2-Benzyl-3-hy­droxy-3-methyl-2,3-dihydro-1H-isoindol-1-one

Wang, H.-Y.; Yang, J.-K.

doi:10.1107/S1600536812021575

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1795

doi:10.1107/S1600536812021575

Open

access

2-Benzyl-3-hydroxy-3-methyl-2,3-dihydro-1H-isoindol-1-one

Hong-Yao Wang ^a ^* and Jing-Kui Yang ^a

^aCollege of Chemistry and Chemical Engineering, Graduate University of Chinese Academy of Sciences, Beijing 100049, People's Republic of China
^*Correspondence e-mail: why5421700@163.com

(Received 26 April 2012; accepted 12 May 2012; online 19 May 2012)

In the title compound, C₁₆H₁₅NO₂, the isoindoline ring system is approximately planar (mean deviation = 0.0186 Å) and makes a dihedral angle of 61.91 (4)° with the phenyl ring. In the crystal, molecules form inversion dimers via pairs of O—H⋯O hydrogen bonds.

Related literature

For background to the synthesis of the title compound, see: Griffiths et al. (1983 ); For its applications in synthesis, see: Winn & Zaugg (1968 ); Katsuhiko et al. (2006 ). For related structures, see: Wang et al. (2008 ); Orzeszko et al. (1998 ); Liu et al. (2009 ); Rosamilia et al. (2002 ).

Experimental

Crystal data

C₁₆H₁₅NO₂
M_r = 253.29
Monoclinic, C 2/c
a = 11.093 (4) Å
b = 11.604 (4) Å
c = 21.226 (7) Å
β = 101.777 (5)°
V = 2674.7 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 153 K
0.47 × 0.34 × 0.23 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
11602 measured reflections
3479 independent reflections
2673 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.114
S = 1.11
3479 reflections
177 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2ⁱ	0.960 (15)	1.836 (15)	2.7938 (14)	175.3 (12)
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812021575/nr2026sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021575/nr2026Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812021575/nr2026Isup3.cml

checkCIF report

Comment top

The title compound was obtained as a byproduct in the preparation of 2-benzyl-1,1,3,3-tetramethylisoindoline, an important intermediate in the synthesis of the radical 1,1,3,3-Tetramethylisoindolin-2-yloxyl (TMIO), which is used as spin probe and radical scavenger (Griffiths et al., 1983). The title compound can be applied in the synthesis of heterocyclic amines through intramolecular amidoalkylation (Winn & Zaugg, 1968) and anionic ring-enlarging reaction (Katsuhiko et al., 2006).

The molecular structure of the title compound is shown in Fig. 1 and there are some similiar stuctures reported before (Wang et al., 2008; Orzeszko et al., 1998; Liu et al., 2009; Rosamilia et al., 2002). In the molecule, the isoindol ring system is approximately planar [mean deviation = 0.0186 Å] and has a dihedral angle of 61.91 (4)° with the benzene ring. In the crystal (Fig. 2), molecules form centrosymmetric dimers via pairs of O—H···O hydrogen bonds (Table 1).

Related literature top

For background to the synthesis of the title compound, see: Griffiths et al. (1983); For its applications in synthesis, see: Winn & Zaugg (1968); Katsuhiko et al. (2006). For related structures, see: Wang et al. (2008); Orzeszko et al. (1998); Liu et al. (2009); Rosamilia et al. (2002).

Experimental top

1.4 ml me thyl magnesium bromide solution (3 M in ether) was added to a 25 ml round-bottom flask filled with nitrogen and heated to 60 °C. A solution of N-benzylphthalimides (500 mg, 2.11 mmol) in toluene (15 ml) was added dropwise with stirring at a sufficient rate to maintain this temperature. When the addition was complete, the solution was heated to 110 °C and maintained at this temperature for 4 h. The reaction mixture was cooled to room temperature and petroleum was added. The mixture turned purple after stirring in air for 12 h. At the end, the mixture was filtered on celite and the filtrate obtained was dried, giving a precipitate which was separated by column chromatography on silica gel (eluent: ethyl acetate/petroleum ether, 1:3). The title compound was obtained as a colorless solid (123 mg, 23%) and evaporation of a solution in ethanol for 24 h afforded colorless single crystals suitable for X-ray diffraction.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular conformation of the title compound showing 50% probability displacement ellipsoids.
	Fig. 2. Molecular packing of the title compound.

2-Benzyl-3-hydroxy-3-methyl-2,3-dihydro-1H-isoindol-1-one top

Crystal data top

C₁₆H₁₅NO₂	F(000) = 1072
M_r = 253.29	D_x = 1.258 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.093 (4) Å	Cell parameters from 4918 reflections
b = 11.604 (4) Å	θ = 2.6–29.1°
c = 21.226 (7) Å	µ = 0.08 mm⁻¹
β = 101.777 (5)°	T = 153 K
V = 2674.7 (15) Å³	Block, colorless
Z = 8	0.47 × 0.34 × 0.23 mm

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	2673 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.032
Graphite monochromator	θ_max = 29.1°, θ_min = 2.6°
Detector resolution: 28.5714 pixels mm^-1	h = −12→15
phi and ω scans	k = −15→15
11602 measured reflections	l = −28→28
3479 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.056P)² + 0.0264P] where P = (F_o² + 2F_c²)/3
3479 reflections	(Δ/σ)_max < 0.001
177 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₅NO₂	V = 2674.7 (15) Å³
M_r = 253.29	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 11.093 (4) Å	µ = 0.08 mm⁻¹
b = 11.604 (4) Å	T = 153 K
c = 21.226 (7) Å	0.47 × 0.34 × 0.23 mm
β = 101.777 (5)°

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	2673 reflections with I > 2σ(I)
11602 measured reflections	R_int = 0.032
3479 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.21 e Å⁻³
3479 reflections	Δρ_min = −0.18 e Å⁻³
177 parameters

Special details top

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	U_iso*/U_eq
O1	0.48310 (7)	0.73617 (7)	0.04556 (4)	0.0310 (2)
O2	0.49294 (7)	0.35635 (7)	0.07278 (4)	0.0321 (2)
N1	0.46720 (9)	0.54981 (8)	0.09038 (4)	0.0256 (2)
C1	0.53806 (10)	0.65930 (9)	0.09452 (5)	0.0263 (2)
C2	0.66237 (10)	0.61485 (9)	0.08633 (5)	0.0242 (2)
C3	0.76900 (10)	0.67523 (10)	0.08427 (5)	0.0300 (3)
H3	0.7719	0.7568	0.0880	0.036*
C4	0.87197 (11)	0.61253 (10)	0.07655 (6)	0.0314 (3)
H4	0.9459	0.6525	0.0746	0.038*
C5	0.86960 (11)	0.49285 (10)	0.07166 (5)	0.0290 (3)
H5	0.9418	0.4523	0.0672	0.035*
C6	0.76204 (10)	0.43254 (9)	0.07334 (5)	0.0257 (3)
H6	0.7589	0.3509	0.0699	0.031*
C7	0.65951 (10)	0.49583 (9)	0.08021 (5)	0.0227 (2)
C8	0.53351 (11)	0.45578 (9)	0.08088 (5)	0.0247 (2)
C9	0.33419 (10)	0.54720 (10)	0.08518 (5)	0.0295 (3)
H9A	0.3006	0.4809	0.0578	0.035*
H9B	0.2989	0.6181	0.0628	0.035*
C10	0.29071 (10)	0.53813 (10)	0.14795 (5)	0.0283 (3)
C11	0.33512 (12)	0.45438 (11)	0.19347 (6)	0.0352 (3)
H11	0.4002	0.4052	0.1873	0.042*
C12	0.28499 (13)	0.44209 (12)	0.24794 (6)	0.0409 (3)
H12	0.3159	0.3844	0.2788	0.049*
C13	0.19061 (13)	0.51312 (13)	0.25754 (6)	0.0433 (3)
H13	0.1557	0.5037	0.2945	0.052*
C14	0.14733 (12)	0.59773 (14)	0.21325 (7)	0.0470 (4)
H14	0.0832	0.6475	0.2200	0.056*
C15	0.19722 (11)	0.61047 (12)	0.15877 (6)	0.0391 (3)
H15	0.1671	0.6693	0.1285	0.047*
C16	0.54084 (11)	0.71985 (10)	0.15828 (6)	0.0339 (3)
H16A	0.5928	0.7887	0.1609	0.041*
H16B	0.5745	0.6675	0.1938	0.041*
H16C	0.4570	0.7423	0.1613	0.041*
H1O	0.4958 (12)	0.7058 (13)	0.0054 (7)	0.059 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0387 (5)	0.0236 (4)	0.0314 (4)	0.0059 (3)	0.0092 (4)	0.0017 (3)
O2	0.0404 (5)	0.0228 (4)	0.0347 (5)	−0.0094 (3)	0.0114 (4)	−0.0022 (3)
N1	0.0259 (5)	0.0244 (5)	0.0278 (5)	−0.0027 (4)	0.0085 (4)	−0.0011 (4)
C1	0.0305 (6)	0.0207 (5)	0.0280 (6)	−0.0010 (4)	0.0069 (5)	−0.0011 (4)
C2	0.0286 (6)	0.0202 (5)	0.0240 (5)	−0.0011 (4)	0.0060 (4)	−0.0005 (4)
C3	0.0333 (6)	0.0208 (5)	0.0357 (6)	−0.0046 (5)	0.0063 (5)	−0.0001 (5)
C4	0.0281 (6)	0.0308 (6)	0.0355 (6)	−0.0052 (5)	0.0067 (5)	0.0040 (5)
C5	0.0290 (6)	0.0295 (6)	0.0290 (6)	0.0023 (5)	0.0073 (5)	0.0025 (5)
C6	0.0331 (7)	0.0202 (5)	0.0242 (5)	0.0007 (4)	0.0068 (5)	0.0009 (4)
C7	0.0287 (6)	0.0193 (5)	0.0202 (5)	−0.0024 (4)	0.0054 (4)	0.0007 (4)
C8	0.0322 (6)	0.0225 (5)	0.0201 (5)	−0.0037 (4)	0.0071 (4)	0.0001 (4)
C9	0.0266 (6)	0.0361 (6)	0.0260 (6)	−0.0022 (5)	0.0059 (5)	0.0008 (5)
C10	0.0238 (6)	0.0353 (6)	0.0256 (6)	−0.0062 (5)	0.0050 (4)	−0.0023 (5)
C11	0.0401 (7)	0.0376 (7)	0.0284 (6)	0.0017 (5)	0.0080 (5)	−0.0007 (5)
C12	0.0494 (9)	0.0469 (8)	0.0259 (6)	−0.0046 (6)	0.0069 (6)	0.0030 (5)
C13	0.0405 (8)	0.0640 (9)	0.0279 (6)	−0.0108 (7)	0.0132 (5)	−0.0030 (6)
C14	0.0350 (7)	0.0681 (10)	0.0419 (8)	0.0064 (7)	0.0174 (6)	0.0024 (7)
C15	0.0292 (7)	0.0531 (8)	0.0367 (7)	0.0031 (6)	0.0107 (5)	0.0069 (6)
C16	0.0387 (7)	0.0311 (6)	0.0325 (6)	0.0011 (5)	0.0086 (5)	−0.0084 (5)

Geometric parameters (Å, º) top

O1—C1	1.4102 (13)	C7—C8	1.4757 (16)
O1—H1O	0.960 (15)	C9—C10	1.5103 (16)
O2—C8	1.2377 (13)	C9—H9A	0.9900
N1—C8	1.3538 (14)	C9—H9B	0.9900
N1—C9	1.4573 (16)	C10—C11	1.3880 (17)
N1—C1	1.4871 (14)	C10—C15	1.3894 (17)
C1—C2	1.5151 (16)	C11—C12	1.3888 (18)
C1—C16	1.5196 (15)	C11—H11	0.9500
C2—C3	1.3831 (15)	C12—C13	1.380 (2)
C2—C7	1.3870 (15)	C12—H12	0.9500
C3—C4	1.3918 (16)	C13—C14	1.376 (2)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.3925 (17)	C14—C15	1.3879 (18)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.3900 (16)	C15—H15	0.9500
C5—H5	0.9500	C16—H16A	0.9800
C6—C7	1.3864 (15)	C16—H16B	0.9800
C6—H6	0.9500	C16—H16C	0.9800

C1—O1—H1O	107.6 (9)	N1—C9—C10	115.80 (10)
C8—N1—C9	122.99 (10)	N1—C9—H9A	108.3
C8—N1—C1	113.62 (9)	C10—C9—H9A	108.3
C9—N1—C1	122.48 (9)	N1—C9—H9B	108.3
O1—C1—N1	110.67 (9)	C10—C9—H9B	108.3
O1—C1—C2	113.42 (9)	H9A—C9—H9B	107.4
N1—C1—C2	100.65 (8)	C11—C10—C15	118.60 (11)
O1—C1—C16	106.91 (9)	C11—C10—C9	122.08 (11)
N1—C1—C16	111.22 (9)	C15—C10—C9	119.16 (11)
C2—C1—C16	113.96 (9)	C10—C11—C12	120.40 (12)
C3—C2—C7	120.32 (10)	C10—C11—H11	119.8
C3—C2—C1	129.45 (10)	C12—C11—H11	119.8
C7—C2—C1	110.23 (9)	C13—C12—C11	120.42 (13)
C2—C3—C4	117.82 (10)	C13—C12—H12	119.8
C2—C3—H3	121.1	C11—C12—H12	119.8
C4—C3—H3	121.1	C14—C13—C12	119.65 (13)
C3—C4—C5	121.78 (10)	C14—C13—H13	120.2
C3—C4—H4	119.1	C12—C13—H13	120.2
C5—C4—H4	119.1	C13—C14—C15	120.15 (13)
C6—C5—C4	120.23 (11)	C13—C14—H14	119.9
C6—C5—H5	119.9	C15—C14—H14	119.9
C4—C5—H5	119.9	C14—C15—C10	120.77 (13)
C7—C6—C5	117.57 (10)	C14—C15—H15	119.6
C7—C6—H6	121.2	C10—C15—H15	119.6
C5—C6—H6	121.2	C1—C16—H16A	109.5
C6—C7—C2	122.26 (10)	C1—C16—H16B	109.5
C6—C7—C8	129.28 (10)	H16A—C16—H16B	109.5
C2—C7—C8	108.44 (9)	C1—C16—H16C	109.5
O2—C8—N1	125.37 (11)	H16A—C16—H16C	109.5
O2—C8—C7	127.62 (10)	H16B—C16—H16C	109.5
N1—C8—C7	106.98 (9)

C8—N1—C1—O1	119.71 (10)	C1—C2—C7—C8	2.63 (12)
C9—N1—C1—O1	−49.64 (13)	C9—N1—C8—O2	−7.00 (17)
C8—N1—C1—C2	−0.51 (11)	C1—N1—C8—O2	−176.29 (10)
C9—N1—C1—C2	−169.86 (9)	C9—N1—C8—C7	171.34 (9)
C8—N1—C1—C16	−121.59 (10)	C1—N1—C8—C7	2.05 (12)
C9—N1—C1—C16	69.06 (12)	C6—C7—C8—O2	−3.10 (19)
O1—C1—C2—C3	60.18 (15)	C2—C7—C8—O2	175.41 (11)
N1—C1—C2—C3	178.40 (11)	C6—C7—C8—N1	178.60 (10)
C16—C1—C2—C3	−62.48 (15)	C2—C7—C8—N1	−2.89 (12)
O1—C1—C2—C7	−119.60 (10)	C8—N1—C9—C10	99.09 (13)
N1—C1—C2—C7	−1.37 (11)	C1—N1—C9—C10	−92.55 (12)
C16—C1—C2—C7	117.75 (11)	N1—C9—C10—C11	−51.07 (15)
C7—C2—C3—C4	−0.60 (16)	N1—C9—C10—C15	133.51 (12)
C1—C2—C3—C4	179.64 (10)	C15—C10—C11—C12	1.30 (18)
C2—C3—C4—C5	−0.64 (17)	C9—C10—C11—C12	−174.15 (11)
C3—C4—C5—C6	1.07 (17)	C10—C11—C12—C13	−0.1 (2)
C4—C5—C6—C7	−0.23 (16)	C11—C12—C13—C14	−1.0 (2)
C5—C6—C7—C2	−1.03 (16)	C12—C13—C14—C15	0.9 (2)
C5—C6—C7—C8	177.31 (10)	C13—C14—C15—C10	0.3 (2)
C3—C2—C7—C6	1.47 (16)	C11—C10—C15—C14	−1.39 (19)
C1—C2—C7—C6	−178.73 (9)	C9—C10—C15—C14	174.19 (12)
C3—C2—C7—C8	−177.17 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2ⁱ	0.960 (15)	1.836 (15)	2.7938 (14)	175.3 (12)

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅NO₂
M_r	253.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	153
a, b, c (Å)	11.093 (4), 11.604 (4), 21.226 (7)
β (°)	101.777 (5)
V (Å³)	2674.7 (15)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.47 × 0.34 × 0.23

Data collection
Diffractometer	Rigaku AFC10/Saturn724+ diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11602, 3479, 2673
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.114, 1.11
No. of reflections	3479
No. of parameters	177
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.18

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2ⁱ	0.960 (15)	1.836 (15)	2.7938 (14)	175.3 (12)

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

We thank the National Natural Science Foundation of China and the Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, for financial support.

References

Griffiths, P. G., Moad, G. & Rizzardo, E. (1983). Aust. J. Chem. 36, 397–401. CrossRef CAS Google Scholar
Katsuhiko, T., Takahiro, T., Takayuki, H. & Kazunobu, I. (2006). Synlett, 15, 2449–2453. Google Scholar
Liu, S., Zhang, X.-L., Zhang, W.-H. & Zhu, H.-J. (2009). Acta Cryst. E65, o3011. Web of Science CSD CrossRef IUCr Journals Google Scholar
Orzeszko, A., Maurin, J. K., Niedzwiecka-Kornas, A. & Kazimierczuk, Z. (1998). Tetrahedron, 54, 7517–7524. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rosamilia, A. E., Mayes, P. A., Papadopoulos, R., Campi, E. M., Jackson, W. R., Rash, L. & Jarrott, B. (2002). Aust. J. Chem. 55, 577–585. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, J. Y., Johnson, D. M. & Tiekink, E. R. T. (2008). Z. Kristallogr. New Cryst. Struct. 223, 25–26. CAS Google Scholar
Winn, M. & Zaugg, H. E. (1968). J. Org. Chem. 33, 3779–3783. CrossRef CAS Web of Science Google Scholar