Ethyl 2-[2-(4-hy-droxy-3-meth-oxy-benzyl-idene)hydrazin-1-yl-idene]-3,4-dimethyl-2,3-dihydro-1,3-thia-zole-5-carboxyl-ate.

The title compound, C(16)H(19)N(3)O(4)S, is almost planar, with a dihedral angle of 2.88 (9)° between the mean planes of the benzene and thia-zole rings. The mol-ecule adopts an E conformation about the two C=N bonds, with a C-N-N-C torsion angle of -177.01 (11)°. An intra-molecular C-H⋯O hydrogen bond exists between a thia-zole methyl group and the formic acid ethyl ester carbonyl O atom. In the crystal, mol-ecules 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 R(2) (2)(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 R(2) (2)(12) ring motifs and C-H⋯π inter-actions, forming an inter-esting three-dimensional supra-molecular 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 = 349.40

Triclinic,

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[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.099

S = 1.02

3316 reflections

222 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.29 e Å−3

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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812043772/su2516sup1.cif

Click here for additional data file.

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

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812043772/su2516Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H19N3O4S	Z = 2
Mr = 349.40	F(000) = 368
Triclinic, P1	Dx = 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

Agilent Xcalibur (Ruby, Gemini) diffractometer	3316 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3254 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 10.5081 pixels mm-1	θmax = 75.2°, θmin = 3.6°
ω scans	h = −8→6
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2011)	k = −12→12
Tmin = 0.508, Tmax = 0.591	l = −14→15
5272 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0628P)2 + 0.3221P] where P = (Fo2 + 2Fc2)/3
3316 reflections	(Δ/σ)max < 0.001
222 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···Cg1iv	0.98	2.96	3.6414 (16)	128
C7—H7C···Cg1v	0.98	2.62	3.4762 (16)	146

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⋯Cg1iv	0.98	2.96	3.6414 (16)	128
C7—H7C⋯Cg1v	0.98	2.62	3.4762 (16)	146

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .