1,5-Bis(4-chloro-phen-yl)-3-(2-thien-yl)pentane-1,5-dione.

In the title mol-ecule, C(21)H(16)Cl(2)O(2)S, the five-membered ring is rotationally disordered between two orientations in a 1:1 ratio. In the crystal structure, weak inter-molecular C-H⋯O hydrogen bonds link mol-ecules related by translation along the a axis into chains, which are further combined into layers parallel to the bc plane via C-H⋯π inter-actions. The crystal studied was a racemic twin with a 0.37 (19):0.63 (19) domain ratio.

Related literature

For the crystal structures of isomers of the title compound, see: Das et al. (1994 ▶); Huang et al. (2006 ▶). For details of the synthesis, see Bose et al. (2004 ▶).

Experimental

Crystal data

C21H16Cl2O2S

M = 403.30

Orthorhombic,

a = 7.148 (3) Å

b = 14.128 (6) Å

c = 19.371 (8) Å

V = 1956.3 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.45 mm−1

T = 298 (2) K

0.50 × 0.18 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.806, T max = 0.935

9549 measured reflections

3430 independent reflections

1466 reflections with I > 2σ(I)

R int = 0.097

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.248

S = 1.01

3430 reflections

274 parameters

93 restraints

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.24 e Å−3

Absolute structure: Flack (1983 ▶); 1650 Friedel pairs

Flack parameter: 0.37 (19)

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808038993/cv2468sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038993/cv2468Isup2.hkl

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

C21H16Cl2O2S	Dx = 1.369 Mg m−3
Mr = 403.30	Mo Kα radiation λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 1035 reflections
a = 7.148 (3) Å	θ = 2.9–18.1º
b = 14.128 (6) Å	µ = 0.45 mm−1
c = 19.371 (8) Å	T = 298 (2) K
V = 1956.3 (14) Å3	Block, colourless
Z = 4	0.50 × 0.18 × 0.15 mm
F000 = 832

Bruker SMART CCD area-detector diffractometer	3430 independent reflections
Radiation source: fine-focus sealed tube	1466 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.097
T = 298(2) K	θmax = 25.0º
φ and ω scans	θmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.806, Tmax = 0.936	k = −16→13
9549 measured reflections	l = −22→23

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.060	w = 1/[σ2(Fo2)]
wR(F2) = 0.248	(Δ/σ)max = 0.049
S = 1.01	Δρmax = 0.22 e Å−3
3430 reflections	Δρmin = −0.24 e Å−3
274 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
93 restraints	Extinction coefficient: 0.007 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983); 1650 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.37 (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.

