1,4-Di­bromo-2,5-di-p-toluoyl­benzene

He, G.-K.; Song, G.-L.; Chen, C.; Zhu, H.-J.

doi:10.1107/S160053681302237X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1444

doi:10.1107/S160053681302237X

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1,4-Dibromo-2,5-di-p-toluoylbenzene

Guang-Ke He,^a Guang-Liang Song,^a Chen Chen ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhjnjut@hotmail.com

(Received 6 August 2013; accepted 9 August 2013; online 17 August 2013)

In the title compound, C₂₂H₁₆Br₂O₂, which has approximate non-crystallographic inversion symmetry, the dihedral angles between the central ring and the pendant rings are 89.1 (4) and 82.4 (3)°; the dihedral angle between the pendant rings is 12.1 (4)°. In the crystal, the packing is influenced by van der Waals forces and no aromatic π–π stacking is observed.

Related literature

For background to the applications of the title compound, see: Shimizu et al. (2011 ). For further synthetic details, see: Chardonnens & Salamin (1968 ).

Experimental

Crystal data

C₂₂H₁₆Br₂O₂
M_r = 472.17
Monoclinic, P 2₁ /n
a = 9.855 (2) Å
b = 12.064 (2) Å
c = 16.345 (3) Å
β = 97.61 (3)°
V = 1926.2 (7) Å³
Z = 4
Mo Kα radiation
μ = 4.22 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.486, T_max = 0.678
3664 measured reflections
3452 independent reflections
1518 reflections with I > 2σ(I)
R_int = 0.054
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.133
S = 1.00
3452 reflections
235 parameters
48 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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 I, s. DOI: 10.1107/S160053681302237X/hb7121sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681302237X/hb7121Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681302237X/hb7121Isup3.cml

checkCIF report

Comment top

The title compound, 1,4-dibromo-2,5-di-p-toluoylbenzene is an important intermediate not only for manufacturing OLED materials, but also for sensing and switching devices that utilize solid-state luminescence as an output. (Shimizu et al., 2011). We now report here its the crystal structure.

The molecular structure of (I) is shown in Fig. 1, and the selected geometric parameters are give in Table 1. The dihedral angles between the phenyl rings in p-toluoyl and the dibromobenzene are 89.14 (2)° and 82.41 (2)°. The phenyl rings are almost parallel with the maximum deviation of 0.26 (8)°. The crystal packing of the molecules in the crystal is influenced by van der Waals forces.

Related literature top

For background to the applications of the title compound, see: Shimizu et al. (2011). For further synthetic details, see: Chardonnens & Salamin (1968).

Experimental top

The title compund was synthesized according to the published procedure (Chardonnens & Salamin, 1968). Colourless blocks were obtained by dissolving it (0.5 g) in tetrahydrofuran (20 ml) and evaporating the solvent slowly at room temperature for about 10 d.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I).

1,4-Dibromo-2,5-di-p-toluoylbenzene top

Crystal data top

C₂₂H₁₆Br₂O₂	F(000) = 936
M_r = 472.17	D_x = 1.628 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 9.855 (2) Å	θ = 10–13°
b = 12.064 (2) Å	µ = 4.22 mm⁻¹
c = 16.345 (3) Å	T = 293 K
β = 97.61 (3)°	Block, colourless
V = 1926.2 (7) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1518 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 25.2°, θ_min = 2.1°
ω/2θ scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
T_min = 0.486, T_max = 0.678	l = 0→19
3664 measured reflections	3 standard reflections every 200 reflections
3452 independent reflections	intensity decay: none

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.050P)²] where P = (F_o² + 2F_c²)/3
3452 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.46 e Å⁻³
48 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₂₂H₁₆Br₂O₂	V = 1926.2 (7) Å³
M_r = 472.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.855 (2) Å	µ = 4.22 mm⁻¹
b = 12.064 (2) Å	T = 293 K
c = 16.345 (3) Å	0.20 × 0.10 × 0.10 mm
β = 97.61 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1518 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.054
T_min = 0.486, T_max = 0.678	3 standard reflections every 200 reflections
3664 measured reflections	intensity decay: none
3452 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	48 restraints
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.46 e Å⁻³
3452 reflections	Δρ_min = −0.40 e Å⁻³
235 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	0.19197 (8)	0.40011 (8)	0.45593 (5)	0.0639 (3)
O1	−0.2881 (7)	0.1341 (5)	0.3699 (4)	0.095 (2)
C1	−0.6659 (9)	0.2445 (8)	0.6544 (5)	0.105 (4)
H1A	−0.6484	0.3109	0.6864	0.158*
H1B	−0.6483	0.1810	0.6897	0.158*
H1C	−0.7597	0.2436	0.6295	0.158*
Br2	−0.44399 (8)	0.39910 (9)	0.28265 (5)	0.0788 (4)
O2	0.0549 (6)	0.6656 (5)	0.3651 (3)	0.0740 (18)
C2	−0.5731 (9)	0.2412 (9)	0.5877 (5)	0.066 (3)
C3	−0.5798 (8)	0.1529 (7)	0.5314 (5)	0.060 (2)
H3A	−0.6427	0.0962	0.5349	0.072*
C4	−0.4954 (8)	0.1491 (7)	0.4718 (5)	0.059 (2)
H4A	−0.5023	0.0903	0.4347	0.071*
C5	−0.3983 (7)	0.2326 (7)	0.4658 (4)	0.045 (2)
C6	−0.3985 (8)	0.3206 (7)	0.5191 (5)	0.058 (2)
H6A	−0.3403	0.3800	0.5138	0.070*
C7	−0.4805 (10)	0.3237 (7)	0.5792 (5)	0.068 (3)
H7A	−0.4738	0.3832	0.6156	0.081*
C8	−0.3040 (8)	0.2209 (7)	0.4062 (5)	0.053 (2)
C9	−0.2155 (7)	0.3172 (6)	0.3889 (4)	0.0425 (18)
C10	−0.0778 (8)	0.3180 (6)	0.4244 (4)	0.0504 (19)
H10A	−0.0436	0.2619	0.4603	0.061*
C11	0.0067 (6)	0.4036 (6)	0.4052 (4)	0.0404 (17)
C12	−0.0358 (7)	0.4850 (6)	0.3498 (4)	0.0422 (18)
C13	−0.1739 (7)	0.4818 (6)	0.3136 (4)	0.0483 (19)
H13A	−0.2061	0.5361	0.2755	0.058*
C14	−0.2627 (7)	0.4003 (7)	0.3332 (4)	0.0464 (18)
C15	0.0537 (8)	0.5788 (7)	0.3286 (4)	0.051 (2)
C16	0.1406 (7)	0.5582 (7)	0.2634 (4)	0.0385 (18)
C17	0.1434 (7)	0.4579 (7)	0.2242 (4)	0.051 (2)
H17A	0.0876	0.4002	0.2374	0.062*
C18	0.2315 (7)	0.4427 (7)	0.1637 (4)	0.050 (2)
H18A	0.2341	0.3739	0.1383	0.060*
C19	0.3118 (7)	0.5248 (8)	0.1418 (4)	0.053 (2)
C20	0.3079 (8)	0.6253 (8)	0.1798 (5)	0.067 (3)
H20A	0.3628	0.6828	0.1652	0.080*
C21	0.2236 (8)	0.6427 (7)	0.2394 (5)	0.065 (2)
H21A	0.2220	0.7120	0.2642	0.078*
C22	0.4080 (8)	0.5080 (8)	0.0781 (4)	0.085 (3)
H22A	0.3981	0.4339	0.0567	0.127*
H22B	0.5006	0.5192	0.1033	0.127*
H22C	0.3864	0.5600	0.0339	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0470 (5)	0.0762 (6)	0.0651 (6)	−0.0002 (5)	−0.0061 (4)	0.0053 (5)
O1	0.116 (6)	0.083 (5)	0.098 (5)	−0.033 (4)	0.055 (4)	−0.022 (4)
C1	0.081 (7)	0.159 (11)	0.087 (7)	0.057 (7)	0.054 (6)	0.042 (7)
Br2	0.0463 (6)	0.1113 (8)	0.0740 (7)	−0.0026 (6)	−0.0098 (4)	0.0075 (6)
O2	0.091 (5)	0.074 (5)	0.064 (4)	−0.010 (4)	0.039 (3)	−0.018 (3)
C2	0.058 (6)	0.095 (8)	0.046 (5)	0.018 (5)	0.013 (5)	0.029 (6)
C3	0.045 (5)	0.065 (6)	0.072 (6)	−0.006 (4)	0.013 (5)	0.018 (5)
C4	0.054 (5)	0.076 (6)	0.049 (5)	0.005 (5)	0.010 (4)	0.011 (5)
C5	0.042 (5)	0.056 (5)	0.040 (5)	−0.009 (4)	0.012 (4)	0.002 (4)
C6	0.052 (5)	0.074 (7)	0.047 (5)	−0.013 (5)	0.002 (4)	−0.009 (5)
C7	0.094 (7)	0.062 (6)	0.053 (6)	0.004 (6)	0.033 (5)	0.006 (5)
C8	0.045 (5)	0.061 (6)	0.052 (5)	−0.003 (5)	0.008 (4)	−0.018 (5)
C9	0.046 (4)	0.051 (5)	0.035 (4)	−0.001 (4)	0.023 (3)	0.002 (3)
C10	0.063 (4)	0.051 (4)	0.040 (4)	0.005 (4)	0.015 (3)	0.008 (4)
C11	0.038 (4)	0.045 (4)	0.041 (4)	0.005 (3)	0.012 (3)	−0.003 (4)
C12	0.050 (4)	0.056 (5)	0.026 (4)	0.002 (4)	0.022 (3)	0.006 (3)
C13	0.054 (4)	0.058 (5)	0.032 (4)	0.010 (4)	0.000 (3)	0.014 (4)
C14	0.047 (4)	0.056 (4)	0.037 (4)	0.001 (4)	0.010 (3)	−0.001 (4)
C15	0.052 (5)	0.071 (7)	0.032 (5)	−0.005 (5)	0.011 (4)	−0.006 (4)
C16	0.034 (4)	0.058 (5)	0.025 (4)	0.005 (4)	0.008 (3)	0.001 (4)
C17	0.043 (5)	0.078 (6)	0.037 (5)	−0.001 (4)	0.023 (4)	−0.001 (4)
C18	0.046 (5)	0.050 (5)	0.055 (5)	0.005 (4)	0.007 (4)	0.001 (4)
C19	0.042 (5)	0.085 (7)	0.032 (5)	0.015 (5)	0.010 (4)	0.010 (5)
C20	0.063 (6)	0.083 (8)	0.056 (6)	−0.025 (5)	0.016 (5)	0.010 (5)
C21	0.065 (6)	0.074 (6)	0.060 (6)	−0.011 (5)	0.019 (5)	0.003 (5)
C22	0.070 (6)	0.136 (9)	0.054 (6)	−0.015 (6)	0.032 (5)	0.004 (6)

