The title compound, C
14H
12N
2O
4, is a potential antiamnesic agent. The pyrrolidinone ring has an envelope conformation. The dihedral angle between the
N-substituted phthalimide moiety and the pyrrolidinone ring is 77.16 (5)°. In the solid state, symmetry-related molecules are linked by weak intermolecular C—H
O interactions, forming a continuous chain.
Supporting information
CCDC reference: 217601
Key indicators
- Single-crystal X-ray study
- T = 160 K
- Mean (C-C) = 0.003 Å
- R factor = 0.047
- wR factor = 0.128
- Data-to-parameter ratio = 13.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
A solution of (1,3-dioxo-1,3-dihydroisoindole-2-yl)acetyl chloride (1.0 g) in dichloromethane was stirred with pyrrolidinone. The dichloromethane was removed and crushed ice was added to the contents. The solid residue obtained was filtered and crystallized from methanol to afford crystals of (I) (yield 0.81 g, 66.5%; m.p. 473 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).
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: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Version 1.07; Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
2-[(2-Oxopyrrolidin-1-yl)carbonylmethyl]-2,3-dihydro-1
H-isoindole-1,3-dione
top
Crystal data top
C14H12N2O4 | Dx = 1.448 Mg m−3 |
Mr = 272.26 | Melting point: 473 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2839 reflections |
a = 10.7480 (2) Å | θ = 2.0–26.0° |
b = 8.3280 (1) Å | µ = 0.11 mm−1 |
c = 27.9084 (4) Å | T = 160 K |
V = 2498.06 (7) Å3 | Plate, colourless |
Z = 8 | 0.18 × 0.18 × 0.05 mm |
F(000) = 1136 | |
Data collection top
Nonius KappaCCD diffractometer | 1620 reflections with I > 2σ(I) |
Radiation source: Nonius FR591 sealed tube generator | Rint = 0.067 |
Horizontally mounted graphite crystal monochromator | θmax = 26.0°, θmin = 2.4° |
Detector resolution: 9 pixels mm-1 | h = 0→13 |
ω scans with κ offsets | k = 0→10 |
29914 measured reflections | l = −34→0 |
2459 independent reflections | |
Refinement top
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0681P)2 + 0.4733P] where P = (Fo2 + 2Fc2)/3 |
2459 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C14H12N2O4 | V = 2498.06 (7) Å3 |
Mr = 272.26 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.7480 (2) Å | µ = 0.11 mm−1 |
b = 8.3280 (1) Å | T = 160 K |
c = 27.9084 (4) Å | 0.18 × 0.18 × 0.05 mm |
Data collection top
Nonius KappaCCD diffractometer | 1620 reflections with I > 2σ(I) |
29914 measured reflections | Rint = 0.067 |
2459 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.17 e Å−3 |
2459 reflections | Δρmin = −0.19 e Å−3 |
181 parameters | |
Special details top
Experimental. Solvent used: MeOH Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.538 (1) Frames collected: 793 Seconds exposure per frame: 77 Degrees rotation per frame: 0.7 Crystal-Detector distance (mm): 42.0 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.04618 (14) | 0.14043 (17) | 0.59049 (5) | 0.0458 (4) | |
O3 | 0.27434 (14) | 0.49855 (18) | 0.58283 (5) | 0.0459 (4) | |
O11 | −0.01451 (14) | 0.48029 (17) | 0.66903 (5) | 0.0446 (4) | |
O13 | 0.25931 (14) | 0.20034 (18) | 0.73247 (5) | 0.0481 (4) | |
N2 | 0.11528 (14) | 0.32121 (18) | 0.59882 (5) | 0.0316 (4) | |
N12 | 0.08877 (15) | 0.37071 (17) | 0.73097 (5) | 0.0308 (4) | |
C1 | 0.02859 (18) | 0.2310 (2) | 0.57284 (7) | 0.0332 (5) | |
C3 | 0.18932 (19) | 0.4147 (2) | 0.56920 (7) | 0.0328 (5) | |
C4 | 0.1863 (2) | 0.4463 (3) | 0.47650 (7) | 0.0423 (5) | |
H4 | 0.2515 | 0.5231 | 0.4752 | 0.051* | |
C5 | 0.1286 (2) | 0.3916 (3) | 0.43516 (7) | 0.0488 (6) | |
H5 | 0.1540 | 0.4328 | 0.4050 | 0.059* | |
C6 | 0.0350 (2) | 0.2784 (3) | 0.43711 (8) | 0.0486 (6) | |
H6 | −0.0022 | 0.2422 | 0.4082 | 0.058* | |
C7 | −0.0060 (2) | 0.2164 (3) | 0.48057 (7) | 0.0427 (5) | |
H7 | −0.0703 | 0.1382 | 0.4819 | 0.051* | |
C8 | 0.05035 (19) | 0.2726 (2) | 0.52169 (6) | 0.0329 (5) | |
C9 | 0.14500 (18) | 0.3841 (2) | 0.51966 (6) | 0.0325 (5) | |
C10 | 0.14576 (19) | 0.2922 (2) | 0.64844 (6) | 0.0345 (5) | |
H101 | 0.2345 | 0.3186 | 0.6538 | 0.041* | |
H102 | 0.1342 | 0.1767 | 0.6556 | 0.041* | |
C11 | 0.06652 (18) | 0.3901 (2) | 0.68244 (7) | 0.0325 (5) | |
C13 | 0.18439 (19) | 0.2856 (2) | 0.75308 (7) | 0.0369 (5) | |
C14 | 0.1779 (2) | 0.3192 (3) | 0.80590 (7) | 0.0461 (6) | |
H141 | 0.2411 | 0.3996 | 0.8154 | 0.055* | |
H142 | 0.1912 | 0.2198 | 0.8247 | 0.055* | |
C15 | 0.0468 (2) | 0.3842 (3) | 0.81345 (7) | 0.0473 (6) | |
H151 | −0.0123 | 0.2963 | 0.8207 | 0.057* | |
H152 | 0.0449 | 0.4632 | 0.8399 | 0.057* | |
C16 | 0.0154 (2) | 0.4634 (2) | 0.76604 (7) | 0.0384 (5) | |
H161 | −0.0747 | 0.4557 | 0.7591 | 0.046* | |
H162 | 0.0402 | 0.5779 | 0.7660 | 0.046* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0429 (9) | 0.0496 (9) | 0.0450 (9) | −0.0089 (8) | −0.0024 (7) | 0.0101 (7) |
O3 | 0.0514 (10) | 0.0470 (9) | 0.0394 (9) | −0.0128 (8) | −0.0014 (7) | −0.0051 (7) |
O11 | 0.0486 (9) | 0.0499 (9) | 0.0352 (9) | 0.0154 (8) | −0.0018 (7) | 0.0027 (7) |
O13 | 0.0457 (9) | 0.0581 (9) | 0.0405 (9) | 0.0131 (8) | −0.0038 (7) | 0.0012 (7) |
N2 | 0.0375 (10) | 0.0346 (9) | 0.0228 (9) | −0.0010 (8) | 0.0002 (7) | 0.0002 (7) |
N12 | 0.0390 (9) | 0.0301 (8) | 0.0233 (9) | 0.0015 (8) | 0.0002 (7) | 0.0004 (7) |
