(E)-3-(Oxolan-2-yl­idene)-1-phenyl­pyrrolidine-2,5-dione

Shao, Y.; Xia, Y.-A.; Wu, Z.-H.; Liu, X.-L.

doi:10.1107/S1600536814007193

organic compounds

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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Page o521

doi:10.1107/S1600536814007193

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(E)-3-(Oxolan-2-ylidene)-1-phenylpyrrolidine-2,5-dione

Ying Shao,^a ^* Yong-An Xia,^a Zhu-Hong Wu ^a and Xiao-Long Liu ^a

^aKey Laboratory of Fine Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, People's Republic of China
^*Correspondence e-mail: shaoying810724@163.com

(Received 19 March 2014; accepted 1 April 2014; online 5 April 2014)

In the title compound, C₁₄H₁₃NO₃, the dihedral angles between the central pyrrolidine ring and the pendant tetrahydrofuran and phenyl rings are 5.34 (18) and 58.99 (17)°, respectively. The tetrahydrofuran ring is almost planar (r.m.s. deviation = 0.008 Å). In the crystal, molecules are linked by C—H⋯O interactions, generating a three-dimensional network.

CCDC reference: 994793

Related literature

For synthetic background, see: Han et al. (2013 ); Sodhi et al. (2012 ).

Experimental

Crystal data

C₁₄H₁₃NO₃
M_r = 243.25
Monoclinic, P 2₁ /n
a = 8.144 (2) Å
b = 13.729 (4) Å
c = 11.160 (3) Å
β = 105.177 (8)°
V = 1204.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.30 × 0.28 × 0.25 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 ) T_min = 0.736, T_max = 0.977
11234 measured reflections
2201 independent reflections
1893 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.161
S = 1.08
2201 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.93	2.59	3.487 (4)	161
C9—H9A⋯O1ⁱⁱ	0.97	2.50	3.403 (3)	154
C14—H14A⋯O2ⁱⁱⁱ	0.97	2.50	3.376 (4)	150
C14—H14B⋯O2^iv	0.97	2.51	3.384 (4)	149
Symmetry codes: (i) -x+1, -y, -z; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku, 2000); 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: SHELXTL.

Supporting information

CCDC reference: 994793

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814007193/hb7212sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814007193/hb7212Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814007193/hb7212Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536814007193/hb7212Isup4.cml

checkCIF report

Comment top

The area of allylic and benzylic oxidation with tert-butyl hydroperoxide (TBHP) in the presence of Co(acac)₂ has been attracted more and more attention (Han, et al., 2013; Sodhi, et al., 2012). The title compound, C₁₄H₁₃NO₃, was synthesized by Co(acac)₂ catalyzed cross-dehydrogenative-coupling (CDC) between 1-phenyl-1H-pyrrole-2,5-dione and tetrahydrofuran in the presence of t-BuOOH as a oxidant in the air. In the molecule of the title compound (Fig. 1), the compound adopts an E conformation. All the non-H atoms of the pyrrolidine-2,5-dione and the tetrahydrofuran fragment, linked by carbon—carbon double bond, are nearly coplanar, with a maximum deviation of 0.056 (1) Å. While the dihedral angle between the benzene ring and the pyrrolidine-2,5-dione ring is 59.9 Å. In the crystal, C—H···O interactions link the molecules (Table 1).

Related literature top

For synthetic background, see: Han et al. (2013); Sodhi et al. (2012).

Experimental top

1-Phenyl-1H-pyrrole-2,5-dione(86.6 mg, 0.5 mmol), THF (0.5 ml, 7.0 mmol), cobalt(II) acetylacetonate (12.9 mg), 1,4-diazabicyclo[2.2.2]octane (70.1 mg, 0.6 mmol), TBHP (2.0 equiv, 70% aqueous solution 140 uL), 1.0 ml acetonitrile, 1.0 ml 1,4-dioxane were added to a tube under air. The reaction mixture was stirred at 60 ^oC for 4 h. Then the reaction mixture was quenched with saturated Na₂SO₃ solution_, extracted repeatedly with ethyl acetate, and dried over Na₂SO₄. It was then removal of the organic solvent in vacuum and followed by flash silica gel column chromatographic purification afforded product with petroleum/ ethyl acetate mixtures. Yield 40%. Colourless crystals were obtained by slow evaporation of ethyl acetate and CH₂Cl₂ mixed solvent.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalStructure (Rigaku, 2000); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title compound, showing 50% probability ellipsoids.
	Fig. 2. Perspective view of the packing of the title compound along a direction.

(E)-3-(Oxolan-2-ylidene)-1-phenylpyrrolidine-2,5-dione top

Crystal data top

C₁₄H₁₃NO₃	F(000) = 512
M_r = 243.25	D_x = 1.342 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2yn	Cell parameters from 4321 reflections
a = 8.144 (2) Å	θ = 3.2–25.3°
b = 13.729 (4) Å	µ = 0.10 mm⁻¹
c = 11.160 (3) Å	T = 296 K
β = 105.177 (8)°	Block, colorless
V = 1204.2 (6) Å³	0.30 × 0.28 × 0.25 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	2201 independent reflections
Radiation source: fine-focus sealed tube	1893 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.3°, θ_min = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	k = −16→15
T_min = 0.736, T_max = 0.977	l = −13→13
11234 measured 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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0555P)² + 0.8273P] where P = (F_o² + 2F_c²)/3
2201 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₃NO₃	V = 1204.2 (6) Å³
M_r = 243.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.144 (2) Å	µ = 0.10 mm⁻¹
b = 13.729 (4) Å	T = 296 K
c = 11.160 (3) Å	0.30 × 0.28 × 0.25 mm
β = 105.177 (8)°

Data collection top

Rigaku Mercury CCD diffractometer	2201 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	1893 reflections with I > 2σ(I)
T_min = 0.736, T_max = 0.977	R_int = 0.035
11234 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.08	Δρ_max = 0.23 e Å⁻³
2201 reflections	Δρ_min = −0.21 e Å⁻³
164 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	0.5949 (3)	0.34863 (14)	0.08693 (17)	0.0660 (6)
O2	0.3330 (3)	0.05454 (15)	−0.01104 (17)	0.0632 (6)
O3	0.4751 (3)	0.32363 (14)	−0.31330 (16)	0.0612 (6)
N1	0.4759 (3)	0.19466 (15)	0.06629 (18)	0.0505 (6)
C1	0.5003 (3)	0.1742 (2)	0.1954 (2)	0.0526 (7)
C2	0.4297 (4)	0.2340 (2)	0.2671 (3)	0.0720 (9)
H2	0.3637	0.2873	0.2323	0.086*
C3	0.4596 (6)	0.2129 (3)	0.3938 (3)	0.0938 (13)
H3	0.4153	0.2531	0.4447	0.113*
C4	0.5547 (6)	0.1324 (4)	0.4428 (3)	0.0986 (14)
H4	0.5739	0.1185	0.5269	0.118*
C5	0.6209 (5)	0.0727 (3)	0.3697 (3)	0.0866 (11)
H5	0.6835	0.0180	0.4035	0.104*
C6	0.5947 (4)	0.0937 (2)	0.2458 (3)	0.0639 (8)
H6	0.6406	0.0536	0.1957	0.077*
C7	0.5310 (3)	0.28121 (19)	0.0200 (2)	0.0514 (6)
C8	0.4917 (3)	0.27047 (19)	−0.1134 (2)	0.0507 (6)
C9	0.4145 (4)	0.1720 (2)	−0.1479 (2)	0.0571 (7)
H9A	0.3038	0.1775	−0.2069	0.069*
H9B	0.4875	0.1319	−0.1838	0.069*
C10	0.3991 (3)	0.1303 (2)	−0.0279 (2)	0.0503 (6)
C11	0.5168 (3)	0.34047 (19)	−0.1899 (2)	0.0508 (7)
C12	0.5857 (4)	0.4404 (2)	−0.1610 (3)	0.0603 (7)
H12A	0.7015	0.4385	−0.1089	0.072*
H12B	0.5161	0.4776	−0.1189	0.072*
C13	0.5797 (6)	0.4839 (3)	−0.2852 (3)	0.0956 (13)
H13A	0.5089	0.5418	−0.2989	0.115*
H13B	0.6932	0.5019	−0.2895	0.115*
C14	0.5080 (4)	0.4095 (2)	−0.3792 (3)	0.0679 (8)
H14A	0.4032	0.4329	−0.4351	0.081*
H14B	0.5878	0.3943	−0.4276	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0912 (15)	0.0522 (11)	0.0478 (11)	−0.0092 (11)	0.0059 (10)	−0.0045 (9)
O2	0.0689 (13)	0.0623 (12)	0.0580 (11)	−0.0180 (10)	0.0161 (9)	−0.0065 (10)
O3	0.0833 (14)	0.0570 (11)	0.0427 (10)	−0.0044 (10)	0.0154 (9)	0.0014 (9)
N1	0.0628 (14)	0.0465 (12)	0.0390 (11)	−0.0043 (10)	0.0080 (9)	−0.0018 (9)
C1	0.0590 (16)	0.0550 (16)	0.0420 (14)	−0.0120 (13)	0.0103 (12)	−0.0030 (12)
C2	0.086 (2)	0.068 (2)	0.0651 (19)	−0.0158 (17)	0.0259 (17)	−0.0166 (16)
C3	0.120 (3)	0.108 (3)	0.066 (2)	−0.048 (3)	0.046 (2)	−0.038 (2)
C4	0.114 (3)	0.128 (4)	0.048 (2)	−0.053 (3)	0.010 (2)	0.008 (2)
C5	0.084 (2)	0.112 (3)	0.056 (2)	−0.020 (2)	0.0052 (17)	0.022 (2)
C6	0.0620 (18)	0.073 (2)	0.0542 (17)	−0.0030 (15)	0.0099 (13)	0.0091 (14)
C7	0.0576 (16)	0.0468 (15)	0.0464 (14)	0.0016 (12)	0.0077 (12)	−0.0012 (12)
C8	0.0559 (16)	0.0484 (14)	0.0445 (14)	0.0023 (12)	0.0074 (11)	−0.0001 (12)
C9	0.0667 (18)	0.0587 (17)	0.0431 (14)	−0.0069 (14)	0.0092 (12)	−0.0059 (12)
C10	0.0478 (15)	0.0512 (15)	0.0496 (15)	0.0000 (12)	0.0085 (11)	−0.0050 (12)
C11	0.0532 (15)	0.0532 (15)	0.0435 (14)	0.0046 (12)	0.0080 (11)	−0.0025 (12)
C12	0.0725 (19)	0.0493 (15)	0.0572 (16)	0.0014 (14)	0.0136 (14)	−0.0015 (13)
C13	0.153 (4)	0.067 (2)	0.069 (2)	−0.030 (2)	0.032 (2)	0.0000 (18)
C14	0.086 (2)	0.0648 (19)	0.0566 (17)	0.0054 (16)	0.0264 (16)	0.0122 (15)

Geometric parameters (Å, º) top

O1—C7	1.217 (3)	C6—H6	0.9300
O2—C10	1.208 (3)	C7—C8	1.447 (4)
O3—C11	1.349 (3)	C8—C11	1.336 (4)
O3—C14	1.451 (3)	C8—C9	1.498 (4)
N1—C10	1.390 (3)	C9—C10	1.492 (4)
N1—C7	1.414 (3)	C9—H9A	0.9700
N1—C1	1.430 (3)	C9—H9B	0.9700
C1—C2	1.372 (4)	C11—C12	1.486 (4)
C1—C6	1.379 (4)	C12—C13	1.498 (4)
C2—C3	1.402 (5)	C12—H12A	0.9700
C2—H2	0.9300	C12—H12B	0.9700
C3—C4	1.378 (6)	C13—C14	1.472 (4)
C3—H3	0.9300	C13—H13A	0.9700
C4—C5	1.364 (6)	C13—H13B	0.9700
C4—H4	0.9300	C14—H14A	0.9700
C5—C6	1.374 (4)	C14—H14B	0.9700
C5—H5	0.9300

C11—O3—C14	110.3 (2)	C10—C9—H9A	110.9
C10—N1—C7	112.4 (2)	C8—C9—H9A	110.9
C10—N1—C1	123.6 (2)	C10—C9—H9B	110.9
C7—N1—C1	124.0 (2)	C8—C9—H9B	110.9
C2—C1—C6	121.0 (3)	H9A—C9—H9B	108.9
C2—C1—N1	120.0 (3)	O2—C10—N1	124.1 (2)
C6—C1—N1	118.9 (3)	O2—C10—C9	128.0 (2)
C1—C2—C3	118.4 (4)	N1—C10—C9	107.9 (2)
C1—C2—H2	120.8	C8—C11—O3	119.3 (2)
C3—C2—H2	120.8	C8—C11—C12	129.6 (2)
C4—C3—C2	119.8 (4)	O3—C11—C12	111.1 (2)
C4—C3—H3	120.1	C11—C12—C13	104.4 (2)
C2—C3—H3	120.1	C11—C12—H12A	110.9
C5—C4—C3	121.0 (3)	C13—C12—H12A	110.9
C5—C4—H4	119.5	C11—C12—H12B	110.9
C3—C4—H4	119.5	C13—C12—H12B	110.9
C4—C5—C6	119.6 (4)	H12A—C12—H12B	108.9
C4—C5—H5	120.2	C14—C13—C12	107.1 (3)
C6—C5—H5	120.2	C14—C13—H13A	110.3
C5—C6—C1	120.1 (3)	C12—C13—H13A	110.3
C5—C6—H6	119.9	C14—C13—H13B	110.3
C1—C6—H6	119.9	C12—C13—H13B	110.3
O1—C7—N1	122.7 (2)	H13A—C13—H13B	108.6
O1—C7—C8	130.7 (3)	O3—C14—C13	107.1 (2)
N1—C7—C8	106.5 (2)	O3—C14—H14A	110.3
C11—C8—C7	123.7 (2)	C13—C14—H14A	110.3
C11—C8—C9	127.5 (2)	O3—C14—H14B	110.3
C7—C8—C9	108.7 (2)	C13—C14—H14B	110.3
C10—C9—C8	104.1 (2)	H14A—C14—H14B	108.6

C10—N1—C1—C2	−120.8 (3)	C11—C8—C9—C10	−173.3 (3)
C7—N1—C1—C2	60.9 (4)	C7—C8—C9—C10	4.4 (3)
C10—N1—C1—C6	58.9 (4)	C7—N1—C10—O2	−175.2 (3)
C7—N1—C1—C6	−119.3 (3)	C1—N1—C10—O2	6.4 (4)
C6—C1—C2—C3	1.7 (4)	C7—N1—C10—C9	4.8 (3)
N1—C1—C2—C3	−178.6 (3)	C1—N1—C10—C9	−173.6 (2)
C1—C2—C3—C4	−1.4 (5)	C8—C9—C10—O2	174.5 (3)
C2—C3—C4—C5	0.1 (6)	C8—C9—C10—N1	−5.5 (3)
C3—C4—C5—C6	0.9 (6)	C7—C8—C11—O3	−179.6 (2)
C4—C5—C6—C1	−0.7 (5)	C9—C8—C11—O3	−2.2 (4)
C2—C1—C6—C5	−0.6 (4)	C7—C8—C11—C12	−0.3 (5)
N1—C1—C6—C5	179.6 (3)	C9—C8—C11—C12	177.1 (3)
C10—N1—C7—O1	176.9 (3)	C14—O3—C11—C8	178.4 (3)
C1—N1—C7—O1	−4.7 (4)	C14—O3—C11—C12	−1.0 (3)
C10—N1—C7—C8	−1.9 (3)	C8—C11—C12—C13	−179.0 (3)
C1—N1—C7—C8	176.5 (2)	O3—C11—C12—C13	0.3 (4)
O1—C7—C8—C11	−2.6 (5)	C11—C12—C13—C14	0.5 (4)
N1—C7—C8—C11	176.1 (2)	C11—O3—C14—C13	1.3 (4)
O1—C7—C8—C9	179.6 (3)	C12—C13—C14—O3	−1.0 (4)
N1—C7—C8—C9	−1.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.59	3.487 (4)	161
C9—H9A···O1ⁱⁱ	0.97	2.50	3.403 (3)	154
C14—H14A···O2ⁱⁱⁱ	0.97	2.50	3.376 (4)	150
C14—H14B···O2^iv	0.97	2.51	3.384 (4)	149

Symmetry codes: (i) −x+1, −y, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1/2, y+1/2, −z−1/2; (iv) x+1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.59	3.487 (4)	161
C9—H9A···O1ⁱⁱ	0.97	2.50	3.403 (3)	154
C14—H14A···O2ⁱⁱⁱ	0.97	2.50	3.376 (4)	150
C14—H14B···O2^iv	0.97	2.51	3.384 (4)	149

Symmetry codes: (i) −x+1, −y, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1/2, y+1/2, −z−1/2; (iv) x+1/2, −y+1/2, z−1/2.

Acknowledgements

We gratefully acknowledge the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), the National Natural Science Foundation of China (grant No. 21302015), and the Natural Science Fundation for Colleges and Universities of Jiangsu Province (grant No. 12KJB150005) for financial support.

References

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