摘要:
1076 J.C.S. DaltonMetal Complexes of Multidentate Ligands containing Carbonyl and a-Di-imine groups. Crystal and Molecular Structure of Aquabis[B-(Z-pyridyl)quinazolin=4(3H) -onato]copper( 11)By Luigi Pietro Battaglia, Anna Bonamartini Corradi. Mario Nardelli, Corrado Pelizzi, and MariaEleonora Vidoni Tani, lstituto di Chimica Generate ed Inorganica, Centro di Studio per la StrutturisticaDiffrattometrica del C.N.R., Parma, ItalyThe title compound (IV) has been prepared and its structure determined from X-ray diffraction data. The structurewas solved by Patterson and Fourier methods and refined using least-squares techniques to R 4.1 % for 3 258 inde-pendent reflections. Crystals are triclinic, space group P i with unit cell dimensions a = 12.20(1), b = 13.91 (1).c = 7.35(1) A; a = 91.7(1),(3 = 112.7(1), y = 103.9(1)".Z = 2.Co-ordination round copper is approximatelysquare pyramidal: a water molecule [Cu-0 2.014(4) A]. a chelate ligand [CU-N(py) 2.022(4), CU-N 1.992(4) A],and one nitrogen atom [Cu-N 1-967(4) A] of the second chelate ligand form the base, and the pyridine nitrogen[Cu-N(py) 2.245(4) 141 of the second ligand forms the apex.DURING recent investigations 1-4 of copper(I1) complexesof organic ligands containing the C=O group and theN-C-C-N system, the ligand behaviour of (I) 2-(2-pyridyl)-2,3-dihydroquinazolin-4( 1 H)-one was considered.(1) (Ligand HL)(11) (Ligand HL')A mixed-chelated iiickel(11) complex with it wasexamined by X-ray diffraction and i.r. spectroscopy.We have now isolated a copper(I1) complex obtainedfrom the reaction of this same ligand with copper(I1)chloride in acetone solution.We now report its spectro-scopic properties and X-ray analysis, and show that theparent ligand has become oxidized to (11), 2-(2-pyridyl)-quinazolin-4(3H)-one.EXPERIMENTALPreparation of (I) 2-( 2-pyridyl)-2,3-dihydroquinazolint-4-( 123)-one.-o-Aminobenzamide and pyridine-2-carbaldehyde(molar ratio 1 : 1) were heated under reflux for 3-4 h inbenzene solution. By slow evaporation of the solvent, acream-coloured microcrystalline product was isolated,m.p. 185 "C (Found: C, 69.2; HI 5.4; N, 18.8. Calc. forPreparation of the Copper(r1) CompZex.-CuC1,*2H20 and(I) (molar ratio 1 : 1) were heated under reflux in acetonesolution for 1 h. After some hours at room temperature, agreen crystalline product of formula Cu (C,,H8N30)Cl-H20was obtained (Found: C, 46.25; H, 3.1; Cu, 19.0;1 A. Mangia, 31.Nardelli, C. Pelizzi, and G. Pelizzi, ActaCryst., 1974, BSO, 17.a A. Mangia, C. Pelizzi, and G. Pelizzi, Acta Cryst., 1974, B30,2146.a P. Domiano, A. Musatti, M. Nardelii, C . Pelizzi, and G.Predieri, J . C . S . Dalton, 1976, 2357.C13H11N30: C, 69.3; H, 5.35; N, 18.65%).N, 12.5. Calc.: C, 46.0; H, 3.0; Cu, 18.7; N, 12.4%).By successive recrystallization of this compound fromboiling dimethyl sulphoxide, green prisms of formulaCu(C,,H,N,O) 2*H20 were obtained (Found : C, 58.6 ;H, 3.6; Cu, 11.75; N, 15.8. Calc.: C, 59.4; H, 3.45;Cu, 12.1; N, 16.0%).1.r. and electronic spectra were recorded on Perkin-Elmer 457 and 402 spectrophotometers respectively.X-Ray intensity data were collected on a Siemens AEDsingle-crystal computer-controlled diffractometer.Crystal Data.