rac-Dimethyl 2-(1H-pyrrole-2-carboxamido)­butane­dioate

Zheng, L.; Hu, F.; Zeng, X.C.; Li, K.P.

doi:10.1107/S1600536811007148

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o752

doi:10.1107/S1600536811007148

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rac-Dimethyl 2-(1H-pyrrole-2-carboxamido)butanedioate

Le Zheng,^a Fang Hu,^a Xiang Chao Zeng ^a ^* and Kai Ping Li ^a

^aDepartment of Chemistry, Jinan University, Guangzhou, Guangdong 510632, People's Republic of China
^*Correspondence e-mail: xczeng@126.com

(Received 22 February 2011; accepted 24 February 2011; online 2 March 2011)

The title compound, C₁₁H₁₄N₂O₅, was synthesized by condensation of (RS)-2-aminosuccinic acid dimethyl ester with 2-trichloroacetylpyrrole at room temperature. The amide group is twisted by 7.4 (1)° from the plane of the pyrrole ring. In the crystal, molecules are linked by intermolecular N—H⋯O hydrogen bonds into chains extending along the c axis.

Related literature

For the bioactivity of pyrrole derivatives, see: Fabio et al. (2007 ); Banwell et al. (2006 ). For related structures, see: Zeng et al. (2010 ); Li et al. (2009 ); Liu et al. (2006 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₅
M_r = 254.24
Monoclinic, P 2₁ /c
a = 9.1387 (8) Å
b = 15.2715 (11) Å
c = 9.6238 (9) Å
β = 105.750 (9)°
V = 1292.69 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.48 × 0.26 × 0.21 mm

Data collection

Oxford Gemini S Ultra area-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.952, T_max = 0.978
5286 measured reflections
2534 independent reflections
1563 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.163
S = 1.05
2534 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	1.96	2.804 (3)	167
N2—H2A⋯O1ⁱ	0.86	1.99	2.845 (3)	176
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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/S1600536811007148/cv5056sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007148/cv5056Isup2.hkl

checkCIF report

Comment top

Pyrrole derivatives show various biological activities, for instance, antitumor activity (Banwell et al., 2006). Some of them are known as metabotropic receptor antagonists (Fabio et al., 2007). Herewith we present the title compound (I), which is a new pyrrole derivative.

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in 1-benzyl-N-methyl-1H-pyrrole-2-carboxamide (Zeng et al., 2010) and 3-(1-ethyl-1H-pyrrole-2-carboxamido) propionic acid monohydrate (Li et al., 2009). In the crystal structure, enantiomorphous molecules are linked by intermolecular N—H···O hydrogen bonds (Table 1) into chains extended along the c axis (Fig. 2).

Related literature top

For the bioactivity of pyrrole derivatives, see: Fabio et al. (2007); Banwell et al. (2006). For related structures, see: Zeng et al. (2010); Li et al. (2009); Liu et al. (2006).

Experimental top

The hydrochloric acid salt of (RS)-2-aminosuccinic acid dimethyl ester (0.99 g, 5 mmol) and 2-trichloroacetylpyrrole (1.27 g, 6 mmol) were added to acetonitrile (12 ml), followed by the dropwise addition of triethylamine (1.4 ml). The mixture was stirred at room temperature for 12 h. After the reaction mixture was filtered, the filtrate was evaporated in vacuo, and then the residue was chromatographed over silica gel using EtOAc-petroleum ether (3:7 v/v) as eluting solvent and the title compound (I) was obtained as a light yellow solid (72.3% yield). Monoclinic crystals suitable for X-ray analysis (m.p. 384 K) grew over a period of five days when the EtOH solution of I was exposed to the air at room temperature.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010; data reduction: CrysAlis PRO (Oxford Diffraction, 2010; 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 molecular structure of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A portion of the crystal packing viewed approximately along the a axis. Dashed lines indicate hydrogen bonds.

(RS)-Dimethyl 2-(1H-pyrrole-2-carboxamido)butanedioate top

Crystal data top

C₁₁H₁₄N₂O₅	D_x = 1.306 Mg m⁻³
M_r = 254.24	Melting point: 384 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1387 (8) Å	Cell parameters from 1891 reflections
b = 15.2715 (11) Å	θ = 3.5–29.4°
c = 9.6238 (9) Å	µ = 0.10 mm⁻¹
β = 105.750 (9)°	T = 293 K
V = 1292.69 (19) Å³	Prism, light yellow
Z = 4	0.48 × 0.26 × 0.21 mm
F(000) = 536

Data collection top

Oxford Gemini S Ultra area-detector diffractometer	2534 independent reflections
Radiation source: fine-focus sealed tube	1563 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 26.0°, θ_min = 3.5°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −11→7
T_min = 0.952, T_max = 0.978	k = −15→18
5286 measured reflections	l = −11→11

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0623P)² + 0.3001P] where P = (F_o² + 2F_c²)/3
2534 reflections	(Δ/σ)_max = 0.012
165 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₁₄N₂O₅	V = 1292.69 (19) Å³
M_r = 254.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.1387 (8) Å	µ = 0.10 mm⁻¹
b = 15.2715 (11) Å	T = 293 K
c = 9.6238 (9) Å	0.48 × 0.26 × 0.21 mm
β = 105.750 (9)°

Data collection top

Oxford Gemini S Ultra area-detector diffractometer	2534 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1563 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.978	R_int = 0.032
5286 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.05	Δρ_max = 0.18 e Å⁻³
2534 reflections	Δρ_min = −0.21 e Å⁻³
165 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
O1	0.8723 (2)	0.22381 (12)	0.93777 (18)	0.0598 (6)
N2	0.8981 (2)	0.20231 (12)	0.7148 (2)	0.0454 (5)
H2A	0.8870	0.2226	0.6292	0.055*
N1	0.7370 (2)	0.36401 (14)	0.6269 (2)	0.0552 (6)
H1A	0.7730	0.3439	0.5594	0.066*
C5	0.8472 (3)	0.24881 (15)	0.8093 (2)	0.0422 (6)
C4	0.7615 (3)	0.32843 (16)	0.7622 (3)	0.0429 (6)
O3	0.9219 (2)	−0.02724 (12)	0.8003 (3)	0.0796 (7)
O5	1.2703 (2)	0.15643 (15)	0.5747 (3)	0.0843 (7)
C7	0.8551 (3)	0.04766 (17)	0.7534 (3)	0.0522 (7)
C3	0.6833 (3)	0.37952 (17)	0.8361 (3)	0.0546 (7)
H3	0.6793	0.3712	0.9307	0.065*
C6	0.9717 (3)	0.11846 (15)	0.7531 (3)	0.0482 (7)
H6	1.0386	0.1232	0.8515	0.058*
C9	1.2137 (3)	0.15003 (18)	0.6855 (4)	0.0585 (7)
C8	1.0705 (3)	0.09670 (17)	0.6529 (3)	0.0546 (7)
H8A	1.0969	0.0350	0.6622	0.065*
H8B	1.0127	0.1072	0.5538	0.065*
O2	0.7223 (2)	0.05805 (14)	0.7203 (3)	0.0953 (9)
O4	1.2728 (3)	0.18044 (18)	0.8018 (3)	0.1036 (9)
C2	0.6111 (3)	0.44624 (19)	0.7425 (4)	0.0681 (9)
H2	0.5493	0.4900	0.7631	0.082*
C1	0.6480 (4)	0.4351 (2)	0.6160 (4)	0.0718 (9)
H1	0.6168	0.4709	0.5351	0.086*
C11	0.8246 (4)	−0.1018 (2)	0.8043 (4)	0.0895 (11)
H11A	0.7600	−0.0886	0.8652	0.134*
H11B	0.8863	−0.1519	0.8418	0.134*
H11C	0.7633	−0.1144	0.7084	0.134*
C10	1.4150 (4)	0.2024 (3)	0.5989 (5)	0.1034 (14)
H10A	1.4106	0.2562	0.6490	0.155*
H10B	1.4344	0.2147	0.5078	0.155*
H10C	1.4951	0.1663	0.6559	0.155*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0845 (15)	0.0672 (12)	0.0320 (10)	0.0113 (10)	0.0231 (9)	0.0068 (9)
N2	0.0597 (14)	0.0481 (12)	0.0324 (11)	0.0102 (9)	0.0190 (10)	0.0027 (9)
N1	0.0586 (15)	0.0614 (14)	0.0459 (13)	0.0154 (11)	0.0147 (11)	0.0060 (11)
C5	0.0451 (14)	0.0481 (14)	0.0354 (13)	−0.0034 (11)	0.0143 (11)	−0.0020 (11)
C4	0.0429 (14)	0.0483 (14)	0.0377 (13)	0.0000 (11)	0.0113 (11)	−0.0031 (11)
O3	0.0615 (14)	0.0542 (12)	0.1168 (19)	0.0094 (10)	0.0136 (13)	0.0197 (12)
O5	0.0604 (14)	0.1133 (18)	0.0853 (17)	0.0004 (12)	0.0300 (13)	0.0117 (14)
C7	0.0528 (17)	0.0549 (16)	0.0487 (16)	0.0091 (13)	0.0135 (13)	0.0059 (12)
C3	0.0487 (16)	0.0610 (17)	0.0569 (17)	0.0007 (12)	0.0192 (14)	−0.0126 (14)
C6	0.0551 (16)	0.0492 (15)	0.0398 (14)	0.0068 (12)	0.0122 (12)	−0.0003 (11)
C9	0.0544 (18)	0.0568 (17)	0.067 (2)	0.0100 (13)	0.0212 (16)	−0.0023 (15)
C8	0.0487 (16)	0.0591 (16)	0.0548 (17)	0.0081 (12)	0.0122 (13)	−0.0084 (13)
O2	0.0527 (14)	0.0739 (15)	0.156 (3)	0.0068 (11)	0.0223 (15)	0.0351 (14)
O4	0.0874 (19)	0.125 (2)	0.097 (2)	−0.0370 (15)	0.0233 (15)	−0.0456 (16)
C2	0.0446 (17)	0.0597 (18)	0.097 (3)	0.0085 (13)	0.0137 (17)	−0.0148 (17)
C1	0.069 (2)	0.070 (2)	0.073 (2)	0.0214 (16)	0.0127 (17)	0.0125 (17)
C11	0.092 (3)	0.0549 (19)	0.117 (3)	−0.0051 (17)	0.020 (2)	0.0205 (19)
C10	0.057 (2)	0.122 (3)	0.138 (4)	−0.004 (2)	0.038 (2)	0.029 (3)

Geometric parameters (Å, º) top

O1—C5	1.254 (3)	C3—H3	0.9300
N2—C5	1.333 (3)	C6—C8	1.526 (3)
N2—C6	1.447 (3)	C6—H6	0.9800
N2—H2A	0.8600	C9—O4	1.197 (4)
N1—C1	1.343 (3)	C9—C8	1.500 (4)
N1—C4	1.372 (3)	C8—H8A	0.9700
N1—H1A	0.8600	C8—H8B	0.9700
C5—C4	1.451 (3)	C2—C1	1.360 (4)
C4—C3	1.378 (3)	C2—H2	0.9300
O3—C7	1.317 (3)	C1—H1	0.9300
O3—C11	1.452 (4)	C11—H11A	0.9600
O5—C9	1.310 (3)	C11—H11B	0.9600
O5—C10	1.458 (4)	C11—H11C	0.9600
C7—O2	1.179 (3)	C10—H10A	0.9600
C7—C6	1.519 (4)	C10—H10B	0.9600
C3—C2	1.401 (4)	C10—H10C	0.9600

C5—N2—C6	121.4 (2)	O4—C9—C8	123.6 (3)
C5—N2—H2A	119.3	O5—C9—C8	112.7 (3)
C6—N2—H2A	119.3	C9—C8—C6	112.4 (2)
C1—N1—C4	109.5 (2)	C9—C8—H8A	109.1
C1—N1—H1A	125.3	C6—C8—H8A	109.1
C4—N1—H1A	125.3	C9—C8—H8B	109.1
O1—C5—N2	120.4 (2)	C6—C8—H8B	109.1
O1—C5—C4	120.1 (2)	H8A—C8—H8B	107.8
N2—C5—C4	119.5 (2)	C1—C2—C3	107.2 (2)
N1—C4—C3	107.0 (2)	C1—C2—H2	126.4
N1—C4—C5	124.3 (2)	C3—C2—H2	126.4
C3—C4—C5	128.7 (2)	N1—C1—C2	108.9 (3)
C7—O3—C11	117.4 (2)	N1—C1—H1	125.6
C9—O5—C10	116.6 (3)	C2—C1—H1	125.6
O2—C7—O3	123.8 (3)	O3—C11—H11A	109.5
O2—C7—C6	125.1 (2)	O3—C11—H11B	109.5
O3—C7—C6	111.0 (2)	H11A—C11—H11B	109.5
C4—C3—C2	107.5 (3)	O3—C11—H11C	109.5
C4—C3—H3	126.3	H11A—C11—H11C	109.5
C2—C3—H3	126.3	H11B—C11—H11C	109.5
N2—C6—C7	110.6 (2)	O5—C10—H10A	109.5
N2—C6—C8	110.2 (2)	O5—C10—H10B	109.5
C7—C6—C8	112.5 (2)	H10A—C10—H10B	109.5
N2—C6—H6	107.8	O5—C10—H10C	109.5
C7—C6—H6	107.8	H10A—C10—H10C	109.5
C8—C6—H6	107.8	H10B—C10—H10C	109.5
O4—C9—O5	123.7 (3)

C6—N2—C5—O1	5.4 (4)	O2—C7—C6—N2	3.4 (4)
C6—N2—C5—C4	−174.2 (2)	O3—C7—C6—N2	−174.5 (2)
C1—N1—C4—C3	0.5 (3)	O2—C7—C6—C8	−120.3 (3)
C1—N1—C4—C5	177.2 (2)	O3—C7—C6—C8	61.8 (3)
O1—C5—C4—N1	175.5 (2)	C10—O5—C9—O4	1.1 (4)
N2—C5—C4—N1	−4.9 (4)	C10—O5—C9—C8	−176.2 (2)
O1—C5—C4—C3	−8.5 (4)	O4—C9—C8—C6	26.0 (4)
N2—C5—C4—C3	171.0 (2)	O5—C9—C8—C6	−156.8 (2)
C11—O3—C7—O2	3.1 (5)	N2—C6—C8—C9	73.9 (3)
C11—O3—C7—C6	−178.9 (3)	C7—C6—C8—C9	−162.1 (2)
N1—C4—C3—C2	0.2 (3)	C4—C3—C2—C1	−0.8 (3)
C5—C4—C3—C2	−176.3 (2)	C4—N1—C1—C2	−1.0 (3)
C5—N2—C6—C7	76.9 (3)	C3—C2—C1—N1	1.1 (4)
C5—N2—C6—C8	−158.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	1.96	2.804 (3)	167
N2—H2A···O1ⁱ	0.86	1.99	2.845 (3)	176

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₅
M_r	254.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.1387 (8), 15.2715 (11), 9.6238 (9)
β (°)	105.750 (9)
V (Å³)	1292.69 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.48 × 0.26 × 0.21

Data collection
Diffractometer	Oxford Gemini S Ultra area-detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.952, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	5286, 2534, 1563
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.163, 1.05
No. of reflections	2534
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis PRO (Oxford Diffraction, 2010, 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—H1A···O1ⁱ	0.86	1.96	2.804 (3)	167
N2—H2A···O1ⁱ	0.86	1.99	2.845 (3)	176

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

We thank the Natural Science Foundation of Guangdong Province, China, for financial support (grant No. 06300581).

References

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