Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005645/bt6023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005645/bt6023Isup2.hkl |
CCDC reference: 165647
The title compound was prepared by a two-step reaction. In the first step, to a stirred solution of methyl 2-pyrrolylcarbocylate (0.1 mol) in CH2Cl2 (300 ml), CH3NO2 (20 ml) and AlCl3 (30 g) was added dropwise a solution of 1,1-dichloromethyl methyl ether in CH2Cl2 (150 ml) at 273 K. After 1 h, the reaction mixture was poured onto ice/water, extracted with chloroform, dried with sodium sulfate, evaporated to dryness and recrystallized from CCl4. To a stirred solution of methyl 4-formylpyrrolyl-2-carboxylate (50 mmol) obtained above in 20 ml of dimethylformamide (DMF) was added potassium tert-butoxide (55 mmol) and tetrabutylammonium bromide (5 mmol) in 20 ml of DMF at 313 K. After 3 h a solution of alkyl bromoacetate (60 mmol) in 20 ml of DMF was added dropwise and stirred for 3 h. The DMF was evaporated, the residue dissolved in 80 ml of H2O, neutralized with concentrated hydrochloric acid and extracted with chloroform. The extract was dried with Na2SO4 and crystallized from toluene-0cyclohexane (m.p. 343–345 K).
Although the H atoms were seen in a difference Fourier map, they were refined with fixed geometry, riding on their carrier atoms, with Uiso set to 1.2 (or 1.5 for the methyl H atoms) times Ueq of the parent atom. Both methyl groups were allowed to rotate about their local threefold axis.
Data collection: Syntex Software (Syntex, 1973); cell refinement: Syntex Software; data reduction: XP21 (Pavelčík, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97.
Fig. 1. View of a molecule of the title compound with its numbering scheme. Displacement ellipsoids are shown at the 35% probability level and H atoms are drawn as spheres of arbitrary radii. |
C10H11NO5 | Dx = 1.395 Mg m−3 Dm = 1.39 (1) Mg m−3 Dm measured by flotation in bromoform/methanol |
Mr = 225.20 | Melting point: 344 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.101 (1) Å | Cell parameters from 15 reflections |
b = 20.098 (4) Å | θ = 7–18° |
c = 10.461 (2) Å | µ = 0.11 mm−1 |
β = 90.31 (3)° | T = 293 K |
V = 1072.4 (4) Å3 | Prism, light yellow |
Z = 4 | 0.35 × 0.28 × 0.25 mm |
F(000) = 472 |
Syntex P21 diffractometer | Rint = 0.038 |
Radiation source: fine-focus sealed tube | θmax = 27.6°, θmin = 2.0° |
Graphite monochromator | h = 0→6 |
θ/2θ scans | k = 0→26 |
2623 measured reflections | l = −13→13 |
2485 independent reflections | 2 standard reflections every 98 reflections |
1469 reflections with I > 2σ(I) | intensity decay: 2% |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.058 | w = 1/[σ2(Fo2) + (0.0356P)2 + 0.4874P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.106 | (Δ/σ)max = 0.002 |
S = 1.04 | Δρmax = 0.13 e Å−3 |
2485 reflections | Δρmin = −0.18 e Å−3 |
147 parameters |
C10H11NO5 | V = 1072.4 (4) Å3 |
Mr = 225.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.101 (1) Å | µ = 0.11 mm−1 |
b = 20.098 (4) Å | T = 293 K |
c = 10.461 (2) Å | 0.35 × 0.28 × 0.25 mm |
β = 90.31 (3)° |
Syntex P21 diffractometer | Rint = 0.038 |