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	Occ. (<1)
Cl1	0.2204 (5)	0.35740 (19)	0.37574 (14)	0.0939 (10)
Cl2	−0.1208 (5)	0.1215 (2)	1.10502 (16)	0.1172 (13)
O1	0.4870 (9)	0.2902 (4)	0.7007 (3)	0.077 (2)
O2	0.5943 (10)	0.1389 (5)	0.8854 (4)	0.092 (2)
S1'	0.4882 (12)	−0.0928 (5)	0.7244 (4)	0.081 (3)	0.501 (11)
C1'	0.670 (3)	−0.1622 (13)	0.7454 (11)	0.072 (6)	0.501 (11)
H1'	0.6698	−0.2277	0.7403	0.086*	0.501 (11)
C2'	0.818 (3)	−0.1125 (15)	0.7705 (12)	0.089 (6)	0.501 (11)
H2'	0.9278	−0.1396	0.7869	0.106*	0.501 (11)
C3'	0.782 (3)	−0.0134 (17)	0.7684 (14)	0.088 (7)	0.501 (11)
H3'	0.8728	0.0324	0.7770	0.106*	0.501 (11)
S1	0.7978 (12)	−0.0198 (6)	0.7932 (5)	0.107 (3)	0.499 (11)
C1	0.772 (3)	−0.1384 (11)	0.7777 (13)	0.085 (6)	0.499 (11)
H1	0.8553	−0.1848	0.7920	0.102*	0.499 (11)
C2	0.609 (4)	−0.1556 (14)	0.7408 (15)	0.096 (7)	0.499 (11)
H2	0.5705	−0.2157	0.7273	0.116*	0.499 (11)
C3	0.510 (4)	−0.0733 (15)	0.7263 (16)	0.097 (7)	0.499 (11)
H3	0.3984	−0.0724	0.7018	0.116*	0.499 (11)
C4	0.5961 (12)	0.0071 (5)	0.7518 (4)	0.059 (2)
C5	0.5207 (13)	0.1047 (6)	0.7477 (4)	0.058 (2)
H5	0.6228	0.1486	0.7585	0.070*
C6	0.4526 (13)	0.1269 (6)	0.6752 (4)	0.060 (2)
H6A	0.5338	0.0954	0.6424	0.072*
H6B	0.3279	0.1009	0.6696	0.072*
C7	0.4467 (13)	0.2307 (6)	0.6581 (5)	0.058 (2)
C8	0.3898 (11)	0.2589 (6)	0.5866 (4)	0.053 (2)
C9	0.3827 (13)	0.3539 (6)	0.5708 (4)	0.062 (2)
H9	0.4142	0.3983	0.6043	0.074*
C10	0.3292 (14)	0.3844 (7)	0.5056 (5)	0.073 (3)
H10	0.3216	0.4486	0.4957	0.088*
C11	0.2880 (14)	0.3186 (7)	0.4564 (4)	0.067 (2)
C12	0.2986 (13)	0.2235 (6)	0.4700 (5)	0.063 (2)
H12	0.2735	0.1796	0.4354	0.076*
C13	0.3468 (12)	0.1938 (6)	0.5352 (5)	0.062 (2)
H13	0.3506	0.1294	0.5451	0.074*
C14	0.3630 (13)	0.1219 (6)	0.7999 (4)	0.060 (2)
H14A	0.2971	0.1793	0.7872	0.072*
H14B	0.2748	0.0699	0.7972	0.072*
C15	0.4286 (14)	0.1311 (6)	0.8727 (5)	0.064 (2)
C16	0.2903 (16)	0.1309 (5)	0.9295 (4)	0.057 (2)
C17	0.1016 (14)	0.1270 (6)	0.9166 (5)	0.061 (2)
H17	0.0591	0.1252	0.8713	0.073*
C18	−0.0272 (14)	0.1257 (7)	0.9706 (5)	0.077 (3)
H18	−0.1550	0.1233	0.9616	0.092*
C19	0.0376 (16)	0.1278 (6)	1.0372 (5)	0.071 (3)
C20	0.2218 (17)	0.1315 (7)	1.0516 (5)	0.080 (3)
H20	0.2633	0.1324	1.0971	0.096*
C21	0.3488 (14)	0.1341 (7)	0.9974 (4)	0.071 (3)
H21	0.4760	0.1379	1.0070	0.085*

