research communications
S,6R)-3,3,6-trimethyl-3,3a,4,5,6,7-hexahydro-2H-indazol-2-yl]thiazol-4(5H)-one
of 2-[(3aaLaboratoire de Physico-Chimie Moléculaire et Synthèse Organique, Département de Chimie, Faculté des Sciences, Semlalia BP 2390, Marrakech 40001, Morocco, bInstitut de Chimie Moléculaire de Reims, CNRS UMR 7312, Bat. Europol'Agr, Moulin de la Housse, UFR Sciences, BP 1039, 51687 Reims Cédex 2, France, and cLaboratoire de Chimie de Coordination, CNRS UPR8241, 205 route de Narbonne, 31077 Toulouse Cedex 04, France
*Correspondence e-mail: a.auhmani@uca.ma
The title compound, C13H19N3OS, is a new thiazolidin-4-one derivative prepared and isolated as the pure (3aS,6R)-diastereisomer from (R)-thiosemicarbazone pulegone. It crystallized with two independent molecules (A and B) in the The compound is composed of a hexhydroindazole ring system (viz. a five-membered dihydropyrazole ring fused to a cyclohexyl ring) with a thiazole-4-one ring system attached to one of the pyrazole N atoms (at position 2). The overall geometry of the two molecules differs slightly, with the mean planes of the pyrazole and thiazole rings being inclined to one another by 10.4 (1)° in molecule A and 0.9 (1)° in molecule B. In the crystal, the A and B molecules are linked via C—H⋯O hydrogen bonds, forming slabs parallel to the ab plane. There are C—H⋯π interactions present within the layers, and between the layers, so forming a three-dimensional structure.
Keywords: crystal structure; absolute structure; heterocyclic compounds; thiazolidinone; indazole; C—H⋯O hydrogen bonding; C—H⋯π interactions.
CCDC reference: 1452670
1. Chemical context
Thiazolidinones constitute an important class of ), antituberculosis (Karali et al., 2007), antiviral (Kaushik-Basu et al., 2008) and anticancer activities (Patel et al., 2014).
containing sulfur and nitrogen in a five-membered ring. They play a vital role due to their wide range of biological activities and industrial importance. Thiazolidin-4-ones are particularly important because of their efficiency towards various pharmacological usages. A recent literature search reveals that thiazolidin-4-one derivatives may exhibit antibacterial (Bonde & Gaikwad, 2004As a part of our endeavour toward the preparation of new heterocyclic systems, we report herein on the structure of a new optically active thiazolidin-4-one (2) synthesized from (R)-thiosemicarbazone pulegone (1); see Scheme. The reaction involves the treatment of thiosemicarbazone (1), in
refluxing ethanol, with ethyl bromoacatete and an excess of sodium acetate. Crystallization from an ethanolic solution of the resulting indazolic thiazolidin-4-one (obtained as a diastereomeric mixture) led to the isolation of compound (2). The structure of (2) was elucidated using spectroscopic (MS and NMR) data, while its was determined as (3aS,6R) based mainly on the synthetic pathway and confirmed by2. Structural commentary
The title compound crystallized with two independent molecules (A and B) in the The compound is composed of a hexhydroindazole ring system [viz. a five-membered dihydropyrazole ring fused to a cyclohexyl ring] with a thiazole-4-one ring system attached to pyrazole N atom N2 (Fig. 1). Molecular fitting of the two molecules (Spek, 2009) shows that they have roughly the same conformation and the same configuration (Fig. 2), even if some slight differences can be observed. The six-membered rings each display a chair conformation, with puckering parameters of θ = 12.96° and φ2 = 113.49° for molecule A and θ = 9.44° and φ2 = 92.43° for molecule B. The five-membered pyrazol rings are almost planar with the largest deviation being 0.081 (3) Å for atom C3 in molecule A and −0.032 (1) for atom C3B in molecule B. The thiazole rings are planar, the largest deviation being −0.011 (1) Å for atom C2′ and 0.005 (1) for atom C5′B in molecules A and B, respectively. In molecule A, the two five-membered rings are slightly twisted with a dihedral angle of 10.4 (1)°, whereas in molecule B the two rings are almost coplanar with a dihedral angle of 0.9 (1)°.
3. Supramolecular features
In the crystal, the two independent molecules are connected via C—H⋯O hydrogen bonds forming layers, or slabs, parallel to the ab plane (Table 1 and Fig. 3). Within the layers there are C—H⋯π interactions present (Fig. 4 and Table 1). The layers are also linked by C—H⋯π interactions (Table 1), forming a three-dimensional structure (Fig. 4).
4. Database survey
A search of the Cambridge Structural Database (CSD, V5.37, update November 2015; Groom & Allen, 2014) using the hexahydroindazole ring system as the main skeleton, revealed the presence of 27 structures. A search for a thiazole ring linked to an N atom of a pyrazole ring, similar to the situation in the title compound, yielded six hits. One of these structures, 2-(3-phenyl-3,3a,4,5-tetrahydro-2H-benzo[g]indazol-2-yl)-1,3-thiazol-4(5H)-one (refcode LUHGAY; Gautam & Chaudhary, 2015), resembles the title compound with an indazole ring system linked to a thiazole ring. The mean plane of the two five-membered rings are inclined to one another by ca 10.05°, similar to the arrangement in molecule A of the title compound.
