1,10-菲啰啉铜配合物的1D p-p堆叠超分子双链结构：合成与晶体研究

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该研究论文探讨了一种新颖的类拉链超分子双链结构，其基础是1D π-π堆积相互作用。标题中提到的化合物是[Cu(phen)(C4H4O4)(H2O)]2·C4H6O4，其中"phen"代表1,10-菲咯啉（1,10-phenanthroline），这是一种重要的有机配体。研究由 Yue-Qing Zheng、Jie Sun 和 Jian-Li Lin 合成并进行了深入的晶体结构分析。实验过程中，通过将草酸（succinic acid）、CuCl2·2H2O、1,10-苯并[a,q] anthraquinone（phen）以及Na2CO3在甲醇±水溶液中反应，成功制备了这种独特的超分子结构。所得晶体属于三斜晶系，空间群P1（No.2），具有晶体参数a=7.493 Å, b=9.758 Å, c=13.517 Å, α=68.89°, β=88.89°, γ=73.32°, Z=1。其结构特征显著，展示了氢键作用下的 Succinic acid 分子以及由 Succinate 建立的一维（1D）拉链状超分子结构，表现为两个[Cu(phen)(C4H4O4)2/2(H2O)]2 双链单元，这些单元之间通过1D π-π堆积相互作用紧密连接，键合距离分别为3.71 Å和3.79 Å。铜原子在此结构中表现出五角锥形配位，由两个1,10-菲咯啉分子提供的氮原子提供五个配位。这种设计使得该化合物展现出独特的结构稳定性和可能的多功能性，因为π-π堆积相互作用对于电子和能量传递有着重要作用。这类研究不仅有助于理解分子间相互作用的基本原理，还可能为新型功能材料的设计，如光致变色材料、传感器或药物载体等领域提供新的思路。这篇论文对基于1D π-π堆积相互作用的超分子化学有重要贡献，通过详细的合成方法和晶体结构解析，为我们揭示了此类复杂分子结构的形成机制，为进一步探索这类系统的潜在应用奠定了基础。

A Zipper-like Supramolecular Double-Chain based on 1 D p-p Stacking

Interactions: Synthesis and Crystal Structure

of [Cu(phen)(C

)(H

O)]

´C

(phen = 1,10-phenanthroline)

Yue-Qing Zheng*, Jie Sun and Jian-Li Lin

Ningbo/P. R. China, Institute for Solid State Chemistry, Chemistry Department of Ningbo University

Received December 20th, 1999

Abstract. [Cu(C

)(C

)(H

O)]

´C

was

prepared by the reaction of succinic acid, CuCl

´2H

1,10-phenanthroline (phen = C

), and Na

in a

OH±H

O solution. The crystal structure (triclinic, P 1

(no. 2), a = 7.493(1), b = 9.758(1), c = 13.517(1) A

;

68.89(1)°, b = 88.89(1)°, c = 73.32(1)°, Z =1, R = 0.0308,

= 0.0799 for 3530 observed reflections (F

³ 2r(F

) out

of 3946 unique reflections) consists of hydrogen bonded

succinic acid molecules and succinato bridged 1 D zipper-

like supramolecular

[Cu(phen)(C

)

2/2

O)]

double

chains based on 1 D p-p stacking interactions between the

chelating phen systems at distances of 3.71 A

and 3.79 A

The Cu atoms are fivefold trigonal bipyramidally coordi-

nated by two N atoms of the bidentate chelating phen ligand

and three O atoms of one water molecule and two bidentate

bridging succinate ligands. The water O atom and one phen

N atom are at the apical positions (equatorial: d(Cu±O) =

1.945, 2.254(2) A

, d(Cu±N) = 2.034(2) A

; axial: d(Cu±O) =

1.971(2) A

, d(Cu±N) = 1.995 A

Keywords: Copper(II) complexes; Crystal structure; p -p

stacking interaction; Supramolecular double-chain

Recently, designing and tailor-making of infinite polymeric

configuration with 1 D to 3 D extended structure by using a

bifunctional ligand, e. g., 4,4'-bipyridine, to link metal ions

have become one of the most active areas of materials re-

search, because incorporation of some active groups into co-

ordination polymers offers an excellent path to develop

functional materials with interesting properties such as elec-

tronic, magnetic, second-order nonlinear optical, inclusion,

and catalytic properties [1±19]. On the other hand, it is well-

known that weak interactions are essential for molecular re-

cognition and self-organization of molecules in supramolecu-

lar chemistry [20±21]. In particular, the stacking interactions

between suitable aromatic moieties of the twofold coordinat-

ing ligands are fascinating [22±24], since p-p stacking interac-

tions have been recognized to be very important in proteins

and protein-DNA systems for protein stabilization and var-

ious regulatory processes [25±26]. Our previous research in-

dicates that

,x-dicarboxylate groups behave as good candi-

dates of bifunctional ligands linking metal ions to build 1 D,

2 D and 3 D polymeric frameworks [27±32], which stimulates

our further research interests to combine the bifunctional

features of

,x-dicarboxylate ligands with aromatic stacking

interactions to study supramolecular complexes. In this

work, we report a novel ternary Cu phen succinato complex

with zipper-like supramolecular double-chains based on 1 D

p-p stacking interactions.

The crystal structure consists of the hydrogen bonded suc-

cinic acid molecules and 1 D

[Cu(phen)(C

)

2/2

O)]

supramolecular double chains. The Cu atoms are fivefold tri-

gonal bipyramidally coordinated by both N atoms of the bi-

dentate chelating phen ligand and by the O atoms of one

water molecule and two bidentate bridging succinate anions

(Fig. 1). The water O atom and one of the phen N atoms are

at the apical positions of the coordination polyhedron with

(Cu±O) = 1.971(2) A

and d

(Cu±N) = 1.995(2) A

.The

equatorial bond lengths are d

(Cu±O) = 1.945(2) A

and

2.254(2) A

as well as d

(Cu±N) = 2.034(2) A

. Evidently, the

coordination polyhedron of the Cu atom is actually distorted

(Table 1). The Cu atom is shifted by 0.124(1) A

from the

equatorial plane toward the apical water molecule. The phen

ligand is nearly perpendicular to the equatorial plane with

the dihedral angle of 88.4(1)°. The succinate ligands bridge

the Cu atoms to form primary neutral 1 D supramolecular

chains

[Cu(phen)(C

)

2/2

O)] along [100] with par-

allel orientated phen ligands at the same side (Fig. 2). The

phen ligands of two adjacent supramolecular chains cover

each other with the quinoline fragments at the alternative

distances of 3.71 A

and 3.79 A

, forming zipper-like supra-

molecular double-chains

[Cu(phen)(C

)

2/2

O)]

(Fig. 2). Apparently, the present spacings of 3.71 A

and

3.79 A

are comparable well with those for the p-p stacking

interactions reported in the literature [33±35]. In this sense,

the title compound represents an unprecedented supra-

molecular complex with zipper-like double-chains formed

by p-p stacking interactions throughout the whole

structure. The bridging succinate ligands are twisted with tor-

sion angle of about 71.3(3)° in the carbon chain. The term-

inal carboxyl groups orientate roughly perpendicular to each

other to meet the requirement of effective p-p stacking inter-

actions.

The additional free succinic acid molecules are imbedded

in voids (Fig. 3). Configuration and bond lengths of the acid

and the anion are different. The terminal carboxyl groups of

the bridging succinate ligands are rotated to form strong in-

trachain hydrogen bonds to water molecules with O±H ´ ´ ´ O

distances of 2.572 A

and 2.613 A

, and O±H ´ ´ ´ O angles of

Z. Anorg. Allg. Chem. 2000, 626, 1501±1504 Ó WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 0044±2313/00/6261501±1504 $ 17.50+.50/0 1501

* Prof. Dr. Y.-Q. Zheng,

Institute for solid state chemistry,

Chemistry Department of Ningbo University,

Ningbo, Zhejiang, 315211 P. R. China,

Telefax: Int. + 5 74/7 60 07 47

e-mail: zhengcm@nbu.edu.cn

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