Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103014823/sk1656sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103014823/sk1656Isup2.hkl |
CCDC reference: 221080
A solution of (4-nitrophenoxy)acetylchloride (1.0 g) in dichloromethane was stirred with pyrrolidinone. Dichloromethane was removed and crushed ice was added to the contents. The solid residue obtained was filtered and crystallized from methanol, affording crystals of (I) (yield 0.78 g, 63.71%; m.p. 413–415 K).
All H atoms were placed in geometrically idealized positions (C—H = 0.95–0.99 Å) and were constrained to ride on their parent atoms with Uiso(H) values equal to 1.2Ueq(C).
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 for Windows (Farrugia, 1997); software used to prepare material for publication: PARST97 (Nardelli, 1995) and PLATON (Spek, 2003).
C12H12N2O5 | Z = 2 |
Mr = 264.24 | F(000) = 276 |
Triclinic, P1 | Dx = 1.507 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.2813 (1) Å | Cell parameters from 3302 reflections |
b = 8.7367 (2) Å | θ = 2.0–30.0° |
c = 12.9843 (3) Å | µ = 0.12 mm−1 |
α = 80.4656 (14)° | T = 160 K |
β = 81.4302 (12)° | Prism, colourless |
γ = 83.883 (1)° | 0.25 × 0.25 × 0.17 mm |
V = 582.17 (2) Å3 |
Nonius KappaCCD diffractometer | 2701 reflections with I > 2σ(I) |
Radiation source: Nonius FR591 sealed tube generator | Rint = 0.033 |
Horizontally mounted graphite crystal monochromator | θmax = 30.0°, θmin = 2.4° |
Detector resolution: 9 pixels mm-1 | h = 0→7 |
ϕ and ω scans with κ offsets | k = −11→12 |
16366 measured reflections | l = −17→18 |
3393 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0735P)2 + 0.0824P] where P = (Fo2 + 2Fc2)/3 |
3393 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C12H12N2O5 | γ = 83.883 (1)° |
Mr = 264.24 | V = 582.17 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.2813 (1) Å | Mo Kα radiation |
b = 8.7367 (2) Å | µ = 0.12 mm−1 |
c = 12.9843 (3) Å | T = 160 K |
α = 80.4656 (14)° | 0.25 × 0.25 × 0.17 mm |
β = 81.4302 (12)° |
Nonius KappaCCD diffractometer | 2701 reflections with I > 2σ(I) |
16366 measured reflections | Rint = 0.033 |
3393 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.36 e Å−3 |
3393 reflections | Δρmin = −0.26 e Å−3 |
172 parameters |
Experimental. Solvent used: MeOH Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.719 (2) Frames collected: 352 Seconds exposure per frame: 46 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 | ||
O7 | −0.15309 (15) | 0.34954 (9) | 0.54930 (6) | 0.02594 (19) | |
O9 | −0.22285 (16) | 0.44936 (10) | 0.73114 (6) | 0.0297 (2) | |
O11 | 0.42580 (16) | 0.13590 (10) | 0.71998 (6) | 0.0301 (2) | |
O16 | 0.04202 (18) | 0.03989 (11) | 0.13850 (7) | 0.0373 (2) | |
