organic papers
Acta Cryst.(2005). E61, o4069–o4070 doi:10.1107/S1600536805036299 Han and Zhen C
21H24O6
o4069
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
3-Ethoxy-4-[3-(2-ethoxy-4-formylphenoxy)-propoxy]benzaldehyde
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: [email protected]
Key indicators
Single-crystal X-ray study T= 293 K
Mean(C–C) = 0.004 A˚ Rfactor = 0.037 wRfactor = 0.100 Data-to-parameter ratio = 9.9
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 title compound, C21H24O6, comprises two ethylvanillin subunits covalently linked to a bridging propyl chain; the molecule has a twofold rotation axis passing through the central C atom of the propyl chain. The two aromatic rings are approximately perpendicular to each other.
Comment
Since their first synthesis by Pedersen (1967), crown ethers have been shown to be of great importance in supramolecular chemistry as they can form supramolecular structures which can be used as models for studying weak interactions. Consequently, numerous derivatives of crown ethers were subsequently developed for many applications (Kim et al., 1999). As part of our interest in the molecular and ionic recognition properties of crown ethers, we investigated the title compound, (I), used as a precursor in the preparation of crown ethers.
The central C11 atom of (I) (Fig. 1 and Table 1) lies on a twofold rotation axis. Atoms C1–C7 and O1–O3 of the ethylvanillin group are coplanar, with an r.m.s. deviation of 0.033 A˚ and this group forms a dihedral angle of 84.70 (3) with its symmetry-related counterpart, indicating a perpendi-cular relationship [symmetry code: (i) 1x, 1 y, z]. The dihedral angle between the plane through the C10—C11— C10iatoms and that through the aromatic ring is 55.96 (6), a result in contrast to the value of 3.0 (3) found in the closely related structure of 4-[6-(4-formyl-2-methoxyphenoxy)hex-yloxy]-3-methoxybenzaldehyde (Diao et al., 2005). All bond lengths and angles for (I) are within normal ranges (Table 1).
Experimental
To a solution of 3-ethoxy-4-hydroxybenzaldehyde (16.6 g, 100 mmol) and potassium carbonate (13.8 g, 100 mmol) in acetonitrile (500 ml), 1,3-dibromohexane (10.1 g, 50 mmol) was added dropwise over a period of 30 min. The mixture was refluxed for 24 h under nitrogen. The solvent was removed and the resultant mixture poured into ice–
water (500 ml). The white precipitate was isolated and recrystallized from ethanol solution to give the pure compound in 51% yield. Colorless single crystals were obtained by slow evaporation of an acetonitrile solution of (I).
Crystal data
C21H24O6 Mr= 372.40
Orthorhombic,P21212
a= 8.7778 (16) A˚
b= 24.029 (4) A˚
c= 4.7259 (9) A˚
V= 996.8 (3) A˚3 Z= 2
Dx= 1.241 Mg m 3
MoKradiation Cell parameters from 2281
reflections
= 2.9–25.8 = 0.09 mm1 T= 293 (2) K Block, colorless 0.240.200.14 mm
Data collection
Bruker SMART CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.968,Tmax= 0.987 5593 measured reflections
1227 independent reflections 949 reflections withI> 2(I)
Rint= 0.027 max= 26.4 h=10!9
k=23!30
l=5!5
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.037 wR(F2) = 0.100 S= 1.09 1227 reflections 124 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0472P)2
+ 0.1241P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.16 e A˚
3 min=0.13 e A˚
3
Table 1
Selected geometric parameters (A˚ ,).
O1—C1 1.209 (4)
O2—C6 1.358 (3)
O2—C8 1.435 (3)
O3—C5 1.357 (3)
O3—C10 1.432 (3)
C6—O2—C8 117.4 (2)
C5—O3—C10 118.43 (18)
O1—C1—C2 125.0 (3)
O3—C5—C4 125.5 (2)
O3—C5—C6 115.16 (19)
O2—C6—C5 114.89 (19)
O2—C6—C7 125.2 (2)
O2—C8—C9 108.4 (3)
O3—C10—C11 107.59 (17)
C10i—C11—C10 114.5 (3)
Symmetry code: (i)xþ1;yþ1;z.
