Dimethyl 3,5-diethyl-1H-pyrrole-2,4-dicarboxyl-ate.

The title pyrrole derivative, C(12)H(17)NO(4), consists of a pyrrole ring with two diagonally attached meth-oxy-carbonyl 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 mol-ecules are assembled into dimers in a head-to-head mode by pairs of inter-molecular 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 = 239.27

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.118

S = 1.08

2285 reflections

155 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.16 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/S1600536811028352/pk2335sup1.cif

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

Supplementary material file. DOI: 10.1107/S1600536811028352/pk2335Isup3.cml

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

C12H17NO4	F(000) = 512
Mr = 239.27	Dx = 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

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

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(Fo2) + (0.0619P)2 + 0.1775P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
2285 reflections	Δρmax = 0.15 e Å−3
155 parameters	Δρmin = −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)

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
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)

	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)

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

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

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) .