organic compounds
2-[(E)-(2S,5R)-2-Isopropyl-5-methylcyclohexylidene]-N-methylhydrazine-1-carbothioamide
aDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, 49100-000 São Cristóvão-SE, Brazil, bInstitut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, D-53121 Bonn, Germany, and cInstituto de Química, Universidade Estadual Paulista, Rua Francisco Degni s/n, 14801-970 Araraquara-SP, Brazil
*Correspondence e-mail: adriano@daad-alumni.de
There are two molecules in the 12H23N3S, which are linked by two strong N—H⋯S hydrogen bonds, building a non-centrosymmetric dimer with graph-set motif R22(8). The molecules are further connected by N—H⋯S interactions into a two-dimensional hydrogen-bonded polymeric structure along the [001] direction. The is based on the of the Flack parameter.
of the title compound, CKeywords: crystal structure; chiral thiosemicarbazone; hydrogen-bonded polymer; non-centrosymmetric dimer.
CCDC reference: 1469055
Structure description
As part of our ongoing research on the synthesis and chemical structure of thiosemicarbazone derivatives from natural products, we report herein the
of a (−)-menthone-thiosemicarbazone compound.In the P21. The molecules are connected by mutual N—H⋯S interactions, building a non-centrosymmetric dimer with an (8) ring. The thiosemicarbazone entities are not planar and the torsion angles N1—N2—C11—N3 and N4—N5—C23—N6 are 2.4 (3) and 12.5 (3)°, respectively. For the N1—N2 and N4—N5 bonds, the E conformation is observed. The cyclohexane rings of the menthone units are in a chair conformation (Fig. 1). Both of these conformations are also observed for the (−)-menthone-3-thiosemicarbazone derivative (Oliveira et al., 2014).
of the title compound, there are two discrete molecules in general positions in the As enantiopure (−)-menthone was used in the chemical reaction, both of the crystallographically independent molecules have the same The atoms C3, C6, C15 and C18 are chiral centres and maintain the of the employed reagent and the obtained product emerges as enantiopure crystals in the non-centrosymmetricIn the crystal, the molecules are also connected by symmetry-generated N—H⋯S hydrogen bonds into a one-dimensional polymer along the b-axis (Fig. 2 and Table 1). In addition, other hydrogen bonds of the same type, with bridging sulfur atoms, connect the molecules into a two-dimensional polymeric chain along [001].
Synthesis and crystallization
The synthesis of the title compound was adapted from a previously reported procedure (Freund & Schander, 1902). In a hydrochloric acid-catalysed reaction, a mixture of (−)-menthone (10 mmol) and 4-methyl-3-thiosemicarbazide (10 mmol) in ethanol (80 mL) was refluxed for 5 h. After cooling and filtering, the title compound was obtained. Colourless plates were obtained by slow evaporation of a solution in the solvent DMSO.
Refinement
Crystal data, data collection and structure . The correct assignment of the was assured by the of 0.00 (7).
details are summarized in Table 2Structural data
CCDC reference: 1469055
10.1107/S2414314616004594/bx4002sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616004594/bx4002Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616004594/bx4002Isup3.cml
The synthesis of the title compound was adapted from a previously reported procedure (Freund & Schander, 1902). In a hydrochloric acid-catalysed reaction, a mixture of (-)-menthone (10 mmol) and 4-methyl-3-thiosemicarbazide (10 mmol) in ethanol (80 ml) was refluxed for 5 h. After cooling and filtering, the title compound was obtained. Colourless plates were obtained by slow evaporation of a solution in the solvent DMSO.
Crystal data, data collection and structure
details are summarized in Table 2. The correct assignment of the was assured by the of 0.00 (7).As part of our ongoing research on the synthesis and chemical structure of thiosemicarbazone derivatives from natural products, we report herein the
of a (-)-menthone-thiosemicarbazone compound.In the
of the title compound, there are two discrete molecules in general positions in the As (-)-menthone was used in the chemical reaction, both of the crystallographically independent molecules have the same The atoms C3, C6, C15 and C18 are chiral centres and maintain the of the employed reagent and the obtained product emerges as crystals in the non-centrosymmetric P21. The molecules are connected by mutual N—H···S interactions, building a non-centrosymmetric dimer with an R22(8) ring. The thiosemicarbazone entities are not planar and the torsion angles N1—N2—C11—N3 and N4—N5—C23—N6 are 2.4 (3) and 12.5 (3)°, respectively. For the N1—N2 and N4—N5 bonds, the E conformation is observed. The cyclohexane rings of the menthone units are in a chair conformation (Fig. 1). Both of these conformations are also observed for the (-)-menthone-3-thiosemicarbazone derivative (Oliveira et al., 2014).In the crystal, the molecules are also connected by symmetry-generated N—H···S hydrogen bonds into a one-dimensional polymer along the b-axis (Fig. 2 and Table 1). In addition, other hydrogen bonds of the same type, with bridging sulfur atoms, connect the molecules into a two-dimensional polymeric structure along [001].
Data collection: COLLECT (Nonius, 1998); cell
SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).Fig. 1. The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. | |
Fig. 2. Partial view of the of the crystal structure of the title compound along the a axis, showing the non non-centrosymmetric dimer and the extended N—H···S interactions along the b axis. The complete two-dimensional hydrogen-bonded polymeric structure is not shown for clarity. Hydrogen bonds are shown as dashed lines; see Table 1 for details. |
C12H23N3S | F(000) = 528 |
Mr = 241.39 | Dx = 1.120 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 80422 reflections |
a = 11.5579 (5) Å | θ = 2.9–27.5° |
b = 9.9279 (4) Å | µ = 0.21 mm−1 |
c = 12.5271 (5) Å | T = 123 K |
β = 95.030 (2)° | Plate, colourless |
V = 1431.90 (10) Å3 | 0.77 × 0.30 × 0.08 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 6380 independent reflections |
Radiation source: fine-focus sealed tube, Nonius KappaCCD | 5069 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.075 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
CCD scans | h = −15→14 |
Absorption correction: analytical (Alcock, 1970) | k = −12→12 |
Tmin = 0.857, Tmax = 0.984 | l = −16→16 |
23116 measured reflections |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0456P)2 + 0.1712P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
6380 reflections | Δρmax = 0.24 e Å−3 |
297 parameters | Δρmin = −0.36 e Å−3 |
1 restraint | Absolute structure: Flack x determined using 1954 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (7) |
C12H23N3S | V = 1431.90 (10) Å3 |
Mr = 241.39 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 11.5579 (5) Å | µ = 0.21 mm−1 |
b = 9.9279 (4) Å | T = 123 K |
c = 12.5271 (5) Å | 0.77 × 0.30 × 0.08 mm |
β = 95.030 (2)° |
Nonius KappaCCD diffractometer | 6380 independent reflections |
Absorption correction: analytical (Alcock, 1970) | 5069 reflections with I > 2σ(I) |
Tmin = 0.857, Tmax = 0.984 | Rint = 0.075 |
23116 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.104 | Δρmax = 0.24 e Å−3 |
S = 1.06 | Δρmin = −0.36 e Å−3 |
6380 reflections | Absolute structure: Flack x determined using 1954 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
297 parameters | Absolute structure parameter: 0.00 (7) |
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 | ||
C1 | 0.73525 (19) | 0.1924 (3) | 0.71879 (19) | 0.0293 (5) | |
C2 | 0.71388 (19) | 0.0693 (3) | 0.78399 (18) | 0.0302 (5) | |
H2A | 0.6428 | 0.0234 | 0.7526 | 0.036* | |
H2B | 0.7005 | 0.0970 | 0.8578 | 0.036* | |
C3 | 0.81593 (19) | −0.0294 (3) | 0.78822 (19) | 0.0365 (5) | |
H3 | 0.8226 | −0.0636 | 0.7139 | 0.044* | |
C4 | 0.9285 (2) | 0.0439 (3) | 0.8247 (2) | 0.0420 (7) | |
H4A | 0.9947 | −0.0193 | 0.8238 | 0.050* | |
H4B | 0.9251 | 0.0763 | 0.8991 | 0.050* | |
C5 | 0.9473 (2) | 0.1634 (3) | 0.7512 (2) | 0.0424 (7) | |
H5A | 0.9547 | 0.1297 | 0.6778 | 0.051* | |
H5B | 1.0210 | 0.2087 | 0.7763 | 0.051* | |
C6 | 0.84778 (19) | 0.2668 (3) | 0.74798 (19) | 0.0330 (5) | |
H6 | 0.8592 | 0.3319 | 0.6889 | 0.040* | |
C7 | 0.8407 (2) | 0.3491 (3) | 0.8524 (2) | 0.0451 (7) | |
H7 | 0.8211 | 0.2855 | 0.9101 | 0.054* | |
C8 | 0.7447 (3) | 0.4539 (3) | 0.8378 (2) | 0.0536 (8) | |
H8A | 0.7419 | 0.5055 | 0.9042 | 0.080* | |
H8B | 0.6700 | 0.4087 | 0.8205 | 0.080* | |
H8C | 0.7602 | 0.5149 | 0.7793 | 0.080* | |
C9 | 0.9558 (3) | 0.4164 (4) | 0.8886 (3) | 0.0687 (10) | |
H9A | 0.9843 | 0.4656 | 0.8284 | 0.103* | |
H9B | 1.0126 | 0.3476 | 0.9137 | 0.103* | |
H9C | 0.9446 | 0.4793 | 0.9471 | 0.103* | |
C10 | 0.7951 (2) | −0.1501 (3) | 0.8595 (2) | 0.0463 (7) | |
H10A | 0.8580 | −0.2155 | 0.8555 | 0.069* | |
H10B | 0.7208 | −0.1925 | 0.8351 | 0.069* | |
H10C | 0.7929 | −0.1198 | 0.9338 | 0.069* | |
C11 | 0.58527 (19) | 0.3497 (2) | 0.49598 (19) | 0.0272 (5) | |
C12 | 0.3993 (2) | 0.2741 (3) | 0.4070 (2) | 0.0376 (6) | |
H12A | 0.3523 | 0.3538 | 0.4193 | 0.056* | |
H12B | 0.3512 | 0.1931 | 0.4095 | 0.056* | |
H12C | 0.4296 | 0.2808 | 0.3366 | 0.056* | |
N1 | 0.65657 (16) | 0.2190 (2) | 0.64304 (16) | 0.0293 (5) | |
N2 | 0.66934 (17) | 0.3292 (2) | 0.57647 (17) | 0.0309 (5) | |
H2 | 0.7296 | 0.3834 | 0.5863 | 0.037* | |
N3 | 0.49569 (16) | 0.2660 (2) | 0.48970 (16) | 0.0306 (5) | |
H3A | 0.4944 | 0.2019 | 0.5382 | 0.037* | |
S1 | 0.59813 (5) | 0.47563 (6) | 0.40686 (5) | 0.03005 (15) | |
C13 | 0.75271 (18) | 0.7836 (3) | 0.26402 (18) | 0.0284 (5) | |
C14 | 0.7259 (2) | 0.6502 (3) | 0.20902 (19) | 0.0322 (5) | |
H14A | 0.7458 | 0.5760 | 0.2602 | 0.039* | |
H14B | 0.7746 | 0.6403 | 0.1483 | 0.039* | |
C15 | 0.5962 (2) | 0.6393 (3) | 0.16702 (19) | 0.0333 (5) | |
H15 | 0.5489 | 0.6421 | 0.2301 | 0.040* | |
C16 | 0.5633 (2) | 0.7605 (3) | 0.0968 (2) | 0.0412 (6) | |
H16A | 0.4794 | 0.7564 | 0.0729 | 0.049* | |
H16B | 0.6070 | 0.7577 | 0.0323 | 0.049* | |
C17 | 0.5897 (2) | 0.8927 (3) | 0.1569 (2) | 0.0425 (6) | |
H17A | 0.5428 | 0.8975 | 0.2192 | 0.051* | |
H17B | 0.5670 | 0.9693 | 0.1089 | 0.051* | |
C18 | 0.7195 (2) | 0.9054 (3) | 0.1962 (2) | 0.0337 (5) | |
H18 | 0.7634 | 0.8985 | 0.1310 | 0.040* | |
C19 | 0.7520 (2) | 1.0418 (3) | 0.2477 (2) | 0.0380 (6) | |
H19 | 0.8317 | 1.0329 | 0.2850 | 0.046* | |
C20 | 0.6707 (2) | 1.0854 (3) | 0.3315 (2) | 0.0486 (7) | |
H20A | 0.5934 | 1.1043 | 0.2961 | 0.073* | |
H20B | 0.7015 | 1.1668 | 0.3681 | 0.073* | |
H20C | 0.6651 | 1.0131 | 0.3841 | 0.073* | |
C21 | 0.7570 (3) | 1.1512 (3) | 0.1618 (3) | 0.0549 (8) | |
H21A | 0.6799 | 1.1620 | 0.1234 | 0.082* | |
H21B | 0.8129 | 1.1249 | 0.1112 | 0.082* | |
H21C | 0.7813 | 1.2366 | 0.1960 | 0.082* | |
C22 | 0.5731 (2) | 0.5053 (3) | 0.1103 (2) | 0.0441 (7) | |
H22A | 0.4907 | 0.4990 | 0.0848 | 0.066* | |
H22B | 0.5936 | 0.4314 | 0.1602 | 0.066* | |
H22C | 0.6203 | 0.4992 | 0.0491 | 0.066* | |
C23 | 0.89897 (19) | 0.7001 (2) | 0.51244 (18) | 0.0264 (5) | |
C24 | 1.0523 (2) | 0.8330 (3) | 0.6096 (2) | 0.0418 (6) | |
H24A | 1.0229 | 0.8081 | 0.6779 | 0.063* | |
H24B | 1.0749 | 0.9282 | 0.6116 | 0.063* | |
H24C | 1.1200 | 0.7774 | 0.5976 | 0.063* | |
N4 | 0.80179 (16) | 0.8028 (2) | 0.35901 (16) | 0.0290 (4) | |
N5 | 0.82468 (16) | 0.6882 (2) | 0.42301 (16) | 0.0284 (4) | |
H5 | 0.7916 | 0.6106 | 0.4055 | 0.034* | |
N6 | 0.96169 (16) | 0.8114 (2) | 0.52266 (16) | 0.0326 (5) | |
H6A | 0.9481 | 0.8756 | 0.4747 | 0.039* | |
S2 | 0.90891 (5) | 0.57300 (6) | 0.60289 (5) | 0.03129 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0226 (11) | 0.0391 (14) | 0.0259 (12) | −0.0002 (10) | 0.0012 (9) | 0.0003 (10) |
C2 | 0.0238 (11) | 0.0398 (14) | 0.0267 (12) | −0.0056 (11) | −0.0003 (9) | 0.0046 (11) |
C3 | 0.0321 (12) | 0.0480 (15) | 0.0286 (12) | 0.0019 (12) | −0.0014 (9) | 0.0066 (12) |
C4 | 0.0287 (12) | 0.0542 (18) | 0.0420 (15) | 0.0028 (12) | −0.0027 (10) | 0.0173 (13) |
C5 | 0.0241 (12) | 0.0587 (18) | 0.0440 (15) | −0.0019 (12) | 0.0000 (10) | 0.0178 (13) |
C6 | 0.0253 (11) | 0.0475 (15) | 0.0251 (12) | −0.0060 (11) | −0.0038 (9) | 0.0073 (11) |
C7 | 0.0456 (15) | 0.0631 (19) | 0.0257 (13) | −0.0186 (14) | −0.0022 (11) | 0.0035 (12) |
C8 | 0.0587 (18) | 0.060 (2) | 0.0449 (17) | −0.0211 (16) | 0.0193 (14) | −0.0158 (14) |
C9 | 0.064 (2) | 0.094 (3) | 0.0449 (19) | −0.034 (2) | −0.0157 (15) | −0.0006 (18) |
C10 | 0.0439 (15) | 0.0507 (17) | 0.0425 (16) | −0.0014 (13) | −0.0061 (12) | 0.0131 (13) |
C11 | 0.0218 (11) | 0.0333 (14) | 0.0264 (13) | 0.0006 (10) | 0.0023 (9) | −0.0010 (10) |
C12 | 0.0234 (11) | 0.0545 (16) | 0.0332 (13) | −0.0072 (12) | −0.0067 (10) | 0.0055 (12) |
N1 | 0.0257 (10) | 0.0340 (11) | 0.0276 (11) | −0.0025 (8) | −0.0012 (8) | 0.0034 (9) |
N2 | 0.0253 (10) | 0.0367 (11) | 0.0296 (11) | −0.0056 (9) | −0.0042 (8) | 0.0044 (9) |
N3 | 0.0228 (9) | 0.0401 (12) | 0.0280 (10) | −0.0045 (9) | −0.0028 (7) | 0.0062 (9) |
S1 | 0.0250 (3) | 0.0327 (3) | 0.0315 (3) | −0.0010 (3) | −0.0026 (2) | 0.0036 (3) |
C13 | 0.0190 (10) | 0.0412 (14) | 0.0249 (12) | 0.0031 (10) | 0.0016 (9) | 0.0014 (11) |
C14 | 0.0268 (12) | 0.0423 (14) | 0.0275 (12) | 0.0002 (11) | 0.0021 (9) | −0.0057 (11) |
C15 | 0.0255 (12) | 0.0468 (15) | 0.0273 (13) | −0.0028 (11) | 0.0002 (9) | −0.0012 (11) |
C16 | 0.0312 (12) | 0.0596 (18) | 0.0309 (13) | −0.0061 (13) | −0.0078 (10) | 0.0042 (13) |
C17 | 0.0320 (13) | 0.0521 (17) | 0.0407 (15) | −0.0039 (12) | −0.0116 (11) | 0.0084 (13) |
C18 | 0.0292 (12) | 0.0405 (14) | 0.0310 (13) | 0.0028 (11) | −0.0004 (10) | 0.0033 (11) |
C19 | 0.0314 (12) | 0.0396 (16) | 0.0416 (15) | 0.0002 (11) | −0.0048 (11) | 0.0042 (12) |
C20 | 0.0408 (14) | 0.0474 (16) | 0.0566 (18) | 0.0070 (13) | −0.0018 (13) | −0.0115 (14) |
C21 | 0.0588 (18) | 0.0495 (18) | 0.0535 (19) | −0.0042 (15) | −0.0122 (14) | 0.0127 (15) |
C22 | 0.0342 (13) | 0.0651 (19) | 0.0330 (14) | −0.0115 (13) | 0.0023 (11) | −0.0111 (13) |
C23 | 0.0221 (11) | 0.0331 (13) | 0.0239 (12) | 0.0025 (10) | 0.0011 (9) | −0.0002 (10) |
C24 | 0.0366 (14) | 0.0486 (16) | 0.0377 (15) | −0.0136 (12) | −0.0115 (11) | 0.0039 (12) |
N4 | 0.0238 (9) | 0.0333 (11) | 0.0295 (11) | 0.0037 (8) | 0.0005 (8) | 0.0013 (9) |
N5 | 0.0252 (10) | 0.0320 (11) | 0.0270 (10) | −0.0022 (8) | −0.0026 (8) | 0.0016 (8) |
N6 | 0.0321 (11) | 0.0357 (12) | 0.0283 (11) | −0.0025 (9) | −0.0065 (8) | 0.0040 (9) |
S2 | 0.0281 (3) | 0.0348 (4) | 0.0302 (3) | −0.0015 (3) | −0.0020 (2) | 0.0035 (3) |
C1—N1 | 1.283 (3) | C13—N4 | 1.287 (3) |
C1—C2 | 1.502 (3) | C13—C18 | 1.508 (4) |
C1—C6 | 1.513 (3) | C13—C14 | 1.512 (4) |
C2—C3 | 1.531 (4) | C14—C15 | 1.549 (3) |
C2—H2A | 0.9900 | C14—H14A | 0.9900 |
C2—H2B | 0.9900 | C14—H14B | 0.9900 |
C3—C4 | 1.525 (4) | C15—C16 | 1.519 (4) |
C3—C10 | 1.526 (4) | C15—C22 | 1.520 (4) |
C3—H3 | 1.0000 | C15—H15 | 1.0000 |
C4—C5 | 1.529 (4) | C16—C17 | 1.531 (4) |
C4—H4A | 0.9900 | C16—H16A | 0.9900 |
C4—H4B | 0.9900 | C16—H16B | 0.9900 |
C5—C6 | 1.539 (4) | C17—C18 | 1.543 (3) |
C5—H5A | 0.9900 | C17—H17A | 0.9900 |
C5—H5B | 0.9900 | C17—H17B | 0.9900 |
C6—C7 | 1.550 (4) | C18—C19 | 1.532 (4) |
C6—H6 | 1.0000 | C18—H18 | 1.0000 |
C7—C8 | 1.521 (4) | C19—C20 | 1.532 (4) |
C7—C9 | 1.522 (4) | C19—C21 | 1.533 (4) |
C7—H7 | 1.0000 | C19—H19 | 1.0000 |
C8—H8A | 0.9800 | C20—H20A | 0.9800 |
C8—H8B | 0.9800 | C20—H20B | 0.9800 |
C8—H8C | 0.9800 | C20—H20C | 0.9800 |
C9—H9A | 0.9800 | C21—H21A | 0.9800 |
C9—H9B | 0.9800 | C21—H21B | 0.9800 |
C9—H9C | 0.9800 | C21—H21C | 0.9800 |
C10—H10A | 0.9800 | C22—H22A | 0.9800 |
C10—H10B | 0.9800 | C22—H22B | 0.9800 |
C10—H10C | 0.9800 | C22—H22C | 0.9800 |
C11—N3 | 1.325 (3) | C23—N6 | 1.322 (3) |
C11—N2 | 1.353 (3) | C23—N5 | 1.356 (3) |
C11—S1 | 1.691 (2) | C23—S2 | 1.693 (2) |
C12—N3 | 1.455 (3) | C24—N6 | 1.459 (3) |
C12—H12A | 0.9800 | C24—H24A | 0.9800 |
C12—H12B | 0.9800 | C24—H24B | 0.9800 |
C12—H12C | 0.9800 | C24—H24C | 0.9800 |
N1—N2 | 1.392 (3) | N4—N5 | 1.403 (3) |
N2—H2 | 0.8800 | N5—H5 | 0.8800 |
N3—H3A | 0.8800 | N6—H6A | 0.8800 |
N1—C1—C2 | 115.5 (2) | N4—C13—C18 | 118.2 (2) |
N1—C1—C6 | 128.1 (2) | N4—C13—C14 | 127.4 (2) |
C2—C1—C6 | 116.4 (2) | C18—C13—C14 | 114.43 (19) |
C1—C2—C3 | 112.13 (19) | C13—C14—C15 | 111.7 (2) |
C1—C2—H2A | 109.2 | C13—C14—H14A | 109.3 |
C3—C2—H2A | 109.2 | C15—C14—H14A | 109.3 |
C1—C2—H2B | 109.2 | C13—C14—H14B | 109.3 |
C3—C2—H2B | 109.2 | C15—C14—H14B | 109.3 |
H2A—C2—H2B | 107.9 | H14A—C14—H14B | 107.9 |
C4—C3—C10 | 111.9 (2) | C16—C15—C22 | 113.4 (2) |
C4—C3—C2 | 109.8 (2) | C16—C15—C14 | 109.1 (2) |
C10—C3—C2 | 111.2 (2) | C22—C15—C14 | 110.2 (2) |
C4—C3—H3 | 107.9 | C16—C15—H15 | 108.0 |
C10—C3—H3 | 107.9 | C22—C15—H15 | 108.0 |
C2—C3—H3 | 107.9 | C14—C15—H15 | 108.0 |
C3—C4—C5 | 110.6 (2) | C15—C16—C17 | 111.4 (2) |
C3—C4—H4A | 109.5 | C15—C16—H16A | 109.3 |
C5—C4—H4A | 109.5 | C17—C16—H16A | 109.3 |
C3—C4—H4B | 109.5 | C15—C16—H16B | 109.3 |
C5—C4—H4B | 109.5 | C17—C16—H16B | 109.3 |
H4A—C4—H4B | 108.1 | H16A—C16—H16B | 108.0 |
C4—C5—C6 | 112.8 (2) | C16—C17—C18 | 111.9 (2) |
C4—C5—H5A | 109.0 | C16—C17—H17A | 109.2 |
C6—C5—H5A | 109.0 | C18—C17—H17A | 109.2 |
C4—C5—H5B | 109.0 | C16—C17—H17B | 109.2 |
C6—C5—H5B | 109.0 | C18—C17—H17B | 109.2 |
H5A—C5—H5B | 107.8 | H17A—C17—H17B | 107.9 |
C1—C6—C5 | 107.8 (2) | C13—C18—C19 | 115.48 (19) |
C1—C6—C7 | 110.70 (19) | C13—C18—C17 | 107.8 (2) |
C5—C6—C7 | 115.1 (2) | C19—C18—C17 | 113.7 (2) |
C1—C6—H6 | 107.7 | C13—C18—H18 | 106.4 |
C5—C6—H6 | 107.7 | C19—C18—H18 | 106.4 |
C7—C6—H6 | 107.7 | C17—C18—H18 | 106.4 |
C8—C7—C9 | 110.2 (3) | C20—C19—C18 | 113.4 (2) |
C8—C7—C6 | 110.5 (2) | C20—C19—C21 | 110.1 (2) |
C9—C7—C6 | 111.9 (2) | C18—C19—C21 | 110.7 (2) |
C8—C7—H7 | 108.0 | C20—C19—H19 | 107.5 |
C9—C7—H7 | 108.0 | C18—C19—H19 | 107.5 |
C6—C7—H7 | 108.0 | C21—C19—H19 | 107.5 |
C7—C8—H8A | 109.5 | C19—C20—H20A | 109.5 |
C7—C8—H8B | 109.5 | C19—C20—H20B | 109.5 |
H8A—C8—H8B | 109.5 | H20A—C20—H20B | 109.5 |
C7—C8—H8C | 109.5 | C19—C20—H20C | 109.5 |
H8A—C8—H8C | 109.5 | H20A—C20—H20C | 109.5 |
H8B—C8—H8C | 109.5 | H20B—C20—H20C | 109.5 |
C7—C9—H9A | 109.5 | C19—C21—H21A | 109.5 |
C7—C9—H9B | 109.5 | C19—C21—H21B | 109.5 |
H9A—C9—H9B | 109.5 | H21A—C21—H21B | 109.5 |
C7—C9—H9C | 109.5 | C19—C21—H21C | 109.5 |
H9A—C9—H9C | 109.5 | H21A—C21—H21C | 109.5 |
H9B—C9—H9C | 109.5 | H21B—C21—H21C | 109.5 |
C3—C10—H10A | 109.5 | C15—C22—H22A | 109.5 |
C3—C10—H10B | 109.5 | C15—C22—H22B | 109.5 |
H10A—C10—H10B | 109.5 | H22A—C22—H22B | 109.5 |
C3—C10—H10C | 109.5 | C15—C22—H22C | 109.5 |
H10A—C10—H10C | 109.5 | H22A—C22—H22C | 109.5 |
H10B—C10—H10C | 109.5 | H22B—C22—H22C | 109.5 |
N3—C11—N2 | 117.1 (2) | N6—C23—N5 | 117.0 (2) |
N3—C11—S1 | 122.56 (18) | N6—C23—S2 | 123.64 (17) |
N2—C11—S1 | 120.29 (18) | N5—C23—S2 | 119.31 (18) |
N3—C12—H12A | 109.5 | N6—C24—H24A | 109.5 |
N3—C12—H12B | 109.5 | N6—C24—H24B | 109.5 |
H12A—C12—H12B | 109.5 | H24A—C24—H24B | 109.5 |
N3—C12—H12C | 109.5 | N6—C24—H24C | 109.5 |
H12A—C12—H12C | 109.5 | H24A—C24—H24C | 109.5 |
H12B—C12—H12C | 109.5 | H24B—C24—H24C | 109.5 |
C1—N1—N2 | 119.97 (19) | C13—N4—N5 | 117.0 (2) |
C11—N2—N1 | 117.26 (19) | C23—N5—N4 | 118.4 (2) |
C11—N2—H2 | 121.4 | C23—N5—H5 | 120.8 |
N1—N2—H2 | 121.4 | N4—N5—H5 | 120.8 |
C11—N3—C12 | 123.6 (2) | C23—N6—C24 | 123.2 (2) |
C11—N3—H3A | 118.2 | C23—N6—H6A | 118.4 |
C12—N3—H3A | 118.2 | C24—N6—H6A | 118.4 |
N1—C1—C2—C3 | 125.8 (2) | N4—C13—C14—C15 | 126.1 (2) |
C6—C1—C2—C3 | −52.4 (3) | C18—C13—C14—C15 | −55.5 (3) |
C1—C2—C3—C4 | 52.6 (3) | C13—C14—C15—C16 | 53.7 (3) |
C1—C2—C3—C10 | 177.1 (2) | C13—C14—C15—C22 | 178.8 (2) |
C10—C3—C4—C5 | 179.6 (2) | C22—C15—C16—C17 | −179.2 (2) |
C2—C3—C4—C5 | −56.4 (3) | C14—C15—C16—C17 | −56.0 (3) |
C3—C4—C5—C6 | 59.1 (3) | C15—C16—C17—C18 | 59.1 (3) |
N1—C1—C6—C5 | −126.7 (3) | N4—C13—C18—C19 | 1.8 (3) |
C2—C1—C6—C5 | 51.2 (3) | C14—C13—C18—C19 | −176.7 (2) |
N1—C1—C6—C7 | 106.7 (3) | N4—C13—C18—C17 | −126.6 (2) |
C2—C1—C6—C7 | −75.4 (3) | C14—C13—C18—C17 | 54.9 (3) |
C4—C5—C6—C1 | −53.9 (3) | C16—C17—C18—C13 | −55.9 (3) |
C4—C5—C6—C7 | 70.1 (3) | C16—C17—C18—C19 | 174.7 (2) |
C1—C6—C7—C8 | −61.2 (3) | C13—C18—C19—C20 | −76.8 (3) |
C5—C6—C7—C8 | 176.3 (2) | C17—C18—C19—C20 | 48.6 (3) |
C1—C6—C7—C9 | 175.6 (2) | C13—C18—C19—C21 | 158.9 (2) |
C5—C6—C7—C9 | 53.1 (3) | C17—C18—C19—C21 | −75.6 (3) |
C2—C1—N1—N2 | −178.62 (19) | C18—C13—N4—N5 | 175.85 (18) |
C6—C1—N1—N2 | −0.7 (4) | C14—C13—N4—N5 | −5.9 (3) |
N3—C11—N2—N1 | 2.4 (3) | N6—C23—N5—N4 | −12.5 (3) |
S1—C11—N2—N1 | −176.24 (16) | S2—C23—N5—N4 | 168.60 (15) |
C1—N1—N2—C11 | 178.0 (2) | C13—N4—N5—C23 | 165.0 (2) |
N2—C11—N3—C12 | −179.2 (2) | N5—C23—N6—C24 | −174.4 (2) |
S1—C11—N3—C12 | −0.6 (3) | S2—C23—N6—C24 | 4.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S2 | 0.88 | 2.79 | 3.671 (2) | 174 |
N3—H3A···S1i | 0.88 | 2.61 | 3.378 (2) | 147 |
N5—H5···S1 | 0.88 | 2.61 | 3.356 (2) | 143 |
N6—H6A···S2ii | 0.88 | 2.79 | 3.445 (2) | 132 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S2 | 0.88 | 2.79 | 3.671 (2) | 174.2 |
N3—H3A···S1i | 0.88 | 2.61 | 3.378 (2) | 146.8 |
N5—H5···S1 | 0.88 | 2.61 | 3.356 (2) | 143.4 |
N6—H6A···S2ii | 0.88 | 2.79 | 3.445 (2) | 132.1 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H23N3S |
Mr | 241.39 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 123 |
a, b, c (Å) | 11.5579 (5), 9.9279 (4), 12.5271 (5) |
β (°) | 95.030 (2) |
V (Å3) | 1431.90 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.77 × 0.30 × 0.08 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.857, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23116, 6380, 5069 |
Rint | 0.075 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.104, 1.06 |
No. of reflections | 6380 |
No. of parameters | 297 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.36 |
Absolute structure | Flack x determined using 1954 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | 0.00 (7) |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).
Acknowledgements
We gratefully acknowledge financial support by the State of North Rhine-Westphalia, Germany. ABO is an associate researcher in the project `Dinitrosyl complexes containing thiol and/or thiosemicarbazone: synthesis, characterization and treatment against cancer`, founded by FAPESP, Proc. 2015/12098–0, and acknowledges Professor José Clayston Melo Pereira (UNESP, Brazil) for his support in this work.
References
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