1-[Bicyclo­[4.2.0]octa-1(6),2,4-trien-3-yl]-3-(but-3-en­yl)imidazolium bromide

Zhu, F.-H.; Yang, J.-X.; Zhang, L.; Xie, R.-G.

doi:10.1107/S1600536807058114

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o433

doi:10.1107/S1600536807058114

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1-[Bicyclo[4.2.0]octa-1(6),2,4-trien-3-yl]-3-(but-3-enyl)imidazolium bromide

Fang-Hua Zhu,^a Jun-Xiao Yang,^b Lin Zhang ^c and Ru-Gang Xie ^a ^*

^aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, ^bSchool of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, People's Republic of China, and ^cChina Academy of Engineering Physics, Mianyang 621900, People's Republic of China
^*Correspondence e-mail: orgxie@scu.edu.cn

(Received 8 November 2007; accepted 12 November 2007; online 11 January 2008)

In the title compound, C₁₅H₁₇N₂⁺·Br⁻, the cyclobutene and benzene rings are coplanar. The dihedral angle between the benzene and imidazolium rings is 21.2 (3)°. In the crystal structure, the C₁₅H₁₇N₂⁺ and Br⁻ ions are linked into a zigzag chain along the b axis by C—H⋯Br hydrogen bonds, and weak C—H⋯π interactions involving the benzene ring of a screw-related cation.

Related literature

For related literature, see: Farona (1996 ); Tan & Arnold (1988 ); Zhang et al. (2005 ).

Experimental

Crystal data

C₁₅H₁₇N₂⁺·Br⁻
M_r = 305.22
Monoclinic, P 2₁ /c
a = 9.342 (3) Å
b = 11.775 (3) Å
c = 13.695 (7) Å
β = 107.76 (3)°
V = 1434.7 (10) Å³
Z = 4
Mo Kα radiation
μ = 2.85 mm⁻¹
T = 291 (2) K
0.30 × 0.25 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2811 measured reflections
2665 independent reflections
1479 reflections with I > 2σ(I)
R_int = 0.005
3 standard reflections every 300 reflections intensity decay: 5.6%

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.144
S = 0.94
2665 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the C1–C4/C7/C9 ring centroid.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯Br	0.93	2.66	3.561 (5)	165
C11—H11⋯Brⁱ	0.93	2.87	3.697 (6)	149
C13—H13A⋯Cg1ⁱ	0.97	2.91	3.735 (7)	143
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: DIFRAC (Gabe & White, 1993 ); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807058114/ci2512sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807058114/ci2512Isup2.hkl

checkCIF report

Comment top

Benzocyclobutene (BCB) based polymeric materials have attracted considerable attention and research interest in the area of electronic applications because of their excellent properties such as low dielectric constant, low dissipation factor, low moisture picking-up, film planarization and high thermal-stability (Farona, 1996; Tan & Arnold, 1988). A number of BCB derivatives, such as BCB-alkyne imide, bis-BCB imide, organosiloxane bridged bis-BCB have been synthesized (Zhang et al., 2005). We report here the crystal structure of the title imidazolium BCB compound, (I), which was synthesized by alkylation of N-imidazolybenzocyclobutene and 4-bromo-1-butene.

The cyclobutene and benzene rings coplanar, with a dihedral angle of 0.7 (4)°. The dihedral angle between the benzene and imidazolium rings is 21.2 (3)°. In the crystal structure of (I), the cations and the bromide ions are linked via C—H···Br hydrogen bonds, and weak C—H···π interactions involving the C13—H13A group and the benzene of a screw-related molecule (Table 1), forming a zigzag chain along the b axis.

Related literature top

For related literature, see: Farona (1996); Tan & Arnold (1988); Zhang et al. (2005).

