5-Amino-4-bromo-2,3-dihydro-1H-inden-1-one

Çelik, Í.; Akkurt, M.; Yılmaz, M.; Tutar, A.; Erenler, R.; García-Granda, S.

doi:10.1107/S1600536812007489

organic compounds

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Volume 68| Part 3| March 2012| Page o833

doi:10.1107/S1600536812007489

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5-Amino-4-bromo-2,3-dihydro-1H-inden-1-one

Ísmail Çelik,^a Mehmet Akkurt,^b ^* Makbule Yılmaz,^c Ahmet Tutar,^c Ramazan Erenler ^d and Santiago García-Granda ^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 ^eDepartamento Química Física y Analítica, Facultad de Química, Universidad Oviedo, C/ Julián Clavería, 8, 33006 Oviedo (Asturias), Spain
^*Correspondence e-mail: akkurt@erciyes.edu.tr

(Received 14 February 2012; accepted 19 February 2012; online 24 February 2012)

In the title compound, C₉H₈BrNO, the non-H-atom framework is essentially planar, with a maximum deviation of 0.087 (3) Å. In the crystal, molecules are interconnected into a three-dimensional network by C—H⋯O and N—H⋯O hydrogen bonds. In addition, C—H⋯π interactions and a π–π stacking interaction, with a centroid–centroid distance of 3.5535 (19) Å, are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₈BrNO
M_r = 226.06
Monoclinic, C 2/c
a = 12.6362 (4) Å
b = 8.3655 (2) Å
c = 17.4913 (5) Å
β = 113.128 (4)°
V = 1700.37 (10) Å³
Z = 8
Cu Kα radiation
μ = 6.16 mm⁻¹
T = 297 K
0.77 × 0.60 × 0.08 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.031, T_max = 0.616
3085 measured reflections
1594 independent reflections
1544 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.134
S = 1.06
1594 reflections
117 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.31 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.83 (4)	2.14 (5)	2.915 (4)	155 (4)
C8—H8B⋯O1ⁱⁱ	0.97	2.50	3.448 (4)	166
C7—H7B⋯Cg2ⁱⁱⁱ	0.97	2.85	3.659 (4)	141
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 1997 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812007489/fj2519sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007489/fj2519Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007489/fj2519Isup3.cml

checkCIF report

Comment top

In ¹H-NMR spectrum, H7 appeared at δ 7.53 as a doublet with coupling constant 8.3 Hz and H6 appeared at δ 6.73 (J = 8.3 Hz) as doublet. NH2 protons were observed at δ 4.82 with broad singlet. Two signal groups (δ 2.98, δ 2.70) observed at aliphatic region fit with the aliphatic protons. In the present study, we describe the molecular and crystal structures of 5-amino-4-bromo-2,3-dihydro-1H-inden-1-one (I), using X-ray diffraction.

As shown in Fig. 1, the molecule of (I), except H atoms, is essentially planar with a maximum deviation of -0.087 (3) Å for O1 atom. Bond lengths and angles observed in (I) are normal (Allen et al., 1987).

The crystal packing is stabilized by intermolecular C—H···O and N—H···O hydrogen bonds (Table 1, Fig. 2) forming a three-dimensional network. In addition, π-π stacking interactions [centroid-centroid distance = 3.5535 (19) Å] between the centroids of the C1–C6 benzene rings of the neighbouring molecules stacking interactions are also observed. C—H···π interactions further help in stabilizing the supramolecular structure (Table 1).

Related literature top

For bond-length data, see: Allen et al. (1987).

Experimental top

To a stirred solution of 5- acetoaminoindanone (0.4 g, 1.95 mmol) in PEG (2.5 g) was added NBS (1.0 g, 5.6 mmol), SiO₂ (1.0 g) and NaClO₄ (0.2 g). The reaction mixture was stirred for 30 days at room temperature, diluted with water (15 ml), extracted with diethyl ether (3×25 ml), dried (Na₂SO₄). After removal of the solvent, the residue was chromatographed on silica gel eluted with chloroform/hexane (4/1) afforded the title compound which was crystallized from dichloromethane-hexane yielded the colourless plate crystal (0.11 g, 25%), ¹H-NMR (400 MHz, CDCl₃); δ 7.53 (d, J = 8.3 Hz, 1H, H7), 6.74 (d, J = 8.3 Hz, 1H, H6), 4.82 (brs, 2H, NH₂), 2.98 (m, 2H, H2), 2.70 (m, 2H, H3).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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, 1999); software used to prepare material for publication: WinGX (Farrugia, 1997) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
	Fig. 2. The packing and hydrogen bonding of (I), viewing down the b axis. H atoms not involved in hydrogen bonding have been omitted.

