2-(2-Amino-1,3-thia­zol-4-yl)acetohydrazide

Pallavi, G.B.; Gowda, R.; Gowda, K.V.A.; Basanagouda, M.; Latha, A.L.

doi:10.1107/S2414314616012736

organic compounds

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ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161273

doi:10.1107/S2414314616012736

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2-(2-Amino-1,3-thiazol-4-yl)acetohydrazide

G. B. Pallavi,^a Ramakrishna Gowda,^b ^* K. V. Arjuna Gowda,^c Mahantesha Basanagouda ^d and A. L. Latha ^e

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 July 2016; accepted 6 August 2016; online 16 August 2016)

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 crystal structure of the title compound (Fig. 1) 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.

Figure 1
The molecular structure of the title compound, showing 40% probability displacement ellipsoids.

The crystal structure features N—H⋯O and N—H⋯N hydrogen bonds, which link the molecules into (010) sheets (Fig. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

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⋯N1^iv	0.83 (2)	2.60 (2)	3.300 (2)	144 (2)
N4—H4D⋯O1^v	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.

Figure 2
The crystal packing diagram of the title compound. The dotted lines indicate intermolecular hydrogen bonds. All H atoms which are not involved in these interactions have been omitted for clarity.

Synthesis 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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₈N₄OS
M_r	172.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.9685 (1), 18.8795 (5), 8.2913 (2)
β (°)	91.448 (2)
V (Å³)	777.50 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.36
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.917, 0.930
No. of measured, independent and observed [I ≥ 2u(I)] reflections	1364, 1364, 1262
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.09
No. of reflections	1364
No. of parameters	131
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.27
Computer programs: APEX2and SAINT (Bruker, 2004), OLEX2 (Dolomanov et al., 2009 ) and olex2.refine (Bourhis et al., 2015 ).

Structural data

CCDC reference: 1498091

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616012736/hb4068sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616012736/hb4068Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616012736/hb4068Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: 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).

2-(2-Amino-1,3-thiazol-4-yl)acetohydrazide top

Crystal data top

C₅H₈N₄OS	F(000) = 360.5934
M_r = 172.21	D_x = 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

Data collection top

Bruker Kappa APEXII CCD diffractometer	1262 reflections with I ≥ 2u(I)
ω and φ scan	R_int = 0.020
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 25.0°, θ_min = 2.2°
T_min = 0.917, T_max = 0.930	h = −5→5
1364 measured reflections	k = 0→22
1364 independent reflections	l = 0→9

Refinement top

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(F_o²) + (0.0366P)² + 0.2878P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.0002
1364 reflections	Δρ_max = 0.28 e Å⁻³
131 parameters	Δρ_min = −0.27 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···N1^iv	0.83 (2)	2.60 (2)	3.300 (2)	144 (2)
N4—H4D···O1^v	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

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