1,4-Bis(4-chloro­phen­yl)butane-1,4-dione

Li, S.; Li, H.

doi:10.1107/S1600536808039251

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2470

doi:10.1107/S1600536808039251

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1,4-Bis(4-chlorophenyl)butane-1,4-dione

Shuqin Li ^a ^* and Huisheng Li ^a

^aDepartment of Chemistry and Biology, Xiangfan University, Xiangfan 441053, People's Republic of China
^*Correspondence e-mail: shuqin2000@yahoo.com.cn

(Received 12 November 2008; accepted 21 November 2008; online 29 November 2008)

The molecule of title compound, C₁₆H₁₂Cl₂O₂, is centrosymmetric. Thus, the asymmetric unit comprises two half-molecules. The two benzene rings are coplanar in each independent molecule (dihedral angles = 0°). The crystal packing exhibits intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions.

Related literature

For applications of the title compound, see: Rao et al. (2004 ); Stauffer & Neier (2000 ); Shridhar et al. (1982 ). For the preparation of the title compound, see: Stetter (1976 ); Nimgirawath et al. (1976 ); Yamamoto et al. (2003 ); Yuguchi et al. (2004 ).

Experimental

Crystal data

C₁₆H₁₂Cl₂O₂
M_r = 307.16
Monoclinic, P 2₁ /c
a = 10.3663 (2) Å
b = 5.2532 (1) Å
c = 26.1125 (6) Å
β = 95.272 (2)°
V = 1415.97 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 298 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.914, T_max = 0.956
14170 measured reflections
2789 independent reflections
1836 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.117
S = 0.97
2789 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O1ⁱ	0.97	2.59	3.553 (3)	173
C11—H11⋯O1ⁱⁱ	0.93	2.50	3.246 (2)	138
C8—H8A⋯Cg1ⁱⁱⁱ	0.97	2.98	3.876 (2)	154
Symmetry codes: (i) x, y+1, z; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 is the centroid of C9–C14.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 1999 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808039251/kp2197sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039251/kp2197Isup2.hkl

checkCIF report

Comment top

1,4-Diketones are very useful intermediates for the synthesis of substituted furans, pyrroles and thiophenes via Paal-Knorr cyclization reaction (Rao et al., 2004; Stauffer et al., 2000; Shridhar et al., 1982). A variety of methods have been reported for the preparation of these 1,4-dicarbonyl compounds (Stetter et al., 1976; Yamamoto et al., 2003; Yuguchi et al., 2004).

The molecule is centrosymmetric. There are two halves of the molecules in the asymmetric unit (Fig. 1). The two phenyl rings are co-planar in both molecules. Intermolecular C—H···O hydrogen bonds and C—H···π interactions stabilize the crystal packing (Table 1).

Related literature top

For applications of the title compound, see: Rao et al. (2004); Stauffer & Neier (2000); Shridhar et al. (1982). For the preparation of the title compound, see: Stetter (1976); Nimgirawath et al. (1976); Yamamoto et al. (2003); Yuguchi et al. (2004).

Experimental top

The title compound was synthesized as previously described by Nimgirawath et al. (1976). Colourless crystals suitable for X-ray data collection were obtained by slow evaporation of a 1:2 (v/v) ratio CH₂Cl₂:CH₃OH solution at 293 K.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 1999); 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 (Sheldrick, 2008).

Figures top

Fig. 1. View of the title molecule showing the atom-labelling scheme. The displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by spheres of arbitrary radius.

1,4-Bis(4-chlorophenyl)butane-1,4-dione top

Crystal data top

C₁₆H₁₂Cl₂O₂	F(000) = 632
M_r = 307.16	D_x = 1.441 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3417 reflections
a = 10.3663 (2) Å	θ = 2.6–23.1°
b = 5.2532 (1) Å	µ = 0.46 mm⁻¹
c = 26.1125 (6) Å	T = 298 K
β = 95.272 (2)°	Block, colourless
V = 1415.97 (5) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2789 independent reflections
Radiation source: fine-focus sealed tube	1836 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −12→12
T_min = 0.914, T_max = 0.956	k = −6→6
14170 measured reflections	l = −31→32

