2-Amino-4-(2-chloro­phen­yl)-5-oxo-5,6,7,8-tetra­hydro-4H-chromene-3-carbonitrile ethanol monosolvate

Yan Qiao; Lingqian Kong; Guifang Chen; Shengli Li; Zhiqing Gao

doi:10.1107/S1600536811043650

. 2011 Oct 29;67(Pt 11):o3099. doi: 10.1107/S1600536811043650

2-Amino-4-(2-chlorophenyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile ethanol monosolvate

Yan Qiao ^a, Lingqian Kong ^a,^b,^*, Guifang Chen ^a, Shengli Li ^a, Zhiqing Gao ^a

PMCID: PMC3247485 PMID: 22220103

Abstract

In the title compound, C₁₆H₁₃ClN₂O₂·C₂H₆O, the fused cyclohexene and pyran rings adopt envelope and flattened boat conformations, respectively. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link the chromene and ethanol solvent molecules into infinite chains along the c axis, and N—H⋯N hydrogen bonds link these chains into a three-dimensional framework. Weak C—H⋯π interactions are also present.

Related literature

For the background, see: Lokaj et al. (1990 ▶); Marco et al. (1993 ▶). For crystal structures similar to the title compound, see: Tu et al. (2001 ▶).

Experimental

Crystal data

C₁₆H₁₃ClN₂O₂·C₂H₆O
M _r = 346.80
Triclinic,
a = 8.7610 (8) Å
b = 9.6281 (9) Å
c = 10.7951 (11) Å
α = 76.878 (1)°
β = 83.028 (2)°
γ = 77.632 (1)°
V = 863.69 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 298 K
0.47 × 0.46 × 0.21 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.896, T _max = 0.952
4606 measured reflections
3003 independent reflections
1428 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.082
wR(F ²) = 0.230
S = 0.90
3003 reflections
219 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811043650/bq2312sup1.cif

e-67-o3099-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811043650/bq2312Isup2.hkl

e-67-o3099-Isup2.hkl^{(147.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811043650/bq2312Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1ⁱ	0.86	2.19	3.037 (5)	167
N2—H2B⋯O3	0.86	1.99	2.851 (5)	178
O3—H3⋯O1ⁱⁱ	0.82	1.97	2.765 (5)	164
C14—H14B⋯Cgⁱⁱⁱ	0.97	2.96	3.704 (5)	135

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

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

supplementary crystallographic information

Comment

The present investigation is a continuation of our work that includes syntheses and structural studies of polyfunctionalized substituted pyran derivatives, owing to their biological activities (Lokaj et al., 1990; Marco et al., 1993).We obtained the title compound, (I), and reported here its crystal structure in the paper.

In the crystal structure, it is observed that structure unit contains a substituted 5,6,7,8-tetrahydro-4H-chromene, a benzene ring and a ethanol solvate. The pyran ring adopts a sofa conformation, the dihedral angle between the (O2/C8-C11) plane and the C8/C7/C11 plane is 16.14 (4)°. Meanwhile, the (O2/C8-C11) plane forms an angle of 88.55 (13)° with the phenyl plane (C1-C6), which means that the pyran ring and the benzene ring is nearly perpendicular. In the crystal, the nitrile group is typical [N≡C = 1.148 (5)Å] and the carbonyl group also is reasonable [C═O =1.223 (6)Å].

Moreover, the plane (C10-C15) also adopts an chair configuration in the compound, and the dihedral angle between the (C10-C15) plane and the (C13-C15) plane is 46.19 (5)°.

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).

In the crystal structure, there exist typical intermolecular N-H···N, N—H···O, O—H···O hydrogen bonds and weak C-H···π interactions (Table 1.). Intermolecular N-H···O and O—H···O hydrogen bonds link the molecules and ethanol solvent into infinite chain along c-axis and intermolecular hydrogen bonds link these chains forming three-dimensional framework.

Experimental

Malononitrile (5 mmol), 1,3-cyclohexanedione (5 mmol) and 2-chorobenzaldehyde (5 mmol) was dissolved in 20 ml DMF in a round-bottom flask. The mixture was warmed, with agitation, to 423 K over a period of 6 h. The resulting solution was cooled. Crystal of (I) suitable for X-ray diffraction analysis were obtained by recrystallized from ethanol.