2,4-Dibromo-2,3-dihydro-1H-inden-1-yl acetate

Çelik, Í.; Akkurt, M.; Yilmaz, M.; Tutar, A.; Erenler, R.; Kazak, C.

doi:10.1107/S1600536812023173

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1884

doi:10.1107/S1600536812023173

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2,4-Dibromo-2,3-dihydro-1H-inden-1-yl acetate

Ísmail Çelik,^a Mehmet Akkurt,^b ^* Makbule Yilmaz,^c Ahmet Tutar,^c Ramazan Erenler ^d and Canan Kazak ^e

^aDepartment of Physics, Faculty of Arts and Sciences, Cumhuriyet University, 58140 Sivas, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cDepartment of Chemistry, Faculty of Art and Science, Sakarya University, 54187 Adapazarı, Turkey, ^dDepartment of Chemistry, Faculty of Art and Science, Gaziosmanpaşa University, 60240 Tokat, Turkey, and ^eDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey
^*Correspondence e-mail: akkurt@erciyes.edu.tr

(Received 16 May 2012; accepted 21 May 2012; online 26 May 2012)

In the title compound, C₁₁H₁₀Br₂O₂, the cyclopentene ring fused to the benzene ring adopts an envelope conformation, with the C atom attached to the Br atom as the flap. The crystal structure does not exhibit any classical hydrogen bonds. The molecular packing is stabilized by van der Waals forces and π–π stacking interactions with a centroid–centroid distance of 3.811 (4) Å.

Related literature

For bromination of hydrocarbons, see: Catto et al. (2010 ); Erenler & Çakmak (2004 ); Erenler et al. (2006 ); McClure et al. (2011 ); Mitrochkine et al. (1995 ); Snyder & Brill (2011 ); Wu (2006 ); Çakmak et al. (2006 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₁H₁₀Br₂O₂
M_r = 333.99
Triclinic, $[P \overline 1]$
a = 8.1423 (7) Å
b = 8.6891 (9) Å
c = 9.0028 (8) Å
α = 76.163 (8)°
β = 68.105 (7)°
γ = 86.397 (8)°
V = 573.60 (10) Å³
Z = 2
Mo Kα radiation
μ = 7.04 mm⁻¹
T = 296 K
0.43 × 0.35 × 0.28 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.152, T_max = 0.243
6542 measured reflections
2635 independent reflections
1958 reflections with I > 2σ(I)
R_int = 0.110

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.178
S = 1.02
2635 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −1.42 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812023173/fj2559sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023173/fj2559Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812023173/fj2559Isup3.cml

checkCIF report

Comment top

Brominations of hydrocarbons are important processes in synthetic chemistry (Çakmak et al., 2006; Erenler et al., 2006; Erenler & Çakmak, 2004). Indanes are important class of molecules due to the pharmacological and medicinal properties (Mitrochkine et al., 1995; Catto et al., 2010; Wu, 2006; McClure et al., 2011) as well as natural product chemistry (Snyder & Brill, 2011).

The five-membered C1C6–C9 cyclopentene ring in the title compound, (Fig. 1), exhibits an envelope-shaped conformation, with the C8 atom attached to Br2 atom at the flap [the puckering parameters (Cremer & Pople, 1975) Q(2) = 0.279 (7) Å, ϕ(2) = 290.5 (13) °]. The Br1–C5–C6–C1, Br2–C8–C9–C1, C9–O1–C10–C11 and C9–O1–C10–O2 torsion angles are -178.0 (4), -152.1 (4), -170.2 (6) and 10.3 (9) °, respectively.

In the crystal, there is no classic hydrogen bonds. The crystal structure is stabilized by van der Waals forces and π-π stacking interactions [Cg2···Cg2(1 - x, 1 - y, 2 - z) = 3.811 (4) Å] between the centroids (Cg2) of the benzene rings of the adjacent molecules. Fig. 2 shows the molecular packing of the title compound along the b axis.

