Experimental. Crystal data. C 33 H 48 N 4 O M r = Monoclinic, P2 1 a = (2) Å b = (2) Å c = (2) Å = 94.

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1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN (2H-Benzotriazol-2-yl)-6-[(dicyclohexylamino)methyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Ming-Jen Chen, a Ban-Hsin Wu, b Chen-Yu Li, b Chia-Her Lin b and Bao-Tsan Ko b * a Department of Applied Cosmetology and Graduate Institute of Cosmetic Science, Hungkuang University, Taichung City 443, Taiwan, and b Department of Chemistry, Chung Yuan Christian University, Chung-Li 320, Taiwan Correspondence btko@cycu.edu.tw Received 5 September 2012; accepted 12 September 2012 Key indicators: single-crystal X-ray study; T = 296 K; mean (C C) = Å; R factor = 0.036; wr factor = 0.101; data-to-parameter ratio = Experimental Crystal data C 33 H 48 N 4 O M r = Monoclinic, P2 1 a = (2) Å b = (2) Å c = (2) Å = (1) Data collection Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2008) T min = 0.968, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 347 parameters V = (5) Å 3 Z =2 Mo K radiation = 0.07 mm 1 T = 296 K mm measured reflections 6650 independent reflections 5895 reflections with I > 2(I) R int = restraint H-atom parameters constrained max = 0.15 e Å 3 min = 0.15 e Å 3 In the title molecule, C 33 H 48 N 4 O, the dihedral angle between the mean planes of the benzotriazole ring system [maximun deviation = (2) Å] and the phenol ring is 16.6 (2). There is an intramolecular O HN hydrogen bond between the phenol and benzotriazole groups. Related literature For background information and potential applications of the title compound, see: Chmura et al. (2006); Gendler et al. (2006); Li et al. (2011). For a related structure: see: Li et al. (2009). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA O H0AN (2) 145 Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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: SHELXTL. We gratefully acknowledge the financial support in part from the National Science Council, Taiwan (NSC M MY2 and NSC M MY3). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5530). References Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Chmura, A. J., Davidson, M. G., Jones, M. D., Lunn, M. D., Mahon, M. F., Johnson, A. F., Khunkamchoo, P., Roberts, S. L. & Wong, S. S. F. (2006). Macromolecules, 39, Gendler, S., Segal, S., Goldberg, I., Goldschmidt, Z. & Kol, M. (2006). Inorg. Chem. 45, Li, J.-Y., Li, C.-Y., Tai, W.-J., Lin, C.-H. & Ko, B.-T. (2011). Inorg. Chem. Commun. 14, Li, J.-Y., Liu, Y.-C., Lin, C.-H. & Ko, B.-T. (2009). Acta Cryst. E65, o2475. Sheldrick, G. M. (2008). Acta Cryst. A64, o2944 Chen et al. doi: /s

2 supporting information [ 2-(2H-Benzotriazol-2-yl)-6-[(dicyclohexylamino)methyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Ming-Jen Chen, Ban-Hsin Wu, Chen-Yu Li, Chia-Her Lin and Bao-Tsan Ko S1. Comment Over the past decade, there has been considerable attention drawn to the development of amine-phenolate titanium alkoxides, due mainly to their applications in polymer preparations of well defined polyesters such as poly(εcaprolactone) (PCL) and poly(lactide) (PLA) (Chmura et al., 2006 & Gendler et al., 2006). Such amine-phenolate type ligands can be easily synthesized via a Mannich condensation from a secondary (or primary) amine, paraformaldehyde, and 2, 4-di-substitute-phenol under reflux conditions. For instance, our group has successfully synthesized and structural characterized amine-phenolate ligands derived from benzotriazole phenoxide (BTP) ligands, and zinc complexes bearing such ligands have been demonstrated to catalyze the ε-caprolactone and β-butyrolactone polymerizations with good catalytic activities in a controlled fashion (Li et al., 2011). However, no amino-btp ligand with sterically bulky pendant arm has been isolated to date. Herein, we present the synthesis and crystal structure of the title compound, (I), a potential ligand for the preparations of group 4 complexes. The molecular structure of (I) is composed of a benzotriazole-phenol moiety and the dicyclohexylamino functionalized group (Fig. 1). The dihedral angle between the mean planes of the benzotriazole unit (maximun deviation (2)Å for C12) and the benzene ring of the phenoxy group is 16.6 (2). There is an intramolecular O H N hydrogen bond between the phenol and benzotriazole groups (Table 1). The distance of N1 H is substantially shorter than the van der Waals distance of 2.75 Å for the N and H distance. It is interesting to note that the six-membered ring (O/C1/C2/N2/N1/H0A) formed from the O H N hydrogen-bond is almost planar with a mean deviation of (2) Å. The bond distances of benzotriazol-phenolate group are similar to those found in the crystal structure of 2-(2Hbenzotriazol-2-yl)-6-((diethylamino)methyl)-4-methylphenol (Li et al., 2009). S2. Experimental The title compound was synthesized by the following procedure (Fig. 2): To a mixture of paraformaldehyde (1.20 g, 40.0 mmol) and dicyclohexylamine (8 ml, 40.0 mmol) was added 2-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2- yl)phenol (3.23 g, 10.0 mmol). The resulting mixture was heated at 383K for 1 day and then dried under reduced pressure to yield the oily residue. The residue was separated by chromatography over silica gel and eluted with hexane/ethyl acetate (95/5) to afford 4.38 g of the title compound in 85% yield. Colorless crystals were obtained from the saturated hexane solution. S3. Refinement The H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C H = 0.93 Å with U iso (H) = 1.2 U eq (C) for benzene hydrogens; 0.96 Å with U iso (H) = 1.5 U eq (C) for CH 3 group; 0.97 Å with U iso (H) = 1.2 U eq (C) for CH 2 group; 0.98 Å with U iso (H) = 1.2 U eq (C) for CH group; O H = 0.85 Å with U iso (H) = 1.5 U eq (O). sup-1

3 Figure 1 The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level. Figure 2 The synthetic procedure. 2-(2H-Benzotriazol-2-yl)-6-[(dicyclohexylamino)methyl]-4-(2,4,4- trimethylpentan-2-yl)phenol Crystal data C 33 H 48 N 4 O M r = Monoclinic, P2 1 Hall symbol: P 2yb a = (2) Å b = (2) Å c = (2) Å β = (1) V = (5) Å 3 Z = 2 F(000) = 564 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 9957 reflections θ = µ = 0.07 mm 1 T = 296 K Columnar, yellow mm sup-2

4 Data collection Bruker APEXII CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: pixels mm -1 φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2008) T min = 0.968, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 347 parameters 1 restraint Primary atom site location: structure-invariant direct methods measured reflections 6650 independent reflections 5895 reflections with I > 2σ(I) R int = θ max = 28.3, θ min = 1.7 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.060P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.15 e Å 3 Δρ min = 0.15 e Å 3 Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq O (8) (10) (8) (3) H0A * N (9) (12) (9) (3) N (9) (11) (8) (2) N (9) (13) (10) (3) N (9) (12) (9) (3) C (10) (13) (10) (3) C (11) (13) (10) (3) C (11) (15) (11) (3) H3B * C (11) (14) (11) (3) C (11) (15) (11) (3) H5A * C (11) (14) (10) (3) C (12) (14) (11) (3) C (15) (16) (13) (4) sup-3

5 H8A * C (17) (18) (15) (5) H9A * C (18) (18) (16) (5) H10A * C (16) (18) (16) (5) H11A * C (12) (15) (12) (3) C (12) (16) (12) (3) C (2) (2) (16) (6) H14A * H14B * H14C * C (14) (2) (18) (6) H15A * H15B * H15C * C (12) (14) (12) (3) H16A * H16B * C (14) (16) (13) (4) C (2) (2) (16) (7) H18A * H18B * H18C * C (19) (3) (2) (7) H19A * H19B * H19C * C (19) (2) (15) (6) H20A * H20B * H20C * C (12) (16) (13) (4) H21A * H21B * C (12) (14) (11) (3) H22A * C (14) (17) (12) (4) H23A * H23B * C (17) (2) (13) (5) H24A * H24B * C (17) (2) (15) (5) H25A * H25B * C (16) (19) (16) (5) sup-4

6 H26A * H26B * C (12) (17) (13) (4) H27A * H27B * C (11) (14) (11) (3) H28A * C (15) (19) (14) (4) H29A * H29B * C (2) (2) (18) (6) H30A * H30B * C (18) (2) (16) (5) H31A * H31B * C (15) (19) (14) (4) H32A * H32C * C (13) (17) (13) (4) H33B * H33A * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 O (5) (6) (6) (4) (4) (5) N (6) (6) (6) (5) (5) (5) N (5) (6) (6) (5) (4) (5) N (6) (7) (7) (5) (5) (6) N (6) (6) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (6) C (7) (7) (6) (5) (5) (5) C (7) (7) (7) (6) (5) (6) C (7) (7) (7) (6) (5) (6) C (7) (7) (7) (6) (6) (6) C (7) (7) (7) (6) (5) (6) C (8) (7) (7) (6) (5) (6) C (10) (8) (9) (7) (7) (7) C (13) (8) (10) (8) (9) (8) C (14) (10) (12) (10) (10) (9) C (9) (10) (13) (8) (9) (9) C (8) (7) (7) (6) (6) (6) C (7) (8) (8) (6) (6) (7) C (15) (13) (11) (12) (10) (10) C (8) (15) (15) (9) (9) (13) C (7) (7) (8) (6) (6) (6) C (9) (8) (9) (7) (7) (7) sup-5

