2′,7′-Di­bromo­spiro­[cyclo­propane-1,9′-fluorene]

Xue, Y.; Qin, Y.

doi:10.1107/S1600536814014585

organic compounds

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ISSN: 2056-9890

Volume 70| Part 7| July 2014| Page o821

https://doi.org/10.1107/S1600536814014585

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2′,7′-Dibromospiro[cyclopropane-1,9′-fluorene]

Yue-yuan Xue ^a and Yong-qi Qin ^b ^*

^aDepartment of Chemistry and Chemical Engineering, Lvliang University, Lvliang, Shanxi 033001, People's Republic of China, and ^bLaboratory of Medicinal Chemistry, Lvliang University, Lvliang, Shanxi 033001, People's Republic of China
^*Correspondence e-mail: qinyq2003@163.com

(Received 3 June 2014; accepted 20 June 2014; online 25 June 2014)

In the title compound, C₁₅H₁₀Br₂, each molecule is situated on special postion mm, so the asymmetric unit contains one-quater of a molecule. The 2,7-dibromo-9H-fluorene fragment and three spirocyclopropane C atoms lie on different planes, which are perpendicular to each other. In the crystal, π–π interactions between aromatic rings [intercentroid distance = 3.699 (3) Å] pack the molecules into stacks extending in [001].

Keywords: crystal structure.

CCDC reference: 1009321

Related literature

For electroluminescence properties of fluorene derivatives, see: Cho et al. (2007 ); Jiang et al. (2005 ); Wei et al. (2008 ). For the crystal structures of related compounds, see: Jason et al. (1981 ); Wang et al. (2007 ).

Experimental

Crystal data

C₁₅H₁₀Br₂
M_r = 350.05
Orthorhombic, C m c m
a = 16.9485 (17) Å
b = 11.0619 (11) Å
c = 6.8127 (10) Å
V = 1277.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 6.32 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
3276 measured reflections
640 independent reflections
471 reflections with I > 2σ(I)
R_int = 0.155

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.100
S = 0.98
640 reflections
53 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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

CCDC reference: 1009321

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536814014585/cv5463sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814014585/cv5463Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814014585/cv5463Isup3.cml

checkCIF report

Comment top

Fluorene derivatives have a wide range of applications in electroluminescence materials (Jiang et al., 2005; Wei et al., 2008) because of their good thermal, light and chemical stability (Cho et al., 2007). Herewith we present the title compound (I), which is a new derivative of fluorene.

In (I) (Fig. 1), all bond lengths and angles are normal and comparable with those observed in the related spiro(cyclopropane-1,9'-(9H)fluorene) (Jason et al., 1981) and 2',7'-diiodospiro(cyclopropane-1,9'-fluorene) (Wang, et al., 2007). In (I), the 2,7-dibromo-9H-fluorene fragment and three carbon atoms of spirocyclopropane lie on different planes m, which are perpendicular to each other, so asymmetric unit contains one fourth of the molecule.

In the crystal, π–π interactions between the aromatic rings [intercentroid distance of 3.699 (3) Å] pack molecules into stacks extended in [001].

Related literature top

For electroluminescence properties of fluorene derivatives, see: Cho et al. (2007); Jiang et al. (2005); Wei et al. (2008). For the crystal structures of related compounds, see: Jason et al. (1981); Wang et al. (2007).

Experimental top

The title compound was prepared by the reaction of 2,7-dibromo-9H-fluorene(0.01 mol), 1,2-dibromethane(0.01 mol) and KOH(0.03 mol) in 1,4-dioxane(20 ml) at 358 K for 3 h. Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Structure description top

In the crystal, π–π interactions between the aromatic rings [intercentroid distance of 3.699 (3) Å] pack molecules into stacks extended in [001].

For electroluminescence properties of fluorene derivatives, see: Cho et al. (2007); Jiang et al. (2005); Wei et al. (2008). For the crystal structures of related compounds, see: Jason et al. (1981); Wang et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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) showing the atomic numbering and 40% probability displacement ellipsoids.

2',7'-Dibromospiro[cyclopropane-1,9'-fluorene] top

Crystal data top

C₁₅H₁₀Br₂	D_x = 1.820 Mg m⁻³
M_r = 350.05	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmcm	Cell parameters from 933 reflections
a = 16.9485 (17) Å	θ = 2.2–25.0°
b = 11.0619 (11) Å	µ = 6.32 mm⁻¹
c = 6.8127 (10) Å	T = 293 K
V = 1277.3 (3) Å³	Block, colourless
Z = 4	0.30 × 0.20 × 0.20 mm
F(000) = 680

Data collection top

Bruker SMART CCD area-detector diffractometer	R_int = 0.155
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.2°
phi and ω scans	h = −20→17
3276 measured reflections	k = −13→12
640 independent reflections	l = −8→7
471 reflections with I > 2σ(I)

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0438P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
640 reflections	Δρ_max = 0.30 e Å⁻³
53 parameters	Δρ_min = −0.68 e Å⁻³

Crystal data top

C₁₅H₁₀Br₂	V = 1277.3 (3) Å³
M_r = 350.05	Z = 4
Orthorhombic, Cmcm	Mo Kα radiation
a = 16.9485 (17) Å	µ = 6.32 mm⁻¹
b = 11.0619 (11) Å	T = 293 K
c = 6.8127 (10) Å	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	471 reflections with I > 2σ(I)
3276 measured reflections	R_int = 0.155
640 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 0.98	Δρ_max = 0.30 e Å⁻³
640 reflections	Δρ_min = −0.68 e Å⁻³
53 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
Br1	0.31110 (3)	0.12115 (5)	0.7500	0.0746 (4)
C1	0.0691 (3)	0.1592 (4)	0.7500	0.0396 (11)
C2	0.1489 (3)	0.1851 (4)	0.7500	0.0470 (12)
H2	0.1666	0.2647	0.7500	0.056*
C3	0.2011 (3)	0.0894 (5)	0.7500	0.0478 (12)
C4	0.1763 (3)	−0.0277 (4)	0.7500	0.0506 (12)
H4	0.2130	−0.0901	0.7500	0.061*
C5	0.0965 (3)	−0.0541 (4)	0.7500	0.0450 (12)
H5	0.0792	−0.1339	0.7500	0.054*
C6	0.0429 (2)	0.0393 (4)	0.7500	0.0380 (10)
C13	0.0000	0.2412 (5)	0.7500	0.0424 (16)
C14	0.0000	0.3609 (3)	0.6418 (11)	0.0725 (18)
H14	0.0485	0.3846	0.5754	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0506 (4)	0.0657 (5)	0.1074 (6)	0.0008 (3)	0.000	0.000
C1	0.054 (3)	0.0309 (19)	0.034 (2)	−0.001 (2)	0.000	0.000
C2	0.056 (3)	0.034 (2)	0.051 (3)	−0.004 (2)	0.000	0.000
C3	0.047 (3)	0.049 (3)	0.047 (3)	0.005 (2)	0.000	0.000
C4	0.059 (3)	0.046 (3)	0.047 (3)	0.012 (2)	0.000	0.000
C5	0.063 (3)	0.031 (2)	0.041 (3)	0.003 (2)	0.000	0.000
C6	0.052 (2)	0.032 (2)	0.031 (2)	0.0006 (19)	0.000	0.000
C13	0.051 (4)	0.028 (3)	0.048 (4)	0.000	0.000	0.000
C14	0.054 (3)	0.039 (3)	0.125 (5)	0.000	0.000	0.030 (3)

Geometric parameters (Å, º) top

Br1—C3	1.897 (5)	C5—C6	1.375 (6)
C1—C2	1.383 (6)	C5—H5	0.9299
C1—C6	1.398 (6)	C6—C6ⁱ	1.454 (8)
C1—C13	1.481 (6)	C13—C1ⁱ	1.481 (6)
C2—C3	1.380 (7)	C13—C14	1.516 (7)
C2—H2	0.9300	C13—C14ⁱⁱ	1.516 (7)
C3—C4	1.361 (7)	C14—C14ⁱⁱ	1.475 (14)
C4—C5	1.384 (6)	C14—H14	0.9741
C4—H4	0.9299

C2—C1—C6	120.5 (4)	C4—C5—H5	120.5
C2—C1—C13	130.3 (4)	C5—C6—C1	120.2 (4)
C6—C1—C13	109.3 (4)	C5—C6—C6ⁱ	131.3 (3)
C3—C2—C1	117.9 (4)	C1—C6—C6ⁱ	108.5 (3)
C3—C2—H2	121.3	C1ⁱ—C13—C1	104.5 (5)
C1—C2—H2	120.8	C1ⁱ—C13—C14	122.36 (19)
C4—C3—C2	122.1 (5)	C1—C13—C14	122.36 (19)
C4—C3—Br1	118.7 (4)	C1ⁱ—C13—C14ⁱⁱ	122.36 (19)
C2—C3—Br1	119.2 (4)	C1—C13—C14ⁱⁱ	122.36 (19)
C3—C4—C5	120.2 (4)	C14—C13—C14ⁱⁱ	58.2 (6)
C3—C4—H4	120.0	C14ⁱⁱ—C14—C13	60.9 (3)
C5—C4—H4	119.8	C14ⁱⁱ—C14—H14	117.6
C6—C5—C4	119.1 (4)	C13—C14—H14	117.4
C6—C5—H5	120.4

C6—C1—C2—C3	0.0	C2—C1—C6—C6ⁱ	180.0
C13—C1—C2—C3	180.0	C13—C1—C6—C6ⁱ	0.0
C1—C2—C3—C4	0.0	C2—C1—C13—C1ⁱ	180.0
C1—C2—C3—Br1	180.0	C6—C1—C13—C1ⁱ	0.0
C2—C3—C4—C5	0.0	C2—C1—C13—C14	35.1 (4)
Br1—C3—C4—C5	180.0	C6—C1—C13—C14	−144.9 (4)
C3—C4—C5—C6	0.0	C2—C1—C13—C14ⁱⁱ	−35.1 (4)
C4—C5—C6—C1	0.0	C6—C1—C13—C14ⁱⁱ	144.9 (4)
C4—C5—C6—C6ⁱ	180.0	C1ⁱ—C13—C14—C14ⁱⁱ	110.6 (3)
C2—C1—C6—C5	0.0	C1—C13—C14—C14ⁱⁱ	−110.6 (3)
C13—C1—C6—C5	180.0

Symmetry codes: (i) −x, y, z; (ii) x, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀Br₂
M_r	350.05
Crystal system, space group	Orthorhombic, Cmcm
Temperature (K)	293
a, b, c (Å)	16.9485 (17), 11.0619 (11), 6.8127 (10)
V (Å³)	1277.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.32
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3276, 640, 471
R_int	0.155
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.100, 0.98
No. of reflections	640
No. of parameters	53
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.68

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Colleges and Universities Technology Project of Shanxi Province (grant No. 20121033) and the Natural Science Fund of Lvliang University (ZRXN201206 and ZRXN201210).

References

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