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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 1| Part 4| April 2016| x160608
doi:10.1107/S2414314616006088

3-tert-Butyl-4-(4-chloro­phen­yl)-1-phenyl-1H-pyrazolo­[3,4-e][1,4]thia­zepin-7(4H,6H,8H)-one

Rodolfo Moreno-Fuquen,a* Juan C. Castillo,b Rodrigo Abonia,a Juan C. Tenorioc and Javier Ellenac

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

Edited by P. C. Healy, Griffith University, Australia (Received 30 March 2016; accepted 12 April 2016; online 22 April 2016)

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].

CCDC reference: 1473503

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

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[Chen, H. & Shi, D. (2011). Tetrahedron, 67, 5686-5692.]).

A perspective view of the title compound, with a folded structure, showing the atomic numbering scheme, is given in Fig. 1[link]. 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)°.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound, with atom labelling and displacement ellipsoids drawn at the 50% probability level.

In the crystal, mol­ecules are linked by pairs of N—H⋯O hydrogen bonds, of moderate strength (Desiraju & Steiner, 1999[Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond, pp. 86-89. Oxford University Press.]), forming inversion dimers enclosing an [R_{2}^{2}](8) ring motif (Table 1[link] and Fig. 2[link]). The dimers are linked via C—H⋯O hydrogen bonds forming ribbons, enclosing R42(20) loops, propagating along the c-axis direction (Table 1[link] and Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

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.
[Figure 2]
Figure 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[link]).

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 thin-layer chromatography. Then, the obtained oily material was purified by column chromatography on silica gel using a mixture of CH2Cl2/EtOAc (10:1) as eluent. 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 refinement details are summarized in Table 2[link].

Table 2
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
No. of measured, independent and observed [I > 2σ(I)] reflections 4362, 4251, 2417
(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[Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.]), DENZO and SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.], SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]).

Structural data

CCDC reference: 1473503

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616006088/hg4005sup1.cif

Supporting information file. DOI: 10.1107/S2414314616006088/hg4005Isup3.cml

Structure factors: contains datablock I. DOI: 10.1107/S2414314616006088/hg4005Isup3.hkl

checkCIF report


Experimental top

Synthesis and crystallization top

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 thin-layer chromatography. Then, the obtained oily material was purified by column chromatography on silica gel using a mixture of CH2Cl2/EtOAc (10:1) as eluent. 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).

Refinement top

Crystal data, data collection and structure refinement 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.

Results and discussion top

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).

Experimental top

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 thin-layer chromatography. Then, the obtained oily material was purified by column chromatography on silica gel using a mixture of CH2Cl2/EtOAc (10:1) as eluent. 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 top

Crystal data, data collection and structure refinement details are summarized in Table 2.

Structure description top

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).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labelling and displacement ellipsoids drawn at the 50% probability level.
[Figure 2] 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).
(I) top
Crystal data top
C22H22ClN3OSDx = 1.313 Mg m−3
Mr = 411.94Melting point: 518(1) K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 9.7478 (3) ÅCell parameters from 7625 reflections
b = 25.2229 (8) Åθ = 3.2–26.4°
c = 8.6354 (2) ŵ = 0.30 mm−1
β = 101.733 (2)°T = 295 K
V = 2078.80 (10) Å3Block, yellow
Z = 40.46 × 0.45 × 0.20 mm
F(000) = 864
Data collection top
Oxford Diffraction Gemini S
diffractometer		2417 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0
Graphite monochromatorθmax = 26.4°, θmin = 3.2°
ω scansh = 0→12
4362 measured reflectionsk = −31→0
4251 independent reflectionsl = −10→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: mixed
wR(F2) = 0.115H 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 parametersΔρmax = 0.40 e Å−3
0 restraintsΔρmin = −0.38 e Å−3
Crystal data top
C22H22ClN3OSV = 2078.80 (10) Å3
Mr = 411.94Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.7478 (3) ŵ = 0.30 mm−1
b = 25.2229 (8) ÅT = 295 K
c = 8.6354 (2) Å0.46 × 0.45 × 0.20 mm
β = 101.733 (2)°
Data collection top
Oxford Diffraction Gemini S
diffractometer		2417 reflections with I > 2σ(I)
4362 measured reflectionsRint = 0
4251 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 0.95Δρmax = 0.40 e Å−3
4251 reflectionsΔρmin = −0.38 e Å−3
257 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.45801 (6)0.54058 (3)0.14582 (7)0.0460 (2)
Cl10.00759 (8)0.36932 (3)0.45897 (8)0.0741 (3)
O10.13987 (16)0.50033 (7)−0.10709 (18)0.0515 (5)
N10.18428 (17)0.67941 (8)0.30062 (19)0.0346 (5)
N20.10134 (17)0.64849 (8)0.18983 (19)0.0338 (5)
N30.1012 (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)
H20.05430.72870.00050.070*
C3−0.1555 (3)0.73149 (12)−0.0774 (4)0.0743 (9)
H3−0.15670.7611−0.14190.089*
C4−0.2783 (3)0.70688 (12)−0.0661 (3)0.0663 (9)
H4−0.36300.7200−0.12270.080*
C5−0.2771 (2)0.66330 (12)0.0276 (3)0.0550 (8)
H5−0.36090.64670.03440.066*
C6−0.1519 (2)0.64363 (10)0.1128 (3)0.0442 (6)
H6−0.15080.61390.17660.053*
C70.1570 (2)0.59975 (9)0.1837 (2)0.0310 (5)
C80.1808 (2)0.53877 (11)−0.0234 (2)0.0402 (6)
C90.3205 (2)0.56410 (10)−0.0200 (2)0.0455 (7)
H910.37950.5507−0.08270.055*
H920.34820.59320.04490.055*
C100.3714 (2)0.54898 (10)0.3150 (2)0.0363 (6)
H1010.44560.55540.40820.044*
C110.2902 (2)0.50020 (9)0.3514 (2)0.0347 (6)
C120.2652 (2)0.45570 (10)0.2574 (2)0.0416 (6)
H120.30670.45280.16980.050*
C130.1798 (2)0.41520 (10)0.2907 (3)0.0449 (6)
H130.16270.38570.22500.054*
C140.1208 (2)0.41892 (10)0.4204 (3)0.0449 (6)
C150.1480 (3)0.46167 (11)0.5211 (3)0.0521 (7)
H150.11050.46330.61180.063*
C160.2314 (3)0.50199 (10)0.4854 (3)0.0479 (7)
H160.24900.53110.55240.057*
C170.2802 (2)0.59764 (9)0.2920 (2)0.0311 (5)
C180.2939 (2)0.64881 (9)0.3612 (2)0.0322 (5)
C190.4095 (2)0.67068 (10)0.4904 (2)0.0389 (6)
C200.3832 (3)0.72886 (10)0.5220 (3)0.0578 (8)
H2010.45720.74190.60390.087*
H2020.38050.74900.42710.087*
H2030.29530.73230.55490.087*
C210.4139 (3)0.63899 (11)0.6429 (3)0.0607 (8)
H2110.48680.65270.72500.091*
H2120.32540.64210.67470.091*
H2130.43210.60240.62460.091*
C220.5510 (2)0.66588 (11)0.4380 (3)0.0549 (7)
H2210.62430.67970.51940.082*
H2220.56940.62930.41950.082*
H2230.54740.68570.34230.082*
H310.029 (2)0.5480 (9)0.080 (2)0.029 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0383 (3)0.0523 (5)0.0503 (4)0.0067 (3)0.0156 (3)0.0009 (3)
