Crystal structure of (Z)-3-{3-(4-chloro-phen-yl)-2-[(4-chloro-phen-yl)imino]-2,3-di-hydro-thia-zol-4-yl}-2H-chromen-2-one.

In the title compound, C24H14Cl2N2O2S, the 2H-chromene ring system is approximately planar, with a maximum deviation of 0.025 (2) Å. The thia-zole ring is almost planar, with an r.m.s. deviation of 0.0022 Å, and makes a dihedral angle of 58.52 (7)° with the chromene ring system. The chromene ring system is inclined at angles of 58.3 (1) and 55.39 (9)° with respect to the two chloro-phenyl rings. The two chloro-phenyl rings show significant deviation from coplanarity, with a dihedral angle between them of 47.69 (8)°. The crystal structure features C-H⋯Cl inter-actions extending in (100) and propagating along the a-axis direction and weak π-π inter-actions [centroid-centroid separation = 3.867 (2) Å].

Related literature

For the bioactivity of coumarin, see: Yusufzai et al. (2012 ▶). For related structures, see: Arshad, Osman, Chan et al. (2010 ▶); Arshad, Osman, Lam et al. (2010a ▶,b ▶). For synthetic chemistry, medicinal chemistry, photochemistry and solid-state chemistry applications of coumarin derivatives, see: Chopra et al. (2009 ▶). For the synthesis, see: Raj Kumar & Rajeswar Rao (2014 ▶).

Experimental

Crystal data

C24H14Cl2N2O2S

M = 465.33

Monoclinic,

a = 9.1491 (7) Å

b = 10.3099 (8) Å

c = 11.9347 (10) Å

β = 111.587 (2)°

V = 1046.80 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.44 mm−1

T = 296 K

0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.897, T max = 1.000

15409 measured reflections

5549 independent reflections

4070 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.075

S = 1.03

5549 reflections

280 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack x determined using 1604 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▶)

Absolute structure parameter: −0.004 (19)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global, 206R. DOI: 10.1107/S1600536814024775/zs2320sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814024775/zs2320Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814024775/zs2320Isup3.cdx

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814024775/zs2320Isup4.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814024775/zs2320fig1.tif

The mol­ecular structure of the title compound showing atom numbering, with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.

a . DOI: 10.1107/S1600536814024775/zs2320fig2.tif

Crystal packing of the title compound in the unit cell, viewed along the a axis, showing C—H⋯Cl inter­actions as dashed lines.

Click here for additional data file.

. DOI: 10.1107/S1600536814024775/zs2320fig3.tif

The partial packing of the title compound, showing the π–π inter­actions.

CCDC reference: 1027667

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

C24H14Cl2N2O2S	F(000) = 476
Mr = 465.33	Dx = 1.476 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 9.1491 (7) Å	Cell parameters from 5853 reflections
b = 10.3099 (8) Å	θ = 4.8–29.9°
c = 11.9347 (10) Å	µ = 0.44 mm−1
β = 111.587 (2)°	T = 296 K
V = 1046.80 (14) Å3	Block, colourless
Z = 2	0.35 × 0.30 × 0.25 mm

Bruker Kappa APEXII CCD diffractometer	5549 independent reflections
Radiation source: fine-focus sealed tube	4070 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω and φ scans	θmax = 30.2°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→12
Tmin = 0.897, Tmax = 1.000	k = −13→14
15409 measured reflections	l = −16→16

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034	w = 1/[σ2(Fo2) + (0.0251P)2 + 0.1767P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.075	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.17 e Å−3
5549 reflections	Δρmin = −0.20 e Å−3
280 parameters	Absolute structure: Flack x determined using 1604 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.004 (19)

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.

	x	y	z	Uiso*/Ueq
Cl1	0.73427 (9)	0.67172 (10)	1.28483 (6)	0.0611 (2)
Cl2	0.07802 (15)	0.15926 (9)	0.32829 (9)	0.0911 (3)
S1	0.42551 (10)	0.84490 (8)	0.71595 (7)	0.0526 (2)
O1	0.2030 (2)	0.7096 (2)	0.17243 (18)	0.0552 (6)
O2	0.3924 (2)	0.6405 (2)	0.33588 (19)	0.0611 (6)
N1	0.3118 (2)	0.6598 (2)	0.56482 (18)	0.0408 (5)
N2	0.4358 (3)	0.5837 (2)	0.7613 (2)	0.0536 (7)
C1	0.2735 (3)	0.7030 (3)	0.2954 (2)	0.0438 (7)
C2	0.1989 (3)	0.7740 (3)	0.3656 (2)	0.0366 (6)
C3	0.0669 (3)	0.8415 (3)	0.3101 (2)	0.0386 (6)
H3	0.0194	0.8846	0.3562	0.046*
C4	−0.0030 (3)	0.8489 (3)	0.1811 (2)	0.0392 (6)
C5	−0.1396 (4)	0.9181 (3)	0.1185 (3)	0.0511 (8)
H5	−0.1912	0.9631	0.1607	0.061*
C6	−0.1983 (4)	0.9202 (4)	−0.0050 (3)	0.0606 (9)
H6	−0.2893	0.9667	−0.0465	0.073*
C7	−0.1228 (4)	0.8536 (4)	−0.0675 (3)	0.0690 (10)
H7	−0.1631	0.8562	−0.1513	0.083*
C8	0.0110 (4)	0.7834 (4)	−0.0087 (3)	0.0645 (9)
H8	0.0611	0.7378	−0.0515	0.077*
C9	0.0692 (3)	0.7822 (3)	0.1157 (2)	0.0452 (7)
C10	0.2782 (3)	0.7744 (3)	0.4978 (2)	0.0379 (6)
C11	0.3305 (4)	0.8795 (3)	0.5646 (3)	0.0462 (7)
H11	0.3174	0.9632	0.5333	0.055*
C12	0.3931 (3)	0.6762 (3)	0.6869 (2)	0.0428 (6)
C13	0.5081 (3)	0.6096 (3)	0.8852 (3)	0.0453 (7)
C14	0.6503 (4)	0.5525 (3)	0.9501 (3)	0.0551 (8)
H14	0.6992	0.5005	0.9106	0.066*
C15	0.7211 (4)	0.5712 (3)	1.0723 (3)	0.0559 (9)
H15	0.8178	0.5330	1.1149	0.067*
C16	0.6480 (3)	0.6468 (3)	1.1310 (2)	0.0422 (6)
C17	0.5071 (3)	0.7039 (3)	1.0692 (3)	0.0531 (8)
H17	0.4584	0.7554	1.1092	0.064*
C18	0.4369 (3)	0.6845 (4)	0.9460 (3)	0.0556 (8)
H18	0.3402	0.7227	0.9036	0.067*
C19	0.1469 (4)	0.3047 (3)	0.4032 (3)	0.0506 (8)
C20	0.3036 (4)	0.3174 (3)	0.4712 (3)	0.0536 (8)
H20	0.3723	0.2485	0.4792	0.064*
C21	0.3576 (4)	0.4336 (3)	0.5275 (3)	0.0492 (8)
H21	0.4636	0.4437	0.5745	0.059*
C22	0.2553 (3)	0.5348 (3)	0.5145 (2)	0.0377 (6)
C23	0.0977 (3)	0.5194 (3)	0.4499 (3)	0.0443 (7)
H23	0.0285	0.5871	0.4448	0.053*
C24	0.0419 (4)	0.4032 (3)	0.3925 (3)	0.0527 (8)
H24	−0.0645	0.3920	0.3476	0.063*

