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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o282.
Published online 2007 December 18. doi:  10.1107/S1600536807066007
PMCID: PMC2915335

trans-Cyclo­hexane-1,4-diyl bis­(4-nitro­phen­yl) dicarbonate

Abstract

In the title crystal structure, C20H18N2O10, there are two independent mol­ecules, both of which lie on crystallographic inversion centres. In one mol­ecule the 4-nitro­phenyl dicarbonate groups are substituted in equatorial (A eq) positions of the chair-form cyclo­hexane ring while in the other mol­ecule the substitution is axial (B ax). The dihedral angles between the atoms of the symmetry-unique carbonate group (O=CO2—) and benzene ring for each mol­ecule are 47.3 (1)° for A eq and 11.7 (2)° for B ax. In B ax, this facilitates the formation of a weak intra­molecular C—H(...)O hydrogen bond, while the packing is stabilized by weak inter­molecular C—H(...)O inter­actions.

Related literature

For related literature, see: Ali et al. (2008 [triangle]).

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Object name is e-64-0o282-scheme1.jpg

Experimental

Crystal data

  • C20H18N2O10
  • M r = 446.36
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o282-efi1.jpg
  • a = 7.6804 (14) Å
  • b = 11.6548 (18) Å
  • c = 12.3092 (11) Å
  • α = 63.201 (8)°
  • β = 87.254 (10)°
  • γ = 82.310 (7)°
  • V = 974.6 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 150 (1) K
  • 0.22 × 0.20 × 0.08 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: multi-scan (SORTAV; Blessing, 1995 [triangle]) T min = 0.768, T max = 0.996
  • 7088 measured reflections
  • 3355 independent reflections
  • 1633 reflections with I > 2σ(I)
  • R int = 0.080

Refinement

  • R[F 2 > 2σ(F 2)] = 0.063
  • wR(F 2) = 0.190
  • S = 0.96
  • 3355 reflections
  • 289 parameters
  • H-atom parameters constrained
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.27 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.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807066007/hb2675sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066007/hb2675Isup2.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 synthesis of title compound is similar to that of cyclohex-2-ene-1,4-diylbis(4-nitrophenyl)dicarbonate (Ali et al., 2008). Here, we used a mixture of cis and trans isomers of cyclohexane-1,4-diol. The trans isomer has been separated from the mixture of cis and trans isomers. Most of the trans isomer remained undissolved in EtOH during the recrystallization at 358 K, after 40 minutes. Pale yellow plates of (I) were obtained after solubilizing this EtOH insoluble solid in dichloromethane. The molecular structure is illustrated in Figs. 1 and 2, showing that one of the two asymmetric molecules possesses equatorial substituents and the other axial. Within the latter, a weak C—H···O interaction (Table 1) occurs. Further C—H···O links help to establish the packing.

Experimental

A solution of 4-nitrophenylchloroformate (5.64 g, 28.0 mmol) in dry dichloromethane (40 ml) was added dropwise via a 100 ml separating funnel into a solution of cyclohexane-1,4-diol (cis and trans isomers) (1.63 g, 14.0 mmol) in anhydrous pyridine (2.15 g, 2.2 ml, 27.1 mmol) and dry dichloromethane (20 ml) in a 250 ml round-bottom flask. A white suspension appeared which was allowed to stir gently at room temperature for 16 h. After this time more dry dichloromethane (40 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 (40 ml). The reaction mixture was transferred to a separating funnel (500 ml), and the lower organic phase was removed. The aqueous phase was washed with dichloromethane (30 ml × 2), and the dichloromethane solutions were combined. These were then washed with deionized water (30 ml × 2), a 1.0% solution of acetic acid (50 ml × 2) and once more with deionized water (40 ml × 2), and then dried over anhydrous magnesium sulfate and filtered. After filtration, the solvent was removed by rotary evaporator. 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 (6.2 g, 84.0%) as a white solid. For recrystallization, the solid was dissolved in 95% EtOH (50 ml) at 358 K, after 40 minutes some of the solid (about 40%) remained undissolved. The warm solution was filtered and the EtOH-insoluble solid was recovered from the filter paper and dissolved in dichloromethane. Pale yellow plates of (I) were obtained by slow evaporation of solvent at room temperature.