2623 measured reflections | 2 standard reflections every 98 reflections |
2485 independent reflections | intensity decay: 2% |
1469 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.13 e Å−3 |
2485 reflections | Δρmin = −0.18 e Å−3 |
147 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.2943 (3) | 0.12052 (8) | 0.80735 (14) | 0.0450 (4) | |
C2 | 0.1398 (4) | 0.16218 (10) | 0.74159 (19) | 0.0498 (5) | |
H2 | 0.0092 | 0.1888 | 0.7765 | 0.060* | |
C3 | 0.2043 (4) | 0.15949 (10) | 0.61475 (19) | 0.0477 (5) | |
C4 | 0.4091 (4) | 0.11323 (10) | 0.60355 (18) | 0.0479 (5) | |
H4 | 0.4922 | 0.1007 | 0.5284 | 0.057* | |
C5 | 0.4638 (4) | 0.09007 (10) | 0.72282 (19) | 0.0448 (5) | |
C6 | 0.2765 (4) | 0.11229 (11) | 0.94437 (17) | 0.0497 (5) | |
H6A | 0.2953 | 0.0655 | 0.9655 | 0.060* | |
H6B | 0.1049 | 0.1267 | 0.9727 | 0.060* | |
C7 | 0.4831 (4) | 0.15139 (10) | 1.01312 (18) | 0.0460 (5) | |
O8 | 0.6520 (3) | 0.18302 (8) | 0.96487 (14) | 0.0616 (4) | |
O9 | 0.4461 (3) | 0.14596 (9) | 1.13692 (13) | 0.0720 (5) | |
C10 | 0.6268 (5) | 0.18183 (15) | 1.2185 (2) | 0.0805 (8) | |
H10A | 0.8034 | 0.1704 | 1.1962 | 0.121* | |
H10B | 0.5958 | 0.1701 | 1.3061 | 0.121* | |
H10C | 0.6012 | 0.2288 | 1.2074 | 0.121* | |
C11 | 0.0775 (5) | 0.19716 (12) | 0.5157 (2) | 0.0635 (6) | |
H11 | −0.0567 | 0.2256 | 0.5403 | 0.076* | |
O12 | 0.1289 (4) | 0.19528 (9) | 0.40404 (15) | 0.0766 (5) | |
C13 | 0.6579 (4) | 0.04184 (10) | 0.7639 (2) | 0.0520 (5) | |
O14 | 0.7106 (3) | 0.02797 (8) | 0.87220 (16) | 0.0720 (5) | |
O15 | 0.7758 (3) | 0.01473 (8) | 0.66302 (16) | 0.0695 (5) | |
C16 | 0.9699 (5) | −0.03517 (12) | 0.6895 (3) | 0.0785 (8) | |
H16A | 1.0705 | −0.0224 | 0.7633 | 0.118* | |
H16B | 1.0841 | −0.0395 | 0.6173 | 0.118* | |
H16C | 0.8850 | −0.0770 | 0.7055 | 0.118* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0446 (9) | 0.0509 (10) | 0.0394 (9) | −0.0022 (8) | −0.0019 (7) | −0.0001 (7) |
C2 | 0.0488 (12) | 0.0506 (12) | 0.0501 (12) | 0.0033 (10) | −0.0034 (9) | −0.0049 (10) |
C3 | 0.0530 (12) | 0.0467 (11) | 0.0433 (11) | 0.0024 (10) | −0.0056 (9) | −0.0018 (9) |
C4 | 0.0530 (12) | 0.0497 (12) | 0.0411 (11) | 0.0004 (10) | 0.0021 (9) | −0.0012 (9) |
C5 | 0.0442 (11) | 0.0437 (11) | 0.0464 (11) | −0.0007 (9) | 0.0002 (9) | −0.0031 (9) |
C6 | 0.0500 (12) | 0.0583 (13) | 0.0407 (10) | −0.0067 (10) | 0.0018 (9) | −0.0002 (10) |
C7 | 0.0465 (11) | 0.0538 (12) | 0.0378 (11) | 0.0054 (10) | 0.0012 (9) | 0.0002 (9) |
O8 | 0.0600 (9) | 0.0771 (11) | 0.0477 (8) | −0.0199 (9) | 0.0024 (7) | −0.0042 (8) |
O9 | 0.0738 (11) | 0.1043 (14) | 0.0378 (8) | −0.0282 (10) | 0.0023 (7) | −0.0020 (8) |
C10 | 0.0829 (18) | 0.117 (2) | 0.0412 (12) | −0.0255 (17) | −0.0112 (12) | −0.0085 (14) |
C11 | 0.0726 (16) | 0.0617 (15) | 0.0562 (15) | 0.0090 (12) | −0.0072 (12) | 0.0002 (11) |
O12 | 0.0946 (13) | 0.0822 (13) | 0.0529 (10) | 0.0120 (10) | −0.0073 (9) | 0.0122 (9) |
C13 | 0.0526 (12) | 0.0434 (11) | 0.0601 (14) | −0.0018 (10) | −0.0019 (11) | 0.0037 (10) |
O14 | 0.0794 (12) | 0.0724 (11) | 0.0640 (10) | 0.0169 (9) | −0.0072 (9) | 0.0138 (9) |
O15 | 0.0736 (11) | 0.0632 (10) | 0.0717 (11) | 0.0216 (9) | 0.0060 (9) | −0.0035 (8) |
C16 | 0.0670 (16) | 0.0527 (14) | 0.116 (2) | 0.0178 (13) | 0.0104 (15) | −0.0018 (15) |
N1—C2 | 1.338 (3) | C7—O9 | 1.314 (2) |
N1—C5 | 1.383 (2) | O9—C10 | 1.446 (3) |
N1—C6 | 1.446 (2) | C10—H10A | 0.9600 |
C2—C3 | 1.370 (3) | C10—H10B | 0.9600 |
C2—H2 | 0.9300 | C10—H10C | 0.9600 |
C3—C4 | 1.404 (3) | C11—O12 | 1.199 (3) |
C3—C11 | 1.434 (3) | C11—H11 | 0.9300 |
C4—C5 | 1.359 (3) | C13—O14 | 1.196 (3) |
C4—H4 | 0.9300 | C13—O15 | 1.334 (3) |
C5—C13 | 1.449 (3) | O15—C16 | 1.435 (3) |
C6—C7 | 1.496 (3) | C16—H16A | 0.9600 |
C6—H6A | 0.9700 | C16—H16B | 0.9600 |
C6—H6B | 0.9700 | C16—H16C | 0.9600 |
C7—O8 | 1.186 (2) | ||
C2—N1—C5 | 108.48 (16) | O8—C7—C6 | 126.07 (18) |
C2—N1—C6 | 122.77 (17) | O9—C7—C6 | 109.00 (18) |
C5—N1—C6 | 128.75 (17) | C7—O9—C10 | 116.48 (18) |
N1—C2—C3 | 109.23 (19) | O9—C10—H10A | 109.5 |
N1—C2—H2 | 125.4 | O9—C10—H10B | 109.5 |
C3—C2—H2 | 125.4 | H10A—C10—H10B | 109.5 |
C2—C3—C4 | 106.84 (18) | O9—C10—H10C | 109.5 |
C2—C3—C11 | 124.7 (2) | H10A—C10—H10C | 109.5 |
C4—C3—C11 | 128.47 (19) | H10B—C10—H10C | 109.5 |
C5—C4—C3 | 107.42 (18) | O12—C11—C3 | 125.9 (2) |
C5—C4—H4 | 126.3 | O12—C11—H11 | 117.0 |
C3—C4—H4 | 126.3 | C3—C11—H11 | 117.0 |
C4—C5—N1 | 108.03 (17) | O14—C13—O15 | 123.6 (2) |
C4—C5—C13 | 129.62 (19) | O14—C13—C5 | 125.9 (2) |
N1—C5—C13 | 122.35 (18) | O15—C13—C5 | 110.44 (18) |
N1—C6—C7 | 111.62 (16) | C13—O15—C16 | 116.53 (19) |
N1—C6—H6A | 109.3 | O15—C16—H16A | 109.5 |
C7—C6—H6A | 109.3 | O15—C16—H16B | 109.5 |
N1—C6—H6B | 109.3 | H16A—C16—H16B | 109.5 |
C7—C6—H6B | 109.3 | O15—C16—H16C | 109.5 |
H6A—C6—H6B | 108.0 | H16A—C16—H16C | 109.5 |
O8—C7—O9 | 124.9 (2) | H16B—C16—H16C | 109.5 |
C5—N1—C2—C3 | 0.2 (2) | C5—N1—C6—C7 | 79.5 (3) |
C6—N1—C2—C3 | 179.49 (17) | N1—C6—C7—O8 | −3.7 (3) |
N1—C2—C3—C4 | 0.2 (2) | N1—C6—C7—O9 | 175.49 (17) |
N1—C2—C3—C11 | 179.4 (2) | O8—C7—O9—C10 | 0.2 (3) |
C2—C3—C4—C5 | −0.6 (2) | C6—C7—O9—C10 | −179.0 (2) |
C11—C3—C4—C5 | −179.8 (2) | C2—C3—C11—O12 | −179.4 (2) |
C3—C4—C5—N1 | 0.7 (2) | C4—C3—C11—O12 | −0.4 (4) |
C3—C4—C5—C13 | −179.9 (2) | C4—C5—C13—O14 | 173.1 (2) |
C2—N1—C5—C4 | −0.6 (2) | N1—C5—C13—O14 | −7.6 (3) |
C6—N1—C5—C4 | −179.83 (18) | C4—C5—C13—O15 | −6.1 (3) |
C2—N1—C5—C13 | 179.96 (19) | N1—C5—C13—O15 | 173.20 (18) |
C6—N1—C5—C13 | 0.7 (3) | O14—C13—O15—C16 | 2.0 (3) |
C2—N1—C6—C7 | −99.6 (2) | C5—C13—O15—C16 | −178.76 (19) |
Experimental details
Crystal data | |
Chemical formula | C10H11NO5 |
Mr | 225.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 5.101 (1), 20.098 (4), 10.461 (2) |
β (°) | 90.31 (3) |
V (Å3) | 1072.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.35 × 0.28 × 0.25 |
Data collection | |
Diffractometer | Syntex P21 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2623, 2485, 1469 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.106, 1.04 |
No. of reflections | 2485 |
No. of parameters | 147 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.18 |
Computer programs: Syntex Software (Syntex, 1973), Syntex Software, XP21 (Pavelčík, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990), SHELXL97.
N1—C2 | 1.338 (3) | C3—C11 | 1.434 (3) |
N1—C5 | 1.383 (2) | C4—C5 | 1.359 (3) |
N1—C6 | 1.446 (2) | C5—C13 | 1.449 (3) |
C2—C3 | 1.370 (3) | C11—O12 | 1.199 (3) |
C3—C4 | 1.404 (3) | C13—O14 | 1.196 (3) |
C2—N1—C5 | 108.48 (16) | C4—C3—C11 | 128.47 (19) |
C2—N1—C6 | 122.77 (17) | C5—C4—C3 | 107.42 (18) |
C5—N1—C6 | 128.75 (17) | C4—C5—N1 | 108.03 (17) |
N1—C2—C3 | 109.23 (19) | C4—C5—C13 | 129.62 (19) |
C2—C3—C4 | 106.84 (18) | N1—C5—C13 | 122.35 (18) |
C2—C3—C11 | 124.7 (2) | ||
C5—N1—C6—C7 | 79.5 (3) | C4—C3—C11—O12 | −0.4 (4) |
N1—C6—C7—O8 | −3.7 (3) | N1—C5—C13—O14 | −7.6 (3) |
Polysubstituted and polycondensed pyrrolyl derivatives have found widespread applications as drugs, polymers, dyes, agrochemicals etc. (Gribble, 1996). The title compound, (I), has also been exploited in the synthesis of other heterocyclic derivatives, such as 4-pyrrolyl-1,4-dihydropyridines or glutaric acid derivatives (Milata et al., 2001), which are of interest because of their calcium channel blocking activity. The present crystal structure determination was undertaken in order to establish the conformation of the substituents bonded to the pyrrole ring and the degree of π-electron conjugation.
A drawing of the molecule is shown in Fig. 1. As expected, the central pyrrole ring is planar within experimental error (r.m.s. deviation 0.003 Å). The distortion of the pyrrole ring from C2v symmetry is considerable and concerns mainly the two N—C bonds which differ by a highly significant amount of 18σ. The 2-methoxycarbonyl group (at C5) is roughly coplanar with the mean plane of the pyrrole ring [dihedral angle 7.0 (2)°]; similarly, the formyl group lies exactly in the pyrrole plane [torsion angle C4—C3—C11—O12 = -0.4 (4)°]. Furthermore, the C3—C11 and C5—C13 bond distances of 1.434 (3) and 1.449 (3) Å, respectively, are significantly shorter than the value of 1.487 (5) Å reported for a Csp2—Csp2 single bond (Shmueli et al., 1973). These results indicate that there is some degree of π-electron delocalization from the heterocyclic ring into the C11—O12 and C13—O14 carbonyl bonds. As revealed by the Cambridge Structural Database (Allen & Kennard, 1993), similar features have also been observed for compounds having electron-withdrawing substituents in the 2- and/or 4-positions of the pyrrole ring. The second methoxycarbonyl group of the molecule is rotated around the N1—C6 and C6—C7 bonds [torsion angles C5—N1—C6—C7 = 79.5 (3)° and N1—C6—C7—O8 = -3.7 (3)°], so that it makes an angle of 76.5 (3)° with the pyrrole plane.
As the molecule has no potential hydrohen-bond donor, the packing is governed by van der Waals interactions.