N Benzyl­phthalimide

organic papers

Acta Cryst.(2006). E62, o2367–o2368 doi:10.1107/S1600536806017971 Warzechaet al. _C

15H11NO2

o2367

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

N

-Benzylphthalimide

Klaus-Dieter Warzecha,* Johann Lex and Axel G. Griesbeck

Institute of Organic Chemistry, University of Cologne, Greinstrasse 4, D-50939 Cologne, Germany

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 100 K

Mean(C–C) = 0.002 A˚

Rfactor = 0.043

wRfactor = 0.108

Data-to-parameter ratio = 11.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 2 May 2006 Accepted 15 May 2006

#2006 International Union of Crystallography All rights reserved

In the roof-shaped molecule of the title compound, C15H11NO2, a planar cyclic imide and a phenyl ring are

tethered by a methylene group. In the crystal structure, parallel layers of phthalimides stack along the a axis with interplanar distances of 3.394 (2) and 3.495 (2)A˚ .

Comment

N-Benzylphthalimide (2-benzylisoindoline-1,3-dione), (I), the lower homologue of the previously described N-(2-pheneth-yl)phthalimide (Warzecha, Lexet al., 2006) was prepared for a mechanistic study on photoinduced electron transfer (PET) reactions with phthalimides as electron acceptors and aryl-alkyl carboxylates as electron donors (Warzecha, Go¨rner & Griesbeck, 2006).

In the course of these synthetically valuable photo-transformations, excitation (exc= 300 nm) of the phthalimide

furnishes its triplet state. Subsequent single electron transfer between the donor and the electronically excited acceptor reduces the phthalimide to its radical anion, thereby oxidizing the arylalkyl carboxylate to the corresponding acyloxy radical. Spontaneous decarboxylation of the latter, followed by recombination of the radical intermediates, gives rise to products identical to those obtained thermally in Grignard-type reactions.

The structure of the title compound, (I), is shown in Fig. 1. The molecule consists of two planar subunits,viz. the phtha-limide chromophore and a phenyl ring, linked via the sp3 -centre C9. The N1—C9—C10 bond angle is 111.18 (13)_.

The C1—N1—C9—C10 and C2—N1—C9—C10 torsion angles from the carbonyl atoms to the benzyl substituent are close to 90 _{[ 86.21 (18) and 90.09 (18), respectively]. The}

pair of torsion angles from the imide N atom to the phenyl ring are virtually the same: N1—C9—C10—C11 = 90.73 (18)and N1—C9—C10—C15 = 86.82 (16). As a result, the title compound exhibits a roof-shaped conformation.

to the centres of the six-membered rings of the next neigh-bours above and below are 3.751 (1) and 3.862 (1)A˚ , respec-tively. The phthalimides are oriented in parallel layers with interplanar distances of 3.394 (2) and 3.495 (2) A˚ .

Experimental

The title compound was prepared by heating equimolar amounts of phthalic anhydride and benzylamine in an open beaker for five successive one-minute periods in a domestic microwave oven (800 W). The liquefied material was carefully treated with acetone and the insoluble residue filtered off. Treament of the filtrate with

water caused precipitation of the crude imide. Subsequent recrys-tallization from ethanol yielded colourless prisms (m.p. 384–385 K) suitable for X-ray diffraction.

Crystal data

C15H11NO2

Mr= 237.25

Triclinic,P1

a= 7.1159 (3) A˚

b= 8.4691 (3) A˚

c= 10.1461 (5) A˚

= 99.480 (2) = 97.648 (2) = 106.745 (2)

V= 566.88 (4) A˚3

Z= 2

Dx= 1.390 Mg m 3

MoKradiation

= 0.09 mm 1

T= 100 (2) K Prism, colourless 0.450.450.30 mm

Data collection

Nonius KappaCCD diffractometer

’and!scans

Absorption correction: none 3760 measured reflections

2441 independent reflections 1709 reflections withI> 2(I)

Rint= 0.057

max= 27.0

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.043

wR(F2_{) = 0.108}

S= 1.00 2441 reflections 209 parameters

All H-atom parameters refined

w= 1/[2_(F

o2) + (0.045P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.014 max= 0.23 e A˚ 3 min= 0.21 e A˚ 3

Extinction correction:SHELXL97

Extinction coefficient: 0.061 (8)

Data collection: COLLECT (Hooft, 1999); cell refinement:

DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics: SCHAKAL99(Keller, 1999); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003) andenCIFer(Allenet al., 2004).

We thank the Deutsche Forschungsgemeinschaft (DFG, Germany) and the Centre National de la Recherche Scientifique (CNRS, France) for their generous financial support.

References

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004).J. Appl. Cryst.37, 335–338.

Hooft, R. W. (1999).COLLECT. Nonius BV, Delft, The Netherlands. Keller, E. (1999).SCHAKAL99. University of Freiburg, Germany. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,

Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Go¨ttingen, Germany.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

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

Warzecha, K.-D., Lex, J., Neudo¨rfl, J. M. & Griesbeck, A. G. (2006).Acta Cryst.

E62, o1580–o1581.

Figure 1

The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as circles of arbitrary size.

Figure 2

supporting information

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Acta Cryst. (2006). E62, o2367–o2368

supporting information

Acta Cryst. (2006). E62, o2367–o2368 [https://doi.org/10.1107/S1600536806017971]

N

-Benzylphthalimide

Klaus-Dieter Warzecha, Johann Lex and Axel G. Griesbeck

2-Benzylisoindoline-1,3-dione

Crystal data C15H11NO2

Mr = 237.25

Triclinic, P1 Hall symbol: -P 1 a = 7.1159 (3) Å b = 8.4691 (3) Å c = 10.1461 (5) Å α = 99.480 (2)° β = 97.648 (2)° γ = 106.745 (2)° V = 566.88 (4) Å3

Z = 2 F(000) = 248 Dx = 1.390 Mg m−3

Melting point = 384–385 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3760 reflections θ = 2.1–27.0°

µ = 0.09 mm−1

T = 100 K

Platelet, colourless 0.45 × 0.45 × 0.30 mm

Data collection Nonius KappaCCD

diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

3760 measured reflections 2441 independent reflections

1709 reflections with I > 2σ(I) Rint = 0.057

θmax = 27.0°, θmin = 2.1°

h = −9→9 k = −10→7 l = −12→12

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.043}

wR(F2_{) = 0.108}

S = 1.00 2441 reflections 209 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

All H-atom parameters refined w = 1/[σ2_(F

o2) + (0.045P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.014

Δρmax = 0.23 e Å−3

Δρmin = −0.21 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Special details

Experimental. IR (neat): 1708, 1432, 1391, 1332, 1063, 938, 716, 696 cm-1_.

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

C1 0.2687 (2) 0.33335 (18) 0.06927 (16) 0.0177 (4)

C2 0.3703 (2) 0.56852 (18) 0.24614 (17) 0.0175 (4)

C3 0.3183 (2) 0.62295 (17) 0.11800 (16) 0.0161 (4)

C4 0.3222 (2) 0.77985 (19) 0.09640 (18) 0.0219 (4)

H4 0.364 (2) 0.8801 (19) 0.1748 (17) 0.023 (4)*

C5 0.2628 (2) 0.7928 (2) −0.03761 (18) 0.0239 (4)

H5 0.264 (3) 0.900 (2) −0.0549 (19) 0.042 (5)*

C6 0.2040 (2) 0.6521 (2) −0.14419 (18) 0.0230 (4)

H6 0.159 (2) 0.6662 (19) −0.2384 (18) 0.022 (4)*

C7 0.2002 (2) 0.4939 (2) −0.12103 (18) 0.0207 (4)

H7 0.155 (2) 0.3944 (19) −0.1967 (17) 0.023 (4)*

C8 0.2577 (2) 0.48172 (17) 0.01130 (16) 0.0169 (4)

C9 0.3558 (2) 0.2873 (2) 0.30685 (18) 0.0197 (4)

H9A 0.464 (2) 0.3598 (19) 0.3860 (17) 0.026 (5)*

H9B 0.394 (2) 0.1932 (19) 0.2585 (16) 0.026 (4)*

C10 0.1609 (2) 0.21752 (18) 0.35308 (16) 0.0181 (4)

C11 0.0233 (2) 0.06337 (19) 0.28379 (17) 0.0218 (4)

H11 0.053 (2) −0.0045 (19) 0.2047 (18) 0.030 (5)*

C12 −0.1583 (3) 0.0027 (2) 0.32373 (19) 0.0265 (4)

H12 −0.255 (2) −0.106 (2) 0.2750 (17) 0.029 (5)*

C13 −0.2046 (3) 0.0959 (2) 0.43241 (18) 0.0282 (4)

H13 −0.337 (3) 0.054 (2) 0.4600 (18) 0.041 (5)*

C14 −0.0688 (3) 0.2502 (2) 0.50149 (18) 0.0270 (4)

H14 −0.101 (3) 0.3177 (19) 0.5754 (18) 0.032 (5)*

C15 0.1133 (2) 0.3103 (2) 0.46305 (17) 0.0215 (4)

H15 0.213 (2) 0.419 (2) 0.5109 (17) 0.027 (4)*

N1 0.33554 (18) 0.39477 (14) 0.20934 (13) 0.0169 (3)

O1 0.22971 (16) 0.18756 (12) 0.01184 (11) 0.0247 (3)

O2 0.43030 (16) 0.65272 (13) 0.36125 (12) 0.0243 (3)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C1 0.0132 (8) 0.0207 (8) 0.0189 (9) 0.0056 (6) 0.0040 (7) 0.0021 (7)

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Acta Cryst. (2006). E62, o2367–o2368

C3 0.0100 (8) 0.0192 (8) 0.0199 (9) 0.0048 (6) 0.0035 (7) 0.0050 (7)

C4 0.0171 (9) 0.0209 (8) 0.0267 (10) 0.0052 (7) 0.0029 (7) 0.0048 (8)

C5 0.0186 (9) 0.0245 (9) 0.0327 (11) 0.0094 (7) 0.0054 (8) 0.0128 (8)

C6 0.0170 (9) 0.0314 (9) 0.0245 (11) 0.0093 (7) 0.0044 (8) 0.0138 (8)

C7 0.0165 (9) 0.0255 (9) 0.0198 (10) 0.0073 (7) 0.0031 (7) 0.0037 (7)

C8 0.0108 (8) 0.0209 (8) 0.0198 (9) 0.0047 (6) 0.0040 (7) 0.0066 (7)

C9 0.0183 (9) 0.0208 (8) 0.0213 (10) 0.0066 (7) 0.0029 (7) 0.0082 (7)

C10 0.0186 (9) 0.0205 (8) 0.0179 (9) 0.0083 (6) 0.0006 (7) 0.0101 (7)

C11 0.0235 (10) 0.0216 (8) 0.0217 (10) 0.0090 (7) 0.0016 (8) 0.0077 (7)

C12 0.0202 (10) 0.0239 (9) 0.0335 (11) 0.0029 (7) −0.0003 (8) 0.0130 (8)

C13 0.0190 (10) 0.0395 (10) 0.0306 (11) 0.0088 (8) 0.0057 (8) 0.0200 (9)

C14 0.0264 (10) 0.0388 (10) 0.0205 (10) 0.0147 (8) 0.0061 (8) 0.0106 (8)

C15 0.0215 (9) 0.0245 (9) 0.0181 (10) 0.0073 (7) 0.0005 (7) 0.0063 (7)

N1 0.0174 (7) 0.0168 (7) 0.0164 (8) 0.0053 (5) 0.0026 (6) 0.0041 (6)

O1 0.0285 (7) 0.0195 (6) 0.0246 (7) 0.0079 (5) 0.0039 (5) 0.0008 (5)

O2 0.0255 (7) 0.0244 (6) 0.0184 (7) 0.0049 (5) 0.0003 (5) 0.0001 (5)

Geometric parameters (Å, º)

C1—O1 1.2098 (17) C9—N1 1.4704 (19)

C1—N1 1.397 (2) C9—C10 1.511 (2)

C1—C8 1.489 (2) C9—H9A 1.009 (17)

C2—O2 1.2134 (18) C9—H9B 0.990 (15)

C2—N1 1.3966 (19) C10—C11 1.391 (2)

C2—C3 1.486 (2) C10—C15 1.394 (2)

C3—C4 1.375 (2) C11—C12 1.387 (2)

C3—C8 1.393 (2) C11—H11 0.991 (16)

C4—C5 1.401 (2) C12—C13 1.381 (2)

C4—H4 1.006 (16) C12—H12 0.978 (16)

C5—C6 1.390 (2) C13—C14 1.387 (2)

C5—H5 0.95 (2) C13—H13 1.000 (18)

C6—C7 1.391 (2) C14—C15 1.382 (2)

C6—H6 1.005 (17) C14—H14 0.961 (16)

C7—C8 1.380 (2) C15—H15 0.989 (16)

C7—H7 0.984 (16)

O1—C1—N1 124.75 (14) C10—C9—H9A 111.2 (9)

O1—C1—C8 129.30 (15) N1—C9—H9B 106.5 (9)

N1—C1—C8 105.95 (12) C10—C9—H9B 109.5 (9)

O2—C2—N1 125.02 (15) H9A—C9—H9B 111.6 (13)

O2—C2—C3 128.94 (13) C11—C10—C15 118.98 (15)

N1—C2—C3 106.04 (13) C11—C10—C9 120.76 (14)

C4—C3—C8 121.63 (15) C15—C10—C9 120.22 (14)

C4—C3—C2 130.27 (15) C12—C11—C10 120.53 (15)

C8—C3—C2 108.11 (13) C12—C11—H11 118.9 (10)

C3—C4—C5 117.44 (15) C10—C11—H11 120.6 (10)

C3—C4—H4 120.6 (9) C13—C12—C11 120.07 (16)

C6—C5—C4 120.90 (15) C11—C12—H12 120.7 (9)

C6—C5—H5 120.2 (11) C12—C13—C14 119.76 (17)

C4—C5—H5 118.9 (11) C12—C13—H13 120.4 (10)

C7—C6—C5 121.14 (16) C14—C13—H13 119.8 (10)

C7—C6—H6 120.4 (9) C15—C14—C13 120.37 (16)

C5—C6—H6 118.4 (9) C15—C14—H14 119.2 (10)

C8—C7—C6 117.69 (15) C13—C14—H14 120.4 (10)

C8—C7—H7 121.6 (9) C14—C15—C10 120.28 (15)

C6—C7—H7 120.7 (9) C14—C15—H15 122.1 (9)

C7—C8—C3 121.20 (14) C10—C15—H15 117.6 (9)

C7—C8—C1 130.82 (14) C2—N1—C1 111.92 (13)

C3—C8—C1 107.98 (13) C2—N1—C9 124.19 (13)

N1—C9—C10 111.20 (13) C1—N1—C9 123.81 (12)