稀土氧化膦取代杯芳烃配合物的合成与结构

合成了一种新的氧化膦取代杯芳烃衍生物的稀土离子(La3+,Eu3+)硝酸盐配合物.通过元素分析和红外光谱对配合物进行了表征.在无水甲醇中培养出了配合物的单晶,用X射线单晶衍射法测定了其晶体结构.硝酸镧配合物晶体L·La(OH2)(NO3)2]NO3{L为四(亚甲基二苯基氧化膦)杯4]芳烃}属四方晶系,空间群P43212,晶胞参数a=b=1.8977(4)nm,c=3.1087(11)nm;Z=4;V=11.196(5)nm3;Dc=1.097g/cm3,F(000)=3712,μ=0.491mm-1,R1=0.1181,wR2=0.1930.硝酸铕配合物晶体L·Eu(OH2)(NO3)2]NO3·CH3OH属单斜晶系,空间群C2/c,晶胞参数a=2.88172(11)nm,b=5.4015(2)nm,c=2.01189(7)nm;β=133.4067(9)°,Z=8;V=22.7511(14)nm3,Dc=1.106g/cm3,F(000)=7464,R1=0.0671,wR2=0.1794.2个配合物的晶体结构相类似,配合物中配体的4个磷氧键上的氧原子、2个双齿配位的硝酸根中的4个氧原子还有1个水分子中的氧原子分别参与了配位.中心离子配位数为9,配位多面体为单帽四方反棱柱体.另外在铕配合物的杯芳烃中还包合了1个甲醇分子.

Syntheses and Crystal Structures of Rare Earth Nitrate Complexes with Phosphinoxide [-CH2P(O)Ph2]-substituted Calix[4]arene

Two rare earth nitrate complexes with phosphinoxide (-CH2P(O)Ph2)-substituted calix arene were prepared and characterized by elemental analysis and IR spectroscopy. Their crystal structures were determined by X-ray diffraction method. Lanthanum nitrate complex L·La(OH2)(NO3)2]NO3( L=tetrakis(methylenediphenylphosphinoxide)calixarene) belongs to tetragonal crystal system, space group P43212 with a=1.897 7(4) nm, b=1.897 7(4) nm, c=3.108 7(11) nm; Z=4; V=11.196(5) nm3; Dc=1.097 g/cm3, F(000)=3 712, μ=0.491 mm-1, R1=0.118 1, wR2=0.193 0. Europium nitrate complex L·Eu(OH2)(NO3)2]NO3·CH3OH belongs to monoclinic crystal system, space group C2/c with a=2.881 72(11) nm, b=5.401 5(2) nm, c=2.011 89(7) nm; β=133.406 7(9)°, Z=8; V=22.751 1(14) nm3, F(000)=7 464, R1=0.067 1, wR2=0.179 4. The structures of the two complexes are very similar, the rare earth atoms are both nine-coordinated with four oxygen atoms from phosphorus-oxygen bonds and four oxygen atoms from two bidentate nitrate anions and one oxygen atom from a water molecule. The coordination polyhedron is a single-capped square antiprism. In the europium complex, a methanol molecule was included in the calixarene.