Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017987/cv6222sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017987/cv6222Isup2.hkl |
CCDC reference: 222885
Methyl 2-(2-naphthyloxy)acetate (0.5 g) was reacted with pyrrolidine. The oily product obtained was treated with water. The precipitate obtained was filtered, dried and crystallized from acetone to afford (I) (yield, 0.51 g, 86.39%; m.p. 397–399 K).
All H atoms were placed in geometrically idealized positions (C—H = 0.95–0.99 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). Reflection 1 0 0 was partially obscured by the beam stop and was omitted.
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
Fig. 1. View of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary radii. |
C16H17NO2 | F(000) = 544 |
Mr = 255.31 | Dx = 1.343 Mg m−3 |
Monoclinic, P21/c | Melting point: 397 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6427 (2) Å | Cell parameters from 3899 reflections |
b = 8.8035 (2) Å | θ = 2.0–30.0° |
c = 14.4306 (2) Å | µ = 0.09 mm−1 |
β = 110.9738 (11)° | T = 160 K |
V = 1262.46 (4) Å3 | Prism, colourless |
Z = 4 | 0.23 × 0.20 × 0.17 mm |
Nonius KappaCCD diffractometer | 2775 reflections with I > 2σ(I) |
Radiation source: Nonius FR591 sealed tube generator | Rint = 0.047 |
Horizontally mounted graphite crystal monochromator | θmax = 30.0°, θmin = 2.8° |
Detector resolution: 9 pixels mm-1 | h = 0→14 |
ϕ and ω scans with κ offsets | k = 0→12 |
33348 measured reflections | l = −20→18 |
3686 independent reflections |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0765P)2 + 0.209P] where P = (Fo2 + 2Fc2)/3 |
3685 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C16H17NO2 | V = 1262.46 (4) Å3 |
Mr = 255.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6427 (2) Å | µ = 0.09 mm−1 |
b = 8.8035 (2) Å | T = 160 K |
c = 14.4306 (2) Å | 0.23 × 0.20 × 0.17 mm |
β = 110.9738 (11)° |
Nonius KappaCCD diffractometer | 2775 reflections with I > 2σ(I) |
33348 measured reflections | Rint = 0.047 |
3686 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.51 e Å−3 |
3685 reflections | Δρmin = −0.30 e Å−3 |
172 parameters |
Experimental. Solvent used: acetone Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.484 (2) Frames collected: 326 Seconds exposure per frame: 40 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 28.0 |
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 | ||
O11 | 0.72111 (8) | 0.52679 (10) | 0.40282 (6) | 0.0258 (2) | |
O13 | 0.91728 (9) | 0.71575 (11) | 0.40863 (6) | 0.0329 (2) | |
N14 | 1.00984 (10) | 0.71437 (12) | 0.57646 (7) | 0.0250 (2) | |
C1 | 0.59653 (11) | 0.36322 (13) | 0.47607 (8) | 0.0225 (3) | |
H1 | 0.6561 | 0.3833 | 0.5418 | 0.027* | |
C2 | 0.61699 (11) | 0.43114 (13) | 0.39705 (8) | 0.0223 (2) | |
C3 | 0.52769 (12) | 0.40350 (14) | 0.29858 (8) | 0.0252 (3) | |
H3 | 0.5418 | 0.4528 | 0.2446 | 0.030* | |
C4 | 0.42181 (12) | 0.30663 (13) | 0.28106 (8) | 0.0247 (3) | |
H4 | 0.3633 | 0.2884 | 0.2148 | 0.030* | |
C5 | 0.28892 (12) | 0.13087 (14) | 0.34436 (9) | 0.0255 (3) | |
H5 | 0.2297 | 0.1106 | 0.2785 | 0.031* | |
C6 | 0.26823 (13) | 0.06134 (14) | 0.42287 (9) | 0.0272 (3) | |
H6 | 0.1954 | −0.0074 | 0.4112 | 0.033* | |