Refinement

The H atoms were placed in calculated positions, with C—H = 0.95–1.00 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
View of one of the independent molecules of the title compound with displacement ellipsoids drawn at the 30% probability level. Unlabeled atoms are related by the symmetry operator (-x, -y, 1 - z).
Fig. 2.
View of the other independent molecule of the title compound with displacement ellipsoids drawn at the 30% probability level. Unlabeled atoms are related by the symmetry operator (2 - x, 1 - y, -z). The dashed line indicates a hydrogen bond.

Crystal data

C20H18N2O10Z = 2
Mr = 446.36F000 = 464
Triclinic, P1Dx = 1.521 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.6804 (14) ÅCell parameters from 7088 reflections
b = 11.6548 (18) Åθ = 2.7–25.2º
c = 12.3092 (11) ŵ = 0.12 mm1
α = 63.201 (8)ºT = 150 (1) K
β = 87.254 (10)ºPlate, pale yellow
γ = 82.310 (7)º0.22 × 0.20 × 0.08 mm
V = 974.6 (3) Å3

Data collection

Nonius KappaCCD diffractometer3355 independent reflections
Radiation source: fine-focus sealed tube1633 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.080
Detector resolution: 9 pixels mm-1θmax = 25.2º
T = 150(2) Kθmin = 2.7º
[var phi] scans and ω scans with κ offsetsh = −9→9
Absorption correction: multi-scan(SORTAV; Blessing, 1995)k = −12→13
Tmin = 0.768, Tmax = 0.996l = −14→14
7088 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)] = 0.063H-atom parameters constrained
wR(F2) = 0.190  w = 1/[σ2(Fo2) + (0.0923P)2] where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max < 0.001
3355 reflectionsΔρmax = 0.30 e Å3
289 parametersΔρmin = −0.27 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
O1A0.1429 (4)0.0985 (3)0.2676 (2)0.0517 (8)
O2A0.4182 (4)−0.0092 (3)0.2921 (2)0.0504 (8)
O3A0.3173 (4)0.1684 (3)0.1182 (2)0.0524 (8)
O4A0.9007 (4)0.1716 (3)−0.2527 (3)0.0685 (10)
O5A1.0631 (5)0.1300 (3)−0.0977 (3)0.0690 (10)
N1A0.9198 (6)0.1542 (3)−0.1481 (4)0.0498 (10)
C1A−0.1660 (6)−0.0576 (4)0.5216 (3)0.0495 (12)
H1A1−0.1245−0.15090.55020.059*
H1A2−0.2960−0.04630.52110.059*
C2A−0.1003 (6)0.0194 (4)0.3939 (3)0.0513 (12)
H2A1−0.1389−0.01450.33960.062*
H2A2−0.15200.11120.36240.062*
C3A0.0979 (6)0.0112 (4)0.3927 (3)0.0474 (12)
H3A0.1518−0.07960.41450.057*
C4A0.3057 (6)0.0763 (4)0.2341 (4)0.0453 (11)
C5A0.4739 (6)0.1635 (4)0.0559 (3)0.0409 (11)
C6A0.6345 (6)0.1517 (4)0.1054 (4)0.0476 (12)
H6AA0.64420.14590.18440.057*
C7A0.7824 (6)0.1483 (4)0.0383 (4)0.0478 (11)
H7AA0.89620.13810.07090.057*
C8A0.7621 (6)0.1599 (4)−0.0766 (3)0.0402 (10)
C9A0.6019 (6)0.1746 (4)−0.1267 (3)0.0459 (11)
H9AA0.59260.1831−0.20680.055*
C10A0.4527 (6)0.1771 (4)−0.0601 (3)0.0455 (11)
H10A0.33910.1878−0.09320.055*
O1B0.9940 (4)0.5357 (3)0.1688 (2)0.0493 (8)
O2B0.9203 (4)0.3799 (3)0.3498 (2)0.0568 (9)
O3B0.8673 (4)0.5951 (3)0.2963 (2)0.0486 (8)
O4B0.4719 (5)0.5191 (3)0.7792 (3)0.0708 (11)
O5B0.4665 (5)0.7279 (4)0.6849 (3)0.0731 (11)
N1B0.5072 (5)0.6198 (4)0.6918 (3)0.0527 (10)
C1B0.8165 (6)0.4921 (4)−0.0214 (4)0.0507 (12)
H1B10.73250.4509−0.04650.061*
H1B20.74800.55650.00080.061*
C2B0.9217 (6)0.3884 (4)0.0905 (3)0.0500 (12)
H2B10.84090.35350.15970.060*
H2B20.97300.31620.07280.060*
C3B1.0669 (6)0.4393 (4)0.1269 (3)0.0497 (12)
H3B1.13920.36590.19380.060*
C4B0.9251 (6)0.4897 (4)0.2793 (4)0.0474 (11)
C5B0.7791 (6)0.5888 (4)0.4005 (3)0.0425 (11)
C6B0.7732 (6)0.4775 (4)0.5097 (3)0.0457 (11)
H6BA0.82990.39600.51890.055*
C7B0.6813 (6)0.4894 (4)0.6054 (4)0.0473 (11)
H7BA0.67350.41490.68100.057*
C8B0.6022 (6)0.6085 (4)0.5905 (3)0.0412 (10)
C9B0.6109 (6)0.7178 (4)0.4819 (3)0.0439 (11)
H9BA0.55540.79960.47270.053*
C10B0.7007 (6)0.7072 (4)0.3872 (3)0.0405 (10)
H10B0.70850.78220.31200.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O1A0.052 (2)0.0532 (18)0.0391 (16)0.0002 (15)0.0040 (14)−0.0132 (14)
O2A0.052 (2)0.0445 (17)0.0441 (16)0.0074 (16)−0.0042 (15)−0.0133 (13)
O3A0.055 (2)0.0517 (17)0.0347 (16)0.0048 (15)0.0035 (14)−0.0093 (14)
O4A0.061 (3)0.087 (2)0.072 (2)−0.0174 (19)0.0189 (18)−0.048 (2)
O5A0.045 (2)0.064 (2)0.078 (2)−0.0100 (18)0.0049 (19)−0.0146 (17)
N1A0.047 (3)0.040 (2)0.059 (3)−0.0088 (19)0.004 (2)−0.0180 (18)
C1A0.051 (3)0.052 (3)0.045 (2)−0.015 (2)0.003 (2)−0.019 (2)
C2A0.056 (3)0.062 (3)0.039 (2)−0.008 (2)−0.001 (2)−0.025 (2)
C3A0.055 (3)0.051 (3)0.036 (2)−0.007 (2)0.001 (2)−0.019 (2)
C4A0.049 (3)0.046 (3)0.044 (3)−0.006 (2)0.008 (2)−0.025 (2)
C5A0.043 (3)0.035 (2)0.041 (2)−0.003 (2)0.010 (2)−0.0155 (18)
C6A0.055 (3)0.048 (3)0.042 (2)−0.003 (2)−0.007 (2)−0.022 (2)
C7A0.043 (3)0.048 (3)0.052 (3)−0.007 (2)−0.005 (2)−0.021 (2)
C8A0.042 (3)0.032 (2)0.044 (2)−0.0007 (19)0.002 (2)−0.0166 (18)
C9A0.054 (3)0.045 (2)0.035 (2)−0.010 (2)−0.001 (2)−0.0141 (19)
C10A0.040 (3)0.050 (3)0.039 (2)−0.008 (2)0.000 (2)−0.0126 (19)
O1B0.059 (2)0.0453 (16)0.0435 (17)−0.0044 (15)0.0073 (14)−0.0209 (13)
O2B0.079 (3)0.0435 (19)0.0430 (17)−0.0046 (16)0.0087 (15)−0.0169 (15)
O3B0.063 (2)0.0411 (17)0.0404 (16)−0.0016 (15)0.0082 (14)−0.0194 (13)
O4B0.077 (3)0.075 (2)0.0455 (19)−0.004 (2)0.0170 (17)−0.0174 (17)
O5B0.084 (3)0.072 (2)0.079 (2)−0.009 (2)0.0228 (19)−0.050 (2)
N1B0.048 (3)0.064 (3)0.048 (2)−0.003 (2)0.0061 (18)−0.029 (2)
C1B0.051 (3)0.049 (3)0.054 (3)−0.002 (2)0.005 (2)−0.027 (2)
C2B0.066 (3)0.045 (3)0.042 (2)−0.009 (2)0.009 (2)−0.022 (2)
C3B0.066 (3)0.042 (2)0.042 (2)−0.003 (2)0.004 (2)−0.021 (2)
C4B0.060 (3)0.043 (3)0.036 (2)−0.008 (2)−0.001 (2)−0.014 (2)
C5B0.046 (3)0.047 (3)0.035 (2)−0.007 (2)−0.0012 (19)−0.0187 (19)
C6B0.048 (3)0.039 (2)0.051 (3)0.002 (2)0.000 (2)−0.022 (2)
C7B0.048 (3)0.047 (3)0.041 (2)−0.008 (2)0.001 (2)−0.015 (2)
C8B0.038 (3)0.046 (3)0.040 (2)−0.005 (2)0.0024 (19)−0.020 (2)
C9B0.043 (3)0.043 (2)0.050 (3)−0.003 (2)−0.003 (2)−0.025 (2)
C10B0.045 (3)0.041 (2)0.037 (2)−0.010 (2)0.0005 (19)−0.0180 (19)

Geometric parameters (Å, °)

O1A—C4A1.327 (5)O1B—C4B1.328 (5)
O1A—C3A1.469 (4)O1B—C3B1.472 (5)
O2A—C4A1.199 (5)O2B—C4B1.184 (5)
O3A—C4A1.352 (5)O3B—C4B1.352 (5)
O3A—C5A1.404 (5)O3B—C5B1.398 (5)
O4A—N1A1.223 (4)O4B—N1B1.236 (4)
O5A—N1A1.224 (5)O5B—N1B1.222 (5)
N1A—C8A1.475 (5)N1B—C8B1.463 (5)
C1A—C2A1.518 (5)C1B—C3Bii1.507 (5)
C1A—C3Ai1.525 (6)C1B—C2B1.535 (5)
C1A—H1A10.9900C1B—H1B10.9900
C1A—H1A20.9900C1B—H1B20.9900
C2A—C3A1.512 (6)C2B—C3B1.503 (6)
C2A—H2A10.9900C2B—H2B10.9900
C2A—H2A20.9900C2B—H2B20.9900
C3A—C1Ai1.525 (6)C3B—C1Bii1.507 (5)
C3A—H3A1.0000C3B—H3B1.0000
C5A—C6A1.365 (6)C5B—C10B1.370 (5)
C5A—C10A1.379 (6)C5B—C6B1.388 (5)
C6A—C7A1.379 (6)C6B—C7B1.395 (6)
C6A—H6AA0.9500C6B—H6BA0.9500
C7A—C8A1.373 (5)C7B—C8B1.373 (6)
C7A—H7AA0.9500C7B—H7BA0.9500
C8A—C9A1.358 (6)C8B—C9B1.375 (5)
C9A—C10A1.381 (6)C9B—C10B1.372 (5)
C9A—H9AA0.9500C9B—H9BA0.9500
C10A—H10A0.9500C10B—H10B0.9500
C4A—O1A—C3A116.0 (3)C4B—O1B—C3B116.4 (3)
C4A—O3A—C5A118.0 (3)C4B—O3B—C5B123.4 (3)
O4A—N1A—O5A123.8 (4)O5B—N1B—O4B123.8 (4)
O4A—N1A—C8A118.7 (4)O5B—N1B—C8B118.3 (4)
O5A—N1A—C8A117.5 (4)O4B—N1B—C8B117.8 (4)
C2A—C1A—C3Ai109.7 (3)C3Bii—C1B—C2B112.3 (4)
C2A—C1A—H1A1109.7C3Bii—C1B—H1B1109.1
C3Ai—C1A—H1A1109.7C2B—C1B—H1B1109.1
C2A—C1A—H1A2109.7C3Bii—C1B—H1B2109.1
C3Ai—C1A—H1A2109.7C2B—C1B—H1B2109.1
H1A1—C1A—H1A2108.2H1B1—C1B—H1B2107.9
C3A—C2A—C1A111.1 (3)C3B—C2B—C1B112.9 (4)
C3A—C2A—H2A1109.4C3B—C2B—H2B1109.0
C1A—C2A—H2A1109.4C1B—C2B—H2B1109.0
C3A—C2A—H2A2109.4C3B—C2B—H2B2109.0
