organic compounds
3-tert-Butyl-4-(4-chlorophenyl)-1-phenyl-1H-pyrazolo[3,4-e][1,4]thiazepin-7(4H,6H,8H)-one
aDepartamento de Química - Facultad de Ciencias Naturales y Exactas, Universidad del Valle, A.A. 25360, Santiago de Cali, Colombia, bDepartamento de Química, Universidad de los Andes, Carrera 1 No 18A-12, Bogotá, Colombia, and cInstituto de Física de São Carlos, IFSC, Universidade de São Paulo, USP, São Carlos, SP, Brazil
*Correspondence e-mail: rodimo26@yahoo.es
In the title molecule, C22H22ClN3OS, the fused 1,4-thiazepinone ring adopts a near twist-boat conformation and the chlorobenzene ring is inclined to the phenyl ring by 88.38 (12)°. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R22(8) ring motif. The dimers are linked via C—H⋯O hydrogen bonds forming ribbons, enclosing R42(20) loops, propagating along [001].
Keywords: crystal structure; 1,4-thiazepinone; hydrogen bonding.
CCDC reference: 1473503
Structure description
The title compound has in its structure the 1,4-thiazepine ring which is one of the most important moieties in nitrogen- and sulfur-containing heterocycles and which has been widely used as a building block for pharmacologically relevant therapeutic agents. Nowadays, the design of 1,4-thiazepines fused with bioactive heteroaromatic scaffolds is highly valuable for medicinal chemistry and drug discovery (Chen & Shi, 2011).
A perspective view of the title compound, with a folded structure, showing the atomic numbering scheme, is given in Fig. 1. From the puckering analysis [q2 = 1.076 (2) Å, φ3 = −106.3 (7)°, q3 = 0.211 (2) Å and φ2 = −167.2 (1)°], the fused 1,4-thiazepinone ring (S1/C9/C8/N3/C7/C17/C10) adopts a near twist-boat conformation. The benzene (C11–C16) and phenyl (C1–C6) rings are normal to one another, with a dihedral anble of 88.38 (12)°.
In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, of moderate strength (Desiraju & Steiner, 1999), forming inversion dimers enclosing an (8) ring motif (Table 1 and Fig. 2). The dimers are linked via C—H⋯O hydrogen bonds forming ribbons, enclosing R42(20) loops, propagating along the c-axis direction (Table 1 and Fig. 2).
Synthesis and crystallization
A 5 ml pyrex test tube was charged with a mixture of 3-(tert-butyl)-1-phenyl-1H-pyrazol-5-amine (111 mg, 0.52 mmol), p-chlorobenzaldehyde (73 mg, 0.52 mmol) and 2-mercaptoacetic acid (57 mg, 0.62 mmol) in the absence of solvent. The mixture was heated in an oil bath at 393 K for 20 min until the starting materials were no longer detected by Then, the obtained oily material was purified by on silica gel using a mixture of CH2Cl2/EtOAc (10:1) as Yellow crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, from a solution in methanol [81% yield, m.p. 518 (1) K].
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1473503
10.1107/S2414314616006088/hg4005sup1.cif
contains datablock I. DOI:Supporting information file. DOI: 10.1107/S2414314616006088/hg4005Isup3.cml
Structure factors: contains datablock I. DOI: 10.1107/S2414314616006088/hg4005Isup3.hkl
A 5 mL pyrex test tube was charged with a mixture of 3-(tert-butyl)-1-phenyl-1H-pyrazol-5-amine (111 mg, 0.52 mmol), p-chlorobenzaldehyde (73 mg, 0.52 mmol) and 2-mercaptoacetic acid (57 mg, 0.62 mmol) in absence of solvent. The mixture was heated in an oil bath at 120°C for 20 min until the starting materials were no longer detected by
Then, the obtained oily material was purified by on silica gel using a mixture of CH2Cl2/EtOAc (10:1) as Yellow crystals of (I) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, from a solution in methanol [81% yield, m.p. 518 (1) K]. Specxtroscopic data: IR (KBr): cm-1, 3424 (N—H), 2972, 2929, 1686 (C=O). MS (IE, 70 eV) m/z (%): 413/411 (16/47) [M+], 366/364 (5/15), 300 (100), 226 (7), 77 (16).Crystal data, data collection and structure
