含N-苯甲酰皮考林酰肼的钒酰、镍及锰配合物的合成和晶体结构

合成了3个含N-苯甲酰皮考林酰肼(简写为HL)的钒、镍和锰配合物VO_2L](1,C_(13)H_(10)N_3O_4V,M_r=323.18),NiL_2]·0.5CH_3OH(2,C_(26.5)H_(22)N_6NiO_(4.5),Mr=555.21)和MnL_2]·0.5CH_3OH(3,C_(26.5)H_(22)MnN_6O_(4.5),Mr=551.44)。配合物1属三斜晶系,空间群为P1,a=0.71241(3)nm,b=0.89625(6)nm,c=1.11706(6)nm,α=94.715(2)°,β=102.053(2)°,γ=112.375(3)°,V=0.63461(7)nm~3,Z=2,F(000)=328,μ(MoKα)=0.802mm~(-1),R=0.0290,wR=0.0816;配合物2属单斜晶系,空间群为C2/c,a=2.5875(1)nm,b=1.4868(1)nm,c=1.8353(1)nm,β=134.470(4)°,V=5.2081(5)nm~3,Z=8,F(000)=2368,μ(MoKα)=0.795mm~(-1),R=0.0459,wR=0.1330;配合物3属单斜晶系,空间群为C2/c,a=2.60113(3)nm,b=1.45231(4)nm,c=1.92903(1)nm,β=132.824(1)°,V=5.3448(2)nm~3,Z=8,F(000)=2344,μ(MoKα)=0.543mm~(-1),R=0.0457,wR=0.1325。在配合物1中,钒(V)原子具有畸变的N_2O_3四角锥配位构型,晶体内每两个分子通过分子间氢键作用形成缔合分子对。在配合物2和配合物3中,镍(Ⅱ)原子和锰(Ⅱ)原子具有扭曲的N_4O_2八面体配位构型,晶体通过分子间氢键作用形成一维的无限链状结构。红外光谱表明,配体在形成配合物后,ν(C=O)和ν(C=N)红移。电

Syntheses and Crystal Structures of Dioxovanadium,Nickel and Manganese Complexes Containing N-phenylpicoloylhydrazide

The three title complexes containing L (HL = N-phenylpicoloylhydrazide) have been synthesized and characterized. They are VO2L (1, C13H10N3O4V, Mr= 323. 18), NiL2] . 0.5CH3OH (2, C26.5H22N6NiO4.5, Mr= 555.21) and MnL2] ,0. 5CH3OH (3, C26.5H22MnN604.5, M, = 551.44). The complex 1 belongs to triclinic system, space group P1, with cell parameters: a =0. 71241(3) nm, 6 =0. 89625(6) nm, c = 1. 1706(6) nm, a = 94.715(2), B=102.053(2), y = 112.375(3), V = 0. 63461(7) nm3, Z =2, Dc = 1.691Mg.m-3 F(000) = 328, u(MoKa) =0. 802mm-1, R=0.0290 and wR=0.0816 for 2545 1> 2o(I)] observed reflections, GOF = 1.064. The complex 2 belongs to monoclinic system, space group C2/c, a =2. 5875(1)nm, b = 1.4868 (1) nm, c =1.8353(1) nm, B= 134. 470(4),V =5.2081(5) nm3, Z = 8, Dc= 1.457Mg. m-3, F(000) = 2368, u(MoKa) =0.795mm-1, R = 0.0459 and wR =0. 1330 for 4144 I>2o( I)] observed reflections, GOF = 1.029. The complex 3 belongs to monoclinic system, space group C2/c, a = 2. 60113(3) nm, b = 1.45231(4) nm, c = 1.92903(1) nm, B= 132.824(1), V = 5. 3448(2) nm3, Z = 8, A = 1. 410Mg . m-3, F(000)=2344, u(MoKa) = 0.543mm-1,R=0.0457, and wR =0.1325 for 4079 I> 2o(I)] observed reflections, GOF = 1. 055. The vanadium atom in the dioxovanadium complex 1 has a distorted square pyramidal geometry with VO2(NNO) coordination, the basal plane being two nitrogen donors and one oxygen donor in L and one oxo oxygen atom. Every two molecules related by centrosymmetric operation in 1 are linked by pairs through the intermolecular hydrogen bonds. The nickel atom in the complex 2 and manganese atom in the complex 3 are in a distorted octahedral environment with Ni(NNO) (NNO) and Mn(NNO) (NNO) coordination models, respectively. The one-dimensional structures in 2 and 3 are formed through the intermolecular hydrogen bonds, respectively. In three title complexes, v(C =0) and v(C-N) are shifted to lower frequencies in IR spectra; charge transitions and d- charge-transitions are observed in their electronic spectra. CCDC: 1, 198070; 2, 198071; 3, 198072.