808 Inorganic Chemistry, V d . 18, No. 3, 1979 Registry No. [Ni,(en),Cl,]CI,,
20647-35-2.
Supplementary Material Avaihble: A listing of observed and calculated structure factors (7 pages). Ordering information is given on any current masthead page.
Freyberg, Mockler, a n d S i n n (7) J. N. McElearney, D. B. Losee, S. Merchant, and R. L. Carlin, Phys. Rev. B, 7, 3314 (1973). (8) S. N. Bhatia, R. L. Carlin, and A. Paduan Filho, Physicn B: -t c‘: (Amsterdam), 82 B + C, 330 (1977). (9) P. W. R. Corfield, R. J. Doedens. and J. A. Ibers, Inoig. Chem., 6, 197
,.
(\ 1- , 967) -,
D. T. Cromer and J. T. Waber, “International Tables for X-Ray Crystallography”, Vol. IV, Kynoch Press, Birmingham, England, 1974. R. F. Stewart, E. R. Davidson, and W. T. Simpson, J. Chem. Phys., 42,
References and Notes (1) (a) University of Illinois at Chicago Circle; (b) University of Virginia. ( 2 ) R. L.Carlin and A. J. van Duyneveldt, “Magnetic Properties of Transition
(3)
(4) (5)
(6)
3175 (1965). D. T. Cromer and J. A. Ibers, ref 9. D. P. Freyberg, G. M. Mcckler, and E. Sinn, J. Chem. Sac., Dalton Yranr., 447 (1976). Supplementary material. F. K. Ross and G.D. Stucky, J. A m . G e m . Soc., 92, 4538 (1970). R. D. Willett, J. C‘hem. Phys., 45, 3737 (1966). Y . Journaux, 0. Kahn, B. Chevalier, J. E. Tourneau. R. Claude, and W. Dworkin, Chem. Phys. Lett.. E;§, 140 (1978). Reference 2, p 139. F. W.Klaaijsen, Z . Dokoupil, and W. J. Huiskamp, Physica B: t C: (Amsterdam), 79 B + C 547 (1975). Note that the zero-field splitting term of these authors enters the Hamiltonian with opposite sign.
Metal Compounds”, Springer-Verlag, New York, 1977, Chapter 4. A. P. Ginsberg, R. L. Martin, R. W. Brookes, and R. C. Sherwood, fnorg. Chem., 11, 2884 (1972). C. G. Barraclough and R. W. Brookes, J. Chem. SOC.,Faraday Trans. 2, 70, 1364 (1974). Reference 2 , Chapters 3 and 10. G. A. Bottomley, L. G. Glossop, C. L. Raston, A. H. White, and A. C. Willis, Aust. J . Chern., 31, 285 (1978), also report the crystal structure of [Niz(en)4C12]C1z.Their final R factor for 1345 reflections is 7.3%, more than twice the value reported here. There are several significant differences in the final analysis of bond lengths and angles from that reported here.
Contribution from the Departments of Chemistry, IJniversity of Virginia, Charlottesville, Virginia 22901, and University of Wollongong, Wollongong, N.S.W., Australia 2500
Properties and Structures of the Five-Coordinate Co per(I1) and S~X-COOP Niekel(I1) Complexes {[CuL].2W20J, and [NiLH20] N,N’-Bis[(2-hydroxy-5-methylphenyl) (4-methylphenyl)methylenel-3-aarahexa~ae-1 amine DEREK P. FREYBERG,la GARRY M . MOCKLER,lb and EKK SINN*Ia
Received September 15, 1978
’
The copper(I1) and nickel(I1) complexes of the potentially pentadentate ligand (2,3-mmbpK) derived from the Schiff base condensation of 3-azahexane-1,6-diamine and 5,4’-dimethyl-2-hydroxybenzophenone have been synthesized and their crystal structures and magnetic and spectral properties determined. For comparison, the copper and nickel complexes of a series of related ligands have also been synthesized and their magnetic and spectral properties deieirnined. The ligands act as pentadentates, in contrast with the coordination reported for some analogous Schiff base ligands with salicylaldehyde. The structurcs of both the copper and nickel complexes with 2,3-mmbpN are unexpected. The copper environment is very close to trigonal tipyramidal, with the amine nitrogen bond being only 0.1 A longer than the imine nitrogen bonds. This amine nitrogen bond, at 2,077 A, is much shorter than the analogous bond in the related complexes [Cu(3,3-mbpN)] (2.374 A) and [Cu(3,4-cbpN)J (2.291 A), and this shortening is ascribed to the steric requirements of the ligand. The nickel environment is close to octahedral, with a molecule of water coordinated to the nickel in a position cis to the amine nitrogen. Such coordination has been previously observed for complexes of cobalt(Ii1) but not for nickel(I1). The hydrogen bonding links neighboring molecules to form weakly linked dimers in the nickel complex, [P\ri(2,3-mmbpN).ti:Ql,, and infinite chains The crystal structures were determined from full-matrix least-squares in the copper complex, ( [Cu(2,3-rnmbpN)].2H20),. refinement of counter data: [Cu(2,3-mmpbN)].2H20, space group C2/c, Z = 4, a = 29.128 A. b -- 8.503 (2) A, c = 13.921 (S) A, 0 = 106.63 (2)O, V = 3304 A3, R = 3.5% for 1718 reflections; [Ni(2,3-mmbpN)H20], space group Pi, Z = 2, a = 10.833 (2) A, b = 12.63 (1) A, c = 13.137 (6) A, ct -- 116.83 ( 5 ) O , 6 = 91.09 (4)O, y = 93.91 (6)”, V = 1598 A3, R = 3.1% for 31 18 reflections.
Introduction A series of bivalent a n d trivalent m e t a l complexes with p e n t a d e n t a t e Schiff base ligands of type 1 have shown a n
Y < o
OH HO
0Y
1: n,m-salH,, R, Y = I % :rz,m-cbpH,, R = C,H,, Y = C1; n,m-mbpH,, R = C,H,, Y = CH,; n,m-mmbpH,, R = p C€I,C, H,, Y = CN,
interesting r a n g e of structures a n d properties. I n particular, indirect s t r u c t u r a l studies on t h e ligand s a l X H z (R = €4, X = IVH, WC6H5,S, 0. PCH3,Y = H) have suggested structures in which t h e donor X w a s frequently u n ~ o o r d i n a t e d . ~ On -~ t h c other h a n d , anajogous ligands based on substituted o-
hydroxybenzophenones (R = C6Mj) have t o d a t e always yielded complexes in which t h e ligand axts as a pentadentate, with X coordinated t o t h e metal.5--10Goniparison of spectral a n d magnetic properties suggests t h a t in a few specific cases, t h e salX complexes also have t h e dorior X coordinated. T h e r e is in fact no reason why t h e salicylaldehyde a n d benzophenone derivatives should behave differently in this respect, except for differences in ligand electronegativities. ’To date, attempts to obtain X - r a y evidence for conipiexes with t h e donor a t o m X uncoordinated have not been successful. Complexes with ligands (1) acting a s pcntadentates have the phenolic oxygen atoms either cis or trans to each other and t h e mechanism that makes o n e structurc preferred over t h e other is not yet clear. T h e differences a p p e a r to be small between t h e ligands of complexes adopting different structural types. In particular, completed a n d preliminary X - r a y studies show t h a t [M(3,3-cbpN)] (M = Ni, Cu, Zn), [ M ( 3 , 4 - c p b N ) ] (M =: Ni,
0020-1669/79/1318-0808$01 .OO/O 0 1979 American Chemical Society
Inorganic Chemistry, Vol. 18, No. 3, I979 809
Cu and Ni Complexes of (2,3-mmbpN) Table I. Analytical Data [Cu(2,3-mmbpN)] , 2 H 2 0 calcd found [Ni(2,3-mmbpN)].2H20 calcd found Ni(2,3-cbpN) calcd found [Cu(2,3-cbpN)J.I/,H,O calcd found [Cu(2,3-mbpN)] ,H,O calcd found [Ni(2,3-mbpN)]. 2 H 2 0 calcd found
C
H
N
66.60 67.03 67.11 67.14 61.73 61.54 60.79 60.79 67.73 68.05 66.24 66.78
6.55 6.36 6.60 6.31 4.51 4.49 4.53 4.54 6.03 6.80 6.23 5.80
6.66 6.28 6.71 6.73 6.97 7.21 6.86 6.74 7.18 6.97 7.02 7.16
Cu), [Zn( 3,3-mbpN)], [Cu( 3,3-cbpS)], and [M( 3,3-cbpS)L] (M = Co, Ni; L = pyridine, 3-methylpyridine), and [Co(3,3-cbpN)NCS] are trans, while [Co(3,3-cbpS)NCS] is cis." All complexes so far studied of bivalent metals with ligands of type 1 are trans. A further common feature of type 1 ligands has been a close structural similarity between their nickel(I1) and copper(I1) complexes, except for a dramatic elongation of the Cu-X bond in each case. However, the complexes with 2,3-mmbpH2 held three surprises in store: the copper and nickel derivatives are not structurally similar either to each other or to any of the analogous complexes previously studied, the Cu-X bond shows little elongation, and the nickel complex has its donor oxygens cis, the first observation of this configuration with nickel.
Experimental Section 2-Hydroxy-4',5-dimethylbenzophenone,Hmmbp, was prepared by Friedelxrafts acylation: 133 g (1 mol) of anhydrous A1CI3 was placed in a 1-L round-bottom flask and 155 g (1 mol) p-tolyl chloride was added. p-Cresol (108 g, 1 mol) was added in portions of about 15 g to the reaction mixture, which rapidly became hot, evolving fumes of HCI. The flask was swirled to encourage mixing of the reactants and was then heated to 180 "C for 30 min. The yellowish brown tarry product mixture was poured, with stirring, into a solution of 300 mL of concentrated HCl dissolved in 1200 mL of water. On cooling of the mixture, a granular precipitate formed, and this was filtered off and washed with water. The Hmmbp was recrystallized from a minimum volume of hot 95% ethanol. The other parent ketones, 3,3'-iminobis(propylamine), and N-(2-aminoethyl)- 1,3-~ropanediamine were purchased from the Aldrich Chemical Co., Inc. The condensation of the ketones with the triamines, to form the Schiff base ligands, and the syntheses of the metal complexes were carried out as previously d e ~ c r i b e d . Analytical ~ data for the new
complexes are given in Table I. Both of the complexes selected for X-ray study retained water molecules from the reaction mixture, leading to empirical formulas Cu(2,3-mmbpN).2H20 and Ni(2,3mmbpN).2H20. One of the water molecules in the nickel complex is readily lost, but the other is retained in the crystals grown for X-ray study, due to being bonded to the metal atom; both water molecules are retained by the copper complex, presumably due to the hydrogen bonding; vide infra. Both complexes were recrystallized from methanol. Magnetic moments were determined by the Gouy method. Visible and near-infrared solution spectra were measured on a Hitachi EPS-3T recording spectrophotometer and solid-state reflectance spectra on a Zeiss PMQII spectrophotometer with an RA-3 reflectance attachment. The spectral data are given in Table 11. Electron spin resonance spectra were obtained on a Varian E-109 spectrometer with an E-102 microwave bridge, operating a t 9 GHz. Crystal data for [Cu(2,3-mmbpN)]-2HzO: C U O ~ N ~ C ~M~, H ~ , , = 631, space group C2/c, a = 29.128 (6) A, b = 8.503 (2) A, c = 1 3 . 9 3 (5) A, p = 106.63 (2)", V = 3304 A3,2 = 4, pc = 1.27 g ~ m - ~ , pa = 1.30 g ~ r n - p(Mo ~, K a ) = 7.3 cm-', green crystal, faces (with distances from centroid in mm) (100) 0.08, (TOO) 0.08, (010) 0.14, (oio) 0.14, (001) 0.14, (oor) 0.14. Crystal data for [Ni(2,3-mmbpN)H20]: Ni03N3C3SH39, M, = 608, space group Pi,a = 10.833 (2) A, b = 12.63 (1) A, c = 13.137 (6) A, a = 116.83 (S)", 0 = 91.09 (4)", y = 93.91 (6)", V = 1598 A3, 2 = 2, pc = 1.27 g ~ m - p~o ,= 1.25 g ~ m - ~~ (, M Ko a ) = 6.5 cm-I, green crystal, faces (with distances from centroid in mm) (100) 0.13, (roo) 0.13, (010) 0.05, (oio) 0.05, ( o i i ) 0.12, ( o i l ) 0.12. For each crystal, the Enraf-Nonius program SEARCH was used to obtain the positions of 15 accurately centered reflections which were then used in the program INDEX to obtain approximate cell dimensions and an orientation matrix for data collection. Refined cell dimensions and their estimated standard deviations were obtained from leastsquares refinement of 28 accurately centered reflections. The mosaicity of each crystal was examined by the w-scan technique and judged to be satisfactory. Collection and Reduction of the Data. Diffraction data were collected at 292 K on an Enraf-Nonius four-circle CAD-4 diffractometer controlled by a PDP-8/M computer, using Mo Ka radiation from a highly oriented graphite crystal monochromator. The 8-28 scan technique was used to obtain the intensities of all nonequivalent reflections for which 1" < 28
