N-(4-Ethoxy­phen­yl)thio­urea

In the title mol­ecule, C₉H₁₂N₂OS, the benzene ring and mean plane of the thio­urea fragment [–N—C(=S)—N] make a dihedral angle of 59.19 (3)°. In the crystal structure, weak inter­molecular N—H...S and N—H...O hydrogen bonds link the mol­ecules into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.033
• wR factor = 0.094
• Data-to-parameter ratio = 17.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C9      ..       5.63 su

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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

Thiazolone derivatives have potential antimicrobial and antitumour properties (Mane et al., 1983). The title compound, (p-ethoxyphenyl)thiourea (I), is an important intermediate in the synthesis of thiazolone derivatives. In our work, we present its crystal structure.

In (I) (Fig. 1), the benzene ring is twisted out of –N1—C9(=S1)—N2 and –O1—C7—C8 planes by the diherdral angles of 59.19 (3)° and 12.26 (3)°, respectively. In the crystal, the weak intermolecular N—H···S and N—H···O hydrogen bonds link the molecules into three-dimensional hydrogen-bonding network (Table 1, Fig. 2).

Related literature

For the synthesis of the title compound, see: Liu et al. (1994). For details of the pharmacological properties of thiazolone derivatives, see: Mane & Ingle (1983).

S2. Experimental

A mixture of 4-Ethoxyaniline(13.7 g,0.1 mol), 36% aqueous HCl(10.1 g,0.1 mol) and ammonium thiocyanate(7.6 g,0.1 mol) was refluxed in water(30 ml) for 4 hrs, then a white precipitate was observed and filtered. The solid was recrystallized from water to give the pure product. The pure product was dissolved in water evaporated gradually at room temperature to afford single crystals of (I). (m.p. 450–451 K). ¹HNMR(CDCl₃)σp.p.m.:7.15(d,2H,J=8.4 Hz),6.92(d,2H,J=8.4 Hz), 4.03(q,2H,CH₂), 1.42(t,3H,CH₃). MS.(m/z,%).196(M,100),163 (35),154 (70),108 (95),80 (35),60 (25).

S3. Refinement

The atoms H1X, H2X and H2Y were located in difference Fourier maps and refined isotropically with the N—H bond restraint of 0.86 (2) Å. Methyl H atoms were placed in calculated positions, with C—H = 0.96 Å, and torsion angles were refined to fit the electron density [U_iso(H) = 1.5U_eq(C)]. Other H atoms were placed in calculated positions, with C—H = 0.93 Å, and refined in riding mode, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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, 2005); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), shown with 30% probability displacement ellipsoids.
	Fig. 2. Crystal structure of (I), viewed down the b axis. N—H···O and N—H···S hydrogen bondings are shown as dashed lines.

N-(4-Ethoxyphenyl)thiourea

Crystal data

C9H12N2OS	F(000) = 832
Mr = 196.27	Dx = 1.274 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3819 reflections
a = 14.8450 (19) Å	θ = 2.8–28.1°
b = 8.2482 (11) Å	µ = 0.28 mm^−1
c = 16.860 (2) Å	T = 293 K
β = 97.489 (1)°	Prismatic, colourless
V = 2046.8 (4) Å^3	0.30 × 0.25 × 0.15 mm
Z = 8

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	2313 independent reflections
Radiation source: fine-focus sealed tube	2082 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
φ and ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→19
Tmin = 0.921, Tmax = 0.949	k = −10→10
6278 measured reflections	l = −19→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)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0558P)^2 + 0.628P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
2313 reflections	Δρmax = 0.22 e Å^−3
132 parameters	Δρmin = −0.20 e Å^−3
3 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0053 (7)

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	0.60518 (2)	1.19209 (4)	0.507891 (19)	0.04179 (14)
O1	0.64641 (7)	0.45160 (12)	0.19824 (6)	0.0506 (3)
N1	0.58619 (7)	0.92414 (14)	0.42155 (7)	0.0415 (3)
H1X	0.5372 (10)	0.9124 (19)	0.4426 (9)	0.047 (4)*
N2	0.71911 (8)	1.06437 (17)	0.41752 (8)	0.0525 (3)
H2X	0.7399 (11)	0.9898 (19)	0.3879 (10)	0.058 (5)*
H2Y	0.7562 (10)	1.1336 (19)	0.4382 (10)	0.052 (4)*
C1	0.60403 (8)	0.80089 (15)	0.36640 (7)	0.0365 (3)
C2	0.61645 (9)	0.84100 (16)	0.28852 (8)	0.0411 (3)
H2	0.6153	0.9492	0.2729	0.049*
C3	0.63050 (9)	0.72167 (16)	0.23422 (7)	0.0415 (3)
H3	0.6393	0.7497	0.1824	0.050*
C4	0.63154 (9)	0.56007 (15)	0.25676 (7)	0.0387 (3)
C5	0.61802 (10)	0.51855 (17)	0.33402 (8)	0.0475 (3)
H5	0.6179	0.4102	0.3493	0.057*
C6	0.60467 (10)	0.63975 (17)	0.38853 (8)	0.0458 (3)
H6	0.5961	0.6120	0.4405	0.055*
C7	0.62819 (11)	0.28480 (17)	0.21063 (10)	0.0515 (4)
H7A	0.5677	0.2719	0.2256	0.062*
H7B	0.6717	0.2415	0.2533	0.062*
C8	0.63544 (13)	0.1967 (2)	0.13409 (10)	0.0625 (4)
H8A	0.5950	0.2450	0.0916	0.094*
H8B	0.6193	0.0849	0.1398	0.094*
H8C	0.6967	0.2035	0.1218	0.094*
C9	0.63966 (8)	1.05019 (15)	0.44530 (7)	0.0360 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0422 (2)	0.0416 (2)	0.0448 (2)	−0.01078 (12)	0.01772 (14)	−0.01294 (12)
O1	0.0699 (7)	0.0407 (5)	0.0453 (5)	−0.0050 (5)	0.0236 (5)	−0.0091 (4)
N1	0.0395 (6)	0.0443 (6)	0.0442 (6)	−0.0121 (5)	0.0187 (5)	−0.0130 (5)
N2	0.0418 (6)	0.0594 (8)	0.0607 (7)	−0.0188 (6)	0.0236 (5)	−0.0276 (6)
C1	0.0340 (6)	0.0407 (6)	0.0359 (6)	−0.0081 (5)	0.0090 (5)	−0.0083 (5)
C2	0.0492 (7)	0.0360 (6)	0.0389 (6)	−0.0021 (5)	0.0085 (5)	−0.0001 (5)
C3	0.0510 (7)	0.0435 (7)	0.0309 (6)	−0.0015 (5)	0.0096 (5)	0.0005 (5)
C4	0.0412 (6)	0.0394 (6)	0.0369 (6)	−0.0037 (5)	0.0105 (5)	−0.0062 (5)
C5	0.0652 (9)	0.0365 (7)	0.0434 (7)	−0.0064 (6)	0.0165 (6)	0.0000 (5)
C6	0.0595 (8)	0.0458 (7)	0.0349 (6)	−0.0098 (6)	0.0159 (6)	−0.0013 (5)
C7	0.0559 (8)	0.0419 (7)	0.0601 (9)	−0.0089 (6)	0.0204 (7)	−0.0099 (6)
C8	0.0717 (11)	0.0540 (9)	0.0624 (10)	−0.0081 (8)	0.0116 (8)	−0.0210 (7)
C9	0.0368 (6)	0.0392 (6)	0.0334 (6)	−0.0065 (5)	0.0096 (4)	−0.0037 (5)

