Ethyl 2-[2-(4-hy­droxy-3-meth­oxy­benzyl­idene)hydrazin-1-yl­idene]-3,4-dimethyl-2,3-dihydro-1,3-thia­zole-5-carboxyl­ate

Öztürk Yildirim, S.; Butcher, R.J.; Köysal, Y.; Kantar, E.N.; Belder, A.

doi:10.1107/S1600536812043772

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages o3213-o3214

doi:10.1107/S1600536812043772

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Ethyl 2-[2-(4-hydroxy-3-methoxybenzylidene)hydrazin-1-ylidene]-3,4-dimethyl-2,3-dihydro-1,3-thiazole-5-carboxylate

Sema Öztürk Yildirim,^a,^b Ray J. Butcher,^a ^* Yavuz Köysal,^c Esen Nur Kantar ^d and Ayşe Belder ^e

^aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cYesilyurt Demir Celik Vocational School, Ondokuz Mayis University, Samsun, Turkey, ^dDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayis University, TR-55139 Samsun, Turkey, and ^eDepartment of Chemistry, Karabük University, 78200 Karabük, Turkey
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 19 October 2012; accepted 22 October 2012; online 27 October 2012)

The title compound, C₁₆H₁₉N₃O₄S, is almost planar, with a dihedral angle of 2.88 (9)° between the mean planes of the benzene and thiazole rings. The molecule adopts an E conformation about the two C=N bonds, with a C—N—N—C torsion angle of −177.01 (11)°. An intramolecular C—H⋯O hydrogen bond exists between a thiazole methyl group and the formic acid ethyl ester carbonyl O atom. In the crystal, molecules are linked by O—-H⋯O hydrogen bonds, forming chains propagating along [2-10]. The chains are linked via C—H⋯O hydrogen bonds with R₂²(12) ring motifs, forming sheets lying parallel to (12-2). The sheets are further linked through out-of-plane C—H⋯N hydrogen bonds with R₂²(12) ring motifs and C—H⋯π interactions, forming an interesting three-dimensional supramolecular architecture.

Related literature

For the various biological activities of 1,3-thiazoles, 1,3,4-thiadiazoles and their derivatives, see: Shucla et al. (1984 ); Desai & Baxi (1992 ); Mullican et al. (1993 ); Chapleo et al. (1986 ); Turner et al. (1988 ); Mazzone et al. (1993 ); Miyamoto et al. (1985 ); Hanna et al. (1995 ); Oh et al. (2002 ). For the antimicrobial activity of thiadiazoles and related compounds, see: Sancak et al. (2007 ). For bond lengths of structurally related molecules, see: Imhof & Wunderle (2012 ); Randell et al. (2012 ). For details of the Cambridge Structural Database, see: Allen (2002 ). For synthetic details, see: Er et al. (2009 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₆H₁₉N₃O₄S
M_r = 349.40
Triclinic, $[P \overline 1]$
a = 6.8957 (3) Å
b = 10.2716 (5) Å
c = 12.7297 (6) Å
α = 74.843 (4)°
β = 87.579 (4)°
γ = 73.304 (4)°
V = 833.06 (7) Å³
Z = 2
Cu Kα radiation
μ = 1.96 mm⁻¹
T = 123 K
0.40 × 0.35 × 0.30 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2011 ) T_min = 0.508, T_max = 0.591
5272 measured reflections
3316 independent reflections
3254 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.099
S = 1.02
3316 reflections
222 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O2	0.98	2.28	3.0111 (19)	130
O4—H4O⋯O2ⁱ	0.84	1.85	2.6878 (14)	176
C16—H16A⋯O4ⁱⁱ	0.98	2.41	3.3824 (18)	171
C8—H8C⋯N3ⁱⁱⁱ	0.98	2.62	3.3986 (19)	137
C6—H6B⋯Cg1^iv	0.98	2.96	3.6414 (16)	128
C7—H7C⋯Cg1^v	0.98	2.62	3.4762 (16)	146
Symmetry codes: (i) x-2, y+1, z; (ii) -x, -y+2, -z+1; (iii) -x+1, -y+1, -z; (iv) -x+1, -y+1, -z+1; (v) x+1, y-1, z.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812043772/su2516sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043772/su2516Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812043772/su2516Isup3.cml

