5,5-Bis(hydroxy­meth­yl)-3-methyl­cyclo­hex-2-enone

Cui, D.; Wang, Q.; Zhang, C.; Gu, J.

doi:10.1107/S1600536808025063

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1745

doi:10.1107/S1600536808025063

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5,5-Bis(hydroxymethyl)-3-methylcyclohex-2-enone

Dongmei Cui,^a ^* Qian Wang,^a Chen Zhang ^b and Jianming Gu ^b

^aCollege of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, and ^bZhejiang University, Hangzhou 310058, People's Republic of China
^*Correspondence e-mail: cuidongmei@zjut.edu.cn

(Received 30 April 2008; accepted 4 August 2008; online 13 August 2008)

In the title compound, C₉H₁₄O₃, the cyclohexenone ring has an envelope conformation; the flap atom (with the hydroxymethyl groups attached) is displaced by 0.582 (4) Å from the plane of the other five ring atoms. The crystal structure contains an intermolecular O—H⋯O hydrogen-bonded ring.

Related literature

For related literature, see: Aghil et al. (1992 ); Hu et al. (2003 ); Li & Strobel (2001 ); Luu et al. (2004 ).

Experimental

Crystal data

C₉H₁₄O₃
M_r = 170.21
Triclinic, $[P \overline 1]$
a = 5.9791 (3) Å
b = 6.2251 (1) Å
c = 13.7493 (8) Å
α = 90.8104 (17)°
β = 91.3285 (12)°
γ = 117.0728 (15)°
V = 455.38 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 (1) K
0.43 × 0.40 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.958, T_max = 0.982
4514 measured reflections
2060 independent reflections
1432 reflections with F² > 2σ(F²)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.195
S = 1.01
2060 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H201⋯O3ⁱ	0.92	1.85	2.738 (2)	163
O3—H301⋯O2ⁱⁱ	0.95	1.84	2.733 (2)	155
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ) and Larson (1970 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025063/ez2128sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025063/ez2128Isup2.hkl

checkCIF report

Comment top

Functionalized cyclohex-2-enone derivatives can be used as precursors in the syntheses of some complex compounds, such as vitamin E, amino acids, terpenes etc. (Hu et al., 2003). In addition, cyclohex-2-enone derivatives have been shown to have a wide range of biological activities such as antimicrobial (Li et al., 2001) and anticancer (Aghil et al., 1992) activities, and are involved in the protection of cerebral neurocytes (Luu et al., 2004). We are interested in their further pharmaceutical activity.

In this paper, we present an X-ray crystallographic analysis of the title compound (I) (Fig. 1). The cyclohexenone ring has an envelope conformation, such that the plane which is composed of atoms C1, C2 and C6 (forming the flap) and the C2, C3, C4, C5, C6 plane form a dihedral angle of 41.80 (4)°. Two molecules are linked together through O—H···O interactions. Since each molecule contains a hydrogen-bond donor group (–OH) at one end and an acceptor (–OH) at the other, a ring of four H-bonds is formed between these two molecules and a neighboring pair in the crystal lattice (Fig. 2).

Related literature top

For related literature, see: Aghil et al. (1992); Hu et al. (2003); Li & Strobel (2001); Luu et al. (2004).

Experimental top

A solution of 4,4-bis(hydroxymethyl)-2,6-heptanedione(188 mg, 1 mmol) and sodium methoxide (54 mg, 1 mmol) in methanol (10 ml) was heated at 323 K for 4 h. The reaction mixture was acidified with dilute aqueous HCl, then concentrated and partitioned between water and dichloromethane. The pure product was obtained through silica gel chromatography (eluant petroleum ether/ethyl acetate, 1:1), and diffraction quality crystals were obtained by slow evaporation of a dichloromethane / petroleum ether (1:3) solution at room temperature.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004) and Larson (1970); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures top

	Fig. 1. The unit of (I) with atom labels, showing 50% probability displacement ellipsoids.
	Fig. 2. A partial packing diagram viewed along the b axis. Hydrogen bonds are drawn as dashed lines.

