4-(4-Chloro­phen­yl)-2,6-bis­(1H-indol-3-yl)-1,4-dihydro­pyridine-3,5-dicarbo­nitrile ethanol monosolvate

Song-Lei Zhu; Jun-Nian Zheng

doi:10.1107/S1600536812013906

. 2012 Apr 4;68(Pt 5):o1300–o1301. doi: 10.1107/S1600536812013906

4-(4-Chlorophenyl)-2,6-bis(1H-indol-3-yl)-1,4-dihydropyridine-3,5-dicarbonitrile ethanol monosolvate

Song-Lei Zhu ^a, Jun-Nian Zheng ^a,^*

PMCID: PMC3344446 PMID: 22590208

Abstract

In the title compound, C₂₉H₁₈ClN₅·C₂H₆O, the dihydropyridine ring adopts a strongly flattened envelope conformation, with a maximum deviation of 0.139 (2) Å from its best plane for the Csp ³ atom. The dihedral angles between the dihydropyridine ring plane and the two indole rings in positions 2 and 6 are 34.28 (5) and 40.50 (6)°, respectively. In turn, the benzene ring and the dihydropyridine ring are oriented at a dihedral angle of 74.69 (6)°. An intramolecular C—H⋯Cl hydrogen bond occurs. In the crystal, molecules are linked by N—H⋯N, N—H⋯O and O—H⋯N hydrogen bonds into layers parallel to (001). There are short C—H⋯Cl contacts between molecules in neighboring layers.

Related literature

For the biological activity of indole and 1,4-dihydropyridine derivatives, see: da Silva et al. (2001 ▶); Joshi & Chand (1982 ▶); Janis & Triggle (1983 ▶). For the synthesis of a series of bisindoles derivatives of 1,4-dihydropyridine, see: Zhu et al. (2008 ▶).

Experimental

Crystal data

C₂₉H₁₈ClN₅·C₂H₆O
M _r = 518.00
Triclinic,
a = 9.2133 (17) Å
b = 11.611 (2) Å
c = 12.473 (2) Å
α = 87.714 (7)°
β = 83.297 (6)°
γ = 89.576 (7)°
V = 1324.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 193 K
0.55 × 0.36 × 0.15 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T _min = 0.787, T _max = 0.974
12971 measured reflections
4803 independent reflections
4095 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.119
S = 1.09
4803 reflections
346 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812013906/gk2473sup1.cif

e-68-o1300-sup1.cif^{(24.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812013906/gk2473Isup2.hkl

e-68-o1300-Isup2.hkl^{(235.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812013906/gk2473Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C31—H31A⋯Cl1	0.99	2.83	3.571 (3)	132
C28—H28⋯Cl1ⁱ	0.95	2.79	3.520 (2)	135
N5—H5⋯O1ⁱⁱ	0.88	2.04	2.907 (2)	167
N2—H2⋯N4ⁱⁱⁱ	0.88	2.18	2.989 (2)	153
N1—H1A⋯O1^iv	0.88	2.04	2.834 (2)	150
O1—H1⋯N3^v	0.84	1.96	2.791 (2)	172

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

Acknowledgments

This work was partially supported by the Open Foundation of the Key Laboratory of Cancer Biotherapy of Xuzhou Medical College (grant No. C0901), the Key Laboratory of Organic Synthesis of Jiangsu Province (grant No. KJS1010), the Natural Science Foundation of Higher Education Institutions of Jiangsu Province (grant No. 09KJB150012) and the Special Presidential Foundation of Xuzhou Medical College (grant Nos. 09KJZ19 and 2010KJZ20).

supplementary crystallographic information

Comment

Indole fragments are important moieties of a large number of natural products and medicinal agents (da Silva et al., 2001). Compounds carrying the indole moiety exhibit antibacterial and fungicidal activities (Joshi & Chand, 1982). In addition, 1,4-dihydropyridine compounds are a well-known classe of calcium channel modulators for the treatment of cardiovascular diseases, for example Nifedipin, Felodipin are clinically useful as vasodilators and antihypertensive agents (Janis & Triggle, 1983). Due to the potent and diverse biological activities of indole and 1,4-dihydropyridine derivatives, we investigated a simple and efficient protocol for synthesis of a series of bisindoles derivatives containing 1,4-dihydropyridine units (Zhu et al., 2008). Herein, we report the crystal structure of the title compound.

In the title molecule (Fig. 1), atoms of the newly formed 1,4-dihydropyridine ring A (N1, C1-C5) are nearly planar, with the maximum deviation of 0.139 (2) Å. The dihedral angles between ring A with attached two indole rings B (N2, C6-C13) and C (N5, C22-C29) are 34.28 (5) and 40.50 (6)°, respectively. Ring A and the benzene ring D (C15-C20) are oriented at a dihedral angle of 74.69 (6)°.

In the crystal, intermolecular N-H···N, N-H···O and O-H···N hydrogen bonds link the molecules into layers parallel to (0 0 1) (Table 1, Fig. 2). There are short C-H···Cl contacts between the molecules from neighboring layers.

Experimental

The title compound was prepared by the reaction of 4-chlorobenzaldehyde (1 mmol), 3-cyanoacetyl indole (2 mmol), ammonium acetate (5 mmol) in glycol solvent (3 mL) under microwave irradiation condition. After irradiating for 8 mins at 413 K, the reaction mixture was cooled and washed with small amount of ethanol. The crude product was filtered and single crystals of the title compound were obtained from ethanol solution by slow evaporation at room temperature (yield: 75%, m.p. > 573 K).