organic compounds
Ethyl 3-amino-4-(4-chlorophenyl)-2-[(4-methoxyphenyl)carbamoyl]-6-phenylthieno[2,3-b]pyridine-5-carboxylate
aChemistry Department, Faculty of Science, Assiut University, Assiut 71516, Egypt, bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, cChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, dChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, eDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and fChemistry Department, Faculty of Science, Sana'a University, Sana'a, Yemen
*Correspondence e-mail: s.mohamed@mmu.ac.uk
The conformation of the title molecule, C30H24ClN3O4S, is partially determined by an intramolecular N—H⋯O hydrogen bond, forming an S(6) loop, and an N—H⋯π interaction involving the centroid of the 4-chlorophenyl ring. The thienopyridine bicyclic system is almost planar with an r.m.s. deviation of 0.019 Å. Its mean plane is inclined to the phenyl ring, the 4-chlorophenyl ring and the 4-methoxyphenyl ring by 36.19 (7), 81.67 (7) and 12.75 (7)°, respectively. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R22(20) ring motif. Within the dimers, which stack along the b-axis direction, there is a weak π–π interaction [centroid-to-centroid distance = 3.7936 (9) Å] involving inversion-related thiophene and pyridine rings.
Keywords: crystal structure; thienopyridines; 3-aminothiophene; ethyl thieno[2,3-b]pyridine-5-carboxylate; hydrogen bonding.
CCDC reference: 1474779
Structure description
Many thieno[2,3-b]pyridines have been synthesized and investigated in relation with their biological and pharmacological importance (Bakhite, 2003; Litvinov et al., 2005). Some of them have been proved to possess antiviral (Schnute et al., 2007; Attaby et al., 2007), antidiabetic (Bahekar et al., 2007), antimicrobial (Abdel-Rahman et al., 2003; Hussein et al., 2000), antitumor (Hayakawa et al., 2004), antiparasitic (Bernardino et al., 2006) and neurotropic activities (Krauze et al.,1999). We report herein on the synthesis and of the new title thienopyridine derivative.
The conformation of the title molecule (Fig. 1) is partially determined by the intramolecular N2—H2B⋯O3 hydrogen bond and the N2—H2A⋯π interaction (H2A⋯Cg = 2.90 Å; N2—H2A⋯Cg = 152°, Cg is the centroid of the 4-chlorophenyl ring; see Table 1). The central thienopyridine bicyclic moiety (S1/N1/C1–C7) is planar to within 0.025 (1) Å, with an r.m.s. deviation of 0.019 Å. The phenyl ring (C8–C13) and the 4-chlorophenyl ring (C17–C22) are inclined to the aforementioned plane by 36.19 (6) and 81.67 (7)°, respectively.
In the crystal, molecules are associated through pairs of N3—H3⋯O1i hydrogen bonds (Table 1 and Fig. 2), generating inversion dimers with an (20) loop. Within the dimers, which stack along the b-axis direction, there is a weak parallel slipped π–π interaction involving inversion-related thiophene and pyridine rings [Cg1⋯Cg2ii = 3.7936 (9) Å, interplanar distance = 3.5684 (6) Å, slippage 1.371 Å, Cg1 and Cg2 are the centroids of rings S1/C4–C7 and N1/C1–C5, respectively; symmetry code: (ii) − x + 1, − y + 1, − z + 1].
Synthesis and crystallization
The title compound was prepared by heating equimolar amounts of ethyl 1,2-dihydro-4-(4-chlorophenyl)-3-cyano-6-phenyl-2-thioxopyridine-5-carboxylate and chloro-N-(4-methoxy-phenyl)acetamide (5 mmol) in absolute ethanol (20 ml) containing sodium ethoxide (0.5 g) on a steam bath for 30 min. The product which separated on cooling was collected and recrystallized from ethanol solution (yield: 82%) giving pale-yellow needle-like crystals.
Spectroscopic and analytical data: IR: 3500, 3300 (NH2), 3200 (NH), 1720 (C=O, ester), 1660 (C=O, amide) cm-1. 1H NMR (CDCl3): δ 9.00 (s, 1H, NH), 7.0–7.8 (m, 13H, ArH), 5.7(s, 2H, NH2), 3.9–4.2 (q, 2H, OCH2), 3.8 (s, 3H, OCH3), 1.0–1.2 (t, 3H, CH3) p.p.m. Elemental analysis calculated for C31H25ClN2O4S (%): C, 66.84; H, 4.52; N, 5.03; S, 5.76. Found (%): C, 67.01; H, 4.44; N, 5.13; S, 5.49; m.p. 466–467 K.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 1474779
10.1107/S241431461600657X/su4032sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S241431461600657X/su4032Isup2.hkl
Supporting information file. DOI: 10.1107/S241431461600657X/su4032Isup3.cml
The title compound was prepared by heating equimolar amounts of ethyl 1,2-dihydro-4-(4-chlorophenyl)-3-cyano-6-phenyl-2-thioxopyridine-5-carboxylate and chloro-N-(4-methoxy-phenyl)acetamide (5 mmol) in absolute ethanol (20 ml) containing sodium ethoxide (0.5 g) on a steam bath for 30 min. The product which separated on cooling was collected and recrystallized from ethanol. (yield: 82%) giving pale-yellow needle-like crystals.
Spectroscopic and analytical data: IR: 3500, 3300 (NH2), 3200 (NH), 1720 (C═O, ester), 1660 (C═O, amide) cm-1. 1H NMR (CDCl3): δ 9.00 (s, 1H, NH), 7.0–7.8 (m, 13H, ArH), 5.7(s, 2H, NH2), 3.9–4.2 (q, 2H, OCH2), 3.8 (s, 3H, OCH3), 1.0–1.2 (t, 3H, CH3) p.p.m. Elemental analysis calculated for C31H25ClN2O4S (%): C, 66.84; H, 4.52; N, 5.03; S, 5.76. Found (%): C, 67.01; H, 4.44; N, 5.13; S, 5.49; m.p. 466–467 K.
Many thieno[2,3-b]pyridines have been synthesized and investigated in relation with their biological and pharmacological importance (Bakhite, 2003; Litvinov et al., 2005). Some of them have been proved to possess antiviral (Schnute et al., 2007; Attaby et al., 2007), antidiabetic (Bahekar et al., 2007), antimicrobial (Abdel-Rahman et al., 2003; Hussein et al., 2000), antitumor (Hayakawa et al., 2004), antiparasitic (Bernardino et al., 2006) and neurotropic activities (Krauze et al.,1999). In view of the above facts, we report herein on the synthesis and
of the new title thienopyridine derivative.The conformation of the title molecule (Fig. 1) is partially determined by the intramolecular N2—H2B···O3 hydrogen bond and the N2—H2A···π interaction (H2A···Cg = 2.90 Å; N2—H2A···Cg = 152°, Cg is the centroid of the 4-chlorophenyl ring; see Table 1). The central thienopyridine bicyclic moiety (S1/N1/C1–C7) is planar to within 0.025 (1) Å, with an r.m.s. deviation of 0.019 Å. The phenyl ring (C8–C13) and the 4-chlorophenyl ring (C17–C22) are inclined to the aforementioned plane by 36.19 (6) and 81.67 (7)°, respectively.
In the crystal, molecules are associated through pairs of intermolecular N3—H3···O1i hydrogen bonds (Table 1 and Fig. 2), generating inversion dimers with an R22(20) loop. Within the dimers, which stack along the b-axis direction, there is a weak parallel slipped π–π interaction involving inversion-related thiophene and pyridine rings [Cg1···Cg2ii = 3.7936 (9) Å, interplanar distance = 3.5684 (6) Å, slippage 1.371 Å, Cg1 and Cg2 are the centroids of rings S1/C4–C7 and N1/C1–C5, respectively; symmetry code: (ii) - x + 1, - y + 1, - z + 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, showing the atom labelling and 50% probability displacement ellipsoids. The N—H···O hydrogen bond and the N—H···π interaction are shown as dashed lines (see Table 1). | |
Fig. 2. The crystal packing of the title compound projected onto (110), with the N—H···O hydrogen bonds shown as dashed lines (see Table 1). |
C30H24ClN3O4S | F(000) = 1160 |
Mr = 558.03 | Dx = 1.396 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 8.8388 (3) Å | Cell parameters from 9974 reflections |
b = 17.7686 (6) Å | θ = 3.6–74.3° |
c = 16.9487 (6) Å | µ = 2.36 mm−1 |
β = 94.159 (2)° | T = 150 K |
