2,6-Bis(2-chloro­benzyl­idene)cyclo­hexanone

Liu, D.

doi:10.1107/S1600536809007648

organic compounds

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Volume 65| Part 4| April 2009| Page o694

doi:10.1107/S1600536809007648

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2,6-Bis(2-chlorobenzylidene)cyclohexanone

Deyun Liu ^a ^*

^aLiaocheng Vocational and Technical College, Liaocheng, 252059, People's Republic of China
^*Correspondence e-mail: lcldy@163.com

(Received 10 February 2009; accepted 2 March 2009; online 6 March 2009)

In the title molecule, C₂₀H₁₆Cl₂O, the central cyclohexanone ring adopts an envelope conformation. The two aromatic rings form a dihedral angle of 30.0 (1)°. The crystal packing exhibits weak intermolecular C—H⋯O hydrogen bonds and short Cl⋯O contacts [3.213 (3) Å].

Related literature

For general background, see: Tanaka & Toda (2000 ). For a similar crystal structure, see: Brinda et al. (2007 ).

Experimental

Crystal data

C₂₀H₁₆Cl₂O
M_r = 343.23
Orthorhombic, P b c a
a = 14.4004 (15) Å
b = 8.1553 (10) Å
c = 28.593 (3) Å
V = 3358.0 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 298 K
0.42 × 0.32 × 0.17 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.854, T_max = 0.937
13876 measured reflections
2962 independent reflections
1762 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.124
S = 1.06
2962 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20—H20⋯O1ⁱ	0.93	2.51	3.352 (4)	151
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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/S1600536809007648/cv2518sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007648/cv2518Isup2.hkl

checkCIF report

Comment top

Development of new solid phase (solvent-free) reactions and transferring solution phase reactions to solid phase are subjects of recent interest in the context of generating libraries of molecules for the discovery of biologically active leads and also for the optimization of potent drug candidates (Tanaka & Toda, 2000).

In this paper, we describe the synthesis of the title compound, (I), starting from the fragrant aldehydes and cyclohexanone in the presence of NaOH under solvent-free conditions. This method can be considered as a general method for the synthesis of benzylidene cyclohexanones.

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in 4-methyl-2,6-bis(2-naphthylmethylene) cyclohexan-1-one (Brinda et al., 2007). The central cyclohexanone ring adopts an envelope conformation, the dihedral angles between the rings C8-C13 and C15-C20 is 30.0 (1)°.

The crystal packing exhibits short Cl···O contacts (Table 1) and weak intermolecular C—H···O hydrogen bonds (Table 2).

Related literature top

For general background, see: Tanaka & Toda (2000). For a similar crystal structure, see: Brinda et al. (2007).

Experimental top

2-Chlorobenzaldehyde (2 mmol) and cyclohexanone (1.0 mmol), NaOH (2.0 mmol) were mixed in 50 ml flash under sovlent-free condtions After stirring 15 min at 293 K, tthe 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: calcd. for C₂₀H₂₆Cl₂O: C 69.98, H 4.70%; found: C 69.93, H 4.65%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. The molecular structure of (I) showing the atomic numbering scheme and 30% probability displacement ellipsoids.

(I) top

Crystal data top

C₂₀H₁₆Cl₂O	D_x = 1.358 Mg m⁻³
M_r = 343.23	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2653 reflections
a = 14.4004 (15) Å	θ = 2.8–43.8°
b = 8.1553 (10) Å	µ = 0.39 mm⁻¹
c = 28.593 (3) Å	T = 298 K
V = 3358.0 (6) Å³	Needle, colourless
Z = 8	0.42 × 0.32 × 0.17 mm
F(000) = 1424

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2962 independent reflections
Radiation source: fine-focus sealed tube	1762 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
phi and ω scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→17
T_min = 0.854, T_max = 0.937	k = −8→9
13876 measured reflections	l = −29→34

