3,3′-Dibromo-1,1′-[(propane-1,3-diyl­dioxy)­bis(nitrilo­methyl­idyne)]dibenzene

Dong, W.-K.; Ding, Y.-J.; Luo, Y.-L.; Lv, Z.-W.; Wang, L.

doi:10.1107/S1600536808018187

organic compounds

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Volume 64| Part 7| July 2008| Page o1324

doi:10.1107/S1600536808018187

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3,3′-Dibromo-1,1′-[(propane-1,3-diyldioxy)bis(nitrilomethylidyne)]dibenzene

Wen-Kui Dong,^a ^* Yu-Jie Ding,^b Ya-Ling Luo,^a Zhong-Wu Lv ^a and Li Wang ^a

^aSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China, and ^bDepartment of Biochemical Engineering, Anhui University of Technology And Science, Wuhu 241000, People's Republic of China
^*Correspondence e-mail: dongwk@mail.lzjtu.cn

(Received 3 June 2008; accepted 16 June 2008; online 21 June 2008)

The molecule of the title compound, C₁₇H₁₆Br₂N₂O₂, lies on a twofold axis that passes through the middle atom of the three-atom trimethylene unit. The two aromatic rings are aligned at an angle of 76.02 (4)°.

Related literature

For similar Schiff bases, see: Aysegul et al. (2005 ); Cordes & Jencks (1962 ); Dong et al. (2008 ); Duan et al. (2007 ); Shi et al. (2007 ); Koehler et al. (1964 ).

Experimental

Crystal data

C₁₇H₁₆Br₂N₂O₂
M_r = 440.14
Monoclinic, C 2/c
a = 24.397 (3) Å
b = 4.4848 (4) Å
c = 17.189 (2) Å
β = 114.009 (2)°
V = 1718.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.73 mm⁻¹
T = 298 (2) K
0.48 × 0.35 × 0.24 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.210, T_max = 0.397 (expected range = 0.170–0.321)
3683 measured reflections
1497 independent reflections
1179 reflections with I > 2σ(I)
R_int = 0.094

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.133
S = 1.07
1497 reflections
105 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Data collection: SMART (Bruker, 1996 ); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT; 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018187/ng2462sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018187/ng2462Isup2.hkl

checkCIF report

Comment top

Schiff base compounds have been widely used as versatile ligands involved in various metal chelations to form transition metal complexes with interesting properties (Aysegul et al., 2005; Dong et al., 2008). Although most of Schiff base derivatives are stable in solution and in solid state, C=N bonds often suffer exchange reaction (Koehler et al., 1964) as well as hydrolysis (Cordes & Jencks, 1962). Rate constants of oxime formation are smaller than those of imine formation and the equilibrium constants are larger by several orders. Hence, bisoxime-type compound should be stable enough to resist the metathesis of the C=N bonds. In this paper, a novel ligand, 3,3'-dibromo-1,1'-[propane-1,3-diyldioxybis(nitrilomethylidyne)]dibenzene (I) was designed and synthesized, and shown in Fig. 1.

The single-crystal structure of (I) is built up by discrete C₁₇H₁₆Br₂N₂O₂ molecules, in which all bond lengths are in normal ranges. There is a crystallographic twofold rotation axis passing through the middle point (symmetry code: -x, y, 1/2 - z) of the C—C unit. The molecule adopts a trans conguration in which two benzane rings are apart from each other and form a dihedral angle of 76.02 (4) Å. The oxime, bromo groups of (I) lie in trans positions relative to the middle point in the N—O—CH₂—CH₂—O—N linkage, which is similar to what is observed in our previously reported salen-type bisoxime compound of 2,2'-[(propane-1,3-diyldioxy)bis(nitrilomethylidyne)]diphenol (Duan et al., 2007). The molecule exhibits a zigzag chain array along a axis.

Related literature top

For similar Schiff bases, see: Aysegul et al. (2005); Cordes & Jencks (1962); Dong et al. (2008); Duan et al. (2007); Shi et al. (2007); Koehler et al. (1964).

Experimental top

3,3'-Dibromo-1,1'-[propane-1,3-diyldioxybis(nitrilomethylidyne)]dibenzene (I) was synthesized according to an analogous method reported earlier (Shi et al., 2007). To an ethanol solution (2 ml) of 3-bromo-benzaldehyde (283.0 mg, 1.48 mmol) was added an ethanol solution (3 ml) of 1,3-bis(aminooxy)propane (78.6 mg, 0.74 mmol). The mixed solution was stirred at 328 K for 6 h. The precipitate was filtered, and washed successively with ethanol and ethanol-hexane (1:4), respectively. The product was dried under vacuum to yield 157.5 mg of (I). Yield, 48.3%. mp. 350.5–352.5 K. Anal. Calc. for C₁₇H₁₆Br₂N₂O₂: C, 45.76; H, 3.49; N, 6.47. Found: C, 45.66; H, 3.43; N, 6.29.

Colorless needle-like single crystals suitable for X-ray diffraction studies were obtained after several weeks by slow evaporation from a methanol-tetrahydrofuran-ethyl acetate mixed solution of (I).

Computing details top

Data collection: SMART (Bruker, 1996); cell refinement: SMART (Bruker, 1996); data reduction: SAINT (Bruker, 1996); 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. The molecule structure of (I) with atom numbering. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.

3,3'-Dibromo-1,1'-[(propane-1,3-diyldioxy)bis(nitrilomethylidyne)]dibenzene top

Crystal data top

C₁₇H₁₆Br₂N₂O₂	F(000) = 872
M_r = 440.14	D_x = 1.702 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2255 reflections
a = 24.397 (3) Å	θ = 2.5–27.9°
b = 4.4848 (4) Å	µ = 4.73 mm⁻¹
c = 17.189 (2) Å	T = 298 K
β = 114.009 (2)°	Rod, colorless
V = 1718.0 (3) Å³	0.48 × 0.35 × 0.24 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1497 independent reflections
Radiation source: fine-focus sealed tube	1179 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.094
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −27→28
T_min = 0.210, T_max = 0.397	k = −5→5
3683 measured reflections	l = −20→15

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.061P)²] where P = (F_o² + 2F_c²)/3
1497 reflections	(Δ/σ)_max = 0.001
105 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

C₁₇H₁₆Br₂N₂O₂	V = 1718.0 (3) Å³
M_r = 440.14	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.397 (3) Å	µ = 4.73 mm⁻¹
b = 4.4848 (4) Å	T = 298 K
c = 17.189 (2) Å	0.48 × 0.35 × 0.24 mm
β = 114.009 (2)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1497 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1179 reflections with I > 2σ(I)
T_min = 0.210, T_max = 0.397	R_int = 0.094
3683 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.07	Δρ_max = 0.60 e Å⁻³
1497 reflections	Δρ_min = −0.66 e Å⁻³
105 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	Occ. (<1)
Br1	0.78652 (2)	1.12437 (15)	0.11896 (3)	0.0608 (3)
O1	0.53639 (12)	0.3149 (7)	−0.13426 (18)	0.0393 (8)
N1	0.58506 (15)	0.4899 (10)	−0.0798 (2)	0.0352 (9)
C1	0.5538 (2)	0.1605 (10)	−0.1934 (3)	0.0369 (11)
H1A	0.5876	0.0299	−0.1635	0.044*
H1B	0.5653	0.3011	−0.2270	0.044*
C2	0.5000	−0.0186 (16)	−0.2500	0.0371 (15)
H2A	0.4880	−0.1465	−0.2142	0.044*	0.50
H2B	0.5120	−0.1465	−0.2858	0.044*	0.50
C3	0.5704 (2)	0.6276 (10)	−0.0265 (3)	0.0398 (12)
H3	0.5317	0.6039	−0.0296	0.048*
C4	0.6117 (2)	0.8206 (10)	0.0390 (3)	0.0350 (11)
C5	0.6701 (2)	0.8759 (10)	0.0463 (3)	0.0368 (11)
H5	0.6836	0.7885	0.0083	0.044*
C6	0.7070 (2)	1.0573 (11)	0.1091 (3)	0.0391 (12)
C7	0.6887 (2)	1.1924 (12)	0.1666 (3)	0.0472 (13)
H7	0.7144	1.3178	0.2087	0.057*
C8	0.6313 (3)	1.1373 (11)	0.1600 (3)	0.0504 (14)
H8	0.6185	1.2245	0.1988	0.061*
C9	0.5930 (2)	0.9556 (12)	0.0972 (3)	0.0444 (13)
H9	0.5544	0.9222	0.0935	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0451 (4)	0.0844 (6)	0.0468 (4)	−0.0215 (3)	0.0126 (3)	−0.0037 (3)
O1	0.0346 (18)	0.042 (2)	0.0377 (19)	−0.0112 (15)	0.0110 (15)	−0.0071 (16)
N1	0.030 (2)	0.036 (2)	0.033 (2)	−0.0059 (17)	0.0067 (17)	0.0016 (19)
C1	0.038 (3)	0.036 (3)	0.035 (2)	0.003 (2)	0.014 (2)	0.007 (2)
C2	0.039 (4)	0.026 (4)	0.043 (4)	0.000	0.013 (3)	0.000
C3	0.037 (3)	0.040 (3)	0.039 (3)	−0.009 (2)	0.012 (2)	0.002 (2)
C4	0.040 (3)	0.035 (3)	0.029 (2)	0.000 (2)	0.013 (2)	0.009 (2)
C5	0.040 (3)	0.041 (3)	0.027 (2)	−0.001 (2)	0.012 (2)	0.003 (2)
C6	0.043 (3)	0.044 (3)	0.026 (2)	−0.006 (2)	0.009 (2)	0.005 (2)
C7	0.059 (3)	0.042 (3)	0.030 (2)	−0.007 (3)	0.008 (2)	−0.005 (2)
C8	0.066 (4)	0.052 (4)	0.041 (3)	0.001 (3)	0.029 (3)	−0.007 (3)
C9	0.047 (3)	0.040 (3)	0.050 (3)	0.000 (2)	0.024 (3)	0.001 (3)