-C2,H,8CuN,03, M = 526, Triclinic, a =12.20(1), b = 13.91(1), c = 7.35(1) A, a = 91.7(1), fl =112.7(1), y = 103.9(1)*, U = 1 112 A3, Dm = 1.59 g cmP3,2 = 2, D, = 1.57 g ~ m - ~ , F(000) = 546. Cu-K, radiation7, = 1.5418 A, ~(CU-K,) = 17.9 cm-l.Space group Pifrom structural analysis.Cell dimensions were determined from rotation andWeissenberg photographs and refined from diffractometermeasurements.Intensity Data Collection.-A sample was aligned with its[OOl] axis along the 9 axis of the diffractometer and all re-flections with 6" < 20 < 120" were collected. In this waythe intensities of 3 258 independent reflections weremeasured, and 2 878 of them, having I > 20(I), were con-sidered observed and were used in the structure analysis.There was no evidence for decomposition of the sampleduring the X-ray exposure as shown by the constantintensity of a standard reflection measured every 20reflections.After the usual data reduction structure amplitudes wereput on an absolute scale first by Wilson's method,6 then bycomparison with the calculated values.Absorption cor-rections were not applied, in view of the low absorbance ofthe sample (pF 0.13).Structure Determination and Refinement.-The structurewas solved by the heavy-atom technique, taking copperco-ordinates obtained from a three-dimensional Pattersoncalculation.Refinement by block-diagonal anisotropicleast-squares gave R 5.6%. The function minimized wasCwlAFI2, first with unit weights, then with the weightingscheme w = 1/(A + BF,)2, where A = 2.40 and B = 0.02.In the last stages of the refinement the hydrogen atoms,which had been located from a difference-Fourier map,were included and refined isotropically, to give a finalR of 4.1%.C . Pelizzi and G. Predieri, Gazsstta, 1976, 105, 413.A. Bonamartini Corradi, C. Grasselli Pdmieri, M. Nardelli,A. J. C . Wilson, Nature, 1942,150. 161and C. Pelizzi, J.C.S. Dalton, 1974, 1501976 1077Final positional parameters with their standard devi-ations are given in Tables l and 2. Observed and cal-culated structure factors with thermal parameters andTABLE 1Final atoinic fractional co-ordinates ( x lo4) with estimatedstandard deviations in parenthesesc u 2 337(1) 2 233( 1) 2 694( 1)267(2) 3 109(2) 506(4)4 663(3) 2 201(2) 1624(5)2 146(2) 701(2) 3 628(4)638(2) 1671(2) 1716(4)-1 126(2) 260(2) 1332(4)2 461(3) 3 067(2) 6 l06(4)4 133(2) 2 932(2) 3 762(6)6 642(3) 4 168(2) 6 439(6)962(3) 182(2) 3 063(6)621(3) -779(3) 3 496(6)1636(4) -1 220(3) 4 614(6)2 753(4) - 703 (3) 5 094(6)3 017(3) 266(3) 4 606(6)2 256(3) 747(6)-1 933(3) 817(3) 417(6)xla Y / b ZICO(1)O(2)O(3)N(1)N(2)N(3)N(4)N(6)N(6)C(1)C(2)C(3)(74)C(5)C(6)C(7)C(8)C(9)C(10)C(11)C(12)C(13)C(14)C(15)C(16)C(17)C(WCP9)C(20)C(21)C(22)Ct23)(324)C(25)C(26)2 299(2) 1 SOS(2) 23(4)726(2) 1967(5)-1 625(3) 1806(3) 86(5)47(3)- 198(3)-3 209(3) 383(3) - 189(6)-4 019(3) 929(3) -1 073(6)-3 604(4) 1916(3) -1 419(6)-2 368(4) 2 346(3) - 847(6)1663(3) 3 053(3) 6 742(6)1736(4) 3 627(3) 7 428(6)3 813(4) 4 280(4) 7 828(7)3 573(3) 3 654(3) 6 172(5)4 637(3) 3 602(3) 6 426(5)4 973(3) 2 790(3) 3 032(6)6 247( 3) 3 393(3) 4 111(6)6 623(3) 4 064(3) 6 748(6)7 749(4) 4 671(3) 6 780(7)8 637(4) 4 666(3) 6 126(8)8 368(4) 3 872(3) 4 496(8)7 165(4) 3 286(3) 3 460(7)2 883(5) 4 