Literature DB >> 21580724

Ethyl 2-(tert-butoxy-carbonyl-amino)-1,3-benzothia-zole-6-carboxyl-ate.

Can Lei, Xin Fang, Hai-Yang Yu, Ming-Dong Huang, Jun-Dong Wang.

Abstract

In the crystal of the title compound, C(15)H(18)N(2)O(4)S, inversion dimers are formed by inter-molecular N-H⋯N hydrogen bonds and weak C-H⋯O contacts. These dimers stack up along [100] through inversion-related π-π inter-actions between thia-zole rings [centroid-centroid distance = 3.790 (2) Å] and the thia-zole and benzene rings [centroid-centroid distance = 3.845 (2) Å] and C-H⋯π contacts.

Entities: CellLine Chemical Disease Species

Year: 2010 PMID： 21580724 PMCID： PMC2984018 DOI： 10.1107/S160053681001024X

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For benzothiazole derivatives with anti-tumor activity, see: Brantley et al. (2004 ▶); Ćaleta et al. (2009 ▶); Mortimer et al. (2006 ▶) and for anti-tuberculous benzothiazolines, see: Palmer et al. (1971 ▶). For related benzothiazole structures, see: Lynch et al. (2002 ▶); Matković-Čalogović et al. (2003 ▶).

Experimental

Crystal data

C15H18N2O4S M = 322.37 Triclinic, a = 6.3026 (13) Å b = 10.791 (2) Å c = 11.909 (2) Å α = 80.58 (3)° β = 86.61 (3)° γ = 81.57 (3)° V = 789.9 (3) Å3 Z = 2 Mo Kα radiation μ = 0.22 mm−1 T = 293 K 0.70 × 0.05 × 0.02 mm

Data collection

Rigaku Saturn 724 CCD area-detector diffractometer Absorption correction: numerical (NUMABS; Higashi, 2000 ▶) T min = 0.987, T max = 0.995 6644 measured reflections 3469 independent reflections 2412 reflections with I > 2σ(I) R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.088 wR(F 2) = 0.203 S = 1.11 3469 reflections 199 parameters H-atom parameters constrained Δρmax = 0.26 e Å−3 Δρmin = −0.30 e Å−3 Data collection: CrystalClear (Rigaku, 2007 ▶); 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: ORTEX (McArdle, 1995 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶). Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681001024X/si2244sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S160053681001024X/si2244Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₅H₁₈N₂O₄S	Z = 2
M_r = 322.37	F(000) = 340
Triclinic, P1	D_x = 1.355 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3026 (13) Å	Cell parameters from 2354 reflections
b = 10.791 (2) Å	θ = 12–18°
c = 11.909 (2) Å	µ = 0.22 mm⁻¹
α = 80.58 (3)°	T = 293 K
β = 86.61 (3)°	Needle, colorless
γ = 81.57 (3)°	0.70 × 0.05 × 0.02 mm
V = 789.9 (3) Å³

Rigaku Saturn 724 CCD area-detector diffractometer	3469 independent reflections
Radiation source: fine-focus sealed tube	2412 reflections with I > 2σ(I)
Graphite	R_int = 0.049
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
dtprofit.ref scans	h = −7→8
Absorption correction: numerical (NUMABS; Higashi, 2000)	k = −13→11
T_min = 0.987, T_max = 0.995	l = −15→15
6644 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)] = 0.088	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.203	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0613P)² + 0.839P] where P = (F_o² + 2F_c²)/3
3469 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	U_iso*/U_eq
S1	−0.00627 (16)	0.75048 (10)	0.94306 (9)	0.0535 (3)
O1	−0.5534 (4)	0.6760 (2)	1.1764 (2)	0.0535 (7)
N1	−0.4017 (5)	0.8086 (3)	1.0445 (3)	0.0463 (7)
H1	−0.5187	0.8593	1.0515	0.056*
O4	0.6440 (4)	0.9028 (3)	0.6602 (2)	0.0544 (7)
N2	−0.2502 (5)	0.9692 (3)	0.9263 (2)	0.0425 (7)
O2	−0.2352 (5)	0.6079 (3)	1.0923 (3)	0.0736 (10)
O3	0.5621 (5)	1.1131 (3)	0.6102 (3)	0.0702 (9)
C1	−0.6011 (11)	0.4579 (5)	1.1729 (5)	0.101 (2)
H1A	−0.6143	0.3772	1.2185	0.151*
H1B	−0.4776	0.4496	1.1221	0.151*
H1C	−0.7275	0.4866	1.1295	0.151*
C2	−0.3890 (9)	0.5131 (6)	1.3253 (5)	0.113 (2)
H2A	−0.4042	0.4330	1.3717	0.169*
H2B	−0.3848	0.5759	1.3733	0.169*
H2C	−0.2583	0.5050	1.2798	0.169*
C3	−0.7806 (8)	0.5823 (5)	1.3176 (5)	0.0844 (17)
H3A	−0.8094	0.5075	1.3685	0.127*
H3B	−0.8973	0.6104	1.2671	0.127*
H3C	−0.7654	0.6480	1.3608	0.127*
C4	−0.5758 (7)	0.5525 (4)	1.2490 (4)	0.0599 (11)
C5	−0.3848 (6)	0.6882 (4)	1.1045 (3)	0.0497 (9)
C6	−0.2382 (6)	0.8519 (4)	0.9732 (3)	0.0426 (8)
C7	−0.0652 (5)	0.9890 (3)	0.8612 (3)	0.0410 (8)
C8	−0.0223 (6)	1.1047 (4)	0.7995 (3)	0.0483 (9)
H8	−0.1213	1.1775	0.8004	0.058*
C9	0.1687 (6)	1.1096 (4)	0.7373 (3)	0.0506 (9)
H9	0.1980	1.1866	0.6962	0.061*
C10	0.3196 (5)	1.0007 (4)	0.7350 (3)	0.0448 (9)
C11	0.2781 (6)	0.8856 (4)	0.7956 (3)	0.0479 (9)
H11	0.3769	0.8129	0.7938	0.057*
C12	0.0869 (6)	0.8803 (3)	0.8590 (3)	0.0438 (8)
C13	0.5180 (6)	1.0144 (4)	0.6628 (3)	0.0500 (9)
C14	0.8351 (6)	0.9081 (4)	0.5871 (3)	0.0554 (10)
H14A	0.9345	0.9534	0.6178	0.066*
H14B	0.7982	0.9520	0.5116	0.066*
C15	0.9356 (9)	0.7748 (5)	0.5812 (5)	0.0817 (15)
H15A	1.0624	0.7757	0.5324	0.123*
H15B	0.8357	0.7307	0.5512	0.123*
H15C	0.9734	0.7326	0.6561	0.123*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0453 (6)	0.0497 (6)	0.0608 (6)	−0.0027 (4)	0.0103 (4)	−0.0027 (5)
O1	0.0468 (15)	0.0474 (15)	0.0610 (17)	−0.0030 (12)	0.0131 (13)	−0.0014 (13)
N1	0.0382 (16)	0.0485 (18)	0.0490 (18)	−0.0047 (13)	0.0040 (14)	−0.0009 (14)
O4	0.0382 (14)	0.0655 (18)	0.0594 (17)	−0.0122 (13)	0.0127 (12)	−0.0099 (14)
N2	0.0373 (16)	0.0482 (18)	0.0424 (16)	−0.0074 (13)	−0.0003 (13)	−0.0073 (14)
O2	0.0594 (19)	0.0573 (18)	0.090 (2)	0.0079 (15)	0.0272 (17)	0.0049 (16)
O3	0.0549 (18)	0.065 (2)	0.085 (2)	−0.0168 (15)	0.0138 (16)	0.0076 (17)
C1	0.128 (5)	0.060 (3)	0.113 (5)	−0.028 (3)	0.036 (4)	−0.013 (3)
C2	0.071 (4)	0.144 (6)	0.099 (4)	−0.015 (4)	−0.011 (3)	0.057 (4)
C3	0.072 (3)	0.070 (3)	0.097 (4)	−0.010 (2)	0.040 (3)	0.013 (3)
C4	0.054 (2)	0.049 (2)	0.071 (3)	−0.0094 (19)	0.010 (2)	0.008 (2)
C5	0.040 (2)	0.051 (2)	0.056 (2)	−0.0070 (17)	0.0093 (18)	−0.0075 (19)
C6	0.0377 (18)	0.049 (2)	0.0417 (19)	−0.0057 (15)	−0.0012 (15)	−0.0082 (16)
C7	0.0324 (17)	0.047 (2)	0.0438 (19)	−0.0050 (15)	−0.0003 (15)	−0.0094 (16)
C8	0.0395 (19)	0.046 (2)	0.059 (2)	−0.0067 (16)	0.0004 (17)	−0.0060 (18)
C9	0.045 (2)	0.052 (2)	0.055 (2)	−0.0145 (17)	0.0038 (18)	−0.0057 (19)
C10	0.0319 (18)	0.055 (2)	0.049 (2)	−0.0094 (16)	0.0022 (15)	−0.0106 (18)
C11	0.0381 (19)	0.053 (2)	0.050 (2)	−0.0017 (16)	0.0021 (16)	−0.0076 (18)
C12	0.0391 (19)	0.051 (2)	0.0417 (19)	−0.0065 (16)	0.0012 (15)	−0.0077 (16)
C13	0.0357 (19)	0.063 (3)	0.051 (2)	−0.0116 (18)	−0.0027 (16)	−0.0047 (19)
C14	0.042 (2)	0.073 (3)	0.052 (2)	−0.0156 (19)	0.0139 (18)	−0.012 (2)
C15	0.078 (3)	0.081 (3)	0.084 (4)	−0.008 (3)	0.027 (3)	−0.020 (3)

S1—C12	1.738 (4)	C3—C4	1.509 (6)
S1—C6	1.750 (4)	C3—H3A	0.9600
O1—C5	1.332 (4)	C3—H3B	0.9600
O1—C4	1.486 (5)	C3—H3C	0.9600
N1—C5	1.369 (5)	C7—C8	1.396 (5)
N1—C6	1.382 (5)	C7—C12	1.404 (5)
N1—H1	0.8600	C8—C9	1.379 (5)
O4—C13	1.345 (5)	C8—H8	0.9300
O4—C14	1.446 (4)	C9—C10	1.402 (5)
N2—C6	1.290 (4)	C9—H9	0.9300
N2—C7	1.385 (4)	C10—C11	1.382 (5)
O2—C5	1.203 (5)	C10—C13	1.487 (5)
O3—C13	1.205 (4)	C11—C12	1.388 (5)
C1—C4	1.501 (7)	C11—H11	0.9300
C1—H1A	0.9600	C14—C15	1.495 (6)
C1—H1B	0.9600	C14—H14A	0.9700
C1—H1C	0.9600	C14—H14B	0.9700
C2—C4	1.499 (7)	C15—H15A	0.9600
C2—H2A	0.9600	C15—H15B	0.9600
C2—H2B	0.9600	C15—H15C	0.9600
C2—H2C	0.9600

C12—S1—C6	87.89 (18)	N2—C6—S1	117.2 (3)
C5—O1—C4	120.7 (3)	N1—C6—S1	121.5 (3)
C5—N1—C6	122.6 (3)	N2—C7—C8	125.6 (3)
C5—N1—H1	118.7	N2—C7—C12	114.9 (3)
C6—N1—H1	118.7	C8—C7—C12	119.5 (3)
C13—O4—C14	115.5 (3)	C9—C8—C7	119.1 (4)
C6—N2—C7	110.1 (3)	C9—C8—H8	120.4
C4—C1—H1A	109.5	C7—C8—H8	120.4
C4—C1—H1B	109.5	C8—C9—C10	121.2 (4)
H1A—C1—H1B	109.5	C8—C9—H9	119.4
C4—C1—H1C	109.5	C10—C9—H9	119.4
H1A—C1—H1C	109.5	C11—C10—C9	120.1 (3)
H1B—C1—H1C	109.5	C11—C10—C13	122.5 (3)
C4—C2—H2A	109.5	C9—C10—C13	117.3 (3)
C4—C2—H2B	109.5	C10—C11—C12	119.0 (4)
H2A—C2—H2B	109.5	C10—C11—H11	120.5
C4—C2—H2C	109.5	C12—C11—H11	120.5
H2A—C2—H2C	109.5	C11—C12—C7	121.2 (3)
H2B—C2—H2C	109.5	C11—C12—S1	128.9 (3)
C4—C3—H3A	109.5	C7—C12—S1	109.9 (3)
C4—C3—H3B	109.5	O3—C13—O4	122.8 (4)
H3A—C3—H3B	109.5	O3—C13—C10	124.7 (4)
C4—C3—H3C	109.5	O4—C13—C10	112.5 (3)
H3A—C3—H3C	109.5	O4—C14—C15	107.8 (3)
H3B—C3—H3C	109.5	O4—C14—H14A	110.1
O1—C4—C2	109.9 (4)	C15—C14—H14A	110.1
O1—C4—C1	108.4 (4)	O4—C14—H14B	110.1
C2—C4—C1	113.7 (5)	C15—C14—H14B	110.1
O1—C4—C3	102.9 (3)	H14A—C14—H14B	108.5
C2—C4—C3	110.7 (5)	C14—C15—H15A	109.5
C1—C4—C3	110.7 (4)	C14—C15—H15B	109.5
O2—C5—O1	126.7 (4)	H15A—C15—H15B	109.5
O2—C5—N1	123.0 (3)	C14—C15—H15C	109.5
O1—C5—N1	110.3 (3)	H15A—C15—H15C	109.5
N2—C6—N1	121.3 (3)	H15B—C15—H15C	109.5

Cg2 is the centroid of the C7–C12 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.86	2.22	3.054 (14)	162
C8—H8···O1ⁱ	0.93	2.43	3.334 (14)	164
C14—H14A···Cg2ⁱⁱ	0.97	2.66	3.523 (18)	149

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C7–C12 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.86	2.22	3.054 (14)	162
C8—H8⋯O1ⁱ	0.93	2.43	3.334 (14)	164
C14—H14A⋯Cg2ⁱⁱ	0.97	2.66	3.523 (18)	149

Symmetry codes: (i) ; (ii) .

7 in total

1. Antitumor benzothiazoles. 26.(1) 2-(3,4-dimethoxyphenyl)-5-fluorobenzothiazole (GW 610, NSC 721648), a simple fluorinated 2-arylbenzothiazole, shows potent and selective inhibitory activity against lung, colon, and breast cancer cell lines.

Authors: Catriona G Mortimer; Geoffrey Wells; Jean-Philippe Crochard; Erica L Stone; Tracey D Bradshaw; Malcolm F G Stevens; Andrew D Westwell
Journal: J Med Chem Date: 2006-01-12 Impact factor: 7.446

2. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

3. 1,3-Benzothiazole-6-carboxamidinium chloride dihydrate.

Authors: Dubravka Matković-Calogović; Zora Popović; Vesna Tralić-Kulenović; Livio Racanè; Grace Karminski-Zamola
Journal: Acta Crystallogr C Date: 2003-03-11 Impact factor: 1.172

4. Benzothiazolines as antituberculous agents.

Authors: P J Palmer; R B Trigg; J V Warrington
Journal: J Med Chem Date: 1971-03 Impact factor: 7.446

5. Fluorinated 2-(4-amino-3-methylphenyl)benzothiazoles induce CYP1A1 expression, become metabolized, and bind to macromolecules in sensitive human cancer cells.

Authors: Eileen Brantley; Valentina Trapani; Michael C Alley; Curtis D Hose; Tracey D Bradshaw; Malcolm F G Stevens; Edward A Sausville; Sherman F Stinson
Journal: Drug Metab Dispos Date: 2004-09-08 Impact factor: 3.922

6. Novel cyano- and amidinobenzothiazole derivatives: synthesis, antitumor evaluation, and X-ray and quantitative structure-activity relationship (QSAR) analysis.

Authors: Irena Caleta; Marijeta Kralj; Marko Marjanović; Branimir Bertosa; Sanja Tomić; Gordana Pavlović; Kresimir Pavelić; Grace Karminski-Zamola
Journal: J Med Chem Date: 2009-03-26 Impact factor: 7.446

7. Structure validation in chemical crystallography.

Authors: Anthony L Spek
Journal: Acta Crystallogr D Biol Crystallogr Date: 2009-01-20