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

Abstract

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].

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,

• a = 16.9485 (17) Å

• b = 11.0619 (11) Å

• c = 6.8127 (10) Å

• V = 1277.3 (3) ų

• 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[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 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.

Supplementary Material

CCDC reference: 1009321

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

S1. Comment

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].

S2. Experimental

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.

S3. Refinement

H atoms were fixed geometrically and allowed to ride on their parent atoms, with C—H distances = 0.93–0.97 Å; and with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of (I) showing the atomic numbering and 40% probability displacement ellipsoids.

Crystal data

C15H10Br2	Dx = 1.820 Mg m−3
Mr = 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

Bruker SMART CCD area-detector diffractometer	Rint = 0.155
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 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

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(Fo2) + (0.0438P)2] where P = (Fo2 + 2Fc2)/3
S = 0.98	(Δ/σ)max < 0.001
640 reflections	Δρmax = 0.30 e Å−3
53 parameters	Δρmin = −0.68 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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.