organic compounds
2-(2-Amino-1,3-thiazol-4-yl)acetohydrazide
aP.G. Department of Physics and Research Centre, Bharathi College, K. M. Doddi, Mandya 571 422, Karnataka, India, bDepartment of Physics, Govt. College for Women, Kolar 563 101, Karnataka, India, cDepartment of Physics, Govt. College for Women, Mandya 571 401, Karnataka, India, dDepartment of Chemistry, P.C. Jabin Science College, Hubli 580 031, Karnataka, India, and eDepartment of Physics, Govt. First Grade College for Women, Vijayanagara, Mysore 570 018, Karnataka, India
*Correspondence e-mail: rkgowdaphy@gmail.com
In the title compound, C5H8N4OS, the dihedral angle between the acetohydrazide moiety and the thiazole ring is 80.96 (8)°. In the crystal, molecules are linked by N—H⋯O and N—H⋯N hydrogen bonds generating (010) sheets.
Keywords: crystal structure; aminothiazole; hydrogen bonding.
CCDC reference: 1498091
Structure description
2-Aminothiazole is an important and versatile five-membered heterocyclic scaffold which is applied extensively in various branches of chemistry including dyes and pharmaceutical industries. Derivatives of 2-aminothiazoles are used widely by medicinal chemists in drug discovery research: Famotidine is used in the treatment of peptic ulcers and controls gastroesophageal reflux, Abafungin is an antimicrobial agent used for the treatment of dermatomycoses and Cefdinir is used for the treatment of pneumonia, chronic bronchitis, sinusitis, pharyngitis and tonsillitis. Non-steroidal anti-inflammatory drugs (NSAIDs) such as Sudoxicam and Meloxicam are used in arthritis, dysmenorrhea and fever while Pramipexole (Mirapex) has been evaluated as a selective serotonin reuptake inhibitor (SSRI) antidepressant and demonstrated in a placebo-controlled proof of concept study in bipolar disorder which have been reviewed (Das et al. 2016).
The ) reveals an L-shaped conformation for the molecule: the dihedral angle between the acetohydrazide moiety and the thiazole ring (r.m.s. deviation = 0.011 Å) is 80.96 (8)°. The C2—S1—C1 bond angle of 88.76 (8)° reflects the presence of an un-delocalized lone pair of electrons and is similar to that observed in other thiazoles.
of the title compound (Fig. 1 features N—H⋯O and N—H⋯N hydrogen bonds, which link the molecules into (010) sheets (Fig. 2Synthesis and crystallization
A solution of (2-amino-thiazol-4-yl)-acetic acid ethyl ester (0.0116 mol) was refluxed with hydrazine hydrate (Hardy et al. 1984) (0.035 mol) in absolute ethanol for 24 h (the completion of the reaction was monitored by thin-layer chromatography). The reaction mixture was concentrated in vacuo to obtain the crude product, which was filtered and washed with cold methanol to remove any traces of impurities of hydrazine. Brown blocks of the title compound were obtained by recrystallization from an ethanol and ethyl acetate solvent mixture by slow evaporation
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
