2-[N-(2,4-Dimeth­oxy­phen­yl)acetamido]-1,3-thia­zol-4-yl acetate

Horishny, V.; Lesyk, R.; Kowiel, M.; Gzella, A.K.

doi:10.1107/S1600536813003474

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Pages o356-o357

doi:10.1107/S1600536813003474

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2-[N-(2,4-Dimethoxyphenyl)acetamido]-1,3-thiazol-4-yl acetate

Volodymyr Horishny,^a Roman Lesyk,^a Marcin Kowiel ^b and Andrzej K. Gzella ^b,^c ^*

^aDepartment of Pharmaceutical, Organic and Bioorganic Chemistry, Danylo Halytsky Lviv National Medical University, Pekarska 69, Lviv, 79010, Ukraine, ^bDepartment of Organic Chemistry, Poznan University of Medical Sciences, ul. Grunwaldzka 6, 60-780 Poznań, Poland, and ^cFaculty of Pharmacy, Ludwik Rydygier Collegium Medicum in Bydgoszcz, Nicolaus Copernicus University in Torun, ul. A. Jurasza 2, 85-089 Bydgoszcz, Poland
^*Correspondence e-mail: akgzella@ump.edu.pl

(Received 1 February 2013; accepted 4 February 2013; online 9 February 2013)

The title compound, C₁₅H₁₆N₂O₅S, is a product of the reaction of 2-(2,4-dimethoxyphenylamino)-1,3-thiazol-4(5H)-one with acetic anhydride. The presence of the acetyl and acetoxy groups in the molecule indicates that the starting thiazole exists as a tautomer in the reaction mixture with exocyclic amino and enol moieties. The acetyl group is tilted slightly from the heterocyclic ring plane [dihedral angle = 4.46 (11)°], while the acetoxy group is almost perpendicular to this ring [dihedral angle = 88.14 (12)°]. An intramolecular acetyl–methoxy C—H⋯O interaction is noted. In the crystal, molecules are connected into a three-dimensional architecture by C—H⋯O interactions.

Related literature

For the biological activity of 2-arylaminothiazol-4-one derivatives, see: Chen et al. (2007 ); Eriksson et al. (2007 ); Lesyk & Zimenkovsky (2004 ); Lesyk et al. (2011 ); Ottana et al. (2005 ); Subtelna et al. (2010 ); Vassilev et al. (2006 ). For prototropic tautomerism studies, see: Subtelna et al. (2010); Lesyk et al. (2003 ); Vana et al. (2009 ).

Experimental

Crystal data

C₁₅H₁₆N₂O₅S
M_r = 336.36
Triclinic, $[P \overline 1]$
a = 9.1486 (11) Å
b = 9.3592 (13) Å
c = 10.2823 (8) Å
α = 69.212 (10)°
β = 82.910 (8)°
γ = 77.220 (11)°
V = 801.73 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 130 K
0.30 × 0.30 × 0.10 mm

Data collection

Agilent Xcalibur Atlas diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 $[Agilent (2011). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.919, T_max = 1.000
10576 measured reflections
3822 independent reflections
3281 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.093
S = 1.06
3822 reflections
212 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O16	0.96	2.57	3.1838 (19)	122
C5—H5⋯O18ⁱ	0.93	2.47	3.2465 (18)	141
C15—H15⋯O8ⁱⁱ	0.93	2.52	3.3117 (18)	143
C17—H17C⋯O8ⁱⁱⁱ	0.96	2.35	3.2945 (19)	170
Symmetry codes: (i) x, y-1, z+1; (ii) -x+1, -y+1, -z; (iii) -x, -y+1, -z.

Data collection: CrysAlis PRO (Agilent, 2011 $[Agilent (2011). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813003474/tk5194sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813003474/tk5194Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813003474/tk5194Isup3.cml

checkCIF report

Comment top

2-Arylaminothiazol-4-one derivatives are of great importance in modern medicinal chemistry of anticancer agents (Lesyk & Zimenkovsky, 2004; Lesyk et al., 2011). In particular, these heterocycles demonstrated inhibition of the HT29 cell line (colon cancer), characterized by a high COX-2 expression (Ottana et al., 2005), as well as CDK1/cyclin B inhibition (Chen et al., 2007). These effects were achieved by block of cell cycle progression at the G2/M phase border in reversible manner and induction of apoptosis (Vassilev et al., 2006). Antagonizing stimulatory effects of free fatty acids at cell proliferation (inhibitory effect on tumor survival) in human breast cancer cell line (MDA-MB-231) was reported as well for the benzylidene-2-arylaminothiazol-4-ones (Eriksson et al., 2007). Series of novel 5-arylidene-2-arylaminothiazol-4(5H)-ones were evaluated for the anticancer potential, in vitro, against the standard US National Cancer Institute's panel of 60 cancer cell lines. The majority of compounds showed significant cytotoxicity at micromolar and submicromolar concentrations; mean log(GI₅₀) range -5.77 to -4.35. Some of the most potent compounds possessed selectively high effects on all leukemia cell lines at the submicromolar level (Subtelna et al., 2010).

Prototropic tautomerism of 2-aminothiazol-4-ones presents an interesting target for studies of both molecular structures and spectroscopic properties (Subtelna et al., 2010; Lesyk et al., 2003; Vana et al., 2009). Motivated by previous research of 2-arylaminothiazol-4-one derivatives, the aim of the present work was to synthesize the title compound (I) as a starting substance for further design of new anticancer agents.

The studies on the structure of compound (I), a product of the reaction of 2-(2,4-dimethoxyphenylamino)-1,3-thiazol-4-one with acetic anhydride, showed the presence of acetoxy and acetyl groups attached respectively at C4 and N6 positions of the compound (Fig. 1). This observation indicates that the starting material exists in the reaction mixture as a tautomer with an exocyclic amino nitrogen atom and additionally an enol moiety (H—)C5═C4—OH in the heterocyclic ring. The acetyl and acetoxy groups are oriented differently relative to the planar thiazole ring. The acetyl group at N6 is tilted only slightly [dihedral angle: 4.46 (11)°] whereas the acetoxy group at C4 is almost perpendicular to this ring [dihedral angle: 88.14 (12)°] (Fig. 1). Worthy of mention is the fact that the C7═ O8 and C21═O22 carbonyl groups are synperiplanar in relation to the C2—N6 and C4—O20, respectively. The torsion angles C2—N6—C7—O8 and C4—O20—C21—O22 are -1.16 (19) and 12.0 (2)°, respectively.

The methoxy groups on C11 and C14 of the phenyl ring are tilted to a small but statistically significant extent. The torsional angles C12—C11—O16—C17 and C12—C13—O18—C19 have the same value of 11.2 (2)°.

The phenyl ring of the 2,4-dimethoxyphenylamino substituent forms a dihedral angle of 73.17 (5)° with the planar thiazole ring. Such an orientation is supported by nonclassical C9—H9A···O16 intramolecular and O15—H15···O8ⁱⁱ intermolecular hydrogen bonding (Table 1).

In the crystal lattice, the molecules of compound (I) are connected by three-centre hydrogen bonds C17ⁱ—H17Cⁱ···O8···H15ⁱⁱ—C15ⁱⁱ into ribbons parallel to the a axis. According to the graph method for categorizing hydrogen bonds, this pattern can be classified as ring motifs R₂²(16) and R₂²(12) (Fig. 2). The neighbouring ribbons are linked further through the C5—H5···O18ⁱⁱⁱ contacts into layers growing parallel to the (011) plane (Fig. 3).

Related literature top

For the biological activity of 2-arylaminothiazol-4-one derivatives, see: Chen et al. (2007); Eriksson et al. (2007); Lesyk & Zimenkovsky (2004); Lesyk et al. (2011); Ottana et al. (2005); Subtelna et al. (2010); Vassilev et al. (2006). For prototropic tautomerism studies, see: Subtelna et al. (2010); Lesyk et al. (2003); Vana et al. (2009).

Experimental top

2-(2,4-Dimethoxyphenyl)thiazol-4-one (1 g) in the medium of acetic anhydride was refluxed for 2 h. The obtained solution was evaporated in vacuum and the residue was recrystallized twice from mixtures benzene–hexane (1:1) and CCl₄ – hexane (1:1). Crystals were obtained from its methanol solution by evaporation at room temperature.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) together with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as spheres of arbitrary radii.
	Fig. 2. The hydrogen bonding (dotted lines) in (I), viewed approximately down the c axis. Symmetry codes: (i) -x, 1 - y, -z; (ii) 1 - x, 1 - y, -z. The ring graph symbols are shown. H atoms not involved in hydrogen bonds have been omitted for clarity.
	Fig. 3. The hydrogen bonding (dotted lines) in (I), viewed approximately down the a axis. Symmetry code: (iii) x, -1 + y, 1 + z. H atoms not involved in hydrogen bonds have been omitted for clarity.

2-[N-(2,4-Dimethoxyphenyl)acetamido]-1,3-thiazol-4-yl acetate top

Crystal data top

C₁₅H₁₆N₂O₅S	Z = 2
M_r = 336.36	F(000) = 352
Triclinic, P1	D_x = 1.393 Mg m⁻³
Hall symbol: -P 1	Melting point = 391–393 K
a = 9.1486 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3592 (13) Å	Cell parameters from 4534 reflections
c = 10.2823 (8) Å	θ = 2.1–29.0°
α = 69.212 (10)°	µ = 0.23 mm⁻¹
β = 82.910 (8)°	T = 130 K
γ = 77.220 (11)°	Plate, light-orange
V = 801.73 (16) Å³	0.30 × 0.30 × 0.10 mm

Data collection top

Agilent Xcalibur Atlas diffractometer	3822 independent reflections
Radiation source: fine-focus sealed tube	3281 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 10.3088 pixels mm^-1	θ_max = 29.1°, θ_min = 2.1°
ω scans	h = −11→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→11
T_min = 0.919, T_max = 1.000	l = −13→13
10576 measured reflections

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0432P)² + 0.2365P] where P = (F_o² + 2F_c²)/3
3822 reflections	(Δ/σ)_max < 0.001
212 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₅H₁₆N₂O₅S	γ = 77.220 (11)°
M_r = 336.36	V = 801.73 (16) Å³
Triclinic, P1	Z = 2
a = 9.1486 (11) Å	Mo Kα radiation
b = 9.3592 (13) Å	µ = 0.23 mm⁻¹
c = 10.2823 (8) Å	T = 130 K
α = 69.212 (10)°	0.30 × 0.30 × 0.10 mm
β = 82.910 (8)°

Data collection top

Agilent Xcalibur Atlas diffractometer	3822 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	3281 reflections with I > 2σ(I)
T_min = 0.919, T_max = 1.000	R_int = 0.023
10576 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.06	Δρ_max = 0.27 e Å⁻³
3822 reflections	Δρ_min = −0.31 e Å⁻³
212 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.32458 (4)	0.43206 (4)	0.29160 (4)	0.02952 (11)
C2	0.31474 (13)	0.61823 (14)	0.16952 (13)	0.0216 (3)
N3	0.32110 (12)	0.72722 (12)	0.21915 (11)	0.0230 (2)
C4	0.33664 (14)	0.66136 (16)	0.35971 (14)	0.0263 (3)
C5	0.34049 (15)	0.50714 (17)	0.41887 (15)	0.0310 (3)
H5	0.3502	0.4503	0.5132	0.037*
N6	0.29963 (12)	0.65332 (12)	0.02702 (11)	0.0216 (2)
C7	0.30067 (14)	0.53574 (15)	−0.02554 (15)	0.0260 (3)
O8	0.31721 (12)	0.40055 (11)	0.05240 (12)	0.0346 (2)
C9	0.28173 (17)	0.58190 (17)	−0.17857 (16)	0.0319 (3)
H9A	0.1797	0.6325	−0.1990	0.048*
H9B	0.3057	0.4908	−0.2054	0.048*
H9C	0.3477	0.6521	−0.2293	0.048*
C10	0.27699 (14)	0.81557 (14)	−0.05890 (12)	0.0194 (2)
C11	0.13373 (14)	0.89309 (14)	−0.10249 (12)	0.0190 (2)
C12	0.10876 (14)	1.05180 (14)	−0.18041 (12)	0.0195 (2)
H12	0.0137	1.1044	−0.2108	0.023*
C13	0.22900 (14)	1.13041 (14)	−0.21197 (12)	0.0197 (2)
C14	0.37236 (14)	1.05301 (15)	−0.17013 (13)	0.0215 (3)
H14	0.4517	1.1063	−0.1933	0.026*
C15	0.39576 (14)	0.89529 (14)	−0.09341 (13)	0.0212 (3)
H15	0.4914	0.8424	−0.0648	0.025*
O16	0.02463 (10)	0.80501 (10)	−0.06499 (9)	0.0232 (2)
C17	−0.11652 (15)	0.87342 (16)	−0.12963 (15)	0.0286 (3)
H17A	−0.1002	0.9041	−0.2290	0.043*
H17B	−0.1623	0.9632	−0.1043	0.043*
H17C	−0.1814	0.7988	−0.0988	0.043*
O18	0.21456 (10)	1.28646 (10)	−0.28607 (9)	0.0248 (2)
C19	0.06590 (15)	1.37616 (15)	−0.31019 (16)	0.0302 (3)
H19A	0.0173	1.3412	−0.3677	0.045*
H19B	0.0707	1.4841	−0.3562	0.045*
H19C	0.0099	1.3634	−0.2228	0.045*
O20	0.35830 (11)	0.76068 (12)	0.42650 (10)	0.0312 (2)
C21	0.23193 (17)	0.84306 (18)	0.47107 (14)	0.0322 (3)
O22	0.11015 (12)	0.81482 (15)	0.47434 (13)	0.0452 (3)
C23	0.2701 (2)	0.9684 (2)	0.51145 (18)	0.0450 (4)
H23A	0.3330	0.9221	0.5896	0.067*
H23B	0.1796	1.0297	0.5362	0.067*
H23C	0.3223	1.0338	0.4344	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02693 (19)	0.01603 (17)	0.0364 (2)	−0.00475 (13)	−0.00359 (14)	0.00326 (14)
C2	0.0166 (6)	0.0141 (6)	0.0289 (6)	−0.0034 (4)	−0.0025 (5)	−0.0002 (5)
N3	0.0214 (5)	0.0197 (5)	0.0247 (5)	−0.0049 (4)	−0.0030 (4)	−0.0024 (4)
C4	0.0199 (6)	0.0288 (7)	0.0260 (6)	−0.0061 (5)	−0.0036 (5)	−0.0027 (5)
C5	0.0248 (7)	0.0315 (7)	0.0273 (7)	−0.0073 (6)	−0.0039 (5)	0.0033 (6)
N6	0.0226 (5)	0.0127 (5)	0.0274 (5)	−0.0042 (4)	−0.0026 (4)	−0.0034 (4)
C7	0.0198 (6)	0.0190 (6)	0.0405 (8)	−0.0052 (5)	0.0000 (5)	−0.0113 (6)
O8	0.0358 (6)	0.0157 (5)	0.0515 (7)	−0.0058 (4)	−0.0038 (5)	−0.0094 (4)
C9	0.0333 (8)	0.0275 (7)	0.0409 (8)	−0.0067 (6)	−0.0005 (6)	−0.0187 (6)
C10	0.0245 (6)	0.0127 (5)	0.0204 (6)	−0.0049 (5)	−0.0016 (5)	−0.0038 (5)
C11	0.0206 (6)	0.0179 (6)	0.0200 (6)	−0.0075 (5)	0.0002 (4)	−0.0062 (5)
C12	0.0198 (6)	0.0175 (6)	0.0200 (6)	−0.0041 (4)	−0.0019 (4)	−0.0044 (5)
C13	0.0261 (6)	0.0151 (6)	0.0174 (5)	−0.0064 (5)	0.0000 (5)	−0.0036 (5)
C14	0.0217 (6)	0.0196 (6)	0.0240 (6)	−0.0091 (5)	0.0004 (5)	−0.0059 (5)
C15	0.0196 (6)	0.0194 (6)	0.0243 (6)	−0.0038 (5)	−0.0023 (5)	−0.0065 (5)
O16	0.0211 (4)	0.0170 (4)	0.0303 (5)	−0.0082 (3)	−0.0020 (4)	−0.0035 (4)
C17	0.0240 (7)	0.0261 (7)	0.0361 (7)	−0.0109 (5)	−0.0056 (5)	−0.0061 (6)
O18	0.0244 (5)	0.0154 (4)	0.0291 (5)	−0.0067 (3)	−0.0030 (4)	0.0017 (4)
C19	0.0272 (7)	0.0177 (6)	0.0388 (8)	−0.0046 (5)	−0.0097 (6)	0.0015 (6)
O20	0.0287 (5)	0.0387 (6)	0.0271 (5)	−0.0107 (4)	−0.0029 (4)	−0.0092 (4)
C21	0.0339 (8)	0.0385 (8)	0.0226 (6)	−0.0085 (6)	−0.0043 (5)	−0.0066 (6)
O22	0.0312 (6)	0.0562 (8)	0.0564 (7)	−0.0090 (5)	−0.0007 (5)	−0.0290 (6)
C23	0.0506 (10)	0.0543 (11)	0.0388 (9)	−0.0167 (8)	−0.0028 (7)	−0.0222 (8)

Geometric parameters (Å, º) top

S1—C5	1.7240 (16)	C12—H12	0.9300
S1—C2	1.7394 (13)	C13—O18	1.3714 (14)
C2—N3	1.3067 (17)	C13—C14	1.3884 (18)
C2—N6	1.4008 (17)	C14—C15	1.3865 (17)
N3—C4	1.3669 (17)	C14—H14	0.9300
C4—C5	1.347 (2)	C15—H15	0.9300
C4—O20	1.3941 (17)	O16—C17	1.4364 (16)
C5—H5	0.9300	C17—H17A	0.9600
N6—C7	1.3855 (17)	C17—H17B	0.9600
N6—C10	1.4433 (15)	C17—H17C	0.9600
C7—O8	1.2212 (16)	O18—C19	1.4305 (16)
C7—C9	1.498 (2)	C19—H19A	0.9600
C9—H9A	0.9600	C19—H19B	0.9600
C9—H9B	0.9600	C19—H19C	0.9600
C9—H9C	0.9600	O20—C21	1.3663 (18)
C10—C11	1.3923 (17)	C21—O22	1.1945 (18)
C10—C15	1.3924 (17)	C21—C23	1.494 (2)
C11—O16	1.3667 (14)	C23—H23A	0.9600
C11—C12	1.3967 (17)	C23—H23B	0.9600
C12—C13	1.3989 (17)	C23—H23C	0.9600

C5—S1—C2	88.67 (7)	O18—C13—C12	123.00 (11)
N3—C2—N6	120.83 (11)	C14—C13—C12	121.30 (11)
N3—C2—S1	115.54 (10)	C15—C14—C13	119.16 (11)
N6—C2—S1	123.63 (10)	C15—C14—H14	120.4
C2—N3—C4	108.68 (11)	C13—C14—H14	120.4
C5—C4—N3	118.10 (13)	C14—C15—C10	120.40 (11)
C5—C4—O20	126.10 (12)	C14—C15—H15	119.8
N3—C4—O20	115.62 (12)	C10—C15—H15	119.8
C4—C5—S1	109.00 (10)	C11—O16—C17	117.33 (10)
C4—C5—H5	125.5	O16—C17—H17A	109.5
S1—C5—H5	125.5	O16—C17—H17B	109.5
C7—N6—C2	120.34 (11)	H17A—C17—H17B	109.5
C7—N6—C10	122.54 (11)	O16—C17—H17C	109.5
C2—N6—C10	117.07 (10)	H17A—C17—H17C	109.5
O8—C7—N6	119.83 (13)	H17B—C17—H17C	109.5
O8—C7—C9	122.69 (12)	C13—O18—C19	117.54 (10)
N6—C7—C9	117.48 (12)	O18—C19—H19A	109.5
C7—C9—H9A	109.5	O18—C19—H19B	109.5
C7—C9—H9B	109.5	H19A—C19—H19B	109.5
H9A—C9—H9B	109.5	O18—C19—H19C	109.5
C7—C9—H9C	109.5	H19A—C19—H19C	109.5
H9A—C9—H9C	109.5	H19B—C19—H19C	109.5
H9B—C9—H9C	109.5	C21—O20—C4	116.53 (11)
C11—C10—C15	120.31 (11)	O22—C21—O20	122.45 (14)
C11—C10—N6	119.22 (10)	O22—C21—C23	127.05 (15)
C15—C10—N6	120.42 (11)	O20—C21—C23	110.50 (13)
O16—C11—C10	116.17 (10)	C21—C23—H23A	109.5
O16—C11—C12	123.96 (11)	C21—C23—H23B	109.5
C10—C11—C12	119.87 (11)	H23A—C23—H23B	109.5
C11—C12—C13	118.95 (11)	C21—C23—H23C	109.5
C11—C12—H12	120.5	H23A—C23—H23C	109.5
C13—C12—H12	120.5	H23B—C23—H23C	109.5
O18—C13—C14	115.70 (10)

C5—S1—C2—N3	−0.65 (10)	C15—C10—C11—O16	179.31 (11)
C5—S1—C2—N6	179.91 (11)	N6—C10—C11—O16	−3.12 (17)
N6—C2—N3—C4	−179.64 (11)	C15—C10—C11—C12	−0.44 (18)
S1—C2—N3—C4	0.91 (14)	N6—C10—C11—C12	177.13 (11)
C2—N3—C4—C5	−0.79 (17)	O16—C11—C12—C13	179.61 (11)
C2—N3—C4—O20	174.60 (11)	C10—C11—C12—C13	−0.66 (18)
N3—C4—C5—S1	0.31 (16)	C11—C12—C13—O18	−179.03 (11)
O20—C4—C5—S1	−174.54 (11)	C11—C12—C13—C14	1.49 (18)
C2—S1—C5—C4	0.17 (10)	O18—C13—C14—C15	179.30 (11)
N3—C2—N6—C7	176.71 (11)	C12—C13—C14—C15	−1.19 (19)
S1—C2—N6—C7	−3.88 (17)	C13—C14—C15—C10	0.06 (18)
N3—C2—N6—C10	−5.82 (17)	C11—C10—C15—C14	0.75 (18)
S1—C2—N6—C10	173.58 (9)	N6—C10—C15—C14	−176.78 (11)
C2—N6—C7—O8	−1.16 (19)	C10—C11—O16—C17	−168.59 (11)
C10—N6—C7—O8	−178.48 (11)	C12—C11—O16—C17	11.15 (17)
C2—N6—C7—C9	179.13 (11)	C14—C13—O18—C19	−169.30 (11)
C10—N6—C7—C9	1.80 (18)	C12—C13—O18—C19	11.20 (17)
C7—N6—C10—C11	74.41 (16)	C5—C4—O20—C21	−97.28 (16)
C2—N6—C10—C11	−102.99 (13)	N3—C4—O20—C21	87.75 (14)
C7—N6—C10—C15	−108.02 (14)	C4—O20—C21—O22	12.0 (2)
C2—N6—C10—C15	74.57 (15)	C4—O20—C21—C23	−167.56 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O16	0.96	2.57	3.1838 (19)	122
C5—H5···O18ⁱ	0.93	2.47	3.2465 (18)	141
C15—H15···O8ⁱⁱ	0.93	2.52	3.3117 (18)	143
C17—H17C···O8ⁱⁱⁱ	0.96	2.35	3.2945 (19)	170

Symmetry codes: (i) x, y−1, z+1; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₆N₂O₅S
M_r	336.36
Crystal system, space group	Triclinic, P1
Temperature (K)	130
a, b, c (Å)	9.1486 (11), 9.3592 (13), 10.2823 (8)
α, β, γ (°)	69.212 (10), 82.910 (8), 77.220 (11)
V (Å³)	801.73 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.30 × 0.30 × 0.10

Data collection
Diffractometer	Agilent Xcalibur Atlas diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.919, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10576, 3822, 3281
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.093, 1.06
No. of reflections	3822
No. of parameters	212
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.31

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O16	0.96	2.57	3.1838 (19)	122
C5—H5···O18ⁱ	0.93	2.47	3.2465 (18)	141
C15—H15···O8ⁱⁱ	0.93	2.52	3.3117 (18)	143
C17—H17C···O8ⁱⁱⁱ	0.96	2.35	3.2945 (19)	170

Symmetry codes: (i) x, y−1, z+1; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z.

References

Agilent (2011). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Chen, S., Chen, L., Le, N. T., Zhao, C., Sidduri, A., Lou, J. P., Michoud, C., Portland, L., Jackson, N. & Liu, J. J. (2007). Bioorg. Med. Chem. Lett. 17, 2134-2138. Web of Science CrossRef PubMed CAS Google Scholar
Eriksson, B., Kurz, G., Hedberg, C. & Westman, J. (2007). Patent No. WO2007010273. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Lesyk, R. B. & Zimenkovsky, B. S. (2004). Curr. Org. Chem. 8, 1547–1577. Web of Science CrossRef CAS Google Scholar
Lesyk, R. B., Zimenkovsky, B. S., Kaminskyy, D. V., Kryshchyshyn, A. P., Havrylyuk, D. Ya., Atamanyuk, D. V., Subtel'na, I. Yu. & Khyluk, D. V. (2011). Biopolym. Cell. 27, 107–117. CrossRef CAS Google Scholar
Lesyk, R., Zimenkovsky, B., Subtelna, I., Nektegayev, I. & Kazmirchuk, G. (2003). Acta Pol. Pharm. 60, 457–466. PubMed CAS Google Scholar
Ottana, R., Carotti, S., Maccari, R., Landini, I., Chiricosta, G., Caciagli, B., Vigorita, M. G. & Mini, E. (2005). Bioorg. Med. Chem. Lett. 15, 3930–3933. Web of Science PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Subtelna, I., Atamanyuk, D., Szymańska, E., Kieć-Kononowicz, K., Zimenkovsky, B., Vasylenko, O., Gzella, A. & Lesyk, R. (2010). Bioorg. Med. Chem. 18, 5089–5101. Google Scholar
Vana, J., Hanusek, J., Ruzicka, A. & Sedlak, M. (2009). J. Heterocycl. Chem. 46, 635–639. CAS Google Scholar
Vassilev, L. T., Tovar, C., Chen, S., Knezevic, D., Zhao, X., Sun, H., Heimbrook, D. C. & Chen, L. (2006). Proc. Natl Acad. Sci. USA, 103, 10660–10665. Web of Science CrossRef PubMed CAS Google Scholar

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Volume 69| Part 3| March 2013| Pages o356-o357

doi:10.1107/S1600536813003474

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