2-Ethyl 4-methyl 5-ethyl-3-methyl-1H-pyrrole-2,4-dicarboxyl-ate.

The title pyrrole derivative compound, C(12)H(17)NO(4), was synthesized from methyl 3-oxopenta-noate by a Knorr-type reaction and contains a pyrrole ring to which two diagonal alk-oxy-carbonyl groups and two diagonal alkyl substituents are attached. The methyl-carbonyl and ethyl-carbonyl substituents are approximately co-planar with the pyrrole ring, making dihedral angles of 5.64 (2) and 3.44 (1)°, respectively. In the crystal, adjacent mol-ecules are assembled by pairs of N-H⋯O hydrogen bonds into dimers in a head-to-head mode.

Related literature

For applications of polysubstituted pyrroles, see: Brockmann & Tour, (1995 ▶); Guilard et al. (2001 ▶); Trofimov et al. (2004 ▶). For related structures, see: Lu et al. (2011 ▶); Takaya et al. (2001 ▶). For 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 = 239.27

Triclinic,

a = 7.2827 (10) Å

b = 8.8573 (12) Å

c = 11.1806 (16) Å

α = 77.948 (2)°

β = 73.135 (2)°

γ = 69.970 (2)°

V = 643.62 (15) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.15 × 0.12 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.986, T max = 0.995

3249 measured reflections

2255 independent reflections

1891 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.220

S = 1.11

2255 reflections

159 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.36 e Å−3

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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812001729/vm2149sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812001729/vm2149Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812001729/vm2149Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H17NO4	Z = 2
Mr = 239.27	F(000) = 256
Triclinic, P1	Dx = 1.235 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2827 (10) Å	Cell parameters from 1663 reflections
b = 8.8573 (12) Å	θ = 2.4–26.8°
c = 11.1806 (16) Å	µ = 0.09 mm−1
α = 77.948 (2)°	T = 293 K
β = 73.135 (2)°	Sheet, colorless
γ = 69.970 (2)°	0.15 × 0.12 × 0.06 mm
V = 643.62 (15) Å3

Bruker APEXII CCD area-detector diffractometer	2255 independent reflections
Radiation source: fine-focus sealed tube	1891 reflections with I > 2σ(I)
graphite	Rint = 0.018
φ and ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→6
Tmin = 0.986, Tmax = 0.995	k = −10→9
3249 measured reflections	l = −13→13

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)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.220	w = 1/[σ2(Fo2) + (0.1366P)2 + 0.1514P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max < 0.001
2255 reflections	Δρmax = 0.51 e Å−3
159 parameters	Δρmin = −0.36 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: 0.046 (17)

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.

	x	y	z	Uiso*/Ueq
C10	0.3898 (4)	−0.0962 (3)	−0.1197 (2)	0.0550 (6)
H10A	0.4158	−0.2064	−0.0808	0.082*
H10B	0.5149	−0.0720	−0.1553	0.082*
H10C	0.3217	−0.0814	−0.1849	0.082*
C11	0.2132 (4)	−0.1884 (3)	0.1807 (2)	0.0560 (6)
C12	0.3494 (6)	−0.4707 (4)	0.1703 (3)	0.0963 (11)
H12A	0.4249	−0.5445	0.1089	0.144*
H12B	0.2222	−0.4899	0.2098	0.144*
H12C	0.4232	−0.4871	0.2328	0.144*
O4	0.3164 (3)	−0.3073 (2)	0.10932 (18)	0.0785 (6)
O3	0.1512 (4)	−0.2162 (3)	0.29184 (19)	0.0950 (8)
H1A	0.020 (3)	0.3365 (14)	0.079 (2)	0.052 (7)*
C1	0.1913 (3)	0.1820 (3)	−0.04297 (19)	0.0461 (5)
C2	0.2603 (3)	0.0150 (2)	−0.02273 (19)	0.0439 (5)
C3	0.1853 (3)	−0.0280 (3)	0.1078 (2)	0.0470 (6)
C4	0.0707 (3)	0.1150 (3)	0.1615 (2)	0.0491 (6)
C5	0.2114 (4)	0.3014 (3)	−0.1527 (2)	0.0569 (6)
C6	0.3253 (8)	0.3461 (4)	−0.3746 (3)	0.1147 (15)
H6A	0.1902	0.4037	−0.3852	0.138*
H6B	0.3889	0.4250	−0.3721	0.138*
C7	0.4382 (8)	0.2543 (6)	−0.4772 (3)	0.1304 (17)
H7A	0.4460	0.3259	−0.5547	0.196*
H7B	0.3730	0.1779	−0.4801	0.196*
H7C	0.5715	0.1974	−0.4659	0.196*
C8	−0.0423 (4)	0.1442 (3)	0.2940 (2)	0.0621 (7)
H8A	−0.1565	0.2409	0.2921	0.075*
H8B	−0.0940	0.0540	0.3344	0.075*
C9	0.0830 (5)	0.1639 (4)	0.3707 (3)	0.0857 (9)
H9A	0.0028	0.1823	0.4542	0.129*
H9B	0.1322	0.2546	0.3324	0.129*
H9C	0.1946	0.0676	0.3748	0.129*
N1	0.0782 (3)	0.2382 (2)	0.07013 (17)	0.0503 (5)
O1	0.1384 (3)	0.4462 (2)	−0.15035 (18)	0.0821 (7)
O2	0.3170 (3)	0.2368 (2)	−0.25857 (16)	0.0748 (6)

	U11	U22	U33	U12	U13	U23
C10	0.0654 (14)	0.0407 (12)	0.0528 (13)	−0.0105 (10)	−0.0084 (10)	−0.0104 (10)
C11	0.0628 (13)	0.0460 (13)	0.0535 (13)	−0.0180 (10)	−0.0088 (10)	0.0016 (10)
C12	0.130 (3)	0.0388 (15)	0.097 (2)	−0.0178 (16)	−0.016 (2)	0.0119 (14)
O4	0.1114 (15)	0.0334 (10)	0.0680 (12)	−0.0114 (9)	−0.0062 (11)	0.0025 (8)
O3	0.1393 (19)	0.0586 (12)	0.0578 (12)	−0.0263 (12)	0.0044 (12)	0.0097 (9)
C1	0.0501 (11)	0.0386 (11)	0.0423 (11)	−0.0088 (8)	−0.0071 (8)	−0.0033 (8)
C2	0.0436 (10)	0.0389 (11)	0.0467 (11)	−0.0113 (9)	−0.0087 (8)	−0.0047 (8)
C3	0.0480 (11)	0.0404 (11)	0.0495 (12)	−0.0137 (9)	−0.0083 (9)	−0.0025 (9)
C4	0.0478 (11)	0.0438 (12)	0.0483 (12)	−0.0118 (9)	−0.0047 (9)	−0.0027 (9)
C5	0.0677 (14)	0.0397 (12)	0.0484 (13)	−0.0075 (10)	−0.0055 (10)	−0.0003 (9)
C6	0.183 (4)	0.0601 (18)	0.0511 (17)	−0.014 (2)	0.007 (2)	0.0112 (14)
C7	0.186 (4)	0.123 (3)	0.0515 (19)	−0.033 (3)	−0.008 (2)	0.001 (2)
C8	0.0667 (14)	0.0542 (14)	0.0494 (13)	−0.0144 (11)	0.0032 (11)	−0.0029 (10)
C9	0.104 (2)	0.101 (2)	0.0500 (15)	−0.0386 (19)	−0.0048 (14)	−0.0093 (15)
N1	0.0533 (10)	0.0370 (10)	0.0479 (11)	−0.0050 (8)	−0.0044 (8)	−0.0040 (8)
O1	0.1135 (15)	0.0386 (10)	0.0600 (11)	−0.0033 (9)	0.0023 (10)	0.0007 (8)
O2	0.1088 (14)	0.0453 (10)	0.0434 (10)	−0.0087 (9)	0.0013 (9)	−0.0001 (7)

C10—C2	1.500 (3)	C4—C8	1.498 (3)
C10—H10A	0.9600	C5—O1	1.211 (3)
C10—H10B	0.9600	C5—O2	1.331 (3)
C10—H10C	0.9600	C6—C7	1.428 (5)
C11—O3	1.197 (3)	C6—O2	1.447 (3)
C11—O4	1.330 (3)	C6—H6A	0.9700
C11—C3	1.463 (3)	C6—H6B	0.9700
C12—O4	1.436 (3)	C7—H7A	0.9600
C12—H12A	0.9600	C7—H7B	0.9600
C12—H12B	0.9600	C7—H7C	0.9600
C12—H12C	0.9600	C8—C9	1.491 (4)
C1—N1	1.380 (3)	C8—H8A	0.9700
C1—C2	1.381 (3)	C8—H8B	0.9700
C1—C5	1.451 (3)	C9—H9A	0.9600
C2—C3	1.422 (3)	C9—H9B	0.9600
C3—C4	1.401 (3)	C9—H9C	0.9600
C4—N1	1.335 (3)	N1—H1A	0.839 (10)
C2—C10—H10A	109.5	O2—C5—C1	113.5 (2)
C2—C10—H10B	109.5	C7—C6—O2	108.8 (3)
H10A—C10—H10B	109.5	C7—C6—H6A	109.9
C2—C10—H10C	109.5	O2—C6—H6A	109.9
H10A—C10—H10C	109.5	C7—C6—H6B	109.9
H10B—C10—H10C	109.5	O2—C6—H6B	109.9
O3—C11—O4	121.4 (2)	H6A—C6—H6B	108.3
O3—C11—C3	126.0 (2)	C6—C7—H7A	109.5
O4—C11—C3	112.6 (2)	C6—C7—H7B	109.5
O4—C12—H12A	109.5	H7A—C7—H7B	109.5
O4—C12—H12B	109.5	C6—C7—H7C	109.5
H12A—C12—H12B	109.5	H7A—C7—H7C	109.5
O4—C12—H12C	109.5	H7B—C7—H7C	109.5
H12A—C12—H12C	109.5	C9—C8—C4	113.3 (2)
H12B—C12—H12C	109.5	C9—C8—H8A	108.9
C11—O4—C12	117.6 (2)	C4—C8—H8A	108.9
N1—C1—C2	108.30 (19)	C9—C8—H8B	108.9
N1—C1—C5	117.4 (2)	C4—C8—H8B	108.9
C2—C1—C5	134.3 (2)	H8A—C8—H8B	107.7
C1—C2—C3	105.90 (18)	C8—C9—H9A	109.5
C1—C2—C10	126.4 (2)	C8—C9—H9B	109.5
C3—C2—C10	127.7 (2)	H9A—C9—H9B	109.5
C4—C3—C2	107.89 (19)	C8—C9—H9C	109.5
C4—C3—C11	122.8 (2)	H9A—C9—H9C	109.5
C2—C3—C11	129.3 (2)	H9B—C9—H9C	109.5
N1—C4—C3	107.36 (19)	C4—N1—C1	110.53 (19)
N1—C4—C8	121.0 (2)	C4—N1—H1A	125.5 (17)
C3—C4—C8	131.6 (2)	C1—N1—H1A	124.0 (17)
O1—C5—O2	122.4 (2)	C5—O2—C6	117.1 (2)
O1—C5—C1	124.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.84 (1)	2.07 (1)	2.883 (3)	165 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.84 (1)	2.07 (1)	2.883 (3)	165 (2)

Symmetry code: (i) .