5,5-Bis(hydroxymethyl)-3-methylcyclohex-2-enone top

Crystal data top

C₉H₁₄O₃	Z = 2
M_r = 170.21	F(000) = 184.00
Triclinic, P1	D_x = 1.241 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 5.9791 (3) Å	Cell parameters from 3491 reflections
b = 6.2251 (1) Å	θ = 3.7–27.4°
c = 13.7493 (8) Å	µ = 0.09 mm⁻¹
α = 90.8104 (17)°	T = 296 K
β = 91.3285 (12)°	Chunk, colorless
γ = 117.0728 (15)°	0.43 × 0.40 × 0.20 mm
V = 455.38 (4) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	1432 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.018
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→7
T_min = 0.958, T_max = 0.982	k = −8→8
4514 measured reflections	l = −17→17
2060 independent reflections

Refinement top

Refinement on F²	w = 1/[0.0027F_o² + 5σ(F_o²) + 1]/(4F_o²)
R[F² > 2σ(F²)] = 0.054	(Δ/σ)_max < 0.001
wR(F²) = 0.195	Δρ_max = 0.29 e Å⁻³
S = 1.01	Δρ_min = −0.23 e Å⁻³
2060 reflections	Extinction correction: Larson (1970)
110 parameters	Extinction coefficient: 107 (30)
H-atom parameters constrained

Crystal data top

C₉H₁₄O₃	γ = 117.0728 (15)°
M_r = 170.21	V = 455.38 (4) Å³
Triclinic, P1	Z = 2
a = 5.9791 (3) Å	Mo Kα radiation
b = 6.2251 (1) Å	µ = 0.09 mm⁻¹
c = 13.7493 (8) Å	T = 296 K
α = 90.8104 (17)°	0.43 × 0.40 × 0.20 mm
β = 91.3285 (12)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2060 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1432 reflections with F² > 2σ(F²)
T_min = 0.958, T_max = 0.982	R_int = 0.018
4514 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	110 parameters
wR(F²) = 0.195	H-atom parameters constrained
S = 1.01	Δρ_max = 0.29 e Å⁻³
2060 reflections	Δρ_min = −0.23 e Å⁻³

Special details top

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.1756 (3)	1.1069 (3)	0.16817 (14)	0.0617 (6)
O2	0.8610 (2)	0.5583 (3)	0.38179 (12)	0.0518 (5)
O3	0.3183 (3)	0.5928 (4)	0.43726 (12)	0.0625 (6)
C1	0.6300 (3)	0.7646 (4)	0.31049 (14)	0.0342 (5)
C2	0.4284 (4)	0.7285 (4)	0.23242 (14)	0.0382 (6)
C3	0.5141 (4)	0.7644 (4)	0.13114 (16)	0.0395 (6)
C4	0.7599 (4)	0.8911 (4)	0.11129 (17)	0.0459 (6)
C5	0.9546 (4)	1.0036 (4)	0.18614 (18)	0.0418 (6)
C6	0.8686 (4)	0.9901 (4)	0.29092 (17)	0.0435 (6)
C7	0.3125 (5)	0.6558 (5)	0.05324 (18)	0.0575 (8)
C8	0.6772 (4)	0.5422 (4)	0.31014 (16)	0.0391 (6)
C9	0.5370 (4)	0.7935 (5)	0.41112 (17)	0.0497 (7)
H4	0.8057	0.9066	0.0466	0.055*
H21	0.2949	0.5649	0.2365	0.046*
H22	0.3628	0.8418	0.2467	0.046*
H61	1.0013	0.9953	0.3343	0.052*
H62	0.8404	1.1291	0.3044	0.052*
H71	0.3875	0.6827	−0.0093	0.069*
H72	0.2024	0.7294	0.0564	0.069*
H73	0.2183	0.4855	0.0626	0.069*
H81	0.5204	0.4012	0.3225	0.047*
H82	0.7344	0.5243	0.2465	0.047*
H91	0.6684	0.8209	0.4596	0.060*
H92	0.5042	0.9324	0.4103	0.060*
H201	0.7736	0.4867	0.4357	0.067*
H301	0.1888	0.6149	0.4049	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0437 (10)	0.0582 (12)	0.0750 (14)	0.0149 (8)	0.0195 (9)	0.0154 (10)
O2	0.0403 (9)	0.0843 (13)	0.0433 (9)	0.0383 (9)	0.0072 (7)	0.0232 (8)
O3	0.0444 (9)	0.1166 (18)	0.0398 (9)	0.0471 (11)	0.0123 (7)	0.0284 (10)
C1	0.0325 (10)	0.0441 (13)	0.0296 (10)	0.0205 (9)	0.0006 (8)	−0.0006 (8)
C2	0.0357 (10)	0.0514 (14)	0.0324 (11)	0.0239 (10)	0.0002 (8)	0.0044 (9)
C3	0.0480 (12)	0.0438 (13)	0.0328 (11)	0.0263 (11)	−0.0014 (9)	0.0041 (9)
C4	0.0556 (14)	0.0524 (15)	0.0333 (11)	0.0272 (12)	0.0097 (10)	0.0090 (10)
C5	0.0422 (12)	0.0347 (12)	0.0508 (13)	0.0190 (10)	0.0108 (10)	0.0086 (10)
C6	0.0423 (12)	0.0411 (13)	0.0437 (13)	0.0163 (10)	−0.0014 (10)	−0.0049 (10)
C7	0.0663 (17)	0.0717 (19)	0.0387 (13)	0.0360 (15)	−0.0145 (12)	−0.0003 (12)
C8	0.0371 (11)	0.0488 (14)	0.0366 (11)	0.0238 (10)	−0.0010 (9)	0.0071 (9)
C9	0.0473 (13)	0.0781 (19)	0.0333 (12)	0.0367 (13)	0.0062 (10)	0.0024 (12)

Geometric parameters (Å, º) top

O1—C5	1.211 (2)	O3—H301	0.948
O2—C8	1.426 (3)	C2—H21	0.970
O3—C9	1.395 (2)	C2—H22	0.970
C1—C2	1.530 (3)	C4—H4	0.930
C1—C6	1.512 (2)	C6—H61	0.970
C1—C8	1.534 (4)	C6—H62	0.970
C1—C9	1.541 (3)	C7—H71	0.960
C2—C3	1.480 (3)	C7—H72	0.960
C3—C4	1.351 (3)	C7—H73	0.960
C3—C7	1.495 (3)	C8—H81	0.970
C4—C5	1.445 (3)	C8—H82	0.970
C5—C6	1.531 (3)	C9—H91	0.970
O2—H201	0.915	C9—H92	0.970

C2—C1—C6	109.76 (18)	C3—C4—H4	118.6
C2—C1—C8	109.12 (18)	C5—C4—H4	118.6
C2—C1—C9	109.4 (2)	C1—C6—H61	108.4
C6—C1—C8	110.8 (2)	C1—C6—H62	108.4
C6—C1—C9	108.79 (18)	C5—C6—H61	108.4
C8—C1—C9	109.0 (2)	C5—C6—H62	108.4
C1—C2—C3	115.5 (2)	H61—C6—H62	109.5
C2—C3—C4	121.45 (19)	C3—C7—H71	109.5
C2—C3—C7	115.92 (19)	C3—C7—H72	109.5
C4—C3—C7	122.6 (2)	C3—C7—H73	109.5
C3—C4—C5	122.9 (2)	H71—C7—H72	109.5
O1—C5—C4	122.5 (2)	H71—C7—H73	109.5
O1—C5—C6	120.8 (2)	H72—C7—H73	109.5
C4—C5—C6	116.7 (2)	O2—C8—H81	108.6
C1—C6—C5	113.84 (17)	O2—C8—H82	108.6
O2—C8—C1	113.12 (18)	C1—C8—H81	108.6
O3—C9—C1	113.6 (2)	C1—C8—H82	108.6
C8—O2—H201	105.8	H81—C8—H82	109.5
C9—O3—H301	103.4	O3—C9—H91	108.4
C1—C2—H21	107.9	O3—C9—H92	108.4
C1—C2—H22	107.9	C1—C9—H91	108.4
C3—C2—H21	107.9	C1—C9—H92	108.4
C3—C2—H22	107.9	H91—C9—H92	109.5
H21—C2—H22	109.5

C2—C1—C6—C5	−50.0 (3)	C8—C1—C9—O3	−58.2 (2)
C6—C1—C2—C3	44.7 (3)	C9—C1—C8—O2	−59.9 (2)
C2—C1—C8—O2	−179.24 (16)	C1—C2—C3—C4	−19.9 (4)
C8—C1—C2—C3	−76.9 (2)	C1—C2—C3—C7	161.0 (2)
C2—C1—C9—O3	61.0 (3)	C2—C3—C4—C5	−1.2 (4)
C9—C1—C2—C3	164.0 (2)	C7—C3—C4—C5	177.8 (3)
C6—C1—C8—O2	59.8 (2)	C3—C4—C5—O1	176.3 (3)
C8—C1—C6—C5	70.6 (2)	C3—C4—C5—C6	−4.6 (4)
C6—C1—C9—O3	−179.1 (2)	O1—C5—C6—C1	−149.4 (2)
C9—C1—C6—C5	−169.7 (2)	C4—C5—C6—C1	31.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H201···O3ⁱ	0.92	1.85	2.738 (2)	163
O3—H301···O2ⁱⁱ	0.95	1.85	2.733 (2)	155

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

Experimental details

Crystal data
Chemical formula	C₉H₁₄O₃
M_r	170.21
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.9791 (3), 6.2251 (1), 13.7493 (8)
α, β, γ (°)	90.8104 (17), 91.3285 (12), 117.0728 (15)
V (Å³)	455.38 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.43 × 0.40 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.958, 0.982
No. of measured, independent and observed [F² > 2σ(F²)] reflections	4514, 2060, 1432
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.195, 1.01
No. of reflections	2060
No. of parameters	110
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.23

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004) and Larson (1970), SIR97 (Altomare et al., 1999), CRYSTALS (Watkin et al., 1996), ORTEP-3 for Windows (Farrugia, 1997), CrystalStructure (Rigaku/MSC, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H201···O3ⁱ	0.915	1.849	2.738 (2)	163.3
O3—H301···O2ⁱⁱ	0.948	1.845	2.733 (2)	154.7

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

Acknowledgements

This work was partially supported by the Natural Science Foundation of China (20572094, 20672099). Mr Xinju Ma of the College of Pharmaceutical Science of Zhejiang University of Technology is acknowledged for assistance with the crystal structure analysis.

References

Aghil, O., Bibby, M. C., Carrington, S. J., Douglas, K. T., Phillips, R. M. & Shing, T. K. M. (1992). Anti-Cancer Drug Des. 7, 67–82. PubMed CAS Web of Science Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hu, B. C., Lv, C. X. & Liu, Z. L. (2003). Yingyong Huaxue, 20, 1012–1014. CAS Google Scholar
Larson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, pp. 291–294. Copenhagen: Munksgaard. Google Scholar
Li, J. Y. & Strobel, G. A. (2001). Phytochemistry, 57, 261–265. Web of Science CrossRef PubMed CAS Google Scholar
Luu, B., Kudo, Y., Yamada, M., Uchida, M., Suma, Y. & Suzuki, H. (2004). US Patent No. 0 152 786. Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar