organic papers
Acta Cryst.(2005). E61, o4049–o4050 doi:10.1107/S1600536805036135 Han and Zhen C
20H22O6
o4049
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
3-[4-(5-Formyl-2-methoxyphenoxy)butoxy]-4-methoxybenzaldehyde
Jian-Rong Han* and Xiao-Li Zhen
College of Sciences, Hebei University of Science & Technology, Shijiazhuang 050018, People’s Republic of China
Correspondence e-mail: han_jianrong@163.com
Key indicators
Single-crystal X-ray study T= 294 K
Mean(C–C) = 0.004 A˚ Rfactor = 0.049 wRfactor = 0.131
Data-to-parameter ratio = 15.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
The molecule of the title compound, C20H22O6, lies on
crystallographic center of symmetry. The isovanillin group makes a dihedral angle of 2.8 (5)with the four C atoms of the
central chain. A weak intermolecular C—H O hydrogen
bond links molecules into extended one-dimensional chains.
Comment
Since the early work on macrocyclic crown ethers was carried out by Pedersen (1967), considerable effort has been devoted to the study of these species (Kimet al., 1999). Crown ethers are capable of forming stable and selective complexes with metal cations, halide anions and small organic molecules. We are interested in the molecular and ionic recognition of these crown ethers. As part of this study, we report the synthesis and structure of the title compound, (I), used as a precursor in their preparation.
In (I) (Fig. 1), a crystallographic center of symmetry is located at the mid-point of the central C—C bond. The bond lengths and angles are as expected. The isovanillin group (C1– C7/O1/O2/O3) is essentially planar, with an r.m.s. deviation for the fitted atoms of 0.0261 A˚ . The torsion angle of 176.8 (2)for
C6—C1—O1—C9, in conjunction with the value of 2.8 (5)for
the dihedral angle between the central chain of C atoms and the isovanillin group, confirm the nearly planar conformation of the molecule. The geometry is similar to that in 4-[6-(4- formyl-2-methoxyphenoxy)hexyloxy]-3-methoxybenzalde-hyde (Diaoet al., 2005), in which the dihedral angle between the central C-atom chain and the atoms of the isovanillin group is 3.0 (3)
A weak intermolecular C—H O hydrogen bond (Table 1)
links molecules into extended one-dimensional chains (Fig. 2).
Experimental
To a solution of 3-hydroxy-4-methoxybenzaldehyde (15.2 g, 100 mmol) and potassium carbonate (13.8 g, 100 mmol) in aceto-nitrile (500 ml), 1,4-dibromobutane (10.8 g, 50 mmol) was added dropwise over a period of 30 min, and the mixture refluxed for 24 h under nitrogen. The solvent was removed and the resultant mixture poured into ice-water (500 ml). The white precipitate was then
isolated and recrystallized from ethanol to give the pure compound in 51% yield. Colorless single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an acetonitrile solution.
Crystal data
C20H22O6
Mr= 358.38 Monoclinic,P21=n
a= 7.828 (2) A˚
b= 7.261 (2) A˚
c= 16.445 (4) A˚
= 94.499 (5) V= 931.9 (4) A˚3
Z= 2
Dx= 1.277 Mg m3 MoKradiation Cell parameters from 1180
reflections
= 3.0–24.3
= 0.09 mm1
T= 294 (2) K Block, colorless 0.220.200.14 mm
Data collection
Bruker SMART-CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.972,Tmax= 0.987
5085 measured reflections
1907 independent reflections 1109 reflections withI> 2(I)
Rint= 0.039 max= 26.4
h=9!9
k=8!9
l=20!12
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.049
wR(F2) = 0.131
S= 1.14 1907 reflections 120 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0515P)2
+ 0.0565P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.005 max= 0.39 e A˚
3 min=0.24 e A˚
3
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
C8—H8B O1i
0.96 2.57 3.512 (4) 167
Symmetry code: (i)x;yþ2;zþ2.
H atoms were included in calculated positions and refined using a riding-model approximation, with C—H bond lengths and isotropicU parameters as follows: 0.93 A˚ andUiso(H) = 1.2Ueq(C) for aromatic CH; 0.97 A˚ andUiso(H) = 1.2Ueq(C) for methylene CH2; 0.96 A˚ and Uiso(H) = 1.5Ueq(C) for methyl CH3.
Data collection:SMART(Bruker, 1999); cell refinement:SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL(Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.
References
Bruker (1999).SMART(Version 5.0) andSAINT(Version 4.0) for Windows NT. Bruker AXS Inc., Madison, Wisconsin, USA.
Diao, C.-H., Guo, M.-J., Yu, M., Chen, X. & Jing, Z.-L. (2005).Acta Cryst.E61, o3670–o3671.
Kim, J., Shamsipur, M., Huang, S. Z., Huang, R. H. & Dye, J. L. (1999).J. Phys. Chem. A,103, 5615–5620.
Pedersen, C. J. (1967).J. Am. Chem. Soc.89, 7017–7036.
Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of
Go¨ttingen, Germany.
Sheldrick, G. M. (1997b).SHELXTL. Version 5.10 for Windows NT. Bruker AXS Inc., Madison, Wisconsin, USA.
Figure 2
[image:2.610.314.565.70.223.2] [image:2.610.313.565.284.481.2]Partial packing diagram, showing hydrogen-bonding interactions as dashed lines.
Figure 1
supporting information
sup-1 Acta Cryst. (2005). E61, o4049–o4050
supporting information
Acta Cryst. (2005). E61, o4049–o4050 [https://doi.org/10.1107/S1600536805036135]
3-[4-(5-Formyl-2-methoxyphenoxy)butoxy]-4-methoxybenzaldehyde
Jian-Rong Han and Xiao-Li Zhen
3-[4-(5-Formyl-2-methoxyphenoxy)butoxy]-4-methoxybenzaldehyde
Crystal data
C20H22O6 Mr = 358.38
Monoclinic, P21/n Hall symbol: -P 2yn a = 7.828 (2) Å b = 7.261 (2) Å c = 16.445 (4) Å β = 94.499 (5)° V = 931.9 (4) Å3 Z = 2
F(000) = 380 Dx = 1.277 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1180 reflections θ = 3.0–24.3°
µ = 0.09 mm−1 T = 294 K Block, colorless 0.22 × 0.20 × 0.14 mm
Data collection
Bruker SMART-CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.972, Tmax = 0.987
5085 measured reflections 1907 independent reflections 1109 reflections with I > 2σ(I) Rint = 0.039
θmax = 26.4°, θmin = 2.5° h = −9→9
k = −8→9 l = −20→12
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.049 wR(F2) = 0.131 S = 1.14 1907 reflections 120 parameters 6 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0515P)2 + 0.0565P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.005 Δρmax = 0.39 e Å−3 Δρmin = −0.24 e Å−3
Special details
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 > 2σ(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)
x y z Uiso*/Ueq
O1 0.3564 (2) 1.1337 (3) 0.93699 (12) 0.0468 (6)
O2 0.1157 (3) 0.8943 (3) 0.93578 (14) 0.0609 (7)
O3 0.7434 (4) 0.9003 (5) 0.7134 (2) 0.1058 (11)
C1 0.3709 (4) 0.9911 (4) 0.88433 (16) 0.0381 (7)
C2 0.4974 (4) 0.9701 (4) 0.83234 (17) 0.0443 (8)
H2 0.5848 1.0568 0.8320 0.053*
C3 0.4958 (4) 0.8187 (5) 0.77955 (19) 0.0511 (9)
C4 0.3672 (5) 0.6902 (5) 0.7810 (2) 0.0594 (10)
H4 0.3675 0.5883 0.7467 0.071*
C5 0.2383 (4) 0.7103 (5) 0.8323 (2) 0.0570 (10)
H5 0.1515 0.6229 0.8322 0.068*
C6 0.2373 (4) 0.8594 (4) 0.88392 (18) 0.0444 (8)
C7 0.6247 (5) 0.7975 (6) 0.7213 (2) 0.0749 (12)
H7 0.6149 0.6955 0.6871 0.090*
C8 −0.0297 (4) 0.7735 (5) 0.9342 (3) 0.0820 (13)
H8A −0.0870 0.7728 0.8804 0.123*
H8B −0.1072 0.8158 0.9725 0.123*
H8C 0.0080 0.6511 0.9485 0.123*
C9 0.4826 (4) 1.2768 (4) 0.93739 (17) 0.0419 (8)
H9A 0.4840 1.3305 0.8834 0.050*
H9B 0.5954 1.2272 0.9531 0.050*
C10 0.4365 (4) 1.4205 (4) 0.99753 (17) 0.0401 (8)
