Crystal structure of 5-diethylamino-2-({[4-(diethylamino) phenyl] imino ...

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Sep 3, 2015 - Mr = 339.47. Orthorhombic, P212121 ... C. Vidya Rani, G. Chakkaravarthi, N. Indra Gandhi and G. Rajagopal. S1. Comment. Schiff base ...

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ISSN 2056-9890

Crystal structure of 5-diethylamino-2({[4-(diethylamino)phenyl]imino}methyl)phenol C. Vidya Rani,a G. Chakkaravarthi,b* N. Indra Gandhic* and G. Rajagopala a

PG & Research Department of Chemistry, Chikkanna Government Arts College, Tiruppur 641 602, India, bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, and cPG & Research Department of Chemistry, Presidency College (Autonomous), Chennai 600 005, India. *Correspondence e-mail: [email protected], [email protected]

2. Experimental 2.1. Crystal data ˚3 V = 1944.38 (16) A Z=4 Mo K radiation  = 0.07 mm1 T = 295 K 0.28  0.26  0.24 mm

C21H29N3O Mr = 339.47 Orthorhombic, P21 21 21 ˚ a = 8.1986 (4) A ˚ b = 9.7128 (4) A ˚ c = 24.4172 (12) A

2.2. Data collection

Received 1 September 2015; accepted 3 September 2015 Edited by V. Rybakov, Moscow State University, Russia

In the title compound, C21H29N3O, the dihedral angle between the planes of the aromatic rings is 8.1 (2) . The ethyl groups at one terminal site of the compound are disordered over two sets of sites with occupancies of 0.775 (9) and 0.225 (9). The molecule has an E conformation about the N C bond. The molecular structure features an intramolecular O—H  N hydrogen bond, which closes an S(6) loop. In the crystal, weak C—H   interactions leads to the formation of a threedimensional network. Keywords: crystal structure; phenol; Schiff base; intramolecular hydrogen bond; C—H   interactions; biological activity; pharmacological activity.

Bruker Kappa APEX II CCD diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.980, Tmax = 0.983

29557 measured reflections 3556 independent reflections 2130 reflections with I > 2(I) Rint = 0.046

2.3. Refinement R[F 2 > 2(F 2)] = 0.064 wR(F 2) = 0.205 S = 1.07 3556 reflections 272 parameters 10 restraints

H atoms treated by a mixture of independent and constrained refinement ˚ 3 max = 0.44 e A ˚ 3 min = 0.20 e A

Table 1 ˚ ,  ). Hydrogen-bond geometry (A Cg1 and Cg2 are the centroids of the C5–C10 and C12–C17 rings, respectively.

CCDC reference: 1422036

1. Related literature For biological and pharmacological activities of Schiff base compounds and their derivatives, see: Khandar et al. (2005); Chen et al. (2006); Kidwai et al. (2000). For similar structures, see: Manvizhi et al. (2011); Thirugnanasundar et al. (2011); Rani et al. (2015).

D—H  A


H  A

D  A

D—H  A

O1—H1  N2 C18—H18A  Cg2i C1A—H1A1  Cg1ii

0.86 (2) 0.97 0.96

1.81 (4) 2.92 2.80

2.563 (5) 3.660 (5) 3.49 (4)

144 (6) 134 130

Symmetry codes: (i) x þ 52; y  1; z þ 12; (ii) x  1; y þ 32; z þ 12.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Acknowledgements The authors acknowledge the SAIF, IIT, Madras, for the data collection.


Rani et al.


Acta Cryst. (2015). E71, o712–o713

data reports Supporting information for this paper is available from the IUCr electronic archives (Reference: RK2432).

References Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Chen, Y., Zhao, Y., Lu, C., Tzeng, C. & Wang, J. (2006). Bioorg. Med. Chem. 14, 4373–4378.

Acta Cryst. (2015). E71, o712–o713

Khandar, A. A., Hosseini-Yazdi, S. A. & Zarei, S. A. (2005). Inorg. Chim. Acta, 358, 3211–3217. Kidwai, M., Bhushan, K., Sapra, P., Saxena, R. & Gupta, R. (2000). Bioorg. Med. Chem. 8, 69–72. Manvizhi, K., Chakkaravarthi, G., Anbalagan, G. & Rajagopal, G. (2011). Acta Cryst. E67, o2500. Rani, C. V., Chakkaravarthi, G. & Rajagopal, G. (2015). Acta Cryst. E71, o503. Sheldrick, G. M. (1996). SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Spek, A. L. (2009). Acta Cryst. D65, 148–155. Thirugnanasundar, A., Suresh, J., Ramu, A. & RajaGopal, G. (2011). Acta Cryst. E67, o2303.

Rani et al.



supporting information

supporting information Acta Cryst. (2015). E71, o712–o713


Crystal structure of 5-diethylamino-2-({[4-(diethylamino)phenyl]imino}methyl)phenol C. Vidya Rani, G. Chakkaravarthi, N. Indra Gandhi and G. Rajagopal S1. Comment Schiff base derivatives serve as intermediates in certain enzymatic reactions and are also found in proteins that form the connective tissue (Khandar et al., 2005; Chen et al., 2006) and in the pharmaceutical field (Kidwai et al., 2000). We herein report the crystal structure of the title compound (Fig.1). The geometric parameters of the title compound are comparable to the reported structures (Manvizhi et al., 2011; Thirugnanasundar et al., 2011; Rani et al., 2015). The dihedral angle between the rings (C5–C10) and (C12–C17) is 8.1 (2)°. The ethyl groups at one terminal site (N1) of the compound are disordered over two positions, with the site occupancies of 0.775 (9) and 0.225 (9). The molecular structure is stabilized by weak intramolecular O—H···N hydrogen bond (Table 1). The crystal structure is influenced by weak C—H···π (Table 1) interactions to form a three dimensional network. S2. Experimental For the preparation of Schiff base, an ethanolic solution (10 ml) of 5–(diethylamino)–2–hydroxybenzaldehyde (0.5 mol) and the same volume of ethanolic solution of N,N–diethylbenzene–1,4–diamine (0.5 mol) are mixed. The solution is mixed on magnetic stirrer with addition of 2 to 3 drops of glacial acetic acid. The reaction mixture is refluxed for 2 hrs and allowed to cool down to room temperature, crystalline solid precipitate from the mixture is separated out. Crystalline products are washed with ice cold ethanol and dried in vacuo over anhydrous CaCl2. Single crystals suitable for the X-ray diffraction are obtained by slow evaporation of a solution of the title compound in DMF at room temperature. S3. Refinement The H atoms were positioned geometrically and refined using riding model with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H, C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for CH2, C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for CH3. H atom for O atom is found from Fourier map and refined freely with Uiso(H) = 1.5Ueq(O) and distance restraint 0.82 Å. The components of the anisotropic displacement parameters in the direction of the bond between C9 and O1 were restrained to be equal within an effective standard deviation of 0.001 using the DELU command. The N1—C2, N1—C3, N1—C2A, N1—C3A distances were restraint to 1.46 (1) Å and C1—C2, C1A—C2A, C3—C4 and C3A—C4A distances were restraint to 1.53 (1) Å

Acta Cryst. (2015). E71, o712–o713


supporting information

Figure 1 The molecular structure of title compaund, with the atom–numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius. The intramolecular hydrogen bond is depicted by a dashed line. Only the major occupancy component of the disordered diethylamino–group [—N1(C2H5)2] is shown. 5-Diethylamino-2-({[4-(diethylamino)phenyl]imino}methyl)phenol Crystal data C21H29N3O Mr = 339.47 Orthorhombic, P212121 Hall symbol: P 2ac 2ab a = 8.1986 (4) Å b = 9.7128 (4) Å c = 24.4172 (12) Å V = 1944.38 (16) Å3 Z=4

F(000) = 736 Dx = 1.160 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 7089 reflections θ = 2.5–25.3° µ = 0.07 mm−1 T = 295 K Block, colourless 0.28 × 0.26 × 0.24 mm

Data collection Bruker Kappa APEX II CCD diffractometer Radiation source: fine–focus sealed tube Graphite monochromator ω and φ scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.980, Tmax = 0.983

29557 measured reflections 3556 independent reflections 2130 reflections with I > 2σ(I) Rint = 0.046 θmax = 25.4°, θmin = 2.3° h = −9→9 k = −11→11 l = −29→29

Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.064 wR(F2) = 0.205 S = 1.07 3556 reflections 272 parameters 10 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Acta Cryst. (2015). E71, o712–o713

Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0727P)2 + 1.5032P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.44 e Å−3 Δρmin = −0.20 e Å−3 Absolute structure: Flack (1983), 1466 Friedel pairs


supporting information Special details Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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)

C1 H1A H1B H1C C2 H2A H2B C3 H3A H3B C4 H4A H4B H4C C1A H1A1 H1A2 H1A3 C2A H2A1 H2A2 C3A H3A1 H3A2 C4A H4A1 H4A2 H4A3 C5 C6 H6 C7 H7 C8 C9





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