Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019334/na6018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019334/na6018Isup2.hkl |
CCDC reference: 155901
A solution of 3-carboxy-2,2,5,5-tetramethyl-1H-2,5-dihydropyrrol-1-yloxyl (1.84 g, 0.01 mol), dicyclohexylcarbodiimide (2.1 g, 0.01 mol), ethanol (1 g, 0.022 mol) and 4-(pyrrol-1-yl)pyridine (0.1 g) in 20 ml dichloromethane was stirred overnight. After filtering off the dicyclohexylurea, the solution was extracted with 5% solution of sodium hydrogencarbonate and dried with magnesium sulfate. The methylene chloride was evaporated and the crude product was crystallized from hexane solution.
Two reflections 011 and 101 were omitted from the final refinement due to the large beam stop used. The systematic absences showed two possible space groups, non-centrosymmetric Pn21a and centrosymmetric Pnma. The phase problem was solved in the space group Pnma. All H atoms were found in the difference Fourier maps and freely refined with isotropic displacement parameters. The refinement in non-centrosymetric Pn21a led to lowering the R value from 0.044 to 0.042. However, the refinement in this space group was less stable and led to unrealistic positions of H atoms. Free refinement in Pnma gave C—H bond distances in the interval 0.96–1.03 Å and free refinement in Pn21a gave deviations of non-H atoms from planarity less than 2 s.u.'s and C—H bonds in the range 0.85–1.35 Å. Therefore, the Pnma group was prefered.
Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and ORTEP-3.
C11H18NO3 | Dx = 1.164 Mg m−3 |
Mr = 212.26 | Melting point: 105-107 C K |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71070 Å |
a = 10.4710 (4) Å | Cell parameters from 12475 reflections |
b = 9.3700 (3) Å | θ = 1.0–27.5° |
c = 12.3500 (4) Å | µ = 0.08 mm−1 |
V = 1211.70 (7) Å3 | T = 150 K |
Z = 4 | Prism, yellow |
F(000) = 460 | 0.4 × 0.3 × 0.2 mm |
Nonius KappaCCD area-detector diffractometer | 1216 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 27.5°, θmin = 3.3° |
ϕ and ω scans | h = −13→13 |
15701 measured reflections | k = −12→12 |
1464 independent reflections | l = −15→16 |
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)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.152 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.22 | (Δ/σ)max = 0.009 |
1462 reflections | Δρmax = 0.27 e Å−3 |
123 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00003 (1) |
C11H18NO3 | V = 1211.70 (7) Å3 |
Mr = 212.26 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 10.4710 (4) Å | µ = 0.08 mm−1 |
b = 9.3700 (3) Å | T = 150 K |
c = 12.3500 (4) Å | 0.4 × 0.3 × 0.2 mm |
Nonius KappaCCD area-detector diffractometer | 1216 reflections with I > 2σ(I) |
15701 measured reflections | Rint = 0.028 |
1464 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.152 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.22 | Δρmax = 0.27 e Å−3 |
1462 reflections | Δρmin = −0.15 e Å−3 |
123 parameters |
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. Two strong reflections 101 and 011 were omitted from the final refinement due inaccuracy in measurement. |
x | y | z | Uiso*/Ueq | ||
N1 | −0.18529 (12) | 0.2500 | 0.62264 (11) | 0.0421 (4) | |
C2 | −0.14572 (14) | 0.2500 | 0.50795 (12) | 0.0331 (4) | |
C3 | −0.00289 (14) | 0.2500 | 0.52252 (11) | 0.0308 (4) | |
C4 | 0.03176 (14) | 0.2500 | 0.62623 (11) | 0.0326 (4) | |
C5 | −0.07972 (13) | 0.2500 | 0.70199 (13) | 0.0340 (4) | |
O6 | −0.30192 (11) | 0.2500 | 0.65080 (11) | 0.0662 (5) | |
C7 | −0.19680 (13) | 0.11609 (12) | 0.45207 (11) | 0.0462 (4) | |
C8 | 0.08547 (15) | 0.2500 | 0.42918 (12) | 0.0346 (4) | |
O9 | 0.05073 (12) | 0.2500 | 0.33631 (10) | 0.0522 (4) | |
O10 | 0.20763 (11) | 0.2500 | 0.45910 (8) | 0.0403 (4) | |
C11 | 0.30171 (17) | 0.2500 | 0.37204 (15) | 0.0532 (5) | |
C12 | 0.4288 (2) | 0.2500 | 0.4199 (2) | 0.0906 (10) | |
C13 | −0.08471 (13) | 0.3840 (1) | 0.77207 (10) | 0.0426 (4) | |
H1 | 0.1239 (17) | 0.2500 | 0.6551 (15) | 0.044 (5)* | |
H2 | −0.0108 (13) | 0.3868 (13) | 0.8198 (12) | 0.051 (3)* | |
H3 | −0.0784 (12) | 0.4699 (17) | 0.7274 (11) | 0.054 (4)* | |
H4 | −0.2888 (15) | 0.1179 (15) | 0.4577 (10) | 0.050 (4)* | |
H5 | −0.1663 (14) | 0.3828 (15) | 0.8143 (14) | 0.059 (4)* | |
H6 | −0.1693 (13) | 0.1170 (16) | 0.3737 (13) | 0.060 (4)* | |
H7 | −0.1639 (12) | 0.0314 (17) | 0.4861 (12) | 0.052 (3)* | |
H8 | 0.492 (2) | 0.2500 | 0.358 (2) | 0.083 (8)* | |
H9 | 0.2852 (16) | 0.162 (2) | 0.3302 (15) | 0.081 (5)* | |
H10 | 0.446 (2) | 0.179 (3) | 0.475 (2) | 0.138 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0289 (7) | 0.0623 (9) | 0.0350 (8) | 0.000 | 0.0006 (5) | 0.000 |
C2 | 0.0346 (8) | 0.0341 (7) | 0.0306 (8) | 0.000 | −0.0039 (6) | 0.000 |
C3 | 0.0378 (8) | 0.0259 (7) | 0.0287 (9) | 0.000 | 0.0010 (5) | 0.000 |
C4 | 0.0319 (8) | 0.0368 (7) | 0.0291 (8) | 0.000 | 0.0016 (6) | 0.000 |
C5 | 0.0313 (7) | 0.0412 (8) | 0.0295 (8) | 0.000 | 0.0004 (6) | 0.000 |
O6 | 0.0269 (7) | 0.1213 (13) | 0.0503 (9) | 0.000 | 0.0041 (5) | 0.000 |
C7 | 0.0480 (8) | 0.0370 (7) | 0.0536 (8) | −0.0059 (5) | −0.0075 (6) | −0.0039 (5) |
C8 | 0.0441 (9) | 0.0310 (7) | 0.0287 (8) | 0.000 | 0.0033 (6) | 0.000 |
O9 | 0.0583 (8) | 0.0714 (8) | 0.0268 (7) | 0.000 | 0.0008 (5) | 0.000 |
O10 | 0.0392 (7) | 0.0527 (7) | 0.0288 (6) | 0.000 | 0.0099 (4) | 0.000 |
C11 | 0.0478 (11) | 0.0773 (14) | 0.0343 (10) | 0.000 | 0.0155 (7) | 0.000 |
C12 | 0.0468 (12) | 0.183 (3) | 0.0422 (13) | 0.000 | 0.0162 (10) | 0.000 |
C13 | 0.0462 (7) | 0.0436 (7) | 0.0380 (7) | 0.0028 (5) | 0.0054 (5) | −0.0039 (5) |
N1—O6 | 1.270 (2) | C7—H6 | 1.01 (2) |
N1—C5 | 1.477 (2) | C7—H7 | 0.96 (2) |
N1—C2 | 1.476 (2) | C8—O9 | 1.203 (2) |
C2—C3 | 1.506 (2) | C8—O10 | 1.331 (2) |
C2—C7 | 1.529 (1) | O10—C11 | 1.458 (2) |
C2—C7i | 1.529 (1) | C11—C12 | 1.456 (3) |
C3—C4 | 1.331 (2) | C11—H9 | 0.99 (2) |
C3—C8 | 1.478 (2) | C12—H8 | 1.01 (3) |
C4—C5 | 1.496 (2) | C12—H10 | 0.97 (3) |
C4—H1 | 1.029 (18) | C13—H2 | 0.97 (2) |
C5—C13i | 1.526 (1) | C13—H3 | 0.98 (1) |
C5—C13 | 1.526 (1) | C13—H5 | 1.00 (2) |
C7—H4 | 0.97 (2) | ||
O6—N1—C5 | 122.5 (1) | C2—C7—H6 | 109.0 (9) |
O6—N1—C2 | 122.2 (1) | H4—C7—H6 | 111 (1) |
C5—N1—C2 | 115.2 (1) | C2—C7—H7 | 110.8 (9) |
N1—C2—C3 | 99.4 (1) | H4—C7—H7 | 110 (1) |
N1—C2—C7 | 109.58 (9) | H6—C7—H7 | 109 (1) |
C3—C2—C7 | 113.66 (8) | O9—C8—O10 | 123.7 (1) |
N1—C2—C7i | 109.57 (9) | O9—C8—C3 | 123.6 (1) |
C3—C2—C7i | 113.66 (8) | O10—C8—C3 | 112.6 (1) |
C7—C2—C7i | 110.3 (1) | C8—O10—C11 | 116.4 (1) |
C4—C3—C8 | 125.4 (1) | O10—C11—C12 | 108.5 (2) |
C4—C3—C2 | 112.7 (1) | O10—C11—H9 | 106 (1) |
C8—C3—C2 | 121.9 (1) | C12—C11—H9 | 112 (1) |
C3—C4—C5 | 112.9 (1) | C11—C12—H8 | 108 (2) |
C3—C4—H1 | 126 (1) | C11—C12—H10 | 118 (2) |
C5—C4—H1 | 121 (1) | H8—C12—H10 | 114 (2) |
N1—C5—C4 | 99.7 (1) | C5—C13—H2 | 109.8 (7) |
N1—C5—C13i | 110.53 (8) | C5—C13—H3 | 110.8 (8) |
C4—C5—C13i | 112.42 (8) | H2—C13—H3 | 105 (1) |
N1—C5—C13 | 110.53 (8) | C5—C13—H5 | 108.4 (8) |
C4—C5—C13 | 112.42 (8) | H2—C13—H5 | 111 (1) |
C13i—C5—C13 | 110.7 (1) | H3—C13—H5 | 111 (1) |
C2—C7—H4 | 107.6 (8) |
Symmetry code: (i) x, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C11H18NO3 |
Mr | 212.26 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 150 |
a, b, c (Å) | 10.4710 (4), 9.3700 (3), 12.3500 (4) |
V (Å3) | 1211.70 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15701, 1464, 1216 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.152, 1.22 |
No. of reflections | 1462 |
No. of parameters | 123 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.15 |
Computer programs: COLLECT (Hooft, 1998) and DENZO (Otwinowski, 1997), COLLECT and DENZO, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97 and ORTEP-3.
N1—O6 | 1.270 (2) | C4—C5 | 1.496 (2) |
N1—C5 | 1.477 (2) | C5—C13 | 1.526 (1) |
N1—C2 | 1.476 (2) | C8—O9 | 1.203 (2) |
C2—C3 | 1.506 (2) | C8—O10 | 1.331 (2) |
C2—C7 | 1.529 (1) | O10—C11 | 1.458 (2) |
C3—C4 | 1.331 (2) | C11—C12 | 1.456 (3) |
C3—C8 | 1.478 (2) | ||
O6—N1—C5 | 122.5 (1) | N1—C5—C4 | 99.7 (1) |
C5—N1—C2 | 115.2 (1) | N1—C5—C13 | 110.53 (8) |
N1—C2—C3 | 99.4 (1) | C4—C5—C13 | 112.42 (8) |
N1—C2—C7 | 109.58 (9) | C13i—C5—C13 | 110.7 (1) |
C3—C2—C7 | 113.66 (8) | O9—C8—O10 | 123.7 (1) |
C7—C2—C7i | 110.3 (1) | O9—C8—C3 | 123.6 (1) |
C4—C3—C8 | 125.4 (1) | O10—C8—C3 | 112.6 (1) |
C4—C3—C2 | 112.7 (1) | C8—O10—C11 | 116.4 (1) |
C3—C4—C5 | 112.9 (1) | O10—C11—C12 | 108.5 (2) |
Symmetry code: (i) x, −y+1/2, z. |
The title molecule, (I), and the labeling scheme are shown in Fig. 1. As expected, the part of the molecule containing the pyrrol ring with the ethoxycarbonyl group is planar with standard bond distances and angles similar to that in hexa-2,4-diyne-6-(2,2,5,5-tetramethyl-1-oxyl-3-pyrrolin-3-carboxylate)-1-ol (Wiley, 1991). Two atoms, C12 and O6, showed higher values of atomic displacement parameters perpendicular to the plane of molecule, i.e. ellipsoids are prolonged along the b axis direction. In contrast (Wiley, 1991), there are no hydrogen bonds because of a lack of donor atoms. The packing diagram of the structure is presented in Fig. 2.