Geometric parameters (Å, º) top

Br1—C11	1.904 (6)	C10—C11	1.388 (9)
O1—C8	1.224 (8)	C10—H10A	0.9300
C1—C2	1.514 (10)	C11—C12	1.363 (9)
C1—H1A	0.9600	C12—C13	1.410 (9)
C1—H1B	0.9600	C12—C15	1.503 (9)
C1—H1C	0.9600	C13—C14	1.382 (9)
Br2—C14	1.867 (7)	C13—H13A	0.9300
O2—C15	1.204 (8)	C15—C16	1.475 (9)
C2—C7	1.369 (11)	C16—C17	1.371 (9)
C2—C3	1.403 (11)	C16—C21	1.395 (10)
C3—C4	1.363 (9)	C17—C18	1.411 (9)
C3—H3A	0.9300	C17—H17A	0.9300
C4—C5	1.402 (10)	C18—C19	1.346 (9)
C4—H4A	0.9300	C18—H18A	0.9300
C5—C6	1.374 (9)	C19—C20	1.365 (10)
C5—C8	1.439 (9)	C19—C22	1.512 (9)
C6—C7	1.352 (9)	C20—C21	1.378 (10)
C6—H6A	0.9300	C20—H20A	0.9300
C7—H7A	0.9300	C21—H21A	0.9300
C8—C9	1.502 (10)	C22—H22A	0.9600
C9—C14	1.391 (9)	C22—H22B	0.9600
C9—C10	1.404 (9)	C22—H22C	0.9600

C2—C1—H1A	109.5	C11—C12—C13	117.0 (7)
C2—C1—H1B	109.5	C11—C12—C15	123.8 (7)
H1A—C1—H1B	109.5	C13—C12—C15	119.1 (7)
C2—C1—H1C	109.5	C14—C13—C12	121.8 (7)
H1A—C1—H1C	109.5	C14—C13—H13A	119.1
H1B—C1—H1C	109.5	C12—C13—H13A	119.1
C7—C2—C3	117.3 (8)	C13—C14—C9	119.8 (6)
C7—C2—C1	121.9 (9)	C13—C14—Br2	120.1 (6)
C3—C2—C1	120.8 (9)	C9—C14—Br2	120.1 (6)
C4—C3—C2	120.9 (8)	O2—C15—C16	122.5 (7)
C4—C3—H3A	119.5	O2—C15—C12	120.5 (7)
C2—C3—H3A	119.5	C16—C15—C12	117.0 (7)
C3—C4—C5	120.9 (8)	C17—C16—C21	117.7 (7)
C3—C4—H4A	119.6	C17—C16—C15	122.4 (7)
C5—C4—H4A	119.6	C21—C16—C15	119.9 (7)
C6—C5—C4	116.9 (7)	C16—C17—C18	119.6 (7)
C6—C5—C8	124.1 (8)	C16—C17—H17A	120.2
C4—C5—C8	119.0 (8)	C18—C17—H17A	120.2
C7—C6—C5	122.2 (8)	C19—C18—C17	121.9 (8)
C7—C6—H6A	118.9	C19—C18—H18A	119.0
C5—C6—H6A	118.9	C17—C18—H18A	119.0
C6—C7—C2	121.6 (9)	C18—C19—C20	118.7 (7)
C6—C7—H7A	119.2	C18—C19—C22	121.9 (8)
C2—C7—H7A	119.2	C20—C19—C22	119.4 (9)
O1—C8—C5	123.2 (8)	C19—C20—C21	120.8 (8)
O1—C8—C9	117.1 (7)	C19—C20—H20A	119.6
C5—C8—C9	119.7 (7)	C21—C20—H20A	119.6
C14—C9—C10	119.1 (7)	C20—C21—C16	121.2 (8)
C14—C9—C8	121.9 (7)	C20—C21—H21A	119.4
C10—C9—C8	118.8 (7)	C16—C21—H21A	119.4
C11—C10—C9	119.2 (7)	C19—C22—H22A	109.5
C11—C10—H10A	120.4	C19—C22—H22B	109.5
C9—C10—H10A	120.4	H22A—C22—H22B	109.5
C12—C11—C10	123.1 (7)	C19—C22—H22C	109.5
C12—C11—Br1	119.9 (5)	H22A—C22—H22C	109.5
C10—C11—Br1	117.0 (6)	H22B—C22—H22C	109.5

C7—C2—C3—C4	1.1 (12)	C11—C12—C13—C14	0.1 (10)
C1—C2—C3—C4	−179.3 (7)	C15—C12—C13—C14	−177.3 (7)
C2—C3—C4—C5	0.8 (12)	C12—C13—C14—C9	−1.3 (11)
C3—C4—C5—C6	−3.8 (11)	C12—C13—C14—Br2	−179.4 (5)
C3—C4—C5—C8	175.1 (7)	C10—C9—C14—C13	0.1 (10)
C4—C5—C6—C7	5.0 (11)	C8—C9—C14—C13	−174.2 (7)
C8—C5—C6—C7	−173.8 (7)	C10—C9—C14—Br2	178.2 (5)
C5—C6—C7—C2	−3.2 (13)	C8—C9—C14—Br2	3.9 (9)
C3—C2—C7—C6	0.0 (12)	C11—C12—C15—O2	−92.6 (10)
C1—C2—C7—C6	−179.6 (8)	C13—C12—C15—O2	84.6 (9)
C6—C5—C8—O1	166.2 (8)	C11—C12—C15—C16	86.1 (8)
C4—C5—C8—O1	−12.7 (12)	C13—C12—C15—C16	−96.7 (8)
C6—C5—C8—C9	−11.4 (11)	O2—C15—C16—C17	177.2 (7)
C4—C5—C8—C9	169.8 (7)	C12—C15—C16—C17	−1.4 (10)
O1—C8—C9—C14	98.5 (9)	O2—C15—C16—C21	−2.9 (11)
C5—C8—C9—C14	−83.8 (9)	C12—C15—C16—C21	178.4 (7)
O1—C8—C9—C10	−75.8 (9)	C21—C16—C17—C18	1.8 (10)
C5—C8—C9—C10	101.9 (8)	C15—C16—C17—C18	−178.4 (6)
C14—C9—C10—C11	2.1 (10)	C16—C17—C18—C19	−1.3 (11)
C8—C9—C10—C11	176.6 (6)	C17—C18—C19—C20	0.4 (11)
C9—C10—C11—C12	−3.4 (10)	C17—C18—C19—C22	178.9 (7)
C9—C10—C11—Br1	179.7 (5)	C18—C19—C20—C21	0.0 (12)
C10—C11—C12—C13	2.2 (10)	C22—C19—C20—C21	−178.5 (7)
Br1—C11—C12—C13	179.1 (5)	C19—C20—C21—C16	0.5 (12)
C10—C11—C12—C15	179.5 (7)	C17—C16—C21—C20	−1.4 (11)
Br1—C11—C12—C15	−3.6 (9)	C15—C16—C21—C20	178.7 (7)

Experimental details

Crystal data
Chemical formula	C₂₂H₁₆Br₂O₂
M_r	472.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.855 (2), 12.064 (2), 16.345 (3)
β (°)	97.61 (3)
V (Å³)	1926.2 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.22
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.486, 0.678
No. of measured, independent and observed [I > 2σ(I)] reflections	3664, 3452, 1518
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.133, 1.00
No. of reflections	3452
No. of parameters	235
No. of restraints	48
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.40

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Center of Test and Analysis, Nanjing University, for the data collection.

References

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Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
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