2,10-Bis(3-bromo­phen­yl)-3,7,11,15-tetra­oxa-8,16-diaza­tricyclo­[12.2.1.16,9]octa­deca-1(16),6(18),8,14(17)-tetra­ene

Ha, K.; Park, S.B.; Lee, Y.J.; Kim, H.J.

doi:10.1107/S1600536810028813

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2120

https://doi.org/10.1107/S1600536810028813

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2,10-Bis(3-bromophenyl)-3,7,11,15-tetraoxa-8,16-diazatricyclo[12.2.1.1^6,9]octadeca-1(16),6(18),8,14(17)-tetraene

Kwang Ha,^a Sae Byul Park,^a Young Ju Lee ^b and Hyung Jin Kim ^a ^*

^aSchool of Applied Chemical Engineering, Chonnam National University, Gwangju 500-757, Republic of Korea, and ^bGwangju Branch, Korea Basic Science Institute, Gwangju 500-757, Republic of Korea
^*Correspondence e-mail: hyungkim@chonnam.ac.kr

(Received 19 July 2010; accepted 19 July 2010; online 24 July 2010)

The title compound, C₂₄H₂₀Br₂N₂O₄, is an 18-membered tricycle including two isoxazole rings. The asymmetric unit contains one half of the formula unit; a centre of inversion is located at the centroid of the compound. The dihedral angle between adjacent isoxazole and benzene rings is 84.0 (2)°. The compound displays intra- and intermolecular π–π stacking interactions between the isoxazole rings, the shortest centroid–centroid distances being 3.837 (3) and 3.634 (3) Å, respectively. The molecules are stacked in columns along the a axis with short Br⋯Br contacts [3.508 (1) Å].

Related literature

For the biological activity of isoxazole derivatives, see: Kim et al. (1994 , 1997 ); Lang & Lin (1984 ). For the syntheses of various pyrano[3,4-c]isoxzole derivatives, see: Kim et al. (1999 ).

Experimental

Crystal data

C₂₄H₂₀Br₂N₂O₄
M_r = 560.24
Triclinic, $[P \overline 1]$
a = 5.6446 (4) Å
b = 7.3703 (5) Å
c = 13.701 (1) Å
α = 93.735 (1)°
β = 99.564 (1)°
γ = 102.363 (1)°
V = 546.03 (7) Å³
Z = 1
Mo Kα radiation
μ = 3.75 mm⁻¹
T = 200 K
0.34 × 0.26 × 0.17 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.797, T_max = 1.000
4051 measured reflections
2645 independent reflections
2040 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.152
S = 1.30
2645 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 1.25 e Å⁻³
Δρ_min = −1.87 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810028813/ng5004sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028813/ng5004Isup2.hkl

checkCIF report

Comment top

Many isoxazole derivatives are known to have a variety of biological activities in pharmaceutical and agricultural areas (Kim et al., 1994, 1997; Lang & Lin, 1984). Recently we reported that the syntheses of various pyrano[3,4-c]isoxzole derivatives by means of the intramolecular 1,3-dipolar cycloaddition of a nitrile oxide containing an alkyne moiety within the structure and that these fused isoxazoles displayed fungicidal activities against some plant pathogens (Kim et al., 1999). During the chromatographic purification of the crude product, we isolated an unexpected macrocylic isoxazole compound which was formed by intermolecular cycloaddition process.

The asymmetric unit of the title compound, C₂₄H₂₀Br₂N₂O₄, contains one half of the formula unit; a centre of inversion is located at the midpoint of the compound (Fig. 1). The C7 and C11 atoms lie in the isoxazole ring plane with the largest deviation of 0.055 (9) Å (C7) from the least-squares plane of the isoxazole ring. The compound displays intra- and intermolecular π-π interactions between the isoxazole rings (the symmetry operations for second planes: -x,-y,-z and -x,1 - y,-z, respectively), the shortest centroid-centroid distance being 3.837 (3) Å and 3.634 (3) Å, respectively. The parallel planes are shifted for 1.048 Å and 1.936 Å, respectively (Fig. 2). There may also be weak intermolecular π-π interactions between adjacent benzene rings, with a shortest centroid-centroid distance of 4.453 (4) Å. The molecules are stacked in columns along the a axis and the Br···Br contacts are present. The shortest Br1···Br1^a [symmetry code: (a) 2 - x,-y,1 - z] distance is 3.508 (1) Å.

Related literature top

For the biological activity of isoxazole derivatives, see: Kim et al. (1994, 1997); Lang & Lin (1984). For the syntheses of various pyrano[3,4-c]isoxzole derivatives, see: Kim et al. (1999).

