tert-Butyl 2-(1H-imidazol-1-yl)acetate

Al-Mohammed, N.N.; Alias, Y.; Abdullah, Z.; Khaledi, H.

doi:10.1107/S1600536812001067

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o445

doi:10.1107/S1600536812001067

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tert-Butyl 2-(1H-imidazol-1-yl)acetate

Nassir N. Al-Mohammed,^a Yatimah Alias,^a Zanariah Abdullah ^a and Hamid Khaledi ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: khaledi@siswa.um.edu.my

(Received 9 January 2012; accepted 10 January 2012; online 18 January 2012)

In the title compound, C₉H₁₄N₂O₂, the imidazole ring and the acetate O—C=O plane make a dihedral angle of 80.54 (12)°. In the crystal, molecules are connected via pairs of C—H⋯O hydrogen bonds, forming centrosymmetric dimers.

Related literature

For related structures, see: Pak et al. (2003 ); Wang et al. (2010 ).

Experimental

Crystal data

C₉H₁₄N₂O₂
M_r = 182.22
Monoclinic, P 2₁ /n
a = 10.558 (2) Å
b = 9.287 (2) Å
c = 11.047 (2) Å
β = 117.157 (4)°
V = 963.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.33 × 0.27 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.971, T_max = 0.996
6535 measured reflections
2208 independent reflections
1688 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.097
S = 1.05
2208 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯O2ⁱ	0.99	2.56	3.3768 (18)	140
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812001067/is5051sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001067/is5051Isup2.hkl

checkCIF report

Comment top

The title compound was obtained through the condensation reaction of imidazole with tert-butyl chloroacetate. The imidazole ring and the plane passing through C5/O1/O2, make a dihedral angle of 80.54 (12)°. This value is comparable to those calculated for some similar structures (Pak et al., 2003; Wang et al., 2010). In the crystal, each two molecules are connected via a pair of C—H···O bonds around a center of inversion.

Related literature top

For related structures, see: Pak et al. (2003); Wang et al. (2010).

Experimental top

Sodium hydroxide (1.32 g, 0.033 mol) was added to a solution of imidazole (1.5 g, 0.022 mol) in DMF (20 ml), followed by addition of tert-butyl chloroacetate (3.15 ml, 0.022 mol). The mixture was refluxed for 1 h. The reaction mass was quenched with cold water (50 ml) and extracted by dichloromethane (3 × 25 ml). The combined organic layers was washed with cold water and brine and dried over anhydrous sodium sulfate. The solvent was evaporated under vacuum and the formed amorphous solid was stirred in n-hexane (30 ml) at room temperature. The solid was filtered, washed with hexane (2 × 20 ml), and recrystallized from ethyl acetate to afford off-white crystals of the title compound (melting point = 384–386 K).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of the title compound showing displacement ellipsoids at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

tert-Butyl 2-(1H-imidazol-1-yl)acetate top

Crystal data top

C₉H₁₄N₂O₂	F(000) = 392
M_r = 182.22	D_x = 1.256 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 771 reflections
a = 10.558 (2) Å	θ = 3.0–29.0°
b = 9.287 (2) Å	µ = 0.09 mm⁻¹
c = 11.047 (2) Å	T = 100 K
β = 117.157 (4)°	Plate, colorless
V = 963.9 (4) Å³	0.33 × 0.27 × 0.05 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2208 independent reflections
Radiation source: fine-focus sealed tube	1688 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→13
T_min = 0.971, T_max = 0.996	k = −12→12
6535 measured reflections	l = −14→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0352P)² + 0.2973P] where P = (F_o² + 2F_c²)/3
2208 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₉H₁₄N₂O₂	V = 963.9 (4) Å³
M_r = 182.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.558 (2) Å	µ = 0.09 mm⁻¹
b = 9.287 (2) Å	T = 100 K
c = 11.047 (2) Å	0.33 × 0.27 × 0.05 mm
β = 117.157 (4)°

Data collection top

Bruker APEXII CCD diffractometer	2208 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1688 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.996	R_int = 0.035
6535 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	Δρ_max = 0.23 e Å⁻³
2208 reflections	Δρ_min = −0.27 e Å⁻³
121 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	0.58413 (11)	0.82030 (11)	0.21337 (11)	0.0244 (3)
O2	0.42983 (10)	0.63596 (10)	0.11631 (10)	0.0177 (2)
N1	1.01459 (13)	0.74927 (14)	0.30780 (13)	0.0250 (3)
N2	0.79333 (12)	0.67798 (12)	0.17766 (12)	0.0164 (3)
C1	0.91215 (15)	0.66189 (16)	0.29694 (15)	0.0210 (3)
H1	0.9207	0.5949	0.3653	0.025*
C2	0.95672 (16)	0.82623 (16)	0.18788 (16)	0.0231 (3)
H2	1.0055	0.8989	0.1650	0.028*
C3	0.82115 (15)	0.78441 (15)	0.10713 (15)	0.0197 (3)
H3	0.7584	0.8211	0.0198	0.024*
C4	0.65738 (15)	0.60761 (15)	0.13621 (15)	0.0188 (3)
H4A	0.6720	0.5166	0.1876	0.023*
H4B	0.6155	0.5835	0.0382	0.023*
C5	0.55466 (15)	0.70313 (15)	0.16122 (14)	0.0169 (3)
C6	0.30955 (14)	0.69930 (15)	0.13399 (14)	0.0178 (3)
C7	0.35240 (16)	0.71586 (17)	0.28396 (15)	0.0228 (3)
H7A	0.3916	0.6247	0.3308	0.034*
H7B	0.2688	0.7420	0.2957	0.034*
H7C	0.4245	0.7916	0.3225	0.034*
C8	0.26438 (16)	0.84140 (16)	0.05766 (16)	0.0230 (3)
H8A	0.3393	0.9133	0.1028	0.035*
H8B	0.1761	0.8747	0.0572	0.035*
H8C	0.2487	0.8278	−0.0362	0.035*
C9	0.19439 (15)	0.58562 (16)	0.06881 (15)	0.0230 (3)
H9A	0.1688	0.5775	−0.0281	0.034*
H9B	0.1102	0.6134	0.0790	0.034*
H9C	0.2299	0.4927	0.1135	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0231 (6)	0.0202 (5)	0.0320 (6)	−0.0045 (4)	0.0144 (5)	−0.0086 (4)
O2	0.0141 (5)	0.0182 (5)	0.0222 (5)	−0.0015 (4)	0.0096 (4)	−0.0035 (4)
N1	0.0185 (7)	0.0306 (7)	0.0238 (7)	−0.0012 (5)	0.0077 (6)	−0.0052 (6)
N2	0.0143 (6)	0.0174 (6)	0.0177 (6)	−0.0016 (5)	0.0075 (5)	−0.0027 (5)
C1	0.0195 (7)	0.0230 (7)	0.0192 (7)	0.0036 (6)	0.0076 (6)	0.0006 (6)
C2	0.0199 (7)	0.0233 (7)	0.0290 (8)	−0.0039 (6)	0.0138 (7)	−0.0026 (6)
C3	0.0213 (8)	0.0209 (7)	0.0191 (7)	0.0001 (6)	0.0111 (6)	0.0010 (6)
C4	0.0159 (7)	0.0177 (7)	0.0241 (8)	−0.0026 (5)	0.0102 (6)	−0.0037 (6)
C5	0.0163 (7)	0.0188 (7)	0.0148 (7)	−0.0015 (5)	0.0064 (6)	0.0003 (5)
C6	0.0147 (7)	0.0191 (7)	0.0210 (7)	0.0024 (5)	0.0094 (6)	−0.0002 (6)
C7	0.0218 (8)	0.0268 (8)	0.0216 (8)	0.0020 (6)	0.0116 (6)	−0.0015 (6)
C8	0.0216 (8)	0.0222 (7)	0.0259 (8)	0.0028 (6)	0.0114 (7)	0.0028 (6)
C9	0.0165 (8)	0.0241 (7)	0.0288 (8)	−0.0011 (6)	0.0107 (7)	−0.0011 (6)

Geometric parameters (Å, º) top

O1—C5	1.2039 (17)	C4—H4B	0.9900
O2—C5	1.3325 (16)	C6—C7	1.513 (2)
O2—C6	1.4910 (16)	C6—C9	1.5207 (19)
N1—C1	1.3131 (19)	C6—C8	1.5209 (19)
N1—C2	1.379 (2)	C7—H7A	0.9800
N2—C1	1.3503 (18)	C7—H7B	0.9800
N2—C3	1.3709 (18)	C7—H7C	0.9800
N2—C4	1.4482 (17)	C8—H8A	0.9800
C1—H1	0.9500	C8—H8B	0.9800
C2—C3	1.353 (2)	C8—H8C	0.9800
C2—H2	0.9500	C9—H9A	0.9800
C3—H3	0.9500	C9—H9B	0.9800
C4—C5	1.5208 (19)	C9—H9C	0.9800
C4—H4A	0.9900

C5—O2—C6	121.56 (10)	O2—C6—C9	102.05 (11)
C1—N1—C2	104.32 (12)	C7—C6—C9	111.34 (12)
C1—N2—C3	106.85 (12)	O2—C6—C8	109.88 (11)
C1—N2—C4	127.15 (12)	C7—C6—C8	112.35 (12)
C3—N2—C4	125.75 (12)	C9—C6—C8	111.06 (12)
N1—C1—N2	112.36 (13)	C6—C7—H7A	109.5
N1—C1—H1	123.8	C6—C7—H7B	109.5
N2—C1—H1	123.8	H7A—C7—H7B	109.5
C3—C2—N1	110.88 (13)	C6—C7—H7C	109.5
C3—C2—H2	124.6	H7A—C7—H7C	109.5
N1—C2—H2	124.6	H7B—C7—H7C	109.5
C2—C3—N2	105.60 (13)	C6—C8—H8A	109.5
C2—C3—H3	127.2	C6—C8—H8B	109.5
N2—C3—H3	127.2	H8A—C8—H8B	109.5
N2—C4—C5	111.43 (11)	C6—C8—H8C	109.5
N2—C4—H4A	109.3	H8A—C8—H8C	109.5
C5—C4—H4A	109.3	H8B—C8—H8C	109.5
N2—C4—H4B	109.3	C6—C9—H9A	109.5
C5—C4—H4B	109.3	C6—C9—H9B	109.5
H4A—C4—H4B	108.0	H9A—C9—H9B	109.5
O1—C5—O2	126.65 (13)	C6—C9—H9C	109.5
O1—C5—C4	124.35 (13)	H9A—C9—H9C	109.5
O2—C5—C4	108.99 (11)	H9B—C9—H9C	109.5
O2—C6—C7	109.68 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···O2ⁱ	0.99	2.56	3.3768 (18)	140

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₉H₁₄N₂O₂
M_r	182.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.558 (2), 9.287 (2), 11.047 (2)
β (°)	117.157 (4)
V (Å³)	963.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.33 × 0.27 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.971, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	6535, 2208, 1688
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.097, 1.05
No. of reflections	2208
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.27

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···O2ⁱ	0.99	2.56	3.3768 (18)	139.8

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

The authors thank the University of Malaya for funding this study (FRGS grant No. FP001/2010 A).

References

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