supplementary materials


fy2100 scheme

Acta Cryst. (2013). E69, o1594-o1595    [ doi:10.1107/S160053681302638X ]

2-Benzyl-5-methoxyisoindoline-1,3-dione

N. Vila, M. C. Costas-Lago, P. Besada and C. Terán

Abstract top

The title N-benzylphthalimide derivative, C16H13NO3, consists of two planar moieties, viz. the phthalimide system (r.m.s. deviation = 0.007 Å) and the phenyl ring, which make a dihedral angle of 84.7 (6)°. The methoxy group is almost coplanar with the phathalimide ring, as shown by the C-C-O-C torsion angle of -171.5 (2)°. In the crystal, the molecules are self-assembled via non-classical C-H...O hydrogen bonds, forming a tape motif along [110].

Comment top

Phthalimide derivatives represent a significant family of organic compounds because of their numerous applications in different fields of chemistry. They are not only useful intermediates for synthesis (Luzzio, 2005), but are also important scaffolds for new materials (Barooah & Baruah, 2007) and drug design (Sharma et al., 2010). Among the phthalimide analogues, there are very well known N-benzyl substituted derivatives, some of them prepared for mechanistic studies on photoreactions (Warzecha, Görner et al., 2006). Reaction of phthalic acid derivatives with benzylamines at high temperature or in the presence of a Lewis acid are the classical methods for obtaining N-benzylphthalimides (Favor et al., 2008; Haj-Yehia & Khan, 2004; Luzzio, 2005). In addition, unconventional approaches were also developed, such as carbonylative cyclizations of arenes with amines catalyzed by transition metals (Cao & Alper, 2010) or microwave-assisted synthesis (Vidal et al., 2000).

The title compound (I) is a N-benzylphthalimide substituted at C5 with a methoxy group. It was obtained by the reaction of dimethyl phthalimide with benzyl hydrazine under microwave irradiation.

The molecular structure of (I) is illustrated in Figure 1. There are some similar structures reported before (Warzecha et al., 2006a; Warzecha et al., 2006b; Warzecha et al., 2006c; Jiang et al., 2008). The molecule consists of two planar moieties, the phthalimide system and the phenyl ring, linked by the methylene group C9 (N2—C9—C10 bond angle of 114.4°), resulting in a non-planar structure. The two planar subunits make a dihedral angle of 84.7 (6)°, which is similar to the value reported for the same angle in the crystal structure of the monoclinic form of the parent N-benzylphthalimide (Jiang et al., 2008). Furthermore, the methoxy group at C5 is almost coplanar with the phathalimide ring [torsion angle C4—C5—O5—C8 of -171.5 (2)°].

In addition, the C1—N2—C9—C10 and C3—N2—C9—C10 torsion angles of 93.1 (3)° and -86.0 (3)°, respectively, are also very similar to those of N-benzylphthalimide (Jiang et al., 2008) and they corroborate that the phenyl group is virtually orthogonal to the phthalimide benzene ring. In the crystal structure, the molecules are self-assembled via non-classical C—H···O hydrogen bonds, involving CH and CH3 groups as donors and oxygen atoms as acceptors, to form a one-dimensional supramolecular organization (Table 1, Figure 2).

Related literature top

For background to the applications of phthalimide derivatives, see: Luzzio (2005); Barooah & Baruah (2007); Sharma et al. (2010); Warzecha et al. (2006). For different approaches to synthesize N-benzylphalimides, see: Luzzio (2005); Cao & Alper (2010); Vidal et al. (2000). For the synthesis of the title compound, see: Favor et al. (2008); Haj-Yehia & Khan (2004). For related structures, see: Warzecha et al. (2006a,b,c); Jiang et al. (2008).

Experimental top

The synthesis of 2-benzyl-5-methoxyisoindoline-1,3-dione was carried out in a microwave oven (CEM discover system 908010, monomode) according to the following protocol: a solution of dimethyl 4-methoxyphthalate (50 mg, 0.22 mmol), benzylhydrazine dihydrochloride (174 mg, 0.89 mmol) and triethylamine (0.37 ml, 2.65 mmol), in ethanol (5 ml) was introduced in a Pyrex flask and submitted to microwave irradiation (280 W, 185 °C) for 30 min. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel (hexane/ethyl acetate 40:1 20:1) to afford a white solid (9.3 mg, 15%). The product was dissolved in ethyl acetate (3 ml) and the solution was kept at room temperature for 1 d. Natural evaporation gave colourless block-like crystals of the title compound (m.p. 448–449 K) suitable for X-ray diffraction analysis.

Refinement top

All H-atoms were positioned and refined using a riding model with d(C—H)= 0.95 Å, Uiso = 1.2Ueq(C) for aromatic CH, d(C—H)= 0.99 Å, Uiso = 1.2Ueq(C) for CH2 group and d(C—H)= 0.98 Å, Uiso = 1.5Ueq(C) for CH3 group.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. View of the supramolecular tape motif in the crystal structure of the title compound.
[Figure 3] Fig. 3. View of the unit-cell contents of (I).
2-Benzyl-5-methoxyisoindoline-1,3-dione top
Crystal data top
C16H13NO3F(000) = 560
Mr = 267.27Dx = 1.409 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.476 (4) ÅCell parameters from 1091 reflections
b = 5.264 (3) Åθ = 2.6–24.8°
c = 28.295 (13) ŵ = 0.10 mm1
β = 93.589 (9)°T = 100 K
V = 1260.0 (11) Å3Prism, colourless
Z = 40.49 × 0.13 × 0.07 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
2204 independent reflections
Radiation source: fine-focus sealed tube1433 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.083
φ and ω scansθmax = 25.1°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 109
Tmin = 0.954, Tmax = 0.993k = 56
5768 measured reflectionsl = 3331
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.137 w = 1/[σ2(Fo2) + (0.0548P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2204 reflectionsΔρmax = 0.30 e Å3
183 parametersΔρmin = 0.27 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.022 (4)
Crystal data top
C16H13NO3V = 1260.0 (11) Å3
Mr = 267.27Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.476 (4) ŵ = 0.10 mm1
b = 5.264 (3) ÅT = 100 K
c = 28.295 (13) Å0.49 × 0.13 × 0.07 mm
β = 93.589 (9)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
2204 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1433 reflections with I > 2σ(I)
Tmin = 0.954, Tmax = 0.993Rint = 0.083
5768 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.137Δρmax = 0.30 e Å3
S = 1.00Δρmin = 0.27 e Å3
2204 reflectionsAbsolute structure: ?
183 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. 1H NMR (400 MHz, CDCl3) δ p.p.m.: 7.77 (d, J = 8.3 Hz, 1H, H7), 7.44 (m, 2H, H—Ph), 7.31 (m, 4H, H4, 3xH-Ph), 7.16 (dd, J = 8.3 Hz, 2.3 Hz, 1H, H6), 4.85 (s, 2H, CH2), 3.95 (s, 3H, OCH3). 13C MNR (100 MHz, CDCl3) δ p.p.m.: 167.9 (2xCO), 164.7 (C5), 136.5 (C), 134.7 (C), 128.7 (CH—Ar), 128.6 (CH—Ar), 127.8 (CH—Ar), 125.1 (C7), 124.0 (C), 119.7 (C6), 108.2 (C4), 56.1 (CH3), 41.6 (CH2). EMAR (ESI) calcld. for: [C16H14NO3]+ 268.09682; Found: 268.09697

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
xyzUiso*/Ueq
C10.3240 (3)0.6996 (5)0.92388 (10)0.0213 (6)
O10.4087 (2)0.5180 (4)0.91838 (6)0.0267 (5)
N20.2352 (3)0.8192 (4)0.88663 (7)0.0211 (6)
C30.1503 (3)1.0257 (5)0.90228 (10)0.0215 (7)
O30.0646 (2)1.1594 (4)0.87683 (7)0.0288 (5)
C3A0.1874 (3)1.0402 (5)0.95430 (9)0.0195 (6)
C40.1349 (3)1.2090 (5)0.98669 (10)0.0231 (7)
H40.06491.34350.97740.028*
C50.1887 (3)1.1749 (5)1.03403 (9)0.0217 (6)
O50.1292 (2)1.3429 (4)1.06478 (6)0.0270 (5)
C60.2935 (3)0.9800 (5)1.04724 (10)0.0230 (7)
H60.33030.96261.07950.028*
C70.3447 (3)0.8103 (5)1.01369 (10)0.0241 (7)
H70.41470.67541.02270.029*
C7A0.2915 (3)0.8428 (5)0.96708 (9)0.0197 (6)
C80.1941 (3)1.3450 (6)1.11298 (10)0.0310 (8)
H8A0.17161.18251.12810.047*
H8B0.14621.48341.13030.047*
H8C0.30871.37041.11340.047*
C90.2351 (3)0.7371 (5)0.83788 (9)0.0232 (7)
H9A0.13270.78450.82150.028*
H9B0.24320.54950.83720.028*
C100.3673 (3)0.8478 (5)0.81074 (9)0.0195 (6)
C110.3994 (3)0.7401 (5)0.76729 (9)0.0232 (7)
H110.34240.59370.75650.028*
C120.5122 (3)0.8419 (6)0.73974 (10)0.0253 (7)
H120.53130.76730.71010.030*
C130.5972 (3)1.0524 (6)0.75539 (10)0.0281 (7)
H130.67531.12310.73660.034*
C140.5679 (3)1.1605 (5)0.79876 (10)0.0277 (7)
H140.62671.30500.80960.033*
C150.4534 (3)1.0593 (5)0.82639 (10)0.0226 (7)
H150.43401.13480.85600.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0199 (14)0.0202 (15)0.0238 (16)0.0009 (12)0.0017 (12)0.0003 (12)
O10.0280 (11)0.0264 (11)0.0255 (11)0.0068 (10)0.0011 (9)0.0021 (9)
N20.0249 (13)0.0229 (13)0.0156 (12)0.0022 (10)0.0021 (10)0.0003 (10)
C30.0205 (14)0.0225 (15)0.0219 (15)0.0000 (13)0.0047 (12)0.0022 (12)
O30.0307 (11)0.0333 (12)0.0222 (11)0.0097 (9)0.0004 (9)0.0040 (9)
C3A0.0157 (13)0.0227 (15)0.0201 (15)0.0023 (11)0.0027 (11)0.0035 (12)
C40.0216 (14)0.0237 (15)0.0245 (16)0.0014 (12)0.0058 (12)0.0017 (12)
C50.0202 (14)0.0248 (15)0.0207 (15)0.0026 (13)0.0059 (12)0.0024 (13)
O50.0278 (11)0.0317 (11)0.0213 (11)0.0052 (9)0.0000 (9)0.0049 (9)
C60.0237 (15)0.0268 (16)0.0182 (15)0.0041 (13)0.0001 (12)0.0008 (13)
C70.0224 (15)0.0241 (15)0.0257 (16)0.0017 (12)0.0001 (12)0.0039 (13)
C7A0.0205 (14)0.0192 (14)0.0197 (15)0.0022 (12)0.0043 (12)0.0020 (12)
C80.0300 (17)0.0402 (19)0.0231 (16)0.0028 (14)0.0029 (13)0.0070 (14)
C90.0256 (16)0.0252 (16)0.0190 (15)0.0025 (12)0.0017 (12)0.0026 (12)
C100.0193 (14)0.0223 (15)0.0167 (14)0.0054 (12)0.0008 (11)0.0005 (12)
C110.0213 (15)0.0257 (16)0.0223 (16)0.0008 (12)0.0014 (13)0.0036 (12)
C120.0244 (15)0.0313 (17)0.0202 (15)0.0030 (13)0.0019 (12)0.0031 (13)
C130.0240 (15)0.0374 (18)0.0232 (16)0.0008 (14)0.0044 (13)0.0011 (14)
C140.0279 (16)0.0269 (16)0.0279 (17)0.0027 (13)0.0026 (13)0.0001 (14)
C150.0247 (15)0.0254 (16)0.0177 (15)0.0034 (13)0.0015 (12)0.0017 (12)
Geometric parameters (Å, º) top
C1—O11.211 (3)C8—H8A0.9800
