trans-4-[(Phenyl­sulfon­yloxy)meth­yl]cyclo­hexa­necarboxylic acid

Liang, Y.-F.; Qi, Q.-R.; Zheng, H.

doi:10.1107/S1600536808024513

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1703

doi:10.1107/S1600536808024513

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trans-4-[(Phenylsulfonyloxy)methyl]cyclohexanecarboxylic acid

Yu-Feng Liang,^a Qing-Rong Qi ^a and Hu Zheng ^a ^*

^aDepartment of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: wcums416@yahoo.com.cn

(Received 15 July 2008; accepted 31 July 2008; online 6 August 2008)

The title compound, C₁₄H₁₈O₅S, is an important intermediate for the synthesis of poly(amidoamine) dendrimers. The cyclohexane ring adopts a chair conformation with its two substituents in equatorial positions. In the crystal structure, molecules form centrosymmetric dimers via O—H⋯O hydrogen bonds.

Related literature

For related literature, see: Ahmed et al. (2001 ); Grabchev et al. (2003 ); Wang et al. (2004 ).

Experimental

Crystal data

C₁₄H₁₈O₅S
M_r = 298.34
Monoclinic, P 2₁ /c
a = 17.097 (5) Å
b = 5.960 (3) Å
c = 14.919 (4) Å
β = 107.09 (3)°
V = 1453.2 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 292 (2) K
0.32 × 0.32 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
3702 measured reflections
2691 independent reflections
1323 reflections with I > 2σ(I)
R_int = 0.008
3 standard reflections every 250 reflections intensity decay: 0.9%

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.142
S = 1.00
2691 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O5ⁱ	0.82	1.86	2.677 (3)	174
Symmetry code: (i) -x+1, -y, -z+2.

Data collection: DIFRAC (Gabe & White, 1993 ); cell refinement: DIFRAC; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024513/bt2749sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024513/bt2749Isup2.hkl

checkCIF report

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 periphery of PAMAM dendrimer which aimed to change the physical or chemical properties of PAMAM dendrimers, 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.

The crystal structure shows that molecules are mainly linked by O—H···.O hydrogen bonds and the cyclohexane ring of the title compound exists in the chair conformation.

Related literature top

For related literature, see: Ahmed et al. (2001); Grabchev et al. (2003); 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), benzenesulfonyl chloride (11 mmol) was dropped with vigorous stirring at room temperature, after 1 h the reaction was quenched by addition of water. The organic layer separated was evaporated to give an oil and the oil was hydrolyzed in methanol and aqueous NaOH (11 mmol) solution for 5 h at 323 K. Then the title compound was obtained by acidification with hydrochloride and recrystallized from acetone. Colorless crystals suitable for X-ray analysis were obtained by slow evaporation in cyclohexane and acetone at room temperature.

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

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram of the title compound. Intermolecular hydrogen bonds are shown as dashed lines.

trans-4-[(Phenylsulfonyloxy)methyl]cyclohexanecarboxylic acid top

Crystal data top

C₁₄H₁₈O₅S	F(000) = 632
M_r = 298.34	D_x = 1.364 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.097 (5) Å	Cell parameters from 24 reflections
b = 5.960 (3) Å	θ = 4.4–8.7°
c = 14.919 (4) Å	µ = 0.24 mm⁻¹
β = 107.09 (3)°	T = 292 K
V = 1453.2 (10) Å³	Block, colourless
Z = 4	0.32 × 0.32 × 0.13 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 1.3°
Graphite monochromator	h = −2→20
ω/2θ scans	k = −7→0
3702 measured reflections	l = −18→17
2691 independent reflections	3 standard reflections every 250 reflections
1323 reflections with I > 2σ(I)	intensity decay: 0.9%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.0729P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2691 reflections	Δρ_max = 0.27 e Å⁻³
183 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0076 (16)

Crystal data top

C₁₄H₁₈O₅S	V = 1453.2 (10) Å³
M_r = 298.34	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.097 (5) Å	µ = 0.24 mm⁻¹
b = 5.960 (3) Å	T = 292 K
c = 14.919 (4) Å	0.32 × 0.32 × 0.13 mm
β = 107.09 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
3702 measured reflections	3 standard reflections every 250 reflections
2691 independent reflections	intensity decay: 0.9%
1323 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.00	Δρ_max = 0.27 e Å⁻³
2691 reflections	Δρ_min = −0.25 e Å⁻³
183 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.15478 (7)	0.60525 (16)	0.42320 (6)	0.0631 (4)
O1	0.15724 (19)	0.8419 (4)	0.42806 (17)	0.0942 (11)
O2	0.10478 (16)	0.4829 (4)	0.46844 (17)	0.0782 (8)
O3	0.24614 (15)	0.5294 (4)	0.46482 (16)	0.0705 (8)
O4	0.4357 (2)	−0.1520 (5)	0.8999 (2)	0.1010 (11)
H4	0.4645	−0.1623	0.9545	0.151*
O5	0.46270 (19)	0.2062 (5)	0.92678 (18)	0.0973 (11)
C1	0.0928 (2)	0.3172 (6)	0.2785 (2)	0.0558 (10)
H1	0.0855	0.2167	0.3231	0.067*
C2	0.0687 (2)	0.2625 (7)	0.1846 (3)	0.0694 (12)
H2	0.0457	0.1227	0.1654	0.083*
C3	0.0785 (3)	0.4130 (9)	0.1199 (3)	0.0786 (14)
H3	0.0615	0.3752	0.0567	0.094*
C4	0.1127 (3)	0.6184 (9)	0.1467 (3)	0.0807 (13)
H4A	0.1184	0.7202	0.1017	0.097*
C5	0.1386 (2)	0.6739 (6)	0.2393 (2)	0.0636 (11)
H5	0.1632	0.8122	0.2579	0.076*
C6	0.12814 (18)	0.5243 (5)	0.3051 (2)	0.0434 (9)
C7	0.2647 (2)	0.2958 (6)	0.4899 (2)	0.0634 (11)
H7A	0.2877	0.2257	0.4447	0.076*
H7B	0.2147	0.2168	0.4885	0.076*
C8	0.3248 (2)	0.2787 (6)	0.5868 (2)	0.0543 (10)
H8	0.3740	0.3632	0.5870	0.065*
C9	0.2910 (2)	0.3764 (6)	0.6619 (2)	0.0560 (10)
H9A	0.2390	0.3056	0.6579	0.067*
H9B	0.2812	0.5356	0.6504	0.067*
C10	0.3488 (2)	0.3433 (6)	0.7602 (2)	0.0595 (11)
H10A	0.3985	0.4287	0.7669	0.071*
H10B	0.3232	0.3991	0.8058	0.071*
C11	0.3702 (2)	0.0971 (6)	0.7794 (2)	0.0540 (10)
H11	0.3193	0.0165	0.7753	0.065*
C12	0.4053 (2)	−0.0003 (6)	0.7056 (2)	0.0685 (12)
H12A	0.4147	−0.1597	0.7169	0.082*
H12B	0.4577	0.0699	0.7109	0.082*
C13	0.3484 (2)	0.0350 (6)	0.6063 (2)	0.0688 (12)
H13A	0.3754	−0.0171	0.5614	0.083*
H13B	0.2993	−0.0540	0.5981	0.083*
C14	0.4275 (2)	0.0573 (7)	0.8757 (3)	0.0637 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0904 (8)	0.0477 (6)	0.0373 (5)	0.0035 (6)	−0.0028 (5)	−0.0010 (5)
O1	0.152 (3)	0.0478 (16)	0.0584 (17)	0.0040 (17)	−0.0069 (17)	−0.0068 (14)
O2	0.103 (2)	0.0828 (19)	0.0552 (16)	0.0009 (16)	0.0327 (15)	0.0129 (15)
O3	0.0844 (18)	0.0586 (15)	0.0488 (15)	−0.0147 (13)	−0.0111 (13)	0.0161 (12)
O4	0.129 (3)	0.0696 (19)	0.0663 (19)	−0.0009 (17)	−0.0307 (17)	0.0240 (15)
O5	0.125 (3)	0.0689 (18)	0.0601 (18)	−0.0064 (17)	−0.0309 (17)	0.0143 (15)
C1	0.060 (2)	0.053 (2)	0.049 (2)	−0.0035 (18)	0.0074 (18)	0.0019 (18)
C2	0.062 (2)	0.065 (3)	0.065 (3)	0.005 (2)	−0.006 (2)	−0.022 (2)
C3	0.086 (3)	0.104 (4)	0.034 (2)	0.034 (3)	−0.001 (2)	−0.006 (3)
C4	0.105 (3)	0.091 (3)	0.046 (2)	0.020 (3)	0.023 (2)	0.023 (3)
C5	0.077 (3)	0.058 (2)	0.051 (2)	0.004 (2)	0.012 (2)	0.014 (2)
C6	0.049 (2)	0.0432 (19)	0.0327 (18)	0.0033 (16)	0.0031 (15)	0.0025 (15)
C7	0.078 (3)	0.055 (2)	0.046 (2)	0.006 (2)	0.0014 (19)	0.0017 (19)
C8	0.057 (2)	0.053 (2)	0.044 (2)	0.0011 (17)	0.0010 (18)	0.0034 (18)
C9	0.060 (2)	0.054 (2)	0.046 (2)	0.0115 (18)	0.0023 (17)	0.0113 (19)
C10	0.068 (2)	0.064 (2)	0.0378 (19)	0.010 (2)	0.0006 (17)	0.0036 (18)
C11	0.051 (2)	0.057 (2)	0.045 (2)	0.0009 (18)	0.0007 (17)	0.0120 (19)
C12	0.072 (2)	0.063 (2)	0.058 (2)	0.017 (2)	0.000 (2)	0.009 (2)
C13	0.078 (3)	0.067 (3)	0.048 (2)	0.020 (2)	−0.003 (2)	−0.0003 (18)
C14	0.060 (2)	0.066 (3)	0.056 (2)	0.004 (2)	0.0020 (19)	0.020 (2)

Geometric parameters (Å, º) top

S1—O1	1.412 (3)	C7—H7A	0.9700
S1—O2	1.434 (3)	C7—H7B	0.9700
S1—O3	1.568 (3)	C8—C13	1.513 (5)
S1—C6	1.754 (3)	C8—C9	1.521 (5)
O3—C7	1.453 (4)	C8—H8	0.9800
O4—C14	1.295 (4)	C9—C10	1.521 (4)
O4—H4	0.8200	C9—H9A	0.9700
O5—C14	1.209 (4)	C9—H9B	0.9700
C1—C2	1.378 (5)	C10—C11	1.519 (4)
C1—C6	1.380 (4)	C10—H10A	0.9700
C1—H1	0.9300	C10—H10B	0.9700
C2—C3	1.364 (6)	C11—C14	1.501 (4)
C2—H2	0.9300	C11—C12	1.516 (5)
C3—C4	1.365 (6)	C11—H11	0.9800
C3—H3	0.9300	C12—C13	1.529 (4)
C4—C5	1.362 (5)	C12—H12A	0.9700
C4—H4A	0.9300	C12—H12B	0.9700
C5—C6	1.376 (4)	C13—H13A	0.9700
C5—H5	0.9300	C13—H13B	0.9700
C7—C8	1.510 (4)

O1—S1—O2	119.8 (2)	C13—C8—H8	108.2
O1—S1—O3	104.85 (16)	C9—C8—H8	108.2
O2—S1—O3	109.22 (15)	C8—C9—C10	112.4 (3)
O1—S1—C6	108.74 (16)	C8—C9—H9A	109.1
O2—S1—C6	108.57 (16)	C10—C9—H9A	109.1
O3—S1—C6	104.66 (16)	C8—C9—H9B	109.1
C7—O3—S1	119.6 (2)	C10—C9—H9B	109.1
C14—O4—H4	109.5	H9A—C9—H9B	107.9
C2—C1—C6	118.6 (4)	C11—C10—C9	111.1 (3)
C2—C1—H1	120.7	C11—C10—H10A	109.4
C6—C1—H1	120.7	C9—C10—H10A	109.4
C3—C2—C1	120.1 (4)	C11—C10—H10B	109.4
C3—C2—H2	119.9	C9—C10—H10B	109.4
C1—C2—H2	119.9	H10A—C10—H10B	108.0
C2—C3—C4	120.9 (4)	C14—C11—C12	110.4 (3)
C2—C3—H3	119.5	C14—C11—C10	112.7 (3)
C4—C3—H3	119.5	C12—C11—C10	110.9 (3)
C5—C4—C3	119.9 (4)	C14—C11—H11	107.5
C5—C4—H4A	120.1	C12—C11—H11	107.5
C3—C4—H4A	120.1	C10—C11—H11	107.5
C4—C5—C6	119.6 (4)	C11—C12—C13	112.1 (3)
C4—C5—H5	120.2	C11—C12—H12A	109.2
C6—C5—H5	120.2	C13—C12—H12A	109.2
C5—C6—C1	120.8 (3)	C11—C12—H12B	109.2
C5—C6—S1	119.3 (3)	C13—C12—H12B	109.2
C1—C6—S1	119.8 (3)	H12A—C12—H12B	107.9
O3—C7—C8	110.3 (3)	C8—C13—C12	112.1 (3)
O3—C7—H7A	109.6	C8—C13—H13A	109.2
C8—C7—H7A	109.6	C12—C13—H13A	109.2
O3—C7—H7B	109.6	C8—C13—H13B	109.2
C8—C7—H7B	109.6	C12—C13—H13B	109.2
H7A—C7—H7B	108.1	H13A—C13—H13B	107.9
C7—C8—C13	108.5 (3)	O5—C14—O4	122.6 (3)
C7—C8—C9	112.4 (3)	O5—C14—C11	123.5 (3)
C13—C8—C9	111.3 (3)	O4—C14—C11	113.9 (3)
C7—C8—H8	108.2

O1—S1—O3—C7	166.4 (3)	S1—O3—C7—C8	−132.0 (3)
O2—S1—O3—C7	36.9 (3)	O3—C7—C8—C13	−174.7 (3)
C6—S1—O3—C7	−79.2 (3)	O3—C7—C8—C9	61.8 (4)
C6—C1—C2—C3	−1.2 (5)	C7—C8—C9—C10	175.6 (3)
C1—C2—C3—C4	0.6 (6)	C13—C8—C9—C10	53.7 (4)
C2—C3—C4—C5	0.8 (6)	C8—C9—C10—C11	−55.3 (4)
C3—C4—C5—C6	−1.6 (6)	C9—C10—C11—C14	179.8 (3)
C4—C5—C6—C1	1.0 (5)	C9—C10—C11—C12	55.4 (4)
C4—C5—C6—S1	−175.4 (3)	C14—C11—C12—C13	179.5 (3)
C2—C1—C6—C5	0.4 (5)	C10—C11—C12—C13	−54.7 (4)
C2—C1—C6—S1	176.7 (3)	C7—C8—C13—C12	−176.5 (3)
O1—S1—C6—C5	20.1 (3)	C9—C8—C13—C12	−52.4 (4)
O2—S1—C6—C5	151.9 (3)	C11—C12—C13—C8	53.6 (5)
O3—S1—C6—C5	−91.5 (3)	C12—C11—C14—O5	113.9 (5)
O1—S1—C6—C1	−156.3 (3)	C10—C11—C14—O5	−10.8 (6)
O2—S1—C6—C1	−24.4 (3)	C12—C11—C14—O4	−66.6 (5)
O3—S1—C6—C1	92.1 (3)	C10—C11—C14—O4	168.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5ⁱ	0.82	1.86	2.677 (3)	174

Symmetry code: (i) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈O₅S
M_r	298.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	17.097 (5), 5.960 (3), 14.919 (4)
β (°)	107.09 (3)
V (Å³)	1453.2 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.32 × 0.32 × 0.13

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3702, 2691, 1323
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.607

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.143, 1.00
No. of reflections	2691
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.25

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5ⁱ	0.82	1.86	2.677 (3)	173.7

Symmetry code: (i) −x+1, −y, −z+2.

References

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Volume 64| Part 9| September 2008| Page o1703

doi:10.1107/S1600536808024513

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