4-Bromo-2-(4-fluoro­benzyl­idene)indan-1-one

Zhou, Y.-X.; Wang, J.-Q.; Du, R.-J.; Tang, J.-G.; Guo, C.

doi:10.1107/S1600536809025781

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1936

doi:10.1107/S1600536809025781

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4-Bromo-2-(4-fluorobenzylidene)indan-1-one

Yi-Xin Zhou,^a Jian-Qiang Wang,^a Ren-Jun Du,^a Jian-Guo Tang ^a and Cheng Guo ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 26 June 2009; accepted 3 July 2009; online 18 July 2009)

In the molecule of the title compound, C₁₆H₁₀BrFO, the indane ring system is planar with a maximum deviation of 0.020 (3) Å. An intramolecular C—H⋯O interaction results in the formation of a planar ring, which is oriented at dihedral angles of 2.24 (3) and 2.34 (3)° with respect to the adjacent rings. π–π contacts between the benzene and indane rings [centroid–centroid distances = 3.699 (1) and 3.786 (1)Å] may stabilize the crystal structure.

Related literature

For a related structure, see: Deeni & Ravi (2001 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₀BrFO
M_r = 317.15
Triclinic, $[P \overline 1]$
a = 7.3580 (15) Å
b = 7.4630 (15) Å
c = 13.140 (3) Å
α = 101.45 (3)°
β = 96.80 (3)°
γ = 111.72 (3)°
V = 642.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 3.20 mm⁻¹
T = 294 K
0.10 × 0.10 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.740, T_max = 0.856
2518 measured reflections
2319 independent reflections
1351 reflections with I > 2σ(I)
R_int = 0.027
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.137
S = 1.00
2319 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O	0.93	2.14	2.972 (8)	149

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025781/hk2723sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025781/hk2723Isup2.hkl

checkCIF report

Comment top

Some derivatives of 2,3-dihydro-1H-inden-1-one alcohol are important chemical materials. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6), B (C8-C10/C15/C16) and C (C10-C15) are, of course, planar and the dihedral angles between them are A/B = 4.49 (3), A/C = 5.44 (3) and B/C = 0.96 (3) °. Intramolecular C-H···O interaction (Table 1) results in the formation of a planar ring (O/C3/C4/C7-C9/H3A), which is oriented with respect to the adjacent rings A and B at dihedral angles of 2.24 (3) and 2.34 (3) °, respectively. The indane ring system is planar with a maximum deviation of -0.020 (3) Å for atom C9. Atoms Br, O and C7 are 0.026 (3), -0.066 (3) and 0.075 (3) Å away from the plane of the indane ring system, respectively.

In the crystal structure, the π–π contacts between the benzene and the indane rings, Cg2—Cg1ⁱ and Cg1—Cg3ⁱⁱ [symmetry codes: (i) 1 - x, 2 - y, -z, (ii) 1 - x, 1 - y, -z, where Cg1, Cg2 and Cg3 are centroids of the rings A (C1-C6), B (C8-C10/C15/C16) and C (C10-C15), respectively] may further stabilize the structure, with centroid-centroid distances of 3.699 (1) and 3.786 (1) Å, respectively.

Related literature top

For a related structure, see: Deeni & Ravi (2001). For bond-length data, see: Allen et al. (1987).

Experimental top

4-fluoro-benzaldehyde (10 mmol), 4-bromo-2,3-dihydro-1H-inden-1-one (10 mmol), anhydrous ethanol (10 ml) and 5 drops of piperidine were mixed in a three necked flask (50 ml). The flask was placed in a microwave synthesis system and irradiated for 7 min at 373 K with power 400 W. Then, the reaction mixture was slowly added with shaking to water (100 ml) and left to stand overnight. The precipitate was filtered, washed with water and dried (Deeni & Ravi, 2001). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

