5-(1H-Inden-2-yl)-1,3-benzodioxole

Deng, R.-X.; Zhou, W.-Y.; Deng, X.-J.; Sun, L.-D.

doi:10.1107/S1600536808001578

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o492

doi:10.1107/S1600536808001578

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5-(1H-Inden-2-yl)-1,3-benzodioxole

Rui-Xue Deng,^a Wei-Yi Zhou,^b Xiao-Juan Deng ^b and Liang-Dong Sun ^a ^*

^aDepartment of Chemistry, Tianjin University, Tianjin 300072, People's Republic of China, and ^bAnalysis Center, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: dengliu20022002@yahoo.com.cn

(Received 17 November 2007; accepted 15 January 2008; online 23 January 2008)

In the title compound, C₁₆H₁₂O₂, the non-H atoms are coplanar with a mean r.m.s. deviation of 0.0260 (2) Å. The deviations of the bond angles from normal values at the indenyl junction C atom and the indenyl bridgehead C atom nearest the junction are imposed by the five-membered ring geometry. Due to conjugation, the single bond linking the two ring systems [1.455 (3) Å] is significantly shorter than the formal single bonds in the five-membered carbocyclic ring [1.500 (3) and 1.489 (3) Å].

Related literature

For related literature, see: Rayabarapu et al. (2003 ); Senanayake et al. (1995 ).

Experimental

Crystal data

C₁₆H₁₂O₂
M_r = 236.26
Orthorhombic, P c a 2₁
a = 22.277 (10) Å
b = 6.892 (3) Å
c = 7.580 (3) Å
V = 1163.7 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 294 (2) K
0.24 × 0.22 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.979, T_max = 0.990
6325 measured reflections
1286 independent reflections
1072 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.091
S = 1.08
1286 reflections
164 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001578/kp2152sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001578/kp2152Isup2.hkl

checkCIF report

Comment top

Indene ring frameworks are present in a large number of biologically active compounds, and their metallocene complexes are able to catalyze olefin polymerization (Senanayake et al., 1995; Rayabarapu et al., 2003). Some derivatives have shown analgesic and myorelaxation activity whereas others are used as valuable intermediates for the synthesis of indenyl chrysanthemates that possess insecticidal properties. In the recent three decades, many chemists have been attracted by the synthesis of indenes. In this context, we report the synthesis and crystal structure of the title compound, (I). The molecul of (I) (Fig. 1) is almost planar (except the H atoms) with the mean value of r.m.s. deviation of 0.0260 (2) Å. The bonding angles of C16—C8—C5 and C16—C8—C9 are 128.3 (2) and 108.88 (19)°, respectively; their deviations from ideal values are imposed by request of a five-ring geometry. The similar deviation is also observed for the C15 with the angles of C14—C15—C16 [132.2 (2)°] and C10—C15—C16 [108.1 (2)°]. Due to the π-π conjugation of the C5?C6 and C8?C16, the single bond distance of the C5—C8 [1.455 (3) Å] is significantly shorter than that of C8—C9 [1.500 (3) Å].

Related literature top

For related literature, see: Rayabarapu et al. (2003); Senanayake et al. (1995).

Experimental top

o-Bromobenzyl zinc bromide (3.5 mmol, 3.5 equiv) in 3.5 ml CH₂Cl₂ was added to a degassed refluxing CH₂Cl₂ solution (8 ml) of 5-ethynyl benzo [1,3] dioxole (1.0 mmol, 1.0 equiv) and Ni(PPh₃)₂I₂ (0.1 mmol, 0.1 equiv). After stirring at 313 K for 6 h, the solution was cooled to room temperature. The solution obtained was diluted with 50 ml e thyl acetate. The organic layer was washed with 10 ml aqueous HCl solution, saturated by NaCl. The aqueous layer was back-extracted with ethyl acetate. The combined organic layer was dried over anhydrous Na₂SO₄. After filtration, the solvent was removed under reduced pressure and the residue was purified via flash chromatography (SiO₂) to afford the compound. Crystals suitale for X-ray analysis were obtained by slow evaporation from a CH₂Cl₂ solution at 298 K.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level.

