具有扩展的双链结构的Mn(III)酰腙配合物的合成和晶体结构①

1、23卷12期结构化学(JIEGOU HUAXUEV ol. 23, No. 12 2004. 12 Chinese J. Struct. Chem. 14321435具有扩展的双链结构的Mn(III酰腙配合物的合成和晶体结构李卫鹏刘世雄(福州大学中心实验室, 福州 350002合成了含有水杨醛缩(4-甲氧基苯氧乙酰腙(以下简写为H2L的锰配合物Mn(L(acac- (EtOHH2O (MnC23H29 N2O8, M r= 516.42。配合物晶体属三斜晶系, 空间群为P, 晶胞参数为:a = 7.6942(3,b = 11.2422(4,c = 14.9230(6 Å, = 95.

2、656(2, = 104.848(2, = 95.642(2°, V =1231.37(8 Å3, Z = 2, D c = 1.393 g/cm3, µ = 0.585 mm1, F(000 = 540。对于4374 (I > 2(I 个可观察点, R = 0.0439, wR = 0.1150。在配合物中, 中心Mn(I I I离子具有扭曲的NO5八面体配位构型。晶体通过分子内与分子间的氢键作用形成平行排列的无限双链结构。关键词: Mn(I I I配合物, 水杨醛缩(4甲氧基苯氧乙酰腙, 晶体结构含有Mn(I I I离子的多啮Schiff碱配合物的设计,

3、 合成及其生物活性的研究一直为人们所关注。我们合成了多个含有Mn(I I I离子的多啮Schiff碱配合物13。二酮类化合物4近来被发现对生命活动中的一些酶具有抑制作用。酰肼类化合物与生物体内的微量元素作用具有抗结核和抗肿瘤的效果。因为酰肼的NH2基团有一定的毒性, 所以人们多研究氨基与羰基缩合的腙或酰肼类化合物57。这一类化合物对于探讨他们的生物活性机理很有意义。但是, 迄今为止关于取代乙酰肼与羰基缩合的腙的化合物的报道8,9却不多。本文报道含有水杨醛缩(4-甲氧基苯氧乙酰腙(H2L的Mn(I I I配合物Mn(L(acac(EtOHH2O的合成与晶体结构, 它具有扩展双链的结构。1 实验部

4、分除三乙酰丙酮锰是由我们依照文献17合成外,所用其余试剂均为市售分析纯试剂, 使用前未经进一步提纯。1. 1 配体(H2L的合成以对甲氧基苯酚和氯乙酸为原料,参照文献10方法合成(4-甲氧基苯氧乙酸。以二氯亚砜为脱水剂, (4-甲氧基苯氧乙酸和无水乙醇反应生成(4-甲氧基苯氧乙酸乙酯。所得的酯与85%的水合肼反应得到的(4-甲氧基苯氧乙酰肼和水杨醛在乙醇中反应制备水杨醛缩(4-甲氧基苯氧乙酰腙。1. 2 配合物的制备0.05mmol三乙酰丙酮合锰和0.05mmol水杨醛缩(4-甲氧基苯氧乙酰腙用1mL DMF和10mL 95的乙醇溶解, 并继续搅拌3小时后过滤得到棕红色的溶液。滤液静置一周后得

5、到黑色块状晶体。1. 3 晶体结构的测定选取大小为0.10 mm ×0.40 mm ×0.40 mm的标题化合物晶体, 在带有石墨单色器的Rigaku 18KW RAXIS-RAPID Weissenberg Imaging Plate衍射仪上进行衍射实验。晶体属三斜晶系, 空间群为P1, 晶胞参数: a = 7.6942(3, b = 11.2422(4, c = 14.9230(6 Å, = 95.656(2, = 104.848(2, = 95.642(2°, V = 1231.37(8 Å3, Z = 2, D c = 1.393 g/

6、cm3, µ = 0.585 mm1, F(000 = 540。用Mo K射线(= 0.71073Å和扫描方式, 在2.84°254.96°范围内收集到5588个独立衍射点(R int = 0.026281, 其中4374个(I > 2(I的可观测点用于结构修正。衍射数据用TEXSAN程序进行还原处理11衍射强度经Lp因子和吸收校正12。晶体结构分析工作在Pentium III PC 计算机上用SHELXL 97程序18进行。晶体结构由直接法和差值Fourier合成法解出。对所有非氢原2003-12-15收到; 2004-03-13接受(CCDC

7、254376福建省自然科学基金资助项目(E0110010联系人. E-mail: shixiongliu1433 结构化学(JIEGOU HUAXUE Chinese J. Struct. Chem. 2004 V ol. 23子的坐标和各向异性温度因子进行最小二乘修正。所有氢原子通过差值Fourier法和理论加氢得到。氢原子的坐标和各向同性温度因子参加修正。最终偏差因子R = 0.0439, wR = 0.1150, w = 2(F o2+(0.0695P2 + 0.5321P1, P = (F o2+2F c2/3, S = 1.076, (/max = 0.000。差值Fourier图上

8、的最大残余峰为0.512(0.731e/Å.表1 原子坐标表(× 104和热参数(Å2 × 103Table 1. Atomic Coordinates (× 104 and Thermal Displacement Parameters (Å2 × 103 Atom x y z U eq Atom x y z U eqMn(1 2771(1 2637(1 1482(1 30(1 N(1 2170(3 4219(2 1104(1 30(1N(2 2286(3 4393(2 197(1 35(1 O(1 2583(3 3110

9、(2 2685(1 44(1O(2 3066(2 2473(1 225(1 35(1 O(3 2314(3 2471(2 1716(1 42(1O(4 3856(4 1658(3 5127(2 80(1 O(5 3343(2 1058(2 1717(1 39(1O(6 40(2 1880(2 993(1 40(1 O(7 5716(3 3386(2 1950(1 48(1C(1 2146(3 4126(2 3050(2 37(1 C(2 1630(3 5083(2 2536(2 36(1C(3 1109(4 6098(3 2980(2 47(1 C(4 1147(5 6197(3 3906(2

10、 58(1C(5 1723(5 5278(3 4414(2 59(1 C(6 2209(4 4262(3 4003(2 52(1C(7 1682(3 5084(2 1583(2 35(1 C(8 2814(3 3437(2 170(2 33(1C(9 3237(4 3501(2 1093(2 38(1 C(10 2714(3 2315(2 2568(2 35(1C(11 1945(4 1234(3 3130(2 48(1 C(12 2282(5 990(3 3995(2 56(1C(13 3381(4 1820(3 4298(2 51(1 C(14 4118(4 2892(3 3741(2 4

11、8(1C(15 3789(4 3151(2 2880(2 40(1 C(16 2929(7 738(5 5802(4 103(2C(17 3265(5 1007(3 1859(3 57(1 C(18 2294(4 62(2 1609(2 36(1C(19 429(4 88(2 1296(2 40(1 C(20 660(3 806(2 1011(2 34(1C(21 2685(4 475(3 720(2 48(1 C(22 6913(5 3507(3 2872(2 62(1C(23 7651(6 2398(4 3113(3 85(1 O(1W 7446(3 3445(2 610(2 63(1U

12、is defined as one third of the trace of the orthogonalized Ueq ijtensor表2.主要的键长和键角Table 2. Selected Bond Lengths (Å and Bond Angles (ºBond Dist.Bond Dist.Bond Dist. Mn(1O(1 1.868(2Mn(1O(5 1.914(2Mn(1O(21.939(2 Mn(1N(1 1.980(2Mn(1O(6 2.155(2Mn(1O(72.243(2N(1C(7 1.292(3N(1N(2 1.410(3N(2C(81.

13、306(3 O(1C(1 1.328(3O(2C(8 1.292(3O(3C(101.382(3 O(3C(9 1.414(3O(4C(161.369(5O(4C(131.377(3 O(5C(18 1.286(3O(6C(20 1.259(3O(7C(221.431(4 Angle (° Angle (° Angle (°O(1Mn(1O(5 95.15(8O(1Mn(1O(2 169.04(7O(5Mn(1O(294.85(7O(1Mn(1N(1 90.65(8O(5Mn(1N(1 174.17(8O(2Mn(1N(179.43(7O(1Mn(1O(6 92.

