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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o385.
Published online 2008 January 9. doi:  10.1107/S1600536808000068
PMCID: PMC2960325

trans-4-Nitro­phenyl 4-(tosyl­oxymeth­yl)cyclo­hexa­necarboxyl­ate

Abstract

The title compound, C21H23NO7S, is an important inter­mediate in the synthesis of poly(amido­amine) dendrimers. The cyclo­hexane ring adopts a chair conformation. The dihedral angle between the two aromatic rings is 69.5 (2)°. The mol­ecules are linked into a zigzag chain along the b axis by C—H(...)O hydrogen bonds.

Related literature

For related literature, see: Bucourt & Hainaut (1965 [triangle]); Dunitz & Strickler (1966 [triangle]); Sewald & Jakubke (2002 [triangle]); Luger et al. (1972 [triangle]); van Koningsveld & Jansen (1984 [triangle]).

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Object name is e-64-0o385-scheme1.jpg

Experimental

Crystal data

  • C21H23NO7S
  • M r = 433.46
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o385-efi1.jpg
  • a = 20.499 (5) Å
  • b = 6.111 (3) Å
  • c = 17.250 (4) Å
  • β = 102.04 (3)°
  • V = 2113.4 (13) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.20 mm−1
  • T = 292 (2) K
  • 0.40 × 0.38 × 0.30 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 4094 measured reflections
  • 3627 independent reflections
  • 1850 reflections with I > 2σ(I)
  • R int = 0.004
  • 3 standard reflections every 300 reflections intensity decay: 2.1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.191
  • S = 1.06
  • 3627 reflections
  • 272 parameters
  • H-atom parameters constrained
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.53 e Å−3

Data collection: DIFRAC (Gabe & White, 1993 [triangle]); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (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/S1600536808000068/ci2549sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000068/ci2549Isup2.hkl

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

supplementary crystallographic information

Comment

Activated esters are commonly used in peptide synthesis to facilitate the reaction of carboxylic acid and amine to obtain amide. trans-Nitrophenyl ester of N-protected amino acid can react with amino group quickly at room temperature with fairly good yields (Sewald et al.,2002). In our work, cyclohexane derivatives were designed to be linked to poly(amidoamine)dendrimer[PAMAM] through the amide bond which could be formed by the reaction of terminal amino groups of PAMAM dendrimer and cyclohexanecarboxylic acid. So the title compound, a p-nitrophenyl ester of trans-4-(tosyloxymethyl) cyclohexanecarboxylic acid was synthesized. As expected, the modification of periphery of PAMAM dendrimer effectively is realised under mild conditions. We report here the crystal structure of the title compound.

The cyclohexane ring of the title compound adopts a chair conformation. The average C—C bond length of the cyclohexane ring is 1.521 (5) Å, which is close to that of trans-1,4-cyclohexanedicarboxylic acid (1.523 (3) Å, Von Luger et al., 1972). The mean endocyclic angle of the cyclohexane is 111.08 (3)°, which is close to that observed for cyclohexane rings (111.1°, Bucourt & Hainaut, 1965; 111.4 (4)°, Dunitz & Strickler, 1966; Von Luger et al., 1972).

The molecules are linked into a zigzag chain along the b axis by C—H···O hydrogen bonds (Table 1).

Experimental

trans-4-(Tosyloxymethyl)cyclohexanecarboxylic acid (10 mmol) and p-nitrophenol (11 mmol) were dissolved in ethyl acetate (10 ml) and the solution was cooled to 273 K in an ice bath. Then a solution of DCC (11 mmol) in ethyl acetate (5 ml) was added dropwsie with stirring. After the addition, the stirring was continued for 30 min at 273 K and for 24 h at room temperature. Then acetic acid (0.5 ml) was added and after 30 min the reaction solution was filtered and the filtrate was evaporated to leave a yellow solid. The title compound was recrystallized from acetone. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a acetone-water solution at room temperature.

Refinement

H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined using a riding model, with Uiso(H) = 1.2–1.5Ueq(C).

Figures

Fig. 1.
The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids drawn at the 30% probability level.

