9,10-Dihydro-7H-benzo[de]imidazo[2,1-a]isoquinolin-7-one

Abstract

In the title compound, C₁₄H₁₀N₂O, all non-H atoms are essentially coplanar (r.m.s. deviation = 0.013 Å). The crystal structure is stabilized by π–π stacking inter­actions [centroid–centroid distance = 3.506 (3) Å].

Related literature  

For the use of rigid ligands in the formation of metal-organic coordination polymers, see: Chen et al. (2006 ▶); Yang et al. (2009 ▶).

Experimental  

Crystal data  

• C₁₄H₁₀N₂O

• M _r = 222.24

• Orthorhombic,

• a = 4.4949 (2) Å

• b = 14.9891 (9) Å

• c = 15.1357 (8) Å

• V = 1019.76 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 296 K

• 0.20 × 0.05 × 0.05 mm

Data collection  

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.982, T _max = 0.995

• 8736 measured reflections

• 1837 independent reflections

• 1207 reflections with I > 2σ(I)

• R _int = 0.046

Refinement  

• R[F ² > 2σ(F ²)] = 0.075

• wR(F ²) = 0.202

• S = 1.01

• 1837 reflections

• 154 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The title compound, C₁₄H₁₀N₂O, (I) can be used as a rigid ligand to form metal-organic coordination polymers, such as [Ag(C₁₄H₁₀N₂O)(NO₃)]_n, [Ag(C₁₄H₁₀N₂O)₂(NO₃)]_n, [Ag(C₁₄H₁₀N₂O)₂ (BF₄)]_n (Yang et al., 2009) and [Cu₂(CH₃COO)₄(C₁₄H₁₀N₂O)₂]_n (Chen et al., 2006). However, the crystal structure of 9,10-dihydro-7H-benzo[de]imidazo[2,1-a]-isoquinolin-7-one have not been reported so far. We report herein the synthesize and the crystal structure of (I). In the title molecule , C₁₄H₁₀N₂O, all non-H atoms are essentially coplanar (r.m.s. 0.013 Å). The crystal structure is stabilized by π–π stacking interactions (centroid -centroid distance 3.506 (3)Å, Cg =C4/C5/C6/C7/C8/C9 ; Cgⁱ =C4/C5/C6/C7/C8/C9 ; symmetry code (i) x-1, y, z)

Experimental

White prism-shaped single crystals of 9,10-dihydro-7H-benzo[de]imidazo[2,1-a]-isoquinolin-7-one were initially obtained from the hydrothermal reaction of Naphthalene-1,8-dicarboxylic anhydride (0.3 g), ethylenediamine (5 ml) and H₂O (10 ml) using Teflon lined bomb at 160°C for 5 days and then cooled to room temperature. A few single crystals suitable for X-ray diffraction analysis were obtained.

Refinement

Constraint instruction 'DELU 0.01 C14 N2' was used in the refinement. The final difference map shows that the highest peak is 0.27 e/ų at 1.55 Å from O(1), while the deepest hole is -0.33 e/ų at 0.16 Å from H(13B). H atoms were placed in geometrically calculated positions with C—H distances in the range 0.93-0.97Å and were refined using a riding model, with U_iso(H)=1.2U_eq(C). Friedel pairs (715) were merged.

Figures

Fig. 1.

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C14H10N2O	F(000) = 464
Mr = 222.24	Dx = 1.448 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 946 reflections
a = 4.4949 (2) Å	θ = 2.7–19.8°
b = 14.9891 (9) Å	µ = 0.09 mm−1
c = 15.1357 (8) Å	T = 296 K
V = 1019.76 (9) Å3	Prism, colourless
Z = 4	0.20 × 0.05 × 0.05 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1837 independent reflections
Radiation source: fine-focus sealed tube	1207 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 83.33 pixels mm-1	θmax = 25.5°, θmin = 1.9°
ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −18→16
Tmin = 0.982, Tmax = 0.995	l = −18→16
8736 measured reflections

