2-Amino-5-oxo-4-phenyl-5,6,7,8-tetra­hydro-4H-chromene-3-carbonitrile

Wang, X.

doi:10.1107/S1600536811008130

organic compounds

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Volume 67| Part 4| April 2011| Page o832

doi:10.1107/S1600536811008130

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2-Amino-5-oxo-4-phenyl-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile

Xiaoli Wang ^a ^*

^aSchool of Petrochemical Engineering, Shenyang University of Technology, Liaoyang 111003, People's Republic of China
^*Correspondence e-mail: xlwangsut@163.com

(Received 12 January 2011; accepted 3 March 2011; online 9 March 2011)

In the title molecule, C₁₆H₁₄N₂O₂, the fused cyclohexene and pyran rings adopt an envelope and a flattened boat conformation, respectively. In the crystal, N—H⋯N and N—H⋯O hydrogen bonds link the molecules into corrugated sheets parallel to the bc plane.

Related literature

For the biological activities of substituted pyran derivatives, see: Lokaj et al. (1990 ); Marco et al. (1993 ). For the crystal structure of a related compound, see: Tu et al. (2001 ).

Experimental

Crystal data

C₁₆H₁₄N₂O₂
M_r = 266.29
Monoclinic, C 2/c
a = 20.210 (2) Å
b = 8.8161 (5) Å
c = 16.3862 (13) Å
β = 99.537 (1)°
V = 2879.2 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.32 × 0.21 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.974, T_max = 0.988
7077 measured reflections
2535 independent reflections
1083 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.114
S = 0.81
2535 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.11 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	3.007 (3)	170
N1—H1B⋯O2ⁱⁱ	0.86	2.00	2.848 (2)	169
Symmetry codes: (i) -x, -y+1, -z+2; (ii) $[x, -y+2, z+{\script{1\over 2}}]$ .

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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008130/cv5040sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008130/cv5040Isup2.hkl

checkCIF report

Comment top

Much interest has recently been paid to the design of polyfunctionalized substituted pyran derivatives, owing to their wide range of biological activities (Lokaj et al., 1990; Marco et al., 1993). We obtained the title compound, (I), and report here its crystal structure.

In (I) (Fig. 1), the bond lengths and angles of the main molecule are normal and correspond to those observed in 2-amino-7,7-dimethyl- 5-oxo-4-phenyl-5,6,7,8-tetra- hydro-4H-chromene-3-carbonitrile (Tu et al., 2001). The fused cyclohexene and pyran rings adopt an envelope and a flattened bath conformations, respecteviley. The dihedral angle between the O1/C1/C2/C5/C6 and C2/C4/C5 planes is 16.67 (14) °. The O1/ C1/C2/C5/C6 plane forms an angle of 89.01 (8)° with the phenyl plane. In the crystal, the nitrile group is typical [N≡C = 1.146 (3) Å] and the carbonyl group also is reasonable [C═O =1.228 (3) Å]. The C5/C6/C7/C8/C9/C10 plane also adopt an chair configuration in the compound, and the the dihedral angle between the C5/C6/C7/C9/C10 plane and the C7/C8/C9 plane is 46.14 (3)°.

In the crystal structure, there exist typical intermolecular N—H···O and N—H···N hydrogen bonds (Table 1). The amino N1 atom of one molecule links through H1B to the nitrile N2 atom of another molecule, creating a dimer. The amino N1 atom of one molecule also links through H1A to the keto O2 atom of another molecule to form the two-dimensional framework.

Related literature top

For the biological activities of substituted pyran derivatives, see: Lokaj et al. (1990); Marco et al. (1993). For the crystal structure of a related compound, see: Tu et al. (2001).

Experimental top

Malononitrile (10 mmol), 1,3-cyclohexanedione (10 mmol),and benzaldehyde(10 mmol)was dissolved in 20 ml e thanol ml in a round-bottom flask. The mixture was warmed, with agitation, to 353 K over a period of 3 h. The resulting solution was cooled. Crystal 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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of (I) showing the atomic numbering and 30% probability displacement ellipsoids.

