Buy article online - an online subscription or single-article purchase is required to access this article.
Treatment of thiosemicarbazones prepared from sesquiterpenes with ethyl 2-bromoacetate in the presence of sodium acetate afforded the corresponding thiazolidin-4-ones. The structures of all the newly synthesized compounds were established by considering spectral and single-crystal X-ray diffraction data. The title compound, ethyl 2-((
Z)-2-{(
Z)-[(1a
R,5a
R,9a
S)-1,1-dichloro-1a,5,5,7-tetramethyl-1a,2,3,4,5,5a,8,9-octahydro-1
H-benzo[
a]cyclopropa[
b][7]annulen-8-ylidene]hydrazono}-4-oxothiazolidin-3-yl)acetate, C
23H
31Cl
2N
3O
3S,
5, crystallizes in the orthorhombic noncentrosymmetric space group
P2
12
12
1 with
Z = 4. Within the molecule in the crystal structure, the cyclohexene ring has an envelope conformation and the cycloheptane ring, to which it is fused, has a boat conformation. In the crystal, molecules are linked by C—H
Cl hydrogen bonds forming chains propagating along the
b-axis direction. The absolute configuration of the molecule in the crystal could be fully confirmed from anomalous dispersion effects [Flack parameter = −0.04 (2)]. Thiosemicarbazones
1 and
2 are efficient inhibitors for steel corrosion in 1
M H
2SO
4 solution, with a maximum efficiency of 92.28% at 10
−3 M. Furthermore, thiosemicarbazone compounds were found to be more efficient than thiazolidin-4-one derivatives. In addition, cyclic voltammetry was used to characterize the tested molecules, as well to estimate the experimental value of the energy band gap.
Supporting information
CCDC reference: 1911992
Data collection: DUO in APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Putz,
2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).
Ethyl
2-{(
Z)-2-{(
Z)-[(1a
R,5a
R,9a
S)-1,1-dichloro-1a,5,5,7-tetramethyl-1a,2,3,4,5,5a,8,9-octahydro-1
H-benzo[
a]cyclopropa[
b][7]annulen-8-ylidene]hydrazono}-4-oxothiazolidin-3-yl)acetate
top
Crystal data top
C23H31Cl2N3O3S | Dx = 1.316 Mg m−3 |
Mr = 500.47 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 5789 reflections |
a = 10.2769 (7) Å | θ = 2.0–27.5° |
b = 12.2445 (7) Å | µ = 0.37 mm−1 |
c = 20.0804 (13) Å | T = 299 K |
V = 2526.8 (3) Å3 | Block, colourless |
Z = 4 | 0.34 × 0.21 × 0.11 mm |
F(000) = 1056 | |
Data collection top
Bruker DUO APEXII CCD diffractometer | 4306 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.056 |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | θmax = 27.5°, θmin = 2.0° |