Experimental top

4-(N-imidazolyl)benzocyclobutene (5 mmol, 850 mg) and 4-bromo-1-butene (6 mmol, 810 mg,) were placed in a two-necked round-bottomed flask under a nitrogen atmosphere and the mixture was heated at 353 K for 5 h. A light-yellow solid was obtained after the surplus 4-bromo-1-butene was removed under vacuum. Colourless crystals of compound (I) were obtained by recrystallization of the solid from methanol-ethyl ether (1:4 v/v) solution (yield: 1.278 g). ¹ H NMR (400 MHz, CDCl₃): δ 10.80 (s, 1H), 7.74 (s, 1H), 7.61 (s, 1H), 7.49 (2 d, J = 7.6 Hz, 1H), 7.42 (s, 1H), 7.21 (d, J = 7.6 Hz, 1H), 5.86–5.95 (m, 1H), 5.11 (d, J = 14.4 Hz, 2H), 4.75 (t, 2H), 3.23 (s, 4H,), 2.76 (q, 2H); ¹³C NMR (100 MHz, CDCl₃): δ 148.22, 147.96, 135.57, 133.50, 132.65, 124.46, 123.48, 121.12, 120.97, 119.49, 116.80, 49.30, 34.60, 29.54, 29.46 p.p.m..

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering.

1-[Bicyclo[4.2.0]octa-1(6),2,4-trien-3-yl]-3-(but-3-enyl)imidazolium bromide top

Crystal data top

C₁₅H₁₇N₂⁺·Br⁻	F(000) = 624
M_r = 305.22	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 24 reflections
a = 9.342 (3) Å	θ = 4.8–9.6°
b = 11.775 (3) Å	µ = 2.85 mm⁻¹
c = 13.695 (7) Å	T = 291 K
β = 107.76 (3)°	Block, colourless
V = 1434.7 (10) Å³	0.30 × 0.25 × 0.25 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.005
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 2.3°
Graphite monochromator	h = −11→10
ω/2θ scans	k = 0→14
2811 measured reflections	l = −6→16
2665 independent reflections	3 standard reflections every 300 reflections
1479 reflections with I > 2σ(I)	intensity decay: 5.6%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.144	w = 1/[σ²(F_o²) + (0.0861P)²] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max = 0.001
2665 reflections	Δρ_max = 0.43 e Å⁻³
166 parameters	Δρ_min = −0.54 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.029 (3)

Crystal data top

C₁₅H₁₇N₂⁺·Br⁻	V = 1434.7 (10) Å³
M_r = 305.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.342 (3) Å	µ = 2.85 mm⁻¹
b = 11.775 (3) Å	T = 291 K
c = 13.695 (7) Å	0.30 × 0.25 × 0.25 mm
β = 107.76 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.005
2811 measured reflections	3 standard reflections every 300 reflections
2665 independent reflections	intensity decay: 5.6%
1479 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 0.94	Δρ_max = 0.43 e Å⁻³
2665 reflections	Δρ_min = −0.54 e Å⁻³
166 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
Br	0.66118 (7)	0.64239 (5)	0.09316 (5)	0.0607 (3)
N1	0.2215 (4)	0.5236 (3)	0.1168 (3)	0.0378 (9)
N2	0.3774 (5)	0.3946 (4)	0.1964 (3)	0.0480 (11)
C1	0.1596 (5)	0.6215 (4)	0.0546 (4)	0.0367 (11)
C2	0.0346 (6)	0.6742 (5)	0.0674 (4)	0.0457 (13)
H2	−0.0101	0.6444	0.1138	0.068 (7)*
C3	−0.0254 (6)	0.7700 (5)	0.0128 (4)	0.0502 (14)
H3	−0.1096	0.8056	0.0215	0.068 (7)*
C4	0.0439 (6)	0.8108 (5)	−0.0547 (4)	0.0476 (13)
C5	0.0411 (7)	0.9018 (5)	−0.1342 (5)	0.0641 (16)
H5A	0.0602	0.9781	−0.1065	0.104 (8)*
H5B	−0.0470	0.8995	−0.1942	0.104 (8)*
C6	0.1832 (7)	0.8406 (5)	−0.1486 (5)	0.0650 (17)
H6A	0.1669	0.8072	−0.2159	0.104 (8)*
H6B	0.2742	0.8860	−0.1284	0.104 (8)*
C7	0.1696 (6)	0.7568 (5)	−0.0671 (4)	0.0462 (13)
C8	0.2313 (6)	0.6611 (4)	−0.0145 (4)	0.0449 (13)
H8	0.3147	0.6251	−0.0240	0.068 (7)*
C9	0.3604 (5)	0.4861 (4)	0.1372 (4)	0.0429 (12)
H9	0.4347	0.5185	0.1140	0.068 (7)*
C10	0.1468 (6)	0.4519 (5)	0.1661 (4)	0.0498 (14)
H10	0.0470	0.4580	0.1649	0.068 (7)*
C11	0.2442 (6)	0.3735 (5)	0.2151 (4)	0.0516 (14)
H11	0.2253	0.3148	0.2550	0.068 (7)*
C12	0.5169 (7)	0.3289 (5)	0.2334 (5)	0.0627 (17)
H12A	0.5421	0.2980	0.1751	0.104 (8)*
H12B	0.5009	0.2657	0.2743	0.104 (8)*
C13	0.6461 (7)	0.3988 (6)	0.2966 (5)	0.0742 (19)
H13A	0.7326	0.3497	0.3229	0.104 (8)*
H13B	0.6715	0.4547	0.2525	0.104 (8)*
C14	0.6175 (8)	0.4578 (8)	0.3828 (6)	0.089 (2)
H14	0.5856	0.4122	0.4276	0.068 (7)*
C15	0.6302 (9)	0.5617 (9)	0.4043 (7)	0.107 (3)
H15A	0.6616	0.6119	0.3625	0.104 (8)*
H15B	0.6082	0.5884	0.4620	0.104 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0601 (4)	0.0638 (4)	0.0677 (4)	−0.0167 (3)	0.0337 (3)	−0.0169 (3)
N1	0.040 (2)	0.041 (2)	0.033 (2)	−0.0065 (19)	0.0113 (18)	−0.0035 (19)
N2	0.057 (3)	0.042 (3)	0.045 (2)	0.003 (2)	0.016 (2)	0.005 (2)
C1	0.036 (3)	0.043 (3)	0.029 (2)	−0.007 (2)	0.006 (2)	−0.006 (2)
C2	0.040 (3)	0.064 (4)	0.033 (3)	−0.001 (3)	0.010 (2)	−0.002 (3)
C3	0.041 (3)	0.063 (4)	0.047 (3)	0.011 (3)	0.015 (3)	−0.003 (3)
C4	0.046 (3)	0.046 (3)	0.044 (3)	0.004 (3)	0.004 (3)	0.004 (3)
C5	0.069 (4)	0.059 (4)	0.061 (4)	0.015 (3)	0.014 (3)	0.011 (3)
C6	0.070 (4)	0.069 (4)	0.056 (4)	0.008 (3)	0.020 (3)	0.017 (3)
C7	0.047 (3)	0.052 (3)	0.037 (3)	−0.001 (3)	0.010 (3)	0.002 (3)
C8	0.040 (3)	0.053 (3)	0.044 (3)	0.003 (2)	0.017 (2)	−0.001 (3)
C9	0.039 (3)	0.047 (3)	0.041 (3)	0.001 (2)	0.012 (2)	0.004 (2)
C10	0.052 (3)	0.057 (3)	0.045 (3)	−0.017 (3)	0.021 (3)	−0.001 (3)
C11	0.058 (4)	0.048 (3)	0.050 (3)	−0.009 (3)	0.017 (3)	0.007 (3)
C12	0.069 (4)	0.050 (4)	0.072 (4)	0.014 (3)	0.024 (3)	0.010 (3)
C13	0.062 (4)	0.076 (5)	0.075 (5)	0.023 (4)	0.008 (4)	0.013 (4)
C14	0.075 (5)	0.110 (7)	0.067 (5)	0.015 (5)	−0.002 (4)	0.001 (5)
C15	0.078 (6)	0.118 (8)	0.104 (7)	0.006 (5)	−0.003 (5)	−0.025 (6)

