supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

wn2233 scheme

Acta Cryst. (2008). E64, o405    [ doi:10.1107/S1600536807068572 ]

trans-4-(Tosyloxymethyl)cyclohexanecarboxylic acid

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

Abstract top

The title compound, C15H20O5S, is an intermediate in the synthesis of a new type of poly(amidoamine) (PAMAM) dendrimer. The cyclohexane ring exhibits a chair conformation, with C-C bond lengths in the range 1.518 (3)-1.531 (3) Å and C-C-C angles in the range 110.45 (19)-112.09 (19)°; these agree well with the values in other cyclohexane derivatives described in the literature. In the crystal structure, adjacent molecules are linked by O-H...·O hydrogen bonds. The H atoms of the methyl group are disordered equally over two positions.

Comment top

PAMAM (poly(amidoamine)) dendrimers have attracted much interest for their symmetry, high degree of branching and high density of terminal functional groups, which can participate in different reactions. The modification of the periphery of PAMAM dendrimers, aimed to change their physical or chemical properties, have been reported recently (Grabchev et al.,2003; Ahmed et al.,2001; Wang et al.,2004). To improve the lipophilicity of PAMAM dendrimers and provide a new type of linker with special stereostructure, a series of cyclohexane derivatives were synthesized. In our synthetic work on PAMAM dendrimers, we obtained the title compound, and report here its crystal structure.

The crystal structure shows that molecules are linked by O—H···.O hydrogen bonds and the cyclohexane ring exists in the chair conformation. The mean C—C bond length of the cyclohexane ring is 1.524 (3) Å, which is close to the value in trans-1,4-cyclohexane dicarboxylic acid (1.523 (3) Å; Luger et al., 1972). The mean endocyclic angle is 111.3 (2)°, which is close to the value for an ideal cyclohexane ring, (C—C—C 111.1°; Bucourt & Hainaut, 1965) and the mean value in trans-1,4-cyclohexanedicarboxylic acid (111.4 (4)°; Dunitz & Strickler, 1966; Luger et al., 1972).

Related literature top

For related literature, see: Ahmed et al. (2001); Bucourt & Hainaut (1965); Dunitz & Strickler (1966); Grabchev et al. (2003); Luger et al. (1972); Wang et al. (2004).

Experimental top

trans-4-(Methoxycarbonyl)cyclohexanemethanol (10 mmol), triethylamine (10 mmol) and a small amount of trimethylamine hydrochloride were suspended in dichloromethane (20 ml), and p-toluenesulfonyl chloride (11 mmol) was added dropwise with vigorous stirring at room temperature; after 1 h the reaction was quenched by addition of water. The organic layer which separated was evaporated to give an oil and the oil was hydrolyzed in a methanol and aqueous NaOH (11 mmol) solution for 5 h at 323 K. The title compound was then obtained by acidification with hydrochloric acid and recrystallized from acetone. Colorless crystals suitable for X-ray analysis were obtained by slow evaporation of a cyclohexane and acetone solution at room temperature.

Refinement top

The carboxyl H was located in a difference Fourier map and refined freely to an O—H value of 0.89 (4) Å. The other H atoms were placed in calculated positions and refined in the riding model approximation, with C—H = 0.93, 0.96, 0.97, or 0.98 Å for benzene, methyl, methylene or methine H atoms, respectively. For carbon-bound H atoms, Uiso(H) = 1.2Ueq(C). The H atoms of the methyl group are disordered equally over two positions.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 20% probability level.
[Figure 2] Fig. 2. A packing diagram of the title compound. Intermolecular hydrogen bonds are shown as dashed lines.
trans-4-(Tosyloxymethyl)cyclohexanecarboxylic acid top
Crystal data top
C15H20O5SZ = 2
Mr = 312.37F000 = 332
Triclinic, P1Dx = 1.326 Mg m−3
a = 5.9006 (5) ÅMo Kα radiation
λ = 0.71073 Å
b = 7.0880 (9) ÅCell parameters from 5250 reflections
c = 20.2754 (18) Åθ = 3.1–27.5º
α = 90.371 (3)ºµ = 0.23 mm−1
β = 97.479 (2)ºT = 293 (2) K
γ = 111.222 (2)ºBlock, colourless
V = 782.44 (14) Å30.53 × 0.48 × 0.12 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3562 independent reflections
Radiation source: Rotating Anode2442 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 293(2) Kθmax = 27.5º
ω scansθmin = 3.1º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −6→7
Tmin = 0.890, Tmax = 0.974k = −9→9
7685 measured reflectionsl = −26→26
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.044  w = 1/[σ2(Fo2) + (0.1018P)2 + 0.285P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.179(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.30 e Å−3
3562 reflectionsΔρmin = −0.48 e Å−3
195 parametersExtinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.047 (7)
Secondary atom site location: difference Fourier map
Crystal data top
C15H20O5Sγ = 111.222 (2)º
Mr = 312.37V = 782.44 (14) Å3
Triclinic, P1Z = 2
a = 5.9006 (5) ÅMo Kα
b = 7.0880 (9) ŵ = 0.23 mm−1
c = 20.2754 (18) ÅT = 293 (2) K
α = 90.371 (3)º0.53 × 0.48 × 0.12 mm
β = 97.479 (2)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3562 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2442 reflections with I > 2σ(I)
Tmin = 0.890, Tmax = 0.974Rint = 0.024
7685 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044195 parameters
wR(F2) = 0.179H atoms treated by a mixture of
independent and constrained refinement
S = 1.01Δρmax = 0.30 e Å−3
3562 reflectionsΔρmin = −0.48 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*/UeqOcc. (<1)
S10.95047 (11)0.96589 (9)0.20554 (3)0.0486 (2)
O10.8978 (3)0.9010 (3)0.27746 (8)0.0470 (4)
O20.8958 (4)1.1432 (3)0.19236 (10)0.0610 (5)
O31.1925 (3)0.9708 (3)0.20334 (10)0.0655 (5)
O4−0.1018 (4)0.1728 (3)0.44904 (11)0.0642 (6)
O50.2394 (4)0.1042 (3)0.46193 (10)0.0624 (5)
C10.5304 (5)0.5148 (3)0.31242 (13)0.0497 (6)
H1A0.40910.48970.27290.060*
H1B0.68010.51060.29880.060*
C20.4366 (5)0.3497 (4)0.36070 (13)0.0518 (6)
H2A0.39810.21810.33830.062*
H2B0.56460.36660.39800.062*
C30.2093 (4)0.3565 (3)0.38646 (11)0.0431 (5)
H30.07900.32900.34840.052*
C40.2559 (5)0.5666 (3)0.41785 (12)0.0486 (6)
H4A0.10410.56990.43030.058*
H4B0.37420.59240.45800.058*
C50.3526 (5)0.7314 (4)0.36991 (13)0.0514 (6)
H5A0.39150.86290.39240.062*
H5B0.22550.71540.33250.062*
C60.5811 (4)0.7245 (3)0.34417 (11)0.0408 (5)
H60.71220.75160.38200.049*
C70.1191 (4)0.1984 (3)0.43585 (11)0.0425 (5)
C80.6621 (4)0.8906 (3)0.29618 (12)0.0436 (5)
H8A0.53990.86200.25680.052*
H8B0.67941.01950.31710.052*
C90.7391 (4)0.7608 (4)0.15427 (12)0.0478 (6)
C100.7786 (5)0.5806 (4)0.15077 (14)0.0583 (7)
H100.92180.57120.17310.070*
C110.6055 (6)0.4147 (5)0.11411 (15)0.0655 (8)
H110.63340.29400.11160.079*
C120.3903 (6)0.4259 (5)0.08091 (14)0.0629 (7)
C130.3540 (5)0.6067 (5)0.08475 (15)0.0657 (8)
H130.21060.61580.06240.079*
C140.5257 (5)0.7752 (4)0.12102 (14)0.0581 (7)
H140.49850.89630.12310.070*
C150.1990 (7)0.2410 (6)0.04226 (17)0.0855 (11)
H15A0.25580.13000.04510.103*0.50
H15B0.17160.2706−0.00360.103*0.50
H15C0.04810.20510.06080.103*0.50
H15D0.06120.27380.02310.103*0.50
H15E0.14540.13320.07170.103*0.50
H15F0.26890.19870.00740.103*0.50
H4O−0.145 (6)0.081 (5)0.4795 (18)0.085 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0436 (4)0.0492 (4)0.0561 (4)0.0181 (3)0.0138 (3)0.0168 (3)
O10.0410 (8)0.0506 (9)0.0490 (9)0.0158 (7)0.0070 (7)0.0125 (7)
O20.0630 (12)0.0484 (10)0.0761 (12)0.0226 (9)0.0186 (10)0.0222 (9)
O30.0395 (9)0.0834 (14)0.0793 (13)0.0239 (9)0.0234 (9)0.0198 (10)
O40.0575 (11)0.0653 (12)0.0795 (13)0.0268 (10)0.0295 (10)0.0342 (10)
O50.0615 (11)0.0614 (11)0.0751 (12)0.0295 (9)0.0257 (10)0.0298 (9)
C10.0605 (15)0.0417 (12)0.0521 (13)0.0198 (11)0.0224 (11)0.0060 (10)
C20.0639 (15)0.0373 (12)0.0632 (15)0.0235 (11)0.0254 (12)0.0101 (10)
C30.0470 (12)0.0366 (11)0.0454 (12)0.0136 (9)0.0107 (10)0.0065 (9)
C40.0595 (14)0.0382 (12)0.0528 (13)0.0191 (11)0.0206 (11)0.0057 (10)
C50.0641 (15)0.0374 (12)0.0616 (14)0.0237 (11)0.0246 (12)0.0111 (10)
C60.0454 (12)0.0363 (11)0.0419 (11)0.0149 (9)0.0104 (9)0.0093 (8)
C70.0440 (12)0.0367 (11)0.0474 (12)0.0138 (9)0.0117 (10)0.0049 (9)
C80.0446 (12)0.0401 (11)0.0502 (12)0.0178 (10)0.0143 (10)0.0119 (9)
C90.0486 (13)0.0572 (14)0.0464 (12)0.0277 (11)0.0131 (10)0.0120 (10)
C100.0613 (16)0.0627 (16)0.0602 (15)0.0345 (13)0.0065 (13)0.0108 (12)
C110.085 (2)0.0545 (16)0.0618 (16)0.0309 (15)0.0104 (15)0.0065 (12)
C120.0669 (18)0.0685 (18)0.0484 (14)0.0174 (14)0.0123 (13)0.0065 (12)
C130.0554 (16)0.085 (2)0.0592 (16)0.0309 (15)−0.0002 (13)0.0036 (14)
C140.0601 (16)0.0658 (17)0.0585 (15)0.0349 (13)0.0078 (12)0.0094 (12)
C150.087 (2)0.082 (2)0.0660 (19)0.0063 (18)0.0072 (17)−0.0036 (16)
Geometric parameters (Å, °) top
S1—O31.4226 (18)C5—H5B0.9700
S1—O21.4250 (19)C6—C81.513 (3)
S1—O11.5678 (17)C6—H60.9800
S1—C91.755 (3)C8—H8A0.9700
O1—C81.465 (3)C8—H8B0.9700
O4—C71.313 (3)C9—C101.382 (4)
O4—H4O0.89 (4)C9—C141.387 (4)
O5—C71.216 (3)C10—C111.378 (4)
C1—C21.524 (3)C10—H100.9300
C1—C61.525 (3)C11—C121.387 (4)
C1—H1A0.9700C11—H110.9300
C1—H1B0.9700C12—C131.377 (4)
C2—C31.518 (3)C12—C151.514 (4)
C2—H2A0.9700C13—C141.383 (4)
C2—H2B0.9700C13—H130.9300
C3—C71.505 (3)C14—H140.9300
C3—C41.531 (3)C15—H15A0.9600
C3—H30.9800C15—H15B0.9600
C4—C51.520 (3)C15—H15C0.9600
C4—H4A0.9700C15—H15D0.9600
C4—H4B0.9700C15—H15E0.9600
C5—C61.525 (3)C15—H15F0.9600
C5—H5A0.9700
O3—S1—O2119.63 (12)O4—C7—C3113.7 (2)
O3—S1—O1104.45 (11)O1—C8—C6108.88 (18)
O2—S1—O1109.39 (11)O1—C8—H8A109.9
O3—S1—C9109.50 (12)C6—C8—H8A109.9
O2—S1—C9109.39 (12)O1—C8—H8B109.9
O1—S1—C9103.13 (10)C6—C8—H8B109.9
C8—O1—S1117.51 (13)H8A—C8—H8B108.3
C7—O4—H4O110 (2)C10—C9—C14120.2 (3)
C2—C1—C6111.4 (2)C10—C9—S1119.55 (19)
C2—C1—H1A109.4C14—C9—S1120.1 (2)
C6—C1—H1A109.4C11—C10—C9119.9 (2)
C2—C1—H1B109.4C11—C10—H10120.1
C6—C1—H1B109.4C9—C10—H10120.1
H1A—C1—H1B108.0C10—C11—C12120.7 (3)
C3—C2—C1111.5 (2)C10—C11—H11119.6
C3—C2—H2A109.3C12—C11—H11119.6
C1—C2—H2A109.3C13—C12—C11118.7 (3)
C3—C2—H2B109.3C13—C12—C15121.2 (3)
C1—C2—H2B109.3C11—C12—C15120.1 (3)
H2A—C2—H2B108.0C12—C13—C14121.6 (3)
C7—C3—C2112.18 (19)C12—C13—H13119.2
C7—C3—C4109.70 (19)C14—C13—H13119.2
C2—C3—C4111.24 (19)C13—C14—C9118.9 (3)
C7—C3—H3107.8C13—C14—H14120.5
C2—C3—H3107.8C9—C14—H14120.5
C4—C3—H3107.8C12—C15—H15A109.5
C5—C4—C3111.32 (19)C12—C15—H15B109.5
C5—C4—H4A109.4H15A—C15—H15B109.5
C3—C4—H4A109.4C12—C15—H15C109.5
C5—C4—H4B109.4H15A—C15—H15C109.5
C3—C4—H4B109.4H15B—C15—H15C109.5
H4A—C4—H4B108.0C12—C15—H15D109.5
C4—C5—C6112.09 (19)H15A—C15—H15D141.1
C4—C5—H5A109.2H15B—C15—H15D56.3
C6—C5—H5A109.2H15C—C15—H15D56.3
C4—C5—H5B109.2C12—C15—H15E109.5
C6—C5—H5B109.2H15A—C15—H15E56.3
H5A—C5—H5B107.9H15B—C15—H15E141.1
C8—C6—C5108.55 (18)H15C—C15—H15E56.3
C8—C6—C1112.53 (19)H15D—C15—H15E109.5
C5—C6—C1110.45 (19)C12—C15—H15F109.5
C8—C6—H6108.4H15A—C15—H15F56.3
C5—C6—H6108.4H15B—C15—H15F56.3
C1—C6—H6108.4H15C—C15—H15F141.1
O5—C7—O4122.8 (2)H15D—C15—H15F109.5
O5—C7—C3123.5 (2)H15E—C15—H15F109.5
O3—S1—O1—C8177.44 (16)C5—C6—C8—O1173.23 (17)
O2—S1—O1—C848.24 (18)C1—C6—C8—O1−64.2 (3)
C9—S1—O1—C8−68.10 (17)O3—S1—C9—C1037.0 (2)
C6—C1—C2—C356.1 (3)O2—S1—C9—C10169.9 (2)
C1—C2—C3—C7−178.2 (2)O1—S1—C9—C10−73.7 (2)
C1—C2—C3—C4−54.9 (3)O3—S1—C9—C14−147.2 (2)
C7—C3—C4—C5178.8 (2)O2—S1—C9—C14−14.3 (3)
C2—C3—C4—C554.1 (3)O1—S1—C9—C14102.0 (2)
C3—C4—C5—C6−54.7 (3)C14—C9—C10—C110.0 (4)
C4—C5—C6—C8179.1 (2)S1—C9—C10—C11175.7 (2)
C4—C5—C6—C155.3 (3)C9—C10—C11—C12−0.5 (4)
C2—C1—C6—C8−177.1 (2)C10—C11—C12—C130.7 (5)
C2—C1—C6—C5−55.6 (3)C10—C11—C12—C15−178.4 (3)
C2—C3—C7—O513.6 (3)C11—C12—C13—C14−0.4 (5)
C4—C3—C7—O5−110.5 (3)C15—C12—C13—C14178.7 (3)
C2—C3—C7—O4−167.2 (2)C12—C13—C14—C9−0.1 (4)
C4—C3—C7—O468.6 (3)C10—C9—C14—C130.2 (4)
S1—O1—C8—C6147.88 (16)S1—C9—C14—C13−175.4 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4O···O5i0.89 (4)1.76 (4)2.654 (3)178 (3)
Symmetry codes: (i) −x, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4O···O5i0.89 (4)1.76 (4)2.654 (3)178 (3)
Symmetry codes: (i) −x, −y, −z+1.
Acknowledgements top

The authors thank Mr Kai-Bei Yu of the Chengdu Branch of the Chinese Academy of Science for the X-ray measurements.

references
References top

Ahmed, S. M., Budd, P. M., McKeown, N. B., Evans, K. P., Beaumont, G. L., Donaldson, C. & Brennan, C. M. (2001). Polymer, 42, 889–896.

Bucourt, R. & Hainaut, D. (1965). Bull. Soc. Chim. Fr. 5, 1366–1378.

Dunitz, J. D. & Strickler, P. (1966). Helv. Chim. Acta, 49, 290–291.

Grabchev, I., Chovelon, J. M., Bojinov, V. & Ivanova, G. (2003). Tetrahedron, 59, 9591–9598.

Higashi, T. (1995). ABSCOR. Rigaku Corporation,Tokyo, Japan.

Koningsveld, H. van & Jansen, J. C. (1984). Acta Cryst. B40, 420–424. [Reference not cited - may it be removed?]

Luger, P., Plieth, K. & Ruban, G. (1972). Acta Cryst. B28, 706–710.

Rigaku (2004). RAPID-AUTO. Version 3.0. Rigaku Corporation, Tokyo, Japan.

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

Sheldrick, G. M. (1997b). SHELXTL. Version 5.0. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Wang, B.-B., Zhang, X., Jia, X.-R., Luo, Y.-F., Sun, Z., Yang, L., Ji, Y. & Wei, Y. (2004). Polymer, 45, 8395–8402.