N-[4-(Prop-2-yn­yloxy)phen­yl]maleimide

Li, Z.-X.; Ren, C.-M.; Yang, S.; Yao, G.-J.; Shi, Q.-Z.

doi:10.1107/S1600536808035885

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o65

doi:10.1107/S1600536808035885

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N-[4-(Prop-2-ynyloxy)phenyl]maleimide

Zhan-Xian Li,^a Cai-Mei Ren,^a Sen Yang,^a Guang-Jun Yao ^a and Qiu-Zhi Shi ^a ^*

^aDepartment of Chemistry, Zhengzhou University, Zhengzhou 450001, People's Republic of China
^*Correspondence e-mail: qzshi@zzu.edu.cn

(Received 24 October 2008; accepted 1 November 2008; online 10 December 2008)

In the title compound, C₁₃H₉NO₃, the dihedral angle between the benzene and maleimide rings is 64.1 (2)°. In the crystal structure, molecules interact via C—H⋯O interactions.

Related literature

N-substituted maleimides can be used in free-radical-initiated polymerization processes upon exposure to light, see: Chang et al. (1999 ); Hoyle et al. (1999 ). For related structures, see: Moreno-Fuquen et al. (2006 , 2008a ,b ). For the effect of benzene ring substituents on the dihedral angle between the benzene and imidic rings, see: Miller et al. (2000 ).

Experimental

Crystal data

C₁₃H₉NO₃
M_r = 227.21
Monoclinic, P 2₁ /n
a = 9.0428 (18) Å
b = 11.491 (2) Å
c = 11.492 (2) Å
β = 102.00 (3)°
V = 1168.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 292 (3) K
0.30 × 0.26 × 0.20 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.968, T_max = 0.981
6107 measured reflections
2053 independent reflections
1368 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.224
S = 1.35
2053 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.93	2.50	3.179 (12)	130
C9—H9⋯O2ⁱⁱ	0.93	2.18	3.103 (10)	169
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808035885/hg2436sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035885/hg2436Isup2.hkl

checkCIF report

Comment top

N-substituted maleimides can be used in free radical initiated polymerization process upon exposure to light (Chang, et al., 1999; Hoyle, et al.,1999). N-(3-Nitrophenyl)maleimide (Moreno-Fuquen, et al., 2006), N-(3-Chlorophenyl)maleimide (Moreno-Fuquen, et al., 2008a) and N-(4-Chlorophenyl)maleimide (Moreno-Fuquen, et al., 2008b) has reported and could be taken as a reference to compare with the structural characteristics of (I).

Perspective view of (I), showing the atomic numbering scheme, can be seen in Fig. 1. The dihedral angle between the benzene and imidic rings influences on the polymerization process, and subsituents of the benzene ring can effect the value of dihedral angle (Miller et al. 2000). In the title compound (I), the dihedral angle between the benzene and maleimide is 64.1 (2)°. This angle is 46.46 (5) ° for N-(3-Chlorophenyl)maleimide (Moreno-Fuquen, et al., 2008:1) and 47.54 (9) ° for N-(4-Chlorophenyl)maleimide (Moreno-Fuquen, et al., 2008:2). The crystal structure of (I) is stabilized by weak intermolecular C—H···O hydrogen bonds.

Related literature top

N-substituted maleimides can be used in free-radical-initiated polymerization processes upon exposure to light, see: Chang et al. (1999); Hoyle et al. (1999). For related structures, see: Moreno-Fuquen et al. (2006, 2008a,b). For the effect of benzene ring substituents on the dihedral angle between the benzene and imidic rings, see: Miller et al. (2000);