5-(1H-Inden-2-yl)-1,3-benzodioxole top

Crystal data top

C₁₆H₁₂O₂	F(000) = 496
M_r = 236.26	D_x = 1.348 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2528 reflections
a = 22.277 (10) Å	θ = 2.7–25.2°
b = 6.892 (3) Å	µ = 0.09 mm⁻¹
c = 7.580 (3) Å	T = 294 K
V = 1163.7 (9) Å³	Plate, colourless
Z = 4	0.24 × 0.22 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1286 independent reflections
Radiation source: fine-focus sealed tube	1072 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 26.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −27→13
T_min = 0.979, T_max = 0.990	k = −8→8
6325 measured reflections	l = −8→9

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0567P)² + 0.0272P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.091	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.12 e Å⁻³
1286 reflections	Δρ_min = −0.11 e Å⁻³
164 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.006 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: indeterminate
Secondary atom site location: difference Fourier map

Crystal data top

C₁₆H₁₂O₂	V = 1163.7 (9) Å³
M_r = 236.26	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 22.277 (10) Å	µ = 0.09 mm⁻¹
b = 6.892 (3) Å	T = 294 K
c = 7.580 (3) Å	0.24 × 0.22 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1286 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1072 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.990	R_int = 0.035
6325 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	1 restraint
wR(F²) = 0.091	H-atom parameters constrained
S = 1.08	Δρ_max = 0.12 e Å⁻³
1286 reflections	Δρ_min = −0.11 e Å⁻³
164 parameters	Absolute structure: indeterminate

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
O1	0.33678 (7)	0.3967 (2)	0.9508 (3)	0.0629 (5)
O2	0.41993 (8)	0.2623 (2)	1.0832 (3)	0.0676 (6)
C1	0.35772 (11)	0.2393 (4)	1.0539 (5)	0.0686 (8)
H1A	0.3366	0.2362	1.1658	0.082*
H1B	0.3502	0.1180	0.9929	0.082*
C2	0.38388 (9)	0.5252 (3)	0.9457 (3)	0.0472 (5)
C3	0.38568 (10)	0.7034 (3)	0.8718 (4)	0.0512 (6)
H3	0.3523	0.7568	0.8162	0.061*
C4	0.43988 (10)	0.8035 (3)	0.8829 (3)	0.0480 (5)
H4	0.4425	0.9262	0.8326	0.058*
C5	0.49008 (9)	0.7272 (3)	0.9662 (3)	0.0415 (5)
C6	0.48641 (10)	0.5410 (3)	1.0401 (3)	0.0468 (5)
H6	0.5192	0.4849	1.0966	0.056*
C7	0.43337 (10)	0.4460 (3)	1.0263 (3)	0.0472 (5)
C8	0.54537 (9)	0.8392 (3)	0.9756 (3)	0.0417 (5)
C9	0.55116 (10)	1.0396 (3)	0.9004 (3)	0.0482 (5)
H9A	0.5435	1.0394	0.7744	0.058*
H9B	0.5234	1.1284	0.9570	0.058*
C10	0.61447 (10)	1.0948 (3)	0.9384 (3)	0.0488 (6)
C11	0.64540 (11)	1.2630 (4)	0.9035 (4)	0.0606 (7)
H11	0.6271	1.3649	0.8438	0.073*
C12	0.70444 (12)	1.2778 (4)	0.9592 (4)	0.0703 (8)
H12	0.7259	1.3910	0.9372	0.084*
C13	0.73163 (11)	1.1275 (4)	1.0462 (4)	0.0692 (8)
H13	0.7714	1.1399	1.0822	0.083*
C14	0.70099 (10)	0.9578 (4)	1.0814 (4)	0.0611 (7)
H14	0.7198	0.8564	1.1405	0.073*
C15	0.64208 (10)	0.9406 (3)	1.0277 (3)	0.0489 (6)
C16	0.59838 (10)	0.7872 (3)	1.0480 (3)	0.0483 (5)
H16	0.6057	0.6691	1.1032	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0482 (8)	0.0638 (10)	0.0767 (12)	−0.0047 (7)	−0.0055 (9)	0.0074 (10)
O2	0.0584 (10)	0.0524 (10)	0.0920 (15)	−0.0043 (8)	−0.0100 (10)	0.0205 (10)
C1	0.0586 (15)	0.0618 (15)	0.085 (2)	−0.0056 (12)	−0.0049 (15)	0.0124 (16)
C2	0.0460 (12)	0.0512 (12)	0.0443 (12)	0.0027 (9)	−0.0027 (11)	−0.0031 (11)
C3	0.0485 (13)	0.0532 (12)	0.0519 (13)	0.0110 (10)	−0.0098 (11)	0.0034 (12)
C4	0.0531 (13)	0.0433 (11)	0.0477 (12)	0.0069 (10)	−0.0060 (11)	0.0016 (10)
C5	0.0479 (12)	0.0410 (10)	0.0357 (10)	0.0080 (8)	−0.0030 (10)	−0.0034 (9)
C6	0.0482 (12)	0.0446 (12)	0.0476 (12)	0.0082 (9)	−0.0083 (10)	0.0005 (11)
C7	0.0523 (12)	0.0428 (11)	0.0466 (12)	0.0080 (10)	−0.0005 (11)	−0.0005 (10)
C8	0.0470 (11)	0.0414 (10)	0.0365 (10)	0.0086 (9)	−0.0040 (9)	−0.0039 (9)
C9	0.0536 (12)	0.0425 (11)	0.0485 (13)	0.0069 (10)	−0.0049 (11)	−0.0001 (10)
C10	0.0521 (13)	0.0539 (12)	0.0404 (12)	0.0021 (10)	0.0062 (10)	−0.0082 (11)
C11	0.0640 (16)	0.0615 (15)	0.0564 (15)	−0.0072 (12)	0.0080 (13)	−0.0007 (12)
C12	0.0664 (17)	0.0803 (18)	0.0644 (16)	−0.0188 (13)	0.0157 (16)	−0.0118 (16)
C13	0.0431 (13)	0.094 (2)	0.0701 (18)	−0.0063 (13)	0.0081 (14)	−0.0234 (17)
C14	0.0461 (14)	0.0761 (18)	0.0612 (16)	0.0082 (12)	0.0014 (12)	−0.0127 (13)
C15	0.0450 (12)	0.0569 (13)	0.0450 (12)	0.0079 (10)	0.0026 (11)	−0.0102 (11)
C16	0.0517 (12)	0.0459 (11)	0.0473 (12)	0.0076 (10)	−0.0047 (11)	−0.0022 (11)

Geometric parameters (Å, º) top

O1—C2	1.374 (3)	C8—C9	1.500 (3)
O1—C1	1.416 (3)	C9—C10	1.489 (3)
O2—C7	1.370 (3)	C9—H9A	0.9700
O2—C1	1.412 (3)	C9—H9B	0.9700
C1—H1A	0.9700	C10—C11	1.375 (3)
C1—H1B	0.9700	C10—C15	1.402 (3)
C2—C3	1.351 (3)	C11—C12	1.385 (4)
C2—C7	1.373 (3)	C11—H11	0.9300
C3—C4	1.393 (3)	C12—C13	1.369 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.387 (3)	C13—C14	1.380 (4)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.402 (3)	C14—C15	1.379 (3)
C5—C8	1.455 (3)	C14—H14	0.9300
C6—C7	1.355 (3)	C15—C16	1.446 (3)
C6—H6	0.9300	C16—H16	0.9300
C8—C16	1.350 (3)

C2—O1—C1	104.93 (18)	C5—C8—C9	122.86 (17)
C7—O2—C1	105.56 (18)	C10—C9—C8	104.06 (17)
O2—C1—O1	108.9 (2)	C10—C9—H9A	110.9
O2—C1—H1A	109.9	C8—C9—H9A	110.9
O1—C1—H1A	109.9	C10—C9—H9B	110.9
O2—C1—H1B	109.9	C8—C9—H9B	110.9
O1—C1—H1B	109.9	H9A—C9—H9B	109.0
H1A—C1—H1B	108.3	C11—C10—C15	120.8 (2)
C3—C2—C7	121.5 (2)	C11—C10—C9	130.8 (2)
C3—C2—O1	128.4 (2)	C15—C10—C9	108.4 (2)
C7—C2—O1	110.1 (2)	C10—C11—C12	118.6 (3)
C2—C3—C4	116.8 (2)	C10—C11—H11	120.7
C2—C3—H3	121.6	C12—C11—H11	120.7
C4—C3—H3	121.6	C13—C12—C11	120.8 (3)
C5—C4—C3	122.6 (2)	C13—C12—H12	119.6
C5—C4—H4	118.7	C11—C12—H12	119.6
C3—C4—H4	118.7	C12—C13—C14	121.0 (2)
C4—C5—C6	118.8 (2)	C12—C13—H13	119.5
C4—C5—C8	120.23 (19)	C14—C13—H13	119.5
C6—C5—C8	120.99 (18)	C15—C14—C13	119.1 (3)
C7—C6—C5	117.51 (19)	C15—C14—H14	120.4
C7—C6—H6	121.2	C13—C14—H14	120.4
C5—C6—H6	121.2	C14—C15—C10	119.7 (2)
C6—C7—O2	127.8 (2)	C14—C15—C16	132.2 (2)
C6—C7—C2	122.8 (2)	C10—C15—C16	108.1 (2)
O2—C7—C2	109.38 (19)	C8—C16—C15	110.6 (2)
C16—C8—C5	128.3 (2)	C8—C16—H16	124.7
C16—C8—C9	108.88 (19)	C15—C16—H16	124.7

C7—O2—C1—O1	10.4 (3)	C4—C5—C8—C9	0.9 (3)
C2—O1—C1—O2	−9.7 (3)	C6—C5—C8—C9	−179.3 (2)
C1—O1—C2—C3	−176.1 (3)	C16—C8—C9—C10	0.3 (2)
C1—O1—C2—C7	5.4 (3)	C5—C8—C9—C10	−179.4 (2)
C7—C2—C3—C4	−0.7 (3)	C8—C9—C10—C11	−178.7 (2)
O1—C2—C3—C4	−179.0 (2)	C8—C9—C10—C15	−0.2 (2)
C2—C3—C4—C5	−0.4 (4)	C15—C10—C11—C12	−0.3 (4)
C3—C4—C5—C6	0.9 (4)	C9—C10—C11—C12	178.0 (3)
C3—C4—C5—C8	−179.3 (2)	C10—C11—C12—C13	0.4 (4)
C4—C5—C6—C7	−0.3 (3)	C11—C12—C13—C14	−0.2 (4)
C8—C5—C6—C7	179.9 (2)	C12—C13—C14—C15	−0.1 (4)
C5—C6—C7—O2	177.9 (2)	C13—C14—C15—C10	0.1 (4)
C5—C6—C7—C2	−0.8 (4)	C13—C14—C15—C16	−178.2 (3)
C1—O2—C7—C6	174.2 (3)	C11—C10—C15—C14	0.1 (3)
C1—O2—C7—C2	−7.0 (3)	C9—C10—C15—C14	−178.6 (2)
C3—C2—C7—C6	1.3 (4)	C11—C10—C15—C16	178.8 (2)
O1—C2—C7—C6	179.9 (2)	C9—C10—C15—C16	0.1 (3)
C3—C2—C7—O2	−177.6 (2)	C5—C8—C16—C15	179.4 (2)
O1—C2—C7—O2	1.0 (3)	C9—C8—C16—C15	−0.2 (3)
C4—C5—C8—C16	−178.7 (2)	C14—C15—C16—C8	178.6 (2)
C6—C5—C8—C16	1.1 (4)	C10—C15—C16—C8	0.1 (3)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂O₂
M_r	236.26
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	294
a, b, c (Å)	22.277 (10), 6.892 (3), 7.580 (3)
V (Å³)	1163.7 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.24 × 0.22 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.979, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	6325, 1286, 1072
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.091, 1.08
No. of reflections	1286
No. of parameters	164
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.11
Absolute structure	Indeterminate

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Bruker (1997). SMART (Version 5.611), SAINT (Version 6.0) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Rayabarapu, D. K., Yang, C. H. & Cheng, C. H. (2003). J. Org. Chem. 68, 6726–6731. Web of Science CrossRef PubMed CAS Google Scholar
Senanayake, C. H., Roberts, F. E., DiMichele, L. M., Ryan, K. M., Liu, J., Fredenburgh, L. E., Foster, B. S., Douglas, A. W., Larsen, R. D., Verhoeven, T. R. & Reider, P. J. (1995). Tetrahedron Lett. 36, 3993–3996. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar