2,6-Bis(4-methoxy­benzyl­idene)cyclo­hexa­none

Liu, D.; Chen, G.

doi:10.1107/S160053680901112X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o928

doi:10.1107/S160053680901112X

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2,6-Bis(4-methoxybenzylidene)cyclohexanone

Deyun Liu ^a ^* and Guohua Chen ^a

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

(Received 12 March 2009; accepted 25 March 2009; online 31 March 2009)

In the title molecule, C₂₂H₂₂O₃, the central cyclohexanone ring adopts an envelope conformation. The two outer aromatic rings form a dihedral angle of 19.3 (2)°. The crystal packing exhibits weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For background, see: Tanaka et al. (2000 ). For a related structure, see: Brinda, Mudakavi et al. (2007 ).

Experimental

Crystal data

C₂₂H₂₂O₃
M_r = 334.40
Monoclinic, P 2₁ /c
a = 9.0129 (8) Å
b = 9.4874 (10) Å
c = 20.9416 (17) Å
β = 100.518 (1)°
V = 1760.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.45 × 0.17 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.964, T_max = 0.988
9092 measured reflections
3105 independent reflections
1233 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.170
S = 0.87
3105 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯O2ⁱ	0.96	2.67	3.512 (5)	146
C4—H4A⋯O1ⁱⁱ	0.97	2.61	3.510 (5)	154
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y, -z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901112X/cv2532sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901112X/cv2532Isup2.hkl

checkCIF report

Comment top

The use of organic syntheses without volatile, often flammable, expensive and toxic solvents strongly reduces the waste production and many fundamental processes have proven to be achievable through efficient procedures characterized by high simplicity of set-up and work-up (Tanaka et al., 2000). In this paper, we describe a solvent-free protocol used in the synthesis of the title compound, (I), starting from the fragrant aldehydes and cyclohexanone in the presence of NaOH.

In (I) (Fig. 1), the bond lengths and angles are normal and correspond to those observed in 4-methyl-2,6-bis(2-naphthylmethylene) cyclohexan-1-one (Brinda, Mudakavi et al., 2007). The central cyclohexanone ring adopts an envelope conformation. The mean planes of two rings - C8—C13 and C16—C21 - form a dihedral angle of 19.3 (2)°. The crystal packing exhibits weak intermolecular C—H···O hydrogen bonds (Table 1).

Related literature top

For background, see Tanaka et al. (2000). For similar crystal structures, see Brinda, Mudakavi et al. (2007).

Experimental top

2-Methoxylbenzaldehyde (4 mmol) and cyclohexanone (2.0 mmol), NaOH (4.0 mmol) were mixed in 50 ml flash under sovlent-free condtions After stirring for 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: calculated for C₂₂H₂₂O₃: C 79.02, H 6.63%; found: C 69.93, H 6.65%.

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. View of (I) showing the atomic numbering scheme and 40% probability displacement ellipsoids.

2,6-Bis(4-methoxybenzylidene)cyclohexanone top

Crystal data top

C₂₂H₂₂O₃	F(000) = 712
M_r = 334.40	D_x = 1.262 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.0129 (8) Å	Cell parameters from 935 reflections
b = 9.4874 (10) Å	θ = 2.4–25.2°
c = 20.9416 (17) Å	µ = 0.08 mm⁻¹
β = 100.518 (1)°	T = 298 K
V = 1760.6 (3) Å³	Prism, yellow
Z = 4	0.45 × 0.17 × 0.15 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3105 independent reflections
Radiation source: fine-focus sealed tube	1233 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.964, T_max = 0.988	k = −11→11
9092 measured reflections	l = −23→24

