2,4-Di-tert-butyl-6-({[2-(di­methyl­amino)­eth­yl](2-hy­droxy­benz­yl)amino}­meth­yl)phenol

Grzegorz P Spaleniak; Elwira Bisz; Marzena Białek; Bartosz Zarychta

doi:10.1107/S1600536814010241

. 2014 May 17;70(Pt 6):o678. doi: 10.1107/S1600536814010241

2,4-Di-tert-butyl-6-({[2-(dimethylamino)ethyl](2-hydroxybenzyl)amino}methyl)phenol

Grzegorz P Spaleniak ^a, Elwira Bisz ^a, Marzena Białek ^a, Bartosz Zarychta ^a,^*

PMCID: PMC4051019 PMID: 24940258

Abstract

The title compound, C₂₆H₄₀N₂O₂, has both its N atoms in trigonal-pyramidal geometries. The molecular structure is stabilized by O—H⋯N and C—H⋯O hydrogen bonds. In the crystal, C—H⋯π interactions lead to the formation of a supramolecular helical chain along the b-axis direction.

Related literature

For general background to the use of diaminebis(aryloxido) compounds as tetradentate ligands, see: Hirotsu et al. (1997 ▶, 1998 ▶); Dutta et al. (2011 ▶). For related structures, see: Abrahams et al. (2009 ▶); Maity et al. (2006 ▶); Janas et al. (2012 ▶).

Experimental

Crystal data

C₂₆H₄₀N₂O₂
M _r = 412.60
Monoclinic,
a = 12.3002 (7) Å
b = 13.3758 (7) Å
c = 15.5662 (9) Å
β = 96.377 (5)°
V = 2545.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 150 K
0.40 × 0.37 × 0.35 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
17015 measured reflections
4964 independent reflections
2292 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.099
S = 0.78
4964 reflections
277 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814010241/bt6979sup1.cif

e-70-0o678-sup1.cif^{(699.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814010241/bt6979Isup2.hkl

e-70-0o678-Isup2.hkl^{(272.2KB, hkl)}

Click here for additional data file.^{(8.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814010241/bt6979Isup3.cml

CCDC reference: 1001222

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

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

Cg is the centroid of the C13–C18 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.96 (2)	2.59 (2)	3.1610 (19)	118.5 (16)
O1—H1A⋯N2	0.96 (2)	1.89 (2)	2.824 (2)	162.4 (19)
O2—H2A⋯N1	0.88 (2)	1.95 (2)	2.7563 (18)	152.1 (18)
C3—H3A⋯O2	0.96	2.64	3.411 (3)	137
C9—H9A⋯Cg ⁱ	0.93	2.77	3.593 (2)	148

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by a research grant (grant No. N N209 140840 within 2011–2014) from the Polish National Science Centre. EB is a recipient of a PhD fellowship from a project funded by the European Social Fund.

supplementary crystallographic information

1. Comment

Diamine bis(phenolate) compounds and its derivatives represent the dominant class of compounds that are used as tripodal tetradentate ligands with an N₂O₂ donor set (Hirotsu et al., 1997, 1998). The steric factors of substituents in the tetradentate ligands are especially important in complexation of agents for polymerization reactions.

The molecular structure of the title compound and the atom-numbering scheme are shown in Figure 1. The crystal structure shows trigonal pyramidal geometries around N1 [sum of C—N—C angles = 332.05 (18)° and N2 [sum of C—N—C angles = 330.37 (13)°], and is comparable with related structures (Abrahams et al., 2009; Maity et al., 2006; Janas et al., 2012). The aromatic ring which is substituted with tert-butyl groups is slightly more distorted in comparison to unsubstituted one due to the steric hindrance. The molecular structure is stabilized by three hydrogen bonds between hydroxyl groups and amine nitrogen atoms (Figure 1) and one of a C—H···O type. This pattern of interactions influences the dihedral angle between aromatic moieties which amounts 73.88 (57)°. Such stabilization is also observed for structures when both aromatic rings are substituted (Maity et al., 2006; Janas et al., 2012), in contrast to the unsubstituted molecule (Abrahams et al., 2009). All remaining bond distances and angles are normal and in good agreement with the geometries of other diamine bis(phenolates) (Abrahams et al., 2009; Maity et al., 2006; Janas et al., 2012). Strong intermolecular interactions were not found in the crystal. The structure is stabilized by weak C—H···π interactions.

2. Experimental

The compound was prepared according to literature procedure (Dutta et al., 2011). Crystals suitable for X-ray crystal structure analysis were grown from methanol.