tert-Butyl 4-formyl-1H-imidazole-1-carboxyl­ate

Kang, J.-T.; Li, Z.-G.; Xu, J.-W.; Wei, Y.

doi:10.1107/S1600536810029247

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2185

https://doi.org/10.1107/S1600536810029247

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tert-Butyl 4-formyl-1H-imidazole-1-carboxylate

Jun-Tao Kang,^a Zhi-Gang Li,^a Jing-Wei Xu ^a ^* and Yang Wei ^a ^*

^aThe State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China
^*Correspondence e-mail: jwxu@ciac.jl.cn, yangwei1988@ciac.jl.cn

(Received 20 February 2010; accepted 22 July 2010; online 31 July 2010)

In the crystal structure of the title compound, C₉H₁₂N₂O₃, weak intermolecular C—H⋯O hydrogen bonds link the molecules into chains. Further weak C—H⋯O hydrogen bonds together with π–π interactions [centroid–centroid distance = 3.672 (4) Å] between neighbouring chains lead to a double-chain structure propagating in [100].

Related literature

For uses of imidazole direvatives, see: Matuszak et al. (1976 ), Verras et al. (2004 ). For the synthesis of the title compound, see: Metobo et al. (2006 ).

Experimental

Crystal data

C₉H₁₂N₂O₃
M_r = 196.21
Triclinic, $[P \overline 1]$
a = 5.972 (3) Å
b = 7.173 (7) Å
c = 12.164 (11) Å
α = 79.630 (16)°
β = 86.620 (15)°
γ = 89.326 (15)°
V = 511.7 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.14 × 0.11 × 0.03 mm

Data collection

Bruker APEX CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.987, T_max = 0.997
2633 measured reflections
1769 independent reflections
915 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.149
S = 0.99
1769 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3ⁱ	0.93	2.36	3.251 (5)	160
C9—H9C⋯O1ⁱⁱ	0.96	2.65	3.531 (5)	153
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810029247/su2164sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029247/su2164Isup2.hkl

checkCIF report

Comment top

Imidazole derivatives are very useful compounds (Matuszak et al., 1976; Verras et al., 2004), and herein we report on the molecular and crystal structure of the title compound, illustrated in Fig. 1.

In the crystal packing of the title compound (Fig. 2), C2—H2···O3 hydrogen bonds involving adjacent molecules lead to the formation of a one-dimensional chain structure. Moverover, via weak C9—H9C···O1 hydrogen bonds and π-π interactions involving two neighbouring chains [the nearest atom-to-atom distance between neighbouring imidazole rings is 3.405 (5) Å], a tubular polymer structure, propagating in [100], is formed.

Related literature top

For uses of imidazole direvatives, see: Matuszak et al. (1976), Verras et al. (2004). For the synthesis of the title compound, see: Metobo et al. (2006).

Experimental top

The title compund was synthesized according to the reported procedure (Metobo et al., 2006). Colourless plate-like crystals, suitable for X-ray diffraction, were obtained by slow evaporation of a solution of the title compound in Diethyl ether at room temperature.

Structure description top

For uses of imidazole direvatives, see: Matuszak et al. (1976), Verras et al. (2004). For the synthesis of the title compound, see: Metobo et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of the title compound, with the atom-labeling scheme and 30% probability displacement ellipsoids.
	Fig. 2. Perspective view along the a-axis of the crystal packing of the title compound, showing the C-H···O interactions as dashed lines [H-atoms not involved in the motif shown have been omitted for clarity].

tert-Butyl 4-formyl-1H-imidazole-1-carboxylate top

Crystal data top

C₉H₁₂N₂O₃	V = 511.7 (8) Å³
M_r = 196.21	Z = 2
Triclinic, P1	F(000) = 208
Hall symbol: -P 1	D_x = 1.274 Mg m⁻³
a = 5.972 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.173 (7) Å	Cell parameters from 360 reflections
c = 12.164 (11) Å	µ = 0.10 mm⁻¹
α = 79.630 (16)°	T = 293 K
β = 86.620 (15)°	Plate, colourless
γ = 89.326 (15)°	0.14 × 0.11 × 0.03 mm

Data collection top

Bruker APEX CCD area detector diffractometer	1769 independent reflections
Radiation source: fine-focus sealed tube	915 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→7
T_min = 0.987, T_max = 0.997	k = −8→8
2633 measured reflections	l = −14→8

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0655P)²] where P = (F_o² + 2F_c²)/3
1769 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₉H₁₂N₂O₃	γ = 89.326 (15)°
M_r = 196.21	V = 511.7 (8) Å³
Triclinic, P1	Z = 2
a = 5.972 (3) Å	Mo Kα radiation
b = 7.173 (7) Å	µ = 0.10 mm⁻¹
c = 12.164 (11) Å	T = 293 K
α = 79.630 (16)°	0.14 × 0.11 × 0.03 mm
β = 86.620 (15)°

Data collection top

Bruker APEX CCD area detector diffractometer	1769 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	915 reflections with I > 2σ(I)
T_min = 0.987, T_max = 0.997	R_int = 0.022
2633 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 0.99	Δρ_max = 0.17 e Å⁻³
1769 reflections	Δρ_min = −0.17 e Å⁻³
130 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.3982 (5)	0.3453 (4)	0.8094 (2)	0.0910 (9)
O2	0.3540 (3)	0.2118 (3)	0.27957 (17)	0.0501 (6)
O3	−0.0065 (4)	0.2329 (4)	0.34612 (19)	0.0794 (9)
N1	0.5369 (4)	0.2729 (4)	0.5822 (2)	0.0562 (8)
N2	0.2860 (4)	0.2475 (4)	0.4569 (2)	0.0480 (7)
C1	0.3197 (5)	0.2938 (4)	0.6277 (3)	0.0505 (9)
C2	0.5087 (5)	0.2466 (4)	0.4808 (3)	0.0503 (9)
H2	0.6262	0.2289	0.4301	0.060*
C3	0.1660 (5)	0.2779 (4)	0.5522 (3)	0.0529 (9)
H3	0.0110	0.2859	0.5627	0.063*
C4	0.2649 (7)	0.3323 (5)	0.7404 (3)	0.0668 (11)
H4	0.1142	0.3480	0.7606	0.080*
C5	0.1920 (6)	0.2290 (5)	0.3551 (3)	0.0519 (9)
C6	0.3044 (5)	0.1971 (5)	0.1619 (3)	0.0470 (8)
C7	0.5376 (5)	0.1878 (5)	0.1061 (3)	0.0634 (10)
H7A	0.6202	0.2993	0.1119	0.095*
H7B	0.5257	0.1806	0.0286	0.095*
H7C	0.6144	0.0775	0.1426	0.095*
C8	0.1737 (5)	0.0162 (5)	0.1638 (3)	0.0702 (11)
H8A	0.2552	−0.0899	0.2017	0.105*
H8B	0.1532	−0.0001	0.0884	0.105*
H8C	0.0299	0.0243	0.2023	0.105*
C9	0.1821 (5)	0.3734 (5)	0.1092 (3)	0.0662 (11)
H9A	0.0359	0.3771	0.1460	0.099*
H9B	0.1674	0.3714	0.0312	0.099*
H9C	0.2654	0.4835	0.1168	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.117 (2)	0.095 (2)	0.0680 (19)	−0.0003 (17)	−0.0229 (17)	−0.0287 (16)
O2	0.0374 (12)	0.0691 (16)	0.0448 (14)	−0.0015 (10)	0.0004 (10)	−0.0143 (12)
O3	0.0360 (14)	0.139 (3)	0.0686 (18)	0.0020 (13)	−0.0019 (12)	−0.0330 (17)
N1	0.0523 (18)	0.064 (2)	0.0522 (19)	−0.0018 (13)	−0.0066 (14)	−0.0074 (15)
N2	0.0376 (15)	0.0592 (19)	0.0468 (18)	−0.0004 (12)	−0.0004 (14)	−0.0089 (14)
C1	0.057 (2)	0.046 (2)	0.049 (2)	−0.0062 (16)	0.0026 (18)	−0.0079 (17)
C2	0.0387 (18)	0.055 (2)	0.055 (2)	−0.0014 (15)	−0.0029 (16)	−0.0051 (19)
C3	0.0437 (19)	0.060 (2)	0.054 (2)	−0.0038 (16)	0.0089 (18)	−0.0105 (19)
C4	0.085 (3)	0.054 (3)	0.062 (3)	−0.007 (2)	−0.005 (2)	−0.013 (2)
C5	0.040 (2)	0.064 (2)	0.051 (2)	−0.0007 (16)	0.0038 (18)	−0.0114 (18)
C6	0.0434 (18)	0.058 (2)	0.041 (2)	0.0034 (16)	−0.0065 (15)	−0.0121 (17)
C7	0.047 (2)	0.086 (3)	0.057 (2)	−0.0012 (18)	0.0030 (17)	−0.016 (2)
C8	0.055 (2)	0.074 (3)	0.086 (3)	−0.0117 (19)	−0.0017 (19)	−0.026 (2)
C9	0.067 (2)	0.068 (3)	0.063 (3)	0.0089 (19)	−0.0101 (19)	−0.007 (2)

Geometric parameters (Å, º) top

O1—C4	1.206 (4)	C4—H4	0.9300
O2—C5	1.315 (4)	C6—C9	1.512 (4)
O2—C6	1.501 (4)	C6—C8	1.518 (5)
O3—C5	1.196 (3)	C6—C7	1.519 (4)
N1—C2	1.301 (4)	C7—H7A	0.9600
N1—C1	1.398 (4)	C7—H7B	0.9600
N2—C3	1.376 (4)	C7—H7C	0.9600
N2—C2	1.378 (4)	C8—H8A	0.9600
N2—C5	1.417 (4)	C8—H8B	0.9600
C1—C3	1.356 (4)	C8—H8C	0.9600
C1—C4	1.464 (5)	C9—H9A	0.9600
C2—H2	0.9300	C9—H9B	0.9600
C3—H3	0.9300	C9—H9C	0.9600

C5—O2—C6	121.3 (2)	C9—C6—C8	113.1 (3)
C2—N1—C1	104.5 (3)	O2—C6—C7	102.4 (2)
C3—N2—C2	106.1 (3)	C9—C6—C7	110.8 (3)
C3—N2—C5	125.2 (3)	C8—C6—C7	111.5 (3)
C2—N2—C5	128.7 (3)	C6—C7—H7A	109.5
C3—C1—N1	110.6 (3)	C6—C7—H7B	109.5
C3—C1—C4	124.5 (3)	H7A—C7—H7B	109.5
N1—C1—C4	124.9 (3)	C6—C7—H7C	109.5
N1—C2—N2	112.7 (3)	H7A—C7—H7C	109.5
N1—C2—H2	123.6	H7B—C7—H7C	109.5
N2—C2—H2	123.6	C6—C8—H8A	109.5
C1—C3—N2	106.1 (3)	C6—C8—H8B	109.5
C1—C3—H3	126.9	H8A—C8—H8B	109.5
N2—C3—H3	126.9	C6—C8—H8C	109.5
O1—C4—C1	125.7 (4)	H8A—C8—H8C	109.5
O1—C4—H4	117.2	H8B—C8—H8C	109.5
C1—C4—H4	117.2	C6—C9—H9A	109.5
O3—C5—O2	129.1 (3)	C6—C9—H9B	109.5
O3—C5—N2	121.5 (3)	H9A—C9—H9B	109.5
O2—C5—N2	109.4 (3)	C6—C9—H9C	109.5
O2—C6—C9	109.5 (2)	H9A—C9—H9C	109.5
O2—C6—C8	109.0 (3)	H9B—C9—H9C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3ⁱ	0.93	2.36	3.251 (5)	160
C9—H9C···O1ⁱⁱ	0.96	2.65	3.531 (5)	153

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

Experimental details

Crystal data
Chemical formula	C₉H₁₂N₂O₃
M_r	196.21
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.972 (3), 7.173 (7), 12.164 (11)
α, β, γ (°)	79.630 (16), 86.620 (15), 89.326 (15)
V (Å³)	511.7 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.14 × 0.11 × 0.03

Data collection
Diffractometer	Bruker APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.987, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	2633, 1769, 915
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.149, 0.99
No. of reflections	1769
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.17

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3ⁱ	0.93	2.36	3.251 (5)	160
C9—H9C···O1ⁱⁱ	0.96	2.65	3.531 (5)	153

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

Acknowledgements

This work was supported by the State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry.

References

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