Crystal structure of N-[3-(2-chloro-benzo-yl)-5-ethyl-thio-phen-2-yl]-2-[(E)-(2-hy-droxy-benzyl-idene)amino]-acetamide.

In the title compound, C22H19ClN2O3S, the dihedral angle between the mean planes of the thio-phene ring and the chloro-phenyl and hy-droxy-phenyl rings are 70.1 (1) and 40.2 (4)°, respectively. The benzene rings are twisted with respect to each other by 88.9 (3)°. The imine bond lies in an E conformation. Intra-molecular O-H⋯N and N-H⋯O hydrogen bonds each generate S(6) ring motifs. In the crystal, weak C-H⋯O inter-actions link the mol-ecules, forming chains along the c axis and zigzag chains along the b axis, generating sheets lying parallel to (100).

Related literature

For background to thio­phene derivatives, see: Molvi et al. (2007 ▶); Rai et al. (2008 ▶). For applications of 2-amino­thio­phene derivatives, see: Puterová et al. (2010 ▶); Cannito et al. (1990 ▶); Nikolakopoulos et al. (2006 ▶). For biological and industrial applications of Schiff bases, see: Desai et al. (2001 ▶); Singh & Dash (1988 ▶); Aydogan et al. (2001 ▶); Taggi et al. (2002 ▶). For a related structure, see: Fun et al. (2012 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C22H19ClN2O3S

M = 426.90

Monoclinic,

a = 9.7888 (2) Å

b = 16.9476 (3) Å

c = 12.2863 (3) Å

β = 90.6654 (19)°

V = 2038.11 (7) Å3

Z = 4

Cu Kα radiation

μ = 2.84 mm−1

T = 173 K

0.32 × 0.28 × 0.18 mm

Data collection

Agilent Xcalibur Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.802, T max = 1.000

14124 measured reflections

3909 independent reflections

3459 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.102

S = 1.02

3909 reflections

264 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.29 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814018224/zs2311sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018224/zs2311Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814018224/zs2311Isup3.cml

Click here for additional data file.

22 19 2 3 . DOI: 10.1107/S1600536814018224/zs2311fig1.tif

ORTEP drawing of C22H19N2O3SCl showing the labeling scheme of the mol­ecule with 30% probability displacement ellipsoids. Dashed lines inidicate O—H⋯N and N—H⋯O intra­molecular hydrogen bonds.

Click here for additional data file.

22 19 2 3 a b c . DOI: 10.1107/S1600536814018224/zs2311fig2.tif

Mol­ecular packing for C22H19ClN2O3S in the unit cell viewed along the a axis. Dashed lines indicate weak C—H⋯O inter­molecular inter­actions which inter­link the mol­ecules forming chains along the b and c axes. H atoms not involved in hydrogen- bonding have been removed for clarity.

CCDC reference: 1018596

Additional supporting information: crystallographic information; 3D view; checkCIF report

C22H19ClN2O3S	F(000) = 888
Mr = 426.90	Dx = 1.391 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 9.7888 (2) Å	Cell parameters from 6410 reflections
b = 16.9476 (3) Å	θ = 4.4–71.5°
c = 12.2863 (3) Å	µ = 2.84 mm−1
β = 90.6654 (19)°	T = 173 K
V = 2038.11 (7) Å3	Irregular, pale yellow
Z = 4	0.32 × 0.28 × 0.18 mm

Agilent Xcalibur Eos Gemini diffractometer	3909 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3459 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm-1	Rint = 0.028
ω scans	θmax = 71.4°, θmin = 4.5°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −12→10
Tmin = 0.802, Tmax = 1.000	k = −15→20
14124 measured reflections	l = −15→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H-atom parameters constrained
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.0595P)2 + 0.7231P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
3909 reflections	Δρmax = 0.42 e Å−3
264 parameters	Δρmin = −0.29 e Å−3
0 restraints

Experimental. 1H NMR (400 MHz, CDCl3): δ 12.39 (s, 1H), 12.18 (s, 1H), 8.51 (s, 1H), 7.45-7.28 (m, 6H), 7.06 (d, J = 8.4 Hz, 1H), 6.92 (t, J = 7.6 Hz, 1H), 6.38 (d, J = 1.2 Hz, 1H), 4.61 (s, 2H), 2.70 (q, J = 7.6 Hz, 2H), 1.27-1.23 (m, 3H).13C NMR (400 MHz, CDCl3): δ 191.0, 169.4, 166.8, 160.7, 148.4, 139.4, 137.4, 133.3, 132.3, 130.7, 130.5, 129.9, 128.3, 126.6, 121.3, 121.2, 121.1, 119.0, 118.4, 117.4, 62.8, 22.8, 15.5. MS: m/z = 426.91 (Calculated), m/z = 426.94 [M]+ (found).

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.

	x	y	z	Uiso*/Ueq
Cl1	0.51629 (5)	0.31401 (3)	0.21556 (4)	0.04758 (15)
S1	0.72524 (4)	0.53992 (2)	−0.03408 (3)	0.03034 (13)
O1	0.90220 (15)	0.32692 (8)	0.14607 (11)	0.0450 (4)
O2	0.89582 (15)	0.48587 (9)	−0.19425 (12)	0.0488 (4)
O3	1.20084 (14)	0.26518 (8)	0.07197 (10)	0.0389 (3)
H3	1.1619	0.2959	0.0304	0.058*
N1	0.89927 (14)	0.41330 (9)	−0.04031 (11)	0.0298 (3)
H1	0.9353	0.3731	−0.0084	0.036*
N2	1.09746 (14)	0.31536 (9)	−0.11697 (11)	0.0296 (3)
C1	0.81400 (18)	0.37146 (11)	0.18143 (14)	0.0337 (4)
C2	0.75997 (17)	0.43810 (10)	0.12005 (14)	0.0301 (4)
C3	0.65870 (17)	0.49297 (10)	0.15660 (14)	0.0312 (4)
H3A	0.6172	0.4893	0.2241	0.037*
C4	0.62912 (17)	0.55044 (10)	0.08380 (14)	0.0303 (4)
C5	0.80425 (17)	0.45664 (10)	0.01659 (14)	0.0277 (3)
C6	0.76476 (19)	0.35931 (11)	0.29613 (14)	0.0347 (4)
C7	0.6345 (2)	0.33302 (10)	0.31984 (15)	0.0361 (4)
C8	0.5958 (2)	0.31975 (11)	0.42645 (17)	0.0459 (5)
H8	0.5078	0.3025	0.4416	0.055*
C9	0.6891 (3)	0.33232 (14)	0.50999 (17)	0.0542 (6)
H9	0.6642	0.3226	0.5816	0.065*
C10	0.8190 (3)	0.35918 (16)	0.48780 (18)	0.0579 (6)
H10	0.8811	0.3679	0.5443	0.069*
C11	0.8567 (2)	0.37316 (14)	0.38070 (17)	0.0479 (5)
H11	0.9438	0.3919	0.3658	0.058*
C12	0.93954 (17)	0.42990 (11)	−0.14303 (14)	0.0325 (4)
C13	1.04302 (19)	0.37442 (12)	−0.19171 (14)	0.0366 (4)
H13A	1.0007	0.3476	−0.2531	0.044*
H13B	1.1184	0.4054	−0.2193	0.044*
C14	1.13375 (17)	0.24926 (10)	−0.15744 (13)	0.0288 (3)
H14	1.1191	0.2404	−0.2314	0.035*
C15	1.19709 (17)	0.18724 (10)	−0.09226 (14)	0.0285 (3)
C16	1.22675 (17)	0.19676 (10)	0.01912 (13)	0.0289 (3)
C17	1.28505 (19)	0.13503 (12)	0.07805 (15)	0.0376 (4)
H17	1.3040	0.1412	0.1519	0.045*
C18	1.3150 (2)	0.06443 (12)	0.02676 (18)	0.0461 (5)
H18	1.3542	0.0234	0.0665	0.055*
C19	1.2869 (2)	0.05440 (12)	−0.08316 (19)	0.0483 (5)
H19	1.3071	0.0068	−0.1171	0.058*
C20	1.2291 (2)	0.11509 (11)	−0.14174 (15)	0.0387 (4)
H20	1.2109	0.1082	−0.2156	0.046*
C21	0.52840 (19)	0.61717 (10)	0.09042 (17)	0.0373 (4)
H21A	0.4703	0.6163	0.0259	0.045*
H21B	0.5780	0.6667	0.0907	0.045*
C22	0.43888 (19)	0.61370 (11)	0.19068 (16)	0.0387 (4)
H22A	0.4948	0.6193	0.2549	0.058*
H22B	0.3922	0.5639	0.1927	0.058*
H22C	0.3731	0.6557	0.1877	0.058*

	U11	U22	U33	U12	U13	U23
Cl1	0.0494 (3)	0.0435 (3)	0.0499 (3)	−0.0040 (2)	0.0038 (2)	−0.0039 (2)
S1	0.0306 (2)	0.0277 (2)	0.0327 (2)	0.00170 (15)	−0.00142 (16)	0.00588 (15)
O1	0.0500 (8)	0.0504 (8)	0.0350 (7)	0.0261 (6)	0.0130 (6)	0.0114 (6)
O2	0.0476 (8)	0.0570 (9)	0.0421 (8)	0.0170 (7)	0.0090 (6)	0.0233 (7)
O3	0.0495 (8)	0.0438 (7)	0.0234 (6)	0.0149 (6)	−0.0037 (5)	−0.0071 (5)
N1	0.0283 (7)	0.0330 (7)	0.0281 (7)	0.0051 (6)	0.0024 (5)	0.0060 (6)
N2	0.0289 (7)	0.0377 (8)	0.0222 (7)	0.0016 (6)	0.0019 (5)	0.0006 (6)
C1	0.0326 (9)	0.0373 (9)	0.0313 (9)	0.0087 (7)	0.0046 (7)	0.0046 (7)
C2	0.0282 (8)	0.0329 (9)	0.0292 (8)	0.0048 (7)	0.0022 (6)	0.0026 (7)
C3	0.0300 (8)	0.0319 (8)	0.0318 (9)	0.0039 (7)	0.0013 (7)	0.0003 (7)
C4	0.0290 (8)	0.0273 (8)	0.0346 (9)	0.0004 (6)	−0.0021 (7)	−0.0009 (7)
C5	0.0263 (8)	0.0279 (8)	0.0287 (8)	−0.0002 (6)	−0.0025 (6)	0.0032 (6)
C6	0.0397 (9)	0.0348 (9)	0.0298 (9)	0.0162 (7)	0.0055 (7)	0.0061 (7)
C7	0.0450 (10)	0.0277 (8)	0.0358 (9)	0.0076 (7)	0.0076 (8)	0.0017 (7)
C8	0.0620 (13)	0.0324 (9)	0.0438 (11)	0.0026 (9)	0.0207 (10)	0.0019 (8)
C9	0.0804 (17)	0.0517 (13)	0.0308 (10)	0.0159 (11)	0.0193 (10)	0.0085 (9)
C10	0.0647 (15)	0.0753 (16)	0.0335 (11)	0.0231 (12)	−0.0056 (10)	0.0055 (10)
C11	0.0395 (10)	0.0667 (14)	0.0376 (10)	0.0179 (9)	0.0027 (8)	0.0057 (9)
C12	0.0276 (8)	0.0414 (10)	0.0284 (8)	0.0007 (7)	0.0002 (6)	0.0081 (7)
C13	0.0366 (9)	0.0484 (10)	0.0248 (8)	0.0064 (8)	0.0062 (7)	0.0085 (7)
C14	0.0292 (8)	0.0382 (9)	0.0190 (7)	−0.0056 (7)	0.0013 (6)	−0.0014 (6)
C15	0.0268 (8)	0.0330 (8)	0.0259 (8)	−0.0054 (6)	0.0029 (6)	−0.0027 (6)
C16	0.0261 (8)	0.0356 (9)	0.0251 (8)	0.0002 (6)	0.0044 (6)	−0.0024 (7)
C17	0.0362 (9)	0.0472 (10)	0.0296 (9)	0.0042 (8)	0.0031 (7)	0.0032 (8)
C18	0.0521 (12)	0.0377 (10)	0.0486 (12)	0.0065 (9)	0.0031 (9)	0.0087 (9)
C19	0.0615 (13)	0.0306 (9)	0.0529 (12)	0.0017 (9)	0.0053 (10)	−0.0071 (9)
C20	0.0465 (10)	0.0366 (10)	0.0330 (9)	−0.0048 (8)	0.0006 (8)	−0.0080 (7)
C21	0.0339 (9)	0.0270 (8)	0.0511 (11)	0.0046 (7)	−0.0016 (8)	0.0019 (8)
C22	0.0364 (9)	0.0349 (9)	0.0447 (10)	0.0069 (7)	−0.0049 (8)	−0.0103 (8)

Cl1—C7	1.746 (2)	C9—C10	1.381 (4)
S1—C4	1.7453 (18)	C10—H10	0.9300
S1—C5	1.7223 (16)	C10—C11	1.391 (3)
O1—C1	1.230 (2)	C11—H11	0.9300
O2—C12	1.214 (2)	C12—C13	1.511 (3)
O3—H3	0.8200	C13—H13A	0.9700
O3—C16	1.354 (2)	C13—H13B	0.9700
N1—H1	0.8600	C14—H14	0.9300
N1—C5	1.382 (2)	C14—C15	1.456 (2)
N1—C12	1.356 (2)	C15—C16	1.405 (2)
N2—C13	1.455 (2)	C15—C20	1.403 (2)
N2—C14	1.278 (2)	C16—C17	1.391 (3)
C1—C2	1.454 (2)	C17—H17	0.9300
C1—C6	1.509 (2)	C17—C18	1.385 (3)
C2—C3	1.435 (2)	C18—H18	0.9300
C2—C5	1.384 (2)	C18—C19	1.386 (3)
C3—H3A	0.9300	C19—H19	0.9300
C3—C4	1.351 (2)	C19—C20	1.373 (3)
C4—C21	1.503 (2)	C20—H20	0.9300
C6—C7	1.385 (3)	C21—H21A	0.9700
C6—C11	1.387 (3)	C21—H21B	0.9700
C7—C8	1.386 (3)	C21—C22	1.521 (3)
C8—H8	0.9300	C22—H22A	0.9600
C8—C9	1.382 (4)	C22—H22B	0.9600
C9—H9	0.9300	C22—H22C	0.9600
C5—S1—C4	91.60 (8)	N1—C12—C13	116.29 (15)
C16—O3—H3	109.5	N2—C13—C12	114.87 (14)
C5—N1—H1	117.8	N2—C13—H13A	108.5
C12—N1—H1	117.8	N2—C13—H13B	108.5
C12—N1—C5	124.42 (15)	C12—C13—H13A	108.5
C14—N2—C13	117.32 (14)	C12—C13—H13B	108.5
O1—C1—C2	123.10 (16)	H13A—C13—H13B	107.5
O1—C1—C6	118.64 (15)	N2—C14—H14	118.7
C2—C1—C6	118.17 (14)	N2—C14—C15	122.52 (15)
C3—C2—C1	126.12 (15)	C15—C14—H14	118.7
C5—C2—C1	122.47 (15)	C16—C15—C14	122.33 (15)
C5—C2—C3	111.41 (15)	C20—C15—C14	119.14 (15)
C2—C3—H3A	123.1	C20—C15—C16	118.53 (16)
C4—C3—C2	113.79 (16)	O3—C16—C15	121.85 (15)
C4—C3—H3A	123.1	O3—C16—C17	118.19 (15)
C3—C4—S1	111.23 (13)	C17—C16—C15	119.97 (16)
C3—C4—C21	129.94 (17)	C16—C17—H17	120.0
C21—C4—S1	118.82 (14)	C18—C17—C16	120.03 (17)
N1—C5—S1	123.71 (13)	C18—C17—H17	120.0
N1—C5—C2	124.32 (15)	C17—C18—H18	119.7
C2—C5—S1	111.96 (13)	C17—C18—C19	120.58 (19)
C7—C6—C1	123.05 (17)	C19—C18—H18	119.7
C7—C6—C11	119.20 (17)	C18—C19—H19	120.2
C11—C6—C1	117.73 (17)	C20—C19—C18	119.65 (18)
C6—C7—Cl1	120.58 (14)	C20—C19—H19	120.2
C6—C7—C8	120.9 (2)	C15—C20—H20	119.4
C8—C7—Cl1	118.52 (17)	C19—C20—C15	121.23 (18)
C7—C8—H8	120.3	C19—C20—H20	119.4
C9—C8—C7	119.4 (2)	C4—C21—H21A	108.9
C9—C8—H8	120.3	C4—C21—H21B	108.9
C8—C9—H9	119.8	C4—C21—C22	113.53 (16)
C10—C9—C8	120.41 (19)	H21A—C21—H21B	107.7
C10—C9—H9	119.8	C22—C21—H21A	108.9
C9—C10—H10	120.1	C22—C21—H21B	108.9
C9—C10—C11	119.9 (2)	C21—C22—H22A	109.5
C11—C10—H10	120.1	C21—C22—H22B	109.5
C6—C11—C10	120.2 (2)	C21—C22—H22C	109.5
C6—C11—H11	119.9	H22A—C22—H22B	109.5
C10—C11—H11	119.9	H22A—C22—H22C	109.5
O2—C12—N1	122.69 (17)	H22B—C22—H22C	109.5
O2—C12—C13	121.02 (16)
Cl1—C7—C8—C9	178.20 (15)	C5—S1—C4—C21	−178.57 (14)
S1—C4—C21—C22	172.69 (13)	C5—N1—C12—O2	0.9 (3)
O1—C1—C2—C3	−179.10 (19)	C5—N1—C12—C13	−179.01 (16)
O1—C1—C2—C5	−0.1 (3)	C5—C2—C3—C4	−0.4 (2)
O1—C1—C6—C7	−111.3 (2)	C6—C1—C2—C3	−2.5 (3)
O1—C1—C6—C11	66.8 (3)	C6—C1—C2—C5	176.43 (17)
O2—C12—C13—N2	173.46 (17)	C6—C7—C8—C9	−0.6 (3)
O3—C16—C17—C18	−179.09 (18)	C7—C6—C11—C10	1.3 (3)
N1—C12—C13—N2	−6.6 (2)	C7—C8—C9—C10	1.1 (3)
N2—C14—C15—C16	−2.1 (2)	C8—C9—C10—C11	−0.5 (4)
N2—C14—C15—C20	177.49 (16)	C9—C10—C11—C6	−0.8 (4)
C1—C2—C3—C4	178.67 (17)	C11—C6—C7—Cl1	−179.40 (15)
C1—C2—C5—S1	−178.41 (14)	C11—C6—C7—C8	−0.7 (3)
C1—C2—C5—N1	2.3 (3)	C12—N1—C5—S1	−1.4 (2)
C1—C6—C7—Cl1	−1.3 (2)	C12—N1—C5—C2	177.77 (17)
C1—C6—C7—C8	177.39 (16)	C13—N2—C14—C15	176.28 (15)
C1—C6—C11—C10	−176.8 (2)	C14—N2—C13—C12	149.92 (16)
C2—C1—C6—C7	72.0 (2)	C14—C15—C16—O3	−1.5 (3)
C2—C1—C6—C11	−110.0 (2)	C14—C15—C16—C17	178.81 (15)
C2—C3—C4—S1	−0.1 (2)	C14—C15—C20—C19	−178.92 (18)
C2—C3—C4—C21	178.74 (17)	C15—C16—C17—C18	0.6 (3)
C3—C2—C5—S1	0.69 (19)	C16—C15—C20—C19	0.7 (3)
C3—C2—C5—N1	−178.61 (16)	C16—C17—C18—C19	−0.2 (3)
C3—C4—C21—C22	−6.1 (3)	C17—C18—C19—C20	0.1 (3)
C4—S1—C5—N1	178.67 (15)	C18—C19—C20—C15	−0.4 (3)
C4—S1—C5—C2	−0.63 (14)	C20—C15—C16—O3	178.86 (16)
C5—S1—C4—C3	0.40 (14)	C20—C15—C16—C17	−0.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N2	0.82	1.94	2.6611 (19)	146
N1—H1···O1	0.86	2.08	2.7177 (19)	130
C14—H14···O3i	0.93	2.56	3.405 (2)	152
C20—H20···O2ii	0.93	2.57	3.209 (2)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N2	0.82	1.94	2.6611 (19)	146
N1—H1⋯O1	0.86	2.08	2.7177 (19)	130
C14—H14⋯O3i	0.93	2.56	3.405 (2)	152
C20—H20⋯O2ii	0.93	2.57	3.209 (2)	126

Symmetry codes: (i) ; (ii) .