C7 | 0.35519 (13) | 0.09200 (14) | 0.52097 (9) | 0.0273 (3) | |
H7 | 0.3402 | 0.0439 | 0.5750 | 0.033* | |
C8 | 0.46083 (12) | 0.19043 (13) | 0.53880 (8) | 0.0248 (3) | |
H8 | 0.5180 | 0.2105 | 0.6052 | 0.030* | |
C9 | 0.48618 (11) | 0.26294 (13) | 0.45948 (8) | 0.0214 (2) | |
C10 | 0.39775 (11) | 0.23241 (13) | 0.36073 (8) | 0.0218 (2) | |
C12 | 0.81293 (12) | 0.56020 (14) | 0.49915 (8) | 0.0236 (3) | |
H121 | 0.8574 | 0.4659 | 0.5323 | 0.028* | |
H122 | 0.7648 | 0.6060 | 0.5396 | 0.028* | |
C13 | 0.91719 (12) | 0.67071 (14) | 0.48940 (8) | 0.0238 (3) | |
C15 | 1.01720 (12) | 0.66274 (15) | 0.67521 (9) | 0.0277 (3) | |
H151 | 1.0330 | 0.5518 | 0.6828 | 0.033* | |
H152 | 0.9335 | 0.6876 | 0.6870 | 0.033* | |
C16 | 1.13665 (16) | 0.75073 (18) | 0.74576 (11) | 0.0421 (4) | |
H161 | 1.1198 | 0.7810 | 0.8064 | 0.051* | |
H162 | 1.2197 | 0.6887 | 0.7652 | 0.051* | |
C17 | 1.14902 (18) | 0.88943 (19) | 0.68716 (11) | 0.0456 (4) | |
H171 | 1.0868 | 0.9708 | 0.6909 | 0.055* | |
H172 | 1.2421 | 0.9294 | 0.7120 | 0.055* | |
C18 | 1.11106 (12) | 0.83033 (15) | 0.58232 (9) | 0.0286 (3) | |
H181 | 1.0729 | 0.9121 | 0.5332 | 0.034* | |
H182 | 1.1898 | 0.7855 | 0.5712 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0235 (4) | 0.0310 (5) | 0.0208 (4) | −0.0041 (3) | 0.0054 (3) | 0.0001 (3) |
O13 | 0.0333 (5) | 0.0406 (5) | 0.0250 (4) | −0.0040 (4) | 0.0106 (4) | 0.0043 (4) |
N14 | 0.0218 (5) | 0.0271 (5) | 0.0245 (5) | −0.0022 (4) | 0.0063 (4) | 0.0008 (4) |
C1 | 0.0209 (5) | 0.0261 (6) | 0.0189 (5) | 0.0036 (4) | 0.0051 (4) | −0.0006 (4) |
C2 | 0.0209 (5) | 0.0235 (6) | 0.0226 (6) | 0.0017 (4) | 0.0081 (4) | −0.0007 (4) |
C3 | 0.0281 (6) | 0.0281 (6) | 0.0196 (6) | 0.0004 (5) | 0.0087 (5) | 0.0008 (4) |
C4 | 0.0266 (6) | 0.0273 (6) | 0.0176 (5) | 0.0012 (5) | 0.0047 (4) | −0.0009 (4) |
C5 | 0.0237 (6) | 0.0285 (6) | 0.0229 (5) | 0.0005 (5) | 0.0068 (4) | −0.0042 (4) |
C6 | 0.0271 (6) | 0.0279 (6) | 0.0287 (6) | −0.0025 (5) | 0.0126 (5) | −0.0032 (5) |
C7 | 0.0317 (7) | 0.0291 (6) | 0.0242 (6) | 0.0019 (5) | 0.0135 (5) | 0.0012 (5) |
C8 | 0.0266 (6) | 0.0280 (6) | 0.0196 (5) | 0.0027 (5) | 0.0079 (5) | −0.0001 (4) |
C9 | 0.0214 (5) | 0.0230 (6) | 0.0202 (5) | 0.0050 (4) | 0.0080 (4) | 0.0002 (4) |
C10 | 0.0227 (5) | 0.0234 (6) | 0.0196 (5) | 0.0037 (4) | 0.0078 (4) | −0.0012 (4) |
C12 | 0.0216 (5) | 0.0273 (6) | 0.0205 (5) | 0.0003 (5) | 0.0061 (4) | −0.0007 (4) |
C13 | 0.0210 (5) | 0.0254 (6) | 0.0251 (6) | 0.0031 (5) | 0.0083 (4) | 0.0013 (4) |
C15 | 0.0257 (6) | 0.0323 (7) | 0.0230 (6) | −0.0008 (5) | 0.0061 (5) | 0.0021 (5) |
C16 | 0.0444 (8) | 0.0446 (9) | 0.0286 (7) | −0.0122 (7) | 0.0023 (6) | −0.0005 (6) |
C17 | 0.0513 (9) | 0.0408 (8) | 0.0407 (8) | −0.0156 (7) | 0.0117 (7) | −0.0075 (6) |
C18 | 0.0232 (6) | 0.0262 (6) | 0.0355 (7) | −0.0021 (5) | 0.0095 (5) | 0.0006 (5) |
O11—C2 | 1.3703 (14) | C7—C8 | 1.3690 (17) |
O11—C12 | 1.4147 (14) | C7—H7 | 0.9500 |
O13—C13 | 1.2315 (15) | C8—C9 | 1.4182 (16) |
N14—C13 | 1.3459 (15) | C8—H8 | 0.9500 |
N14—C18 | 1.4643 (16) | C9—C10 | 1.4243 (16) |
N14—C15 | 1.4709 (15) | C12—C13 | 1.5197 (17) |
C1—C2 | 1.3723 (16) | C12—H121 | 0.9900 |
C1—C9 | 1.4194 (17) | C12—H122 | 0.9900 |
C1—H1 | 0.9500 | C15—C16 | 1.5252 (19) |
C2—C3 | 1.4194 (16) | C15—H151 | 0.9900 |
C3—C4 | 1.3626 (17) | C15—H152 | 0.9900 |
C3—H3 | 0.9500 | C16—C17 | 1.518 (2) |
C4—C10 | 1.4231 (16) | C16—H161 | 0.9900 |
C4—H4 | 0.9500 | C16—H162 | 0.9900 |
C5—C6 | 1.3732 (18) | C17—C18 | 1.512 (2) |
C5—C10 | 1.4144 (17) | C17—H171 | 0.9900 |
C5—H5 | 0.9500 | C17—H172 | 0.9900 |
C6—C7 | 1.4126 (17) | C18—H181 | 0.9900 |
C6—H6 | 0.9500 | C18—H182 | 0.9900 |
C2—O11—C12 | 116.52 (9) | O11—C12—C13 | 108.21 (9) |
C13—N14—C18 | 122.07 (10) | O11—C12—H121 | 110.1 |
C13—N14—C15 | 125.67 (10) | C13—C12—H121 | 110.1 |
C18—N14—C15 | 112.12 (9) | O11—C12—H122 | 110.1 |
C2—C1—C9 | 119.91 (10) | C13—C12—H122 | 110.1 |
C2—C1—H1 | 120.0 | H121—C12—H122 | 108.4 |
C9—C1—H1 | 120.0 | O13—C13—N14 | 122.89 (11) |
O11—C2—C1 | 125.64 (10) | O13—C13—C12 | 122.80 (10) |
O11—C2—C3 | 113.79 (10) | N14—C13—C12 | 114.31 (10) |
C1—C2—C3 | 120.57 (11) | N14—C15—C16 | 103.44 (10) |
C4—C3—C2 | 120.40 (11) | N14—C15—H151 | 111.1 |
C4—C3—H3 | 119.8 | C16—C15—H151 | 111.1 |
C2—C3—H3 | 119.8 | N14—C15—H152 | 111.1 |
C3—C4—C10 | 120.89 (10) | C16—C15—H152 | 111.1 |
C3—C4—H4 | 119.6 | H151—C15—H152 | 109.0 |
C10—C4—H4 | 119.6 | C17—C16—C15 | 104.74 (11) |
C6—C5—C10 | 120.50 (11) | C17—C16—H161 | 110.8 |
C6—C5—H5 | 119.8 | C15—C16—H161 | 110.8 |
C10—C5—H5 | 119.8 | C17—C16—H162 | 110.8 |
C5—C6—C7 | 120.04 (11) | C15—C16—H162 | 110.8 |
C5—C6—H6 | 120.0 | H161—C16—H162 | 108.9 |
C7—C6—H6 | 120.0 | C18—C17—C16 | 103.61 (12) |
C8—C7—C6 | 120.58 (11) | C18—C17—H171 | 111.0 |
C8—C7—H7 | 119.7 | C16—C17—H171 | 111.0 |
C6—C7—H7 | 119.7 | C18—C17—H172 | 111.0 |
C7—C8—C9 | 120.92 (10) | C16—C17—H172 | 111.0 |
C7—C8—H8 | 119.5 | H171—C17—H172 | 109.0 |
C9—C8—H8 | 119.5 | N14—C18—C17 | 103.02 (11) |
C8—C9—C1 | 121.92 (10) | N14—C18—H181 | 111.2 |
C8—C9—C10 | 118.30 (11) | C17—C18—H181 | 111.2 |
C1—C9—C10 | 119.78 (10) | N14—C18—H182 | 111.2 |
C5—C10—C4 | 121.91 (10) | C17—C18—H182 | 111.2 |
C5—C10—C9 | 119.65 (11) | H181—C18—H182 | 109.1 |
C4—C10—C9 | 118.44 (11) | ||
C12—O11—C2—C1 | −1.55 (17) | C8—C9—C10—C5 | −0.53 (16) |
C12—O11—C2—C3 | 179.33 (10) | C1—C9—C10—C5 | 179.16 (10) |
C9—C1—C2—O11 | −178.29 (10) | C8—C9—C10—C4 | 179.13 (10) |
C9—C1—C2—C3 | 0.77 (18) | C1—C9—C10—C4 | −1.17 (16) |
O11—C2—C3—C4 | 177.85 (10) | C2—O11—C12—C13 | −178.34 (9) |
C1—C2—C3—C4 | −1.31 (18) | C18—N14—C13—O13 | 5.85 (19) |
C2—C3—C4—C10 | 0.58 (18) | C15—N14—C13—O13 | −178.70 (11) |
C10—C5—C6—C7 | 0.57 (18) | C18—N14—C13—C12 | −174.56 (10) |
C5—C6—C7—C8 | −0.23 (19) | C15—N14—C13—C12 | 0.90 (17) |
C6—C7—C8—C9 | −0.50 (18) | O11—C12—C13—O13 | −1.60 (16) |
C7—C8—C9—C1 | −178.81 (11) | O11—C12—C13—N14 | 178.81 (10) |
C7—C8—C9—C10 | 0.88 (17) | C13—N14—C15—C16 | −178.27 (12) |
C2—C1—C9—C8 | −179.84 (11) | C18—N14—C15—C16 | −2.43 (14) |
C2—C1—C9—C10 | 0.47 (17) | N14—C15—C16—C17 | 23.52 (15) |
C6—C5—C10—C4 | −179.83 (11) | C15—C16—C17—C18 | −35.72 (16) |
C6—C5—C10—C9 | −0.18 (17) | C13—N14—C18—C17 | 156.45 (12) |
C3—C4—C10—C5 | −179.69 (11) | C15—N14—C18—C17 | −19.56 (14) |
C3—C4—C10—C9 | 0.65 (17) | C16—C17—C18—N14 | 33.41 (15) |
Experimental details
Crystal data | |
Chemical formula | C16H17NO2 |
Mr | 255.31 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 160 |
a, b, c (Å) | 10.6427 (2), 8.8035 (2), 14.4306 (2) |
β (°) | 110.9738 (11) |
V (Å3) | 1262.46 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.23 × 0.20 × 0.17 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33348, 3686, 2775 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.144, 1.05 |
No. of reflections | 3685 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.30 |
Computer programs: COLLECT (Nonius, 2000), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97 and PLATON (Spek, 2003).
O11—C2—C1 | 125.64 (10) | ||
C2—O11—C12—C13 | −178.34 (9) | O11—C12—C13—N14 | 178.81 (10) |
The conformation of molecules with anti-amnesic activity has attracted considerable interest (Amato et al., 1991). The pyrrolidine moiety is a requisite for several active compounds currently used in the therapy of pathological brain-aging phenomena (Piracetam, Oxyracetam and Pramiracetam). The ring-extended N-analogues of 2-pyrrolidinone, viz. 2-aryl-3-piperazinone compounds, have been found to possess the characteristic nootropic pharmacological profile (Amato et al., 1991). The present paper reports the structure and conformation of the title compound, (I), which was determined as a continuation of the investigation of a new class of anti-amnesic agents (Thamotharan, Parthasarathi, Gupta et al., 2003a,b,c; Thamotharan, Parthasarathi, Malik et al., 2003a,b).
Fig. 1 shows a view of the molecule of (I), with the atomic numbering scheme. The bond lengths and angles in (I) are comparable with those in the related structures of 1-(2-naphthyloxymethylcarbonyl)piperidine and 3-methyl-1-(2-naphthyloxymethylcarbonyl)piperidine (Thamotharan, Parthasarathi, Malik et al., 2003a), 4-(2-naphthyloxymethylcarbonyl)morpholine and 4-methyl-1-(2-naphthyloxymethylcarbonyl)piperazine (Thamotharan, Parthasarathi, Gupta et al., 2003a), as well as N,N-dimethyl-2-(2-naphthyloxy)acetamide monohydrate (Thamotharan, Parthasarathi, Gupta et al., 2003c). In (I), the central fragment C2—O11—C12—C13—N14 is planar, with a maximum deviation of 0.0223 (13) Å for atom C12. This central unit is virtually coplanar with the plane of the naphthalene moiety, the angle between the planes being 1.48 (5)°. The C2—O11—C12—C13 and O11—C12—C13—N14 torsion angles show that the central unit has an antiperiplanar conformation.
The pyrrolidine ring in nootropics usually has a half-chair (C2, twist-envelope) conformation, (Thamotharan, Parthasarathi, Malik et al., 2003b and references therein). In (I), however, the pyrrolidine ring adopts an envelope conformation, with atom C17 as the flap, a pseudo-rotation angle Δ = 86.0 (1)° and a maximum torsion angle ϕm = 36.5 (1)° (Rao et al., 1981) for the atom sequence N14—C15—C16—C17—C18. Ignoring C17, the mean plane through the remainder of the pyrrolidine ring is almost coplanar with the plane of the naphthalene moiety, the angle between the planes being 3.55 (9)°. Thus, the entire molecule is essentially planar.
The exocyclic bond angle C1—C2—O11 deviates significantly from the normal value of 120° (Table 1) and this may be due to steric repulsion (H1···H121 =2.31 Å, H1···H122 = 2.28 Å). The crystal packing is influenced only by normal van der Waals contacts.