organic compounds
2,4-Dichloro-N-[ethyl(2-hydroxyethyl)carbamothioyl]benzamide
aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
*Correspondence e-mail: Aishah80@ukm.my
In the title compound, C12H14Cl2N2O2S, the molecule adopts a cis conformation with respect to the dichlorobenzoyl group against the thiono group about the C—N bond. However, the dichlorobenzene group and the thiourea moiety are twisted by 75.41 (8)°. An intramolecular N—H⋯O hydrogen bond occurs between the amido H atom and hydroxyl O atom. In the crystal, O—H⋯S and O—H⋯O hydrogen bonds link the molecules, forming chains along the b-axis direction.
CCDC reference: 975069
Related literature
For bond-length data, see: Allen et al. (1987). For related structures of thiourea derivatives, see: Hassan et al. (2010); Nasir et al. (2011); Al-abbasi et al. (2012); Yamin et al. (2013).
Experimental
Crystal data
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Data collection: SMART (Bruker,2009); cell 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, PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 975069
https://doi.org/10.1107/S1600536813032881/rn2121sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813032881/rn2121Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813032881/rn2121Isup3.cml
An acetone (30 ml) solution of (ethylamino)ethanol (0.18 g, 2 mmol) was added to a round-bottomed flask containing 2,4-dichlorobenzoyl isothiocyanate (0.58 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.
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 Uiso(H)= 1.2Ueq[C (methylene and aromatic),N] and 1.5 Ueq [C (methyl)]. The hydroxyl hydrogen atom was located from Fourier map and refined isotropically with O-H restraint to 0.82Å with an esd of 0.01.
Most of the aroyl or carbonoyl thiourea compounds reported so far are based on primary
The two amino hydrogen atoms play an important role on the geometry of the thiourea moiety such as that in 3-chloro-N-[N-(furan-2-carbonyl)hydrazinocarbothioyl]benzamide (Yamin et al., 2013) where it adopts trans geometry. However, in the secondary amine based thiourea, only the amido hydrogen atom is present (Nasir et al., 2011; Al-abbasi et al., 2012). Therefore, it can be expected that in the secondary amine carbonoyl thiourea, cis configuration is more likely to occur due to the absence of intrahydrogen bond involving the carbonyl oxygen atom and thioamide hydrogen atom. The title compound consists of dichloro substituted benzoyl and ethylethanol groups attached to the terminal nitrogen atoms respectively (Fig.1). The dichlorobenzoyl group is cis against thiono group across the C7—N1 bond. They are not coplanar but twisted by the dihedral angle between thiourea fragment S1/N1/N2/C8 and the dichlorobenzene ring, Cl1/Cl2/C1-C6, of 75.41 (8)°. Each fragment is planar with the maximum deviation of 0.025 (1)Å for atom Cl1 from the least-squares plane. The bond lengths and angles are in normal ranges (Allen et al.,1987). There is an intramolecular hydrogen bond N1–H1A···O2 between the amido hydrogen and hydroxyl oxygen atom. In the the molecules are linked by O2–H2A···S1 and O2–H2A···O1 intermolecular hydrogen bonds (see Table 1 for symmetry codes) to form one-dimensional chains along the b-axis (Fig.2).For bond-length data, see: Allen et al. (1987). For related structures of thiourea derivatives, see: Hassan et al. (2010); Nasir et al. (2011); Al-abbasi et al. (2012); Yamin et al. (2013)
Data collection: SMART (Bruker,2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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), PLATON (Spek, 2009) and publCIF (Westrip, 2010).C12H14Cl2N2O2S | F(000) = 664 |
Mr = 321.21 | Dx = 1.489 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 18947 reflections |
a = 6.9712 (4) Å | θ = 2.8–26.5° |
b = 10.6989 (6) Å | µ = 0.60 mm−1 |
c = 19.3288 (10) Å | T = 300 K |
β = 96.441 (2)° | Block, colourless |
V = 1432.52 (14) Å3 | 0.50 × 0.40 × 0.18 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 2967 independent reflections |
Radiation source: fine-focus sealed tube | 2619 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 83.66 pixels mm-1 | θmax = 26.5°, θmin = 2.8° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −13→13 |
Tmin = 0.754, Tmax = 0.900 | l = −24→24 |
30240 measured reflections |
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) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0666P)2 + 0.6739P] where P = (Fo2 + 2Fc2)/3 |
2967 reflections | (Δ/σ)max = 0.002 |
176 parameters | Δρmax = 0.44 e Å−3 |
1 restraint | Δρmin = −0.36 e Å−3 |
C12H14Cl2N2O2S | V = 1432.52 (14) Å3 |
Mr = 321.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.9712 (4) Å | µ = 0.60 mm−1 |
b = 10.6989 (6) Å | T = 300 K |
c = 19.3288 (10) Å | 0.50 × 0.40 × 0.18 mm |
β = 96.441 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 2967 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 2619 reflections with I > 2σ(I) |
Tmin = 0.754, Tmax = 0.900 | Rint = 0.036 |
30240 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 1 restraint |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | Δρmax = 0.44 e Å−3 |
2967 reflections | Δρmin = −0.36 e Å−3 |
176 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.89241 (10) | 0.71322 (6) | 0.93151 (4) | 0.0554 (2) | |
Cl2 | 0.70111 (8) | 1.08652 (6) | 1.09352 (3) | 0.04474 (18) | |
S1 | 0.75350 (9) | 0.90835 (6) | 0.64182 (3) | 0.04555 (19) | |
O1 | 0.7295 (4) | 0.8000 (2) | 0.78711 (10) | 0.0845 (9) | |
