rac-(S)-2-(1H-Imidazol-1-yl)-3-methyl­butan-1-ol

Song, G.; Xue, F.; Li, D.

doi:10.1107/S1600536809004565

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o525

doi:10.1107/S1600536809004565

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rac-(S)-2-(1H-Imidazol-1-yl)-3-methylbutan-1-ol

Guangfu Song,^a ^* Fang Xue ^a and Dongliang Li ^a

^aTechnical Research Center, China Tabacco Chuanyu Industrial Corporation, Chengdu 610066, People's Republic of China
^*Correspondence e-mail: songguangfu@pride56.com

(Received 5 February 2009; accepted 9 February 2009; online 13 February 2009)

In the crystal structure of the title compound, C₈H₁₄N₂O, intermolecular O—H⋯N hydrogen bonds link molecules related by translation along the a axis into chains. Weak intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions enhance the crystal packing stability.

Related literature

For useful applications of imidazole derivatives, see Lu et al. (2006 ); Zou et al. (2006 ). For details of the synthesis, see Bao et al. (2003 ); Guo et al. (2006 ).

Experimental

Crystal data

C₈H₁₄N₂O
M_r = 154.21
Monoclinic, P 2₁ /n
a = 7.356 (4) Å
b = 7.212 (3) Å
c = 16.549 (5) Å
β = 90.54 (3)°
V = 877.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 292 K
0.58 × 0.54 × 0.42 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
1931 measured reflections
1630 independent reflections
965 reflections with I > 2σ(I)
R_int = 0.004
3 standard reflections every 120 reflections intensity decay: 0.3%

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.197
S = 1.18
1630 reflections
104 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.82	1.93	2.751 (3)	176
C1—H1A⋯O1ⁱⁱ	0.93	2.43	3.353 (4)	173
C4—H4⋯Cgⁱⁱ	0.98	2.86	3.716 (4)	146
Symmetry codes: (i) x-1, y, z; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg is the centroid of the C1–C3/N1/N2 ring.

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: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004565/cv2517sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004565/cv2517Isup2.hkl

checkCIF report

Comment top

Imidazole is important for biological systems, and its derivatives have attracted widespread interest due to their further expanded application in perfume chemistry and in the construction of some interesting metal–organic frameworks (Lu et al. 2006; Zou et al. 2006). Here, we report the crystal structure of the title compound, (I), which is a basic unit of constructing chiral receptors and could be applied for the preparation of perfume.

As shown in Fig. 1, there is a chiral center at C4 derived from the source L-valine. In the crystal, intermolecular O—H···N hydrogen bonds (Table 1) link the molecules related by translation along axis a into chains. Weak intermolecular C—H···O hydrogen bonds and C—H···π interactions (Table 1) enhance the crystal packing stability.

Related literature top

For useful applications of imidazole derivatives, see Lu et al. (2006); Zou et al. (2006). For details of the synthesis, see Bao et al. (2003); Guo et al. (2006).

Experimental top

The title compound was prepared according to the literature (Guo et al. 2006). Starting from L-valine, methyl 2-(1H-imidazol-1-yl)-3-methylbutanoate was easily prepared according to literature procedure (Bao et al. 2003). Following, NaBH₄ (1.52 g, 40 mmol) was added to methyl 2-(1H-imidazol-1-yl)-3-methylbutanoate (1.82 g, 10.0 mmol) in ethanol (50 ml) at 273 K during 30 min. The mixture was stirred at 333 K for another 20 h and then evaporated under vacuum. The residue was diluted with 50 ml saturated K₂CO₃ and extracted with 30 ml ethyl acetate. The organic layer was dried over anhydrous Na₂SO₄ and concentrated under reduced pressure. The resulting residue was purified by column chromatography on silica gel eluting with CH₂Cl₂/CH₃OH (20/1, v/v). Then, colourless crystals suitable for X-ray analysis can be obtained by recrystallization of the compound from ethyl acetate.

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: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering.

rac-(S)-2-(1H-Imidazol-1-yl)-3-methylbutan-1-ol top

Crystal data top

C₈H₁₄N₂O	F(000) = 336
M_r = 154.21	D_x = 1.167 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 21 reflections
a = 7.356 (4) Å	θ = 4.6–7.4°
b = 7.212 (3) Å	µ = 0.08 mm⁻¹
c = 16.549 (5) Å	T = 292 K
β = 90.54 (3)°	Block, colourless
V = 877.9 (7) Å³	0.58 × 0.54 × 0.42 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.004
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 2.5°
Graphite monochromator	h = −8→8
ω/2θ scans	k = 0→8
1931 measured reflections	l = −7→20
1630 independent reflections	3 standard reflections every 120 reflections
965 reflections with I > 2σ(I)	intensity decay: 0.3%

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)] = 0.067	H-atom parameters constrained
wR(F²) = 0.197	w = 1/[σ²(F_o²) + (0.0941P)²] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max < 0.001
1630 reflections	Δρ_max = 0.31 e Å⁻³
104 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXS97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.046 (11)

Crystal data top

C₈H₁₄N₂O	V = 877.9 (7) Å³
M_r = 154.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.356 (4) Å	µ = 0.08 mm⁻¹
b = 7.212 (3) Å	T = 292 K
c = 16.549 (5) Å	0.58 × 0.54 × 0.42 mm
β = 90.54 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.004
1931 measured reflections	3 standard reflections every 120 reflections
1630 independent reflections	intensity decay: 0.3%
965 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.197	H-atom parameters constrained
S = 1.18	Δρ_max = 0.31 e Å⁻³
1630 reflections	Δρ_min = −0.24 e Å⁻³
104 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
O1	0.4065 (2)	0.1870 (3)	0.31165 (14)	0.0557 (7)
H1	0.3011	0.1697	0.3255	0.084*
N1	0.7629 (3)	0.0340 (3)	0.34211 (14)	0.0459 (7)
N2	1.0479 (3)	0.1263 (4)	0.34916 (16)	0.0598 (8)
C4	0.6043 (3)	−0.0816 (4)	0.32307 (17)	0.0456 (8)
H4	0.6473	−0.1848	0.2898	0.055*
C5	0.4713 (4)	0.0284 (4)	0.27157 (18)	0.0480 (8)
H5A	0.5306	0.0660	0.2221	0.058*
H5B	0.3692	−0.0503	0.2570	0.058*
C1	0.9353 (4)	0.0047 (4)	0.31778 (19)	0.0514 (8)
H1A	0.9698	−0.0901	0.2830	0.062*
C3	0.7676 (4)	0.1855 (4)	0.39170 (18)	0.0559 (8)
H3	0.6696	0.2406	0.4174	0.067*
C6	0.5261 (4)	−0.1657 (4)	0.39954 (16)	0.0487 (8)
H6	0.4769	−0.0643	0.4322	0.058*
C2	0.9438 (4)	0.2392 (4)	0.3958 (2)	0.0597 (9)
H2	0.9875	0.3387	0.4260	0.072*
C7	0.3712 (5)	−0.2990 (5)	0.3805 (2)	0.0693 (10)
H7A	0.4164	−0.4013	0.3495	0.104*
H7B	0.2786	−0.2355	0.3500	0.104*
H7C	0.3208	−0.3444	0.4300	0.104*
C8	0.6711 (5)	−0.2629 (5)	0.4495 (2)	0.0761 (11)
H8A	0.6199	−0.3035	0.4996	0.114*
H8B	0.7693	−0.1786	0.4602	0.114*
H8C	0.7157	−0.3681	0.4202	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0302 (11)	0.0505 (12)	0.0864 (15)	0.0012 (9)	−0.0025 (10)	−0.0011 (11)
N1	0.0288 (13)	0.0493 (13)	0.0595 (15)	0.0029 (11)	−0.0026 (10)	−0.0055 (11)
N2	0.0307 (14)	0.0628 (16)	0.086 (2)	−0.0005 (12)	−0.0039 (13)	−0.0031 (14)
C4	0.0325 (15)	0.0424 (15)	0.0617 (18)	−0.0002 (12)	−0.0060 (13)	−0.0027 (14)
C5	0.0355 (16)	0.0499 (16)	0.0586 (17)	−0.0024 (13)	−0.0038 (13)	−0.0008 (14)
C1	0.0334 (16)	0.0518 (17)	0.069 (2)	0.0086 (14)	0.0035 (14)	−0.0014 (14)
C3	0.0353 (16)	0.0655 (19)	0.0669 (19)	0.0006 (15)	−0.0020 (14)	−0.0129 (16)
C6	0.0407 (16)	0.0520 (17)	0.0532 (17)	0.0002 (14)	−0.0043 (13)	0.0040 (14)
C2	0.0405 (17)	0.0628 (19)	0.075 (2)	−0.0027 (15)	−0.0125 (15)	−0.0133 (16)
C7	0.066 (2)	0.071 (2)	0.071 (2)	−0.0228 (19)	0.0010 (17)	0.0087 (18)
C8	0.063 (2)	0.085 (2)	0.081 (2)	0.0034 (19)	−0.0120 (19)	0.025 (2)

Geometric parameters (Å, º) top

O1—C5	1.408 (3)	C3—C2	1.354 (4)
O1—H1	0.8200	C3—H3	0.9300
N1—C1	1.351 (4)	C6—C8	1.515 (4)
N1—C3	1.367 (3)	C6—C7	1.522 (4)
N1—C4	1.466 (3)	C6—H6	0.9800
N2—C1	1.310 (3)	C2—H2	0.9300
N2—C2	1.362 (4)	C7—H7A	0.9600
C4—C5	1.516 (3)	C7—H7B	0.9600
C4—C6	1.521 (4)	C7—H7C	0.9600
C4—H4	0.9800	C8—H8A	0.9600
C5—H5A	0.9700	C8—H8B	0.9600
C5—H5B	0.9700	C8—H8C	0.9600
C1—H1A	0.9300

C5—O1—H1	109.5	N1—C3—H3	126.9
C1—N1—C3	106.6 (2)	C8—C6—C4	111.6 (2)
C1—N1—C4	126.5 (2)	C8—C6—C7	110.0 (3)
C3—N1—C4	126.8 (2)	C4—C6—C7	111.6 (2)
C1—N2—C2	105.6 (2)	C8—C6—H6	107.8
N1—C4—C5	109.4 (2)	C4—C6—H6	107.8
N1—C4—C6	110.8 (2)	C7—C6—H6	107.8
C5—C4—C6	115.4 (2)	C3—C2—N2	110.1 (3)
N1—C4—H4	107.0	C3—C2—H2	125.0
C5—C4—H4	107.0	N2—C2—H2	125.0
C6—C4—H4	107.0	C6—C7—H7A	109.5
O1—C5—C4	112.3 (2)	C6—C7—H7B	109.5
O1—C5—H5A	109.1	H7A—C7—H7B	109.5
C4—C5—H5A	109.1	C6—C7—H7C	109.5
O1—C5—H5B	109.1	H7A—C7—H7C	109.5
C4—C5—H5B	109.1	H7B—C7—H7C	109.5
H5A—C5—H5B	107.9	C6—C8—H8A	109.5
N2—C1—N1	111.6 (3)	C6—C8—H8B	109.5
N2—C1—H1A	124.2	H8A—C8—H8B	109.5
N1—C1—H1A	124.2	C6—C8—H8C	109.5
C2—C3—N1	106.1 (3)	H8A—C8—H8C	109.5
C2—C3—H3	126.9	H8B—C8—H8C	109.5

C1—N1—C4—C5	−115.0 (3)	C1—N1—C3—C2	−0.8 (3)
C3—N1—C4—C5	69.3 (3)	C4—N1—C3—C2	175.7 (2)
C1—N1—C4—C6	116.8 (3)	N1—C4—C6—C8	−51.7 (3)
C3—N1—C4—C6	−59.0 (3)	C5—C4—C6—C8	−176.6 (2)
N1—C4—C5—O1	−61.5 (3)	N1—C4—C6—C7	−175.2 (2)
C6—C4—C5—O1	64.2 (3)	C5—C4—C6—C7	59.9 (3)
C2—N2—C1—N1	0.0 (3)	N1—C3—C2—N2	0.8 (4)
C3—N1—C1—N2	0.5 (3)	C1—N2—C2—C3	−0.5 (4)
C4—N1—C1—N2	−175.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.82	1.93	2.751 (3)	176
C1—H1A···O1ⁱⁱ	0.93	2.43	3.353 (4)	173
C4—H4···Cgⁱⁱ	0.98	2.86	3.716 (4)	146

Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₄N₂O
M_r	154.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	292
a, b, c (Å)	7.356 (4), 7.212 (3), 16.549 (5)
β (°)	90.54 (3)
V (Å³)	877.9 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.58 × 0.54 × 0.42

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1931, 1630, 965
R_int	0.004
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.197, 1.18
No. of reflections	1630
No. of parameters	104
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.24

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.82	1.93	2.751 (3)	176
C1—H1A···O1ⁱⁱ	0.93	2.43	3.353 (4)	173
C4—H4···Cgⁱⁱ	0.98	2.86	3.716 (4)	146

Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

The authors are grateful to the Science and Technology Bureau of Sichuan Province of China (grant No. 2008JY0142 and 2008JY0143) for financial support.

References

Bao, W. L., Wang, Z. M. & Li, Y. X. (2003). J. Org. Chem. 68, 591–593. Web of Science CrossRef PubMed CAS Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gabe, E. J. & White, P. S. (1993). DIFRAC. American Crystallographic Association, Pittsburgh Meeting. Abstract PA104. Google Scholar
Guo, S. J., Luo, K., Wang, W. H., Zhang, S. Y., Jiang, H. Y., Lan, J. B. & Xie, R. G. (2006). Gaodeng Xuexiao Huaxue Xuebao, 27, 1664–1668. CAS Google Scholar
Lu, W. G., Su, C. Y., Lu, T. B., Jiang, L. & Chen, J. M. (2006). J. Am. Chem. Soc. 128, 34–35. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zou, R., Sakurai, H. & Xu, Q. (2006). Angew. Chem. Int. Ed. 45, 2542–2546. Web of Science CSD CrossRef CAS Google Scholar