N-(2,6-Dimethylphenyl)-N′-propanoyl­thiourea

Abstract

In the title compound, C₁₂H₁₆N₂OS, an intra­molecular N—H⋯O hydrogen bond forms an S(6) ring motif. The propionyl­thio­urea group is approximately planar [with a maximum deviation of 0.135 (2) Å] and forms a dihedral angle of 83.39 (7)° with the benzene ring. In the crystal, mol­ecules are linked by pairs of N—H⋯S hydrogen bonds, forming centrosymmetric dimers and generating R ² ₂(8) ring motifs.

Related literature  

For related structures, see: Yamin & Othman (2008 ▶); Usman et al. (2002 ▶); Sultana et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental  

Crystal data  

• C₁₂H₁₆N₂OS

• M _r = 236.33

• Triclinic,

• a = 7.8069 (3) Å

• b = 8.4770 (3) Å

• c = 10.1426 (3) Å

• α = 103.782 (2)°

• β = 90.342 (2)°

• γ = 109.928 (2)°

• V = 610.07 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 0.25 mm⁻¹

• T = 100 K

• 0.23 × 0.18 × 0.06 mm

Data collection  

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T _min = 0.946, T _max = 0.985

• 6225 measured reflections

• 3211 independent reflections

• 2664 reflections with I > 2σ(I)

• R _int = 0.025

Refinement  

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.100

• S = 1.00

• 3211 reflections

• 156 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.40 e Å⁻³

• Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2009) ▶; cell refinement: SAINT (Bruker, 2009) ▶; data reduction: SAINT ▶; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812009233/lh5423Isup3.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
N2—H1N2⋯O1	0.85 (2)	1.98 (2)	2.6661 (19)	138 (2)
N1—H1N1⋯S1i	0.87 (2)	2.54 (2)	3.3765 (15)	162.0 (16)

Symmetry code: (i) .

supplementary crystallographic information

Comment

The title compound is analogous to N-propionylthiourea, (Yamin & Othman, 2008) except that the hydogen atom at the N terminal atom is replaced by a 2,6-dimethylphenyl group.

In the molecular structure (Fig. 1), an intramolecular N2—H1N2···O1 hydrogen bond (Table 1) generates an S(6) ring motif (Bernstein et al., 1995). The propionylthiourea group (S1/N1/N2/O1/C1-C4) is approximately planar (with a maximum deviation of 0.135 (2)Å for C1) and forms a dihedral angle of 83.39 (7)° with the benzene ring (C5-C10). The bond lengths and angles are within normal ranges and are comparable to related structures (Usman et al., 2002; Sultana et al., 2007).

The crystal packing is shown in Fig. 2. The molecules are linked by pairs of intermolecular N1—H1N1···S1ⁱ hydrogen bonds (Table 1) to form dimers, generating R²₂(8) ring motifs (Bernstein et al., 1995).

Experimental

To a stirring acetone solution (75 ml) of propionyl chloride (2.42 g, 0.03 mol) and ammonium thiocyanate (2.0 g, 0.03 mol), 2,6-dimethylaniline (3.64 g, 0.03 mol) in 40 ml of acetone was added dropwise. The mixture was refluxed reflux for 1 h. The resulting solution was poured into a beaker containing ice blocks. The white precipitate was filtered off and washed with distilled water and cold ethanol before being dried under vacuum. Good quality crystals were obtained by recrystallization from DMSO.

Refinement

N-bound H atoms were located from the difference map and refined freely, [N–H = 0.85 (2) and 0.87 (2) Å]. The remaining H atoms were positioned geometrically [C–H = 0.95-0.99 Å] and refined using a riding model with U_iso(H) = 1.2 or 1.5 U_eq(C). A rotating group model was applied to the methyl groups.

Figures

Fig. 1.

The molecular structure of the title compound with 30% probability displacement ellipsoids.

Fig. 2.

The crystal packing of the title compound. The H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

Crystal data

C12H16N2OS	Z = 2
Mr = 236.33	F(000) = 252
Triclinic, P1	Dx = 1.287 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8069 (3) Å	Cell parameters from 2626 reflections
b = 8.4770 (3) Å	θ = 2.8–30.1°
c = 10.1426 (3) Å	µ = 0.25 mm−1
α = 103.782 (2)°	T = 100 K
β = 90.342 (2)°	Plate, colourless
γ = 109.928 (2)°	0.23 × 0.18 × 0.06 mm
V = 610.07 (4) Å3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	3211 independent reflections
Radiation source: fine-focus sealed tube	2664 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 29.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→5
Tmin = 0.946, Tmax = 0.985	k = −11→11
6225 measured reflections	l = −13→13

Refinement

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0263P)2 + 0.6043P] where P = (Fo2 + 2Fc2)/3
3211 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.29160 (6)	0.31937 (5)	0.83787 (4)	0.02011 (12)
N1	0.48198 (18)	0.65151 (17)	0.86755 (14)	0.0150 (3)
H1N1	0.537 (3)	0.634 (2)	0.934 (2)	0.018 (5)*
N2	0.23611 (18)	0.53214 (18)	0.70040 (14)	0.0159 (3)
H1N2	0.269 (3)	0.634 (3)	0.690 (2)	0.032 (6)*
O1	0.45702 (17)	0.86360 (15)	0.77368 (12)	0.0218 (3)
C1	0.7853 (2)	1.1145 (2)	0.90542 (19)	0.0243 (4)
H1A	0.8956	1.1898	0.9662	0.036*
H1B	0.6927	1.1697	0.9161	0.036*
H1C	0.8158	1.0959	0.8107	0.036*
C2	0.7107 (2)	0.9413 (2)	0.94142 (17)	0.0184 (3)
H2A	0.8052	0.8867	0.9313	0.022*
H2B	0.6838	0.9612	1.0380	0.022*
C3	0.5388 (2)	0.8192 (2)	0.85224 (16)	0.0153 (3)
C4	0.3335 (2)	0.5086 (2)	0.79737 (16)	0.0152 (3)
C5	0.0741 (2)	0.3969 (2)	0.62443 (16)	0.0153 (3)
C6	0.0916 (2)	0.2808 (2)	0.50703 (17)	0.0187 (3)
C7	−0.0683 (3)	0.1516 (2)	0.43662 (18)	0.0229 (4)
H7A	−0.0605	0.0696	0.3569	0.027*
C8	−0.2383 (2)	0.1413 (2)	0.48146 (19)	0.0251 (4)
H8A	−0.3457	0.0529	0.4322	0.030*
C9	−0.2519 (2)	0.2590 (2)	0.59732 (19)	0.0239 (4)
H9A	−0.3691	0.2508	0.6270	0.029*
C10	−0.0956 (2)	0.3906 (2)	0.67187 (17)	0.0188 (3)
C11	−0.1090 (3)	0.5156 (2)	0.79955 (19)	0.0254 (4)
H11A	−0.0389	0.5064	0.8760	0.038*
H11B	−0.2376	0.4883	0.8180	0.038*
H11C	−0.0594	0.6340	0.7884	0.038*
C12	0.2756 (3)	0.2913 (2)	0.45815 (19)	0.0252 (4)
H12A	0.3586	0.2987	0.5341	0.038*
H12B	0.3259	0.3946	0.4234	0.038*
H12C	0.2622	0.1874	0.3852	0.038*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0208 (2)	0.01442 (19)	0.0210 (2)	0.00006 (15)	−0.00808 (16)	0.00615 (15)
N1	0.0141 (6)	0.0134 (6)	0.0152 (6)	0.0021 (5)	−0.0051 (5)	0.0037 (5)
N2	0.0152 (7)	0.0128 (6)	0.0165 (7)	0.0013 (5)	−0.0038 (5)	0.0033 (5)
O1	0.0238 (6)	0.0167 (6)	0.0229 (6)	0.0041 (5)	−0.0069 (5)	0.0061 (5)
C1	0.0232 (9)	0.0169 (8)	0.0260 (9)	−0.0010 (7)	−0.0023 (7)	0.0052 (7)
C2	0.0179 (8)	0.0140 (7)	0.0199 (8)	0.0028 (6)	−0.0038 (6)	0.0025 (6)
C3	0.0150 (7)	0.0145 (7)	0.0141 (7)	0.0037 (6)	0.0009 (6)	0.0019 (5)
C4	0.0135 (7)	0.0154 (7)	0.0142 (7)	0.0032 (6)	0.0002 (6)	0.0019 (6)
C5	0.0152 (7)	0.0131 (7)	0.0153 (7)	0.0019 (6)	−0.0044 (6)	0.0043 (6)
C6	0.0197 (8)	0.0171 (8)	0.0179 (8)	0.0044 (6)	−0.0033 (6)	0.0051 (6)
C7	0.0283 (9)	0.0165 (8)	0.0179 (8)	0.0020 (7)	−0.0081 (7)	0.0025 (6)
C8	0.0212 (9)	0.0211 (9)	0.0260 (9)	−0.0028 (7)	−0.0126 (7)	0.0091 (7)
C9	0.0161 (8)	0.0267 (9)	0.0289 (9)	0.0033 (7)	−0.0035 (7)	0.0134 (7)
C10	0.0192 (8)	0.0195 (8)	0.0191 (8)	0.0070 (6)	−0.0011 (6)	0.0072 (6)
C11	0.0220 (9)	0.0285 (9)	0.0275 (9)	0.0114 (7)	0.0038 (7)	0.0069 (7)
C12	0.0263 (9)	0.0268 (9)	0.0207 (9)	0.0096 (7)	0.0026 (7)	0.0024 (7)