Cl10.0895 (6)0.0602 (6)0.0791 (5)−0.0211 (4)0.0326 (4)0.0031 (4)
O10.0585 (11)0.0504 (13)0.0452 (9)−0.0022 (9)0.0098 (8)−0.0194 (9)
N10.0331 (10)0.0306 (12)0.0381 (10)−0.0008 (9)0.0020 (8)−0.0035 (9)
N20.0298 (10)0.0320 (13)0.0357 (10)0.0047 (9)−0.0022 (8)−0.0062 (9)
N30.0321 (11)0.0355 (13)0.0383 (11)0.0000 (10)0.0044 (9)−0.0080 (10)
C10.0336 (13)0.0321 (15)0.0354 (12)0.0047 (11)−0.0001 (10)−0.0082 (11)
C20.0475 (16)0.0399 (19)0.0778 (18)−0.0054 (13)−0.0097 (14)0.0099 (15)
C30.068 (2)0.043 (2)0.095 (2)0.0040 (16)−0.0237 (17)0.0180 (16)
C40.0500 (18)0.050 (2)0.084 (2)0.0145 (15)−0.0217 (15)−0.0162 (18)
C50.0325 (14)0.066 (2)0.0627 (16)0.0041 (14)0.0009 (12)−0.0188 (16)
C60.0402 (14)0.0478 (18)0.0427 (13)−0.0001 (13)0.0043 (11)−0.0038 (12)
C70.0301 (12)0.0286 (15)0.0331 (12)0.0019 (11)0.0039 (10)−0.0047 (11)
C80.0455 (14)0.0437 (17)0.0297 (12)0.0056 (13)0.0038 (11)0.0021 (13)
C90.0425 (14)0.0595 (19)0.0368 (13)−0.0027 (13)0.0130 (11)−0.0078 (12)
C100.0339 (12)0.0406 (16)0.0324 (12)0.0047 (11)0.0020 (9)−0.0018 (11)
C110.0374 (13)0.0354 (16)0.0305 (12)0.0094 (11)0.0051 (10)0.0019 (11)
C120.0531 (15)0.0390 (17)0.0345 (12)0.0072 (13)0.0134 (11)0.0007 (12)
C130.0620 (16)0.0349 (17)0.0379 (13)0.0033 (13)0.0105 (12)−0.0032 (12)
C140.0491 (14)0.0391 (17)0.0465 (14)−0.0018 (13)0.0098 (12)0.0067 (13)
C150.0767 (18)0.0451 (19)0.0406 (14)−0.0013 (15)0.0262 (13)0.0020 (14)
C160.0697 (17)0.0371 (17)0.0384 (13)−0.0002 (14)0.0145 (12)−0.0074 (12)
C170.0316 (12)0.0292 (15)0.0318 (11)0.0017 (11)0.0049 (10)0.0015 (11)
C180.0318 (12)0.0328 (15)0.0318 (11)0.0002 (11)0.0058 (9)0.0000 (11)
C190.0356 (13)0.0371 (16)0.0394 (12)−0.0018 (11)−0.0031 (10)−0.0034 (12)
C200.0535 (16)0.051 (2)0.0612 (16)−0.0043 (14)−0.0062 (13)−0.0178 (14)
C210.0670 (17)0.066 (2)0.0409 (14)−0.0129 (15)−0.0092 (12)0.0001 (14)
C220.0379 (14)0.053 (2)0.0690 (17)−0.0065 (13)0.0006 (12)−0.0006 (15)
Geometric parameters (Å, º) top
S1—C101.842 (2)C10—C111.530 (3)
S1—C91.849 (2)C10—H1010.9800
Cl1—C141.745 (2)C11—C121.378 (3)
O1—C81.226 (3)C11—C161.392 (3)
N1—C181.336 (3)C12—C131.385 (3)
N1—N21.365 (2)C12—H120.9300
N2—C71.349 (3)C13—C141.362 (3)
N2—C11.436 (2)C13—H130.9300
N3—C81.355 (3)C14—C151.377 (3)
N3—C71.402 (3)C15—C161.376 (3)
N3—H310.81 (2)C15—H150.9300
C1—C21.365 (3)C16—H160.9300
C1—C61.373 (3)C17—C181.417 (3)
C2—C31.385 (3)C18—C191.519 (3)
C2—H20.9300C19—C201.524 (3)
C3—C41.369 (4)C19—C211.534 (3)
C3—H30.9300C19—C221.541 (3)
C4—C51.364 (4)C20—H2010.9600
C4—H40.9300C20—H2020.9600
C5—C61.383 (3)C20—H2030.9600
C5—H50.9300C21—H2110.9600
C6—H60.9300C21—H2120.9600
C7—C171.365 (3)C21—H2130.9600
C8—C91.499 (3)C22—H2210.9600
C9—H910.9300C22—H2220.9600
C9—H920.9300C22—H2230.9600
C10—C171.505 (3)
C10—S1—C9101.56 (10)C16—C11—C10117.6 (2)
C18—N1—N2104.91 (17)C11—C12—C13121.3 (2)
C7—N2—N1111.25 (16)C11—C12—H12119.3
C7—N2—C1128.48 (17)C13—C12—H12119.3
N1—N2—C1120.23 (18)C14—C13—C12119.5 (2)
C8—N3—C7121.5 (2)C14—C13—H13120.3
C8—N3—H31119.9 (15)C12—C13—H13120.3
C7—N3—H31116.1 (15)C13—C14—C15121.0 (2)
C2—C1—C6121.0 (2)C13—C14—Cl1119.8 (2)
C2—C1—N2119.7 (2)C15—C14—Cl1119.25 (19)
C6—C1—N2119.4 (2)C16—C15—C14118.9 (2)
C1—C2—C3119.6 (2)C16—C15—H15120.5
C1—C2—H2120.2C14—C15—H15120.5
C3—C2—H2120.2C15—C16—C11121.6 (2)
C4—C3—C2119.7 (3)C15—C16—H16119.2
C4—C3—H3120.1C11—C16—H16119.2
C2—C3—H3120.1C7—C17—C18104.37 (18)
C5—C4—C3120.4 (2)C7—C17—C10122.4 (2)
C5—C4—H4119.8C18—C17—C10133.19 (18)
C3—C4—H4119.8N1—C18—C17111.19 (17)
C4—C5—C6120.3 (3)N1—C18—C19119.5 (2)
C4—C5—H5119.8C17—C18—C19129.26 (19)
C6—C5—H5119.8C18—C19—C20110.76 (18)
C1—C6—C5119.0 (2)C18—C19—C21109.17 (19)
C1—C6—H6120.5C20—C19—C21108.9 (2)
C5—C6—H6120.5C18—C19—C22109.26 (18)
N2—C7—C17108.26 (18)C20—C19—C22108.7 (2)
N2—C7—N3123.23 (17)C21—C19—C22109.96 (19)
C17—C7—N3128.1 (2)C19—C20—H201109.5
O1—C8—N3122.1 (2)C19—C20—H202109.5
O1—C8—C9122.3 (2)H201—C20—H202109.5
N3—C8—C9115.6 (2)C19—C20—H203109.5
C8—C9—S1113.04 (16)H201—C20—H203109.5
C8—C9—H91120.0H202—C20—H203109.5
S1—C9—H9184.1C19—C21—H211109.5
C8—C9—H92120.0C19—C21—H212109.5
S1—C9—H9273.2H211—C21—H212109.5
H91—C9—H92120.0C19—C21—H213109.5
C17—C10—C11111.46 (17)H211—C21—H213109.5
C17—C10—S1110.06 (14)H212—C21—H213109.5
C11—C10—S1114.23 (15)C19—C22—H221109.5
C17—C10—H101106.9C19—C22—H222109.5
C11—C10—H101106.9H221—C22—H222109.5
S1—C10—H101106.9C19—C22—H223109.5
C12—C11—C16117.6 (2)H221—C22—H223109.5
C12—C11—C10124.8 (2)H222—C22—H223109.5
C18—N1—N2—C70.9 (2)C16—C11—C12—C132.8 (3)
C18—N1—N2—C1178.85 (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—C261.2 (3)C12—C13—C14—C15−1.7 (3)
C7—N2—C1—C658.3 (3)C12—C13—C14—Cl1177.52 (18)
N1—N2—C1—C6−119.2 (2)C13—C14—C15—C162.7 (4)
C6—C1—C2—C30.4 (4)Cl1—C14—C15—C16−176.60 (18)
N2—C1—C2—C3179.9 (2)C14—C15—C16—C11−0.8 (4)
C1—C2—C3—C40.0 (4)C12—C11—C16—C15−1.9 (3)
C2—C3—C4—C5−0.3 (4)C10—C11—C16—C15175.1 (2)
C3—C4—C5—C60.3 (4)N2—C7—C17—C18−0.7 (2)
C2—C1—C6—C5−0.5 (3)N3—C7—C17—C18172.0 (2)
N2—C1—C6—C5179.99 (19)N2—C7—C17—C10−179.07 (19)
C4—C5—C6—C10.2 (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—C772.2 (2)
N1—N2—C7—N3−173.25 (19)C11—C10—C17—C18126.5 (2)
C1—N2—C7—N39.1 (3)S1—C10—C17—C18−105.7 (2)
C8—N3—C7—N2125.2 (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—O1169.2 (2)C7—C17—C18—N11.3 (2)
C7—N3—C8—C9−12.1 (3)C10—C17—C18—N1179.5 (2)
O1—C8—C9—S1−96.7 (2)C7—C17—C18—C19179.6 (2)
N3—C8—C9—S184.6 (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—C20177.5 (2)
C9—S1—C10—C1190.69 (16)N1—C18—C19—C21115.6 (2)
C17—C10—C11—C12117.2 (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—C2257.7 (3)
S1—C10—C11—C16174.91 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H31···O1i0.81 (2)2.10 (2)2.897 (3)170 (2)
C15—H15···O1ii0.932.563.372 (3)146
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H31···O1i0.81 (2)2.10 (2)2.897 (3)170 (2)
C15—H15···O1ii0.932.563.372 (3)145.7
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC22H22ClN3OS
Mr411.94
Crystal system, space groupMonoclinic, 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)
Z4
Radiation typeMo Kα
µ (mm−1)0.30
Crystal size (mm)0.46 × 0.45 × 0.20
Data collection
DiffractometerOxford Diffraction Gemini S
Absorption correction–
No. of measured, independent and
observed [I > 2σ(I)] reflections		4362, 4251, 2417
Rint0
(sin θ/λ)max (Å−1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.115, 0.95
No. of reflections4251
No. of parameters257
H-atom treatmentH 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.

References

First citationChen, H. & Shi, D. (2011). Tetrahedron, 67, 5686–5692.  CrossRef CAS Google Scholar
 First citationDesiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond, pp. 86–89. Oxford University Press.  Google Scholar
 First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationMacrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationNonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
 First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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ISSN: 2414-3146
Volume 1| Part 4| April 2016| x160608
doi:10.1107/S2414314616006088
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