Ethyl (Z)-2-[2-(4-methylphenyl)hydrazin-1-ylidene]-3-oxo-3-(thiazol-2-ylamino)propanoate

El-Hiti, G.A.; Mohamed, H.A.; Abdel-Wahab, B.F.; Alotaibi, M.H.; Hegazy, A.S.; Kariuki, B.M.

doi:10.1107/S2414314617018521

organic compounds

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ISSN: 2414-3146

Volume 3| Part 1| January 2018| x171852

https://doi.org/10.1107/S2414314617018521

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Ethyl (Z)-2-[2-(4-methylphenyl)hydrazin-1-ylidene]-3-oxo-3-(thiazol-2-ylamino)propanoate

Gamal A. El-Hiti,^a ^* Hanan A. Mohamed,^b,^c Bakr F. Abdel-Wahab,^b,^c Mohammad Hayal Alotaibi,^d Amany S. Hegazy ^e and Benson M. Kariuki ^e ‡

^aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bDepartment of Chemistry, College of Science and Humanities, Shaqra University, Duwadimi, Saudi Arabia, ^cApplied Organic Chemistry Department, National Research Centre, Dokki, Giza, Egypt, ^dNational Center for Petrochemicals Technology, King Abdulaziz City for Science and Technology, PO Box 6086, Riyadh 11442, Saudi Arabia, and ^eSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 30 December 2017; accepted 30 December 2017; online 9 January 2018)

In the title compound, C₁₅H₁₆N₄O₃S, the dihedral angle between the aromatic rings is 15.90 (19)°. The molecule features two intramolecular N—H⋯O hydrogen bonds, which both close S(6) rings. In the crystal, weak C—H⋯O interactions link the molecules into [010] chains.

Keywords: crystal structure; thiazole; hydrogen bonding.

CCDC reference: 1814070

Structure description

Azo dyes containing thiazole ring systems have various industrial applications (e.g. Hunger, 2003 ; El-Shishtawy et al., 2013 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound (Fig. 1).

Figure 1
The molecular structure showing 50% displacement ellipsoids.

The central atoms (C4/C5/C6/O1/O2/O3/N2/N3/N4) are almost coplanar (r.m.s. deviation = 0.037 Å) and subtend dihedral angles of 10.35 (16) and 6.63 (15)° with the five- and six-membered rings, respectively. The dihedral angle between the rings is 15.90 (19)°. The terminal CH₃ group of the ethyl side-chain is twisted away from the rest of the molecule [C6—O3—C7—C8 = 81.4 (5)°]. The molecule features two intramolecular N—H⋯O hydrogen bonds (Table 1), which both generate S(6) rings. In the crystal, weak C—H⋯O interactions link the molecules into [010] C(8) chains (Fig. 2), with adjacent molecules related by the 2₁ screw axis.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2	0.86	1.93	2.639 (4)	139
N4—H4⋯O1	0.86	1.91	2.590 (4)	135
C10—H10⋯O2ⁱ	0.93	2.44	3.255 (5)	147
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
A view down the a axis of the crystal packing.

Synthesis and crystallization

1-Chloro-2-(4-tolyl)diazene and ethyl 3-oxo-3-(thiazol-2-ylamino)propanoate were dissolved in ethanol containing sodium acetate trihydrate and placed in an ice-bath for 2 h. The resulting solid was filtered, washed with ethanol, dried and recrystallized from dimethylformamide solution to give yellow blocks, m.p. 152–153°C.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₆N₄O₃S
M_r	332.38
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	5.6487 (3), 16.7479 (11), 16.9726 (14)
V (Å³)	1605.67 (19)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.22
Crystal size (mm)	0.18 × 0.18 × 0.11

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Multi-scan (CrysAlis PRO; Agilent 2014 )
T_min, T_max	0.756, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5888, 3601, 2691
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.698

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.130, 1.07
No. of reflections	3601
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19
Absolute structure	Flack x determined using 863 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.02 (5)
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS2013 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 20015), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Structural data

CCDC reference: 1814070

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617018521/hb4198sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617018521/hb4198Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617018521/hb4198Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 20015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

Ethyl (Z)-2-[2-(4-methylphenyl)hydrazin-1-ylidene]-3-oxo-3-(thiazol-2-ylamino)propanoate top

Crystal data top

C₁₅H₁₆N₄O₃S	D_x = 1.375 Mg m⁻³
M_r = 332.38	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 1846 reflections
a = 5.6487 (3) Å	θ = 3.8–26.8°
b = 16.7479 (11) Å	µ = 0.22 mm⁻¹
c = 16.9726 (14) Å	T = 298 K
V = 1605.67 (19) Å³	Block, yellow
Z = 4	0.18 × 0.18 × 0.11 mm
F(000) = 696

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	2691 reflections with I > 2σ(I)
ω scans	R_int = 0.022
Absorption correction: multi-scan (CrysAlisPro; Agilent 2014)	θ_max = 29.8°, θ_min = 3.4°
T_min = 0.756, T_max = 1.000	h = −7→5
5888 measured reflections	k = −23→15
3601 independent reflections	l = −22→14

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.048	w = 1/[σ²(F_o²) + (0.0542P)² + 0.2718P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.130	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.18 e Å⁻³
3601 reflections	Δρ_min = −0.19 e Å⁻³
210 parameters	Absolute structure: Flack x determined using 863 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.02 (5)

Special details top

Experimental. Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET) (compiled Dec 9 2014,15:38:47) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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. All hydrogen atoms were placed in calculated positions and refined using a riding model. Methyl C—H bonds were fixed at 0.96 Å, with displacement parameters 1.5 times U_eq(C), and were allowed to spin about the C—C bonds. The N—H bonds were was fixed at 0.86 Å, ethyl C—H were fixed at 0.97 Å and aromatic C—H distances were set to 0.93 Å and their U(iso) set to 1.2 times the U_eq for the atoms to which they are bonded.

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

	x	y	z	U_iso*/U_eq
C1	0.5357 (7)	−0.0268 (2)	0.3815 (2)	0.0505 (8)
C2	0.2323 (7)	−0.0349 (3)	0.4602 (2)	0.0648 (11)
H2	0.0977	−0.0579	0.4820	0.078*
C3	0.3136 (8)	0.0352 (3)	0.4845 (3)	0.0663 (11)
H3	0.2458	0.0657	0.5244	0.080*
C4	0.8791 (6)	−0.0096 (2)	0.2963 (2)	0.0466 (8)
C5	1.0331 (6)	−0.0486 (2)	0.2376 (2)	0.0460 (8)
C6	0.9915 (7)	−0.1316 (2)	0.2118 (2)	0.0547 (9)
C7	1.1328 (9)	−0.2416 (2)	0.1390 (3)	0.0760 (13)
H7A	1.0872	−0.2732	0.1844	0.091*
H7B	1.2855	−0.2607	0.1209	0.091*
C8	0.9588 (13)	−0.2523 (3)	0.0768 (4)	0.113 (2)
H8A	0.8081	−0.2325	0.0942	0.170*
H8B	0.9454	−0.3080	0.0642	0.170*
H8C	1.0079	−0.2233	0.0308	0.170*
C9	1.4593 (6)	0.09900 (19)	0.1852 (2)	0.0441 (7)
C10	1.4866 (7)	0.1794 (2)	0.1996 (2)	0.0570 (9)
H10	1.3856	0.2053	0.2346	0.068*
C11	1.6640 (7)	0.2217 (2)	0.1622 (3)	0.0595 (10)
H11	1.6807	0.2761	0.1718	0.071*
C12	1.8173 (6)	0.1838 (2)	0.1106 (2)	0.0576 (10)
C13	1.7886 (7)	0.1027 (2)	0.0987 (2)	0.0582 (10)
H13	1.8923	0.0762	0.0651	0.070*
C14	1.6118 (6)	0.0601 (2)	0.1349 (2)	0.0506 (8)
H14	1.5954	0.0056	0.1256	0.061*
C15	2.0080 (7)	0.2309 (3)	0.0683 (3)	0.0792 (13)
H15A	2.1610	0.2117	0.0840	0.119*
H15B	1.9941	0.2864	0.0817	0.119*
H15C	1.9898	0.2245	0.0124	0.119*
N1	0.3575 (6)	−0.07177 (19)	0.40072 (19)	0.0589 (8)
N2	0.6934 (6)	−0.05218 (19)	0.32443 (18)	0.0545 (7)
H2A	0.6717	−0.0991	0.3051	0.065*
N3	1.2153 (5)	−0.01322 (15)	0.20449 (17)	0.0466 (7)
N4	1.2696 (5)	0.05964 (17)	0.22258 (17)	0.0486 (7)
H4	1.1887	0.0843	0.2579	0.058*
O1	0.9189 (4)	0.05855 (15)	0.32087 (15)	0.0554 (6)
O2	0.8283 (6)	−0.17229 (15)	0.2343 (2)	0.0779 (9)
O3	1.1534 (5)	−0.15850 (15)	0.16202 (17)	0.0660 (8)
S1	0.5615 (2)	0.06154 (6)	0.43218 (7)	0.0657 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0535 (19)	0.0531 (18)	0.0449 (19)	0.0073 (18)	0.0004 (17)	0.0047 (16)
C2	0.057 (2)	0.082 (3)	0.055 (2)	0.009 (2)	0.0076 (19)	0.004 (2)
C3	0.069 (2)	0.073 (3)	0.057 (2)	0.017 (2)	0.012 (2)	−0.001 (2)
C4	0.0492 (19)	0.0473 (18)	0.0432 (19)	0.0053 (15)	−0.0005 (16)	0.0061 (16)
C5	0.0506 (18)	0.0463 (17)	0.0411 (18)	0.0036 (16)	0.0013 (15)	0.0031 (15)
C6	0.065 (2)	0.0471 (17)	0.052 (2)	0.0013 (18)	0.007 (2)	0.0016 (17)
C7	0.092 (3)	0.049 (2)	0.087 (3)	0.004 (2)	0.013 (3)	−0.014 (2)
C8	0.154 (5)	0.078 (3)	0.109 (4)	−0.006 (4)	−0.015 (5)	−0.017 (3)
C9	0.0419 (16)	0.0476 (16)	0.0427 (18)	0.0029 (15)	−0.0039 (15)	0.0034 (15)
C10	0.056 (2)	0.0488 (18)	0.066 (3)	0.0071 (17)	0.001 (2)	−0.0044 (18)
C11	0.056 (2)	0.0474 (19)	0.075 (3)	−0.0039 (17)	−0.002 (2)	0.0031 (19)
C12	0.0449 (18)	0.073 (2)	0.055 (2)	0.0000 (19)	−0.0072 (19)	0.010 (2)
C13	0.048 (2)	0.076 (2)	0.051 (2)	0.0026 (19)	0.0016 (18)	−0.0035 (19)
C14	0.0485 (18)	0.0523 (19)	0.051 (2)	0.0036 (17)	−0.0027 (16)	−0.0048 (18)
C15	0.060 (2)	0.099 (3)	0.078 (3)	−0.015 (2)	−0.001 (2)	0.020 (3)
N1	0.0590 (18)	0.066 (2)	0.0521 (18)	−0.0005 (16)	0.0080 (16)	0.0017 (16)
N2	0.0598 (17)	0.0491 (15)	0.0545 (18)	0.0006 (15)	0.0110 (15)	−0.0029 (14)
N3	0.0504 (16)	0.0443 (14)	0.0452 (16)	0.0040 (13)	−0.0026 (14)	0.0020 (13)
N4	0.0494 (15)	0.0457 (14)	0.0508 (17)	0.0036 (14)	0.0051 (13)	−0.0029 (14)
O1	0.0627 (15)	0.0486 (13)	0.0549 (15)	0.0013 (13)	0.0058 (12)	−0.0047 (12)
O2	0.090 (2)	0.0508 (14)	0.094 (2)	−0.0145 (15)	0.035 (2)	−0.0115 (15)
O3	0.0793 (18)	0.0462 (13)	0.0725 (19)	−0.0003 (13)	0.0211 (16)	−0.0099 (13)
S1	0.0756 (6)	0.0558 (5)	0.0656 (6)	0.0035 (5)	0.0145 (5)	−0.0067 (5)

Geometric parameters (Å, º) top

C1—N1	1.299 (5)	C8—H8B	0.9600
C1—N2	1.383 (5)	C8—H8C	0.9600
C1—S1	1.718 (4)	C9—C14	1.377 (5)
C2—C3	1.326 (6)	C9—C10	1.378 (5)
C2—N1	1.378 (5)	C9—N4	1.409 (4)
C2—H2	0.9300	C10—C11	1.381 (5)
C3—S1	1.717 (4)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.385 (6)
C4—O1	1.236 (4)	C11—H11	0.9300
C4—N2	1.354 (4)	C12—C13	1.382 (5)
C4—C5	1.476 (5)	C12—C15	1.516 (5)
C5—N3	1.313 (4)	C13—C14	1.373 (5)
C5—C6	1.475 (5)	C13—H13	0.9300
C6—O2	1.209 (4)	C14—H14	0.9300
C6—O3	1.325 (4)	C15—H15A	0.9600
C7—O3	1.451 (4)	C15—H15B	0.9600
C7—C8	1.454 (7)	C15—H15C	0.9600
C7—H7A	0.9700	N2—H2A	0.8600
C7—H7B	0.9700	N3—N4	1.295 (4)
C8—H8A	0.9600	N4—H4	0.8600

N1—C1—N2	119.8 (3)	C10—C9—N4	117.6 (3)
N1—C1—S1	116.1 (3)	C9—C10—C11	120.0 (4)
N2—C1—S1	124.1 (3)	C9—C10—H10	120.0
C3—C2—N1	116.6 (4)	C11—C10—H10	120.0
C3—C2—H2	121.7	C10—C11—C12	120.7 (4)
N1—C2—H2	121.7	C10—C11—H11	119.7
C2—C3—S1	110.4 (3)	C12—C11—H11	119.7
C2—C3—H3	124.8	C13—C12—C11	117.9 (4)
S1—C3—H3	124.8	C13—C12—C15	121.7 (4)
O1—C4—N2	120.5 (3)	C11—C12—C15	120.4 (4)
O1—C4—C5	121.9 (3)	C14—C13—C12	122.1 (4)
N2—C4—C5	117.5 (3)	C14—C13—H13	119.0
N3—C5—C6	115.0 (3)	C12—C13—H13	119.0
N3—C5—C4	123.5 (3)	C13—C14—C9	119.1 (4)
C6—C5—C4	121.5 (3)	C13—C14—H14	120.5
O2—C6—O3	122.4 (3)	C9—C14—H14	120.5
O2—C6—C5	124.0 (3)	C12—C15—H15A	109.5
O3—C6—C5	113.6 (3)	C12—C15—H15B	109.5
O3—C7—C8	111.5 (4)	H15A—C15—H15B	109.5
O3—C7—H7A	109.3	C12—C15—H15C	109.5
C8—C7—H7A	109.3	H15A—C15—H15C	109.5
O3—C7—H7B	109.3	H15B—C15—H15C	109.5
C8—C7—H7B	109.3	C1—N1—C2	108.8 (3)
H7A—C7—H7B	108.0	C4—N2—C1	125.7 (3)
C7—C8—H8A	109.5	C4—N2—H2A	117.1
C7—C8—H8B	109.5	C1—N2—H2A	117.1
H8A—C8—H8B	109.5	N4—N3—C5	120.6 (3)
C7—C8—H8C	109.5	N3—N4—C9	121.0 (3)
H8A—C8—H8C	109.5	N3—N4—H4	119.5
H8B—C8—H8C	109.5	C9—N4—H4	119.5
C14—C9—C10	120.2 (3)	C6—O3—C7	116.3 (3)
C14—C9—N4	122.2 (3)	C3—S1—C1	88.2 (2)

N1—C2—C3—S1	0.5 (5)	N2—C1—N1—C2	178.0 (3)
O1—C4—C5—N3	−3.2 (5)	S1—C1—N1—C2	−0.6 (4)
N2—C4—C5—N3	178.4 (3)	C3—C2—N1—C1	0.0 (5)
O1—C4—C5—C6	176.7 (3)	O1—C4—N2—C1	−0.9 (5)
N2—C4—C5—C6	−1.7 (5)	C5—C4—N2—C1	177.6 (3)
N3—C5—C6—O2	−177.8 (4)	N1—C1—N2—C4	176.6 (3)
C4—C5—C6—O2	2.3 (6)	S1—C1—N2—C4	−4.9 (5)
N3—C5—C6—O3	3.3 (5)	C6—C5—N3—N4	−179.8 (3)
C4—C5—C6—O3	−176.6 (3)	C4—C5—N3—N4	0.1 (5)
C14—C9—C10—C11	1.5 (5)	C5—N3—N4—C9	−177.6 (3)
N4—C9—C10—C11	−177.5 (3)	C14—C9—N4—N3	−7.5 (5)
C9—C10—C11—C12	−0.6 (6)	C10—C9—N4—N3	171.5 (3)
C10—C11—C12—C13	−0.8 (6)	O2—C6—O3—C7	−3.4 (6)
C10—C11—C12—C15	178.6 (4)	C5—C6—O3—C7	175.5 (3)
C11—C12—C13—C14	1.4 (6)	C8—C7—O3—C6	81.4 (5)
C15—C12—C13—C14	−178.0 (4)	C2—C3—S1—C1	−0.7 (3)
C12—C13—C14—C9	−0.5 (5)	N1—C1—S1—C3	0.8 (3)
C10—C9—C14—C13	−0.9 (5)	N2—C1—S1—C3	−177.8 (3)
N4—C9—C14—C13	178.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2	0.86	1.93	2.639 (4)	139
N4—H4···O1	0.86	1.91	2.590 (4)	135
C10—H10···O2ⁱ	0.93	2.44	3.255 (5)	147

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Footnotes

‡Additional corresponding author, e-mail: kariukib@cardiff.ac.uk.

Funding information

The project was supported by King Saud University, Deanship of Scientific Research, Research Chairs.

References

Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
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Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethyl (Z)-2-[2-(4-methylphenyl)hydrazin-1-yl­idene]-3-oxo-3-(thiazol-2-ylamino)propanoate

Structure description

Synthesis and crystallization

Refinement

Structural data

Footnotes

Funding information

References

organic compounds

Ethyl (Z)-2-[2-(4-methylphenyl)hydrazin-1-ylidene]-3-oxo-3-(thiazol-2-ylamino)propanoate