Dimethyl 3,5-diethyl-1H-pyrrole-2,4-dicarboxyl­ate

Lu, G.-F.; Lin, W.-S.; Zhu, W.-H.; Ou, Z.-P.

doi:10.1107/S1600536811028352

organic compounds

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Volume 67| Part 8| August 2011| Page o2097

doi:10.1107/S1600536811028352

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Dimethyl 3,5-diethyl-1H-pyrrole-2,4-dicarboxylate

Gui-Fen Lu,^a Wen-Sheng Lin,^a Wei-Hua Zhu ^a and Zhong-Ping Ou ^a ^*

^aSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: zpou2011@126.com

(Received 29 June 2011; accepted 15 July 2011; online 23 July 2011)

The title pyrrole derivative, C₁₂H₁₇NO₄, consists of a pyrrole ring with two diagonally attached methoxycarbonyl groups and two diagonally attached ethyl groups. The two carbonyl groups are approximately in the same plane as the pyrrole ring, making dihedral angles of 3.50 (19) and 6.70 (19)°. In the crystal, adjacent molecules are assembled into dimers in a head-to-head mode by pairs of intermolecular N—H⋯O hydrogen bonds.

Related literature

For applications of polysubstituted pyrroles, see: Brockmann & Tour (1995 ); Guilard et al. (2001 ); Trofimov et al. (2004 ). For related structures, see: Takaya et al. (2001 ). For background to complexes of pyrrole derivatives, see: Fan et al. (2008 ); Ou et al. (2009 ); Paixão et al. (2003 ); Yamamoto et al. (1986 ).

Experimental

Crystal data

C₁₂H₁₇NO₄
M_r = 239.27
Monoclinic, P 2₁ /c
a = 4.4697 (7) Å
b = 14.616 (2) Å
c = 19.784 (3) Å
β = 90.467 (2)°
V = 1292.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.982, T_max = 0.991
6296 measured reflections
2285 independent reflections
1977 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.118
S = 1.08
2285 reflections
155 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 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—H1N⋯O4ⁱ	0.85	2.07	2.8773 (15)	160
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811028352/pk2335sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028352/pk2335Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028352/pk2335Isup3.cml

checkCIF report

Comment top

Polysubstituted pyrroles have been paid much attention because of their wide application in the preparation of porphyrin (Trofimov et al., 2004), corrole (Guilard et al., 2001), and as monomers for polymer chemistry (Brockmann & Tour, 1995). In particular, 2-(alkoxycarbonyl)pyrrole derivatives have attracted intense interest in the design and synthesis of functional materials (Fan et al., 2008). The title compound was synthesized as a precursor to corrole compounds.

As shown in Fig. 1, the compound has a five-membered pyrrole ring as skeleton and four substituents. Two diagonally related methoxycarbonyl groups and two diagonally related ethyl substituents are attached to the pyrrole ring. Pairs of intermolecular N1—H1n···O4ⁱ (symmetry code i: -x + 1, -y, -z + 1) hydrogen bonds assemble adjacent molecules in a head-to-head manner, as shown in Fig. 2. All bond distances are in the normal range for this type of compound, as reported by Yamamoto et al. (1986).

Related literature top

For applications of polysubstituted pyrroles, see: Brockmann & Tour (1995); Guilard et al. (2001); Trofimov et al. (2004). For related structures, see: Takaya et al. (2001). For background to complexes of pyrrole derivatives, see: Fan et al. (2008); Ou et al. (2009); Paixão et al. (2003); Yamamoto et al. (1986).

Experimental top

The title compound was synthesized from methyl 3-oxopentanoate by a Knorr-type reaction according to the method reported by Ou et al. (2009). Single crystals were grown from ethyl alcohol by slow evaporation.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The two-dimensional supramolecular configuration, viewed down the a axis.

Dimethyl 3,5-diethyl-1H-pyrrole-2,4-dicarboxylate top

Crystal data top

C₁₂H₁₇NO₄	F(000) = 512
M_r = 239.27	D_x = 1.230 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3745 reflections
a = 4.4697 (7) Å	θ = 2.8–27.4°
b = 14.616 (2) Å	µ = 0.09 mm⁻¹
c = 19.784 (3) Å	T = 298 K
β = 90.467 (2)°	Block, colorless
V = 1292.4 (4) Å³	0.20 × 0.15 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2285 independent reflections
Radiation source: fine-focus sealed tube	1977 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −5→5
T_min = 0.982, T_max = 0.991	k = −15→17
6296 measured reflections	l = −23→21

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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0619P)² + 0.1775P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2285 reflections	Δρ_max = 0.15 e Å⁻³
155 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.110 (8)

Crystal data top

C₁₂H₁₇NO₄	V = 1292.4 (4) Å³
M_r = 239.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.4697 (7) Å	µ = 0.09 mm⁻¹
b = 14.616 (2) Å	T = 298 K
c = 19.784 (3) Å	0.20 × 0.15 × 0.10 mm
β = 90.467 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2285 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1977 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.991	R_int = 0.037
6296 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.118	H-atom parameters constrained
S = 1.08	Δρ_max = 0.15 e Å⁻³
2285 reflections	Δρ_min = −0.16 e Å⁻³
155 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
C1	1.0716 (4)	−0.06793 (13)	0.67868 (10)	0.0771 (5)
H1A	1.1839	−0.0662	0.7202	0.116*
H1B	1.2038	−0.0808	0.6419	0.116*
H1C	0.9220	−0.1149	0.6812	0.116*
C2	0.7645 (3)	0.02789 (10)	0.61180 (6)	0.0485 (4)
C3	0.6201 (3)	0.11655 (9)	0.60495 (6)	0.0429 (3)
C4	0.6275 (3)	0.19623 (9)	0.64214 (6)	0.0428 (3)
C5	0.4354 (3)	0.25896 (9)	0.60761 (6)	0.0440 (3)
C6	0.3161 (3)	0.21461 (9)	0.55064 (6)	0.0422 (3)
C7	0.1103 (3)	0.24441 (10)	0.49502 (7)	0.0504 (4)
H7A	−0.0305	0.2888	0.5126	0.060*
H7B	−0.0030	0.1920	0.4789	0.060*
C8	0.2772 (4)	0.28646 (14)	0.43641 (8)	0.0753 (5)
H8A	0.1370	0.3043	0.4018	0.113*
H8B	0.4146	0.2425	0.4184	0.113*
H8C	0.3857	0.3393	0.4519	0.113*
C9	0.3744 (3)	0.35270 (11)	0.62967 (7)	0.0548 (4)
C10	0.1230 (6)	0.49089 (14)	0.60468 (13)	0.1063 (8)
H10A	0.0056	0.5182	0.5692	0.159*
H10B	0.2992	0.5270	0.6126	0.159*
H10C	0.0071	0.4882	0.6453	0.159*
C11	0.8015 (3)	0.21297 (11)	0.70625 (7)	0.0530 (4)
H11A	0.8638	0.2765	0.7077	0.064*
H11B	0.9803	0.1754	0.7062	0.064*
C12	0.6215 (4)	0.19160 (16)	0.76897 (8)	0.0802 (6)
H12A	0.7415	0.2033	0.8085	0.120*
H12B	0.5628	0.1284	0.7683	0.120*
H12C	0.4463	0.2296	0.7698	0.120*
N1	0.4307 (2)	0.12986 (7)	0.55029 (5)	0.0439 (3)
H1N	0.3918	0.0897	0.5207	0.053*
O1	0.2088 (3)	0.39946 (8)	0.58509 (7)	0.0858 (4)
O2	0.4557 (3)	0.38626 (9)	0.68180 (7)	0.0867 (4)
O3	0.9285 (3)	0.01959 (7)	0.66768 (5)	0.0619 (3)
O4	0.7364 (3)	−0.03336 (7)	0.57103 (5)	0.0725 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0872 (12)	0.0737 (11)	0.0700 (11)	0.0164 (9)	−0.0229 (9)	0.0148 (9)
C2	0.0557 (8)	0.0537 (8)	0.0361 (7)	−0.0007 (6)	−0.0071 (6)	0.0027 (6)
C3	0.0452 (7)	0.0510 (8)	0.0324 (6)	−0.0027 (6)	−0.0039 (5)	0.0028 (5)
C4	0.0428 (7)	0.0518 (7)	0.0337 (6)	−0.0065 (5)	0.0008 (5)	−0.0004 (5)
C5	0.0448 (7)	0.0501 (7)	0.0370 (7)	−0.0040 (6)	0.0018 (5)	−0.0018 (5)
C6	0.0426 (7)	0.0485 (7)	0.0356 (7)	−0.0011 (5)	0.0022 (5)	0.0011 (5)
C7	0.0499 (7)	0.0581 (8)	0.0430 (7)	0.0065 (6)	−0.0060 (6)	−0.0012 (6)
C8	0.0784 (11)	0.0967 (13)	0.0507 (9)	0.0129 (10)	−0.0038 (8)	0.0251 (9)
C9	0.0604 (9)	0.0543 (8)	0.0497 (8)	−0.0030 (7)	0.0003 (7)	−0.0054 (7)
C10	0.144 (2)	0.0585 (11)	0.1155 (18)	0.0297 (12)	−0.0188 (16)	−0.0147 (12)
C11	0.0521 (8)	0.0635 (9)	0.0432 (8)	−0.0057 (7)	−0.0091 (6)	−0.0072 (6)
C12	0.0775 (12)	0.1278 (17)	0.0351 (8)	−0.0093 (11)	−0.0089 (7)	−0.0013 (9)
N1	0.0515 (7)	0.0469 (6)	0.0332 (6)	−0.0012 (5)	−0.0062 (5)	−0.0037 (4)
O1	0.1210 (11)	0.0572 (7)	0.0788 (8)	0.0254 (7)	−0.0276 (8)	−0.0122 (6)
O2	0.1163 (11)	0.0700 (8)	0.0733 (8)	0.0097 (7)	−0.0253 (7)	−0.0288 (6)
O3	0.0770 (7)	0.0614 (7)	0.0468 (6)	0.0075 (5)	−0.0213 (5)	0.0043 (5)
O4	0.1030 (9)	0.0579 (7)	0.0560 (7)	0.0185 (6)	−0.0278 (6)	−0.0112 (5)

Geometric parameters (Å, º) top

C1—O3	1.446 (2)	C7—H7B	0.9700
C1—H1A	0.9600	C8—H8A	0.9600
C1—H1B	0.9600	C8—H8B	0.9600
C1—H1C	0.9600	C8—H8C	0.9600
C2—O4	1.2109 (17)	C9—O2	1.1959 (18)
C2—O3	1.3270 (16)	C9—O1	1.335 (2)
C2—C3	1.453 (2)	C10—O1	1.444 (2)
C3—C4	1.3779 (19)	C10—H10A	0.9600
C3—N1	1.3816 (16)	C10—H10B	0.9600
C4—C5	1.4266 (19)	C10—H10C	0.9600
C4—C11	1.5024 (18)	C11—C12	1.517 (2)
C5—C6	1.4017 (17)	C11—H11A	0.9700
C5—C9	1.464 (2)	C11—H11B	0.9700
C6—N1	1.3404 (17)	C12—H12A	0.9600
C6—C7	1.4935 (18)	C12—H12B	0.9600
C7—C8	1.514 (2)	C12—H12C	0.9600
C7—H7A	0.9700	N1—H1N	0.8457

O3—C1—H1A	109.5	C7—C8—H8C	109.5
O3—C1—H1B	109.5	H8A—C8—H8C	109.5
H1A—C1—H1B	109.5	H8B—C8—H8C	109.5
O3—C1—H1C	109.5	O2—C9—O1	121.51 (15)
H1A—C1—H1C	109.5	O2—C9—C5	125.79 (15)
H1B—C1—H1C	109.5	O1—C9—C5	112.69 (13)
O4—C2—O3	122.75 (13)	O1—C10—H10A	109.5
O4—C2—C3	123.61 (12)	O1—C10—H10B	109.5
O3—C2—C3	113.64 (12)	H10A—C10—H10B	109.5
C4—C3—N1	108.11 (12)	O1—C10—H10C	109.5
C4—C3—C2	134.03 (12)	H10A—C10—H10C	109.5
N1—C3—C2	117.86 (11)	H10B—C10—H10C	109.5
C3—C4—C5	106.00 (11)	C4—C11—C12	112.50 (12)
C3—C4—C11	126.77 (13)	C4—C11—H11A	109.1
C5—C4—C11	127.23 (12)	C12—C11—H11A	109.1
C6—C5—C4	108.15 (12)	C4—C11—H11B	109.1
C6—C5—C9	127.00 (13)	C12—C11—H11B	109.1
C4—C5—C9	124.85 (12)	H11A—C11—H11B	107.8
N1—C6—C5	106.78 (11)	C11—C12—H12A	109.5
N1—C6—C7	119.92 (12)	C11—C12—H12B	109.5
C5—C6—C7	133.28 (13)	H12A—C12—H12B	109.5
C6—C7—C8	112.23 (12)	C11—C12—H12C	109.5
C6—C7—H7A	109.2	H12A—C12—H12C	109.5
C8—C7—H7A	109.2	H12B—C12—H12C	109.5
C6—C7—H7B	109.2	C6—N1—C3	110.97 (11)
C8—C7—H7B	109.2	C6—N1—H1N	124.6
H7A—C7—H7B	107.9	C3—N1—H1N	124.4
C7—C8—H8A	109.5	C9—O1—C10	116.33 (15)
C7—C8—H8B	109.5	C2—O3—C1	116.55 (12)
H8A—C8—H8B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4ⁱ	0.85	2.07	2.8773 (15)	160

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₇NO₄
M_r	239.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	4.4697 (7), 14.616 (2), 19.784 (3)
β (°)	90.467 (2)
V (Å³)	1292.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.982, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	6296, 2285, 1977
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.118, 1.08
No. of reflections	2285
No. of parameters	155
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.16

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4ⁱ	0.85	2.07	2.8773 (15)	159.5

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

This work was supported by the Natural Science Foundation of China (No. 21001054) and the Natural Science Fund for Colleges and Universities in Jiangsu Province (No. 10KJB150003)

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