research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 3| March 2016| Pages 297-299
doi:10.1107/S2056989016001341

Crystal structure of ethyl 3-amino-6-methyl-2-[(4-methyl­phen­yl)carbamo­yl]-4-[(E)-2-phenyl­ethen­yl]thieno[2,3-b]pyridine-5-carboxyl­ate monohydrate

CROSSMARK_Color_square_no_text.svg
Joel T. Mague,a Mehmet Akkurt,b Shaaban K. Mohamed,c,d Etify A. Bakhitee and Mustafa R. Albayatif*

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

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 13 January 2016; accepted 21 January 2016; online 6 February 2016)

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[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]). Acta Cryst. C71, 9–18]. The given chemical formula and other crystal data do not take into account the unknown solvent molecule(s).

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[Bakhite, E. A. (2003). Phosphorus Sulfur Silicon, 178, 929-992.]). They are versatile synthons such that a variety of new heterocycles with good pharmaceutical profiles can be designed (Litvinov et al., 2005[Litvinov, V. P., Dotsenko, V. V. & Krivokolysko, S. G. (2005). Russ. Chem. Bull. 54, 864-904.]). 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[Litvinov, V. P., Dotsenko, V. V. & Krivokolysko, S. G. (2005). Russ. Chem. Bull. 54, 864-904.]). 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[Ho, Y. W. & Wang, I. J. (1995). J. Heterocycl. Chem. 32, 819-825.]). The above findings promoted us to synthesize the title compound and characterize its crystal structure.

[Scheme 1]

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[link] and Fig. 1[link]).

Table 1
Hydrogen-bond geometry (Å, °)

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+{\script{3\over 2}}]; (ii) -x+1, -y+1, -z+1.
[Figure 1]
Figure 1
The mol­ecular structure of the title compound, shown with 50% probability ellipsoids. Hydrogen bonds are shown by dotted lines.

3. Supra­molecular features

In the crystal, complementary N1—H1A⋯O2i [symmetry code: (i) 1 − x, y, [{3\over 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 water mol­ecules of crystallization (Fig. 2[link] and Table 1[link]).

[Figure 2]
Figure 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.

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 refinement details are summarized in Table 2[link]. 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[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]).

Table 2
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[Bruker (2015). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.])
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 and SAINT (Bruker, 2015[Bruker (2015). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]), SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg & Putz, 2012[Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany.]).

Supporting information

CCDC reference: 1448789

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989016001341/rz5183sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016001341/rz5183Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989016001341/rz5183Isup3.cml

checkCIF report


Chemical context top

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.

Structural commentary top

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).

Supra­molecular features top

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).

Synthesis and crystallization top

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).

Refinement top

Crystal data, data collection and structure refinement 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).

Structure description top

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).

Synthesis and crystallization top

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).

Refinement details top

Crystal data, data collection and structure refinement 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).

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, shown with 50% probability ellipsoids. Hydrogen bonds are shown by dotted lines.
[Figure 2] 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.
Ethyl 3-amino-6-methyl-2-[(4-methylphenyl)carbamoyl]-4-[(E)-2-phenylethenyl]thieno[2,3-b]pyridine-5-carboxylate monohydrate top
Crystal data top
C27H25N3O3S·H2OF(000) = 2064
Mr = 489.57Dx = 1.244 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 31.083 (3) ÅCell parameters from 7720 reflections
b = 12.0766 (10) Åθ = 2.2–28.7°
c = 14.7678 (12) ŵ = 0.16 mm−1
β = 109.446 (1)°T = 150 K
V = 5227.2 (7) Å3Column, yellow
Z = 80.28 × 0.15 × 0.10 mm
Data collection top
Bruker SMART APEX CCD
diffractometer		6682 independent reflections
Radiation source: fine-focus sealed tube4746 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 8.3333 pixels mm-1θmax = 29.0°, θmin = 1.4°
φ and ω scansh = −41→42
Absorption correction: multi-scan
(SADABS; Bruker, 2015)		k = −16→16
Tmin = 0.86, Tmax = 0.98l = −20→20
24570 measured reflections
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)] = 0.047Hydrogen site location: mixed
wR(F2) = 0.140H-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 parametersΔρmax = 0.56 e Å−3
0 restraintsΔρmin = −0.65 e Å−3
Crystal data top
C27H25N3O3S·H2OV = 5227.2 (7) Å3
Mr = 489.57Z = 8
Monoclinic, C2/cMo Kα radiation
a = 31.083 (3) ŵ = 0.16 mm−1
b = 12.0766 (10) ÅT = 150 K
c = 14.7678 (12) Å0.28 × 0.15 × 0.10 mm
β = 109.446 (1)°
Data collection top
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 = 0.98Rint = 0.036
24570 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.140H-atom parameters constrained
S = 1.08Δρmax = 0.56 e Å−3
6682 reflectionsΔρmin = −0.65 e Å−3
319 parameters
Special details top

