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

Abstract

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,

• a = 17.097 (5) Å

• b = 5.960 (3) Å

• c = 14.919 (4) Å

• β = 107.09 (3)°

• V = 1453.2 (10) ų

• 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[F ² > 2σ(F ²)] = 0.054

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically (C—H = 0.93–0.98 Å, O—H = 0.82 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C,O).

Figures

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.

Crystal data

C14H18O5S	F000 = 632
Mr = 298.34	Dx = 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 = 4.4–8.7º
c = 14.919 (4) Å	µ = 0.24 mm−1
β = 107.09 (3)º	T = 292 (2) K
V = 1453.2 (10) Å3	Block, colourless
Z = 4	0.32 × 0.32 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.008
Radiation source: fine-focus sealed tube	θmax = 25.5º
Monochromator: graphite	θmin = 1.3º
T = 292(2) K	h = −2→20
ω/2θ scans	k = −7→0
Absorption correction: none	l = −18→17
3702 measured reflections	3 standard reflections
2691 independent reflections	every 250 reflections
1323 reflections with I > 2σ(I)	intensity decay: 0.9%

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.054	w = 1/[σ2(Fo2) + (0.0729P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.143	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.27 e Å−3
2691 reflections	Δρmin = −0.25 e Å−3
183 parameters	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)
Secondary atom site location: difference Fourier map

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) −x+1, −y, −z+2.