134 Acta Chim. Slov. 2011, 58, 134–138
Slyvka et al.:  First Silver(I) – Complexes with Tetrazole Allyl Derivatives. Synthesis and Crystal Structure of ...
Scientific paper
First Silver(I) – Complexes with Tetrazole Allyl Derivatives.
Synthesis and Crystal Structure of
[Ag2(C10H10N4S)2(H2O)2](BF4)2 and [Ag(C10H9ClN4S)(NO3)]
π-Compounds (C10H10N4S and C10H9ClN4S – 5-
(Allylthio)-1-phenyl- and 5-(Allylthio)-1-(4-chlorophenyl)-
1H-tetrazole)
Yuriy Slyvka,1,* Oleksiy Pavlyuk,1 Nazariy Pokhodylo,1 Bogdan Ardan,1
Zoran Mazej2 and Evgeny Goreshnik2
1 Department of Chemistry, Ivan Franko National University of Lviv, 
Kyryla i Mefodiya St, 6, 79005, Ukraine
2 Department of Inorganic Chemistry and Technology, Jo`ef Stefan Institute, 
Jamova 39, SI-1000 Ljubljana, Slovenia
* Corresponding author: E-mail: slyvkayu@gmail.com
Tel.: +380 32 2394 506
Received: 25-10-2010
Abstract
Crystalline silver(I) π-complexes [Ag2(atpt)2(H2O)2](BF4)2 (1) (atpt – 5-(allylthio)-1-phenyl-1H-tetrazole (C10H10N4S))
and [Ag(atcpt)(NO3)] (2) (atcpt – 5-(allylthio)-1-(4-chlorophenyl)-1H-tetrazole (C10H9ClN4S)) complexes have been
obtained using silver salt and the organic ligands. Compounds were characterized by X-ray single crystal diffraction: for
1 space group P21/n, a = 10.4560(5), b = 11.4008(5), c = 12.7550(7) Å, β = 98.128(3)°, V = 1505.21(13) Å
3 at 200 K,
Z = 2; for 2: space group P21 /a, a = 8.6790(8), b = 13.7324(10), c = 12.4597(13) Å, β = 102.288(5)°, V = 1451.0(2) Å
3
at 200 K, Z = 4. In both structures silver(I) atoms possess a trigonal pyramidal coordination environment with essen-
tially different coordination modes of organic ligands. The Ag(I) arrangement in 1 involves the N3 and N4 atoms of two
adjacent atpt molecules, an olefin C=C bond and a water molecule at the apical position. In crystal structure of 2 two O
atoms from NO3
– anions occupy two equatorial position of silver(I) coordination polyhedron, and atcpt is attached to
the metal centre through the N4 atom of tetrazole core only. The weakly bound C=C bond is located at the apical posi-
tion of Ag(I) environment.
Keywords: Tetrazole; Silver(I); π-Complex; Crystal structure
1. Introduction
Tetrazole derivatives may serve as suitable ligands
for a design and self-organization of molecules through
the coordination to transition metal ions by different nitro-
gen atoms of tetrazole ring and other donor atoms of sub-
stituents.1 Use of the olefin-containing derivatives would
improve specific coordination property of tetrazole mo-
iety and therefore provide a formation of unexpected
compounds.
Recently investigated [CuX(3atpy)] (3atpy – 3-(2-
allyl-2H-tetrazole-5-yl)pyridine, X = Cl, Br),2–3 [Cu2Cl2
(4atpy)2] (4atpy – 4-(2-allyl-2H-tetrazole-5-yl)pyridine),
4
[CuBr(4atpy)],5 [Cu2(atcpt)2(H2O)2](NO3)2 · C2H5OH and
[Cu3(atcpt)Cl3] (atcpt – C10H9ClN4S 5-(allylthio)-1-(4-
chlorophenyl)-1H-tetrazole (C10H9Cl N4S)),
6 are the only
representatives among Cu(I) tetrazole π-compounds. The
5-allylthiosubstituted tetrazoles (atcpt) show a good affi-
nity to Cu(I) and act as a topologically interesting coordi-
nation agent, being attached simultaneously to the metal
with two N atoms of tetrazole core and through the olefin
135Acta Chim. Slov. 2011, 58, 134–138
Slyvka et al.:  First Silver(I) – Complexes with Tetrazole Allyl Derivatives. Synthesis and Crystal Structure of ...
C=C bond from S-allyl group by chelating mode. N-allyl
derivatives of tetrazoles (3atpy and 4atpy) do not promo-
te participation of other nitrogen atoms of the ring in me-
tal coordination and therefore they are bonded to Cu(I)
by olefin C=C bond and pyridine type nitrogen atom on-
ly.
However, corresponding Ag(I) π-complexes with
tertrazoles appeared to be unknown. In order to study 5-
(allylthio)-1-phenyl tetrazoles coordination behavior re-
garding to silver(I) ion we have obtained crystalline
[Ag2(atpt)2(H2O)2](BF4)2 (1) (atpt – 5-(allylthio)-1-
phenyl-1H-tetrazole (C10H10N4S)) and [Ag(atcpt)(NO3)]
(2) π-complexes and performed their single crystal X-ray
structure characterization.
2. Experimental Section
2. 1. Synthesis of C10H10N4S and C10H9ClN4S
The target ligands IV (C10H10N4S (a) and C10H9Cl-
N4S (b)) were synthesized from commercially available
aniline (I a) and 4-chloroaniline (I b) by several procedu-
res (Scheme 1). Appropriated 4-R-aniline I was converted
into 4-R-isothiocyanatobenzene II by the reaction with
dithioxomethane and the following treatment with ethyl
chlorocarbonate and HCl according to the modified Kalu-
za method.7 By 1,3-dipolar cycloaddition reaction of the
obtained isothiocyanatobenzene II with azide ion, 1-(4-R-
phenyl)-1H-tetrazole-5-thiol III was formed and readily
reacted with 3-bromoprop-1-ene in the presence of KOH
yielding corresponding ligand IV.8,9
Scheme 1. Synthesis of C10H10N4S and C10H9ClN4S.
2. 2. Preparation of
[Ag2(C10H10N4S)2(H2O)2](BF4)2
To a solution of C10H10N4S (0.8 mmol) in 1.5 mL of
methanol Ag2CO3 precipitate (0.3 mmol) was added at
room temperature. The suspension acidity was adjusted to
pH∼3 using HBF4 (AgBF4 appeared in situ).
10 A white-red
precipitate is formed. Keeping of the reactor at room tem-
perature during 24 h led to colorless crystals of
[Ag2(C10H10N4S)2(H2O)2](BF4)2 which have appeared on
the precipitate surface.
2. 3. Preparation of [Ag(C10H9ClN4S)(NO3)]
The solutions of C10H9ClN4S (0.8 mmol) in 0.5 mL
of methanol and AgNO3 (0.8 mmol) in 0.8 mL of water-
methanol (0.5 mL of CH3OH and 0.3 mL of H2O) prepa-
red at 60 °C were mixed and microcrystalline powder of 2
appeared after slow cooling to room temperature. A for-
mation of colorless prismatic crystals of [Ag(C10H9Cl-
N4S)(NO3)] (2) was observed after keeping of the reactor
at –6 °C over 48 h.
3. X–Ray Crystal Structure 
Determination
The crystallographic parameters and summaries of
data collection for 1 and 2 are represented in Table 1. Sin-
gle-crystal data were collected on a Rigaku AFC7 diffrac-
tometer equipped with a Mercury CCD area detector, us-
ing graphite monochromatized MoKα radiation. Data we-
re treated using the Rigaku CrystalClear software suite
program package.11 Both structures were solved by direct
methods using SIR-92 and SHELXS-97 programs (teXan
crystallographic software package of Molecular Structure
Corporation) and refined with SHELXL-97 software, im-
plemented in program package WinGX.12–16 In both struc-
tures non-hydrogen atoms were found by direct methods.
Full–matrix least–squares refinements based on F2 were
carried out for the positional and thermal parameters for all
non-hydrogen atoms. For 1 and 2 structures positions of H
atoms were treated as riding atoms and refined with C–H
fixed distances and with Uiso(H) values of 1.2Ueq(C). The
figures were prepared using DIAMOND 3.1 software.17
4. Results and Discussion
In the crystal structure of [Ag2(atpt)2(H2O)2](BF4)2
(1) atpt molecule is coordinated to Ag(I) atom through a
C=C-bond of the allyl group and two nucleophilic N
Figure 1. Fragment of crystal structure 1. Symmetry code: (i) –x,
–y, 2–z. Hydrogen O–H···F bonds are depicted as dot lines.
136 Acta Chim. Slov. 2011, 58, 134–138
Slyvka et al.:  First Silver(I) – Complexes with Tetrazole Allyl Derivatives. Synthesis and Crystal Structure of ...
atoms of tetrazole ring (Fig. 1). As in the earlier studied
[Cu2(atcpt)2(H2O)2](NO3)2 · C2H5OH (3) and [Cu3(atcpt)
Cl3] (4) π-complexes with Cu(I),
6 Ag(I) atoms in 1 pos-
sess trigonal pyramidal coordination environment arran-
ged by two N3 and N4 atoms of adjacent tetrazole core
and the C=C bond from the S-allyl group. The apical posi-
tion of the metal coordination polyhedron is occupied by a
water molecule (Figure 1, Table 2). 
Table 2. Selected bond length (in Å) and angle (in deg) values in
the 1 structure.
Ag–C(9)i 2.385(5) N(3)–Ag–m 138.9(2)
Ag–C(10)i 2.340(6) N(4)i–Ag–m 101.8(2)
Ag–m [a] 2.265(6) O–Ag–m 109.5(2)
Ag–N(3) 2.246(5) N(3)–Ag–N(4)i 114.1(2)
Ag–N(4)i 2.298(5) N(3)–Ag–O 85.1(2)
Ag–O 2.438(6) N(4)i–Ag–O 98.4(2)
C(9)=C(10) 1.346(8) C(9)i–Ag–C(10)i 33.1(2)
C(8)–C(9) 1.491(9) C(10)=C(9)–C(8) 124.0(6)
Symmetry code: (i) –x, –y, 2–z.
[a] m – middle point of C(9)=C(10) bond. 
So, in the case of AgBF4 (1) the organic ligand is at-
tached to silver(I) atoms almost by its entire coordinating
active sites similarly that in 3 and 4. The atpt acts as a tri-
dentate N,N,(S-C3H5) chelate-bridging ligand connecting
two Ag(I) atoms into centrosymmetric cationic
[Ag2(atpt)2(H2O)2]
2+ dimers with one almost planar six-
membered {Ag2N4} cycle and two seven-membered {Ag-
NC4S} rings. 
Essential role of coordinated water molecule in the
structure stabilizing is also observed. The H2O moiety
acts as a bridge between Ag+ cation and BF4
– anion by
means of H···F hydrogen contacts,18,19 which occur bet-
ween the water hydrogen atoms and fluorine atoms of
BF4
– anion ((Ow)H(11)···F(1) 1.95 Å, (Ow)H(12)···F(2)
1.92 Å). So, the H2O molecule in 1 plays similar bridging
role to that in earlier studied structure of [Cu2(atcpt)2
(H2O)2](NO3)2 · C2H5OH (3),
6 where the water bridge
connects Cu+ cation and NO3
– anion.
Although Ag(I) atom is deviated by 0.29 Å from the
base of the trigonal pyramid, and the distance Ag–m (m is
a middle point of C=C bond) is equal to 2.265(6) Å, a no-
ticeable difference between Ag–C(9) (2.385(5) Å) and
Ag–C(10) (2.340(6) Å) bonds lengths, as well as rather
Table 1. Crystal data and structure refinement for the compounds 1–3[a].
1 2
Empirical formula C20H24Ag2N8O2S2 · 2(BF4) C10H9AgClN5O3S
Formula weight 861.97 g/mol 422.60 g/mol
Temperature, K 200(2) 200(2) 
Wavelength 0.71069 Å 0.71069 Å
Crystal system, space group monoclinic, P21/n monoclinic, P21/a
Unit cell dimensions, Å
a, Å 10.4560(5) 8.6790(8) 
b, Å 11.4008(5) 13.7324(10) 
c, Å 12.7550(7) 12.4597(13) 
α, ° 90.00 90.00
β, ° 98.128(3) 102.288(5)
γ, ° 90.00 90.00
V, Å3 1505.21(13) 1451.0(2) 
Z 2 4
Calculated density, g/cm3 1.90 1.94
Absorption coeff., mm–1 1.53 1.73 
F(000) 848 832
Crystal size, mm 0.1 × 0.08 × 0.07 0.1 × 0.1 × 0.08
Color colorless colorless
Theta range for data collection 2–29 deg 2–29 deg
Limiting indices –13 ≤ h ≤ 14, –14 ≤ k ≤ 14, –17 ≤ l ≤ 17 –11 ≤ h ≤ 8, –15 ≤ k ≤ 17, –9 ≤ l ≤ 16
Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2
Measured reflections 12077 6495
Used in refinement 3435 3370
Free parameters 199 190
Goodness-of-fit on F2 1.17 1.049
R indices R1 = 0.069, wR1 =0.1493 R1 = 0.0995, wR1 = 0.3362
Largest diff. peak and hole 1.27 and –0.75 e Å–3 1.54 and –1.11 e Å–3
[a] CCDC 772787, 792001 contain the supplementary crystallographic data for this paper. Copies of the data can be obtained free of charge on
applications to the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: int.code+(1223)336–033; e–mail for inquiry: fileserv-
@ccdc.cam.ac.uk).
137
large angle between olefin C=C bond and the base of the
trigonal pyramid of 12.37, indicate the less effective
Ag–(C=C) π-interaction comparatively to Cu(I)–(C=C)
ones in 3 and 4. Similar tendency was also observed
among analogous Ag(I) and Cu(I) π-complexes.20–23
Use atcpt instead of atcpt in the presence of NO3
–
anion leads to a quite different structure of [Ag(atcpt)
(NO3)] (2) π-complex. More covalent character of
Ag+–O(NO2
–) interaction in comparison to ionic
Ag+···BF4
– one promotes participation of O atoms in the
silver(I) coordination. Thus, in crystal structure of 2 Ag(I)
possesses a trigonal-pyramidal coordination environment
comprising the two O atoms from different NO3
– anions,
the only nitrogen atom from the ligand moiety and the
C=C-bond from another ligand molecule at the apical po-
sition (Figure 3, Table 3). Nitrate anions play a role of
pseudo-halide bridge connecting Ag+ ions into infinite
chains {AgNO3}n.
One may note that location of the olefin group at the
apical position in the silver surrounding appears to be very
unusual and indicates a weakness of Ag–(C=C) π-interaction.
Atcpt molecule acts as a bidentate N,(S–C3H5)– bridging li-
Acta Chim. Slov. 2011, 58, 134–138
Slyvka et al.:  First Silver(I) – Complexes with Tetrazole Allyl Derivatives. Synthesis and Crystal Structure of ...
Figure 2. Mutual orientation of topological units in crystal structu-
re of [Ag2(atpt)2(H2O)2](BF4)2.
Figure 3. Fragment of structure 2. Symmetry codes: (i) 0.5 + x, 0.5
– y, z; (ii) –0.5 + x, 0.5 – y, z.
Figure 4. Projection of 2 crystal structure on yz plane.
Table 3. Selected bond length (in Å) and angle (in deg) values in
the 2 structure.
Ag–C(9)i 2.853(14) N(4)–Ag–m 97.00(22)
Ag–C(10)i 2.770(20) O(3)–Ag–m 87.04(18)
Ag–m [a] 2.745(18) N(4)–Ag–O(3) 117.7(3)
Ag–N(4) 2.311(9) N(4)–Ag–O(3)ii 106.0(3)
Ag–O(3)ii 2.353(8) O(3)–Ag–O(3)ii 134.6(3)
Ag–O(3) 2.408(7) C(9)i–Ag–C(10)i 25.0(5)
C(9)=C(10) 1.22(2) C(10)=C(9)–C(8) 127.9(18)
Symmetry codes: (i) 0.5 + x, 0.5 – y, z; (ii) –0.5 + x, 0.5 – y, z.
[a] m – middle point of C(9)=C(10) bond.
138 Acta Chim. Slov. 2011, 58, 134–138
Slyvka et al.:  First Silver(I) – Complexes with Tetrazole Allyl Derivatives. Synthesis and Crystal Structure of ...
gand, additionally connecting Ag(I) atoms in {AgNO3}n
chains. Crystal packing of 2 is shown in Figure 4.
5. Acknolegment
The authors thank the Slovenian Research Agency
(ARRS) and Ukrainian Ministry for Science and Higher
Education for financial support.
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Povzetek
Iz srebrovega karbonata in organskih ligandov smo pripravili kristalini~na π-kompleksa srebra(I) [Ag2(atpt)2
(H2O)2](BF4)2 (1) (atpt – 5-(aliltio)-1-fenil-1H-tetrazol (C10H10N4S)) in [Ag(atcpt)(NO3)] (2) (atcpt – 5-(aliltio)-1-(4-
klorofenil)-1H-tetrazol (C10H9ClN4S)). Dobljeni spojini smo okarakterizirali z rentgensko strukturno analizo: za 1 je
prostorska skupina P21/n, a = 10.4560(5), b = 11.4008(5), c = 12.7550(7) A, β = 98.128(3)°, V = 1505.21(13) A
3 pri
200 K, Z = 2; za 2: prostorska skupina P21/a, a = 8.6790(8), b = 13.7324(10), c = 12.4597(13) A, α = 102.288(5)°, V =
1451.0(2) A3 pri 200 K, Z = 4. V obeh strukturah je koordinacijski polieder srebra(I) trikotna piramida, vendar je na~in
koordinacije organskega liganda razli~en. V spojini 1 sta na vsak atom srebra koordinirana N3 in N4 atom iz dveh so-
sednjih atpt molekul, olefinska C=C vez in v apikalnem polo`aju molekula vode. V kristalni strukturi spojine 2 dva ek-
vatorialna polo`aja v koordinacijskem poliedru srebra(I) zavzemata kisikova atoma dveh razli~nih NO3
– anionov, mole-
kula atcpt pa je na kovinski atom koordinirana le preko N4 atoma tetrazolovega obro~a. V apikalnem polo`aju je na
Ag(I) {ibko vezana C=C vez.