V = 2654.84 (16) Å3 | Needle, pale-yellow |
Z = 4 | 0.16 × 0.07 × 0.07 mm |
Bruker D8 VENTURE PHOTON 100 CMOS diffractometer | 5277 independent reflections |
Radiation source: INCOATEC IµS micro–focus source | 4468 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.040 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 74.5°, θmin = 3.6° |
ω scans | h = −11→10 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −19→22 |
Tmin = 0.75, Tmax = 0.85 | l = −17→20 |
20325 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.0439P)2 + 1.0305P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
5277 reflections | Δρmax = 0.30 e Å−3 |
367 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00154 (15) |
C30H24ClN3O4S | V = 2654.84 (16) Å3 |
Mr = 558.03 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 8.8388 (3) Å | µ = 2.36 mm−1 |
b = 17.7686 (6) Å | T = 150 K |
c = 16.9487 (6) Å | 0.16 × 0.07 × 0.07 mm |
β = 94.159 (2)° |
Bruker D8 VENTURE PHOTON 100 CMOS diffractometer | 5277 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | 4468 reflections with I > 2σ(I) |
Tmin = 0.75, Tmax = 0.85 | Rint = 0.040 |
20325 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.30 e Å−3 |
5277 reflections | Δρmin = −0.22 e Å−3 |
367 parameters |
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 > 2sigma(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) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.93057 (7) | 0.55123 (3) | 0.07821 (3) | 0.05299 (16) | |
S1 | 0.61224 (5) | 0.59156 (2) | 0.59762 (2) | 0.02643 (11) | |
O1 | 0.74915 (13) | 0.32446 (7) | 0.34507 (7) | 0.0320 (3) | |
O2 | 0.98542 (13) | 0.37180 (7) | 0.36461 (7) | 0.0322 (3) | |
O3 | 0.64084 (15) | 0.78617 (7) | 0.48736 (7) | 0.0366 (3) | |
O4 | 0.31751 (16) | 1.03614 (7) | 0.69484 (8) | 0.0399 (3) | |
N1 | 0.70552 (15) | 0.45194 (7) | 0.56600 (7) | 0.0254 (3) | |
N2 | 0.70828 (18) | 0.66939 (9) | 0.38878 (9) | 0.0333 (3) | |
H2A | 0.763 (2) | 0.6506 (13) | 0.3521 (13) | 0.044 (6)* | |
H2B | 0.704 (2) | 0.7185 (14) | 0.3956 (13) | 0.048 (6)* | |
N3 | 0.50338 (17) | 0.75521 (8) | 0.59171 (8) | 0.0295 (3) | |
H3 | 0.461 (3) | 0.7179 (13) | 0.6165 (13) | 0.049 (6)* | |
C1 | 0.76387 (17) | 0.40248 (9) | 0.51642 (9) | 0.0247 (3) | |
C2 | 0.79742 (17) | 0.42332 (9) | 0.43908 (9) | 0.0245 (3) | |
C3 | 0.77840 (17) | 0.49702 (9) | 0.41263 (9) | 0.0237 (3) | |
C4 | 0.72153 (17) | 0.54956 (9) | 0.46494 (9) | 0.0237 (3) | |
C5 | 0.68559 (17) | 0.52221 (9) | 0.53961 (9) | 0.0241 (3) | |
C6 | 0.63015 (18) | 0.65820 (9) | 0.52280 (9) | 0.0268 (3) | |
C7 | 0.68925 (18) | 0.62898 (9) | 0.45635 (9) | 0.0261 (3) | |
C8 | 0.79395 (19) | 0.32535 (9) | 0.54762 (9) | 0.0269 (3) | |
C9 | 0.6953 (2) | 0.29235 (10) | 0.59818 (10) | 0.0314 (4) | |
H9 | 0.6103 | 0.3196 | 0.6141 | 0.038* | |
C10 | 0.7224 (2) | 0.21932 (10) | 0.62509 (11) | 0.0401 (4) | |
H10 | 0.6550 | 0.1966 | 0.6592 | 0.048* | |
C11 | 0.8467 (3) | 0.17944 (10) | 0.60255 (11) | 0.0427 (5) | |
H11 | 0.8627 | 0.1291 | 0.6201 | 0.051* | |
C12 | 0.9478 (2) | 0.21265 (11) | 0.55452 (11) | 0.0407 (4) | |
H12 | 1.0343 | 0.1856 | 0.5401 | 0.049* | |
C13 | 0.9221 (2) | 0.28560 (10) | 0.52754 (10) | 0.0341 (4) | |
H13 | 0.9922 | 0.3087 | 0.4952 | 0.041* | |
C14 | 0.83919 (18) | 0.36646 (9) | 0.37896 (9) | 0.0260 (3) | |
C15 | 1.0348 (2) | 0.32705 (13) | 0.29932 (12) | 0.0469 (5) | |
H15A | 1.1261 | 0.3504 | 0.2792 | 0.056* | |
H15B | 0.9539 | 0.3268 | 0.2557 | 0.056* | |
C16 | 1.0705 (3) | 0.24785 (15) | 0.32371 (17) | 0.0703 (8) | |
H16A | 1.1103 | 0.2206 | 0.2794 | 0.105* | |
H16B | 0.9780 | 0.2231 | 0.3390 | 0.105* | |
H16C | 1.1466 | 0.2479 | 0.3687 | 0.105* | |
C17 | 0.81286 (17) | 0.51549 (9) | 0.32963 (9) | 0.0244 (3) | |
C18 | 0.70985 (19) | 0.49708 (10) | 0.26706 (10) | 0.0313 (4) | |
H18 | 0.6144 | 0.4761 | 0.2773 | 0.038* | |
C19 | 0.7451 (2) | 0.50915 (11) | 0.18947 (10) | 0.0363 (4) | |
H19 | 0.6740 | 0.4969 | 0.1467 | 0.044* | |
C20 | 0.8838 (2) | 0.53903 (10) | 0.17525 (10) | 0.0320 (4) | |
C21 | 0.9873 (2) | 0.55861 (11) | 0.23643 (11) | 0.0367 (4) | |
H21 | 1.0821 | 0.5801 | 0.2257 | 0.044* | |
C22 | 0.9521 (2) | 0.54672 (10) | 0.31378 (10) | 0.0332 (4) | |
H22 | 1.0232 | 0.5599 | 0.3562 | 0.040* | |
C23 | 0.59152 (19) | 0.73833 (9) | 0.53178 (9) | 0.0279 (3) | |
C24 | 0.45659 (18) | 0.82863 (9) | 0.61364 (10) | 0.0277 (3) | |
C25 | 0.4291 (2) | 0.88638 (10) | 0.55940 (10) | 0.0306 (4) | |
H25 | 0.4431 | 0.8781 | 0.5050 | 0.037* | |
C26 | 0.3810 (2) | 0.95634 (10) | 0.58454 (10) | 0.0319 (4) | |
H26 | 0.3626 | 0.9959 | 0.5473 | 0.038* | |
C27 | 0.35998 (19) | 0.96856 (9) | 0.66361 (10) | 0.0295 (4) | |
C28 | 0.3847 (2) | 0.91026 (10) | 0.71805 (10) | 0.0313 (4) | |
H28 | 0.3687 | 0.9182 | 0.7722 | 0.038* | |
C29 | 0.43253 (19) | 0.84107 (9) | 0.69294 (10) | 0.0300 (4) | |
H29 | 0.4493 | 0.8014 | 0.7301 | 0.036* | |
C30 | 0.2967 (3) | 1.09714 (12) | 0.64081 (14) | 0.0578 (7) | |
H30A | 0.2724 | 1.1429 | 0.6697 | 0.087* | |
H30B | 0.2133 | 1.0855 | 0.6014 | 0.087* | |
H30C | 0.3901 | 1.1051 | 0.6141 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0659 (3) | 0.0684 (4) | 0.0269 (2) | −0.0027 (3) | 0.0192 (2) | 0.0049 (2) |
S1 | 0.0347 (2) | 0.0231 (2) | 0.0222 (2) | 0.00087 (15) | 0.00689 (14) | 0.00014 (14) |
O1 | 0.0371 (6) | 0.0291 (6) | 0.0303 (6) | −0.0034 (5) | 0.0048 (5) | −0.0045 (5) |
O2 | 0.0303 (6) | 0.0372 (7) | 0.0298 (6) | 0.0027 (5) | 0.0067 (5) | −0.0067 (5) |
O3 | 0.0489 (7) | 0.0249 (6) | 0.0383 (7) | 0.0011 (5) | 0.0182 (6) | 0.0045 (5) |