Crystal data

C21H23NO7SF000 = 912
Mr = 433.46Dx = 1.362 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 33 reflections
a = 20.499 (5) Åθ = 4.5–7.6º
b = 6.111 (3) ŵ = 0.20 mm1
c = 17.250 (4) ÅT = 292 (2) K
β = 102.04 (3)ºBlock, colourless
V = 2113.4 (13) Å30.40 × 0.38 × 0.30 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.004
Radiation source: fine-focus sealed tubeθmax = 25.0º
Monochromator: graphiteθmin = 1.0º
T = 292(2) Kh = −8→24
ω/2θ scansk = −7→0
Absorption correction: nonel = −20→19
4094 measured reflections3 standard reflections
3627 independent reflections every 300 reflections
1850 reflections with I > 2σ(I) intensity decay: 2.1%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.060H-atom parameters constrained
wR(F2) = 0.191  w = 1/[σ2(Fo2) + (0.097P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
3627 reflectionsΔρmax = 0.40 e Å3
272 parametersΔρmin = −0.53 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
S10.30112 (5)−0.15510 (18)0.17299 (7)0.0556 (4)
O10.30040 (14)−0.0770 (6)0.09454 (16)0.0702 (9)
O20.30099 (14)−0.3830 (5)0.1871 (2)0.0763 (10)
O30.23652 (12)−0.0742 (5)0.19982 (18)0.0632 (8)
O4−0.09447 (15)0.2718 (6)0.1532 (2)0.0885 (12)
O5−0.08914 (13)0.5252 (5)0.06303 (18)0.0686 (9)
O6−0.39478 (15)0.7233 (6)−0.0126 (2)0.0813 (11)
O7−0.36075 (17)0.9887 (7)0.0674 (2)0.0936 (12)
N1−0.35100 (18)0.8235 (8)0.0323 (2)0.0635 (10)
C10.39156 (18)0.1686 (7)0.2212 (2)0.0500 (10)
H10.37400.23670.17320.060*
C20.44258 (19)0.2665 (7)0.2753 (2)0.0536 (11)
H20.45890.40160.26330.064*
C30.46966 (18)0.1673 (8)0.3465 (2)0.0526 (10)
C40.4444 (2)−0.0304 (9)0.3636 (3)0.0650 (13)
H40.4618−0.09730.41190.078*
C50.3931 (2)−0.1337 (8)0.3100 (2)0.0593 (12)
H50.3769−0.26900.32200.071*
C60.36691 (17)−0.0320 (6)0.2393 (2)0.0440 (9)
C70.5248 (2)0.2787 (10)0.4050 (3)0.0811 (16)
H7A0.51250.42790.41210.122*
H7B0.56520.27530.38520.122*
H7C0.53160.20370.45500.122*
C80.21871 (19)0.1584 (7)0.1883 (3)0.0657 (12)
H8A0.22860.21040.13890.079*
H8B0.24420.24480.23130.079*
C90.14546 (17)0.1807 (7)0.1864 (2)0.0507 (10)
H90.13700.12300.23640.061*
C100.10207 (18)0.0551 (7)0.1192 (2)0.0527 (10)
H10A0.1131−0.09920.12490.063*
H10B0.11150.10460.06920.063*
C110.02817 (18)0.0850 (8)0.1176 (2)0.0564 (11)
H11A0.01780.02380.16550.068*
H11B0.00230.00670.07260.068*
C120.00917 (18)0.3266 (7)0.1115 (2)0.0525 (11)
H120.01750.38360.06140.063*
C130.05248 (19)0.4533 (7)0.1792 (3)0.0614 (12)
H13A0.04260.40500.22910.074*