H atoms were included in the riding-model approximation, with C—H = 0.93 (aromatic C), 0.97 (methylene C) and 0.96 A˚ (methyl H), and with Uiso(H) = 1.2Ueq(aromatic and methylene C) and
1.5Ueq(methyl C). In the absence of significant anomalous dispersion
effects, Friedel pairs were averaged.
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.
[image:2.610.311.566.70.275.2]Sheldrick, G. M. (1997b).SHELXTL97. Version 5.10 for Windows NT. Bruker AXS Inc., Madison, Wisconsin, USA.
Figure 1
supporting information
sup-1 Acta Cryst. (2005). E61, o4069–o4070
supporting information
Acta Cryst. (2005). E61, o4069–o4070 [https://doi.org/10.1107/S1600536805036299]
3-Ethoxy-4-[3-(2-ethoxy-4-formylphenoxy)propoxy]benzaldehyde
Jian-Rong Han and Xiao-Li Zhen
3-Ethoxy-4-[3-(2-ethoxy-4-formylphenoxy)propoxy]benzaldehyde
Crystal data C21H24O6
Mr = 372.40
Orthorhombic, P21212
Hall symbol: P 2 2ab a = 8.7778 (16) Å b = 24.029 (4) Å c = 4.7259 (9) Å V = 996.8 (3) Å3
Z = 2
F(000) = 396 Dx = 1.241 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2281 reflections θ = 2.9–25.8°
µ = 0.09 mm−1
T = 293 K Block, colorless 0.24 × 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 = 0.968, Tmax = 0.987
5593 measured reflections 1227 independent reflections 949 reflections with I > 2σ(I) Rint = 0.027
θmax = 26.4°, θmin = 1.7°
h = −10→9 k = −23→30 l = −5→5
Refinement Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.037
wR(F2) = 0.100
S = 1.09 1227 reflections 124 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) + (0.0472P)2 + 0.1241P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.16 e Å−3
Δρmin = −0.13 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 Occ. (<1)
O1 0.4802 (3) 0.22311 (9) −0.4685 (6) 0.1031 (8) O2 0.24665 (19) 0.39332 (7) 0.0478 (4) 0.0640 (5) O3 0.45807 (17) 0.42912 (6) 0.3722 (3) 0.0526 (4) C1 0.5764 (4) 0.24645 (12) −0.3294 (7) 0.0803 (9)
H1 0.6753 0.2327 −0.3389 0.096*
C2 0.5491 (3) 0.29480 (10) −0.1469 (6) 0.0583 (7) C3 0.6640 (3) 0.31501 (11) 0.0218 (6) 0.0630 (7)
H3 0.7595 0.2983 0.0167 0.076*
C4 0.6389 (3) 0.36003 (10) 0.1998 (6) 0.0568 (6)
H4 0.7174 0.3734 0.3132 0.068*
C5 0.4968 (3) 0.38499 (9) 0.2082 (5) 0.0459 (5) C6 0.3800 (3) 0.36485 (9) 0.0316 (5) 0.0471 (5) C7 0.4067 (3) 0.31984 (9) −0.1407 (5) 0.0546 (6)
H7 0.3287 0.3061 −0.2540 0.065*
C8 0.1307 (3) 0.37985 (12) −0.1549 (8) 0.0830 (10)
H8A 0.0919 0.3427 −0.1198 0.100*
H8B 0.1726 0.3809 −0.3447 0.100*
C9 0.0092 (4) 0.4200 (2) −0.1287 (13) 0.146 (2)
H9A −0.0331 0.4181 0.0584 0.219*
H9B −0.0687 0.4119 −0.2652 0.219*
H9C 0.0487 0.4567 −0.1618 0.219*
C10 0.5742 (3) 0.45496 (10) 0.5394 (5) 0.0542 (6)
H10A 0.6522 0.4707 0.4179 0.065*
H10B 0.6215 0.4278 0.6630 0.065*
C11 0.5 0.5 0.7112 (7) 0.0570 (9)
H11A 0.4236 0.4832 0.8325 0.068* 0.50
H11B 0.5764 0.5168 0.8325 0.068* 0.50
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3 Acta Cryst. (2005). E61, o4069–o4070
C7 0.0726 (16) 0.0452 (11) 0.0458 (13) −0.0058 (12) 0.0028 (13) 0.0001 (11) C8 0.0694 (17) 0.0777 (18) 0.102 (3) −0.0085 (15) −0.027 (2) −0.0103 (19) C9 0.086 (2) 0.141 (3) 0.211 (5) 0.023 (2) −0.048 (4) −0.035 (4) C10 0.0627 (14) 0.0549 (13) 0.0451 (12) −0.0162 (12) −0.0098 (12) 0.0045 (11) C11 0.081 (2) 0.0526 (17) 0.0368 (17) −0.0205 (18) 0 0
Geometric parameters (Å, º)
O1—C1 1.209 (4) C6—C7 1.374 (3)
O2—C6 1.358 (3) C7—H7 0.9300
O2—C8 1.435 (3) C8—C9 1.443 (5)
O3—C5 1.357 (3) C8—H8A 0.9700
O3—C10 1.432 (3) C8—H8B 0.9700
C1—C2 1.467 (4) C9—H9A 0.9600
C1—H1 0.9300 C9—H9B 0.9600
C2—C3 1.374 (4) C9—H9C 0.9600
C2—C7 1.388 (4) C10—C11 1.502 (3)
C3—C4 1.388 (4) C10—H10A 0.9700
C3—H3 0.9300 C10—H10B 0.9700
C4—C5 1.385 (3) C11—C10i 1.502 (3)
C4—H4 0.9300 C11—H11A 0.9700
C5—C6 1.408 (3) C11—H11B 0.9700
C6—O2—C8 117.4 (2) O2—C8—H8A 110.0
C5—O3—C10 118.43 (18) C9—C8—H8A 110.0
O1—C1—C2 125.0 (3) O2—C8—H8B 110.0
O1—C1—H1 117.5 C9—C8—H8B 110.0
C2—C1—H1 117.5 H8A—C8—H8B 108.4
C3—C2—C7 119.7 (2) C8—C9—H9A 109.5
C3—C2—C1 120.1 (3) C8—C9—H9B 109.5
C7—C2—C1 120.2 (3) H9A—C9—H9B 109.5
C2—C3—C4 120.7 (2) C8—C9—H9C 109.5
C2—C3—H3 119.6 H9A—C9—H9C 109.5
C4—C3—H3 119.6 H9B—C9—H9C 109.5
C5—C4—C3 119.8 (2) O3—C10—C11 107.59 (17)
C5—C4—H4 120.1 O3—C10—H10A 110.2
C3—C4—H4 120.1 C11—C10—H10A 110.2
O3—C5—C4 125.5 (2) O3—C10—H10B 110.2
O3—C5—C6 115.16 (19) C11—C10—H10B 110.2
C4—C5—C6 119.3 (2) H10A—C10—H10B 108.5
O2—C6—C5 114.89 (19) C10i—C11—C10 114.5 (3)
O2—C6—C7 125.2 (2) C10i—C11—H11A 108.6
C7—C6—C5 119.9 (2) C10—C11—H11A 108.6
C6—C7—C2 120.5 (2) C10i—C11—H11B 108.6
C6—C7—H7 119.8 C10—C11—H11B 108.6
C2—C7—H7 119.8 H11A—C11—H11B 107.6
O1—C1—C2—C3 174.1 (3) O3—C5—C6—O2 1.2 (3) O1—C1—C2—C7 −5.0 (5) C4—C5—C6—O2 −177.7 (2)
C7—C2—C3—C4 0.4 (4) O3—C5—C6—C7 −179.2 (2)
C1—C2—C3—C4 −178.7 (2) C4—C5—C6—C7 1.8 (3)
C2—C3—C4—C5 0.0 (4) O2—C6—C7—C2 178.0 (2)
C10—O3—C5—C4 4.2 (3) C5—C6—C7—C2 −1.5 (3) C10—O3—C5—C6 −174.71 (19) C3—C2—C7—C6 0.4 (4) C3—C4—C5—O3 −179.9 (2) C1—C2—C7—C6 179.4 (2) C3—C4—C5—C6 −1.1 (3) C6—O2—C8—C9 −171.5 (3) C8—O2—C6—C7 −8.1 (4) C5—O3—C10—C11 −176.82 (18) C8—O2—C6—C5 171.4 (2) O3—C10—C11—C10i −61.02 (13)
