N-[Eth­yl(2-hy­droxy­eth­yl)carbamo­thio­yl]-2-methyl­benzamide

Yamin, B.M.; Hizam, S.M.M.; Yusoff, S.F.M.; Hasbullah, S.A.

doi:10.1107/S1600536814008952

organic compounds

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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Page o602

doi:10.1107/S1600536814008952

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N-[Ethyl(2-hydroxyethyl)carbamothioyl]-2-methylbenzamide

Bohari M. Yamin,^a Sara Maira M. Hizam,^b Siti Fairus M. Yusoff ^b and Siti Aishah Hasbullah ^b ^*

^aLow Carbon Research Group, School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia, and ^bSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
^*Correspondence e-mail: aishah80@ukm.my

(Received 5 April 2014; accepted 19 April 2014; online 26 April 2014)

The title compound, C₁₃H₁₈N₂O₂S, adopts a cis conformation between the methylbenzoyl and thiono groups across their thiourea C—N bond. However, the methylbenzoyl group and N₂CS thiourea moiety are twisted by 15.03 (3)°. In the molecule there is an N—H⋯O hydrogen bond. In the crystal, molecules are linked by O—H⋯O interactions, generating chains extending along the c-axis direction.

CCDC reference: 998473

Related literature

For bond-length data, see: Allen et al. (1987 ). For related structures of thiourea derivatives, see: Awang et al. (2013 ); Sapari et al. (2013 ).

Experimental

Crystal data

C₁₃H₁₈N₂O₂S
M_r = 266.35
Monoclinic, P 2₁ /c
a = 11.393 (4) Å
b = 8.989 (3) Å
c = 14.467 (5) Å
β = 109.940 (9)°
V = 1392.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 K
0.35 × 0.34 × 0.06 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.924, T_max = 0.986
28196 measured reflections
2583 independent reflections
2005 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.088
S = 1.06
2583 reflections
169 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.86	1.98	2.750 (2)	149
O2—H2A⋯O1ⁱ	0.81 (2)	1.91 (2)	2.716 (2)	171 (2)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 998473

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814008952/lr2125sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814008952/lr2125Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814008952/lr2125Isup3.cml

checkCIF report

Experimental top

Synthesis and crystallization top

An acetone (30 ml) solution of 2-(ethylamino)ethanol (0.18 g, 2 mmol) was added to a round-bottomed flask containing 2-methylbenzoyl isothiocyanate (0.31 g,2 mmol). The mixture was refluxed for 3h. After cooling the solution was filtered off and the filtrate was left to evaporate at room temperature. The solid formed was washed with water and cold ethanol. Crystals suitable for X-ray study were obtained by recrystallization from DMSO.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms attached to C and N atoms were fixed geometrically and treated as riding with C—H= 0.93-0.97Å and N–H = 0.86Å with U_iso(H)= 1.2U_eq[C (methylene and aromatic),N] and 1.5 U_eq [C (methyl)]. The hydroxyl hydrogen atom was located from Fourier map and refined isotropically with O—H restraint to 0.81Å with esd of 0.01.

Results and discussion top

The carbonoylthiourea derivatives with a secondary amine group at the terminal thiourea moiety are expected to adopt a cis conformation with respect to the position of the carbonoyl against the thiono group. Such a configuration will allow the ligand to chelate with metals in bidentate manner. Thus, 2,4-dichloro-N-[ethyl(hydroxyethyl)carbamothioyl]benzamide (Sapari et al.,2013) and N[ethyl(hydroxyethyl)carbamothioyl]-2-iodo-benzamide (Awang et al., 2013) adopt the said conformation. The title compound is analogous to the two compounds but having a methyl group attached at position-2 of the benzene ring (Fig.1). However, the title molecule maintains a cis conformation between the carbonyl and thiono groups across the C8—N1 bond and twisted by torsion angle of O1—C8—N1—C9 and S1—C9—N1—C8 of 7.1 (3)and 47.1 (2)° respectively. Both S1/N1/N2/C9 thiourea moiety and (C1—C8) benzyl fragments are planar with maximum deviation of 0.031 (2)Å for C4 atom from the least square plane of the benzyl fragment. The two planes make dihedral angle of 15.03 (3)°. The bond lengths and angles are in normal ranges (Allen et al.,1987) and comparable to those in the two analogs. There is an intramolecular hydrogen bond N1–H1A···O2 between the amido hydrogen and hydroxyl oxygen atom. In the crystal structure, the molecules are linked by O2–H2A···O1 intermolecular hydrogen bond (see Table 1 for symmetry codes) to form one-dimensional chains along the c-axis direction (Fig.2). In addition, there is a C—H.. π bond between H12B and (C1—C6) centroid (-x,1-y,-z) with the H12B···C_g distance of 2.84Å and C12—H12B—C_g angle, 137°.

Related literature top

For bond-length data, see: Allen et al. (1987). For related structures of thiourea derivatives, see: Awang et al. (2013); Sapari et al. (2013) .

Computing details top

Data collection: SMART (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsods drawn at the 50% probability level. The dashed line indicates the intramolecular hydrogen bond.
	Fig. 2. Packing of (I) viewed down the a-axis. The dashed lines indicate intermolecular hydrogen bonds.

N-[Ethyl(2-hydroxyethyl)carbamothioyl]-2-methylbenzamide top

Crystal data top

C₁₃H₁₈N₂O₂S	F(000) = 568
M_r = 266.35	D_x = 1.270 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 21535 reflections
a = 11.393 (4) Å	θ = 2.8–26.5°
b = 8.989 (3) Å	µ = 0.23 mm⁻¹
c = 14.467 (5) Å	T = 296 K
β = 109.940 (9)°	Block, colorless
V = 1392.7 (7) Å³	0.35 × 0.34 × 0.06 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2583 independent reflections
Radiation source: fine-focus sealed tube	2005 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 83.66 pixels mm^-1	θ_max = 25.5°, θ_min = 3.6°
ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −10→10
T_min = 0.924, T_max = 0.986	l = −17→17
28196 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0285P)² + 0.6558P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2583 reflections	Δρ_max = 0.20 e Å⁻³
169 parameters	Δρ_min = −0.20 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0087 (13)

Crystal data top

C₁₃H₁₈N₂O₂S	V = 1392.7 (7) Å³
M_r = 266.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.393 (4) Å	µ = 0.23 mm⁻¹
b = 8.989 (3) Å	T = 296 K
c = 14.467 (5) Å	0.35 × 0.34 × 0.06 mm
β = 109.940 (9)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2583 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2005 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.986	R_int = 0.048
28196 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	1 restraint
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.20 e Å⁻³
2583 reflections	Δρ_min = −0.20 e Å⁻³
169 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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

	x	y	z	U_iso*/U_eq
S1	0.41046 (5)	0.21117 (6)	0.04784 (4)	0.05354 (18)
O1	0.13506 (12)	0.29922 (15)	−0.09305 (9)	0.0484 (3)
O2	0.19987 (15)	0.33465 (18)	0.26307 (10)	0.0605 (4)
N1	0.19870 (12)	0.29892 (16)	0.07400 (10)	0.0349 (3)
H1A	0.1715	0.2966	0.1226	0.042*
N2	0.37657 (13)	0.41992 (16)	0.16698 (10)	0.0360 (3)
C1	−0.06300 (17)	0.3318 (2)	0.04619 (13)	0.0440 (4)
H1	−0.0132	0.4036	0.0876	0.053*
C2	−0.18157 (19)	0.3051 (3)	0.04839 (16)	0.0563 (6)
H2	−0.2126	0.3604	0.0893	0.068*
C3	−0.25302 (18)	0.1954 (3)	−0.01084 (16)	0.0588 (6)
H3	−0.3319	0.1741	−0.0086	0.071*
C4	−0.20788 (17)	0.1171 (2)	−0.07337 (15)	0.0516 (5)
H4	−0.2572	0.0427	−0.1123	0.062*
C5	−0.09168 (16)	0.1453 (2)	−0.08036 (12)	0.0399 (4)
C6	−0.01715 (15)	0.25332 (19)	−0.01686 (12)	0.0346 (4)
C7	−0.0495 (2)	0.0586 (2)	−0.15221 (14)	0.0544 (5)
H7A	−0.1073	−0.0209	−0.1794	0.082*
H7B	0.0320	0.0181	−0.1190	0.082*
H7C	−0.0464	0.1232	−0.2041	0.082*
C8	0.11165 (16)	0.28421 (18)	−0.01751 (12)	0.0347 (4)
C9	0.32863 (15)	0.31759 (18)	0.09763 (12)	0.0345 (4)
C10	0.51197 (17)	0.4398 (2)	0.21078 (14)	0.0500 (5)
H10A	0.5529	0.3457	0.2089	0.060*
H10B	0.5326	0.4682	0.2792	0.060*
C11	0.5611 (2)	0.5562 (3)	0.15845 (18)	0.0699 (7)
H11A	0.5440	0.5266	0.0913	0.105*
H11B	0.6497	0.5665	0.1905	0.105*
H11C	0.5211	0.6496	0.1602	0.105*
C12	0.30146 (18)	0.5213 (2)	0.20352 (13)	0.0428 (4)
H12A	0.2226	0.5397	0.1514	0.051*
H12B	0.3449	0.6156	0.2205	0.051*
C13	0.2756 (2)	0.4621 (3)	0.29216 (14)	0.0573 (6)
H13A	0.3534	0.4367	0.3436	0.069*
H13B	0.2332	0.5370	0.3175	0.069*
H2A	0.187 (2)	0.300 (3)	0.3107 (13)	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0491 (3)	0.0548 (3)	0.0672 (4)	−0.0036 (2)	0.0334 (3)	−0.0109 (3)
O1	0.0528 (8)	0.0629 (9)	0.0344 (7)	−0.0094 (7)	0.0212 (6)	−0.0071 (6)
O2	0.0835 (11)	0.0669 (10)	0.0426 (8)	−0.0108 (8)	0.0366 (8)	0.0027 (7)
N1	0.0331 (7)	0.0443 (9)	0.0310 (7)	−0.0087 (6)	0.0154 (6)	−0.0054 (6)
N2	0.0360 (8)	0.0361 (8)	0.0327 (7)	−0.0062 (6)	0.0075 (6)	0.0006 (6)
C1	0.0438 (10)	0.0458 (11)	0.0438 (10)	−0.0005 (8)	0.0166 (8)	0.0022 (9)
C2	0.0465 (12)	0.0715 (15)	0.0579 (12)	0.0127 (11)	0.0271 (10)	0.0137 (11)
C3	0.0309 (10)	0.0753 (15)	0.0669 (14)	−0.0008 (10)	0.0124 (10)	0.0274 (12)
C4	0.0380 (11)	0.0535 (13)	0.0514 (12)	−0.0092 (9)	0.0000 (9)	0.0140 (10)
C5	0.0364 (9)	0.0389 (10)	0.0362 (9)	−0.0025 (8)	0.0015 (7)	0.0094 (8)
C6	0.0338 (9)	0.0350 (9)	0.0331 (9)	−0.0017 (7)	0.0092 (7)	0.0051 (7)
C7	0.0601 (13)	0.0485 (12)	0.0466 (11)	−0.0125 (10)	0.0078 (10)	−0.0101 (9)
C8	0.0410 (9)	0.0300 (9)	0.0353 (9)	−0.0045 (7)	0.0161 (8)	−0.0052 (7)
C9	0.0372 (9)	0.0346 (9)	0.0337 (9)	−0.0058 (7)	0.0146 (7)	0.0041 (7)
C10	0.0376 (10)	0.0569 (12)	0.0442 (11)	−0.0096 (9)	−0.0007 (8)	0.0021 (9)
C11	0.0515 (13)	0.0740 (16)	0.0800 (16)	−0.0247 (12)	0.0170 (12)	0.0045 (13)
C12	0.0530 (11)	0.0336 (10)	0.0396 (10)	−0.0037 (8)	0.0127 (8)	−0.0036 (8)
C13	0.0747 (15)	0.0627 (14)	0.0372 (10)	0.0000 (11)	0.0227 (10)	−0.0080 (9)

Geometric parameters (Å, º) top

S1—C9	1.6617 (17)	C4—H4	0.9300
O1—C8	1.2176 (19)	C5—C6	1.406 (2)
O2—C13	1.410 (3)	C5—C7	1.503 (3)
O2—H2A	0.815 (10)	C6—C8	1.497 (2)
N1—C8	1.363 (2)	C7—H7A	0.9600
N1—C9	1.411 (2)	C7—H7B	0.9600
N1—H1A	0.8600	C7—H7C	0.9600
N2—C9	1.333 (2)	C10—C11	1.507 (3)
N2—C10	1.465 (2)	C10—H10A	0.9700
N2—C12	1.467 (2)	C10—H10B	0.9700
C1—C2	1.383 (3)	C11—H11A	0.9600
C1—C6	1.388 (2)	C11—H11B	0.9600
C1—H1	0.9300	C11—H11C	0.9600
C2—C3	1.376 (3)	C12—C13	1.507 (3)
C2—H2	0.9300	C12—H12A	0.9700
C3—C4	1.377 (3)	C12—H12B	0.9700
C3—H3	0.9300	C13—H13A	0.9700
C4—C5	1.385 (3)	C13—H13B	0.9700