Experimental top

A mixture of 1-bromo-3-[1-(but-3-ynyloxy)-2-nitroethyl]benzene (1.49 g, 5 mmol), phenyl isocyanate (2.97 g, 25 mmol) and Et₃N (51 mg, 0.5 mmol) in dry benzene (30 ml) was stirred for 12 h at 25 °C under nitrogen atmosphere. Water (1 ml) was added and the mixture was stirred for 2 h at which time the solids were removed by vacuum filtration. The filtrate was dried (MgSO₄) and concentrated in vacuo to give crude product, which was column chromatographed (SiO₂) by eluting with a mixture of n-hexane/EtOAc (10:1) to afford the title compound (34 mg, 1.2%) as a white solid. Crystals suitable for X-ray analysis were obtained by slow evaporation from an n-hexane/EtOAc solution. Mp 231 °C. ¹H NMR (600 MHz, CDCl₃): δ 7.57 (s, 2H, Ar), 7.41–7.18 (m, 6H, Ar), 5.41 (s, 2H, isoxazole), 5.37 (s, 2H, –O—CH-C₆H₄Br), 4.19 (dt, 2H, J = 10.2 Hz, 3.0 Hz, –CH₂CHH—O), 3.67 (bt, 2H, J = 10.2 Hz, –CH₂CHH-O–), 3.15 (ddd, 2H, J = 16.2 Hz, 12.6 Hz, 3.0 Hz, –CHH—CH₂O–), 2.77 (bd, J = 16.2 Hz, –CHH-CH₂O–). ¹³C NMR (150 MHz, CDCl₃): δ 172.71, 164.13, 141.11, 131.00, 129.98, 128.74, 124.43, 122.61, 98.90, 74.22, 67.40, 27.91.

Structure description top

For the biological activity of isoxazole derivatives, see: Kim et al. (1994, 1997); Lang & Lin (1984). For the syntheses of various pyrano[3,4-c]isoxzole derivatives, see: Kim et al. (1999).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 50% probability level for non-H atoms [Symmetry code: (i) -x, -y, -z].
	Fig. 2. View of the unit-cell contents of the title compound.

2,10-Bis(3-bromophenyl)-3,7,11,15-tetraoxa-8,16- diazatricyclo[12.2.1.1^6,9]octadeca-1(16),6(18),8,14 (17)-tetraene top

Crystal data top

C₂₄H₂₀Br₂N₂O₄	Z = 1
M_r = 560.24	F(000) = 280
Triclinic, P1	D_x = 1.704 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6446 (4) Å	Cell parameters from 2388 reflections
b = 7.3703 (5) Å	θ = 2.8–28.1°
c = 13.701 (1) Å	µ = 3.75 mm⁻¹
α = 93.735 (1)°	T = 200 K
β = 99.564 (1)°	Plate, colorless
γ = 102.363 (1)°	0.34 × 0.26 × 0.17 mm
V = 546.03 (7) Å³

Data collection top

Bruker SMART 1000 CCD diffractometer	2645 independent reflections
Radiation source: fine-focus sealed tube	2040 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
φ and ω scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→6
T_min = 0.797, T_max = 1.000	k = −9→9
4051 measured reflections	l = −16→18

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 1.30	w = 1/[σ²(F_o²) + (0.P)² + 3.5324P] where P = (F_o² + 2F_c²)/3
2645 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 1.25 e Å⁻³
0 restraints	Δρ_min = −1.87 e Å⁻³

Crystal data top

C₂₄H₂₀Br₂N₂O₄	γ = 102.363 (1)°
M_r = 560.24	V = 546.03 (7) Å³
Triclinic, P1	Z = 1
a = 5.6446 (4) Å	Mo Kα radiation
b = 7.3703 (5) Å	µ = 3.75 mm⁻¹
c = 13.701 (1) Å	T = 200 K
α = 93.735 (1)°	0.34 × 0.26 × 0.17 mm
β = 99.564 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2645 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2040 reflections with I > 2σ(I)
T_min = 0.797, T_max = 1.000	R_int = 0.015
4051 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.30	Δρ_max = 1.25 e Å⁻³
2645 reflections	Δρ_min = −1.87 e Å⁻³
145 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
Br1	0.78777 (12)	0.13416 (10)	0.45968 (6)	0.0464 (2)
O1	−0.0873 (7)	0.2957 (6)	−0.0511 (3)	0.0304 (9)
O2	−0.0557 (7)	−0.0026 (5)	0.2100 (3)	0.0323 (9)
N1	−0.1737 (8)	0.2688 (7)	0.0394 (4)	0.0315 (10)
C1	0.5786 (11)	0.2773 (8)	0.3908 (4)	0.0336 (12)
C2	0.3670 (11)	0.1843 (8)	0.3295 (4)	0.0333 (12)
H2	0.3226	0.0517	0.3216	0.040*
C3	0.2166 (10)	0.2874 (8)	0.2784 (4)	0.0288 (11)
C4	0.2855 (12)	0.4808 (8)	0.2927 (5)	0.0383 (14)
H4	0.1827	0.5521	0.2588	0.046*
C5	0.5037 (13)	0.5714 (9)	0.3561 (5)	0.0443 (16)
H5	0.5493	0.7040	0.3655	0.053*
C6	0.6540 (12)	0.4683 (9)	0.4054 (5)	0.0411 (15)
H6	0.8049	0.5278	0.4482	0.049*
C7	−0.0170 (10)	0.1934 (7)	0.2048 (4)	0.0286 (11)
H7	−0.1606	0.2385	0.2229	0.034*
C8	0.0115 (9)	0.2363 (7)	0.1015 (4)	0.0254 (11)
C9	0.2206 (10)	0.2402 (7)	0.0570 (4)	0.0273 (11)
H9	0.3764	0.2208	0.0867	0.033*
C10	0.1503 (9)	0.2772 (7)	−0.0368 (4)	0.0263 (11)
C11	0.2785 (10)	0.2954 (8)	−0.1230 (4)	0.0303 (12)
H11A	0.4454	0.3774	−0.1016	0.036*
H11B	0.1857	0.3539	−0.1749	0.036*
C12	−0.2998 (10)	−0.1054 (8)	0.1658 (4)	0.0310 (12)
H12A	−0.3729	−0.0385	0.1125	0.037*
H12B	−0.4066	−0.1201	0.2166	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0331 (3)	0.0454 (4)	0.0559 (4)	0.0092 (3)	−0.0055 (3)	0.0045 (3)
O1	0.0248 (19)	0.038 (2)	0.031 (2)	0.0108 (16)	0.0029 (16)	0.0109 (17)
O2	0.029 (2)	0.029 (2)	0.032 (2)	−0.0001 (16)	−0.0033 (16)	0.0014 (16)
N1	0.023 (2)	0.040 (3)	0.032 (3)	0.008 (2)	0.0034 (19)	0.005 (2)
C1	0.034 (3)	0.034 (3)	0.033 (3)	0.011 (2)	0.005 (2)	0.006 (2)
C2	0.035 (3)	0.027 (3)	0.035 (3)	0.002 (2)	0.009 (2)	−0.006 (2)
C3	0.031 (3)	0.026 (3)	0.027 (3)	0.004 (2)	0.003 (2)	0.003 (2)
C4	0.042 (3)	0.029 (3)	0.038 (3)	0.007 (3)	−0.006 (3)	0.002 (3)
C5	0.052 (4)	0.026 (3)	0.042 (4)	−0.004 (3)	−0.008 (3)	0.000 (3)
C6	0.033 (3)	0.044 (4)	0.035 (3)	−0.008 (3)	−0.004 (3)	0.002 (3)
C7	0.028 (3)	0.025 (3)	0.031 (3)	0.006 (2)	0.003 (2)	0.000 (2)
C8	0.025 (3)	0.022 (2)	0.030 (3)	0.007 (2)	0.002 (2)	0.002 (2)
C9	0.022 (2)	0.026 (3)	0.034 (3)	0.005 (2)	0.002 (2)	0.004 (2)
C10	0.022 (2)	0.022 (2)	0.032 (3)	0.0018 (19)	0.002 (2)	0.004 (2)
C11	0.029 (3)	0.027 (3)	0.032 (3)	0.002 (2)	0.005 (2)	0.004 (2)
C12	0.023 (3)	0.031 (3)	0.038 (3)	0.003 (2)	0.005 (2)	0.007 (2)

Geometric parameters (Å, º) top

Br1—C1	1.921 (6)	C5—H5	0.9500
O1—C10	1.360 (6)	C6—H6	0.9500
O1—N1	1.416 (6)	C7—C8	1.497 (8)
O2—C7	1.423 (6)	C7—H7	1.0000
O2—C12	1.433 (6)	C8—C9	1.412 (7)
N1—C8	1.308 (7)	C9—C10	1.344 (7)
C1—C2	1.358 (8)	C9—H9	0.9500
C1—C6	1.372 (9)	C10—C11	1.483 (8)
C2—C3	1.391 (8)	C11—C12ⁱ	1.520 (8)
C2—H2	0.9500	C11—H11A	0.9900
C3—C4	1.386 (8)	C11—H11B	0.9900
C3—C7	1.521 (7)	C12—C11ⁱ	1.520 (8)
C4—C5	1.391 (8)	C12—H12A	0.9900
C4—H4	0.9500	C12—H12B	0.9900
C5—C6	1.381 (9)

C10—O1—N1	107.8 (4)	O2—C7—H7	109.7
C7—O2—C12	114.0 (4)	C8—C7—H7	109.7
C8—N1—O1	105.5 (4)	C3—C7—H7	109.7
C2—C1—C6	123.7 (6)	N1—C8—C9	111.9 (5)
C2—C1—Br1	118.4 (5)	N1—C8—C7	120.4 (5)
C6—C1—Br1	117.9 (5)	C9—C8—C7	127.6 (5)
C1—C2—C3	118.6 (5)	C10—C9—C8	104.7 (5)
C1—C2—H2	120.7	C10—C9—H9	127.6
C3—C2—H2	120.7	C8—C9—H9	127.6
C4—C3—C2	119.1 (5)	C9—C10—O1	110.0 (5)
C4—C3—C7	119.1 (5)	C9—C10—C11	132.4 (5)
C2—C3—C7	121.7 (5)	O1—C10—C11	117.5 (5)
C3—C4—C5	120.7 (6)	C10—C11—C12ⁱ	110.7 (5)
C3—C4—H4	119.6	C10—C11—H11A	109.5
C5—C4—H4	119.6	C12ⁱ—C11—H11A	109.5
C6—C5—C4	119.8 (6)	C10—C11—H11B	109.5
C6—C5—H5	120.1	C12ⁱ—C11—H11B	109.5
C4—C5—H5	120.1	H11A—C11—H11B	108.1
C1—C6—C5	118.0 (6)	O2—C12—C11ⁱ	107.4 (4)
C1—C6—H6	121.0	O2—C12—H12A	110.2
C5—C6—H6	121.0	C11ⁱ—C12—H12A	110.2
O2—C7—C8	109.7 (4)	O2—C12—H12B	110.2
O2—C7—C3	107.8 (4)	C11ⁱ—C12—H12B	110.2
C8—C7—C3	110.1 (5)	H12A—C12—H12B	108.5

C10—O1—N1—C8	0.0 (6)	C2—C3—C7—C8	−113.0 (6)
C6—C1—C2—C3	−0.1 (10)	O1—N1—C8—C9	0.0 (6)
Br1—C1—C2—C3	−179.2 (4)	O1—N1—C8—C7	−177.6 (4)
C1—C2—C3—C4	−0.8 (9)	O2—C7—C8—N1	100.4 (6)
C1—C2—C3—C7	177.1 (6)	C3—C7—C8—N1	−141.0 (5)
C2—C3—C4—C5	0.8 (10)	O2—C7—C8—C9	−76.8 (7)
C7—C3—C4—C5	−177.1 (6)	C3—C7—C8—C9	41.8 (7)
C3—C4—C5—C6	0.1 (11)	N1—C8—C9—C10	0.0 (6)
C2—C1—C6—C5	1.1 (10)	C7—C8—C9—C10	177.4 (5)
Br1—C1—C6—C5	−179.9 (5)	C8—C9—C10—O1	0.0 (6)
C4—C5—C6—C1	−1.0 (11)	C8—C9—C10—C11	−178.2 (5)
C12—O2—C7—C8	−76.1 (6)	N1—O1—C10—C9	0.0 (6)
C12—O2—C7—C3	164.0 (5)	N1—O1—C10—C11	178.6 (4)
C4—C3—C7—O2	−175.5 (5)	C9—C10—C11—C12ⁱ	73.1 (7)
C2—C3—C7—O2	6.6 (7)	O1—C10—C11—C12ⁱ	−105.0 (5)
C4—C3—C7—C8	64.8 (7)	C7—O2—C12—C11ⁱ	147.7 (5)

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₂₄H₂₀Br₂N₂O₄
M_r	560.24
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	5.6446 (4), 7.3703 (5), 13.701 (1)
α, β, γ (°)	93.735 (1), 99.564 (1), 102.363 (1)
V (Å³)	546.03 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	3.75
Crystal size (mm)	0.34 × 0.26 × 0.17

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.797, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4051, 2645, 2040
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.152, 1.30
No. of reflections	2645
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.25, −1.87

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Acknowledgements

This study was supported financially by Chonnam National University, 2008.

References

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