	U11	U22	U33	U12	U13	U23
Cl1	0.119 (2)	0.0946 (19)	0.0679 (17)	0.0109 (16)	−0.0102 (16)	0.0201 (14)
Cl2	0.114 (3)	0.163 (3)	0.075 (2)	0.021 (2)	0.0267 (17)	−0.0001 (17)
O1	0.106 (6)	0.060 (4)	0.063 (4)	−0.004 (4)	−0.015 (4)	−0.002 (3)
O2	0.063 (5)	0.147 (6)	0.067 (5)	−0.005 (4)	−0.010 (4)	−0.016 (4)
S1'	0.099 (6)	0.075 (5)	0.070 (4)	−0.012 (4)	0.003 (4)	0.007 (3)
C1'	0.091 (12)	0.063 (10)	0.062 (10)	0.013 (9)	0.010 (10)	0.018 (8)
C2'	0.106 (13)	0.077 (11)	0.083 (11)	−0.001 (10)	−0.002 (10)	0.011 (10)
C3'	0.101 (13)	0.081 (12)	0.083 (11)	0.012 (11)	−0.013 (11)	0.009 (10)
S1	0.092 (5)	0.084 (5)	0.146 (8)	0.026 (3)	−0.034 (5)	−0.004 (4)
C1	0.086 (12)	0.048 (10)	0.122 (13)	0.014 (10)	0.005 (11)	0.013 (9)
C2	0.099 (12)	0.072 (11)	0.118 (13)	0.019 (11)	−0.001 (11)	0.016 (10)
C3	0.093 (13)	0.063 (12)	0.135 (14)	0.018 (11)	−0.003 (12)	0.013 (11)
C4	0.056 (6)	0.067 (6)	0.054 (5)	0.000 (5)	−0.006 (4)	0.010 (4)
C5	0.051 (6)	0.061 (5)	0.063 (6)	0.000 (4)	−0.004 (4)	0.003 (4)
C6	0.057 (6)	0.064 (6)	0.058 (6)	−0.002 (4)	0.005 (4)	0.011 (4)
C7	0.054 (6)	0.067 (6)	0.055 (5)	0.009 (5)	0.003 (4)	0.016 (5)
C8	0.044 (5)	0.060 (6)	0.056 (5)	0.006 (4)	0.000 (4)	0.010 (5)
C9	0.065 (6)	0.059 (6)	0.062 (6)	0.000 (5)	−0.016 (5)	−0.001 (4)
C10	0.081 (8)	0.069 (6)	0.070 (7)	0.004 (5)	−0.009 (6)	0.016 (5)
C11	0.076 (7)	0.069 (6)	0.057 (6)	−0.002 (5)	−0.001 (5)	0.015 (5)
C12	0.057 (6)	0.071 (6)	0.062 (6)	0.001 (5)	0.004 (4)	0.005 (5)
C13	0.061 (7)	0.061 (6)	0.064 (6)	0.010 (4)	0.004 (4)	0.006 (5)
C14	0.060 (6)	0.070 (6)	0.051 (5)	0.001 (4)	−0.008 (4)	0.004 (4)
C15	0.059 (6)	0.082 (6)	0.050 (5)	0.003 (5)	−0.009 (5)	−0.005 (4)
C16	0.074 (7)	0.049 (5)	0.047 (5)	0.002 (5)	−0.007 (5)	−0.007 (4)
C17	0.068 (7)	0.067 (6)	0.048 (5)	0.013 (5)	−0.003 (5)	0.002 (4)
C18	0.056 (7)	0.106 (8)	0.068 (7)	0.009 (5)	−0.004 (6)	0.002 (5)
C19	0.092 (9)	0.064 (6)	0.058 (6)	0.001 (5)	0.005 (6)	−0.015 (4)
C20	0.090 (9)	0.106 (8)	0.044 (5)	−0.015 (6)	−0.009 (6)	0.003 (5)
C21	0.070 (7)	0.090 (7)	0.053 (6)	−0.007 (5)	−0.013 (5)	−0.009 (4)

Cl1—C11	1.724 (9)	C6—H6B	0.9700
Cl2—C19	1.736 (11)	C7—C8	1.498 (11)
O1—C7	1.213 (10)	C8—C9	1.377 (10)
O2—C15	1.215 (10)	C8—C13	1.389 (11)
S1'—C1'	1.678 (16)	C9—C10	1.387 (12)
S1'—C4	1.694 (10)	C9—H9	0.9300
C1'—C2'	1.359 (17)	C10—C11	1.364 (13)
C1'—H1'	0.9300	C10—H10	0.9300
C2'—C3'	1.423 (18)	C11—C12	1.371 (12)
C2'—H2'	0.9300	C12—C13	1.376 (12)
C3'—C4	1.401 (18)	C12—H12	0.9300
C3'—H3'	0.9300	C13—H13	0.9300
S1—C4	1.693 (10)	C14—C15	1.490 (12)
S1—C1	1.713 (16)	C14—H14A	0.9700
C1—C2	1.385 (18)	C14—H14B	0.9700
C1—H1	0.9300	C15—C16	1.479 (13)
C2—C3	1.390 (18)	C16—C17	1.373 (12)
C2—H2	0.9300	C16—C21	1.381 (12)
C3—C4	1.383 (19)	C17—C18	1.393 (13)
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.482 (10)	C18—C19	1.372 (14)
C5—C6	1.518 (11)	C18—H18	0.9300
C5—C14	1.535 (13)	C19—C20	1.347 (14)
C5—H5	0.9800	C20—C21	1.389 (14)
C6—C7	1.504 (10)	C20—H20	0.9300
C6—H6A	0.9700	C21—H21	0.9300
C1'—S1'—C4	93.3 (9)	C9—C8—C13	118.6 (7)
C2'—C1'—S1'	112.8 (13)	C9—C8—C7	118.3 (7)
C2'—C1'—H1'	123.6	C13—C8—C7	123.1 (7)
S1'—C1'—H1'	123.6	C8—C9—C10	120.9 (8)
C1'—C2'—C3'	111.1 (17)	C8—C9—H9	119.5
C1'—C2'—H2'	124.5	C10—C9—H9	119.5
C3'—C2'—H2'	124.4	C11—C10—C9	119.0 (9)
C4—C3'—C2'	112.3 (17)	C11—C10—H10	120.5
C4—C3'—H3'	123.8	C9—C10—H10	120.5
C2'—C3'—H3'	123.8	C10—C11—C12	121.4 (8)
C4—S1—C1	92.5 (9)	C10—C11—Cl1	118.6 (7)
C2—C1—S1	110.7 (13)	C12—C11—Cl1	120.1 (7)
C2—C1—H1	124.6	C11—C12—C13	119.3 (9)
S1—C1—H1	124.6	C11—C12—H12	120.4
C1—C2—C3	112.6 (17)	C13—C12—H12	120.4
C1—C2—H2	123.7	C12—C13—C8	120.7 (8)
C3—C2—H2	123.7	C12—C13—H13	119.6
C4—C3—C2	112.9 (18)	C8—C13—H13	119.6
C4—C3—H3	123.5	C15—C14—C5	114.0 (8)
C2—C3—H3	123.5	C15—C14—H14A	108.8
C3—C4—C3'	109.4 (15)	C5—C14—H14A	108.8
C3—C4—C5	125.7 (13)	C15—C14—H14B	108.8
C3'—C4—C5	123.5 (12)	C5—C14—H14B	108.8
C3—C4—S1	111.3 (12)	H14A—C14—H14B	107.7
C3'—C4—S1	15.2 (13)	O2—C15—C16	120.0 (9)
C5—C4—S1	123.0 (7)	O2—C15—C14	120.4 (9)
C3—C4—S1'	2.8 (15)	C16—C15—C14	119.6 (9)
C3'—C4—S1'	109.4 (11)	C17—C16—C21	118.1 (9)
C5—C4—S1'	126.3 (7)	C17—C16—C15	121.4 (8)
S1—C4—S1'	110.4 (6)	C21—C16—C15	120.4 (9)
C4—C5—C6	111.1 (7)	C16—C17—C18	120.9 (8)
C4—C5—C14	112.3 (7)	C16—C17—H17	119.5
C6—C5—C14	109.9 (7)	C18—C17—H17	119.5
C4—C5—H5	107.8	C19—C18—C17	118.9 (9)
C6—C5—H5	107.8	C19—C18—H18	120.6