C13—O2—H2A	109.2 (19)	O1—C8—N1	123.46 (15)
C8—N1—C9	127.05 (13)	O1—C8—C6	122.79 (15)
C8—N1—H1A	116.5	N1—C8—C6	113.71 (14)
C9—N1—H1A	116.5	N2—C9—N1	113.03 (14)
C9—N2—C10	120.68 (15)	N2—C9—S1	125.24 (13)
C9—N2—C12	124.08 (14)	N1—C9—S1	121.59 (12)
C10—N2—C12	115.22 (14)	N2—C10—C11	112.60 (16)
C2—C1—C6	121.06 (18)	N2—C10—H10A	109.1
C2—C1—H1	119.5	C11—C10—H10A	109.1
C6—C1—H1	119.5	N2—C10—H10B	109.1
C3—C2—C1	119.02 (19)	C11—C10—H10B	109.1
C3—C2—H2	120.5	H10A—C10—H10B	107.8
C1—C2—H2	120.5	C10—C11—H11A	109.5
C2—C3—C4	120.08 (18)	C10—C11—H11B	109.5
C2—C3—H3	120.0	H11A—C11—H11B	109.5
C4—C3—H3	120.0	C10—C11—H11C	109.5
C3—C4—C5	122.36 (19)	H11A—C11—H11C	109.5
C3—C4—H4	118.8	H11B—C11—H11C	109.5
C5—C4—H4	118.8	N2—C12—C13	113.24 (16)
C4—C5—C6	117.25 (18)	N2—C12—H12A	108.9
C4—C5—C7	119.64 (17)	C13—C12—H12A	108.9
C6—C5—C7	123.09 (16)	N2—C12—H12B	108.9
C1—C6—C5	120.12 (16)	C13—C12—H12B	108.9
C1—C6—C8	119.94 (15)	H12A—C12—H12B	107.7
C5—C6—C8	119.94 (15)	O2—C13—C12	108.07 (15)
C5—C7—H7A	109.5	O2—C13—H13A	110.1
C5—C7—H7B	109.5	C12—C13—H13A	110.1
H7A—C7—H7B	109.5	O2—C13—H13B	110.1
C5—C7—H7C	109.5	C12—C13—H13B	110.1
H7A—C7—H7C	109.5	H13A—C13—H13B	108.4
H7B—C7—H7C	109.5

C6—C1—C2—C3	2.1 (3)	C5—C6—C8—O1	45.3 (2)
C1—C2—C3—C4	−2.0 (3)	C1—C6—C8—N1	43.5 (2)
C2—C3—C4—C5	−0.7 (3)	C5—C6—C8—N1	−136.79 (16)
C3—C4—C5—C6	3.2 (3)	C10—N2—C9—N1	171.38 (14)
C3—C4—C5—C7	−178.29 (18)	C12—N2—C9—N1	−10.0 (2)
C2—C1—C6—C5	0.4 (3)	C10—N2—C9—S1	−4.2 (2)
C2—C1—C6—C8	−179.82 (17)	C12—N2—C9—S1	174.43 (13)
C4—C5—C6—C1	−3.0 (2)	C8—N1—C9—N2	137.07 (16)
C7—C5—C6—C1	178.51 (17)	C8—N1—C9—S1	−47.1 (2)
C4—C5—C6—C8	177.27 (15)	C9—N2—C10—C11	92.3 (2)
C7—C5—C6—C8	−1.2 (3)	C12—N2—C10—C11	−86.5 (2)
C9—N1—C8—O1	−7.0 (3)	C9—N2—C12—C13	92.0 (2)
C9—N1—C8—C6	175.12 (15)	C10—N2—C12—C13	−89.25 (19)
C1—C6—C8—O1	−134.39 (18)	N2—C12—C13—O2	−65.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	1.98	2.750 (2)	149
O2—H2A···O1ⁱ	0.81 (2)	1.91 (2)	2.716 (2)	171 (2)

Symmetry code: (i) x, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	1.98	2.750 (2)	149
O2—H2A···O1ⁱ	0.81 (2)	1.91 (2)	2.716 (2)	171 (2)

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

The authors would like to thank Universiti Kebangsaan Malaysia and the Ministry of Science and Technology, Malaysia, for research grants GUP-2103-022, DIP-2012-11, LRGS/BU/2011/USM-UKM/PG-02 and the Centre of Research and Instrumentation (CRIM) for research facilities.

References

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Volume 70| Part 5| May 2014| Page o602

doi:10.1107/S1600536814008952

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