4,4,5,5-Tetra­methyl-2-[1,3,6,8-tetra­bromo-7-(4,4,5,5-tetra­methyl-1,3,2-dioxaborolan-2-yl)pyren-2-yl]-1,3,2-dioxaborolane

Chen, Y.; Yu, W.; Liu, Z.; Yu, P.

doi:10.1107/S1600536812006095

organic compounds

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4,4,5,5-Tetramethyl-2-[1,3,6,8-tetrabromo-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyren-2-yl]-1,3,2-dioxaborolane

Ying Chen,^a Wen-tao Yu,^b Zhi-qiang Liu ^b and Ping Yu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China, and ^bState Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: yupping@sdu.edu.cn

(Received 14 January 2012; accepted 11 February 2012; online 17 February 2012)

The complete molecule of the title compound, C₂₈H₂₈B₂Br₄O₄, is generated by the application of a centre of inversion. In the molecule, the BO₂ plane is perpendicular to that through the pyrene ring [dihedral angle = 86.27 (13)°]. In the crystal, molecules stack into columns along the b axis, the closest contact between these being of the type C—Br⋯π.

Related literature

For background to the reactions of pyrene, see: Miura & Yamano (1995 ). For the structure of the non-brominated derivative, see: Coventry et al. (2005 ).

Experimental

Crystal data

C₂₈H₂₈B₂Br₄O₄
M_r = 769.76
Monoclinic, P 2₁ /c
a = 15.5047 (10) Å
b = 7.5136 (5) Å
c = 13.9191 (9) Å
β = 113.961 (1)°
V = 1481.78 (17) Å³
Z = 2
Mo Kα radiation
μ = 5.46 mm⁻¹
T = 296 K
0.34 × 0.24 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.258, T_max = 0.475
8745 measured reflections
3344 independent reflections
2488 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.109
S = 1.01
3344 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C3–C5/C8/C9/C14 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—Br2⋯Cg1ⁱ	1.90 (1)	3.48 (1)	4.921 (3)	130 (1)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX-2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812006095/tk5049sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812006095/tk5049Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812006095/tk5049Isup3.cml

checkCIF report

Comment top

The chemistry of pyrene is strongly position-dependent. For example, in the bromination reaction of 2,7-di-t-butylpyrene, the bromide atoms were connected at the 4,5,9,10-positions of pyrene (Miura & Yamano, 1995). However, to our surprise, when the t-butyl group is changed to pinacol boronate, the bromination reaction resulted in bromination at the 1,3,6,8-positions as confirmed by the crystal structure described herein.

The molecule, Fig. 1, is centrosymmetric. Before bromination, the two BO₂ groups are nearly co-planar with the pyrene ring (Coventry et al., 2005). However, they become nearly perpendicular after bromination (dihedral angle 86.27 (13)°).

The molecules pack into columns along the b axis, Fig. 2. The most prominent contacts in the structure appear to be of the type C—Br···π, Table 1.

Related literature top

For background to the reactions of pyrene, see: Miura & Yamano (1995). For the structure of the non-brominated derivative, see: Coventry et al. (2005).

Experimental top

The title compound was synthesized via a one-step bromination reaction. The precursor compound, 2,7-di-Bpinpyrene (pin = O₂C₂Me₄) was prepared using the method of Ir-catalyzed borylation (Coventry et al., 2005). To a stirred mixture of 1.36 g (3.0 mmol) of 2,7-di-Bpinpyrene and a small amount of Fe powder (ca 0.10 g) in 80 ml of CCl₄ was added drop-wise a solution of 2.88 g (0.78 mL, 18 mmol) of bromine in 20 ml of CCl₄ at room temperature. After stirring for 5 h, the mixture was slowly poured into ice water. Then the organic layer was collected and washed with aqueous Na₂S₂O₃ and dried over MgSO₄. After evaporation, the residue was crystallized from hexane, giving 1.80 g (78% yield) of gray powdered product. Crystals were grown by slow evaporation from its hexane/dichloromethane solution.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX-2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at 50% probability level.
	Fig. 2. The packing in the title molecules in crystal viewed approximately down the b axis. Intermolecular Br···C (3.414 (3) Å) contacts, being representative of the Br···π contacts are shown as dashed lines.

4,4,5,5-Tetramethyl-2-[1,3,6,8-tetrabromo-7-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)pyren-2-yl]-1,3,2-dioxaborolane top

Crystal data top

C₂₈H₂₈B₂Br₄O₄	F(000) = 756
M_r = 769.76	D_x = 1.725 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3344 reflections
a = 15.5047 (10) Å	θ = 2.9–27.4°
b = 7.5136 (5) Å	µ = 5.46 mm⁻¹
c = 13.9191 (9) Å	T = 296 K
β = 113.961 (1)°	Pod, colourless
V = 1481.78 (17) Å³	0.34 × 0.24 × 0.16 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	3344 independent reflections
Radiation source: fine-focus sealed tube	2488 reflections with i > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −20→18
T_min = 0.258, T_max = 0.475	k = −9→9
8745 measured reflections	l = −9→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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0653P)² + 0.4343P] where P = (F_o² + 2F_c²)/3
3344 reflections	(Δ/σ)_max = 0.007
176 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

C₂₈H₂₈B₂Br₄O₄	V = 1481.78 (17) Å³
M_r = 769.76	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.5047 (10) Å	µ = 5.46 mm⁻¹
b = 7.5136 (5) Å	T = 296 K
c = 13.9191 (9) Å	0.34 × 0.24 × 0.16 mm
β = 113.961 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3344 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2488 reflections with i > 2σ(I)
T_min = 0.258, T_max = 0.475	R_int = 0.026
8745 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.01	Δρ_max = 0.60 e Å⁻³
3344 reflections	Δρ_min = −0.67 e Å⁻³
176 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	0.77662 (3)	0.70726 (6)	0.97202 (4)	0.07199 (18)
Br2	0.58141 (3)	0.07842 (5)	0.79828 (3)	0.06680 (17)
O1	0.73711 (17)	0.4128 (3)	0.75325 (18)	0.0521 (6)
O2	0.81831 (17)	0.2540 (4)	0.89972 (18)	0.0603 (7)
C1	0.8075 (4)	0.3192 (8)	0.6352 (3)	0.0949 (17)
H1A	0.7619	0.2248	0.6114	0.142*
H1B	0.8652	0.2812	0.6316	0.142*
H1C	0.7835	0.4218	0.5914	0.142*
C2	0.8258 (2)	0.3653 (5)	0.7461 (3)	0.0537 (9)
C3	0.6666 (2)	0.4017 (4)	0.8923 (2)	0.0380 (6)
C4	0.5917 (2)	0.2876 (4)	0.8788 (2)	0.0395 (7)
C5	0.5247 (2)	0.3199 (4)	0.9201 (2)	0.0377 (6)
C6	0.4480 (2)	0.2033 (4)	0.9060 (3)	0.0503 (8)
H6	0.4417	0.0985	0.8681	0.060*
C7	0.3844 (2)	0.2413 (5)	0.9460 (3)	0.0522 (9)
H7	0.3348	0.1628	0.9345	0.063*
C8	0.6087 (2)	0.6003 (4)	0.9941 (2)	0.0404 (7)
C9	0.6728 (2)	0.5543 (4)	0.9499 (3)	0.0424 (7)
C10	0.8662 (3)	0.2212 (5)	0.8302 (3)	0.0588 (10)
C11	0.8343 (5)	0.0358 (6)	0.7828 (6)	0.119 (2)
H11A	0.8451	−0.0486	0.8382	0.178*
H11B	0.8697	0.0015	0.7429	0.178*
H11C	0.7683	0.0387	0.7375	0.178*
C12	0.8844 (4)	0.5382 (7)	0.7748 (5)	0.0971 (17)
H12A	0.8460	0.6359	0.7364	0.146*
H12B	0.9378	0.5261	0.7571	0.146*
H12C	0.9059	0.5600	0.8489	0.146*
C13	0.9711 (3)	0.2251 (10)	0.8940 (4)	0.113 (2)
H13A	0.9882	0.3348	0.9325	0.169*
H13B	1.0032	0.2160	0.8479	0.169*
H13C	0.9889	0.1269	0.9423	0.169*
C14	0.53370 (18)	0.4799 (4)	0.9788 (2)	0.0340 (6)
B1	0.7425 (2)	0.3542 (5)	0.8473 (3)	0.0397 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0592 (3)	0.0748 (3)	0.1085 (4)	−0.02956 (19)	0.0614 (3)	−0.0371 (2)
Br2	0.0623 (3)	0.0677 (3)	0.0883 (3)	−0.01639 (18)	0.0490 (2)	−0.0388 (2)
O1	0.0482 (13)	0.0696 (15)	0.0472 (13)	0.0173 (11)	0.0281 (11)	0.0108 (11)
O2	0.0525 (14)	0.0954 (19)	0.0458 (13)	0.0283 (13)	0.0331 (12)	0.0213 (13)
C1	0.124 (4)	0.122 (4)	0.058 (3)	0.044 (4)	0.056 (3)	0.016 (3)
C2	0.053 (2)	0.070 (2)	0.0533 (19)	0.0117 (17)	0.0365 (17)	0.0064 (17)
C3	0.0304 (14)	0.0502 (17)	0.0361 (15)	0.0019 (12)	0.0164 (12)	−0.0025 (13)
C4	0.0353 (15)	0.0459 (16)	0.0396 (15)	0.0015 (12)	0.0175 (13)	−0.0087 (13)
C5	0.0303 (14)	0.0468 (16)	0.0389 (15)	−0.0028 (12)	0.0171 (13)	−0.0058 (13)
C6	0.0470 (18)	0.0480 (19)	0.066 (2)	−0.0136 (14)	0.0337 (17)	−0.0207 (16)
C7	0.0449 (18)	0.0520 (19)	0.072 (2)	−0.0169 (15)	0.0358 (18)	−0.0202 (17)
C8	0.0342 (15)	0.0481 (17)	0.0442 (16)	−0.0061 (13)	0.0213 (13)	−0.0086 (13)
C9	0.0312 (15)	0.0519 (18)	0.0493 (18)	−0.0071 (13)	0.0218 (14)	−0.0045 (14)
C10	0.054 (2)	0.073 (2)	0.070 (2)	0.0207 (18)	0.0466 (19)	0.0189 (19)
C11	0.192 (7)	0.055 (3)	0.183 (6)	0.007 (3)	0.153 (6)	0.004 (3)
C12	0.103 (4)	0.078 (3)	0.144 (5)	−0.016 (3)	0.086 (4)	−0.003 (3)
C13	0.057 (3)	0.197 (7)	0.090 (4)	0.045 (4)	0.035 (3)	0.029 (4)
C14	0.0288 (13)	0.0408 (15)	0.0354 (15)	−0.0024 (11)	0.0162 (12)	−0.0050 (12)
B1	0.0338 (17)	0.0473 (19)	0.0427 (19)	0.0011 (14)	0.0204 (15)	−0.0029 (15)

Geometric parameters (Å, º) top

Br1—C9	1.899 (3)	C6—H6	0.9300
Br2—C4	1.899 (3)	C7—C8ⁱ	1.432 (4)
O1—B1	1.351 (4)	C7—H7	0.9300
O1—C2	1.463 (4)	C8—C9	1.408 (4)
O2—B1	1.336 (4)	C8—C14	1.419 (4)
O2—C10	1.460 (4)	C8—C7ⁱ	1.432 (4)
C1—C2	1.492 (5)	C10—C13	1.504 (6)
C1—H1A	0.9600	C10—C11	1.535 (7)
C1—H1B	0.9600	C11—H11A	0.9600
C1—H1C	0.9600	C11—H11B	0.9600
C2—C10	1.530 (5)	C11—H11C	0.9600
C2—C12	1.542 (6)	C12—H12A	0.9600
C3—C9	1.380 (4)	C12—H12B	0.9600
C3—C4	1.394 (4)	C12—H12C	0.9600
C3—B1	1.583 (4)	C13—H13A	0.9600
C4—C5	1.397 (4)	C13—H13B	0.9600
C5—C6	1.425 (4)	C13—H13C	0.9600
C5—C14	1.428 (4)	C14—C14ⁱ	1.426 (5)
C6—C7	1.345 (4)

