N-(2,2-Di­methyl­propano­yl)-N′-(2-meth­­oxy­phen­yl)thio­urea

In the title compound, C₁₃H₁₈N₂O₂S, the carbonyl­thio­urea fragment is nearly planar with an r.m.s. deviation of 0.0096 Å. The dihedral angle between carbonyl­thio­urea group and the benzene ring is 19.16 (16)°. There are two intra­molecular N—H⋯O hydrogen bonds, which lead to two pseudo-six-membered rings. Weak intra­molecular C—H⋯S hydrogen bonding also occurs.

Related literature

For related structures, see: Saeed & Flörke (2007); Yusof et al. (2008); Shoukat et al. (2007). For standard bond lengths, see: Allen et al. (1987).

Experimental

Crystal data

• C₁₃H₁₈N₂O₂S

• M_r = 266.35

• Orthorhombic, P 2₁ 2₁ 2₁

• a = 5.9181 (10) Å

• b = 13.492 (2) Å

• c = 17.592 (3) Å

• V = 1404.7 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.23 mm⁻¹

• T = 273 K

• 0.50 × 0.14 × 0.09 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2000) T_min = 0.895, T_max = 0.980

• 8711 measured reflections

• 2763 independent reflections

• 2227 reflections with I > 2σ(I)

• R_int = 0.045

Refinement

• R[F² > 2σ(F²)] = 0.068

• wR(F²) = 0.147

• S = 1.13

• 2763 reflections

• 163 parameters

• H-atom parameters constrained

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

• Absolute structure: Flack (1983), 1141

• Flack parameter: 0.63 (15)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	1.89	2.619 (4)	142
N2—H2A⋯O2	0.86	2.17	2.575 (4)	109
C12—H12A⋯S1	0.93	2.62	3.235 (4)	124

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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 PARST (Nardelli, 1995).

Supporting information

S1. Comment

The title compound is analogous to the previously reported, 1-(2-Nitrophenyl)-3-pivaloylthiourea (Saeed and Flörke, 2007) except that the nitro group is replace with methoxy group (Fig. 1). The bond lengths are in normal ranges (Allen et al., 1987) and comparable with other similar molecule reported (Yusof et al. 2008; Shoukat et al. 2007).

The carbonylthiourea (S1/N1/N2/O1/C4–C7) and phenyl fragments are essentially planar, with rms deviations of 0.0096 Å and 0.0064 Å, respectively. These two fragments inclined at each other at an angle of 19.16(0.16)°. There are two intramolecular hydrogen bonds, N2—H2A···O1 and N2—H2A···O2 leading to two pseudo-six membered rings. Weak C-H···S intramolecular H-bonding is also exist. There is no intermolecular hydrogen bond in the crystal structure.

Related literature

For related structures, see: Saeed & Flörke (2007); Yusof et al. (2008); Shoukat et al. (2007). For standard bond lengths, see: Allen et al. (1987).

S2. Experimental

To a stirring acetone solution (75 ml) of pivaloyl chloride (5.0 g, 0.04 mol) and ammonium thiocyanate (3.15 g, 0.04 mol), 2-methoxyaniline (0.49 g, 0.04 mol) in 40 ml of acetone was added dropwise. The solution mixture was refluxed for 1 h. The resulting solution was poured into a beaker containing some 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 DMF.

S3. Refinement

H atoms on C were positioned geometrically with C—H 0.93, 0.96 Å, for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms with U_iso(H)= xU_eq(C) where x=1.5 for methyl H and x=1.2 for aromatic H atoms. The H atom attached to oxygen atoms were located from the Fourier difference map and refined isotropically.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PARST (Nardelli, 1995).

Figures

Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. Dashed lines show H-bondings.

N-(2,2-Dimethylpropanoyl)-N'-(2-methoxyphenyl)thiourea

Crystal data

C13H18N2O2S	F(000) = 568
Mr = 266.35	Dx = 1.259 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 770 reflections
a = 5.9181 (10) Å	θ = 1.9–26.0°
b = 13.492 (2) Å	µ = 0.23 mm^−1
c = 17.592 (3) Å	T = 273 K
V = 1404.7 (4) Å^3	Slab, colourless
Z = 4	0.50 × 0.14 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2763 independent reflections
Radiation source: fine-focus sealed tube	2227 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 83.66 pixels mm^-1	θmax = 26.0°, θmin = 1.9°
ω scan	h = −7→6
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −16→16
Tmin = 0.895, Tmax = 0.980	l = −20→21
8711 measured reflections

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)] = 0.068	H-atom parameters constrained
wR(F^2) = 0.147	w = 1/[σ^2(Fo^2) + (0.0655P)^2 + 0.2181P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max < 0.001
2763 reflections	Δρmax = 0.32 e Å^−3
163 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1141 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.63 (15)

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	0.1312 (2)	0.79180 (7)	0.57763 (7)	0.0693 (4)
O1	0.3640 (5)	0.47260 (17)	0.56305 (13)	0.0559 (7)
O2	0.7537 (5)	0.5571 (2)	0.67865 (15)	0.0662 (8)
C6	0.2391 (6)	0.6781 (2)	0.58348 (19)	0.0442 (8)
N2	0.3935 (5)	0.6446 (2)	0.63138 (15)	0.0453 (7)
H2A	0.4306	0.5836	0.6243	0.054*
N1	0.1602 (5)	0.60835 (18)	0.53095 (15)	0.0427 (7)
H1A	0.0573	0.6290	0.5003	0.051*
C5	0.2250 (6)	0.5112 (2)	0.52178 (18)	0.0384 (8)
C8	0.7025 (7)	0.6429 (3)	0.71748 (19)	0.0474 (9)
C9	0.8272 (8)	0.6805 (3)	0.7766 (2)	0.0623 (11)
H9A	0.9588	0.6489	0.7924	0.075*
C4	0.1096 (6)	0.4544 (2)	0.45732 (18)	0.0445 (8)
C7	0.5083 (7)	0.6910 (2)	0.69201 (17)	0.0434 (9)
C3	0.2134 (8)	0.3508 (3)	0.4531 (2)	0.0682 (12)
H3A	0.1901	0.3171	0.5005	0.102*
H3B	0.3724	0.3562	0.4432	0.102*
H3C	0.1427	0.3140	0.4128	0.102*
C2	0.1488 (9)	0.5089 (3)	0.3823 (2)	0.0726 (13)
H2B	0.0831	0.5738	0.3850	0.109*
H2C	0.0798	0.4724	0.3416	0.109*
H2D	0.3082	0.5146	0.3731	0.109*
C12	0.4381 (8)	0.7757 (3)	0.7293 (2)	0.0599 (12)
H12A	0.3061	0.8075	0.7142	0.072*
C11	0.5629 (10)	0.8133 (3)	0.7888 (2)	0.0731 (15)
H11A	0.5165	0.8711	0.8129	0.088*
C10	0.7544 (9)	0.7660 (3)	0.8125 (2)	0.0714 (14)
H10A	0.8365	0.7915	0.8532	0.086*
C13	0.9241 (8)	0.4949 (3)	0.7089 (2)	0.0744 (13)
H13A	0.9422	0.4379	0.6769	0.112*
H13B	0.8817	0.4740	0.7591	0.112*
H13C	1.0642	0.5307	0.7113	0.112*
C1	−0.1417 (7)	0.4454 (3)	0.4742 (3)	0.0734 (12)
H1B	−0.2072	0.5103	0.4777	0.110*
H1C	−0.1626	0.4110	0.5215	0.110*
H1D	−0.2141	0.4090	0.4341	0.110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0848 (8)	0.0424 (5)	0.0806 (7)	0.0145 (6)	−0.0263 (7)	−0.0102 (5)
O1	0.0650 (17)	0.0465 (13)	0.0562 (14)	0.0105 (13)	−0.0175 (14)	−0.0061 (11)
O2	0.068 (2)	0.0701 (18)	0.0609 (15)	0.0127 (16)	−0.0192 (15)	−0.0080 (14)
C6	0.045 (2)	0.0429 (18)	0.0448 (18)	−0.0036 (16)	0.0009 (18)	0.0016 (15)
N2	0.0535 (19)	0.0360 (14)	0.0465 (16)	0.0025 (14)	−0.0089 (15)	−0.0053 (12)
N1	0.0445 (17)	0.0396 (15)	0.0440 (15)	0.0033 (13)	−0.0109 (14)	−0.0057 (12)
C5	0.0366 (19)	0.0403 (17)	0.0385 (17)	−0.0044 (15)	0.0033 (15)	0.0015 (14)
C8	0.054 (2)	0.048 (2)	0.0405 (18)	−0.0111 (18)	−0.0028 (17)	0.0069 (16)
C9	0.061 (3)	0.074 (3)	0.051 (2)	−0.020 (2)	−0.010 (2)	0.008 (2)
C4	0.039 (2)	0.0484 (19)	0.0462 (19)	−0.0020 (17)	0.0003 (16)	−0.0068 (15)
C7	0.057 (2)	0.0386 (18)	0.0351 (18)	−0.0119 (18)	−0.0021 (17)	0.0025 (14)
C3	0.074 (3)	0.057 (2)	0.074 (3)	0.002 (2)	−0.016 (2)	−0.027 (2)
C2	0.100 (4)	0.078 (3)	0.039 (2)	−0.011 (3)	−0.004 (2)	−0.0070 (19)
C12	0.085 (3)	0.050 (2)	0.045 (2)	−0.007 (2)	−0.003 (2)	−0.0055 (17)
C11	0.119 (5)	0.050 (2)	0.050 (2)	−0.015 (3)	−0.002 (3)	−0.0072 (18)
C10	0.100 (4)	0.068 (3)	0.046 (2)	−0.041 (3)	−0.016 (3)	0.000 (2)
C13	0.063 (3)	0.088 (3)	0.073 (3)	0.012 (2)	−0.007 (2)	0.008 (2)
C1	0.051 (3)	0.080 (3)	0.090 (3)	−0.014 (2)	−0.002 (2)	−0.021 (2)

Geometric parameters (Å, º)

