2-[N-(4-Meth-oxy-phen-yl)acetamido]-1,3-thia-zol-4-yl acetate.

The structural analysis of the title compound, C14H14N2O4S, particularly the presence of an acetyl group at the exocyclic N atom and the C(H)-C(O2CMe)-N acet-oxy group in the thia-zole ring, may indicate that one of the starting materials, i.e. 2-(4-meth-oxy-anilino)-1,3-thia-zol-4(5H)-one, exists in the reaction mixture, at least partially, as a tautomer with an exocyclic amine N atom and an enol group. The acet-oxy and acetyl groups deviate from the thia-zole plane by 69.17 (6) and 7.25 (19)°, respectively. The thia-zole and benzene rings form a dihedral angle of 73.50 (4)°. In the crystal, centrosymmetrically related mol-ecules are connected into dimeric aggregates via C-H⋯O inter-actions.

Related literature

For the biological activity of 2-ar­yl(heter­yl)amino­thia­zol-4-one derivatives, see: Ates et al. (2000 ▶); Eleftheriou et al. (2012 ▶); Eriksson et al. (2007 ▶); Lesyk & Zimenkovsky (2004 ▶); Lesyk et al. (2003 ▶, 2011 ▶); Rout & Mahapatra (1955 ▶); Subtel’na et al. (2010 ▶). For prototropic tautomerism studies, see: Lesyk et al. (2003 ▶); Subtel’na et al. (2010 ▶). For bond-length data, see: Allen et al. (1987 ▶). For a related structural study, see: Horishny et al. (2013 ▶).

Experimental

Crystal data

C14H14N2O4S

M = 306.33

Triclinic,

a = 8.9445 (5) Å

b = 9.5736 (8) Å

c = 9.9078 (9) Å

α = 115.509 (9)°

β = 93.381 (6)°

γ = 108.144 (6)°

V = 708.95 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.25 mm−1

T = 130 K

0.50 × 0.50 × 0.10 mm

Data collection

Agilent Xcalibur Atlas diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.860, T max = 1.000

12469 measured reflections

3445 independent reflections

3075 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.095

S = 1.06

3445 reflections

193 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813004236/tk5195sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813004236/tk5195Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813004236/tk5195Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H14N2O4S	Z = 2
Mr = 306.33	F(000) = 320
Triclinic, P1	Dx = 1.435 Mg m−3
Hall symbol: -P 1	Melting point = 399–401 K
a = 8.9445 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5736 (8) Å	Cell parameters from 5310 reflections
c = 9.9078 (9) Å	θ = 2.3–29.1°
α = 115.509 (9)°	µ = 0.25 mm−1
β = 93.381 (6)°	T = 130 K
γ = 108.144 (6)°	Block, yellow
V = 708.95 (10) Å3	0.50 × 0.50 × 0.10 mm

Agilent Xcalibur Atlas diffractometer	3445 independent reflections
Radiation source: fine-focus sealed tube	3075 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 10.3088 pixels mm-1	θmax = 29.1°, θmin = 2.3°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→12
Tmin = 0.860, Tmax = 1.000	l = −12→13
12469 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.045P)2 + 0.2987P] where P = (Fo2 + 2Fc2)/3
3445 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	−0.09020 (4)	0.14762 (4)	0.45516 (4)	0.02269 (10)
C2	0.03052 (15)	0.08180 (16)	0.32947 (14)	0.0177 (2)
N3	0.16077 (13)	0.19958 (13)	0.34043 (12)	0.0191 (2)
C4	0.16774 (16)	0.34906 (16)	0.45435 (15)	0.0215 (3)
C5	0.04751 (17)	0.34910 (17)	0.52956 (16)	0.0249 (3)
H5	0.0399	0.4428	0.6090	0.030*
N6	−0.00495 (12)	−0.08552 (13)	0.22511 (12)	0.0182 (2)
C7	−0.14419 (16)	−0.20995 (17)	0.21360 (16)	0.0233 (3)
O8	−0.24272 (12)	−0.17289 (13)	0.28765 (13)	0.0308 (2)
C9	−0.16476 (18)	−0.38706 (18)	0.10871 (18)	0.0305 (3)
H9A	−0.2535	−0.4615	0.1245	0.046*
H9B	−0.0678	−0.4040	0.1305	0.046*
H9C	−0.1861	−0.4089	0.0040	0.046*
C10	0.11162 (15)	−0.12397 (15)	0.13403 (14)	0.0182 (2)
C11	0.25487 (16)	−0.11824 (17)	0.20057 (15)	0.0220 (3)
H11	0.2770	−0.0887	0.3042	0.026*
C12	0.36650 (16)	−0.15662 (17)	0.11261 (16)	0.0237 (3)
H12	0.4633	−0.1527	0.1569	0.028*
C13	0.33070 (16)	−0.20089 (16)	−0.04265 (16)	0.0229 (3)
C14	0.18573 (17)	−0.20726 (17)	−0.10887 (15)	0.0240 (3)
H14	0.1623	−0.2383	−0.2128	0.029*
C15	0.07619 (16)	−0.16761 (16)	−0.02071 (15)	0.0213 (3)
H15	−0.0201	−0.1701	−0.0645	0.026*
O16	0.42891 (13)	−0.24239 (14)	−0.14095 (12)	0.0321 (2)
C17	0.57663 (19)	−0.2456 (2)	−0.0825 (2)	0.0358 (4)
H17A	0.6389	−0.1390	0.0039	0.054*
H17B	0.6368	−0.2696	−0.1611	0.054*
H17C	0.5537	−0.3304	−0.0509	0.054*
O18	0.30433 (12)	0.49009 (12)	0.49350 (11)	0.0263 (2)
C19	0.31110 (16)	0.56737 (17)	0.40442 (16)	0.0238 (3)
O20	0.20654 (12)	0.51567 (14)	0.29430 (12)	0.0311 (2)
C21	0.46079 (18)	0.7203 (2)	0.4657 (2)	0.0372 (4)
H21A	0.5421	0.6945	0.4116	0.056*
H21B	0.4991	0.7596	0.5730	0.056*
H21C	0.4376	0.8053	0.4520	0.056*

	U11	U22	U33	U12	U13	U23
S1	0.02568 (18)	0.02852 (19)	0.02403 (18)	0.01508 (14)	0.01369 (13)	0.01672 (15)
C2	0.0191 (6)	0.0226 (6)	0.0167 (6)	0.0101 (5)	0.0062 (4)	0.0118 (5)
N3	0.0194 (5)	0.0210 (5)	0.0186 (5)	0.0081 (4)	0.0053 (4)	0.0102 (4)
C4	0.0252 (6)	0.0201 (6)	0.0195 (6)	0.0085 (5)	0.0027 (5)	0.0098 (5)
C5	0.0336 (7)	0.0255 (7)	0.0211 (6)	0.0165 (6)	0.0092 (5)	0.0117 (6)
N6	0.0182 (5)	0.0195 (5)	0.0183 (5)	0.0067 (4)	0.0064 (4)	0.0100 (4)
C7	0.0215 (6)	0.0257 (7)	0.0246 (7)	0.0057 (5)	0.0047 (5)	0.0157 (6)
O8	0.0236 (5)	0.0334 (6)	0.0390 (6)	0.0084 (4)	0.0141 (4)	0.0207 (5)
C9	0.0312 (7)	0.0221 (7)	0.0329 (8)	0.0028 (6)	0.0072 (6)	0.0135 (6)
C10	0.0212 (6)	0.0159 (5)	0.0181 (6)	0.0069 (5)	0.0075 (5)	0.0084 (5)
C11	0.0238 (6)	0.0241 (6)	0.0188 (6)	0.0087 (5)	0.0057 (5)	0.0110 (5)
C12	0.0208 (6)	0.0247 (6)	0.0258 (7)	0.0086 (5)	0.0051 (5)	0.0122 (6)
C13	0.0286 (7)	0.0173 (6)	0.0235 (7)	0.0086 (5)	0.0122 (5)	0.0095 (5)
C14	0.0343 (7)	0.0217 (6)	0.0158 (6)	0.0108 (5)	0.0068 (5)	0.0084 (5)
C15	0.0249 (6)	0.0200 (6)	0.0196 (6)	0.0085 (5)	0.0036 (5)	0.0098 (5)
O16	0.0367 (6)	0.0362 (6)	0.0288 (5)	0.0192 (5)	0.0182 (4)	0.0148 (5)
C17	0.0318 (8)	0.0345 (8)	0.0471 (10)	0.0178 (7)	0.0216 (7)	0.0192 (7)
O18	0.0276 (5)	0.0202 (5)	0.0259 (5)	0.0053 (4)	0.0000 (4)	0.0097 (4)
C19	0.0227 (6)	0.0233 (6)	0.0278 (7)	0.0112 (5)	0.0095 (5)	0.0120 (6)
O20	0.0288 (5)	0.0357 (6)	0.0291 (5)	0.0071 (4)	0.0047 (4)	0.0194 (5)
C21	0.0253 (7)	0.0317 (8)	0.0537 (10)	0.0046 (6)	0.0024 (7)	0.0245 (8)

S1—C5	1.7233 (15)	C11—H11	0.9300
S1—C2	1.7379 (12)	C12—C13	1.3944 (19)
C2—N3	1.3046 (16)	C12—H12	0.9300
C2—N6	1.3979 (17)	C13—O16	1.3649 (16)
N3—C4	1.3678 (17)	C13—C14	1.390 (2)
C4—C5	1.3439 (19)	C14—C15	1.3835 (18)
C4—O18	1.3899 (16)	C14—H14	0.9300
C5—H5	0.9300	C15—H15	0.9300
N6—C7	1.3876 (16)	O16—C17	1.4258 (19)
N6—C10	1.4494 (15)	C17—H17A	0.9600
C7—O8	1.2196 (17)	C17—H17B	0.9600
C7—C9	1.501 (2)	C17—H17C	0.9600
C9—H9A	0.9600	O18—C19	1.3677 (17)
C9—H9B	0.9600	C19—O20	1.1984 (17)
C9—H9C	0.9600	C19—C21	1.491 (2)
C10—C11	1.3801 (18)	C21—H21A	0.9600
C10—C15	1.3907 (18)	C21—H21B	0.9600
C11—C12	1.3953 (18)	C21—H21C	0.9600
C5—S1—C2	88.70 (6)	C13—C12—C11	119.01 (12)
N3—C2—N6	121.23 (11)	C13—C12—H12	120.5
N3—C2—S1	115.46 (10)	C11—C12—H12	120.5
N6—C2—S1	123.30 (9)	O16—C13—C14	114.88 (12)
C2—N3—C4	108.79 (11)	O16—C13—C12	124.64 (13)
C5—C4—N3	118.01 (12)	C14—C13—C12	120.48 (12)
C5—C4—O18	123.64 (12)	C15—C14—C13	120.23 (12)
N3—C4—O18	118.17 (11)	C15—C14—H14	119.9
C4—C5—S1	109.03 (10)	C13—C14—H14	119.9
C4—C5—H5	125.5	C14—C15—C10	119.31 (12)
S1—C5—H5	125.5	C14—C15—H15	120.3
C7—N6—C2	120.87 (11)	C10—C15—H15	120.3
C7—N6—C10	121.59 (11)	C13—O16—C17	117.97 (12)
C2—N6—C10	117.51 (10)	O16—C17—H17A	109.5
O8—C7—N6	119.90 (12)	O16—C17—H17B	109.5
O8—C7—C9	123.04 (12)	H17A—C17—H17B	109.5
N6—C7—C9	117.05 (12)	O16—C17—H17C	109.5
C7—C9—H9A	109.5	H17A—C17—H17C	109.5
C7—C9—H9B	109.5	H17B—C17—H17C	109.5
H9A—C9—H9B	109.5	C19—O18—C4	117.42 (10)
C7—C9—H9C	109.5	O20—C19—O18	122.46 (12)
H9A—C9—H9C	109.5	O20—C19—C21	126.78 (13)
H9B—C9—H9C	109.5	O18—C19—C21	110.75 (12)
C11—C10—C15	120.86 (12)	C19—C21—H21A	109.5
C11—C10—N6	120.11 (11)	C19—C21—H21B	109.5
C15—C10—N6	119.03 (11)	H21A—C21—H21B	109.5
C10—C11—C12	120.11 (12)	C19—C21—H21C	109.5
C10—C11—H11	119.9	H21A—C21—H21C	109.5
C12—C11—H11	119.9	H21B—C21—H21C	109.5
C5—S1—C2—N3	−0.81 (10)	C7—N6—C10—C15	75.64 (16)
C5—S1—C2—N6	177.79 (11)	C2—N6—C10—C15	−106.51 (13)
N6—C2—N3—C4	−177.87 (11)	C15—C10—C11—C12	−0.1 (2)
S1—C2—N3—C4	0.76 (13)	N6—C10—C11—C12	179.45 (11)
C2—N3—C4—C5	−0.29 (16)	C10—C11—C12—C13	−0.1 (2)
C2—N3—C4—O18	174.95 (10)	C11—C12—C13—O16	−179.44 (12)
N3—C4—C5—S1	−0.30 (15)	C11—C12—C13—C14	−0.2 (2)
O18—C4—C5—S1	−175.25 (10)	O16—C13—C14—C15	−179.91 (12)
C2—S1—C5—C4	0.58 (10)	C12—C13—C14—C15	0.8 (2)
N3—C2—N6—C7	−179.65 (11)	C13—C14—C15—C10	−1.00 (19)
S1—C2—N6—C7	1.83 (17)	C11—C10—C15—C14	0.63 (19)
N3—C2—N6—C10	2.48 (17)	N6—C10—C15—C14	−178.89 (11)
S1—C2—N6—C10	−176.04 (9)	C14—C13—O16—C17	−177.34 (12)
C2—N6—C7—O8	4.96 (19)	C12—C13—O16—C17	1.9 (2)
C10—N6—C7—O8	−177.26 (12)	C5—C4—O18—C19	−102.83 (15)
C2—N6—C7—C9	−174.65 (12)	N3—C4—O18—C19	82.22 (15)
C10—N6—C7—C9	3.14 (18)	C4—O18—C19—O20	−1.67 (19)
C7—N6—C10—C11	−103.88 (14)	C4—O18—C19—C21	177.30 (12)
C2—N6—C10—C11	73.97 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O20i	0.93	2.53	3.200 (2)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O20i	0.93	2.53	3.200 (2)	129

Symmetry code: (i) .