Crystal structure of the bis[zinc(II)-hydroxide-(μ-perchlorate)-triaqua] complex

Article abstract of DOI:10.1002/zaac.200400201

Colorless single crystals of the title compound were accidentally obtained by a reaction of p-sulfophenylalanine with zinc perchlorate. The crystal structure (monoclinic, P2₁/c, Z = 4, a = 5.9031(7), b = 13.5404(16), c = 9.7932(8) A, β = 126.438(5)°, V = 629.74(12) A³, R₁[I>2σ(I)] = 0.0276, wR ₂(all) = 0.0844) reveals a discrete dinuclear [Zn(OH)(μ-ClO ₄)(H₂O)₃]₂ in which each perchlorate anion acts as a bidentate bridging linker to bind two Zn atoms whereas the hydroxy group is a terminal group. Thus, the local surrounding around the zinc atom can be best described as a slightly distorted octahedron.

Full text of DOI:10.1002/zaac.200400201

Crystal Structure of the Bis[zinc(II)-hydroxide-(µ-perchlorate)-triaqua] Complex
Yong-Hua Li, Qiong Ye, Yun-Zhi Tang, and Ren-Gen Xiong*
Nanjing / P. R. China, Nanjing University, Coordination Chemistry Institute, The State Key Laboratory of Coordination Chemistry
Received June 2nd, 2004.
Abstract. Colorless single crystals of the title compound were acci-
dentally obtained by a reaction of p-sulfophenylalanine with zinc
perchlorate. The crystal structure (monoclinic, P21/c, Z ϭ 4, a ϭ
chlorate anion acts as a bidentate bridging linker to bind two Zn
atoms whereas the hydroxy group is a terminal group. Thus, the
local surrounding around the zinc atom can be best described as a
slightly distorted octahedron.
˚
5.9031(7), b ϭ 13.5404(16), c ϭ 9.7932(8) A, β ϭ 126.438(5)°, V ϭ
3
˚
629.74(12) A , R1[I>2σ(I)] ϭ 0.0276, wR2(all) ϭ 0.0844) reveals a
discrete dinuclear [Zn(OH)(µ-ClO4)(H2O)3]2 in which each per-
Keywords: Crystal structure; Zinc; Hydrogen bonding; Perchlorate
The structural diversity in the inorganozinc perchlorates is well
documented [1, 2]. Amongst these, the structures in which per-
chlorate anion acting as bridging ligand are rather rare. To the best
of our knowledge, inorganozinc perchlorate compound containing
two bridging perchlorate anions has not been reported. Here we
report on the molecular and crystal structure of the title compound
[Zn(OH)(µ-ClO4)(H2O)3]2. This title compound is an example of
the broader class of inorganozinc perchlorates.
Caution. Single crystals of [Zn(OH)(µ-ClO4)(H2O)3]2 decompose
upon heating and applied pressure. Dry powder samples, especially
in larger quantities, should be handled with great care.
Figure 2 The packing perspective view of [Zn(OH)(µ-ClO4)(H2O)3]2
along [100] direction.
Crystal Structure of [Zn(OH)(µ-ClO4)(H2O)3]2
The reaction of Zn(ClO4)2·6H2O with 4-sulfophenylalanine offers
a precipitate which may be mono(4-sulfo-phenylalanine)(diaqua)-
zinc(II) [3]. The evaporation of this mother liquid gives the title
compound. X-ray crystallographic analysis indicates that the cen-
trosymmetric dinuclear structure of [Zn(OH)(µ-ClO4)(H2O)3]2,
crystallizes with the monoclinic space group P21/c with four for-
mula units in the unit cell [4]. The molecular structure of the title
compound (Fig. 1) features two bidentate perchlorate ligands that
µ2-bridge via two oxygen atoms each to two zinc atoms leading to
the formation of an eight-membered ring. Other coordination sites
were occupied by three water molecules and one hydroxy anion.
This arrangement leads to six-coordinate zinc atoms that are best
described as existing in square bipyramidal coordination. The
Zn-O (perchlorate group and water molecule) bond distances
˚
(2.085-2.109 A) are quite similar to normal Zn-O bond distances
˚
˚
(2.050-2.132 A) [1]. Zn-OH bond length (2.071 A) also has a typical
Figure 1 Molecular structure of [Zn(OH)(µ-ClO4)(H2O)3]2 with hy-
drogen atoms of water omitted.
˚
bond distance (2.020 A) [5], the intramolecular Zn-Zn bond dis-
˚
˚
tance is 4.502 A and Cl-O distances range from 1.459 to 1.479 A.
The extensive intermolecular hydrogen bonding interactions give
rise to a three-dimensional network structure (Fig. 2).
Prof. Dr. Ren-Gen Xiong
Coordination Chemistry Institute, The State Key Laboratory of
Coordination Chemistry, Nanjing University,
Nanjing, 210093, P. R. China
Experimental Details
A solution of Zn(ClO4)2·6H2O(0.5 mmol) in methanol(5 mL) was
added to a solution of 4-sulfophenylalanine(0.5 mmol) prepared by
E-mail: xiongrg@netra.nju.edu.cn
Z. Anorg. Allg. Chem. 2004, 630, 1553Ϫ1554
DOI: 10.1002/zaac.200400201
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1553

Y.-H. Li, Q. Ye, Y.-Z. Tang, R.-G. Xiong
Table 1 Atomic coordinates, equivalent temperature factors, dis-
tances (in A) and angles (in deg) for [Zn(OH)(µ-ClO4)(H2O)3]2.
intensity data set with the aid of the same diffractometer at 293 K.
For structure solution and refinement see ref. [4] and for crystal
data Table 1.
˚
Atom
x/a
y/b
z/c
Ueq
Zn
0.15(1)
0.1035(1)
0.1074(1)
0.0758(2)
0.1265(2)
0.1409(2)
0.0485(2)
0.2486(2)
0.0737(2)
0.2115(2)
0.0917(2)
0.2818(1)
0.3243(1)
0.1453(3)
0.0599(3)
0.4148(3)
0.2569(3)
0.2841(3)
0.4983(3)
0.3213(3)
0.2169(3)
0.016(1)
0.017(1)
0.023(1)
0.031(1)
0.025(1)
0.020(1)
0.024(1)
0.021(1)
0.021(1)
0.022(1)
[1] S. Ghosh, M. Mukherjee, A. Seal, S. Ray, Acta Crystallogr.
1997, B53, 639.
[2] M. Ghosh, S. Ray, Z. Kristallogr. 1977, 145, 146.
[3] Y.-R. Xie, R.-G. Xiong, X. Xue, X.-T. Chen, Z. Xue, X.-Z.
You, Inorg. Chem. 2002, 41, 3323.
Cl(2)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
0.3705(2)
0.0085(5)
0.5537(6)
0.3143(5)
0.2462(5)
0.0374(5)
0.2532(4)
0.3099(5)
0.6788(5)
[4] [Zn(OH)(µ-ClO4)(H2O)3]2: Colourless single crystal; dif-
fractometer Bruker P4; Mo-Kα radiation, graphite mono-
˚
chromator, λ ϭ 0.71073 A; T ϭ 293(2) K; monoclinic, P21/c,
Zn-O(2)
Zn-O(4)
Zn-O(5)
Cl(2)-O(8)
O(2)-Zn-O(6)
O(9)-Cl(2)-O(7)
2.071(2)
2.096(2)
2.109(2)
1.459(2)
85.16(10)
108.14(13)
Zn-O(6)
2.074(2)
2.092(2)
1.479(2)
1.479(2)
87.50(9)
109.25(13)
˚
Z ϭ 4, a ϭ 5.9031(7), b ϭ 13.5404(16), c ϭ 9.7932(8) A, β ϭ
Zn-O(7)A
Cl(2)-O(7)
Cl(2)-O(5)
O(2)-Zn-O(7)A
O(5)-Cl(2)-O(7)
3
˚
126.438(5)°,
V
ϭ
629.74(12) A ; F(000)
ϭ
472,
µ
ϭ
4.321 cmϪ1; θmin ϭ 2.99°, θmax ϭ 26°, Ϫ7<h<7, Ϫ16<k<13,
Ϫ12<l<12; 3700 reflection intensities measured of which 1238
were symmetrically independent, Rint ϭ 0.0307, 117 param-
Symmetry transformations used to generate equivalent atoms: A, Ϫx, Ϫy, Ϫzϩ1
Ϫ3
˚
eters. Largest diffraction peak and hole 0.64 and Ϫ0.76 eA
.
Structure solution and refinement with the programs
SHELXS-97 and SHELXL-97 (G. M. Sheldrick, Göttingen),
scattering factors from Int. Tables for X-ray Crystallogr., Vol
C. R values: R1/wR2 for 1121 reflections with I0 > 2σ(I0):
0.0276/0.0826 and for all data: 0.0312/0.0844; Goof: 1.084.
Further details may be obtained from the Fachinformations-
zentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen, crys-
data@FIZ-Karlsruhe.de, referring to CSD No. 413949, the au-
thors and the journal citation.
standard methods in methanol/water (5 mL/5 mL). This mixture
was stirred at 60 °C for 2 h and the precipitated compound (may
be mono(4-sulfo-phenylalanine)(diaqua)zinc(II)) [3] was filtered
off. Colorless crystals were obtained from the slow evaporation of
the mother liquid. Some of these were selected and sealed in thin-
walled glass capillaries of 0.1-0.2 mm outer diameter and were
tested for their quality on a single-crystal X-ray diffractometer
(Bruker P4). The best specimen was used to collect a complete
[5] V. W. Nowachi, J. N. Silverman, Z. Kristallogr. 1961, 115, 21.
1554
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 1553Ϫ1554