organic compounds
N-[Ethyl(2-hydroxyethyl)carbamothioyl]-3-fluorobenzamide
aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia, and bLow Carbon Research Group, School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
*Correspondence e-mail: sitifairus@ukm.edu.my
In the title compound, C12H15FN2O2S, the molecule adopts a cis configuration of the fluorobenzoyl group with respect to the thiono group about their C—N bond. The dihedral angle between the fluorobenzoyl group and the thiourea N2CS fragment is 69.60 (11)°. An intramolecular N—H⋯O hydrogen bond occurs. In the crystal, molecules form chains along the b-axis direction via O—H⋯S and C—H⋯O hydrogen bonds.
CCDC reference: 996752
Related literature
For bond length data see: Allen et al. (1987). For a related structure, see: Yamin et al. (2014).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); 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 and PLATON (Spek, 2009).
Supporting information
CCDC reference: 996752
10.1107/S1600536814008174/bq2395sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814008174/bq2395Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814008174/bq2395Isup3.cml
A mixture of acetone (30 ml) solution and 2-(ethylamino)ethanol (0.18 g, 2 mmol) was added into round-bottom flask containing 4-fluorobenzoyl isothiocyanate (0.36 g, 2 mmol). The mixture was refluxed for 3 h. The mixture then cooled and filtered off. 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 ethanol.
After their location in the difference map, the H-atoms attached to the C and N atoms were fixed geometrically at ideal positions and allowed to ride on the parent atoms with C—H = 0.93 Å, with Uiso(H)=1.2Ueq(C). The hydrogen atom attached to oxygen atom was located from Fourier map and refined isotropically with O—H restraint to 0.82 with an e.s.d. of 0.01. The rotating model was applied for the
of methyl H atoms.Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL2013 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).C12H15FN2O2S | F(000) = 568 |
Mr = 270.32 | Dx = 1.347 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 11689 reflections |
a = 6.0205 (3) Å | θ = 3.1–28.2° |
b = 12.9441 (6) Å | µ = 0.25 mm−1 |
c = 17.1071 (9) Å | T = 296 K |
V = 1333.16 (11) Å3 | Block, colorless |
Z = 4 | 0.50 × 0.50 × 0.29 mm |
Bruker SMART APEX CCD area-detector diffractometer | 3290 independent reflections |
Radiation source: fine-focus sealed tube | 2864 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 28.2°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −8→7 |
Tmin = 0.885, Tmax = 0.931 | k = −17→16 |
21708 measured reflections | l = −21→22 |
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) = 0.086 | w = 1/[σ2(Fo2) + (0.0367P)2 + 0.3143P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
3290 reflections | Δρmax = 0.22 e Å−3 |
168 parameters | Δρmin = −0.18 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1378 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.05 (8) |