Refinement

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.202	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0818P)2 + 0.9931P] where P = (Fo2 + 2Fc2)/3
1837 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.27 e Å−3
1 restraint	Δρmin = −0.33 e Å−3
1 constraint

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.8099 (9)	0.5958 (3)	0.5858 (3)	0.0586 (11)
C9	0.4344 (11)	0.4484 (3)	0.5830 (3)	0.0526 (11)
C10	0.5848 (10)	0.4693 (3)	0.6615 (3)	0.0537 (11)
C12	0.6647 (12)	0.5790 (3)	0.5059 (3)	0.0614 (14)
C11	0.7765 (11)	0.5470 (3)	0.6614 (3)	0.0556 (11)
C5	0.0907 (13)	0.3543 (4)	0.4989 (4)	0.0772 (17)
H5	−0.0366	0.3055	0.4963	0.093*
C1	0.5498 (12)	0.4169 (4)	0.7347 (3)	0.0692 (14)
H1	0.6487	0.4308	0.7868	0.083*
O1	0.7130 (11)	0.6295 (2)	0.4429 (2)	0.0886 (14)
C8	0.4680 (11)	0.5014 (3)	0.5046 (3)	0.0557 (12)
C4	0.2423 (12)	0.3730 (3)	0.5796 (3)	0.0620 (13)
C7	0.3183 (12)	0.4788 (4)	0.4287 (3)	0.0673 (14)
H7	0.3457	0.5130	0.3781	0.081*
N2	0.9310 (11)	0.5775 (3)	0.7269 (3)	0.0773 (13)
C3	0.2118 (14)	0.3213 (4)	0.6554 (4)	0.0774 (16)
H3	0.0863	0.2720	0.6547	0.093*
C13	1.0057 (13)	0.6648 (3)	0.6011 (4)	0.0778 (17)
H13A	0.9115	0.7223	0.5921	0.093*
H13B	1.1794	0.6604	0.5633	0.093*
C6	0.1267 (13)	0.4058 (4)	0.4255 (4)	0.0805 (17)
H6	0.0242	0.3924	0.3738	0.097*
C2	0.3623 (14)	0.3418 (4)	0.7303 (4)	0.0825 (18)
H2	0.3413	0.3055	0.7797	0.099*
C14	1.0800 (16)	0.6516 (4)	0.6897 (5)	0.100 (2)
H14A	1.0297	0.7048	0.7230	0.120*
H14B	1.2931	0.6425	0.6945	0.120*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.061 (3)	0.056 (2)	0.060 (3)	0.003 (2)	0.006 (2)	−0.006 (2)
C9	0.052 (3)	0.054 (3)	0.051 (3)	0.013 (2)	0.011 (2)	−0.003 (2)
C10	0.050 (2)	0.061 (3)	0.051 (3)	0.012 (2)	0.006 (2)	0.002 (2)
C12	0.068 (3)	0.054 (3)	0.062 (3)	0.016 (3)	0.011 (3)	0.002 (2)
C11	0.047 (3)	0.061 (3)	0.059 (3)	0.010 (3)	0.005 (2)	−0.008 (2)
C5	0.057 (3)	0.079 (4)	0.095 (5)	−0.001 (3)	0.011 (3)	−0.028 (3)
C1	0.066 (3)	0.083 (4)	0.059 (3)	0.018 (3)	0.007 (3)	0.005 (3)
O1	0.118 (3)	0.074 (2)	0.074 (2)	0.006 (3)	0.021 (3)	0.021 (2)
C8	0.050 (3)	0.058 (2)	0.060 (3)	0.014 (2)	0.003 (2)	0.001 (2)
C4	0.051 (3)	0.060 (3)	0.075 (3)	0.009 (3)	0.011 (3)	−0.008 (3)
C7	0.067 (3)	0.081 (4)	0.054 (3)	0.015 (3)	0.000 (3)	−0.004 (3)
N2	0.077 (3)	0.081 (3)	0.074 (3)	0.003 (3)	−0.007 (3)	−0.014 (2)
C3	0.070 (4)	0.067 (3)	0.095 (4)	0.006 (3)	0.023 (3)	0.007 (3)
C13	0.068 (4)	0.059 (3)	0.106 (5)	0.011 (3)	0.019 (3)	−0.020 (3)
C6	0.072 (4)	0.098 (4)	0.072 (4)	0.005 (4)	−0.008 (3)	−0.023 (4)
C2	0.081 (4)	0.084 (4)	0.083 (4)	0.014 (3)	0.019 (3)	0.024 (3)
C14	0.083 (4)	0.097 (5)	0.120 (6)	0.010 (4)	0.015 (4)	−0.041 (4)

Geometric parameters (Å, º)

N1—C11	1.367 (5)	C1—H1	0.9300
N1—C13	1.377 (6)	C8—C7	1.375 (7)
N1—C12	1.397 (6)	C4—C3	1.391 (7)
C9—C10	1.402 (6)	C7—C6	1.392 (7)
C9—C4	1.423 (6)	C7—H7	0.9300
C9—C8	1.436 (6)	N2—C14	1.414 (8)
C10—C1	1.367 (7)	C3—C2	1.355 (8)
C10—C11	1.448 (6)	C3—H3	0.9300
C12—O1	1.236 (5)	C13—C14	1.396 (8)
C12—C8	1.462 (7)	C13—H13A	0.9700
C11—N2	1.295 (6)	C13—H13B	0.9700
C5—C6	1.363 (8)	C6—H6	0.9300
C5—C4	1.426 (7)	C2—H2	0.9300
C5—H5	0.9300	C14—H14A	0.9700
C1—C2	1.408 (8)	C14—H14B	0.9700
C11—N1—C13	109.4 (4)	C9—C4—C5	118.5 (5)
C11—N1—C12	125.2 (4)	C8—C7—C6	121.7 (5)
C13—N1—C12	125.4 (5)	C8—C7—H7	119.2
C10—C9—C4	120.1 (4)	C6—C7—H7	119.2
C10—C9—C8	121.7 (4)	C11—N2—C14	103.1 (5)
C4—C9—C8	118.2 (4)	C2—C3—C4	121.0 (6)
C1—C10—C9	120.2 (5)	C2—C3—H3	119.5
C1—C10—C11	122.1 (5)	C4—C3—H3	119.5
C9—C10—C11	117.8 (4)	N1—C13—C14	102.0 (5)
O1—C12—N1	118.4 (5)	N1—C13—H13A	111.4
O1—C12—C8	125.7 (5)	C14—C13—H13A	111.4
N1—C12—C8	116.0 (4)	N1—C13—H13B	111.4
N2—C11—N1	113.1 (4)	C14—C13—H13B	111.4
N2—C11—C10	127.0 (5)	H13A—C13—H13B	109.2
N1—C11—C10	119.8 (4)	C5—C6—C7	119.3 (5)
C6—C5—C4	122.0 (6)	C5—C6—H6	120.3
C6—C5—H5	119.0	C7—C6—H6	120.3
C4—C5—H5	119.0	C3—C2—C1	121.3 (5)
C10—C1—C2	119.3 (5)	C3—C2—H2	119.3
C10—C1—H1	120.3	C1—C2—H2	119.3
C2—C1—H1	120.3	C13—C14—N2	112.4 (6)
C7—C8—C9	120.2 (5)	C13—C14—H14A	109.1
C7—C8—C12	120.3 (5)	N2—C14—H14A	109.1
C9—C8—C12	119.6 (4)	C13—C14—H14B	109.1
C3—C4—C9	118.1 (5)	N2—C14—H14B	109.1
C3—C4—C5	123.4 (6)	H14A—C14—H14B	107.9