Two Succinato-bridged Zinc(II) Phenanthroline Complexes:
[Zn(phen)L
2/2
](H
2
L) and [(phen)
2
Zn(µ-L)Zn(phen)
2
]L · 11H
2
O with
H
2
L 5 Succinic Acid
Yue-Qing Zheng
a,*
, Wen-Han Liu
b
, and Jian-Li Lin
a
a
Ningbo/P. R. China, Municipal Key Laboratory of Inorganic Materials Chemistry, Institute for Solid State Chemistry,
Ningbo University
b
Hangzhou/P. R. China, Department of Chemical Engineering, Zhejiang University of Technology
Received July 27th, 2001.
Abstract. Two mixed ligand Zn
II
complexes [Zn(phen)L
2/2
](H
2
L)
(1) and [(phen)
2
Zn(µ-L)Zn(phen)
2
]L · 11H
2
O(2) with H
2
L 5 suc-
cinic acid were prepared and crystallographically characterized.
Complex 1 crystallizes in the monoclinic space group C2/c (no. 15)
with a 5 13.618(1) A
˚
, b 5 9.585(1) A
˚
, c 5 15.165(1) A
˚
, β 5
96.780(6)°, V 5 1965.6(3) A
˚
3
, Z 5 4 and complex 2 in the triclinic
space group P 1
¯
(no. 2) with a 5 12.989(2) A
˚
, b 5 14.464(2) A
˚
,
c 5 18.025(3) A
˚
, a 5 90.01(1)°, β 5 109.69(1)°, γ 5 112.32(1)°,
V 5 2917.4(8) A
˚
3
, Z 5 2. 1 consists of succinic acid molecules and
1D zigzag
1
`
[Zn(phen)(C
4
H
4
O
4
)
2/2
] polymeric chains, in which the
tetrahedrally coordinated Zn atoms are bridged by bis - monodent-
ate succinato ligands. Succinic acid molecules play an important
role in supramolecular assemblies of the polymeric chains into 2D
Succinatverbrückte Zink-Phenanthrolin-Komplexe: [Zn(phen)L
2/2
](H
2
L) und
[(phen)
2
Zn(µ-L)Zn(phen)
2
]L · 11H
2
O mit H
2
L 5 Bernsteinsäure
Inhaltsübersicht. Die Zn
II
2Komplexe [Zn(phen)L
2/2
](H
2
L) (1) und
[(phen)
2
Zn(µ2L)Zn(phen)
2
]L·11H
2
O(2) mit H
2
L 5 Bernstein-
säure wurden dargestellt und röntgenographisch charakterisiert. 1
kristallisiert in der monoklinen Raumgruppe C2/c (Nr. 15) mit a 5
13,618(1) A
˚
, b 5 9,585(1) A
˚
, c 5 15,165(1) A
˚
, β 5 96,780(6)°, V 5
1965,6(3) A
˚
3
, Z 5 4 und 2 in der triklinen Raumgruppe P 1
¯
(Nr. 2)
mit a 5 12,989(2) A
˚
, b 5 14,464(2) A
˚
, c 5 18,025(3) A
˚
, α 5
90,01(1)°, β 5 109,69(1)°, γ 5 112,32(1)°, V 5 2917,4(8) A
˚
3
, Z 5
2. 1 setzt sich aus Bernsteinsäure-Molekülen und zickzackfömigen
1
`
[Zn(phen)(C
4
H
4
O
4
)
2/2
]2Ketten, in denen tetraederisch koordinierte
Zn-Atome über bis-einzähnige Succinato-Liganden verbrückt sind,
Introduction
Previous investigations show that α,ω2dicarboxylate
anions are interesting flexible bridging ligands to interlink
metal atoms into supramolecular architectures with specific
topologies [124]. As a lower member of the α,ω2dicar-
boxylate family, the succinate (C
4
H
4
O
4
)
22
anion has proven
to be a versatile polyfunctional ligand. For example, the
* Prof. Dr. Yue-Qing Zheng
Institute for Solid State Chemistry
Ningbo University, Ningbo
315211 P. R. China
Telefax: Int. 1574/87600747
e-mail: zhengcm@nbu.edu.cn
620
WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 004422313/02/628/6202624 $ 17.501.50/0 Z. Anorg. Allg. Chem. 2002, 628,6202624
layers as well as in the stacking of 2D layers. 2 is composed of
[(phen)
2
Zn(µ-L)Zn(phen)
2
]
21
complex cations, succinate anions
and hydrogen bonded water molecules. Within the divalent cations,
Zn atoms are octahedrally coordinated by four N atoms of two
phen ligands and two O atoms of one bis-chelating succinato li-
gand. Through the intermolecular π2π stacking interactions, the
complex cations form positively charged 2D layers, between which
the noncoordinating succinate anions and water molecules are
sandwiched.
Keywords: Zinc; Succinato complexes; Phenanthroline complexes;
π2π Stacking interactions
zusammen. Die Bernsteinsäure-Moleküle spielen eine wichtige
Rolle beim supramolekularen Aufbau der polymeren Ketten zu 2D-
Schichten. 2 wird von den [(phen)
2
Zn(µ2L)Zn(phen)
2
]
21
-Katio-
nen, den Succinat-Anionen und den über H-Brücken gebundenen
H
2
O2Molekülen gebildet. Innerhalb der zweiwertigen Kationen
sind Zn-Atome oktaedrisch von vier N-Atomen zweier Phen-Li-
ganden und zwei O-Atomen eines bis-chelatisierenden Succinato-
Liganden koordiniert. Durch intermolekulare π2π2Wech-
selwirkungen bilden die komplexen Kationen positiv geladene 2D-
Schichten, zwischen denen die nicht-koordinierenden Succinat-An-
ionen und H
2
O-Moleküle eingelagert sind.
succinate ions bridge transition metal atoms to form 1D
polymeric chains [5, 6, 7a]. In addition, the succinato li-
gands polydentately link metal atoms to form 2D and 3D
networks [7b, 8210]. Interestingly, self-assembly of tran-
sition metal ions with succinate anions under hydrothermal
synthetic conditions affords new organic-inorganic hybrid
materials which have currently been attracting enormous at-
tention [11213]. Our research indicates that self-assembly
of Zn
21
with succinate anions can yield novel nonlinear
optical materials [10, 14]. On the other hand, synergetic co-
ordination of α,ω2dicarboxylato ligands and the phen-
anthroline ligand to Cu ions led to a variety of mixed ligand
complexes of interesting structure types with π2π stacking
interactions [15]. Under the influence of the phen ligand,
succinate anions can chelate the Mn ion to form a seven-
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