C 34 H 32 Cu 2 I 2 N 6 O 10 S 2 ,monoclinic, P 12 1 / c 1(no. 14), a =8.028(3) Å, b =12.957(3) Å, c =18.236(4) Å, b =95.54(4)°, V =1888.0 Å 3 , Z =2, R gt (F) =0.040, wRref(F) =0.041, T =295 K.
Source of materialThe ligand 1-iodo-4-[bis(2-pyridyl)amino]benzene (Ibdpam) was synthesized according to the standard Ullmann procedure (cf. [1]). The titlecomplex wasobtained by stirring aslight excess of Ibdpam (0.447 g, 1.2 mmol) with 0.244 g(1mmol) of CuSO4 ·5H 2 Oin a 20 mLethanol-water solution (1:1, v / v )for twenty four hours. The finalblue-green solution wasdistilled to dryness,forming ablue precipitate.This waswashed severaltimes with chloroformand ether to remove the excess of the ligand and finally recrystallized from methanol (yield 89 %with respect to CuSO4 ·5H 2 O). Crystals of thet itle compound were obtained after recrystallization and slow evaporation in methanol-water solution atambient temperature. They were air and X-raystable.
DiscussionThe copper(II)(chelate)n (dianion) complexes formulated as Cu(chelate)n X with chelate being 2,2¢ -bipyridyl (bipy), n =1 ,2 and X asvarious dianions, coordinated or not, are known to displayalarge variation of non-regularstereochemistry, presenting alarge number of investigated structuraldata [2][3][4]. When the coordinated ligand is the more flexible bis(2-pyridyl)-amine, structurald ataa re more limited [5][6][7]. Moreover, structurald ataof copper(II)complexes with N -substituted dpamchelates are rather rare [8,9]. Inthe case X represents CO 3 2-or SO 4 2-,severalclasses of localm oleculars tructures like monomeric, dimeric or polymeric square pyramids with unidentate,b identate or tridentate oxy-dianions were established [10]. The unit cell of the titlecrystalstructure contains two dinuclear neutralCu(II)c omplexes and four methanol molecules. Each metalcation is bonded to one ligand Ibdpaminabidentate chelating mode and to two oxygen atoms of the sulfate anion. One further oxygen atom from aneighboring sulfate anion is finally coordinated to the copper ion resulting in asquare based distorted pyramidale nvironment. The finalc oordination mode of each oxy-dianion is tridentate.The Cu1···Cu1adistance is 4.539(1) Å showing no interaction betweenthem. The bond distances and the bite angle of Ibdpamaswell asthe remaining coordination distances and angles are similartothose found for other analogous copper complexes [5][6][7][8][9][10][11]. The square pyramidalbase is formed from N1, N2, O1and O2atoms,while the axialposition is occupied by O3a.The atoms forming the basalplane practically present no deviation from the planarity (smaller or equalt hant he e.s.d.). The Cuatom is placed 0.199(4)Åabove this plane, while the apicalO3aatom hasadistance of 1.165(4) Å.Each pyridyl ring aswell asthe phenyl ring of the Ibdpamligand are planaras expected. The angle between the best planes of the two pyridyl rings is 146.59(4)°.Considering ameanp lane passing through the two pyridyl rings, the phenyl ring is nearly perpendicularto this plane forming anangle of 91.06(4)°. ...