1,4-Bis(4-chloro­phen­yl)-2-hydroxy­butane-1,4-dione

Liu, Y.; Yang, K.; Song, W.; Qi, Y.

doi:10.1107/S1600536810018027

organic compounds

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Volume 66| Part 6| June 2010| Page o1426

https://doi.org/10.1107/S1600536810018027

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1,4-Bis(4-chlorophenyl)-2-hydroxybutane-1,4-dione

Yongjun Liu,^a ^* Kuiwei Yang,^a Weiling Song ^a and Yan Qi ^a

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: pubsliu@163.com

(Received 30 April 2010; accepted 15 May 2010; online 22 May 2010)

In the title compound, C₁₆H₁₂Cl₂O₃, the benzene rings form a dihedral angle of 2.0 (3)°. Within the central O=C—CH₂C(H)OH—C=O unit, the carbonyl groups are coplanar and lie to opposite sides [O—C⋯C—O = −170.1 (6)°]. In the crystal, intermolecular O—H⋯O hydrogen bonds formed between the hydroxy groups lead to a supramolecular chain along the c axis. In addition, the crystal packing features some very weak C—H⋯π interactions.

Related literature

For the synthesis and applications of 1,4-dicarbonyl compounds, see: Ellison (1973 ); Hassner (1991 ); Ohno et al. (2001 ).

Experimental

Crystal data

C₁₆H₁₂Cl₂O₃
M_r = 323.16
Monoclinic, C c
a = 34.800 (8) Å
b = 7.4221 (14) Å
c = 5.6535 (13) Å
β = 95.925 (2)°
V = 1452.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 273 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.947, T_max = 0.964
3531 measured reflections
1256 independent reflections
998 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.163
S = 1.05
1256 reflections
190 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1—C6 and C11—C16 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O2ⁱ	0.82	2.10	2.894 (6)	163
C1—H1⋯Cg1ⁱⁱ	0.93	2.89	3.507 (6)	125
C4—H4⋯Cg1ⁱⁱⁱ	0.93	2.97	3.600 (6)	126
C13—H13⋯Cg2ⁱⁱ	0.93	2.88	3.517 (6)	127
C16—H16⋯Cg2ⁱⁱⁱ	0.93	2.90	3.544 (6)	128
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810018027/tk2670sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018027/tk2670Isup2.hkl

checkCIF report

Comment top

1,4-Dicarbonyl compounds constitute key intermediates in various natural product syntheses, and are important synthetic precursors of cyclopentenones, cyclopenta-1,3-diones, butenolides, and derivatives of furan and pyrrole (Hassner, 1991). For this reason, a number of methods for their synthesis have been developed and applied (Ellison, 1973; Ohno et al., 2001).

In the title compound, Fig. 1, the benzene rings form a dihedral angle of 2.0 (3) °. Intermolecular O2—H2A···O2 hydrogen bonds lead to the formation of a supramolecular chain along the c axis (Table 1, Fig. 2). In addition, the crystal packing is stabilized by intermolecular C—H···π interactions (Table 1) and short Cl···Clⁱ contacts (3.434 (3) Å for i: 1/2+x, 1/2-y, -1/2+z).

Related literature top

For the synthesis and applications of 1,4-dicarbonyl compounds, see: Ellison (1973); Hassner (1991); Ohno et al. (2001).

Experimental top

The title compound was obtained as a by-product in the coupling reaction between 4-ClC₆H₄COCH₂Br and benzaldehyde, a reaction which is being studied in our laboratory. Colourless single crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution over a period of 20 days.

Structure description top

For the synthesis and applications of 1,4-dicarbonyl compounds, see: Ellison (1973); Hassner (1991); Ohno et al. (2001).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing atom labels and 50% probability displacement ellipsoids.
	Fig. 2. The packing diagram for the title compound, viewed down the a axis, showing the intermolecular hydrogen bonds (dashed lines).