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).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.56861 (2)0.53645 (3)0.64405 (3)0.02434 (12)
O10.61317 (4)0.23972 (11)0.61342 (10)0.0415 (3)
O20.35098 (4)0.52166 (10)0.63445 (8)0.0294 (3)
O30.35101 (4)0.47141 (10)0.48800 (8)0.0312 (3)
N10.65244 (4)0.38651 (11)0.69843 (9)0.0247 (3)
H1A0.64990.44810.73180.030*
N20.52169 (5)0.22909 (12)0.60780 (12)0.0374 (4)
H2A0.54510.18050.61690.045*
H2B0.50280.21050.64100.045*
N30.48792 (4)0.62120 (11)0.63560 (9)0.0238 (3)
C10.69789 (5)0.34988 (13)0.71843 (11)0.0236 (3)
C20.71060 (6)0.26439 (15)0.66984 (14)0.0351 (4)
H20.68800.22520.62070.042*
C30.75638 (6)0.23609 (15)0.69314 (14)0.0367 (4)
H30.76460.17760.65900.044*
C40.79040 (6)0.29031 (15)0.76441 (13)0.0326 (4)
C50.77717 (5)0.37692 (15)0.81137 (13)0.0322 (4)
H50.79980.41660.85990.039*
C60.73187 (5)0.40666 (14)0.78915 (12)0.0276 (4)
H60.72380.46630.82240.033*
C70.83973 (6)0.25687 (19)0.79060 (16)0.0463 (5)
H7A0.84960.22090.85370.070*
H7B0.85850.32280.79280.070*
H7C0.84320.20520.74240.070*
C80.61337 (5)0.33272 (14)0.64630 (11)0.0259 (3)
C90.57069 (5)0.39261 (14)0.63448 (11)0.0246 (3)
C100.52928 (5)0.34191 (14)0.61994 (11)0.0262 (3)
C110.49407 (5)0.42133 (13)0.61750 (11)0.0229 (3)
C120.51150 (5)0.52967 (13)0.63232 (10)0.0218 (3)
C130.44362 (5)0.60840 (13)0.62383 (11)0.0238 (3)
C140.41817 (6)0.71201 (14)0.62923 (14)0.0325 (4)
H14A0.41400.71630.69210.049*
H14B0.38830.71110.57850.049*
H14C0.43560.77650.62060.049*
C150.42213 (5)0.50379 (14)0.60392 (11)0.0233 (3)
C160.44682 (5)0.40837 (13)0.60086 (11)0.0235 (3)
C170.42494 (5)0.29814 (14)0.57731 (12)0.0266 (3)
H170.42930.25820.52570.032*
C180.39976 (6)0.25193 (13)0.62341 (12)0.0270 (4)
H180.39560.29290.67480.032*
C190.37747 (5)0.14278 (13)0.60252 (12)0.0261 (3)
C200.38580 (6)0.06826 (14)0.53845 (13)0.0317 (4)
H200.40680.08720.50680.038*
C210.36377 (7)−0.03324 (15)0.52028 (14)0.0384 (4)
H210.3696−0.08330.47610.046*
C220.33324 (6)−0.06161 (15)0.56647 (15)0.0409 (5)
H220.3181−0.13110.55380.049*
C230.32477 (6)0.01048 (16)0.63069 (15)0.0389 (4)
H230.3039−0.00930.66250.047*
C240.34676 (6)0.11200 (15)0.64895 (13)0.0327 (4)
H240.34090.16130.69360.039*
C250.37130 (5)0.49932 (14)0.58031 (11)0.0241 (3)
C260.30137 (6)0.45925 (16)0.45613 (13)0.0360 (4)
H26A0.28890.46620.38530.043*
H26B0.28820.51930.48420.043*
C270.28784 (6)0.34965 (16)0.48538 (13)0.0353 (4)
H27A0.30250.29020.46110.053*
H27B0.25460.34140.45860.053*
H27C0.29750.34560.55560.053*
O40.52863 (6)0.82044 (15)0.59700 (12)0.0721 (5)
H4A0.51800.76680.62040.087*
H4B0.51070.82460.53930.087*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0185 (2)0.0275 (2)0.0272 (2)−0.00112 (15)0.00795 (16)0.00181 (16)
O10.0280 (7)0.0383 (8)0.0555 (9)0.0006 (5)0.0101 (6)−0.0201 (6)
O20.0242 (6)0.0343 (7)0.0320 (6)−0.0004 (5)0.0125 (5)0.0014 (5)
O30.0201 (6)0.0462 (8)0.0243 (6)−0.0060 (5)0.0034 (5)0.0045 (5)
N10.0203 (6)0.0260 (7)0.0276 (7)0.0027 (5)0.0078 (5)−0.0034 (6)
N20.0270 (8)0.0276 (8)0.0534 (10)−0.0002 (6)0.0077 (7)−0.0095 (7)
N30.0214 (7)0.0265 (7)0.0240 (7)−0.0003 (5)0.0080 (5)0.0021 (5)
C10.0203 (7)0.0264 (8)0.0265 (8)0.0029 (6)0.0109 (6)0.0043 (6)
C20.0285 (9)0.0325 (10)0.0461 (11)−0.0018 (7)0.0148 (8)−0.0099 (8)
C30.0337 (10)0.0288 (9)0.0538 (12)0.0065 (7)0.0227 (9)−0.0034 (8)
C40.0252 (8)0.0368 (10)0.0402 (10)0.0069 (7)0.0169 (8)0.0102 (8)
C50.0217 (8)0.0402 (10)0.0340 (9)0.0002 (7)0.0082 (7)−0.0002 (8)
C60.0261 (8)0.0300 (9)0.0283 (9)0.0026 (7)0.0113 (7)−0.0002 (7)
C70.0299 (10)0.0544 (13)0.0575 (13)0.0145 (9)0.0183 (9)0.0090 (10)
C80.0238 (8)0.0308 (9)0.0237 (8)0.0020 (7)0.0087 (6)−0.0029 (7)
C90.0221 (8)0.0276 (8)0.0227 (8)0.0004 (6)0.0058 (6)−0.0032 (6)
C100.0232 (8)0.0271 (8)0.0260 (8)0.0008 (6)0.0050 (6)−0.0047 (7)
C110.0212 (8)0.0264 (8)0.0201 (8)−0.0011 (6)0.0052 (6)−0.0012 (6)
C120.0189 (7)0.0295 (9)0.0166 (7)−0.0006 (6)0.0054 (6)0.0023 (6)
C130.0224 (8)0.0279 (8)0.0215 (8)0.0005 (6)0.0077 (6)0.0029 (6)
C140.0263 (9)0.0285 (9)0.0449 (10)0.0027 (7)0.0148 (8)0.0034 (8)
C150.0194 (7)0.0325 (8)0.0180 (7)−0.0012 (6)0.0064 (6)0.0009 (6)
C160.0213 (8)0.0289 (9)0.0198 (7)−0.0038 (6)0.0060 (6)−0.0016 (6)
C170.0230 (8)0.0283 (8)0.0269 (8)−0.0021 (6)0.0059 (6)−0.0049 (7)
C180.0278 (8)0.0261 (9)0.0269 (8)−0.0001 (7)0.0090 (7)−0.0030 (7)
C190.0226 (8)0.0244 (8)0.0292 (9)0.0009 (6)0.0058 (7)0.0004 (7)
C200.0320 (9)0.0291 (9)0.0344 (9)0.0008 (7)0.0114 (8)−0.0011 (7)
C210.0416 (11)0.0247 (9)0.0439 (11)0.0019 (8)0.0076 (9)−0.0053 (8)
C220.0349 (10)0.0233 (9)0.0583 (13)−0.0047 (8)0.0072 (9)0.0029 (8)
C230.0334 (10)0.0334 (10)0.0508 (12)−0.0021 (8)0.0152 (9)0.0087 (9)
C240.0316 (9)0.0305 (9)0.0385 (10)−0.0001 (7)0.0150 (8)−0.0002 (8)
C250.0219 (8)0.0257 (8)0.0234 (8)−0.0009 (6)0.0058 (6)0.0056 (6)
C260.0211 (8)0.0486 (11)0.0317 (9)−0.0066 (8)−0.0001 (7)0.0104 (8)
C270.0273 (9)0.0415 (10)0.0354 (10)−0.0079 (8)0.0081 (8)0.0008 (8)
O40.0651 (11)0.0779 (12)0.0635 (11)−0.0336 (9)0.0082 (9)0.0187 (9)
Geometric parameters (Å, º) top
S1—C121.7271 (15)C11—C161.415 (2)
S1—C91.7459 (17)C13—C151.413 (2)
O1—C81.223 (2)C13—C141.497 (2)
O2—C251.2030 (19)C14—H14A0.9800
O3—C251.341 (2)C14—H14B0.9800
O3—C261.4630 (19)C14—H14C0.9800
N1—C81.366 (2)C15—C161.394 (2)
N1—C11.4145 (19)C15—C251.501 (2)
N1—H1A0.9101C16—C171.483 (2)
N2—C101.384 (2)C17—C181.320 (2)
N2—H2A0.9102C17—H170.9500
N2—H2B0.9102C18—C191.473 (2)
N3—C121.336 (2)C18—H180.9500
N3—C131.3383 (19)C19—C201.391 (2)
C1—C21.388 (2)C19—C241.398 (2)
C1—C61.394 (2)C20—C211.386 (3)
C2—C31.391 (2)C20—H200.9500
C2—H20.9500C21—C221.384 (3)
C3—C41.383 (3)C21—H210.9500
C3—H30.9500C22—C231.376 (3)
C4—C51.391 (2)C22—H220.9500
C4—C71.506 (2)C23—C241.386 (3)
C5—C61.382 (2)C23—H230.9500
C5—H50.9500C24—H240.9500
C6—H60.9500C26—C271.496 (2)
C7—H7A0.9800C26—H26A0.9900
C7—H7B0.9800C26—H26B0.9900
C7—H7C0.9800C27—H27A0.9800
C8—C91.469 (2)C27—H27B0.9800
C9—C101.376 (2)C27—H27C0.9800
C10—C111.447 (2)O4—H4A0.8502
C11—C121.405 (2)O4—H4B0.8504
C12—S1—C990.52 (7)C13—C14—H14B109.5
C25—O3—C26116.17 (13)H14A—C14—H14B109.5
C8—N1—C1127.41 (14)C13—C14—H14C109.5
C8—N1—H1A118.3H14A—C14—H14C109.5
C1—N1—H1A113.7H14B—C14—H14C109.5
C10—N2—H2A121.4C16—C15—C13121.24 (14)
C10—N2—H2B106.6C16—C15—C25120.74 (14)
H2A—N2—H2B113.0C13—C15—C25117.92 (14)
C12—N3—C13116.93 (13)C15—C16—C11117.00 (14)
C2—C1—C6118.58 (14)C15—C16—C17122.37 (14)
C2—C1—N1124.13 (15)C11—C16—C17120.58 (14)
C6—C1—N1117.24 (14)C18—C17—C16124.27 (15)
C1—C2—C3119.92 (17)C18—C17—H17117.9
C1—C2—H2120.0C16—C17—H17117.9
C3—C2—H2120.0C17—C18—C19126.06 (15)
C4—C3—C2122.14 (17)C17—C18—H18117.0
C4—C3—H3118.9C19—C18—H18117.0
C2—C3—H3118.9C20—C19—C24118.26 (15)
C3—C4—C5117.21 (15)C20—C19—C18122.69 (15)
C3—C4—C7121.56 (17)C24—C19—C18119.05 (15)
C5—C4—C7121.23 (17)C21—C20—C19120.80 (17)
C6—C5—C4121.60 (16)C21—C20—H20119.6
C6—C5—H5119.2C19—C20—H20119.6
C4—C5—H5119.2C22—C21—C20119.96 (18)
C5—C6—C1120.53 (16)C22—C21—H21120.0
C5—C6—H6119.7C20—C21—H21120.0
C1—C6—H6119.7C23—C22—C21120.21 (17)
C4—C7—H7A109.5C23—C22—H22119.9
C4—C7—H7B109.5C21—C22—H22119.9
H7A—C7—H7B109.5C22—C23—C24119.92 (18)
C4—C7—H7C109.5C22—C23—H23120.0
H7A—C7—H7C109.5C24—C23—H23120.0
H7B—C7—H7C109.5C23—C24—C19120.86 (17)
O1—C8—N1123.12 (15)C23—C24—H24119.6
O1—C8—C9121.32 (15)C19—C24—H24119.6
N1—C8—C9115.52 (14)O2—C25—O3123.99 (14)
C10—C9—C8124.06 (15)O2—C25—C15125.62 (14)
C10—C9—S1113.42 (12)O3—C25—C15110.33 (13)
C8—C9—S1122.44 (12)O3—C26—C27111.33 (14)
C9—C10—N2124.64 (15)O3—C26—H26A109.4
C9—C10—C11111.68 (14)C27—C26—H26A109.4
N2—C10—C11123.67 (14)O3—C26—H26B109.4
C12—C11—C16117.02 (14)C27—C26—H26B109.4
C12—C11—C10111.35 (13)H26A—C26—H26B108.0
C16—C11—C10131.61 (15)C26—C27—H27A109.5
N3—C12—C11126.03 (14)C26—C27—H27B109.5
N3—C12—S1120.99 (12)H27A—C27—H27B109.5
C11—C12—S1112.96 (11)C26—C27—H27C109.5
N3—C13—C15121.66 (14)H27A—C27—H27C109.5
N3—C13—C14115.83 (14)H27B—C27—H27C109.5
C15—C13—C14122.46 (14)H4A—O4—H4B104.0
C13—C14—H14A109.5
C8—N1—C1—C215.6 (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—C30.9 (3)C12—N3—C13—C14179.16 (14)
N1—C1—C2—C3178.41 (16)N3—C13—C15—C163.5 (2)
C1—C2—C3—C40.3 (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—C7178.42 (18)C14—C13—C15—C254.6 (2)
C3—C4—C5—C61.1 (3)C13—C15—C16—C11−0.7 (2)
C7—C4—C5—C6−178.63 (17)C25—C15—C16—C11175.66 (13)
C4—C5—C6—C10.1 (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—O14.0 (3)C10—C11—C16—C15179.78 (16)