5. Synthesis and crystallization
The synthesis of the title compound is illustrated in the Scheme. A mixture of thiosemicarbazone (1) (1.5 mmol, 1 eq), ethyl 2-bromoacetate (0.24 ml, 1.5 mmol) and anhydrous sodium acetate (0.37 g, 4.5 mmol, 3 eq) in absolute ethanol (30 ml) was heated under reflux until the completion of the reaction (1–3 h). The solvent was then evaporated under reduced pressure and the crude product was purified by on silica gel (230–400 mesh) using hexane/ethyl acetate (90:10) as to give pure indazolic thiazolidin-4-one in 60% yield as a diastereomeric mixture. Slow evaporation from an ethanolic solution gives crystals of the pure diastereoisomer of the title compound (2) suitable for crystallographic analysis.
6. Refinement
Crystal data, data collection and structure . The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.96–0.98 Å with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1452670
10.1107/S2056989016002498/su5277sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016002498/su5277Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016002498/su5277Isup3.cml
Thiazolidinones constitute an important class of
containing sulfur and nitrogen in a five-membered ring. They play a vital role due to their wide range of biological activities and industrial importance. Thiazolidin-4-ones are particularly important because of their efficiency towards various pharmacological usages. A recent literature search reveals that thiazolidin-4-one derivatives may exhibit antibacterial (Bonde & Gaikwad, 2004), antituberculosis (Karali et al., 2007), antiviral (Kaushik-Basu et al., 2008) and anticancer activities (Patel et al., 2014).As a part of our endeavour toward the preparation of new heterocyclic systems, we report herein on the structure of a new optically active thiazolidin-4-one (2) synthesized from (R)-thiosemicarbazone pulegone (1); see Scheme. The reaction involves the treatment of thiosemicarbazone (1), in refluxing ethanol, with ethyl bromoacatete and an excess of sodium acetate. Crystallization from an ethanolic solution of the resulting indazolic thiazolidin-4-one (obtained as a diastereomeric mixture) led to the isolation of compound (2). The structure of (2) was elucidated using spectroscopic (MS and NMR) data, while its
was determined as (3aS,6R) based mainly on the synthetic pathway and confirmed by resonant scattering.The title compound crystallized with two independent molecules (A and B) in the θ = 12.96° and φ2 = 113.49° for molecule A and θ = 9.44° and φ2 = 92.43° for molecule B. The five-membered pyrazol rings are almost planar with the largest deviation being 0.081 (3) Å for atom C3 in molecule A and −0.032 (1) for atom C3B in molecule B. The thiazole rings are planar, the largest deviation being −0.011 (1) Å for atom C2' and 0.005 (1) for atom C5'B in molecules A and B, respectively. In molecule A, the two five-membered rings are slightly twisted with a dihedral angle of 10.4 (1)°, whereas in molecule B the two rings are almost coplanar with a dihedral angle of 0.9 (1)°.
The compound is composed of a hexhydroindazole ring system [viz. a five-membered dihydropyrazole ring fused to a cyclohexyl ring] with a thiazole-4-one ring system attached to pyrazole N atom N2 (Fig. 1). Molecular fitting of the two molecules (Spek, 2009) shows that they have roughly the same conformation and the same configuration (Fig. 2), even if some slight differences can be observed. The six-membered rings each display a chair conformation, with puckering parameters ofIn the crystal, the two independent molecules are connected via C—H···O hydrogen bonds forming layers, or slabs, parallel to the ab plane (Table 1 and Fig. 3). Within the layers there are C—H···π interactions present (Fig. 4 and Table 1). The layers are also linked by C—H···π interactions (Table 1), forming a three-dimensional structure (Fig. 4).
\ A search of the Cambridge Structural Database (CSD, V5.37, update November 2015; Groom & Allen, 2014) using the hexahydroindazole ring system as the main skeleton, revealed the presence of 27 structures. A search for a thiazole ring linked to an N atom of a pyrazole ring, similar to the situation in the title compound, yielded six hits. One of these structures, 2-(3-phenyl-3,3a,4,5-tetrahydro-2H-benzo[g]indazol-2-yl)-1,3-\ thiazol-4(5H)-one (refcode LUHGAY; Gautam & Chaudhary, 2015), resembles the title compound with an indazole ring system linked to a thiazole ring. The mean plane of the two five-membered rings are inclined to one another by ca 10.05°, similar to the arrangement in molecule A of the title compound.
