Z. Kristallogr. NCS 228 (2013) 69-70 / DOI 10.1524/ncrs.2013.0044
69
© by Oldenbourg Wissenschaftsverlag, München
Crystal structure of aqua-di-$-hydroxy-bis(3-(pyridin-3-yl-oxy)-benzene1,2-dicarboxylato)tri-zinc(II), C26H18N2O13Zn3
Guan-Feng Li, Xun Feng*, Zhi-Qiang Shi and Shi-Yu Xie
I
Luoyang Normal University, College of Chemistry and Chemical Engineering, Luoyang 471022, Henan Province, P. R. China
Received September 22, 2012, accepted November 21, 2012, available online March 01, 2013, CCDC no. 1267/3909
Experimental details
Positions of hydrogen atoms of water were located from the difference Fourier syntheses and refined. All Uiso values were restrained on Ueq values of the parent atoms.
Abstract
C26H18N2O13Zn3, monoclinic, C2/c (no. 15), a = 24.794(5) Å,
b = 9.362(2) Å, c = 11.950(2) Å, $ = 112.452(4)°,
V = 2563.7 Å3, Z = 4, Rgt(F) = 0.0681, wRref(F2) = 0.1855,
T = 293 K.
Table 1. Data collection and handling.
Crystal:
Wavelength:
#:
Diffractometer, scan mode:
2"max:
N(hkl)measured, N(hkl)unique:
Criterion for Iobs, N(hkl)gt:
N(param)refined:
Programs:
colourless blocks, size 0.15#0.18#0.20 mm
Mo K! radiation (0.71073 Å)
28.63 cm"1
CCD area detector, % and &
50°
6149, 2249
Iobs > 2 !(Iobs), 1395
202
SHELX [10]
Source of material
3-(Pyridin-3-yl-oxy)benzene-1,2-dicarboxylic acid (H2PBDA)
(52 mg, 0.2 mmol) in a solution of water / alcohol (v/v = 1.2, 10
mL) were mixed with an aqueous solution (10 mL) of 0.2 mmol
Zn(ClO4)2, (0.031 g). After stirring for 20 min the pH value was
adjusted to 5.5 with nitric acid. Then the mixture was placed into a
25 mL Teflon-lined stainless steel autoclave under autogenous
pressure being heated at 155 °C for 72 h. The autoclave was
cooled over a period of 24 h at a rate 5 °C/h. After filtration the
product was washed with distilled water and then dried, yielding
colourless crystals. Yield: 0.014 g (61 %).
Elemental analysis For C26H18N2O13Zn3: calcd., %: C, 54.94;
H, 3.57; N; 4.93. Found, %: C, 54.85; H,3.66; N, 4.98.
IR (KBr pellet, cm–1): 3250br, 3023s, 1533.7vs, 1421.1s,
1328.4s, 1254s, 845.0s, 712.1m, 510.8m, 465m.
_____________
* Correspondence author (e-mail: [email protected])
Discussion
Particular attention has been paid to the synthesis and crystal
structure of carboxylic compounds and their analogues [1, 2]. It is
well known that benzenedicarboxylate compounds and their derivatives play the important role to construct high dimensional
frameworks in coordination chemistry. They usually adopt binding modes diverse as terminal monodentate, chelating to one
metal center, bridging bidentate in a syn-syn, syn-anti, and antianti configuration to link two metal centers, and bridging
tridentate to two metal centers [3, 4]. Multidentate N- or O-donor
ligands have been employed extensively as organic spacers in the
construction of extended structures, such as 4,4'-bipyridine, 1,4benzenedicarboxylate, and 1,3,5-benzene-tricarboxylate [5, 6].
Furthermore, zinc, as one of the most important trace elements,
plays a versatile role in biological systems caused by its structural
and catalytic role in enzymes [ 7, 8]. In order to further study on
the coordination behavior and role of the late transition cation in
the self-assembly processes in the presence of nitrogenheterocyclic dicarboxylates, a new complex has been synthesized
and structurally characterized. The title compound crystallizes in
the monoclinic space group C2/c. There are two crystallographically independent Zn(II) cations and one PBDA ligand, as well as
one coordinated water molecule and one Zn-Zn-bridging
hydroxyl group in the asymmetric unit of title compound, as
shown in the figure. The coordination geometry around the Zn(1)
ion is a slightly distorted tetragonal pyramid. The Zn(1) cation is
coordinated by two oxygen atoms from carboxylate groups of
two different PBDA ligands and two oxygen atoms of hydroxyl
groups, as well as one oxygen atom from a water molecule. The
bond distances of Zn(1)–O(1), Zn(1)–O(6), Zn(1)–O(1w) are
2.185(7), 1.889(6), 1.992(10) Å, respectively. In the basal plane,
the bond angle of O(6)#1–Zn(1)–O(6)#2 is 129.2(4)°, while, the
a ng l e s O ( 6 ) - Z n ( 1 ) - O( 1 ) # 1 , O ( 6) # 1 - Z n ( 1 ) - O( 1 ) # 1 ,
O(1)#1–Zn(1)–O(1) and O(6)–Zn(1)–O(1) are 91.5(3), 87.4(2),
177.3(3) and 91.31(15)°, respectively. Zn(2) is fourfold-coordinated by two oxygen atoms from two different carboxlyic groups,
one oxygen atom from a hydroxyl group and one nitrogen atom
from a PBDA ligand. The bond distances of Zn(2)–O(6),
Zn(2)–O(2), Zn(2)–O(3), and Zn(2)–N(1) are 1.894(6), 1.934(6),
1.907(6), and 2.021(8) Å, respectively, giving the slightly distorted tetrahedral arrangement.Within one PBDA moiety, the dihedral angle between benzene and pyridine plane is 88.4°. The
first category of oxygen is from hydroxyl group, it acts as bisdentate bridging, linking adjacent two Zn(1) and Zn(2) ions, with
the separation of Zn(1)–Zn(2) of 3.1553(12) Å. Three adjacent
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70
C26H18N2O13Zn3
zinc cations are connected by two PBDA ligands using the 2carboxylic oxygen atoms, forming a macrocyclo-like configuration, while the oxygen atom (O(1w)) of water just acts as a terminal ligand, being coordinated to Zn(1) ion. The starting material
H2PBDA has been completely deprotonated. The PBDA exhibits
diverse coordination configurations and modes owing to its flexibility [11]. Both of two neighboring PBDA ligands acts as trichelate ligands and connect three adjacent Zn(II) center in bis(bridging) bidentate and monodentate fashion, emplying the
carboxylic oxygen atoms as well as the pyridine nitrogen atom.
The pyridine nitrogen atom (N1), further connects these tri-nuclear units, into one dimensional chains along the c axis. In addition, there are several obvious hydrogen bonding interactions
between the adjacent units mentioned above involving the water
oxygen atoms, benzene dicarboxylic groups as follows:
O(6)–H(6)···O(4) [O···O = 2.821(9) Å, O–H···O = 122.7°];
O1(w)–H(1w)···O(4)#4 [O···O = 2.819(6) Å, O–H ···O = 153.8
Å]. All the hydrogen atoms of coordinated water molecule participate in the hydrogen bonding. The extensive hydrogen bonds
further links the 1D chain into a 1D double ribbon-like structure.
Table 2. Atomic coordinates and displacement parameters (in Å2).
Atom
Site
x
y
z
Uiso
H(6)
H(1)
H(5)
H(6A)
H(7)
H(9)
H(10)
H(11)
H(13)
8f
8f
8f
8f
8f
8f
8f
8f
8f
0.4937
0.4733
0.2505
0.2354
0.2885
0.4554
0.4529
0.3906
0.3374
0.7524
0.3753
0.9464
1.0097
0.9051
0.9261
1.0422
0.9622
0.6611
0.5691
0.7710
0.2056
0.3772
0.5575
0.0102
0.1743
0.2654
0.0134
0.063
0.093
0.054
0.052
0.046
0.049
0.056
0.048
0.052
Table 3. Atomic coordinates and displacement parameters (in Å2).
Atom
Site
x
y
Zn(1)
Zn(2)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(1w)
N(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
4e
8f
8f
8f
8f
8f
8f
8f
4e
8f
8f
8f
8f
8f
8f
8f
8f
8f
8f
8f
8f
8f
8f
!
0.59579(5)
0.4084(3)
0.3579(3)
0.3640(3)
0.4339(3)
0.3162(3)
0.5179(3)
!
0.3963(4)
0.3696(4)
0.3351(4)
0.3448(4)
0.3122(4)
0.2716(4)
0.2630(4)
0.2945(4)
0.3854(4)
0.4297(4)
0.4287(4)
0.3916(4)
0.3562(4)
0.3606(4)
0.6179(2)
0.6719(1)
0.6234(6)
0.7568(6)
0.4967(6)
0.6524(7)
0.7492(7)
0.7044(6)
0.405(1)
0.7853(8)
0.711(1)
0.7746(9)
0.7337(9)
0.799(1)
0.903(1)
0.941(1)
0.8779(9)
0.620(1)
0.895(1)
0.964(1)
0.918(1)
0.8046(9)
0.741(1)
z
"
0.6410(1)
0.6266(6)
0.7045(6)
0.3728(6)
0.3913(6)
0.1831(6)
0.6255(6)
"
"0.0042(8)
0.6175(8)
0.4960(8)
0.3956(8)
0.2879(8)
0.279(1)
0.3812(9)
0.4882(9)
0.3885(8)
0.0447(9)
0.143(1)
0.1965(9)
0.1440(8)
0.0463(8)
U11
U22
U33
0.054(1)
0.0451(8)
0.053(4)
0.061(4)
0.056(4)
0.029(4)
0.054(4)
0.042(4)
0.063(8)
0.047(5)
0.029(5)
0.035(5)
0.034(5)
0.041(6)
0.049(6)
0.046(6)
0.039(6)
0.032(6)
0.035(6)
0.042(6)
0.043(6)
0.045(6)
0.058(7)
0.0318(9)
0.0306(7)
0.034(4)
0.036(4)
0.026(4)
0.051(4)
0.040(4)
0.043(4)
0.044(6)
0.034(4)
0.036(5)
0.036(5)
0.031(5)
0.045(6)
0.040(6)
0.043(6)
0.039(5)
0.041(6)
0.047(6)
0.042(6)
0.035(5)
0.036(5)
0.040(6)
0.050(1)
0.0360(7)
0.041(4)
0.037(4)
0.052(4)
0.046(4)
0.041(4)
0.049(4)
0.098(9)
0.052(5)
0.034(5)
0.032(5)
0.036(5)
0.035(6)
0.045(6)
0.040(6)
0.046(6)
0.031(5)
0.045(6)
0.055(7)
0.043(6)
0.028(5)
0.037(6)
Acknowledgments. This work was supported by the National Natural Science
Foundation of China (nos. 21271098 and 21273101), the Foundation of the
Program for Backbone Teachers in Universities of Henan Province, China
(no. 2012GGJS158) and the Foundation of Education Committee of Henan
province, China (no 2011B150022).
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U12
0
0.0005(5)
0.006(3)
0.011(3)
0.008(3)
0.001(3)
"0.011(3)
0.012(3)
0
0.002(4)
"0.006(4)
"0.011(4)
0.001(4)
0.001(4)
0.005(5)
0.016(5)
0.006(4)
0.008(4)
"0.002(5)
0.000(5)
0.004(4)
0.006(4)
"0.004(5)
U13
0.0316(9)
0.0212(5)
0.021(3)
0.029(3)
0.025(4)
0.015(3)
0.030(4)
0.028(3)
0.052(7)
0.028(4)
0.011(4)
0.017(4)
0.018(4)
0.021(5)
0.016(5)
0.017(5)
0.027(5)
0.013(4)
0.020(5)
0.017(5)
0.018(5)
0.019(4)
0.023(5)
U23
0
"0.0011(5)
0.001(3)
0.006(3)
"0.003(3)
"0.005(3)
"0.006(3)
0.016(3)
0
0.001(4)
"0.002(4)
0.003(4)
0.000(4)
"0.004(5)
0.013(5)
0.004(5)
0.002(5)
0.009(4)
0.011(5)
"0.001(5)
"0.005(4)
0.004(4)
0.001(5)
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