O2 | 1.0855 (3) | 1.20198 (15) | 0.81005 (9) | 0.0448 (4) | |
N1 | 0.9083 (3) | 0.97467 (17) | 0.77030 (9) | 0.0367 (4) | |
H1A | 0.9742 | 1.0316 | 0.7937 | 0.044* | |
N2 | 1.0766 (3) | 1.03352 (17) | 0.68075 (9) | 0.0336 (4) | |
C1 | 0.8163 (3) | 0.8659 (2) | 0.93868 (12) | 0.0347 (5) | |
C2 | 0.7904 (3) | 0.9090 (2) | 1.00426 (11) | 0.0341 (5) | |
H2B | 0.8090 | 0.8564 | 1.0427 | 0.041* | |
C3 | 0.7364 (3) | 1.0320 (2) | 1.01142 (11) | 0.0331 (4) | |
C4 | 0.7097 (3) | 1.1128 (2) | 0.95552 (12) | 0.0383 (5) | |
H4A | 0.6744 | 1.1956 | 0.9616 | 0.046* | |
C5 | 0.7369 (3) | 1.0677 (2) | 0.89040 (12) | 0.0389 (5) | |
H5A | 0.7198 | 1.1211 | 0.8523 | 0.047* | |
C6 | 0.7895 (3) | 0.9437 (2) | 0.88045 (11) | 0.0348 (5) | |
C7 | 0.8036 (4) | 0.8964 (2) | 0.80809 (12) | 0.0446 (6) | |
C8 | 0.9215 (3) | 0.97372 (19) | 0.69876 (11) | 0.0322 (4) | |
C9 | 1.0983 (4) | 1.0593 (2) | 0.60741 (11) | 0.0422 (5) | |
H9A | 1.1651 | 1.1382 | 0.6043 | 0.051* | |
H9B | 0.9712 | 1.0677 | 0.5817 | 0.051* | |
C10 | 1.2073 (4) | 0.9592 (3) | 0.57421 (14) | 0.0611 (8) | |
H10A | 1.2171 | 0.9808 | 0.5265 | 0.092* | |
H10B | 1.1404 | 0.8811 | 0.5761 | 0.092* | |
H10C | 1.3344 | 0.9516 | 0.5987 | 0.092* | |
C11 | 1.2412 (3) | 1.0729 (2) | 0.73058 (12) | 0.0409 (5) | |
H11A | 1.3576 | 1.0700 | 0.7074 | 0.049* | |
H11B | 1.2566 | 1.0134 | 0.7687 | 0.049* | |
C12 | 1.2214 (4) | 1.2026 (2) | 0.76032 (14) | 0.0524 (6) | |
H12A | 1.3459 | 1.2306 | 0.7824 | 0.063* | |
H12B | 1.1792 | 1.2604 | 0.7230 | 0.063* | |
H2A | 1.000 (4) | 1.253 (3) | 0.8004 (19) | 0.081 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0691 (4) | 0.0333 (3) | 0.0679 (4) | −0.0079 (3) | 0.0262 (3) | −0.0030 (3) |
Cl2 | 0.0400 (3) | 0.0580 (4) | 0.0379 (3) | −0.0032 (2) | 0.0114 (2) | −0.0079 (2) |
S1 | 0.0486 (4) | 0.0481 (4) | 0.0379 (3) | −0.0119 (3) | −0.0042 (3) | −0.0043 (2) |
O1 | 0.134 (2) | 0.0746 (15) | 0.0452 (11) | −0.0699 (15) | 0.0110 (12) | −0.0104 (10) |
O2 | 0.0520 (10) | 0.0357 (9) | 0.0459 (9) | 0.0000 (7) | 0.0017 (8) | −0.0053 (7) |
N1 | 0.0424 (10) | 0.0378 (10) | 0.0308 (9) | −0.0154 (8) | 0.0083 (7) | −0.0074 (7) |
N2 | 0.0371 (9) | 0.0357 (9) | 0.0283 (9) | −0.0033 (7) | 0.0053 (7) | −0.0009 (7) |
C1 | 0.0263 (9) | 0.0346 (11) | 0.0446 (12) | −0.0094 (8) | 0.0101 (8) | −0.0020 (9) |
C2 | 0.0248 (9) | 0.0414 (12) | 0.0366 (11) | −0.0071 (8) | 0.0059 (8) | 0.0043 (9) |
C3 | 0.0216 (9) | 0.0454 (12) | 0.0329 (10) | −0.0039 (8) | 0.0061 (7) | −0.0021 (9) |
C4 | 0.0310 (10) | 0.0399 (12) | 0.0451 (12) | 0.0016 (9) | 0.0090 (9) | 0.0016 (9) |
C5 | 0.0321 (11) | 0.0462 (13) | 0.0390 (12) | −0.0038 (9) | 0.0065 (9) | 0.0078 (9) |
C6 | 0.0275 (9) | 0.0429 (12) | 0.0349 (11) | −0.0120 (8) | 0.0072 (8) | −0.0015 (9) |
C7 | 0.0516 (13) | 0.0450 (13) | 0.0378 (12) | −0.0214 (11) | 0.0077 (10) | −0.0044 (10) |
C8 | 0.0383 (11) | 0.0268 (10) | 0.0316 (10) | 0.0000 (8) | 0.0047 (8) | −0.0035 (8) |
C9 | 0.0478 (13) | 0.0489 (13) | 0.0306 (11) | −0.0012 (10) | 0.0070 (9) | 0.0062 (9) |
C10 | 0.0576 (16) | 0.087 (2) | 0.0398 (13) | 0.0117 (15) | 0.0123 (12) | −0.0085 (14) |
C11 | 0.0362 (11) | 0.0508 (13) | 0.0362 (11) | −0.0079 (10) | 0.0064 (9) | −0.0002 (10) |
C12 | 0.0644 (16) | 0.0461 (14) | 0.0464 (14) | −0.0239 (12) | 0.0055 (12) | −0.0024 (11) |
Cl1—C1 | 1.728 (2) | C4—C5 | 1.381 (3) |
Cl2—C3 | 1.734 (2) | C4—H4A | 0.9300 |
S1—C8 | 1.668 (2) | C5—C6 | 1.395 (3) |
O1—C7 | 1.203 (3) | C5—H5A | 0.9300 |
O2—C12 | 1.423 (3) | C6—C7 | 1.501 (3) |
O2—H2A | 0.815 (10) | C9—C10 | 1.498 (4) |
N1—C7 | 1.374 (3) | C9—H9A | 0.9700 |
N1—C8 | 1.396 (3) | C9—H9B | 0.9700 |
N1—H1A | 0.8600 | C10—H10A | 0.9600 |
N2—C8 | 1.336 (3) | C10—H10B | 0.9600 |
N2—C9 | 1.468 (3) | C10—H10C | 0.9600 |
N2—C11 | 1.474 (3) | C11—C12 | 1.514 (4) |
C1—C2 | 1.380 (3) | C11—H11A | 0.9700 |
C1—C6 | 1.395 (3) | C11—H11B | 0.9700 |
C2—C3 | 1.380 (3) | C12—H12A | 0.9700 |
C2—H2B | 0.9300 | C12—H12B | 0.9700 |
C3—C4 | 1.380 (3) | ||
C12—O2—H2A | 112 (3) | N2—C8—N1 | 113.57 (17) |
C7—N1—C8 | 128.33 (18) | N2—C8—S1 | 123.90 (16) |
C7—N1—H1A | 115.8 | N1—C8—S1 | 122.48 (16) |
C8—N1—H1A | 115.8 | N2—C9—C10 | 113.0 (2) |
C8—N2—C9 | 121.02 (18) | N2—C9—H9A | 109.0 |
C8—N2—C11 | 124.05 (17) | C10—C9—H9A | 109.0 |
C9—N2—C11 | 114.86 (17) | N2—C9—H9B | 109.0 |
C2—C1—C6 | 121.5 (2) | C10—C9—H9B | 109.0 |
C2—C1—Cl1 | 117.57 (17) | H9A—C9—H9B | 107.8 |
C6—C1—Cl1 | 120.91 (17) | C9—C10—H10A | 109.5 |
C1—C2—C3 | 118.5 (2) | C9—C10—H10B | 109.5 |
C1—C2—H2B | 120.8 | H10A—C10—H10B | 109.5 |
C3—C2—H2B | 120.8 | C9—C10—H10C | 109.5 |
C2—C3—C4 | 122.2 (2) | H10A—C10—H10C | 109.5 |
C2—C3—Cl2 | 118.74 (16) | H10B—C10—H10C | 109.5 |
C4—C3—Cl2 | 119.03 (17) | N2—C11—C12 | 114.4 (2) |
C3—C4—C5 | 118.3 (2) | N2—C11—H11A | 108.7 |
C3—C4—H4A | 120.8 | C12—C11—H11A | 108.7 |
C5—C4—H4A | 120.8 | N2—C11—H11B | 108.7 |
C4—C5—C6 | 121.6 (2) | C12—C11—H11B | 108.7 |
C4—C5—H5A | 119.2 | H11A—C11—H11B | 107.6 |
C6—C5—H5A | 119.2 | O2—C12—C11 | 110.37 (19) |
C1—C6—C5 | 118.0 (2) | O2—C12—H12A | 109.6 |
C1—C6—C7 | 122.3 (2) | C11—C12—H12A | 109.6 |
C5—C6—C7 | 119.6 (2) | O2—C12—H12B | 109.6 |
O1—C7—N1 | 125.2 (2) | C11—C12—H12B | 109.6 |
O1—C7—C6 | 122.2 (2) | H12A—C12—H12B | 108.1 |
N1—C7—C6 | 112.59 (18) | ||
C6—C1—C2—C3 | 0.2 (3) | C1—C6—C7—O1 | 44.6 (4) |
Cl1—C1—C2—C3 | 177.72 (15) | C5—C6—C7—O1 | −131.6 (3) |
C1—C2—C3—C4 | −0.7 (3) | C1—C6—C7—N1 | −135.5 (2) |
C1—C2—C3—Cl2 | 179.34 (15) | C5—C6—C7—N1 | 48.4 (3) |
C2—C3—C4—C5 | 0.6 (3) | C9—N2—C8—N1 | −170.21 (19) |
Cl2—C3—C4—C5 | −179.50 (16) | C11—N2—C8—N1 | 12.9 (3) |
C3—C4—C5—C6 | 0.2 (3) | C9—N2—C8—S1 | 7.5 (3) |
C2—C1—C6—C5 | 0.5 (3) | C11—N2—C8—S1 | −169.33 (17) |
Cl1—C1—C6—C5 | −176.96 (15) | C7—N1—C8—N2 | −160.2 (2) |
C2—C1—C6—C7 | −175.70 (19) | C7—N1—C8—S1 | 22.0 (3) |
Cl1—C1—C6—C7 | 6.8 (3) | C8—N2—C9—C10 | −92.3 (3) |
C4—C5—C6—C1 | −0.7 (3) | C11—N2—C9—C10 | 84.8 (3) |
C4—C5—C6—C7 | 175.6 (2) | C8—N2—C11—C12 | −89.9 (3) |
C8—N1—C7—O1 | 13.0 (5) | C9—N2—C11—C12 | 93.1 (2) |
C8—N1—C7—C6 | −167.0 (2) | N2—C11—C12—O2 | 74.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.86 | 1.99 | 2.796 (3) | 155 |
C9—H9B···S1 | 0.97 | 2.64 | 3.031 (3) | 105 |
O2—H2A···S1i | 0.81 (3) | 2.75 (3) | 3.438 (2) | 143 (3) |
O2—H2A···O1i | 0.81 (3) | 2.25 (3) | 2.920 (3) | 140 (3) |
Symmetry code: (i) −x+3/2, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.86 | 1.99 | 2.796 (3) | 155 |
C9—H9B···S1 | 0.97 | 2.64 | 3.031 (3) | 105 |
O2—H2A···S1i | 0.81 (3) | 2.75 (3) | 3.438 (2) | 143 (3) |
O2—H2A···O1i | 0.81 (3) | 2.25 (3) | 2.920 (3) | 140 (3) |
Symmetry code: (i) −x+3/2, y+1/2, −z+3/2. |
Acknowledgements
The authors would like to thank Universiti Kebangsaan Malaysia and the Ministry of Science and Technology, Malaysia, for research grants FRGS/1/2013/ST01/UKM/03/4 and DIP-2012–11 and the Centre of Research and Instrumentation (CRIM) for the research facilities.
References
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Most of the aroyl or carbonoyl thiourea compounds reported so far are based on primary amines. The two amino hydrogen atoms play an important role on the geometry of the thiourea moiety such as that in 3-chloro-N-[N-(furan-2-carbonyl)hydrazinocarbothioyl]benzamide (Yamin et al., 2013) where it adopts trans geometry. However, in the secondary amine based thiourea, only the amido hydrogen atom is present (Nasir et al., 2011; Al-abbasi et al., 2012). Therefore, it can be expected that in the secondary amine carbonoyl thiourea, cis configuration is more likely to occur due to the absence of intrahydrogen bond involving the carbonyl oxygen atom and thioamide hydrogen atom. The title compound consists of dichloro substituted benzoyl and ethylethanol groups attached to the terminal nitrogen atoms respectively (Fig.1). The dichlorobenzoyl group is cis against thiono group across the C7—N1 bond. They are not coplanar but twisted by the dihedral angle between thiourea fragment S1/N1/N2/C8 and the dichlorobenzene ring, Cl1/Cl2/C1-C6, of 75.41 (8)°. Each fragment is planar with the maximum deviation of 0.025 (1)Å for atom Cl1 from the least-squares plane. The bond lengths and angles are in normal ranges (Allen et al.,1987). 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···S1 and O2–H2A···O1 intermolecular hydrogen bonds (see Table 1 for symmetry codes) to form one-dimensional chains along the b-axis (Fig.2).