1-(3-Amino-1H-inden-2-yl)ethanone

Hu, D.-Y.; Qu, Z.-R.

doi:10.1107/S1600536808033485

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2239

doi:10.1107/S1600536808033485

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1-(3-Amino-1H-inden-2-yl)ethanone

Dong-Yue Hu ^a and Zhi-Rong Qu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: quzr@seu.edu.cn

(Received 30 September 2008; accepted 15 October 2008; online 31 October 2008)

The title compound, C₁₁H₁₁NO, was synthesized by the reaction of 2-(bromomethyl)benzonitrile and acetylacetone in the presence of KOH. In the crystal packing, molecules are linked by intermolecular N—H⋯O hydrogen bonds into chains running parallel to the b axis. Centrosymmetrically-related chains interact further through weak C—H⋯π interactions.

Related literature

For the crystal structures of related compounds, see: Choi et al. (1999 ); Fu & Zhao (2007 ).

Experimental

Crystal data

C₁₁H₁₁NO
M_r = 173.21
Monoclinic, P 2₁ /c
a = 8.1794 (4) Å
b = 10.6905 (5) Å
c = 10.5602 (6) Å
β = 93.783 (8)°
V = 921.39 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 (2) K
0.25 × 0.16 × 0.14 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.980, T_max = 0.989
9369 measured reflections
2108 independent reflections
1385 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.171
S = 1.04
2108 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C11/C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.86	2.17	2.766 (2)	126
N1—H1B⋯O2ⁱ	0.86	2.09	2.924 (2)	164
C2—H2B⋯Cg1ⁱⁱ	0.97	2.77	3.631 (2)	148
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+2, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033485/rz2252sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033485/rz2252Isup2.hkl

checkCIF report

Comment top

In recent years, the synthesis and characterization of new ligands containing amino donor groups has received considerable attention due to the potential applications in coordination chemistry (Choi et al., 1999; Fu & Zhao, 2007). We report here the crystal structure of the title compound, which was obtained by the reaction of o-(bromomethyl)benzonitrile and acetylacetone in the presence of KOH.

In the molecule of the title compound (Fig. 1), the five-membered ring formed through the reaction is planar, and the geometric parameters are in the usual ranges. The molecular conformation is stabilized by an intramolecular N—H···O hydrogen bond (Table 1). In the crystal structure (Fig. 2), molecules are connected by intermolecular N—H···O hydrogen bonds into chains running parallel to the b axis (Table 1). Centrosymmetrically-related chains are further interacting through weak C—H···π interactions (Table 1).

Related literature top

For the crystal structures of related compounds, see: Choi et al. (1999); Fu & Zhao (2007).

Experimental top

Acetylacetone (0.5 g, 0.5 mmol) and o-(bromomethyl)-benzonitrile (0.98 g, 0.5 mmol) were dissolved in methanol (30 ml) in the presence of KOH (0.28 g, 0.5 mmol) and the mixture refluxed for 24 h at 393K. After cooling to room temperature, most of the solvent was removed by vacuum filtration. Colourless crystals of the title compound suitable for X-ray diffraction analysis were obtained by slow evaporation of the remaining solvent.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Packing diagram of the title compound. Intermolecular hydrogen bonds are shown as dashed lines.

1-(3-Amino-1H-inden-2-yl)ethanone top

Crystal data top

C₁₁H₁₁NO	F(000) = 368
M_r = 173.21	D_x = 1.249 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4430 reflections
a = 8.1794 (4) Å	θ = 3.1–27.4°
b = 10.6905 (5) Å	µ = 0.08 mm⁻¹
c = 10.5602 (6) Å	T = 293 K
β = 93.783 (8)°	Block, colourless
V = 921.39 (8) Å³	0.25 × 0.16 × 0.14 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2108 independent reflections
Radiation source: fine-focus sealed tube	1385 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD profile fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
T_min = 0.980, T_max = 0.989	l = −13→13
9369 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.171	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0814P)² + 0.2011P] where P = (F_o² + 2F_c²)/3
2108 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₁H₁₁NO	V = 921.39 (8) Å³
M_r = 173.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1794 (4) Å	µ = 0.08 mm⁻¹
b = 10.6905 (5) Å	T = 293 K
c = 10.5602 (6) Å	0.25 × 0.16 × 0.14 mm
β = 93.783 (8)°

