Ethyl 5-methyl-1H-pyrrole-2-carboxyl­ate

Zhang, Z.-P.; Wang, Y.; Li, X.-X.

doi:10.1107/S1600536811021180

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1585

doi:10.1107/S1600536811021180

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Ethyl 5-methyl-1H-pyrrole-2-carboxylate

Zhao-Po Zhang,^a Yuan Wang ^a ^* and Xiao-Xia Li ^b

^aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiaozuo 454000, People's Republic of China, and ^bInstitute of Functional Materials, Jiangxi University of Finance and Economics, Nanchang 330013, People's Republic of China
^*Correspondence e-mail: wangyuan08@hpu.edu.cn

(Received 1 June 2011; accepted 1 June 2011; online 4 June 2011)

In the title molecule, C₈H₁₁NO₂, the r.m.s. deviation of non-H atoms from their best plane is 0.031 Å. Molecules are connected via a pair of N—H⋯O hydrogen bonds into a centrosymmetric dimer.

Related literature

For the crystal structure of the 5-cyano analogue of the title compound, see: Zhang et al. (2003 ). For the synthesis of the title compound, see: Motekaitis et al. (1970 ).

Experimental

Crystal data

C₈H₁₁NO₂
M_r = 153.18
Monoclinic, P 2₁ /c
a = 7.0759 (3) Å
b = 18.0705 (9) Å
c = 6.6606 (3) Å
β = 101.349 (3)°
V = 835.01 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.984, T_max = 0.989
7496 measured reflections
1991 independent reflections
1157 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.143
S = 1.02
1991 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	1.99	2.8363 (19)	167
Symmetry code: (i) -x+1, -y+1, -z+2.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811021180/gk2381sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021180/gk2381Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811021180/gk2381Isup3.cml

checkCIF report

Comment top

As part of our studies on hydrazone ligands bearing pyrrole unit the title compound was synthesized and characterized by X-ray diffraction.

The non-hydrogen atoms of the title molecule (Fig. 1) are situated in a fair plane (r.m.s. deviation of the non-hydrogen atoms being 0.0306 Å). In the crystal, the molecules are linked into a centrosymmetric dimer by two intermolecular N—H···O hydrogen bonds, forming a R₂²(10) ring motif (Table 1, Fig. 2).

Related literature top

For the crystal structure of the 5-cyano analogue of the title compound, see: Zhang et al. (2003). For the synthesis of the title compound, see: Motekaitis et al. (1970).

Experimental top

The title compound was synthesized according to the literature procedure (Motekaitis et al., 1970). The crude orange solid was washed well with ice water and dried in air. Colorless plates of the title compound were obtained by slow evaporation of petroleum ether/ethyl acetate (100:1) solution.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The title compound with the displacement ellipsoids shown at the 50% probability level.
	Fig. 2. The centrosymmetric dimer via N-H···O hydrogen bonds of the title compound (hydrogen bonds shown as dashed lines, symmetry code:: 1 - x, 1 - y, 2 - z).

Ethyl 5-methyl-1H-pyrrole-2-carboxylate top

Crystal data top

C₈H₁₁NO₂	F(000) = 328
M_r = 153.18	D_x = 1.218 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2070 reflections
a = 7.0759 (3) Å	θ = 2.3–24.2°
b = 18.0705 (9) Å	µ = 0.09 mm⁻¹
c = 6.6606 (3) Å	T = 296 K
β = 101.349 (3)°	Plate, colorless
V = 835.01 (7) Å³	0.20 × 0.15 × 0.13 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1991 independent reflections
Radiation source: fine-focus sealed tube	1157 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 27.9°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
T_min = 0.984, T_max = 0.989	k = −23→23
7496 measured reflections	l = −8→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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0683P)² + 0.0738P] where P = (F_o² + 2F_c²)/3
1991 reflections	(Δ/σ)_max < 0.001
102 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₈H₁₁NO₂	V = 835.01 (7) Å³
M_r = 153.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0759 (3) Å	µ = 0.09 mm⁻¹
b = 18.0705 (9) Å	T = 296 K
c = 6.6606 (3) Å	0.20 × 0.15 × 0.13 mm
β = 101.349 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1991 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1157 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.989	R_int = 0.029
7496 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.02	Δρ_max = 0.16 e Å⁻³
1991 reflections	Δρ_min = −0.16 e Å⁻³
102 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
O2	0.12507 (16)	0.64959 (6)	0.92921 (18)	0.0629 (4)
N1	0.52408 (19)	0.57393 (7)	0.7402 (2)	0.0581 (4)
H1	0.5637	0.5360	0.8146	0.087*
C6	0.2631 (2)	0.60036 (9)	0.9187 (3)	0.0585 (4)
O1	0.2888 (2)	0.54602 (8)	1.0272 (2)	0.0861 (5)
C5	0.3729 (2)	0.61798 (9)	0.7644 (2)	0.0548 (4)
C2	0.6023 (2)	0.59835 (10)	0.5831 (3)	0.0600 (5)
C8	−0.1423 (3)	0.69326 (11)	1.0591 (3)	0.0768 (6)
H8A	−0.0794	0.7400	1.0916	0.115*
H8B	−0.2268	0.6837	1.1527	0.115*
H8C	−0.2159	0.6946	0.9217	0.115*
C4	0.3561 (2)	0.67196 (10)	0.6178 (3)	0.0651 (5)
H4	0.2658	0.7100	0.5976	0.078*
C7	0.0051 (3)	0.63353 (10)	1.0768 (3)	0.0691 (5)
H7A	0.0825	0.6324	1.2142	0.083*
H7B	−0.0569	0.5858	1.0480	0.083*
C1	0.7719 (3)	0.56133 (11)	0.5261 (3)	0.0780 (6)
H1A	0.8862	0.5893	0.5791	0.117*
H1B	0.7543	0.5585	0.3796	0.117*
H1C	0.7847	0.5123	0.5827	0.117*
C3	0.4987 (3)	0.65956 (10)	0.5044 (3)	0.0712 (5)
H3	0.5200	0.6879	0.3944	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0581 (7)	0.0624 (7)	0.0748 (8)	0.0073 (5)	0.0294 (6)	0.0035 (6)
N1	0.0533 (8)	0.0560 (8)	0.0691 (9)	0.0001 (6)	0.0221 (7)	0.0000 (6)
C6	0.0519 (9)	0.0563 (9)	0.0698 (11)	0.0019 (8)	0.0182 (8)	−0.0026 (9)
O1	0.0847 (10)	0.0820 (9)	0.1032 (11)	0.0273 (8)	0.0467 (8)	0.0332 (8)
C5	0.0486 (9)	0.0532 (9)	0.0649 (11)	−0.0015 (7)	0.0165 (8)	−0.0035 (8)
C2	0.0539 (9)	0.0652 (10)	0.0644 (11)	−0.0091 (8)	0.0202 (8)	−0.0063 (8)
C8	0.0689 (12)	0.0819 (13)	0.0884 (15)	0.0074 (10)	0.0373 (11)	−0.0054 (10)
C4	0.0587 (10)	0.0616 (10)	0.0766 (12)	0.0036 (8)	0.0172 (9)	0.0060 (9)
C7	0.0635 (11)	0.0788 (12)	0.0716 (12)	0.0050 (9)	0.0293 (9)	0.0048 (9)
C1	0.0664 (12)	0.0894 (14)	0.0867 (14)	−0.0022 (10)	0.0360 (10)	−0.0094 (11)
C3	0.0683 (11)	0.0781 (12)	0.0715 (12)	−0.0023 (10)	0.0246 (10)	0.0107 (10)

Geometric parameters (Å, º) top

C2—C1	1.487 (2)	C1—H1A	0.9600
C2—C3	1.373 (3)	C1—H1B	0.9600
C4—C3	1.392 (2)	C1—H1C	0.9600
C5—C4	1.369 (2)	C3—H3	0.9300
N1—C2	1.351 (2)	C4—H4	0.9300
N1—C5	1.368 (2)	C7—H7A	0.9700
C6—C5	1.440 (2)	C7—H7B	0.9700
C6—O1	1.212 (2)	C8—H8A	0.9600
O2—C6	1.3333 (19)	C8—H8B	0.9600
O2—C7	1.4490 (19)	C8—H8C	0.9600
C8—C7	1.490 (2)	N1—H1	0.8600

C6—O2—C7	115.81 (13)	C5—C4—C3	107.57 (16)
C2—N1—C5	110.53 (14)	C5—C4—H4	126.2
C2—N1—H1	124.7	C3—C4—H4	126.2
C5—N1—H1	124.7	O2—C7—C8	107.22 (15)
O1—C6—O2	122.31 (15)	O2—C7—H7A	110.3
O1—C6—C5	124.50 (15)	C8—C7—H7A	110.3
O2—C6—C5	113.19 (15)	O2—C7—H7B	110.3
C4—C5—N1	106.89 (14)	C8—C7—H7B	110.3
C4—C5—C6	133.09 (16)	H7A—C7—H7B	108.5
N1—C5—C6	119.97 (15)	C2—C1—H1A	109.5
N1—C2—C3	106.81 (15)	C2—C1—H1B	109.5
N1—C2—C1	121.69 (16)	H1A—C1—H1B	109.5
C3—C2—C1	131.48 (17)	C2—C1—H1C	109.5
C7—C8—H8A	109.5	H1A—C1—H1C	109.5
C7—C8—H8B	109.5	H1B—C1—H1C	109.5
H8A—C8—H8B	109.5	C2—C3—C4	108.20 (16)
C7—C8—H8C	109.5	C2—C3—H3	125.9
H8A—C8—H8C	109.5	C4—C3—H3	125.9
H8B—C8—H8C	109.5

C7—O2—C6—O1	−0.9 (2)	C5—N1—C2—C3	−0.1 (2)
C7—O2—C6—C5	177.93 (14)	C5—N1—C2—C1	178.73 (15)
C2—N1—C5—C4	−0.12 (19)	N1—C5—C4—C3	0.26 (19)
C2—N1—C5—C6	177.58 (14)	C6—C5—C4—C3	−177.02 (18)
O1—C6—C5—C4	173.57 (18)	C6—O2—C7—C8	−178.10 (14)
O2—C6—C5—C4	−5.3 (3)	N1—C2—C3—C4	0.2 (2)
O1—C6—C5—N1	−3.4 (3)	C1—C2—C3—C4	−178.40 (18)
O2—C6—C5—N1	177.75 (13)	C5—C4—C3—C2	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	1.99	2.8363 (19)	167

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₈H₁₁NO₂
M_r	153.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.0759 (3), 18.0705 (9), 6.6606 (3)
β (°)	101.349 (3)
V (Å³)	835.01 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.15 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.984, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	7496, 1991, 1157
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.143, 1.02
No. of reflections	1991
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16

Computer programs: APEX2 (Bruker, 2007), SAINT (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
N1—H1···O1ⁱ	0.86	1.99	2.8363 (19)	167.4

Symmetry code: (i) −x+1, −y+1, −z+2.

Acknowledgements

The authors are grateful to the National Natural Science Foundation of China for financial support (grant No. 21001040).

References

Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Motekaitis, R. J., Heinert, H. D. & Martell, A. E. (1970). J. Org. Chem. 35, 2504–2511. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, Y.-H., Yin, Z., Li, X.-F., He, J. & Cheng, J.-P. (2003). Acta Cryst. E59, o1881–o1882. Web of Science CSD CrossRef IUCr Journals Google Scholar