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0353P)² + 3.2692P] where P = (F_o² + 2F_c²)/3
2962 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₂₀H₁₆Cl₂O	V = 3358.0 (6) Å³
M_r = 343.23	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 14.4004 (15) Å	µ = 0.39 mm⁻¹
b = 8.1553 (10) Å	T = 298 K
c = 28.593 (3) Å	0.42 × 0.32 × 0.17 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2962 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1762 reflections with I > 2σ(I)
T_min = 0.854, T_max = 0.937	R_int = 0.064
13876 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
2962 reflections	Δρ_min = −0.32 e Å⁻³
208 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
Cl1	1.01278 (6)	1.01596 (12)	0.34622 (3)	0.0568 (3)
Cl2	0.72695 (8)	0.83897 (15)	0.07162 (3)	0.0783 (4)
O1	0.86474 (15)	0.7337 (3)	0.22424 (7)	0.0515 (7)
C1	0.7861 (2)	0.7354 (4)	0.24087 (10)	0.0342 (8)
C2	0.7724 (2)	0.7802 (4)	0.29170 (10)	0.0347 (8)
C3	0.6741 (2)	0.8022 (5)	0.30951 (11)	0.0472 (9)
H3A	0.6726	0.8954	0.3306	0.057*
H3B	0.6567	0.7058	0.3273	0.057*
C4	0.6032 (2)	0.8289 (5)	0.27104 (11)	0.0455 (9)
H4A	0.6145	0.9334	0.2559	0.055*
H4B	0.5413	0.8313	0.2844	0.055*
C5	0.6099 (2)	0.6916 (4)	0.23542 (11)	0.0399 (8)
H5A	0.6006	0.5870	0.2509	0.048*
H5B	0.5615	0.7046	0.2122	0.048*
C6	0.7032 (2)	0.6928 (4)	0.21178 (10)	0.0335 (7)
C7	0.8490 (2)	0.8002 (4)	0.31767 (10)	0.0412 (8)
H7	0.9051	0.7861	0.3020	0.049*
C8	0.8563 (2)	0.8412 (5)	0.36743 (11)	0.0458 (9)
C9	0.9282 (2)	0.9410 (5)	0.38404 (11)	0.0485 (9)
C10	0.9346 (3)	0.9856 (6)	0.43068 (13)	0.0654 (12)
H10	0.9817	1.0555	0.4406	0.078*
C11	0.8710 (3)	0.9260 (7)	0.46211 (14)	0.0806 (15)
H11	0.8753	0.9550	0.4935	0.097*
C12	0.8011 (3)	0.8238 (7)	0.44739 (14)	0.0836 (15)
H12	0.7585	0.7832	0.4689	0.100*
C13	0.7935 (3)	0.7809 (6)	0.40090 (12)	0.0626 (12)
H13	0.7461	0.7108	0.3915	0.075*
C14	0.7172 (2)	0.6681 (4)	0.16580 (11)	0.0399 (8)
H14	0.7776	0.6812	0.1549	0.048*
C15	0.6467 (2)	0.6227 (4)	0.13110 (10)	0.0382 (8)
C16	0.6448 (2)	0.6917 (4)	0.08648 (11)	0.0444 (9)
C17	0.5785 (3)	0.6500 (5)	0.05364 (12)	0.0561 (10)
H17	0.5785	0.7002	0.0244	0.067*
C18	0.5126 (3)	0.5339 (5)	0.06440 (13)	0.0610 (11)
H18	0.4672	0.5062	0.0426	0.073*
C19	0.5141 (3)	0.4588 (5)	0.10758 (13)	0.0588 (11)
H19	0.4707	0.3781	0.1146	0.071*
C20	0.5795 (2)	0.5029 (4)	0.14024 (11)	0.0461 (9)
H20	0.5791	0.4515	0.1693	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0448 (5)	0.0640 (7)	0.0615 (6)	−0.0018 (5)	−0.0062 (5)	−0.0015 (5)
Cl2	0.1071 (9)	0.0832 (8)	0.0447 (5)	−0.0501 (7)	−0.0081 (6)	0.0118 (5)
O1	0.0311 (14)	0.086 (2)	0.0376 (13)	−0.0010 (13)	0.0065 (11)	0.0017 (12)
C1	0.0311 (19)	0.037 (2)	0.0346 (17)	0.0016 (15)	0.0042 (15)	0.0061 (14)
C2	0.0328 (19)	0.038 (2)	0.0338 (17)	−0.0009 (15)	0.0062 (14)	0.0039 (14)
C3	0.038 (2)	0.060 (3)	0.0431 (19)	−0.0041 (18)	0.0083 (16)	−0.0082 (17)
C4	0.0317 (19)	0.051 (2)	0.054 (2)	0.0072 (16)	0.0020 (16)	−0.0050 (18)
C5	0.0316 (19)	0.046 (2)	0.0419 (18)	−0.0017 (16)	0.0002 (15)	0.0013 (16)
C6	0.0296 (18)	0.037 (2)	0.0336 (17)	0.0031 (14)	0.0025 (14)	0.0066 (14)
C7	0.032 (2)	0.054 (2)	0.0376 (18)	0.0038 (16)	0.0037 (15)	0.0027 (16)
C8	0.045 (2)	0.058 (2)	0.0338 (18)	0.0056 (18)	−0.0014 (16)	−0.0029 (17)
C9	0.050 (2)	0.055 (3)	0.040 (2)	0.0114 (19)	−0.0070 (17)	−0.0024 (17)
C10	0.068 (3)	0.078 (3)	0.050 (2)	0.011 (2)	−0.011 (2)	−0.014 (2)
C11	0.085 (4)	0.120 (4)	0.036 (2)	0.017 (3)	−0.008 (2)	−0.015 (3)
C12	0.076 (3)	0.134 (5)	0.041 (2)	0.001 (3)	0.010 (2)	0.007 (3)
C13	0.058 (3)	0.091 (3)	0.039 (2)	−0.003 (2)	0.0029 (19)	0.006 (2)
C14	0.0346 (19)	0.045 (2)	0.0405 (19)	−0.0006 (16)	0.0013 (15)	0.0063 (16)
C15	0.0365 (19)	0.044 (2)	0.0337 (17)	0.0016 (16)	0.0025 (15)	−0.0040 (15)
C16	0.058 (2)	0.041 (2)	0.0345 (18)	−0.0080 (18)	0.0020 (16)	−0.0019 (15)
C17	0.077 (3)	0.060 (3)	0.0318 (18)	−0.007 (2)	−0.0099 (19)	−0.0037 (18)
C18	0.062 (3)	0.070 (3)	0.051 (2)	−0.014 (2)	−0.010 (2)	−0.015 (2)
C19	0.054 (2)	0.066 (3)	0.056 (2)	−0.018 (2)	0.004 (2)	−0.009 (2)
C20	0.049 (2)	0.053 (2)	0.0370 (18)	−0.0034 (19)	0.0034 (16)	0.0057 (17)

Geometric parameters (Å, º) top

Cl1—C9	1.739 (4)	C9—C10	1.385 (5)
Cl2—C16	1.738 (3)	C10—C11	1.372 (6)
O1—C1	1.228 (3)	C10—H10	0.9300
C1—C6	1.496 (4)	C11—C12	1.374 (6)
C1—C2	1.511 (4)	C11—H11	0.9300
C2—C7	1.340 (4)	C12—C13	1.379 (5)
C2—C3	1.514 (4)	C12—H12	0.9300
C3—C4	1.517 (4)	C13—H13	0.9300
C3—H3A	0.9700	C14—C15	1.467 (4)
C3—H3B	0.9700	C14—H14	0.9300
C4—C5	1.517 (4)	C15—C16	1.395 (4)
C4—H4A	0.9700	C15—C20	1.400 (4)
C4—H4B	0.9700	C16—C17	1.381 (5)
C5—C6	1.504 (4)	C17—C18	1.376 (5)
C5—H5A	0.9700	C17—H17	0.9300
C5—H5B	0.9700	C18—C19	1.378 (5)
C6—C14	1.345 (4)	C18—H18	0.9300
C7—C8	1.465 (4)	C19—C20	1.374 (5)
C7—H7	0.9300	C19—H19	0.9300
C8—C9	1.400 (5)	C20—H20	0.9300
C8—C13	1.405 (5)

Cl1···O1ⁱ	3.213 (3)

C9—Cl1—O1ⁱ	165.55 (13)	C10—C9—Cl1	117.4 (3)
O1—C1—C6	121.2 (3)	C8—C9—Cl1	120.8 (3)
O1—C1—C2	119.7 (3)	C11—C10—C9	119.6 (4)
C6—C1—C2	119.1 (3)	C11—C10—H10	120.2
C7—C2—C1	117.0 (3)	C9—C10—H10	120.2
C7—C2—C3	124.7 (3)	C10—C11—C12	120.2 (4)
C1—C2—C3	118.3 (3)	C10—C11—H11	119.9
C2—C3—C4	113.7 (3)	C12—C11—H11	119.9
C2—C3—H3A	108.8	C11—C12—C13	120.5 (4)
C4—C3—H3A	108.8	C11—C12—H12	119.8
C2—C3—H3B	108.8	C13—C12—H12	119.8
C4—C3—H3B	108.8	C12—C13—C8	121.1 (4)
H3A—C3—H3B	107.7	C12—C13—H13	119.4
C3—C4—C5	109.8 (3)	C8—C13—H13	119.4
C3—C4—H4A	109.7	C6—C14—C15	126.6 (3)
C5—C4—H4A	109.7	C6—C14—H14	116.7
C3—C4—H4B	109.7	C15—C14—H14	116.7
C5—C4—H4B	109.7	C16—C15—C20	116.0 (3)
H4A—C4—H4B	108.2	C16—C15—C14	122.0 (3)
C6—C5—C4	110.7 (3)	C20—C15—C14	121.9 (3)
C6—C5—H5A	109.5	C17—C16—C15	122.4 (3)
C4—C5—H5A	109.5	C17—C16—Cl2	118.3 (3)
C6—C5—H5B	109.5	C15—C16—Cl2	119.3 (3)
C4—C5—H5B	109.5	C18—C17—C16	119.6 (3)
H5A—C5—H5B	108.1	C18—C17—H17	120.2
C14—C6—C1	117.4 (3)	C16—C17—H17	120.2
C14—C6—C5	124.9 (3)	C17—C18—C19	119.7 (3)
C1—C6—C5	117.7 (3)	C17—C18—H18	120.2
C2—C7—C8	128.7 (3)	C19—C18—H18	120.2
C2—C7—H7	115.7	C20—C19—C18	120.2 (4)
C8—C7—H7	115.7	C20—C19—H19	119.9
C9—C8—C13	116.6 (3)	C18—C19—H19	119.9
C9—C8—C7	121.0 (3)	C19—C20—C15	122.0 (3)
C13—C8—C7	122.4 (3)	C19—C20—H20	119.0
C10—C9—C8	121.9 (4)	C15—C20—H20	119.0

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···O1ⁱⁱ	0.93	2.51	3.352 (4)	151

Symmetry code: (ii) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₆Cl₂O
M_r	343.23
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	14.4004 (15), 8.1553 (10), 28.593 (3)
V (Å³)	3358.0 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.42 × 0.32 × 0.17

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.854, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	13876, 2962, 1762
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.124, 1.06
No. of reflections	2962
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.32

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected interatomic distances (Å) top

Cl1···O1ⁱ

3.213 (3)

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···O1ⁱⁱ	0.93	2.51	3.352 (4)	151.3

Symmetry code: (ii) −x+3/2, y−1/2, z.

Acknowledgements

This project was supported by the Foundation of Liaocheng Vocational and Technical College.

References

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Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Systems Inc., Madison, Wisconsin, USA. Google Scholar
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