Related literature top

For bromination of hydrocarbons, see: Catto et al. (2010); Erenler & Çakmak (2004); Erenler et al. (2006); McClure et al. (2011); Mitrochkine et al. (1995); Snyder & Brill (2011); Wu (2006); Çakmak et al. (2006). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

To a cooled solution (273 K) of 2,4-dibromo-1-hyodroxyindane (0.2 g, 0.68 mmol) in pyridine (6.0 ml) was added acetic anhydride (1.0 ml) dropwise. After completion of the reaction for 4 h at room temperature, the solvent was removed under reduced pressure to form the solid product which was crystalized from dichloromethane/hexane to yield the 1-acetate-2,4-dibromo-indane (0.21 g, 95%). ¹H-NMR (300 MHz, CDCl₃) δ 7.40–7.60 (m, 3H), 6.0 (d, 1H), 4.90 (dt, 1H), 3.50 (m, 2H), 2.20 (s, 3H).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. An ORTEP drawing of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
	Fig. 2. View of the packing of the title compound, along the b axis. H atoms are omitted for the sake of clarity.

2,4-Dibromo-2,3-dihydro-1H-inden-1-yl acetate top

Crystal data top

C₁₁H₁₀Br₂O₂	Z = 2
M_r = 333.99	F(000) = 324
Triclinic, P1	D_x = 1.934 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1423 (7) Å	Cell parameters from 9714 reflections
b = 8.6891 (9) Å	θ = 2.4–28.1°
c = 9.0028 (8) Å	µ = 7.04 mm⁻¹
α = 76.163 (8)°	T = 296 K
β = 68.105 (7)°	Prism, colourless
γ = 86.397 (8)°	0.43 × 0.35 × 0.28 mm
V = 573.60 (10) Å³

Data collection top

Stoe IPDS 2 diffractometer	2635 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1958 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.110
Detector resolution: 6.67 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
ω scans	h = −10→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −11→10
T_min = 0.152, T_max = 0.243	l = −11→11
6542 measured reflections

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.1053P)²] where P = (F_o² + 2F_c²)/3
2635 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −1.42 e Å⁻³

Crystal data top

C₁₁H₁₀Br₂O₂	γ = 86.397 (8)°
M_r = 333.99	V = 573.60 (10) Å³
Triclinic, P1	Z = 2
a = 8.1423 (7) Å	Mo Kα radiation
b = 8.6891 (9) Å	µ = 7.04 mm⁻¹
c = 9.0028 (8) Å	T = 296 K
α = 76.163 (8)°	0.43 × 0.35 × 0.28 mm
β = 68.105 (7)°

