20 ml acetone and 4-methylquinoline (0.50 g, ... wise addition of 0.85 g (13 mmol) of NaN3 dis ... stand over several days to produce black crystals of 2. .... 100.0(1). N 1 -C u -N 2 3. 94.0(1). N 1- C u -C u A. 129.8(1). N 1- C u - N 11 A 160.1(1).
Preparation, Spectral and Structural Characterization of Two Polymeric 1:1 Mixed Ligand Complexes of Copper(II) Azide with 4-Methylquinoline and 2-Methylpyridine M ohamed A. S. G o h e r and Franz A. M autner*+ * + D epartm ent o f C hem istry, F aculty o f Science, A lex an d ria U niversity, A lexandria, Egypt ++ Institut für Physikalische und T heoretische C hem ie, Technische U niversität G raz, A -8010G raz, R ech b au erstraß e 12, A ustria Z. N aturforsch. 46b, 6 8 7 -6 9 2 (1991); received A u gust 28, 1990 C opper(II) Azide, C rystal S tructure, 4-M ethylquinoline, 2-M ethylpyridine, Spectroscopic Studies Two 1:1 mixed ligand com plexes o f co pper(II) azide w ith substituted quinoline an d pyri dine, namely catena d i-/i(l,l)-azid o -(4 -m eth y lq u in o lin e)co p p er(II) (1) and catena d i-//(l,3)azido-[di-//(l,l)-azido-bis(2-m ethylpyridine)dicopper(II)] (2) have been prepared and ch arac terized by X -ray crystallography. Crystal data: 1, C 10H 9N 7Cu, space group P 2 Jc, a = 577.8(2), b = 2202.3(5), c = 919.9(2) pm ,/? = 93.92(2)°, Z = 4, an d R = 0.035 fo r 1293 observed M o K « data; 2, C 6H 7N 7Cu, space group P 2 ,/a , a = 823.7(2), b = 1303.8(4), c = 895.3(3) p m ,/? = 112.23(2)°, Z = 4, and R = 0.022 for 2133 observed M o K a d iffracto m eter d a ta . In the stru ctu re o f 1, the C u(II) has a strongly distorted trigonal bypyram idal co o rd in atio n , w here b o th azido groups function as //(1,1) bridging ligands resulting in a co lu m n ar stru c tu re along the a axis. The polym eric com plex 2 has a less d istorted square pyram idal structure; one h a lf o f the azide groups act as //(1,1) bridging ligands to form centrosym m etric dim ers. T hese dim eric units are fu rth er connected by the rem aining ,«(1,3) bridging azido groups to form layers w ithin the aA-plane. Infrared and electronic spectral d a ta are also presented and discussed.
Introduction
Experimental
Azide ligand binding to protein binuclear centres has played a key role in bioinorganic stud ies. This is because o f strong charge transfer ab sorption in the visible region, accessibility by IR and ESR spectroscopic techniques and its variable mode of bonding [1]. Terminal, end-on and endto-end bridging azido ligands are all known in cop per chemistry [2]. Recently we reported the syn thesis and structural characterizations of a series of copper azide complexes [3-6] in order to inves tigate the factors influencing the bonding modes of azide in these complexes. Now we have synthe sized two new 1:1 complexes of copper(II) azide with 4-methylquinoline (4-MeQ) and 2-methylpyridine (2-pic) and characterized them by X-ray crystallography, IR and reflectance spectra.
Preparation o f polymeric Cu( 4-M eQ ) (N 3) 2 (I)
* R eprint requests to D r. F. A. M autner. Verlag der Zeitschrift für N aturforschung, D-7400 Tübingen 0932 - 0776/91 /0500- 0687/$ 01.00/0
C u (N 0 3)3-3 H 20 (0.972 g, 4 mmol) dissolved in 20 ml acetone and 4-methylquinoline (0.50 g, 3.5 mmol) dissolved in 30 ml acetone were mixed together followed by the addition of N aN 3 (0.534 g, 8 mmol) dissolved in a minimum o f wa ter. The final mixture was boiled for several m in utes, cooled and allowed to stand until black wellformed crystals of 1 separated. C 10H 9N 7C u (290.8) Calcd C 41.32 H 3.12 N 33.70 Cu 21.85, Found C 41.08 H 3.41 N 33.52 Cu 21.80. Preparation o f polymeric Cu(2-pic) ( N3) 2 (2)
An ethanolic solution of 2-picoline (0.74 g, 8 mmol) was added to C u (N 0 3)2-3 H 20 (1.46 g, 6 mmol) dissolved in 40 ml ethanol. After dropwise addition of 0.85 g (13 mmol) of N aN 3 dis solved in 5 ml water to the stirred solution, the fin al mixture was heated and filtered. The filtrate was boiled for about 15 minutes, cooled and allowed to stand over several days to produce black crystals o f 2. C6H 7N 7Cu (240.7) Calcd C 29.95 H 2.93 N 40.73 Cu 26.39, Found C 29.78 H 3.02 N 40.61 Cu 26.22.
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M. A. S. G o h e r - F . A. M a u tn e r • Polym erie C u (4 -M cQ )(N 3); an d C u(2-pic)(N ,),
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T able I. C rystallographic d ata.
C o m pound
1
2
Chem ical form ula F o rm u lar mass C rystal system Cell constants
C 10H 9N 7C u 290.8 m onoclinic a = 577.8(2) pm b = 2202.3(5) pm c = 919.9(2) pm ß = 93.92(2) V = 1167.8(6)x 106 pm 3
C 6H 7N 7C u 240.7 m onoclinic a = 823.7(2) pm h = 1303.8(4) pm c = 895.3(3) pm ß = 112.23(2) V = 890.0(5) x 106 pm 3 P 2 ,/a 4 484 1.796 M g /m 3 103(2) K 0.23x0.21 x 0.20 mm 2 0 < 64 hkl: - 1 2 ,0 ,0 /1 2 , 19,13 w -scan, A to = 1.4 2133 155 /;(M o K a ) = 2.43 m m ” 1 0.022 0.024 60.551