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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o281.
Published online 2007 December 18. doi:  10.1107/S1600536807065993
PMCID: PMC2915334

trans-Cyclo­hex-2-ene-1,4-diyl bis­(4-nitro­phen­yl) dicarbonate

Abstract

Although the title mol­ecule, C20H16N2O10, does not possess mol­ecular inversion symmetry, it lies on a crystallographic inversion centre which imposes disorder on the central cyclo­hexene ring. In addition, the cyclo­hexene ring has non-symmetry-related disorder over two sites, with the ratio of the major and minor components being 0.54:0.46. The overall effect is to produce four disorder components for the atoms of the cyclo­hexene ring. The side chain is perfectly ordered and the dihedral angle between the atoms of the carbonate group (O=CO2—) and the benzene ring is 72.99 (6)°.

Related literature

For related literature, see: Ali et al. (2008 [triangle]); Ericsson & Hult (1991 [triangle]); Fréchet et al. (1986 [triangle], 1987 [triangle]).

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Object name is e-64-0o281-scheme1.jpg

Experimental

Crystal data

  • C20H16N2O10
  • M r = 444.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o281-efi1.jpg
  • a = 5.6874 (4) Å
  • b = 13.4958 (10) Å
  • c = 12.7017 (5) Å
  • β = 96.453 (4)°
  • V = 968.76 (11) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 150 (1) K
  • 0.40 × 0.18 × 0.12 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: multi-scan (SORTAV; Blessing, 1995 [triangle]) T min = 0.560, T max = 0.987
  • 9286 measured reflections
  • 2222 independent reflections
  • 1408 reflections with I > 2σ(I)
  • R int = 0.068

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.167
  • S = 1.05
  • 2222 reflections
  • 185 parameters
  • 58 restraints
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.35 e Å−3

Data collection: COLLECT (Nonius, 2002 [triangle]); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO–SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 [triangle]); program(s) used to refine structure: SHELXTL/PC (Sheldrick, 2001 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]) ; software used to prepare material for publication: SHELXTL/PC.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807065993/hb2674sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065993/hb2674Isup2.hkl

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

Acknowledgments

The authors acknowledge funding from the Higher Education Commission (HEC) of Pakistan, Materials and Manufacturing Ontario (MMO), Canada, NSERC Canada and the University of Toronto.

supplementary crystallographic information

Comment

The title compound, (I), was synthesized two decades ago (Fréchet et al., 1986) as a mixture of cis and trans isomers starting with a cis and trans mixture of cyclohex-2-ene-1,4-diol to obtain electrophilic character of diols. This compound has been used to obtain a wide variety of thermally and acid labile polymers for a variety of applications (Fréchet et al., 1987; Ericsson & Hult, 1991). We have used the trans isomer of this alcohol for the synthesis of a number of homo and copolycarbonates (Ali et al., 2008).

We report here the crystal structure of (I). Figures 1 and 2 show the two non-symmetry related components of disorder for the cyclohexene ring in (I). The crystallograhic inversion related disorder is not shown.

Experimental

A solution of 4-nitrophenylchloroformate (1.41 g, 7.0 mmol) in dry dichloromethane (20 ml) was added dropwise via a 100 ml separating funnel into a solution of cyclohex-2-ene-1,4-diol (trans isomer) (0.40 g, 3.5 mmol) in anhydrous pyridine (0.49 g, 0.5 ml, 6.2 mmol) and dry dichloromethane (10 ml) in a 100 ml round-bottom flask. A white suspension appeared which was allowed to stir gently at room temperature for 12 h. After this time more dry dichloromethane (25 ml) was added, which dissolved the suspension and then the reaction mixture was stirred for another 6 h. Then it was quenched by adding deionized water (30 ml). The reaction mixture was transferred to a separating funnel (250 ml), and the lower organic phase was removed. The aqueous phase was washed with dichloromethane (20 ml × 2), and all the dichloromethane solutions were combined. These were then washed with deionized water (20 ml × 2), a 1.0% solution of acetic acid (30 ml × 2) and once more with deionized water (25 ml × 2), and then dried over anhydrous magnesium sulfate and filtered. After filtration, the solvent was removed by rotary evaporation. The product was dried in air overnight in a fume hood and then in a vacuum oven for 24 h at room temperature (< 1 Torr). The desired product was obtained in good yield (1.35 g, 86.5%) as a white crystalline solid. The product was recrystallized in dichloromethane and colourless needles of (I) were obtained by slow evaporation of solvent at room temperature. In addition to the X-ray structure determination, the structure of the crystalline sample was confirmed by Mass and NMR (1H and 13C)Spectroscopy.

Refinement

All the hydrogen atoms were placed in calculated positions with C—H = 0.95 - 1.00 Å and refined as riding with Uiso(H) = 1.2Ueq(C). The components of the two symmetry independent disorder sites refined to 0.2680 (13) and 0.2320 (13). The disorder was modelled by creating two full rings for each component and by using suitable constraints and restraints to give each ring component similar geometries.

Figures

Fig. 1.
The molecular structure of (I) showing one component of disorder in the cyclohexene ring. Displacement ellipsoids drawn at the 30% probability level. Unlabeled atoms are related by the symmetry operator (1 - x, 1 - y, 1 - z).
Fig. 2.
The molecular structure of (I) showing another component of disorder in the cyclohexene ring. Displacement ellipsoids drawn at the 30% probability level. Unlabeled atoms are related by the symmetry operator (1 - x, 1 - y, 1 - z).

Crystal data

C20H16N2O10F000 = 460
Mr = 444.35Dx = 1.523 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9286 reflections
a = 5.6874 (4) Åθ = 3–27.5º
b = 13.4958 (10) ŵ = 0.13 mm1
c = 12.7017 (5) ÅT = 150 (1) K
β = 96.453 (4)ºNeedle, colourless
V = 968.76 (11) Å30.40 × 0.18 × 0.12 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer2222 independent reflections
Radiation source: fine-focus sealed tube1408 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.068
Detector resolution: 9 pixels mm-1θmax = 27.5º
T = 150(2) Kθmin = 3.0º
[var phi] scans and ω scans with κ offsetsh = −7→7
Absorption correction: multi-scan(SORTAV; Blessing, 1995)k = −17→17
Tmin = 0.560, Tmax = 0.987l = −16→16
9286 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.167  w = 1/[σ2(Fo2) + (0.0883P)2 + 0.1379P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2222 reflectionsΔρmax = 0.24 e Å3
185 parametersΔρmin = −0.35 e Å3
58 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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*/UeqOcc. (<1)
N10.1105 (3)0.66892 (13)1.23307 (12)0.0413 (4)
O10.2311 (3)0.72664 (14)1.28816 (11)0.0724 (5)
O2−0.0346 (3)0.61480 (13)1.26762 (11)0.0677 (5)
C10.1364 (3)0.66467 (13)1.12001 (13)0.0337 (4)
C2−0.0422 (3)0.62192 (14)1.05264 (14)0.0382 (4)
H2−0.17860.59551.07930.046*
C3−0.0189 (4)0.61836 (14)0.94586 (14)0.0422 (5)
H3−0.13990.58990.89760.051*
C40.1818 (4)0.65644 (15)0.91015 (14)0.0431 (5)
C50.3600 (3)0.69951 (16)0.97755 (15)0.0455 (5)
H50.49660.72540.95060.055*
C60.3380 (3)0.70468 (15)1.08455 (14)0.0406 (5)
H60.45730.73471.13250.049*
O30.1941 (3)0.65488 (13)0.80041 (10)0.0582 (4)
C70.3396 (3)0.58846 (15)0.76418 (14)0.0394 (5)
O40.4698 (2)0.53485 (11)0.81690 (10)0.0491 (4)
O50.3066 (3)0.59665 (13)0.65942 (10)0.0551 (4)
C8A0.4218 (17)0.5118 (9)0.6065 (8)0.0423 (9)0.2680 (13)
H8A0.46510.45830.65970.051*0.2680 (13)
C9A0.6450 (17)0.5568 (7)0.5726 (7)0.0341 (18)0.2680 (13)
H9A0.75670.57210.63600.041*0.2680 (13)
H9B0.60590.61950.53410.041*0.2680 (13)
C10A0.7618 (16)0.4853 (7)0.5010 (6)0.0509 (19)0.2680 (13)
H10A0.92250.50810.48970.061*0.2680 (13)
H10B0.77210.41770.53140.061*0.2680 (13)
C11A0.5965 (18)0.4882 (9)0.3987 (9)0.0423 (9)0.2680 (13)
H11A0.61390.55190.36030.051*0.2680 (13)
C12A0.3392 (18)0.4672 (7)0.4093 (7)0.037 (2)0.2680 (13)
H12A0.22980.45430.34870.045*0.2680 (13)
C13A0.2677 (17)0.4674 (6)0.5102 (5)0.0435 (17)0.2680 (13)
H13A0.11880.43920.52030.052*0.2680 (13)
C8B0.496 (2)0.5532 (8)0.6018 (9)0.0423 (9)0.2320 (13)
H8B0.65510.56050.64380.051*0.2320 (13)
C9B0.4298 (19)0.4460 (8)0.5879 (8)0.0341 (18)0.2320 (13)
H9C0.26130.44100.55870.041*0.2320 (13)
H9D0.44890.41270.65780.041*0.2320 (13)
C10B0.5814 (19)0.3938 (10)0.5141 (8)0.0509 (19)0.2320 (13)
H10C0.55270.32140.51390.061*0.2320 (13)
H10D0.75150.40620.53590.061*0.2320 (13)
C11B0.506 (2)0.4379 (8)0.4055 (9)0.0423 (9)0.2320 (13)
H11B0.34740.41240.37590.051*0.2320 (13)
C12B0.5147 (19)0.5479 (9)0.3997 (9)0.037 (2)0.2320 (13)
H12B0.53300.58140.33530.045*0.2320 (13)
C13B0.4943 (19)0.5999 (9)0.4934 (7)0.0435 (17)0.2320 (13)
H13B0.47770.66980.48870.052*0.2320 (13)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0430 (9)0.0476 (10)0.0351 (8)−0.0026 (8)0.0119 (7)−0.0027 (7)
O10.0743 (11)0.1030 (14)0.0427 (8)−0.0408 (10)0.0191 (7)−0.0301 (8)
O20.0728 (11)0.0881 (13)0.0447 (9)−0.0339 (10)0.0181 (7)0.0035 (8)
C10.0384 (10)0.0327 (9)0.0311 (9)0.0052 (8)0.0090 (7)−0.0006 (7)
C20.0388 (10)0.0342 (10)0.0420 (10)0.0021 (8)0.0060 (8)0.0018 (8)
C30.0487 (11)0.0407 (11)0.0357 (10)0.0075 (9)−0.0021 (8)−0.0036 (8)
C40.0485 (11)0.0510 (12)0.0305 (9)0.0232 (9)0.0071 (8)0.0028 (8)
C50.0383 (11)0.0579 (13)0.0431 (10)0.0087 (9)0.0164 (8)0.0066 (9)
C60.0382 (10)0.0470 (11)0.0375 (10)0.0010 (8)0.0080 (7)−0.0016 (8)
O30.0684 (10)0.0769 (11)0.0302 (7)0.0395 (8)0.0100 (6)0.0045 (6)
C70.0377 (10)0.0498 (11)0.0306 (9)0.0040 (9)0.0033 (7)−0.0026 (8)
O40.0554 (9)0.0584 (9)0.0326 (7)0.0197 (7)0.0006 (6)−0.0061 (6)
O50.0578 (9)0.0801 (11)0.0278 (7)0.0220 (8)0.0059 (6)−0.0007 (6)
C8A0.052 (3)0.043 (3)0.0314 (14)−0.0076 (18)0.0046 (15)−0.0078 (17)
C9A0.040 (4)0.037 (4)0.025 (3)−0.001 (3)−0.001 (3)−0.001 (2)
C10A0.051 (4)0.056 (4)0.047 (4)−0.019 (4)0.013 (3)−0.006 (3)
C11A0.052 (3)0.043 (3)0.0314 (14)−0.0076 (18)0.0046 (15)−0.0078 (17)
C12A0.037 (4)0.041 (4)0.032 (4)0.002 (3)−0.002 (3)0.004 (3)
C13A0.061 (4)0.039 (3)0.032 (3)−0.024 (3)0.013 (3)−0.004 (2)
C8B0.052 (3)0.043 (3)0.0314 (14)−0.0076 (18)0.0046 (15)−0.0078 (17)
C9B0.040 (4)0.037 (4)0.025 (3)−0.001 (3)−0.001 (3)−0.001 (2)
C10B0.051 (4)0.056 (4)0.047 (4)−0.019 (4)0.013 (3)−0.006 (3)
C11B0.052 (3)0.043 (3)0.0314 (14)−0.0076 (18)0.0046 (15)−0.0078 (17)
C12B0.037 (4)0.041 (4)0.032 (4)0.002 (3)−0.002 (3)0.004 (3)
C13B0.061 (4)0.039 (3)0.032 (3)−0.024 (3)0.013 (3)−0.004 (2)

Geometric parameters (Å, °)

N1—O11.208 (2)C9A—H9A0.9900
N1—O21.220 (2)C10A—C11A1.516 (10)
N1—C11.461 (2)C10A—H10A0.9900
C1—C21.379 (3)C10A—H10B0.9900
C1—C61.387 (3)C11A—O5i1.500 (10)
C2—C31.378 (3)C11A—C12A1.511 (10)
C2—H20.9500C11A—H11A1.0000
C3—C41.374 (3)C12A—C13A1.387 (11)
C3—H30.9500C12A—H12A0.9500
C4—C51.379 (3)C13A—H13A0.9500
C4—O31.403 (2)C8B—C9B1.502 (11)
C5—C61.381 (3)C8B—C13B1.513 (10)
C5—H50.9500C8B—H8B1.0000
C6—H60.9500C9B—C10B1.517 (11)
O3—C71.336 (2)C9B—H9C0.9900
C7—O41.187 (2)C9B—H9D0.9900
C7—O51.327 (2)C10B—C11B1.519 (11)
O5—C8B1.491 (10)C10B—H10C0.9900
O5—C11Bi1.491 (10)C10B—H10D0.9900
O5—C11Ai1.500 (10)C11B—C12B1.489 (11)
O5—C8A1.515 (9)C11B—O5i1.491 (10)
C8A—C9A1.513 (10)C11B—H11B1.0000
C8A—C13A1.543 (9)C12B—C13B1.397 (13)
C8A—H8A1.0000C12B—H12B0.9500
C9A—C10A1.527 (10)C13B—H13B0.9500
O1—N1—O2122.74 (16)O5i—C11A—C12A108.3 (7)
O1—N1—C1118.76 (16)O5i—C11A—C10A100.1 (7)
O2—N1—C1118.49 (16)C12A—C11A—C10A115.6 (9)
C2—C1—C6122.64 (17)O5i—C11A—H11A110.8
C2—C1—N1118.54 (16)C12A—C11A—H11A110.8
C6—C1—N1118.82 (16)C10A—C11A—H11A110.8
C3—C2—C1118.65 (18)C13A—C12A—C11A118.0 (9)
C3—C2—H2120.7C13A—C12A—H12A121.0
C1—C2—H2120.7C11A—C12A—H12A121.0
C4—C3—C2119.16 (18)C12A—C13A—C8A122.2 (9)
C4—C3—H3120.4C12A—C13A—H13A118.9
C2—C3—H3120.4C8A—C13A—H13A118.9
C3—C4—C5122.15 (17)O5—C8B—C9B104.4 (9)
C3—C4—O3117.26 (18)O5—C8B—C13B110.5 (8)
C5—C4—O3120.50 (19)C9B—C8B—C13B108.5 (10)
C4—C5—C6119.38 (18)O5—C8B—H8B111.0
C4—C5—H5120.3C9B—C8B—H8B111.0
C6—C5—H5120.3C13B—C8B—H8B111.0
C5—C6—C1118.01 (18)C8B—C9B—C10B111.5 (9)
C5—C6—H6121.0C8B—C9B—H9C109.3
C1—C6—H6121.0C10B—C9B—H9C109.3
C7—O3—C4116.99 (14)C8B—C9B—H9D109.3
O4—C7—O5128.71 (18)C10B—C9B—H9D109.3
O4—C7—O3125.86 (17)H9C—C9B—H9D108.0
O5—C7—O3105.43 (16)C9B—C10B—C11B105.0 (9)
C7—O5—C8B115.5 (5)C9B—C10B—H10C110.7
C7—O5—C8A111.3 (5)C11B—C10B—H10C110.7
C9A—C8A—O5104.0 (8)C9B—C10B—H10D110.7
C9A—C8A—C13A110.5 (8)C11B—C10B—H10D110.7
O5—C8A—C13A114.2 (7)H10C—C10B—H10D108.8
C9A—C8A—H8A109.3C12B—C11B—O5i104.8 (8)
O5—C8A—H8A109.3C12B—C11B—C10B115.4 (11)
C13A—C8A—H8A109.3O5i—C11B—C10B103.6 (8)
C8A—C9A—C10A110.5 (8)C12B—C11B—H11B110.9
C8A—C9A—H9A109.5O5i—C11B—H11B110.9
C10A—C9A—H9A109.5C10B—C11B—H11B110.9
C11A—C10A—C9A103.0 (8)C13B—C12B—C11B116.9 (11)
C11A—C10A—H10A111.2C13B—C12B—H12B121.6
C9A—C10A—H10A111.2C11B—C12B—H12B121.6
C11A—C10A—H10B111.2C12B—C13B—C8B125.0 (11)
C9A—C10A—H10B111.2C12B—C13B—H13B117.5
H10A—C10A—H10B109.1C8B—C13B—H13B117.5

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2674).

References

  • Ali, S. N., Ghafouri, S., Yin, Z., Froimowicz, P., Begum, S. & Winnik, M. A. (2008). In preparation.
  • Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst.27, 435.
  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • Ericsson, J. & Hult, A. (1991). Makromol. Chem.192, 1609–1619.
  • Fréchet, J. M. J., Bouchard, F., Eichler, E., Houlihan, F. M., Ilzawa, T., Kryczka, B. & Willson, C. G. (1987). Polym. J.19, 31–49.
  • Fréchet, J. M. J., Bouchard, F., Houlihan, F. M., Eichler, E., Ktyczka, B. & Willson, C. G. (1986). Macromol. Chem. Rapid Commun.7, 121–126.
  • Nonius (2002). 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. (2001). SHELXTL/PC Version 6.1. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

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