Geometric parameters (Å, º) top

N1—C9	1.317 (6)	C6—H6A	0.97
N1—C10	1.394 (6)	C6—H6B	0.97
N1—C1	1.444 (6)	C7—C8	1.368 (7)
N2—C9	1.329 (6)	C8—H8	0.93
N2—C11	1.367 (7)	C9—H9	0.93
N2—C12	1.466 (7)	C10—C11	1.327 (7)
C1—C2	1.380 (7)	C10—H10	0.93
C1—C8	1.396 (7)	C11—H11	0.93
C2—C3	1.374 (7)	C12—C13	1.499 (9)
C2—H2	0.93	C12—H12A	0.97
C3—C4	1.368 (7)	C12—H12B	0.97
C3—H3	0.93	C13—C14	1.463 (10)
C4—C7	1.390 (7)	C13—H13A	0.97
C4—C5	1.523 (8)	C13—H13B	0.97
C5—C6	1.576 (8)	C14—C15	1.255 (11)
C5—H5A	0.97	C14—H14	0.93
C5—H5B	0.97	C15—H15A	0.93
C6—C7	1.523 (7)	C15—H15B	0.93

C9—N1—C10	107.4 (4)	C4—C7—C6	93.2 (4)
C9—N1—C1	125.8 (4)	C7—C8—C1	114.9 (5)
C10—N1—C1	126.8 (4)	C7—C8—H8	122.6
C9—N2—C11	108.4 (5)	C1—C8—H8	122.6
C9—N2—C12	124.5 (5)	N1—C9—N2	109.2 (4)
C11—N2—C12	127.1 (5)	N1—C9—H9	125.4
C2—C1—C8	122.3 (5)	N2—C9—H9	125.4
C2—C1—N1	119.1 (4)	C11—C10—N1	107.4 (5)
C8—C1—N1	118.5 (4)	C11—C10—H10	126.3
C3—C2—C1	121.4 (5)	N1—C10—H10	126.3
C3—C2—H2	119.3	C10—C11—N2	107.6 (5)
C1—C2—H2	119.3	C10—C11—H11	126.2
C4—C3—C2	117.2 (5)	N2—C11—H11	126.2
C4—C3—H3	121.4	N2—C12—C13	112.6 (5)
C2—C3—H3	121.4	N2—C12—H12A	109.1
C3—C4—C7	121.0 (5)	C13—C12—H12A	109.1
C3—C4—C5	145.3 (5)	N2—C12—H12B	109.1
C7—C4—C5	93.7 (4)	C13—C12—H12B	109.1
C4—C5—C6	86.3 (4)	H12A—C12—H12B	107.8
C4—C5—H5A	114.3	C14—C13—C12	114.4 (6)
C6—C5—H5A	114.3	C14—C13—H13A	108.7
C4—C5—H5B	114.3	C12—C13—H13A	108.7
C6—C5—H5B	114.3	C14—C13—H13B	108.7
H5A—C5—H5B	111.4	C12—C13—H13B	108.7
C7—C6—C5	86.7 (4)	H13A—C13—H13B	107.6
C7—C6—H6A	114.2	C15—C14—C13	128.6 (9)
C5—C6—H6A	114.2	C15—C14—H14	115.7
C7—C6—H6B	114.2	C13—C14—H14	115.7
C5—C6—H6B	114.2	C14—C15—H15A	120.0
H6A—C6—H6B	111.4	C14—C15—H15B	120.0
C8—C7—C4	123.2 (5)	H15A—C15—H15B	120.0
C8—C7—C6	143.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Br	0.93	2.66	3.561 (5)	165
C11—H11···Brⁱ	0.93	2.87	3.697 (6)	149
C13—H13A···Cg1ⁱ	0.97	2.91	3.735 (7)	143

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₇N₂⁺·Br⁻
M_r	305.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	9.342 (3), 11.775 (3), 13.695 (7)
β (°)	107.76 (3)
V (Å³)	1434.7 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.85
Crystal size (mm)	0.30 × 0.25 × 0.25

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2811, 2665, 1479
R_int	0.005
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.144, 0.94
No. of reflections	2665
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.54

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Br	0.93	2.66	3.561 (5)	165
C11—H11···Brⁱ	0.93	2.87	3.697 (6)	149
C13—H13A···Cg1ⁱ	0.97	2.91	3.735 (7)	143

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors are grateful to the National Natural Science Foundation of China (grant No. 20574046) for financial support.

References

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