C12H15FN2O2S | V = 1333.16 (11) Å3 |
Mr = 270.32 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.0205 (3) Å | µ = 0.25 mm−1 |
b = 12.9441 (6) Å | T = 296 K |
c = 17.1071 (9) Å | 0.50 × 0.50 × 0.29 mm |
Bruker SMART APEX CCD area-detector diffractometer | 3290 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2864 reflections with I > 2σ(I) |
Tmin = 0.885, Tmax = 0.931 | Rint = 0.031 |
21708 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.086 | Δρmax = 0.22 e Å−3 |
S = 1.07 | Δρmin = −0.18 e Å−3 |
3290 reflections | Absolute structure: Flack (1983), 1378 Friedel pairs |
168 parameters | Absolute structure parameter: −0.05 (8) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
F1 | −0.5492 (2) | 0.22048 (12) | 0.06124 (8) | 0.0690 (4) | |
S1 | 0.25957 (10) | 0.08756 (4) | 0.35274 (3) | 0.05288 (15) | |
O1 | 0.2778 (3) | 0.02641 (9) | 0.17285 (8) | 0.0537 (4) | |
O2 | 0.0320 (2) | 0.39036 (10) | 0.21034 (9) | 0.0501 (3) | |
H2A | −0.053 (3) | 0.4382 (14) | 0.2024 (14) | 0.067 (7)* | |
N1 | 0.1564 (2) | 0.18174 (10) | 0.21762 (8) | 0.0369 (3) | |
H1A | 0.0836 | 0.2359 | 0.2039 | 0.044* | |
N2 | 0.3727 (2) | 0.27479 (10) | 0.30261 (8) | 0.0360 (3) | |
C1 | −0.2089 (3) | 0.16654 (13) | 0.11163 (9) | 0.0382 (4) | |
H1 | −0.2228 | 0.2134 | 0.1526 | 0.046* | |
C2 | −0.3693 (3) | 0.15905 (16) | 0.05543 (10) | 0.0438 (4) | |
C3 | −0.3574 (4) | 0.09202 (19) | −0.00610 (11) | 0.0556 (5) | |
H3 | −0.4698 | 0.0890 | −0.0433 | 0.067* | |
C4 | −0.1751 (4) | 0.02952 (18) | −0.01123 (13) | 0.0625 (6) | |
H4 | −0.1633 | −0.0167 | −0.0526 | 0.075* | |
C5 | −0.0084 (4) | 0.03385 (15) | 0.04385 (11) | 0.0497 (5) | |
H5 | 0.1148 | −0.0091 | 0.0394 | 0.060* | |
C6 | −0.0245 (3) | 0.10242 (12) | 0.10612 (10) | 0.0341 (3) | |
C7 | 0.1516 (3) | 0.09866 (12) | 0.16784 (10) | 0.0349 (3) | |
C8 | 0.2701 (3) | 0.18551 (11) | 0.28899 (10) | 0.0348 (3) | |
C9 | 0.4712 (4) | 0.29815 (16) | 0.37932 (11) | 0.0546 (5) | |
H9A | 0.3884 | 0.2621 | 0.4196 | 0.066* | |
H9B | 0.4587 | 0.3717 | 0.3893 | 0.066* | |
C10 | 0.7126 (4) | 0.26688 (19) | 0.38404 (16) | 0.0765 (8) | |
H10A | 0.7259 | 0.1941 | 0.3743 | 0.115* | |
H10B | 0.7690 | 0.2823 | 0.4352 | 0.115* | |
H10C | 0.7964 | 0.3044 | 0.3456 | 0.115* | |
C11 | 0.4091 (3) | 0.35433 (13) | 0.24232 (10) | 0.0366 (4) | |
H11A | 0.4176 | 0.3211 | 0.1916 | 0.044* | |
H11B | 0.5505 | 0.3879 | 0.2520 | 0.044* | |
C12 | 0.2301 (4) | 0.43491 (12) | 0.24008 (11) | 0.0447 (4) | |
H12A | 0.2041 | 0.4615 | 0.2923 | 0.054* | |
H12B | 0.2760 | 0.4919 | 0.2070 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0511 (7) | 0.0961 (10) | 0.0598 (7) | 0.0225 (7) | −0.0128 (6) | −0.0004 (7) |
S1 | 0.0634 (3) | 0.0408 (2) | 0.0544 (3) | −0.0138 (2) | −0.0199 (3) | 0.0157 (2) |
O1 | 0.0596 (9) | 0.0393 (6) | 0.0622 (8) | 0.0182 (7) | −0.0127 (7) | −0.0037 (6) |
O2 | 0.0487 (8) | 0.0337 (7) | 0.0677 (9) | 0.0113 (6) | −0.0071 (7) | −0.0017 (6) |
N1 | 0.0404 (8) | 0.0252 (6) | 0.0451 (8) | 0.0027 (6) | −0.0149 (6) | 0.0016 (6) |
N2 | 0.0388 (8) | 0.0307 (7) | 0.0385 (7) | −0.0034 (6) | −0.0073 (6) | −0.0005 (6) |
C1 | 0.0421 (10) | 0.0422 (8) | 0.0301 (7) | 0.0018 (8) | −0.0015 (7) | −0.0009 (6) |
C2 | 0.0367 (9) | 0.0559 (11) | 0.0389 (9) | 0.0023 (8) | −0.0004 (8) | 0.0067 (8) |
C3 | 0.0562 (12) | 0.0745 (14) | 0.0360 (9) | −0.0134 (12) | −0.0118 (9) | 0.0010 (10) |
C4 | 0.0816 (17) | 0.0612 (13) | 0.0446 (11) | −0.0042 (13) | −0.0055 (11) | −0.0176 (10) |
C5 | 0.0578 (12) | 0.0452 (10) | 0.0460 (11) | 0.0046 (9) | −0.0001 (9) | −0.0088 (9) |
C6 | 0.0377 (8) | 0.0304 (8) | 0.0343 (8) | −0.0033 (7) | −0.0008 (7) | 0.0019 (6) |
C7 | 0.0355 (8) | 0.0278 (7) | 0.0413 (9) | −0.0010 (7) | −0.0014 (7) | 0.0033 (6) |
C8 | 0.0304 (8) | 0.0315 (7) | 0.0427 (8) | 0.0003 (7) | −0.0065 (7) | 0.0005 (6) |
C9 | 0.0727 (14) | 0.0475 (11) | 0.0437 (10) | −0.0147 (10) | −0.0170 (10) | −0.0025 (9) |
C10 | 0.0724 (17) | 0.0650 (14) | 0.0920 (17) | −0.0156 (13) | −0.0453 (15) | 0.0178 (13) |
C11 | 0.0368 (9) | 0.0304 (8) | 0.0425 (9) | −0.0040 (7) | −0.0002 (7) | 0.0001 (7) |
C12 | 0.0554 (12) | 0.0275 (7) | 0.0512 (10) | 0.0047 (9) | −0.0025 (10) | −0.0039 (7) |
F1—C2 | 1.347 (2) | C4—C5 | 1.377 (3) |
S1—C8 | 1.6736 (16) | C4—H4 | 0.9300 |
O1—C7 | 1.208 (2) | C5—C6 | 1.390 (2) |
O2—C12 | 1.419 (2) | C5—H5 | 0.9300 |
O2—H2A | 0.816 (10) | C6—C7 | 1.497 (2) |
N1—C7 | 1.372 (2) | C9—C10 | 1.511 (3) |
N1—C8 | 1.401 (2) | C9—H9A | 0.9700 |
N1—H1A | 0.8600 | C9—H9B | 0.9700 |
N2—C8 | 1.331 (2) | C10—H10A | 0.9600 |
N2—C9 | 1.471 (2) | C10—H10B | 0.9600 |
N2—C11 | 1.474 (2) | C10—H10C | 0.9600 |
C1—C2 | 1.366 (2) | C11—C12 | 1.500 (3) |
C1—C6 | 1.389 (2) | C11—H11A | 0.9700 |
C1—H1 | 0.9300 | C11—H11B | 0.9700 |
C2—C3 | 1.366 (3) | C12—H12A | 0.9700 |
C3—C4 | 1.366 (3) | C12—H12B | 0.9700 |
C3—H3 | 0.9300 | ||
C12—O2—H2A | 106.3 (18) | N2—C8—N1 | 114.19 (13) |
C7—N1—C8 | 125.36 (13) | N2—C8—S1 | 124.15 (13) |
C7—N1—H1A | 117.3 | N1—C8—S1 | 121.54 (12) |
C8—N1—H1A | 117.3 | N2—C9—C10 | 112.35 (19) |
C8—N2—C9 | 121.44 (15) | N2—C9—H9A | 109.1 |
C8—N2—C11 | 123.58 (14) | C10—C9—H9A | 109.1 |
C9—N2—C11 | 114.88 (14) | N2—C9—H9B | 109.1 |
C2—C1—C6 | 118.34 (16) | C10—C9—H9B | 109.1 |
C2—C1—H1 | 120.8 | H9A—C9—H9B | 107.9 |
C6—C1—H1 | 120.8 | C9—C10—H10A | 109.5 |
F1—C2—C3 | 118.29 (17) | C9—C10—H10B | 109.5 |
F1—C2—C1 | 118.32 (16) | H10A—C10—H10B | 109.5 |
C3—C2—C1 | 123.38 (18) | C9—C10—H10C | 109.5 |
C2—C3—C4 | 117.89 (18) | H10A—C10—H10C | 109.5 |
C2—C3—H3 | 121.1 | H10B—C10—H10C | 109.5 |
C4—C3—H3 | 121.1 | N2—C11—C12 | 113.38 (15) |
C3—C4—C5 | 121.14 (19) | N2—C11—H11A | 108.9 |
C3—C4—H4 | 119.4 | C12—C11—H11A | 108.9 |
C5—C4—H4 | 119.4 | N2—C11—H11B | 108.9 |
C4—C5—C6 | 120.0 (2) | C12—C11—H11B | 108.9 |
C4—C5—H5 | 120.0 | H11A—C11—H11B | 107.7 |
C6—C5—H5 | 120.0 | O2—C12—C11 | 109.28 (13) |
C1—C6—C5 | 119.29 (16) | O2—C12—H12A | 109.8 |
C1—C6—C7 | 122.51 (15) | C11—C12—H12A | 109.8 |
C5—C6—C7 | 118.06 (16) | O2—C12—H12B | 109.8 |
O1—C7—N1 | 123.33 (15) | C11—C12—H12B | 109.8 |
O1—C7—C6 | 121.38 (15) | H12A—C12—H12B | 108.3 |
N1—C7—C6 | 115.29 (14) | ||
C6—C1—C2—F1 | 179.31 (16) | C1—C6—C7—N1 | −18.5 (2) |
C6—C1—C2—C3 | −0.2 (3) | C5—C6—C7—N1 | 165.87 (16) |
F1—C2—C3—C4 | −179.56 (19) | C9—N2—C8—N1 | 170.60 (17) |
C1—C2—C3—C4 | 0.0 (3) | C11—N2—C8—N1 | −13.3 (2) |
C2—C3—C4—C5 | 0.0 (3) | C9—N2—C8—S1 | −5.4 (3) |
C3—C4—C5—C6 | 0.2 (3) | C11—N2—C8—S1 | 170.74 (13) |
C2—C1—C6—C5 | 0.5 (2) | C7—N1—C8—N2 | 139.06 (17) |
C2—C1—C6—C7 | −175.11 (16) | C7—N1—C8—S1 | −44.8 (2) |
C4—C5—C6—C1 | −0.5 (3) | C8—N2—C9—C10 | 91.8 (2) |
C4—C5—C6—C7 | 175.31 (19) | C11—N2—C9—C10 | −84.6 (2) |
C8—N1—C7—O1 | −14.3 (3) | C8—N2—C11—C12 | 93.48 (19) |
C8—N1—C7—C6 | 165.10 (16) | C9—N2—C11—C12 | −90.17 (19) |
C1—C6—C7—O1 | 160.93 (17) | N2—C11—C12—O2 | −70.51 (19) |
C5—C6—C7—O1 | −14.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.86 | 2.03 | 2.805 (2) | 150 |
C9—H9A···S1 | 0.97 | 2.65 | 3.043 (3) | 105 |
O2—H2A···S1i | 0.82 (3) | 2.49 (3) | 3.2805 (19) | 166 (3) |
C11—H11B···O1ii | 0.97 | 2.44 | 3.259 (3) | 142 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.86 | 2.03 | 2.805 (2) | 150 |
O2—H2A···S1i | 0.82 (3) | 2.49 (3) | 3.2805 (19) | 166 (3) |
C11—H11B···O1ii | 0.97 | 2.44 | 3.259 (3) | 142 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
Acknowledgements
The authors would like to thank Universiti Kebangsaan Malaysia for research grants DLP-2013–009 and DIP-2012–11. Research facilities provided by the Centre of Research and Instrumentation (CRIM) is very much appreciated.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yamin, B. M., Sapari, S. & Hasbullah, S. A. (2014). Acta Cryst. E70, o33. CSD CrossRef IUCr Journals Google Scholar
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The expected cis configuration of the carbonoyl with respect to the thione group was observed when one terminal of the thiourea moiety is a secondary amine as in the case of 2,4-dichloro-N-[ethyl(2-hydroxyethyl)- carbamothioyl]benzamide (Yamin et al., 2014). Such configuration will enhance its property as bidentate ligand in a complexation reaction with metals. The title compound is similar but having a monosubstituted flourine atom at position-3 of the benzene ring (Fig 1). The fluorobenzoyl group is also cis to the thiono group, C8—S1 about the N1—C8 bond. The thiourea moiety S1/N1/N2/C8 and fluorobenzene ring F1/(C1—C6) are planar with maximum deviation of 0.022 (2) Å for C8 atom from the least square plane of the thiourea moiety fragment. The two planes make dihedral angle of 69.60 (11)°, slightly less than that of the analog (75.41 (8)°). The bond lengths and angles are in normal ranges (Allen et al., 1987). There is intramolecular hydrogen bond between hydroxyl oxygen atom, (O2) and the hydrogen of the amide group. In the crystal structure, molecules are linked by O2—H2A···S1 and C11—H11B···O1 intermolecular hydrogen bonds (see Table 1 for symmetry codes) to form one-dimensional chain along the b axis (Fig.2).