H10A 0.4338 1.3646 1.0510 0.048*
H10B 0.3228 1.4675 0.9816 0.048*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.0509 (13) 0.0364 (13) 0.0548 (13) −0.0134 (10) 0.0154 (10) −0.0120 (10) O2 0.0524 (14) 0.0518 (15) 0.0803 (17) −0.0198 (11) 0.0159 (12) −0.0125 (12) O3 0.1102 (15) 0.1046 (16) 0.1098 (15) −0.0033 (12) 0.0536 (12) −0.0201 (12) C1 0.0443 (17) 0.0305 (17) 0.0392 (17) −0.0022 (13) −0.0002 (14) −0.0037 (13) C2 0.0497 (18) 0.0366 (19) 0.0465 (18) −0.0029 (15) 0.0023 (15) −0.0012 (15)
C3 0.063 (2) 0.043 (2) 0.0461 (19) 0.0090 (17) 0.0006 (16) −0.0065 (15)
C4 0.077 (2) 0.043 (2) 0.056 (2) −0.0012 (19) −0.0084 (19) −0.0181 (16)
C5 0.060 (2) 0.043 (2) 0.066 (2) −0.0107 (17) −0.0081 (19) −0.0102 (18)
C6 0.0456 (18) 0.0371 (19) 0.0495 (19) −0.0047 (15) −0.0024 (15) −0.0010 (14)
C7 0.090 (3) 0.066 (3) 0.071 (3) 0.006 (2) 0.021 (2) −0.018 (2)
C8 0.058 (2) 0.068 (3) 0.122 (3) −0.031 (2) 0.021 (2) −0.018 (3)
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sup-3 Acta Cryst. (2005). E61, o4049–o4050
C10 0.0430 (16) 0.0338 (17) 0.0444 (17) −0.0069 (13) 0.0084 (14) −0.0017 (13)
Geometric parameters (Å, º)
O1—C1 1.360 (3) C5—C6 1.376 (4)
O1—C9 1.434 (3) C5—H5 0.9300
O2—C6 1.351 (3) C7—H7 0.9300
O2—C8 1.436 (4) C8—H8A 0.9600
O3—C7 1.207 (4) C8—H8B 0.9600
C1—C2 1.366 (4) C8—H8C 0.9600
C1—C6 1.417 (4) C9—C10 1.501 (4)
C2—C3 1.400 (4) C9—H9A 0.9700
C2—H2 0.9300 C9—H9B 0.9700
C3—C4 1.374 (4) C10—C10i 1.522 (5)
C3—C7 1.452 (5) C10—H10A 0.9700
C4—C5 1.374 (5) C10—H10B 0.9700
C4—H4 0.9300
C1—O1—C9 117.6 (2) O3—C7—H7 117.1
C6—O2—C8 118.0 (3) C3—C7—H7 117.1
O1—C1—C2 125.7 (3) O2—C8—H8A 109.5
O1—C1—C6 114.7 (3) O2—C8—H8B 109.5
C2—C1—C6 119.5 (3) H8A—C8—H8B 109.5
C1—C2—C3 120.3 (3) O2—C8—H8C 109.5
C1—C2—H2 119.9 H8A—C8—H8C 109.5
C3—C2—H2 119.9 H8B—C8—H8C 109.5
C4—C3—C2 119.6 (3) O1—C9—C10 107.8 (2)
C4—C3—C7 119.1 (3) O1—C9—H9A 110.1
C2—C3—C7 121.3 (3) C10—C9—H9A 110.1
C5—C4—C3 120.8 (3) O1—C9—H9B 110.1
C5—C4—H4 119.6 C10—C9—H9B 110.1
C3—C4—H4 119.6 H9A—C9—H9B 108.5
C4—C5—C6 120.2 (3) C9—C10—C10i 111.9 (3)
C4—C5—H5 119.9 C9—C10—H10A 109.2
C6—C5—H5 119.9 C10i—C10—H10A 109.2
O2—C6—C5 125.1 (3) C9—C10—H10B 109.2
O2—C6—C1 115.3 (3) C10i—C10—H10B 109.2
C5—C6—C1 119.6 (3) H10A—C10—H10B 107.9
O3—C7—C3 125.9 (4)
C9—O1—C1—C2 1.2 (4) C4—C5—C6—O2 178.8 (3)
C9—O1—C1—C6 −176.8 (2) C4—C5—C6—C1 −0.6 (5)
O1—C1—C2—C3 −178.5 (3) O1—C1—C6—O2 −0.1 (4)
C6—C1—C2—C3 −0.6 (4) C2—C1—C6—O2 −178.3 (3)
C1—C2—C3—C4 −0.7 (5) O1—C1—C6—C5 179.4 (3)
C1—C2—C3—C7 177.4 (3) C2—C1—C6—C5 1.2 (4)
C2—C3—C4—C5 1.3 (5) C4—C3—C7—O3 179.6 (4)
C3—C4—C5—C6 −0.7 (5) C1—O1—C9—C10 178.0 (2)
C8—O2—C6—C5 −3.9 (5) O1—C9—C10—C10i 180.0 (3)
C8—O2—C6—C1 175.6 (3)
Symmetry code: (i) −x+1, −y+3, −z+2.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
C8—H8B···O1ii 0.96 2.57 3.512 (4) 167