2-Amino-4-[4-(dimethyl­amino)­phen­yl]-5-oxo-5,6,7,8-tetra­hydro-4H-chromene-3-carbonitrile

Qiao, Y.; Chen, G.; Kong, L.; Ju, X.; Gao, Z.

doi:10.1107/S1600536811043662

organic compounds

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Volume 67| Part 11| November 2011| Page o3067

doi:10.1107/S1600536811043662

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2-Amino-4-[4-(dimethylamino)phenyl]-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile

Yan Qiao,^a Guifang Chen,^a Lingqian Kong,^a,^b ^* Xiuping Ju ^a and Zhiqing Gao ^a

^aDongchang College, Liaocheng University, Liaocheng 250059, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 250059, People's Republic of China
^*Correspondence e-mail: konglingqian08@163.com

(Received 13 October 2011; accepted 21 October 2011; online 29 October 2011)

In the title molecule, C₁₈H₁₉N₃O₂, the fused cyclohexenone and pyran rings adopt sofa conformations. Intermolecular N—H⋯N and N—H⋯O hydrogen bonds link molecules into corrugated layers parallel to the bc plane.

Related literature

For the crystal structures of related compounds, see: Kong et al. (2011 ); Wang (2011 ).

Experimental

Crystal data

C₁₈H₁₉N₃O₂
M_r = 309.36
Monoclinic, C 2/c
a = 25.021 (3) Å
b = 8.8724 (8) Å
c = 16.3827 (16) Å
β = 114.721 (2)°
V = 3303.5 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.40 × 0.36 × 0.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.968, T_max = 0.982
8056 measured reflections
2907 independent reflections
1411 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.187
S = 1.01
2907 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.86	2.16	3.014 (4)	171
N1—H1B⋯O2ⁱⁱ	0.86	2.02	2.867 (4)	169
Symmetry codes: (i) -x, -y+1, -z; (ii) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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 I, global. DOI: 10.1107/S1600536811043662/cv5176sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043662/cv5176Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811043662/cv5176Isup3.cml

checkCIF report

Comment top

In continuation of our structural studies of benzopyran derivatives (Kong et al., 2011), we present here the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal and comparable with those in close compounds (Kong et al., 2011; Wang, 2011). The dihedral angle between the C2/C1/O1/C9/C4 plane and the (C2-C4) plane is 9.86( 4 )°. The C2/C1/O1/C9/C4 plane forms an angle of 86.43 (12 )° with the phenyl plane C11-C16.

In the crystal structure, intermolecular N—H···N and N—H···O hydrogen bonds (Table 1) link molecules into corrugated layers parallel to bc plane.

Related literature top

For the crystal structures of related compounds, see: Kong et al. (2011); Wang (2011).

Experimental top

Malononitrile (6 mmol), 1,3-cyclohexanedione (6 mmol) and N,N-dimethylbenzaldehyde (6 mmol) were dissolved in 20 ml ethanol ml in a round-bottom flask. The mixture was warmed, with agitation, to 363 K over a period of 5 h. The resulting solution was cooled. Crystals of (I) suitable for X-ray diffraction analysis were obtained by slow evaporation.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. The title molecule with the atomic numbering scheme. The displacement ellipsoids are shown at the 30% probability level.

2-Amino-4-[4-(dimethylamino)phenyl]-5-oxo-5,6,7,8-tetrahydro- 4H-chromene-3-carbonitrile top

Crystal data top

C₁₈H₁₉N₃O₂	F(000) = 1312
M_r = 309.36	D_x = 1.244 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.021 (3) Å	Cell parameters from 1265 reflections
b = 8.8724 (8) Å	θ = 2.5–21.3°
c = 16.3827 (16) Å	µ = 0.08 mm⁻¹
β = 114.721 (2)°	T = 298 K
V = 3303.5 (5) Å³	Block, red
Z = 8	0.40 × 0.36 × 0.22 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2907 independent reflections
Radiation source: fine-focus sealed tube	1411 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
phi and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→25
T_min = 0.968, T_max = 0.982	k = −10→8
8056 measured reflections	l = −19→19

