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Acta Cryst. (2007). E63, o3933    [ doi:10.1107/S1600536807042298 ]

Norbornane-2,7-diyl 1',2'-phenylene orthocarbonate

R. Betz and P. Klüfers

Abstract top

In the title compound, C14H14O4, which was synthesized in order to compare its NMR spectroscopic data with those of similar silicon compounds, the incorporation of chelating hydroxyl groups into the parent rigid bicyclic framework ensures that the resulting six-membered chelate ring has a boat conformation.

Comment top

The title compound, C14H14O4, was prepared for the purpose of collecting NMR data on orthocarbonates and for comparison with similar silicon compounds. The incorporation of the chelating hydroxyl groups into the rigid bicyclic framework ensures the six-membered chelate ring to be present in a boat conformation. The markedly large range of the C—O distances at the spiro center is in agreement with a DFT calculation on a single molecule, i. e., it is not indicative of special packing forces in the crystalline state.

The molecular structure (Fig. 1) shows a norbornane-2,7-dioxy and a a benzene-1,2-dioxy fragment attached to a carbon atom.

The molecular packing is shown in Figure 2.

Related literature top

For synthesis, see Mues & Buysch (1990).

Experimental top

The title compound was prepared according to standard procedures (Mues & Buysch, 1990) upon reaction of 2,2-dichlorobenzo[1.3]dioxole with 2,7-norbornanediol in the presence of pyridine in dichloromethane. Crystals suitable for X-ray analysis were directly obtained from the recrystallized reaction product.

Refinement top

All H atoms were located in a difference map and refined as riding on their parent atoms. One common isotropic displacement parameter for all H atoms was refined to Uiso(H) = 0.0463 (14).

Computing details top

Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular of (I). Anisotropic displacement ellipsoids are drawn at the 50%-probability level for non-H atoms.
[Figure 2] Fig. 2. The packing of (I) viewed along [1 0 0].
Norbornane-2,7-diyl 1',2'-phenylene orthocarbonate top
Crystal data top
C14H14O4F000 = 520
Mr = 246.26Dx = 1.445 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 11723 reflections
a = 6.0509 (2) Åθ = 3.1–27.5º
b = 18.1250 (6) ŵ = 0.11 mm−1
c = 10.3711 (3) ÅT = 200 (2) K
β = 95.689 (2)ºBlock, colourless
V = 1131.82 (6) Å30.16 × 0.15 × 0.10 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		1779 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.028
Monochromator: MONTEL, graded multilayered X-ray opticsθmax = 27.5º
T = 200(2) Kθmin = 3.6º
CCD; rotation images; thick slices scansh = −7→7
Absorption correction: nonek = −23→23
5009 measured reflectionsl = −13→13
2573 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Only H-atom displacement parameters refined
wR(F2) = 0.117  w = 1/[σ2(Fo2) + (0.0525P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2573 reflectionsΔρmax = 0.19 e Å−3
164 parametersΔρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C14H14O4V = 1131.82 (6) Å3
Mr = 246.26Z = 4
Monoclinic, P21/nMo Kα
a = 6.0509 (2) ŵ = 0.11 mm−1
b = 18.1250 (6) ÅT = 200 (2) K
c = 10.3711 (3) Å0.16 × 0.15 × 0.10 mm
β = 95.689 (2)º
Data collection top
Nonius KappaCCD
diffractometer		2573 independent reflections
Absorption correction: none1779 reflections with I > 2σ(I)
5009 measured reflectionsRint = 0.028
Refinement top
R[F2 > 2σ(F2)] = 0.044164 parameters
wR(F2) = 0.117Only H-atom displacement parameters refined
S = 1.03Δρmax = 0.19 e Å−3
2573 reflectionsΔρmin = −0.20 e Å−3
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 > 2sigma(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
xyzUiso*/Ueq
O120.83506 (19)0.08057 (6)0.82385 (11)0.0373 (3)
O170.97730 (18)0.02608 (6)0.64946 (11)0.0327 (3)
O211.13089 (19)0.12882 (6)0.73797 (11)0.0377 (3)
O220.78699 (19)0.13656 (6)0.62400 (11)0.0382 (3)
C100.9290 (3)0.09008 (9)0.71081 (16)0.0320 (4)
C110.5901 (3)−0.00278 (9)0.69471 (17)0.0350 (4)
H110.51020.03990.65030.0463 (14)*
C120.7030 (3)0.01341 (9)0.82865 (16)0.0358 (4)
H120.59170.01810.89340.0463 (14)*
C130.8536 (3)−0.05454 (9)0.85779 (16)0.0393 (4)
H1311.0068−0.03950.88940.0463 (14)*
H1320.7944−0.08700.92300.0463 (14)*
C140.8472 (3)−0.09294 (9)0.72612 (17)0.0359 (4)
H140.9839−0.12160.71180.0463 (14)*
C150.6297 (3)−0.13617 (10)0.70228 (19)0.0415 (4)
H1510.6115−0.17110.77390.0463 (14)*
H1520.6220−0.16370.61950.0463 (14)*
C160.4545 (3)−0.07430 (10)0.69715 (19)0.0427 (4)
H1610.3488−0.07870.61830.0463 (14)*
H1620.3706−0.07590.77430.0463 (14)*
C170.7989 (3)−0.02808 (9)0.63485 (16)0.0324 (4)
H170.7652−0.04430.54280.0463 (14)*
C211.1277 (3)0.18638 (8)0.64979 (15)0.0316 (4)
C220.9223 (3)0.19053 (8)0.58122 (15)0.0317 (4)
C230.8708 (3)0.24313 (9)0.48849 (16)0.0370 (4)
H230.72820.24570.44130.0463 (14)*
C241.0393 (3)0.29288 (9)0.46697 (16)0.0389 (4)
H241.01140.33030.40340.0463 (14)*
C251.2457 (3)0.28872 (9)0.53632 (17)0.0391 (4)
H251.35650.32350.51940.0463 (14)*
C261.2961 (3)0.23468 (9)0.63083 (16)0.0365 (4)
H261.43780.23160.67890.0463 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O120.0485 (7)0.0298 (6)0.0347 (6)−0.0033 (5)0.0092 (5)−0.0051 (5)
O170.0337 (6)0.0282 (6)0.0374 (6)−0.0027 (5)0.0089 (5)−0.0021 (5)
O210.0360 (7)0.0316 (6)0.0436 (7)−0.0057 (5)−0.0059 (5)0.0068 (5)
O220.0330 (6)0.0328 (6)0.0476 (7)−0.0042 (5)−0.0030 (5)0.0084 (5)
C100.0333 (9)0.0272 (8)0.0346 (8)−0.0008 (7)−0.0005 (7)0.0016 (7)
C110.0299 (9)0.0331 (9)0.0419 (9)0.0010 (7)0.0025 (7)0.0050 (7)
C120.0425 (10)0.0318 (9)0.0354 (9)−0.0015 (7)0.0143 (8)−0.0020 (7)
C130.0448 (11)0.0357 (9)0.0364 (9)−0.0001 (8)−0.0009 (8)0.0059 (7)
C140.0353 (9)0.0290 (8)0.0443 (9)0.0015 (7)0.0075 (8)−0.0007 (7)
C150.0427 (10)0.0348 (9)0.0475 (10)−0.0067 (8)0.0066 (8)−0.0010 (8)
C160.0337 (10)0.0438 (10)0.0506 (11)−0.0060 (8)0.0043 (8)0.0033 (8)
C170.0349 (9)0.0306 (8)0.0323 (8)−0.0070 (7)0.0066 (7)−0.0031 (7)
C210.0376 (9)0.0241 (8)0.0328 (8)−0.0006 (7)0.0024 (7)−0.0002 (6)
C220.0351 (9)0.0246 (8)0.0356 (8)−0.0035 (7)0.0042 (7)−0.0013 (6)
C230.0407 (10)0.0318 (9)0.0369 (9)−0.0008 (7)−0.0038 (8)0.0012 (7)
C240.0515 (11)0.0298 (9)0.0350 (9)−0.0030 (8)0.0019 (8)0.0036 (7)
C250.0450 (11)0.0323 (9)0.0407 (9)−0.0102 (8)0.0070 (8)−0.0003 (7)
C260.0354 (9)0.0335 (9)0.0397 (9)−0.0040 (7)−0.0002 (7)−0.0025 (7)
Geometric parameters (Å, °) top
O12—C101.364 (2)C14—C151.530 (2)
O12—C121.4598 (19)C14—H141.0000
O17—C101.3685 (19)C15—C161.541 (2)
O17—C171.4557 (18)C15—H1510.9900
O21—C211.3862 (19)C15—H1520.9900
O21—C101.4129 (19)C16—H1610.9900
O22—C221.3770 (18)C16—H1620.9900
O22—C101.4510 (19)C17—H171.0000
C11—C121.515 (3)C21—C221.371 (2)
C11—C171.532 (2)C21—C261.372 (2)
C11—C161.536 (2)C22—C231.368 (2)
C11—H111.0000C23—C241.395 (2)
C12—C131.544 (2)C23—H230.9500
C12—H121.0000C24—C251.380 (3)
C13—C141.530 (2)C24—H240.9500
C13—H1310.9900C25—C261.398 (2)
C13—H1320.9900C25—H250.9500
C14—C171.519 (2)C26—H260.9500
C10—O12—C12114.27 (12)C14—C15—H151111.3
C10—O17—C17115.45 (12)C16—C15—H151111.3
C21—O21—C10106.68 (12)C14—C15—H152111.3
C22—O22—C10106.13 (12)C16—C15—H152111.3
O12—C10—O17114.77 (13)H151—C15—H152109.2
O12—C10—O21108.50 (13)C11—C16—C15104.34 (13)
O17—C10—O21107.08 (13)C11—C16—H161110.9
O12—C10—O22109.58 (13)C15—C16—H161110.9
O17—C10—O22110.14 (13)C11—C16—H162110.9
O21—C10—O22106.40 (12)C15—C16—H162110.9
C12—C11—C1796.58 (14)H161—C16—H162108.9
C12—C11—C16109.98 (14)O17—C17—C14111.23 (13)
C17—C11—C16102.57 (13)O17—C17—C11112.88 (13)
C12—C11—H11115.2C14—C17—C1195.42 (12)
C17—C11—H11115.2O17—C17—H17112.1
C16—C11—H11115.2C14—C17—H17112.1
O12—C12—C11109.20 (13)C11—C17—H17112.1
O12—C12—C13110.93 (14)C22—C21—C26122.57 (15)
C11—C12—C13103.22 (13)C22—C21—O21109.65 (13)
O12—C12—H12111.1C26—C21—O21127.77 (15)
C11—C12—H12111.1C23—C22—C21122.30 (15)
C13—C12—H12111.1C23—C22—O22128.34 (15)
C14—C13—C12103.05 (13)C21—C22—O22109.34 (14)
C14—C13—H131111.2C22—C23—C24116.35 (16)
C12—C13—H131111.2C22—C23—H23121.8
C14—C13—H132111.2C24—C23—H23121.8
C12—C13—H132111.2C25—C24—C23121.26 (15)
H131—C13—H132109.1C25—C24—H24119.4
C17—C14—C13100.98 (13)C23—C24—H24119.4
C17—C14—C15100.74 (14)C24—C25—C26121.81 (16)
C13—C14—C15108.81 (14)C24—C25—H25119.1
C17—C14—H14114.9C26—C25—H25119.1
C13—C14—H14114.9C21—C26—C25115.72 (16)
C15—C14—H14114.9C21—C26—H26122.1
C14—C15—C16102.17 (13)C25—C26—H26122.1
C12—O12—C10—O17−29.50 (19)C14—C15—C16—C119.50 (18)
C12—O12—C10—O21−149.20 (12)C10—O17—C17—C14−107.09 (15)
C12—O12—C10—O2295.01 (15)C10—O17—C17—C11−1.20 (18)
C17—O17—C10—O1248.45 (18)C13—C14—C17—O1762.57 (16)
C17—O17—C10—O21168.94 (11)C15—C14—C17—O17174.35 (12)
C17—O17—C10—O22−75.77 (15)C13—C14—C17—C11−54.55 (15)
C21—O21—C10—O12−130.62 (13)C15—C14—C17—C1157.24 (14)
C21—O21—C10—O17104.97 (13)C12—C11—C17—O17−54.39 (16)
C21—O21—C10—O22−12.80 (15)C16—C11—C17—O17−166.60 (13)
C22—O22—C10—O12130.32 (13)C12—C11—C17—C1461.39 (14)
C22—O22—C10—O17−102.52 (14)C16—C11—C17—C14−50.83 (15)
C22—O22—C10—O2113.21 (15)C10—O21—C21—C227.81 (17)
C10—O12—C12—C11−34.36 (18)C10—O21—C21—C26−173.44 (16)
C10—O12—C12—C1378.75 (16)C26—C21—C22—C230.2 (3)
C17—C11—C12—O1272.75 (14)O21—C21—C22—C23179.04 (14)
C16—C11—C12—O12178.71 (12)C26—C21—C22—O22−178.16 (14)
C17—C11—C12—C13−45.31 (15)O21—C21—C22—O220.67 (17)
C16—C11—C12—C1360.65 (17)C10—O22—C22—C23173.13 (16)
O12—C12—C13—C14−104.89 (14)C10—O22—C22—C21−8.63 (16)
C11—C12—C13—C1411.96 (17)C21—C22—C23—C240.0 (2)
C12—C13—C14—C1726.56 (16)O22—C22—C23—C24178.00 (15)
C12—C13—C14—C15−78.90 (16)C22—C23—C24—C25−0.1 (2)
C17—C14—C15—C16−42.05 (16)C23—C24—C25—C260.1 (3)
C13—C14—C15—C1663.58 (17)C22—C21—C26—C25−0.2 (2)
C12—C11—C16—C15−75.92 (17)O21—C21—C26—C25−178.81 (15)
C17—C11—C16—C1525.97 (18)C24—C25—C26—C210.0 (2)
Selected geometric parameters (Å) top
O12—C101.364 (2)O21—C101.4129 (19)
O17—C101.3685 (19)O22—C101.4510 (19)
Acknowledgements top

The authors thank Sandra Albrecht for professional support.

references
References top

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Mues, P. & Buysch, H.-J. (1990). Synthesis, pp. 249–252.

Nonius (2004). COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.