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