1-Bromo­pyrene

Taylor, R.E.; Raithby, P.R.; Teat, S.J.

doi:10.1107/S160053680601052X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 4| April 2006| Pages o1604-o1605

https://doi.org/10.1107/S160053680601052X

1-Bromopyrene¹ ¹

Robert E. Taylor,^a Paul R. Raithby ^a,^b ^* and Simon J. Teat ^a

^aDepartment of Chemistry, University of Bath, Bath BA2 7AY, England, and ^bCCLRC Daresbury Laboratory, Daresbury, Warrington WA4 4AD, England
^*Correspondence e-mail: p.r.raithby@bath.ac.uk

(Received 20 March 2006; accepted 22 March 2006; online 29 March 2006)

1-Bromopyrene, C₁₆H₉Br, is a planar, fused aromatic organic compound. The molecule is approximately planar with an r.m.s. deviation of 0.0243 Å for the ring C atoms and 0.0261 Å for all non-H atoms. A herringbone packing motif based on π-π interactions is observed, with a perpendicular distance between adjacent stacked molecules of 3.519 Å.

Comment

We report here the structural characterization of the title compound, (I), which is a planar, fused aromatic organic compound. Its structure was determined to establish whether π–π stacking occurred in the solid state, and to relate the nature of the packing to some of the physical properties of the material, including triboluminescence. Similar fused aromatic compounds have exhibited π–π interactions (Desiraju & Gavezzotti, 1989 ) which, we believe, may be a requirement for aromatic materials to show triboluminescent activity (Sweeting et al., 1997 ).

The molecule (Fig. 1) is shown to be approximately planar, with an r.m.s. deviation of 0.0243 Å for the ring C atoms and 0.0261 Å for all non-H atoms. A herringbone packing motif based on π-π interactions is observed (Fig. 2), with a perpendicular distance between adjacent stacked molecules of 3.519 Å. No C—H⋯π contacts shorter than 2.91 Å are observed.

Figure 1
The molecular structure of (I)

with atom labels and 50% probability ellipsoids for non-H atoms.

Figure 2
Two views of the packing, perpendicular to (010) and to (001), with 50% probability ellipsoids for non-H atoms. H atoms have been omitted for clarity.

Experimental

1-Bromopyrene was purchased as a yellow powder from the Aldrich Chemical Company. Small orange crystals suitable for X-ray diffraction were grown by slow evaporation of a solution in benzene stored at 278 K.

Crystal data

C₁₆H₉Br
M_r = 281.14
Monoclinic, P 2₁ /c
a = 14.530 (3) Å
b = 3.9490 (8) Å
c = 20.277 (4) Å
β = 108.163 (3)°
V = 1105.5 (4) Å³
Z = 4
D_x = 1.689 Mg m⁻³
Synchrotron radiation
λ = 0.6775 Å
Cell parameters from 1772 reflections
θ = 2.8–23.3°
μ = 3.69 mm⁻¹
T = 200 (2) K
Block, orange
0.05 × 0.05 × 0.03 mm

Data collection

Bruker APEX-II CCD diffractometer
Narrow–frame ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.817, T_max = 0.895
7895 measured reflections
1888 independent reflections
1284 reflections with I > 2σ(I)
R_int = 0.149
θ_max = 24.7°
h = −17 → 17
k = −4 → 4
l = −23 → 23

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.126
S = 0.95
1888 reflections
154 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0527P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.67 e Å⁻³

H atoms were constrained as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). The value of R_int is rather high due to the poor quality of the crystal, which required the use of synchrotron radiation for any diffraction to be observed.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053680601052X/cf2017sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680601052X/cf2017Isup2.hkl

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

(I) top

Crystal data top

C₁₆H₉Br	F(000) = 560
M_r = 281.14	D_x = 1.689 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.6775 Å
a = 14.530 (3) Å	Cell parameters from 1772 reflections
b = 3.9490 (8) Å	θ = 2.8–23.3°
c = 20.277 (4) Å	µ = 3.69 mm⁻¹
β = 108.163 (3)°	T = 200 K
V = 1105.5 (4) Å³	Block, orange
Z = 4	0.05 × 0.05 × 0.03 mm