266(4) 8 494( 7)TABLE 2Final fractional co-ordinates ( x lo3) and isotropic thermalparameter ( x lo2 A2) of hydrogen atoms, with estimatedstandard deviations in parenthesesxla Y lb ZlC B-22(3) -111(3) 316(6) 42(8)133(3) -190(3) 481(6) 49(9)HC ( 2)331(4) - lOO(3) 547(6) 53(9)HC(3)386(3) 67(3) 496(5) 49(9)HC(4)HC(11) -489(3) 63(3) -143(6) 46(9)HC(13) -203(3) 299(3) - 113(6) 52(9)HC( 16) 304(4) 473(3)EE[%) -349(3) -32(3) 3(5) 40(8)::[?I)::[;i)HC(12) -418(4) 230(3) -200(6) 66(10)262(3) 491(6)786(6)974( 7) 73(12)HC( 14)HC( 16) 105(4)HC( 17) 462(4) 472(3) 849(6) 70( 11)HC(23) 797(3) 618(3) 799(6)HC( 24) 950(4) 496(3) 690(6)HC( 25) 900(4) 380(3) 404(6) 68(11)HC(26) 696(4) 280(3) 225(6) 68( 11)H(1)0(3) 189(4) 117(3) -56(6) 57(10)H(2)0(3) 308(4) 190(3) 28(6) 68(10)individual bond lengths and angles in the organic ligandsare listed in Supplementary Publication No.SUP 21636(17 pp., 1 microfiche).* Atomic scattering factors used* See Notice to Authors No.7, in J.C.S. Dalton, 1975, Indexissue.D. T. Cromer and J. B. Mann, Acta Cvyst., 1968, AN, 321.74(3) 369(3)throughout the calculations were taken from ref. 7 for non-hydrogen atoms and for hydrogen atoms from ref. 8.All calculations were performed on a CDC 6600 computerat the Centro di Calcolo Interuniversitario dell’Italia Nord-Orientale with programs of Irnmir~i.~RESULTS AND DISCUSSIONI.Y. Spectra.-Table 3 lists the main vibrational bandswith their assignments for the organic ligand (I), and ofthe two copper complexes (111) and (IV). The spectraof the two complexes are characterized by the disap-pearance of the vibrational modes due to the N-H groupsTABLE 3Main vibrational bands (cm-l) for (I), CuL’Cl*H,O (III),and CuL’,*H,O (IV) .(1)3 290ms3 180m3 060m2 920m1663vs1610s1 690m1670mAssignmentY (N-H)u(N-H)v(C-H) 3 lOOm 3 060m3 060m 3 040sh v (C-H)6(N-H)W I ) (IV)1630sh 1 630vs u(c=O)1 606sh 1 606s PY1680s 1 686s PY1 660m PY 1670sh ~.1 645sh1 6 3 0 ~ s ) v(c=N)1636s1610ms Y(C--N)1 485m 1 476sh1468vs 1470m1 450m 1 445mm = medium, ms = medium strong, sli = shoulder, s =strong, vs = very strong.PY1 473s PYPY1486sh1 460mand by the presence of the absorptions bands of G O ,C=N, and aromatic rings. In particular, the band atca. 1540 cm-l is likely to be due to the stretchingvibration of the imine C=N group. The band at 1663cm-l in the spectrum of (I) was assigned to v(C0); theoccurrence of such a band in the complexes (1 630 cm-l)at lower frequencies is a consequence of the deproton-ation of the CONH system.Several pyridine bands areshifted towards higher frequencies in the region 1 600-1 400 cm-l, indicating that the nitrogen atom is involvedin co-ordination.Ebctronic Spectra .-The electronic absorption spectraof the two copper(rr) complexes have been measured indimethyl sulphoxide solution and in the solid state bydiffuse reflectance. In the U.V. region, both compoundsshow a strong band at 325 nm, with shoulders at 280 and340 nm, which can be attributed to electronic transitionsin the ligand (a probable metal-ligand charge-transferis present in the 340 nm shoulder). The spectrum ofCuL‘CI*H,O (111) dissolved in dimethyl sulphoxide showsa broad band at ’140 nm (at 700 nm in diffuse reflectancespectrum) indicating probable