2-Amino-5-oxo-4-phenyl-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile top

Crystal data top

C₁₆H₁₄N₂O₂	F(000) = 1120
M_r = 266.29	D_x = 1.229 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.210 (2) Å	Cell parameters from 851 reflections
b = 8.8161 (5) Å	θ = 2.5–19.1°
c = 16.3862 (13) Å	µ = 0.08 mm⁻¹
β = 99.537 (1)°	T = 298 K
V = 2879.2 (4) Å³	Block, red
Z = 8	0.32 × 0.21 × 0.15 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2535 independent reflections
Radiation source: fine-focus sealed tube	1083 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→17
T_min = 0.974, T_max = 0.988	k = −10→10
7077 measured reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0454P)²] where P = (F_o² + 2F_c²)/3
S = 0.81	(Δ/σ)_max = 0.001
2535 reflections	Δρ_max = 0.12 e Å⁻³
182 parameters	Δρ_min = −0.11 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0017 (2)

Crystal data top

C₁₆H₁₄N₂O₂	V = 2879.2 (4) Å³
M_r = 266.29	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 20.210 (2) Å	µ = 0.08 mm⁻¹
b = 8.8161 (5) Å	T = 298 K
c = 16.3862 (13) Å	0.32 × 0.21 × 0.15 mm
β = 99.537 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2535 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1083 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.988	R_int = 0.063
7077 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 0.81	Δρ_max = 0.12 e Å⁻³
2535 reflections	Δρ_min = −0.11 e Å⁻³
182 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
O1	0.10075 (8)	0.98207 (19)	1.01594 (9)	0.0666 (5)
C1	0.07153 (12)	0.8416 (3)	1.00139 (16)	0.0571 (7)
C5	0.09662 (11)	1.0170 (3)	0.87111 (15)	0.0550 (7)
C2	0.05849 (11)	0.7806 (3)	0.92527 (13)	0.0501 (6)
N1	0.05983 (10)	0.7810 (2)	1.07271 (11)	0.0759 (7)
H1A	0.0419	0.6926	1.0729	0.091*
H1B	0.0703	0.8305	1.1182	0.091*
C4	0.08060 (11)	0.8555 (3)	0.85109 (13)	0.0549 (7)
H4	0.0427	0.8528	0.8053	0.066*
O2	0.08103 (10)	1.0779 (2)	0.73126 (12)	0.0897 (7)
C10	0.09649 (13)	1.1227 (3)	0.80287 (19)	0.0686 (8)
C11	0.13891 (14)	0.7707 (3)	0.82384 (15)	0.0569 (7)
C3	0.02554 (13)	0.6406 (4)	0.91435 (14)	0.0586 (7)
C6	0.10774 (12)	1.0700 (3)	0.94811 (17)	0.0604 (7)
N2	−0.00226 (12)	0.5272 (3)	0.90338 (13)	0.0839 (8)
C7	0.12867 (14)	1.2263 (3)	0.97399 (16)	0.0790 (8)
H7A	0.1622	1.2225	1.0237	0.095*
H7B	0.0903	1.2825	0.9865	0.095*
C9	0.11266 (18)	1.2848 (4)	0.82299 (19)	0.1061 (11)
H9A	0.0712	1.3400	0.8232	0.127*
H9B	0.1346	1.3279	0.7799	0.127*
C16	0.13116 (16)	0.6985 (3)	0.74839 (18)	0.0867 (9)
H16	0.0904	0.7056	0.7127	0.104*