C14—C5—H5	107.8	C17—C18—H18	120.6
C7—C6—C5	114.5 (7)	C20—C19—C18	121.7 (10)
C7—C6—H6A	108.6	C20—C19—Cl2	118.9 (8)
C5—C6—H6A	108.6	C18—C19—Cl2	119.4 (9)
C7—C6—H6B	108.6	C19—C20—C21	118.9 (9)
C5—C6—H6B	108.6	C19—C20—H20	120.6
H6A—C6—H6B	107.6	C21—C20—H20	120.6
O1—C7—C8	120.7 (8)	C16—C21—C20	121.5 (10)
O1—C7—C6	121.2 (8)	C16—C21—H21	119.3
C8—C7—C6	118.1 (8)	C20—C21—H21	119.3
C4—S1'—C1'—C2'	−2.6 (7)	C5—C6—C7—C8	177.1 (8)
S1'—C1'—C2'—C3'	−3.5 (9)	O1—C7—C8—C9	−0.6 (13)
C1'—C2'—C3'—C4	9.7 (17)	C6—C7—C8—C9	179.5 (8)
C4—S1—C1—C2	0.2 (7)	O1—C7—C8—C13	178.3 (9)
S1—C1—C2—C3	−0.1 (10)	C6—C7—C8—C13	−1.5 (12)
C1—C2—C3—C4	−0.1 (19)	C13—C8—C9—C10	1.6 (14)
C2—C3—C4—C3'	16 (3)	C7—C8—C9—C10	−179.4 (9)
C2—C3—C4—C5	−176.9 (13)	C8—C9—C10—C11	−1.7 (16)
C2—C3—C4—S1	0(2)	C9—C10—C11—C12	0.0 (16)
C2—C3—C4—S1'	−73 (26)	C9—C10—C11—Cl1	179.6 (8)
C2'—C3'—C4—C3	−14 (2)	C10—C11—C12—C13	1.8 (14)
C2'—C3'—C4—C5	178.6 (12)	Cl1—C11—C12—C13	−177.8 (8)
C2'—C3'—C4—S1	85 (5)	C11—C12—C13—C8	−1.9 (14)
C2'—C3'—C4—S1'	−11.3 (19)	C9—C8—C13—C12	0.2 (13)
C1—S1—C4—C3	−0.3 (15)	C7—C8—C13—C12	−178.8 (9)
C1—S1—C4—C3'	−86 (4)	C4—C5—C14—C15	73.6 (9)
C1—S1—C4—C5	176.9 (11)	C6—C5—C14—C15	−162.3 (7)
C1—S1—C4—S1'	2.5 (10)	C5—C14—C15—O2	11.0 (12)
C1'—S1'—C4—C3	100 (27)	C5—C14—C15—C16	−169.3 (7)
C1'—S1'—C4—C3'	7.9 (13)	O2—C15—C16—C17	176.7 (8)
C1'—S1'—C4—C5	177.6 (10)	C14—C15—C16—C17	−3.1 (12)
C1'—S1'—C4—S1	−8.2 (9)	O2—C15—C16—C21	−3.8 (13)
C3—C4—C5—C6	−47.4 (19)	C14—C15—C16—C21	176.4 (8)
C3'—C4—C5—C6	117.6 (16)	C21—C16—C17—C18	−0.4 (12)
S1—C4—C5—C6	135.8 (8)	C15—C16—C17—C18	179.1 (8)
S1'—C4—C5—C6	−50.7 (11)	C16—C17—C18—C19	−0.3 (13)
C3—C4—C5—C14	76.2 (18)	C17—C18—C19—C20	0.2 (14)
C3'—C4—C5—C14	−118.8 (15)	C17—C18—C19—Cl2	−177.5 (7)
S1—C4—C5—C14	−100.6 (9)	C18—C19—C20—C21	0.6 (14)
S1'—C4—C5—C14	72.9 (10)	Cl2—C19—C20—C21	178.3 (7)
C4—C5—C6—C7	−156.7 (8)	C17—C16—C21—C20	1.2 (13)
C14—C5—C6—C7	78.5 (10)	C15—C16—C21—C20	−178.3 (8)
C5—C6—C7—O1	−2.7 (13)	C19—C20—C21—C16	−1.3 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O2i	0.93	2.33	3.175 (12)	150
C10—H10···Cgii	0.93	2.57	3.489 (10)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯O2i	0.93	2.33	3.175 (12)	150
C10—H10⋯Cgii	0.93	2.57	3.489 (10)	171

Symmetry codes: (i) ; (ii) . Cg is the centroid of the C16–C21 ring.