14、72(8O(5Mn(1O(6 88.04(7O(2Mn(1O(692.11(7N(1Mn(1O(6 91.07(7O(1Mn(1O(7 89.09(8O(5Mn(1O(791.12(8O(2Mn(1O(7 86.22(8N(1Mn(1O(7 89.58(8O(6Mn(1O(7178.06(8C(7N(1N(2 117.5(2C(7N(1Mn(1127.9(2N(2N(1Mn(1114.6(1C(8N(2N(1 108.7(2C(1O(1Mn(1130.6(2C(8O(2Mn(1112.7(2C(10O(3C(9 116.5(2C(16O(4C(13119.3(4C(18O(5Mn(1130.2

15、(2C(20O(6Mn(1 125.7(2C(22O(7Mn(1 127.8(2 O(1C(1C(6 118.2(2O(1C(1C(2 123.7(2N(1C(7C(2 124.2(2O(2C(8N(2124.4(2O(2C(8C(9 118.6(2N(2C(8C(9 116.9(2O(3C(9C(8108.8(2O(3C(10C(15 124.5(2O(3C(10C(11 115.7(2 C(14C(13O(4115.3(3O(4C(13C(12 125.1(3O(5C(18C(19 125.9(2 O(5C(18C(17114.4(2C(18C(19C(20 126.3(2O(6C(20C

16、(19 123.7(2 O(6C(20C(21117.9(2O(7C(22C(23 113.4(3No. 12 李卫鹏等:具有扩展的双链结构的Mn(I I I酰腙配合物的合成和晶体结构14342结果与讨论配合物的非氢原子坐标和热参数列于表1,配合物的主要键长和键角分别列于表2, 晶体结构示于图1。配合物由Mn(I I I阳离子、L2配阴离子、acac1配阴离子、配位乙醇和溶剂水组成。中心Mn(I I I离子由L2的酚氧(O1, 酰氧(O2和肼氮(N1, acac1的2个氧(O5和O6和配位乙醇分子的氧(O7构成扭曲的配位八面体。其中, O(1, O(2, N(1, O(5组成配位八面体的赤道平

17、面, Mn(I I I离子偏离赤道平面0.0418Å并偏向O(6原子, O(6和O(7分别位于2个轴向位置。其中, Mn(1O(1的键长为1.868(2Å与文献13值1.875(2Å基本一致。Mn(1O(2的键长为1.939(2Å与文献13值1.931(2Å基本一致。Mn(1N(1的键长为1.980(2Å与文献13值1.967(3Å基本一致。Mn(1O(7的键长2.243(2 Å与文献13值2.269(3Å基本一致。Mn(1O(5的键长1.914(2Å与文献14值1.942(3Å基本一

18、致。Mn(1O(6的键长2.155(2Å比文献14值2.112(4 Å略长。O(1, C(1, C(2, C(7, N(1和Mn构成的六员螯合环的面上平均偏差为0.0290Å, 该平面与邻近苯环平面间的二面角是4.2(0.1°。在L2配阴离子中, O(1C(1的键长1.328(3与Mn(I I I与酚羟基配位的化合物Di-µ-methoxobis- salicylaldehyde anthraniloylhydrazonato(2-diman- ganese(I I I-Bismethanol中的相应键长1.326(8Å一致15。C(

19、7N(1的键长1.292(3Å与文献15值1.304(8 Å一致。C(8N(2的键长1.306(3Å与烯醇化酰腙配合物15中的CN键长(1.309(2Å相符; C(8O(2的键长 1.292(3Å与文献15值1.318(6 Å接近; N(1N(2的键长1.410(3Å与文献15值1.412(6Å一致。可见, 配合物中的L2配阴离子从酮式结构转化成为烯醇式结构, C=NN=C出现一定程度的共轭作用。C(10O(3键长1.382(3Å与文献16值(1.38(1Å一致。配体L2中的2个苯环平面的夹角为

20、54.58(9°, 说明配体发生了较大的扭曲。图1. 标题化合物的分子结构图2.标题化合物的氢键及相互作用Fig. 1. Molecular structure of the title compound Fig. 2. Scheme of the hydrogen bonding interactionsshown by the dotted lines in the title compoundTable 3. Hydrogen Bond Geometry (ÅDH···A DHH···AD·

21、3;·ADH···A O(7H(07 ···O(1w 0.945 1.735 2.674(3 172.4O(1wH(01 ···O(6a 0.928 1.834 2.732(3 162.3O(1wH(02 ···N(2b 0.908 1.979 2.830(3 155.3Symmetry codes: a: x+1, y, z; b: x+1, y+1, z标题化合物中, 乙酰丙酮脱去1个氢原子, 它的各键长键角与文献14的相应键长键角一致。1433 结构化学(JI

22、EGOU HUAXUE Chinese J. Struct. Chem. 2004 V ol. 23如图2和表3所示, 晶体中存在OH(water··· O(acac, OH(water···N(肼和OH (EtOH··· O(water 氢键。结晶水分子作为3个氢键的中心, 它联系了3个相互独立的分子,从而通过分子内与分子间氢键的相互作用形成了扩展的双链结构。参考文献(1 Liu, S. X.; Feng, Y. L. Polyhedron1996, 15, 41954201(2 Feng, Y. L.

23、; Liu, S. X. J. Coord. Chem.1998,44, 8190(3 Feng, Y. L.; Liu, S. X. Chinese. J. Struct. Chem. 1988, 17, 125128(4 Wang, J. L.; Yang, Y.; Zhang, Z. M.; Zhang, X.; Miao, F. M. Chinese. J. Struct. Chem. 2003,351354(5 Ferrai, M. B.; Fava, G. G.; Pelizzi, C.; Pelosi, G.; Tarasconi, P. Inorg. Chim. Acta 19

24、98, 269, 297301(6 Wang, Z. X.; Jian, F. F.; Duan, C. Y.; Bai, Z.; You, X. Z. Acta Cryst.1998, C54, 19271929(7 Kovala-Demertzi, D.; Miller, J. R.; Kourkoumelis, N.; Hadjikakou, S. K.; Demertzis,M. A.Polyhedron1999, 18, 10051013(8 Adams, H.; Fenton, D. E.; Minardi, G.; Mura, E.; Pistuddi, A. M.; Solin

25、as, C. Inorg. Chem. Comm. 2000, 3, 2428(9 (a Bacchi, A.; Battaglia, L. P.; Carcelli, M.; Pelizzi, C.; Pelizzi, G.; Solinas, C.; Zoroddu, M. A. J. Chem. Soc., Dalton Trans. 1993,775779;(b Chen, X. H.; Liu S. X. Chinese. J. Struct. Chem. 2004, 23, 3337(10 Fan, N. T. Dict. of Org. Synth. Beijing Instit

26、ute of Science and Technology University Press. 280281(11 Rigaku Molecular Structure Corporation, TEXSAN, Version 1. 10. MSC, 9009 New Trails Drive, The Woodlands 1999, TX 773815209, U. S. A.(12 North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta Cryst. 1968, A24, 351.(13 Dutta, S.; Manivannan, V.

27、; Babu, L. G.; Pal, S. Acta Cryst. 1995, C51, 813815(14 Stults, B. R.; Marianelli, R. S.; Day, V. W. Inorg. Chem. 1979,18, 18531858(15 Mangia, A.; Nardelli, M.; Pelizzi, C.; Pelizzi G. J. Chem. Soc., Dalton Trans. 1973, 11411145(16 McCan, M.; Casey, M. T.; Devereux, M.; Curran, M.; Cardin, C.; Todd,

28、 A. polyhedron 1996, 15, 21172120(17 Japanese Chem. Soc., Translated by Cao, H. M. The Handbook of Inorganic Synthesis V ol. .;Chemical Industry Press: Beijing 1988, 607607(18 Sheldrick, G. M. SHELX-97: Program for Refinement of Crystal Structure. University of Göttingen, Germany 1997.Synthesis and Crystal Structure of ExtendedBicartinarian Mn(III Compl