Geometric parameters (Å, º)

S1—C9	1.6989 (12)	C3—C4	1.3855 (18)
O1—C4	1.3708 (15)	C3—H3	0.9300
O1—C7	1.4228 (17)	C4—C5	1.3866 (18)
N1—C9	1.3374 (16)	C5—C6	1.3894 (19)
N1—C1	1.4255 (15)	C5—H5	0.9300
N1—H1X	0.855 (13)	C6—H6	0.9300
N2—C9	1.3297 (16)	C7—C8	1.497 (2)
N2—H2X	0.874 (14)	C7—H7A	0.9700
N2—H2Y	0.836 (14)	C7—H7B	0.9700
C1—C6	1.3802 (19)	C8—H8A	0.9599
C1—C2	1.3895 (18)	C8—H8B	0.9599
C2—C3	1.3785 (18)	C8—H8C	0.9599
C2—H2	0.9300
C4—O1—C7	118.29 (10)	C4—C5—H5	120.2
C9—N1—C1	126.59 (10)	C6—C5—H5	120.2
C9—N1—H1X	117.9 (11)	C1—C6—C5	120.71 (12)
C1—N1—H1X	115.5 (11)	C1—C6—H6	119.6
C9—N2—H2X	122.4 (11)	C5—C6—H6	119.6
C9—N2—H2Y	118.6 (11)	O1—C7—C8	107.86 (13)
H2X—N2—H2Y	117.1 (16)	O1—C7—H7A	110.1
C6—C1—C2	119.18 (11)	C8—C7—H7A	110.1
C6—C1—N1	120.38 (11)	O1—C7—H7B	110.1
C2—C1—N1	120.36 (11)	C8—C7—H7B	110.1
C3—C2—C1	120.52 (12)	H7A—C7—H7B	108.4
C3—C2—H2	119.7	C7—C8—H8A	109.5
C1—C2—H2	119.7	C7—C8—H8B	109.5
C2—C3—C4	120.13 (11)	H8A—C8—H8B	109.5
C2—C3—H3	119.9	C7—C8—H8C	109.5
C4—C3—H3	119.9	H8A—C8—H8C	109.5
O1—C4—C3	115.32 (11)	H8B—C8—H8C	109.5
O1—C4—C5	124.86 (12)	N2—C9—N1	118.82 (11)
C3—C4—C5	119.83 (12)	N2—C9—S1	120.74 (10)
C4—C5—C6	119.62 (12)	N1—C9—S1	120.42 (9)
C9—N1—C1—C6	123.61 (15)	O1—C4—C5—C6	179.21 (13)
C9—N1—C1—C2	−59.64 (19)	C3—C4—C5—C6	−0.8 (2)
C6—C1—C2—C3	−0.9 (2)	C2—C1—C6—C5	0.4 (2)
N1—C1—C2—C3	−177.68 (12)	N1—C1—C6—C5	177.14 (13)
C1—C2—C3—C4	0.6 (2)	C4—C5—C6—C1	0.5 (2)
C7—O1—C4—C3	−165.98 (13)	C4—O1—C7—C8	171.20 (13)
C7—O1—C4—C5	14.0 (2)	C1—N1—C9—N2	−1.7 (2)
C2—C3—C4—O1	−179.75 (12)	C1—N1—C9—S1	176.65 (10)
C2—C3—C4—C5	0.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1X···S1^i	0.86 (1)	2.52 (1)	3.3594 (11)	166 (1)
N2—H2X···O1^ii	0.87 (1)	2.39 (2)	3.1105 (15)	141 (1)
N2—H2Y···S1^iii	0.84 (1)	2.58 (1)	3.4008 (13)	168 (2)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+3/2, −y+5/2, −z+1.