Journal of Structural Chemistry. Vol. 51, No. 2, pp.

382-385, 2010
Original Russian Text Copyright © 2010 by Y. Kim, H. G. Koo, D. H. Shin, L. O. Park, J. H. Lee, H. G. Jang, and C. Kim

ZINC CITRATE WITH ALKALI METAL AND

AMMONIUM CATIONS:
CRYSTAL STRUCTURE OF K4[Zn(Citrate)2]

Y. Kim,1 H. G. Koo,2 D. H. Shin,2 L. O. Park,3 UDC 548.73

J. H. Lee,4 H. G. Jang,4 and C. Kim2

In the crystal of K4[Zn(Citrate)2], two citrate anions coordinate Zn(II) cation with octahedral geometry in
the [Zn(Citrate)2]4– complex anion, and the charge is balanced by four potassium ions. Crystal data:
monoclinic, P21/c, a = 8.502(2) Å, b = 13.210(3) Å, c = 8.942(2) Å, E = 113.132(4)°, V = 923.5(4) Å3,
Z = 2, R = 0.0229.
Keywords: zinc citrate, synthesis, crystal structure, citric acid.

Citric acid is a tricarboxylic acid which can undergo different degrees of deprotonation [1-3] and thus can form
various reaction products with alkali and transition metals such as sodium [1, 4], potassium [5], magnesium[6], iron [7, 8],
zinc [9], nickel [10], manganese [11], cobalt [12], vanadium [13] with different molar ratios. Its most important role is the
solubilization of metal ions and thus enhancement of their bioavailability and subsequent absorption by biological tissues.
This prominent function of the citric acid is directly related to its metal-chelating capacity, which is manifested in its
multimodal coordination to biologically significant metal ions, zinc and nickel. Acrodennatitis enteropathica is a genetic
disorder of zinc metabolism [2, 14]. The signs of zinc deficiency appear when infants with the disorder are fed with cow’s
milk or can be alleviated by human milk, even though cowcs milk generally contains more zinc than human milk. We
presume that this disorder could be caused by different binding ability of citrate ion to zinc metal and alkali metals such as
sodium and potassium. Therefore, the need to understand (a) the relative binding interaction of the zinc, sodium and
potassium ions with the citrate ligand and (b) the ability of the citrate ion as an organic cofactor to efficiently mobilize these
essential elements and enhance its availability to biological sites prompted us to investigate the competitive reaction between
zinc and alkali metals, sodium and potassium, to citrate ion in aqueous solutions. We report herein the synthesis, isolation,
and structural characterization of the first mononuclear zinc citrate complex containing potassium cation in aqueous solution.
Experimental. The (NH4)4[Zn(Citrate)2] (1) and [Na3(Citrate)]˜5.5H2O (2) were reported previously [2, 4], but we
synthesized them and re-collected data for the crystal structures. The parameters of the crystal structures were very similar to
those previously reported.
Preparation of K4[Zn(Citrate)2] (3): 33.4 mg (0.016 mmol) of ZnCl2 and 465.8 mg (0.16 mmol) of citric acid were
dissolved in 15 ml water and then pH of the solution was adjusted to 7.0 by adding KOH. The solution was carefully layered
by 15 ml MeOH.

1
Department of Chemistry and Nano Science, Ewha Womans Univeristy, Seoul 120-750, South Korea. 2Deartment
of Fine Chemistry, and Eco-Product and Materials Education Center, Seoul National University of Technology, Seoul 139-
743, South Korea; [email protected]. 3Tongil Obstetrics and Gynecology, 56-3 Banpo-Dong, Seocho-Gu, Seoul 137-040,
South Korea. 4Department of Chemistry, Korea University, Seoul 136-701, South Korea; [email protected]. The text was
submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 51, No. 2, pp. 396-398, March-April, 2010. Original
article submitted March 17, 2009.
382 0022-4766/10/5102-0382 © 2010 Springer Science+Business Media, Inc.
 TABLE 1. Crystallographic Data for Compounds 1, 2, and 3

Parameter 1a 2b 3

Empirical formula C12H26N4O14Zn C6H5Na3O12.5 C12H10K4O14Zn

Formula weight 515.74 346.07 599.97
Temperature, K 170(2) 293(2) 293(2)
Wavelength, Å 0.71073 0.71073 0.71073
Space group P21/c Pnma P21/c
a, Å 8.7566(16) 16.456(3) 8.502(2)
b, Å 13.494(3) 26.429(4) 13.210(3)
c, Å 9.0546(17) 6.4345(10) 8.942(2)
E, deg 113.459(3) 90 113.132(4)
Volume, Å3 981.5(3) 2798.4(7) 923.5(4)
Z 2 4 2
Density (calc), g/cm3 1.745 1.638 2.158
Absorption coeff., mm–1 1.334 0.236 2.308
Crystal size, mm 0.25u0.20u0.10 0.20u0.15u0.15 0.15u0.10u0.10
Reflections collected 5318 16735 5040
Independent reflections 1907 [R(int) = 0.1101] 3476 [R(int) = 0.1016] 1805 [R(int) = 0.0309]
Data/restraints/parameters 1907 / 8 / 178 3476 / 0 / 203 1805 / 0 / 146
GOOF on F2 1.002 0.819 0.924
Final R indices [I > 2V(I)] R1 = 0.0360, wR2 = 0.0925 R1 = 0.0480, wR2 = 0.1213 R1 = 0.0229, wR2 = 0.0505
R indices (all data) R1 = 0.0418, wR2 = 0.0936 R1 = 0.1299, wR2 = 0.1283 R1 = 0.0287, wR2 = 0.0512
Largest peak and hole, e˜Å–3 0.66 and –0.75 0.47 and –0.27 0.30 and –0.32
a
Practically identical to previously reported [2].
b
Practically identical to previously reported [4].

X-Ray Diffraction Analysis: The X-ray diffraction data for the two compounds were collected on a Bruker
SMART APX diffractometer equipped with monochromated MoKD (O = 0.71073 Å) source. Each crystal was mounted on a
glass fiber. The data on reflection intensities were integrated and scaled using the Bruker-SAINT software package, and the
structure was solved and refined using SHEXTL V6.12 [15]. All hydrogen atoms were placed in calculated positions.
Structural information for 3 was deposited at the Cambridge Crystallographic Data Center (CCDC reference number
628842). The crystallographic data for compounds 1, 2 and 3 are listed in Table 1.
Results and Discussion. [Zn(Citrate)2]4– complex ion containing two triply ionized citrates has been reported, and
the charge balance was achieved by four ammonium ions [2]. In the crystal of 1, the zinc ion lies on an inversion center,
octahedrally coordinated by two equivalent citrates. [Zn(Citrate)2]4– complex ions are indirectly cross-linked into a three-
dimensional network through hydrogen bonds between oxygen atoms of citrates and ammonium hydrogen atoms.

Scheme 1

In order to deeper investigate possible structures of zinc citrate ions, we have changed the counter cations balancing
the charge from ammonium ions to sodium and potassium ions (see Scheme 1). If the sodium ion was used as a counter

383
 Fig. 1. The structure of the Fig. 2. The coordination geometry of K+ ions in 3.
[Zn(Citrate)2]4– anion in 3 with
50% ellipsoids. Selected bond
distances: Zn1—O21
2.093(2) Å, Zn1–O41
2.047(2) Å, Zn–O1 2.135(2) Å.

Fig. 3. The unit cell contents of 3.

cation, citrates did not coordinate the zinc ion to form a zinc complex but yielded trisodium citrate 5.5-hydrate (2) whose
structure was determined previously [4]. Final result is that the potassium ions can replace the ammonium positions in the
crystal structures while the sodium ions can not act as a counter cation but can be directly coordinated by triply ionized
citrate. The result could be explained by the hard-soft acid-base (HSAB). The oxygen atoms of the citrate ion are hard, and
they like hard sodium ions. The potassium and ammonium ions are slightly softer, so they are not directly coordinated by
hard oxygen atoms of citrates and act just as counter cations. So, it seems to be important to select appropriate counter cation
for the formation of a [Zn(Citrate)2]4– complex ion.
In the crystal of K4[Zn(Citrate)2] (3), two citrate anions coordinate Zn(II) cation, with octahedral geometry in the
[Zn(Citrate)2]4– complex anion being similar to that previously reported for 2 [2] (Fig. 1). The distance from the zinc ion to a
hydroxyl oxygen atom of the citrate (2.135(2) Å) is significantly longer than those from zinc to acid oxygen atoms
(2.047(2) Å and 2.093(2) Å). The [Zn(Citrate)2]4– complex anion of 3 is surrounded by K+ ions. The K+ ions of 3 are
coordinated by oxygen atoms of citrate ions, yielding a coordination number of 5, with trigonal bipyramidal geometry
(Fig. 2). Fig. 3 shows the unit cell contents of 3.

384
 Financial support from Korea Ministry Environment “ET-Human Resource Development Project,” the Korean
Science & Engineering Foundation (R01-2008-000-20704-0), and a Korea University Grant is gratefully acknowledged.

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