C1A—C2A—H2A2109.4C1B—C2B—H2B2109.0
H2A1—C2A—H2A2108.0H2B1—C2B—H2B2107.8
O1A—C3A—C2A105.7 (3)O1B—C3B—C2B110.5 (4)
O1A—C3A—C1Ai108.5 (3)O1B—C3B—C1Bii106.1 (3)
C2A—C3A—C1Ai111.9 (4)C2B—C3B—C1Bii111.9 (3)
O1A—C3A—H3A110.2O1B—C3B—H3B109.4
C2A—C3A—H3A110.2C2B—C3B—H3B109.4
C1Ai—C3A—H3A110.2C1Bii—C3B—H3B109.4
O2A—C4A—O1A127.8 (4)O2B—C4B—O1B127.6 (4)
O2A—C4A—O3A126.7 (4)O2B—C4B—O3B127.0 (4)
O1A—C4A—O3A105.5 (4)O1B—C4B—O3B105.3 (3)
C6A—C5A—C10A122.8 (4)C10B—C5B—C6B121.5 (4)
C6A—C5A—O3A122.0 (4)C10B—C5B—O3B113.0 (3)
C10A—C5A—O3A115.1 (4)C6B—C5B—O3B125.5 (4)
C5A—C6A—C7A118.6 (4)C5B—C6B—C7B117.8 (4)
C5A—C6A—H6AA120.7C5B—C6B—H6BA121.1
C7A—C6A—H6AA120.7C7B—C6B—H6BA121.1
C8A—C7A—C6A118.8 (4)C8B—C7B—C6B120.1 (4)
C8A—C7A—H7AA120.6C8B—C7B—H7BA120.0
C6A—C7A—H7AA120.6C6B—C7B—H7BA120.0
C9A—C8A—C7A122.5 (4)C7B—C8B—C9B121.2 (4)
C9A—C8A—N1A118.4 (4)C7B—C8B—N1B119.6 (3)
C7A—C8A—N1A119.0 (4)C9B—C8B—N1B119.2 (4)
C8A—C9A—C10A119.3 (4)C10B—C9B—C8B119.2 (4)
C8A—C9A—H9AA120.3C10B—C9B—H9BA120.4
C10A—C9A—H9AA120.3C8B—C9B—H9BA120.4
C5A—C10A—C9A117.9 (4)C5B—C10B—C9B120.2 (3)
C5A—C10A—H10A121.0C5B—C10B—H10B119.9
C9A—C10A—H10A121.0C9B—C10B—H10B119.9

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C10A—H10A···O5Aiii0.952.323.205 (6)155
C6B—H6BA···O2B0.952.242.812 (5)118
C9B—H9BA···O2Aiv0.952.483.184 (5)131

Symmetry codes: (iii) x−1, y, z; (iv) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2675).

References

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