organic compounds
2-({5-[(4-Chlorophenoxy)methyl]-4-phenyl-4H-1,2,4-triazol-3-yl}sulfanyl)-N-phenylacetamide
aDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, bChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, cChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, eChemistry Department, Faculty of Science, Assiut University, Assiut 71516, Egypt, and fKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
*Correspondence e-mail: shaabankamel@yahoo.com
The title molecule, C23H19ClN4O2S, is in an `extended' conformation. In the crystal, pairwise N—H⋯N and C—H⋯O hydrogen bonds lead to the formation of `stair-step' chains. C—H⋯π interactions further contribute to the consolidation of the molecular packing. The 4-chlorophenyl group is disordered over two sets of sites in a 0.948 (2):0.052 (2) ratio. The dihedral angle between the two components of the disordered chloro-substituted benzene ring is 15.76 (9) °.
Keywords: crystal structure; triazoles; phenoxides; amides.
CCDC reference: 1468942
Structure description
In the last few years, the chemistry of 1,2,4-triazoles has received considerable attention owing to their synthetic and effective biological importance (Shaker, 2006). Many triazole compounds exhibited different biological properties such as antifungal, anti-bacterial, anti-inflammatory, ant-cancer, anti-malarial and analgesic activity (Bektaş et al., 2010; Jawad et al., 2012; Singhal et al., 2011).
In the solid state, the molecule of the title compound (Fig. 1) is in an `extended' conformation. The 1,2,4-triazole ring (N1–N3/C8/C9) forms dihedral angles of 62.57 (8) and 33.48 (8)°, with the phenyl ring (C10–C15) attached to the 1,2,4-triazol ring and the phenyl ring (C18–C23) of the N-phenylacetamide group, respectively. The dihedral angle between the two components of the disordered chloro-substituted benzene ring is 15.76 (9)°.
In the crystal, pairwise N4—H4⋯N1i [symmetry code: (i) −x + 1, −y + 1, −z + 1] hydrogen bonds form dimers, which are then associated into `stair-step' chains through pairwise C7—H7B⋯O2ii [symmetry code: (ii) x + , y − , z] hydrogen bonds (Table 1 and Fig. 2). In addition, C—H⋯π interactions are observed in the (Table 1).
Synthesis and crystallization
A suspension of 5-(4-chlorphenoxy)methyl-4-phenyl-1,2,4-triazoline-3-thione (10 mmol), chloro(N-phenyl)acetamide (10 mol) and anhydrous K2CO3 (2.0 g) in dry acetone (50 ml) was heated under reflux with stirring for 3 h. The hot reaction mixture was filtered to remove K2CO3 and the clear filtrate was evaporated till dryness. The solid residue was crystallized from ethanol to give the title compound. Yield: 80%; m.p. 463 K. IR: 3300 (NH), 1670 (C=O) cm.-1 1H NMR (DMSO-d6): δ = 8.8 (s, 1H, NH), 6.5–7.8 (m, 14H, ArH), 4.9 (s, 2H, OCH2), 3.9 (s, 2H,SCH2).
Refinement
Crystal data, data collection and structure . The 4-chlorophenyl group is disordered over two orientations in a 0.948 (2): 0.052 (2) ratio. The minor component was refined as a rigid hexagon.
details are summarized in Table 2
|
Structural data
CCDC reference: 1468942
10.1107/S2414314616004533/rz4002sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616004533/rz4002Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616004533/rz4002Isup3.cml
In the last few years, the chemistry of 1,2,4-triazoles has received considerable attention owing to their synthetic and effective biological importance (Shaker, 2006). Many triazole compounds exhibited different biological applications such as antifungal, anti-bacterial, anti-inflammatory, ant-cancer, anti-malarial and analgesic activity (Bektaş et al., 2010; Jawad et al., 2012; Singhal et al., 2011).
In the solid, the molecule (Fig. 1) is in an "extended" conformation. The 1,2,4-triazol ring (N1–N3/C8/C9) forms dihedral angles of 62.57 (8) and 33.48 (8)°, with the phenyl ring (C10—C15) attached to the 1,2,4-triazol ring and the phenyl ring (C18—C23) of the N-phenylacetamide group, respectively. The dihedral angle between the two components of the disordered chloro-substituted benzene ring is 15.76 (9) °.
Pairwise N4—H4···N1i (i: −x + 1, −y + 1, −z + 1) hydrogen bonds form dimers which are then associated into "stair-step" chains through pairwise C7—H7B···O2ii (ii: x + 1/2, y − 1/2, z) hydrogen bonds (Table 1 and Fig. 2). In addition, C—H···π interactions are observed in the (Table 1).
A suspension of 5-(4-chlorphenoxy)methyl-4-phenyl-1,2,4-triazoline-3-thione (10 mmol), chloro(N-phenyl)acetamide (10 mol) and anhydrous K2CO3 (2.0 g) in dry acetone (50 ml) was heated under reflux with stirring for 3 h. The hot reaction mixture was filtered to remove K2CO3 and the clear filtrate was evaporated till dryness. The solid residue was crystallized from ethanol to give the title compound. Yield: 80%; m.p. 463 K. IR: 3300 (NH), 1670 (C=O) cm.−1 1H NMR (DMSO-d6): δ = 8.8 (s, 1H, NH), 6.5–7.8 (m, 14H, ArH), 4.9 (s, 2H, OCH2), 3.9 (s, 2H,SCH2).
H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 − 0.99 Å) while that attached to nitrogen was placed in a location derived from a difference map and its coordinates adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms. The 4-chlorophenyl group is disordered over two orientations in a 95:5 ratio. The minor component was refined as a rigid hexagon. Crystal data, data collection and structure
details are summarized in Table 2.A suspension of 5-(4-chlorphenoxy)methyl-4-phenyl-1,2,4-triazoline-3-thione (10 mmol), chloro(N-phenyl)acetamide (10 mol) and anhydrous K2CO3 (2.0 g) in dry acetone (50 ml) was heated under reflux with stirring for 3 h. The hot reaction mixture was filtered to remove K2CO3 and the clear filtrate was evaporated till dryness. The solid residue was crystallized from ethanol to give the title compound. Yield: 80%; m.p. 463 K. IR: 3300 (NH), 1670 (C=O) cm.-1 1H NMR (DMSO-d6): δ = 8.8 (s, 1H, NH), 6.5–7.8 (m, 14H, ArH), 4.9 (s, 2H, OCH2), 3.9 (s, 2H,SCH2).
Crystal data, data collection and structure
details are summarized in Table 2. The 4-chlorophenyl group is disordered over two orientations in a 0.948 (2): 0.052 (2) ratio. The minor component was refined as a rigid hexagon.In the last few years, the chemistry of 1,2,4-triazoles has received considerable attention owing to their synthetic and effective biological importance (Shaker, 2006). Many triazole compounds exhibited different biological properties such as antifungal, anti-bacterial, anti-inflammatory, ant-cancer, anti-malarial and analgesic activity (Bektaş et al., 2010; Jawad et al., 2012; Singhal et al., 2011).
In the solid state, the molecule of the title compound (Fig. 1) is in an `extended' conformation. The 1,2,4-triazole ring (N1–N3/C8/C9) forms dihedral angles of 62.57 (8) and 33.48 (8)°, with the phenyl ring (C10–C15) attached to the 1,2,4-triazol ring and the phenyl ring (C18–C23) of the N-phenylacetamide group, respectively. The dihedral angle between the two components of the disordered chloro-substituted benzene ring is 15.76 (9)°.
In the crystal, pairwise N4—H4···N1i [symmetry code: (i) −x + 1, −y + 1, −z + 1] hydrogen bonds form dimers which are then associated into `stair-step' chains through pairwise C7—H7B···O2ii [symmetry code: (ii) x + 1/2, y − 1/2, z] hydrogen bonds (Table 1 and Fig. 2). In addition, C—H···π interactions are observed in the (Table 1).
Data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound with 50% probability ellipsoids. | |
Fig. 2. Packing projected onto (110). N—H···N and C—H···O hydrogen bonds are shown, respectively, as blue and purple dotted lines. Displacement ellipsoids are drawn at the 50% probability level. |
C23H19ClN4O2S | F(000) = 1872 |
Mr = 450.93 | Dx = 1.371 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.7940 (12) Å | Cell parameters from 9935 reflections |
b = 11.1864 (8) Å | θ = 2.3–28.9° |
c = 24.8212 (18) Å | µ = 0.30 mm−1 |
β = 95.128 (1)° | T = 150 K |
V = 4367.8 (6) Å3 | Block, colourless |
Z = 8 | 0.24 × 0.20 × 0.11 mm |
Bruker SMART APEX CCD diffractometer | 5886 independent reflections |
Radiation source: fine-focus sealed tube | 4471 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 8.3333 pixels mm-1 | θmax = 29.2°, θmin = 1.7° |
φ and ω scans | h = −21→21 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −14→15 |
Tmin = 0.86, Tmax = 0.97 | l = −33→34 |
41579 measured reflections |
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)] = 0.043 | Hydrogen site location: mixed |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0604P)2 + 1.3119P] where P = (Fo2 + 2Fc2)/3 |
5886 reflections | (Δ/σ)max < 0.001 |
287 parameters | Δρmax = 0.41 e Å−3 |
2 restraints | Δρmin = −0.21 e Å−3 |
C23H19ClN4O2S | V = 4367.8 (6) Å3 |
Mr = 450.93 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.7940 (12) Å | µ = 0.30 mm−1 |
b = 11.1864 (8) Å | T = 150 K |
c = 24.8212 (18) Å | 0.24 × 0.20 × 0.11 mm |
β = 95.128 (1)° |
Bruker SMART APEX CCD diffractometer | 5886 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | 4471 reflections with I > 2σ(I) |
Tmin = 0.86, Tmax = 0.97 | Rint = 0.045 |
41579 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 2 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.41 e Å−3 |
5886 reflections | Δρmin = −0.21 e Å−3 |
287 parameters |
Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = −30.00 and 210.00°. The scan time was 20 sec/frame. |
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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 − 0.99 Å) while that attached to nitrogen was placed in a location derived from a difference map and its coordinates adjusted to give N—H = 0.91%A. All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms. The 4-chlorophenyl group is disordered over two orientations in a 95:5 ratio. The minor component was refined as a rigid hexagon. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.58100 (3) | −0.46695 (4) | 0.30292 (2) | 0.06539 (18) | |
S1 | 0.33857 (2) | 0.45849 (3) | 0.39103 (2) | 0.02814 (10) | |
O1 | 0.50609 (7) | 0.00496 (9) | 0.38890 (4) | 0.0346 (2) | |
O2 | 0.26017 (7) | 0.68130 (9) | 0.39453 (4) | 0.0356 (3) | |
N1 | 0.53671 (8) | 0.27205 (11) | 0.44169 (5) | 0.0323 (3) | |
N2 | 0.48065 (8) | 0.36629 (11) | 0.44741 (5) | 0.0298 (3) | |
N3 | 0.43815 (7) | 0.26509 (9) | 0.37347 (4) | 0.0226 (2) | |
N4 | 0.33954 (7) | 0.76835 (10) | 0.46533 (5) | 0.0257 (2) | |
H4 | 0.3802 | 0.7527 | 0.4927 | 0.031* | |
C1 | 0.52663 (12) | −0.10073 (13) | 0.36507 (7) | 0.0287 (4) | 0.948 (2) |
C2 | 0.60655 (11) | −0.12626 (15) | 0.35021 (8) | 0.0393 (4) | 0.948 (2) |
H2 | 0.6499 | −0.0672 | 0.3536 | 0.047* | 0.948 (2) |
C3 | 0.62341 (12) | −0.23890 (16) | 0.33017 (8) | 0.0452 (5) | 0.948 (2) |
H3 | 0.6786 | −0.2580 | 0.3204 | 0.054* | 0.948 (2) |
C4 | 0.55925 (12) | −0.32265 (15) | 0.32458 (7) | 0.0379 (4) | 0.948 (2) |
C5 | 0.47874 (12) | −0.29637 (15) | 0.33764 (8) | 0.0410 (4) | 0.948 (2) |
H5 | 0.4349 | −0.3545 | 0.3328 | 0.049* | 0.948 (2) |
C6 | 0.46197 (11) | −0.18450 (15) | 0.35786 (7) | 0.0383 (4) | 0.948 (2) |
H6 | 0.4063 | −0.1651 | 0.3668 | 0.046* | 0.948 (2) |
C1A | 0.5373 (18) | −0.1082 (12) | 0.3766 (10) | 0.0287 (4) | 0.052 (2) |
C2A | 0.5741 (17) | −0.1263 (15) | 0.3285 (9) | 0.0393 (4) | 0.052 (2) |
H2A | 0.5901 | −0.0597 | 0.3079 | 0.047* | 0.052 (2) |
C3A | 0.5875 (17) | −0.2418 (19) | 0.3104 (8) | 0.0452 (5) | 0.052 (2) |
H3A | 0.6126 | −0.2542 | 0.2775 | 0.054* | 0.052 (2) |
C4A | 0.5641 (19) | −0.3392 (13) | 0.3406 (9) | 0.0379 (4) | 0.052 (2) |
C5A | 0.5273 (16) | −0.3211 (13) | 0.3887 (9) | 0.0410 (4) | 0.052 (2) |
H5A | 0.5113 | −0.3877 | 0.4093 | 0.049* | 0.052 (2) |
C6A | 0.5139 (15) | −0.2056 (16) | 0.4068 (8) | 0.0383 (4) | 0.052 (2) |
H6A | 0.4887 | −0.1932 | 0.4397 | 0.046* | 0.052 (2) |
C7 | 0.55380 (9) | 0.10811 (12) | 0.37635 (6) | 0.0300 (3) | |
H7A | 0.5558 | 0.1153 | 0.3367 | 0.036* | |
H7B | 0.6128 | 0.1021 | 0.3934 | 0.036* | |
C8 | 0.51050 (9) | 0.21362 (12) | 0.39776 (6) | 0.0262 (3) | |
C9 | 0.42313 (8) | 0.36036 (11) | 0.40612 (5) | 0.0238 (3) | |
C10 | 0.38827 (8) | 0.22517 (12) | 0.32540 (5) | 0.0226 (3) | |
C11 | 0.37983 (10) | 0.29843 (13) | 0.28040 (6) | 0.0327 (3) | |
H11 | 0.4063 | 0.3747 | 0.2811 | 0.039* | |
C12 | 0.33191 (11) | 0.25847 (14) | 0.23410 (6) | 0.0386 (4) | |
H12 | 0.3247 | 0.3085 | 0.2031 | 0.046* | |
C13 | 0.29497 (10) | 0.14698 (14) | 0.23290 (6) | 0.0349 (3) | |
H13 | 0.2630 | 0.1199 | 0.2010 | 0.042* | |
C14 | 0.30446 (10) | 0.07439 (14) | 0.27815 (6) | 0.0339 (3) | |
H14 | 0.2793 | −0.0028 | 0.2771 | 0.041* | |
C15 | 0.35049 (9) | 0.11348 (12) | 0.32500 (6) | 0.0269 (3) | |
H15 | 0.3560 | 0.0644 | 0.3563 | 0.032* | |
C16 | 0.36384 (11) | 0.56155 (13) | 0.44629 (6) | 0.0328 (3) | |
H16A | 0.3468 | 0.5275 | 0.4805 | 0.039* | |
H16B | 0.4257 | 0.5776 | 0.4506 | 0.039* | |
C17 | 0.31512 (9) | 0.67619 (12) | 0.43258 (5) | 0.0260 (3) | |
C18 | 0.31242 (9) | 0.88903 (12) | 0.46004 (5) | 0.0253 (3) | |
C19 | 0.36564 (11) | 0.97533 (13) | 0.48553 (6) | 0.0340 (3) | |
H19 | 0.4176 | 0.9520 | 0.5050 | 0.041* | |
C20 | 0.34301 (13) | 1.09500 (14) | 0.48259 (7) | 0.0426 (4) | |
H20 | 0.3795 | 1.1534 | 0.5001 | 0.051* | |
C21 | 0.26751 (13) | 1.12977 (14) | 0.45431 (7) | 0.0441 (4) | |
H21 | 0.2521 | 1.2118 | 0.4522 | 0.053* | |
C22 | 0.21490 (12) | 1.04423 (14) | 0.42929 (7) | 0.0413 (4) | |
H22 | 0.1628 | 1.0680 | 0.4102 | 0.050* | |
C23 | 0.23653 (10) | 0.92380 (14) | 0.43150 (6) | 0.0326 (3) | |
H23 | 0.2000 | 0.8659 | 0.4137 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0626 (3) | 0.0424 (3) | 0.0857 (4) | 0.0196 (2) | −0.0237 (3) | −0.0402 (3) |
S1 | 0.02955 (18) | 0.02184 (18) | 0.0311 (2) | 0.00325 (13) | −0.00802 (14) | −0.00773 (13) |
O1 | 0.0408 (6) | 0.0215 (5) | 0.0433 (6) | 0.0016 (4) | 0.0128 (5) | −0.0058 (4) |
O2 | 0.0428 (6) | 0.0307 (6) | 0.0301 (6) | 0.0088 (5) | −0.0134 (5) | −0.0077 (4) |
N1 | 0.0330 (6) | 0.0258 (6) | 0.0359 (7) | 0.0051 (5) | −0.0098 (5) | −0.0085 (5) |
N2 | 0.0341 (6) | 0.0230 (6) | 0.0303 (6) | 0.0038 (5) | −0.0086 (5) | −0.0072 (5) |
N3 | 0.0261 (5) | 0.0176 (5) | 0.0233 (6) | −0.0010 (4) | −0.0026 (4) | −0.0039 (4) |
N4 | 0.0307 (6) | 0.0210 (6) | 0.0242 (6) | 0.0047 (4) | −0.0045 (5) | −0.0031 (4) |
C1 | 0.0375 (9) | 0.0215 (7) | 0.0267 (9) | 0.0059 (6) | 0.0009 (7) | −0.0028 (6) |
C2 | 0.0271 (8) | 0.0300 (8) | 0.0598 (12) | 0.0046 (6) | −0.0020 (8) | −0.0135 (8) |
C3 | 0.0313 (9) | 0.0409 (10) | 0.0618 (13) | 0.0121 (8) | −0.0047 (9) | −0.0187 (9) |
C4 | 0.0446 (9) | 0.0289 (9) | 0.0373 (10) | 0.0125 (7) | −0.0117 (8) | −0.0140 (7) |
C5 | 0.0467 (10) | 0.0269 (8) | 0.0496 (10) | −0.0044 (7) | 0.0051 (8) | −0.0071 (7) |
C6 | 0.0394 (9) | 0.0290 (8) | 0.0482 (10) | 0.0002 (7) | 0.0137 (8) | −0.0044 (7) |
C1A | 0.0375 (9) | 0.0215 (7) | 0.0267 (9) | 0.0059 (6) | 0.0009 (7) | −0.0028 (6) |
C2A | 0.0271 (8) | 0.0300 (8) | 0.0598 (12) | 0.0046 (6) | −0.0020 (8) | −0.0135 (8) |
C3A | 0.0313 (9) | 0.0409 (10) | 0.0618 (13) | 0.0121 (8) | −0.0047 (9) | −0.0187 (9) |
C4A | 0.0446 (9) | 0.0289 (9) | 0.0373 (10) | 0.0125 (7) | −0.0117 (8) | −0.0140 (7) |
C5A | 0.0467 (10) | 0.0269 (8) | 0.0496 (10) | −0.0044 (7) | 0.0051 (8) | −0.0071 (7) |
C6A | 0.0394 (9) | 0.0290 (8) | 0.0482 (10) | 0.0002 (7) | 0.0137 (8) | −0.0044 (7) |
C7 | 0.0275 (7) | 0.0239 (7) | 0.0380 (8) | 0.0010 (5) | −0.0008 (6) | −0.0060 (6) |
C8 | 0.0264 (6) | 0.0218 (7) | 0.0294 (7) | 0.0005 (5) | −0.0028 (5) | −0.0029 (5) |
C9 | 0.0275 (6) | 0.0187 (6) | 0.0245 (7) | −0.0005 (5) | −0.0022 (5) | −0.0038 (5) |
C10 | 0.0256 (6) | 0.0208 (6) | 0.0210 (6) | −0.0012 (5) | 0.0006 (5) | −0.0057 (5) |
C11 | 0.0475 (9) | 0.0235 (7) | 0.0265 (7) | −0.0070 (6) | −0.0006 (6) | −0.0020 (6) |
C12 | 0.0575 (10) | 0.0342 (8) | 0.0227 (7) | −0.0004 (7) | −0.0044 (7) | 0.0004 (6) |
C13 | 0.0389 (8) | 0.0392 (8) | 0.0253 (7) | 0.0004 (6) | −0.0047 (6) | −0.0114 (6) |
C14 | 0.0362 (8) | 0.0295 (7) | 0.0350 (8) | −0.0081 (6) | −0.0015 (6) | −0.0098 (6) |
C15 | 0.0313 (7) | 0.0239 (7) | 0.0251 (7) | −0.0050 (5) | 0.0006 (6) | −0.0026 (5) |
C16 | 0.0482 (9) | 0.0246 (7) | 0.0237 (7) | 0.0112 (6) | −0.0077 (6) | −0.0076 (5) |
C17 | 0.0324 (7) | 0.0235 (7) | 0.0216 (6) | 0.0036 (5) | −0.0003 (5) | −0.0029 (5) |
C18 | 0.0346 (7) | 0.0204 (6) | 0.0214 (6) | 0.0029 (5) | 0.0053 (5) | −0.0020 (5) |
C19 | 0.0411 (8) | 0.0271 (8) | 0.0341 (8) | −0.0014 (6) | 0.0042 (7) | −0.0052 (6) |
C20 | 0.0661 (11) | 0.0245 (8) | 0.0388 (9) | −0.0061 (7) | 0.0130 (8) | −0.0062 (7) |
C21 | 0.0768 (13) | 0.0228 (8) | 0.0344 (9) | 0.0115 (8) | 0.0142 (8) | 0.0005 (6) |
C22 | 0.0579 (10) | 0.0332 (9) | 0.0328 (8) | 0.0173 (7) | 0.0041 (8) | 0.0045 (7) |
C23 | 0.0418 (8) | 0.0277 (7) | 0.0279 (7) | 0.0078 (6) | 0.0004 (6) | −0.0007 (6) |
Cl1—C4A | 1.741 (11) | C4A—C5A | 1.3900 |
Cl1—C4 | 1.7452 (16) | C5A—C6A | 1.3900 |
S1—C9 | 1.7434 (14) | C5A—H5A | 0.9500 |
S1—C16 | 1.8089 (14) | C6A—H6A | 0.9500 |
O1—C1 | 1.3738 (17) | C7—C8 | 1.4861 (19) |
O1—C1A | 1.402 (11) | C7—H7A | 0.9900 |
O1—C7 | 1.4277 (18) | C7—H7B | 0.9900 |
O2—C17 | 1.2257 (17) | C10—C11 | 1.3822 (19) |
N1—C8 | 1.3065 (18) | C10—C15 | 1.3843 (18) |
N1—N2 | 1.3920 (16) | C11—C12 | 1.392 (2) |
N2—C9 | 1.3092 (17) | C11—H11 | 0.9500 |
N3—C8 | 1.3703 (17) | C12—C13 | 1.376 (2) |
N3—C9 | 1.3724 (16) | C12—H12 | 0.9500 |
N3—C10 | 1.4405 (16) | C13—C14 | 1.383 (2) |
N4—C17 | 1.3477 (17) | C13—H13 | 0.9500 |
N4—C18 | 1.4189 (17) | C14—C15 | 1.3858 (19) |
N4—H4 | 0.9098 | C14—H14 | 0.9500 |
C1—C2 | 1.376 (2) | C15—H15 | 0.9500 |
C1—C6 | 1.386 (2) | C16—C17 | 1.5184 (19) |
C2—C3 | 1.389 (2) | C16—H16A | 0.9900 |
C2—H2 | 0.9500 | C16—H16B | 0.9900 |
C3—C4 | 1.378 (3) | C18—C23 | 1.392 (2) |
C3—H3 | 0.9500 | C18—C19 | 1.394 (2) |
C4—C5 | 1.372 (3) | C19—C20 | 1.386 (2) |
C5—C6 | 1.383 (2) | C19—H19 | 0.9500 |
C5—H5 | 0.9500 | C20—C21 | 1.384 (3) |
C6—H6 | 0.9500 | C20—H20 | 0.9500 |
C1A—C2A | 1.3900 | C21—C22 | 1.378 (3) |
C1A—C6A | 1.3900 | C21—H21 | 0.9500 |
C2A—C3A | 1.3900 | C22—C23 | 1.390 (2) |
C2A—H2A | 0.9500 | C22—H22 | 0.9500 |
C3A—C4A | 1.3900 | C23—H23 | 0.9500 |
C3A—H3A | 0.9500 | ||
C9—S1—C16 | 97.21 (6) | H7A—C7—H7B | 108.5 |
C1—O1—C7 | 116.88 (12) | N1—C8—N3 | 110.29 (12) |
C1A—O1—C7 | 118.7 (10) | N1—C8—C7 | 125.05 (13) |
C8—N1—N2 | 107.88 (11) | N3—C8—C7 | 124.65 (12) |
C9—N2—N1 | 106.56 (11) | N2—C9—N3 | 110.93 (12) |
C8—N3—C9 | 104.34 (11) | N2—C9—S1 | 126.94 (10) |
C8—N3—C10 | 127.37 (11) | N3—C9—S1 | 122.12 (10) |
C9—N3—C10 | 128.26 (11) | C11—C10—C15 | 121.26 (12) |
C17—N4—C18 | 127.18 (12) | C11—C10—N3 | 119.45 (12) |
C17—N4—H4 | 116.6 | C15—C10—N3 | 119.29 (12) |
C18—N4—H4 | 116.1 | C10—C11—C12 | 118.87 (13) |
O1—C1—C2 | 123.47 (16) | C10—C11—H11 | 120.6 |
O1—C1—C6 | 115.96 (15) | C12—C11—H11 | 120.6 |
C2—C1—C6 | 120.54 (14) | C13—C12—C11 | 120.47 (14) |
C1—C2—C3 | 119.60 (17) | C13—C12—H12 | 119.8 |
C1—C2—H2 | 120.2 | C11—C12—H12 | 119.8 |
C3—C2—H2 | 120.2 | C12—C13—C14 | 119.96 (14) |
C4—C3—C2 | 119.34 (16) | C12—C13—H13 | 120.0 |
C4—C3—H3 | 120.3 | C14—C13—H13 | 120.0 |
C2—C3—H3 | 120.3 | C13—C14—C15 | 120.45 (14) |
C5—C4—C3 | 121.28 (15) | C13—C14—H14 | 119.8 |
C5—C4—Cl1 | 118.89 (15) | C15—C14—H14 | 119.8 |
C3—C4—Cl1 | 119.78 (14) | C10—C15—C14 | 118.97 (13) |
C4—C5—C6 | 119.43 (16) | C10—C15—H15 | 120.5 |
C4—C5—H5 | 120.3 | C14—C15—H15 | 120.5 |
C6—C5—H5 | 120.3 | C17—C16—S1 | 107.17 (10) |
C5—C6—C1 | 119.73 (16) | C17—C16—H16A | 110.3 |
C5—C6—H6 | 120.1 | S1—C16—H16A | 110.3 |
C1—C6—H6 | 120.1 | C17—C16—H16B | 110.3 |
C2A—C1A—C6A | 120.0 | S1—C16—H16B | 110.3 |
C2A—C1A—O1 | 120.0 (14) | H16A—C16—H16B | 108.5 |
C6A—C1A—O1 | 118.4 (14) | O2—C17—N4 | 125.02 (12) |
C1A—C2A—C3A | 120.0 | O2—C17—C16 | 121.46 (12) |
C1A—C2A—H2A | 120.0 | N4—C17—C16 | 113.51 (12) |
C3A—C2A—H2A | 120.0 | C23—C18—C19 | 119.62 (13) |
C2A—C3A—C4A | 120.0 | C23—C18—N4 | 123.51 (13) |
C2A—C3A—H3A | 120.0 | C19—C18—N4 | 116.87 (13) |
C4A—C3A—H3A | 120.0 | C20—C19—C18 | 120.19 (15) |
C3A—C4A—C5A | 120.0 | C20—C19—H19 | 119.9 |
C3A—C4A—Cl1 | 107.1 (13) | C18—C19—H19 | 119.9 |
C5A—C4A—Cl1 | 132.6 (13) | C21—C20—C19 | 120.30 (16) |
C6A—C5A—C4A | 120.0 | C21—C20—H20 | 119.9 |
C6A—C5A—H5A | 120.0 | C19—C20—H20 | 119.9 |
C4A—C5A—H5A | 120.0 | C22—C21—C20 | 119.39 (15) |
C5A—C6A—C1A | 120.0 | C22—C21—H21 | 120.3 |
C5A—C6A—H6A | 120.0 | C20—C21—H21 | 120.3 |
C1A—C6A—H6A | 120.0 | C21—C22—C23 | 121.27 (16) |
O1—C7—C8 | 107.16 (12) | C21—C22—H22 | 119.4 |
O1—C7—H7A | 110.3 | C23—C22—H22 | 119.4 |
C8—C7—H7A | 110.3 | C22—C23—C18 | 119.23 (15) |
O1—C7—H7B | 110.3 | C22—C23—H23 | 120.4 |
C8—C7—H7B | 110.3 | C18—C23—H23 | 120.4 |
C8—N1—N2—C9 | −0.32 (16) | N1—N2—C9—N3 | 0.68 (16) |
C7—O1—C1—C2 | 28.4 (2) | N1—N2—C9—S1 | −177.94 (11) |
C7—O1—C1—C6 | −153.50 (14) | C8—N3—C9—N2 | −0.75 (15) |
O1—C1—C2—C3 | 175.06 (16) | C10—N3—C9—N2 | 177.55 (12) |
C6—C1—C2—C3 | −3.0 (3) | C8—N3—C9—S1 | 177.94 (10) |
C1—C2—C3—C4 | 1.2 (3) | C10—N3—C9—S1 | −3.76 (19) |
C2—C3—C4—C5 | 1.0 (3) | C16—S1—C9—N2 | 2.70 (15) |
C2—C3—C4—Cl1 | −176.55 (15) | C16—S1—C9—N3 | −175.77 (12) |
C3—C4—C5—C6 | −1.3 (3) | C8—N3—C10—C11 | −117.80 (16) |
Cl1—C4—C5—C6 | 176.23 (14) | C9—N3—C10—C11 | 64.27 (19) |
C4—C5—C6—C1 | −0.5 (3) | C8—N3—C10—C15 | 61.47 (18) |
O1—C1—C6—C5 | −175.53 (16) | C9—N3—C10—C15 | −116.46 (15) |
C2—C1—C6—C5 | 2.7 (3) | C15—C10—C11—C12 | 0.3 (2) |
C7—O1—C1A—C2A | −40.3 (19) | N3—C10—C11—C12 | 179.60 (13) |
C7—O1—C1A—C6A | 154.0 (11) | C10—C11—C12—C13 | −1.2 (2) |
C6A—C1A—C2A—C3A | 0.0 | C11—C12—C13—C14 | 0.8 (2) |
O1—C1A—C2A—C3A | −166 (2) | C12—C13—C14—C15 | 0.5 (2) |
C1A—C2A—C3A—C4A | 0.0 | C11—C10—C15—C14 | 0.9 (2) |
C2A—C3A—C4A—C5A | 0.0 | N3—C10—C15—C14 | −178.32 (13) |
C2A—C3A—C4A—Cl1 | 175 (2) | C13—C14—C15—C10 | −1.4 (2) |
C3A—C4A—C5A—C6A | 0.0 | C9—S1—C16—C17 | 162.90 (11) |
Cl1—C4A—C5A—C6A | −173 (3) | C18—N4—C17—O2 | −5.4 (2) |
C4A—C5A—C6A—C1A | 0.0 | C18—N4—C17—C16 | 173.55 (13) |
C2A—C1A—C6A—C5A | 0.0 | S1—C16—C17—O2 | 10.32 (18) |
O1—C1A—C6A—C5A | 166 (2) | S1—C16—C17—N4 | −168.65 (10) |
C1—O1—C7—C8 | 169.54 (13) | C17—N4—C18—C23 | 22.5 (2) |
C1A—O1—C7—C8 | −175.2 (13) | C17—N4—C18—C19 | −157.94 (14) |
N2—N1—C8—N3 | −0.15 (16) | C23—C18—C19—C20 | 0.2 (2) |
N2—N1—C8—C7 | 178.55 (13) | N4—C18—C19—C20 | −179.40 (14) |
C9—N3—C8—N1 | 0.54 (16) | C18—C19—C20—C21 | −0.1 (2) |
C10—N3—C8—N1 | −177.78 (13) | C19—C20—C21—C22 | 0.3 (3) |
C9—N3—C8—C7 | −178.17 (13) | C20—C21—C22—C23 | −0.6 (3) |
C10—N3—C8—C7 | 3.5 (2) | C21—C22—C23—C18 | 0.7 (2) |
O1—C7—C8—N1 | 103.81 (16) | C19—C18—C23—C22 | −0.5 (2) |
O1—C7—C8—N3 | −77.67 (17) | N4—C18—C23—C22 | 179.06 (14) |
Cg3 and Cg4 are the centroids of the C10–C15 and C18–C23 phenyl rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1i | 0.91 | 2.02 | 2.9230 (17) | 174 |
C7—H7B···O2ii | 0.99 | 2.49 | 3.3518 (18) | 146 |
C3—H3···Cg3iii | 0.95 | 2.92 | 3.867 (2) | 174 |
C15—H15···Cg4iv | 0.95 | 2.86 | 3.6871 (16) | 146 |
C16—H16A···Cg4v | 0.99 | 2.80 | 3.6488 (18) | 144 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, y−1/2, z; (iii) −x, −y−1, −z; (iv) x, y−1, z; (v) −x+1/2, −y+3/2, −z+1. |
Cg3 and Cg4 are the centroids of the C10–C15 and C18–C23 phenyl rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1i | 0.91 | 2.02 | 2.9230 (17) | 174 |
C7—H7B···O2ii | 0.99 | 2.49 | 3.3518 (18) | 146 |
C3—H3···Cg3iii | 0.95 | 2.92 | 3.867 (2) | 174 |
C15—H15···Cg4iv | 0.95 | 2.86 | 3.6871 (16) | 146 |
C16—H16A···Cg4v | 0.99 | 2.80 | 3.6488 (18) | 144 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, y−1/2, z; (iii) −x, −y−1, −z; (iv) x, y−1, z; (v) −x+1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C23H19ClN4O2S |
Mr | 450.93 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 15.7940 (12), 11.1864 (8), 24.8212 (18) |
β (°) | 95.128 (1) |
V (Å3) | 4367.8 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.24 × 0.20 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2016) |
Tmin, Tmax | 0.86, 0.97 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 41579, 5886, 4471 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.686 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.118, 1.06 |
No. of reflections | 5886 |
No. of parameters | 287 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.21 |
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012), SHELXTL (Sheldrick, 2008).
Acknowledgements
JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.
References
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