C8	0.15751 (17)	1.3064 (3)	0.9057 (2)	0.1100 (12)
H8A	0.1621	1.4139	0.9181	0.132*
H8B	0.2018	1.2663	0.9029	0.132*
C12	0.19982 (16)	0.7600 (3)	0.87459 (18)	0.0894 (10)
H12	0.2064	0.8083	0.9258	0.107*
C15	0.1828 (2)	0.6155 (4)	0.7246 (3)	0.1201 (14)
H15	0.1766	0.5667	0.6736	0.144*
C14	0.2420 (2)	0.6057 (5)	0.7757 (3)	0.1254 (17)
H14	0.2767	0.5492	0.7600	0.150*
C13	0.25165 (18)	0.6783 (5)	0.8505 (3)	0.1215 (14)
H13	0.2930	0.6727	0.8850	0.146*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0811 (13)	0.0612 (12)	0.0571 (11)	−0.0126 (10)	0.0103 (9)	0.0013 (10)
C1	0.0571 (17)	0.0574 (18)	0.0580 (17)	−0.0072 (14)	0.0135 (14)	0.0012 (15)
C5	0.0524 (16)	0.0553 (18)	0.0593 (17)	0.0015 (13)	0.0151 (13)	0.0061 (15)
C2	0.0532 (16)	0.0537 (17)	0.0443 (15)	−0.0037 (13)	0.0104 (12)	−0.0004 (13)
N1	0.1060 (19)	0.0758 (16)	0.0488 (13)	−0.0279 (13)	0.0216 (13)	−0.0051 (12)
C4	0.0530 (16)	0.0653 (18)	0.0462 (15)	−0.0032 (14)	0.0073 (12)	0.0070 (13)
O2	0.1089 (16)	0.0947 (16)	0.0703 (13)	0.0135 (12)	0.0287 (13)	0.0276 (12)
C10	0.071 (2)	0.063 (2)	0.078 (2)	0.0115 (15)	0.0308 (18)	0.0157 (18)
C11	0.0616 (18)	0.0584 (17)	0.0533 (16)	−0.0055 (14)	0.0177 (15)	0.0073 (14)
C3	0.0683 (18)	0.066 (2)	0.0439 (16)	−0.0033 (16)	0.0159 (14)	0.0034 (14)
C6	0.0599 (18)	0.0542 (18)	0.0675 (18)	−0.0019 (14)	0.0115 (14)	0.0077 (16)
N2	0.110 (2)	0.0755 (18)	0.0680 (16)	−0.0249 (16)	0.0210 (14)	−0.0018 (14)
C7	0.084 (2)	0.062 (2)	0.093 (2)	−0.0100 (16)	0.0226 (17)	−0.0057 (17)
C9	0.150 (3)	0.072 (2)	0.110 (3)	0.007 (2)	0.061 (2)	0.019 (2)
C16	0.100 (3)	0.088 (2)	0.076 (2)	−0.0078 (18)	0.0265 (18)	−0.0177 (18)
C8	0.137 (3)	0.064 (2)	0.141 (3)	−0.031 (2)	0.058 (3)	−0.008 (2)
C12	0.066 (2)	0.116 (3)	0.088 (2)	0.015 (2)	0.018 (2)	0.0002 (19)
C15	0.162 (4)	0.091 (3)	0.130 (4)	0.003 (3)	0.089 (3)	−0.020 (2)
C14	0.119 (4)	0.101 (3)	0.181 (5)	0.021 (3)	0.098 (4)	0.025 (3)
C13	0.071 (2)	0.144 (4)	0.155 (4)	0.023 (2)	0.036 (3)	0.018 (3)

Geometric parameters (Å, º) top

O1—C1	1.376 (3)	C6—C7	1.482 (3)
O1—C6	1.381 (3)	C7—C8	1.520 (3)
C1—N1	1.341 (3)	C7—H7A	0.9700
C1—C2	1.344 (3)	C7—H7B	0.9700
C5—C6	1.329 (3)	C9—C8	1.512 (4)
C5—C10	1.455 (3)	C9—H9A	0.9700
C5—C4	1.484 (3)	C9—H9B	0.9700
C2—C3	1.400 (3)	C16—C15	1.382 (4)
C2—C4	1.514 (3)	C16—H16	0.9300
N1—H1A	0.8600	C8—H8A	0.9700
N1—H1B	0.8600	C8—H8B	0.9700
C4—C11	1.524 (3)	C12—C13	1.382 (4)
C4—H4	0.9800	C12—H12	0.9300
O2—C10	1.228 (3)	C15—C14	1.344 (5)
C10—C9	1.491 (4)	C15—H15	0.9300
C11—C12	1.370 (3)	C14—C13	1.368 (5)
C11—C16	1.376 (3)	C14—H14	0.9300
C3—N2	1.146 (3)	C13—H13	0.9300

C1—O1—C6	117.64 (19)	C8—C7—H7A	109.6
N1—C1—C2	127.8 (2)	C6—C7—H7B	109.6
N1—C1—O1	109.9 (2)	C8—C7—H7B	109.6
C2—C1—O1	122.3 (2)	H7A—C7—H7B	108.1
C6—C5—C10	118.9 (3)	C10—C9—C8	113.3 (3)
C6—C5—C4	122.9 (2)	C10—C9—H9A	108.9
C10—C5—C4	118.1 (2)	C8—C9—H9A	108.9
C1—C2—C3	119.2 (2)	C10—C9—H9B	108.9
C1—C2—C4	122.1 (2)	C8—C9—H9B	108.9
C3—C2—C4	118.6 (2)	H9A—C9—H9B	107.7
C1—N1—H1A	120.0	C11—C16—C15	121.3 (3)
C1—N1—H1B	120.0	C11—C16—H16	119.4
H1A—N1—H1B	120.0	C15—C16—H16	119.4
C5—C4—C2	108.9 (2)	C9—C8—C7	110.8 (3)
C5—C4—C11	112.61 (19)	C9—C8—H8A	109.5
C2—C4—C11	111.50 (19)	C7—C8—H8A	109.5
C5—C4—H4	107.9	C9—C8—H8B	109.5
C2—C4—H4	107.9	C7—C8—H8B	109.5
C11—C4—H4	107.9	H8A—C8—H8B	108.1
O2—C10—C5	119.7 (3)	C11—C12—C13	120.6 (3)
O2—C10—C9	122.1 (3)	C11—C12—H12	119.7
C5—C10—C9	118.1 (3)	C13—C12—H12	119.7
C12—C11—C16	118.1 (3)	C14—C15—C16	119.7 (4)
C12—C11—C4	121.1 (2)	C14—C15—H15	120.2
C16—C11—C4	120.8 (3)	C16—C15—H15	120.2
N2—C3—C2	178.2 (3)	C15—C14—C13	120.4 (4)
C5—C6—O1	122.9 (2)	C15—C14—H14	119.8
C5—C6—C7	126.4 (2)	C13—C14—H14	119.8
O1—C6—C7	110.7 (2)	C14—C13—C12	119.9 (4)
C6—C7—C8	110.3 (2)	C14—C13—H13	120.0
C6—C7—H7A	109.6	C12—C13—H13	120.0

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	3.007 (3)	170
N1—H1B···O2ⁱⁱ	0.86	2.00	2.848 (2)	169

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄N₂O₂
M_r	266.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	20.210 (2), 8.8161 (5), 16.3862 (13)
β (°)	99.537 (1)
V (Å³)	2879.2 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.21 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.974, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	7077, 2535, 1083
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.114, 0.81
No. of reflections	2535
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.11

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in 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	3.007 (3)	169.9
N1—H1B···O2ⁱⁱ	0.86	2.00	2.848 (2)	169.2

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

Acknowledgements

The author acknowledges financial support from the Shenyang University of Technology.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lokaj, J., Kettmann, V., Pavelčík, F., Ilavský, D. & Marchalín, Š. (1990). Acta Cryst. C46, 788–791. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Marco, J. L., Martin, G., Martin, N., Martinez-Grau, A., Seoane, C., Albert, A. & Cano, F. H. (1993). Tetrahedron, 49, 7133–7144. CSD 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
Tu, S.-J., Deng, X., Fang, Y.-Y., Guo, Y.-M., Du, M. & Liu, X.-H. (2001). Acta Cryst. E57, o358–o359. Web of Science CSD CrossRef IUCr Journals Google Scholar