The synthesis of the title compound is illustrated in the Scheme. A mixture of thiosemicarbazone (1) (1.5 mmol, 1 eq), ethyl 2-bromoacetate (0.24 ml, 1.5 mmol) and anhydrous sodium acetate (0.37 g, 4.5 mmol, 3 eq) in absolute ethanol (30 ml) was heated under reflux until the completion of the reaction (1–3 h). The solvent was then evaporated under reduced pressure and the crude product was purified by
on silica gel (230–400 mesh) using hexane/ethyl acetate (90:10) as to give pure indazolic thiazolidin-4-one in 60% yield as a diastereomeric mixture. Slow evaporation from an ethanolic solution gives crystals of the pure diastereoisomer of the title compound (2) suitable for crystallographic analysis.Thiazolidinones constitute an important class of
containing sulfur and nitrogen in a five-membered ring. They play a vital role due to their wide range of biological activities and industrial importance. Thiazolidin-4-ones are particularly important because of their efficiency towards various pharmacological usages. A recent literature search reveals that thiazolidin-4-one derivatives may exhibit antibacterial (Bonde & Gaikwad, 2004), antituberculosis (Karali et al., 2007), antiviral (Kaushik-Basu et al., 2008) and anticancer activities (Patel et al., 2014).As a part of our endeavour toward the preparation of new heterocyclic systems, we report herein on the structure of a new optically active thiazolidin-4-one (2) synthesized from (R)-thiosemicarbazone pulegone (1); see Scheme. The reaction involves the treatment of thiosemicarbazone (1), in refluxing ethanol, with ethyl bromoacatete and an excess of sodium acetate. Crystallization from an ethanolic solution of the resulting indazolic thiazolidin-4-one (obtained as a diastereomeric mixture) led to the isolation of compound (2). The structure of (2) was elucidated using spectroscopic (MS and NMR) data, while its
was determined as (3aS,6R) based mainly on the synthetic pathway and confirmed by resonant scattering.The title compound crystallized with two independent molecules (A and B) in the θ = 12.96° and φ2 = 113.49° for molecule A and θ = 9.44° and φ2 = 92.43° for molecule B. The five-membered pyrazol rings are almost planar with the largest deviation being 0.081 (3) Å for atom C3 in molecule A and −0.032 (1) for atom C3B in molecule B. The thiazole rings are planar, the largest deviation being −0.011 (1) Å for atom C2' and 0.005 (1) for atom C5'B in molecules A and B, respectively. In molecule A, the two five-membered rings are slightly twisted with a dihedral angle of 10.4 (1)°, whereas in molecule B the two rings are almost coplanar with a dihedral angle of 0.9 (1)°.
The compound is composed of a hexhydroindazole ring system [viz. a five-membered dihydropyrazole ring fused to a cyclohexyl ring] with a thiazole-4-one ring system attached to pyrazole N atom N2 (Fig. 1). Molecular fitting of the two molecules (Spek, 2009) shows that they have roughly the same conformation and the same configuration (Fig. 2), even if some slight differences can be observed. The six-membered rings each display a chair conformation, with puckering parameters ofIn the crystal, the two independent molecules are connected via C—H···O hydrogen bonds forming layers, or slabs, parallel to the ab plane (Table 1 and Fig. 3). Within the layers there are C—H···π interactions present (Fig. 4 and Table 1). The layers are also linked by C—H···π interactions (Table 1), forming a three-dimensional structure (Fig. 4).
\ A search of the Cambridge Structural Database (CSD, V5.37, update November 2015; Groom & Allen, 2014) using the hexahydroindazole ring system as the main skeleton, revealed the presence of 27 structures. A search for a thiazole ring linked to an N atom of a pyrazole ring, similar to the situation in the title compound, yielded six hits. One of these structures, 2-(3-phenyl-3,3a,4,5-tetrahydro-2H-benzo[g]indazol-2-yl)-1,3-\ thiazol-4(5H)-one (refcode LUHGAY; Gautam & Chaudhary, 2015), resembles the title compound with an indazole ring system linked to a thiazole ring. The mean plane of the two five-membered rings are inclined to one another by ca 10.05°, similar to the arrangement in molecule A of the title compound.
The synthesis of the title compound is illustrated in the Scheme. A mixture of thiosemicarbazone (1) (1.5 mmol, 1 eq), ethyl 2-bromoacetate (0.24 ml, 1.5 mmol) and anhydrous sodium acetate (0.37 g, 4.5 mmol, 3 eq) in absolute ethanol (30 ml) was heated under reflux until the completion of the reaction (1–3 h). The solvent was then evaporated under reduced pressure and the crude product was purified by
on silica gel (230–400 mesh) using hexane/ethyl acetate (90:10) as to give pure indazolic thiazolidin-4-one in 60% yield as a diastereomeric mixture. Slow evaporation from an ethanolic solution gives crystals of the pure diastereoisomer of the title compound (2) suitable for crystallographic analysis. detailsCrystal data, data collection and structure
details are summarized in Table 2. The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.96–0.98 Å with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.Data collection: CrysAlis PRO (Agilent, 2014); cell
CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015).Fig. 1. View of the molecular structure of the two independent molecules (A and B) of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. Molecular fitting of independent molecules A (black) and B (red). | |
Fig. 3. A view along the a axis of the crystal packing of the title compound, showing the formation of layers parallel to the ab plane via C—H···O hydrogen bonds (see Table 1). H atoms not involved in these interactions have been omitted for clarity. | |
Fig. 4. A view along the a axis of the crystal packing of the title compound, showing the C—H···O hydrogen bonds (dashed lines), and the C—H···π interactions (represented by blue arrows) linking the A (black) and B (red) molecules within and between the layers (see Table 1). H atoms not involved in these interactions have been omitted for clarity. |
C13H19N3OS | F(000) = 568 |
Mr = 265.37 | Dx = 1.301 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.5519 (2) Å | Cell parameters from 5859 reflections |
b = 18.9335 (4) Å | θ = 3.6–29.2° |
c = 8.9165 (3) Å | µ = 0.23 mm−1 |
β = 110.203 (3)° | T = 180 K |
V = 1354.91 (7) Å3 | Prismatic, colourless |
Z = 4 | 0.25 × 0.21 × 0.18 mm |
Agilent Xcalibur Eos Gemini ultra diffractometer | 6147 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 5674 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 16.1978 pixels mm-1 | θmax = 29.5°, θmin = 3.3° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −23→25 |
Tmin = 0.939, Tmax = 1.000 | l = −12→11 |
15302 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0364P)2 + 0.1555P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.077 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.22 e Å−3 |
6147 reflections | Δρmin = −0.19 e Å−3 |
331 parameters | Absolute structure: Flack x determined using 2349 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
1 restraint | Absolute structure parameter: −0.08 (3) |
C13H19N3OS | V = 1354.91 (7) Å3 |
Mr = 265.37 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.5519 (2) Å | µ = 0.23 mm−1 |
b = 18.9335 (4) Å | T = 180 K |
c = 8.9165 (3) Å | 0.25 × 0.21 × 0.18 mm |
β = 110.203 (3)° |
Agilent Xcalibur Eos Gemini ultra diffractometer | 6147 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | 5674 reflections with I > 2σ(I) |
