4,4′,6,6′-Tetra-tert-butyl-2,2′-[1,3-diazinane-1,3-diylbis(methyl­ene)]diphenol 0.25-hydrate

Manman Zhang; Li Li; Fugen Yuan; Hui Qian

doi:10.1107/S1600536812026505

. 2012 Jun 16;68(Pt 7):o2123. doi: 10.1107/S1600536812026505

4,4′,6,6′-Tetra-tert-butyl-2,2′-[1,3-diazinane-1,3-diylbis(methylene)]diphenol 0.25-hydrate

Manman Zhang ^a, Li Li ^a, Fugen Yuan ^a,^*, Hui Qian ^a

PMCID: PMC3393934 PMID: 22798799

Abstract

The title compound, C₃₄H₅₄N₂O₂·0.25H₂O, the organic molecule, a potential tetradentate ligand with a bulky phenolic donor, has overall mirror symmetry. A partially occupied water molecule of solvation is present in the lattice. The six-membered 1,3-diazinane ring displays a chair conformation. An intramolecular O—H⋯N hydrogen bond ocurs. In the crystal, molecules are linked by O—H⋯O interactions.

Related literature

For aminobisphenolato ligands in coordination chemistry, see: Wichmann et al. (2012 ▶). For applications of their metal complexes, see: Barroso et al. (2010 ▶); Wong et al. (2010 ▶); Kannan et al. (2008 ▶); Pang et al. (2008 ▶); Tshuva et al. (2001 ▶). For background to the synthetic procedure and related structures, see: Hancock et al. (2011 ▶); Manna et al. (2008 ▶); Mohanty et al. (2008 ▶); Guo et al. (2003 ▶).

Experimental

Crystal data

C₃₄H₅₄N₂O₂·0.25H₂O
M _r = 527.30
Orthorhombic,
a = 8.7292 (8) Å
b = 37.428 (3) Å
c = 10.1806 (9) Å
V = 3326.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.33 × 0.24 × 0.16 mm

Data collection

Bruker SMART APEXII CCD diffractometer
29196 measured reflections
3908 independent reflections
3411 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.130
S = 1.05
3908 reflections
180 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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, global. DOI: 10.1107/S1600536812026505/fj2558sup1.cif

e-68-o2123-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026505/fj2558Isup2.hkl

e-68-o2123-Isup2.hkl^{(191.7KB, hkl)}

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
O1—H1⋯N1	0.82	2.00	2.6880 (13)	142
O2—H2⋯O1ⁱ	0.85	2.22	3.036 (5)	161

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Jiangsu Key Laboratory for Environment Functional Materials, a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) and the Innovation Program for graduate students of USTS is gratefully acknowledged.

supplementary crystallographic information

Comment

In coordination chemistry, various ligands are used to control the environment of the metal. Especially, the electronic and steric properties of ligands are used to control the reactivity of metal species. Aminobisphenolato ligand is attractive, because its substituents at the phenolate rings as well as the position and nature of the side chain donor are easily tuneable features; thus different electronic and steric properties are available (Wichmann et al. 2012). Such metal complexes have been found to display catalytic activity for polymerization of cyclic esters (Hancock et al., 2011) (biodegradable polymers) and polymerization of olefins (Tshuva et al., 2001). They can also catalyse Tischenko reactions (Pang et al., 2008), sulfoxidations (Barroso et al., 2010), olefin epoxidation (Wong et al., 2010), hydrogenation of ketones (Kannan et al., 2008) and Mizorokie-Heck coupling reaction (Mohanty et al., 2008). Generally, aminobisphenolato ligands are prepared by Mannich condensation from formaldehyde, phenol and a primary amine (Manna et al., 2008; Guo et al., 2003). Herein we present a new ligand, in which two substituted phenols are bridge-linked by a tetrahydropyrimidine ring. The molecules form a mirror symmetric structure, as illustrated in Scheme 1.

In the title compound, the C—N bond distances are between 1.4580 (14) to 1.4763 (15) Å whereas the bond length of C—O is 1.3763 (15) Å. The bond angles around the nitrogen atoms range from 110.35 (12)^o to 112.08 (10)^o, which is in agreement with those in similar structure (Guo et al., 2003). Two phenolate groups are linked by a tetrahydropyrimidine ring. The overall geometry is mirror-symmetric (Fig.1). The six-member 1,3-diazacyclohexane ring displays in a chair-configuration. Compound molecules were stabilized by hydrogen bonds including intra-molecular O—H···N interaction and inter-molecular O—H···O interaction (Fig. 2).

Experimental

The title compound was prepared as follows. To a solution of 2,4-di-butylphenol (24.77 g, 0.12 mol) in 20 ml of methanol was added 7 ml of formaldehyde(0.08 mol) and 2.0 ml 1,3-propanediamine. The mixture was refluxed for 3 d at 65 ^oC. In the process white precipitates were produced gradually. After being filtered and washed with methanol for 3 times, white product of C₁₃₆H₂₁₈N₈O₉ was obtained in a yield of 90.7% (based on diamine). Single crystals were grown from ethyl acetate, m.p. = 185 °C, Anal. calcd for C₁₃₆H₂₁₈N₈O₉: C, 77.44; H, 10.42; N, 5.31; Found: C, 77.02; H, 10.55; N, 5.27. IR(KBr, cm^-1) 3434(w), 2956(s), 2906(s), 2870(s), 2806(s), 2726(m), 2680(m), 1607(m), 1480(s), 1459(s), 1442(s), 1392(m), 1362(s), 1307(s), 1286(w), 1235(s), 1204(m), 1189(m), 1167(m), 1123(w), 1110(m), 1095(m), 989(m), 883(m), 822(w), 797(w), 761(w), 724(w), 682(w), 460(w).