Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807036689/im2028sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807036689/im2028Isup2.hkl |
CCDC reference: 660316
The procedure for synthesizing benzyl (S)-2-(5-methyl-2-pyridylaminocarbonyl)-pyrrolidine-1-carboxylate (He, 2006) was used, with 6-methylpyridyl-2-amine in place of 5-methylpyridyl-2-amine. Crystals were grown from an ethanolic solution of the compound.
The carbon-bound hydrogen atoms were placed at calculated positions (C–H 0.95 to 0.99 Å) and were inlcuded in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5 Ueq(C). The amido hydrogen atom was located in a difference Fourier map and was refined with a distance restraint of N–H 0.88 ± 0.01 Å; its temperature factor was freely refined.
A recent study of benzyl (S)-2-(5-methyl-2-pyridylaminocarbonyl)-pyrrolidine-1-carboxylate shows a hydrogen-bonded chain [N···O 2.927 (2) Å] that runs along b-axis [11.4256 (3) Å] of the orthorhombic unit cell. In the isomeric title compound, the molecules are linked by the corresponding amido-carbonyl hydrogen bond [N···O 3.036 (2) Å] into a helical chain that runs along the a-axis of the orthorhombic cell. The mode of propagation differs between the two, as noted from the pitch of the helix.
For benzyl (S)-2-(5-methyl-2-pyridylaminocarbonyl)-pyrrolidine-2-carboxylate, see He (2006).
For related literature, see: Flack (1983).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
Fig. 1. Thermal ellipsoid plot of C19H21N3O3. Displacement ellipsoids are drawn at the 70% probability level, H atoms are drawn as spheres of arbitrary radiui. |
C19H21N3O3 | F(000) = 720 |
Mr = 339.39 | Dx = 1.309 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 16166 reflections |
a = 6.9065 (1) Å | θ = 3.2–27.5° |
b = 15.7480 (4) Å | µ = 0.09 mm−1 |
c = 15.8380 (4) Å | T = 153 K |
V = 1722.60 (7) Å3 | Block, colorless |
Z = 4 | 0.45 × 0.44 × 0.22 mm |
Rigaku R-AXIS RAPID IP diffractometer | 2261 independent reflections |
Radiation source: rotating anode tube | 2207 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −8→8 |
Tmin = 0.961, Tmax = 0.981 | k = −20→20 |
16810 measured reflections | l = −20→20 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0611P)2 + 0.4025P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.092 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.53 e Å−3 |
2261 reflections | Δρmin = −0.20 e Å−3 |
232 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
8 restraints | Extinction coefficient: 0.033 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Friedel pairs were merged |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0 |
C19H21N3O3 | V = 1722.60 (7) Å3 |
