PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2454.
Published online 2008 November 26. doi:  10.1107/S1600536808038993
PMCID: PMC2959928

1,5-Bis(4-chloro­phen­yl)-3-(2-thien­yl)pentane-1,5-dione

Abstract

In the title mol­ecule, C21H16Cl2O2S, the five-membered ring is rotationally disordered between two orientations in a 1:1 ratio. In the crystal structure, weak inter­molecular C—H(...)O hydrogen bonds link mol­ecules related by translation along the a axis into chains, which are further combined into layers parallel to the bc plane via C—H(...)π inter­actions. 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 [triangle]); Huang et al. (2006 [triangle]). For details of the synthesis, see Bose et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2454-scheme1.jpg

Experimental

Crystal data

  • C21H16Cl2O2S
  • M r = 403.30
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2454-efi1.jpg
  • 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 [triangle]) 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 [triangle]); 1650 Friedel pairs
  • Flack parameter: 0.37 (19)

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

The authors acknowledge the financial support of the University Student Science and Technology Culture Foundation of Liaocheng University (grant No. SRT07013HX2).

supplementary crystallographic information

Comment

In an earlier publication, the "Grindstone Chemistry" method for conducting exothermic reactions in the solvent-free mode has been described (Bose et al., 2004). We tested energy-saving procedures developed in our laboratory for the preparation of 1,5-diketones starting from the fragrant aldehydes and fragrant ketones in the presence of NaOH under solvent-free conditions. Using this method we obtained the title compound, (I).

In (I) (Fig. 1), the bond lengths and angles are normal and correspond to those observed in 1,3,5-triphenyl-pentane-1,5-diketone (Das et al., 1994) and 1,5-diphenyl-3-(2-pyridyl)pentane-1,5-dione (Huang et al., 2006). However, the five-membered ring in (I) is rotationally disordered.

In the crystal, the weak intermolecular C—H···O hydrogen bonds (Table 1) link the molecules related by translations along a axis into one-dimensional linear chains, which are further combined into layers parallel to a(b-c) plane via C—H···π interactions (Table 1).

Experimental

4-Chloroacetophenone (6.25 mmol) and thiophene-2-carbaldehyde (3.125 mmol), NaOH (6.25 mmol) were aggregated with glass paddle in an open flask. The resulting mixture was washed with water for several times for removing NaOH, and recrystalized from ethanol, and afforded the title compound as a crystalline solid. Elemental analysis: calculated for C21 H16 Cl2O2 S: C 62.54, H 4.00%; Found: C 62.58, H 4.03%.

Refinement

All H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.98 Å and Uiso(H) = Ueq(C). The five-membered ring was treated as disordered between two orientations with nearly equal occupancies refined to 0.501 (11) and 0.499 (11), respectively. The geometries and anisotropic displacement parameters of disordered atoms were refined with soft restraints using the SHELXL commands DFIX, FLAT and SIMU.

Figures

Fig. 1.
View of (I) showing the atomic labelling and displacement ellipsoids at the 30% level. Only one component of the disordered ring (S1,C1-C4) is shown. Hydrogen atoms are omitted for clarity.

Crystal data

C21H16Cl2O2SDx = 1.369 Mg m3
Mr = 403.30Mo Kα radiation λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 1035 reflections
a = 7.148 (3) Åθ = 2.9–18.1º
b = 14.128 (6) ŵ = 0.45 mm1
c = 19.371 (8) ÅT = 298 (2) K
V = 1956.3 (14) Å3Block, colourless
Z = 40.50 × 0.18 × 0.15 mm
F000 = 832

Data collection

Bruker SMART CCD area-detector diffractometer3430 independent reflections
Radiation source: fine-focus sealed tube1466 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.097
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −8→8
Tmin = 0.806, Tmax = 0.936k = −16→13
9549 measured reflectionsl = −22→23

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.060  w = 1/[σ2(Fo2)]
wR(F2) = 0.248(Δ/σ)max = 0.049
S = 1.01Δρmax = 0.22 e Å3
3430 reflectionsΔρmin = −0.24 e Å3
274 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
93 restraintsExtinction coefficient: 0.007 (3)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983); 1650 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.37 (19)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Cl10.2204 (5)0.35740 (19)0.37574 (14)0.0939 (10)
Cl2−0.1208 (5)0.1215 (2)1.10502 (16)0.1172 (13)
O10.4870 (9)0.2902 (4)0.7007 (3)0.077 (2)
O20.5943 (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)
H1'0.6698−0.22770.74030.086*0.501 (11)
C2'0.818 (3)−0.1125 (15)0.7705 (12)0.089 (6)0.501 (11)
H2'0.9278−0.13960.78690.106*0.501 (11)
C3'0.782 (3)−0.0134 (17)0.7684 (14)0.088 (7)0.501 (11)
H3'0.87280.03240.77700.106*0.501 (11)
S10.7978 (12)−0.0198 (6)0.7932 (5)0.107 (3)0.499 (11)
C10.772 (3)−0.1384 (11)0.7777 (13)0.085 (6)0.499 (11)
H10.8553−0.18480.79200.102*0.499 (11)
C20.609 (4)−0.1556 (14)0.7408 (15)0.096 (7)0.499 (11)
H20.5705−0.21570.72730.116*0.499 (11)
C30.510 (4)−0.0733 (15)0.7263 (16)0.097 (7)0.499 (11)
H30.3984−0.07240.70180.116*0.499 (11)
C40.5961 (12)0.0071 (5)0.7518 (4)0.059 (2)
C50.5207 (13)0.1047 (6)0.7477 (4)0.058 (2)
H50.62280.14860.75850.070*
C60.4526 (13)0.1269 (6)0.6752 (4)0.060 (2)
H6A0.53380.09540.64240.072*
H6B0.32790.10090.66960.072*
C70.4467 (13)0.2307 (6)0.6581 (5)0.058 (2)
C80.3898 (11)0.2589 (6)0.5866 (4)0.053 (2)
C90.3827 (13)0.3539 (6)0.5708 (4)0.062 (2)
H90.41420.39830.60430.074*
C100.3292 (14)0.3844 (7)0.5056 (5)0.073 (3)
H100.32160.44860.49570.088*
C110.2880 (14)0.3186 (7)0.4564 (4)0.067 (2)
C120.2986 (13)0.2235 (6)0.4700 (5)0.063 (2)
H120.27350.17960.43540.076*
C130.3468 (12)0.1938 (6)0.5352 (5)0.062 (2)
H130.35060.12940.54510.074*
C140.3630 (13)0.1219 (6)0.7999 (4)0.060 (2)
H14A0.29710.17930.78720.072*
H14B0.27480.06990.79720.072*
C150.4286 (14)0.1311 (6)0.8727 (5)0.064 (2)
C160.2903 (16)0.1309 (5)0.9295 (4)0.057 (2)
C170.1016 (14)0.1270 (6)0.9166 (5)0.061 (2)
H170.05910.12520.87130.073*
C18−0.0272 (14)0.1257 (7)0.9706 (5)0.077 (3)
H18−0.15500.12330.96160.092*
C190.0376 (16)0.1278 (6)1.0372 (5)0.071 (3)
C200.2218 (17)0.1315 (7)1.0516 (5)0.080 (3)
H200.26330.13241.09710.096*
C210.3488 (14)0.1341 (7)0.9974 (4)0.071 (3)
H210.47600.13791.00700.085*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.119 (2)0.0946 (19)0.0679 (17)0.0109 (16)−0.0102 (16)0.0201 (14)
Cl20.114 (3)0.163 (3)0.075 (2)0.021 (2)0.0267 (17)−0.0001 (17)
O10.106 (6)0.060 (4)0.063 (4)−0.004 (4)−0.015 (4)−0.002 (3)
O20.063 (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)
S10.092 (5)0.084 (5)0.146 (8)0.026 (3)−0.034 (5)−0.004 (4)
C10.086 (12)0.048 (10)0.122 (13)0.014 (10)0.005 (11)0.013 (9)
C20.099 (12)0.072 (11)0.118 (13)0.019 (11)−0.001 (11)0.016 (10)
C30.093 (13)0.063 (12)0.135 (14)0.018 (11)−0.003 (12)0.013 (11)
C40.056 (6)0.067 (6)0.054 (5)0.000 (5)−0.006 (4)0.010 (4)
C50.051 (6)0.061 (5)0.063 (6)0.000 (4)−0.004 (4)0.003 (4)
C60.057 (6)0.064 (6)0.058 (6)−0.002 (4)0.005 (4)0.011 (4)
C70.054 (6)0.067 (6)0.055 (5)0.009 (5)0.003 (4)0.016 (5)
C80.044 (5)0.060 (6)0.056 (5)0.006 (4)0.000 (4)0.010 (5)
C90.065 (6)0.059 (6)0.062 (6)0.000 (5)−0.016 (5)−0.001 (4)
C100.081 (8)0.069 (6)0.070 (7)0.004 (5)−0.009 (6)0.016 (5)
C110.076 (7)0.069 (6)0.057 (6)−0.002 (5)−0.001 (5)0.015 (5)
C120.057 (6)0.071 (6)0.062 (6)0.001 (5)0.004 (4)0.005 (5)
C130.061 (7)0.061 (6)0.064 (6)0.010 (4)0.004 (4)0.006 (5)
C140.060 (6)0.070 (6)0.051 (5)0.001 (4)−0.008 (4)0.004 (4)
C150.059 (6)0.082 (6)0.050 (5)0.003 (5)−0.009 (5)−0.005 (4)
C160.074 (7)0.049 (5)0.047 (5)0.002 (5)−0.007 (5)−0.007 (4)
C170.068 (7)0.067 (6)0.048 (5)0.013 (5)−0.003 (5)0.002 (4)
C180.056 (7)0.106 (8)0.068 (7)0.009 (5)−0.004 (6)0.002 (5)
C190.092 (9)0.064 (6)0.058 (6)0.001 (5)0.005 (6)−0.015 (4)
C200.090 (9)0.106 (8)0.044 (5)−0.015 (6)−0.009 (6)0.003 (5)
C210.070 (7)0.090 (7)0.053 (6)−0.007 (5)−0.013 (5)−0.009 (4)

Geometric parameters (Å, °)

Cl1—C111.724 (9)C6—H6B0.9700
Cl2—C191.736 (11)C7—C81.498 (11)
O1—C71.213 (10)C8—C91.377 (10)
O2—C151.215 (10)C8—C131.389 (11)
S1'—C1'1.678 (16)C9—C101.387 (12)
S1'—C41.694 (10)C9—H90.9300
C1'—C2'1.359 (17)C10—C111.364 (13)
C1'—H1'0.9300C10—H100.9300
C2'—C3'1.423 (18)C11—C121.371 (12)
C2'—H2'0.9300C12—C131.376 (12)
C3'—C41.401 (18)C12—H120.9300
C3'—H3'0.9300C13—H130.9300
S1—C41.693 (10)C14—C151.490 (12)
S1—C11.713 (16)C14—H14A0.9700
C1—C21.385 (18)C14—H14B0.9700
C1—H10.9300C15—C161.479 (13)
C2—C31.390 (18)C16—C171.373 (12)
C2—H20.9300C16—C211.381 (12)
C3—C41.383 (19)C17—C181.393 (13)
C3—H30.9300C17—H170.9300
C4—C51.482 (10)C18—C191.372 (14)
C5—C61.518 (11)C18—H180.9300
C5—C141.535 (13)C19—C201.347 (14)
C5—H50.9800C20—C211.389 (14)
C6—C71.504 (10)C20—H200.9300
C6—H6A0.9700C21—H210.9300
C1'—S1'—C493.3 (9)C9—C8—C13118.6 (7)
C2'—C1'—S1'112.8 (13)C9—C8—C7118.3 (7)
C2'—C1'—H1'123.6C13—C8—C7123.1 (7)
S1'—C1'—H1'123.6C8—C9—C10120.9 (8)
C1'—C2'—C3'111.1 (17)C8—C9—H9119.5
C1'—C2'—H2'124.5C10—C9—H9119.5
C3'—C2'—H2'124.4C11—C10—C9119.0 (9)
C4—C3'—C2'112.3 (17)C11—C10—H10120.5
C4—C3'—H3'123.8C9—C10—H10120.5
C2'—C3'—H3'123.8C10—C11—C12121.4 (8)
C4—S1—C192.5 (9)C10—C11—Cl1118.6 (7)
C2—C1—S1110.7 (13)C12—C11—Cl1120.1 (7)
C2—C1—H1124.6C11—C12—C13119.3 (9)
S1—C1—H1124.6C11—C12—H12120.4
C1—C2—C3112.6 (17)C13—C12—H12120.4
C1—C2—H2123.7C12—C13—C8120.7 (8)
C3—C2—H2123.7C12—C13—H13119.6
C4—C3—C2112.9 (18)C8—C13—H13119.6
C4—C3—H3123.5C15—C14—C5114.0 (8)
C2—C3—H3123.5C15—C14—H14A108.8
C3—C4—C3'109.4 (15)C5—C14—H14A108.8
C3—C4—C5125.7 (13)C15—C14—H14B108.8
C3'—C4—C5123.5 (12)C5—C14—H14B108.8
C3—C4—S1111.3 (12)H14A—C14—H14B107.7
C3'—C4—S115.2 (13)O2—C15—C16120.0 (9)
C5—C4—S1123.0 (7)O2—C15—C14120.4 (9)
C3—C4—S1'2.8 (15)C16—C15—C14119.6 (9)
C3'—C4—S1'109.4 (11)C17—C16—C21118.1 (9)
C5—C4—S1'126.3 (7)C17—C16—C15121.4 (8)
S1—C4—S1'110.4 (6)C21—C16—C15120.4 (9)
C4—C5—C6111.1 (7)C16—C17—C18120.9 (8)
C4—C5—C14112.3 (7)C16—C17—H17119.5
C6—C5—C14109.9 (7)C18—C17—H17119.5
C4—C5—H5107.8C19—C18—C17118.9 (9)
C6—C5—H5107.8C19—C18—H18120.6
C14—C5—H5107.8C17—C18—H18120.6
C7—C6—C5114.5 (7)C20—C19—C18121.7 (10)
C7—C6—H6A108.6C20—C19—Cl2118.9 (8)
C5—C6—H6A108.6C18—C19—Cl2119.4 (9)
C7—C6—H6B108.6C19—C20—C21118.9 (9)
C5—C6—H6B108.6C19—C20—H20120.6
H6A—C6—H6B107.6C21—C20—H20120.6
O1—C7—C8120.7 (8)C16—C21—C20121.5 (10)
O1—C7—C6121.2 (8)C16—C21—H21119.3
C8—C7—C6118.1 (8)C20—C21—H21119.3
C4—S1'—C1'—C2'−2.6 (7)C5—C6—C7—C8177.1 (8)
S1'—C1'—C2'—C3'−3.5 (9)O1—C7—C8—C9−0.6 (13)
C1'—C2'—C3'—C49.7 (17)C6—C7—C8—C9179.5 (8)
C4—S1—C1—C20.2 (7)O1—C7—C8—C13178.3 (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—C101.6 (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—S10(2)C9—C10—C11—C120.0 (16)
C2—C3—C4—S1'−73 (26)C9—C10—C11—Cl1179.6 (8)
C2'—C3'—C4—C3−14 (2)C10—C11—C12—C131.8 (14)
C2'—C3'—C4—C5178.6 (12)Cl1—C11—C12—C13−177.8 (8)
C2'—C3'—C4—S185 (5)C11—C12—C13—C8−1.9 (14)
C2'—C3'—C4—S1'−11.3 (19)C9—C8—C13—C120.2 (13)
C1—S1—C4—C3−0.3 (15)C7—C8—C13—C12−178.8 (9)
C1—S1—C4—C3'−86 (4)C4—C5—C14—C1573.6 (9)
C1—S1—C4—C5176.9 (11)C6—C5—C14—C15−162.3 (7)
C1—S1—C4—S1'2.5 (10)C5—C14—C15—O211.0 (12)
C1'—S1'—C4—C3100 (27)C5—C14—C15—C16−169.3 (7)
C1'—S1'—C4—C3'7.9 (13)O2—C15—C16—C17176.7 (8)
C1'—S1'—C4—C5177.6 (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—C21176.4 (8)
C3'—C4—C5—C6117.6 (16)C21—C16—C17—C18−0.4 (12)
S1—C4—C5—C6135.8 (8)C15—C16—C17—C18179.1 (8)
S1'—C4—C5—C6−50.7 (11)C16—C17—C18—C19−0.3 (13)
C3—C4—C5—C1476.2 (18)C17—C18—C19—C200.2 (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—C210.6 (14)
S1'—C4—C5—C1472.9 (10)Cl2—C19—C20—C21178.3 (7)
C4—C5—C6—C7−156.7 (8)C17—C16—C21—C201.2 (13)
C14—C5—C6—C778.5 (10)C15—C16—C21—C20−178.3 (8)
C5—C6—C7—O1−2.7 (13)C19—C20—C21—C16−1.3 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C18—H18···O2i0.932.333.175 (12)150
C10—H10···Cgii0.932.573.489 (10)171

Symmetry codes: (i) x−1, y, z; (ii) −x+1/2, y+1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2468).

References

  • Bose, A. K., Pednekar, S., Ganguly, S. N., Chakraborty, G. & Manhas, M. S. (2004). Tetrahedron Lett.45, 8351–8353.
  • Das, G. C., Hursthouse, M. B., Malik, K. M. A., Rahman, M. M., Rahman, M. T. & Olsson, T. (1994). J. Chem. Crystallogr.24, 511–515.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Huang, X.-Q., Wang, D.-Q., Dou, J.-M. & Wang, J.-X. (2006). Acta Cryst. E62, o60–o61.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1995). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography