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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1191.
Published online 2010 April 28. doi:  10.1107/S1600536810014741
PMCID: PMC2979257

3,9-Di-1-naphthyl-2,4,8,10-tetra­oxa­spiro­[5.5]undeca­ne

Abstract

In the title compound, C27H24O4, the 1,3-dioxane rings have chair conformations. The mol­ecule has non-crystallographic twofold rotation symmetry. The dihedral angle between the naphthalene ring systems is 17.96(4)° In the crystal structure, weak inter­molecular C—H(...)π inter­actions contribute to the crystal packing.

Related literature

For a related 3,9-diphenyl structure, see: Wang et al. (2006 [triangle]). For other oxaspiro structures, see: Mihis et al. (2008 [triangle]); Shi et al. (2009 [triangle]).

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Object name is e-66-o1191-scheme1.jpg

Experimental

Crystal data

  • C27H24O4
  • M r = 412.46
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1191-efi1.jpg
  • a = 14.9040 (15) Å
  • b = 5.7761 (6) Å
  • c = 24.238 (2) Å
  • β = 95.447 (2)°
  • V = 2077.1 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 295 K
  • 0.22 × 0.21 × 0.19 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2003 [triangle]) T min = 0.981, T max = 0.984
  • 11731 measured reflections
  • 4067 independent reflections
  • 2961 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.158
  • S = 1.03
  • 4067 reflections
  • 280 parameters
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2003 [triangle]); cell refinement: SAINT (Bruker, 2003 [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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810014741/si2258sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014741/si2258Isup2.hkl

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

Acknowledgments

The authors are grateful to Jiangsu Polytechnic University and the Natural Science Foundation of China (No.20872051) for financial support.

supplementary crystallographic information

Comment

The title compound is an important intermediate in the synthesis of pesticides. Several related structures were synthesized and reported (Wang et al.,2006; Mihis et al.,2008; Shi et al.,2009). The X-ray structural analysis confirmed the assignment of the structure of the title compound from spectroscopic data. The molecular structure is depicted in Fig. 1. The title molecule has a non-crystallographic twofold rotation symmetry. In the molecules, the naphthalene planes make a dihedral angle of 17.96 (4) °. Weak intermolecular C–H···π interactions contribute to the crystal packing (Table 1).

Experimental

Pentaerythritol (0.22 g, 1.6 mmol), α-naphthaldehyde (0.5 g, 3.2 mmol), p-toluene sulphonic acid (0.02 g, 0.12 mmol) and dimethylbenzene (10 ml) were heated for six hours. The mixture was cooled and then filtered. The organic phase was evaporated on a rotary evaporator and the resulting solid was recrystallized in ethyl acetate, yielding the title compound (0.53 g, 80%); m.p. 445-446 K.

Refinement

All H atoms were fixed geometrically and treated as riding with C—H=0.93 Å, 0.97 Å or 0.98 Å, and Uiso(H)=1.2Ueq(C-methylene, C-aromatic).

Figures

Fig. 1.
Molecular structure of the title compound with the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as small spheres of arbitrary radii.

Crystal data

C27H24O4F(000) = 872
Mr = 412.46Dx = 1.319 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.9040 (15) ÅCell parameters from 4101 reflections
b = 5.7761 (6) Åθ = 2.8–28.9°
c = 24.238 (2) ŵ = 0.09 mm1
β = 95.447 (2)°T = 295 K
V = 2077.1 (4) Å3Block, colorless
Z = 40.22 × 0.21 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer4067 independent reflections
Radiation source: fine-focus sealed tube2961 reflections with I > 2σ(I)
graphiteRint = 0.024
[var phi] and ω scansθmax = 26.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)h = −18→16
Tmin = 0.981, Tmax = 0.984k = −6→7
11731 measured reflectionsl = −29→29

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.1P)2 + 0.1334P] where P = (Fo2 + 2Fc2)/3
4067 reflections(Δ/σ)max = 0.001
280 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = −0.17 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O10.13414 (8)0.84377 (18)0.45655 (4)0.0446 (3)
O20.22638 (8)0.6064 (2)0.40974 (4)0.0515 (3)
O30.26584 (7)0.18521 (18)0.56082 (5)0.0480 (3)
O40.36401 (8)0.4833 (2)0.54471 (5)0.0547 (3)
C10.34069 (15)−0.1745 (4)0.71697 (8)0.0678 (6)
H10.2942−0.17320.74000.081*
C20.40805 (16)−0.3418 (4)0.72465 (9)0.0720 (6)
H20.4063−0.45130.75270.086*
C30.47631 (14)−0.3452 (3)0.69128 (9)0.0650 (6)
H30.5207−0.45840.69650.078*
C40.48080 (12)−0.1802 (3)0.64906 (8)0.0539 (5)
C50.55262 (13)−0.1798 (4)0.61468 (9)0.0700 (6)
H50.5969−0.29340.61930.084*
C60.55731 (14)−0.0168 (4)0.57552 (10)0.0790 (7)
H60.6062−0.01490.55430.095*
C70.48923 (13)0.1507 (4)0.56622 (9)0.0653 (5)
H70.49330.26110.53860.078*
C80.41737 (12)0.1540 (3)0.59693 (7)0.0488 (4)
C90.41222 (11)−0.0103 (3)0.64054 (7)0.0463 (4)
C100.34223 (12)−0.0132 (3)0.67623 (7)0.0556 (5)
H100.29660.09700.67170.067*
C110.34087 (11)0.3197 (3)0.58327 (7)0.0460 (4)
H110.32590.39800.61710.055*
C120.18859 (11)0.3248 (3)0.54602 (7)0.0488 (4)
H12A0.16790.39170.57930.059*
H12B0.14060.22830.52880.059*
C130.29204 (12)0.6434 (3)0.53143 (7)0.0523 (5)
H13A0.31040.75750.50540.063*
H13B0.27840.72390.56480.063*
C140.20848 (10)0.5180 (3)0.50633 (6)0.0406 (4)
C150.12684 (12)0.6778 (3)0.49917 (7)0.0495 (4)
H15A0.07290.58570.49040.059*
H15B0.12070.75760.53380.059*
C160.22281 (12)0.4224 (3)0.44935 (7)0.0506 (4)
H16A0.27870.33530.45150.061*
H16B0.17390.31790.43730.061*
C170.14617 (11)0.7325 (3)0.40554 (6)0.0413 (4)
H170.09540.62810.39560.050*
C180.14747 (11)0.9196 (3)0.36260 (6)0.0430 (4)
C190.22421 (13)0.9714 (3)0.33883 (7)0.0554 (5)
H190.27550.88130.34700.066*
C200.22692 (15)1.1598 (4)0.30208 (8)0.0674 (6)
H200.27961.19160.28580.081*
C210.15360 (16)1.2942 (4)0.29038 (7)0.0670 (6)
H210.15691.42060.26690.080*
C220.07234 (14)1.2462 (3)0.31316 (7)0.0535 (5)
C230.06793 (12)1.0532 (3)0.34917 (6)0.0442 (4)
C24−0.01615 (12)1.0029 (3)0.36927 (7)0.0543 (5)
H24−0.02070.87750.39290.065*
C25−0.09045 (14)1.1344 (4)0.35467 (8)0.0687 (6)
H25−0.14521.09510.36760.082*
C26−0.08524 (17)1.3280 (4)0.32048 (9)0.0761 (7)
H26−0.13591.41930.31140.091*
C27−0.00558 (17)1.3820 (4)0.30050 (8)0.0711 (6)
H27−0.00241.51140.27800.085*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0659 (7)0.0329 (6)0.0345 (6)0.0103 (5)0.0018 (5)0.0004 (4)
O20.0625 (8)0.0500 (7)0.0416 (6)0.0150 (6)0.0034 (5)−0.0012 (5)
O30.0504 (7)0.0305 (6)0.0603 (7)0.0003 (5)−0.0103 (5)0.0055 (5)
O40.0552 (7)0.0417 (7)0.0639 (8)−0.0075 (5)−0.0122 (6)0.0112 (6)
C10.0774 (14)0.0711 (14)0.0534 (11)−0.0021 (11)−0.0019 (9)0.0115 (10)
C20.0816 (15)0.0645 (14)0.0651 (12)−0.0064 (11)−0.0180 (11)0.0232 (10)
C30.0643 (12)0.0498 (11)0.0750 (13)−0.0001 (9)−0.0245 (10)0.0110 (9)
C40.0495 (10)0.0471 (10)0.0603 (10)−0.0024 (8)−0.0204 (8)0.0018 (8)
C50.0489 (11)0.0699 (14)0.0879 (15)0.0110 (10)−0.0104 (10)0.0089 (12)
C60.0557 (12)0.0890 (17)0.0927 (16)0.0088 (12)0.0089 (11)0.0187 (14)
C70.0582 (12)0.0679 (13)0.0684 (12)−0.0001 (10)−0.0016 (9)0.0152 (10)
C80.0509 (10)0.0427 (9)0.0494 (9)−0.0029 (8)−0.0131 (7)−0.0005 (7)
C90.0490 (9)0.0402 (9)0.0458 (9)−0.0050 (7)−0.0161 (7)−0.0032 (7)
C100.0614 (11)0.0527 (11)0.0502 (10)0.0036 (9)−0.0078 (8)0.0022 (8)
C110.0553 (10)0.0358 (9)0.0443 (8)−0.0043 (7)−0.0088 (7)−0.0008 (7)
C120.0504 (10)0.0360 (9)0.0587 (10)0.0043 (7)−0.0019 (8)0.0086 (7)
C130.0690 (12)0.0320 (9)0.0525 (10)−0.0035 (8)−0.0110 (8)0.0037 (7)
C140.0500 (9)0.0295 (8)0.0410 (8)0.0029 (7)−0.0025 (7)−0.0009 (6)
C150.0640 (11)0.0422 (9)0.0428 (9)0.0111 (8)0.0075 (8)0.0072 (7)
C160.0658 (11)0.0363 (9)0.0476 (9)0.0127 (8)−0.0055 (8)−0.0054 (7)
C170.0498 (9)0.0358 (8)0.0369 (8)0.0040 (7)−0.0028 (6)−0.0062 (6)
C180.0547 (10)0.0423 (9)0.0307 (7)−0.0015 (8)−0.0035 (6)−0.0065 (7)
C190.0613 (11)0.0614 (12)0.0429 (9)−0.0007 (9)0.0020 (8)−0.0036 (8)
C200.0767 (14)0.0766 (15)0.0497 (11)−0.0168 (12)0.0099 (10)0.0028 (10)
C210.1016 (17)0.0567 (12)0.0406 (9)−0.0183 (12)−0.0041 (10)0.0068 (8)
C220.0810 (13)0.0434 (9)0.0326 (8)0.0004 (9)−0.0125 (8)−0.0030 (7)
C230.0622 (10)0.0398 (9)0.0283 (7)0.0006 (8)−0.0074 (7)−0.0060 (6)
C240.0612 (11)0.0571 (11)0.0429 (9)0.0068 (9)−0.0034 (8)−0.0002 (8)
C250.0664 (13)0.0836 (15)0.0534 (11)0.0179 (11)−0.0090 (9)−0.0104 (10)
C260.0882 (16)0.0758 (16)0.0589 (12)0.0347 (13)−0.0216 (11)−0.0084 (11)
C270.1127 (19)0.0499 (11)0.0449 (10)0.0161 (12)−0.0234 (11)0.0012 (9)

Geometric parameters (Å, °)

O1—C171.4198 (18)C12—H12B0.9700
O1—C151.4211 (19)C13—C141.517 (2)
O2—C171.3954 (18)C13—H13A0.9700
O2—C161.437 (2)C13—H13B0.9700
O3—C121.4233 (18)C14—C161.521 (2)
O3—C111.4265 (19)C14—C151.524 (2)
O4—C111.395 (2)C15—H15A0.9700
O4—C131.429 (2)C15—H15B0.9700
C1—C101.360 (3)C16—H16A0.9700
C1—C21.393 (3)C16—H16B0.9700
C1—H10.9300C17—C181.502 (2)
C2—C31.359 (3)C17—H170.9800
C2—H20.9300C18—C191.362 (2)
C3—C41.404 (3)C18—C231.426 (2)
C3—H30.9300C19—C201.409 (3)
C4—C51.418 (3)C19—H190.9300
C4—C91.418 (2)C20—C211.349 (3)
C5—C61.343 (3)C20—H200.9300
C5—H50.9300C21—C221.406 (3)
C6—C71.405 (3)C21—H210.9300
C6—H60.9300C22—C271.411 (3)
C7—C81.361 (3)C22—C231.421 (2)
C7—H70.9300C23—C241.417 (2)
C8—C91.428 (2)C24—C251.362 (3)
C8—C111.502 (2)C24—H240.9300
C9—C101.417 (3)C25—C261.398 (3)
C10—H100.9300C25—H250.9300
C11—H110.9800C26—C271.360 (3)
C12—C141.521 (2)C26—H260.9300
C12—H12A0.9700C27—H270.9300
C17—O1—C15110.63 (12)C13—C14—C16110.89 (14)
C17—O2—C16110.43 (13)C12—C14—C16111.14 (13)
C12—O3—C11111.94 (13)C13—C14—C15111.88 (14)
C11—O4—C13111.16 (14)C12—C14—C15108.36 (13)
C10—C1—C2120.7 (2)C16—C14—C15107.20 (12)
C10—C1—H1119.6O1—C15—C14112.09 (13)
C2—C1—H1119.6O1—C15—H15A109.2
C3—C2—C1120.09 (19)C14—C15—H15A109.2
C3—C2—H2120.0O1—C15—H15B109.2
C1—C2—H2120.0C14—C15—H15B109.2
C2—C3—C4120.93 (19)H15A—C15—H15B107.9
C2—C3—H3119.5O2—C16—C14110.83 (13)
C4—C3—H3119.5O2—C16—H16A109.5
C3—C4—C5121.35 (18)C14—C16—H16A109.5
C3—C4—C9119.49 (19)O2—C16—H16B109.5
C5—C4—C9119.16 (17)C14—C16—H16B109.5
C6—C5—C4120.62 (19)H16A—C16—H16B108.1
C6—C5—H5119.7O2—C17—O1110.54 (11)
C4—C5—H5119.7O2—C17—C18111.03 (13)
C5—C6—C7120.7 (2)O1—C17—C18106.80 (12)
C5—C6—H6119.6O2—C17—H17109.5
C7—C6—H6119.6O1—C17—H17109.5
C8—C7—C6121.05 (19)C18—C17—H17109.5
C8—C7—H7119.5C19—C18—C23119.86 (16)
C6—C7—H7119.5C19—C18—C17121.19 (15)
C7—C8—C9119.73 (16)C23—C18—C17118.84 (14)
C7—C8—C11120.58 (16)C18—C19—C20120.83 (18)
C9—C8—C11119.59 (16)C18—C19—H19119.6
C10—C9—C4117.72 (16)C20—C19—H19119.6
C10—C9—C8123.65 (16)C21—C20—C19120.41 (19)
C4—C9—C8118.63 (17)C21—C20—H20119.8
C1—C10—C9121.03 (18)C19—C20—H20119.8
C1—C10—H10119.5C20—C21—C22121.00 (18)
C9—C10—H10119.5C20—C21—H21119.5
O4—C11—O3110.36 (12)C22—C21—H21119.5
O4—C11—C8110.41 (14)C21—C22—C27121.80 (19)
O3—C11—C8106.74 (13)C21—C22—C23119.21 (18)
O4—C11—H11109.8C27—C22—C23118.98 (19)
O3—C11—H11109.8C24—C23—C22117.77 (16)
C8—C11—H11109.8C24—C23—C18123.62 (15)
O3—C12—C14111.92 (13)C22—C23—C18118.60 (16)
O3—C12—H12A109.2C25—C24—C23121.35 (19)
C14—C12—H12A109.2C25—C24—H24119.3
O3—C12—H12B109.2C23—C24—H24119.3
C14—C12—H12B109.2C24—C25—C26120.7 (2)
H12A—C12—H12B107.9C24—C25—H25119.7
O4—C13—C14110.57 (13)C26—C25—H25119.7
O4—C13—H13A109.5C27—C26—C25119.58 (19)
C14—C13—H13A109.5C27—C26—H26120.2
O4—C13—H13B109.5C25—C26—H26120.2
C14—C13—H13B109.5C26—C27—C22121.57 (19)
H13A—C13—H13B108.1C26—C27—H27119.2
C13—C14—C12107.37 (13)C22—C27—H27119.2
C10—C1—C2—C30.0 (3)C17—O1—C15—C1456.96 (17)
C1—C2—C3—C40.6 (3)C13—C14—C15—O170.48 (17)
C2—C3—C4—C5178.8 (2)C12—C14—C15—O1−171.34 (13)
C2—C3—C4—C9−1.1 (3)C16—C14—C15—O1−51.30 (18)
C3—C4—C5—C6−178.1 (2)C17—O2—C16—C14−59.81 (17)
C9—C4—C5—C61.9 (3)C13—C14—C16—O2−70.38 (17)
C4—C5—C6—C7−2.7 (4)C12—C14—C16—O2170.25 (13)
C5—C6—C7—C80.7 (3)C15—C14—C16—O252.01 (18)
C6—C7—C8—C92.1 (3)C16—O2—C17—O163.95 (16)
C6—C7—C8—C11−174.38 (18)C16—O2—C17—C18−177.72 (12)
C3—C4—C9—C101.0 (2)C15—O1—C17—O2−62.50 (17)
C5—C4—C9—C10−178.95 (17)C15—O1—C17—C18176.62 (13)
C3—C4—C9—C8−179.18 (15)O2—C17—C18—C19−9.1 (2)
C5—C4—C9—C80.9 (2)O1—C17—C18—C19111.48 (16)
C7—C8—C9—C10177.00 (17)O2—C17—C18—C23174.59 (12)
C11—C8—C9—C10−6.5 (2)O1—C17—C18—C23−64.84 (17)
C7—C8—C9—C4−2.8 (2)C23—C18—C19—C201.7 (2)
C11—C8—C9—C4173.70 (14)C17—C18—C19—C20−174.60 (15)
C2—C1—C10—C9−0.1 (3)C18—C19—C20—C210.9 (3)
C4—C9—C10—C1−0.4 (2)C19—C20—C21—C22−1.8 (3)
C8—C9—C10—C1179.76 (17)C20—C21—C22—C27−178.67 (17)
C13—O4—C11—O362.51 (17)C20—C21—C22—C230.2 (3)
C13—O4—C11—C8−179.72 (12)C21—C22—C23—C24−176.99 (15)
C12—O3—C11—O4−59.83 (17)C27—C22—C23—C241.9 (2)
C12—O3—C11—C8−179.84 (13)C21—C22—C23—C182.3 (2)
C7—C8—C11—O4−11.1 (2)C27—C22—C23—C18−178.80 (14)
C9—C8—C11—O4172.40 (13)C19—C18—C23—C24176.01 (15)
C7—C8—C11—O3108.84 (19)C17—C18—C23—C24−7.6 (2)
C9—C8—C11—O3−67.62 (18)C19—C18—C23—C22−3.2 (2)
C11—O3—C12—C1455.23 (17)C17—C18—C23—C22173.15 (13)
C11—O4—C13—C14−60.70 (17)C22—C23—C24—C250.0 (2)
O4—C13—C14—C1253.24 (18)C18—C23—C24—C25−179.21 (16)
O4—C13—C14—C16−68.36 (17)C23—C24—C25—C26−1.8 (3)
O4—C13—C14—C15172.01 (13)C24—C25—C26—C271.6 (3)
O3—C12—C14—C13−51.13 (18)C25—C26—C27—C220.4 (3)
O3—C12—C14—C1670.32 (17)C21—C22—C27—C26176.72 (19)
O3—C12—C14—C15−172.14 (13)C23—C22—C27—C26−2.2 (3)

Hydrogen-bond geometry (Å, °)

Cg5 and Cg6 are the centroids of the C18–C23 and C22–C27 naphthyl rings, respectively.
D—H···AD—HH···AD···AD—H···A
C16—H16B···Cg5i0.972.953.5827 (19)124
C27—H27···Cg6ii0.932.943.754 (2)147

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2258).

References

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