S1—C6	1.665 (3)	C7—C12	1.382 (5)
O1—C5	1.215 (4)	C3—H3A	0.9600
O2—C8	1.378 (5)	C3—H3B	0.9600
O2—C13	1.416 (5)	C3—H3C	0.9600
C6—N2	1.323 (4)	C2—H2B	0.9600
C6—N1	1.399 (4)	C2—H2C	0.9600
N2—C7	1.411 (4)	C2—H2D	0.9600
N2—H2A	0.8600	C12—C11	1.378 (6)
N1—C5	1.375 (4)	C12—H12A	0.9300
N1—H1A	0.8600	C11—C10	1.366 (7)
C5—C4	1.530 (5)	C11—H11A	0.9300
C8—C9	1.373 (5)	C10—H10A	0.9300
C8—C7	1.394 (5)	C13—H13A	0.9600
C9—C10	1.385 (6)	C13—H13B	0.9600
C9—H9A	0.9300	C13—H13C	0.9600
C4—C1	1.522 (5)	C1—H1B	0.9600
C4—C2	1.529 (5)	C1—H1C	0.9600
C4—C3	1.529 (5)	C1—H1D	0.9600
C8—O2—C13	117.9 (3)	C4—C3—H3C	109.5
N2—C6—N1	114.9 (3)	H3A—C3—H3C	109.5
N2—C6—S1	128.3 (3)	H3B—C3—H3C	109.5
N1—C6—S1	116.8 (3)	C4—C2—H2B	109.5
C6—N2—C7	131.5 (3)	C4—C2—H2C	109.5
C6—N2—H2A	114.3	H2B—C2—H2C	109.5
C7—N2—H2A	114.3	C4—C2—H2D	109.5
C5—N1—C6	128.7 (3)	H2B—C2—H2D	109.5
C5—N1—H1A	115.7	H2C—C2—H2D	109.5
C6—N1—H1A	115.7	C11—C12—C7	120.2 (4)
O1—C5—N1	121.9 (3)	C11—C12—H12A	119.9
O1—C5—C4	122.0 (3)	C7—C12—H12A	119.9
N1—C5—C4	116.1 (3)	C10—C11—C12	120.4 (4)
C9—C8—O2	124.6 (4)	C10—C11—H11A	119.8
C9—C8—C7	121.0 (4)	C12—C11—H11A	119.8
O2—C8—C7	114.4 (3)	C11—C10—C9	120.5 (4)
C8—C9—C10	119.1 (4)	C11—C10—H10A	119.7
C8—C9—H9A	120.5	C9—C10—H10A	119.7
C10—C9—H9A	120.5	O2—C13—H13A	109.5
C1—C4—C2	110.8 (4)	O2—C13—H13B	109.5
C1—C4—C3	109.2 (3)	H13A—C13—H13B	109.5
C2—C4—C3	109.6 (3)	O2—C13—H13C	109.5
C1—C4—C5	109.4 (3)	H13A—C13—H13C	109.5
C2—C4—C5	109.4 (3)	H13B—C13—H13C	109.5
C3—C4—C5	108.4 (3)	C4—C1—H1B	109.5
C12—C7—C8	118.7 (3)	C4—C1—H1C	109.5
C12—C7—N2	125.5 (4)	H1B—C1—H1C	109.5
C8—C7—N2	115.7 (3)	C4—C1—H1D	109.5
C4—C3—H3A	109.5	H1B—C1—H1D	109.5
C4—C3—H3B	109.5	H1C—C1—H1D	109.5
H3A—C3—H3B	109.5
N1—C6—N2—C7	−178.8 (3)	O1—C5—C4—C3	−4.2 (5)
S1—C6—N2—C7	2.0 (6)	N1—C5—C4—C3	176.6 (3)
N2—C6—N1—C5	−1.5 (5)	C9—C8—C7—C12	−2.3 (5)
S1—C6—N1—C5	177.9 (3)	O2—C8—C7—C12	177.6 (3)
C6—N1—C5—O1	2.2 (5)	C9—C8—C7—N2	−179.4 (3)
C6—N1—C5—C4	−178.6 (3)	O2—C8—C7—N2	0.5 (4)
C13—O2—C8—C9	10.6 (5)	C6—N2—C7—C12	19.9 (6)
C13—O2—C8—C7	−169.3 (3)	C6—N2—C7—C8	−163.3 (3)
O2—C8—C9—C10	−178.1 (3)	C8—C7—C12—C11	2.2 (6)
C7—C8—C9—C10	1.7 (5)	N2—C7—C12—C11	178.9 (3)
O1—C5—C4—C1	114.7 (4)	C7—C12—C11—C10	−1.4 (6)
N1—C5—C4—C1	−64.5 (4)	C12—C11—C10—C9	0.8 (6)
O1—C5—C4—C2	−123.7 (4)	C8—C9—C10—C11	−1.0 (6)
N1—C5—C4—C2	57.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.89	2.619 (4)	142
N2—H2A···O2	0.86	2.17	2.575 (4)	109
C12—H12A···S1	0.93	2.62	3.235 (4)	124