2-[(1R*,4R*)-1,4-Dihy­dr­oxy­cyclo­hex­yl]acetic acid

The title compound, C₈H₁₄O₄, is an isolation product of the aerial parts of Senecio desfontanei. The acetic acid group is oriented at a dihedral angle of 48.03 (9)° with respect to the basal plane of the cyclo­hexane-1,4-diol chair. An intra­molecular O—H⋯O hydrogen bond generates an S(6) ring with an envelope conformation. In the crystal, mol­ecules are linked by O—H⋯O hydrogen bonds, resulting in R₃³(20) ring motifs and C(2) O—H⋯O—H⋯O—H⋯ chains. Overall, a three-dimensional polymeric network arises. A C—H⋯O contact is also present.

Related literature

For related structures, see: Jasinski et al. (2009); Vasudev et al. (2008). For graph-set notation, see: Bernstein et al. (1995).

Experimental

Crystal data

• C₈H₁₄O₄

• M_r = 174.19

• Triclinic, P 1

• a = 5.7301 (4) Å

• b = 6.3493 (3) Å

• c = 6.4964 (4) Å

• α = 92.863 (2)°

• β = 97.223 (1)°

• γ = 108.258 (2)°

• V = 221.67 (2) ų

• Z = 1

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 296 K

• 0.28 × 0.12 × 0.10 mm

Data collection

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005) T_min = 0.935, T_max = 0.965

• 3664 measured reflections

• 1092 independent reflections

• 932 reflections with I > 2σ(I)

• R_int = 0.025

Refinement

• R[F² > 2σ(F²)] = 0.037

• wR(F²) = 0.091

• S = 1.07

• 1092 reflections

• 118 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.22 e Å⁻³

• Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3^i	0.83 (3)	1.78 (3)	2.608 (3)	177 (3)
O3—H3⋯O4^ii	0.86 (3)	1.90 (3)	2.756 (2)	175 (3)
O4—H4⋯O1^iii	0.83 (3)	2.39 (3)	3.007 (3)	131 (3)
O4—H4⋯O2	0.83 (3)	2.20 (3)	2.789 (3)	128 (3)
C5—H5A⋯O1^iv	0.97	2.60	3.511 (3)	157
Symmetry codes: (i) x-1, y-1, z-1; (ii) x, y, z+1; (iii) x+1, y, z; (iv) x+1, y, z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON.

Supporting information

S1. Comment

The crystal structure of (1-(aminomethyl)cyclohexane)acetic acid hydrochloride hemihydrate (Jasinski et al., 2009) and 1-ammoniocyclohexaneacetic acid chloride monohydrate (Vasudev et al., 2008) have been published which are related to the title compound (I, Fig. 1).

In (I), there are cyclohexane-1,4-diol and acetic acid moieties. The basal plane of cyclohexane A (C4,C5,C7,C8) and the acetic acid moiety B (O1/C1/C2/O2) are planar with r. m. s. deviation of 0.0022 and 0.0016 Å, respectively. The dihedral angle between A/B is 48.03 (9)°. The hydroxy atoms O3 and O4 are at a distance of 2.0320 (26) and -2.0535 (23) Å respectively, from the basal plane whereas the C-atoms C3 and C6 are at a distance of -0.6862 (29) and -0.6195 (23) Å respectively, from it. There exist an intra molecular H-bonding of O—H···O type (Table 1, Fig. 2) forming an S(6) and R₃³(20) ring motifs (Bernstein et al., 1995). The molecules are stabilized in the form of three dimensional polymeric network with O—H···O—H···O—H··· chains (Fig. 2).

Related literature

For related structures, see: Jasinski et al. (2009); Vasudev et al. (2008). For graph-set notation, see: Bernstein et al. (1995).

S2. Experimental

The air dried and pulverized aerial parts of Senecio desfontanei (12 kg), collected from Kaghan, KPK, Pakistan, in July 2008, were subjected to cold extraction with methanol (MeOH) in percolator. The MeOH extract was concentrated in vacuo to give dark greenish crude extract (300 g) which was then suspended in distilled water and successively partitioned with n-hexane, dichloromethane (DCM), ethyl acetate (EtOAc). The EtOAc fraction (90 g) was subjected to column chromatography (CC) on silica gel and n-hexane: EtOAc (100:0 → 0:100) as eluting system. This resulted in total of 20 subfractions i.e. 1 A-20 A compiled on the basis of TLC profiles. Subfraction 12 A was resubjected to CC on silica gel and eluted with n-hexane: EtOAc (20:80) yielding a crystalline compound containing minor impurities. The impurity was washed off with DCM. Transparent needles of the title compound were obtained by recrystallization using a mixture of EtOAc:MeOH (85:15).

S3. Refinement

In the absence of significant anomolous scattering, the Friedal pairs were merged before refinement.

The coordinates of the hydroxy H-atoms were refined. The H-atoms were positioned geometrically (O—H = 0.82, C–H = 0.97–0.98 Å) and refined as riding with U_iso(H) = xU_eq(C, O), where x = 1.2 for all H-atoms.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing of the title compound, which shows that molecules form polymeric network with ring motifs.

2-[(1R*,4R*)-1,4-dihydroxycyclohexyl]acetic acid

Crystal data

C8H14O4	Z = 1
Mr = 174.19	F(000) = 94
Triclinic, P1	Dx = 1.305 Mg m^−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7301 (4) Å	Cell parameters from 933 reflections
b = 6.3493 (3) Å	θ = 3.2–28.4°
c = 6.4964 (4) Å	µ = 0.10 mm^−1
α = 92.863 (2)°	T = 296 K
β = 97.223 (1)°	Needle, colorless
γ = 108.258 (2)°	0.28 × 0.12 × 0.10 mm
V = 221.67 (2) Å^3

Data collection

Bruker Kappa APEXII CCD diffractometer	1092 independent reflections
Radiation source: fine-focus sealed tube	932 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 7.50 pixels mm^-1	θmax = 28.4°, θmin = 3.2°
ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→8
Tmin = 0.935, Tmax = 0.965	l = −8→8
3664 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 0.0008P] where P = (Fo^2 + 2Fc^2)/3
1092 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.15 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O1	−0.1847 (3)	0.0914 (3)	−0.1705 (3)	0.0440 (5)
O2	0.1853 (4)	0.0521 (4)	−0.1685 (4)	0.0773 (9)
O3	0.6317 (3)	0.6910 (3)	0.6378 (3)	0.0431 (5)
O4	0.5902 (3)	0.4332 (3)	−0.0313 (2)	0.0359 (5)
C1	0.0589 (4)	0.1643 (4)	−0.1287 (3)	0.0417 (7)
C2	0.1589 (4)	0.4007 (4)	−0.0290 (4)	0.0401 (7)
C3	0.4158 (4)	0.4631 (3)	0.1003 (3)	0.0304 (6)
C4	0.4181 (4)	0.3231 (3)	0.2851 (3)	0.0382 (7)
C5	0.6749 (5)	0.3888 (4)	0.4164 (4)	0.0414 (7)
C6	0.7759 (4)	0.6356 (4)	0.4899 (3)	0.0391 (7)
C7	0.7640 (4)	0.7782 (4)	0.3096 (4)	0.0379 (7)
C8	0.5067 (4)	0.7087 (3)	0.1812 (3)	0.0341 (7)
H1	−0.238 (5)	−0.036 (5)	−0.231 (5)	0.0528*
H2A	0.04354	0.42391	0.05989	0.0481*
H2B	0.16539	0.50069	−0.13778	0.0481*
H3	0.627 (5)	0.610 (5)	0.740 (5)	0.0517*
H4	0.556 (5)	0.301 (5)	−0.077 (4)	0.0430*
H4A	0.29895	0.34223	0.37184	0.0458*
H4B	0.36752	0.16699	0.23368	0.0458*
H5A	0.66520	0.30369	0.53680	0.0497*
H5B	0.78917	0.35099	0.33472	0.0497*
H6	0.94896	0.67271	0.55625	0.0469*
H7A	0.80965	0.93295	0.36434	0.0455*
H7B	0.88352	0.76609	0.22023	0.0455*
H8A	0.51074	0.79800	0.06399	0.0409*
H8B	0.39057	0.73763	0.26622	0.0409*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0402 (9)	0.0388 (9)	0.0490 (10)	0.0100 (7)	0.0025 (7)	−0.0051 (7)
O2	0.0475 (11)	0.0688 (13)	0.1084 (19)	0.0249 (10)	−0.0090 (11)	−0.0466 (13)
O3	0.0573 (10)	0.0406 (9)	0.0293 (8)	0.0122 (7)	0.0094 (7)	0.0006 (7)
O4	0.0380 (8)	0.0414 (9)	0.0320 (8)	0.0167 (7)	0.0106 (6)	0.0001 (7)
C1	0.0380 (12)	0.0476 (12)	0.0379 (12)	0.0158 (10)	−0.0004 (9)	−0.0073 (10)
C2	0.0357 (11)	0.0408 (12)	0.0448 (13)	0.0158 (9)	0.0042 (10)	−0.0056 (10)
C3	0.0343 (10)	0.0324 (10)	0.0265 (10)	0.0126 (8)	0.0087 (8)	0.0002 (8)
C4	0.0492 (12)	0.0295 (10)	0.0346 (12)	0.0093 (9)	0.0103 (10)	0.0032 (9)
C5	0.0574 (14)	0.0424 (12)	0.0315 (12)	0.0253 (11)	0.0073 (10)	0.0079 (9)
C6	0.0381 (11)	0.0468 (13)	0.0322 (12)	0.0151 (10)	0.0025 (9)	0.0006 (9)
C7	0.0422 (12)	0.0336 (10)	0.0352 (12)	0.0069 (9)	0.0097 (9)	0.0024 (9)
C8	0.0412 (12)	0.0311 (10)	0.0322 (12)	0.0138 (9)	0.0076 (9)	0.0045 (9)

Geometric parameters (Å, º)

O1—C1	1.313 (3)	C6—C7	1.524 (3)
O2—C1	1.205 (3)	C7—C8	1.520 (3)
O3—C6	1.441 (3)	C2—H2A	0.9700
O4—C3	1.443 (3)	C2—H2B	0.9700
O1—H1	0.83 (3)	C4—H4A	0.9700
O3—H3	0.86 (3)	C4—H4B	0.9700
O4—H4	0.83 (3)	C5—H5A	0.9700
C1—C2	1.507 (3)	C5—H5B	0.9700
C2—C3	1.523 (3)	C6—H6	0.9800
C3—C8	1.523 (3)	C7—H7A	0.9700
C3—C4	1.530 (3)	C7—H7B	0.9700
C4—C5	1.527 (4)	C8—H8A	0.9700
C5—C6	1.519 (3)	C8—H8B	0.9700
C1—O1—H1	112 (2)	H2A—C2—H2B	108.00
C6—O3—H3	111 (2)	C3—C4—H4A	109.00
C3—O4—H4	112 (2)	C3—C4—H4B	109.00
O1—C1—O2	122.7 (2)	C5—C4—H4A	109.00
O1—C1—C2	112.7 (2)	C5—C4—H4B	109.00
O2—C1—C2	124.7 (2)	H4A—C4—H4B	108.00
C1—C2—C3	114.80 (19)	C4—C5—H5A	109.00
O4—C3—C8	106.40 (17)	C4—C5—H5B	109.00
O4—C3—C4	109.61 (17)	C6—C5—H5A	109.00
C4—C3—C8	109.02 (15)	C6—C5—H5B	109.00
C2—C3—C4	112.02 (18)	H5A—C5—H5B	108.00
C2—C3—C8	110.55 (18)	O3—C6—H6	109.00
O4—C3—C2	109.09 (17)	C5—C6—H6	109.00
C3—C4—C5	111.86 (18)	C7—C6—H6	109.00
C4—C5—C6	112.5 (2)	C6—C7—H7A	109.00
O3—C6—C7	107.08 (19)	C6—C7—H7B	109.00
O3—C6—C5	110.6 (2)	C8—C7—H7A	109.00
C5—C6—C7	111.52 (18)	C8—C7—H7B	109.00
C6—C7—C8	112.19 (19)	H7A—C7—H7B	108.00
C3—C8—C7	112.17 (18)	C3—C8—H8A	109.00
C1—C2—H2A	109.00	C3—C8—H8B	109.00
C1—C2—H2B	109.00	C7—C8—H8A	109.00
C3—C2—H2A	109.00	C7—C8—H8B	109.00
C3—C2—H2B	109.00	H8A—C8—H8B	108.00
O1—C1—C2—C3	156.30 (19)	C2—C3—C8—C7	−179.47 (19)
O2—C1—C2—C3	−24.2 (3)	C4—C3—C8—C7	57.0 (2)
C1—C2—C3—O4	59.4 (2)	C3—C4—C5—C6	54.8 (3)
C1—C2—C3—C4	−62.1 (2)	C4—C5—C6—O3	67.6 (2)
C1—C2—C3—C8	176.07 (18)	C4—C5—C6—C7	−51.4 (3)
O4—C3—C4—C5	59.7 (2)	O3—C6—C7—C8	−69.5 (2)
C2—C3—C4—C5	−179.04 (19)	C5—C6—C7—C8	51.6 (3)
C8—C3—C4—C5	−56.4 (2)	C6—C7—C8—C3	−55.6 (2)
O4—C3—C8—C7	−61.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^i	0.83 (3)	1.78 (3)	2.608 (3)	177 (3)
O3—H3···O4^ii	0.86 (3)	1.90 (3)	2.756 (2)	175 (3)
O4—H4···O1^iii	0.83 (3)	2.39 (3)	3.007 (3)	131 (3)
O4—H4···O2	0.83 (3)	2.20 (3)	2.789 (3)	128 (3)
C5—H5A···O1^iv	0.97	2.60	3.511 (3)	157

Symmetry codes: (i) x−1, y−1, z−1; (ii) x, y, z+1; (iii) x+1, y, z; (iv) x+1, y, z+1.