Tmin = 0.710, Tmax = 0.746 | h = −13→13 |
58280 measured reflections | k = −15→15 |
5789 independent reflections | l = −25→25 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0393P)2 + 0.3269P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.089 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.26 e Å−3 |
5789 reflections | Δρmin = −0.19 e Å−3 |
294 parameters | Absolute structure: Flack x determined using 1538 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
0 restraints | Absolute structure parameter: −0.04 (2) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.91689 (9) | 0.40874 (6) | 0.28176 (4) | 0.0521 (2) | |
Cl2 | 0.92163 (8) | 0.64247 (6) | 0.28263 (4) | 0.0456 (2) | |
S1' | 0.41368 (9) | 0.18868 (7) | 0.16736 (5) | 0.0572 (3) | |
O1 | 0.5447 (3) | −0.10510 (19) | 0.14607 (15) | 0.0719 (8) | |
O2 | 0.7293 (3) | 0.0766 (2) | 0.02640 (14) | 0.0716 (8) | |
O3 | 0.9255 (3) | 0.0866 (3) | 0.07238 (13) | 0.0816 (9) | |
N1 | 0.6044 (2) | 0.3561 (2) | 0.15782 (13) | 0.0447 (6) | |
N2 | 0.6657 (3) | 0.2530 (2) | 0.15405 (14) | 0.0441 (7) | |
N3' | 0.6216 (2) | 0.06903 (19) | 0.15379 (14) | 0.0447 (7) | |
C1 | 0.9428 (3) | 0.5258 (2) | 0.23193 (14) | 0.0334 (6) | |
C1A | 1.0446 (3) | 0.5220 (2) | 0.17788 (15) | 0.0341 (7) | |
C2 | 1.1211 (3) | 0.6249 (2) | 0.16433 (16) | 0.0418 (7) | |
H2A | 1.2050 | 0.6198 | 0.1863 | 0.050* | |
H2B | 1.0751 | 0.6868 | 0.1831 | 0.050* | |
C3 | 1.1421 (3) | 0.6439 (3) | 0.08995 (18) | 0.0538 (9) | |
H3A | 1.2185 | 0.6032 | 0.0761 | 0.065* | |
H3B | 1.1605 | 0.7208 | 0.0830 | 0.065* | |
C4 | 1.0282 (3) | 0.6115 (3) | 0.04491 (17) | 0.0509 (9) | |
H4A | 1.0515 | 0.6310 | −0.0004 | 0.061* | |
H4B | 1.0207 | 0.5326 | 0.0464 | 0.061* | |
C5 | 0.8934 (3) | 0.6590 (2) | 0.05887 (15) | 0.0425 (8) | |
C5A | 0.8460 (3) | 0.6323 (2) | 0.13161 (14) | 0.0338 (7) | |
H5A | 0.8799 | 0.6908 | 0.1600 | 0.041* | |
C6 | 0.7006 (3) | 0.6342 (3) | 0.13993 (15) | 0.0406 (7) | |
H6 | 0.6597 | 0.7019 | 0.1379 | 0.049* | |
C7 | 0.6253 (3) | 0.5472 (2) | 0.14991 (15) | 0.0387 (7) | |
C8 | 0.6826 (3) | 0.4371 (2) | 0.14911 (15) | 0.0357 (7) | |
C9 | 0.8265 (3) | 0.4258 (2) | 0.13597 (16) | 0.0361 (7) | |
H9A | 0.8412 | 0.4166 | 0.0886 | 0.043* | |
H9B | 0.8594 | 0.3614 | 0.1585 | 0.043* | |
C9A | 0.8990 (3) | 0.5258 (2) | 0.16040 (13) | 0.0300 (6) | |
C10 | 1.1226 (3) | 0.4187 (2) | 0.16751 (19) | 0.0466 (8) | |
H10A | 1.0659 | 0.3566 | 0.1703 | 0.070* | |
H10B | 1.1885 | 0.4134 | 0.2013 | 0.070* | |
H10C | 1.1630 | 0.4206 | 0.1244 | 0.070* | |
C11 | 0.8944 (4) | 0.7841 (3) | 0.05106 (19) | 0.0587 (10) | |
H11A | 0.9255 | 0.8029 | 0.0074 | 0.088* | |
H11B | 0.9507 | 0.8156 | 0.0840 | 0.088* | |
H11C | 0.8078 | 0.8119 | 0.0568 | 0.088* | |
C12 | 0.8010 (4) | 0.6128 (3) | 0.00546 (17) | 0.0591 (10) | |
H12A | 0.8294 | 0.6361 | −0.0378 | 0.089* | |
H12B | 0.7143 | 0.6389 | 0.0134 | 0.089* | |
H12C | 0.8017 | 0.5344 | 0.0075 | 0.089* | |
C13 | 0.4803 (3) | 0.5579 (3) | 0.1594 (2) | 0.0581 (10) | |
H13A | 0.4360 | 0.5206 | 0.1240 | 0.087* | |
H13B | 0.4566 | 0.6338 | 0.1589 | 0.087* | |
H13C | 0.4560 | 0.5263 | 0.2013 | 0.087* | |
C2' | 0.5817 (3) | 0.1767 (2) | 0.15774 (15) | 0.0414 (7) | |
C4' | 0.5249 (3) | −0.0091 (3) | 0.15382 (17) | 0.0501 (9) | |
C5' | 0.3940 (3) | 0.0420 (3) | 0.1651 (2) | 0.0565 (9) | |
H5'A | 0.3576 | 0.0164 | 0.2068 | 0.068* | |
H5'B | 0.3351 | 0.0218 | 0.1294 | 0.068* | |
C6' | 0.7568 (3) | 0.0426 (3) | 0.14311 (17) | 0.0479 (8) | |
H6'A | 0.7701 | −0.0348 | 0.1508 | 0.057* | |
H6'B | 0.8099 | 0.0826 | 0.1748 | 0.057* | |
C7' | 0.7990 (4) | 0.0707 (3) | 0.07342 (19) | 0.0493 (9) | |
C8' | 0.9852 (5) | 0.1165 (6) | 0.0093 (2) | 0.1041 (19) | |
H8'A | 1.0096 | 0.0512 | −0.0151 | 0.125* | |
H8'B | 0.9239 | 0.1576 | −0.0176 | 0.125* | |
C9' | 1.0974 (7) | 0.1811 (5) | 0.0221 (3) | 0.133 (3) | |
H9'A | 1.1409 | 0.1969 | −0.0191 | 0.199* | |
H9'B | 1.1553 | 0.1417 | 0.0510 | 0.199* | |
H9'C | 1.0718 | 0.2481 | 0.0431 | 0.199* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0539 (5) | 0.0422 (4) | 0.0601 (5) | 0.0043 (4) | 0.0065 (5) | 0.0198 (4) |
Cl2 | 0.0503 (5) | 0.0425 (4) | 0.0441 (4) | 0.0020 (4) | −0.0012 (4) | −0.0076 (3) |
S1' | 0.0366 (5) | 0.0501 (5) | 0.0849 (7) | −0.0068 (4) | 0.0104 (5) | −0.0062 (4) |
O1 | 0.076 (2) | 0.0378 (13) | 0.102 (2) | −0.0106 (12) | 0.0121 (16) | −0.0047 (13) |
O2 | 0.0620 (19) | 0.097 (2) | 0.0559 (17) | −0.0111 (16) | −0.0092 (16) | −0.0069 (14) |
O3 | 0.0451 (18) | 0.150 (3) | 0.0499 (16) | −0.0113 (19) | 0.0077 (14) | 0.0047 (16) |
N1 | 0.0343 (15) | 0.0404 (13) | 0.0595 (17) | −0.0021 (13) | 0.0024 (13) | −0.0069 (12) |
N2 | 0.0354 (15) | 0.0366 (14) | 0.0602 (18) | −0.0060 (12) | 0.0039 (14) | −0.0043 (12) |
N3' | 0.0388 (17) | 0.0356 (13) | 0.0597 (18) | −0.0024 (11) | 0.0036 (14) | −0.0034 (12) |
C1 | 0.0333 (17) | 0.0264 (13) | 0.0404 (16) | 0.0001 (13) | −0.0001 (13) | 0.0027 (12) |
C1A | 0.0274 (16) | 0.0292 (13) | 0.0456 (17) | 0.0018 (12) | 0.0017 (13) | 0.0024 (13) |
C2 | 0.0284 (17) | 0.0387 (16) | 0.058 (2) | −0.0035 (13) | 0.0029 (15) | 0.0018 (14) |
C3 | 0.041 (2) | 0.056 (2) | 0.065 (2) | −0.0024 (17) | 0.0117 (18) | 0.0132 (18) |
C4 | 0.052 (2) | 0.053 (2) | 0.047 (2) | 0.0064 (17) | 0.0104 (17) | 0.0089 (16) |
C5 | 0.049 (2) | 0.0374 (16) | 0.0415 (18) | 0.0039 (15) | −0.0017 (16) | 0.0042 (12) |
C5A | 0.0336 (17) | 0.0287 (14) | 0.0391 (16) | 0.0035 (13) | −0.0022 (13) | 0.0010 (12) |
C6 | 0.0351 (18) | 0.0371 (16) | 0.0496 (19) | 0.0112 (14) | −0.0046 (15) | 0.0006 (14) |
C7 | 0.0298 (17) | 0.0434 (17) | 0.0429 (18) | 0.0051 (13) | −0.0020 (14) | −0.0071 (13) |
C8 | 0.0289 (17) | 0.0377 (16) | 0.0406 (18) | −0.0004 (13) | −0.0006 (14) | −0.0046 (13) |
C9 | 0.0288 (17) | 0.0292 (14) | 0.0501 (19) | 0.0032 (12) | 0.0006 (14) | −0.0034 (13) |
C9A | 0.0245 (15) | 0.0264 (12) | 0.0392 (15) | 0.0025 (12) | 0.0007 (13) | −0.0014 (12) |
C10 | 0.0324 (18) | 0.0387 (16) | 0.069 (2) | 0.0074 (14) | 0.0046 (17) | 0.0030 (15) |
C11 | 0.073 (3) | 0.0444 (19) | 0.059 (2) | 0.003 (2) | −0.004 (2) | 0.0173 (15) |
C12 | 0.069 (3) | 0.061 (2) | 0.048 (2) | 0.007 (2) | −0.0091 (19) | 0.0008 (17) |
C13 | 0.033 (2) | 0.066 (2) | 0.075 (3) | 0.0113 (17) | −0.0009 (19) | −0.011 (2) |
C2' | 0.0361 (17) | 0.0424 (16) | 0.0456 (18) | −0.0061 (15) | 0.0042 (16) | −0.0044 (13) |
C4' | 0.051 (2) | 0.046 (2) | 0.054 (2) | −0.0124 (16) | 0.0059 (17) | 0.0001 (16) |
C5' | 0.044 (2) | 0.054 (2) | 0.071 (2) | −0.0187 (17) | 0.0089 (19) | −0.0073 (17) |
C6' | 0.040 (2) | 0.0479 (19) | 0.056 (2) | 0.0009 (16) | 0.0027 (16) | −0.0011 (16) |
C7' | 0.043 (2) | 0.051 (2) | 0.053 (2) | −0.0010 (17) | 0.0023 (19) | −0.0078 (16) |
C8' | 0.069 (3) | 0.194 (6) | 0.049 (3) | −0.023 (4) | 0.021 (2) | −0.005 (3) |
C9' | 0.171 (7) | 0.148 (5) | 0.079 (4) | −0.076 (5) | 0.042 (4) | −0.027 (3) |
Geometric parameters (Å, º) top
Cl1—C1 | 1.768 (3) | C5A—H5A | 0.9800 |
Cl2—C1 | 1.768 (3) | C6—C7 | 1.332 (4) |
S1'—C2' | 1.744 (3) | C6—H6 | 0.9300 |
S1'—C5' | 1.808 (3) | C7—C8 | 1.472 (4) |
O1—C4' | 1.203 (4) | C7—C13 | 1.508 (5) |
O2—C7' | 1.188 (4) | C8—C9 | 1.509 (4) |
O3—C7' | 1.315 (5) | C9—C9A | 1.515 (4) |
O3—C8' | 1.455 (5) | C9—H9A | 0.9700 |
N1—C8 | 1.288 (4) | C9—H9B | 0.9700 |
N1—N2 | 1.413 (3) | C10—H10A | 0.9600 |
N2—C2' | 1.274 (4) | C10—H10B | 0.9600 |
N3'—C4' | 1.380 (4) | C10—H10C | 0.9600 |