Geometric parameters (Å, º) top

Br1—C6	1.900 (4)	C3—H3	0.9300
O1—N1	1.413 (4)	C4—C9	1.396 (6)
O1—C1	1.431 (5)	C4—C5	1.400 (6)
N1—C3	1.270 (6)	C5—C6	1.359 (6)
C1—C2	1.508 (6)	C5—H5	0.9300
C1—H1A	0.9700	C6—C7	1.381 (6)
C1—H1B	0.9700	C7—C8	1.379 (7)
C2—C1ⁱ	1.508 (6)	C7—H7	0.9300
C2—H2A	0.9700	C8—C9	1.372 (7)
C2—H2B	0.9700	C8—H8	0.9300
C3—C4	1.453 (6)	C9—H9	0.9300

N1—O1—C1	109.1 (3)	C9—C4—C3	119.2 (4)
C3—N1—O1	109.9 (3)	C5—C4—C3	122.3 (4)
O1—C1—C2	106.5 (3)	C6—C5—C4	120.0 (4)
O1—C1—H1A	110.4	C6—C5—H5	120.0
C2—C1—H1A	110.4	C4—C5—H5	120.0
O1—C1—H1B	110.4	C5—C6—C7	121.8 (4)
C2—C1—H1B	110.4	C5—C6—Br1	119.3 (3)
H1A—C1—H1B	108.6	C7—C6—Br1	118.9 (4)
C1—C2—C1ⁱ	115.7 (5)	C8—C7—C6	118.5 (5)
C1—C2—H2A	108.4	C8—C7—H7	120.8
C1ⁱ—C2—H2A	108.4	C6—C7—H7	120.8
C1—C2—H2B	108.4	C9—C8—C7	121.0 (4)
C1ⁱ—C2—H2B	108.4	C9—C8—H8	119.5
H2A—C2—H2B	107.4	C7—C8—H8	119.5
N1—C3—C4	122.6 (4)	C8—C9—C4	120.3 (4)
N1—C3—H3	118.7	C8—C9—H9	119.8
C4—C3—H3	118.7	C4—C9—H9	119.8
C9—C4—C5	118.4 (4)

C1—O1—N1—C3	−179.7 (4)	C4—C5—C6—C7	−0.3 (7)
N1—O1—C1—C2	−179.4 (4)	C4—C5—C6—Br1	179.0 (3)
O1—C1—C2—C1ⁱ	65.8 (3)	C5—C6—C7—C8	0.7 (7)
O1—N1—C3—C4	178.7 (4)	Br1—C6—C7—C8	−178.6 (4)
N1—C3—C4—C9	−177.6 (4)	C6—C7—C8—C9	−0.8 (8)
N1—C3—C4—C5	2.1 (7)	C7—C8—C9—C4	0.6 (8)
C9—C4—C5—C6	0.0 (6)	C5—C4—C9—C8	−0.1 (7)
C3—C4—C5—C6	−179.7 (4)	C3—C4—C9—C8	179.6 (5)

Symmetry code: (i) −x+1, y, −z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H3···C3#	0.93	2.36	3.189	148

Experimental details

Crystal data
Chemical formula	C₁₇H₁₆Br₂N₂O₂
M_r	440.14
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	24.397 (3), 4.4848 (4), 17.189 (2)
β (°)	114.009 (2)
V (Å³)	1718.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.73
Crystal size (mm)	0.48 × 0.35 × 0.24

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.210, 0.397
No. of measured, independent and observed [I > 2σ(I)] reflections	3683, 1497, 1179
R_int	0.094
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.133, 1.07
No. of reflections	1497
No. of parameters	105
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.66

Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was generously supported by the Foundation of the Education Department of Gansu Province (No. 0604–01) and the `Qing Lan' Talent Engineering Funds of Lanzhou Jiaotong University (No. QL-03–01 A).

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