1,4-Bis(4-chlorophenyl)-2-hydroxybutane-1,4-dione top

Crystal data top

C₁₆H₁₂Cl₂O₃	F(000) = 664
M_r = 323.16	D_x = 1.478 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1044 reflections
a = 34.800 (8) Å	θ = 2.4–24.4°
b = 7.4221 (14) Å	µ = 0.45 mm⁻¹
c = 5.6535 (13) Å	T = 273 K
β = 95.925 (2)°	Column, colourless
V = 1452.4 (5) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1256 independent reflections
Radiation source: fine-focus sealed tube	998 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
phi and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −38→40
T_min = 0.947, T_max = 0.964	k = −7→8
3531 measured reflections	l = −6→6

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.163	w = 1/[σ²(F_o²) + (0.1063P)² + 0.4654P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1256 reflections	Δρ_max = 0.40 e Å⁻³
190 parameters	Δρ_min = −0.21 e Å⁻³
9 restraints	Absolute structure: nd
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₆H₁₂Cl₂O₃	V = 1452.4 (5) Å³
M_r = 323.16	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 34.800 (8) Å	µ = 0.45 mm⁻¹
b = 7.4221 (14) Å	T = 273 K
c = 5.6535 (13) Å	0.12 × 0.10 × 0.08 mm
β = 95.925 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1256 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	998 reflections with I > 2σ(I)
T_min = 0.947, T_max = 0.964	R_int = 0.025
3531 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	9 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.05	Δρ_max = 0.40 e Å⁻³
1256 reflections	Δρ_min = −0.21 e Å⁻³
190 parameters	Absolute structure: nd

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	1.04214 (18)	0.1713 (8)	0.3400 (11)	0.0369 (15)
H1	1.0356	0.1204	0.4809	0.044*
C2	1.0810 (2)	0.1845 (10)	0.2991 (14)	0.053 (2)
H2	1.1002	0.1385	0.4089	0.063*
C3	1.0905 (2)	0.2672 (9)	0.0921 (14)	0.049 (2)
C4	1.0605 (2)	0.3249 (10)	−0.0726 (13)	0.049 (2)
H4	1.0664	0.3745	−0.2154	0.058*
C5	1.0234 (2)	0.3116 (8)	−0.0327 (12)	0.0403 (16)
H5	1.0043	0.3556	−0.1448	0.048*
C6	1.0133 (2)	0.2332 (8)	0.1732 (12)	0.0357 (16)
C7	0.9724 (2)	0.2035 (8)	0.2253 (12)	0.0374 (16)
C8	0.9403 (2)	0.2685 (8)	0.0412 (13)	0.0383 (14)
H8	0.9443	0.2140	−0.1121	0.046*
C9	0.9007 (2)	0.2137 (9)	0.1027 (12)	0.0412 (15)
H9A	0.8999	0.0839	0.1210	0.049*
H9B	0.8961	0.2678	0.2533	0.049*
C10	0.8693 (2)	0.2712 (9)	−0.0860 (13)	0.0454 (18)
C11	0.8287 (2)	0.2621 (8)	−0.0279 (12)	0.0362 (16)
C12	0.8185 (2)	0.1854 (9)	0.1838 (11)	0.0444 (18)
H12	0.8377	0.1432	0.2964	0.053*
C13	0.7794 (2)	0.1712 (10)	0.2287 (12)	0.0465 (19)
H13	0.7725	0.1146	0.3649	0.056*
C14	0.7524 (2)	0.2427 (10)	0.0672 (14)	0.053 (2)
C15	0.7606 (2)	0.3157 (9)	−0.1456 (15)	0.0489 (18)
H15	0.7409	0.3558	−0.2564	0.059*
C16	0.7982 (2)	0.3280 (9)	−0.1908 (12)	0.0473 (18)
H16	0.8040	0.3809	−0.3319	0.057*
Cl1	1.13745 (6)	0.2822 (4)	0.0298 (3)	0.0922 (9)
Cl2	0.70386 (6)	0.2245 (4)	0.1208 (4)	0.0948 (10)
O1	0.96490 (15)	0.1328 (6)	0.4095 (9)	0.0515 (12)
O2	0.94303 (14)	0.4587 (5)	0.0178 (8)	0.0501 (10)
H2A	0.9434	0.5058	0.1492	0.075*
O3	0.87583 (16)	0.3179 (10)	−0.2824 (10)	0.084 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.043 (4)	0.037 (3)	0.030 (3)	−0.007 (3)	0.002 (3)	−0.001 (3)
C2	0.066 (5)	0.056 (5)	0.035 (4)	0.005 (4)	0.000 (4)	0.001 (3)
C3	0.060 (6)	0.047 (4)	0.040 (4)	−0.008 (3)	0.000 (4)	−0.012 (3)
C4	0.057 (6)	0.053 (4)	0.037 (4)	−0.006 (3)	0.008 (4)	−0.001 (3)
C5	0.047 (4)	0.033 (3)	0.040 (4)	−0.009 (3)	0.001 (3)	0.002 (3)
C6	0.042 (4)	0.033 (3)	0.033 (4)	0.009 (3)	0.008 (3)	−0.001 (3)
C7	0.057 (4)	0.026 (3)	0.030 (4)	0.006 (3)	0.009 (3)	−0.001 (3)
C8	0.048 (3)	0.033 (3)	0.033 (3)	0.011 (2)	0.000 (3)	0.002 (3)
C9	0.047 (3)	0.047 (4)	0.031 (3)	−0.007 (3)	0.008 (3)	0.003 (3)
C10	0.043 (4)	0.057 (4)	0.037 (4)	0.006 (3)	0.008 (3)	0.003 (3)
C11	0.047 (4)	0.029 (3)	0.032 (4)	−0.010 (2)	0.003 (3)	−0.004 (3)
C12	0.053 (5)	0.055 (4)	0.026 (3)	0.013 (3)	0.004 (3)	0.006 (3)
C13	0.054 (5)	0.058 (4)	0.029 (3)	−0.017 (4)	0.013 (3)	0.005 (3)
C14	0.034 (4)	0.069 (5)	0.058 (6)	−0.011 (3)	0.014 (4)	−0.004 (4)
C15	0.027 (3)	0.055 (4)	0.062 (5)	−0.008 (3)	−0.011 (3)	0.003 (4)
C16	0.061 (5)	0.042 (3)	0.037 (4)	0.001 (3)	−0.002 (4)	0.004 (3)
Cl1	0.0472 (14)	0.147 (3)	0.0842 (18)	−0.0177 (14)	0.0152 (13)	0.0093 (17)
Cl2	0.0469 (15)	0.150 (3)	0.089 (2)	−0.0122 (14)	0.0178 (13)	0.0072 (17)
O1	0.052 (3)	0.057 (3)	0.047 (3)	0.002 (2)	0.012 (2)	0.019 (2)
O2	0.064 (3)	0.039 (2)	0.048 (2)	0.0037 (19)	0.0072 (18)	0.0049 (19)
O3	0.048 (3)	0.172 (6)	0.033 (3)	0.010 (3)	0.011 (2)	0.033 (3)

Geometric parameters (Å, º) top

C1—C6	1.384 (10)	C9—C10	1.507 (11)
C1—C2	1.398 (10)	C9—H9A	0.9700
C1—H1	0.9300	C9—H9B	0.9700
C2—C3	1.391 (12)	C10—O3	1.206 (9)
C2—H2	0.9300	C10—C11	1.485 (10)
C3—C4	1.393 (11)	C11—C12	1.404 (9)
C3—Cl1	1.711 (8)	C11—C16	1.419 (10)
C4—C5	1.334 (9)	C12—C13	1.413 (9)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.380 (9)	C13—C14	1.349 (11)
C5—H5	0.9300	C13—H13	0.9300
C6—C7	1.499 (10)	C14—C15	1.376 (12)
C7—O1	1.218 (8)	C14—Cl2	1.753 (8)
C7—C8	1.525 (10)	C15—C16	1.361 (10)
C8—O2	1.422 (7)	C15—H15	0.9300
C8—C9	1.509 (7)	C16—H16	0.9300
C8—H8	0.9800	O2—H2A	0.8200

C6—C1—C2	120.7 (6)	C10—C9—H9A	109.3
C6—C1—H1	119.7	C8—C9—H9A	109.3
C2—C1—H1	119.7	C10—C9—H9B	109.3
C3—C2—C1	119.2 (7)	C8—C9—H9B	109.3
C3—C2—H2	120.4	H9A—C9—H9B	107.9
C1—C2—H2	120.4	O3—C10—C11	119.3 (6)
C2—C3—C4	118.1 (8)	O3—C10—C9	122.8 (6)
C2—C3—Cl1	121.1 (6)	C11—C10—C9	117.8 (6)
C4—C3—Cl1	120.6 (6)	C12—C11—C16	117.0 (7)
C5—C4—C3	122.3 (7)	C12—C11—C10	122.6 (6)
C5—C4—H4	118.8	C16—C11—C10	120.4 (6)
C3—C4—H4	118.8	C11—C12—C13	121.2 (6)
C4—C5—C6	120.7 (7)	C11—C12—H12	119.4
C4—C5—H5	119.7	C13—C12—H12	119.4
C6—C5—H5	119.7	C14—C13—C12	117.7 (6)
C5—C6—C1	118.9 (7)	C14—C13—H13	121.2
C5—C6—C7	124.0 (6)	C12—C13—H13	121.2
C1—C6—C7	117.1 (6)	C13—C14—C15	123.6 (7)
O1—C7—C6	121.4 (6)	C13—C14—Cl2	117.9 (6)
O1—C7—C8	120.9 (7)	C15—C14—Cl2	118.2 (6)
C6—C7—C8	117.6 (6)	C16—C15—C14	118.8 (7)
O2—C8—C9	111.2 (5)	C16—C15—H15	120.6
O2—C8—C7	109.0 (5)	C14—C15—H15	120.6
C9—C8—C7	112.3 (5)	C15—C16—C11	121.6 (7)
O2—C8—H8	108.1	C15—C16—H16	119.2
C9—C8—H8	108.1	C11—C16—H16	119.2
C7—C8—H8	108.1	C8—O2—H2A	109.5
C10—C9—C8	111.8 (5)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1—C6 and C11—C16 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O2ⁱ	0.82	2.10	2.894 (6)	163
C1—H1···Cg1ⁱⁱ	0.93	2.89	3.507 (6)	125
C4—H4···Cg1ⁱⁱⁱ	0.93	2.97	3.600 (6)	126
C13—H13···Cg2ⁱⁱ	0.93	2.88	3.517 (6)	127
C16—H16···Cg2ⁱⁱⁱ	0.93	2.90	3.544 (6)	128

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂Cl₂O₃
M_r	323.16
Crystal system, space group	Monoclinic, Cc
Temperature (K)	273
a, b, c (Å)	34.800 (8), 7.4221 (14), 5.6535 (13)
β (°)	95.925 (2)
V (Å³)	1452.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.947, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	3531, 1256, 998
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.163, 1.05
No. of reflections	1256
No. of parameters	190
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.21
Absolute structure	Nd

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

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1—C6 and C11—C16 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O2ⁱ	0.82	2.10	2.894 (6)	163
C1—H1···Cg1ⁱⁱ	0.93	2.89	3.507 (6)	125
C4—H4···Cg1ⁱⁱⁱ	0.93	2.97	3.600 (6)	126
C13—H13···Cg2ⁱⁱ	0.93	2.88	3.517 (6)	127
C16—H16···Cg2ⁱⁱⁱ	0.93	2.90	3.544 (6)	128

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

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ellison, R. A. (1973). Synthesis, pp. 397–412. CrossRef Google Scholar
Hassner, A. (1991). Comprehensive Organic Synthesis, Vol. 1, edited by B. M. Trost, pp. 541–577. Oxford: Pergamon. Google Scholar
Ohno, T., Sakai, M., Ishino, Y., Shibata, T., Maekawa, H. & Nishiguchi, I. (2001). Org. Lett. 3, 3439–3442. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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