Tmin = 0.939, Tmax = 1.000 | Rint = 0.024 |
15302 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.077 | Δρmax = 0.22 e Å−3 |
S = 1.04 | Δρmin = −0.19 e Å−3 |
6147 reflections | Absolute structure: Flack x determined using 2349 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
331 parameters | Absolute structure parameter: −0.08 (3) |
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. |
x | y | z | Uiso*/Ueq | ||
S1' | 0.77265 (7) | 0.51418 (3) | 0.26117 (7) | 0.02894 (15) | |
O6' | 1.2287 (2) | 0.54265 (10) | 0.5307 (3) | 0.0410 (5) | |
N1 | 0.6528 (2) | 0.37534 (10) | 0.2176 (2) | 0.0258 (4) | |
N2 | 0.8216 (2) | 0.37680 (10) | 0.3163 (2) | 0.0246 (4) | |
N3' | 1.0511 (3) | 0.44868 (11) | 0.4370 (2) | 0.0269 (4) | |
C2' | 0.8954 (3) | 0.43930 (12) | 0.3469 (3) | 0.0232 (5) | |
C4' | 1.0915 (3) | 0.51929 (14) | 0.4524 (3) | 0.0290 (5) | |
C5' | 0.9500 (3) | 0.56889 (15) | 0.3626 (3) | 0.0358 (6) | |
H5'1 | 0.9808 | 0.5970 | 0.2862 | 0.043* | |
H5'2 | 0.9245 | 0.6005 | 0.4366 | 0.043* | |
C3 | 0.8934 (3) | 0.30406 (12) | 0.3685 (3) | 0.0241 (5) | |
C3A | 0.7284 (3) | 0.26108 (13) | 0.3219 (3) | 0.0266 (5) | |
H3A | 0.7035 | 0.2524 | 0.4197 | 0.032* | |
C4 | 0.7166 (3) | 0.19101 (16) | 0.2363 (3) | 0.0389 (6) | |
H4A | 0.7865 | 0.1564 | 0.3091 | 0.047* | |
H4B | 0.7564 | 0.1965 | 0.1474 | 0.047* | |
C5 | 0.5357 (4) | 0.16515 (15) | 0.1746 (4) | 0.0406 (7) | |
H5A | 0.5305 | 0.1200 | 0.1216 | 0.049* | |
H5B | 0.4984 | 0.1580 | 0.2645 | 0.049* | |
C6 | 0.4191 (3) | 0.21710 (15) | 0.0582 (3) | 0.0356 (6) | |
H6 | 0.4574 | 0.2231 | −0.0327 | 0.043* | |
C7 | 0.4263 (3) | 0.28925 (13) | 0.1385 (3) | 0.0318 (5) | |
H7A | 0.3692 | 0.3240 | 0.0583 | 0.038* | |
H7B | 0.3690 | 0.2864 | 0.2151 | 0.038* | |
C7A | 0.6020 (3) | 0.31236 (12) | 0.2218 (3) | 0.0257 (5) | |
C9 | 1.0058 (3) | 0.28524 (14) | 0.2749 (3) | 0.0318 (5) | |
H9A | 0.9442 | 0.2890 | 0.1625 | 0.048* | |
H9B | 1.0454 | 0.2377 | 0.2997 | 0.048* | |
H9C | 1.0988 | 0.3171 | 0.3031 | 0.048* | |
C8 | 0.9873 (3) | 0.30082 (14) | 0.5474 (3) | 0.0331 (6) | |
H8A | 1.0870 | 0.3286 | 0.5732 | 0.050* | |
H8B | 1.0161 | 0.2527 | 0.5787 | 0.050* | |
H8C | 0.9182 | 0.3191 | 0.6033 | 0.050* | |
C10 | 0.2398 (4) | 0.1906 (2) | −0.0055 (4) | 0.0551 (8) | |
H10A | 0.2358 | 0.1458 | −0.0573 | 0.083* | |
H10B | 0.1715 | 0.2240 | −0.0808 | 0.083* | |
H10C | 0.1990 | 0.1852 | 0.0816 | 0.083* | |
S1'B | 0.72290 (7) | 0.19227 (3) | 0.77175 (8) | 0.02873 (15) | |
O6'B | 0.2793 (2) | 0.16136 (10) | 0.4764 (3) | 0.0430 (5) | |
N1B | 0.8189 (2) | 0.33287 (10) | 0.8585 (2) | 0.0256 (4) | |
N2B | 0.6558 (2) | 0.32950 (10) | 0.7482 (2) | 0.0251 (4) | |
N3'B | 0.4417 (3) | 0.25589 (11) | 0.5972 (2) | 0.0285 (4) | |
C2'B | 0.5933 (3) | 0.26630 (13) | 0.6977 (3) | 0.0231 (5) | |
C4'B | 0.4099 (3) | 0.18550 (14) | 0.5654 (3) | 0.0297 (5) | |
C5'B | 0.5556 (3) | 0.13661 (14) | 0.6521 (3) | 0.0323 (6) | |
H5'3 | 0.5899 | 0.1101 | 0.5756 | 0.039* | |
H5'4 | 0.5236 | 0.1035 | 0.7194 | 0.039* | |
C3B | 0.5720 (3) | 0.40092 (12) | 0.7089 (3) | 0.0243 (5) | |
C3AB | 0.7198 (3) | 0.44937 (13) | 0.8040 (3) | 0.0272 (5) | |
H3AB | 0.6873 | 0.4763 | 0.8825 | 0.033* | |
C4B | 0.7936 (4) | 0.50042 (17) | 0.7135 (4) | 0.0458 (7) | |
H4B1 | 0.7139 | 0.5375 | 0.6651 | 0.055* | |
H4B2 | 0.8175 | 0.4754 | 0.6290 | 0.055* | |
C5B | 0.9540 (4) | 0.53296 (16) | 0.8284 (4) | 0.0483 (8) | |
H5B1 | 0.9978 | 0.5662 | 0.7701 | 0.058* | |
H5B2 | 0.9282 | 0.5590 | 0.9106 | 0.058* | |
C6B | 1.0865 (3) | 0.47829 (14) | 0.9071 (3) | 0.0334 (6) | |
H6B | 1.1154 | 0.4540 | 0.8231 | 0.040* | |
C7B | 1.0200 (3) | 0.42344 (13) | 0.9955 (3) | 0.0309 (5) | |
H7B1 | 1.0964 | 0.3838 | 1.0262 | 0.037* | |
H7B2 | 1.0117 | 0.4442 | 1.0919 | 0.037* | |