five-co-or&nation.lO Theband at 750 nm in the solid-state spectrum of (IV), which isin agreement with five-co-ordination for copper, disap-pears when the complex is dissolved in dimethyl sul-phoxide, to be replaced by a broad band at 630 nm,8 R.F. Stewart, E. R. Davidson, and W. 7’. Simpson, J. Chem.Phys.. 1966, 42, 3175.A. Immirzi, Ricerca Sci., 1967, 34, 743.10 B. J. Hathaway, J.C.S. Dalton, 1972, 11961078 J.C.S. DaltonTABLE tiBond distances (A) and angles (") with their estimated standard deviations in parentheses(a) In the co-ordination polyhedronCu-N(l) 2.245(4) N( 1)-Cu-N (2) 76.9 (2) N( 2)-Cu-N (5) 1 74.2 ( 3.1)Cu-N(2) 1.967(4) N( l)-Cu-N(4) 101.6( 3) N( 2)-Cu-O( 3) 91.1 (3)CU-N( 4) 2.022( 4) N(l)-Cu-N(5) 107.6(3) N(4)-Cu-N (5) 82.1 (3)Cu-N(5) 1.992(4) N ( l)-Cu-O ( 3) 96.1 ( 3) N (4)-Cu-O (3) 163.3 ( 1.8)C~-0(3) 2.014(4) N( 2)-Cu-N( 4) 93.5 (3) N( 5)-Cu-O (3) 92.2 (3)( b ) In the organic ligands (means for two independent molecules)N(4)-C(14), N(l)-C(6) 1.340( 4) C( 4)-C( 5), C( 14)-C( 15)C( 3)-C (4), C ( 15)-C ( 16) C (2)-C (3), C( 16)-C ( 17)C( 1)-C( 2), C( 17)-C( 18) 1.379 (4) N(4)-C(18).N(l)-C(l)C(l)-C(6), C(18)-C(19) N( 2)-C( 6), N( 5)-C( 19)~ ( 2 ~ 7 1 , ~ ( 5 ) - ~ ( 2 0 ) 1.370(4) O( 1)-C(7), 0(2)-C(20)C(7)-C(8), C(20)-C(21) N( 3)-C ( 9), N ( 6)-C( 22)N (3)-C( 6), N (6)-C (1 9) C( 8)-C( 9), C( 21)-C( 22)1.3 72 (4)1.49 1 (4)1.461 (4)1.302( 3)(C-C) (benzene ring) 1.394(2)C(l)-N(l)-C(5), C(14)-N(4)-C(18)N( l)-C( 1 )-C( 2).N (4)-C( 18)-C( 17)C( 2)<( 3)-C( 4), C( 1 7)-C( 16)-C( 16)N(4)<(18)-C(19), N(l)-C(l)-C(6)N (5)-C( 19)-C( 8), N(2)-C (6)-C( 1)0(1)-C(7)-C(8), C(20)-C(21)-0(2)N (2)-C( 6)-N (3), N( 5)-C( 19)-N( 6)N (2)-C (7) -C (8), N (5)-C (20)-C (2 1)C (7)-C( 8)-C ( 1 3), C (20)-C ( 2 1 )-C( 26)N (3)-C (9)-C ( lo), N (6)-C (22)-C (2 3)(C-C-C) (benzene ring) 119.9(2)1 1 8.1 (6)122.2( 5)119.3( 6)115.1 (5)1 15.0( 4)122.9( 5 )1 27.4 (5)1 16.0( 4)120.3 (6)11 9.7 (5)N( 1)-C( 5)-C( 4), N( 4)-C( 14)-C ( 15)C( l)-C( 2)-C( 3), C( 18)-C( 17)-C( 16)C(3)-C(4)-C(5), C( 16)-C( 14)-C( 15)C( 17)-C( 18)-C( 19), C(2)-C( l)-C(6)N( 6)-C( 19)-C( 18), N( 3)-C( 6)-C( 1)0 (1)-C( 7)-N (2), 0 (2)-C (20)-N (6)C ( 6)-N (2)-C (7), C( 19)-N (5)-C (20)C(7)-C(8)-C(9), C(20)-C(2L)-C(22)C( 8)-C( 9)-N( 3), C( 2 1)-C( 22)-N( 6)C( 9)-N (3)-C( 6), C( 22)-N( 6)-C( 19)1.378(4)1.382( 5)1.3 35 (3)1.358( 3)1.233(4)1.384 (4)1.3 93 (4)123.4 (6)1 18.9(6)118.2(6)122.8( 6)118.2(5)120.3 (6)120.3 (5)1 18.7 (5)122.3( 6)115.5(6)(c) Bond distances involving the hydrogen atoms are in the range 0.84-1.03 fL; those involving the water molecules are 0.87 and0.90 AFIGURE 1 Clinographic projection of the complex moleculeindicating that the co-ordination has changed, probablyto octahedral.X-Ray Structure.-In agreement with the disappear-ance of the N-H vibrational bands in the i.r.spectrum,the X-ray analysis confirms the deprotonation of theoriginal ligand (I) and its oxidation, which produced a1.31 and C(19)-N(6) 1.29 A (theoretical 1.265Co-ordination of copper invo, qes two organic molecu !es,which act as bidentate ligands through the pyridinenitrogen and the quinazoline nitrogen adjacent to theC=O group, to form two five-membered chelate rings(Figure 1). In this way, the co-ordination polyhedronresults in a distorted square pyramid involving fourig56,g, 655.c=N bond localized between C(6)-N(3) 11 J. Donohue, L. R. Lavine, and J. S. Rollett, A& Cryst.1976 1079nitrogen atoms and the oxygen atom of the water per atom is out of the basal plane N(2),N(4),N(5),0(3) bymolecule. The water molecule is not situated at the 0.17 A.apex of the pyramid, as is frequently found in five-co- A sixth co-ordination site, severely distorted fromordinate copper(r1) comple~es,l~.~~ but it is at the base of octahedral, is occupied by a carbonyl oxygen atom whichthe pyramid.This unusual behaviour can be explained is 2.994 away from copper. This 5 + 1 distortedby the rather strong intermolecular hydrogen bonding arrangement has been observed in many copper(I1)1FIGURE 2 The crystal packing(2.566 A) formed by the water molecule with a G Ogroup of an adjacent ligand.The bonds formed by the two pyridine nitrogenatoms with copper are of different lengths, the longerbeing that involving the apex of the pyramid. As aconsequence of these effects, the co-ordination poly-hedron is distorted with respect to the ideal squarepyramid suggested by Gillespie, on the basis of thevalence-shell electron-pair repulsion t heory.14 The cop-A.Mangia, M. Nardelli, C. Pelizzi, and G. Pelizzi, J.C.S.Dalton, 1972, 2483.18 T. S. Cameron, K. Rout, F. J. C. Rossotti, and D. Steele,J.C.S. Dalton, 1973,2626.complexes.l5 Both ligands are nearly planar, and co-planar with their chelation rings, displacements from themean least-squares planes being in the range 0.014.12A. The dihedral angle between the two organic mole-cules is 78.85". Bond distances and angles in theseligands are as expected (Table 4); the only featureworthy of note is that the double bonds are not com-pletely localized at C(6)-N(3) and C(19)-N(6) but a smallx-delocalization is extended onto the adjacent N(3)-C(9), C(6)-N(2), and N(6)-C(22), C(19)-N(5) bonds shownl4 R. J. Gillespie, J . Chem. SOC., 1963, 4670,4672.15 B. F. Hoskins and F. D. Williams, Co-ordination Chem. Rev.,1972, 9, 3651080 J.C.S. Daltonby their lengths, which are a little shorter than thetheoretical value (1.44 A) for a C(sp2)-N(sp2) single bond.Some x-delocalization is also present along the O(l),C(7),-N(2) and 0(2),C(20),N(5) amide groups.Comparison of the conformation of the organic ligand(11) in the copper complex with that of (I) in the nickelcomplex5 shows that the pyridine group assumesdifferent orientations in the two complexes, in order toallow bidentate chelation in each.The water molecule forms two hydrogen bonds: oneintramolecular [0(3)-H O(2) 2.566 A] which israther short, the other intermolecular [0(3)-H N(3I)2.837 A] which is normal. The complex molecule ispacked in the crystal in such a way that the organicligands are facing their analogues in adjacent moleculesthrough the centre of symmetry at O,O,O and Q,i,#, thusforming ribbons along [lll] (Figure 2). The othercontacts (3.50 A are: O(3) C(2I) 3.412(7),O(3) C(10II) 3.472(6), 0(1) C(15II) 3.393(7), andO(3) C(15II) 3.263(6), where superscripts refer to theequivalent positions I at 2, y, 2, and I1 at x, y, x - 1.[5/1406 Received, 171h J d y , 1975
ISSN:1477-9226
DOI:10.1039/DT9760001076
出版商:RSC
年代:1976
数据来源: RSC