O17 | −0.28845 (19) | 0.20168 (11) | 0.10914 (7) | 0.0373 (2) | |
N10 | 0.13145 (17) | 0.31977 (10) | 0.79120 (7) | 0.0219 (2) | |
N15 | −0.12317 (19) | 0.14158 (11) | 0.16452 (7) | 0.0260 (2) | |
C1 | −0.1311 (2) | 0.29202 (12) | 0.45630 (8) | 0.0214 (2) | |
C2 | 0.0669 (2) | 0.18582 (12) | 0.42193 (8) | 0.0235 (2) | |
H2 | 0.1983 | 0.1473 | 0.4645 | 0.028* | |
C3 | 0.0712 (2) | 0.13667 (12) | 0.32514 (9) | 0.0240 (2) | |
H3 | 0.2058 | 0.0652 | 0.3003 | 0.029* | |
C4 | −0.1245 (2) | 0.19388 (12) | 0.26572 (8) | 0.0216 (2) | |
C5 | −0.3230 (2) | 0.29975 (12) | 0.29858 (8) | 0.0225 (2) | |
H5 | −0.4546 | 0.3372 | 0.2560 | 0.027* | |
C6 | −0.3259 (2) | 0.34963 (12) | 0.39422 (8) | 0.0232 (2) | |
H6 | −0.4593 | 0.4227 | 0.4179 | 0.028* | |
C8 | 0.0375 (2) | 0.28918 (13) | 0.61578 (8) | 0.0239 (2) | |
H81 | 0.2095 | 0.3172 | 0.5807 | 0.029* | |
H82 | 0.0405 | 0.1743 | 0.6320 | 0.029* | |
C9 | −0.0330 (2) | 0.36052 (12) | 0.71558 (8) | 0.0217 (2) | |
C11 | 0.3410 (2) | 0.20721 (12) | 0.79208 (8) | 0.0233 (2) | |
C12 | 0.4296 (2) | 0.19012 (13) | 0.89878 (9) | 0.0275 (2) | |
H121 | 0.6196 | 0.1788 | 0.8925 | 0.033* | |
H122 | 0.3614 | 0.0983 | 0.9458 | 0.033* | |
C13 | 0.3218 (2) | 0.34010 (13) | 0.94052 (9) | 0.0270 (2) | |
H131 | 0.4433 | 0.4219 | 0.9185 | 0.032* | |
H132 | 0.2847 | 0.3223 | 1.0184 | 0.032* | |
C14 | 0.0746 (2) | 0.38539 (13) | 0.89048 (8) | 0.0246 (2) | |
H141 | −0.0741 | 0.3393 | 0.9361 | 0.030* | |
H142 | 0.0386 | 0.5000 | 0.8768 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O7 | 0.0267 (4) | 0.0302 (4) | 0.0219 (4) | 0.0061 (3) | −0.0090 (3) | −0.0072 (3) |
O9 | 0.0250 (4) | 0.0345 (4) | 0.0287 (4) | 0.0098 (3) | −0.0067 (3) | −0.0070 (3) |
O11 | 0.0308 (4) | 0.0312 (4) | 0.0291 (4) | 0.0107 (3) | −0.0081 (3) | −0.0117 (3) |
O16 | 0.0340 (5) | 0.0435 (5) | 0.0366 (5) | 0.0089 (4) | −0.0041 (4) | −0.0204 (4) |
O17 | 0.0446 (5) | 0.0426 (5) | 0.0265 (4) | 0.0092 (4) | −0.0155 (4) | −0.0091 (4) |
N10 | 0.0222 (4) | 0.0224 (4) | 0.0213 (4) | 0.0037 (3) | −0.0055 (3) | −0.0050 (3) |
N15 | 0.0269 (5) | 0.0270 (5) | 0.0245 (5) | −0.0002 (4) | −0.0037 (4) | −0.0058 (4) |
C1 | 0.0224 (5) | 0.0206 (5) | 0.0212 (5) | −0.0013 (4) | −0.0031 (4) | −0.0029 (4) |
C2 | 0.0215 (5) | 0.0240 (5) | 0.0252 (5) | 0.0021 (4) | −0.0072 (4) | −0.0031 (4) |
C3 | 0.0225 (5) | 0.0215 (5) | 0.0274 (5) | 0.0019 (4) | −0.0037 (4) | −0.0044 (4) |
C4 | 0.0224 (5) | 0.0217 (5) | 0.0209 (5) | −0.0008 (4) | −0.0028 (4) | −0.0045 (4) |
C5 | 0.0205 (5) | 0.0234 (5) | 0.0231 (5) | 0.0016 (4) | −0.0052 (4) | −0.0024 (4) |
C6 | 0.0206 (5) | 0.0248 (5) | 0.0237 (5) | 0.0019 (4) | −0.0036 (4) | −0.0039 (4) |
C8 | 0.0247 (5) | 0.0241 (5) | 0.0233 (5) | 0.0028 (4) | −0.0082 (4) | −0.0034 (4) |
C9 | 0.0221 (5) | 0.0213 (5) | 0.0209 (5) | 0.0006 (4) | −0.0042 (4) | −0.0012 (4) |
