Ethyl 5-formyl-3,4-dimethyl-1H-pyrrole-2-carboxyl­ate

Wu, W.-N.; Wang, Y.; Wang, Q.-F.

doi:10.1107/S160053680902323X

organic compounds

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Volume 65| Part 7| July 2009| Page o1661

doi:10.1107/S160053680902323X

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Ethyl 5-formyl-3,4-dimethyl-1H-pyrrole-2-carboxylate

Wei-Na Wu,^a Yuan Wang ^a ^* and Qiu-Fen Wang ^a

^aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiaozuo 454000, People's Republic of China
^*Correspondence e-mail: wangyuan08@hpu.edu.cn

(Received 14 May 2009; accepted 17 June 2009; online 20 June 2009)

The molecule of the title compound, C₁₀H₁₃NO₃, is approximately planar (maximum deviation 0.1424 Å). In the crystal, molecules are linked into inversion dimers by pairs of N—H⋯O hydrogen bonds, and the dimeric units are linked by non-classical C—H⋯O hydrogen bonds, forming a layered structure.

Related literature

For a related structure, see: Kang et al. (2008 ). For our studies of bis(pyrrol-2-yl-methyleneamine) ligands, see: Wang et al. (2008 , 2009 ). For the synthesis, see: Wang et al. (2008).

Experimental

Crystal data

C₁₀H₁₃NO₃
M_r = 195.21
Triclinic, $[P \overline 1]$
a = 7.2223 (12) Å
b = 7.4347 (12) Å
c = 10.0488 (17) Å
α = 78.412 (2)°
β = 84.191 (2)°
γ = 79.051 (2)°
V = 517.84 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.30 × 0.18 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.980, T_max = 0.986
6232 measured reflections
2416 independent reflections
1692 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.212
S = 1.07
2416 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	2.07	2.919 (2)	169
C5—H5A⋯O1ⁱⁱ	0.93	2.54	3.347 (3)	145
Symmetry codes: (i) -x, -y+2, -z+2; (ii) -x+1, -y+2, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXL97 (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/S160053680902323X/gw2066sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680902323X/gw2066Isup2.hkl

checkCIF report

Comment top

Schiff Base bearing pyrrole units have been extensively investigated for a long time because they could stabilize mono- or binuclear metal complexes which have various structures and special properties. As part of our owning studies of bis(pyrrol-2-yl-methyleneamine) ligands (Wang et al., 2008), we report here the crystal structure of the title compound, (I), (Fig. 1), which is approximately planar.

The molecules are joined to dimers via intermolecular N—H···O hydrogen bonds (Table 1), and the dimeric units are linked with each other by nonclassical C—H···O hydrogen bonds (Table 1) to form a layered geometry (Fig. 2).

Related literature top

For a related structure, see: Kang(2008). For our owning studies of bis(pyrrol-2-yl-methyleneamine) ligands, see: Wang et al. (2008, 2009). For the synthesis, see: Wang et al. (2008).

Experimental top

A quantity of POCl₃ (2.30 g, 0.015 mol) was added dropwise to DMF (1.10 g, 0.015 mol) under stirring on an ice-water bath, then a CH₂Cl₂solution (30 ml) containing 3,4-dimethyl-2-ethoxycarbonyl-pyrrole (2.51 g, 0.015 mol) was added. After stirring at room temperature for 4 h, a 10% Na₂CO₃ solution (80 ml) was added. The reaction mixture was refluxing for 0.5 h, then cooled to room temperature, extracted with CH₂Cl₂ (3×10 ml), and dried with anhydrous Na₂CO₃. The solvent was evaporated under reduced pressure. The crude product was treated with column chromatography on silica gel [petroleum ether-ethyl acetate (100:1)] to yield (I) 2.25 g (77%). Colorless prisms of (I) were obtained by slow evaporation of an ethanol solution.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXL97 (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 molecular structure of the title compound shown with 50% probability displacement ellipsoids.
	Fig. 2. Layered structure of the title compound. Hydrogen-bonding interactions are shown as dashed lines.

Ethyl 5-formyl-3,4-dimethyl-1H-pyrrole-2-carboxylate top

Crystal data top

C₁₀H₁₃NO₃	Z = 2
M_r = 195.21	F(000) = 208
Triclinic, P1	D_x = 1.252 Mg m⁻³
a = 7.2223 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.4347 (12) Å	Cell parameters from 2123 reflections
c = 10.0488 (17) Å	θ = 2.1–27.7°
α = 78.412 (2)°	µ = 0.09 mm⁻¹
β = 84.191 (2)°	T = 296 K
γ = 79.051 (2)°	Prism, colorless
V = 517.84 (15) Å³	0.30 × 0.18 × 0.15 mm

Data collection top

Bruker SMART CCD diffractometer	2416 independent reflections
Radiation source: fine-focus sealed tube	1692 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 27.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.980, T_max = 0.986	k = −9→9
6232 measured reflections	l = −13→13

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.212	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1226P)² + 0.0669P] where P = (F_o² + 2F_c²)/3
2416 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₀H₁₃NO₃	γ = 79.051 (2)°
M_r = 195.21	V = 517.84 (15) Å³
Triclinic, P1	Z = 2
a = 7.2223 (12) Å	Mo Kα radiation
b = 7.4347 (12) Å	µ = 0.09 mm⁻¹
c = 10.0488 (17) Å	T = 296 K
α = 78.412 (2)°	0.30 × 0.18 × 0.15 mm
β = 84.191 (2)°

Data collection top

Bruker SMART CCD diffractometer	2416 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1692 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.986	R_int = 0.017
6232 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.212	H-atom parameters constrained
S = 1.07	Δρ_max = 0.29 e Å⁻³
2416 reflections	Δρ_min = −0.29 e Å⁻³
129 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
C4	0.3634 (3)	0.8003 (2)	1.03572 (18)	0.0519 (5)
C8	0.2197 (3)	0.8074 (3)	1.1488 (2)	0.0593 (5)
C3	0.5533 (3)	0.7196 (2)	1.0262 (2)	0.0556 (5)
C1	0.4613 (3)	0.8683 (3)	0.8185 (2)	0.0585 (5)
C2	0.6149 (3)	0.7620 (3)	0.8883 (2)	0.0605 (5)
C5	0.4495 (4)	0.9519 (4)	0.6766 (2)	0.0780 (7)
H5A	0.5582	0.9328	0.6195	0.094*
C7	0.6715 (3)	0.6084 (3)	1.1392 (2)	0.0720 (6)
H7A	0.7978	0.5703	1.1030	0.108*
H7B	0.6181	0.5001	1.1808	0.108*
H7C	0.6741	0.6836	1.2060	0.108*
C9	0.1496 (4)	0.7387 (5)	1.3863 (3)	0.1023 (10)
H9A	0.1126	0.8660	1.4008	0.123*
H9B	0.0375	0.6948	1.3693	0.123*
C10	0.2342 (5)	0.6221 (6)	1.5051 (3)	0.1191 (12)
H10A	0.1453	0.6265	1.5826	0.179*
H10B	0.3450	0.6663	1.5212	0.179*
H10C	0.2687	0.4960	1.4906	0.179*
C6	0.8106 (3)	0.7039 (4)	0.8285 (3)	0.0872 (8)
H6A	0.8884	0.6318	0.8993	0.131*
H6B	0.8631	0.8128	0.7869	0.131*
H6C	0.8059	0.6301	0.7612	0.131*
O3	0.2874 (2)	0.7315 (2)	1.26943 (15)	0.0771 (5)
O2	0.0572 (2)	0.8726 (3)	1.13418 (17)	0.0899 (6)
O1	0.3095 (3)	1.0448 (3)	0.62612 (17)	0.1053 (7)
N1	0.3105 (2)	0.8889 (2)	0.90931 (15)	0.0539 (4)
H1A	0.1993	0.9484	0.8903	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C4	0.0506 (9)	0.0554 (9)	0.0481 (10)	−0.0087 (7)	−0.0052 (7)	−0.0051 (7)
C8	0.0550 (11)	0.0682 (11)	0.0493 (10)	−0.0082 (8)	−0.0053 (8)	0.0004 (8)
C3	0.0517 (10)	0.0526 (9)	0.0619 (11)	−0.0072 (7)	−0.0068 (8)	−0.0095 (8)
C1	0.0601 (11)	0.0638 (11)	0.0518 (11)	−0.0101 (8)	0.0033 (8)	−0.0155 (8)
C2	0.0555 (11)	0.0608 (10)	0.0652 (12)	−0.0072 (8)	0.0024 (9)	−0.0180 (9)
C5	0.0779 (15)	0.1027 (17)	0.0473 (12)	−0.0053 (13)	0.0084 (11)	−0.0156 (11)
C7	0.0584 (12)	0.0679 (12)	0.0837 (15)	0.0005 (9)	−0.0165 (10)	−0.0048 (10)
C9	0.0778 (16)	0.148 (3)	0.0571 (14)	−0.0005 (16)	0.0093 (12)	0.0119 (14)
C10	0.108 (2)	0.161 (3)	0.0668 (17)	−0.010 (2)	0.0026 (16)	0.0126 (18)
C6	0.0651 (14)	0.0912 (16)	0.0983 (19)	−0.0010 (12)	0.0157 (13)	−0.0233 (14)
O3	0.0625 (9)	0.1094 (12)	0.0475 (8)	−0.0070 (8)	−0.0043 (7)	0.0061 (7)
O2	0.0552 (9)	0.1288 (15)	0.0616 (10)	0.0092 (9)	0.0013 (7)	0.0126 (9)
O1	0.0927 (14)	0.1528 (19)	0.0505 (10)	0.0128 (12)	−0.0006 (9)	−0.0065 (10)
N1	0.0507 (8)	0.0637 (9)	0.0445 (8)	−0.0055 (7)	−0.0028 (6)	−0.0083 (6)

Geometric parameters (Å, º) top

C4—N1	1.364 (2)	C7—H7B	0.9600
C4—C3	1.390 (3)	C7—H7C	0.9600
C4—C8	1.461 (3)	C9—C10	1.443 (4)
C8—O2	1.194 (2)	C9—O3	1.463 (3)
C8—O3	1.330 (2)	C9—H9A	0.9700
C3—C2	1.405 (3)	C9—H9B	0.9700
C3—C7	1.500 (3)	C10—H10A	0.9600
C1—N1	1.354 (2)	C10—H10B	0.9600
C1—C2	1.396 (3)	C10—H10C	0.9600
C1—C5	1.440 (3)	C6—H6A	0.9600
C2—C6	1.498 (3)	C6—H6B	0.9600
C5—O1	1.206 (3)	C6—H6C	0.9600
C5—H5A	0.9300	N1—H1A	0.8600
C7—H7A	0.9600

N1—C4—C3	108.93 (17)	H7B—C7—H7C	109.5
N1—C4—C8	117.47 (17)	C10—C9—O3	108.7 (3)
C3—C4—C8	133.61 (18)	C10—C9—H9A	109.9
O2—C8—O3	123.29 (19)	O3—C9—H9A	109.9
O2—C8—C4	123.38 (19)	C10—C9—H9B	109.9
O3—C8—C4	113.32 (17)	O3—C9—H9B	109.9
C4—C3—C2	106.33 (17)	H9A—C9—H9B	108.3
C4—C3—C7	127.64 (19)	C9—C10—H10A	109.5
C2—C3—C7	126.03 (19)	C9—C10—H10B	109.5
N1—C1—C2	108.25 (17)	H10A—C10—H10B	109.5
N1—C1—C5	121.70 (19)	C9—C10—H10C	109.5
C2—C1—C5	130.0 (2)	H10A—C10—H10C	109.5
C1—C2—C3	107.43 (18)	H10B—C10—H10C	109.5
C1—C2—C6	126.8 (2)	C2—C6—H6A	109.5
C3—C2—C6	125.8 (2)	C2—C6—H6B	109.5
O1—C5—C1	125.0 (2)	H6A—C6—H6B	109.5
O1—C5—H5A	117.5	C2—C6—H6C	109.5
C1—C5—H5A	117.5	H6A—C6—H6C	109.5
C3—C7—H7A	109.5	H6B—C6—H6C	109.5
C3—C7—H7B	109.5	C8—O3—C9	115.39 (18)
H7A—C7—H7B	109.5	C1—N1—C4	109.06 (16)
C3—C7—H7C	109.5	C1—N1—H1A	125.5
H7A—C7—H7C	109.5	C4—N1—H1A	125.5

N1—C4—C8—O2	6.4 (3)	C7—C3—C2—C1	−179.66 (18)
C3—C4—C8—O2	−173.7 (2)	C4—C3—C2—C6	−179.9 (2)
N1—C4—C8—O3	−174.52 (16)	C7—C3—C2—C6	−0.1 (3)
C3—C4—C8—O3	5.4 (3)	N1—C1—C5—O1	−0.2 (4)
N1—C4—C3—C2	−0.1 (2)	C2—C1—C5—O1	−178.7 (2)
C8—C4—C3—C2	179.9 (2)	O2—C8—O3—C9	−2.1 (4)
N1—C4—C3—C7	−179.99 (18)	C4—C8—O3—C9	178.8 (2)
C8—C4—C3—C7	0.1 (3)	C10—C9—O3—C8	169.4 (3)
N1—C1—C2—C3	−0.7 (2)	C2—C1—N1—C4	0.6 (2)
C5—C1—C2—C3	178.0 (2)	C5—C1—N1—C4	−178.23 (18)
N1—C1—C2—C6	179.8 (2)	C3—C4—N1—C1	−0.3 (2)
C5—C1—C2—C6	−1.5 (4)	C8—C4—N1—C1	179.68 (15)
C4—C3—C2—C1	0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.07	2.919 (2)	169
C5—H5A···O1ⁱⁱ	0.93	2.54	3.347 (3)	145

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃NO₃
M_r	195.21
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.2223 (12), 7.4347 (12), 10.0488 (17)
α, β, γ (°)	78.412 (2), 84.191 (2), 79.051 (2)
V (Å³)	517.84 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.980, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	6232, 2416, 1692
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.654

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.212, 1.07
No. of reflections	2416
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.29

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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—H1A···O2ⁱ	0.86	2.07	2.919 (2)	169.0
C5—H5A···O1ⁱⁱ	0.93	2.54	3.347 (3)	145.3

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

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kang, S.-S., Li, H.-L., Zeng, H.-S. & Wang, H.-B. (2008). Acta Cryst. E64, o1125. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Y., Wu, W.-N. & Yang, Z.-Y. (2009). X-ray Struct. Anal. Online, 25, 33-34. CSD CrossRef CAS Google Scholar
Wang, Y., Yang, Z.-Y. & Chen, Z.-N. (2008). Bioorg. Med. Chem. Lett., 18, 298-303. Web of Science CSD CrossRef PubMed CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1661

doi:10.1107/S160053680902323X

Open

access