	U11	U22	U33	U12	U13	U23
Cl1	0.0589 (4)	0.0805 (6)	0.0361 (4)	−0.0094 (4)	0.0086 (3)	0.0030 (4)
Cl2	0.1509 (9)	0.0438 (4)	0.0690 (6)	−0.0333 (6)	0.0292 (6)	−0.0135 (5)
S1	0.0634 (5)	0.0460 (4)	0.0382 (4)	−0.0074 (4)	0.0069 (3)	−0.0095 (3)
O1	0.0514 (11)	0.0756 (15)	0.0401 (11)	0.0026 (11)	0.0187 (10)	−0.0100 (10)
O2	0.0481 (12)	0.0787 (17)	0.0577 (13)	0.0119 (12)	0.0209 (10)	−0.0019 (12)
N1	0.0441 (12)	0.0374 (11)	0.0330 (11)	−0.0043 (11)	0.0050 (9)	−0.0020 (11)
N2	0.0641 (17)	0.0458 (15)	0.0380 (13)	−0.0036 (12)	0.0037 (12)	−0.0006 (11)
C1	0.0427 (15)	0.0492 (16)	0.0404 (15)	−0.0036 (14)	0.0162 (13)	−0.0047 (13)
C2	0.0404 (15)	0.0341 (13)	0.0357 (14)	−0.0053 (12)	0.0144 (12)	−0.0038 (11)
C3	0.0476 (15)	0.0300 (12)	0.0390 (14)	−0.0045 (13)	0.0170 (12)	−0.0054 (12)
C4	0.0445 (14)	0.0337 (13)	0.0367 (13)	−0.0076 (13)	0.0117 (12)	−0.0020 (12)
C5	0.0561 (19)	0.0434 (16)	0.0460 (17)	0.0003 (14)	0.0096 (15)	0.0001 (14)
C6	0.063 (2)	0.058 (2)	0.0460 (18)	0.0005 (17)	0.0026 (16)	0.0053 (16)
C7	0.078 (2)	0.082 (2)	0.0355 (16)	−0.005 (2)	0.0079 (17)	0.0021 (19)
C8	0.066 (2)	0.088 (3)	0.0402 (17)	−0.007 (2)	0.0208 (16)	−0.0091 (18)
C9	0.0461 (16)	0.0518 (17)	0.0372 (15)	−0.0077 (14)	0.0146 (13)	−0.0026 (13)
C10	0.0371 (14)	0.0396 (15)	0.0352 (14)	−0.0007 (12)	0.0112 (12)	−0.0027 (12)
C11	0.0566 (19)	0.0402 (17)	0.0398 (16)	−0.0039 (13)	0.0154 (14)	−0.0043 (12)
C12	0.0399 (13)	0.0471 (17)	0.0370 (14)	−0.0047 (14)	0.0090 (11)	−0.0071 (14)
C13	0.0475 (16)	0.0430 (15)	0.0381 (15)	−0.0052 (13)	0.0069 (13)	0.0019 (13)
C14	0.066 (2)	0.0477 (17)	0.0456 (17)	0.0145 (16)	0.0142 (16)	0.0030 (14)
C15	0.0490 (18)	0.061 (2)	0.0464 (18)	0.0120 (15)	0.0039 (15)	0.0077 (15)
C16	0.0402 (14)	0.0489 (16)	0.0332 (13)	−0.0061 (13)	0.0086 (11)	0.0064 (13)
C17	0.0462 (16)	0.072 (2)	0.0430 (16)	0.0079 (16)	0.0182 (13)	0.0052 (15)
C18	0.0384 (14)	0.081 (2)	0.0429 (16)	0.0096 (17)	0.0095 (13)	0.0070 (18)
C19	0.079 (2)	0.0358 (15)	0.0362 (15)	−0.0115 (15)	0.0207 (15)	−0.0025 (12)
C20	0.072 (2)	0.0378 (17)	0.0506 (18)	0.0081 (14)	0.0218 (17)	0.0017 (13)
C21	0.0434 (17)	0.0474 (18)	0.0496 (18)	0.0029 (14)	0.0089 (14)	−0.0011 (14)
C22	0.0441 (16)	0.0356 (14)	0.0315 (13)	−0.0028 (12)	0.0118 (12)	−0.0021 (11)
C23	0.0390 (15)	0.0445 (17)	0.0459 (16)	−0.0006 (12)	0.0114 (13)	−0.0011 (13)
C24	0.0486 (17)	0.0565 (19)	0.0447 (17)	−0.0186 (16)	0.0075 (14)	0.0003 (15)

Cl1—C16	1.731 (3)	C8—C9	1.380 (4)
Cl2—C19	1.741 (3)	C8—H8	0.9300
S1—C11	1.729 (3)	C10—C11	1.326 (4)
S1—C12	1.777 (3)	C11—H11	0.9300
O1—C1	1.371 (3)	C13—C18	1.376 (4)
O1—C9	1.382 (4)	C13—C14	1.378 (4)
O2—C1	1.203 (3)	C14—C15	1.374 (4)
N1—C12	1.381 (3)	C14—H14	0.9300
N1—C10	1.396 (4)	C15—C16	1.375 (4)
N1—C22	1.436 (3)	C15—H15	0.9300
N2—C12	1.263 (4)	C16—C17	1.362 (4)
N2—C13	1.406 (4)	C17—C18	1.386 (4)
C1—C2	1.457 (4)	C17—H17	0.9300
C2—C3	1.339 (4)	C18—H18	0.9300
C2—C10	1.474 (4)	C19—C20	1.369 (5)
C3—C4	1.435 (3)	C19—C24	1.371 (5)
C3—H3	0.9300	C20—C21	1.373 (4)
C4—C9	1.378 (4)	C20—H20	0.9300
C4—C5	1.394 (4)	C21—C22	1.371 (4)
C5—C6	1.371 (4)	C21—H21	0.9300
C5—H5	0.9300	C22—C23	1.371 (4)
C6—C7	1.372 (5)	C23—C24	1.381 (4)
C6—H6	0.9300	C23—H23	0.9300
C7—C8	1.372 (5)	C24—H24	0.9300
C7—H7	0.9300
C11—S1—C12	90.84 (13)	N2—C12—N1	123.8 (3)
C1—O1—C9	122.3 (2)	N2—C12—S1	128.0 (2)
C12—N1—C10	114.9 (2)	N1—C12—S1	108.2 (2)
C12—N1—C22	121.5 (2)	C18—C13—C14	118.4 (3)
C10—N1—C22	123.41 (19)	C18—C13—N2	122.1 (3)
C12—N2—C13	120.0 (3)	C14—C13—N2	119.4 (3)
O2—C1—O1	117.1 (3)	C15—C14—C13	121.0 (3)
O2—C1—C2	125.8 (3)	C15—C14—H14	119.5
O1—C1—C2	117.1 (2)	C13—C14—H14	119.5
C3—C2—C1	120.3 (2)	C14—C15—C16	119.5 (3)
C3—C2—C10	121.8 (2)	C14—C15—H15	120.2
C1—C2—C10	117.8 (2)	C16—C15—H15	120.2
C2—C3—C4	121.5 (3)	C17—C16—C15	120.7 (3)
C2—C3—H3	119.2	C17—C16—Cl1	118.8 (2)
C4—C3—H3	119.2	C15—C16—Cl1	120.5 (2)
C9—C4—C5	118.3 (3)	C16—C17—C18	119.2 (3)
C9—C4—C3	117.6 (2)	C16—C17—H17	120.4
C5—C4—C3	124.1 (3)	C18—C17—H17	120.4
C6—C5—C4	120.2 (3)	C13—C18—C17	121.1 (3)
C6—C5—H5	119.9	C13—C18—H18	119.5
C4—C5—H5	119.9	C17—C18—H18	119.5
C5—C6—C7	120.0 (3)	C20—C19—C24	121.9 (3)
C5—C6—H6	120.0	C20—C19—Cl2	119.3 (3)
C7—C6—H6	120.0	C24—C19—Cl2	118.7 (3)
C6—C7—C8	121.2 (3)	C19—C20—C21	118.9 (3)
C6—C7—H7	119.4	C19—C20—H20	120.5
C8—C7—H7	119.4	C21—C20—H20	120.5
C7—C8—C9	118.3 (3)	C22—C21—C20	120.0 (3)
C7—C8—H8	120.9	C22—C21—H21	120.0
C9—C8—H8	120.9	C20—C21—H21	120.0
C4—C9—C8	122.0 (3)	C23—C22—C21	120.6 (3)
C4—C9—O1	121.1 (2)	C23—C22—N1	118.7 (2)
C8—C9—O1	117.0 (3)	C21—C22—N1	120.7 (2)
C11—C10—N1	113.1 (2)	C22—C23—C24	120.0 (3)
C11—C10—C2	124.9 (3)	C22—C23—H23	120.0
N1—C10—C2	121.9 (2)	C24—C23—H23	120.0
C10—C11—S1	113.0 (2)	C19—C24—C23	118.5 (3)
C10—C11—H11	123.5	C19—C24—H24	120.7
S1—C11—H11	123.5	C23—C24—H24	120.7
C9—O1—C1—O2	−177.6 (3)	C13—N2—C12—N1	−175.3 (3)
C9—O1—C1—C2	1.5 (4)	C13—N2—C12—S1	5.4 (4)
O2—C1—C2—C3	179.3 (3)	C10—N1—C12—N2	−178.8 (3)
O1—C1—C2—C3	0.3 (4)	C22—N1—C12—N2	6.4 (4)
O2—C1—C2—C10	2.7 (4)	C10—N1—C12—S1	0.5 (3)
O1—C1—C2—C10	−176.4 (2)	C22—N1—C12—S1	−174.3 (2)
C1—C2—C3—C4	−1.5 (4)	C11—S1—C12—N2	178.9 (3)
C10—C2—C3—C4	175.0 (2)	C11—S1—C12—N1	−0.4 (2)
C2—C3—C4—C9	1.0 (4)	C12—N2—C13—C18	56.7 (4)
C2—C3—C4—C5	−179.7 (3)	C12—N2—C13—C14	−127.2 (3)
C9—C4—C5—C6	−0.7 (4)	C18—C13—C14—C15	−1.0 (5)
C3—C4—C5—C6	179.9 (3)	N2—C13—C14—C15	−177.2 (3)
C4—C5—C6—C7	0.2 (5)	C13—C14—C15—C16	0.8 (5)
C5—C6—C7—C8	0.5 (6)	C14—C15—C16—C17	−0.5 (5)
C6—C7—C8—C9	−0.6 (6)	C14—C15—C16—Cl1	179.9 (3)
C5—C4—C9—C8	0.6 (4)	C15—C16—C17—C18	0.4 (5)
C3—C4—C9—C8	−180.0 (3)	Cl1—C16—C17—C18	−180.0 (3)
C5—C4—C9—O1	−178.6 (3)	C14—C13—C18—C17	0.9 (5)
C3—C4—C9—O1	0.8 (4)	N2—C13—C18—C17	177.0 (3)
C7—C8—C9—C4	0.1 (5)	C16—C17—C18—C13	−0.6 (5)
C7—C8—C9—O1	179.3 (3)	C24—C19—C20—C21	−1.9 (5)
C1—O1—C9—C4	−2.0 (4)	Cl2—C19—C20—C21	178.3 (2)
C1—O1—C9—C8	178.7 (3)	C19—C20—C21—C22	−0.4 (5)
C12—N1—C10—C11	−0.4 (3)	C20—C21—C22—C23	3.0 (5)
C22—N1—C10—C11	174.3 (3)	C20—C21—C22—N1	−175.1 (3)
C12—N1—C10—C2	177.1 (2)	C12—N1—C22—C23	122.6 (3)
C22—N1—C10—C2	−8.2 (4)	C10—N1—C22—C23	−51.8 (4)
C3—C2—C10—C11	−58.0 (4)	C12—N1—C22—C21	−59.4 (4)
C1—C2—C10—C11	118.6 (3)	C10—N1—C22—C21	126.3 (3)
C3—C2—C10—N1	124.9 (3)	C21—C22—C23—C24	−3.2 (4)
C1—C2—C10—N1	−58.5 (4)	N1—C22—C23—C24	174.9 (3)
N1—C10—C11—S1	0.0 (3)	C20—C19—C24—C23	1.7 (5)
C2—C10—C11—S1	−177.3 (2)	Cl2—C19—C24—C23	−178.6 (2)
C12—S1—C11—C10	0.2 (3)	C22—C23—C24—C19	0.9 (4)