Mr = 339.39 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.9065 (1) Å | µ = 0.09 mm−1 |
b = 15.7480 (4) Å | T = 153 K |
c = 15.8380 (4) Å | 0.45 × 0.44 × 0.22 mm |
Rigaku R-AXIS RAPID IP diffractometer | 2261 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2207 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.981 | Rint = 0.019 |
16810 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.092 | Δρmax = 0.53 e Å−3 |
S = 1.04 | Δρmin = −0.20 e Å−3 |
2261 reflections | Absolute structure: Friedel pairs were merged |
232 parameters | Absolute structure parameter: 0 |
8 restraints |
x | y | z | Uiso*/Ueq | ||
O1 | 0.9391 (2) | 0.09533 (8) | 0.58395 (7) | 0.0265 (3) | |
O2 | 0.91177 (19) | 0.29212 (8) | 0.61477 (7) | 0.0234 (3) | |
O3 | 1.00096 (19) | 0.27940 (8) | 0.75267 (7) | 0.0226 (3) | |
N1 | 0.9295 (2) | 0.09490 (8) | 0.31762 (8) | 0.0196 (3) | |
N2 | 1.0429 (2) | 0.12574 (9) | 0.44994 (8) | 0.0198 (3) | |
H2 | 1.134 (3) | 0.1534 (12) | 0.4225 (13) | 0.032 (6)* | |
N3 | 1.1779 (2) | 0.21679 (9) | 0.65344 (8) | 0.0196 (3) | |
C1 | 0.8381 (3) | 0.07319 (13) | 0.17138 (10) | 0.0289 (4) | |
H1A | 0.9745 | 0.0672 | 0.1554 | 0.043* | |
H1B | 0.7958 | 0.1317 | 0.1611 | 0.043* | |
H1C | 0.7592 | 0.0342 | 0.1376 | 0.043* | |
C2 | 0.8148 (2) | 0.05246 (10) | 0.26361 (10) | 0.0215 (3) | |
C3 | 0.6786 (3) | −0.00678 (11) | 0.29092 (11) | 0.0254 (4) | |
H3 | 0.6003 | −0.0365 | 0.2515 | 0.030* | |
C4 | 0.6600 (3) | −0.02138 (11) | 0.37685 (12) | 0.0277 (4) | |
H4 | 0.5674 | −0.0612 | 0.3969 | 0.033* | |
C5 | 0.7765 (3) | 0.02218 (11) | 0.43353 (10) | 0.0245 (4) | |
H5 | 0.7653 | 0.0134 | 0.4927 | 0.029* | |
C6 | 0.9107 (2) | 0.07922 (9) | 0.40043 (10) | 0.0188 (3) | |
C7 | 1.0491 (2) | 0.13158 (9) | 0.53608 (9) | 0.0183 (3) | |
C8 | 1.2178 (2) | 0.18583 (10) | 0.56818 (9) | 0.0183 (3) | |
H8 | 1.2434 | 0.2343 | 0.5289 | 0.022* | |
C9 | 1.4007 (3) | 0.13120 (11) | 0.57953 (11) | 0.0249 (4) | |
H9A | 1.3667 | 0.0703 | 0.5837 | 0.030* | |
H9B | 1.4907 | 0.1392 | 0.5315 | 0.030* | |
C10 | 1.4912 (3) | 0.16248 (13) | 0.66126 (11) | 0.0301 (4) | |
H10A | 1.5743 | 0.2127 | 0.6511 | 0.036* | |
H10B | 1.5698 | 0.1174 | 0.6881 | 0.036* | |
C11 | 1.3167 (3) | 0.18557 (11) | 0.71607 (10) | 0.0239 (4) | |
H11A | 1.2658 | 0.1353 | 0.7463 | 0.029* | |
H11B | 1.3499 | 0.2302 | 0.7576 | 0.029* | |
C12 | 1.0218 (2) | 0.26492 (10) | 0.66888 (9) | 0.0181 (3) | |
C13 | 0.8416 (3) | 0.33562 (11) | 0.77456 (10) | 0.0251 (4) | |
H13A | 0.7232 | 0.3188 | 0.7436 | 0.030* | |
H13B | 0.8739 | 0.3949 | 0.7591 | 0.030* | |
C14 | 0.8084 (2) | 0.32899 (10) | 0.86799 (10) | 0.0193 (3) | |
C15 | 0.7404 (3) | 0.25312 (11) | 0.90256 (11) | 0.0242 (3) | |
H15 | 0.7205 | 0.2052 | 0.8671 | 0.029* | |
C16 | 0.7017 (3) | 0.24711 (14) | 0.98825 (12) | 0.0309 (4) | |
H16 | 0.6578 | 0.1950 | 1.0116 | 0.037* | |
C17 | 0.7273 (3) | 0.31743 (15) | 1.03973 (11) | 0.0344 (5) | |
H17 | 0.6986 | 0.3136 | 1.0983 | 0.041* | |
C18 | 0.7942 (3) | 0.39275 (13) | 1.00651 (12) | 0.0322 (4) | |
H18 | 0.8111 | 0.4408 | 1.0420 | 0.039* | |
C19 | 0.8372 (3) | 0.39844 (11) | 0.92059 (11) | 0.0250 (3) | |
H19 | 0.8863 | 0.4500 | 0.8980 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0286 (6) | 0.0308 (6) | 0.0200 (5) | −0.0078 (6) | 0.0056 (5) | 0.0008 (5) |
O2 | 0.0228 (6) | 0.0309 (6) | 0.0167 (5) | 0.0053 (5) | −0.0015 (5) | 0.0009 (4) |
O3 | 0.0220 (5) | 0.0312 (6) | 0.0145 (5) | 0.0091 (5) | −0.0007 (4) | −0.0024 (4) |
N1 | 0.0188 (6) | 0.0221 (6) | 0.0179 (6) | −0.0021 (6) | −0.0003 (5) | −0.0033 (5) |
N2 | 0.0201 (7) | 0.0229 (6) | 0.0163 (6) | −0.0061 (5) | 0.0015 (5) | 0.0002 (5) |
N3 | 0.0199 (7) | 0.0260 (6) | 0.0129 (5) | 0.0038 (6) | −0.0018 (5) | −0.0020 (5) |
C1 | 0.0268 (9) | 0.0396 (9) | 0.0204 (7) | −0.0062 (8) | −0.0010 (7) | −0.0081 (7) |
C2 | 0.0170 (7) | 0.0251 (7) | 0.0224 (7) | 0.0008 (7) | −0.0003 (6) | −0.0068 (6) |
C3 | 0.0204 (8) | 0.0257 (7) | 0.0299 (8) | −0.0041 (7) | −0.0022 (7) | −0.0079 (7) |
C4 | 0.0224 (9) | 0.0256 (8) | 0.0352 (9) | −0.0076 (7) | 0.0029 (7) | −0.0013 (7) |
C5 | 0.0246 (8) | 0.0258 (8) | 0.0230 (7) | −0.0052 (7) | 0.0016 (7) | 0.0011 (7) |
C6 | 0.0176 (7) | 0.0181 (6) | 0.0207 (7) | 0.0001 (6) | 0.0006 (6) | −0.0024 (5) |
C7 | 0.0198 (8) | 0.0178 (6) | 0.0174 (7) | 0.0007 (6) | 0.0002 (6) | 0.0009 (5) |
C8 | 0.0197 (7) | 0.0221 (7) | 0.0131 (6) | −0.0003 (6) | 0.0007 (6) | −0.0016 (5) |
C9 | 0.0206 (8) | 0.0313 (8) | 0.0227 (7) | 0.0052 (7) | 0.0012 (7) | −0.0030 (7) |
C10 | 0.0258 (9) | 0.0345 (9) | 0.0301 (9) | 0.0048 (8) | −0.0021 (8) | −0.0008 (7) |
C11 | 0.0250 (8) | 0.0313 (8) | 0.0155 (7) | 0.0069 (7) | −0.0044 (7) | 0.0004 (6) |
C12 | 0.0185 (7) | 0.0209 (6) | 0.0150 (6) | −0.0008 (6) | −0.0001 (6) | −0.0004 (5) |
C13 | 0.0247 (8) | 0.0308 (8) | 0.0198 (7) | 0.0110 (7) | 0.0020 (7) | 0.0008 (6) |
C14 | 0.0141 (7) | 0.0247 (7) | 0.0189 (7) | 0.0043 (6) | −0.0004 (6) | −0.0013 (6) |
C15 | 0.0215 (8) | 0.0259 (8) | 0.0252 (8) | −0.0020 (7) | −0.0026 (7) | −0.0033 (6) |
C16 | 0.0215 (8) | 0.0409 (9) | 0.0302 (9) | −0.0044 (8) | 0.0016 (7) | 0.0095 (8) |
C17 | 0.0240 (9) | 0.0612 (13) | 0.0180 (8) | 0.0038 (9) | 0.0023 (7) | −0.0025 (8) |
C18 | 0.0266 (9) | 0.0422 (10) | 0.0277 (8) | 0.0050 (8) | −0.0014 (8) | −0.0162 (8) |
C19 | 0.0212 (8) | 0.0235 (7) | 0.0302 (8) | 0.0010 (7) | 0.0009 (7) | −0.0044 (7) |
O1—C7 | 1.216 (2) | C8—C9 | 1.539 (2) |
O2—C12 | 1.223 (2) | C8—H8 | 1.0000 |
O3—C12 | 1.3541 (18) | C9—C10 | 1.520 (2) |
O3—C13 | 1.455 (2) | C9—H9A | 0.9900 |
N1—C6 | 1.341 (2) | C9—H9B | 0.9900 |
N1—C2 | 1.344 (2) | C10—C11 | 1.530 (2) |
N2—C7 | 1.3682 (19) | C10—H10A | 0.9900 |
N2—C6 | 1.409 (2) | C10—H10B | 0.9900 |
N2—H2 | 0.880 (10) | C11—H11A | 0.9900 |
N3—C12 | 1.341 (2) | C11—H11B | 0.9900 |
N3—C8 | 1.4618 (18) | C13—C14 | 1.501 (2) |
N3—C11 | 1.4642 (19) | C13—H13A | 0.9900 |
C1—C2 | 1.505 (2) | C13—H13B | 0.9900 |
C1—H1A | 0.9800 | C14—C19 | 1.389 (2) |
C1—H1B | 0.9800 | C14—C15 | 1.396 (2) |
C1—H1C | 0.9800 | C15—C16 | 1.386 (2) |
C2—C3 | 1.393 (2) | C15—H15 | 0.9500 |
C3—C4 | 1.386 (2) | C16—C17 | 1.387 (3) |
C3—H3 | 0.9500 | C16—H16 | 0.9500 |
C4—C5 | 1.387 (2) | C17—C18 | 1.377 (3) |
C4—H4 | 0.9500 | C17—H17 | 0.9500 |
C5—C6 | 1.393 (2) | C18—C19 | 1.396 (2) |
C5—H5 | 0.9500 | C18—H18 | 0.9500 |
C7—C8 | 1.531 (2) | C19—H19 | 0.9500 |
C12—O3—C13 | 114.62 (13) | C8—C9—H9B | 110.8 |
C6—N1—C2 | 118.28 (14) | H9A—C9—H9B | 108.9 |
C7—N2—C6 | 127.62 (14) | C9—C10—C11 | 103.66 (14) |
C7—N2—H2 | 115.9 (15) | C9—C10—H10A | 111.0 |
C6—N2—H2 | 116.4 (15) | C11—C10—H10A | 111.0 |
C12—N3—C8 | 120.57 (13) | C9—C10—H10B | 111.0 |
C12—N3—C11 | 126.34 (13) | C11—C10—H10B | 111.0 |
C8—N3—C11 | 112.99 (13) | H10A—C10—H10B | 109.0 |
C2—C1—H1A | 109.5 | N3—C11—C10 | 102.19 (13) |
C2—C1—H1B | 109.5 | N3—C11—H11A | 111.3 |
H1A—C1—H1B | 109.5 | C10—C11—H11A | 111.3 |
C2—C1—H1C | 109.5 | N3—C11—H11B | 111.3 |
H1A—C1—H1C | 109.5 | C10—C11—H11B | 111.3 |
H1B—C1—H1C | 109.5 | H11A—C11—H11B | 109.2 |
N1—C2—C3 | 122.23 (15) | O2—C12—N3 | 124.75 (14) |
N1—C2—C1 | 116.52 (15) | O2—C12—O3 | 124.17 (15) |
C3—C2—C1 | 121.24 (15) | N3—C12—O3 | 111.08 (13) |
C4—C3—C2 | 118.59 (16) | O3—C13—C14 | 107.95 (13) |
C4—C3—H3 | 120.7 | O3—C13—H13A | 110.1 |
C2—C3—H3 | 120.7 | C14—C13—H13A | 110.1 |
C3—C4—C5 | 119.96 (17) | O3—C13—H13B | 110.1 |
C3—C4—H4 | 120.0 | C14—C13—H13B | 110.1 |
C5—C4—H4 | 120.0 | H13A—C13—H13B | 108.4 |
C4—C5—C6 | 117.47 (16) | C19—C14—C15 | 119.13 (15) |
C4—C5—H5 | 121.3 | C19—C14—C13 | 120.97 (16) |
C6—C5—H5 | 121.3 | C15—C14—C13 | 119.85 (15) |
N1—C6—C5 | 123.45 (15) | C16—C15—C14 | 120.49 (17) |
N1—C6—N2 | 112.70 (14) | C16—C15—H15 | 119.8 |
C5—C6—N2 | 123.84 (14) | C14—C15—H15 | 119.8 |
O1—C7—N2 | 124.79 (15) | C15—C16—C17 | 119.77 (19) |
O1—C7—C8 | 122.04 (14) | C15—C16—H16 | 120.1 |
N2—C7—C8 | 113.10 (14) | C17—C16—H16 | 120.1 |
N3—C8—C7 | 110.45 (13) | C18—C17—C16 | 120.39 (16) |
N3—C8—C9 | 103.48 (12) | C18—C17—H17 | 119.8 |
C7—C8—C9 | 110.57 (13) | C16—C17—H17 | 119.8 |
N3—C8—H8 | 110.7 | C17—C18—C19 | 119.94 (17) |
C7—C8—H8 | 110.7 | C17—C18—H18 | 120.0 |
C9—C8—H8 | 110.7 | C19—C18—H18 | 120.0 |
C10—C9—C8 | 104.84 (13) | C14—C19—C18 | 120.25 (16) |
C10—C9—H9A | 110.8 | C14—C19—H19 | 119.9 |
C8—C9—H9A | 110.8 | C18—C19—H19 | 119.9 |
C10—C9—H9B | 110.8 | ||
C6—N1—C2—C3 | −0.1 (2) | C7—C8—C9—C10 | −139.34 (14) |
C6—N1—C2—C1 | 178.90 (15) | C8—C9—C10—C11 | 34.49 (18) |
N1—C2—C3—C4 | 0.8 (3) | C12—N3—C11—C10 | −161.55 (16) |
C1—C2—C3—C4 | −178.13 (17) | C8—N3—C11—C10 | 21.96 (18) |
C2—C3—C4—C5 | −0.5 (3) | C9—C10—C11—N3 | −33.99 (18) |
C3—C4—C5—C6 | −0.5 (3) | C8—N3—C12—O2 | −6.1 (2) |
C2—N1—C6—C5 | −1.0 (2) | C11—N3—C12—O2 | 177.70 (16) |
C2—N1—C6—N2 | 178.20 (14) | C8—N3—C12—O3 | 173.69 (14) |
C4—C5—C6—N1 | 1.3 (3) | C11—N3—C12—O3 | −2.6 (2) |
C4—C5—C6—N2 | −177.80 (16) | C13—O3—C12—O2 | −3.9 (2) |
C7—N2—C6—N1 | 172.46 (15) | C13—O3—C12—N3 | 176.36 (14) |
C7—N2—C6—C5 | −8.4 (3) | C12—O3—C13—C14 | 166.87 (14) |
C6—N2—C7—O1 | 1.0 (3) | O3—C13—C14—C19 | 115.82 (17) |
C6—N2—C7—C8 | 178.08 (14) | O3—C13—C14—C15 | −66.7 (2) |
C12—N3—C8—C7 | −59.16 (18) | C19—C14—C15—C16 | 0.1 (3) |
C11—N3—C8—C7 | 117.55 (15) | C13—C14—C15—C16 | −177.40 (17) |
C12—N3—C8—C9 | −177.53 (14) | C14—C15—C16—C17 | 1.2 (3) |
C11—N3—C8—C9 | −0.81 (18) | C15—C16—C17—C18 | −1.1 (3) |
O1—C7—C8—N3 | −24.6 (2) | C16—C17—C18—C19 | −0.2 (3) |
N2—C7—C8—N3 | 158.28 (13) | C15—C14—C19—C18 | −1.5 (3) |
O1—C7—C8—C9 | 89.38 (19) | C13—C14—C19—C18 | 176.02 (17) |
N2—C7—C8—C9 | −87.78 (16) | C17—C18—C19—C14 | 1.5 (3) |
N3—C8—C9—C10 | −21.06 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2i | 0.88 (1) | 2.18 (1) | 3.036 (2) | 163 (2) |
Symmetry code: (i) x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C19H21N3O3 |
Mr | 339.39 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 153 |
a, b, c (Å) | 6.9065 (1), 15.7480 (4), 15.8380 (4) |
V (Å3) | 1722.60 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.45 × 0.44 × 0.22 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID IP |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.961, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16810, 2261, 2207 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.092, 1.04 |
No. of reflections | 2261 |
No. of parameters | 232 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.53, −0.20 |
Absolute structure | Friedel pairs were merged |
Absolute structure parameter | 0 |
Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2i | 0.88 (1) | 2.18 (1) | 3.036 (2) | 163 (2) |
Symmetry code: (i) x+1/2, −y+1/2, −z+1. |
A recent study of benzyl (S)-2-(5-methyl-2-pyridylaminocarbonyl)-pyrrolidine-1-carboxylate shows a hydrogen-bonded chain [N···O 2.927 (2) Å] that runs along b-axis [11.4256 (3) Å] of the orthorhombic unit cell. In the isomeric title compound, the molecules are linked by the corresponding amido-carbonyl hydrogen bond [N···O 3.036 (2) Å] into a helical chain that runs along the a-axis of the orthorhombic cell. The mode of propagation differs between the two, as noted from the pitch of the helix.