2-Benzyl­isoindoline-1,3-dione: a monoclinic polymorph

Abstract

In the molecule of the title compound, C₁₅H₁₁NO₂, the dihedral angle between the ring systems is 81.3 (2)°. In the crystal structure, mol­ecules are held together via C—H⋯O inter­actions.

Related literature

For the crystal structure of the triclinic form, see: Warzecha, Lex & Griesbeck (2006 ▶). For related literature, see: Warzecha, Görner & Griesbeck (2006 ▶); Orzeszko et al. (2000 ▶).

Experimental

Crystal data

• C₁₅H₁₁NO₂

• M _r = 237.25

• Monoclinic,

• a = 8.8324 (6) Å

• b = 5.3656 (4) Å

• c = 25.1926 (18) Å

• β = 98.851 (3)°

• V = 1179.69 (15) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 298 (2) K

• 0.8 × 0.2 × 0.1 mm

Data collection

• Rigaku R-AXIS RAPID IP diffractometer

• Absorption correction: none

• 3668 measured reflections

• 2083 independent reflections

• 1439 reflections with I > 2σ(I)

• R _int = 0.048

Refinement

• R[F ² > 2σ(F ²)] = 0.097

• wR(F ²) = 0.192

• S = 1.26

• 2083 reflections

• 208 parameters

• All H-atom parameters refined

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2006 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEX (McArdle, 1995 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H7⋯O1i	1.03 (6)	2.43 (6)	3.425 (6)	161 (5)
C3—H1⋯O2ii	0.98 (5)	2.54 (5)	3.363 (7)	142 (4)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The title compound, N-Benzylphthalimide (2-benzylisoindoline-1,3-dione) (I), plays an important role in photoinduced electron transfer (PET) reactions (Warzecha, Görner & Griesbeck, 2006). Warzecha, Lex & Griesbeck (2006) also reported the crystal structure of the triclinic form of (I). Herein, the crystal structure of a monoclinic form is described.

The molecular structure of (I), Fig. 1, shows two planar subunits, i.e. a phthalimide moiety and a phenyl ring, being linked by a methylene-C9 atom with a N1—C9—C10 bond angle of 114.2 (5)°. The dihedral angle formed between the least-squares planes through each of the subunits is 81.3 (2)°. The C8—N1—C9—C10 and C7—N1—C9—C10 torsion angles of 91.3 (6)Å and -88.0 (6)°, respectively, highlight the orthogonal relationship within the molecule.

The crystal packing is stabilized by C—H···O interactions (Table 1).

Experimental

Compound (I) was purified by silica-gel column chromatography with alcohol-hexane (v/v = 3/7) as eluent. Single crystals were obtained by slow evaporation of the eluting solution at room temperature.

Refinement

The H atoms were refined: range of C—H = 0.91 (6) - 1.04 (6) Å.

Figures

Fig. 1.

The molecular structure of (I) showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 35% probability level.

Crystal data

C15H11N1O2	F000 = 496
Mr = 237.25	Dx = 1.336 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 3962 reflections
a = 8.8324 (6) Å	θ = 1.2–25.0º
b = 5.3656 (4) Å	µ = 0.09 mm−1
c = 25.1926 (18) Å	T = 298 (2) K
β = 98.851 (3)º	Needle, colorless
V = 1179.69 (15) Å3	0.8 × 0.2 × 0.1 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer	1439 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode generator	Rint = 0.048
Monochromator: Graphite Monochromator	θmax = 25.0º
T = 298(2) K	θmin = 1.6º
ω scans	h = −10→9
Absorption correction: none	k = −6→6
3668 measured reflections	l = −29→13
2083 independent reflections

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.097	w = 1/[σ2(Fo2) + (0.0216P)2 + 2.0256P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.192	(Δ/σ)max < 0.001
S = 1.26	Δρmax = 0.24 e Å−3
2083 reflections	Δρmin = −0.19 e Å−3
208 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.008 (2)
Secondary atom site location: difference Fourier map

Special details

Experimental. collimator diameter: 0.800000 mm

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 (Ų)

	x	y	z	Uiso*/Ueq
O2	0.5810 (4)	0.7318 (7)	0.08609 (13)	0.0656 (10)
N1	0.7327 (4)	1.0824 (8)	0.09212 (14)	0.0520 (11)
O1	0.8908 (4)	1.4018 (7)	0.07261 (13)	0.0679 (11)
H1	0.579 (6)	0.595 (10)	−0.030 (2)	0.081*
H5	0.631 (6)	1.076 (10)	0.1573 (18)	0.070 (15)*
H10	1.040 (6)	1.130 (11)	0.309 (2)	0.085*
H4	0.895 (6)	1.300 (11)	−0.042 (2)	0.085*
H6	0.717 (7)	1.326 (13)	0.149 (2)	0.11 (2)*
H11	0.834 (6)	1.292 (12)	0.244 (2)	0.10 (2)*
H9	1.167 (6)	0.743 (11)	0.291 (2)	0.090 (18)*
H2	0.666 (6)	0.677 (11)	−0.112 (2)	0.082 (17)*
H3	0.815 (6)	1.037 (10)	−0.120 (2)	0.081 (16)*
H8	1.099 (7)	0.588 (12)	0.204 (2)	0.10 (2)*
H7	0.905 (7)	0.729 (12)	0.140 (2)	0.115*
C1	0.7860 (5)	1.0946 (9)	0.00582 (17)	0.0476 (12)
C2	0.6932 (5)	0.8927 (9)	0.00966 (17)	0.0483 (12)
C3	0.6470 (6)	0.7357 (11)	−0.0330 (2)	0.0599 (14)
C4	0.6984 (7)	0.7930 (12)	−0.0809 (2)	0.0670 (15)
C5	0.7910 (6)	0.9958 (12)	−0.0849 (2)	0.0676 (16)
C6	0.8377 (6)	1.1518 (11)	−0.0419 (2)	0.0600 (14)
C7	0.8157 (5)	1.2218 (9)	0.05865 (18)	0.0495 (12)
C8	0.6581 (5)	0.8804 (10)	0.06590 (18)	0.0509 (12)
C9	0.7296 (7)	1.1484 (13)	0.1487 (2)	0.0620 (14)
C10	0.8568 (5)	1.0365 (9)	0.18740 (17)	0.0495 (12)
C11	0.8977 (7)	1.1438 (12)	0.2375 (2)	0.0652 (15)
C12	1.0108 (8)	1.0414 (13)	0.2747 (2)	0.0787 (19)
C13	1.0886 (7)	0.8336 (13)	0.2625 (2)	0.0744 (17)
C14	1.0491 (7)	0.7241 (13)	0.2137 (2)	0.0711 (16)
C15	0.9351 (6)	0.8245 (10)	0.1757 (2)	0.0581 (13)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O2	0.069 (2)	0.063 (2)	0.066 (2)	−0.012 (2)	0.0146 (17)	0.0088 (19)
N1	0.058 (2)	0.052 (3)	0.046 (2)	0.001 (2)	0.0091 (18)	−0.002 (2)
O1	0.073 (2)	0.054 (2)	0.077 (2)	−0.012 (2)	0.0135 (18)	−0.015 (2)
C1	0.045 (2)	0.041 (3)	0.056 (3)	0.003 (2)	0.007 (2)	0.004 (2)
C2	0.048 (2)	0.049 (3)	0.047 (2)	0.008 (2)	0.0045 (19)	0.005 (2)
C3	0.058 (3)	0.064 (4)	0.056 (3)	−0.003 (3)	0.004 (2)	−0.002 (3)
C4	0.075 (4)	0.068 (4)	0.057 (3)	0.004 (3)	0.008 (3)	−0.008 (3)
C5	0.070 (3)	0.083 (4)	0.052 (3)	0.013 (3)	0.016 (3)	0.008 (3)
C6	0.058 (3)	0.064 (4)	0.060 (3)	0.000 (3)	0.017 (2)	0.006 (3)
C7	0.048 (3)	0.041 (3)	0.059 (3)	0.005 (2)	0.004 (2)	−0.004 (2)
C8	0.049 (3)	0.051 (3)	0.053 (3)	0.004 (3)	0.005 (2)	0.004 (3)
C9	0.069 (3)	0.064 (4)	0.055 (3)	0.010 (3)	0.017 (2)	−0.005 (3)
C10	0.060 (3)	0.047 (3)	0.045 (2)	−0.007 (3)	0.017 (2)	0.001 (2)
C11	0.080 (4)	0.065 (4)	0.052 (3)	−0.005 (3)	0.014 (3)	−0.008 (3)
C12	0.101 (5)	0.088 (5)	0.044 (3)	−0.017 (4)	0.002 (3)	−0.005 (3)
C13	0.074 (4)	0.080 (5)	0.067 (4)	−0.002 (4)	0.004 (3)	0.013 (4)
C14	0.072 (4)	0.067 (4)	0.074 (4)	0.007 (3)	0.011 (3)	0.003 (3)
C15	0.064 (3)	0.055 (3)	0.056 (3)	−0.001 (3)	0.012 (2)	−0.001 (3)

Geometric parameters (Å, °)

O2—C8	1.210 (5)	C6—H4	0.94 (6)
N1—C8	1.383 (6)	C9—C10	1.496 (7)
N1—C7	1.413 (6)	C9—H5	1.01 (5)
N1—C9	1.473 (6)	C9—H6	0.96 (7)
O1—C7	1.193 (5)	C10—C11	1.383 (6)
C1—C2	1.371 (6)	C10—C15	1.386 (7)
C1—C6	1.384 (6)	C11—C12	1.376 (8)
C1—C7	1.483 (6)	C11—H11	1.00 (6)
C2—C3	1.377 (7)	C12—C13	1.370 (8)
C2—C8	1.498 (6)	C12—H10	0.99 (5)
C3—C4	1.388 (7)	C13—C14	1.359 (8)
C3—H1	0.98 (5)	C13—H9	1.04 (6)
C4—C5	1.374 (8)	C14—C15	1.385 (7)
C4—H2	1.00 (5)	C14—H8	0.91 (6)
C5—C6	1.382 (7)	C15—H7	1.03 (6)
C5—H3	0.97 (5)
C8—N1—C7	112.5 (4)	N1—C8—C2	105.3 (4)
C8—N1—C9	124.9 (4)	N1—C9—C10	114.2 (4)
C7—N1—C9	122.6 (4)	N1—C9—H5	105 (3)
C2—C1—C6	121.1 (4)	C10—C9—H5	107 (3)
C2—C1—C7	109.0 (4)	N1—C9—H6	105 (4)
C6—C1—C7	129.8 (5)	C10—C9—H6	118 (4)
C1—C2—C3	122.5 (4)	H5—C9—H6	106 (5)
C1—C2—C8	108.3 (4)	C11—C10—C15	117.8 (5)
C3—C2—C8	129.2 (5)	C11—C10—C9	119.5 (5)
C2—C3—C4	116.5 (5)	C15—C10—C9	122.7 (4)
C2—C3—H1	122 (3)	C12—C11—C10	121.1 (6)
C4—C3—H1	122 (3)	C12—C11—H11	124 (3)
C5—C4—C3	121.1 (5)	C10—C11—H11	114 (3)
C5—C4—H2	123 (3)	C13—C12—C11	120.5 (6)
C3—C4—H2	116 (3)	C13—C12—H10	121 (3)
C4—C5—C6	122.1 (5)	C11—C12—H10	118 (3)
C4—C5—H3	117 (3)	C14—C13—C12	119.2 (6)
C6—C5—H3	120 (3)	C14—C13—H9	118 (3)
C5—C6—C1	116.7 (5)	C12—C13—H9	122 (3)
C5—C6—H4	127 (3)	C13—C14—C15	121.0 (6)
C1—C6—H4	116 (3)	C13—C14—H8	122 (4)
O1—C7—N1	124.6 (4)	C15—C14—H8	117 (4)
O1—C7—C1	130.6 (5)	C14—C15—C10	120.4 (5)
N1—C7—C1	104.8 (4)	C14—C15—H7	118 (3)
O2—C8—N1	125.0 (4)	C10—C15—H7	122 (3)
O2—C8—C2	129.7 (5)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H7···O1i	1.03 (6)	2.43 (6)	3.425 (6)	161 (5)
C3—H1···O2ii	0.98 (5)	2.54 (5)	3.363 (7)	142 (4)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z.