details are summarized in Table 1. The H-atoms bounded to C were positioned geometrically [C—H = 0.93 Å for aromatic and methylene, C—H= 0.96 Å for methyl and C—H = 0.98 Å for methane] and were refined in riding modes with Uiso(H) = 1.2 times Ueq of the parent atom. H31 atom was found from the Fourier maps and its coordinates were refined freely.The compound 3-tert-butyl-4-(4-chlorophenyl)-1-phenyl-1H-pyrazolo[3,4-e][1,4]thiazepin-7(4H,6H,8H)-one (I), has in its structure the 1,4-thiazepine ring which is one of the most important moieties in nitrogen- and sulfur-containing heterocycles and it has been widely used as building block for pharmacologically relevant therapeutic agents. Nowadays, the design of 1,4-thiazepines fused with bioactive heteroaromatic scaffolds is highly valuable for medicinal chemistry and drug discovery (Chen et al., 2011). A perspective view of the molecule of the title compound, with a folded structure, showing the atomic numbering scheme, is given in Fig. 1. From the puckering analysis, the fused 1,4-thiazepinone ring (S1/C9/C8/N3/C7/C17/C10) adopts a near twist-boat conformation with q2= 1.076 (2)Å, φ3= -106.3 (7)°, q3= 0.211 (2) Å and φ2= -167.2 (1)°. Molecules of (I) are held together by intermolecular N—H···O hydrogen bonds of moderate strength (Desiraju & Steiner, 1999) and C—H···O interactions. The N3—H31 group in the molecule at (x,y,z) acts as hydrogen bond donor to O1 atom of the carbonyl group in the molecule at (-x,-y+1,-z) and C15—H15 group in the molecule at (x,y,z) acts as hydrogen bond donor to O1 atom in the molecule at (x,+y,+z+1). These interactions generate R22(8) and R24(20) rings along [100] and they are observed to contribute to the crystal packing stability (see Fig. 2).
A 5 ml pyrex test tube was charged with a mixture of 3-(tert-butyl)-1-phenyl-1H-pyrazol-5-amine (111 mg, 0.52 mmol), p-chlorobenzaldehyde (73 mg, 0.52 mmol) and 2-mercaptoacetic acid (57 mg, 0.62 mmol) in the absence of solvent. The mixture was heated in an oil bath at 393 K for 20 min until the starting materials were no longer detected by
Then, the obtained oily material was purified by on silica gel using a mixture of CH2Cl2/EtOAc (10:1) as Yellow crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, from a solution in methanol [81% yield, m.p. 518 (1) K].The title compound has in its structure the 1,4-thiazepine ring which is one of the most important moieties in nitrogen- and sulfur-containing heterocycles and which has been widely used as a building block for pharmacologically relevant therapeutic agents. Nowadays, the design of 1,4-thiazepines fused with bioactive heteroaromatic scaffolds is highly valuable for medicinal chemistry and drug discovery (Chen & Shi, 2011).
A perspective view of the title compound, with a folded structure, showing the atomic numbering scheme, is given in Fig. 1. From the puckering analysis [q2 = 1.076 (2) Å, φ3 = -106.3 (7)°, q3 = 0.211 (2) Å and φ2 = -167.2 (1)°], the fused 1,4-thiazepinone ring (S1/C9/C8/N3/C7/C17/C10) adopts a near twist-boat conformation. The benzene (C11–C16) and phenyl (C1–C6) rings are normal to one another, with a dihedral anble of 88.38 (12)°.
In the crystal, molecules are linked by pairs of N—H···O hydrogen bonds, of moderate strength (Desiraju & Steiner, 1999), forming inversion dimers enclosing an R22(8) ring motif (Table 1 and Fig. 2). The dimers are linked via C—H···O hydrogen bonds forming ribbons, enclosing R24(20) loops, propagating along the c-axis direction (Table 1 and Fig. 2).
Data collection: COLLECT (Nonius, 2000); 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: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).Fig. 1. The molecular structure of the title compound, with atom labelling and displacement ellipsoids drawn at the 50% probability level. | |
Fig. 2. A partial view along the a axis of the crystal packing of the title compound, with hydrogen bonds shown as dashed lines (see Table 1). |
C22H22ClN3OS | Dx = 1.313 Mg m−3 |
Mr = 411.94 | Melting point: 518(1) K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7478 (3) Å | Cell parameters from 7625 reflections |
b = 25.2229 (8) Å | θ = 3.2–26.4° |
c = 8.6354 (2) Å | µ = 0.30 mm−1 |
β = 101.733 (2)° | T = 295 K |
V = 2078.80 (10) Å3 | Block, yellow |
Z = 4 | 0.46 × 0.45 × 0.20 mm |
F(000) = 864 |
Oxford Diffraction Gemini S diffractometer | 2417 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0 |
Graphite monochromator | θmax = 26.4°, θmin = 3.2° |
ω scans | h = 0→12 |
4362 measured reflections | k = −31→0 |
4251 independent reflections | l = −10→10 |
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)] = 0.048 | Hydrogen site location: mixed |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0442P)2] where P = (Fo2 + 2Fc2)/3 |
4251 reflections | (Δ/σ)max < 0.001 |
257 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C22H22ClN3OS | V = 2078.80 (10) Å3 |
Mr = 411.94 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.7478 (3) Å | µ = 0.30 mm−1 |
b = 25.2229 (8) Å | T = 295 K |
c = 8.6354 (2) Å | 0.46 × 0.45 × 0.20 mm |
β = 101.733 (2)° |
Oxford Diffraction Gemini S diffractometer | 2417 reflections with I > 2σ(I) |
4362 measured reflections | Rint = 0 |
4251 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | Δρmax = 0.40 e Å−3 |
4251 reflections | Δρmin = −0.38 e Å−3 |
257 parameters |
Experimental. IR spectra was recorded on a FT—IR SHIMADZU IR-Affinity-1 spectrophotometer. IR (KBr): cm-1, 3424 (N-H), 2972, 2929, 1686 (C=O). MS (IE, 70 eV) m/z (%): 413/411 (16/47) [M+], 366/364 (5/15), 300 (100), 226 (7), 77 (16). |
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 > 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 | ||
S1 | 0.45801 (6) | 0.54058 (3) | 0.14582 (7) | 0.0460 (2) | |
Cl1 | 0.00759 (8) | 0.36932 (3) | 0.45897 (8) | 0.0741 (3) | |
O1 | 0.13987 (16) | 0.50033 (7) | −0.10709 (18) | 0.0515 (5) | |
N1 | 0.18428 (17) | 0.67941 (8) | 0.30062 (19) | 0.0346 (5) | |
N2 | 0.10134 (17) | 0.64849 (8) | 0.18983 (19) | 0.0338 (5) | |
N3 | 0.1012 (2) | 0.56179 (8) | 0.0695 (2) | 0.0357 (5) | |
C1 | −0.0292 (2) | 0.66867 (10) | 0.1018 (2) | 0.0347 (6) | |
C2 | −0.0295 (3) | 0.71213 (11) | 0.0076 (3) | 0.0582 (8) | |
H2 | 0.0543 | 0.7287 | 0.0005 | 0.070* | |
C3 | −0.1555 (3) | 0.73149 (12) | −0.0774 (4) | 0.0743 (9) | |
H3 | −0.1567 | 0.7611 | −0.1419 | 0.089* | |
C4 | −0.2783 (3) | 0.70688 (12) | −0.0661 (3) | 0.0663 (9) | |
H4 | −0.3630 | 0.7200 | −0.1227 | 0.080* | |
C5 | −0.2771 (2) | 0.66330 (12) | 0.0276 (3) | 0.0550 (8) | |
H5 | −0.3609 | 0.6467 | 0.0344 | 0.066* | |
C6 | −0.1519 (2) | 0.64363 (10) | 0.1128 (3) | 0.0442 (6) | |
H6 | −0.1508 | 0.6139 | 0.1766 | 0.053* | |
C7 | 0.1570 (2) | 0.59975 (9) | 0.1837 (2) | 0.0310 (5) | |
C8 | 0.1808 (2) | 0.53877 (11) | −0.0234 (2) | 0.0402 (6) | |
C9 | 0.3205 (2) | 0.56410 (10) | −0.0200 (2) | 0.0455 (7) | |
H91 | 0.3795 | 0.5507 | −0.0827 | 0.055* | |
H92 | 0.3482 | 0.5932 | 0.0449 | 0.055* | |
C10 | 0.3714 (2) | 0.54898 (10) | 0.3150 (2) | 0.0363 (6) | |
H101 | 0.4456 | 0.5554 | 0.4082 | 0.044* | |
C11 | 0.2902 (2) | 0.50020 (9) | 0.3514 (2) | 0.0347 (6) | |
C12 | 0.2652 (2) | 0.45570 (10) | 0.2574 (2) | 0.0416 (6) | |
H12 | 0.3067 | 0.4528 | 0.1698 | 0.050* | |
C13 | 0.1798 (2) | 0.41520 (10) | 0.2907 (3) | 0.0449 (6) | |
H13 | 0.1627 | 0.3857 | 0.2250 | 0.054* | |
C14 | 0.1208 (2) | 0.41892 (10) | 0.4204 (3) | 0.0449 (6) | |
C15 | 0.1480 (3) | 0.46167 (11) | 0.5211 (3) | 0.0521 (7) | |
H15 | 0.1105 | 0.4633 | 0.6118 | 0.063* | |
C16 | 0.2314 (3) | 0.50199 (10) | 0.4854 (3) | 0.0479 (7) | |
H16 | 0.2490 | 0.5311 | 0.5524 | 0.057* | |
C17 | 0.2802 (2) | 0.59764 (9) | 0.2920 (2) | 0.0311 (5) | |
C18 | 0.2939 (2) | 0.64881 (9) | 0.3612 (2) | 0.0322 (5) | |
C19 | 0.4095 (2) | 0.67068 (10) | 0.4904 (2) | 0.0389 (6) | |
C20 | 0.3832 (3) | 0.72886 (10) | 0.5220 (3) | 0.0578 (8) | |
H201 | 0.4572 | 0.7419 | 0.6039 | 0.087* | |
H202 | 0.3805 | 0.7490 | 0.4271 | 0.087* | |
H203 | 0.2953 | 0.7323 | 0.5549 | 0.087* | |
C21 | 0.4139 (3) | 0.63899 (11) | 0.6429 (3) | 0.0607 (8) | |
H211 | 0.4868 | 0.6527 | 0.7250 | 0.091* | |
H212 | 0.3254 | 0.6421 | 0.6747 | 0.091* | |
H213 | 0.4321 | 0.6024 | 0.6246 | 0.091* | |
C22 | 0.5510 (2) | 0.66588 (11) | 0.4380 (3) | 0.0549 (7) | |
H221 | 0.6243 | 0.6797 | 0.5194 | 0.082* | |
H222 | 0.5694 | 0.6293 | 0.4195 | 0.082* | |
H223 | 0.5474 | 0.6857 | 0.3423 | 0.082* | |
H31 | 0.029 (2) | 0.5480 (9) | 0.080 (2) | 0.029 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0383 (3) | 0.0523 (5) | 0.0503 (4) | 0.0067 (3) | 0.0156 (3) | 0.0009 (3) |
Cl1 | 0.0895 (6) | 0.0602 (6) | 0.0791 (5) | −0.0211 (4) | 0.0326 (4) | 0.0031 (4) |
O1 | 0.0585 (11) | 0.0504 (13) | 0.0452 (9) | −0.0022 (9) | 0.0098 (8) | −0.0194 (9) |
N1 | 0.0331 (10) | 0.0306 (12) | 0.0381 (10) | −0.0008 (9) | 0.0020 (8) | −0.0035 (9) |
N2 | 0.0298 (10) | 0.0320 (13) | 0.0357 (10) | 0.0047 (9) | −0.0022 (8) | −0.0062 (9) |
N3 | 0.0321 (11) | 0.0355 (13) | 0.0383 (11) | 0.0000 (10) | 0.0044 (9) | −0.0080 (10) |
C1 | 0.0336 (13) | 0.0321 (15) | 0.0354 (12) | 0.0047 (11) | −0.0001 (10) | −0.0082 (11) |
C2 | 0.0475 (16) | 0.0399 (19) | 0.0778 (18) | −0.0054 (13) | −0.0097 (14) | 0.0099 (15) |
C3 | 0.068 (2) | 0.043 (2) | 0.095 (2) | 0.0040 (16) | −0.0237 (17) | 0.0180 (16) |
C4 | 0.0500 (18) | 0.050 (2) | 0.084 (2) | 0.0145 (15) | −0.0217 (15) | −0.0162 (18) |
C5 | 0.0325 (14) | 0.066 (2) | 0.0627 (16) | 0.0041 (14) | 0.0009 (12) | −0.0188 (16) |
C6 | 0.0402 (14) | 0.0478 (18) | 0.0427 (13) | −0.0001 (13) | 0.0043 (11) | −0.0038 (12) |
C7 | 0.0301 (12) | 0.0286 (15) | 0.0331 (12) | 0.0019 (11) | 0.0039 (10) | −0.0047 (11) |
C8 | 0.0455 (14) | 0.0437 (17) | 0.0297 (12) | 0.0056 (13) | 0.0038 (11) | 0.0021 (13) |
C9 | 0.0425 (14) | 0.0595 (19) | 0.0368 (13) | −0.0027 (13) | 0.0130 (11) | −0.0078 (12) |
C10 | 0.0339 (12) | 0.0406 (16) | 0.0324 (12) | 0.0047 (11) | 0.0020 (9) | −0.0018 (11) |
C11 | 0.0374 (13) | 0.0354 (16) | 0.0305 (12) | 0.0094 (11) | 0.0051 (10) | 0.0019 (11) |
C12 | 0.0531 (15) | 0.0390 (17) | 0.0345 (12) | 0.0072 (13) | 0.0134 (11) | 0.0007 (12) |
C13 | 0.0620 (16) | 0.0349 (17) | 0.0379 (13) | 0.0033 (13) | 0.0105 (12) | −0.0032 (12) |
C14 | 0.0491 (14) | 0.0391 (17) | 0.0465 (14) | −0.0018 (13) | 0.0098 (12) | 0.0067 (13) |
C15 | 0.0767 (18) | 0.0451 (19) | 0.0406 (14) | −0.0013 (15) | 0.0262 (13) | 0.0020 (14) |
C16 | 0.0697 (17) | 0.0371 (17) | 0.0384 (13) | −0.0002 (14) | 0.0145 (12) | −0.0074 (12) |
C17 | 0.0316 (12) | 0.0292 (15) | 0.0318 (11) | 0.0017 (11) | 0.0049 (10) | 0.0015 (11) |
C18 | 0.0318 (12) | 0.0328 (15) | 0.0318 (11) | 0.0002 (11) | 0.0058 (9) | 0.0000 (11) |
C19 | 0.0356 (13) | 0.0371 (16) | 0.0394 (12) | −0.0018 (11) | −0.0031 (10) | −0.0034 (12) |
C20 | 0.0535 (16) | 0.051 (2) | 0.0612 (16) | −0.0043 (14) | −0.0062 (13) | −0.0178 (14) |
C21 | 0.0670 (17) | 0.066 (2) | 0.0409 (14) | −0.0129 (15) | −0.0092 (12) | 0.0001 (14) |
C22 | 0.0379 (14) | 0.053 (2) | 0.0690 (17) | −0.0065 (13) | 0.0006 (12) | −0.0006 (15) |
S1—C10 | 1.842 (2) | C10—C11 | 1.530 (3) |
S1—C9 | 1.849 (2) | C10—H101 | 0.9800 |
Cl1—C14 | 1.745 (2) | C11—C12 | 1.378 (3) |
O1—C8 | 1.226 (3) | C11—C16 | 1.392 (3) |
N1—C18 | 1.336 (3) | C12—C13 | 1.385 (3) |
N1—N2 | 1.365 (2) | C12—H12 | 0.9300 |
N2—C7 | 1.349 (3) | C13—C14 | 1.362 (3) |
N2—C1 | 1.436 (2) | C13—H13 | 0.9300 |
N3—C8 | 1.355 (3) | C14—C15 | 1.377 (3) |
N3—C7 | 1.402 (3) | C15—C16 | 1.376 (3) |
N3—H31 | 0.81 (2) | C15—H15 | 0.9300 |
C1—C2 | 1.365 (3) | C16—H16 | 0.9300 |
C1—C6 | 1.373 (3) | C17—C18 | 1.417 (3) |
C2—C3 | 1.385 (3) | C18—C19 | 1.519 (3) |
C2—H2 | 0.9300 | C19—C20 | 1.524 (3) |
C3—C4 | 1.369 (4) | C19—C21 | 1.534 (3) |
C3—H3 | 0.9300 | C19—C22 | 1.541 (3) |
C4—C5 | 1.364 (4) | C20—H201 | 0.9600 |
C4—H4 | 0.9300 | C20—H202 | 0.9600 |
C5—C6 | 1.383 (3) | C20—H203 | 0.9600 |
C5—H5 | 0.9300 | C21—H211 | 0.9600 |
C6—H6 | 0.9300 | C21—H212 | 0.9600 |
C7—C17 | 1.365 (3) | C21—H213 | 0.9600 |
C8—C9 | 1.499 (3) | C22—H221 | 0.9600 |
C9—H91 | 0.9300 | C22—H222 | 0.9600 |
C9—H92 | 0.9300 | C22—H223 | 0.9600 |
C10—C17 | 1.505 (3) | ||
C10—S1—C9 | 101.56 (10) | C16—C11—C10 | 117.6 (2) |
C18—N1—N2 | 104.91 (17) | C11—C12—C13 | 121.3 (2) |
C7—N2—N1 | 111.25 (16) | C11—C12—H12 | 119.3 |
C7—N2—C1 | 128.48 (17) | C13—C12—H12 | 119.3 |
N1—N2—C1 | 120.23 (18) | C14—C13—C12 | 119.5 (2) |
C8—N3—C7 | 121.5 (2) | C14—C13—H13 | 120.3 |
C8—N3—H31 | 119.9 (15) | C12—C13—H13 | 120.3 |
C7—N3—H31 | 116.1 (15) | C13—C14—C15 | 121.0 (2) |
C2—C1—C6 | 121.0 (2) | C13—C14—Cl1 | 119.8 (2) |
C2—C1—N2 | 119.7 (2) | C15—C14—Cl1 | 119.25 (19) |
C6—C1—N2 | 119.4 (2) | C16—C15—C14 | 118.9 (2) |
C1—C2—C3 | 119.6 (2) | C16—C15—H15 | 120.5 |
C1—C2—H2 | 120.2 | C14—C15—H15 | 120.5 |
C3—C2—H2 | 120.2 | C15—C16—C11 | 121.6 (2) |
C4—C3—C2 | 119.7 (3) | C15—C16—H16 | 119.2 |
C4—C3—H3 | 120.1 | C11—C16—H16 | 119.2 |
C2—C3—H3 | 120.1 | C7—C17—C18 | 104.37 (18) |
C5—C4—C3 | 120.4 (2) | C7—C17—C10 | 122.4 (2) |
C5—C4—H4 | 119.8 | C18—C17—C10 | 133.19 (18) |
C3—C4—H4 | 119.8 | N1—C18—C17 | 111.19 (17) |
C4—C5—C6 | 120.3 (3) | N1—C18—C19 | 119.5 (2) |
C4—C5—H5 | 119.8 | C17—C18—C19 | 129.26 (19) |
C6—C5—H5 | 119.8 | C18—C19—C20 | 110.76 (18) |
C1—C6—C5 | 119.0 (2) | C18—C19—C21 | 109.17 (19) |
C1—C6—H6 | 120.5 | C20—C19—C21 | 108.9 (2) |
C5—C6—H6 | 120.5 | C18—C19—C22 | 109.26 (18) |
N2—C7—C17 | 108.26 (18) | C20—C19—C22 | 108.7 (2) |
N2—C7—N3 | 123.23 (17) | C21—C19—C22 | 109.96 (19) |
C17—C7—N3 | 128.1 (2) | C19—C20—H201 | 109.5 |
O1—C8—N3 | 122.1 (2) | C19—C20—H202 | 109.5 |
O1—C8—C9 | 122.3 (2) | H201—C20—H202 | 109.5 |
N3—C8—C9 | 115.6 (2) | C19—C20—H203 | 109.5 |
C8—C9—S1 | 113.04 (16) | H201—C20—H203 | 109.5 |
C8—C9—H91 | 120.0 | H202—C20—H203 | 109.5 |
S1—C9—H91 | 84.1 | C19—C21—H211 | 109.5 |
C8—C9—H92 | 120.0 | C19—C21—H212 | 109.5 |
S1—C9—H92 | 73.2 | H211—C21—H212 | 109.5 |
H91—C9—H92 | 120.0 | C19—C21—H213 | 109.5 |
C17—C10—C11 | 111.46 (17) | H211—C21—H213 | 109.5 |
C17—C10—S1 | 110.06 (14) | H212—C21—H213 | 109.5 |
C11—C10—S1 | 114.23 (15) | C19—C22—H221 | 109.5 |
C17—C10—H101 | 106.9 | C19—C22—H222 | 109.5 |
C11—C10—H101 | 106.9 | H221—C22—H222 | 109.5 |
S1—C10—H101 | 106.9 | C19—C22—H223 | 109.5 |
C12—C11—C16 | 117.6 (2) | H221—C22—H223 | 109.5 |
C12—C11—C10 | 124.8 (2) | H222—C22—H223 | 109.5 |
C18—N1—N2—C7 | 0.9 (2) | C16—C11—C12—C13 | 2.8 (3) |
C18—N1—N2—C1 | 178.85 (19) | C10—C11—C12—C13 | −173.9 (2) |
C7—N2—C1—C2 | −121.2 (3) | C11—C12—C13—C14 | −1.1 (3) |
N1—N2—C1—C2 | 61.2 (3) | C12—C13—C14—C15 | −1.7 (3) |
C7—N2—C1—C6 | 58.3 (3) | C12—C13—C14—Cl1 | 177.52 (18) |
N1—N2—C1—C6 | −119.2 (2) | C13—C14—C15—C16 | 2.7 (4) |
C6—C1—C2—C3 | 0.4 (4) | Cl1—C14—C15—C16 | −176.60 (18) |
N2—C1—C2—C3 | 179.9 (2) | C14—C15—C16—C11 | −0.8 (4) |
C1—C2—C3—C4 | 0.0 (4) | C12—C11—C16—C15 | −1.9 (3) |
C2—C3—C4—C5 | −0.3 (4) | C10—C11—C16—C15 | 175.1 (2) |
C3—C4—C5—C6 | 0.3 (4) | N2—C7—C17—C18 | −0.7 (2) |
C2—C1—C6—C5 | −0.5 (3) | N3—C7—C17—C18 | 172.0 (2) |
N2—C1—C6—C5 | 179.99 (19) | N2—C7—C17—C10 | −179.07 (19) |
C4—C5—C6—C1 | 0.2 (4) | N3—C7—C17—C10 | −6.4 (3) |
N1—N2—C7—C17 | −0.2 (2) | C11—C10—C17—C7 | −55.6 (3) |
C1—N2—C7—C17 | −177.8 (2) | S1—C10—C17—C7 | 72.2 (2) |
N1—N2—C7—N3 | −173.25 (19) | C11—C10—C17—C18 | 126.5 (2) |
C1—N2—C7—N3 | 9.1 (3) | S1—C10—C17—C18 | −105.7 (2) |
C8—N3—C7—N2 | 125.2 (2) | N2—N1—C18—C17 | −1.4 (2) |
C8—N3—C7—C17 | −46.5 (3) | N2—N1—C18—C19 | −179.90 (18) |
C7—N3—C8—O1 | 169.2 (2) | C7—C17—C18—N1 | 1.3 (2) |
C7—N3—C8—C9 | −12.1 (3) | C10—C17—C18—N1 | 179.5 (2) |
O1—C8—C9—S1 | −96.7 (2) | C7—C17—C18—C19 | 179.6 (2) |
N3—C8—C9—S1 | 84.6 (2) | C10—C17—C18—C19 | −2.2 (4) |
C10—S1—C9—C8 | −50.4 (2) | N1—C18—C19—C20 | −4.3 (3) |
C9—S1—C10—C17 | −35.57 (17) | C17—C18—C19—C20 | 177.5 (2) |
C9—S1—C10—C11 | 90.69 (16) | N1—C18—C19—C21 | 115.6 (2) |
C17—C10—C11—C12 | 117.2 (2) | C17—C18—C19—C21 | −62.6 (3) |
S1—C10—C11—C12 | −8.3 (3) | N1—C18—C19—C22 | −124.1 (2) |
C17—C10—C11—C16 | −59.6 (2) | C17—C18—C19—C22 | 57.7 (3) |
S1—C10—C11—C16 | 174.91 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H31···O1i | 0.81 (2) | 2.10 (2) | 2.897 (3) | 170 (2) |
C15—H15···O1ii | 0.93 | 2.56 | 3.372 (3) | 146 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H31···O1i | 0.81 (2) | 2.10 (2) | 2.897 (3) | 170 (2) |
C15—H15···O1ii | 0.93 | 2.56 | 3.372 (3) | 145.7 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C22H22ClN3OS |
Mr | 411.94 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 9.7478 (3), 25.2229 (8), 8.6354 (2) |
β (°) | 101.733 (2) |
V (Å3) | 2078.80 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.46 × 0.45 × 0.20 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini S |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4362, 4251, 2417 |
Rint | 0 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.115, 0.95 |
No. of reflections | 4251 |
No. of parameters | 257 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.38 |
Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997, SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006).
Acknowledgements
RMF and RA are grateful to the Universidad del Valle, Colombia, for partial financial support. JCC acknowledges his doctoral fellowship granted by COLCIENCIAS.
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