Data collection top

Rigaku SCXmini diffractometer	2108 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1385 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.989	R_int = 0.049
9369 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 1.04	Δρ_max = 0.21 e Å⁻³
2108 reflections	Δρ_min = −0.20 e Å⁻³
119 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
C2	0.6932 (2)	0.90032 (19)	−0.07286 (18)	0.0447 (5)
H2A	0.7446	0.8647	−0.1448	0.054*
H2B	0.5859	0.8630	−0.0672	0.054*
C4	0.7981 (2)	0.88190 (18)	0.04815 (17)	0.0393 (5)
C5	0.8500 (2)	0.76630 (18)	0.1034 (2)	0.0434 (5)
C6	0.8406 (2)	0.99769 (18)	0.10065 (17)	0.0363 (4)
C7	0.7680 (2)	1.09672 (19)	0.01929 (18)	0.0389 (5)
C8	0.5992 (3)	1.1144 (2)	−0.1751 (2)	0.0584 (6)
H8	0.5401	1.0783	−0.2440	0.070*
C9	0.6815 (2)	1.0401 (2)	−0.08348 (18)	0.0439 (5)
C10	0.6928 (3)	1.2986 (3)	−0.0592 (2)	0.0629 (7)
H10	0.6952	1.3853	−0.0521	0.076*
C11	0.7750 (3)	1.2260 (2)	0.0329 (2)	0.0490 (6)
H11	0.8332	1.2626	0.1019	0.059*
C12	0.7998 (3)	0.6463 (2)	0.0355 (3)	0.0667 (7)
H12A	0.8792	0.5824	0.0570	0.100*
H12B	0.7939	0.6602	−0.0545	0.100*
H12C	0.6945	0.6204	0.0608	0.100*
C13	0.6070 (3)	1.2432 (2)	−0.1617 (2)	0.0664 (7)
H13	0.5533	1.2936	−0.2231	0.080*
N1	0.9314 (2)	1.01839 (16)	0.20784 (15)	0.0490 (5)
H1A	0.9702	0.9564	0.2522	0.059*
H1B	0.9512	1.0938	0.2328	0.059*
O2	0.93402 (18)	0.75969 (13)	0.20655 (14)	0.0527 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0439 (11)	0.0511 (13)	0.0384 (11)	0.0004 (9)	−0.0018 (8)	−0.0056 (9)
C4	0.0376 (10)	0.0419 (11)	0.0383 (10)	−0.0022 (8)	0.0014 (8)	−0.0035 (8)
C5	0.0434 (11)	0.0401 (12)	0.0470 (12)	−0.0014 (9)	0.0046 (9)	−0.0010 (8)
C6	0.0332 (9)	0.0403 (11)	0.0354 (10)	−0.0004 (8)	0.0023 (7)	0.0010 (8)
C7	0.0346 (9)	0.0424 (11)	0.0399 (11)	0.0010 (8)	0.0036 (8)	0.0024 (8)
C8	0.0553 (13)	0.0740 (18)	0.0446 (13)	0.0109 (12)	−0.0053 (10)	0.0031 (11)
C9	0.0392 (10)	0.0544 (14)	0.0380 (11)	0.0049 (9)	0.0023 (8)	0.0025 (9)
C10	0.0714 (16)	0.0487 (13)	0.0685 (17)	0.0096 (12)	0.0037 (13)	0.0164 (12)
C11	0.0484 (12)	0.0456 (14)	0.0526 (12)	0.0016 (10)	0.0007 (9)	0.0042 (10)
C12	0.0854 (18)	0.0415 (13)	0.0719 (16)	−0.0014 (12)	−0.0041 (13)	−0.0100 (11)
C13	0.0691 (16)	0.0700 (17)	0.0593 (15)	0.0214 (13)	−0.0016 (12)	0.0218 (12)
N1	0.0605 (11)	0.0381 (9)	0.0461 (10)	−0.0026 (8)	−0.0137 (8)	0.0000 (7)
O2	0.0660 (10)	0.0415 (8)	0.0493 (9)	0.0033 (7)	−0.0075 (7)	0.0062 (6)

Geometric parameters (Å, º) top

C2—C9	1.501 (3)	C8—C9	1.391 (3)
C2—C4	1.505 (3)	C8—H8	0.9300
C2—H2A	0.9700	C10—C11	1.383 (3)
C2—H2B	0.9700	C10—C13	1.384 (3)
C4—C6	1.391 (3)	C10—H10	0.9300
C4—C5	1.420 (3)	C11—H11	0.9300
C5—O2	1.251 (2)	C12—H12A	0.9600
C5—C12	1.513 (3)	C12—H12B	0.9600
C6—N1	1.331 (2)	C12—H12C	0.9600
C6—C7	1.464 (3)	C13—H13	0.9300
C7—C11	1.391 (3)	N1—H1A	0.8600
C7—C9	1.394 (3)	N1—H1B	0.8600
C8—C13	1.385 (4)

C9—C2—C4	102.92 (15)	C8—C9—C7	119.4 (2)
C9—C2—H2A	111.2	C8—C9—C2	130.2 (2)
C4—C2—H2A	111.2	C7—C9—C2	110.33 (17)
C9—C2—H2B	111.2	C11—C10—C13	120.5 (3)
C4—C2—H2B	111.2	C11—C10—H10	119.7
H2A—C2—H2B	109.1	C13—C10—H10	119.7
C6—C4—C5	123.41 (18)	C10—C11—C7	118.1 (2)
C6—C4—C2	109.61 (17)	C10—C11—H11	121.0
C5—C4—C2	126.98 (18)	C7—C11—H11	121.0
O2—C5—C4	122.65 (18)	C5—C12—H12A	109.5
O2—C5—C12	118.77 (19)	C5—C12—H12B	109.5
C4—C5—C12	118.6 (2)	H12A—C12—H12B	109.5
N1—C6—C4	126.71 (18)	C5—C12—H12C	109.5
N1—C6—C7	124.11 (17)	H12A—C12—H12C	109.5
C4—C6—C7	109.18 (16)	H12B—C12—H12C	109.5
C11—C7—C9	121.81 (19)	C10—C13—C8	121.5 (2)
C11—C7—C6	130.23 (19)	C10—C13—H13	119.2
C9—C7—C6	107.96 (18)	C8—C13—H13	119.2
C13—C8—C9	118.7 (2)	C6—N1—H1A	120.0
C13—C8—H8	120.7	C6—N1—H1B	120.0
C9—C8—H8	120.7	H1A—N1—H1B	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	2.17	2.766 (2)	126
N1—H1B···O2ⁱ	0.86	2.09	2.924 (2)	164
C2—H2B···Cg1ⁱⁱ	0.97	2.77	3.631 (2)	148

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁NO
M_r	173.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.1794 (4), 10.6905 (5), 10.5602 (6)
β (°)	93.783 (8)
V (Å³)	921.39 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.25 × 0.16 × 0.14

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.980, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	9369, 2108, 1385
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.171, 1.04
No. of reflections	2108
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	2.17	2.766 (2)	125.8
N1—H1B···O2ⁱ	0.86	2.09	2.924 (2)	164.2
C2—H2B···Cg1ⁱⁱ	0.97	2.77	3.631 (2)	148.1

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

Acknowledgements

This work was supported by a Start-up Grant from Southeast University to ZRQ.

References

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