C1 | 0.0342 (11) | 0.0327 (11) | 0.0327 (11) | 0.0026 (9) | −0.0023 (9) | 0.0009 (9) |
C3 | 0.0385 (12) | 0.0297 (10) | 0.0302 (11) | 0.0024 (9) | 0.0018 (9) | −0.0028 (9) |
C4 | 0.0486 (13) | 0.0461 (13) | 0.0322 (12) | 0.0052 (11) | 0.0062 (10) | 0.0033 (10) |
C5 | 0.0617 (16) | 0.0573 (14) | 0.0275 (12) | 0.0177 (13) | 0.0019 (11) | 0.0030 (10) |
C6 | 0.0585 (15) | 0.0562 (14) | 0.0310 (12) | 0.0165 (13) | −0.0097 (11) | −0.0104 (11) |
C7 | 0.0475 (13) | 0.0435 (12) | 0.0370 (12) | 0.0064 (10) | −0.0102 (10) | −0.0083 (10) |
C8 | 0.0383 (11) | 0.0324 (11) | 0.0280 (11) | 0.0069 (9) | −0.0028 (9) | −0.0029 (8) |
C9 | 0.0397 (11) | 0.0318 (10) | 0.0260 (11) | 0.0053 (9) | 0.0007 (9) | −0.0010 (8) |
C10 | 0.0391 (11) | 0.0389 (11) | 0.0254 (11) | 0.0029 (9) | −0.0025 (9) | 0.0004 (9) |
C11 | 0.0347 (11) | 0.0328 (10) | 0.0302 (11) | −0.0007 (10) | −0.0002 (9) | 0.0020 (9) |
C13 | 0.0392 (12) | 0.0351 (11) | 0.0366 (12) | −0.0025 (10) | 0.0007 (10) | −0.0002 (10) |
C14 | 0.0574 (14) | 0.0510 (13) | 0.0299 (12) | −0.0032 (12) | −0.0063 (10) | 0.0010 (10) |
C15 | 0.0654 (15) | 0.0459 (13) | 0.0305 (12) | 0.0023 (12) | 0.0042 (11) | −0.0025 (10) |
C16 | 0.0461 (13) | 0.0344 (11) | 0.0346 (12) | 0.0002 (10) | 0.0070 (10) | −0.0046 (9) |
Geometric parameters (Å, º) top
O1—C1 | 1.207 (2) | C6—C7 | 1.390 (3) |
O3—C3 | 1.211 (2) | C6—H6 | 0.9500 |
O11—C11 | 1.209 (2) | C7—C8 | 1.380 (3) |
O13—C13 | 1.218 (2) | C7—H7 | 0.9500 |
N2—C3 | 1.387 (2) | C8—C9 | 1.379 (3) |
N2—C1 | 1.399 (2) | C10—C11 | 1.514 (3) |
N2—C10 | 1.443 (2) | C10—H101 | 0.9900 |
N12—C11 | 1.385 (2) | C10—H102 | 0.9900 |
N12—C13 | 1.392 (3) | C13—C14 | 1.502 (3) |
N12—C16 | 1.475 (2) | C14—C15 | 1.524 (3) |
C1—C8 | 1.488 (3) | C14—H141 | 0.9900 |
C3—C9 | 1.484 (3) | C14—H142 | 0.9900 |
C4—C9 | 1.384 (3) | C15—C16 | 1.516 (3) |
C4—C5 | 1.387 (3) | C15—H151 | 0.9900 |
C4—H4 | 0.9500 | C15—H152 | 0.9900 |
C5—C6 | 1.380 (3) | C16—H161 | 0.9900 |
C5—H5 | 0.9500 | C16—H162 | 0.9900 |
| | | |
C3—N2—C1 | 112.00 (16) | N2—C10—C11 | 112.54 (16) |
C3—N2—C10 | 122.39 (16) | N2—C10—H101 | 109.1 |
C1—N2—C10 | 123.94 (15) | C11—C10—H101 | 109.1 |
C11—N12—C13 | 128.34 (17) | N2—C10—H102 | 109.1 |
C11—N12—C16 | 119.70 (15) | C11—C10—H102 | 109.1 |
C13—N12—C16 | 111.52 (15) | H101—C10—H102 | 107.8 |
O1—C1—N2 | 124.56 (18) | O11—C11—N12 | 119.97 (17) |
O1—C1—C8 | 129.92 (18) | O11—C11—C10 | 123.09 (17) |
N2—C1—C8 | 105.52 (16) | N12—C11—C10 | 116.93 (16) |
O3—C3—N2 | 124.70 (18) | O13—C13—N12 | 125.12 (18) |
O3—C3—C9 | 129.32 (18) | O13—C13—C14 | 127.08 (19) |
N2—C3—C9 | 105.94 (16) | N12—C13—C14 | 107.80 (17) |
C9—C4—C5 | 117.2 (2) | C13—C14—C15 | 104.18 (17) |
C9—C4—H4 | 121.4 | C13—C14—H141 | 110.9 |
C5—C4—H4 | 121.4 | C15—C14—H141 | 110.9 |
C6—C5—C4 | 121.2 (2) | C13—C14—H142 | 110.9 |
C6—C5—H5 | 119.4 | C15—C14—H142 | 110.9 |
C4—C5—H5 | 119.4 | H141—C14—H142 | 108.9 |
C5—C6—C7 | 121.3 (2) | C16—C15—C14 | 103.84 (17) |
C5—C6—H6 | 119.4 | C16—C15—H151 | 111.0 |
C7—C6—H6 | 119.4 | C14—C15—H151 | 111.0 |
C8—C7—C6 | 117.4 (2) | C16—C15—H152 | 111.0 |
C8—C7—H7 | 121.3 | C14—C15—H152 | 111.0 |
C6—C7—H7 | 121.3 | H151—C15—H152 | 109.0 |
C9—C8—C7 | 121.24 (18) | N12—C16—C15 | 103.45 (16) |
C9—C8—C1 | 108.19 (16) | N12—C16—H161 | 111.1 |
C7—C8—C1 | 130.56 (19) | C15—C16—H161 | 111.1 |
C8—C9—C4 | 121.61 (18) | N12—C16—H162 | 111.1 |
C8—C9—C3 | 108.32 (16) | C15—C16—H162 | 111.1 |
C4—C9—C3 | 130.05 (19) | H161—C16—H162 | 109.0 |
| | | |
C3—N2—C1—O1 | 179.98 (18) | O3—C3—C9—C8 | 176.3 (2) |
C10—N2—C1—O1 | 14.4 (3) | N2—C3—C9—C8 | −1.5 (2) |
C3—N2—C1—C8 | −0.2 (2) | O3—C3—C9—C4 | −2.1 (4) |
C10—N2—C1—C8 | −165.72 (16) | N2—C3—C9—C4 | −179.95 (19) |
C1—N2—C3—O3 | −176.99 (18) | C3—N2—C10—C11 | 104.0 (2) |
C10—N2—C3—O3 | −11.2 (3) | C1—N2—C10—C11 | −91.9 (2) |
C1—N2—C3—C9 | 1.0 (2) | C13—N12—C11—O11 | −173.23 (18) |
C10—N2—C3—C9 | 166.82 (16) | C16—N12—C11—O11 | −1.5 (3) |
C9—C4—C5—C6 | −0.8 (3) | C13—N12—C11—C10 | 7.9 (3) |
C4—C5—C6—C7 | 0.8 (3) | C16—N12—C11—C10 | 179.58 (16) |
C5—C6—C7—C8 | 0.2 (3) | N2—C10—C11—O11 | 1.2 (3) |
C6—C7—C8—C9 | −1.0 (3) | N2—C10—C11—N12 | −179.98 (15) |
C6—C7—C8—C1 | −179.83 (19) | C11—N12—C13—O13 | −7.2 (3) |
O1—C1—C8—C9 | 179.0 (2) | C16—N12—C13—O13 | −179.49 (18) |
N2—C1—C8—C9 | −0.8 (2) | C11—N12—C13—C14 | 172.47 (18) |
O1—C1—C8—C7 | −2.1 (4) | C16—N12—C13—C14 | 0.2 (2) |
N2—C1—C8—C7 | 178.08 (19) | O13—C13—C14—C15 | −162.0 (2) |
C7—C8—C9—C4 | 1.0 (3) | N12—C13—C14—C15 | 18.3 (2) |
C1—C8—C9—C4 | −179.97 (17) | C13—C14—C15—C16 | −29.0 (2) |
C7—C8—C9—C3 | −177.60 (17) | C11—N12—C16—C15 | 168.35 (16) |
C1—C8—C9—C3 | 1.4 (2) | C13—N12—C16—C15 | −18.6 (2) |
C5—C4—C9—C8 | 0.0 (3) | C14—C15—C16—N12 | 28.8 (2) |
C5—C4—C9—C3 | 178.21 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H152···O1i | 0.99 | 2.44 | 3.426 (3) | 175 |
C16—H162···O13ii | 0.99 | 2.56 | 3.261 (3) | 128 |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1/2, y+1/2, z. |
Experimental details
Crystal data |
Chemical formula | C14H12N2O4 |
Mr | 272.26 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 160 |
a, b, c (Å) | 10.7480 (2), 8.3280 (1), 27.9084 (4) |
V (Å3) | 2498.06 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.18 × 0.18 × 0.05 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29914, 2459, 1620 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.129, 1.03 |
No. of reflections | 2459 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.19 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H152···O1i | 0.99 | 2.44 | 3.426 (3) | 175 |
C16—H162···O13ii | 0.99 | 2.56 | 3.261 (3) | 128 |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1/2, y+1/2, z. |
The conformations of molecules with anti-amnesic activity have attracted considerable interest (Amato et al., 1991), and the structure determination of the title compound, (I), was carried out to continue the investigation of a new class of anti-amnesic agents (Thamotharan, Parthasarathi, Malik et al., 2003; Thamotharan, Parthasarathi, Gupta et al., 2003).
Fig. 1 shows the asymmetric unit of (I) with the atom-numbering scheme. The geometric parameters of the N-substituted phthalimide moiety in (I) are almost the same as those in 2-(5-chloropyridin-2-yl)-2,3-dihydro-1H-isoindole-1,3-dione (Holband et al., 2001). The angles C5—C4—C9 [117.2 (2)°] and C6—C7—C8 [117.4 (2)°] are significantly smaller than the other angles in the benzene ring. Similar observations have been made in related structures (Christensen & Thom, 1971, and references therein). This angular distortioncan be explained by the strain caused by fusion with the five-membered ring.
In (I), the five-membered pyrrolidinone ring exhibits an envelope conformation, with atom C15 as the flap, a pseudo-rotation angle Δ = 270.3 (2)° and a maximum torsion angle ϕm = 30.7 (1)° for the atom sequence N12—C13—C14—C15—C16 (Rao et al., 1981). The dihedral angle between the N-substituted phthalimide moiety and pyrrolidinone ring is 77.16 (5)°. The planar central moiety, N2—C10—C11—N12, is oriented at angles of 7.62 (11) and 84.67 (10)° with respect to the pyrrolidinone and N-substituted phthalimide moieties, respectively.
In the crystal structure, atom C15 acts as a donor for a weak intermolecular C—H···O interaction with carbonyl atom O1 of an adjacent molecule. This interaction links the molecules into a chain, which runs parallel to the b axis and has a graph-set motif of C(9) (Bernstein et al., 1995). Atom C16 has a weak intermolecular C—H···O interaction with carbonyl atom O13 of a different adjacent molecule. This interaction also links the molecules into a chain, which runs parallel to the b axis and has a graph-set motif of C(5) (Table 1) (Bernstein et al., 1995). A short intermolecular contact is observed, O3···C1i 2.883 (3) Å [symmetry code: (i) −x + 1/2, y + 1/2, z].