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) = 0.187	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0818P)² + 1.1159P] where P = (F_o² + 2F_c²)/3
2907 reflections	(Δ/σ)_max < 0.001
210 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₈H₁₉N₃O₂	V = 3303.5 (5) Å³
M_r = 309.36	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.021 (3) Å	µ = 0.08 mm⁻¹
b = 8.8724 (8) Å	T = 298 K
c = 16.3827 (16) Å	0.40 × 0.36 × 0.22 mm
β = 114.721 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2907 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1411 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.982	R_int = 0.062
8056 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.187	H-atom parameters constrained
S = 1.01	Δρ_max = 0.24 e Å⁻³
2907 reflections	Δρ_min = −0.21 e Å⁻³
210 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N1	0.05600 (14)	0.2235 (3)	−0.03033 (19)	0.0617 (9)
H1A	0.0417	0.3129	−0.0433	0.074*
H1B	0.0652	0.1742	−0.0679	0.074*
N2	0.00475 (15)	0.4788 (4)	0.0962 (2)	0.0641 (10)
N3	0.23314 (16)	0.5169 (4)	0.4808 (3)	0.0788 (11)
O1	0.08809 (11)	0.0187 (2)	0.05519 (15)	0.0530 (7)
O2	0.07367 (12)	−0.0804 (3)	0.32595 (18)	0.0683 (8)
C1	0.06404 (14)	0.1610 (4)	0.0482 (2)	0.0422 (9)
C2	0.05254 (14)	0.2195 (3)	0.1146 (2)	0.0389 (8)
C3	0.06843 (14)	0.1431 (3)	0.2039 (2)	0.0383 (8)
H3	0.0327	0.1385	0.2145	0.046*
C4	0.08682 (14)	−0.0157 (3)	0.1978 (2)	0.0390 (8)
C5	0.08851 (16)	−0.1218 (4)	0.2673 (3)	0.0543 (10)
C6	0.1057 (2)	−0.2815 (4)	0.2617 (3)	0.0838 (15)
H6A	0.0704	−0.3419	0.2335	0.101*
H6B	0.1276	−0.3199	0.3220	0.101*
C7	0.1428 (2)	−0.2992 (4)	0.2089 (3)	0.0866 (15)
H7A	0.1814	−0.2557	0.2427	0.104*
H7B	0.1479	−0.4055	0.2003	0.104*
C8	0.11417 (18)	−0.2228 (4)	0.1188 (3)	0.0613 (11)
H8A	0.1417	−0.2193	0.0911	0.074*
H8B	0.0801	−0.2805	0.0799	0.074*
C9	0.09573 (14)	−0.0674 (4)	0.1286 (2)	0.0449 (9)
C10	0.02665 (16)	0.3637 (4)	0.1031 (2)	0.0428 (9)
C11	0.11413 (14)	0.2331 (3)	0.2807 (2)	0.0386 (8)
C12	0.16973 (16)	0.2606 (4)	0.2860 (3)	0.0555 (10)
H12	0.1808	0.2171	0.2438	0.067*
C13	0.20934 (17)	0.3510 (4)	0.3524 (3)	0.0633 (11)
H13	0.2464	0.3673	0.3537	0.076*
C14	0.19513 (17)	0.4180 (4)	0.4172 (3)	0.0522 (10)
C15	0.13956 (18)	0.3880 (4)	0.4126 (2)	0.0572 (10)
H15	0.1283	0.4297	0.4551	0.069*
C16	0.10079 (15)	0.2973 (4)	0.3461 (2)	0.0490 (9)
H16	0.0640	0.2788	0.3454	0.059*
C17	0.2940 (2)	0.5246 (5)	0.4932 (4)	0.1074 (19)
H17A	0.3129	0.4299	0.5158	0.161*
H17B	0.3139	0.6030	0.5354	0.161*
H17C	0.2953	0.5460	0.4367	0.161*
C18	0.2225 (2)	0.5576 (6)	0.5575 (3)	0.1047 (18)
H18A	0.1839	0.6007	0.5377	0.157*
H18B	0.2513	0.6299	0.5932	0.157*
H18C	0.2251	0.4694	0.5929	0.157*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.104 (3)	0.0475 (19)	0.046 (2)	0.0274 (17)	0.0439 (19)	0.0138 (15)
N2	0.092 (3)	0.048 (2)	0.059 (2)	0.0198 (19)	0.038 (2)	0.0132 (16)
N3	0.069 (3)	0.064 (2)	0.079 (3)	−0.0101 (19)	0.006 (2)	−0.019 (2)
O1	0.0782 (18)	0.0426 (15)	0.0480 (16)	0.0211 (13)	0.0360 (14)	0.0096 (12)
O2	0.097 (2)	0.0645 (18)	0.0472 (17)	−0.0115 (15)	0.0338 (16)	0.0095 (14)
C1	0.050 (2)	0.038 (2)	0.040 (2)	0.0075 (16)	0.0202 (17)	0.0037 (16)
C2	0.045 (2)	0.037 (2)	0.0331 (19)	0.0050 (15)	0.0149 (16)	0.0038 (15)
C3	0.042 (2)	0.0386 (19)	0.037 (2)	0.0015 (15)	0.0187 (16)	0.0036 (15)
C4	0.047 (2)	0.0325 (19)	0.0336 (19)	−0.0056 (15)	0.0128 (16)	0.0051 (15)
C5	0.066 (3)	0.046 (2)	0.040 (2)	−0.0094 (19)	0.011 (2)	0.0049 (18)
C6	0.139 (4)	0.039 (2)	0.061 (3)	0.002 (2)	0.030 (3)	0.015 (2)
C7	0.120 (4)	0.046 (3)	0.081 (3)	0.025 (3)	0.029 (3)	0.016 (2)
C8	0.074 (3)	0.040 (2)	0.067 (3)	0.0051 (19)	0.027 (2)	0.0000 (19)
C9	0.052 (2)	0.035 (2)	0.045 (2)	0.0021 (16)	0.0178 (18)	0.0088 (17)
C10	0.060 (2)	0.039 (2)	0.033 (2)	0.0017 (18)	0.0232 (17)	0.0030 (16)
C11	0.044 (2)	0.0339 (19)	0.036 (2)	0.0044 (15)	0.0153 (16)	0.0061 (15)
C12	0.049 (2)	0.064 (3)	0.058 (3)	−0.001 (2)	0.026 (2)	−0.007 (2)
C13	0.042 (2)	0.070 (3)	0.074 (3)	−0.004 (2)	0.021 (2)	−0.008 (2)
C14	0.056 (3)	0.033 (2)	0.052 (2)	0.0002 (18)	0.008 (2)	0.0012 (18)
C15	0.073 (3)	0.051 (2)	0.051 (2)	−0.005 (2)	0.029 (2)	−0.0125 (19)
C16	0.049 (2)	0.052 (2)	0.048 (2)	−0.0072 (18)	0.0225 (19)	−0.0072 (18)
C17	0.062 (3)	0.083 (4)	0.132 (5)	−0.018 (3)	−0.003 (3)	−0.018 (3)
C18	0.124 (4)	0.085 (3)	0.072 (4)	−0.020 (3)	0.009 (3)	−0.037 (3)

Geometric parameters (Å, º) top

N1—C1	1.337 (4)	C7—C8	1.505 (5)
N1—H1A	0.8600	C7—H7A	0.9700
N1—H1B	0.8600	C7—H7B	0.9700
N2—C10	1.141 (4)	C8—C9	1.484 (5)
N3—C14	1.390 (5)	C8—H8A	0.9700
N3—C18	1.435 (6)	C8—H8B	0.9700
N3—C17	1.450 (5)	C11—C16	1.372 (4)
O1—C9	1.369 (4)	C11—C12	1.379 (5)
O1—C1	1.383 (4)	C12—C13	1.381 (5)
O2—C5	1.222 (4)	C12—H12	0.9300
C1—C2	1.341 (4)	C13—C14	1.387 (5)
C2—C10	1.411 (5)	C13—H13	0.9300
C2—C3	1.507 (4)	C14—C15	1.386 (5)
C3—C4	1.498 (4)	C15—C16	1.376 (5)
C3—C11	1.524 (4)	C15—H15	0.9300
C3—H3	0.9800	C16—H16	0.9300
C4—C9	1.326 (4)	C17—H17A	0.9600
C4—C5	1.464 (5)	C17—H17B	0.9600
C5—C6	1.495 (5)	C17—H17C	0.9600
C6—C7	1.517 (6)	C18—H18A	0.9600
C6—H6A	0.9700	C18—H18B	0.9600
C6—H6B	0.9700	C18—H18C	0.9600

C1—N1—H1A	120.0	C7—C8—H8A	109.5
C1—N1—H1B	120.0	C9—C8—H8B	109.5
H1A—N1—H1B	120.0	C7—C8—H8B	109.5
C14—N3—C18	119.7 (4)	H8A—C8—H8B	108.1
C14—N3—C17	118.9 (4)	C4—C9—O1	123.1 (3)
C18—N3—C17	115.7 (4)	C4—C9—C8	125.8 (3)
C9—O1—C1	118.6 (2)	O1—C9—C8	111.1 (3)
N1—C1—C2	128.6 (3)	N2—C10—C2	177.2 (4)
N1—C1—O1	110.1 (3)	C16—C11—C12	116.5 (3)
C2—C1—O1	121.3 (3)	C16—C11—C3	121.2 (3)
C1—C2—C10	119.0 (3)	C12—C11—C3	122.3 (3)
C1—C2—C3	123.7 (3)	C11—C12—C13	121.7 (3)
C10—C2—C3	117.3 (3)	C11—C12—H12	119.2
C4—C3—C2	108.8 (3)	C13—C12—H12	119.2
C4—C3—C11	113.7 (3)	C12—C13—C14	121.5 (4)
C2—C3—C11	111.5 (3)	C12—C13—H13	119.2
C4—C3—H3	107.5	C14—C13—H13	119.2
C2—C3—H3	107.5	C15—C14—C13	116.6 (3)
C11—C3—H3	107.5	C15—C14—N3	121.2 (4)
C9—C4—C5	118.8 (3)	C13—C14—N3	122.1 (4)
C9—C4—C3	123.3 (3)	C16—C15—C14	121.0 (3)
C5—C4—C3	117.6 (3)	C16—C15—H15	119.5
O2—C5—C4	119.9 (3)	C14—C15—H15	119.5
O2—C5—C6	121.6 (3)	C11—C16—C15	122.7 (3)
C4—C5—C6	118.5 (4)	C11—C16—H16	118.6
C5—C6—C7	113.2 (3)	C15—C16—H16	118.6
C5—C6—H6A	108.9	N3—C17—H17A	109.5
C7—C6—H6A	108.9	N3—C17—H17B	109.5
C5—C6—H6B	108.9	H17A—C17—H17B	109.5
C7—C6—H6B	108.9	N3—C17—H17C	109.5
H6A—C6—H6B	107.8	H17A—C17—H17C	109.5
C8—C7—C6	111.0 (4)	H17B—C17—H17C	109.5
C8—C7—H7A	109.4	N3—C18—H18A	109.5
C6—C7—H7A	109.4	N3—C18—H18B	109.5
C8—C7—H7B	109.4	H18A—C18—H18B	109.5
C6—C7—H7B	109.4	N3—C18—H18C	109.5
H7A—C7—H7B	108.0	H18A—C18—H18C	109.5
C9—C8—C7	110.8 (3)	H18B—C18—H18C	109.5
C9—C8—H8A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.16	3.014 (4)	171
N1—H1B···O2ⁱⁱ	0.86	2.02	2.867 (4)	169

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₉N₃O₂
M_r	309.36
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	25.021 (3), 8.8724 (8), 16.3827 (16)
β (°)	114.721 (2)
V (Å³)	3303.5 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.36 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.968, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	8056, 2907, 1411
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.187, 1.01
No. of reflections	2907
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.16	3.014 (4)	170.6
N1—H1B···O2ⁱⁱ	0.86	2.02	2.867 (4)	169.0

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

Acknowledgements

This project was supported by the Foundation of Dongchang College, Liaocheng University (grant No. LG0801).

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kong, L., Ju, X., Qiao, Y., Zhang, J. & Gao, Z. (2011). Acta Cryst. E67. In the press. CrossRef IUCr Journals 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
Wang, X. (2011). Acta Cryst. E67, o832. Web of Science CSD CrossRef IUCr Journals Google Scholar

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2-Amino-4-[4-(di­methyl­amino)­phen­yl]-5-oxo-5,6,7,8-tetra­hydro-4H-chromene-3-carbo­nitrile

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-Amino-4-[4-(dimethylamino)phenyl]-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile