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

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.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.042
• wR factor = 0.121
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.737     0.950
            Tmin(prime) and Tmax expected:      0.945     0.955
            RR(prime) =      0.784
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.78
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C9

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C8     = ...          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = xU_eq(C,N), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Computing details

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

	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.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
	Fig. 3. The formation of the title compound.

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

Crystal data

C12H15N3OS	Dx = 1.236 Mg m^−3
Mr = 249.33	Melting point: 365 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3793 reflections
a = 13.785 (5) Å	θ = 2.2–23.3°
b = 10.664 (4) Å	µ = 0.23 mm^−1
c = 18.233 (6) Å	T = 294 K
V = 2680.2 (16) Å^3	Block, colorless
Z = 8	0.24 × 0.22 × 0.20 mm
F(000) = 1056

Data collection

Bruker SMART CCD area-detector diffractometer	2371 independent reflections
Radiation source: fine-focus sealed tube	1825 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −16→15
Tmin = 0.737, Tmax = 0.950	k = −12→10
13556 measured reflections	l = −21→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0509P)^2 + 1.1474P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2371 reflections	Δρmax = 0.49 e Å^−3
156 parameters	Δρmin = −0.50 e Å^−3
0 restraints	Extinction correction: SHELXL97
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0045 (6)

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.20197 (6)	0.31298 (7)	0.39880 (4)	0.0880 (3)
N1	0.06932 (13)	0.68893 (15)	0.47218 (10)	0.0573 (5)
N2	0.17241 (13)	0.52421 (15)	0.47711 (9)	0.0540 (4)
H2A	0.1972	0.5695	0.5113	0.065*
N3	0.29367 (13)	0.39256 (16)	0.51506 (10)	0.0562 (4)
H3A	0.3287	0.3279	0.5056	0.067*
O1	0.28019 (13)	0.55553 (14)	0.59591 (9)	0.0729 (5)
C1	0.03215 (16)	0.5184 (2)	0.39285 (12)	0.0603 (6)
H1	0.0484	0.4401	0.3741	0.072*
C2	−0.04982 (17)	0.5802 (2)	0.36940 (14)	0.0669 (6)
H2	−0.0898	0.5435	0.3343	0.080*
C3	−0.07274 (17)	0.6952 (2)	0.39747 (13)	0.0639 (6)
H3	−0.1282	0.7378	0.3826	0.077*
C4	−0.01104 (17)	0.7452 (2)	0.44817 (13)	0.0637 (6)
H4	−0.0260	0.8237	0.4672	0.076*
C5	0.08957 (14)	0.57576 (17)	0.44482 (11)	0.0483 (5)
C6	0.22019 (15)	0.41698 (19)	0.46441 (11)	0.0533 (5)
C7	0.31854 (17)	0.45635 (19)	0.57795 (13)	0.0580 (5)
C8	0.39334 (18)	0.3926 (2)	0.62153 (13)	0.0682 (6)
H8	0.4317	0.3302	0.5948	0.082*
C9	0.37782 (19)	0.3640 (2)	0.70296 (13)	0.0662 (6)
C10	0.4473 (2)	0.4617 (3)	0.68099 (15)	0.0853 (8)
H10A	0.5158	0.4435	0.6869	0.102*
H10B	0.4295	0.5483	0.6901	0.102*
C11	0.4160 (3)	0.2389 (2)	0.72840 (16)	0.0987 (10)
H11A	0.4792	0.2251	0.7080	0.148*
H11B	0.3729	0.1736	0.7125	0.148*
H11C	0.4200	0.2384	0.7810	0.148*
C12	0.2849 (2)	0.4015 (3)	0.73987 (16)	0.0930 (9)
H12A	0.2951	0.4065	0.7919	0.139*
H12B	0.2358	0.3402	0.7296	0.139*
H12C	0.2645	0.4818	0.7218	0.139*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.1028 (6)	0.0876 (5)	0.0736 (4)	0.0359 (4)	−0.0289 (4)	−0.0302 (4)
N1	0.0604 (11)	0.0481 (10)	0.0633 (11)	0.0035 (8)	−0.0025 (9)	0.0014 (8)
N2	0.0589 (11)	0.0453 (9)	0.0578 (10)	0.0006 (8)	−0.0089 (8)	−0.0005 (8)
N3	0.0603 (11)	0.0498 (9)	0.0585 (10)	0.0080 (8)	−0.0079 (8)	−0.0016 (8)
O1	0.0922 (12)	0.0477 (9)	0.0788 (11)	0.0052 (8)	−0.0285 (9)	−0.0096 (8)
C1	0.0607 (13)	0.0535 (12)	0.0666 (14)	0.0020 (10)	−0.0064 (11)	−0.0032 (10)
C2	0.0616 (14)	0.0668 (14)	0.0723 (15)	0.0002 (11)	−0.0125 (12)	0.0005 (12)
C3	0.0530 (13)	0.0641 (14)	0.0746 (15)	0.0041 (10)	−0.0014 (11)	0.0110 (12)
C4	0.0662 (14)	0.0500 (12)	0.0750 (14)	0.0073 (11)	0.0027 (12)	0.0020 (11)
C5	0.0507 (11)	0.0443 (10)	0.0500 (11)	−0.0022 (9)	0.0036 (9)	0.0079 (9)
C6	0.0575 (13)	0.0521 (12)	0.0503 (11)	0.0018 (10)	−0.0005 (9)	0.0045 (9)
C7	0.0634 (13)	0.0463 (12)	0.0642 (13)	−0.0039 (10)	−0.0111 (10)	0.0014 (10)
C8	0.0709 (15)	0.0659 (14)	0.0680 (14)	0.0114 (12)	−0.0183 (12)	−0.0063 (11)
C9	0.0790 (17)	0.0526 (12)	0.0671 (14)	0.0036 (11)	−0.0261 (12)	−0.0049 (11)
C10	0.0817 (18)	0.0794 (17)	0.0947 (19)	−0.0100 (14)	−0.0385 (15)	0.0026 (15)
C11	0.140 (3)	0.0620 (15)	0.094 (2)	0.0146 (17)	−0.0489 (19)	0.0006 (14)
C12	0.098 (2)	0.108 (2)	0.0722 (18)	0.0091 (18)	−0.0160 (15)	0.0025 (16)