C1—N1—C8—C9−178.01 (14)C12—C11—C16—C17175.39 (14)
O1—C8—C9—C1024.8 (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—C18127.21 (18)
N1—C8—C9—S123.2 (2)C16—C17—C18—C19−179.93 (15)
C12—S1—C9—C101.85 (13)C17—C18—C19—C209.1 (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—C210.8 (3)
S1—C9—C10—N2178.41 (13)C18—C19—C20—C21−179.43 (16)
C8—C9—C10—C11176.00 (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—C240.2 (3)
N2—C10—C11—C12179.74 (15)C22—C23—C24—C190.3 (3)
C9—C10—C11—C16177.14 (16)C20—C19—C24—C23−0.8 (3)
N2—C10—C11—C16−2.1 (3)C18—C19—C24—C23179.43 (16)
C13—N3—C12—C110.1 (2)C26—O3—C25—O2−5.3 (2)
C13—N3—C12—S1178.62 (11)C26—O3—C25—C15177.44 (13)
C16—C11—C12—N32.6 (2)C16—C15—C25—O2117.80 (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—S12.45 (17)C13—C15—C25—O3111.48 (16)
C9—S1—C12—N3178.87 (13)C25—O3—C26—C27−79.71 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.912.172.9900 (17)149
N2—H2A···O10.912.252.820 (2)120
O4—H4A···N30.852.042.863 (2)163
O4—H4B···N2ii0.852.172.967 (2)157
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.912.172.9900 (17)149
N2—H2A···O10.912.252.820 (2)120
O4—H4A···N30.852.042.863 (2)163
O4—H4B···N2ii0.852.172.967 (2)157
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formulaC27H25N3O3S·H2O
Mr489.57
Crystal system, space groupMonoclinic, 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)
Z8
Radiation typeMo Kα
µ (mm−1)0.16
Crystal size (mm)0.28 × 0.15 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2015)
Tmin, Tmax0.86, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections		24570, 6682, 4746
Rint0.036
(sin θ/λ)max (Å−1)0.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.140, 1.08
No. of reflections6682
No. of parameters319
H-atom treatmentH-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

First citationBakhite, E. A. (2003). Phosphorus Sulfur Silicon, 178, 929–992.  Web of Science CrossRef CAS Google Scholar
 First citationBrandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
 First citationBruker (2015). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationHo, Y. W. & Wang, I. J. (1995). J. Heterocycl. Chem. 32, 819–825.  CrossRef CAS Google Scholar
 First citationLitvinov, V. P., Dotsenko, V. V. & Krivokolysko, S. G. (2005). Russ. Chem. Bull. 54, 864–904.  Web of Science CrossRef CAS 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. (2015a). Acta Cryst. A71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
 First citationSpek, A. L. (2015). Acta Cryst. C71, 9–18.  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.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 3| March 2016| Pages 297-299
doi:10.1107/S2056989016001341
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