Refinement top

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0637P)²] where P = (F_o² + 2F_c²)/3
2789 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₆H₁₂Cl₂O₂	V = 1415.97 (5) Å³
M_r = 307.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.3663 (2) Å	µ = 0.46 mm⁻¹
b = 5.2532 (1) Å	T = 298 K
c = 26.1125 (6) Å	0.20 × 0.10 × 0.10 mm
β = 95.272 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2789 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	1836 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.956	R_int = 0.058
14170 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 0.97	Δρ_max = 0.21 e Å⁻³
2789 reflections	Δρ_min = −0.23 e Å⁻³
181 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.3102 (2)	0.4151 (4)	0.32315 (8)	0.0609 (5)
C2	0.3437 (2)	0.2160 (4)	0.35628 (8)	0.0658 (6)
H2	0.4069	0.0995	0.3488	0.079*
C3	0.2824 (2)	0.1933 (4)	0.40024 (8)	0.0612 (6)
H3	0.3041	0.0584	0.4225	0.073*
C4	0.18851 (19)	0.3661 (3)	0.41264 (8)	0.0524 (5)
C5	0.1579 (2)	0.5660 (4)	0.37840 (8)	0.0590 (5)
H5	0.0960	0.6851	0.3859	0.071*
C6	0.2175 (2)	0.5899 (4)	0.33398 (8)	0.0627 (6)
H6	0.1955	0.7228	0.3113	0.075*
C7	0.1272 (2)	0.3362 (4)	0.46133 (8)	0.0559 (5)
C8	0.0298 (2)	0.5308 (4)	0.47540 (7)	0.0576 (5)
H8A	−0.0386	0.5432	0.4476	0.069*
H8B	0.0719	0.6955	0.4790	0.069*
C9	0.1559 (2)	0.7318 (4)	0.15908 (8)	0.0593 (5)
C10	0.1743 (2)	0.6200 (4)	0.11264 (8)	0.0623 (6)
H10	0.1275	0.4755	0.1019	0.075*
C11	0.2621 (2)	0.7227 (4)	0.08217 (8)	0.0575 (5)
H11	0.2745	0.6459	0.0509	0.069*
C12	0.33228 (18)	0.9383 (3)	0.09714 (7)	0.0508 (5)
C13	0.3118 (2)	1.0476 (4)	0.14417 (8)	0.0628 (6)
H13	0.3581	1.1926	0.1549	0.075*
C14	0.2249 (2)	0.9467 (4)	0.17514 (8)	0.0674 (6)
H14	0.2127	1.0220	0.2066	0.081*
C15	0.42674 (19)	1.0574 (4)	0.06459 (7)	0.0537 (5)
C16	0.45259 (19)	0.9285 (4)	0.01517 (8)	0.0558 (5)
H16A	0.3713	0.9095	−0.0061	0.067*
H16B	0.4865	0.7594	0.0229	0.067*
Cl1	0.04740 (6)	0.59996 (12)	0.19828 (2)	0.0828 (2)
Cl2	0.38806 (6)	0.44975 (15)	0.26764 (2)	0.0908 (3)
O1	0.15594 (16)	0.1582 (3)	0.48988 (6)	0.0830 (5)
O2	0.48192 (15)	1.2536 (3)	0.07810 (6)	0.0746 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0561 (13)	0.0641 (12)	0.0619 (13)	−0.0073 (11)	0.0012 (10)	−0.0094 (10)
C2	0.0571 (13)	0.0598 (13)	0.0800 (15)	0.0045 (11)	0.0034 (12)	−0.0096 (12)
C3	0.0596 (14)	0.0472 (11)	0.0746 (14)	0.0029 (10)	−0.0055 (11)	0.0030 (10)
C4	0.0524 (12)	0.0432 (10)	0.0596 (12)	−0.0020 (9)	−0.0061 (10)	0.0006 (9)
C5	0.0639 (14)	0.0499 (11)	0.0632 (13)	0.0086 (10)	0.0063 (10)	0.0010 (10)
C6	0.0705 (15)	0.0559 (12)	0.0609 (13)	0.0026 (11)	0.0023 (11)	0.0044 (10)
C7	0.0566 (13)	0.0454 (11)	0.0637 (13)	−0.0034 (9)	−0.0049 (10)	0.0052 (9)
C8	0.0648 (14)	0.0473 (11)	0.0600 (12)	−0.0027 (10)	0.0017 (10)	0.0039 (9)
C9	0.0569 (13)	0.0607 (12)	0.0600 (13)	0.0043 (10)	0.0036 (10)	0.0077 (10)
C10	0.0634 (14)	0.0543 (12)	0.0682 (14)	−0.0080 (10)	0.0007 (11)	−0.0027 (10)
C11	0.0614 (13)	0.0531 (11)	0.0575 (12)	−0.0005 (10)	0.0036 (10)	−0.0074 (9)
C12	0.0530 (12)	0.0478 (10)	0.0504 (11)	0.0042 (9)	−0.0017 (9)	−0.0011 (9)
C13	0.0733 (15)	0.0528 (12)	0.0609 (13)	−0.0079 (11)	−0.0011 (11)	−0.0067 (10)
C14	0.0807 (16)	0.0673 (14)	0.0543 (12)	−0.0008 (12)	0.0064 (11)	−0.0065 (11)
C15	0.0502 (12)	0.0520 (11)	0.0577 (12)	0.0030 (10)	−0.0020 (9)	−0.0021 (9)
C16	0.0504 (12)	0.0559 (11)	0.0599 (12)	0.0011 (9)	−0.0012 (9)	−0.0014 (9)
Cl1	0.0788 (5)	0.0941 (5)	0.0772 (4)	−0.0099 (3)	0.0169 (3)	0.0112 (3)
Cl2	0.0818 (5)	0.1167 (6)	0.0764 (4)	0.0026 (4)	0.0215 (3)	−0.0058 (4)
O1	0.0957 (13)	0.0697 (10)	0.0855 (11)	0.0224 (9)	0.0175 (9)	0.0298 (9)
O2	0.0803 (11)	0.0631 (9)	0.0819 (11)	−0.0212 (8)	0.0150 (8)	−0.0150 (8)

Geometric parameters (Å, º) top

C1—C6	1.377 (3)	C9—C14	1.381 (3)
C1—C2	1.381 (3)	C9—Cl1	1.733 (2)
C1—Cl2	1.732 (2)	C10—C11	1.373 (3)
C2—C3	1.368 (3)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.383 (3)
C3—C4	1.391 (3)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.390 (3)
C4—C5	1.397 (3)	C12—C15	1.492 (3)
C4—C7	1.481 (3)	C13—C14	1.371 (3)
C5—C6	1.369 (3)	C13—H13	0.9300
C5—H5	0.9300	C14—H14	0.9300
C6—H6	0.9300	C15—O2	1.215 (2)
C7—O1	1.216 (2)	C15—C16	1.503 (3)
C7—C8	1.506 (3)	C16—C16ⁱⁱ	1.517 (4)
C8—C8ⁱ	1.511 (4)	C16—H16A	0.9700
C8—H8A	0.9700	C16—H16B	0.9700
C8—H8B	0.9700	Cl1—Cl2	3.8985 (9)
C9—C10	1.376 (3)

C6—C1—C2	121.1 (2)	C10—C9—Cl1	120.01 (17)
C6—C1—Cl2	119.31 (17)	C14—C9—Cl1	119.58 (16)
C2—C1—Cl2	119.60 (18)	C11—C10—C9	119.75 (19)
C3—C2—C1	118.8 (2)	C11—C10—H10	120.1
C3—C2—H2	120.6	C9—C10—H10	120.1
C1—C2—H2	120.6	C10—C11—C12	121.17 (19)
C2—C3—C4	121.84 (19)	C10—C11—H11	119.4
C2—C3—H3	119.1	C12—C11—H11	119.4
C4—C3—H3	119.1	C11—C12—C13	117.95 (19)
C3—C4—C5	117.68 (19)	C11—C12—C15	122.57 (17)
C3—C4—C7	119.70 (18)	C13—C12—C15	119.47 (17)
C5—C4—C7	122.62 (19)	C14—C13—C12	121.59 (19)
C6—C5—C4	121.17 (19)	C14—C13—H13	119.2
C6—C5—H5	119.4	C12—C13—H13	119.2
C4—C5—H5	119.4	C13—C14—C9	119.2 (2)
C5—C6—C1	119.39 (19)	C13—C14—H14	120.4
C5—C6—H6	120.3	C9—C14—H14	120.4
C1—C6—H6	120.3	O2—C15—C12	120.42 (18)
O1—C7—C4	120.50 (19)	O2—C15—C16	120.99 (19)
O1—C7—C8	120.30 (19)	C12—C15—C16	118.58 (17)
C4—C7—C8	119.20 (16)	C15—C16—C16ⁱⁱ	113.6 (2)
C7—C8—C8ⁱ	113.5 (2)	C15—C16—H16A	108.8
C7—C8—H8A	108.9	C16ⁱⁱ—C16—H16A	108.8
C8ⁱ—C8—H8A	108.9	C15—C16—H16B	108.8
C7—C8—H8B	108.9	C16ⁱⁱ—C16—H16B	108.8
C8ⁱ—C8—H8B	108.9	H16A—C16—H16B	107.7
H8A—C8—H8B	107.7	C9—Cl1—Cl2	75.29 (7)
C10—C9—C14	120.4 (2)	C1—Cl2—Cl1	86.46 (7)

C6—C1—C2—C3	0.5 (3)	C10—C11—C12—C13	0.3 (3)
Cl2—C1—C2—C3	179.23 (15)	C10—C11—C12—C15	−178.93 (18)
C1—C2—C3—C4	−0.6 (3)	C11—C12—C13—C14	0.0 (3)
C2—C3—C4—C5	0.2 (3)	C15—C12—C13—C14	179.26 (19)
C2—C3—C4—C7	−178.57 (18)	C12—C13—C14—C9	−0.2 (3)
C3—C4—C5—C6	0.5 (3)	C10—C9—C14—C13	0.2 (3)
C7—C4—C5—C6	179.23 (18)	Cl1—C9—C14—C13	179.13 (16)
C4—C5—C6—C1	−0.7 (3)	C11—C12—C15—O2	176.53 (19)
C2—C1—C6—C5	0.2 (3)	C13—C12—C15—O2	−2.7 (3)
Cl2—C1—C6—C5	−178.55 (15)	C11—C12—C15—C16	−3.9 (3)
C3—C4—C7—O1	−1.9 (3)	C13—C12—C15—C16	176.85 (17)
C5—C4—C7—O1	179.45 (18)	O2—C15—C16—C16ⁱⁱ	−2.1 (3)
C3—C4—C7—C8	177.44 (18)	C12—C15—C16—C16ⁱⁱ	178.39 (19)
C5—C4—C7—C8	−1.2 (3)	C10—C9—Cl1—Cl2	107.86 (17)
O1—C7—C8—C8ⁱ	−3.6 (3)	C14—C9—Cl1—Cl2	−71.11 (16)
C4—C7—C8—C8ⁱ	177.0 (2)	C6—C1—Cl2—Cl1	−43.73 (16)
C14—C9—C10—C11	0.1 (3)	C2—C1—Cl2—Cl1	137.48 (16)
Cl1—C9—C10—C11	−178.83 (15)	C9—Cl1—Cl2—C1	158.48 (10)
C9—C10—C11—C12	−0.4 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1ⁱⁱⁱ	0.97	2.59	3.553 (3)	173
C11—H11···O1^iv	0.93	2.50	3.246 (2)	138
C8—H8A···Cg1^v	0.97	2.98	3.876 (2)	154

Symmetry codes: (iii) x, y+1, z; (iv) x, −y+1/2, z−1/2; (v) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂Cl₂O₂
M_r	307.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.3663 (2), 5.2532 (1), 26.1125 (6)
β (°)	95.272 (2)
V (Å³)	1415.97 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.914, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	14170, 2789, 1836
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.117, 0.97
No. of reflections	2789
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.23

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1ⁱ	0.97	2.59	3.553 (3)	172.9
C11—H11···O1ⁱⁱ	0.93	2.50	3.246 (2)	137.5
C8—H8A···Cg1ⁱⁱⁱ	0.97	2.98	3.876 (2)	154

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

Acknowledgements

The authors are grateful to Xiangfan University for financial support.

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