Observation of a direct interaction between the carbonyl oxygen, O(6), of a N(7)-bonded 6-oxopurine and a metal center. Preparation and crystal and molecular structure of (N-3,4-benzosalicylidene-N',N'-dimethylethylenediamine)-(theophyllinato)copper (II) monohydrate.
Observation of a direct interaction between the carbonyl oxygen, O(6), of a N(7)-bonded 6-oxopurine and a metal center. Preparation and crystal and molecular structure of (N-3,4-benzosalicylidene-N',N'-dimethylethylenediamine)-(theophyllinato)copper (II) monohydrate.
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DOI：
10.1021/ja00442a010
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发表时间：
1976-12
影响因子：
15
通讯作者：
D. Szalda;T. Kistenmacher;L. Marzilli
中科院分区：
文献类型：
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作者：
D. Szalda;T. Kistenmacher;L. Marzilli
报道了(7V-3，4-苯并水杨基-Ar‘，A“-二甲基苯二胺)(茶氨酸)铜(II)配合物的合成、晶体结构和分子结构。该络合物在95%乙醇作溶剂的反应混合物中结晶成一水合物。晶体为单斜晶系，空间群为Pc，a=100.27(2)，b=6.925(3)，c=15.463(4)A，β=100.27(2)，Z=2，V=1126.2，α=1.50(2)g cm~(-3)，áca，Cd=1.48g cm~(-3)。7359个测量的反射随后被简化为3138个强度的对称独立集合，用于结构求解和精化。使用标准的重原子帕特森和傅立叶方法来求解结构，并通过基于F的全矩阵最小二乘进行细化，最终得到R值为0.037。铜(II)的配位几何构型为(4+1)，赤道位置为三齿席夫碱与茶碱的N(7)配位，Cu-N(7)键长为1.956(3)A，其中一个轴向位置被嘌呤环系C(6)上的羰基氧占据，Cu-0(6)距离为2.919(3)A。这是首次观察到6-氧嘌呤的羰基氧与金属中心之间显著的直接相互作用。配合物通过O(10)(席夫碱)沿a轴连接。HO-Fl.，0(2)(茶碱钼阴离子)氢键体系，涉及翻译相关的络合物。进一步的晶体稳定性是通过乙二胺末端的甲基和茶氨酸单阴离子环上的甲基钉扎Schiff碱络合物的萘环而获得的。最近对金属离子和金属络合物与核酸及其组分的结合的研究进行了总结。这一区域的活性既受到生命系统中这种相互作用的重要性的刺激，也受到金属结合在铂(II)癌症化疗药物作用中的潜在重要性的刺激。
The preparation and crystal and molecular structure of the complex (7V-3, 4-benzosalicylidene-Ar', A"-dimethyleth-ylenediamine)(theophyllinato) copper (II) are reported. The complex crystallizes, as the monohydrate, from the reaction mix-ture with 95% ethanol as the solvent. The crystals are monoclinic, space group Pc, with a= 10.689 (2), b= 6.925 (3), c= 15.463 (4) A, ß= 100.27 (2), Z= 2, V= 1126.2 A3,¿ measd= 1.50 (2) g cm” 3, áca, cd= 1.48 g cm'3. The 7359 reflections in the+ h hemisphere to26= 60 were collected by counter methods on an automated diffractometer, employing crystal-monochromated radiation and the-2 scan technique. The 7359 measured reflections were subsequently reduced to a sym-metry independent set of 3138 intensities, which were used in the structural solution and refinement. Standard heavy-atom Patterson and Fourier methods were used to solve the structure, and refinement by full-matrix least squares, based on F, has led to a final R value of 0.037. The coordination geometry about the copper (II) is (4+ 1) with the equatorial positions occu-pied by the tridentate Schiff base chelate and N (7) of the theophylline monoanion, Cu-N (7) bond length= 1.956 (3) A, and one of the axial positions is occupied by the carbonyl oxygen at C (6) of the purine ring system, Cu-0 (6) distance= 2.919 (3) A. Thisrepresents the first observation of a significant, direct interaction between the carbonyl oxygen of a 6-oxopurine and a metal center. The complexes are connected along the a axis by an O (10)(Schiff base)... HO-Fl.., 0 (2)(theophylline mo-noanion) hydrogen bond system involving translationally related complexes. Further crystal stability is obtained by a “pin-ning” of the naphthylidene rings of the Schiff base chelate by methyl groups from the ethylenediamine terminus and the theo-phylline monoanion ring.Investigations into the binding of metal ions and metal complexes to nucleic acids and their constituents, both in so-lution1 and in the solid state, 2 have recently been summarized. Activity in this area has been stimulated by both the impor-tance of such interactions in living systems, and also the po-tential importance of metal binding in the functioning of pla-tinum (II) cancer chemotherapeutics.