Crystal structure of ethyl 4-(2,4-di-chloro-phen-yl)-2-methyl-4H-benzo[4,5]thia-zolo[3,2-a]pyrimidine-3-carboxyl-ate.

In the title compound, C20H16Cl2N2O2S, the pyrimidine ring has a screw-boat conformation. The attached di-chloro-phenyl ring is twisted at an angle of 89.29 (13)° with respect to the pyrimidine ring mean plane. The benzo-thia-zole group is approximately planar (r.m.s. deviation = 0.008 Å) and inclined to the pyrimidine ring mean plane by 3.04 (10)°. The carboxyl-ate group assumes an extended conformation with respect to the pyrimidine ring, which can be seen from the O=C-O-C torsion angle of 3.2 (4) °. In the crystal, mol-ecules are linked via C-H⋯O and C-H⋯N hydrogen bonds, forming slabs lying parallel to (100).

Related literature

For general background and literature on the biological properties of pyrimidine derivatives, see: Kumar et al. (2002 ▸; Baraldi et al. (2002 ▸); Nasr & Gineinah (2002 ▸).

Experimental

Crystal data

C20H16Cl2N2O2S

M = 419.31

Monoclinic,

a = 38.654 (8) Å

b = 11.787 (3) Å

c = 8.774 (2) Å

β = 102.415 (14)°

V = 3904.1 (15) Å3

Z = 8

Cu Kα radiation

μ = 4.14 mm−1

T = 296 K

0.30 × 0.27 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.370, T max = 0.424

10089 measured reflections

3114 independent reflections

2519 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.139

S = 1.04

3114 reflections

246 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; 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 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015007033/su5114sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007033/su5114Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015007033/su5114Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015007033/su5114fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

c . DOI: 10.1107/S2056989015007033/su5114fig2.tif

The crystal packing of the mol­ecules viewed down the c axis.

CCDC reference: 1056200

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

C20H16Cl2N2O2S	F(000) = 1728
Mr = 419.31	Dx = 1.427 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 3114 reflections
a = 38.654 (8) Å	θ = 5.1–64.1°
b = 11.787 (3) Å	µ = 4.14 mm−1
c = 8.774 (2) Å	T = 296 K
β = 102.415 (14)°	Block, yellow
V = 3904.1 (15) Å3	0.30 × 0.27 × 0.25 mm
Z = 8

Bruker SMART APEXII CCD diffractometer	3114 independent reflections
Radiation source: fine-focus sealed tube	2519 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω and φ scans	θmax = 64.1°, θmin = 5.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −43→44
Tmin = 0.370, Tmax = 0.424	k = −12→12
10089 measured reflections	l = −10→9

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0772P)2 + 2.6744P] where P = (Fo2 + 2Fc2)/3
3114 reflections	(Δ/σ)max < 0.001
246 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.31 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
N1	0.29291 (6)	0.8365 (2)	0.6499 (3)	0.0540 (6)
C2	0.29669 (6)	0.7278 (2)	0.6518 (3)	0.0450 (6)
S3	0.267722 (17)	0.63964 (6)	0.72345 (9)	0.0552 (3)
C4	0.28999 (6)	0.5193 (2)	0.6806 (3)	0.0446 (6)
C5	0.28233 (7)	0.4079 (2)	0.7057 (3)	0.0520 (7)
H5	0.2631	0.3891	0.7488	0.062*
C6	0.30359 (8)	0.3250 (3)	0.6658 (4)	0.0561 (7)
H6	0.2990	0.2492	0.6832	0.067*
C7	0.33195 (8)	0.3533 (2)	0.5997 (4)	0.0560 (7)
H7	0.3460	0.2958	0.5730	0.067*
C8	0.33984 (7)	0.4649 (2)	0.5723 (3)	0.0484 (7)
H8	0.3589	0.4831	0.5276	0.058*
C9	0.31847 (6)	0.5488 (2)	0.6136 (3)	0.0406 (6)
N10	0.32157 (5)	0.66662 (18)	0.5982 (2)	0.0417 (5)
C11	0.35145 (6)	0.7226 (2)	0.5479 (3)	0.0411 (6)
H11	0.3537	0.6908	0.4474	0.049*
C12	0.34297 (7)	0.8489 (2)	0.5275 (3)	0.0463 (6)
C13	0.31608 (7)	0.8979 (2)	0.5811 (3)	0.0513 (7)
C14	0.30725 (9)	1.0217 (3)	0.5713 (4)	0.0694 (9)
H14A	0.3263	1.0638	0.6345	0.104*
H14B	0.2859	1.0344	0.6084	0.104*
H14C	0.3038	1.0464	0.4649	0.104*
C15	0.38581 (6)	0.7024 (2)	0.6676 (3)	0.0409 (6)
C16	0.38873 (7)	0.7454 (2)	0.8175 (3)	0.0472 (6)
H16	0.3695	0.7836	0.8417	0.057*
C17	0.41907 (8)	0.7332 (3)	0.9307 (4)	0.0608 (8)
H17	0.4205	0.7630	1.0300	0.073*
C18	0.44751 (8)	0.6758 (3)	0.8946 (4)	0.0627 (8)
C19	0.44582 (7)	0.6332 (3)	0.7486 (4)	0.0612 (8)
H19	0.4651	0.5953	0.7251	0.073*
C20	0.41531 (7)	0.6470 (2)	0.6369 (3)	0.0491 (7)
Cl21	0.41503 (2)	0.59197 (7)	0.45153 (10)	0.0706 (3)
Cl22	0.48585 (3)	0.65809 (11)	1.03772 (14)	0.1075 (4)
C23	0.36748 (8)	0.9170 (3)	0.4592 (3)	0.0556 (7)
O24	0.36870 (7)	1.0189 (2)	0.4524 (3)	0.0880 (8)
O25	0.39033 (6)	0.8507 (2)	0.4043 (3)	0.0734 (7)
C26	0.41805 (13)	0.9061 (4)	0.3433 (5)	0.1021 (15)
H26A	0.4088	0.9754	0.2903	0.122*
H26B	0.4253	0.8568	0.2674	0.122*
C27	0.44862 (13)	0.9328 (5)	0.4666 (8)	0.134 (2)
H27A	0.4416	0.9836	0.5400	0.201*
H27B	0.4665	0.9682	0.4221	0.201*
H27C	0.4579	0.8642	0.5190	0.201*