C7AB | 0.8528 (3) | 0.39813 (13) | 0.8913 (3) | 0.0250 (5) | |
C9B | 0.5074 (3) | 0.41293 (14) | 0.5291 (3) | 0.0328 (6) | |
H9B1 | 0.4216 | 0.3791 | 0.4788 | 0.049* | |
H9B2 | 0.5971 | 0.4075 | 0.4886 | 0.049* | |
H9B3 | 0.4625 | 0.4598 | 0.5064 | 0.049* | |
C8B | 0.4338 (3) | 0.40513 (15) | 0.7789 (3) | 0.0321 (6) | |
H8B1 | 0.3807 | 0.4505 | 0.7553 | 0.048* | |
H8B2 | 0.4799 | 0.3988 | 0.8926 | 0.048* | |
H8B3 | 0.3533 | 0.3687 | 0.7330 | 0.048* | |
C10B | 1.2448 (3) | 0.51173 (18) | 1.0226 (4) | 0.0468 (7) | |
H10D | 1.2862 | 0.5463 | 0.9669 | 0.070* | |
H10E | 1.3276 | 0.4758 | 1.0650 | 0.070* | |
H10F | 1.2202 | 0.5341 | 1.1085 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1' | 0.0251 (3) | 0.0232 (3) | 0.0350 (3) | 0.0039 (3) | 0.0059 (3) | 0.0028 (2) |
O6' | 0.0283 (10) | 0.0288 (10) | 0.0563 (12) | −0.0043 (8) | 0.0025 (10) | −0.0012 (9) |
N1 | 0.0204 (10) | 0.0254 (10) | 0.0294 (11) | 0.0025 (8) | 0.0058 (8) | −0.0001 (8) |
N2 | 0.0189 (10) | 0.0229 (10) | 0.0299 (10) | 0.0017 (8) | 0.0059 (8) | 0.0029 (8) |
N3' | 0.0226 (10) | 0.0242 (10) | 0.0311 (11) | 0.0008 (8) | 0.0057 (9) | 0.0023 (8) |
C2' | 0.0254 (12) | 0.0218 (12) | 0.0237 (11) | 0.0035 (9) | 0.0103 (10) | 0.0022 (9) |
C4' | 0.0276 (13) | 0.0272 (13) | 0.0320 (12) | −0.0002 (11) | 0.0100 (11) | 0.0012 (11) |
C5' | 0.0315 (14) | 0.0259 (14) | 0.0447 (15) | −0.0006 (12) | 0.0065 (13) | 0.0030 (11) |
C3 | 0.0236 (11) | 0.0207 (11) | 0.0265 (12) | 0.0019 (9) | 0.0068 (10) | 0.0049 (9) |
C3A | 0.0271 (12) | 0.0266 (12) | 0.0260 (11) | −0.0003 (10) | 0.0089 (10) | 0.0019 (10) |
C4 | 0.0365 (15) | 0.0238 (13) | 0.0521 (17) | 0.0023 (12) | 0.0098 (13) | −0.0040 (13) |
C5 | 0.0401 (16) | 0.0269 (14) | 0.0529 (17) | −0.0061 (12) | 0.0138 (14) | −0.0103 (13) |
C6 | 0.0362 (15) | 0.0388 (14) | 0.0319 (13) | −0.0079 (12) | 0.0121 (12) | −0.0107 (12) |
C7 | 0.0255 (12) | 0.0298 (13) | 0.0381 (14) | −0.0006 (10) | 0.0083 (11) | −0.0009 (11) |
C7A | 0.0262 (12) | 0.0255 (12) | 0.0261 (12) | 0.0021 (9) | 0.0099 (10) | −0.0025 (9) |
C9 | 0.0302 (13) | 0.0313 (13) | 0.0353 (13) | 0.0074 (11) | 0.0130 (11) | 0.0061 (11) |
C8 | 0.0343 (14) | 0.0337 (14) | 0.0273 (13) | −0.0018 (11) | 0.0055 (11) | 0.0051 (10) |
C10 | 0.0411 (17) | 0.0507 (19) | 0.064 (2) | −0.0136 (17) | 0.0065 (16) | −0.0210 (17) |
S1'B | 0.0231 (3) | 0.0223 (3) | 0.0364 (3) | 0.0027 (2) | 0.0046 (3) | 0.0057 (2) |
O6'B | 0.0303 (11) | 0.0298 (10) | 0.0540 (12) | −0.0032 (9) | −0.0044 (10) | −0.0025 (9) |
N1B | 0.0193 (9) | 0.0254 (11) | 0.0285 (10) | −0.0003 (8) | 0.0037 (8) | 0.0039 (8) |
N2B | 0.0201 (10) | 0.0224 (10) | 0.0283 (10) | 0.0031 (8) | 0.0025 (8) | 0.0012 (8) |
N3'B | 0.0249 (11) | 0.0225 (10) | 0.0324 (11) | 0.0010 (9) | 0.0025 (9) | 0.0008 (9) |
C2'B | 0.0215 (12) | 0.0232 (12) | 0.0254 (11) | 0.0024 (9) | 0.0089 (10) | 0.0034 (9) |
C4'B | 0.0268 (13) | 0.0262 (13) | 0.0335 (13) | −0.0005 (11) | 0.0072 (11) | 0.0009 (11) |
C5'B | 0.0287 (14) | 0.0204 (13) | 0.0422 (15) | 0.0004 (11) | 0.0054 (12) | 0.0033 (11) |
C3B | 0.0243 (12) | 0.0206 (11) | 0.0256 (12) | 0.0048 (9) | 0.0056 (10) | 0.0000 (9) |
C3AB | 0.0257 (12) | 0.0250 (12) | 0.0306 (13) | 0.0032 (9) | 0.0093 (10) | −0.0053 (10) |
C4B | 0.0447 (17) | 0.0318 (16) | 0.0514 (18) | −0.0054 (12) | 0.0043 (14) | 0.0139 (13) |
C5B | 0.0503 (18) | 0.0270 (15) | 0.062 (2) | −0.0110 (13) | 0.0127 (16) | 0.0076 (13) |
C6B | 0.0315 (14) | 0.0320 (14) | 0.0414 (15) | −0.0078 (11) | 0.0187 (12) | −0.0081 (11) |
C7B | 0.0247 (12) | 0.0320 (13) | 0.0341 (13) | −0.0027 (10) | 0.0077 (10) | −0.0014 (11) |
C7AB | 0.0260 (12) | 0.0281 (12) | 0.0230 (11) | −0.0009 (10) | 0.0111 (10) | 0.0021 (9) |
C9B | 0.0398 (14) | 0.0280 (13) | 0.0285 (13) | 0.0026 (11) | 0.0090 (12) | 0.0000 (10) |
C8B | 0.0262 (12) | 0.0385 (14) | 0.0315 (13) | 0.0035 (11) | 0.0100 (11) | −0.0004 (11) |
C10B | 0.0370 (16) | 0.0417 (17) | 0.0629 (19) | −0.0179 (15) | 0.0190 (15) | −0.0129 (16) |
S1'—C2' | 1.772 (2) | S1'B—C2'B | 1.767 (2) |
S1'—C5' | 1.801 (3) | S1'B—C5'B | 1.800 (3) |
O6'—C4' | 1.222 (3) | O6'B—C4'B | 1.214 (3) |
N1—C7A | 1.274 (3) | N1B—C7AB | 1.280 (3) |
N1—N2 | 1.408 (3) | N1B—N2B | 1.404 (3) |
N2—C2' | 1.324 (3) | N2B—C2'B | 1.324 (3) |
N2—C3 | 1.514 (3) | N2B—C3B | 1.513 (3) |
N3'—C2' | 1.308 (3) | N3'B—C2'B | 1.312 (3) |
N3'—C4' | 1.376 (3) | N3'B—C4'B | 1.370 (3) |
C4'—C5' | 1.523 (4) | C4'B—C5'B | 1.531 (3) |
C5'—H5'1 | 0.9700 | C5'B—H5'3 | 0.9700 |
C5'—H5'2 | 0.9700 | C5'B—H5'4 | 0.9700 |
C3—C9 | 1.517 (3) | C3B—C8B | 1.517 (3) |
C3—C8 | 1.519 (3) | C3B—C9B | 1.522 (3) |
C3—C3A | 1.556 (3) | C3B—C3AB | 1.555 (3) |
C3A—C7A | 1.497 (3) | C3AB—C7AB | 1.493 (3) |
C3A—C4 | 1.517 (4) | C3AB—C4B | 1.529 (4) |
C3A—H3A | 0.9800 | C3AB—H3AB | 0.9800 |
C4—C5 | 1.532 (4) | C4B—C5B | 1.529 (4) |
C4—H4A | 0.9700 | C4B—H4B1 | 0.9700 |
C4—H4B | 0.9700 | C4B—H4B2 | 0.9700 |
C5—C6 | 1.524 (4) | C5B—C6B | 1.516 (4) |
C5—H5A | 0.9700 | C5B—H5B1 | 0.9700 |
C5—H5B | 0.9700 | C5B—H5B2 | 0.9700 |
C6—C10 | 1.525 (4) | C6B—C10B | 1.527 (4) |
C6—C7 | 1.534 (4) | C6B—C7B | 1.528 (3) |
C6—H6 | 0.9800 | C6B—H6B | 0.9800 |
C7—C7A | 1.493 (3) | C7B—C7AB | 1.490 (3) |
C7—H7A | 0.9700 | C7B—H7B1 | 0.9700 |
C7—H7B | 0.9700 | C7B—H7B2 | 0.9700 |
C9—H9A | 0.9600 | C9B—H9B1 | 0.9600 |
C9—H9B | 0.9600 | C9B—H9B2 | 0.9600 |
C9—H9C | 0.9600 | C9B—H9B3 | 0.9600 |
C8—H8A | 0.9600 | C8B—H8B1 | 0.9600 |
C8—H8B | 0.9600 | C8B—H8B2 | 0.9600 |
C8—H8C | 0.9600 | C8B—H8B3 | 0.9600 |
C10—H10A | 0.9600 | C10B—H10D | 0.9600 |
C10—H10B | 0.9600 | C10B—H10E | 0.9600 |
C10—H10C | 0.9600 | C10B—H10F | 0.9600 |
C2'—S1'—C5' | 88.45 (12) | C2'B—S1'B—C5'B | 88.60 (12) |
C7A—N1—N2 | 106.63 (19) | C7AB—N1B—N2B | 107.21 (19) |
C2'—N2—N1 | 117.31 (18) | C2'B—N2B—N1B | 117.75 (19) |
C2'—N2—C3 | 129.48 (19) | C2'B—N2B—C3B | 128.74 (19) |
N1—N2—C3 | 113.19 (17) | N1B—N2B—C3B | 113.44 (18) |
C2'—N3'—C4' | 111.1 (2) | C2'B—N3'B—C4'B | 111.5 (2) |
N3'—C2'—N2 | 124.0 (2) | N3'B—C2'B—N2B | 123.7 (2) |
N3'—C2'—S1' | 118.80 (18) | N3'B—C2'B—S1'B | 118.70 (18) |
N2—C2'—S1' | 117.20 (17) | N2B—C2'B—S1'B | 117.56 (17) |
O6'—C4'—N3' | 124.6 (2) | O6'B—C4'B—N3'B | 125.0 (2) |
O6'—C4'—C5' | 120.6 (2) | O6'B—C4'B—C5'B | 120.5 (2) |
N3'—C4'—C5' | 114.8 (2) | N3'B—C4'B—C5'B | 114.5 (2) |
C4'—C5'—S1' | 106.73 (19) | C4'B—C5'B—S1'B | 106.68 (18) |
C4'—C5'—H5'1 | 110.4 | C4'B—C5'B—H5'3 | 110.4 |
S1'—C5'—H5'1 | 110.4 | S1'B—C5'B—H5'3 | 110.4 |
C4'—C5'—H5'2 | 110.4 | C4'B—C5'B—H5'4 | 110.4 |
S1'—C5'—H5'2 | 110.4 | S1'B—C5'B—H5'4 | 110.4 |
H5'1—C5'—H5'2 | 108.6 | H5'3—C5'B—H5'4 | 108.6 |
N2—C3—C9 | 108.11 (18) | N2B—C3B—C8B | 109.00 (19) |
N2—C3—C8 | 111.76 (19) | N2B—C3B—C9B | 110.36 (19) |
C9—C3—C8 | 111.3 (2) | C8B—C3B—C9B | 112.0 (2) |
N2—C3—C3A | 99.17 (17) | N2B—C3B—C3AB | 99.81 (18) |
C9—C3—C3A | 114.7 (2) | C8B—C3B—C3AB | 110.28 (19) |
C8—C3—C3A | 111.2 (2) | C9B—C3B—C3AB | 114.7 (2) |
C7A—C3A—C4 | 111.0 (2) | C7AB—C3AB—C4B | 107.9 (2) |
C7A—C3A—C3 | 102.81 (19) | C7AB—C3AB—C3B | 103.32 (19) |
C4—C3A—C3 | 119.2 (2) | C4B—C3AB—C3B | 119.4 (2) |
C7A—C3A—H3A | 107.8 | C7AB—C3AB—H3AB | 108.6 |
C4—C3A—H3A | 107.8 | C4B—C3AB—H3AB | 108.6 |
C3—C3A—H3A | 107.8 | C3B—C3AB—H3AB | 108.6 |
C3A—C4—C5 | 110.1 (2) | C3AB—C4B—C5B | 109.9 (2) |
C3A—C4—H4A | 109.6 | C3AB—C4B—H4B1 | 109.7 |
C5—C4—H4A | 109.6 | C5B—C4B—H4B1 | 109.7 |
C3A—C4—H4B | 109.6 | C3AB—C4B—H4B2 | 109.7 |
C5—C4—H4B | 109.6 | C5B—C4B—H4B2 | 109.7 |
H4A—C4—H4B | 108.2 | H4B1—C4B—H4B2 | 108.2 |
C6—C5—C4 | 112.3 (2) | C6B—C5B—C4B | 112.9 (3) |