Geometric parameters (Å, º)

S1—C4	1.6756 (16)	C5—C10	1.400 (2)
N1—C3	1.385 (2)	C6—C7	1.397 (2)
N1—C4	1.393 (2)	C6—C12	1.503 (2)
N1—H1N1	0.87 (2)	C7—C8	1.386 (3)
N2—C4	1.331 (2)	C7—H7A	0.9500
N2—C5	1.445 (2)	C8—C9	1.380 (3)
N2—H1N2	0.85 (2)	C8—H8A	0.9500
O1—C3	1.219 (2)	C9—C10	1.401 (2)
C1—C2	1.517 (2)	C9—H9A	0.9500
C1—H1A	0.9800	C10—C11	1.495 (2)
C1—H1B	0.9800	C11—H11A	0.9800
C1—H1C	0.9800	C11—H11B	0.9800
C2—C3	1.511 (2)	C11—H11C	0.9800
C2—H2A	0.9900	C12—H12A	0.9800
C2—H2B	0.9900	C12—H12B	0.9800
C5—C6	1.393 (2)	C12—H12C	0.9800
C3—N1—C4	127.85 (14)	C5—C6—C7	117.67 (16)
C3—N1—H1N1	117.2 (13)	C5—C6—C12	121.57 (15)
C4—N1—H1N1	114.7 (13)	C7—C6—C12	120.75 (16)
C4—N2—C5	122.62 (13)	C8—C7—C6	120.93 (17)
C4—N2—H1N2	116.3 (15)	C8—C7—H7A	119.5
C5—N2—H1N2	120.9 (15)	C6—C7—H7A	119.5
C2—C1—H1A	109.5	C9—C8—C7	120.23 (16)
C2—C1—H1B	109.5	C9—C8—H8A	119.9
H1A—C1—H1B	109.5	C7—C8—H8A	119.9
C2—C1—H1C	109.5	C8—C9—C10	121.04 (17)
H1A—C1—H1C	109.5	C8—C9—H9A	119.5
H1B—C1—H1C	109.5	C10—C9—H9A	119.5
C3—C2—C1	112.25 (14)	C5—C10—C9	117.38 (16)
C3—C2—H2A	109.2	C5—C10—C11	121.28 (15)
C1—C2—H2A	109.2	C9—C10—C11	121.31 (16)
C3—C2—H2B	109.2	C10—C11—H11A	109.5
C1—C2—H2B	109.2	C10—C11—H11B	109.5
H2A—C2—H2B	107.9	H11A—C11—H11B	109.5
O1—C3—N1	122.77 (15)	C10—C11—H11C	109.5
O1—C3—C2	123.23 (14)	H11A—C11—H11C	109.5
N1—C3—C2	114.00 (14)	H11B—C11—H11C	109.5
N2—C4—N1	117.11 (14)	C6—C12—H12A	109.5
N2—C4—S1	124.53 (12)	C6—C12—H12B	109.5
N1—C4—S1	118.36 (12)	H12A—C12—H12B	109.5
C6—C5—C10	122.74 (15)	C6—C12—H12C	109.5
C6—C5—N2	119.40 (14)	H12A—C12—H12C	109.5
C10—C5—N2	117.85 (15)	H12B—C12—H12C	109.5
C4—N1—C3—O1	2.3 (3)	C10—C5—C6—C12	179.71 (15)
C4—N1—C3—C2	−177.72 (15)	N2—C5—C6—C12	0.8 (2)
C1—C2—C3—O1	−9.3 (2)	C5—C6—C7—C8	0.9 (2)
C1—C2—C3—N1	170.72 (14)	C12—C6—C7—C8	179.91 (16)
C5—N2—C4—N1	−177.10 (14)	C6—C7—C8—C9	−0.2 (3)
C5—N2—C4—S1	4.1 (2)	C7—C8—C9—C10	−0.1 (3)
C3—N1—C4—N2	2.4 (2)	C6—C5—C10—C9	1.0 (2)
C3—N1—C4—S1	−178.77 (13)	N2—C5—C10—C9	179.92 (14)
C4—N2—C5—C6	−87.4 (2)	C6—C5—C10—C11	179.02 (15)
C4—N2—C5—C10	93.64 (19)	N2—C5—C10—C11	−2.0 (2)
C10—C5—C6—C7	−1.2 (2)	C8—C9—C10—C5	−0.3 (2)
N2—C5—C6—C7	179.82 (14)	C8—C9—C10—C11	−178.34 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1	0.85 (2)	1.98 (2)	2.6661 (19)	138 (2)
N1—H1N1···S1i	0.87 (2)	2.54 (2)	3.3765 (15)	162.0 (16)

Symmetry code: (i) −x+1, −y+1, −z+2.