N3'—C2' | 1.383 (4) | C11—H11A | 0.9600 |
N3'—C6' | 1.442 (4) | C11—H11B | 0.9600 |
C1—C9A | 1.505 (4) | C11—H11C | 0.9600 |
C1—C1A | 1.508 (4) | C12—H12A | 0.9600 |
C1A—C2 | 1.509 (4) | C12—H12B | 0.9600 |
C1A—C10 | 1.512 (4) | C12—H12C | 0.9600 |
C1A—C9A | 1.538 (4) | C13—H13A | 0.9600 |
C2—C3 | 1.527 (5) | C13—H13B | 0.9600 |
C2—H2A | 0.9700 | C13—H13C | 0.9600 |
C2—H2B | 0.9700 | C4'—C5' | 1.501 (5) |
C3—C4 | 1.532 (5) | C5'—H5'A | 0.9700 |
C3—H3A | 0.9700 | C5'—H5'B | 0.9700 |
C3—H3B | 0.9700 | C6'—C7' | 1.505 (5) |
C4—C5 | 1.529 (5) | C6'—H6'A | 0.9700 |
C4—H4A | 0.9700 | C6'—H6'B | 0.9700 |
C4—H4B | 0.9700 | C8'—C9' | 1.421 (7) |
C5—C11 | 1.539 (4) | C8'—H8'A | 0.9700 |
C5—C12 | 1.540 (5) | C8'—H8'B | 0.9700 |
C5—C5A | 1.574 (4) | C9'—H9'A | 0.9600 |
C5A—C6 | 1.504 (4) | C9'—H9'B | 0.9600 |
C5A—C9A | 1.527 (4) | C9'—H9'C | 0.9600 |
| | | |
C2'—S1'—C5' | 91.40 (15) | C1—C9A—C9 | 117.1 (2) |
C7'—O3—C8' | 117.9 (3) | C1—C9A—C5A | 117.9 (2) |
C8—N1—N2 | 113.7 (2) | C9—C9A—C5A | 113.1 (2) |
C2'—N2—N1 | 110.5 (3) | C1—C9A—C1A | 59.40 (19) |
C4'—N3'—C2' | 116.6 (3) | C9—C9A—C1A | 121.9 (2) |
C4'—N3'—C6' | 122.6 (3) | C5A—C9A—C1A | 117.3 (2) |
C2'—N3'—C6' | 120.5 (3) | C1A—C10—H10A | 109.5 |
C9A—C1—C1A | 61.37 (18) | C1A—C10—H10B | 109.5 |
C9A—C1—Cl1 | 119.7 (2) | H10A—C10—H10B | 109.5 |
C1A—C1—Cl1 | 119.2 (2) | C1A—C10—H10C | 109.5 |
C9A—C1—Cl2 | 120.84 (19) | H10A—C10—H10C | 109.5 |
C1A—C1—Cl2 | 121.6 (2) | H10B—C10—H10C | 109.5 |
Cl1—C1—Cl2 | 108.09 (15) | C5—C11—H11A | 109.5 |
C1—C1A—C2 | 117.8 (2) | C5—C11—H11B | 109.5 |
C1—C1A—C10 | 119.5 (2) | H11A—C11—H11B | 109.5 |
C2—C1A—C10 | 113.4 (2) | C5—C11—H11C | 109.5 |
C1—C1A—C9A | 59.22 (18) | H11A—C11—H11C | 109.5 |
C2—C1A—C9A | 116.2 (2) | H11B—C11—H11C | 109.5 |
C10—C1A—C9A | 120.6 (2) | C5—C12—H12A | 109.5 |
C1A—C2—C3 | 112.2 (3) | C5—C12—H12B | 109.5 |
C1A—C2—H2A | 109.2 | H12A—C12—H12B | 109.5 |
C3—C2—H2A | 109.2 | C5—C12—H12C | 109.5 |
C1A—C2—H2B | 109.2 | H12A—C12—H12C | 109.5 |
C3—C2—H2B | 109.2 | H12B—C12—H12C | 109.5 |
H2A—C2—H2B | 107.9 | C7—C13—H13A | 109.5 |
C2—C3—C4 | 115.5 (3) | C7—C13—H13B | 109.5 |
C2—C3—H3A | 108.4 | H13A—C13—H13B | 109.5 |
C4—C3—H3A | 108.4 | C7—C13—H13C | 109.5 |
C2—C3—H3B | 108.4 | H13A—C13—H13C | 109.5 |
C4—C3—H3B | 108.4 | H13B—C13—H13C | 109.5 |
H3A—C3—H3B | 107.5 | N2—C2'—N3' | 119.6 (3) |
C5—C4—C3 | 119.1 (3) | N2—C2'—S1' | 128.0 (2) |
C5—C4—H4A | 107.6 | N3'—C2'—S1' | 112.3 (2) |
C3—C4—H4A | 107.6 | O1—C4'—N3' | 123.8 (3) |
C5—C4—H4B | 107.6 | O1—C4'—C5' | 125.3 (3) |
C3—C4—H4B | 107.6 | N3'—C4'—C5' | 110.9 (3) |
H4A—C4—H4B | 107.0 | C4'—C5'—S1' | 108.5 (2) |
C4—C5—C11 | 110.7 (3) | C4'—C5'—H5'A | 110.0 |
C4—C5—C12 | 106.9 (3) | S1'—C5'—H5'A | 110.0 |
C11—C5—C12 | 107.4 (3) | C4'—C5'—H5'B | 110.0 |
C4—C5—C5A | 111.8 (3) | S1'—C5'—H5'B | 110.0 |
C11—C5—C5A | 107.7 (3) | H5'A—C5'—H5'B | 108.4 |
C12—C5—C5A | 112.3 (3) | N3'—C6'—C7' | 111.4 (3) |
C6—C5A—C9A | 109.0 (2) | N3'—C6'—H6'A | 109.3 |
C6—C5A—C5 | 114.0 (2) | C7'—C6'—H6'A | 109.3 |
C9A—C5A—C5 | 114.7 (2) | N3'—C6'—H6'B | 109.3 |
C6—C5A—H5A | 106.1 | C7'—C6'—H6'B | 109.3 |
C9A—C5A—H5A | 106.1 | H6'A—C6'—H6'B | 108.0 |
C5—C5A—H5A | 106.1 | O2—C7'—O3 | 125.1 (4) |
C7—C6—C5A | 125.5 (3) | O2—C7'—C6' | 125.4 (3) |
C7—C6—H6 | 117.2 | O3—C7'—C6' | 109.5 (3) |
C5A—C6—H6 | 117.2 | C9'—C8'—O3 | 108.9 (4) |
C6—C7—C8 | 119.9 (3) | C9'—C8'—H8'A | 109.9 |
C6—C7—C13 | 121.6 (3) | O3—C8'—H8'A | 109.9 |
C8—C7—C13 | 118.5 (3) | C9'—C8'—H8'B | 109.9 |
N1—C8—C7 | 117.0 (3) | O3—C8'—H8'B | 109.9 |
N1—C8—C9 | 124.4 (3) | H8'A—C8'—H8'B | 108.3 |
C7—C8—C9 | 118.6 (3) | C8'—C9'—H9'A | 109.5 |
C8—C9—C9A | 110.5 (2) | C8'—C9'—H9'B | 109.5 |
C8—C9—H9A | 109.5 | H9'A—C9'—H9'B | 109.5 |
C9A—C9—H9A | 109.5 | C8'—C9'—H9'C | 109.5 |
C8—C9—H9B | 109.5 | H9'A—C9'—H9'C | 109.5 |
C9A—C9—H9B | 109.5 | H9'B—C9'—H9'C | 109.5 |
H9A—C9—H9B | 108.1 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···Cl2i | 0.96 | 2.79 | 3.557 (3) | 137 |
C2—H2B···Cl1ii | 0.97 | 2.81 | 3.661 (3) | 147 |
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) −x+2, y+1/2, −z+1/2. |
Selected geometric parameters (Å, °) for 5 (reported here) and
a–c (reported previously) topBond lengths | 5 | a* | b** | c*** |
Cl1—C1 | 1.768 (3) | 1.757 (3) | 1.763 (6) | 1.769 (2) |
Cl2—C1 | 1.768 (3) | 1.762 (3) | 1.766 (6) | 1.761 (2) |
N1—C8 | 1.287 (4) | —– | 1.283 (7) | 1.288 (2) |
C6—C7 | 1.331 (5) | 1.318 (4) | 1.342 (8) | 1.326 (3) |
C7—C8 | 1.472 (4) | 1.486 (4) | 1.474 (8) | 1.472 (2) |
C8—C9 | 1.509 (4) | 1.511 (4) | 1.512 (7) | 1.504 (2) |
| | | | |
Cl1—C1—Cl2 | 108.1 (2) | 107.6 (2) | 108.2 (3) | 108.8 (1) |
C7—C8—C9 | 118.6 (3) | 114.8 (2) | 118.2 (4) | 119.6 (2) |
C6—C7—C8 | 119.9 (3) | 121.4 (3) | 120.2 (4) | 119.0 (2) |
N1—C8—C7 | 117.0 (3) | —– | 116.3 (4) | 116.3 (2) |
N1—C8—C9 | 124.3 (3) | —– | 125.4 (5) | 124.2 (2) |
References: (*) Auhmani et al. (1999); (**) Benharref et
al. (2016); (***)
Ourhriss et al. (2005). |
Comparison of main bond lengths (Å) and C═N—N═C torsions
angles (°) in the title compound and related structures topN1—N2 | C2'—N2 | N1—C8 | S1'—C2' | N3'—C2' | C═N—N═C | Reference |
1.413 (4) | 1.275 (5) | 1.288 (4) | 1.744 (4) | 1.383 (4) | -174.7 (3) | This study |
1.417 (3) | 1.269 (3) | 1.291 (3) | 1.756 (3) | 1.380 (3) | 173.8 (3) | Gautam & Chaudhary (2015) |
1.406 (2) | 1.277 (2) | 1.287 (2) | 1.769 (2) | 1.386 (2) | 179.0 (2) | Hassan et al. (2017) |
1.405 (3) | 1.274 (3) | 1.286 (4) | 1.756 (3) | 1.398 (3) | -168.9 (2) | N'ait Ousidi et al. (2017) |
1.407 (2) | 1.281 (2) | 1.291 (2) | 1.761 (2) | 1.392 (2) | 179.4 (2) | Mague et al. (2014) |
1.414 (2) | 1.278 (2) | 1.278 (2) | 1.749 (2) | 1.367 (2) | -177.3 (2) | Ramachandran et al. (2009) |
1.417 (7) | 1.256 (7) | 1.268 (8) | 1.759 (5) | 1.412 (8) | -177.6 (8) | Gupta & Chaudhary (2013) |
1.410 (6) | 1.279 (7) | 1.279 (7) | 1.767 (5) | 1.364 (7) | 174.9 (7) | Gautam et al. (2013) |
Tafel parameters and corresponding inhibition efficiency derived from
potentiodynamic polarization curves topInhibitor | Ecorr (mV versus SCE) | icorr (mA cm-2) | η (%) |
Blank | -378.7 | 305.9 | – |
1 | -330.3 | 112.8 | 63.12 |
3 | -327.7 | 129.9 | 57.53 |
5 | -369.4 | 202.5 | 33.80 |
2 | -376.2 | 23.6 | 92.28 |
4 | -327.8 | 187.4 | 38.73 |
6 | -311.3 | 132.2 | 56.78 |
Cyclic voltammetry parameters for the different tested molecules in a
solution of 0.2 M Et4NClO4/acetonitrile at 100 mV s-1. topMolecules | Eoxonset | EHOMO | Eredonset | ELUMO | ΔE |
1 | 0.235 | -5.035 | 0.102 | -4.902 | 0.133 |
2 | -0.235 | -4.565 | -0.324 | -4.476 | 0.089 |
3 | 0.537 | -5.337 | 0.235 | -5.035 | 0.302 |
4 | 0.271 | -5.071 | 0.129 | -4.929 | 0.142 |
5 | 0.572 | -5.372 | 0.226 | -5.026 | 0.346 |
6 | 0.182 | -4.982 | 0.031 | -4.831 | 0.151 |
Molecular properties of thiosemicarbazone and thiazolidin-4-one derivatives
calculated using DFT at the B3LYP/6-31G(d) basis set. topMolecule | 1 | 2 | 4 | 6 | 3 | 5 |
EHOMO | -0.201 | -0.203 | -0.216 | -0.212 | -0.217 | -0.213 |
ELUMO | -0.051 | -0.053 | -0.054 | -0.053 | -0.055 | -0.053 |
ΔE | 0.150 | 0.150 | 0.162 | 0.158 | 0.161 | 0.159 |
η | 0.075 | 0.075 | 0.081 | 0.079 | 0.080 | 0.079 |
ΔET | -0.01875 | -0.018 | -0.020 | -0.0198 | -0.0202 | -0.0198 |
ΔN | 45.821 | 45.651 | 42.307 | 43.294 | 42.393 | 43.150 |
Dipôle/moment | 7.295 | 6.696 | 3.738 | 3.834 | 3.881 | 4.085 |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.