	U11	U22	U33	U12	U13	U23
N1	0.0535 (13)	0.0408 (15)	0.0701 (16)	0.0048 (10)	0.0185 (12)	−0.0012 (11)
C2	0.0429 (13)	0.0401 (17)	0.0513 (15)	0.0021 (11)	0.0086 (11)	−0.0025 (12)
S3	0.0456 (4)	0.0476 (5)	0.0771 (5)	0.0017 (3)	0.0239 (3)	0.0002 (3)
C4	0.0394 (12)	0.0424 (17)	0.0512 (15)	−0.0019 (11)	0.0077 (11)	0.0004 (12)
C5	0.0495 (15)	0.0455 (18)	0.0619 (17)	−0.0077 (13)	0.0142 (13)	0.0038 (13)
C6	0.0656 (18)	0.0351 (16)	0.0682 (19)	−0.0063 (13)	0.0155 (15)	0.0017 (13)
C7	0.0608 (17)	0.0400 (18)	0.0682 (19)	0.0019 (13)	0.0163 (15)	−0.0035 (14)
C8	0.0491 (14)	0.0408 (17)	0.0574 (17)	−0.0014 (12)	0.0162 (12)	−0.0049 (13)
C9	0.0420 (13)	0.0351 (15)	0.0429 (14)	−0.0045 (11)	0.0050 (11)	−0.0022 (11)
N10	0.0421 (11)	0.0343 (13)	0.0502 (12)	−0.0013 (9)	0.0136 (10)	−0.0016 (9)
C11	0.0462 (13)	0.0366 (15)	0.0432 (14)	−0.0043 (11)	0.0154 (11)	−0.0037 (11)
C12	0.0538 (15)	0.0379 (16)	0.0450 (15)	−0.0023 (11)	0.0058 (12)	0.0034 (11)
C13	0.0560 (16)	0.0381 (16)	0.0563 (17)	0.0024 (12)	0.0044 (13)	0.0004 (12)
C14	0.075 (2)	0.0404 (19)	0.092 (2)	0.0083 (15)	0.0153 (18)	0.0044 (16)
C15	0.0456 (13)	0.0315 (14)	0.0479 (14)	−0.0041 (11)	0.0152 (11)	−0.0003 (11)
C16	0.0526 (14)	0.0401 (16)	0.0513 (15)	0.0009 (12)	0.0165 (12)	−0.0034 (12)
C17	0.0724 (19)	0.057 (2)	0.0495 (17)	−0.0046 (16)	0.0048 (15)	−0.0073 (14)
C18	0.0493 (16)	0.063 (2)	0.070 (2)	−0.0035 (15)	0.0002 (14)	0.0069 (16)
C19	0.0433 (15)	0.057 (2)	0.085 (2)	0.0012 (13)	0.0171 (15)	0.0003 (17)
C20	0.0490 (14)	0.0414 (16)	0.0623 (17)	−0.0040 (12)	0.0241 (13)	−0.0068 (13)
Cl21	0.0700 (5)	0.0747 (6)	0.0771 (5)	−0.0009 (4)	0.0375 (4)	−0.0252 (4)
Cl22	0.0677 (6)	0.1307 (10)	0.1058 (8)	0.0037 (6)	−0.0221 (5)	0.0064 (7)
C23	0.0678 (18)	0.048 (2)	0.0501 (17)	−0.0049 (14)	0.0103 (14)	0.0078 (13)
O24	0.0960 (18)	0.0479 (16)	0.127 (2)	−0.0077 (12)	0.0385 (16)	0.0245 (14)
O25	0.0905 (16)	0.0654 (16)	0.0767 (15)	−0.0168 (12)	0.0455 (13)	−0.0005 (11)
C26	0.126 (3)	0.104 (3)	0.098 (3)	−0.039 (3)	0.071 (3)	−0.006 (2)
C27	0.088 (3)	0.143 (5)	0.182 (6)	−0.025 (3)	0.050 (4)	−0.008 (4)

