Crystal structure of (2,6-diisopropyl-phenyl)-[6-(2,6-dimethylphenyI)- pyridin-2-yl-methylene]-amine, C26H30N2

Content Provider	Semantic Scholar
Author	Maisel, Heidi E. Keller, Sandra Irrgang, Torsten Kempe, Rhett
Copyright Year	2005
Abstract	C26H30N2, monoclinic, C12/cl (no. 15), a = 20.434(2) A, b = 8.551(1) A, c = 26.498(2) A,/? = 102.889(1)°, V= 4513.4 A, Z= 8, RpfF) = 0.062, wRnf(F) = 0.187, Τ =293 Κ. Source of material First, 2.0 g (10.7 mmol) of 6-bromopyridine-2-carbaldehyde and 2.03 mL (1.91 g, 10.7 mmol) of 2,6-diisopropylaniline were dissolved in 30 mL of ethanol and the mixture was heated at reflux for 2 h. The solvent was removed under reduced pressure and 3.59 g (97 %) of pale yellow crystalline material (I) was obtained and used without further purification. A solution of 1.39 mL (1.93 g, 10.4 mmol) of 2-bromo-m-xylene in 30 mL THF was added to 0.30 g (12.5 mmol) magnesium turnings and the resulting suspension stirred and activated using 0.2 mL of 1,2-bromoethane. An exothermic reaction took place and an ice bath was used to cool the reaction mixture when the reaction became too vigorous. The reaction mixture was stirred at room temperature for 2 h, then filtered and the filtrate (Π) directly used. To a solution of 3.0 g (8.69 mmol) I in 30 mL of dioxane was added a suspension of 0.11 g (0.87 mmol) FeCh in 10 mL of THF. The Grignard solution Π was then slowly added to the stirred suspension. The reaction mixture was heated to 70 °C for 48 h. 100 mL of water and 80 mL of diethyl ether were added and the resulting suspension transferred to a 500 mL separating funnel. The organic phase was collected and the inorganic phase washed with diethyl ether two times and extracted. The combined organic phases were washed with a saturated sodium chloride solution and dried with Na2S04. The organic phase was concentrated to dryness under vacuum resulting in a brown oily product. The oil was purified using silica chromatography (pentane) and then crystallized from pentane at -25 °C to afford pale yellow crystals suitable for X-ray crystal structure analysis (yield 1.16 g (39 %), m.p. 142.5 °C). Discussion As neutral metal complexes are required for selective oligomerization of ethylene or bis-alkoxycarbonylation of styrene, Bianchini and co-workers developed a series of substituted iminopyridine ligands [1-3]. The title compound, our search by SciFinder proceeded without any results, is a new sterically demanding member of this type of ligands. The bulky phenyl substituents in the 6-position of the pyridine and at the imino Ν atom are twisted with regard to the pyridine ring, and the dihedral angles are 118.6° and 98.1 respectively. Both phenyl rings form a dihedral angle of 68.8°. The significant shortening of the C6—N2 bond (1.25 A) indicates the imino function. In the uncoordinated ligand, the free electron pairs at the Npyndine and Njmino atoms are transoid. The C6-N2-C7 angle with 119.8° is much smaller than the C5-C6-N2 angle with 123.0°. Table 1. Data collection and handling. Crystal: Wavelength: μ· Diffractometer, scan mode: 20nux: WAUVasoitd. Nfhklhwpc: Criterion for /ote, Nfhkl)^: AYparamAefined·' Programs: pale yellow prism, size 0.4 χ 0.5 χ 0.6 mm Mo K„ radiation (0.71069 A) 0.63 cm Stoe IPDS Π, ω/φ 52.12° 31342,4468 /obs>2CTf/obs;, 3001 253 SIR97 [4], SHELXL-97 [5] Table 2. Atomic coordinates and displacement parameters (in A). * Correspondence author (e-mail: kempe@uni-bayreuth.de) Atom Site X y ζ Uiso H(2) 8/ -0.0275 -0.3555 0.3104 0.088 H(3) 8/ -0.0779 -0.2539 0.3733 0.098 H(4) 8/ -0.0126 -0.1203 0.4430 0.085 H(6) 8/ 0.1650 -0.0608 0.4627 0.074 H(9) 8/ 0.2317 0.0372 0.6549 0.092 H(10) 8/ 0.2624 0.2883 0.6421 0.102 H(ll) 8/ 0.2184 0.4149 0.5656 0.096 H(13) 8/ 0.1314 0.2503 0.4509 0.093 H(14A) 8/ 0.0399 0.4166 0.4461 0.203 H(14B) 8/ 0.0564 0.4292 0.5066 0.203 H(14C) 8/ 0.0339 0.2686 0.4797 0.203 H(15A) 8/ 0.2161 0.4401 0.4711 0.154 H(15B) 8/ 0.1690 0.5446 0.4963 0.154 H(15C) 8/ 0.1505 0.5113 0.4366 0.154 H(16) 8/ 0.1242 -0.2013 0.5611 0.102 H(17A) 8/ 0.0986 -0.2793 0.6390 0.286
Starting Page	483
Ending Page	484
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DOI	10.1524/ncrs.2005.220.14.483
Volume Number	220
Alternate Webpage(s)	http://www.degruyter.com/downloadpdf/j/ncrs.2005.220.issue-1-4/ncrs.2005.220.14.483/ncrs.2005.220.14.483.xml
Alternate Webpage(s)	https://doi.org/10.1524/ncrs.2005.220.14.483
Language	English
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