Geometric parameters (Å, º)

S1—C6	1.651 (2)	C4—H4	0.9300
N1—C4	1.334 (3)	C7—C8	1.469 (3)
N1—C5	1.335 (2)	C8—C10	1.507 (3)
N2—C6	1.340 (3)	C8—H8	0.9800
N2—C5	1.397 (3)	C9—C8	1.531 (3)
N2—H2A	0.8600	C9—C10	1.471 (4)
N3—C7	1.377 (3)	C9—C11	1.507 (3)
N3—C6	1.395 (3)	C9—C12	1.501 (4)
N3—H3A	0.8600	C10—H10A	0.9700
O1—C7	1.227 (3)	C10—H10B	0.9700
C1—C2	1.376 (3)	C11—H11A	0.9600
C1—C5	1.378 (3)	C11—H11B	0.9600
C1—H1	0.9300	C11—H11C	0.9600
C2—H2	0.9300	C12—H12A	0.9600
C3—C4	1.365 (3)	C12—H12B	0.9600
C3—C2	1.366 (3)	C12—H12C	0.9600
C3—H3	0.9300
C4—N1—C5	117.24 (19)	C7—C8—C9	121.3 (2)
C6—N2—C5	131.66 (18)	C10—C8—C9	57.90 (16)
C6—N2—H2A	114.2	C7—C8—H8	115.1
C5—N2—H2A	114.2	C10—C8—H8	115.1
C7—N3—C6	129.78 (18)	C9—C8—H8	115.1
C7—N3—H3A	115.1	C10—C9—C12	119.3 (2)
C6—N3—H3A	115.1	C10—C9—C11	118.9 (2)
C2—C1—C5	118.2 (2)	C12—C9—C11	113.3 (3)
C2—C1—H1	120.9	C10—C9—C8	60.25 (17)
C5—C1—H1	120.9	C12—C9—C8	120.1 (2)
C3—C2—C1	120.2 (2)	C11—C9—C8	115.2 (2)
C3—C2—H2	119.9	C9—C10—C8	61.85 (17)
C1—C2—H2	119.9	C9—C10—H10A	117.6
C4—C3—C2	117.4 (2)	C8—C10—H10A	117.6
C4—C3—H3	121.3	C9—C10—H10B	117.6
C2—C3—H3	121.3	C8—C10—H10B	117.6
N1—C4—C3	124.4 (2)	H10A—C10—H10B	114.7
N1—C4—H4	117.8	C9—C11—H11A	109.5
C3—C4—H4	117.8	C9—C11—H11B	109.5
N1—C5—C1	122.53 (19)	H11A—C11—H11B	109.5
N1—C5—N2	111.65 (18)	C9—C11—H11C	109.5
C1—C5—N2	125.78 (19)	H11A—C11—H11C	109.5
N2—C6—N3	113.69 (17)	H11B—C11—H11C	109.5
N2—C6—S1	128.60 (16)	C9—C12—H12A	109.5
N3—C6—S1	117.70 (15)	C9—C12—H12B	109.5
O1—C7—N3	122.8 (2)	H12A—C12—H12B	109.5
O1—C7—C8	123.8 (2)	C9—C12—H12C	109.5
N3—C7—C8	113.38 (19)	H12A—C12—H12C	109.5
C7—C8—C10	120.7 (2)	H12B—C12—H12C	109.5
C5—N1—C4—C3	−0.6 (3)	C4—C3—C2—C1	0.7 (4)
C4—N1—C5—C1	1.3 (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—C10	164.6 (2)
C6—N2—C5—C1	5.1 (3)	O1—C7—C8—C9	52.1 (3)
C5—N2—C6—N3	−172.60 (19)	N3—C7—C8—C9	−126.7 (2)
C5—N2—C6—S1	6.5 (3)	C7—C8—C10—C9	109.9 (3)
C7—N3—C6—N2	5.6 (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—C7	140.9 (2)
C6—N3—C7—C8	173.2 (2)	C12—C9—C8—C10	108.7 (3)
C5—C1—C2—C3	0.0 (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—N2	176.8 (2)	C11—C9—C10—C8	104.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.93	2.648 (2)	141
N3—H3A···N1^i	0.86	2.13	2.982 (3)	170

Symmetry code: (i) −x+1/2, y−1/2, z.