O4 | 0.0604 (8) | 0.0258 (6) | 0.0358 (7) | 0.0099 (6) | 0.0179 (6) | 0.0026 (5) |
N1 | 0.0294 (7) | 0.0247 (7) | 0.0219 (6) | −0.0003 (5) | 0.0013 (5) | 0.0007 (5) |
N2 | 0.0491 (9) | 0.0246 (8) | 0.0280 (8) | 0.0039 (7) | 0.0146 (6) | 0.0050 (6) |
N3 | 0.0384 (8) | 0.0217 (7) | 0.0295 (7) | −0.0007 (6) | 0.0106 (6) | 0.0003 (5) |
C1 | 0.0266 (8) | 0.0249 (8) | 0.0222 (8) | −0.0003 (6) | −0.0001 (6) | −0.0003 (6) |
C2 | 0.0262 (8) | 0.0259 (8) | 0.0216 (7) | 0.0019 (6) | 0.0021 (6) | −0.0014 (6) |
C3 | 0.0244 (7) | 0.0258 (8) | 0.0210 (7) | −0.0004 (6) | 0.0016 (5) | 0.0006 (6) |
C4 | 0.0256 (7) | 0.0241 (8) | 0.0216 (7) | −0.0005 (6) | 0.0030 (6) | 0.0019 (6) |
C5 | 0.0267 (7) | 0.0245 (8) | 0.0213 (7) | −0.0008 (6) | 0.0022 (6) | −0.0004 (6) |
C6 | 0.0314 (8) | 0.0241 (8) | 0.0253 (8) | −0.0008 (6) | 0.0049 (6) | 0.0014 (6) |
C7 | 0.0281 (8) | 0.0251 (8) | 0.0255 (8) | 0.0003 (6) | 0.0042 (6) | 0.0021 (6) |
C8 | 0.0349 (8) | 0.0250 (8) | 0.0201 (7) | 0.0020 (7) | −0.0023 (6) | −0.0001 (6) |
C9 | 0.0409 (9) | 0.0287 (9) | 0.0243 (8) | 0.0003 (7) | 0.0003 (7) | 0.0008 (6) |
C10 | 0.0564 (12) | 0.0317 (9) | 0.0316 (9) | −0.0057 (8) | −0.0012 (8) | 0.0070 (7) |
C11 | 0.0667 (13) | 0.0251 (9) | 0.0345 (10) | 0.0073 (9) | −0.0074 (9) | 0.0028 (7) |
C12 | 0.0530 (12) | 0.0352 (10) | 0.0332 (9) | 0.0158 (9) | −0.0020 (8) | −0.0001 (8) |
C13 | 0.0409 (10) | 0.0332 (9) | 0.0280 (9) | 0.0076 (8) | 0.0012 (7) | 0.0020 (7) |
C14 | 0.0313 (8) | 0.0246 (8) | 0.0225 (8) | 0.0021 (6) | 0.0039 (6) | 0.0021 (6) |
C15 | 0.0409 (10) | 0.0611 (13) | 0.0406 (11) | 0.0006 (9) | 0.0151 (8) | −0.0203 (9) |
C16 | 0.0657 (16) | 0.0581 (15) | 0.0864 (19) | 0.0208 (12) | 0.0002 (13) | −0.0338 (14) |
C17 | 0.0282 (8) | 0.0238 (7) | 0.0218 (7) | 0.0027 (6) | 0.0055 (6) | 0.0008 (6) |
C18 | 0.0281 (8) | 0.0390 (9) | 0.0269 (8) | −0.0030 (7) | 0.0037 (6) | 0.0032 (7) |
C19 | 0.0375 (9) | 0.0473 (11) | 0.0237 (8) | −0.0020 (8) | 0.0003 (7) | 0.0000 (7) |
C20 | 0.0394 (9) | 0.0329 (9) | 0.0247 (8) | 0.0037 (7) | 0.0103 (7) | 0.0026 (7) |
C21 | 0.0309 (9) | 0.0447 (11) | 0.0356 (10) | −0.0041 (8) | 0.0104 (7) | 0.0037 (8) |
C22 | 0.0306 (9) | 0.0400 (10) | 0.0291 (9) | −0.0052 (7) | 0.0025 (7) | 0.0016 (7) |
C23 | 0.0334 (8) | 0.0243 (8) | 0.0263 (8) | −0.0008 (6) | 0.0052 (6) | −0.0003 (6) |
C24 | 0.0309 (8) | 0.0224 (8) | 0.0302 (8) | 0.0001 (6) | 0.0055 (6) | −0.0018 (6) |
C25 | 0.0378 (9) | 0.0305 (9) | 0.0239 (8) | 0.0037 (7) | 0.0042 (6) | 0.0005 (6) |
C26 | 0.0380 (9) | 0.0292 (9) | 0.0289 (9) | 0.0065 (7) | 0.0048 (7) | 0.0039 (7) |
C27 | 0.0345 (9) | 0.0239 (8) | 0.0310 (9) | 0.0033 (7) | 0.0076 (7) | −0.0007 (6) |
C28 | 0.0408 (9) | 0.0293 (9) | 0.0248 (8) | 0.0013 (7) | 0.0096 (7) | 0.0005 (6) |
C29 | 0.0390 (9) | 0.0250 (8) | 0.0267 (8) | 0.0004 (7) | 0.0069 (7) | 0.0034 (6) |
C30 | 0.0977 (19) | 0.0300 (10) | 0.0491 (13) | 0.0253 (11) | 0.0278 (12) | 0.0084 (9) |
Cl1—C20 | 1.7383 (17) | C11—H11 | 0.9500 |
S1—C5 | 1.7314 (16) | C12—C13 | 1.388 (2) |
S1—C6 | 1.7504 (16) | C12—H12 | 0.9500 |
O1—C14 | 1.206 (2) | C13—H13 | 0.9500 |
O2—C14 | 1.336 (2) | C15—C16 | 1.494 (4) |
O2—C15 | 1.455 (2) | C15—H15A | 0.9900 |
O3—C23 | 1.236 (2) | C15—H15B | 0.9900 |
O4—C27 | 1.375 (2) | C16—H16A | 0.9800 |
O4—C30 | 1.422 (2) | C16—H16B | 0.9800 |
N1—C5 | 1.334 (2) | C16—H16C | 0.9800 |
N1—C1 | 1.344 (2) | C17—C18 | 1.386 (2) |
N2—C7 | 1.372 (2) | C17—C22 | 1.394 (2) |
N2—H2A | 0.88 (2) | C18—C19 | 1.390 (2) |
N2—H2B | 0.88 (2) | C18—H18 | 0.9500 |
N3—C23 | 1.358 (2) | C19—C20 | 1.373 (3) |
N3—C24 | 1.426 (2) | C19—H19 | 0.9500 |
N3—H3 | 0.88 (2) | C20—C21 | 1.377 (3) |
C1—C2 | 1.414 (2) | C21—C22 | 1.386 (2) |
C1—C8 | 1.486 (2) | C21—H21 | 0.9500 |
C2—C3 | 1.390 (2) | C22—H22 | 0.9500 |
C2—C14 | 1.500 (2) | C24—C25 | 1.387 (2) |
C3—C4 | 1.405 (2) | C24—C29 | 1.394 (2) |
C3—C17 | 1.497 (2) | C25—C26 | 1.391 (2) |
C4—C5 | 1.413 (2) | C25—H25 | 0.9500 |
C4—C7 | 1.445 (2) | C26—C27 | 1.383 (2) |
C6—C7 | 1.377 (2) | C26—H26 | 0.9500 |
C6—C23 | 1.475 (2) | C27—C28 | 1.394 (2) |
C8—C9 | 1.395 (2) | C28—C29 | 1.377 (2) |
C8—C13 | 1.398 (2) | C28—H28 | 0.9500 |
C9—C10 | 1.390 (2) | C29—H29 | 0.9500 |
C9—H9 | 0.9500 | C30—H30A | 0.9800 |
C10—C11 | 1.385 (3) | C30—H30B | 0.9800 |
C10—H10 | 0.9500 | C30—H30C | 0.9800 |
C11—C12 | 1.384 (3) | ||
C5—S1—C6 | 90.74 (7) | O2—C15—H15B | 109.2 |
C14—O2—C15 | 116.56 (13) | C16—C15—H15B | 109.2 |
C27—O4—C30 | 116.34 (14) | H15A—C15—H15B | 107.9 |
C5—N1—C1 | 116.72 (13) | C15—C16—H16A | 109.5 |
C7—N2—H2A | 119.9 (15) | C15—C16—H16B | 109.5 |
C7—N2—H2B | 113.5 (15) | H16A—C16—H16B | 109.5 |
H2A—N2—H2B | 120 (2) | C15—C16—H16C | 109.5 |
C23—N3—C24 | 126.17 (14) | H16A—C16—H16C | 109.5 |
C23—N3—H3 | 118.5 (15) | H16B—C16—H16C | 109.5 |
C24—N3—H3 | 114.9 (15) | C18—C17—C22 | 119.13 (15) |
N1—C1—C2 | 121.60 (14) | C18—C17—C3 | 120.01 (14) |
N1—C1—C8 | 116.57 (14) | C22—C17—C3 | 120.73 (14) |
C2—C1—C8 | 121.82 (14) | C17—C18—C19 | 120.50 (16) |
C3—C2—C1 | 121.13 (14) | C17—C18—H18 | 119.7 |
C3—C2—C14 | 116.44 (14) | C19—C18—H18 | 119.7 |
C1—C2—C14 | 122.13 (14) | C20—C19—C18 | 119.34 (16) |
C2—C3—C4 | 117.55 (14) | C20—C19—H19 | 120.3 |
C2—C3—C17 | 118.78 (14) | C18—C19—H19 | 120.3 |
C4—C3—C17 | 123.62 (14) | C19—C20—C21 | 121.23 (16) |
C3—C4—C5 | 116.78 (14) | C19—C20—Cl1 | 119.40 (14) |
C3—C4—C7 | 131.47 (14) | C21—C20—Cl1 | 119.36 (14) |
C5—C4—C7 | 111.75 (14) | C20—C21—C22 | 119.42 (16) |
N1—C5—C4 | 126.12 (14) | C20—C21—H21 | 120.3 |
N1—C5—S1 | 121.45 (12) | C22—C21—H21 | 120.3 |
C4—C5—S1 | 112.43 (12) | C21—C22—C17 | 120.36 (16) |
C7—C6—C23 | 123.57 (14) | C21—C22—H22 | 119.8 |
C7—C6—S1 | 113.39 (12) | C17—C22—H22 | 119.8 |
C23—C6—S1 | 123.00 (12) | O3—C23—N3 | 123.41 (15) |
N2—C7—C6 | 124.19 (15) | O3—C23—C6 | 120.45 (15) |
N2—C7—C4 | 124.04 (15) | N3—C23—C6 | 116.12 (14) |
C6—C7—C4 | 111.70 (14) | C25—C24—C29 | 119.35 (15) |
C9—C8—C13 | 119.38 (15) | C25—C24—N3 | 122.96 (15) |
C9—C8—C1 | 120.17 (15) | C29—C24—N3 | 117.64 (15) |
C13—C8—C1 | 120.44 (15) | C24—C25—C26 | 120.06 (16) |
C10—C9—C8 | 119.59 (17) | C24—C25—H25 | 120.0 |
C10—C9—H9 | 120.2 | C26—C25—H25 | 120.0 |
C8—C9—H9 | 120.2 | C27—C26—C25 | 120.17 (16) |
C11—C10—C9 | 120.53 (18) | C27—C26—H26 | 119.9 |
C11—C10—H10 | 119.7 | C25—C26—H26 | 119.9 |
C9—C10—H10 | 119.7 | O4—C27—C26 | 124.71 (15) |
C12—C11—C10 | 120.22 (17) | O4—C27—C28 | 115.35 (15) |
C12—C11—H11 | 119.9 | C26—C27—C28 | 119.93 (15) |
C10—C11—H11 | 119.9 | C29—C28—C27 | 119.72 (15) |
C11—C12—C13 | 119.68 (18) | C29—C28—H28 | 120.1 |
C11—C12—H12 | 120.2 | C27—C28—H28 | 120.1 |
C13—C12—H12 | 120.2 | C28—C29—C24 | 120.74 (15) |
C12—C13—C8 | 120.51 (18) | C28—C29—H29 | 119.6 |
C12—C13—H13 | 119.7 | C24—C29—H29 | 119.6 |
C8—C13—H13 | 119.7 | O4—C30—H30A | 109.5 |
O1—C14—O2 | 124.83 (15) | O4—C30—H30B | 109.5 |
O1—C14—C2 | 123.65 (15) | H30A—C30—H30B | 109.5 |
O2—C14—C2 | 111.40 (13) | O4—C30—H30C | 109.5 |
O2—C15—C16 | 111.91 (18) | H30A—C30—H30C | 109.5 |
O2—C15—H15A | 109.2 | H30B—C30—H30C | 109.5 |
C16—C15—H15A | 109.2 | ||
C5—N1—C1—C2 | −2.2 (2) | C1—C8—C13—C12 | −177.88 (16) |
C5—N1—C1—C8 | 176.70 (14) | C15—O2—C14—O1 | 4.6 (2) |
N1—C1—C2—C3 | 3.3 (2) | C15—O2—C14—C2 | −171.53 (15) |
C8—C1—C2—C3 | −175.53 (14) | C3—C2—C14—O1 | −99.45 (19) |
N1—C1—C2—C14 | −170.19 (14) | C1—C2—C14—O1 | 74.3 (2) |
C8—C1—C2—C14 | 11.0 (2) | C3—C2—C14—O2 | 76.68 (17) |
C1—C2—C3—C4 | −1.4 (2) | C1—C2—C14—O2 | −109.56 (17) |
C14—C2—C3—C4 | 172.46 (14) | C14—O2—C15—C16 | −83.3 (2) |
C1—C2—C3—C17 | −178.82 (14) | C2—C3—C17—C18 | 77.9 (2) |
C14—C2—C3—C17 | −5.0 (2) | C4—C3—C17—C18 | −99.37 (19) |
C2—C3—C4—C5 | −1.3 (2) | C2—C3—C17—C22 | −97.89 (19) |
C17—C3—C4—C5 | 176.03 (14) | C4—C3—C17—C22 | 84.8 (2) |
C2—C3—C4—C7 | 179.85 (16) | C22—C17—C18—C19 | 0.4 (3) |
C17—C3—C4—C7 | −2.8 (3) | C3—C17—C18—C19 | −175.48 (16) |
C1—N1—C5—C4 | −0.7 (2) | C17—C18—C19—C20 | 0.5 (3) |
C1—N1—C5—S1 | −179.70 (11) | C18—C19—C20—C21 | −1.3 (3) |
C3—C4—C5—N1 | 2.5 (2) | C18—C19—C20—Cl1 | 177.86 (14) |
C7—C4—C5—N1 | −178.43 (15) | C19—C20—C21—C22 | 1.2 (3) |
C3—C4—C5—S1 | −178.46 (11) | Cl1—C20—C21—C22 | −177.99 (15) |
C7—C4—C5—S1 | 0.62 (17) | C20—C21—C22—C17 | −0.2 (3) |
C6—S1—C5—N1 | 178.69 (14) | C18—C17—C22—C21 | −0.5 (3) |
C6—S1—C5—C4 | −0.41 (12) | C3—C17—C22—C21 | 175.32 (16) |
C5—S1—C6—C7 | 0.08 (13) | C24—N3—C23—O3 | −1.1 (3) |
C5—S1—C6—C23 | −177.49 (14) | C24—N3—C23—C6 | 177.44 (15) |
C23—C6—C7—N2 | −5.2 (3) | C7—C6—C23—O3 | −16.0 (3) |
S1—C6—C7—N2 | 177.27 (13) | S1—C6—C23—O3 | 161.36 (13) |
C23—C6—C7—C4 | 177.81 (15) | C7—C6—C23—N3 | 165.42 (16) |
S1—C6—C7—C4 | 0.25 (18) | S1—C6—C23—N3 | −17.3 (2) |
C3—C4—C7—N2 | 1.3 (3) | C23—N3—C24—C25 | 32.6 (3) |
C5—C4—C7—N2 | −177.58 (15) | C23—N3—C24—C29 | −149.90 (17) |
C3—C4—C7—C6 | 178.34 (16) | C29—C24—C25—C26 | 1.3 (3) |
C5—C4—C7—C6 | −0.56 (19) | N3—C24—C25—C26 | 178.83 (16) |
N1—C1—C8—C9 | 36.8 (2) | C24—C25—C26—C27 | −0.2 (3) |
C2—C1—C8—C9 | −144.34 (16) | C30—O4—C27—C26 | −1.0 (3) |
N1—C1—C8—C13 | −142.32 (16) | C30—O4—C27—C28 | 177.92 (19) |
C2—C1—C8—C13 | 36.5 (2) | C25—C26—C27—O4 | 177.84 (17) |
C13—C8—C9—C10 | −2.7 (2) | C25—C26—C27—C28 | −1.0 (3) |
C1—C8—C9—C10 | 178.12 (15) | O4—C27—C28—C29 | −177.85 (16) |
C8—C9—C10—C11 | 0.5 (3) | C26—C27—C28—C29 | 1.1 (3) |
C9—C10—C11—C12 | 1.7 (3) | C27—C28—C29—C24 | 0.0 (3) |
C10—C11—C12—C13 | −1.4 (3) | C25—C24—C29—C28 | −1.2 (3) |
C11—C12—C13—C8 | −0.9 (3) | N3—C24—C29—C28 | −178.88 (16) |
C9—C8—C13—C12 | 3.0 (3) |
Cg is the centroid of the C17–C22 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O3 | 0.88 (2) | 2.07 (2) | 2.756 (2) | 133.6 (19) |
N2—H2A···Cg | 0.88 (2) | 2.90 | 3.698 | 152 |
N3—H3···O1i | 0.88 (2) | 2.15 (2) | 2.912 (2) | 145 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Cg is the centroid of the C17–C22 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O3 | 0.88 (2) | 2.07 (2) | 2.756 (2) | 133.6 (19) |
N2—H2A···Cg | 0.88 (2) | 2.90 | 3.698 | 152 |
N3—H3···O1i | 0.88 (2) | 2.15 (2) | 2.912 (2) | 145 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C30H24ClN3O4S |
Mr | 558.03 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 8.8388 (3), 17.7686 (6), 16.9487 (6) |
β (°) | 94.159 (2) |
V (Å3) | 2654.84 (16) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.36 |
Crystal size (mm) | 0.16 × 0.07 × 0.07 |
Data collection | |
Diffractometer | Bruker D8 VENTURE PHOTON 100 CMOS |
Absorption correction | Multi-scan (SADABS; Bruker, 2016) |
Tmin, Tmax | 0.75, 0.85 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20325, 5277, 4468 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.094, 1.02 |
No. of reflections | 5277 |
No. of parameters | 367 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.22 |
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012), SHELXTL (Sheldrick, 2008).
Acknowledgements
The support of NSF–MRI Grant No 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.
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