N1—C2	1.290 (4)	C14—H14A	0.9600
N1—C13	1.387 (4)	C14—H14B	0.9600
C2—N10	1.364 (3)	C14—H14C	0.9600
C2—S3	1.741 (3)	C15—C20	1.390 (3)
S3—C4	1.741 (3)	C15—C16	1.392 (4)
C4—C5	1.375 (4)	C16—C17	1.372 (4)
C4—C9	1.399 (3)	C16—H16	0.9300
C5—C6	1.369 (4)	C17—C18	1.384 (4)
C5—H5	0.9300	C17—H17	0.9300
C6—C7	1.387 (4)	C18—C19	1.365 (5)
C6—H6	0.9300	C18—Cl22	1.737 (3)
C7—C8	1.383 (4)	C19—C20	1.371 (4)
C7—H7	0.9300	C19—H19	0.9300
C8—C9	1.385 (4)	C20—Cl21	1.748 (3)
C8—H8	0.9300	C23—O24	1.204 (4)
C9—N10	1.403 (3)	C23—O25	1.343 (4)
N10—C11	1.478 (3)	O25—C26	1.452 (4)
C11—C15	1.524 (3)	C26—C27	1.455 (7)
C11—C12	1.527 (4)	C26—H26A	0.9700
C11—H11	0.9800	C26—H26B	0.9700
C12—C13	1.358 (4)	C27—H27A	0.9600
C12—C23	1.465 (4)	C27—H27B	0.9600
C13—C14	1.497 (4)	C27—H27C	0.9600
C2—N1—C13	116.2 (2)	C13—C14—H14B	109.5
N1—C2—N10	127.4 (2)	H14A—C14—H14B	109.5
N1—C2—S3	121.2 (2)	C13—C14—H14C	109.5
N10—C2—S3	111.4 (2)	H14A—C14—H14C	109.5
C4—S3—C2	91.26 (12)	H14B—C14—H14C	109.5
C5—C4—C9	121.3 (2)	C20—C15—C16	116.8 (2)
C5—C4—S3	127.6 (2)	C20—C15—C11	124.7 (2)
C9—C4—S3	111.0 (2)	C16—C15—C11	118.4 (2)
C6—C5—C4	118.6 (3)	C17—C16—C15	121.9 (3)
C6—C5—H5	120.7	C17—C16—H16	119.0
C4—C5—H5	120.7	C15—C16—H16	119.0
C5—C6—C7	120.5 (3)	C16—C17—C18	118.9 (3)
C5—C6—H6	119.8	C16—C17—H17	120.6
C7—C6—H6	119.7	C18—C17—H17	120.6
C8—C7—C6	121.6 (3)	C19—C18—C17	121.0 (3)
C8—C7—H7	119.2	C19—C18—Cl22	119.7 (3)
C6—C7—H7	119.2	C17—C18—Cl22	119.3 (3)
C7—C8—C9	117.9 (3)	C18—C19—C20	119.2 (3)
C7—C8—H8	121.1	C18—C19—H19	120.4
C9—C8—H8	121.1	C20—C19—H19	120.4
C8—C9—C4	120.0 (2)	C19—C20—C15	122.2 (3)
C8—C9—N10	127.8 (2)	C19—C20—Cl21	117.0 (2)
C4—C9—N10	112.2 (2)	C15—C20—Cl21	120.9 (2)
C2—N10—C9	114.1 (2)	O24—C23—O25	121.8 (3)
C2—N10—C11	121.4 (2)	O24—C23—C12	127.0 (3)
C9—N10—C11	124.0 (2)	O25—C23—C12	111.2 (3)
N10—C11—C15	110.2 (2)	C23—O25—C26	117.7 (3)
N10—C11—C12	108.0 (2)	O25—C26—C27	111.6 (4)
C15—C11—C12	111.5 (2)	O25—C26—H26A	109.3
N10—C11—H11	109.0	C27—C26—H26A	109.3
C15—C11—H11	109.0	O25—C26—H26B	109.3
C12—C11—H11	109.0	C27—C26—H26B	109.3
C13—C12—C23	121.3 (3)	H26A—C26—H26B	108.0
C13—C12—C11	122.4 (2)	C26—C27—H27A	109.5
C23—C12—C11	116.1 (2)	C26—C27—H27B	109.5
C12—C13—N1	122.9 (3)	H27A—C27—H27B	109.5
C12—C13—C14	125.2 (3)	C26—C27—H27C	109.5
N1—C13—C14	111.9 (3)	H27A—C27—H27C	109.5
C13—C14—H14A	109.5	H27B—C27—H27C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N1i	0.93	2.59	3.515 (4)	176
C16—H16···O24ii	0.93	2.53	3.180 (4)	128

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C5H5N1i	0.93	2.59	3.515(4)	176
C16H16O24ii	0.93	2.53	3.180(4)	128

Symmetry codes: (i) ; (ii) .