organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Upadhyaya, D. J., Barge, A., Stefania, R. & Cravotto, G. (2007). Tetrahedron Lett. 48, 8318-8322.]). For the bioactivity of thia­zoles, see: Barradas et al. (2011[Barradas, J. S., Errea, M. I., D'Accorso, N., Sepúlveda, C. S. & Damonte, E. B. (2011). Eur. J. Med. Chem. 46, 259-264.]); Zaharia et al. (2010[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.]). For related structures, see: Liu et al. (2011[Liu, Z.-J., Fu, X.-K., Hu, Z.-K., Wu, X.-J. & Wu, L. (2011). Acta Cryst. E67, o1562.]); Wang (2011[Wang, M.-F. (2011). Acta Cryst. E67, o1581.]).

[Scheme 1]

Experimental

Crystal data
  • C11H16N2O4S

  • Mr = 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[Rigaku (2005). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.938, Tmax = 0.947

  • 11392 measured reflections

  • 3180 independent reflections

  • 2177 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.46 e Å−3

  • Δρmin = −0.46 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2005). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: CrystalStructure (Rigaku, 2005[Rigaku (2005). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.]).

Supporting information


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%).

Refinement top

The H atoms linked to the C atoms were fixed geometrically and treated as riding with C—H = 0.95 Å (aromatic), 0.98 Å (ethyl), 0.99 Å (methylene) with Uiso(H) = 1.2–1.5Ueq(C).

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
[Figure 1] Fig. 1. Structure of the title compound, with displacement ellipsoids drawn at 50% probability level.
[Figure 2] 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
C11H16N2O4SF(000) = 576
Mr = 272.32Dx = 1.345 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 5.8258 (12) ÅCell parameters from 2589 reflections
b = 9.4916 (19) Åθ = 2.3–28.0°
c = 24.350 (5) ŵ = 0.25 mm1
β = 92.37 (3)°T = 113 K
V = 1345.3 (5) Å3Block, colourless
Z = 40.26 × 0.24 × 0.22 mm
Data collection top
Rigaku Saturn CCD
diffractometer
3180 independent reflections
Radiation source: rotating anode2177 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.057
Detector resolution: 7.31 pixels mm-1θmax = 28.0°, θmin = 2.3°
ω and ϕ scansh = 77
Absorption correction: multi-scan
CrystalClear (Rigaku, 2005)
k = 1212
Tmin = 0.938, Tmax = 0.947l = 3230
11392 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.155 w = 1/[σ2(Fo2) + (0.0806P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
3180 reflectionsΔρmax = 0.46 e Å3
172 parametersΔρmin = 0.46 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.014 (4)
Crystal data top
C11H16N2O4SV = 1345.3 (5) Å3
Mr = 272.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.8258 (12) ŵ = 0.25 mm1
b = 9.4916 (19) ÅT = 113 K
c = 24.350 (5) Å0.26 × 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)
Tmin = 0.938, Tmax = 0.947Rint = 0.057
11392 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.155H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.46 e Å3
3180 reflectionsΔρmin = 0.46 e Å3
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
xyzUiso*/Ueq
S10.48801 (9)0.74851 (5)0.499500 (19)0.0218 (2)
O10.4912 (3)0.86694 (18)0.65493 (6)0.0358 (4)
O20.2511 (3)0.91136 (16)0.58203 (6)0.0277 (4)
O30.5169 (3)0.68642 (17)0.39011 (6)0.0287 (4)
O40.7506 (3)0.51367 (14)0.35826 (6)0.0211 (4)
N10.8382 (3)0.60995 (19)0.54014 (7)0.0240 (4)
N20.7723 (3)0.5693 (2)0.44654 (7)0.0229 (4)
C10.7172 (4)0.6345 (2)0.49427 (9)0.0211 (5)
C20.7472 (4)0.6836 (2)0.58220 (9)0.0251 (5)
H20.81210.67960.61860.030*
C30.5600 (4)0.7625 (2)0.56921 (8)0.0217 (5)
C40.4342 (4)0.8514 (2)0.60725 (9)0.0257 (5)
C50.1173 (5)1.0034 (3)0.61617 (11)0.0347 (6)
H5A0.21881.07270.63550.042*
H5B0.03770.94760.64400.042*
C60.0552 (4)1.0780 (3)0.57876 (11)0.0353 (6)
H6A0.02571.13410.55180.053*
H6B0.15021.14020.60050.053*
H6C0.15321.00840.55950.053*
C70.6642 (4)0.5978 (2)0.39667 (9)0.0222 (5)
C80.6805 (4)0.5341 (2)0.29934 (8)0.0203 (5)
C90.4230 (4)0.5149 (2)0.29012 (10)0.0253 (5)
H9A0.37790.42260.30420.038*
H9B0.38280.52040.25070.038*
H9C0.34230.58920.30950.038*
C100.7627 (4)0.6774 (2)0.28086 (10)0.0295 (5)
H10A0.67560.75130.29890.044*
H10B0.73910.68570.24090.044*
H10C0.92650.68790.29090.044*
C110.8063 (4)0.4163 (2)0.27124 (9)0.0257 (5)
H11A0.97180.42550.27930.039*
H11B0.77520.42200.23140.039*
H11C0.75310.32520.28480.039*
H2A0.881 (5)0.512 (3)0.4476 (13)0.047 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0254 (3)0.0232 (3)0.0166 (3)0.0059 (2)0.0008 (2)0.0012 (2)
O10.0432 (11)0.0404 (10)0.0237 (9)0.0136 (8)0.0007 (7)0.0049 (8)
O20.0284 (9)0.0279 (9)0.0267 (9)0.0098 (7)0.0011 (6)0.0062 (7)
O30.0319 (9)0.0309 (9)0.0231 (8)0.0136 (7)0.0018 (6)0.0013 (7)
O40.0237 (8)0.0235 (8)0.0161 (8)0.0064 (6)0.0018 (6)0.0022 (6)
N10.0288 (10)0.0242 (10)0.0188 (9)0.0043 (8)0.0004 (7)0.0005 (7)
N20.0262 (10)0.0241 (10)0.0182 (9)0.0082 (8)0.0007 (7)0.0010 (7)
C10.0236 (11)0.0178 (11)0.0219 (11)0.0005 (9)0.0019 (8)0.0002 (8)
C20.0302 (12)0.0247 (12)0.0202 (11)0.0027 (9)0.0010 (8)0.0003 (9)
C30.0257 (11)0.0208 (11)0.0185 (10)0.0001 (9)0.0005 (8)0.0014 (8)
C40.0296 (12)0.0230 (12)0.0246 (12)0.0013 (10)0.0033 (9)0.0007 (9)
C50.0353 (14)0.0347 (14)0.0342 (15)0.0132 (11)0.0041 (11)0.0099 (11)
C60.0294 (13)0.0291 (13)0.0478 (16)0.0058 (10)0.0052 (11)0.0024 (12)
C70.0241 (11)0.0204 (11)0.0221 (11)0.0022 (9)0.0018 (8)0.0011 (9)
