research communications
E)-2-phenylethenyl]thieno[2,3-b]pyridine-5-carboxylate monohydrate
of ethyl 3-amino-6-methyl-2-[(4-methylphenyl)carbamoyl]-4-[(aDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, cChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, dChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, 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
In the title molecule, C27H25N3O3S·H2O, the dihedral angle between the planes of the thienyl ring and the pendant p-tolyl group is 39.25 (6)°, while that between the pyridine ring and the pendant phenyl ring is 44.37 (6)°. In addition, there is a slight twist in the bicyclic core, with a dihedral angle of 2.39 (4)° between the thienyl and pyridine rings. The conformation of the carbamoyl moiety is partially determined by an intramolecular N—H⋯O hydrogen bond. In the crystal, complementary N—H⋯O hydrogen bonds form dimers which are then associated into chains parallel to the c axis through O—H⋯N hydrogen bonds involving the water molecule of crystallization. Electron density associated with an additional solvent molecule of partial occupancy and disordered about a twofold axis was removed with the SQUEEZE procedure in PLATON [Spek (2015). Acta Cryst. C71, 9–18]. The given chemical formula and other crystal data do not take into account the unknown solvent molecule(s).
Keywords: crystal structure; thienyl ring; pyridine ring; dimer; PLATON SQUEEZE.
CCDC reference: 1448789
1. Chemical context
Recently, considerable interest has been focused on the synthesis and pharmacological activities of thieno[2,3-b]pyridine derivatives (Bakhite, 2003). They are versatile synthons such that a variety of new heterocycles with good pharmaceutical profiles can be designed (Litvinov et al., 2005). These thieno[2,3-b]pyridines are usually prepared through S-alkylation of 3-cyanopyridine-2(1H)-thiones and subsequent Thorpe–Ziegler isomerization of the resulting 2-(alkylthio)pyridine-3-carbonitriles (Litvinov et al., 2005). On the other hand, a literature survey revealed that only a few 4-(2-phenylethylene)thieno[2,3-b]pyridines, without any X-ray diffraction analyses, have been reported (Ho & Wang, 1995). The above findings promoted us to synthesize the title compound and characterize its crystal structure.
2. Structural commentary
In the title molecule, the dihedral angle between the thienyl ring and the pendant p-tolyl group is 39.25 (6)° while that between the pyridine ring and the pendant phenyl ring is 44.37 (6)°. In addition there is a slight twist in the bicyclic core with a dihedral angle of 2.39 (4)° between the thienyl and pyridine rings. The conformation of the carbamoyl moiety is partially determined by an intramolecular N2—H2A⋯O1 hydrogen bond (Table 1 and Fig. 1).
3. Supramolecular features
In the crystal, complementary N1—H1A⋯O2i [symmetry code: (i) 1 − x, y, − z] form dimers which are then associated into chains parallel to the c axis through O4—H4A⋯N3 and O4—H4B⋯N2ii [symmetry code: (ii) 1 − x, 1 − y, 1 − z] hydrogen bonds involving the water molecules of crystallization (Fig. 2 and Table 1).
4. Synthesis and crystallization
The title compound was prepared by heating equimolar quantities of ethyl 3-cyano-1,2-dihydro-6-methyl-4-(2-phenylethenyl)-2-thioxopyridine-5-carboxylate and chloro(N-(4-methylphenyl)acetamide (10 mmol) in absolute ethanol (25 ml) containing sodium ethoxide (0.3 g) on a steam bath for 30 mins. The product that formed on cooling was collected by filtration and recrystallized from ethanol 95% as yellow needles. Yield (73%); m.p. IR (KBr) ν = 3500, 3350, (NH2, NH), 1701 (C=O, ester), 1638 (C=O, amide) cm−1. 1H NMR (DMSO-d6): 9.41 (s, 1H, NH), 7.73–7.75 (d, J = 16 Hz, 1H, ethene proton), 7.64–7.66 (d, J = 16 Hz, 2H, ArH), 7.55–7.56 (d, J = 8 Hz, 2H, ArH), 7.38–7.44 (m, 3H, ArH), 7.13–7.15 (d, J = 16 Hz, 2H, ArH), 6.81–6.85 (d, J = 16 Hz, 1H, ethene proton).
5. Refinement
Crystal data, data collection and structure . C-bound H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) while those attached to N or O atoms were placed in locations derived from a difference Fourier map and their coordinates adjusted to give N—H = 0.91 and O—H = 0.85 Å. All were included as riding contributions with isotropic displacement parameters 1.2–1.5 times those of the attached atoms. Electron density associated with an additional solvent molecule of partial occupancy and disordered about a twofold axis was removed with the SQUEEZE procedure in PLATON (Spek, 2015).
details are summarized in Table 2Supporting information
CCDC reference: 1448789
10.1107/S2056989016001341/rz5183sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016001341/rz5183Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016001341/rz5183Isup3.cml
The chemistry of different pyridine compounds has generated intensive scientific studies throughout the world. Special interest has been focused on the synthesis and pharmacological activities of thieno[2,3-b]pyridine derivatives (Bakhite, 2003). They are versatile synthons such that a variety of novel heterocycles with good pharmaceutical profiles can be designed (Litvinov et al., 2005). These thieno[2,3-b]pyridines are usually prepared through S-alkylation of 3-cyanopyridine-2(1H)-thiones and subsequent Thorpe–Ziegler isomerization of the resulting 2-(alkylthio)pyridine-3-carbonitriles (Litvinov et al., 2005). On the other hand, a literature survey revealed that only a few 4-(2-phenylethylene)thieno[2,3-b]pyridines, without any X-ray diffraction analyses, have been reported (Ho & Wang, 1995). The above findings promoted us to synthesize the title compound and characterize its crystal structure.
In the title molecule, the dihedral angle between the thienyl ring and the pendant p-tolyl group is 39.25 (6)° while that between the pyridine ring and the pendant phenyl ring is 44.37 (6)°. In addition there is a slight twist in the bicyclic core with a dihedral angle of 2.39 (4)° between the thienyl and pyridine rings. The conformation of the carbamoyl moiety is partially determined by an intramolecular N2—H2A···O1 hydrogen bond (Table 1 and Fig. 1).
In the crystal, complementary N1—H1A···O2i [symmetry code: (i) 1 − x, y, 3/2 − z] form dimers which are then associated into chains parallel to the c axis through O4—H4A···N3 and O4—H4B···N2ii [symmetry code: (ii) 1 − x, 1 − y, 1 − z] hydrogen bonds involving the lattice water molecule (Fig. 2 and Table 1).
The title compound was prepared by heating equimolar quantities of ethyl 3-cyano-1,2-dihydro-6-methyl-4-(2-phenylethenyl)-2-thioxopyridine-5-carboxylate and chloro(N-(4-methylphenyl)acetamide (10 mmol) in absolute ethanol (25 ml) containing sodium ethoxide (0.3 g) on a steam bath for 30 min. The product that formed on cooling was collected by filtration and recrystallized from ethanol 95% as yellow needles. Yield (73%); m.p. IR (KBr) ν = 3500, 3350, (NH2, NH), 1701(C=O, ester), 1638 (C═O, amide) cm−1. 1H NMR (DMSO-d6): 9.41 (s, 1H, NH), 7.73–7.75 (d, J = 16 Hz, 1H, ethene proton), 7.64–7.66 (d, J = 16 Hz, 2H, ArH), 7.55–7.56 (d, J = 8 Hz, 2H, ArH), 7.38–7.44 (m, 3H, ArH), 7.13–7.15 (d, J = 16 Hz, 2H, ArH), 6.81–6.85 (d, J =16 Hz, 1H, ethene proton).
Crystal data, data collection and structure
details are summarized in Table 2. H atoms attached to carbon were placed in calculated positions (C—H = 0.95–0.99 Å) while those attached to nitrogen and oxygen were placed in locations derived from a difference Fourier map and their coordinates adjusted to give N—H = 0.91 and O—H = 0.85 Å. All were included as riding contributions with isotropic displacement parameters 1.2–1.5 times those of the attached atoms. Density associated with an additional lattice water molecule of partial occupancy and disordered about a twofold axis was removed with the SQUEEZE procedure in PLATON (Spek, 2015).The chemistry of different pyridine compounds has generated intensive scientific studies throughout the world. Special interest has been focused on the synthesis and pharmacological activities of thieno[2,3-b]pyridine derivatives (Bakhite, 2003). They are versatile synthons such that a variety of novel heterocycles with good pharmaceutical profiles can be designed (Litvinov et al., 2005). These thieno[2,3-b]pyridines are usually prepared through S-alkylation of 3-cyanopyridine-2(1H)-thiones and subsequent Thorpe–Ziegler isomerization of the resulting 2-(alkylthio)pyridine-3-carbonitriles (Litvinov et al., 2005). On the other hand, a literature survey revealed that only a few 4-(2-phenylethylene)thieno[2,3-b]pyridines, without any X-ray diffraction analyses, have been reported (Ho & Wang, 1995). The above findings promoted us to synthesize the title compound and characterize its crystal structure.
In the title molecule, the dihedral angle between the thienyl ring and the pendant p-tolyl group is 39.25 (6)° while that between the pyridine ring and the pendant phenyl ring is 44.37 (6)°. In addition there is a slight twist in the bicyclic core with a dihedral angle of 2.39 (4)° between the thienyl and pyridine rings. The conformation of the carbamoyl moiety is partially determined by an intramolecular N2—H2A···O1 hydrogen bond (Table 1 and Fig. 1).
In the crystal, complementary N1—H1A···O2i [symmetry code: (i) 1 − x, y, 3/2 − z] form dimers which are then associated into chains parallel to the c axis through O4—H4A···N3 and O4—H4B···N2ii [symmetry code: (ii) 1 − x, 1 − y, 1 − z] hydrogen bonds involving the lattice water molecule (Fig. 2 and Table 1).
The title compound was prepared by heating equimolar quantities of ethyl 3-cyano-1,2-dihydro-6-methyl-4-(2-phenylethenyl)-2-thioxopyridine-5-carboxylate and chloro(N-(4-methylphenyl)acetamide (10 mmol) in absolute ethanol (25 ml) containing sodium ethoxide (0.3 g) on a steam bath for 30 min. The product that formed on cooling was collected by filtration and recrystallized from ethanol 95% as yellow needles. Yield (73%); m.p. IR (KBr) ν = 3500, 3350, (NH2, NH), 1701(C=O, ester), 1638 (C═O, amide) cm−1. 1H NMR (DMSO-d6): 9.41 (s, 1H, NH), 7.73–7.75 (d, J = 16 Hz, 1H, ethene proton), 7.64–7.66 (d, J = 16 Hz, 2H, ArH), 7.55–7.56 (d, J = 8 Hz, 2H, ArH), 7.38–7.44 (m, 3H, ArH), 7.13–7.15 (d, J = 16 Hz, 2H, ArH), 6.81–6.85 (d, J =16 Hz, 1H, ethene proton).
detailsCrystal data, data collection and structure
details are summarized in Table 2. H atoms attached to carbon were placed in calculated positions (C—H = 0.95–0.99 Å) while those attached to nitrogen and oxygen were placed in locations derived from a difference Fourier map and their coordinates adjusted to give N—H = 0.91 and O—H = 0.85 Å. All were included as riding contributions with isotropic displacement parameters 1.2–1.5 times those of the attached atoms. Density associated with an additional lattice water molecule of partial occupancy and disordered about a twofold axis was removed with the SQUEEZE procedure in PLATON (Spek, 2015).Data collection: APEX2 (Bruker, 2015); cell
SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); 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, shown with 50% probability ellipsoids. Hydrogen bonds are shown by dotted lines. | |
Fig. 2. View of the hydrogen-bonded dimer with half of each of two adjacent dimers as the basic elements of the one-dimensional chains. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted. Displacement ellipsoids are drawn at the 50% probability level. |
C27H25N3O3S·H2O | F(000) = 2064 |
Mr = 489.57 | Dx = 1.244 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 31.083 (3) Å | Cell parameters from 7720 reflections |
b = 12.0766 (10) Å | θ = 2.2–28.7° |
c = 14.7678 (12) Å | µ = 0.16 mm−1 |
β = 109.446 (1)° | T = 150 K |
V = 5227.2 (7) Å3 | Column, yellow |
Z = 8 | 0.28 × 0.15 × 0.10 mm |
Bruker SMART APEX CCD diffractometer | 6682 independent reflections |
Radiation source: fine-focus sealed tube | 4746 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 8.3333 pixels mm-1 | θmax = 29.0°, θmin = 1.4° |
φ and ω scans | h = −41→42 |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | k = −16→16 |
Tmin = 0.86, Tmax = 0.98 | l = −20→20 |
24570 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)] = 0.047 | Hydrogen site location: mixed |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0777P)2 + 0.6476P] where P = (Fo2 + 2Fc2)/3 |
6682 reflections | (Δ/σ)max = 0.001 |
319 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
C27H25N3O3S·H2O | V = 5227.2 (7) Å3 |
Mr = 489.57 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 31.083 (3) Å | µ = 0.16 mm−1 |
b = 12.0766 (10) Å | T = 150 K |
c = 14.7678 (12) Å | 0.28 × 0.15 × 0.10 mm |
β = 109.446 (1)° |
Bruker SMART APEX CCD diffractometer | 6682 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | 4746 reflections with I > 2σ(I) |
Tmin = 0.86, Tmax = 0.98 | Rint = 0.036 |
24570 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.56 e Å−3 |
6682 reflections | Δρmin = −0.65 e Å−3 |
319 parameters |
Experimental. The diffraction data were collected in three sets of 363 frames (0.5° width in ω) at φ = 0, 120 and 240°. A scan time of 80 sec/frame was used. |
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 andgoodness 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 those attached to nitrogen and oxygen were placed in locations derived from a difference map and their coordinates adjusted to give N—H = 0.91 and O—H = 0.85%A. All were included as riding contributions with isotropic displacement parameters 1.2 − 1.5 times those of the attached atoms. Density associated with an additional lattice water molecule of partial occupancy and disordered about a 2-fold axis was removed with PLATON SQUEEZE (Spek, 2015). |
x | y | z | Uiso*/Ueq | ||
S1 | 0.56861 (2) | 0.53645 (3) | 0.64405 (3) | 0.02434 (12) | |
O1 | 0.61317 (4) | 0.23972 (11) | 0.61342 (10) | 0.0415 (3) | |
O2 | 0.35098 (4) | 0.52166 (10) | 0.63445 (8) | 0.0294 (3) | |
O3 | 0.35101 (4) | 0.47141 (10) | 0.48800 (8) | 0.0312 (3) | |
N1 | 0.65244 (4) | 0.38651 (11) | 0.69843 (9) | 0.0247 (3) | |
H1A | 0.6499 | 0.4481 | 0.7318 | 0.030* | |
N2 | 0.52169 (5) | 0.22909 (12) | 0.60780 (12) | 0.0374 (4) | |
H2A | 0.5451 | 0.1805 | 0.6169 | 0.045* | |
H2B | 0.5028 | 0.2105 | 0.6410 | 0.045* | |
N3 | 0.48792 (4) | 0.62120 (11) | 0.63560 (9) | 0.0238 (3) | |
C1 | 0.69789 (5) | 0.34988 (13) | 0.71843 (11) | 0.0236 (3) | |
C2 | 0.71060 (6) | 0.26439 (15) | 0.66984 (14) | 0.0351 (4) | |
H2 | 0.6880 | 0.2252 | 0.6207 | 0.042* | |
C3 | 0.75638 (6) | 0.23609 (15) | 0.69314 (14) | 0.0367 (4) | |
H3 | 0.7646 | 0.1776 | 0.6590 | 0.044* | |
C4 | 0.79040 (6) | 0.29031 (15) | 0.76441 (13) | 0.0326 (4) | |
C5 | 0.77717 (5) | 0.37692 (15) | 0.81137 (13) | 0.0322 (4) | |
H5 | 0.7998 | 0.4166 | 0.8599 | 0.039* | |
C6 | 0.73187 (5) | 0.40666 (14) | 0.78915 (12) | 0.0276 (4) | |
H6 | 0.7238 | 0.4663 | 0.8224 | 0.033* | |
C7 | 0.83973 (6) | 0.25687 (19) | 0.79060 (16) | 0.0463 (5) | |
H7A | 0.8496 | 0.2209 | 0.8537 | 0.070* | |
H7B | 0.8585 | 0.3228 | 0.7928 | 0.070* | |
H7C | 0.8432 | 0.2052 | 0.7424 | 0.070* | |
C8 | 0.61337 (5) | 0.33272 (14) | 0.64630 (11) | 0.0259 (3) | |
C9 | 0.57069 (5) | 0.39261 (14) | 0.63448 (11) | 0.0246 (3) | |
C10 | 0.52928 (5) | 0.34191 (14) | 0.61994 (11) | 0.0262 (3) | |
C11 | 0.49407 (5) | 0.42133 (13) | 0.61750 (11) | 0.0229 (3) | |
C12 | 0.51150 (5) | 0.52967 (13) | 0.63232 (10) | 0.0218 (3) | |
C13 | 0.44362 (5) | 0.60840 (13) | 0.62383 (11) | 0.0238 (3) | |
C14 | 0.41817 (6) | 0.71201 (14) | 0.62923 (14) | 0.0325 (4) | |
H14A | 0.4140 | 0.7163 | 0.6921 | 0.049* | |
H14B | 0.3883 | 0.7111 | 0.5785 | 0.049* | |
H14C | 0.4356 | 0.7765 | 0.6206 | 0.049* | |
C15 | 0.42213 (5) | 0.50379 (14) | 0.60392 (11) | 0.0233 (3) | |
C16 | 0.44682 (5) | 0.40837 (13) | 0.60086 (11) | 0.0235 (3) | |
C17 | 0.42494 (5) | 0.29814 (14) | 0.57731 (12) | 0.0266 (3) | |
H17 | 0.4293 | 0.2582 | 0.5257 | 0.032* | |
C18 | 0.39976 (6) | 0.25193 (13) | 0.62341 (12) | 0.0270 (4) | |
H18 | 0.3956 | 0.2929 | 0.6748 | 0.032* | |
C19 | 0.37747 (5) | 0.14278 (13) | 0.60252 (12) | 0.0261 (3) | |
C20 | 0.38580 (6) | 0.06826 (14) | 0.53845 (13) | 0.0317 (4) | |
H20 | 0.4068 | 0.0872 | 0.5068 | 0.038* | |
C21 | 0.36377 (7) | −0.03324 (15) | 0.52028 (14) | 0.0384 (4) | |
H21 | 0.3696 | −0.0833 | 0.4761 | 0.046* | |
C22 | 0.33324 (6) | −0.06161 (15) | 0.56647 (15) | 0.0409 (5) | |
H22 | 0.3181 | −0.1311 | 0.5538 | 0.049* | |
C23 | 0.32477 (6) | 0.01048 (16) | 0.63069 (15) | 0.0389 (4) | |
H23 | 0.3039 | −0.0093 | 0.6625 | 0.047* | |
C24 | 0.34676 (6) | 0.11200 (15) | 0.64895 (13) | 0.0327 (4) | |
H24 | 0.3409 | 0.1613 | 0.6936 | 0.039* | |
C25 | 0.37130 (5) | 0.49932 (14) | 0.58031 (11) | 0.0241 (3) | |
C26 | 0.30137 (6) | 0.45925 (16) | 0.45613 (13) | 0.0360 (4) | |
H26A | 0.2889 | 0.4662 | 0.3853 | 0.043* | |
H26B | 0.2882 | 0.5193 | 0.4842 | 0.043* | |
C27 | 0.28784 (6) | 0.34965 (16) | 0.48538 (13) | 0.0353 (4) | |
H27A | 0.3025 | 0.2902 | 0.4611 | 0.053* | |
H27B | 0.2546 | 0.3414 | 0.4586 | 0.053* | |
H27C | 0.2975 | 0.3456 | 0.5556 | 0.053* | |
O4 | 0.52863 (6) | 0.82044 (15) | 0.59700 (12) | 0.0721 (5) | |
H4A | 0.5180 | 0.7668 | 0.6204 | 0.087* | |
H4B | 0.5107 | 0.8246 | 0.5393 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0185 (2) | 0.0275 (2) | 0.0272 (2) | −0.00112 (15) | 0.00795 (16) | 0.00181 (16) |
O1 | 0.0280 (7) | 0.0383 (8) | 0.0555 (9) | 0.0006 (5) | 0.0101 (6) | −0.0201 (6) |
O2 | 0.0242 (6) | 0.0343 (7) | 0.0320 (6) | −0.0004 (5) | 0.0125 (5) | 0.0014 (5) |
O3 | 0.0201 (6) | 0.0462 (8) | 0.0243 (6) | −0.0060 (5) | 0.0034 (5) | 0.0045 (5) |
N1 | 0.0203 (6) | 0.0260 (7) | 0.0276 (7) | 0.0027 (5) | 0.0078 (5) | −0.0034 (6) |
N2 | 0.0270 (8) | 0.0276 (8) | 0.0534 (10) | −0.0002 (6) | 0.0077 (7) | −0.0095 (7) |
N3 | 0.0214 (7) | 0.0265 (7) | 0.0240 (7) | −0.0003 (5) | 0.0080 (5) | 0.0021 (5) |
C1 | 0.0203 (7) | 0.0264 (8) | 0.0265 (8) | 0.0029 (6) | 0.0109 (6) | 0.0043 (6) |
C2 | 0.0285 (9) | 0.0325 (10) | 0.0461 (11) | −0.0018 (7) | 0.0148 (8) | −0.0099 (8) |
C3 | 0.0337 (10) | 0.0288 (9) | 0.0538 (12) | 0.0065 (7) | 0.0227 (9) | −0.0034 (8) |
C4 | 0.0252 (8) | 0.0368 (10) | 0.0402 (10) | 0.0069 (7) | 0.0169 (8) | 0.0102 (8) |
C5 | 0.0217 (8) | 0.0402 (10) | 0.0340 (9) | 0.0002 (7) | 0.0082 (7) | −0.0002 (8) |
C6 | 0.0261 (8) | 0.0300 (9) | 0.0283 (9) | 0.0026 (7) | 0.0113 (7) | −0.0002 (7) |
C7 | 0.0299 (10) | 0.0544 (13) | 0.0575 (13) | 0.0145 (9) | 0.0183 (9) | 0.0090 (10) |
C8 | 0.0238 (8) | 0.0308 (9) | 0.0237 (8) | 0.0020 (7) | 0.0087 (6) | −0.0029 (7) |
C9 | 0.0221 (8) | 0.0276 (8) | 0.0227 (8) | 0.0004 (6) | 0.0058 (6) | −0.0032 (6) |
C10 | 0.0232 (8) | 0.0271 (8) | 0.0260 (8) | 0.0008 (6) | 0.0050 (6) | −0.0047 (7) |
C11 | 0.0212 (8) | 0.0264 (8) | 0.0201 (8) | −0.0011 (6) | 0.0052 (6) | −0.0012 (6) |
C12 | 0.0189 (7) | 0.0295 (9) | 0.0166 (7) | −0.0006 (6) | 0.0054 (6) | 0.0023 (6) |
C13 | 0.0224 (8) | 0.0279 (8) | 0.0215 (8) | 0.0005 (6) | 0.0077 (6) | 0.0029 (6) |
C14 | 0.0263 (9) | 0.0285 (9) | 0.0449 (10) | 0.0027 (7) | 0.0148 (8) | 0.0034 (8) |
C15 | 0.0194 (7) | 0.0325 (8) | 0.0180 (7) | −0.0012 (6) | 0.0064 (6) | 0.0009 (6) |
C16 | 0.0213 (8) | 0.0289 (9) | 0.0198 (7) | −0.0038 (6) | 0.0060 (6) | −0.0016 (6) |
C17 | 0.0230 (8) | 0.0283 (8) | 0.0269 (8) | −0.0021 (6) | 0.0059 (6) | −0.0049 (7) |
C18 | 0.0278 (8) | 0.0261 (9) | 0.0269 (8) | −0.0001 (7) | 0.0090 (7) | −0.0030 (7) |
C19 | 0.0226 (8) | 0.0244 (8) | 0.0292 (9) | 0.0009 (6) | 0.0058 (7) | 0.0004 (7) |
C20 | 0.0320 (9) | 0.0291 (9) | 0.0344 (9) | 0.0008 (7) | 0.0114 (8) | −0.0011 (7) |
C21 | 0.0416 (11) | 0.0247 (9) | 0.0439 (11) | 0.0019 (8) | 0.0076 (9) | −0.0053 (8) |
C22 | 0.0349 (10) | 0.0233 (9) | 0.0583 (13) | −0.0047 (8) | 0.0072 (9) | 0.0029 (8) |
C23 | 0.0334 (10) | 0.0334 (10) | 0.0508 (12) | −0.0021 (8) | 0.0152 (9) | 0.0087 (9) |
C24 | 0.0316 (9) | 0.0305 (9) | 0.0385 (10) | −0.0001 (7) | 0.0150 (8) | −0.0002 (8) |
C25 | 0.0219 (8) | 0.0257 (8) | 0.0234 (8) | −0.0009 (6) | 0.0058 (6) | 0.0056 (6) |
C26 | 0.0211 (8) | 0.0486 (11) | 0.0317 (9) | −0.0066 (8) | −0.0001 (7) | 0.0104 (8) |
C27 | 0.0273 (9) | 0.0415 (10) | 0.0354 (10) | −0.0079 (8) | 0.0081 (8) | 0.0008 (8) |
O4 | 0.0651 (11) | 0.0779 (12) | 0.0635 (11) | −0.0336 (9) | 0.0082 (9) | 0.0187 (9) |
S1—C12 | 1.7271 (15) | C11—C16 | 1.415 (2) |
S1—C9 | 1.7459 (17) | C13—C15 | 1.413 (2) |
O1—C8 | 1.223 (2) | C13—C14 | 1.497 (2) |
O2—C25 | 1.2030 (19) | C14—H14A | 0.9800 |
O3—C25 | 1.341 (2) | C14—H14B | 0.9800 |
O3—C26 | 1.4630 (19) | C14—H14C | 0.9800 |
N1—C8 | 1.366 (2) | C15—C16 | 1.394 (2) |
N1—C1 | 1.4145 (19) | C15—C25 | 1.501 (2) |
N1—H1A | 0.9101 | C16—C17 | 1.483 (2) |
N2—C10 | 1.384 (2) | C17—C18 | 1.320 (2) |
N2—H2A | 0.9102 | C17—H17 | 0.9500 |
N2—H2B | 0.9102 | C18—C19 | 1.473 (2) |
N3—C12 | 1.336 (2) | C18—H18 | 0.9500 |
N3—C13 | 1.3383 (19) | C19—C20 | 1.391 (2) |
C1—C2 | 1.388 (2) | C19—C24 | 1.398 (2) |
C1—C6 | 1.394 (2) | C20—C21 | 1.386 (3) |
C2—C3 | 1.391 (2) | C20—H20 | 0.9500 |
C2—H2 | 0.9500 | C21—C22 | 1.384 (3) |
C3—C4 | 1.383 (3) | C21—H21 | 0.9500 |
C3—H3 | 0.9500 | C22—C23 | 1.376 (3) |
C4—C5 | 1.391 (2) | C22—H22 | 0.9500 |
C4—C7 | 1.506 (2) | C23—C24 | 1.386 (3) |
C5—C6 | 1.382 (2) | C23—H23 | 0.9500 |
C5—H5 | 0.9500 | C24—H24 | 0.9500 |
C6—H6 | 0.9500 | C26—C27 | 1.496 (2) |
C7—H7A | 0.9800 | C26—H26A | 0.9900 |
C7—H7B | 0.9800 | C26—H26B | 0.9900 |
C7—H7C | 0.9800 | C27—H27A | 0.9800 |
C8—C9 | 1.469 (2) | C27—H27B | 0.9800 |
C9—C10 | 1.376 (2) | C27—H27C | 0.9800 |
C10—C11 | 1.447 (2) | O4—H4A | 0.8502 |
C11—C12 | 1.405 (2) | O4—H4B | 0.8504 |
C12—S1—C9 | 90.52 (7) | C13—C14—H14B | 109.5 |
C25—O3—C26 | 116.17 (13) | H14A—C14—H14B | 109.5 |
C8—N1—C1 | 127.41 (14) | C13—C14—H14C | 109.5 |
C8—N1—H1A | 118.3 | H14A—C14—H14C | 109.5 |
C1—N1—H1A | 113.7 | H14B—C14—H14C | 109.5 |
C10—N2—H2A | 121.4 | C16—C15—C13 | 121.24 (14) |
C10—N2—H2B | 106.6 | C16—C15—C25 | 120.74 (14) |
H2A—N2—H2B | 113.0 | C13—C15—C25 | 117.92 (14) |
C12—N3—C13 | 116.93 (13) | C15—C16—C11 | 117.00 (14) |
C2—C1—C6 | 118.58 (14) | C15—C16—C17 | 122.37 (14) |
C2—C1—N1 | 124.13 (15) | C11—C16—C17 | 120.58 (14) |
C6—C1—N1 | 117.24 (14) | C18—C17—C16 | 124.27 (15) |
C1—C2—C3 | 119.92 (17) | C18—C17—H17 | 117.9 |
C1—C2—H2 | 120.0 | C16—C17—H17 | 117.9 |
C3—C2—H2 | 120.0 | C17—C18—C19 | 126.06 (15) |
C4—C3—C2 | 122.14 (17) | C17—C18—H18 | 117.0 |
C4—C3—H3 | 118.9 | C19—C18—H18 | 117.0 |
C2—C3—H3 | 118.9 | C20—C19—C24 | 118.26 (15) |
C3—C4—C5 | 117.21 (15) | C20—C19—C18 | 122.69 (15) |
C3—C4—C7 | 121.56 (17) | C24—C19—C18 | 119.05 (15) |
C5—C4—C7 | 121.23 (17) | C21—C20—C19 | 120.80 (17) |
C6—C5—C4 | 121.60 (16) | C21—C20—H20 | 119.6 |
C6—C5—H5 | 119.2 | C19—C20—H20 | 119.6 |
C4—C5—H5 | 119.2 | C22—C21—C20 | 119.96 (18) |
C5—C6—C1 | 120.53 (16) | C22—C21—H21 | 120.0 |
C5—C6—H6 | 119.7 | C20—C21—H21 | 120.0 |
C1—C6—H6 | 119.7 | C23—C22—C21 | 120.21 (17) |
C4—C7—H7A | 109.5 | C23—C22—H22 | 119.9 |
C4—C7—H7B | 109.5 | C21—C22—H22 | 119.9 |
H7A—C7—H7B | 109.5 | C22—C23—C24 | 119.92 (18) |
C4—C7—H7C | 109.5 | C22—C23—H23 | 120.0 |
H7A—C7—H7C | 109.5 | C24—C23—H23 | 120.0 |
H7B—C7—H7C | 109.5 | C23—C24—C19 | 120.86 (17) |
O1—C8—N1 | 123.12 (15) | C23—C24—H24 | 119.6 |
O1—C8—C9 | 121.32 (15) | C19—C24—H24 | 119.6 |
N1—C8—C9 | 115.52 (14) | O2—C25—O3 | 123.99 (14) |
C10—C9—C8 | 124.06 (15) | O2—C25—C15 | 125.62 (14) |
C10—C9—S1 | 113.42 (12) | O3—C25—C15 | 110.33 (13) |
C8—C9—S1 | 122.44 (12) | O3—C26—C27 | 111.33 (14) |
C9—C10—N2 | 124.64 (15) | O3—C26—H26A | 109.4 |
C9—C10—C11 | 111.68 (14) | C27—C26—H26A | 109.4 |
N2—C10—C11 | 123.67 (14) | O3—C26—H26B | 109.4 |
C12—C11—C16 | 117.02 (14) | C27—C26—H26B | 109.4 |
C12—C11—C10 | 111.35 (13) | H26A—C26—H26B | 108.0 |
C16—C11—C10 | 131.61 (15) | C26—C27—H27A | 109.5 |
N3—C12—C11 | 126.03 (14) | C26—C27—H27B | 109.5 |
N3—C12—S1 | 120.99 (12) | H27A—C27—H27B | 109.5 |
C11—C12—S1 | 112.96 (11) | C26—C27—H27C | 109.5 |
N3—C13—C15 | 121.66 (14) | H27A—C27—H27C | 109.5 |
N3—C13—C14 | 115.83 (14) | H27B—C27—H27C | 109.5 |
C15—C13—C14 | 122.46 (14) | H4A—O4—H4B | 104.0 |
C13—C14—H14A | 109.5 | ||
C8—N1—C1—C2 | 15.6 (3) | C9—S1—C12—C11 | −2.44 (12) |
C8—N1—C1—C6 | −166.89 (15) | C12—N3—C13—C15 | −3.2 (2) |
C6—C1—C2—C3 | 0.9 (3) | C12—N3—C13—C14 | 179.16 (14) |
N1—C1—C2—C3 | 178.41 (16) | N3—C13—C15—C16 | 3.5 (2) |
