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Acta Cryst. (2008). E64, o385    [ doi:10.1107/S1600536808000068 ]

trans-4-Nitrophenyl 4-(tosyloxymethyl)cyclohexanecarboxylate

Q.-R. Qi, W.-C. Huang, Z.-H. Mao and H. Zheng

Abstract top

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.

Comment top

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).

Related literature top

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

Experimental top

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 top

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).

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids drawn at the 30% probability level.
trans-4-Nitrophenyl 4-(tosyloxymethyl)cyclohexanecarboxylate top
Crystal data top
C21H23NO7SF000 = 912
Mr = 433.46Dx = 1.362 Mg m−3
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 mm−1
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 top
Enraf–Nonius CAD-4
diffractometer		Rint = 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 top
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 Å−3
272 parametersΔρmin = −0.53 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C21H23NO7SV = 2113.4 (13) Å3
Mr = 433.46Z = 4
Monoclinic, P21/cMo Kα
a = 20.499 (5) ŵ = 0.20 mm−1
b = 6.111 (3) ÅT = 292 (2) K
c = 17.250 (4) Å0.40 × 0.38 × 0.30 mm
β = 102.04 (3)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.004
Absorption correction: none3 standard reflections
4094 measured reflections every 300 reflections
3627 independent reflections intensity decay: 2.1%
1850 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.060272 parameters
wR(F2) = 0.191H-atom parameters constrained
S = 1.06Δρmax = 0.40 e Å−3
3627 reflectionsΔρmin = −0.53 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 > 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) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
references
References top

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.