Ethyl 2-[(tert-but­oxy­carbon­yl)amino]­thia­zole-5-carboxyl­ate

Wang, W.; Zhong, B.; Shi, W.

doi:10.1107/S1600536812005971

organic compounds

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Volume 68| Part 3| March 2012| Page o747

doi:10.1107/S1600536812005971

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Ethyl 2-[(tert-butoxycarbonyl)amino]thiazole-5-carboxylate

Weisong Wang,^a Bohua Zhong ^a and Weiguo Shi ^a ^*

^aBeijing Institute of Pharmacology and Toxicology, Beijing 100850, People's Republic of China
^*Correspondence e-mail: shiwg1988@126.com

(Received 2 February 2012; accepted 10 February 2012; online 17 February 2012)

In the crystal of the title compound, C₁₁H₁₆N₂O₄S, molecules are linked via pairs of N—H⋯N hydrogen bonds to form inversion dimers. The dimers are linked by a weak C—H⋯O interaction to form chains propagating along direction [100].

Related literature

For details of the synthesis, see: Upadhyaya et al. (2007 ). For the bioactivity of thiazoles, see: Barradas et al. (2011 ); Zaharia et al. (2010 ). For related structures, see: Liu et al. (2011 ); Wang (2011 ).

Experimental

Crystal data

C₁₁H₁₆N₂O₄S
M_r = 272.32
Monoclinic, P 2₁ /c
a = 5.8258 (12) Å
b = 9.4916 (19) Å
c = 24.350 (5) Å
β = 92.37 (3)°
V = 1345.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 113 K
0.26 × 0.24 × 0.22 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan CrystalClear (Rigaku, 2005 ) T_min = 0.938, T_max = 0.947
11392 measured reflections
3180 independent reflections
2177 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.155
S = 1.07
3180 reflections
172 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1ⁱ	0.84 (3)	2.01 (3)	2.844 (3)	172 (3)
C10—H10B⋯O1ⁱⁱ	0.98	2.54	3.418 (3)	149
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku, 2005).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812005971/ff2055sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005971/ff2055Isup4.hkl

Supporting information file. DOI: 10.1107/S1600536812005971/ff2055Isup3.cml

checkCIF report

Related literature top

For details of the synthesis, see: Upadhyaya et al. (2007). For the bioactivity of thiazoles, see: Barradas et al. (2011); Zaharia et al. (2010). For related structures, see: Liu et al. (2011); Wang (2011).

Experimental top

Ethyl 2-aminothiazole-5-carboxylate 5 g (Alfa Aesar) was dissolved in 30 ml 1,4-dioxane, then triethylamine 3 ml and di-tert-butyl carbonate 6 g were added into the solution, the reaction mixture was stirred for 6 h at room temperature. When the reaction was complete as shown by TLC, the solvent was removed under reduced pressure. The residue was added into 200 ml water, ethyl acetate 100 ml was then added into the solution, the mixture was stirred for 10 min. The organic layer was separated and washed by water, brine, and dried over Na₂SO₄. The solvent was removed under reduced pressure to yield product as a white solid (4.7 g, 59.5%).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku, 2005).

Figures top

	Fig. 1. Structure of the title compound, with displacement ellipsoids drawn at 50% probability level.
	Fig. 2. Part of the packing of the title compound, viewed down the a direction. Hydrogen bonds are shown as dashed lines.

Ethyl 2-[(tert-butoxycarbonyl)amino]thiazole-5-carboxylate top

Crystal data top

C₁₁H₁₆N₂O₄S	F(000) = 576
M_r = 272.32	D_x = 1.345 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.8258 (12) Å	Cell parameters from 2589 reflections
b = 9.4916 (19) Å	θ = 2.3–28.0°
c = 24.350 (5) Å	µ = 0.25 mm⁻¹
β = 92.37 (3)°	T = 113 K
V = 1345.3 (5) Å³	Block, colourless
Z = 4	0.26 × 0.24 × 0.22 mm

Data collection top

Rigaku Saturn CCD diffractometer	3180 independent reflections
Radiation source: rotating anode	2177 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.057
Detector resolution: 7.31 pixels mm^-1	θ_max = 28.0°, θ_min = 2.3°
ω and ϕ scans	h = −7→7
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	k = −12→12
T_min = 0.938, T_max = 0.947	l = −32→30
11392 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.155	w = 1/[σ²(F_o²) + (0.0806P)²] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3180 reflections	Δρ_max = 0.46 e Å⁻³
172 parameters	Δρ_min = −0.46 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (4)

Crystal data top

C₁₁H₁₆N₂O₄S	V = 1345.3 (5) Å³
M_r = 272.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8258 (12) Å	µ = 0.25 mm⁻¹
b = 9.4916 (19) Å	T = 113 K
c = 24.350 (5) Å	0.26 × 0.24 × 0.22 mm
β = 92.37 (3)°

Data collection top

Rigaku Saturn CCD diffractometer	3180 independent reflections
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	2177 reflections with I > 2σ(I)
T_min = 0.938, T_max = 0.947	R_int = 0.057
11392 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.46 e Å⁻³
3180 reflections	Δρ_min = −0.46 e Å⁻³
172 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	0.48801 (9)	0.74851 (5)	0.499500 (19)	0.0218 (2)
O1	0.4912 (3)	0.86694 (18)	0.65493 (6)	0.0358 (4)
O2	0.2511 (3)	0.91136 (16)	0.58203 (6)	0.0277 (4)
O3	0.5169 (3)	0.68642 (17)	0.39011 (6)	0.0287 (4)
O4	0.7506 (3)	0.51367 (14)	0.35826 (6)	0.0211 (4)
N1	0.8382 (3)	0.60995 (19)	0.54014 (7)	0.0240 (4)
N2	0.7723 (3)	0.5693 (2)	0.44654 (7)	0.0229 (4)
C1	0.7172 (4)	0.6345 (2)	0.49427 (9)	0.0211 (5)
C2	0.7472 (4)	0.6836 (2)	0.58220 (9)	0.0251 (5)
H2	0.8121	0.6796	0.6186	0.030*
C3	0.5600 (4)	0.7625 (2)	0.56921 (8)	0.0217 (5)
C4	0.4342 (4)	0.8514 (2)	0.60725 (9)	0.0257 (5)
C5	0.1173 (5)	1.0034 (3)	0.61617 (11)	0.0347 (6)
H5A	0.2188	1.0727	0.6355	0.042*
H5B	0.0377	0.9476	0.6440	0.042*
C6	−0.0552 (4)	1.0780 (3)	0.57876 (11)	0.0353 (6)
H6A	0.0257	1.1341	0.5518	0.053*
H6B	−0.1502	1.1402	0.6005	0.053*
H6C	−0.1532	1.0084	0.5595	0.053*
C7	0.6642 (4)	0.5978 (2)	0.39667 (9)	0.0222 (5)
C8	0.6805 (4)	0.5341 (2)	0.29934 (8)	0.0203 (5)
C9	0.4230 (4)	0.5149 (2)	0.29012 (10)	0.0253 (5)
H9A	0.3779	0.4226	0.3042	0.038*
H9B	0.3828	0.5204	0.2507	0.038*
H9C	0.3423	0.5892	0.3095	0.038*
C10	0.7627 (4)	0.6774 (2)	0.28086 (10)	0.0295 (5)
H10A	0.6756	0.7513	0.2989	0.044*
H10B	0.7391	0.6857	0.2409	0.044*
H10C	0.9265	0.6879	0.2909	0.044*
C11	0.8063 (4)	0.4163 (2)	0.27124 (9)	0.0257 (5)
H11A	0.9718	0.4255	0.2793	0.039*
H11B	0.7752	0.4220	0.2314	0.039*
H11C	0.7531	0.3252	0.2848	0.039*
H2A	0.881 (5)	0.512 (3)	0.4476 (13)	0.047 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0254 (3)	0.0232 (3)	0.0166 (3)	0.0059 (2)	−0.0008 (2)	−0.0012 (2)
O1	0.0432 (11)	0.0404 (10)	0.0237 (9)	0.0136 (8)	−0.0007 (7)	−0.0049 (8)
O2	0.0284 (9)	0.0279 (9)	0.0267 (9)	0.0098 (7)	−0.0011 (6)	−0.0062 (7)
O3	0.0319 (9)	0.0309 (9)	0.0231 (8)	0.0136 (7)	−0.0018 (6)	−0.0013 (7)
O4	0.0237 (8)	0.0235 (8)	0.0161 (8)	0.0064 (6)	−0.0018 (6)	−0.0022 (6)
N1	0.0288 (10)	0.0242 (10)	0.0188 (9)	0.0043 (8)	−0.0004 (7)	0.0005 (7)
N2	0.0262 (10)	0.0241 (10)	0.0182 (9)	0.0082 (8)	−0.0007 (7)	−0.0010 (7)
C1	0.0236 (11)	0.0178 (11)	0.0219 (11)	0.0005 (9)	0.0019 (8)	−0.0002 (8)
C2	0.0302 (12)	0.0247 (12)	0.0202 (11)	0.0027 (9)	0.0010 (8)	−0.0003 (9)
C3	0.0257 (11)	0.0208 (11)	0.0185 (10)	0.0001 (9)	−0.0005 (8)	−0.0014 (8)
C4	0.0296 (12)	0.0230 (12)	0.0246 (12)	0.0013 (10)	0.0033 (9)	−0.0007 (9)
C5	0.0353 (14)	0.0347 (14)	0.0342 (15)	0.0132 (11)	0.0041 (11)	−0.0099 (11)
C6	0.0294 (13)	0.0291 (13)	0.0478 (16)	0.0058 (10)	0.0052 (11)	−0.0024 (12)
C7	0.0241 (11)	0.0204 (11)	0.0221 (11)	0.0022 (9)	0.0018 (8)	−0.0011 (9)
C8	0.0221 (11)	0.0246 (11)	0.0140 (10)	0.0005 (9)	−0.0005 (8)	−0.0004 (8)
C9	0.0205 (11)	0.0318 (13)	0.0233 (12)	−0.0004 (9)	−0.0018 (9)	0.0000 (9)
C10	0.0326 (13)	0.0258 (13)	0.0299 (12)	−0.0068 (10)	−0.0027 (9)	0.0015 (10)
C11	0.0231 (12)	0.0313 (13)	0.0228 (11)	0.0028 (9)	0.0029 (8)	−0.0080 (9)