B1—O1—C2	107.2 (3)	C3—C9—Br1	116.9 (2)
B1—O2—C10	107.7 (2)	C8—C9—Br1	118.9 (2)
C2—C1—H1A	109.5	O2—C10—C13	109.0 (3)
C2—C1—H1B	109.5	O2—C10—C2	103.1 (2)
H1A—C1—H1B	109.5	C13—C10—C2	116.5 (4)
C2—C1—H1C	109.5	O2—C10—C11	106.1 (3)
H1A—C1—H1C	109.5	C13—C10—C11	110.7 (5)
H1B—C1—H1C	109.5	C2—C10—C11	110.7 (4)
O1—C2—C1	109.7 (3)	C10—C11—H11A	109.5
O1—C2—C10	103.0 (2)	C10—C11—H11B	109.5
C1—C2—C10	118.3 (4)	H11A—C11—H11B	109.5
O1—C2—C12	104.4 (3)	C10—C11—H11C	109.5
C1—C2—C12	108.0 (4)	H11A—C11—H11C	109.5
C10—C2—C12	112.5 (4)	H11B—C11—H11C	109.5
C9—C3—C4	116.6 (3)	C2—C12—H12A	109.5
C9—C3—B1	122.0 (3)	C2—C12—H12B	109.5
C4—C3—B1	121.4 (3)	H12A—C12—H12B	109.5
C3—C4—C5	123.7 (3)	C2—C12—H12C	109.5
C3—C4—Br2	117.0 (2)	H12A—C12—H12C	109.5
C5—C4—Br2	119.2 (2)	H12B—C12—H12C	109.5
C4—C5—C6	123.7 (3)	C10—C13—H13A	109.5
C4—C5—C14	117.7 (2)	C10—C13—H13B	109.5
C6—C5—C14	118.6 (2)	H13A—C13—H13B	109.5
C7—C6—C5	121.6 (3)	C10—C13—H13C	109.5
C7—C6—H6	119.2	H13A—C13—H13C	109.5
C5—C6—H6	119.2	H13B—C13—H13C	109.5
C6—C7—C8ⁱ	121.6 (3)	C8—C14—C14ⁱ	119.8 (3)
C6—C7—H7	119.2	C8—C14—C5	120.4 (2)
C8ⁱ—C7—H7	119.2	C14ⁱ—C14—C5	119.8 (3)
C9—C8—C14	117.3 (3)	O2—B1—O1	114.1 (3)
C9—C8—C7ⁱ	124.0 (3)	O2—B1—C3	122.8 (3)
C14—C8—C7ⁱ	118.6 (3)	O1—B1—C3	123.1 (3)
C3—C9—C8	124.2 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C3–C5/C8/C9/C14 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—Br2···Cg1ⁱⁱ	1.90 (1)	3.48 (1)	4.921 (3)	130 (1)

Symmetry code: (ii) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₈H₂₈B₂Br₄O₄
M_r	769.76
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	15.5047 (10), 7.5136 (5), 13.9191 (9)
β (°)	113.961 (1)
V (Å³)	1481.78 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.46
Crystal size (mm)	0.34 × 0.24 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.258, 0.475
No. of measured, independent and observed [i > 2σ(I)] reflections	8745, 3344, 2488
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.109, 1.01
No. of reflections	3344
No. of parameters	176
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.67

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX-2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C3–C5/C8/C9/C14 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—Br2···Cg1ⁱ	1.899 (3)	3.4834 (13)	4.921 (3)	129.82 (9)

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Acknowledgements

We gratefully acknowledge financial support from the National Natural Science Foundation of China (grant Nos 20802026 and 50803033).

References

Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Coventry, D. N., Batsanov, A. S., Goeta, A. E. H., Judith, A. K., Marder, T. B. & Perutz, R. N. (2005). Chem. Commun. pp. 2172–2174. Web of Science CSD CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Miura, T. & Yamano, E. (1995). J. Org. Chem. 60, 1070–1073. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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4,4,5,5-Tetra­methyl-2-[1,3,6,8-tetra­bromo-7-(4,4,5,5-tetra­methyl-1,3,2-dioxaborolan-2-yl)pyren-2-yl]-1,3,2-dioxaborolane

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4,4,5,5-Tetramethyl-2-[1,3,6,8-tetrabromo-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyren-2-yl]-1,3,2-dioxaborolane