|
Structural data
CCDC reference: 1498091
10.1107/S2414314616012736/hb4068sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616012736/hb4068Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616012736/hb4068Isup3.cml
Data collection: APEX2 (Bruker, 2004); cell
APEX2 and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009); program(s) used to refine structure: olex2.refine (Bourhis et al., 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C5H8N4OS | F(000) = 360.5934 |
Mr = 172.21 | Dx = 1.471 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 4.9685 (1) Å | Cell parameters from 4593 reflections |
b = 18.8795 (5) Å | θ = 2.5–30.2° |
c = 8.2913 (2) Å | µ = 0.36 mm−1 |
β = 91.448 (2)° | T = 293 K |
V = 777.50 (3) Å3 | Block, brown |
Z = 4 | 0.3 × 0.2 × 0.2 mm |
Bruker Kappa APEXII CCD diffractometer | 1262 reflections with I ≥ 2u(I) |
ω and φ scan | Rint = 0.020 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | θmax = 25.0°, θmin = 2.2° |
Tmin = 0.917, Tmax = 0.930 | h = −5→5 |
1364 measured reflections | k = 0→22 |
1364 independent reflections | l = 0→9 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.030 | All H-atom parameters refined |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0366P)2 + 0.2878P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.0002 |
1364 reflections | Δρmax = 0.28 e Å−3 |
131 parameters | Δρmin = −0.27 e Å−3 |
Experimental. Absorption correction: SADABS-2004/1 (Bruker,2004) was used for absorption correction. R(int) was 0.0304 before and 0.0203 after correction. The Ratio of minimum to maximum transmission is 0.8035. The λ/2 correction factor is 0.0015. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7239 (3) | 0.40966 (9) | 0.56391 (19) | 0.0381 (4) | |
C2 | 0.7249 (4) | 0.29205 (10) | 0.4459 (2) | 0.0468 (4) | |
H2 | 0.755 (4) | 0.2469 (13) | 0.416 (3) | 0.066 (6)* | |
C3 | 0.5557 (3) | 0.33835 (8) | 0.3747 (2) | 0.0376 (4) | |
C4 | 0.3736 (4) | 0.32468 (9) | 0.2323 (2) | 0.0422 (4) | |
H4a | 0.403 (4) | 0.2776 (11) | 0.190 (2) | 0.055 (6)* | |
H4b | 0.197 (4) | 0.3273 (9) | 0.259 (2) | 0.045 (5)* | |
C5 | 0.4288 (3) | 0.37505 (8) | 0.09570 (18) | 0.0340 (4) | |
N1 | 0.7600 (4) | 0.46674 (9) | 0.6572 (2) | 0.0529 (4) | |
N2 | 0.5537 (3) | 0.40546 (7) | 0.44149 (16) | 0.0386 (3) | |
N3 | 0.2152 (3) | 0.40373 (8) | 0.02335 (18) | 0.0441 (4) | |
N4 | 0.2344 (3) | 0.44932 (11) | −0.1106 (2) | 0.0515 (4) | |
S1 | 0.89807 (10) | 0.33134 (2) | 0.60529 (5) | 0.05055 (19) | |
O1 | 0.6576 (2) | 0.38824 (7) | 0.05292 (15) | 0.0462 (3) | |
H1a | 0.687 (4) | 0.5046 (12) | 0.625 (2) | 0.054 (6)* | |
H1b | 0.883 (5) | 0.4656 (12) | 0.725 (3) | 0.064 (7)* | |
H3 | 0.058 (4) | 0.3921 (10) | 0.049 (2) | 0.049 (5)* | |
H4c | 0.358 (5) | 0.4329 (13) | −0.164 (3) | 0.069 (8)* | |
H4d | 0.276 (5) | 0.4936 (15) | −0.073 (3) | 0.082 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0376 (9) | 0.0405 (9) | 0.0361 (8) | 0.0058 (7) | −0.0014 (7) | 0.0067 (7) |
