ELSEVIER InorganicaChimicaActa239 (1995) 13-17

Zinc complexes of dipyridyl-triazoles

U. Hartmann, H. Vahrenkamp *
lnstitut fiir Anorganische und Analytische Chemic der Universit~t Freiburg, Albertstrasse 21, D-79104 Freiburg, Germany
Received 17 January 1995;revised 10 May 1995

Abstract

The ligands 3,5-di(2-pyridyl)-l,2,4-triazole (L) and 3,5-di(2-pyridyl)-4-amino-l,2,4-triazole (L') were reacted with zinc salts. With
ZnC12 1:1 complexes were obtained. Zn(NO3)2, Zn(C104)2 and Zn (BF4)2 produced 2:1 complexes. NMR and IR data indicate varying
bonding modes of the ligands and anions. A crystal structure determination of [(L')2Zn(H20)2] (C104)2 has shown the metal to be
octahedrally coordinated by two water molecules and one triazole and pyridine nitrogen atom each of the two ligands L'.

Keywords: Zinc complexes;Drug-relatedligand complexes;Crystalstructures

1. Introduction

The work reported in this paper is related to our investi-

gations on the coordination chemistry of zinc with drug sub- N--N
stances. As most drugs contain either acidic functions or L
nitrogen heterocycles they are all potential ligands for the
metals in the human body. In the case of zinc it has been
shown quite often that drugs interact (favourably or unfa-
vourably) with zinc-dependent enzymes [1-3] and that
mutual relations exist between the presence of drugs and the N--N
zinc status in the body [4--6]. We are therefore screening
L'
drugs or drug-related organic compounds for their donor
capacity, complex stability, and coordination preferences
towards zinc. The coordinative behaviour of L and L' towards copper,
nickel, cobalt, iron and ruthenium has already been investi-
Triazole derivatives occur in several drug substances
gated by Reedijk and co-workers [8-11]. They found the
among which is the psychopharmacologically active class of
chelating function of the triazole N1 atom and one pyridine
benzodiazepine annelated triazoles [7]. The four nitrogen
nitrogen to be the preferred bonding mode. We expected that
atoms of these molecules offer many modes of donation and
the coordinative flexibility of zinc would allow a variable
chelation thereby making them attractive ligands. We there-
structural chemistry of its complexes with L and L'.
fore wanted to investigate their zinc complex chemistry. In
view of the restricted accessibility of this class of drugs we
modelled the 3-aminomethyl-triazole structural unit of the 2. Experimental
anellated diazepine by a 3- (2-pyridyl)- 1,2,4-triazole unit.
Two compounds with this structural motif which can be pre- The general experimental techniques and physical meas-
pared with a reasonable synthetic effort are the two triazole urements were as described before [ 12]. The ligands L and
derivatives L and L'. L' were prepared according to the published procedures [ 13 ].
All zinc complexes were prepared according to the same
* Corresponding author. procedure. A solution of the zinc salt was dropped into a

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14 U. Hartraann, H. Vahrenkamp / lnorganica Chimica Acta 239 (1995) 13-17

Table 1
Preparative details

Zinc salt Ligand Solvent c Reaction time Product

mg mmol mg mmol ml mg %

ZnC12 61 0.45 L 100 0.45 E 40 5h la 136 85

ZnCI2 57 0.42 L' 100 0.42 EW 60 0.5 h lb 128 82
Zn(NO3)2 a 96 0.42 L' 200 0.84 MW 40 2d 2b 192 69
Zn(CIO4)2 b 166 0.45 L 100 0.45 E 40 3h 3a 105 66
Zn(CIO4)2 t, 79 0.21 L' 100 0.42 EW 60 4d 3b 128 79
Zn(BF4) 2 155 0.45 L 100 0.45 M 20 2d 4a 90 59

a Zn(NO3)2 as the tetrahydrate.

h Zn(CIO4)2 as the hexahydrate.
c Solvents: E = ethanol, M = methanol, EW = ethanol/water 2:1, MW = methanol/water 1:1.

vigourously stirred solution of the ligand. Stirring was con- for the calculations after an empirical absorption correction
tinued for a given amount of time. Then the solution was based on psi scans. The SHELX program system [ 14] was
filtered and reduced in volume in vacuo until the complex used to solve the structure with direct methods and for the
started to precipitate. Then the reaction flask was kept at - 25 full-matrix least-squares refinement with anisotropic temper-
°C for 3 days. The colourless crystalline product was filtered ature factors. Hydrogen atoms were included with fixed
off, washed with a few ml of methanol and dried in vacuo. distances ( C - H = N - H = 0 . 9 6 .&) and a common isotropic
Table 1 lists the reaction conditions; Table 2 the elemental temperature factor. The refinement for 223 parameters con-
analyses. All complexes decompose above 250 °C without verged to an unweighted R value of 0.051 and a GOF of 1.08.
melting. The maxima in the final difference map were + 0.6 and - 0.6
e/~-3. Atomic parameters are given in Table 3; the structure
2.1. Structure determination drawing was produced with the SCHAKAL program [ 15].
See also Section 5.

Crystals of 3b (formula C24H24C12N12OloZn, molecular

weight 776.8) were obtained by very slowly cooling down a
60 °C solution to room temperature, and a colourless block 3. Results and discussion
of size 0.3 X 0.2 × 0.2 mm was chosen for the measurement.
Crystals belong to the monoclinic system, space group 3.1. Reactions and products
P21/n, a = 9 . 9 8 3 ( 2 ) , b = 1 4 . 3 8 4 ( 3 ) , c=10.934(2) /k,
/3=100.08(3) °, V=1545.8(5) ,~3, Z = 2 , Dca~c=1.67 g Four zinc salts were chosen for the reactions with L and
cm -3, /x=10.4 cm -1. All crystallographic data were L': ZnCI2 and Zn (NO 3)2 as species with coordinating anions,
obtained at room temperature with a Nonius CAD4 diffrac- and Zn(CIO4)2 and Zn(BF4)2 as species with non-coordi-
tometer using Mo K a radiation. Of the 6644 reflections nating anions. The identification of the products has shown
obtained with the to/20 technique in the range - h, _ k, _+l, (see below) that the coordinative behaviour of the anions
3134 were independent, and 2407 with I >_2o-(I) were used was as expected. Irrespective of the molar ratio of the reac-
tants only one product was obtained in all cases.
Table 2
Product characterization ZnC12 reacted with L and L' in ethanol to form the 1:1
complexes l a and lb. Their 1:1 composition allowed the
No. Formula Analyses conclusion that not only the triazole ligand but also chloride
(molecular weight) is involved in the bonding to zinc. Once precipitated these
C H N Zn
complexes were of rather low solubility in all common sol-
la CI2H9CI2N5Zn calc. 40.09 2.52 19.48 18.19 vents, thereby indicating that they probably do not have the
(359.5) found 40.81 2.29 19.90 18.43 simple mononuclear constitution LZnCI2. Instead it seems
lb Cl2HloCl2N6Zn calc. 38.48 2.69 22.44 17.46 that they are dimeric, polymeric, or possibly ionic. Conclu-
(374.5) found 37.72 2.92 21.47 17.55 sions of this kind could not be drawn from the composition
2b C24H2oNI406Zn calc. 43.29 3.03 29.45 9.82
or the properties of complex 2b obtained from L' and
(665.9) found 43.70 3.02 28.94 9.71
3a Cz4HisCl2NloOsZn calc. 40.56 2.55 19.71 9.20 Zn(NO3)2 in methanol/water. 2b is of reasonable solubility
(710.8) found 40.94 2.35 19.87 9.15 in polar organic solvents thereby leaving the question open
3b C24H24C12Nt2Oi oZn calc. 37.11 3.11 21.64 8.42 whether it is ionic or neutral.
(776.8) found 37.23 3.12 21.36 8.11
4a C24HIsB2FsN1oZn calc. 42.05 2.65 20.43 9.54
IL' ZnCl2]x IL' • ZnCI2]~, (L')2Zn(NO3)2
(685.5) found 42.95 2.59 21.24 9.87
la lb 2b
 U. Hartmann, H. Vahrenkamp / Inorganica Chimica Acta 239 (1995) 13-17 15

Table 3 Table 4
Atomic coordinates ( 104) and equivalent isotropic displacement parameters IR data (KBr, cm - t )
(pm2× 10 - l ) for2b
Pyridine bands Anion bands
x y z U~
L 1591 1570
Zn 0 0 5000 36(1) L' 1587 1567
N(1) 5636(4) - 1688(3) 5945(4) 64(1) la 1613 1571
N(2) 2897(3) -1008(2) 5727(3) 38(1) lb 1605 1571
N(3) 1653(3) -715(2) 5956(3) 36(1) 2b 1606 1589 1570 1383 1323
N(4) 2811(3) - 1200(2) 7707(2) 33(1) 3a 1610 1595 1570 1108
N(5) 3189(3) - 1317(2) 8998(3) 44(1) 3b 1607 1590 1571 1092
N(6) -594(3) -223(2) 6793(3) 37(1) 4a 1618 1596 1570 1052
C(1) 4931(3) -1736(2) 6921(3) 36(1)
C(2) 5388(3) -2178(2) 7989(3) 35(1)
C(3) 6616(4) -2585(3) 8114(5) 54(1) Table 5
C(4) 7388(4) -2586(3) 7192(5) 57(1) tH NMR data (DMSO-d 6, internal TMS, ppm) a.b
C(5) 6899(4) -2147(3) 6101(5) 58(1)
C(6) 3577(3) -1304(2) 6789(3) 34(1) 3-H 4-H 5-H 6-H
C(7) 1602(3) -853(2) 7140(3) 32(1)
C(8) 355(3) -660(2) 7630(3) 34(1) L 7.20 8.25 8.10 8.25
C(9) 110(4) -936(3) 8786(3) 44(1) L' 7.58 8.23 8.06 8.77
C(10) -1147(4) -739(3) 9095(4) 50(1) lb 7.63 8.30 8.09 8.78
C(ll) -2102(4) -270(3) 8258(4) 49(1) 2b 7.68 8.42 8.16 8.76
C(12) - 1797(4) -29(3) 7124(4) 43(1) 3a 7.68, 7.14 8.21, 8.08 7.84, 7.27 8.42, 8.21
O(11) 936(3) 1312(2) 5681(3) 46(1) 3b 7.70 8.47 8.19 8.74
CI(1) 3864(1) 1373(1) 8272(1) 49(1) 4a 7.70, 7.08 8.21, 8.08 7.82, 7.25 8.42, 8.21
O(1) 4496(9) 631(4) 8871(8) 214(5)
0(2) 4025(7) 1398(7) 7082(5) 195(4) a Complex l a is insoluble in DMSO.
0(3) 2440(5) 1303(6) 8214(6) 144(3) b Assigned according to our experience with other polydentate pyridine-
0(4) 4434(5) 2175(3) 8898(4) 98(2) containing ligands [ 18].

and probably one triazole nitrogen for chelate binding, as was

The complexes 3a and 3b, obtained from L and L', respec-
confirmed by the structure determination of 3b (see below).
tively, and Zn (CIO4) 2 in ethanol or ethanol / water mixtures,
are only soluble in water or very polar organic solvents, With respect to anion binding, the positions of the two nitrate
corresponding to their expected ionic nature. It is noticeable stretching bands of 2b point to a unidentate nitrate coordi-
that 3a crystallizes water-free even from water while 3b con- nation in this complex [ 17]. The perchlorate and tetrafluo-
roborate bands in 3a, 3b and 4a are those of the free anions.
tains water (from Zn (CIO4)2" 6H20) even when prepared in
No conclusion with respect to chloride binding can be drawn
a water-free solvent. Finally, L and Zn(BF4)2 yielded com-
plex 4a which resembles 3a in all respects. Accordingly we from the spectral data.
The 1H NMR spectra (see Table 5) are less informative.
assume that it belongs to the same structural type as 3a.
As the complexes are soluble enough only in the strongly
[ (L)2Zn(CIO4) 2 [ (L') 2Zrl(H20) 2] (CIO4) 2 [ (L)2Zn(BF4)2 coordinating and line-broadening solvent DMSO some
3a 3b 4a detailed information is lost due to ligand exchange and the
occurrence of unresolved multiplets. Thus for each of the
3.2. Spectra and constitutions three complexes of ligand L' only one set of four signals is
observed which have similar positions each time. Thereby
The bonding mode of the ligands and anions can be the difference in ligand bonding seen in the IR spectra is
deduced from the IR spectra of the complexes, see Table 4. wiped out. In contrast the two soluble complexes of ligand L
The indicators for the ligands are the two intensive bands of show (with one superposition) two separate sets of four sig-
the pyridine ring vibrations near 1580 cm-t. Upon pyridine nals, assignable to the coordinated and the uncoordinated
coordination to a metal the higher one of these bands is shifted pyridine units. In these two cases (3a and 4a) the NMR
by about + 15 wavenumbers [ 16]. The IR data show that spectra are so similar, however, that it seems that the coli-
this is the case for both pyridine rings of the ligands in the gands (H20 and NO3-, respectively) have been replaced by
ZnC12 complexes l a and lb. As concluded from the 1:1 DMSO. It can be excluded, though, that DMSO has replaced
composition this means that both pyridine nitrogens together L and L' from zinc as all ligand signals of the complexes
with two of the triazole nitrogens are coordinated to zinc. In show a downfield shift with respect to those of the free
all four other cases there are two IR bands in the 1590-1620 ligands.
c m - t range which can be assigned to one coordinated and For the constitutions of the complexes the following con-
one uncoordinated pyridine ring. This means that in these 2:1 clusions can be drawn (with support from the structure deter-
complexes each triazole ligand uses one pyridine nitrogen mination): (i) complexes 2b and 3b are octahedral with an
16 U. Hartmann, H. Vahrenkamp/ lnorganica ChimicaActa 239 (1995) 13-17

)'"
• ®

,)

Fig. 1. Solidstate structureof complex3b.

N402 coordination by ligand L' and the water and nitrate dral to a very good approximation, being disturbed only by
coligands, respectively; (ii) complexes 3a and 4 a a r e tetra- the narrow chelate angle N3-Zn-N6 (see Table 6). The Zn-
hedral with an N4 coordination by one pyridine and triazole N and Zn-O distances are within the range observed for
nitrogen each of both ligands; (iii) in complexes l a and lb octahedral complexes (2.05-2.25 A) [20]. It is, however,
the ligand uses both pyridine nitrogens for coordination. noticeable that the Zn-N bond to the triazole nitrogen is 0.1
Assuming that chloride is coordinated as well this leaves two /k shorter than that to the pyridine nitrogen. The ligand L' is
alternatives: (a) a coordination polymer in which each ligand close to being completely planar. The orientation of the
links two ZnC12 units by chelating triazole-pyridine groups, uncoordinated pyridine ring is uncertain (i.e. N1 pointing
i.e. a compound with octahedral N4C12 coordination; (b) a 'inward' or 'outward') as its C and N atoms cannot be dis-
coordination polymer in which only the pyridine nitrogens tinguished crystallographically. The perchlorate ions are con-
make up tetrahedral ZnN4 units (i.e. with ZnL2 stoichiometry nected to the water ligands by a hydrogen bridge (2.91 ,~,)
in the cationic polymer backbone) and which contains between 0 3 and O l l . The perchlorate oxygen O1 is also
ZnCI42- counterions. As octahedral ZnN4CI2 complexes are within close contact (3.10 ti,) of the hydrazine nitrogen N5
unusual and as we have observed dismutation with ZnC142- which in turn is in close contact (3.14 A) with O1 of an
formation several times before [ 19] we favour the latter adjacent perchlorate ion.
assignment. The general structural features o f the metal-ligand com-
bination in 3b can be compared with those observed for the
3.3. Structure determination copper, nickel and ruthenium complexes [8-11 ], i.e. the

Complex 3b was chosen for the structure determination Table6

Selectedbond lengths (A) and angles (°) for 3b
because its IR and NMR data gave conflicting information
with respect to the coordination of L'. The X-ray analysis Zn-N3 2.067(3) N3-Zn-N6 77.9(1)
resolved this conflict as shown in Fig. 1, and proved the NMR Zn-N6 2.169(3) N3-Zn-N6' 102.1(1)
data to be misleading. Zn-O11 2.178(3) N3-Zn-O11 90.1( 1)
The zinc ion in 3a is located on an inversion centre relating O l 1 . • •03 2.91( 1) N3-Zn-O11' 89.9( 1)
N6-Zn-O11 89.3( 1)
the two molecules of L', the two water ligands and the two
N6-Zn-O11' 90.7( 1)
perchlorate ions. The coordination of the zinc ion is octahe-
 U. Hartmann, H. Vahrenkamp / lnorganica Chimica Acta 239 (1995) 13-17 17

ligand prefers to be a planar entity, the metal-nitrogen (tri- many, quoting the depository no. CSD-401402, the authors
azole) bond is significantly shorter than the metal-nitrogen and the journal citation.
(pyridine) bond, and the N4 atom of the tfiazole or its amino
substituent do not get involved in the coordination. Unlike in
the metal complexes prepared by Reedijk and co-workers Acknowledgements
[8-10], however, the ligands L and L' do not seem to have
any binucleating tendency towards zinc. A comparable coor- This work was supported by the Deutsche Forschungsge-
dination of zinc by two planar heterocyclic chelate ligands in meinschaft and by the Fonds der Chemischen Industrie.
the equatorial plane and by weakly bound oxygen ligands in
the axial position has been observed in [ Zn(2-pyridyl-acet-
a m i d e ) 2 ( H 2 0 ) 2 ] ( N O 3 ) 2 [21] and in some bis-bipyridyl
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