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 0.87	w = 1/[σ²(F_o²) + (0.076P)²] where P = (F_o² + 2F_c²)/3
3105 reflections	(Δ/σ)_max < 0.001
228 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₂₂H₂₂O₃	V = 1760.6 (3) Å³
M_r = 334.40	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.0129 (8) Å	µ = 0.08 mm⁻¹
b = 9.4874 (10) Å	T = 298 K
c = 20.9416 (17) Å	0.45 × 0.17 × 0.15 mm
β = 100.518 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3105 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1233 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.988	R_int = 0.065
9092 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 0.87	Δρ_max = 0.26 e Å⁻³
3105 reflections	Δρ_min = −0.12 e Å⁻³
228 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
O1	0.1376 (3)	−0.1927 (3)	0.02703 (11)	0.1012 (9)
O2	0.4818 (3)	−0.0038 (2)	0.41111 (13)	0.0905 (8)
O3	0.0867 (3)	0.0536 (3)	−0.35644 (17)	0.1062 (9)
C1	0.1981 (4)	−0.0760 (4)	0.02660 (19)	0.0782 (10)
C2	0.2658 (4)	−0.0065 (3)	0.0884 (2)	0.0729 (10)
C3	0.3239 (4)	0.1430 (3)	0.08487 (18)	0.0941 (12)
H3A	0.3018	0.1963	0.1215	0.113*
H3B	0.4327	0.1404	0.0883	0.113*
C4	0.2551 (5)	0.2176 (4)	0.02279 (19)	0.1055 (14)
H4A	0.1479	0.2305	0.0217	0.127*
H4B	0.3007	0.3101	0.0220	0.127*
C5	0.2779 (5)	0.1360 (4)	−0.03590 (18)	0.0973 (12)
H5A	0.3851	0.1263	−0.0359	0.117*
H5B	0.2331	0.1869	−0.0748	0.117*
C6	0.2063 (4)	−0.0095 (3)	−0.0364 (2)	0.0754 (10)
C7	0.2725 (4)	−0.0772 (3)	0.1430 (2)	0.0744 (10)
H7	0.2294	−0.1662	0.1361	0.089*
C8	0.3302 (4)	−0.0512 (3)	0.21109 (18)	0.0655 (9)
C9	0.4222 (4)	0.0636 (4)	0.2354 (2)	0.0812 (10)
H9	0.4495	0.1291	0.2066	0.097*
C10	0.4728 (4)	0.0810 (3)	0.30125 (19)	0.0760 (10)
H10	0.5326	0.1585	0.3158	0.091*
C11	0.4371 (4)	−0.0127 (4)	0.3454 (2)	0.0746 (10)
C12	0.3475 (4)	−0.1281 (3)	0.3233 (2)	0.0753 (10)
H12	0.3210	−0.1932	0.3525	0.090*
C13	0.2984 (4)	−0.1449 (3)	0.2575 (2)	0.0789 (10)
H13	0.2403	−0.2238	0.2434	0.095*
C14	0.5918 (5)	0.0992 (4)	0.43567 (18)	0.1055 (13)
H14A	0.6829	0.0810	0.4194	0.158*
H14B	0.6125	0.0951	0.4823	0.158*
H14C	0.5545	0.1911	0.4220	0.158*
C15	0.1460 (4)	−0.0755 (3)	−0.0911 (2)	0.0747 (10)
H15	0.1021	−0.1614	−0.0840	0.090*
C16	0.1343 (4)	−0.0418 (3)	−0.1593 (2)	0.0709 (10)
C17	0.0221 (4)	−0.1023 (3)	−0.2053 (2)	0.0777 (10)
H17	−0.0428	−0.1659	−0.1907	0.093*
C18	−0.0001 (4)	−0.0757 (4)	−0.2704 (2)	0.0792 (10)
H18	−0.0786	−0.1184	−0.2988	0.095*
C19	0.0973 (5)	0.0166 (4)	−0.2928 (2)	0.0862 (12)
C20	0.2143 (5)	0.0738 (4)	−0.2494 (2)	0.0884 (12)
H20	0.2823	0.1329	−0.2646	0.106*
C21	0.2335 (4)	0.0466 (4)	−0.1850 (2)	0.0894 (11)
H21	0.3142	0.0874	−0.1572	0.107*
C22	−0.0240 (5)	−0.0063 (4)	−0.4044 (2)	0.1223 (16)
H22A	−0.0036	−0.1049	−0.4082	0.184*
H22B	−0.0231	0.0395	−0.4452	0.184*
H22C	−0.1213	0.0054	−0.3925	0.184*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.117 (2)	0.0614 (16)	0.120 (2)	−0.0281 (15)	0.0088 (15)	0.0043 (14)
O2	0.097 (2)	0.0870 (18)	0.087 (2)	−0.0124 (15)	0.0157 (15)	0.0058 (14)
O3	0.128 (3)	0.090 (2)	0.104 (2)	0.0029 (17)	0.0314 (19)	−0.0034 (17)
C1	0.072 (3)	0.059 (2)	0.105 (3)	0.0060 (19)	0.019 (2)	0.008 (2)
C2	0.066 (2)	0.053 (2)	0.098 (3)	−0.0002 (17)	0.012 (2)	−0.004 (2)
C3	0.107 (3)	0.061 (2)	0.109 (3)	−0.011 (2)	0.005 (2)	0.003 (2)
C4	0.133 (4)	0.053 (2)	0.124 (3)	−0.019 (2)	0.005 (3)	−0.003 (2)
C5	0.108 (3)	0.063 (2)	0.120 (3)	−0.018 (2)	0.017 (2)	0.002 (2)
C6	0.070 (3)	0.054 (2)	0.101 (3)	0.0013 (17)	0.012 (2)	−0.010 (2)
C7	0.065 (2)	0.053 (2)	0.107 (3)	0.0008 (17)	0.021 (2)	0.001 (2)
C8	0.057 (2)	0.047 (2)	0.094 (3)	0.0007 (17)	0.018 (2)	−0.0063 (19)
C9	0.078 (3)	0.069 (2)	0.101 (3)	−0.010 (2)	0.027 (2)	0.010 (2)
C10	0.073 (3)	0.064 (2)	0.090 (3)	−0.0117 (18)	0.014 (2)	0.002 (2)
C11	0.070 (3)	0.067 (2)	0.091 (3)	0.0036 (19)	0.025 (2)	0.009 (2)
C12	0.071 (3)	0.053 (2)	0.104 (3)	−0.0076 (18)	0.022 (2)	0.0050 (19)
C13	0.067 (3)	0.056 (2)	0.116 (3)	−0.0037 (17)	0.021 (2)	0.000 (2)
C14	0.103 (3)	0.083 (3)	0.126 (3)	−0.012 (2)	0.008 (3)	−0.008 (2)
C15	0.067 (2)	0.059 (2)	0.101 (3)	0.0070 (18)	0.022 (2)	0.001 (2)
C16	0.060 (2)	0.050 (2)	0.104 (3)	0.0043 (18)	0.019 (2)	−0.009 (2)
C17	0.072 (3)	0.058 (2)	0.106 (3)	0.0068 (19)	0.023 (2)	−0.007 (2)
C18	0.073 (3)	0.065 (2)	0.101 (3)	0.010 (2)	0.021 (2)	−0.008 (2)
C19	0.102 (4)	0.065 (3)	0.097 (4)	0.026 (2)	0.031 (3)	0.001 (2)
C20	0.090 (3)	0.069 (2)	0.111 (4)	−0.011 (2)	0.031 (3)	−0.010 (2)
C21	0.086 (3)	0.076 (3)	0.109 (4)	−0.007 (2)	0.023 (3)	−0.009 (2)
C22	0.135 (4)	0.134 (4)	0.099 (3)	0.024 (3)	0.025 (3)	−0.013 (3)

Geometric parameters (Å, º) top

O1—C1	1.236 (4)	C10—C11	1.363 (4)
O2—C11	1.364 (4)	C10—H10	0.9300
O2—C14	1.420 (4)	C11—C12	1.388 (4)
O3—C19	1.364 (4)	C12—C13	1.377 (4)
O3—C22	1.400 (4)	C12—H12	0.9300
C1—C6	1.477 (5)	C13—H13	0.9300
C1—C2	1.481 (5)	C14—H14A	0.9600
C2—C7	1.318 (4)	C14—H14B	0.9600
C2—C3	1.518 (4)	C14—H14C	0.9600
C3—C4	1.510 (4)	C15—C16	1.448 (4)
C3—H3A	0.9700	C15—H15	0.9300
C3—H3B	0.9700	C16—C17	1.388 (4)
C4—C5	1.498 (4)	C16—C21	1.403 (5)
C4—H4A	0.9700	C17—C18	1.364 (4)
C4—H4B	0.9700	C17—H17	0.9300
C5—C6	1.523 (4)	C18—C19	1.382 (5)
C5—H5A	0.9700	C18—H18	0.9300
C5—H5B	0.9700	C19—C20	1.372 (5)
C6—C15	1.330 (4)	C20—C21	1.352 (5)
C7—C8	1.447 (4)	C20—H20	0.9300
C7—H7	0.9300	C21—H21	0.9300
C8—C13	1.385 (4)	C22—H22A	0.9600
C8—C9	1.407 (4)	C22—H22B	0.9600
C9—C10	1.380 (4)	C22—H22C	0.9600
C9—H9	0.9300

C11—O2—C14	117.8 (3)	C10—C11—C12	118.9 (4)
C19—O3—C22	120.6 (4)	O2—C11—C12	115.6 (3)
O1—C1—C6	118.9 (3)	C13—C12—C11	119.0 (3)
O1—C1—C2	120.3 (3)	C13—C12—H12	120.5
C6—C1—C2	120.7 (4)	C11—C12—H12	120.5
C7—C2—C1	118.6 (3)	C12—C13—C8	123.9 (3)
C7—C2—C3	123.8 (3)	C12—C13—H13	118.0
C1—C2—C3	117.6 (3)	C8—C13—H13	118.0
C4—C3—C2	112.9 (3)	O2—C14—H14A	109.5
C4—C3—H3A	109.0	O2—C14—H14B	109.5
C2—C3—H3A	109.0	H14A—C14—H14B	109.5
C4—C3—H3B	109.0	O2—C14—H14C	109.5
C2—C3—H3B	109.0	H14A—C14—H14C	109.5
H3A—C3—H3B	107.8	H14B—C14—H14C	109.5
C5—C4—C3	111.6 (3)	C6—C15—C16	133.6 (3)
C5—C4—H4A	109.3	C6—C15—H15	113.2
C3—C4—H4A	109.3	C16—C15—H15	113.2
C5—C4—H4B	109.3	C17—C16—C21	114.5 (4)
C3—C4—H4B	109.3	C17—C16—C15	120.4 (4)
H4A—C4—H4B	108.0	C21—C16—C15	125.0 (4)
C4—C5—C6	110.7 (3)	C18—C17—C16	124.9 (4)
C4—C5—H5A	109.5	C18—C17—H17	117.5
C6—C5—H5A	109.5	C16—C17—H17	117.5
C4—C5—H5B	109.5	C17—C18—C19	118.1 (4)
C6—C5—H5B	109.5	C17—C18—H18	121.0
H5A—C5—H5B	108.1	C19—C18—H18	121.0
C15—C6—C1	119.3 (3)	O3—C19—C20	117.0 (4)
C15—C6—C5	122.6 (3)	O3—C19—C18	124.0 (4)
C1—C6—C5	118.1 (3)	C20—C19—C18	118.9 (4)
C2—C7—C8	136.0 (3)	C21—C20—C19	121.9 (4)
C2—C7—H7	112.0	C21—C20—H20	119.0
C8—C7—H7	112.0	C19—C20—H20	119.0
C13—C8—C9	115.2 (3)	C20—C21—C16	121.5 (4)
C13—C8—C7	119.9 (3)	C20—C21—H21	119.3
C9—C8—C7	124.8 (3)	C16—C21—H21	119.3
C10—C9—C8	121.3 (3)	O3—C22—H22A	109.5
C10—C9—H9	119.3	O3—C22—H22B	109.5
C8—C9—H9	119.3	H22A—C22—H22B	109.5
C11—C10—C9	121.6 (3)	O3—C22—H22C	109.5
C11—C10—H10	119.2	H22A—C22—H22C	109.5
C9—C10—H10	119.2	H22B—C22—H22C	109.5
C10—C11—O2	125.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···O2ⁱ	0.96	2.67	3.512 (5)	146
C4—H4A···O1ⁱⁱ	0.97	2.61	3.510 (5)	154

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

Experimental details

Crystal data
Chemical formula	C₂₂H₂₂O₃
M_r	334.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.0129 (8), 9.4874 (10), 20.9416 (17)
β (°)	100.518 (1)
V (Å³)	1760.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.45 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.964, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	9092, 3105, 1233
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.170, 0.87
No. of reflections	3105
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.12

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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
C14—H14B···O2ⁱ	0.96	2.67	3.512 (5)	146.0
C4—H4A···O1ⁱⁱ	0.97	2.61	3.510 (5)	153.8

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

Acknowledgements

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

References

Brinda, Mudakavi, R., Chopra, D., Murthy, M. S. & Row, T. N. G. (2007). Acta Cryst. E63, o4494. Web of Science CSD CrossRef IUCr Journals Google Scholar
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