Crystal structure of N,N,N-tris­[(1,3-benzo­thia­zol-2-yl)meth­yl]amine

Velabo Mdluli; James A Golen; Arnold L Rheingold; David R Manke

doi:10.1107/S2056989015017417

. 2015 Sep 26;71(Pt 10):o786–o787. doi: 10.1107/S2056989015017417

Crystal structure of N,N,N-tris[(1,3-benzothiazol-2-yl)methyl]amine

Velabo Mdluli ^a, James A Golen ^b, Arnold L Rheingold ^b, David R Manke ^a,^*

PMCID: PMC4647366 PMID: 26594479

Abstract

The title compound, C₂₄H₁₈N₄S₃, exhibits three near planar benzothiazole systems in a pseudo-C ₃ conformation. The dihedral angles between the planes of the benzothiazole groups range from 112.56 (4) to 124.68 (4)° In the crystal, molecules are connected to each other through three short C—H⋯N contacts, forming an infinite chain along [100]. The molecules are also linked by π–π interactions with each of the three five-membered thiazole rings. [inter-centroid distance range: 3.614 (1)–4.074 (1) Å, inter-planar distance range: 3.4806 (17)–3.6902 (15) Å, slippage range: 0.759 (3)–1.887 (3) Å].

Keywords: crystal structure, benzothiazoles, C—H⋯N interactions

Related literature

For synthesis of the title compound and a structure of the ligand bound to copper, see: Thompson et al. (1980 ▸). For a related organic structure, see: Zhang et al. (2009 ▸). For other related structures, see; Bautista & Thompson (1980 ▸); Pandey & Mathur (1995 ▸). For a study of its use as a ligand in azide–alkyne cycloadditions, see: Rodionov, Presolski, Gardinier et al. (2007 ▸); Rodionov, Presolski, Diaz et al. (2007 ▸). graphic file with name e-71-0o786-scheme1.jpg

Experimental

Crystal data

C₂₄H₁₈N₄S₃
M _r = 495.66
Triclinic,
a = 6.6530 (3) Å
b = 14.3098 (6) Å
c = 14.5822 (7) Å
α = 61.471 (1)°
β = 88.474 (2)°
γ = 79.138 (1)°
V = 1194.61 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 100 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T _min = 0.951, T _max = 0.967
4691 measured reflections
4691 independent reflections
3767 reflections with I > 2σ(I)
R _int = 0.000

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.110
S = 1.08
4691 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▸); cell refinement: SAINT (Bruker, 2005 ▸); 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: publCIF (Westrip, 2010 ▸) and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015017417/ff2141sup1.cif

e-71-0o786-sup1.cif^{(28.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017417/ff2141Isup2.hkl

e-71-0o786-Isup2.hkl^{(229.8KB, hkl)}

Supporting information file. DOI: 10.1107/S2056989015017417/ff2141Isup3.txt

e-71-0o786-Isup3.txt^{(561.7KB, txt)}

Click here for additional data file.^{(8.2KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015017417/ff2141Isup4.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015017417/ff2141fig1.tif

Molecular structure of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as spheres of arbitrary radius.

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015017417/ff2141fig2.tif

Molecular packing of the title compound.

CCDC reference: 1425576

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C4H4AN1ⁱ	0.95	2.47	3.376(3)	159
C12H12AN2ⁱ	0.95	2.60	3.449(2)	150
C20H20AN3ⁱ	0.95	2.54	3.490(3)	178

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge support from the National Science Foundation (CHE-1229339 and CHE-1429086).

supplementary crystallographic information

S1. Chemical context

Tripodal ligands with nitrogen donors have become a common motif in coordination chemistry. Herein we report the structure of tris(benzothiazolylmethyl)amine. The bond distances and angles of the complex are similar to the previously reported bis(benzothiazol-2-ylmethyl)amine (Zhang et al., 2009). Copper and cobalt complexes of this ligand have been synthesized (Bautista & Thompson, 1980; Thompson et al., 1980, Pandey & Mathur, 1995) and copper complexes have been explored as catalysts for azide-alkyne cycloadditions (Rodionov, Presolski, Diaz, et al., 2007; Rodionov, Presolski, Gardinier, et al. 2007).

The molecular structure of the title compound is shown in Figure 1. The compound possesses three planar benzothiazoles that demonstrate a pseudo-C₃ configuration. The planes of the three benzothiazole ligands exhibit dihedral angles of 112.555 (2), 123.744 (2) and 124.677 (3). The structure exhibits infinite chains along [100] which result from three C—H···N short contacts. The packing of the title compound is shown in Figure 2.

S2. Synthesis and crystallization

The compound was prepared by literature procedure (Thompson et al., 1980). Crystals suitable for single-crystal X-ray analysis were grown by slow evaporation of a diethyl ether solution.

S3. Refinement details

The structure was solved by direct methods and all non-hydrogen atoms were refined anisotropically by full matrix least squares on F². Hydrogen atoms were placed in calculated positions and then refined with riding models with C—H lengths of 0.99 Å for (CH₂) and 0.95 Å for (CH) with isotropic displacement parameters set to 1.20 times U_eq of the parent C atoms. Diffused solvent (ethyl ether) was treated using Platon (Spek, 2009) program SQUEEZE (found void 157Å³, 48 electrons) and the unit card was adjusted by C₄H₁₀O to address issues of chemical formula, molecular mass, density and F000 value.