C80.0221 (11)0.0246 (11)0.0140 (10)0.0005 (9)0.0005 (8)0.0004 (8)
C90.0205 (11)0.0318 (13)0.0233 (12)0.0004 (9)0.0018 (9)0.0000 (9)
C100.0326 (13)0.0258 (13)0.0299 (12)0.0068 (10)0.0027 (9)0.0015 (10)
C110.0231 (12)0.0313 (13)0.0228 (11)0.0028 (9)0.0029 (8)0.0080 (9)
Geometric parameters (Å, º) top
S1—C11.727 (2)C5—H5A0.9900
S1—C31.737 (2)C5—H5B0.9900
O1—C41.204 (3)C6—H6A0.9800
O2—C41.336 (3)C6—H6B0.9800
O2—C51.455 (3)C6—H6C0.9800
O3—C71.208 (2)C8—C111.515 (3)
O4—C71.343 (2)C8—C101.517 (3)
O4—C81.488 (2)C8—C91.518 (3)
N1—C11.317 (3)C9—H9A0.9800
N1—C21.365 (3)C9—H9B0.9800
N2—C11.367 (3)C9—H9C0.9800
N2—C71.371 (3)C10—H10A0.9800
N2—H2A0.84 (3)C10—H10B0.9800
C2—C31.349 (3)C10—H10C0.9800
C2—H20.9500C11—H11A0.9800
C3—C41.471 (3)C11—H11B0.9800
C5—C61.505 (4)C11—H11C0.9800
C1—S1—C387.93 (10)H6A—C6—H6C109.5
C4—O2—C5115.48 (18)H6B—C6—H6C109.5
C7—O4—C8119.88 (16)O3—C7—O4127.3 (2)
C1—N1—C2109.57 (18)O3—C7—N2123.5 (2)
C1—N2—C7123.24 (19)O4—C7—N2109.13 (18)
C1—N2—H2A118 (2)O4—C8—C11102.75 (16)
C7—N2—H2A119 (2)O4—C8—C10108.99 (17)
N1—C1—N2120.32 (19)C11—C8—C10111.31 (18)
N1—C1—S1115.88 (16)O4—C8—C9110.91 (17)
N2—C1—S1123.78 (16)C11—C8—C9109.73 (18)
C3—C2—N1116.31 (19)C10—C8—C9112.70 (18)
C3—C2—H2121.8C8—C9—H9A109.5
N1—C2—H2121.8C8—C9—H9B109.5
C2—C3—C4126.1 (2)H9A—C9—H9B109.5
C2—C3—S1110.30 (16)C8—C9—H9C109.5
C4—C3—S1123.57 (16)H9A—C9—H9C109.5
O1—C4—O2125.0 (2)H9B—C9—H9C109.5
O1—C4—C3123.6 (2)C8—C10—H10A109.5
O2—C4—C3111.36 (19)C8—C10—H10B109.5
O2—C5—C6107.3 (2)H10A—C10—H10B109.5
O2—C5—H5A110.3C8—C10—H10C109.5
C6—C5—H5A110.3H10A—C10—H10C109.5
O2—C5—H5B110.3H10B—C10—H10C109.5
C6—C5—H5B110.3C8—C11—H11A109.5
H5A—C5—H5B108.5C8—C11—H11B109.5
C5—C6—H6A109.5H11A—C11—H11B109.5
C5—C6—H6B109.5C8—C11—H11C109.5
H6A—C6—H6B109.5H11A—C11—H11C109.5
C5—C6—H6C109.5H11B—C11—H11C109.5
C2—N1—C1—N2178.4 (2)C2—C3—C4—O12.5 (4)
C2—N1—C1—S10.3 (2)S1—C3—C4—O1175.89 (19)
C7—N2—C1—N1175.1 (2)C2—C3—C4—O2177.5 (2)
C7—N2—C1—S16.3 (3)S1—C3—C4—O24.1 (3)
C3—S1—C1—N10.62 (17)C4—O2—C5—C6170.96 (19)
C3—S1—C1—N2178.0 (2)C8—O4—C7—O36.0 (3)
C1—N1—C2—C30.3 (3)C8—O4—C7—N2173.39 (17)
N1—C2—C3—C4179.4 (2)C1—N2—C7—O32.8 (4)
N1—C2—C3—S10.8 (3)C1—N2—C7—O4177.82 (18)
C1—S1—C3—C20.74 (17)C7—O4—C8—C11177.64 (17)
C1—S1—C3—C4179.4 (2)C7—O4—C8—C1064.2 (2)
C5—O2—C4—O11.0 (3)C7—O4—C8—C960.4 (2)
C5—O2—C4—C3179.05 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.84 (3)2.01 (3)2.844 (3)172 (3)
C10—H10B···O1ii0.982.543.418 (3)149
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC11H16N2O4S
Mr272.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)113
a, b, c (Å)5.8258 (12), 9.4916 (19), 24.350 (5)
β (°) 92.37 (3)
V3)1345.3 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.25
Crystal size (mm)0.26 × 0.24 × 0.22
Data collection
DiffractometerRigaku Saturn CCD
diffractometer
Absorption correctionMulti-scan
CrystalClear (Rigaku, 2005)
Tmin, Tmax0.938, 0.947
No. of measured, independent and
observed [I > 2σ(I)] reflections
11392, 3180, 2177
Rint0.057
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.155, 1.07
No. of reflections3180
No. of parameters172
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2A···N1i0.84 (3)2.01 (3)2.844 (3)172 (3)
C10—H10B···O1ii0.982.543.418 (3)149
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y+3/2, z1/2.
 

References

First citationBarradas, 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
First citationLiu, Z.-J., Fu, X.-K., Hu, Z.-K., Wu, X.-J. & Wu, L. (2011). Acta Cryst. E67, o1562.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationRigaku (2005). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationUpadhyaya, D. J., Barge, A., Stefania, R. & Cravotto, G. (2007). Tetrahedron Lett. 48, 8318–8322.  Web of Science CrossRef CAS Google Scholar
First citationWang, M.-F. (2011). Acta Cryst. E67, o1581.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationZaharia, 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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