C1—C2—C3—C4 | 0.3 (3) | C14—C13—C15—C16 | −178.95 (15) |
C2—C3—C4—C5 | −1.3 (3) | N3—C13—C15—C25 | −172.90 (14) |
C2—C3—C4—C7 | 178.42 (18) | C14—C13—C15—C25 | 4.6 (2) |
C3—C4—C5—C6 | 1.1 (3) | C13—C15—C16—C11 | −0.7 (2) |
C7—C4—C5—C6 | −178.63 (17) | C25—C15—C16—C11 | 175.66 (13) |
C4—C5—C6—C1 | 0.1 (3) | C13—C15—C16—C17 | −178.14 (14) |
C2—C1—C6—C5 | −1.1 (2) | C25—C15—C16—C17 | −1.8 (2) |
N1—C1—C6—C5 | −178.79 (15) | C12—C11—C16—C15 | −2.1 (2) |
C1—N1—C8—O1 | 4.0 (3) | C10—C11—C16—C15 | 179.78 (16) |
C1—N1—C8—C9 | −178.01 (14) | C12—C11—C16—C17 | 175.39 (14) |
O1—C8—C9—C10 | 24.8 (3) | C10—C11—C16—C17 | −2.7 (3) |
N1—C8—C9—C10 | −153.29 (16) | C15—C16—C17—C18 | −55.4 (2) |
O1—C8—C9—S1 | −158.72 (14) | C11—C16—C17—C18 | 127.21 (18) |
N1—C8—C9—S1 | 23.2 (2) | C16—C17—C18—C19 | −179.93 (15) |
C12—S1—C9—C10 | 1.85 (13) | C17—C18—C19—C20 | 9.1 (3) |
C12—S1—C9—C8 | −175.01 (14) | C17—C18—C19—C24 | −171.14 (17) |
C8—C9—C10—N2 | −4.8 (3) | C24—C19—C20—C21 | 0.8 (3) |
S1—C9—C10—N2 | 178.41 (13) | C18—C19—C20—C21 | −179.43 (16) |
C8—C9—C10—C11 | 176.00 (14) | C19—C20—C21—C22 | −0.3 (3) |
S1—C9—C10—C11 | −0.79 (18) | C20—C21—C22—C23 | −0.2 (3) |
C9—C10—C11—C12 | −1.04 (19) | C21—C22—C23—C24 | 0.2 (3) |
N2—C10—C11—C12 | 179.74 (15) | C22—C23—C24—C19 | 0.3 (3) |
C9—C10—C11—C16 | 177.14 (16) | C20—C19—C24—C23 | −0.8 (3) |
N2—C10—C11—C16 | −2.1 (3) | C18—C19—C24—C23 | 179.43 (16) |
C13—N3—C12—C11 | 0.1 (2) | C26—O3—C25—O2 | −5.3 (2) |
C13—N3—C12—S1 | 178.62 (11) | C26—O3—C25—C15 | 177.44 (13) |
C16—C11—C12—N3 | 2.6 (2) | C16—C15—C25—O2 | 117.80 (19) |
C10—C11—C12—N3 | −178.94 (14) | C13—C15—C25—O2 | −65.7 (2) |
C16—C11—C12—S1 | −176.03 (11) | C16—C15—C25—O3 | −64.98 (19) |
C10—C11—C12—S1 | 2.45 (17) | C13—C15—C25—O3 | 111.48 (16) |
C9—S1—C12—N3 | 178.87 (13) | C25—O3—C26—C27 | −79.71 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.91 | 2.17 | 2.9900 (17) | 149 |
N2—H2A···O1 | 0.91 | 2.25 | 2.820 (2) | 120 |
O4—H4A···N3 | 0.85 | 2.04 | 2.863 (2) | 163 |
O4—H4B···N2ii | 0.85 | 2.17 | 2.967 (2) | 157 |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.91 | 2.17 | 2.9900 (17) | 149 |
N2—H2A···O1 | 0.91 | 2.25 | 2.820 (2) | 120 |
O4—H4A···N3 | 0.85 | 2.04 | 2.863 (2) | 163 |
O4—H4B···N2ii | 0.85 | 2.17 | 2.967 (2) | 157 |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C27H25N3O3S·H2O |
Mr | 489.57 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 31.083 (3), 12.0766 (10), 14.7678 (12) |
β (°) | 109.446 (1) |
V (Å3) | 5227.2 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.28 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2015) |
Tmin, Tmax | 0.86, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24570, 6682, 4746 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.140, 1.08 |
No. of reflections | 6682 |
No. of parameters | 319 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.56, −0.65 |
Computer programs: APEX2 (Bruker, 2015), SAINT (Bruker, 2015), 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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