4-Bromo-2-(4-fluorobenzylidene)indan-1-one top

Crystal data top

C₁₆H₁₀BrFO	Z = 2
M_r = 317.15	F(000) = 316
Triclinic, P1	D_x = 1.640 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3580 (15) Å	Cell parameters from 25 reflections
b = 7.4630 (15) Å	θ = 9–13°
c = 13.140 (3) Å	µ = 3.20 mm⁻¹
α = 101.45 (3)°	T = 294 K
β = 96.80 (3)°	Block, colorless
γ = 111.72 (3)°	0.10 × 0.10 × 0.05 mm
V = 642.2 (3) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1351 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 25.3°, θ_min = 1.6°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = −8→8
T_min = 0.740, T_max = 0.856	l = −15→15
2518 measured reflections	3 standard reflections every 120 min
2319 independent reflections	intensity decay: 1%

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.067P)²] where P = (F_o² + 2F_c²)/3
2319 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₆H₁₀BrFO	γ = 111.72 (3)°
M_r = 317.15	V = 642.2 (3) Å³
Triclinic, P1	Z = 2
a = 7.3580 (15) Å	Mo Kα radiation
b = 7.4630 (15) Å	µ = 3.20 mm⁻¹
c = 13.140 (3) Å	T = 294 K
α = 101.45 (3)°	0.10 × 0.10 × 0.05 mm
β = 96.80 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1351 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.027
T_min = 0.740, T_max = 0.856	3 standard reflections every 120 min
2518 measured reflections	intensity decay: 1%
2319 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.00	Δρ_max = 0.38 e Å⁻³
2319 reflections	Δρ_min = −0.35 e Å⁻³
172 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
Br	0.47010 (11)	0.25337 (12)	0.59830 (5)	0.0759 (3)
O	0.2276 (6)	0.2064 (7)	1.0423 (3)	0.0688 (12)
F	0.8344 (6)	0.2939 (6)	1.4682 (2)	0.0883 (12)
C1	0.7931 (11)	0.2919 (9)	1.3633 (4)	0.0618 (17)
C2	0.6046 (11)	0.2666 (9)	1.3199 (4)	0.0657 (18)
H2A	0.5071	0.2516	1.3604	0.079*
C3	0.5620 (9)	0.2638 (9)	1.2136 (4)	0.0558 (16)
H3A	0.4348	0.2475	1.1823	0.067*
C4	0.7092 (9)	0.2854 (8)	1.1535 (4)	0.0483 (14)
C5	0.8976 (9)	0.3109 (9)	1.2025 (4)	0.0586 (16)
H5A	0.9979	0.3272	1.1639	0.070*
C6	0.9387 (10)	0.3124 (9)	1.3084 (5)	0.0678 (18)
H6A	1.0648	0.3273	1.3407	0.081*
C7	0.6811 (9)	0.2884 (8)	1.0409 (4)	0.0543 (15)
H7A	0.7986	0.3146	1.0156	0.065*
C8	0.5240 (8)	0.2619 (8)	0.9659 (4)	0.0467 (14)
C9	0.3131 (9)	0.2200 (8)	0.9680 (4)	0.0497 (15)
C10	0.2123 (9)	0.1972 (8)	0.8595 (4)	0.0449 (13)
C11	0.0132 (10)	0.1497 (9)	0.8219 (4)	0.0621 (17)
H11A	−0.0777	0.1254	0.8663	0.075*
C12	−0.0493 (10)	0.1387 (9)	0.7156 (4)	0.0642 (17)
H12A	−0.1827	0.1093	0.6886	0.077*
C13	0.0868 (10)	0.1714 (9)	0.6507 (4)	0.0607 (17)
H13A	0.0442	0.1646	0.5800	0.073*
C14	0.2830 (10)	0.2135 (8)	0.6883 (4)	0.0510 (15)
C15	0.3494 (9)	0.2285 (8)	0.7946 (4)	0.0474 (14)
C16	0.5512 (8)	0.2711 (9)	0.8538 (4)	0.0515 (15)
H16A	0.6460	0.4025	0.8538	0.062*
H16B	0.5987	0.1720	0.8228	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0960 (6)	0.1065 (6)	0.0373 (4)	0.0458 (5)	0.0289 (3)	0.0263 (3)
O	0.063 (3)	0.110 (4)	0.033 (2)	0.030 (3)	0.0189 (19)	0.022 (2)
F	0.117 (3)	0.104 (3)	0.0362 (19)	0.036 (3)	0.0016 (19)	0.0279 (19)
C1	0.085 (5)	0.061 (4)	0.029 (3)	0.022 (4)	0.000 (3)	0.011 (3)
C2	0.087 (5)	0.075 (5)	0.034 (3)	0.029 (4)	0.016 (3)	0.018 (3)
C3	0.063 (4)	0.070 (4)	0.033 (3)	0.028 (4)	0.005 (3)	0.011 (3)
C4	0.058 (4)	0.048 (4)	0.033 (3)	0.017 (3)	0.008 (3)	0.008 (3)
C5	0.055 (4)	0.068 (4)	0.041 (3)	0.017 (3)	0.003 (3)	0.009 (3)
C6	0.069 (5)	0.078 (5)	0.050 (4)	0.027 (4)	−0.005 (3)	0.019 (3)
C7	0.060 (4)	0.064 (4)	0.035 (3)	0.020 (3)	0.015 (3)	0.013 (3)
C8	0.052 (4)	0.058 (4)	0.028 (3)	0.020 (3)	0.013 (3)	0.010 (3)
C9	0.063 (4)	0.055 (4)	0.031 (3)	0.023 (3)	0.017 (3)	0.008 (3)
C10	0.053 (4)	0.052 (4)	0.032 (3)	0.024 (3)	0.009 (3)	0.010 (2)
C11	0.066 (5)	0.081 (5)	0.041 (3)	0.032 (4)	0.017 (3)	0.015 (3)
C12	0.063 (4)	0.087 (5)	0.047 (4)	0.040 (4)	0.004 (3)	0.010 (3)
C13	0.077 (5)	0.084 (5)	0.031 (3)	0.045 (4)	0.007 (3)	0.016 (3)
C14	0.077 (5)	0.055 (4)	0.028 (3)	0.033 (3)	0.015 (3)	0.011 (3)
C15	0.068 (4)	0.042 (3)	0.031 (3)	0.023 (3)	0.009 (3)	0.005 (2)
C16	0.060 (4)	0.060 (4)	0.030 (3)	0.018 (3)	0.016 (3)	0.011 (3)

Geometric parameters (Å, º) top

Br—C14	1.898 (6)	C8—C9	1.470 (8)
O—C9	1.224 (6)	C8—C16	1.521 (7)
F—C1	1.371 (6)	C9—C10	1.473 (7)
C1—C6	1.341 (9)	C10—C11	1.375 (8)
C1—C2	1.365 (8)	C10—C15	1.382 (7)
C2—C3	1.389 (7)	C11—C12	1.394 (7)
C2—H2A	0.9300	C11—H11A	0.9300
C3—C4	1.395 (8)	C12—C13	1.376 (8)
C3—H3A	0.9300	C12—H12A	0.9300
C4—C5	1.385 (7)	C13—C14	1.364 (8)
C4—C7	1.476 (7)	C13—H13A	0.9300
C5—C6	1.385 (7)	C14—C15	1.393 (7)
C5—H5A	0.9300	C15—C16	1.480 (7)
C6—H6A	0.9300	C16—H16A	0.9700
C7—C8	1.352 (7)	C16—H16B	0.9700
C7—H7A	0.9300

C6—C1—C2	123.3 (5)	C8—C9—C10	107.1 (4)
C6—C1—F	118.5 (6)	C11—C10—C15	122.0 (5)
C2—C1—F	118.1 (6)	C11—C10—C9	128.3 (5)
C1—C2—C3	118.3 (6)	C15—C10—C9	109.7 (5)
C1—C2—H2A	120.9	C10—C11—C12	118.4 (6)
C3—C2—H2A	120.9	C10—C11—H11A	120.8
C2—C3—C4	120.3 (6)	C12—C11—H11A	120.8
C2—C3—H3A	119.8	C13—C12—C11	119.9 (6)
C4—C3—H3A	119.8	C13—C12—H12A	120.1
C5—C4—C3	118.4 (5)	C11—C12—H12A	120.1
C5—C4—C7	116.8 (5)	C14—C13—C12	121.2 (5)
C3—C4—C7	124.7 (5)	C14—C13—H13A	119.4
C4—C5—C6	120.9 (6)	C12—C13—H13A	119.4
C4—C5—H5A	119.5	C13—C14—C15	119.9 (5)
C6—C5—H5A	119.5	C13—C14—Br	121.3 (4)
C1—C6—C5	118.7 (6)	C15—C14—Br	118.8 (5)
C1—C6—H6A	120.7	C10—C15—C14	118.5 (5)
C5—C6—H6A	120.7	C10—C15—C16	111.1 (4)
C8—C7—C4	134.8 (5)	C14—C15—C16	130.3 (5)
C8—C7—H7A	112.6	C15—C16—C8	104.5 (4)
C4—C7—H7A	112.6	C15—C16—H16A	110.8
C7—C8—C9	132.6 (5)	C8—C16—H16A	110.8
C7—C8—C16	119.9 (5)	C15—C16—H16B	110.8
C9—C8—C16	107.5 (4)	C8—C16—H16B	110.8
O—C9—C8	129.6 (5)	H16A—C16—H16B	108.9
O—C9—C10	123.4 (5)

C6—C1—C2—C3	−0.6 (10)	O—C9—C10—C15	177.6 (5)
F—C1—C2—C3	−179.8 (5)	C8—C9—C10—C15	−1.8 (6)
C1—C2—C3—C4	0.3 (9)	C15—C10—C11—C12	−1.8 (9)
C2—C3—C4—C5	−0.5 (9)	C9—C10—C11—C12	179.1 (5)
C2—C3—C4—C7	−178.8 (5)	C10—C11—C12—C13	1.2 (9)
C3—C4—C5—C6	0.8 (9)	C11—C12—C13—C14	0.4 (10)
C7—C4—C5—C6	179.3 (5)	C12—C13—C14—C15	−1.4 (9)
C2—C1—C6—C5	1.0 (10)	C12—C13—C14—Br	178.7 (5)
F—C1—C6—C5	−179.9 (5)	C11—C10—C15—C14	0.8 (9)
C4—C5—C6—C1	−1.1 (10)	C9—C10—C15—C14	180.0 (5)
C5—C4—C7—C8	176.9 (6)	C11—C10—C15—C16	−178.2 (5)
C3—C4—C7—C8	−4.8 (11)	C9—C10—C15—C16	0.9 (7)
C4—C7—C8—C9	0.7 (12)	C13—C14—C15—C10	0.9 (8)
C4—C7—C8—C16	−178.4 (6)	Br—C14—C15—C10	−179.3 (4)
C7—C8—C9—O	3.4 (11)	C13—C14—C15—C16	179.7 (6)
C16—C8—C9—O	−177.5 (6)	Br—C14—C15—C16	−0.5 (8)
C7—C8—C9—C10	−177.3 (6)	C10—C15—C16—C8	0.2 (6)
C16—C8—C9—C10	1.9 (6)	C14—C15—C16—C8	−178.7 (5)
O—C9—C10—C11	−3.3 (10)	C7—C8—C16—C15	178.0 (5)
C8—C9—C10—C11	177.4 (6)	C9—C8—C16—C15	−1.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O	0.93	2.14	2.972 (8)	149

Experimental details

Crystal data
Chemical formula	C₁₆H₁₀BrFO
M_r	317.15
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.3580 (15), 7.4630 (15), 13.140 (3)
α, β, γ (°)	101.45 (3), 96.80 (3), 111.72 (3)
V (Å³)	642.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.20
Crystal size (mm)	0.10 × 0.10 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.740, 0.856
No. of measured, independent and observed [I > 2σ(I)] reflections	2518, 2319, 1351
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.137, 1.00
No. of reflections	2319
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.35

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O	0.93	2.14	2.972 (8)	149.00

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Deeni, B. & Ravi, M. R. (2001). Tetrahedron Lett. 42, 3025–3027. Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar