4,6-Di­bromo-N-{3-[(4,6-di­bromo-2,3-di­methyl­phenyl)imino]butan-2-yl­idene}-2,3-di­methyl­aniline

Huang, L.; Du, Z.; Liu, W.; Che, F.

doi:10.1107/S1600536813023921

organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page o1496

doi:10.1107/S1600536813023921

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4,6-Dibromo-N-{3-[(4,6-dibromo-2,3-dimethylphenyl)imino]butan-2-ylidene}-2,3-dimethylaniline

Lina Huang,^a Zhengyin Du,^a ^* Wei Liu ^a and Fushou Che ^a

^aKey Laboratory of Eco-Environment-Related Polymer Materials of the Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: clinton_du@126.com

(Received 11 July 2013; accepted 26 August 2013; online 4 September 2013)

The title compound, C₂₀H₂₀Br₄N₂, is a product of the condensation reaction of 4,6-dibromo-2,3-dimethylaniline and butane-2,3-dione. The molecule has a center of symmetry at the mid-point of the central C—C bond. The dihedral angle between the benzene ring and the 1,4-diazabutadiene plane is 78.3 (2)°. Niether hydrogen bonding nor aromatic stacking is observed in the crystal structure.

Related literature

For applications of diimine–metal catalysts, see: Johnson et al. (1995 ). For related structures, see: Gao et al. (2012 ); Sun et al. (2012 ); Popeney et al. (2012 ); Shi et al. (2012 ); Zhang & Ye (2012 ); Killian et al. (1996 ); Yuan et al. (2005 , 2011 ).

Experimental

Crystal data

C₂₀H₂₀Br₄N₂
M_r = 607.98
Monoclinic, P 2₁ /n
a = 5.5582 (6) Å
b = 12.8881 (15) Å
c = 14.8377 (11) Å
β = 98.782 (8)°
V = 1050.43 (19) Å³
Z = 2
Cu Kα radiation
μ = 9.40 mm⁻¹
T = 150 K
0.29 × 0.17 × 0.16 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ) T_min = 0.688, T_max = 1.000
4675 measured reflections
1921 independent reflections
1777 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.135
S = 1.11
1921 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −1.04 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2013); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009 ); molecular graphics: OLEX2; software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813023921/rk2409sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813023921/rk2409Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813023921/rk2409Isup3.cml

checkCIF report

Comment top

Since Brookhart and co–workers discovered nickel and palladium(II) aryl–substituted α–diimine catalysts for olefin polymerization (Johnson et al., 1995), late transition metal catalysis has attracted increasing attention due to their high functional group tolerance and their ability to produce branched or dendritic polymer (Gao et al., 2012; Sun et al., 2012; Popeney et al., 2012; Shi et al., 2012; Zhang & Ye, 2012; Killian et al., 1996; Yuan et al., 2005;2011). In this study, we designed and synthesized the title compound as abidentate ligand (Fig. 1).

The title molecule placed in center of symmetry (middle of C6—C6ⁱ bond). The dihedral angle between the benzene ring and 1,4–diazabutadiene plane is 78.3 (2)°. Niether hydrogen bonding nor aromatic stacking are observed in the crystal structure.

Related literature top

For applications of diimine–metal catalysts, see: Johnson et al. (1995). For related structures, see: Gao et al. (2012); Sun et al. (2012); Popeney et al. (2012); Shi et al. (2012); Zhang & Ye (2012); Killian et al. (1996); Yuan et al. (2005, 2011).

Experimental top

Formic acid (0.5 ml) was added to a stirred solution of 2,3–butanedione (0.09 g, 1.00 mmol) and 4,6–dibromo–2,3–dimethylaniline (0.61 g, 2.2 mmol) in ethanol (10 ml) (Fig. 2). The mixture was refluxed for 24 h, and then cooled and the precipitate was separated by filtration. The solid was recrystallized from EtOH/CH₂Cl₂ (v:v = 10:1), washed with cold ethanol and dried under vacuum to give the title compound1. Yield is 0.50 g (82%). Crystals suitable for X–ray structure determination were grown from a cyclohexane/dichloromethane (v:v = 1:2) solution. Anal. Calcd. for C₂₀H₂₀Br₄N₂: C, 39.51; H, 3.32; Br, 52.57; N, 4.61. Found: C, 39.49; H, 3.31; Br, 52.60 N, 4.60.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis RED (Agilent, 2013); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. Molecular structure of title compound with the atom numbering scheme. Displacement ellipsoids are shown at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius. Symmetry code: (i) -x+1, -y+1, -z+1.
	Fig. 2. A condensation reaction of 2,3–butanedione and 4,6–dibromo-2,3–dimethylaniline.

4,6-Dibromo-N-{3-[(4,6-dibromo-2,3-dimethylphenyl)imino]butan-2-ylidene}-2,3-dimethylaniline top

Crystal data top

C₂₀H₂₀Br₄N₂	F(000) = 588
M_r = 607.98	D_x = 1.922 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.5418 Å
a = 5.5582 (6) Å	Cell parameters from 2210 reflections
b = 12.8881 (15) Å	θ = 3.4–70.4°
c = 14.8377 (11) Å	µ = 9.40 mm⁻¹
β = 98.782 (8)°	T = 150 K
V = 1050.43 (19) Å³	Block, clear light yellow
Z = 2	0.29 × 0.17 × 0.16 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	1921 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1777 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 16.0733 pixels mm^-1	θ_max = 68.2°, θ_min = 4.6°
ω–scans	h = −6→4
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −15→15
T_min = 0.688, T_max = 1.000	l = −17→17
4675 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0802P)² + 2.2115P] where P = (F_o² + 2F_c²)/3
1921 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −1.04 e Å⁻³

Crystal data top

C₂₀H₂₀Br₄N₂	V = 1050.43 (19) Å³
M_r = 607.98	Z = 2
Monoclinic, P2₁/n	Cu Kα radiation
a = 5.5582 (6) Å	µ = 9.40 mm⁻¹
b = 12.8881 (15) Å	T = 150 K
c = 14.8377 (11) Å	0.29 × 0.17 × 0.16 mm
β = 98.782 (8)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	1921 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	1777 reflections with I > 2σ(I)
T_min = 0.688, T_max = 1.000	R_int = 0.029
4675 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.11	Δρ_max = 0.70 e Å⁻³
1921 reflections	Δρ_min = −1.04 e Å⁻³
121 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Br2	0.84461 (11)	0.31214 (5)	0.68427 (4)	0.0431 (2)
N1	0.5517 (8)	0.5134 (4)	0.6182 (3)	0.0327 (9)
C2	0.2754 (9)	0.4881 (4)	0.8311 (3)	0.0269 (9)
C3	0.6169 (9)	0.3862 (4)	0.7425 (3)	0.0277 (10)
C4	0.4939 (9)	0.4723 (4)	0.7012 (3)	0.0275 (10)
C5	0.3261 (10)	0.5238 (4)	0.7464 (3)	0.0296 (10)
C6	0.4633 (10)	0.4739 (4)	0.5417 (3)	0.0341 (11)
C7	0.5762 (9)	0.3504 (4)	0.8271 (3)	0.0293 (10)
H7	0.6616	0.2939	0.8548	0.035*
C1	0.1862 (10)	0.6189 (4)	0.7022 (3)	0.0341 (11)
H1A	0.0200	0.5999	0.6813	0.051*
H1B	0.2604	0.6422	0.6515	0.051*
H1C	0.1912	0.6736	0.7463	0.051*
C8	0.2980 (12)	0.3814 (5)	0.5268 (3)	0.0438 (14)
H8A	0.1479	0.4010	0.4898	0.066*
H8B	0.2654	0.3560	0.5845	0.066*
H8C	0.3751	0.3278	0.4964	0.066*
C9	0.0867 (10)	0.5414 (4)	0.8773 (4)	0.0378 (12)
H9A	0.1616	0.5968	0.9148	0.057*
H9B	0.0170	0.4924	0.9146	0.057*
H9C	−0.0388	0.5691	0.8321	0.057*
C10	0.4039 (9)	0.4017 (4)	0.8689 (3)	0.0277 (10)
Br1	0.34078 (11)	0.34478 (4)	0.98167 (3)	0.0379 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br2	0.0473 (4)	0.0546 (4)	0.0317 (3)	−0.0012 (3)	0.0199 (3)	−0.0110 (2)
N1	0.043 (2)	0.043 (2)	0.0129 (18)	−0.0155 (19)	0.0064 (16)	0.0029 (17)
C2	0.035 (2)	0.030 (2)	0.017 (2)	−0.0044 (19)	0.0075 (17)	−0.0020 (17)
C3	0.038 (2)	0.032 (2)	0.015 (2)	−0.005 (2)	0.0109 (17)	−0.0075 (18)
C4	0.042 (3)	0.032 (2)	0.0096 (19)	−0.012 (2)	0.0066 (17)	−0.0023 (17)
C5	0.047 (3)	0.026 (2)	0.015 (2)	−0.006 (2)	0.0046 (19)	0.0011 (18)
C6	0.047 (3)	0.044 (3)	0.013 (2)	−0.016 (2)	0.0102 (19)	0.001 (2)
C7	0.042 (3)	0.025 (2)	0.022 (2)	−0.003 (2)	0.007 (2)	−0.0012 (17)
C1	0.053 (3)	0.029 (2)	0.019 (2)	−0.004 (2)	0.001 (2)	0.0107 (19)
C8	0.061 (4)	0.058 (3)	0.013 (2)	−0.031 (3)	0.007 (2)	0.000 (2)
C9	0.045 (3)	0.042 (3)	0.029 (3)	0.005 (2)	0.015 (2)	−0.003 (2)
C10	0.044 (3)	0.030 (2)	0.0102 (18)	−0.004 (2)	0.0077 (17)	0.0000 (17)
Br1	0.0605 (4)	0.0407 (4)	0.0159 (3)	0.0013 (2)	0.0171 (2)	0.00654 (19)

Geometric parameters (Å, º) top

Br2—C3	1.895 (5)	C7—H7	0.9300
N1—C4	1.422 (6)	C7—C10	1.385 (7)
N1—C6	1.273 (6)	C1—H1A	0.9600
C2—C5	1.406 (6)	C1—H1B	0.9600
C2—C9	1.504 (7)	C1—H1C	0.9600
C2—C10	1.395 (7)	C8—H8A	0.9600
C3—C4	1.395 (7)	C8—H8B	0.9600
C3—C7	1.388 (6)	C8—H8C	0.9600
C4—C5	1.397 (7)	C9—H9A	0.9600
C5—C1	1.543 (7)	C9—H9B	0.9600
C6—C6ⁱ	1.518 (9)	C9—H9C	0.9600
C6—C8	1.501 (7)	C10—Br1	1.908 (4)

C6—N1—C4	121.1 (4)	C5—C1—H1B	109.5
C5—C2—C9	120.5 (5)	C5—C1—H1C	109.5
C10—C2—C5	117.4 (4)	H1A—C1—H1B	109.5
C10—C2—C9	122.1 (4)	H1A—C1—H1C	109.5
C4—C3—Br2	121.1 (3)	H1B—C1—H1C	109.5
C7—C3—Br2	117.2 (4)	C6—C8—H8A	109.5
C7—C3—C4	121.6 (4)	C6—C8—H8B	109.5
C3—C4—N1	121.1 (4)	C6—C8—H8C	109.5
C3—C4—C5	119.1 (4)	H8A—C8—H8B	109.5
C5—C4—N1	119.6 (4)	H8A—C8—H8C	109.5
C2—C5—C1	118.9 (5)	H8B—C8—H8C	109.5
C4—C5—C2	120.9 (4)	C2—C9—H9A	109.5
C4—C5—C1	120.2 (4)	C2—C9—H9B	109.5
N1—C6—C6ⁱ	115.8 (6)	C2—C9—H9C	109.5
N1—C6—C8	126.4 (4)	H9A—C9—H9B	109.5
C8—C6—C6ⁱ	117.8 (5)	H9A—C9—H9C	109.5
C3—C7—H7	121.1	H9B—C9—H9C	109.5
C10—C7—C3	117.8 (5)	C2—C10—Br1	120.6 (4)
C10—C7—H7	121.1	C7—C10—C2	123.2 (4)
C5—C1—H1A	109.5	C7—C10—Br1	116.2 (4)

Br2—C3—C4—N1	−6.1 (6)	C5—C2—C10—C7	−0.1 (7)
Br2—C3—C4—C5	179.4 (3)	C5—C2—C10—Br1	−178.0 (4)
Br2—C3—C7—C10	−177.8 (4)	C6—N1—C4—C3	82.4 (7)
N1—C4—C5—C2	−176.5 (4)	C6—N1—C4—C5	−103.1 (6)
N1—C4—C5—C1	5.7 (7)	C7—C3—C4—N1	174.7 (4)
C3—C4—C5—C2	−1.9 (7)	C7—C3—C4—C5	0.2 (7)
C3—C4—C5—C1	−179.7 (4)	C9—C2—C5—C4	−177.4 (5)
C3—C7—C10—C2	−1.5 (7)	C9—C2—C5—C1	0.4 (7)
C3—C7—C10—Br1	176.5 (4)	C9—C2—C10—C7	179.1 (5)
C4—N1—C6—C6ⁱ	179.2 (6)	C9—C2—C10—Br1	1.2 (7)
C4—N1—C6—C8	−1.5 (10)	C10—C2—C5—C4	1.8 (7)
C4—C3—C7—C10	1.5 (7)	C10—C2—C5—C1	179.6 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀Br₄N₂
M_r	607.98
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	5.5582 (6), 12.8881 (15), 14.8377 (11)
β (°)	98.782 (8)
V (Å³)	1050.43 (19)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	9.40
Crystal size (mm)	0.29 × 0.17 × 0.16

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013)
T_min, T_max	0.688, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4675, 1921, 1777
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.135, 1.11
No. of reflections	1921
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −1.04

Computer programs: CrysAlis PRO (Agilent, 2013), CrysAlis RED (Agilent, 2013), SUPERFLIP (Palatinus & Chapuis, 2007), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

We gratefully acknowledge the Natural Science Foundation of China (20702042, 21262028), the Program for Changjiang Scholars and Innovative Research Teams in Universities of the Ministry of Education of China (IRT1177), the Natural Science Foundation of Gansu Province (1208RJZA140) and the NWNU Young Teachers Reseach Improving Program (NWNU–LKQN–10–11) for financial support.

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