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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1556.
Published online 2008 July 19. doi:  10.1107/S1600536808022186
PMCID: PMC2962178

4′-Formyl­benzo-15-crown-5

Abstract

In the title compound (systematic name: 17-formyl-2,5,8,11,14-penta­oxabicyclo­[13.4.0]nona­deca-15,17,19-triene), C15H20O6, the 15-crown-5 ring adopts a twisted conformation. The formyl group is coplanar with the benzene ring. The crystal packing is stabilized by C—H(...)O inter­actions involving the C=O group and ether O atoms as acceptors and methyl­ene CH groups as donors.

Related literature

The unsubstituted benzocrown ether was characterized by Pedersen (1967 [triangle]) and its structure was described by Hanson (1978 [triangle]), while Rogers and co-workers reported 4′-amino- and 4′-nitro-substituted compounds (Rogers, Huggins et al., 1992 [triangle]; Rogers, Henry & Rollins, 1992 [triangle]). For the synthesis of the title compound, see: Hyde et al. (1978 [triangle]).

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Object name is e-64-o1556-scheme1.jpg

Experimental

Crystal data

  • C15H20O6
  • M r = 296.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1556-efi1.jpg
  • a = 18.0091 (8) Å
  • b = 9.6678 (4) Å
  • c = 8.1028 (3) Å
  • β = 91.262 (2)°
  • V = 1410.42 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 90 (2) K
  • 0.60 × 0.39 × 0.05 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.857, T max = 0.995
  • 18190 measured reflections
  • 4523 independent reflections
  • 3716 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.116
  • S = 1.00
  • 4523 reflections
  • 190 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022186/gk2144sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022186/gk2144Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

Financial support from the German Federal Ministry of Economics and Technology (BMWi) under grant No. 16IN0218 ‘ChemoChips’ is gratefully acknowledged. We thank Dr Tobias Gruber for fruitful discussions.

supplementary crystallographic information

Comment

The title compound is a derivative of benzo-15-crown-5 (Pedersen, 1967). It was prepared as part of our studies concerning fluorogenic receptor molecules with possible analytical applications. The O-C-C-O torsion angles within the polyether ring are (±)gauche [69.34° (10), -71.10°(8), -65.61°(11)) and anti (168.42°(9)]) resulting in a twisted crown ether conformation. In the title molecule, the dihedral angle between the aromatic ring plane and the mean plane of ether oxygen atoms is 20.67 (5)°. Worth to note, the torsion angle C3—C4—C7—O1 is 179.75 (10)°, indicating only a very small twist of the formyl group relative to the aromatic ring. Thus, in agreement with a previous report (Rogers, Huggins et al., 1992; Rogers, Henry & Rollins, 1992), the substituent on the benzene ring has negligible influence on the conformation of the benzo-15-crown-5 (Hanson, 1978). Owing to the absence of strong hydrogen bond donors, the crystal packing is stabilized by weak C—H···O hydrogen bonds, involving the O atoms of the crown ether and C==O group as acceptors, and the methylene C-H groups as donors (Table 1). In addition, π—π interaction has also been detected, resulting in a stacking of the molecules along the crystallographic c axis with a distance of 4.211 (2) Å between the centroids of two neighboring aromatic rings (Fig.2).

Experimental

The title compound, 4'-formylbenzo-15-crown-5, was synthesized from benzo-15-crown-5 (Pedersen, 1967) which was reacted with N-methylformanilide and phoshoryl chloride (Hyde et al., 1978). Colourless needles of the title compound suitable for X-ray diffraction analysis were obtained by slow cooling and evaporation of a solution of n-heptane. Fast cooling of the solution resulted in the formation of an orthorhombic polymorph of the title compound.

Refinement

The H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 -0.99 Å, and Uiso=1.2–1.5 Ueq (C).

Figures

Fig. 1.
Molecular structure of the title compound with ellipsoids drawn at the 50% probability level.
Fig. 2.
Packing diagram, viewed down the c axis.

Crystal data

C15H20O6F000 = 632
Mr = 296.31Dx = 1.395 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9008 reflections
a = 18.0091 (8) Åθ = 2.4–33.3º
b = 9.6678 (4) ŵ = 0.11 mm1
c = 8.1028 (3) ÅT = 90 (2) K
β = 91.262 (2)ºPlate, colourless
V = 1410.42 (10) Å30.60 × 0.39 × 0.05 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer4523 independent reflections
Radiation source: fine-focus sealed tube3716 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 90(2) Kθmax = 31.1º
[var phi] and ω scansθmin = 3.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)h = −26→23
Tmin = 0.857, Tmax = 0.995k = −14→12
18190 measured reflectionsl = −11→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.116  w = 1/[σ2(Fo2) + (0.0681P)2 + 0.3911P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
4523 reflectionsΔρmax = 0.28 e Å3
190 parametersΔρmin = −0.22 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
O1−0.03932 (4)0.76211 (8)0.74777 (10)0.02453 (17)
O20.18803 (4)0.54926 (7)0.45384 (9)0.01606 (14)
O30.25972 (4)0.29979 (8)0.55829 (10)0.02217 (17)
O40.42078 (4)0.40116 (8)0.32578 (9)0.01872 (15)
O50.41719 (4)0.72035 (7)0.34545 (8)0.01730 (15)
O60.26420 (4)0.75557 (7)0.36194 (9)0.01609 (14)
C10.15926 (5)0.67447 (9)0.49388 (11)0.01361 (17)
C20.09428 (5)0.69566 (10)0.57629 (11)0.01540 (17)
H20.06500.61900.60840.018*
C30.07132 (5)0.83094 (10)0.61289 (11)0.01618 (18)
C40.11385 (6)0.94299 (10)0.56708 (12)0.01868 (19)
H40.09841.03400.59400.022*
C50.17961 (6)0.92303 (10)0.48118 (12)0.01756 (18)
H50.20851.00020.44870.021*
C60.20225 (5)0.78964 (9)0.44389 (11)0.01396 (17)
C70.00239 (5)0.85268 (11)0.70205 (12)0.02018 (19)
H7−0.01090.94550.72620.024*
C80.14823 (5)0.43015 (9)0.50768 (13)0.01689 (18)
H8A0.09840.42690.45390.020*
H8B0.14220.43290.62880.020*
C90.19286 (5)0.30593 (10)0.46010 (14)0.0203 (2)
H9A0.16330.22090.47690.024*
H9B0.20520.31160.34180.024*
C100.32608 (5)0.28738 (10)0.46689 (14)0.0204 (2)
H10A0.31930.21400.38270.025*
H10B0.36720.25890.54250.025*
C110.34702 (5)0.42146 (10)0.38202 (12)0.01686 (18)
H11A0.31260.44080.28790.020*
H11B0.34530.49990.46040.020*
C120.44456 (5)0.49820 (11)0.20613 (12)0.01883 (19)
H12A0.40240.51850.12950.023*
H12B0.48440.45540.14100.023*
C130.47328 (5)0.63335 (11)0.27812 (12)0.01947 (19)
H13A0.51060.61220.36620.023*
H13B0.49880.68510.19050.023*
C140.37553 (5)0.79418 (10)0.22314 (11)0.01733 (18)
H14A0.35700.72970.13670.021*
H14B0.40740.86420.17050.021*
C150.31127 (5)0.86389 (10)0.30465 (11)0.01632 (18)
H15A0.32910.92170.39820.020*
H15B0.28400.92360.22470.020*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0197 (3)0.0272 (4)0.0269 (4)−0.0004 (3)0.0049 (3)−0.0043 (3)
O20.0180 (3)0.0094 (3)0.0211 (3)−0.0007 (2)0.0051 (2)0.0003 (2)
O30.0173 (3)0.0243 (4)0.0250 (4)0.0025 (3)0.0044 (3)0.0089 (3)
O40.0157 (3)0.0198 (3)0.0208 (3)0.0011 (2)0.0037 (2)0.0046 (3)
O50.0187 (3)0.0205 (3)0.0127 (3)−0.0001 (3)0.0001 (2)0.0022 (2)
O60.0177 (3)0.0122 (3)0.0186 (3)−0.0023 (2)0.0052 (2)0.0007 (2)
C10.0164 (4)0.0108 (4)0.0137 (4)0.0004 (3)−0.0004 (3)0.0002 (3)
C20.0164 (4)0.0140 (4)0.0158 (4)−0.0003 (3)0.0005 (3)0.0001 (3)
C30.0175 (4)0.0163 (4)0.0148 (4)0.0023 (3)−0.0001 (3)−0.0014 (3)
C40.0233 (4)0.0129 (4)0.0199 (4)0.0028 (3)0.0012 (3)−0.0017 (3)
C50.0222 (4)0.0119 (4)0.0186 (4)−0.0003 (3)0.0011 (3)0.0007 (3)
C60.0159 (4)0.0133 (4)0.0127 (4)−0.0004 (3)0.0002 (3)0.0006 (3)
C70.0195 (4)0.0209 (5)0.0201 (4)0.0039 (3)0.0009 (3)−0.0053 (4)
C80.0161 (4)0.0112 (4)0.0235 (5)−0.0019 (3)0.0035 (3)0.0015 (3)
C90.0171 (4)0.0124 (4)0.0314 (5)−0.0006 (3)0.0021 (4)−0.0001 (4)
C100.0169 (4)0.0171 (4)0.0274 (5)0.0023 (3)0.0044 (3)0.0054 (4)
C110.0162 (4)0.0154 (4)0.0191 (4)−0.0003 (3)0.0033 (3)−0.0001 (3)
C120.0193 (4)0.0218 (5)0.0156 (4)0.0005 (3)0.0043 (3)0.0017 (3)
C130.0156 (4)0.0230 (5)0.0199 (4)−0.0019 (3)0.0023 (3)0.0025 (4)
C140.0185 (4)0.0208 (4)0.0127 (4)−0.0019 (3)0.0009 (3)0.0043 (3)
C150.0194 (4)0.0141 (4)0.0156 (4)−0.0040 (3)0.0008 (3)0.0027 (3)

Geometric parameters (Å, °)

O1—C71.2168 (13)C7—H70.9500
O2—C11.3589 (11)C8—C91.5001 (13)
O2—C81.4296 (11)C8—H8A0.9900
O3—C101.4249 (12)C8—H8B0.9900
O3—C91.4297 (13)C9—H9A0.9900
O4—C121.4219 (12)C9—H9B0.9900
O4—C111.4275 (11)C10—C111.5189 (13)
O5—C141.4219 (12)C10—H10A0.9900
O5—C131.4318 (12)C10—H10B0.9900
O6—C61.3516 (11)C11—H11A0.9900
O6—C151.4311 (11)C11—H11B0.9900
C1—C21.3755 (12)C12—C131.5171 (15)
C1—C61.4202 (12)C12—H12A0.9900
C2—C31.4052 (13)C12—H12B0.9900
C2—H20.9500C13—H13A0.9900
C3—C41.3822 (13)C13—H13B0.9900
C3—C71.4651 (13)C14—C151.5044 (13)
C4—C51.4003 (13)C14—H14A0.9900
C4—H40.9500C14—H14B0.9900
C5—C61.3877 (13)C15—H15A0.9900
C5—H50.9500C15—H15B0.9900
C1—O2—C8116.64 (7)H9A—C9—H9B108.2
C10—O3—C9114.84 (8)O3—C10—C11112.51 (8)
C12—O4—C11115.04 (7)O3—C10—H10A109.1
C14—O5—C13113.27 (7)C11—C10—H10A109.1
C6—O6—C15118.83 (7)O3—C10—H10B109.1
O2—C1—C2125.56 (8)C11—C10—H10B109.1
O2—C1—C6114.66 (8)H10A—C10—H10B107.8
C2—C1—C6119.78 (8)O4—C11—C10105.62 (7)
C1—C2—C3119.90 (9)O4—C11—H11A110.6
C1—C2—H2120.0C10—C11—H11A110.6
C3—C2—H2120.0O4—C11—H11B110.6
C4—C3—C2120.36 (9)C10—C11—H11B110.6
C4—C3—C7120.03 (9)H11A—C11—H11B108.7
C2—C3—C7119.61 (9)O4—C12—C13114.29 (8)
C3—C4—C5120.35 (9)O4—C12—H12A108.7
C3—C4—H4119.8C13—C12—H12A108.7
C5—C4—H4119.8O4—C12—H12B108.7
C6—C5—C4119.47 (9)C13—C12—H12B108.7
C6—C5—H5120.3H12A—C12—H12B107.6
C4—C5—H5120.3O5—C13—C12114.52 (8)
O6—C6—C5125.67 (8)O5—C13—H13A108.6
O6—C6—C1114.21 (8)C12—C13—H13A108.6
C5—C6—C1120.12 (8)O5—C13—H13B108.6
O1—C7—C3125.61 (10)C12—C13—H13B108.6
O1—C7—H7117.2H13A—C13—H13B107.6
C3—C7—H7117.2O5—C14—C15108.54 (7)
O2—C8—C9106.94 (7)O5—C14—H14A110.0
O2—C8—H8A110.3C15—C14—H14A110.0
C9—C8—H8A110.3O5—C14—H14B110.0
O2—C8—H8B110.3C15—C14—H14B110.0
C9—C8—H8B110.3H14A—C14—H14B108.4
H8A—C8—H8B108.6O6—C15—C14106.35 (7)
O3—C9—C8109.85 (8)O6—C15—H15A110.5
O3—C9—H9A109.7C14—C15—H15A110.5
C8—C9—H9A109.7O6—C15—H15B110.5
O3—C9—H9B109.7C14—C15—H15B110.5
C8—C9—H9B109.7H15A—C15—H15B108.7
C8—O2—C1—C2−2.33 (13)C2—C1—C6—C51.40 (14)
C8—O2—C1—C6177.50 (8)C4—C3—C7—O1179.75 (10)
O2—C1—C2—C3178.83 (9)C2—C3—C7—O1−1.06 (16)
C6—C1—C2—C3−0.99 (14)C1—O2—C8—C9−176.14 (8)
C1—C2—C3—C4−0.25 (14)C10—O3—C9—C8−127.42 (9)
C1—C2—C3—C7−179.43 (9)O2—C8—C9—O369.34 (10)
C2—C3—C4—C51.12 (15)C9—O3—C10—C1173.81 (11)
C7—C3—C4—C5−179.71 (9)C12—O4—C11—C10164.16 (8)
C3—C4—C5—C6−0.71 (15)O3—C10—C11—O4168.42 (8)
C15—O6—C6—C5−1.01 (14)C11—O4—C12—C1382.80 (10)
C15—O6—C6—C1179.48 (8)C14—O5—C13—C12−78.28 (10)
C4—C5—C6—O6179.97 (9)O4—C12—C13—O5−71.10 (11)
C4—C5—C6—C1−0.54 (14)C13—O5—C14—C15171.27 (8)
O2—C1—C6—O61.10 (12)C6—O6—C15—C14178.69 (8)
C2—C1—C6—O6−179.06 (8)O5—C14—C15—O6−65.61 (9)
O2—C1—C6—C5−178.45 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C13—H13B···O4i0.992.553.3351 (10)137
C14—H14A···O5ii0.992.663.1700 (12)112
C8—H8A···O1iii0.992.663.3775 (13)130

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2144).

References

  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Hanson, I. R. (1978). Acta Cryst. B34, 1026–1028.
  • Hyde, E. M., Shaw, B. L. & Shepherd, I. (1978). J. Chem. Soc. Dalton Trans. pp. 1696–1705.
  • Pedersen, C. J. (1967). J. Am. Chem. Soc 89, 7017–7036.
  • Rogers, R. D., Henry, R. F. & Rollins, A. N. (1992). J. Inclusion Phenom. Macrocycl. Chem.13, 219–232.
  • Rogers, R. D., Huggins, S. E., Henry, R. F. & Bond, A. H. (1992). Supramol. Chem.1, 59–63.
  • Sheldrick, G. M. (2004). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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