C2 | 0.0588 (11) | 0.0353 (9) | 0.0467 (10) | 0.0063 (8) | 0.0089 (8) | 0.0049 (7) |
C3 | 0.0378 (9) | 0.0358 (8) | 0.0397 (8) | −0.0034 (6) | 0.0082 (7) | 0.0037 (7) |
C4 | 0.0360 (9) | 0.0417 (9) | 0.0492 (10) | −0.0106 (7) | 0.0057 (7) | −0.0040 (7) |
C5 | 0.0245 (8) | 0.0383 (8) | 0.0391 (8) | −0.0036 (6) | 0.0004 (6) | −0.0091 (6) |
N1 | 0.0611 (11) | 0.0479 (9) | 0.0484 (9) | 0.0124 (8) | −0.0243 (8) | −0.0043 (7) |
N2 | 0.0381 (7) | 0.0361 (7) | 0.0411 (7) | 0.0034 (6) | −0.0051 (6) | 0.0010 (6) |
N3 | 0.0218 (7) | 0.0591 (9) | 0.0513 (9) | −0.0037 (6) | −0.0007 (6) | 0.0029 (7) |
N4 | 0.0340 (8) | 0.0659 (11) | 0.0542 (10) | −0.0007 (8) | −0.0079 (7) | 0.0077 (8) |
S1 | 0.0572 (3) | 0.0499 (3) | 0.0443 (3) | 0.0186 (2) | −0.0035 (2) | 0.01077 (19) |
O1 | 0.0215 (6) | 0.0620 (8) | 0.0551 (7) | −0.0016 (5) | 0.0026 (5) | 0.0102 (6) |
C1—N1 | 1.336 (2) | C4—C5 | 1.509 (2) |
C1—N2 | 1.307 (2) | C5—N3 | 1.322 (2) |
C1—S1 | 1.7431 (16) | C5—O1 | 1.2254 (18) |
C2—H2 | 0.90 (2) | N1—H1a | 0.84 (2) |
C2—C3 | 1.339 (3) | N1—H1b | 0.82 (2) |
C2—S1 | 1.726 (2) | N3—N4 | 1.411 (2) |
C3—C4 | 1.492 (2) | N3—H3 | 0.84 (2) |
C3—N2 | 1.383 (2) | N4—H4c | 0.83 (3) |
C4—H4a | 0.97 (2) | N4—H4d | 0.91 (3) |
C4—H4b | 0.91 (2) | ||
N2—C1—N1 | 125.00 (15) | N3—C5—C4 | 116.10 (14) |
S1—C1—N1 | 120.76 (13) | O1—C5—C4 | 122.19 (15) |
S1—C1—N2 | 114.18 (13) | O1—C5—N3 | 121.71 (16) |
C3—C2—H2 | 127.3 (14) | H1a—N1—C1 | 117.0 (14) |
S1—C2—H2 | 122.1 (14) | H1b—N1—C1 | 117.5 (16) |
S1—C2—C3 | 110.60 (14) | H1b—N1—H1a | 123 (2) |
C4—C3—C2 | 126.66 (16) | C3—N2—C1 | 110.83 (14) |
N2—C3—C2 | 115.62 (16) | N4—N3—C5 | 122.56 (15) |
N2—C3—C4 | 117.72 (14) | H3—N3—C5 | 121.2 (13) |
H4a—C4—C3 | 110.4 (12) | H3—N3—N4 | 116.0 (13) |
H4b—C4—C3 | 111.3 (12) | H4c—N4—N3 | 105.0 (17) |
H4b—C4—H4a | 107.0 (16) | H4d—N4—N3 | 108.0 (17) |
C5—C4—C3 | 111.54 (13) | H4d—N4—H4c | 111 (2) |
C5—C4—H4a | 106.1 (12) | C2—S1—C1 | 88.76 (8) |
C5—C4—H4b | 110.1 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.84 (2) | 2.14 (2) | 2.976 (2) | 171 (2) |
N1—H1B···N4ii | 0.82 (3) | 2.21 (2) | 3.023 (2) | 172 (2) |
N3—H3···O1iii | 0.84 (2) | 1.99 (2) | 2.8027 (18) | 160.9 (17) |
N4—H4C···N1iv | 0.83 (2) | 2.60 (2) | 3.300 (2) | 144 (2) |
N4—H4D···O1v | 0.91 (3) | 2.26 (3) | 3.148 (2) | 164 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z+1; (iii) x−1, y, z; (iv) x, y, z−1; (v) −x+1, −y+1, −z. |
Acknowledgements
The authors thank the SAIF IIT Madras, Chennai, for the data collection.
References
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Das, D., Sikdar, P. & Bairagi, M. (2016). Eur. J. Med. Chem. 109, 89–98. CrossRef CAS PubMed Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hardy, K. D., Harrington, F. P. & Stachulski, A. V. (1984). J. Chem. Soc. Perkin Trans. 1, pp. 1227–1235. CrossRef Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.