C6—C5—H5A | 109.1 | C6B—C5B—H5B1 | 109.0 |
C4—C5—H5A | 109.1 | C4B—C5B—H5B1 | 109.0 |
C6—C5—H5B | 109.1 | C6B—C5B—H5B2 | 109.0 |
C4—C5—H5B | 109.1 | C4B—C5B—H5B2 | 109.0 |
H5A—C5—H5B | 107.9 | H5B1—C5B—H5B2 | 107.8 |
C5—C6—C10 | 112.2 (3) | C5B—C6B—C10B | 112.1 (2) |
C5—C6—C7 | 110.2 (2) | C5B—C6B—C7B | 110.5 (2) |
C10—C6—C7 | 109.9 (2) | C10B—C6B—C7B | 109.6 (2) |
C5—C6—H6 | 108.1 | C5B—C6B—H6B | 108.2 |
C10—C6—H6 | 108.1 | C10B—C6B—H6B | 108.2 |
C7—C6—H6 | 108.1 | C7B—C6B—H6B | 108.2 |
C7A—C7—C6 | 111.4 (2) | C7AB—C7B—C6B | 110.2 (2) |
C7A—C7—H7A | 109.4 | C7AB—C7B—H7B1 | 109.6 |
C6—C7—H7A | 109.4 | C6B—C7B—H7B1 | 109.6 |
C7A—C7—H7B | 109.4 | C7AB—C7B—H7B2 | 109.6 |
C6—C7—H7B | 109.4 | C6B—C7B—H7B2 | 109.6 |
H7A—C7—H7B | 108.0 | H7B1—C7B—H7B2 | 108.1 |
N1—C7A—C7 | 123.6 (2) | N1B—C7AB—C7B | 123.1 (2) |
N1—C7A—C3A | 116.2 (2) | N1B—C7AB—C3AB | 115.9 (2) |
C7—C7A—C3A | 120.1 (2) | C7B—C7AB—C3AB | 120.7 (2) |
C3—C9—H9A | 109.5 | C3B—C9B—H9B1 | 109.5 |
C3—C9—H9B | 109.5 | C3B—C9B—H9B2 | 109.5 |
H9A—C9—H9B | 109.5 | H9B1—C9B—H9B2 | 109.5 |
C3—C9—H9C | 109.5 | C3B—C9B—H9B3 | 109.5 |
H9A—C9—H9C | 109.5 | H9B1—C9B—H9B3 | 109.5 |
H9B—C9—H9C | 109.5 | H9B2—C9B—H9B3 | 109.5 |
C3—C8—H8A | 109.5 | C3B—C8B—H8B1 | 109.5 |
C3—C8—H8B | 109.5 | C3B—C8B—H8B2 | 109.5 |
H8A—C8—H8B | 109.5 | H8B1—C8B—H8B2 | 109.5 |
C3—C8—H8C | 109.5 | C3B—C8B—H8B3 | 109.5 |
H8A—C8—H8C | 109.5 | H8B1—C8B—H8B3 | 109.5 |
H8B—C8—H8C | 109.5 | H8B2—C8B—H8B3 | 109.5 |
C6—C10—H10A | 109.5 | C6B—C10B—H10D | 109.5 |
C6—C10—H10B | 109.5 | C6B—C10B—H10E | 109.5 |
H10A—C10—H10B | 109.5 | H10D—C10B—H10E | 109.5 |
C6—C10—H10C | 109.5 | C6B—C10B—H10F | 109.5 |
H10A—C10—H10C | 109.5 | H10D—C10B—H10F | 109.5 |
H10B—C10—H10C | 109.5 | H10E—C10B—H10F | 109.5 |
Cg1 is the centroid of the thiazole ring S1'/N3'/C2'/C4'/C5' |
D—H···A | D—H | H···A | D···A | D—H···A |
C5′—H5′2···O6′Bi | 0.97 | 2.43 | 3.304 (4) | 150 |
C9—H9B···O6′Bii | 0.96 | 2.53 | 3.361 (3) | 145 |
C5′B—H5′3···O6′iii | 0.97 | 2.44 | 3.361 (3) | 159 |
C4B—H4B2···Cg1 | 0.96 | 2.93 | 3.737 (4) | 141 |
C7B—H7B2···Cg1iv | 0.96 | 2.90 | 3.867 (4) | 174 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x+1, y, z; (iii) −x+2, y−1/2, −z+1; (iv) x, y, z+1. |
Cg1 is the centroid of the thiazole ring S1'/N3'/C2'/C4'/C5' |
D—H···A | D—H | H···A | D···A | D—H···A |
C5'—H5'2···O6'Bi | 0.97 | 2.43 | 3.304 (4) | 150 |
C9—H9B···O6'Bii | 0.96 | 2.53 | 3.361 (3) | 145 |
C5'B—H5'3···O6'iii | 0.97 | 2.44 | 3.361 (3) | 159 |
C4B—H4B2···Cg1 | 0.96 | 2.93 | 3.737 (4) | 141 |
C7B—H7B2···Cg1iv | 0.96 | 2.90 | 3.867 (4) | 174 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x+1, y, z; (iii) −x+2, y−1/2, −z+1; (iv) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C13H19N3OS |
Mr | 265.37 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 180 |
a, b, c (Å) | 8.5519 (2), 18.9335 (4), 8.9165 (3) |
β (°) | 110.203 (3) |
V (Å3) | 1354.91 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.25 × 0.21 × 0.18 |
Data collection | |
Diffractometer | Agilent Xcalibur Eos Gemini ultra |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2014) |
Tmin, Tmax | 0.939, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15302, 6147, 5674 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.692 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.077, 1.04 |
No. of reflections | 6147 |
No. of parameters | 331 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.19 |
Absolute structure | Flack x determined using 2349 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | −0.08 (3) |
Computer programs: CrysAlis PRO (Agilent, 2014), SIR97 (Altomare et al., 1999), SHELXL2013 (Sheldrick, 2015), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009).
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