Geometric parameters (Å, º) top

S1—C1	1.727 (2)	C5—H5A	0.9900
S1—C3	1.737 (2)	C5—H5B	0.9900
O1—C4	1.204 (3)	C6—H6A	0.9800
O2—C4	1.336 (3)	C6—H6B	0.9800
O2—C5	1.455 (3)	C6—H6C	0.9800
O3—C7	1.208 (2)	C8—C11	1.515 (3)
O4—C7	1.343 (2)	C8—C10	1.517 (3)
O4—C8	1.488 (2)	C8—C9	1.518 (3)
N1—C1	1.317 (3)	C9—H9A	0.9800
N1—C2	1.365 (3)	C9—H9B	0.9800
N2—C1	1.367 (3)	C9—H9C	0.9800
N2—C7	1.371 (3)	C10—H10A	0.9800
N2—H2A	0.84 (3)	C10—H10B	0.9800
C2—C3	1.349 (3)	C10—H10C	0.9800
C2—H2	0.9500	C11—H11A	0.9800
C3—C4	1.471 (3)	C11—H11B	0.9800
C5—C6	1.505 (4)	C11—H11C	0.9800

C1—S1—C3	87.93 (10)	H6A—C6—H6C	109.5
C4—O2—C5	115.48 (18)	H6B—C6—H6C	109.5
C7—O4—C8	119.88 (16)	O3—C7—O4	127.3 (2)
C1—N1—C2	109.57 (18)	O3—C7—N2	123.5 (2)
C1—N2—C7	123.24 (19)	O4—C7—N2	109.13 (18)
C1—N2—H2A	118 (2)	O4—C8—C11	102.75 (16)
C7—N2—H2A	119 (2)	O4—C8—C10	108.99 (17)
N1—C1—N2	120.32 (19)	C11—C8—C10	111.31 (18)
N1—C1—S1	115.88 (16)	O4—C8—C9	110.91 (17)
N2—C1—S1	123.78 (16)	C11—C8—C9	109.73 (18)
C3—C2—N1	116.31 (19)	C10—C8—C9	112.70 (18)
C3—C2—H2	121.8	C8—C9—H9A	109.5
N1—C2—H2	121.8	C8—C9—H9B	109.5
C2—C3—C4	126.1 (2)	H9A—C9—H9B	109.5
C2—C3—S1	110.30 (16)	C8—C9—H9C	109.5
C4—C3—S1	123.57 (16)	H9A—C9—H9C	109.5
O1—C4—O2	125.0 (2)	H9B—C9—H9C	109.5
O1—C4—C3	123.6 (2)	C8—C10—H10A	109.5
O2—C4—C3	111.36 (19)	C8—C10—H10B	109.5
O2—C5—C6	107.3 (2)	H10A—C10—H10B	109.5
O2—C5—H5A	110.3	C8—C10—H10C	109.5
C6—C5—H5A	110.3	H10A—C10—H10C	109.5
O2—C5—H5B	110.3	H10B—C10—H10C	109.5
C6—C5—H5B	110.3	C8—C11—H11A	109.5
H5A—C5—H5B	108.5	C8—C11—H11B	109.5
C5—C6—H6A	109.5	H11A—C11—H11B	109.5
C5—C6—H6B	109.5	C8—C11—H11C	109.5
H6A—C6—H6B	109.5	H11A—C11—H11C	109.5
C5—C6—H6C	109.5	H11B—C11—H11C	109.5

C2—N1—C1—N2	−178.4 (2)	C2—C3—C4—O1	2.5 (4)
C2—N1—C1—S1	0.3 (2)	S1—C3—C4—O1	−175.89 (19)
C7—N2—C1—N1	−175.1 (2)	C2—C3—C4—O2	−177.5 (2)
C7—N2—C1—S1	6.3 (3)	S1—C3—C4—O2	4.1 (3)
C3—S1—C1—N1	−0.62 (17)	C4—O2—C5—C6	170.96 (19)
C3—S1—C1—N2	178.0 (2)	C8—O4—C7—O3	6.0 (3)
C1—N1—C2—C3	0.3 (3)	C8—O4—C7—N2	−173.39 (17)
N1—C2—C3—C4	−179.4 (2)	C1—N2—C7—O3	2.8 (4)
N1—C2—C3—S1	−0.8 (3)	C1—N2—C7—O4	−177.82 (18)
C1—S1—C3—C2	0.74 (17)	C7—O4—C8—C11	−177.64 (17)
C1—S1—C3—C4	179.4 (2)	C7—O4—C8—C10	64.2 (2)
C5—O2—C4—O1	1.0 (3)	C7—O4—C8—C9	−60.4 (2)
C5—O2—C4—C3	−179.05 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1ⁱ	0.84 (3)	2.01 (3)	2.844 (3)	172 (3)
C10—H10B···O1ⁱⁱ	0.98	2.54	3.418 (3)	149

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₆N₂O₄S
M_r	272.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	5.8258 (12), 9.4916 (19), 24.350 (5)
β (°)	92.37 (3)
V (Å³)	1345.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.26 × 0.24 × 0.22

Data collection
Diffractometer	Rigaku Saturn CCD diffractometer
Absorption correction	Multi-scan CrystalClear (Rigaku, 2005)
T_min, T_max	0.938, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	11392, 3180, 2177
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.155, 1.07
No. of reflections	3180
No. of parameters	172
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.46

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1ⁱ	0.84 (3)	2.01 (3)	2.844 (3)	172 (3)
C10—H10B···O1ⁱⁱ	0.98	2.54	3.418 (3)	149

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z−1/2.

References

Barradas, J. S., Errea, M. I., D'Accorso, N., Sepúlveda, C. S. & Damonte, E. B. (2011). Eur. J. Med. Chem. 46, 259–264. Web of Science CrossRef CAS PubMed Google Scholar
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Zaharia, V., Ignat, A., Palibroda, N., Ngameni, B., Kuete, V., Fokunang, C., Moungang, M. L. & Ngadjui, B. T. (2010). Eur. J. Med. Chem. 45, 5080–5085. Web of Science CrossRef CAS PubMed Google Scholar

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