C1—N21.405 (3)C8—H8B0.9800
C1—C7A1.476 (4)C8—H8C0.9800
N2—C31.391 (3)C9—C101.514 (4)
N2—C91.445 (3)C9—H9A0.9900
C3—O31.215 (3)C9—H9B0.9900
C3—C3A1.488 (4)C10—C151.388 (4)
C3A—C41.371 (4)C10—C111.396 (4)
C3A—C7A1.396 (4)C11—C121.379 (4)
C4—C51.399 (4)C11—H110.9500
C4—H40.9500C12—C131.379 (4)
C5—O51.359 (3)C12—H120.9500
C5—C61.393 (4)C13—C141.389 (4)
O5—C81.438 (3)C13—H130.9500
C6—C71.393 (4)C14—C151.390 (4)
C6—H60.9500C14—H140.9500
C7—C7A1.378 (4)C15—H150.9500
C7—H70.9500
O1—C1—N2123.4 (2)O5—C8—H8B109.5
O1—C1—C7A130.7 (2)H8A—C8—H8B109.5
N2—C1—C7A105.9 (2)O5—C8—H8C109.5
C3—N2—C1112.0 (2)H8A—C8—H8C109.5
C3—N2—C9124.6 (2)H8B—C8—H8C109.5
C1—N2—C9123.4 (2)N2—C9—C10114.4 (2)
O3—C3—N2124.5 (3)N2—C9—H9A108.7
O3—C3—C3A129.7 (3)C10—C9—H9A108.7
N2—C3—C3A105.9 (2)N2—C9—H9B108.7
C4—C3A—C7A122.4 (2)C10—C9—H9B108.7
C4—C3A—C3129.6 (2)H9A—C9—H9B107.6
C7A—C3A—C3108.0 (2)C15—C10—C11118.6 (3)
C3A—C4—C5117.2 (2)C15—C10—C9122.5 (2)
C3A—C4—H4121.4C11—C10—C9118.8 (2)
C5—C4—H4121.4C12—C11—C10121.3 (3)
O5—C5—C6124.3 (2)C12—C11—H11119.3
O5—C5—C4114.7 (2)C10—C11—H11119.3
C6—C5—C4121.0 (3)C11—C12—C13119.8 (3)
C5—O5—C8118.5 (2)C11—C12—H12120.1
C5—C6—C7120.7 (2)C13—C12—H12120.1
C5—C6—H6119.6C12—C13—C14119.6 (3)
C7—C6—H6119.6C12—C13—H13120.2
C7A—C7—C6118.4 (3)C14—C13—H13120.2
C7A—C7—H7120.8C13—C14—C15120.6 (3)
C6—C7—H7120.8C13—C14—H14119.7
C7—C7A—C3A120.3 (3)C15—C14—H14119.7
C7—C7A—C1131.5 (2)C10—C15—C14120.0 (3)
C3A—C7A—C1108.3 (2)C10—C15—H15120.0
O5—C8—H8A109.5C14—C15—H15120.0
O1—C1—N2—C3178.9 (3)C6—C7—C7A—C1179.5 (3)
C7A—C1—N2—C30.3 (3)C4—C3A—C7A—C70.5 (4)
O1—C1—N2—C90.3 (4)C3—C3A—C7A—C7179.5 (2)
C7A—C1—N2—C9179.5 (2)C4—C3A—C7A—C1179.7 (2)
C1—N2—C3—O3179.9 (3)C3—C3A—C7A—C10.3 (3)
C9—N2—C3—O30.9 (4)O1—C1—C7A—C71.4 (5)
C1—N2—C3—C3A0.1 (3)N2—C1—C7A—C7179.4 (3)
C9—N2—C3—C3A179.3 (2)O1—C1—C7A—C3A178.7 (3)
O3—C3—C3A—C40.3 (5)N2—C1—C7A—C3A0.4 (3)
N2—C3—C3A—C4179.9 (3)C3—N2—C9—C1093.1 (3)
O3—C3—C3A—C7A179.6 (3)C1—N2—C9—C1086.0 (3)
N2—C3—C3A—C7A0.1 (3)N2—C9—C10—C1516.9 (3)
C7A—C3A—C4—C50.7 (4)N2—C9—C10—C11166.0 (2)
C3—C3A—C4—C5179.3 (3)C15—C10—C11—C121.0 (4)
C3A—C4—C5—O5178.1 (2)C9—C10—C11—C12176.2 (2)
C3A—C4—C5—C61.1 (4)C10—C11—C12—C130.9 (4)
C6—C5—O5—C89.2 (4)C11—C12—C13—C140.2 (4)
C4—C5—O5—C8171.5 (2)C12—C13—C14—C150.3 (4)
O5—C5—C6—C7177.8 (2)C11—C10—C15—C140.5 (4)
C4—C5—C6—C71.4 (4)C9—C10—C15—C14176.6 (2)
C5—C6—C7—C7A1.1 (4)C13—C14—C15—C100.1 (4)
C6—C7—C7A—C3A0.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O5i0.952.573.505 (3)168
C7—H7···O1ii0.952.403.247 (3)149
C8—H8B···O3i0.982.593.432 (4)144
C15—H15···N20.952.562.884 (4)100
Symmetry codes: (i) x, y+3, z+2; (ii) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O5i0.952.573.505 (3)168
C7—H7···O1ii0.952.403.247 (3)149
C8—H8B···O3i0.982.593.432 (4)144
Symmetry codes: (i) x, y+3, z+2; (ii) x+1, y+1, z+2.
Acknowledgements top

This work was supported financially by the Xunta de Galicia (CN 2012/184). The authors gratefully acknowledge Dr Berta Covelo, X-ray service of the University of Vigo, for her valuable assistance. NV thanks the University of Vigo for a PhD fellowship.

references
References top

Barooah, N. & Baruah, J. B. (2007). Mini-Rev. Org. Chem. 4, 292–309.

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madinson, Wisconsin, USA.

Cao, H. & Alper, H. (2010). Org. Lett. 12, 4126–4129.

Favor, D., Powers, J. J., Repine, J. T. & White, A. D. (2008). PCT Int. Appl. WO 020306.

Haj-Yehia, A. I. & Khan, M. A. (2004). PCT Int. Appl. WO 047837.

Jiang, Z., Wang, J.-D., Chen, N.-S. & Huang, J.-L. (2008). Acta Cryst. E64, o324.

Luzzio, F. A. (2005). Science of Synthesis, Vol. 21, edited by S. Veinreb, pp. 259–324. Stuttgart: Thieme Chemistry.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.

Sharma, U., Kumar, P., Kumar, N. & Singh, B. (2010). Mini Rev. Med. Chem. 10, 678–704.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Vidal, T., Petit, A., Loupy, A. & Gedye, R. N. (2000). Tetrahedron, 56, 5473–5478.

Warzecha, K.-D., Görner, H. & Griesbeck, A. G. (2006). J. Phys. Chem. A, 110, 3356–3363.

Warzecha, K.-D., Lex, J. & Griesbeck, A. G. (2006a). Acta Cryst. E62, o2367–o2368.

Warzecha, K.-D., Lex, J. & Griesbeck, A. G. (2006b). Acta Cryst. E62, o5271–o5273.

Warzecha, K.-D., Lex, J. & Griesbeck, A. G. (2006c). Acta Cryst. E62, o5450–o5452.