H13B0.04180.60780.17320.074*
C140.1265 (2)0.4210 (7)0.1814 (3)0.0648 (12)
H14A0.13740.48390.13400.078*
H14B0.15230.49750.22690.078*
C15−0.0628 (2)0.3620 (8)0.1128 (2)0.0545 (11)
C16−0.1560 (2)0.5894 (8)0.0600 (2)0.0574 (12)
C17−0.2075 (2)0.4605 (8)0.0214 (3)0.0662 (13)
H17−0.19940.32490.00080.079*
C18−0.2720 (2)0.5386 (8)0.0140 (3)0.0631 (13)
H18−0.30800.4554−0.01200.076*
C19−0.28246 (19)0.7380 (8)0.0449 (2)0.0509 (10)
C20−0.2310 (2)0.8667 (8)0.0847 (2)0.0623 (12)
H20−0.23921.00130.10590.075*
C21−0.1658 (2)0.7874 (9)0.0920 (3)0.0665 (13)
H21−0.12970.86900.11850.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0444 (6)0.0441 (7)0.0734 (8)0.0019 (5)0.0014 (5)−0.0017 (6)
O10.068 (2)0.082 (2)0.0556 (18)0.0010 (16)0.0017 (14)−0.0056 (17)
O20.0633 (19)0.041 (2)0.114 (3)−0.0006 (15)−0.0060 (17)0.0007 (19)
O30.0386 (15)0.053 (2)0.096 (2)0.0042 (13)0.0114 (14)0.0135 (17)
O40.0562 (19)0.106 (3)0.108 (3)0.0247 (18)0.0286 (18)0.052 (2)
O50.0447 (16)0.079 (2)0.082 (2)0.0155 (15)0.0136 (14)0.0340 (19)
O60.0471 (18)0.101 (3)0.091 (2)0.0097 (18)0.0021 (17)−0.007 (2)
O70.082 (2)0.105 (3)0.095 (3)0.027 (2)0.0196 (19)−0.024 (3)
N10.060 (2)0.073 (3)0.059 (2)0.018 (2)0.0138 (19)0.000 (2)
C10.050 (2)0.047 (3)0.054 (2)0.0062 (19)0.0105 (18)0.002 (2)
C20.052 (2)0.047 (3)0.062 (3)−0.0082 (19)0.012 (2)0.003 (2)
C30.043 (2)0.063 (3)0.054 (2)−0.004 (2)0.0146 (18)−0.001 (2)
C40.064 (3)0.078 (4)0.050 (2)−0.004 (2)0.006 (2)0.011 (2)
C50.061 (3)0.057 (3)0.062 (3)−0.006 (2)0.016 (2)0.009 (2)
C60.043 (2)0.034 (2)0.056 (2)0.0020 (16)0.0105 (17)0.0054 (19)
C70.063 (3)0.106 (5)0.070 (3)−0.017 (3)0.003 (2)−0.013 (3)
C80.043 (2)0.045 (3)0.109 (4)0.0012 (19)0.015 (2)0.001 (3)
C90.041 (2)0.047 (3)0.064 (3)0.0016 (17)0.0104 (18)0.005 (2)
C100.050 (2)0.041 (3)0.068 (3)0.0056 (18)0.0142 (19)−0.006 (2)
C110.047 (2)0.059 (3)0.061 (3)−0.0058 (19)0.0077 (19)−0.011 (2)
C120.042 (2)0.063 (3)0.053 (2)0.008 (2)0.0124 (17)0.010 (2)
C130.048 (2)0.042 (3)0.095 (3)0.0063 (19)0.016 (2)−0.008 (2)
C140.050 (2)0.046 (3)0.098 (3)−0.004 (2)0.013 (2)−0.006 (3)
C150.050 (2)0.056 (3)0.057 (2)0.006 (2)0.010 (2)0.012 (2)
C160.047 (2)0.067 (3)0.057 (3)0.008 (2)0.0088 (19)0.019 (2)
C170.059 (3)0.056 (3)0.079 (3)0.014 (2)0.005 (2)−0.014 (3)
C180.045 (2)0.071 (4)0.067 (3)−0.001 (2)−0.001 (2)−0.004 (3)
C190.048 (2)0.054 (3)0.049 (2)0.005 (2)0.0060 (18)0.001 (2)
C200.062 (3)0.059 (3)0.063 (3)0.007 (2)0.007 (2)−0.004 (2)
C210.056 (3)0.069 (4)0.068 (3)−0.005 (2)−0.003 (2)0.000 (3)

Geometric parameters (Å, °)

S1—O21.414 (3)C9—C101.515 (5)
S1—O11.432 (3)C9—C141.517 (6)
S1—O31.571 (3)C9—H90.98
S1—C61.747 (4)C10—C111.520 (5)
O3—C81.471 (5)C10—H10A0.97
O4—C151.184 (5)C10—H10B0.97
O5—C151.353 (5)C11—C121.525 (6)
O5—C161.416 (5)C11—H11A0.97
O6—N11.221 (5)C11—H11B0.97
O7—N11.214 (5)C12—C151.495 (5)
N1—C191.472 (5)C12—C131.523 (6)
C1—C21.383 (5)C12—H120.98
C1—C61.386 (6)C13—C141.523 (5)
C1—H10.93C13—H13A0.97
C2—C31.379 (6)C13—H13B0.97
C2—H20.93C14—H14A0.97
C3—C41.371 (6)C14—H14B0.97
C3—C71.511 (6)C16—C211.362 (6)
C4—C51.399 (6)C16—C171.374 (6)
C4—H40.93C17—C181.386 (6)
C5—C61.373 (5)C17—H170.93
C5—H50.93C18—C191.365 (6)
C7—H7A0.96C18—H180.93
C7—H7B0.96C19—C201.379 (6)
C7—H7C0.96C20—C211.402 (6)
C8—C91.501 (5)C20—H200.93
C8—H8A0.97C21—H210.93
C8—H8B0.97
O2—S1—O1119.4 (2)C11—C10—H10A109.2
O2—S1—O3103.13 (18)C9—C10—H10B109.2
O1—S1—O3109.29 (18)C11—C10—H10B109.2
O2—S1—C6109.87 (18)H10A—C10—H10B107.9
O1—S1—C6109.28 (19)C10—C11—C12110.9 (3)
O3—S1—C6104.74 (18)C10—C11—H11A109.5
C8—O3—S1117.7 (3)C12—C11—H11A109.5
C15—O5—C16118.9 (3)C10—C11—H11B109.5
O7—N1—O6123.9 (4)C12—C11—H11B109.5
O7—N1—C19118.2 (4)H11A—C11—H11B108.0
O6—N1—C19117.9 (4)C15—C12—C13109.5 (3)
C2—C1—C6119.4 (4)C15—C12—C11112.2 (4)
C2—C1—H1120.3C13—C12—C11109.9 (3)
C6—C1—H1120.3C15—C12—H12108.4
C3—C2—C1121.2 (4)C13—C12—H12108.4
C3—C2—H2119.4C11—C12—H12108.4
C1—C2—H2119.4C12—C13—C14111.8 (4)
C4—C3—C2118.6 (4)C12—C13—H13A109.3
C4—C3—C7121.1 (4)C14—C13—H13A109.3
C2—C3—C7120.2 (4)C12—C13—H13B109.3
C3—C4—C5121.4 (4)C14—C13—H13B109.3
C3—C4—H4119.3H13A—C13—H13B107.9
C5—C4—H4119.3C9—C14—C13111.6 (3)
C6—C5—C4118.9 (4)C9—C14—H14A109.3
C6—C5—H5120.5C13—C14—H14A109.3
C4—C5—H5120.5C9—C14—H14B109.3
C5—C6—C1120.4 (4)C13—C14—H14B109.3
C5—C6—S1119.5 (3)H14A—C14—H14B108.0
C1—C6—S1120.1 (3)O4—C15—O5121.4 (4)
C3—C7—H7A109.5O4—C15—C12127.3 (4)
C3—C7—H7B109.5O5—C15—C12111.2 (4)
H7A—C7—H7B109.5C21—C16—C17122.9 (4)
C3—C7—H7C109.5C21—C16—O5117.0 (4)
H7A—C7—H7C109.5C17—C16—O5120.0 (4)
H7B—C7—H7C109.5C16—C17—C18118.0 (5)
O3—C8—C9108.0 (3)C16—C17—H17121.0
O3—C8—H8A110.1C18—C17—H17121.0
C9—C8—H8A110.1C19—C18—C17119.7 (4)
O3—C8—H8B110.1C19—C18—H18120.1
C9—C8—H8B110.1C17—C18—H18120.1
H8A—C8—H8B108.4C18—C19—C20122.6 (4)
C8—C9—C10113.3 (4)C18—C19—N1118.8 (4)
C8—C9—C14109.4 (3)C20—C19—N1118.6 (4)
C10—C9—C14110.1 (3)C19—C20—C21117.6 (5)
C8—C9—H9107.9C19—C20—H20121.2
C10—C9—H9107.9C21—C20—H20121.2
C14—C9—H9107.9C16—C21—C20119.3 (4)
C9—C10—C11112.2 (3)C16—C21—H21120.4
C9—C10—H10A109.2C20—C21—H21120.4

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C5—H5···O7i0.932.493.290 (6)144

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2549).

References

  • Bucourt, R. & Hainaut, D. (1965). Bull. Soc. Chim. Fr.5, 1366–1378.
  • Dunitz, J. D. & Strickler, P. (1966). Helv. Chim. Acta, 49, 290–291.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst.22, 384–387.
  • Gabe, E. J. & White, P. S. (1993). DIFRAC American Crystallographic Association Meeting, Pittsburgh, Abstract PA 104.
  • Koningsveld, H. van & Jansen, J. C. (1984). Acta Cryst. B40, 420–424.
  • Luger, P., Plieth, K. & Ruban, G. (1972). Acta Cryst. B28, 706–710.
  • Sewald, N. & Jakubke, H. D. (2002). Peptides: Chemistry and Biology, 1st ed. Weinheim: Wiley.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography