[Cu(C_(12)H_8N_2)(H_2O)(C_4H_4O_4)]·2H_2O的合成和晶体结构

Synthesis and Crystal Structure of [Cu(C_(12)H_8N_2)(H_2O)(C_4H_4O_4)]·2H_2O

将适量邻菲啰啉、丁二酸和CuCl_2·2H_2O(摩尔比=1:1:1)溶于水和甲醇的混合溶剂[V(水):V(甲醇)=1:1]后,滴加NaOH溶液至pH=4.8.滤去沉淀物后,滤液于室温下缓慢蒸发得蓝色细长[Cu(phen)(H_2O)(C_4H_4O_4)]·2H_2O晶体.晶体属三斜晶系,P1(No.2)空间群.晶胞参数a=0.7462(1)nm,b=0.9959(1)nm,c=1.2266(1)nm,α=75.02(1)°,β=82.38(1)°,γ=74.76(1)°,V=0.8475(2)nm^3,Z=2,D_c=1.622g/cm^3,F(000)=426,3882个独立衍射点中,2789个可观测点满足F_0~2≥2σ(F_0~2),R=0.0450,wR^2=0.0951.配合物内每个Cu与邻菲啰啉螯合配体中的2个N原子、来自不同羧酸根的2个羧基O和1个水分子O原子配位,形成扭曲的四方锥体,其中一羧基O位于锥顶[d(Ci—N)=0.2006(3)0 .2032(3)nm;赤道d(Cu—0)=0.1972(2),0.1973(2)nm;轴向d(Cu—O)=0.2210(2)nm].双齿桥联丁二酸根连接Cu原子形成平行于[100]方向的多聚超分子链_∞~1[Cu(phen)_2(H_2O)(C_4H_4O_4)_(2/2)].紧邻链分子上的邻菲啰啉配体互相穿插产生芳环堆积作用,并形成沿[100]方向无限延伸的超分子双链_∞~1[Cu(phen)_2(H_2O)·(C_4H_4O_4)_(2/2)]_2.芳环堆积间距交替为0.366nm和0.380nm.未配位的H_2O分子位于超分子双链之间.

Blue slender crystals of [ Cu( phen) (H2O)(C4H4O4)] · 2H2O were obtained from the solution of CuCl2, 1,10- phenanthroline, succinic acid and NaOH in CH3OH/H2O solution. The crystal structure was determined by single crystal X-ray diffraction. The title complex crystallized in the triclinic space group P1 (No.2) with a=0.7462(1)nm,b=0.9959(1)nm,c = 1.2266(1)nm,α=75.02(1)°,β = 82.38(1)°,γ = 74.76(1)°,V = 0.8475(2)nm3,Z = 2,Dc = 1.622g/cm3, F(000) = 426, R = 0.0450, wR2 = 0.0951 for 2789 observed reflections F02≥2σ ( F02) out of 3882 unique reflections. The crystal structure consists of supramolecular double chains ∞1 [Cu(phen) (H2O) (C4H4O4)2/2 ]2 and water molecules, in which each Cu atom is square - pyramidally coordinated by two N atoms of one chelating phen ligand, two O atoms of different bidentate bridging C4H4O42- ligands and one O atom of water molecule with one carboxyl O atom at the apical position [d(Cu-N) = 0.2006(3), 0.2032(3)nm; basal d(Cu-O) = 0.1972(2), 0.1973(2) nm; axial d (Cu-O) = 0. 2210 (2) nm]. The twisted C4H4O42- ligands interlink square - pyramidally coordinated Cu atoms to form supramolecular chain ∞1 [ Cu (phen) ( H2O) ( C4H4O4)2/2 ] with phen ligands extended outwards on one side to form pitches. Intercalation of phen ligands of one supramolecular chain into the pitches of an adjacent chain gives supramolecular double chains parallel to [ 100] with the alternative phen - phen distances of 0. 366 nm and 0. 380 nm, indicating strong π-π stacking interactions. The H2O molecules are hydrogen - bonded to the double chains.