Data collection top

Stoe IPDS 2 diffractometer	2635 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	1958 reflections with I > 2σ(I)
T_min = 0.152, T_max = 0.243	R_int = 0.110
6542 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.02	Δρ_max = 1.20 e Å⁻³
2635 reflections	Δρ_min = −1.42 e Å⁻³
137 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.22277 (8)	0.18390 (9)	1.10206 (9)	0.0641 (3)
Br2	0.91526 (9)	0.24936 (9)	0.49626 (8)	0.0579 (3)
O1	0.9902 (5)	0.1989 (5)	0.8133 (5)	0.0464 (11)
O2	1.2454 (6)	0.3332 (6)	0.6377 (6)	0.0625 (16)
C1	0.7425 (7)	0.3340 (6)	0.9593 (7)	0.0433 (17)
C2	0.7505 (8)	0.3703 (7)	1.0998 (8)	0.0495 (17)
C3	0.6006 (10)	0.3485 (8)	1.2402 (8)	0.0549 (19)
C4	0.4421 (9)	0.2927 (8)	1.2408 (8)	0.0527 (19)
C5	0.4366 (8)	0.2609 (7)	1.1011 (8)	0.0497 (17)
C6	0.5867 (7)	0.2826 (7)	0.9560 (7)	0.0438 (17)
C7	0.6106 (7)	0.2538 (7)	0.7923 (7)	0.0472 (17)
C8	0.7877 (7)	0.3406 (7)	0.6838 (7)	0.0446 (17)
C9	0.8911 (7)	0.3415 (6)	0.7950 (7)	0.0425 (14)
C10	1.1652 (8)	0.2097 (8)	0.7179 (8)	0.0488 (17)
C11	1.2441 (10)	0.0501 (9)	0.7271 (11)	0.065 (3)
H2	0.85540	0.40870	1.09820	0.0590*
H3	0.60410	0.37060	1.33510	0.0660*
H4	0.34100	0.27740	1.33620	0.0630*
H7A	0.51600	0.29880	0.75610	0.0570*
H7B	0.61690	0.14150	0.79440	0.0570*
H8	0.76310	0.45080	0.64130	0.0530*
H9	0.96600	0.43760	0.75890	0.0510*
H11A	1.18960	−0.01350	0.68340	0.0970*
H11B	1.22470	−0.00010	0.83970	0.0970*
H11C	1.36900	0.06100	0.66390	0.0970*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0461 (4)	0.0769 (5)	0.0653 (5)	−0.0077 (3)	−0.0103 (3)	−0.0237 (4)
Br2	0.0559 (4)	0.0717 (5)	0.0471 (4)	0.0049 (3)	−0.0153 (3)	−0.0228 (3)
O1	0.045 (2)	0.0381 (19)	0.056 (2)	0.0031 (15)	−0.0190 (17)	−0.0109 (17)
O2	0.051 (2)	0.061 (3)	0.067 (3)	−0.006 (2)	−0.014 (2)	−0.010 (2)
C1	0.048 (3)	0.036 (3)	0.046 (3)	0.001 (2)	−0.016 (2)	−0.012 (2)
C2	0.054 (3)	0.042 (3)	0.059 (3)	0.001 (2)	−0.026 (3)	−0.015 (3)
C3	0.070 (4)	0.051 (3)	0.053 (3)	0.013 (3)	−0.029 (3)	−0.022 (3)
C4	0.061 (4)	0.051 (3)	0.043 (3)	0.012 (3)	−0.015 (3)	−0.015 (3)
C5	0.051 (3)	0.043 (3)	0.052 (3)	0.008 (2)	−0.016 (2)	−0.012 (2)
C6	0.046 (3)	0.043 (3)	0.043 (3)	0.006 (2)	−0.018 (2)	−0.010 (2)
C7	0.040 (3)	0.052 (3)	0.049 (3)	−0.002 (2)	−0.014 (2)	−0.014 (3)
C8	0.046 (3)	0.045 (3)	0.045 (3)	0.005 (2)	−0.019 (2)	−0.012 (2)
C9	0.040 (2)	0.033 (2)	0.053 (3)	0.0027 (19)	−0.017 (2)	−0.008 (2)
C10	0.042 (3)	0.056 (3)	0.055 (3)	0.007 (2)	−0.022 (2)	−0.020 (3)
C11	0.062 (4)	0.058 (4)	0.086 (5)	0.012 (3)	−0.031 (4)	−0.034 (4)

Geometric parameters (Å, º) top

Br1—C5	1.900 (7)	C7—C8	1.528 (9)
Br2—C8	1.946 (6)	C8—C9	1.531 (8)
O1—C9	1.446 (7)	C10—C11	1.489 (11)
O1—C10	1.357 (8)	C2—H2	0.9300
O2—C10	1.210 (9)	C3—H3	0.9300
C1—C2	1.400 (9)	C4—H4	0.9300
C1—C6	1.384 (9)	C7—H7A	0.9700
C1—C9	1.512 (8)	C7—H7B	0.9700
C2—C3	1.374 (10)	C8—H8	0.9800
C3—C4	1.405 (11)	C9—H9	0.9800
C4—C5	1.368 (9)	C11—H11A	0.9600
C5—C6	1.399 (9)	C11—H11B	0.9600
C6—C7	1.493 (8)	C11—H11C	0.9600

C9—O1—C10	116.4 (5)	C1—C2—H2	121.00
C2—C1—C6	121.9 (6)	C3—C2—H2	121.00
C2—C1—C9	128.1 (6)	C2—C3—H3	120.00
C6—C1—C9	110.0 (5)	C4—C3—H3	120.00
C1—C2—C3	118.9 (6)	C3—C4—H4	120.00
C2—C3—C4	120.1 (6)	C5—C4—H4	120.00
C3—C4—C5	120.0 (6)	C6—C7—H7A	112.00
Br1—C5—C4	120.1 (5)	C6—C7—H7B	111.00
Br1—C5—C6	118.7 (5)	C8—C7—H7A	112.00
C4—C5—C6	121.3 (6)	C8—C7—H7B	112.00
C1—C6—C5	117.8 (6)	H7A—C7—H7B	109.00
C1—C6—C7	112.1 (5)	Br2—C8—H8	108.00
C5—C6—C7	130.1 (6)	C7—C8—H8	108.00
C6—C7—C8	101.3 (5)	C9—C8—H8	108.00
Br2—C8—C7	112.1 (4)	O1—C9—H9	112.00
Br2—C8—C9	113.7 (4)	C1—C9—H9	112.00
C7—C8—C9	107.2 (5)	C8—C9—H9	112.00
O1—C9—C1	106.8 (4)	C10—C11—H11A	109.00
O1—C9—C8	111.9 (5)	C10—C11—H11B	109.00
C1—C9—C8	101.4 (5)	C10—C11—H11C	109.00
O1—C10—O2	124.1 (6)	H11A—C11—H11B	109.00
O1—C10—C11	110.8 (6)	H11A—C11—H11C	109.00
O2—C10—C11	125.0 (7)	H11B—C11—H11C	109.00

C9—O1—C10—C11	−170.2 (6)	C2—C3—C4—C5	−0.4 (11)
C10—O1—C9—C1	−150.4 (5)	C3—C4—C5—C6	0.1 (10)
C10—O1—C9—C8	99.5 (6)	C3—C4—C5—Br1	179.5 (5)
C9—O1—C10—O2	10.3 (9)	Br1—C5—C6—C7	−0.3 (9)
C9—C1—C2—C3	−177.0 (6)	C4—C5—C6—C1	1.4 (9)
C2—C1—C6—C5	−2.7 (9)	C4—C5—C6—C7	179.2 (6)
C2—C1—C6—C7	179.2 (5)	Br1—C5—C6—C1	−178.0 (4)
C6—C1—C2—C3	2.5 (9)	C1—C6—C7—C8	−15.9 (7)
C6—C1—C9—O1	−99.5 (6)	C5—C6—C7—C8	166.3 (6)
C6—C1—C9—C8	17.8 (6)	C6—C7—C8—Br2	152.3 (4)
C2—C1—C9—O1	80.1 (7)	C6—C7—C8—C9	26.7 (6)
C9—C1—C6—C5	176.8 (5)	Br2—C8—C9—C1	−152.1 (4)
C9—C1—C6—C7	−1.3 (7)	C7—C8—C9—O1	86.0 (6)
C2—C1—C9—C8	−162.7 (6)	C7—C8—C9—C1	−27.5 (6)
C1—C2—C3—C4	−0.8 (10)	Br2—C8—C9—O1	−38.6 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O2	0.98	2.36	2.704 (8)	100

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀Br₂O₂
M_r	333.99
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.1423 (7), 8.6891 (9), 9.0028 (8)
α, β, γ (°)	76.163 (8), 68.105 (7), 86.397 (8)
V (Å³)	573.60 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	7.04
Crystal size (mm)	0.43 × 0.35 × 0.28

Data collection
Diffractometer	Stoe IPDS 2 diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.152, 0.243
No. of measured, independent and observed [I > 2σ(I)] reflections	6542, 2635, 1958
R_int	0.110
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.178, 1.02
No. of reflections	2635
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.20, −1.42

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

References

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