C11 | 0.0224 (5) | 0.0223 (5) | 0.0253 (5) | 0.0028 (4) | −0.0057 (4) | −0.0047 (4) |
C12 | 0.0268 (5) | 0.0295 (5) | 0.0273 (5) | 0.0058 (4) | −0.0106 (4) | −0.0062 (4) |
C13 | 0.0248 (5) | 0.0322 (6) | 0.0258 (5) | 0.0034 (4) | −0.0076 (4) | −0.0092 (4) |
C14 | 0.0236 (5) | 0.0287 (5) | 0.0220 (5) | 0.0038 (4) | −0.0037 (4) | −0.0080 (4) |
O7—C1 | 1.3679 (13) | C4—C5 | 1.3882 (14) |
O7—C8 | 1.4252 (12) | C5—C6 | 1.3801 (15) |
O9—C9 | 1.2141 (13) | C5—H5 | 0.9500 |
O11—C11 | 1.2140 (13) | C6—H6 | 0.9500 |
O16—N15 | 1.2293 (13) | C8—C9 | 1.5102 (15) |
O17—N15 | 1.2325 (13) | C8—H81 | 0.9900 |
N10—C9 | 1.3848 (13) | C8—H82 | 0.9900 |
N10—C11 | 1.4000 (13) | C11—C12 | 1.5070 (15) |
N10—C14 | 1.4742 (13) | C12—C13 | 1.5229 (16) |
N15—C4 | 1.4597 (14) | C12—H121 | 0.9900 |
C1—C2 | 1.3947 (15) | C12—H122 | 0.9900 |
C1—C6 | 1.4012 (14) | C13—C14 | 1.5298 (15) |
C2—C3 | 1.3902 (15) | C13—H131 | 0.9900 |
C2—H2 | 0.9500 | C13—H132 | 0.9900 |
C3—C4 | 1.3834 (14) | C14—H141 | 0.9900 |
C3—H3 | 0.9500 | C14—H142 | 0.9900 |
C1—O7—C8 | 115.97 (8) | O7—C8—H82 | 110.3 |
C9—N10—C11 | 127.95 (9) | C9—C8—H82 | 110.3 |
C9—N10—C14 | 119.51 (8) | H81—C8—H82 | 108.6 |
C11—N10—C14 | 112.18 (8) | O9—C9—N10 | 120.18 (9) |
O16—N15—O17 | 123.07 (10) | O9—C9—C8 | 123.20 (9) |
O16—N15—C4 | 118.67 (9) | N10—C9—C8 | 116.62 (9) |
O17—N15—C4 | 118.26 (9) | O11—C11—N10 | 125.01 (10) |
O7—C1—C2 | 124.69 (9) | O11—C11—C12 | 127.95 (10) |
O7—C1—C6 | 114.67 (9) | N10—C11—C12 | 107.01 (9) |
C2—C1—C6 | 120.64 (10) | C11—C12—C13 | 104.40 (9) |
C3—C2—C1 | 119.69 (9) | C11—C12—H121 | 110.9 |
C3—C2—H2 | 120.2 | C13—C12—H121 | 110.9 |
C1—C2—H2 | 120.2 | C11—C12—H122 | 110.9 |
C4—C3—C2 | 118.64 (9) | C13—C12—H122 | 110.9 |
C4—C3—H3 | 120.7 | H121—C12—H122 | 108.9 |
C2—C3—H3 | 120.7 | C12—C13—C14 | 103.60 (9) |
C3—C4—C5 | 122.47 (10) | C12—C13—H131 | 111.0 |
C3—C4—N15 | 119.03 (9) | C14—C13—H131 | 111.0 |
C5—C4—N15 | 118.50 (9) | C12—C13—H132 | 111.0 |
C6—C5—C4 | 118.87 (9) | C14—C13—H132 | 111.0 |
C6—C5—H5 | 120.6 | H131—C13—H132 | 109.0 |
C4—C5—H5 | 120.6 | N10—C14—C13 | 103.08 (8) |
C5—C6—C1 | 119.68 (10) | N10—C14—H141 | 111.1 |
C5—C6—H6 | 120.2 | C13—C14—H141 | 111.1 |
C1—C6—H6 | 120.2 | N10—C14—H142 | 111.1 |
O7—C8—C9 | 106.89 (8) | C13—C14—H142 | 111.1 |
O7—C8—H81 | 110.3 | H141—C14—H142 | 109.1 |
C9—C8—H81 | 110.3 | ||
C8—O7—C1—C2 | −2.70 (15) | C11—N10—C9—O9 | 172.30 (10) |
C8—O7—C1—C6 | 177.99 (9) | C14—N10—C9—O9 | −0.17 (15) |
O7—C1—C2—C3 | −179.25 (10) | C11—N10—C9—C8 | −7.67 (16) |
C6—C1—C2—C3 | 0.02 (16) | C14—N10—C9—C8 | 179.86 (9) |
C1—C2—C3—C4 | −0.68 (16) | O7—C8—C9—O9 | 1.32 (15) |
C2—C3—C4—C5 | 0.78 (17) | O7—C8—C9—N10 | −178.72 (8) |
C2—C3—C4—N15 | −179.32 (9) | C9—N10—C11—O11 | 7.00 (18) |
O16—N15—C4—C3 | 5.06 (15) | C14—N10—C11—O11 | 179.93 (10) |
O17—N15—C4—C3 | −174.99 (10) | C9—N10—C11—C12 | −171.17 (10) |
O16—N15—C4—C5 | −175.03 (10) | C14—N10—C11—C12 | 1.76 (12) |
O17—N15—C4—C5 | 4.92 (16) | O11—C11—C12—C13 | 161.51 (11) |
C3—C4—C5—C6 | −0.18 (16) | N10—C11—C12—C13 | −20.39 (12) |
N15—C4—C5—C6 | 179.91 (9) | C11—C12—C13—C14 | 30.37 (12) |
C4—C5—C6—C1 | −0.49 (16) | C9—N10—C14—C13 | −169.00 (9) |
O7—C1—C6—C5 | 179.92 (9) | C11—N10—C14—C13 | 17.41 (12) |
C2—C1—C6—C5 | 0.58 (16) | C12—C13—C14—N10 | −28.89 (11) |
C1—O7—C8—C9 | −176.59 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O11i | 0.95 | 2.49 | 3.4235 (13) | 166 |
C5—H5···O9ii | 0.95 | 2.40 | 3.0955 (13) | 130 |
C12—H121···O16i | 0.99 | 2.51 | 3.2837 (14) | 134 |
C14—H141···O17iii | 0.99 | 2.53 | 3.4406 (15) | 153 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x−1, −y+1, −z+1; (iii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H12N2O5 |
Mr | 264.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 160 |
a, b, c (Å) | 5.2813 (1), 8.7367 (2), 12.9843 (3) |
α, β, γ (°) | 80.4656 (14), 81.4302 (12), 83.883 (1) |
V (Å3) | 582.17 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.25 × 0.25 × 0.17 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16366, 3393, 2701 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.126, 1.06 |
No. of reflections | 3393 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.26 |
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 for Windows (Farrugia, 1997), PARST97 (Nardelli, 1995) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O11i | 0.95 | 2.49 | 3.4235 (13) | 166 |
C5—H5···O9ii | 0.95 | 2.40 | 3.0955 (13) | 130 |
C12—H121···O16i | 0.99 | 2.51 | 3.2837 (14) | 134 |
C14—H141···O17iii | 0.99 | 2.53 | 3.4406 (15) | 153 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x−1, −y+1, −z+1; (iii) x, y, z+1. |
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The conformations of molecules with antiamnesic activity have attracted considerable interest (Amato, Bandoli, Grassi et al., 1991). This paper is intended to further develop our studies on the conformational properties of cognition activators. Cognition activators are drugs currently employed for the symptomatic treatment of pathological brain aging phenomena, which are usually referred to as senile cognitive decline or age-associated memory impairment (Gamzu et al., 1989; Bandoli et al., 1992). In the light of the growing incidence of such illnesses among the older population, several families of compounds are being tested in laboratory and clinical trials. The nootropics (mind-targeted) family is the forerunner in the field (Giurgea, 1982), and its key feature is the presence of the pyrrolidin-2-one ring. This moiety is a requisite for several active compounds currently used in therapy (piracetam, oxyracetam and pramiracetam). The ring-extended N-analogues of 2-pyrrilidinone, namely 3-aryl-2-piperazinone compounds, have been found to possess the characteristic nootropic pharmacological profile (Amato, Bandoli, Grassi et al., 1991). The present paper reports the the structure and conformation of of the title compound, (I), which was carried out to continue the investigation of a new class of antiamnesic agents (Thamotharan, Parthasarathi, Malik et al., 2003; Thamotharan, Parthasarathi, Gupta et al., 2003a,b,c).
The pyrrolidine ring in nootropics typically has a half-chair (C2, twist-envelope) conformation (Bandoli, Nicolini, Lumbroso et al., 1987; Bandoli, Nicolini, Pappalardo et al., 1987; Amato et al., 1990; Amato, Bandoli, Dolmella et al., 1991). In (I), however, the five-membered pyrrolidinone ring exhibits an envelope conformation, with atom C13 as the flap, a pseudo-rotation angle, Δ, of 86.6 (1)° and a maximum torsion angle, ϕm, of 31.5 (1)° for the atom sequence N10—C11—C12—C13—C14 (Rao et al., 1981). The dihedral angle between the mean planes through the phenyl and pyrrolinone rings is 6.41 (3)°. The mean plane of the central moiety, C1—O7—C8—C9—N10, is oriented at angles of 2.16 (4) and 6.37 (5)° with respect to the planes of the phenyl and pyrrolidinone rings, respectively. The nitro group is almost coplanar with the adjacent phenyl ring. The slightly enlarged exocyclic O7—C1—C2 bond angle [124.69 (9)°] probably results from a repulsive interaction between the H atoms on atoms C2 and C8 (H2···H81 = 2.30 Å and H2···H82 = 2.25 Å). Otherwise, the bond lengths and angles show no unusual features. The C1—O7—C8—C9 [−176.59 (8)°] and O7—C8—C9—N10 [−178.72 (8)°] torsion angles show that the central moiety has an antiperiplanar conformation.
In the crystal, atoms C3 and C12 act as donors for weak intermolecular C—H···O interactions with carbonyl atom O11 of the pyrrolidinone ring and atom O16 of the nitro group of a neighbouring centrosymmetrically related molecule, respectively. Each interaction links the molecules individually into dimers that have a graph-set motif (Bernstein et al., 1995) of R22(20) and R22(26), respectively (Fig. 2). Atom C5 is involved in an intermolecular C—H···O interaction with another carbonyl O atom (O9) of a different neighbouring centrosymmetrically related molecule. This interaction also produces loops that have a graph-set motif of R22(16). Atom C14 forms a weak intermolecular C—H···O interaction with atom O17 of the nitro group of an adjacent molecule. This interaction links the molecules into chains that run parallel to the c axis and have a graph-set motif of C(12).