5-Amino-4-bromo-2,3-dihydro-1H-inden-1-one top

Crystal data top

C₉H₈BrNO	F(000) = 896
M_r = 226.06	D_x = 1.766 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -C 2yc	Cell parameters from 2518 reflections
a = 12.6362 (4) Å	θ = 5.5–70.2°
b = 8.3655 (2) Å	µ = 6.16 mm⁻¹
c = 17.4913 (5) Å	T = 297 K
β = 113.128 (4)°	Plate, colourless
V = 1700.37 (10) Å³	0.77 × 0.60 × 0.08 mm
Z = 8

Data collection top

Agilent Xcalibur Ruby Gemini diffractometer	1594 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1544 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.2673 pixels mm^-1	θ_max = 70.4°, θ_min = 5.5°
ω scans	h = −13→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −6→10
T_min = 0.031, T_max = 0.616	l = −19→21
3085 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.1063P)² + 1.0273P] where P = (F_o² + 2F_c²)/3
1594 reflections	(Δ/σ)_max = 0.001
117 parameters	Δρ_max = 1.31 e Å⁻³
3 restraints	Δρ_min = −0.89 e Å⁻³

Crystal data top

C₉H₈BrNO	V = 1700.37 (10) Å³
M_r = 226.06	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 12.6362 (4) Å	µ = 6.16 mm⁻¹
b = 8.3655 (2) Å	T = 297 K
c = 17.4913 (5) Å	0.77 × 0.60 × 0.08 mm
β = 113.128 (4)°

Data collection top

Agilent Xcalibur Ruby Gemini diffractometer	1594 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1544 reflections with I > 2σ(I)
T_min = 0.031, T_max = 0.616	R_int = 0.026
3085 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	3 restraints
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 1.31 e Å⁻³
1594 reflections	Δρ_min = −0.89 e Å⁻³
117 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	0.52857 (3)	0.21900 (4)	0.63347 (2)	0.0470 (2)
O1	0.2303 (2)	0.4628 (3)	0.26770 (13)	0.0544 (8)
N1	0.3501 (3)	0.4337 (4)	0.66390 (17)	0.0535 (9)
C1	0.3037 (3)	0.4330 (4)	0.41603 (17)	0.0381 (8)
C2	0.2318 (3)	0.5262 (4)	0.44160 (18)	0.0422 (8)
C3	0.2489 (3)	0.5253 (4)	0.5240 (2)	0.0431 (9)
C4	0.3357 (3)	0.4322 (4)	0.58293 (17)	0.0399 (8)
C5	0.4086 (2)	0.3422 (3)	0.55556 (16)	0.0368 (8)
C6	0.3917 (2)	0.3426 (3)	0.47291 (16)	0.0345 (8)
C7	0.4597 (3)	0.2542 (4)	0.4321 (2)	0.0430 (9)
C8	0.4016 (3)	0.3016 (4)	0.3399 (2)	0.0493 (10)
C9	0.3006 (3)	0.4086 (4)	0.33249 (17)	0.0425 (8)
H1N	0.301 (3)	0.472 (5)	0.679 (3)	0.062 (12)*
H2	0.17350	0.58760	0.40350	0.0510*
H2N	0.387 (4)	0.369 (6)	0.701 (3)	0.10 (2)*
H3	0.20180	0.58790	0.54150	0.0520*
H7A	0.45550	0.13960	0.43890	0.0520*
H7B	0.53980	0.28670	0.45540	0.0520*
H8A	0.45530	0.35870	0.32260	0.0590*
H8B	0.37490	0.20740	0.30530	0.0590*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0466 (3)	0.0552 (4)	0.0315 (3)	0.0060 (1)	0.0070 (2)	0.0028 (1)
O1	0.0541 (13)	0.0741 (16)	0.0303 (10)	−0.0051 (12)	0.0114 (10)	0.0072 (10)
N1	0.0619 (17)	0.0712 (18)	0.0322 (13)	0.0012 (15)	0.0237 (13)	−0.0070 (12)
C1	0.0412 (14)	0.0433 (13)	0.0290 (13)	−0.0056 (12)	0.0128 (11)	0.0001 (10)
C2	0.0393 (14)	0.0471 (15)	0.0368 (15)	0.0014 (12)	0.0114 (12)	0.0050 (12)
C3	0.0443 (15)	0.0451 (14)	0.0443 (16)	0.0013 (13)	0.0221 (13)	−0.0033 (12)
C4	0.0444 (14)	0.0451 (14)	0.0305 (14)	−0.0062 (12)	0.0152 (12)	−0.0046 (11)
C5	0.0386 (13)	0.0414 (14)	0.0274 (12)	−0.0026 (12)	0.0098 (10)	−0.0017 (10)
C6	0.0371 (13)	0.0362 (13)	0.0298 (13)	−0.0009 (10)	0.0126 (11)	−0.0008 (10)
C7	0.0438 (17)	0.0496 (13)	0.0376 (17)	0.0024 (14)	0.0182 (14)	−0.0045 (13)
C8	0.0578 (19)	0.0602 (18)	0.0344 (16)	−0.0064 (15)	0.0230 (15)	−0.0064 (13)
C9	0.0474 (15)	0.0501 (15)	0.0299 (14)	−0.0140 (13)	0.0151 (12)	−0.0006 (11)

Geometric parameters (Å, º) top

Br1—C5	1.896 (3)	C5—C6	1.376 (4)
O1—C9	1.220 (4)	C6—C7	1.509 (5)
N1—C4	1.355 (4)	C7—C8	1.539 (5)
N1—H1N	0.83 (4)	C8—C9	1.522 (5)
N1—H2N	0.83 (5)	C2—H2	0.9300
C1—C9	1.461 (4)	C3—H3	0.9300
C1—C2	1.397 (5)	C7—H7A	0.9700
C1—C6	1.389 (4)	C7—H7B	0.9700
C2—C3	1.371 (4)	C8—H8A	0.9700
C3—C4	1.409 (5)	C8—H8B	0.9700
C4—C5	1.411 (5)

H1N—N1—H2N	105 (5)	C7—C8—C9	106.3 (3)
C4—N1—H1N	122 (3)	O1—C9—C1	126.9 (3)
C4—N1—H2N	128 (3)	O1—C9—C8	125.3 (3)
C2—C1—C6	120.9 (3)	C1—C9—C8	107.8 (3)
C2—C1—C9	129.3 (3)	C1—C2—H2	121.00
C6—C1—C9	109.9 (3)	C3—C2—H2	121.00
C1—C2—C3	118.7 (3)	C2—C3—H3	119.00
C2—C3—C4	121.9 (3)	C4—C3—H3	119.00
C3—C4—C5	118.1 (3)	C6—C7—H7A	111.00
N1—C4—C5	121.5 (3)	C6—C7—H7B	111.00
N1—C4—C3	120.4 (3)	C8—C7—H7A	111.00
Br1—C5—C4	119.4 (2)	C8—C7—H7B	111.00
Br1—C5—C6	120.5 (2)	H7A—C7—H7B	109.00
C4—C5—C6	120.2 (2)	C7—C8—H8A	110.00
C1—C6—C5	120.3 (3)	C7—C8—H8B	111.00
C1—C6—C7	111.9 (3)	C9—C8—H8A	110.00
C5—C6—C7	127.9 (3)	C9—C8—H8B	110.00
C6—C7—C8	104.1 (3)	H8A—C8—H8B	109.00

C6—C1—C2—C3	−0.8 (5)	N1—C4—C5—Br1	0.6 (4)
C9—C1—C2—C3	177.4 (4)	N1—C4—C5—C6	179.8 (3)
C2—C1—C6—C5	0.7 (5)	C3—C4—C5—Br1	178.7 (2)
C2—C1—C6—C7	−178.9 (3)	C3—C4—C5—C6	−2.1 (5)
C9—C1—C6—C5	−177.8 (3)	Br1—C5—C6—C1	180.0 (2)
C9—C1—C6—C7	2.7 (4)	Br1—C5—C6—C7	−0.5 (4)
C2—C1—C9—O1	−2.6 (6)	C4—C5—C6—C1	0.8 (4)
C2—C1—C9—C8	177.6 (4)	C4—C5—C6—C7	−179.7 (3)
C6—C1—C9—O1	175.7 (3)	C1—C6—C7—C8	−0.1 (4)
C6—C1—C9—C8	−4.1 (4)	C5—C6—C7—C8	−179.7 (3)
C1—C2—C3—C4	−0.7 (5)	C6—C7—C8—C9	−2.4 (3)
C2—C3—C4—N1	−179.8 (4)	C7—C8—C9—O1	−175.9 (3)
C2—C3—C4—C5	2.1 (5)	C7—C8—C9—C1	4.0 (4)

Hydrogen-bond geometry (Å, º) top

Cg2 is a centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.83 (4)	2.14 (5)	2.915 (4)	155 (4)
N1—H2N···Br1	0.83 (5)	2.80 (5)	3.088 (4)	103 (4)
C8—H8B···O1ⁱⁱ	0.97	2.50	3.448 (4)	166
C7—H7B···Cg2ⁱⁱⁱ	0.97	2.85	3.659 (4)	141

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₈BrNO
M_r	226.06
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	297
a, b, c (Å)	12.6362 (4), 8.3655 (2), 17.4913 (5)
β (°)	113.128 (4)
V (Å³)	1700.37 (10)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	6.16
Crystal size (mm)	0.77 × 0.60 × 0.08

Data collection
Diffractometer	Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.031, 0.616
No. of measured, independent and observed [I > 2σ(I)] reflections	3085, 1594, 1544
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.611

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.134, 1.06
No. of reflections	1594
No. of parameters	117
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.31, −0.89

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1999), WinGX (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg2 is a centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.83 (4)	2.14 (5)	2.915 (4)	155 (4)
C8—H8B···O1ⁱⁱ	0.97	2.50	3.448 (4)	166
C7—H7B···Cg2ⁱⁱⁱ	0.97	2.85	3.659 (4)	141

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.

References

Agilent (2011). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, Oxfordshire, England. Google Scholar
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
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals 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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o833

doi:10.1107/S1600536812007489

Open

access