Experimental top

The title compound was prepared by taking equimolar quantities of 4-(prop-2-ynyloxy)benzenamine (14.7 g, 0.1 mol) and maleic anhydride (9.8 g, 0.1 mol) in 80 ml benzene and 20 ml DMF and refluxing 4 h in the presence of p-toluenesulfonic acid. The reaction product was poured into 500 ml ice water, yellow precipitate product was formed. The crude product was recrystalled from ethanol. Yield 90%. ¹H NMR (300 MHz, DMSO-d₆) δ 7.30, 7.13(d, aromatic), 7.02(s, 2H, maleimide), 4.85(s, 2H, –H₂–), 3.14(s, 1H, ≡-H). Analysis. calculated for C₁₃H₉NO₃: C 68.72, H 3.99, N 6.16%. Found: C 68.39, H 4.02, N 6.21%. The product added in 50 ml ethanol and crystals of (I) suitable for X-ray analysis were obtained by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of complex (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.

N-[4-(Prop-2-ynyloxy)phenyl]maleimide top

Crystal data top

C₁₃H₉NO₃	F(000) = 472
M_r = 227.21	D_x = 1.292 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2053 reflections
a = 9.0428 (18) Å	θ = 2.5–25.0°
b = 11.491 (2) Å	µ = 0.09 mm⁻¹
c = 11.492 (2) Å	T = 292 K
β = 102.00 (3)°	Block, yellow
V = 1168.0 (4) Å³	0.30 × 0.26 × 0.20 mm
Z = 4

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2053 independent reflections
Radiation source: fine-focus sealed tube	1368 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
phi and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.968, T_max = 0.981	k = −13→10
6107 measured reflections	l = −12→12

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.224	H-atom parameters constrained
S = 1.35	w = 1/[σ²(F_o²) + (0.0733P)² + 3.1182P] where P = (F_o² + 2F_c²)/3
2053 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₃H₉NO₃	V = 1168.0 (4) Å³
M_r = 227.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.0428 (18) Å	µ = 0.09 mm⁻¹
b = 11.491 (2) Å	T = 292 K
c = 11.492 (2) Å	0.30 × 0.26 × 0.20 mm
β = 102.00 (3)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2053 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1368 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.981	R_int = 0.088
6107 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.224	H-atom parameters constrained
S = 1.35	Δρ_max = 0.49 e Å⁻³
2053 reflections	Δρ_min = −0.43 e Å⁻³
154 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
C3	0.2361 (11)	0.5326 (8)	0.6724 (8)	0.088 (4)
H3	0.2039	0.5394	0.5904	0.106*
O3	0.0885 (6)	0.1202 (5)	1.2278 (5)	0.0694 (19)
C5	0.1785 (7)	0.3652 (6)	0.9539 (6)	0.052 (2)
O1	0.3695 (7)	0.5806 (5)	0.9313 (5)	0.083 (2)
O2	0.0834 (8)	0.3616 (6)	0.7229 (6)	0.094 (3)
C8	0.1352 (8)	0.1986 (7)	1.1335 (6)	0.048 (2)
C9	0.2725 (8)	0.2328 (7)	1.0900 (6)	0.054 (2)
H9	0.3586	0.1960	1.1323	0.065*
C10	0.3076 (7)	0.3112 (7)	0.9958 (6)	0.053 (2)
H10	0.3992	0.3200	0.9720	0.064*
C7	0.0089 (9)	0.2487 (8)	1.0914 (8)	0.066 (3)
H7	−0.0834	0.2363	1.1129	0.079*
C6	0.0429 (7)	0.3326 (7)	0.9989 (7)	0.059 (2)
H6	−0.0424	0.3736	0.9613	0.071*
C1	0.3150 (9)	0.5431 (8)	0.8502 (7)	0.062 (3)
C4	0.1745 (10)	0.4410 (7)	0.7421 (7)	0.070 (3)
C11	0.2080 (11)	0.0481 (9)	1.2619 (8)	0.077 (3)
H11A	0.1862	0.0016	1.3268	0.093*
H11B	0.2935	0.0971	1.2958	0.093*
C2	0.3280 (11)	0.5958 (8)	0.7276 (8)	0.078 (3)
H2	0.3866	0.6553	0.7059	0.094*
C12	0.2667 (12)	−0.0409 (10)	1.1735 (10)	0.081 (3)
C13	0.3170 (15)	−0.1138 (12)	1.1030 (12)	0.113 (5)
H13	0.3526	−0.1656	1.0530	0.136*
N1	0.2168 (7)	0.4475 (6)	0.8557 (5)	0.0543 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.115 (8)	0.070 (6)	0.055 (6)	0.005 (6)	−0.038 (6)	0.016 (5)
O3	0.068 (4)	0.078 (4)	0.052 (3)	0.000 (3)	−0.010 (3)	0.011 (3)
C5	0.053 (4)	0.053 (5)	0.038 (4)	−0.006 (4)	−0.017 (4)	−0.001 (4)
O1	0.093 (5)	0.077 (4)	0.058 (4)	−0.021 (4)	−0.038 (4)	−0.001 (3)
O2	0.107 (5)	0.068 (4)	0.074 (4)	−0.006 (4)	−0.056 (4)	0.003 (3)
C8	0.064 (5)	0.049 (5)	0.026 (4)	−0.009 (4)	−0.003 (4)	0.009 (3)
C9	0.059 (5)	0.054 (5)	0.039 (4)	−0.021 (4)	−0.010 (4)	0.016 (4)
C10	0.039 (4)	0.068 (5)	0.045 (5)	−0.006 (4)	−0.007 (4)	−0.009 (4)
C7	0.045 (5)	0.075 (6)	0.069 (6)	−0.013 (4)	−0.006 (4)	0.001 (5)
C6	0.057 (5)	0.051 (5)	0.058 (5)	−0.002 (4)	−0.014 (4)	0.007 (4)
C1	0.057 (5)	0.069 (6)	0.047 (5)	0.002 (4)	−0.018 (4)	−0.003 (5)
C4	0.082 (6)	0.052 (5)	0.054 (5)	0.013 (5)	−0.034 (5)	−0.002 (4)
C11	0.082 (6)	0.096 (8)	0.042 (5)	−0.010 (6)	−0.012 (5)	0.036 (5)
C2	0.088 (7)	0.058 (6)	0.072 (6)	−0.011 (5)	−0.020 (5)	0.016 (5)
C12	0.085 (7)	0.083 (8)	0.068 (7)	0.019 (6)	0.000 (6)	0.028 (6)
C13	0.134 (11)	0.098 (9)	0.092 (9)	0.023 (9)	−0.014 (8)	0.019 (8)
N1	0.051 (4)	0.064 (4)	0.036 (4)	0.004 (3)	−0.018 (3)	0.000 (3)

Geometric parameters (Å, º) top

C3—C2	1.184 (11)	C10—H10	0.9300
C3—C4	1.498 (9)	C7—C6	1.513 (11)
C3—H3	0.9300	C7—H7	0.9300
O3—C11	1.353 (10)	C6—H6	0.9300
O3—C8	1.535 (9)	C1—N1	1.422 (11)
C5—C10	1.321 (7)	C1—C2	1.560 (12)
C5—C6	1.475 (8)	C4—N1	1.284 (10)
C5—N1	1.565 (10)	C11—C12	1.608 (16)
O1—C1	1.052 (9)	C11—H11A	0.9700
O2—C4	1.218 (10)	C11—H11B	0.9700
C8—C7	1.281 (10)	C2—H2	0.9300
C8—C9	1.484 (8)	C12—C13	1.311 (16)
C9—C10	1.493 (10)	C13—H13	0.9300
C9—H9	0.9300

C2—C3—C4	116.3 (8)	C7—C6—H6	112.3
C2—C3—H3	121.9	O1—C1—N1	117.3 (9)
C4—C3—H3	121.9	O1—C1—C2	122.1 (9)
C11—O3—C8	104.1 (6)	N1—C1—C2	120.4 (7)
C10—C5—C6	119.3 (7)	O2—C4—N1	106.0 (8)
C10—C5—N1	103.6 (6)	O2—C4—C3	137.9 (8)
C6—C5—N1	136.9 (6)	N1—C4—C3	115.9 (8)
C7—C8—C9	119.8 (7)	O3—C11—C12	123.7 (7)
C7—C8—O3	100.1 (7)	O3—C11—H11A	106.4
C9—C8—O3	139.9 (6)	C12—C11—H11A	106.4
C8—C9—C10	136.3 (6)	O3—C11—H11B	106.4
C8—C9—H9	111.9	C12—C11—H11B	106.4
C10—C9—H9	111.9	H11A—C11—H11B	106.5
C5—C10—C9	104.1 (6)	C3—C2—C1	93.9 (8)
C5—C10—H10	128.0	C3—C2—H2	133.0
C9—C10—H10	128.0	C1—C2—H2	133.0
C8—C7—C6	104.9 (7)	C13—C12—C11	178.9 (10)
C8—C7—H7	127.6	C12—C13—H13	180.0
C6—C7—H7	127.6	C4—N1—C1	93.2 (7)
C5—C6—C7	135.5 (6)	C4—N1—C5	129.4 (7)
C5—C6—H6	112.3	C1—N1—C5	137.1 (5)

C11—O3—C8—C7	169.0 (7)	C4—C3—C2—C1	−4.4 (12)
C11—O3—C8—C9	−16.0 (12)	O1—C1—C2—C3	−172.0 (11)
C7—C8—C9—C10	−5.8 (14)	N1—C1—C2—C3	2.3 (12)
O3—C8—C9—C10	179.9 (8)	O2—C4—N1—C1	−179.3 (7)
C6—C5—C10—C9	−4.1 (9)	C3—C4—N1—C1	−3.7 (9)
N1—C5—C10—C9	179.7 (5)	O2—C4—N1—C5	6.4 (12)
C8—C9—C10—C5	6.6 (12)	C3—C4—N1—C5	−178.0 (7)
C9—C8—C7—C6	1.8 (10)	O1—C1—N1—C4	175.7 (9)
O3—C8—C7—C6	178.1 (6)	C2—C1—N1—C4	1.2 (10)
C10—C5—C6—C7	2.5 (14)	O1—C1—N1—C5	−10.7 (15)
N1—C5—C6—C7	177.1 (8)	C2—C1—N1—C5	174.7 (8)
C8—C7—C6—C5	−0.8 (13)	C10—C5—N1—C4	109.2 (9)
C2—C3—C4—O2	−179.8 (12)	C6—C5—N1—C4	−65.9 (13)
C2—C3—C4—N1	6.5 (14)	C10—C5—N1—C1	−62.5 (11)
C8—O3—C11—C12	−61.5 (10)	C6—C5—N1—C1	122.4 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.93	2.50	3.179 (12)	130
C9—H9···O2ⁱⁱ	0.93	2.18	3.103 (10)	169

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₉NO₃
M_r	227.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	292
a, b, c (Å)	9.0428 (18), 11.491 (2), 11.492 (2)
β (°)	102.00 (3)
V (Å³)	1168.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.26 × 0.20

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.968, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	6107, 2053, 1368
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.224, 1.35
No. of reflections	2053
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.43

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

C1—N1	1.422 (11)	C11—C12	1.608 (16)
C4—N1	1.284 (10)	C12—C13	1.311 (16)

C13—C12—C11	178.9 (10)	C12—C13—H13	180.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.93	2.50	3.179 (12)	130
C9—H9···O2ⁱⁱ	0.93	2.18	3.103 (10)	169

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x+1/2, −y+1/2, z+1/2.

Acknowledgements

This work was supported by the Natural Science Foundation of China (No. 50873093).

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