Data collection top

Bruker APEX-II CCD diffractometer	1284 reflections with I > 2σ(I)
narrow–frame ω scans	R_int = 0.149
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 24.7°, θ_min = 2.1°
T_min = 0.817, T_max = 0.895	h = −17→17
7895 measured reflections	k = −4→4
1888 independent reflections	l = −23→23

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0527P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.126	(Δ/σ)_max < 0.001
S = 0.95	Δρ_max = 0.66 e Å⁻³
1888 reflections	Δρ_min = −0.67 e Å⁻³
154 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1723 (3)	0.1059 (12)	0.1548 (2)	0.0396 (11)
C2	0.1812 (3)	0.1333 (11)	0.2249 (2)	0.0351 (11)
C3	0.1100 (3)	0.2885 (10)	0.2515 (3)	0.0402 (11)
H3	0.0537	0.3879	0.2201	0.048*
C4	0.1221 (4)	0.2940 (11)	0.3195 (3)	0.0432 (12)
H4	0.0726	0.3928	0.3346	0.052*
C5	0.2034 (4)	0.1631 (11)	0.3696 (3)	0.0416 (12)
C6	0.2178 (4)	0.1619 (12)	0.4423 (3)	0.0508 (14)
H6	0.1672	0.2513	0.4576	0.061*
C7	0.2964 (4)	0.0459 (10)	0.4911 (2)	0.0382 (12)
H7	0.3034	0.0608	0.5392	0.046*
C8	0.3709 (4)	−0.1054 (13)	0.4657 (3)	0.0541 (15)
H8	0.4265	−0.2003	0.4986	0.065*
C9	0.3644 (4)	−0.1172 (12)	0.3960 (3)	0.0409 (12)
C10	0.4363 (4)	−0.2660 (11)	0.3704 (3)	0.0428 (12)
H10	0.4931	−0.3593	0.4023	0.051*
C11	0.4251 (4)	−0.2762 (11)	0.3024 (3)	0.0483 (13)
H11	0.4754	−0.3715	0.2876	0.058*
C12	0.3405 (3)	−0.1496 (11)	0.2511 (3)	0.0390 (12)
C13	0.3274 (4)	−0.1702 (11)	0.1800 (3)	0.0414 (12)
H13	0.3762	−0.2694	0.1641	0.05*
C14	0.2428 (4)	−0.0451 (11)	0.1323 (3)	0.0449 (13)
H14	0.2338	−0.0641	0.0839	0.054*
C15	0.2672 (3)	0.0006 (10)	0.2747 (2)	0.0339 (11)
C16	0.2778 (3)	0.0149 (10)	0.3464 (2)	0.0349 (11)
Br1	0.06020 (4)	0.26841 (12)	0.08553 (2)	0.0523 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.035 (3)	0.032 (2)	0.050 (3)	−0.006 (2)	0.009 (2)	−0.002 (2)
C2	0.037 (3)	0.026 (2)	0.040 (3)	−0.0095 (19)	0.010 (2)	−0.0001 (18)
C3	0.028 (2)	0.030 (2)	0.057 (3)	−0.003 (2)	0.006 (2)	−0.004 (2)
C4	0.035 (3)	0.036 (3)	0.062 (3)	0.000 (2)	0.022 (2)	−0.007 (2)
C5	0.039 (3)	0.033 (2)	0.054 (3)	−0.009 (2)	0.016 (3)	−0.006 (2)
C6	0.059 (4)	0.038 (3)	0.065 (4)	−0.011 (2)	0.033 (3)	−0.012 (2)
C7	0.056 (3)	0.027 (2)	0.027 (2)	−0.014 (2)	0.006 (2)	0.0023 (18)
C8	0.056 (4)	0.040 (3)	0.054 (3)	−0.011 (3)	−0.002 (3)	0.011 (2)
C9	0.041 (3)	0.030 (2)	0.048 (3)	−0.008 (2)	0.008 (2)	0.005 (2)
C10	0.034 (3)	0.034 (3)	0.053 (3)	0.003 (2)	0.004 (2)	0.005 (2)
C11	0.034 (3)	0.035 (3)	0.075 (4)	−0.002 (2)	0.015 (3)	0.000 (2)
C12	0.031 (3)	0.027 (2)	0.059 (3)	−0.0024 (18)	0.014 (2)	0.001 (2)
C13	0.040 (3)	0.038 (3)	0.051 (3)	−0.009 (2)	0.021 (2)	−0.007 (2)
C14	0.048 (3)	0.032 (3)	0.055 (3)	−0.011 (2)	0.018 (3)	−0.004 (2)
C15	0.030 (2)	0.026 (2)	0.047 (3)	−0.0077 (18)	0.014 (2)	−0.0018 (18)
C16	0.030 (3)	0.026 (2)	0.045 (3)	−0.0083 (19)	0.007 (2)	0.0007 (18)
Br1	0.0461 (4)	0.0499 (4)	0.0509 (4)	−0.0028 (3)	0.0007 (2)	0.0080 (3)

Geometric parameters (Å, º) top

C1—C14	1.381 (7)	C8—C9	1.389 (7)
C1—C2	1.392 (6)	C8—H8	0.950
C1—Br1	1.900 (5)	C9—C10	1.429 (7)
C2—C15	1.438 (6)	C9—C16	1.441 (6)
C2—C3	1.444 (7)	C10—C11	1.338 (7)
C3—C4	1.334 (7)	C10—H10	0.950
C3—H3	0.950	C11—C12	1.431 (7)
C4—C5	1.395 (7)	C11—H11	0.950
C4—H4	0.950	C12—C13	1.397 (7)
C5—C6	1.424 (7)	C12—C15	1.425 (6)
C5—C16	1.433 (6)	C13—C14	1.396 (7)
C6—C7	1.336 (7)	C13—H13	0.950
C6—H6	0.950	C14—H14	0.950
C7—C8	1.463 (7)	C15—C16	1.414 (6)
C7—H7	0.950

C14—C1—C2	121.9 (5)	C8—C9—C10	123.9 (5)
C14—C1—Br1	117.1 (4)	C8—C9—C16	117.8 (5)
C2—C1—Br1	121.0 (4)	C10—C9—C16	118.2 (4)
C1—C2—C15	118.2 (4)	C11—C10—C9	121.2 (4)
C1—C2—C3	124.4 (4)	C11—C10—H10	119.4
C15—C2—C3	117.4 (4)	C9—C10—H10	119.4
C4—C3—C2	120.8 (4)	C10—C11—C12	122.7 (5)
C4—C3—H3	119.6	C10—C11—H11	118.7
C2—C3—H3	119.6	C12—C11—H11	118.7
C3—C4—C5	123.8 (5)	C13—C12—C15	119.7 (4)
C3—C4—H4	118.1	C13—C12—C11	122.7 (5)
C5—C4—H4	118.1	C15—C12—C11	117.6 (5)
C4—C5—C6	125.0 (5)	C14—C13—C12	120.1 (5)
C4—C5—C16	117.8 (4)	C14—C13—H13	119.9
C6—C5—C16	117.1 (5)	C12—C13—H13	119.9
C7—C6—C5	125.7 (5)	C1—C14—C13	120.5 (5)
C7—C6—H6	117.1	C1—C14—H14	119.7
C5—C6—H6	117.1	C13—C14—H14	119.7
C6—C7—C8	115.8 (4)	C16—C15—C12	120.5 (4)
C6—C7—H7	122.1	C16—C15—C2	119.9 (4)
C8—C7—H7	122.1	C12—C15—C2	119.5 (4)
C9—C8—C7	123.2 (5)	C15—C16—C5	120.2 (4)
C9—C8—H8	118.4	C15—C16—C9	119.7 (4)
C7—C8—H8	118.4	C5—C16—C9	120.2 (4)

Footnotes

¹.

Acknowledgements

We thank the EPSRC and the CCLRC Centre for Molecular Structure and Dynamics for funding.

References

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