具有擴展的雙鏈結構的Mn(III)酰腙配合物的合成和晶體結構①

1、23卷12期結構化學(JIEGOU HUAXUEV ol. 23, No. 12 2004. 12 Chinese J. Struct. Chem. 14321435具有擴展的雙鏈結構的Mn(III酰腙配合物的合成和晶體結構李衛(wèi)鵬劉世雄(福州大學中心實驗室, 福州 350002合成了含有水楊醛縮(4-甲氧基苯氧乙酰腙(以下簡寫為H2L的錳配合物Mn(L(acac- (EtOHH2O (MnC23H29 N2O8, M r= 516.42。配合物晶體屬三斜晶系, 空間群為P, 晶胞參數(shù)為: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。對于4374 (I > 2(I 個可觀察點, R = 0.0439, wR = 0.1150。在配合物中, 中心Mn(I I I離子具有扭曲的NO5八面體配位構型。晶體通過分子內(nèi)與分子間的氫鍵作用形成平行排列的無限雙鏈結構。關鍵詞: Mn(I I I配合物, 水楊醛縮(4甲氧基苯氧乙酰腙, 晶體結構含有Mn(I I I離子的多嚙Schiff堿配合物的設計,

3、 合成及其生物活性的研究一直為人們所關注。我們合成了多個含有Mn(I I I離子的多嚙Schiff堿配合物13。二酮類化合物4近來被發(fā)現(xiàn)對生命活動中的一些酶具有抑制作用。酰肼類化合物與生物體內(nèi)的微量元素作用具有抗結核和抗腫瘤的效果。因為酰肼的NH2基團有一定的毒性, 所以人們多研究氨基與羰基縮合的腙或酰肼類化合物57。這一類化合物對于探討他們的生物活性機理很有意義。但是, 迄今為止關于取代乙酰肼與羰基縮合的腙的化合物的報道8,9卻不多。本文報道含有水楊醛縮(4-甲氧基苯氧乙酰腙(H2L的Mn(I I I配合物Mn(L(acac(EtOHH2O的合成與晶體結構, 它具有擴展雙鏈的結構。1 實驗部

4、分除三乙酰丙酮錳是由我們依照文獻17合成外,所用其余試劑均為市售分析純試劑, 使用前未經(jīng)進一步提純。1. 1 配體(H2L的合成以對甲氧基苯酚和氯乙酸為原料,參照文獻10方法合成(4-甲氧基苯氧乙酸。以二氯亞砜為脫水劑, (4-甲氧基苯氧乙酸和無水乙醇反應生成(4-甲氧基苯氧乙酸乙酯。所得的酯與85%的水合肼反應得到的(4-甲氧基苯氧乙酰肼和水楊醛在乙醇中反應制備水楊醛縮(4-甲氧基苯氧乙酰腙。1. 2 配合物的制備1. 3 晶體結構的測定選取大小為0.10 mm ×0.40 mm ×0.40 mm的標題化合物晶體, 在帶有石墨單色器的Rigaku 18KW RAXIS-R

5、APID Weissenberg Imaging Plate衍射儀上進行衍射實驗。晶體屬三斜晶系, 空間群為P1, 晶胞參數(shù): 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/cm3, µ = 0.585 mm1, F(000 = 540。用Mo K射線(= 0.71073Å和掃描方式, 在2.84°254.96°范圍內(nèi)收集到55

6、88個獨立衍射點(R int = 0.026281, 其中4374個(I > 2(I的可觀測點用于結構修正。衍射數(shù)據(jù)用TEXSAN程序進行還原處理11衍射強度經(jīng)Lp因子和吸收校正12。晶體結構分析工作在Pentium III PC 計算機上用SHELXL 97程序18進行。晶體結構由直接法和差值Fourier合成法解出。對所有非氫原2003-12-15收到; 2004-03-13接受(CCDC 254376福建省自然科學基金資助項目(E01100101433 結構化學(JIEGOU HUAXUE Chinese J. Struct. Chem. 2004 V ol. 23子的坐標和各向異

7、性溫度因子進行最小二乘修正。所有氫原子通過差值Fourier法和理論加氫得到。氫原子的坐標和各向同性溫度因子參加修正。最終偏差因子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圖上的最大殘余峰為0.512(0.731e/Å.表1 原子坐標表(× 104和熱參數(shù)(Å2 × 103Table 1. Atomic Coordinates (× 104 and Thermal D

8、isplacement 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(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 17

9、17(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 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(1

10、C(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 48(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(

11、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 is defined as one third of the trace of the orthogonalized Ueq ijtensor表2.主要的鍵長和鍵角Table 2. Selected Bond Lengths (Å a

12、nd 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(81.306(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(3

13、O(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 92.72(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 8

14、9.58(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(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.

15、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(19 123.7(2 O(6C(20C(21117.9(2O(7C(22C(23 113.4(3No. 12 李衛(wèi)鵬等:具有擴展的雙鏈結構的Mn(I I I酰腙配合物的合成和晶體結構14342結果與討論配合物的非氫原子坐標和熱參數(shù)列于表1,配

16、合物的主要鍵長和鍵角分別列于表2, 晶體結構示于圖1。配合物由Mn(I I I陽離子、L2配陰離子、acac1配陰離子、配位乙醇和溶劑水組成。中心Mn(I I I離子由L2的酚氧(O1, 酰氧(O2和肼氮(N1, acac1的2個氧(O5和O6和配位乙醇分子的氧(O7構成扭曲的配位八面體。其中, O(1, O(2, N(1, O(5組成配位八面體的赤道平面, Mn(I I I離子偏離赤道平面0.0418Å并偏向O(6原子, O(6和O(7分別位于2個軸向位置。其中, Mn(1O(1的鍵長為1.868(2Å與文獻13值1.875(2Å基本一致。Mn(1O(2的鍵長為

17、1.939(2Å與文獻13值1.931(2Å基本一致。Mn(1N(1的鍵長為1.980(2Å與文獻13值1.967(3Å基本一致。Mn(1O(7的鍵長2.243(2 Å與文獻13值2.269(3Å基本一致。Mn(1O(5的鍵長1.914(2Å與文獻14值1.942(3Å基本一致。Mn(1O(6的鍵長2.155(2Å比文獻14值2.112(4 Å略長。O(1, C(1, C(2, C(7, N(1和Mn構成的六員螯合環(huán)的面上平均偏差為0.0290Å, 該平面與鄰近苯環(huán)平面間的二面角是4.

18、2(0.1°。在L2配陰離子中, O(1C(1的鍵長1.328(3與Mn(I I I與酚羥基配位的化合物Di-µ-methoxobis- salicylaldehyde anthraniloylhydrazonato(2-diman- ganese(I I I-Bismethanol中的相應鍵長1.326(8Å一致15。C(7N(1的鍵長1.292(3Å與文獻15值1.304(8 Å一致。C(8N(2的鍵長1.306(3Å與烯醇化酰腙配合物15中的CN鍵長(1.309(2Å相符; C(8O(2的鍵長 1.292(3Å

19、;與文獻15值1.318(6 Å接近; N(1N(2的鍵長1.410(3Å與文獻15值1.412(6Å一致?？梢? 配合物中的L2配陰離子從酮式結構轉化成為烯醇式結構, C=NN=C出現(xiàn)一定程度的共軛作用。C(10O(3鍵長1.382(3Å與文獻16值(1.38(1Å一致。配體L2中的2個苯環(huán)平面的夾角為54.58(9°, 說明配體發(fā)生了較大的扭曲。圖1. 標題化合物的分子結構圖2.標題化合物的氫鍵及相互作用Fig. 1. Molecular structure of the title compound Fig. 2. Scheme

20、 of the hydrogen bonding interactionsshown by the dotted lines in the title compoundTable 3. Hydrogen Bond Geometry (ÅDH···A DHH···AD···ADH···A O(7H(07 ···O(1w 0.945 1.735 2.674(3 172.4O(1wH(01 ···O(6a 0.9

21、28 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標題化合物中, 乙酰丙酮脫去1個氫原子, 它的各鍵長鍵角與文獻14的相應鍵長鍵角一致。1433 結構化學(JIEGOU HUAXUE Chinese J. Struct. Chem. 2004 V ol. 23如圖2和表3所示, 晶體中存在OH(water··· O(acac, OH(water··&#

22、183;N(肼和OH (EtOH··· O(water 氫鍵。結晶水分子作為3個氫鍵的中心, 它聯(lián)系了3個相互獨立的分子,從而通過分子內(nèi)與分子間氫鍵的相互作用形成了擴展的雙鏈結構。參考文獻(1 Liu, S. X.; Feng, Y. L. Polyhedron1996, 15, 41954201(2 Feng, Y. L.; 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.

23、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 1998, 269, 297301(6 Wang, Z. X.; Jian, F. F.; Duan, C. Y.; Bai, Z.; You, X. Z. Acta Cryst.1998, C54, 19271929(7 Kovala-Demer

24、tzi, 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.; Solinas, C. Inorg. Chem. Comm. 2000, 3, 2428(9 (a Bacchi, A.; Battaglia, L. P.; Carcelli, M.; Pelizzi, C.; Pelizzi, G.; Solinas

25、, 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 Institute of Science and Technology University Press. 280281(11 Rigaku Molecular Structure Corporation, TEXSAN, Version 1. 10. M

26、SC, 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.; Babu, L. G.; Pal, S. Acta Cryst. 1995, C51, 813815(14 Stults, B. R.; Marianelli, R. S.; Day, V. W. Inorg. Chem. 1979,18,

27、 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, 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 Complex of Acyl H