checkCIF report

Comment top

1,3-thiazoles, 1,3,4-thiadiazoles and their derivatives exhibit various biological activities, such as antituberculosis (Shucla, et al., 1984), antimicrobial (Desai & Baxi, 1992), anti-inflammatory (Mullican et al., 1993), antiviral, anticonvulsant (Chapleo et al., 1986), antihypertensive (Turner et al., 1988), local anesthetic (Mazzone et al., 1993), anticancer (Miyamoto et al., 1985), hypoglycemic (Hanna et al., 1995), and cytotoxic activities (Oh et al., 2002). Thiadiazoles and related compounds are of great interest in chemistry owing to their bioactivity with certain plant growth regulating effects as well as antimicrobial activity (Sancak et al., 2007). Owing to the importance of these 1,3,4-thiadiazoles derivatives, we report herein on the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The N2—N3 single bond [1.3982 (16) Å] and the N2═C1 double bond [1.2958 (18) Å] distances are in the normal range and are comparable with those found for similar compounds (Imhof & Wunderle, 2012; Randell et al., 2012). Bond lengths and angles can be regarded as normal (Allen, 2002). The molecule adopts an E conformation about the C1═N2 and the C9═N3 bonds with a C9—N3—N2—C1 torsion angle of -177.01 (11) °. The 2-methoxy-phenol ring (C10—C15) and the thiazole ring (C1/N1/C2/C3/S1) are coplanar with a dihedral angle between their mean planes of only 2.88 (9) °. An intramolecular C—H···O hydrogen bond exists between the thiazol methyl group and atom O2 of the formic acid ethyl ester C═O O atom.

In the crystal, an interesting supramolecular architecture is formed as the molecules link up to form sheets in plane (1 2 -2) through both C—H···O R²₂(12) ring motifs (Bernstein et al., 1995) and O—H···O interactions. These sheets are further linked through out-of-plane C—H···N R²₂(12) ring motifs and C-H···π interactions (Table 1 and Fig. 2).

Related literature top

For the various biological activities of 1,3-thiazoles, 1,3,4-thiadiazoles and their derivatives, see: Shucla et al. (1984); Desai & Baxi (1992); Mullican et al. (1993); Chapleo et al. (1986); Turner et al. (1988); Mazzone et al. (1993); Miyamoto et al. (1985); Hanna et al. (1995); Oh et al. (2002). For the antimicrobial activity of thiadiazoles and related compounds, see: Sancak et al. (2007). For bond lengths of structurally related molecules, see: Imhof & Wunderle (2012); Randell et al. (2012). For details of the Cambridge Structural Database, see: Allen (2002). For synthetic details, see: Er et al. (2009). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized according to the published procedure (Er et al., 2009). Crystals were grown by slow evaporation of a 1 3-dichloro-2-propanol solution.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom numbering. The displacement ellipsoids are drawn at the 30% probability level. The intramolecular C—H···O hydrogen bond is shown as a dashed line.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines - see Table 1 for details.

Ethyl 2-[2-(4-hydroxy-3-methoxybenzylidene)hydrazin-1-ylidene]- 3,4-dimethyl-2,3-dihydro-1,3-thiazole-5-carboxylate top

Crystal data top

C₁₆H₁₉N₃O₄S	Z = 2
M_r = 349.40	F(000) = 368
Triclinic, P1	D_x = 1.393 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 6.8957 (3) Å	Cell parameters from 4259 reflections
b = 10.2716 (5) Å	θ = 3.6–75.0°
c = 12.7297 (6) Å	µ = 1.96 mm⁻¹
α = 74.843 (4)°	T = 123 K
β = 87.579 (4)°	Block, yellow
γ = 73.304 (4)°	0.40 × 0.35 × 0.30 mm
V = 833.06 (7) Å³

Data collection top

Agilent Xcalibur (Ruby, Gemini) diffractometer	3316 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3254 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
Detector resolution: 10.5081 pixels mm^-1	θ_max = 75.2°, θ_min = 3.6°
ω scans	h = −8→6
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2011)	k = −12→12
T_min = 0.508, T_max = 0.591	l = −14→15
5272 measured reflections

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0628P)² + 0.3221P] where P = (F_o² + 2F_c²)/3
3316 reflections	(Δ/σ)_max < 0.001
222 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₆H₁₉N₃O₄S	γ = 73.304 (4)°
M_r = 349.40	V = 833.06 (7) Å³
Triclinic, P1	Z = 2
a = 6.8957 (3) Å	Cu Kα radiation
b = 10.2716 (5) Å	µ = 1.96 mm⁻¹
c = 12.7297 (6) Å	T = 123 K
α = 74.843 (4)°	0.40 × 0.35 × 0.30 mm
β = 87.579 (4)°

Data collection top

Agilent Xcalibur (Ruby, Gemini) diffractometer	3316 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2011)	3254 reflections with I > 2σ(I)
T_min = 0.508, T_max = 0.591	R_int = 0.016
5272 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.02	Δρ_max = 0.35 e Å⁻³
3316 reflections	Δρ_min = −0.29 e Å⁻³
222 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

	x	y	z	U_iso*/U_eq
S1	0.70492 (5)	0.40814 (3)	0.24740 (3)	0.02041 (12)
N1	0.66196 (18)	0.27633 (12)	0.10704 (9)	0.0211 (3)
N2	0.36294 (18)	0.44474 (12)	0.12687 (9)	0.0215 (2)
N3	0.28500 (18)	0.54591 (12)	0.18464 (9)	0.0209 (2)
O1	1.09737 (14)	0.30755 (10)	0.35164 (8)	0.0228 (2)
O2	1.25414 (15)	0.14195 (11)	0.26529 (9)	0.0262 (2)
O3	0.01284 (15)	0.91719 (11)	0.41058 (8)	0.0250 (2)
O4	−0.36639 (15)	1.02884 (11)	0.35124 (9)	0.0260 (2)
H4O	−0.4861	1.0602	0.3258	0.031*
C1	0.5524 (2)	0.38117 (14)	0.15329 (11)	0.0197 (3)
C2	0.8616 (2)	0.21847 (14)	0.14284 (11)	0.0209 (3)
C3	0.9110 (2)	0.27517 (14)	0.21950 (11)	0.0207 (3)
C4	1.1041 (2)	0.23365 (14)	0.27913 (11)	0.0209 (3)
C5	1.2838 (2)	0.27620 (15)	0.41589 (11)	0.0229 (3)
H5A	1.3993	0.2794	0.3674	0.027*
H5B	1.3131	0.1810	0.4664	0.027*
C6	1.2533 (2)	0.38483 (16)	0.47858 (12)	0.0277 (3)
H6A	1.3767	0.3671	0.5220	0.042*
H6B	1.1399	0.3799	0.5270	0.042*
H6C	1.2234	0.4786	0.4278	0.042*
C7	0.9959 (2)	0.10729 (15)	0.09540 (12)	0.0256 (3)
H7A	1.1327	0.0781	0.1283	0.038*
H7B	1.0011	0.1449	0.0165	0.038*
H7C	0.9421	0.0260	0.1102	0.038*
C8	0.5613 (2)	0.23358 (15)	0.02873 (12)	0.0250 (3)
H8A	0.4387	0.2114	0.0602	0.037*
H8B	0.6532	0.1502	0.0113	0.037*
H8C	0.5243	0.3105	−0.0379	0.037*
C9	0.0948 (2)	0.60606 (14)	0.16368 (11)	0.0211 (3)
H9A	0.0275	0.5778	0.1138	0.025*
C10	−0.0221 (2)	0.71595 (14)	0.21327 (11)	0.0205 (3)
C11	0.0644 (2)	0.76348 (14)	0.28849 (11)	0.0199 (3)
H11A	0.2047	0.7247	0.3077	0.024*
C12	−0.0528 (2)	0.86614 (14)	0.33475 (11)	0.0206 (3)
C13	−0.2607 (2)	0.92734 (14)	0.30389 (11)	0.0208 (3)
C14	−0.3465 (2)	0.88063 (15)	0.22958 (11)	0.0228 (3)
H14A	−0.4862	0.9207	0.2091	0.027*
C15	−0.2279 (2)	0.77488 (15)	0.18495 (11)	0.0231 (3)
H15A	−0.2880	0.7426	0.1347	0.028*
C16	0.2148 (2)	0.84763 (16)	0.45449 (12)	0.0271 (3)
H16A	0.2424	0.8898	0.5108	0.041*
H16B	0.3111	0.8580	0.3963	0.041*
H16C	0.2290	0.7475	0.4864	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01519 (18)	0.02052 (19)	0.02471 (19)	−0.00053 (13)	−0.00105 (12)	−0.00933 (13)
N1	0.0198 (6)	0.0202 (6)	0.0223 (5)	−0.0022 (5)	−0.0005 (4)	−0.0073 (4)
N2	0.0189 (6)	0.0207 (6)	0.0236 (6)	−0.0022 (4)	−0.0011 (4)	−0.0073 (4)
N3	0.0190 (6)	0.0203 (6)	0.0219 (5)	−0.0023 (5)	0.0000 (4)	−0.0068 (4)
O1	0.0151 (5)	0.0248 (5)	0.0263 (5)	−0.0009 (4)	−0.0017 (4)	−0.0079 (4)
O2	0.0169 (5)	0.0255 (5)	0.0330 (5)	0.0010 (4)	−0.0016 (4)	−0.0095 (4)
O3	0.0170 (5)	0.0275 (5)	0.0296 (5)	0.0007 (4)	−0.0047 (4)	−0.0131 (4)
O4	0.0167 (5)	0.0278 (5)	0.0314 (5)	0.0023 (4)	−0.0019 (4)	−0.0135 (4)
C1	0.0195 (7)	0.0189 (6)	0.0201 (6)	−0.0043 (5)	0.0003 (5)	−0.0052 (5)
C2	0.0188 (6)	0.0182 (6)	0.0226 (6)	−0.0026 (5)	0.0023 (5)	−0.0030 (5)
C3	0.0160 (6)	0.0184 (6)	0.0247 (6)	−0.0005 (5)	0.0024 (5)	−0.0053 (5)
C4	0.0167 (6)	0.0191 (6)	0.0239 (6)	−0.0030 (5)	0.0017 (5)	−0.0027 (5)
C5	0.0150 (6)	0.0254 (7)	0.0250 (7)	−0.0018 (5)	−0.0026 (5)	−0.0049 (5)
C6	0.0235 (7)	0.0273 (7)	0.0301 (7)	−0.0027 (6)	−0.0025 (6)	−0.0080 (6)
C7	0.0248 (7)	0.0225 (7)	0.0268 (7)	−0.0009 (6)	0.0038 (6)	−0.0087 (5)
C8	0.0240 (7)	0.0251 (7)	0.0264 (7)	−0.0039 (6)	−0.0019 (6)	−0.0110 (6)
C9	0.0200 (7)	0.0211 (6)	0.0213 (6)	−0.0048 (5)	−0.0014 (5)	−0.0049 (5)
C10	0.0181 (7)	0.0196 (6)	0.0210 (6)	−0.0028 (5)	0.0003 (5)	−0.0033 (5)
C11	0.0143 (6)	0.0200 (6)	0.0219 (6)	−0.0019 (5)	−0.0008 (5)	−0.0027 (5)
C12	0.0192 (7)	0.0213 (6)	0.0197 (6)	−0.0049 (5)	−0.0004 (5)	−0.0037 (5)
C13	0.0176 (6)	0.0201 (6)	0.0215 (6)	−0.0019 (5)	0.0017 (5)	−0.0041 (5)
C14	0.0146 (6)	0.0251 (7)	0.0255 (7)	−0.0012 (5)	−0.0022 (5)	−0.0055 (5)
C15	0.0195 (7)	0.0248 (7)	0.0244 (7)	−0.0038 (5)	−0.0025 (5)	−0.0075 (5)
C16	0.0189 (7)	0.0310 (7)	0.0303 (7)	−0.0010 (6)	−0.0062 (6)	−0.0121 (6)

Geometric parameters (Å, º) top

S1—C1	1.7507 (14)	C6—H6B	0.9800
S1—C3	1.7626 (14)	C6—H6C	0.9800
N1—C2	1.3773 (18)	C7—H7A	0.9800
N1—C1	1.3795 (18)	C7—H7B	0.9800
N1—C8	1.4599 (17)	C7—H7C	0.9800
N2—C1	1.2958 (18)	C8—H8A	0.9800
N2—N3	1.3982 (16)	C8—H8B	0.9800
N3—C9	1.2847 (18)	C8—H8C	0.9800
O1—C4	1.3315 (17)	C9—C10	1.4592 (19)
O1—C5	1.4624 (16)	C9—H9A	0.9500
O2—C4	1.2247 (17)	C10—C15	1.3951 (19)
O3—C12	1.3601 (17)	C10—C11	1.4039 (19)
O3—C16	1.4307 (16)	C11—C12	1.3808 (19)
O4—C13	1.3551 (17)	C11—H11A	0.9500
O4—H4O	0.8400	C12—C13	1.4159 (19)
C2—C3	1.359 (2)	C13—C14	1.387 (2)
C2—C7	1.4941 (19)	C14—C15	1.394 (2)
C3—C4	1.457 (2)	C14—H14A	0.9500
C5—C6	1.498 (2)	C15—H15A	0.9500
C5—H5A	0.9900	C16—H16A	0.9800
C5—H5B	0.9900	C16—H16B	0.9800
C6—H6A	0.9800	C16—H16C	0.9800

C1—S1—C3	89.88 (6)	C2—C7—H7C	109.5
C2—N1—C1	114.90 (11)	H7A—C7—H7C	109.5
C2—N1—C8	125.69 (12)	H7B—C7—H7C	109.5
C1—N1—C8	119.40 (11)	N1—C8—H8A	109.5
C1—N2—N3	110.82 (11)	N1—C8—H8B	109.5
C9—N3—N2	112.08 (11)	H8A—C8—H8B	109.5
C4—O1—C5	116.48 (11)	N1—C8—H8C	109.5
C12—O3—C16	116.76 (11)	H8A—C8—H8C	109.5
C13—O4—H4O	109.5	H8B—C8—H8C	109.5
N2—C1—N1	121.36 (12)	N3—C9—C10	122.79 (13)
N2—C1—S1	128.22 (11)	N3—C9—H9A	118.6
N1—C1—S1	110.42 (10)	C10—C9—H9A	118.6
C3—C2—N1	112.65 (12)	C15—C10—C11	119.09 (13)
C3—C2—C7	127.97 (13)	C15—C10—C9	118.38 (12)
N1—C2—C7	119.37 (12)	C11—C10—C9	122.53 (12)
C2—C3—C4	127.31 (12)	C12—C11—C10	120.55 (12)
C2—C3—S1	112.14 (10)	C12—C11—H11A	119.7
C4—C3—S1	120.50 (11)	C10—C11—H11A	119.7
O2—C4—O1	123.89 (13)	O3—C12—C11	125.70 (13)
O2—C4—C3	124.66 (13)	O3—C12—C13	114.35 (12)
O1—C4—C3	111.45 (11)	C11—C12—C13	119.95 (13)
O1—C5—C6	107.59 (11)	O4—C13—C14	123.43 (13)
O1—C5—H5A	110.2	O4—C13—C12	116.96 (12)
C6—C5—H5A	110.2	C14—C13—C12	119.61 (13)
O1—C5—H5B	110.2	C13—C14—C15	120.03 (13)
C6—C5—H5B	110.2	C13—C14—H14A	120.0
H5A—C5—H5B	108.5	C15—C14—H14A	120.0
C5—C6—H6A	109.5	C14—C15—C10	120.74 (13)
C5—C6—H6B	109.5	C14—C15—H15A	119.6
H6A—C6—H6B	109.5	C10—C15—H15A	119.6
C5—C6—H6C	109.5	O3—C16—H16A	109.5
H6A—C6—H6C	109.5	O3—C16—H16B	109.5
H6B—C6—H6C	109.5	H16A—C16—H16B	109.5
C2—C7—H7A	109.5	O3—C16—H16C	109.5
C2—C7—H7B	109.5	H16A—C16—H16C	109.5
H7A—C7—H7B	109.5	H16B—C16—H16C	109.5

C1—N2—N3—C9	−177.01 (11)	S1—C3—C4—O2	179.55 (11)
N3—N2—C1—N1	179.73 (11)	C2—C3—C4—O1	−177.28 (13)
N3—N2—C1—S1	0.40 (17)	S1—C3—C4—O1	−0.06 (16)
C2—N1—C1—N2	179.91 (12)	C4—O1—C5—C6	171.31 (11)
C8—N1—C1—N2	−1.54 (19)	N2—N3—C9—C10	−179.74 (11)
C2—N1—C1—S1	−0.65 (15)	N3—C9—C10—C15	179.88 (13)
C8—N1—C1—S1	177.90 (10)	N3—C9—C10—C11	−0.5 (2)
C3—S1—C1—N2	179.35 (13)	C15—C10—C11—C12	0.6 (2)
C3—S1—C1—N1	−0.04 (10)	C9—C10—C11—C12	−178.93 (12)
C1—N1—C2—C3	1.22 (17)	C16—O3—C12—C11	−7.2 (2)
C8—N1—C2—C3	−177.22 (12)	C16—O3—C12—C13	172.68 (12)
C1—N1—C2—C7	−178.01 (11)	C10—C11—C12—O3	177.97 (12)
C8—N1—C2—C7	3.6 (2)	C10—C11—C12—C13	−1.9 (2)
N1—C2—C3—C4	176.20 (13)	O3—C12—C13—O4	1.00 (18)
C7—C2—C3—C4	−4.7 (2)	C11—C12—C13—O4	−179.11 (12)
N1—C2—C3—S1	−1.21 (15)	O3—C12—C13—C14	−178.01 (12)
C7—C2—C3—S1	177.93 (11)	C11—C12—C13—C14	1.9 (2)
C1—S1—C3—C2	0.71 (11)	O4—C13—C14—C15	−179.53 (13)
C1—S1—C3—C4	−176.90 (11)	C12—C13—C14—C15	−0.6 (2)
C5—O1—C4—O2	1.04 (19)	C13—C14—C15—C10	−0.7 (2)
C5—O1—C4—C3	−179.34 (11)	C11—C10—C15—C14	0.7 (2)
C2—C3—C4—O2	2.3 (2)	C9—C10—C15—C14	−179.74 (12)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C10–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O2	0.98	2.28	3.0111 (19)	130
O4—H4O···O2ⁱ	0.84	1.85	2.6878 (14)	176
C16—H16A···O4ⁱⁱ	0.98	2.41	3.3824 (18)	171
C8—H8C···N3ⁱⁱⁱ	0.98	2.62	3.3986 (19)	137
C6—H6B···Cg1^iv	0.98	2.96	3.6414 (16)	128
C7—H7C···Cg1^v	0.98	2.62	3.4762 (16)	146

Symmetry codes: (i) x−2, y+1, z; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z; (iv) −x+1, −y+1, −z+1; (v) x+1, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₉N₃O₄S
M_r	349.40
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	6.8957 (3), 10.2716 (5), 12.7297 (6)
α, β, γ (°)	74.843 (4), 87.579 (4), 73.304 (4)
V (Å³)	833.06 (7)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	1.96
Crystal size (mm)	0.40 × 0.35 × 0.30

Data collection
Diffractometer	Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Agilent, 2011)
T_min, T_max	0.508, 0.591
No. of measured, independent and observed [I > 2σ(I)] reflections	5272, 3316, 3254
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.099, 1.02
No. of reflections	3316
No. of parameters	222
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.29

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C10–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O2	0.98	2.28	3.0111 (19)	130
O4—H4O···O2ⁱ	0.84	1.85	2.6878 (14)	176
C16—H16A···O4ⁱⁱ	0.98	2.41	3.3824 (18)	171
C8—H8C···N3ⁱⁱⁱ	0.98	2.62	3.3986 (19)	137
C6—H6B···Cg1^iv	0.98	2.96	3.6414 (16)	128
C7—H7C···Cg1^v	0.98	2.62	3.4762 (16)	146

Symmetry codes: (i) x−2, y+1, z; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z; (iv) −x+1, −y+1, −z+1; (v) x+1, y−1, z.

Acknowledgements

RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the diffractometer.

References

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Volume 68| Part 11| November 2012| Pages o3213-o3214

doi:10.1107/S1600536812043772

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

Ethyl 2-[2-(4-hy­dr­oxy-3-meth­­oxy­benzyl­­idene)hydrazin-1-yl­­idene]-3,4-di­methyl-2,3-di­hydro-1,3-thia­zole-5-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Ethyl 2-[2-(4-hydroxy-3-methoxybenzylidene)hydrazin-1-ylidene]-3,4-dimethyl-2,3-dihydro-1,3-thiazole-5-carboxylate