7 C (2) (11) (12) (12) (12) (9) C (15) (16) (15) (13) (12) (14) C (15) (13) (10) (12) (10) (10) C (7) (9) (8) (6) (6) (7) C (7) (7) (7) (6) (6) (6) C (9) (9) (8) (7) (6) (7) C (13) (12) (8) (10) (8) (8) C (14) (12) (10) (11) (9) (10) C (11) (10) (14) (8) (10) (10) C (8) (8) (10) (7) (7) (8) C (7) (7) (7) (6) (5) (6) C (10) (10) (10) (8) (8) (9) C (15) (11) (13) (10) (11) (10) C (15) (11) (11) (10) (10) (9) C (10) (10) (9) (8) (7) (8) C (8) (9) (8) (7) (6) (7) Geometric parameters (Å, º) O C (15) C18 H18A O H0A C18 H18B N1 N (16) C18 H18C N1 C (18) C19 H19A N2 N (15) C19 H19B N2 C (17) C19 H19C N3 C (2) C20 H20A N4 C (18) C20 H20B N4 C (19) C20 H20C N4 C (17) C21 H21A C1 C (18) C21 H21B C1 C (18) C22 C (2) C2 C (18) C22 C (2) C3 C (2) C22 H22A C3 H3B C23 C (2) C4 C (19) C23 H23A C4 C (19) C23 H23B C5 C (19) C24 C (3) C5 H5A C24 H24A C6 C (19) C24 H24B C7 C (2) C25 C (3) C7 C (2) C25 H25A C8 C (2) C25 H25B C8 H8A C26 C (3) C9 C (3) C26 H26A C9 H9A C26 H26B C10 C (3) C27 H27A C10 H10A C27 H27B C11 C (2) C28 C (2) sup-6

8 C11 H11A C28 C (2) C13 C (2) C28 H28A C13 C (3) C29 C (3) C13 C (2) C29 H29A C14 H14A C29 H29B C14 H14B C30 C (3) C14 H14C C30 H30A C15 H15A C30 H30B C15 H15B C31 C (3) C15 H15C C31 H31A C16 C (2) C31 H31B C16 H16A C32 C (2) C16 H16B C32 H32A C17 C (3) C32 H32C C17 C (3) C33 H33B C17 C (3) C33 H33A C1 O H0A H19B C19 H19C N2 N1 C (11) C17 C20 H20A N1 N2 N (11) C17 C20 H20B N1 N2 C (10) H20A C20 H20B N3 N2 C (11) C17 C20 H20C N2 N3 C (12) H20A C20 H20C C21 N4 C (12) H20B C20 H20C C21 N4 C (11) N4 C21 C (11) C22 N4 C (10) N4 C21 H21A O C1 C (11) C6 C21 H21A O C1 C (11) N4 C21 H21B C2 C1 C (11) C6 C21 H21B C3 C2 C (12) H21A C21 H21B C3 C2 N (11) N4 C22 C (12) C1 C2 N (11) N4 C22 C (12) C4 C3 C (12) C23 C22 C (12) C4 C3 H3B N4 C22 H22A C2 C3 H3B C23 C22 H22A C3 C4 C (12) C27 C22 H22A C3 C4 C (12) C22 C23 C (14) C5 C4 C (13) C22 C23 H23A C6 C5 C (13) C24 C23 H23A C6 C5 H5A C22 C23 H23B C4 C5 H5A C24 C23 H23B C5 C6 C (12) H23A C23 H23B C5 C6 C (12) C25 C24 C (15) C1 C6 C (12) C25 C24 H24A N1 C7 C (12) C23 C24 H24A N1 C7 C (14) C25 C24 H24B C12 C7 C (14) C23 C24 H24B C9 C8 C (17) H24A C24 H24B sup-7

9 C9 C8 H8A C24 C25 C (14) C7 C8 H8A C24 C25 H25A C8 C9 C (18) C26 C25 H25A C8 C9 H9A C24 C25 H25B C10 C9 H9A C26 C25 H25B C11 C10 C (16) H25A C25 H25B C11 C10 H10A C27 C26 C (15) C9 C10 H10A C27 C26 H26A C10 C11 C (18) C25 C26 H26A C10 C11 H11A C27 C26 H26B C12 C11 H11A C25 C26 H26B N3 C12 C (12) H26A C26 H26B N3 C12 C (15) C26 C27 C (14) C7 C12 C (15) C26 C27 H27A C4 C13 C (13) C22 C27 H27A C4 C13 C (13) C26 C27 H27B C15 C13 C (15) C22 C27 H27B C4 C13 C (11) H27A C27 H27B C15 C13 C (13) N4 C28 C (12) C14 C13 C (14) N4 C28 C (12) C13 C14 H14A C29 C28 C (13) C13 C14 H14B N4 C28 H28A H14A C14 H14B C29 C28 H28A C13 C14 H14C C33 C28 H28A H14A C14 H14C C30 C29 C (16) H14B C14 H14C C30 C29 H29A C13 C15 H15A C28 C29 H29A C13 C15 H15B C30 C29 H29B H15A C15 H15B C28 C29 H29B C13 C15 H15C H29A C29 H29B H15A C15 H15C C31 C30 C (16) H15B C15 H15C C31 C30 H30A C17 C16 C (13) C29 C30 H30A C17 C16 H16A C31 C30 H30B C13 C16 H16A C29 C30 H30B C17 C16 H16B H30A C30 H30B C13 C16 H16B C32 C31 C (16) H16A C16 H16B C32 C31 H31A C18 C17 C (17) C30 C31 H31A C18 C17 C (14) C32 C31 H31B C20 C17 C (14) C30 C31 H31B C18 C17 C (19) H31A C31 H31B C20 C17 C (17) C31 C32 C (16) C16 C17 C (16) C31 C32 H32A C17 C18 H18A C33 C32 H32A C17 C18 H18B C31 C32 H32C H18A C18 H18B C33 C32 H32C C17 C18 H18C H32A C32 H32C sup-8

10 H18A C18 H18C C32 C33 C (14) H18B C18 H18C C32 C33 H33B C17 C19 H19A C28 C33 H33B C17 C19 H19B C32 C33 H33A H19A C19 H19B C28 C33 H33A C17 C19 H19C H33B C33 H33A H19A C19 H19C C7 N1 N2 N (15) C5 C4 C13 C (15) C7 N1 N2 C (11) C3 C4 C13 C (17) N1 N2 N3 C (15) C5 C4 C13 C (18) C2 N2 N3 C (12) C3 C4 C13 C (14) O C1 C2 C (12) C5 C4 C13 C (18) C6 C1 C2 C (19) C4 C13 C16 C (18) O C1 C2 N (19) C15 C13 C16 C (2) C6 C1 C2 N (12) C14 C13 C16 C (15) N1 N2 C2 C (11) C13 C16 C17 C (2) N3 N2 C2 C (18) C13 C16 C17 C (15) N1 N2 C2 C (18) C13 C16 C17 C (2) N3 N2 C2 C (12) C22 N4 C21 C (16) C1 C2 C3 C4 0.9 (2) C28 N4 C21 C (13) N2 C2 C3 C (12) C5 C6 C21 N (2) C2 C3 C4 C5 0.4 (2) C1 C6 C21 N (12) C2 C3 C4 C (13) C21 N4 C22 C (12) C3 C4 C5 C6 0.3 (2) C28 N4 C22 C (15) C13 C4 C5 C (13) C21 N4 C22 C (15) C4 C5 C6 C1 0.6 (2) C28 N4 C22 C (17) C4 C5 C6 C (14) N4 C22 C23 C (13) O C1 C6 C (12) C27 C22 C23 C (18) C2 C1 C6 C (19) C22 C23 C24 C (2) O C1 C6 C (19) C23 C24 C25 C (2) C2 C1 C6 C (13) C24 C25 C26 C (2) N2 N1 C7 C (14) C25 C26 C27 C (19) N2 N1 C7 C (14) N4 C22 C27 C (13) N1 C7 C8 C (15) C23 C22 C27 C (18) C12 C7 C8 C9 1.3 (2) C21 N4 C28 C (15) C7 C8 C9 C (3) C22 N4 C28 C (13) C8 C9 C10 C (3) C21 N4 C28 C (17) C9 C10 C11 C (3) C22 N4 C28 C (15) N2 N3 C12 C (14) N4 C28 C29 C (13) N2 N3 C12 C (17) C33 C28 C29 C (18) N1 C7 C12 N (16) C28 C29 C30 C (2) C8 C7 C12 N (13) C29 C30 C31 C (2) N1 C7 C12 C (15) C30 C31 C32 C (2) C8 C7 C12 C (2) C31 C32 C33 C (19) C10 C11 C12 N (16) N4 C28 C33 C (13) C10 C11 C12 C7 0.2 (3) C29 C28 C33 C (18) C3 C4 C13 C (2) sup-9

11 Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O H0A N (2) 145 sup-10