ORI GIN AL PA PER

Synthesis and Structures of Silver(I) and Copper(I)3,5-Dipentyl-1,2,4-Triazolates

Wen-Hua Zhang • Yong-Hui Wang • Ya-Wei Li •

Guang Yang

Received: 21 October 2011 / Published online: 7 February 2012

� Springer Science+Business Media, LLC 2012

Abstract The Ag(I) and Cu(I) complexes of 4-amino-3,5-dipentyl-4H-1,2,4-tria-

zole (4-NH2-3,5-(C5H11)2tz) and 3,5-dipentyl-1H-1,2,4-triazole (3,5-(C5H11)2tzH)

have been synthesized and characterized. X-Ray analysis shows that {Ag4[4-NH2-

3,5-(C5H11)2tz]6}(BF4)4 is a tetranuclear complex featuring an Ag4tz6 cluster;

{Ag[3,5-(C5H11)2tz]}n exhibits a 3D structure of lvt-a topology; and {Cu2[3,5-

(C5H11)2tz]Br}n is a Cu4Br4-cluster based 3D complex with the dia topology.

Keywords Silver � Copper � Triazole � Synthesis � Structure � Cu4Br4 cluster

Introduction

During the past several years, there has been considerable interest in the metal–

organic frameworks (MOFs) constructed by metals and 1,2,4-triazoles (3-R1,5-R2-

tzH, R1 and R2 denotes 3,5-substituents) [1–3]. We and others have observed a

prominent ‘‘structure effect’’ of 3,5-substituents even if they are only non-

coordinative hydrocarbons; the structures of metal—triazole complexes are, more or

less, dictated by the shape/size of the 3,5-substituents [4–10]. In the study of the

silver(I) adducts with 4-amino-3,5-disubstituted-4H-1,2,4-triazoles, we were able to

distinguish two types of tetranuclear Ag4tz6 clusters (Ag4tz6-a and Ag4tz6-b) based

Electronic supplementary material The online version of this article (doi:10.1007/s10876-012-0445-3)

contains supplementary material, which is available to authorized users.

W.-H. Zhang � Y.-W. Li � G. Yang (&)

Department of Chemistry, Zhengzhou University, Zhengzhou 450001, China

e-mail: yang@zzu.edu.cn

Y.-H. Wang

The Centre of Supervision and Inspection of Quality and Technique at Sanmenxia,

Sanmenxia 472000, China

123

J Clust Sci (2012) 23:411–420

DOI 10.1007/s10876-012-0445-3

on their crystal structure data. We found the shape/size of the 3,5-substituents is the

key factor to determine which type of cluster can be formed [4, 5]. For a series of

binary silver(I) triazolates–Ag(3,5-R2tz), the structural diversity shown has been

suggested to be associated with the shape/size of the 3,5-substituents, which might

act as ‘‘templates’’ to organize the silver—triazole skeletons [6]. Chen et al.

observed that the 3,5-substituents have influence on the dihedral angles between

adjacent Cu2tz2 secondary building units (SBUs), which in turn determine the

structures of Cu(3,5-R2tz) [7, 11].

As far as we know, triazoles carrying 3,5-alkyl groups such as methyl, ethyl,

propyl and butyl have been used to prepare metal complexes. However, little has

been known on the metal complexes with triazoles bearing even bulkier 3,5-alkyls.

In view of the ‘‘structure effect’’ of 3,5-substituents, we extended our research to

cover the pentyl group as 3,5-substituents on the triazole ring, as one part of our

systematic investigation of the coordination chemistry of 1,2,4-triazoles. As far as

we know, 3,5-dipentyl-1H-1,2,4-triazole was once briefly mentioned in a patent

as intermediate in preparation of an antagonist [12]. In this paper, we report

the synthesis of 4-amino-3,5-dipentyl-4H-1,2,4-triazole (4-NH2-3,5-(C5H11)2tz)

and 3,5-dipentyl-1H-1,2,4-triazole (3,5-(C5H11)2tzH), as well as the structures of

three metal complexes, namely {Ag4[4-NH2-3,5-(C5H11)2tz]6}(BF4)4 (1), {Ag[3,5-

(C5H11)2tz]}n (2) and {Cu2[3,5-(C5H11)2tz]Br}n (3).

Results and Discussion

Synthesis and Characterization

4-NH2-3,5-(C5H11)2tz was prepared according to a literature method [13]. 3,5-

(C5H11)2tzH was obtained by deamination of the corresponding 4-amino-triazoles.

Hypophosphorous acid was used, instead of hydrochloric acid, in the deamination

step to improve the yield [14]. The identities of these two compounds have been

verified by the elemental analysis and their 1H NMR spectra (Figs. S1 and S2). The

synthetic route is shown in Scheme 1.

The complexes 1 and 2 were prepared in a straightforward way by mixing the

appropriate silver salts with triazoles; ammonia is needed to deprotonate triazole for

preparation of 2. On the other hand, the complex 3 was obtained hydrothermally

from 3,5-(C5H11)2tzH and CuBr2. Under the hydrothermal conditions, CuII was

reduced to CuI and triazole deprotonated although no base was added to the reaction

system; similar phenomenon has also been observed by Zubieta and his coworkers

[15].

The characteristic peak of BF4- shows itself at 1,083 cm-1 in the IR spectrum of

1. The molar conductivity of 1 was measured to be 476 S cm2 mol-1 in MeCN at

20 �C, indicative of a 1:4 type of electrolyte [16], which coincides with its crystal

structure. It is noteworthy that the vibrational peaks of N–H stretch (3,143 cm-1)

and N–H bend (1,571 cm-1) in the IR spectrum of 3,5-(C5H11)2tzH are absent in the

IR spectra of its metal complexes 2 and 3, indicating the ligand is present in the

deprotonated triazolate form. (Figs. S4, S5, S6, S7, S8).

412 W.-H. Zhang et al.

123

Crystal Structures

{Ag4[4-NH2-3,5-(C5H11)2tz]6}(BF4)4 (1) is a tetranuclear complex, featuring the

Ag4tz6-a cluster (Fig. 1). In our previous papers, we have been able to recognize

two types of Ag4tz6 cluster motifs–Ag4tz6-a and Ag4tz6-b, based on the crystal

structures of the silver-triazole complexes [4, 5]. The Ag4tz6-a cluster can be

derived from an Ag4tz4 metallacyle, further associated by two additional triazoles

upper and down the Ag4 plane. This structural motif has been observed previously

in some silver(I) adducts with 4-amino-3,5-disubstitued-1,2,4-4H-triazoles such as

[Ag4(4-NH2-3,5-iPr2tz)6]X4 (4-NH2-3,5-iPr2-tz = 4-amino-3,5-diisopropyl-4H-

1,2,4-triazole; X = ClO4- or BF4

-) and [Ag4(4-NH2-3,5-Et2tz)6]X4 (4-NH2-3,5-

Et2tz = 4-amino-3,5-diethyl-4H-1,2,4-triazole; X = ClO4- or CF3SO3

-), as well

as in silver(I) 3,5-diphenyl-1,2,4-triazolate (Ag(3,5-Ph2tz)) as the secondary

building unit (SBU) [4–6]. We have noticed that in cases where anions do not

participate in the coordination, the sizes/shapes of 3,5-substituents would impart a

substantial influence on which type of Ag4tz6 motif can be adopted. Usually larger

substituents such as ethyl, isopropyl and pentyl (in this work) would favor an

Ag4tz6-a motif in order to minimize the steric repulsion. The present structure thus

provides a further example to show the structure effect of 3,5-substituents.

{Ag[3,5-(C5H11)2tz]}n (2) crystallizes in the tetragonal space group I41/a and

exhibits a 3D structure. The asymmetric unit consists of one Ag(I) atom and one

3,5-dipentyl triazole molecule. The Ag(I) atom is roughly triangular three-

coordinated and the triazolato anion adopts a l3-N1,N2,N4 bridging mode (Fig. 2a).

Two Ag atoms and two triazolato anions form an Ag2tz2 subunit featuring an

(Ag–N–N)2 ring. The Ag2tz2 subunit is linked with four adjacent Ag2tz2-SBUs from

two Ag atoms and two N4 atoms of triazoles to give rise to the 3D structure

(Fig. 2b). If we take the Ag2tz2-SBU as a square planar 4-connected node, then the

net underlying the crystal structure of {Ag[3,5-(C5H11)2tz]}n is the lvt net [17–20].

The 3D structure of 2 can also be derived from the 41 infinite helices formed by

Ag atoms, N1 (N2) and N4 of triazoles. The 41 infinite helix extends along the c-axis

and each is of the opposite handedness than its four nearest neighbors. Further

Scheme 1 Synthetic route for 3,5-(C5H11)2tzH

Synthesis and Structures of Silver(I) 413

123

connection of the helices via Ag–N2 (N1) bonds affords the 3D structure of {Ag[3,5-

(C5H11)2tz]}n (Fig. 2b). If both the Ag atom and the triazolato ligand are regarded as

the topologically equivalent three-connected nodes, the structure of {Ag[3,5-

(C5H11)2tz]}n can also be simplified as the lvt-a net [17–20].

PLATON analysis shows the porosity of {Ag[3,5-(C5H11)2tz]}n is only 1.6%; the

voids in Ag-tz skeleton are actually occupied by the pentyl groups. This observation

again supports our hypothesis that 3,5-substituents might act as ‘‘templates’’ to

organize the Ag-tz skeleton during the formation of the MOF structure [6]. It is not

surprising to note that {Ag[3,5-(C5H11)2tz]}n is isostructural to our recently reported

[Cu(3,5-Bu2tz)]n, because of the similarity in the coordination chemistry between

Cu(I) and Ag(I) [11]. Checking the M–N distances, we found that the Ag–N

distances are longer than those of Cu–N (2.18–2.25 A vs. 1.95–2.00 A). Therefore

the voids in Ag-tz skeleton should be larger than those in Cu-tz skeleton if both take

the same or similar structure, that is to say, the Ag-tz skeleton can accommodate

larger substituents compared with the substituents dwelled in the Cu-tz skeleton

(C5H11– for Agtz vs C4H9– for Cutz).

TG/DSC measurement shows that {Ag[3,5-(C5H11)2tz]}n is stable up to ca

268 �C under air (Fig. S9). Before the decomposition of the complexes, DSC curve

shows one endothermic peak at 235 �C, which may be indicative of possible phase

transition or structural modification occurring during the measurement. Above

268 �C, this complex experiences successive weight losses, corresponding to the

decomposition of triazolato ligands. The final residue accounts for 34.5% of the

total mass, suggesting the residue might be Ag, based on the calculated residual

percentage (34.1%).

{Cu2[3,5-(C5H11)2tz]Br}n (3) crystallizes in the tetragonal space group I41/a and

exhibits a 3D metal–organic framework (MOF) structure. The asymmetric unit

consists of two crystallographically independent copper(I) atoms (Cu1 and Cu2),

one Br atom and one triazolato ligand. The triazolato ligand adopts l3-N1, N2, N4

bridging mode and the bromide ion acts as the l4 mono-atomic ligand to connect

four Cu atoms (one Cu1 and three Cu2 atoms) to form an irregular polyhedron

Fig. 1 Ball-and-stick diagramof the Ag4tz6-a cluster in thecrystal structure of {Ag4[4-NH2-3,5-(C5H11)2tz]6}(BF4)4. The3,5-pentyl groups and H-atomshave been omitted for clarity

414 W.-H. Zhang et al.

123

(Fig. 3). Cu1 atom is three-coordinated by a N2 atom, N4 atom of triazoles and a Br

atom with the coordination geometry being nearly T-shaped. The Cu1-Br distance is

2.851(1) A, which is much longer than that observed for usual Cu-Br bond (ca

2.4 A), however, still less than the sum of the van der Waals radii for the Cu and Br

atoms (3.25 A) [21]. On the other hand, Cu2 atom is tetrahedrally four-coordinated

by three Br atoms and a N1 atom of triazole, with the Cu2-Br distances being

2.393(1), 2.577(1), and 2.702(1) A, respectively.

The most interesting feature for 3 is the presence of a Cu4I Br4 cluster, formed by

four Cu2 atoms and four Br atoms (Fig. 3a). This cluster can be described as a

distorted cubane, with two types of atoms being located alternatively on the vertices

of the cubane. The distortion of the cubane can be imaginarily achieved by pulling

Fig. 2 a ORTEP diagram of a fragment of {Ag[3,5-(C5H11)2tz]}n, showing the coordinationenvironment around the Ag atom. Selected distances (A) and angles (�): Ag1-N1 = 2.223(5), Ag1-N2a = 2.181(5), Ag1-N3b = 2.253(5); N2a-Ag1-N1 = 131.4(2), N2a-Ag1-N3b = 116.8(2), N1-Ag1-N3b = 110.4(2). Symmetry codes: a) y ? 1/4, -x ? 5/4, z ? 1/4; b) -y ? 3/4, x-1/4, -z ? 7/4.b Packing diagram of {Ag[3,5-(C5H11)2tz]}n viewed down the c-axis. The pentyl groups have beenomitted for clarity

Synthesis and Structures of Silver(I) 415

123

the Br vertices a little bit out of the body of a suppositional regular Cu4Br4 cubane.

The Cu���Cu distances within the cubane are 2.994(1) and 3.022(1) A, which are

longer than the sum of the van der Waals radii for the Cu atoms (2.80 A) [21],

indicative of no or very weak CuI���CuI interaction. The structural chemistry of

Cu4X4 cluster (X = Cl-, Br-, I-) and some other types of copper(I) halide cluster

has been recently reviewed by Li et al. [22].

Each pair of Cu4Br4 clusters are doubly bridged by two Cu1 atoms and two

triazolates, as shown in Fig. 3b. In this way, each Cu4Br4 cluster is linked to its four

nearest Cu4Br4 clusters to form the 3D structure (Fig. S10). Topologically, we can

regard the Cu4Br4 cluster as tetrahedrally four-connected node and the double

bridges between two neighboring Cu4Br4 clusters as a single linker, then, the

structure of 3 can be simplified to the dia net [17–20].

Fig. 3 a Ball-and-stick diagram of the Cu4Br4 cluster in {Cu2[3,5-(C5H11)2tz]Br}n. Selected distances(A) and angles (�): Cu2-Br1 = 2.702(1), Cu2- Br1b = 2.577(1), Cu2-Br1c = 2.393(1); Br1c-Cu2-Br1b = 110.74(2), Br1c-Cu2-Br1 = 104.28(2), Br1b-Cu2-Br1 = 101.58(2). b A fragment of 3 withatom labels, showing the coordination geometries around Cu1 and Cu2 atoms and how two adjacentCu4Br4 clusters are doubly linked. Selected distances (A) and angles (�): Cu1-Br1 = 2.851(1),Cu1-N3 = 1.884(3), Cu1-N2d = 1.893(3); Cu2a-N1d = 1.970(3); N3-Cu1-N2d = 160.92(12),N3-Cu1-Br1 = 101.02(9), N2d-Cu1-Br1 = 97.76(9). Symmetry codes: a y-1/4, -x ? 1/4, -z ? 1/4;b -y ? 1/4, x ? 1/4, -z ? 1/4; c -x, -y ? 1/2, z; d y ? 1/4, -x ? 1/4, z ? 1/4. The pentyl groupshave been omitted for clarity

416 W.-H. Zhang et al.

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Experimental Section

The CHN microanalyses were carried out with a Flash EA 1112 elemental analyzer.

IR spectra (KBr pellets) were recorded on a Nicolet Impact 420 FT-IR spectrometer.1H NMR spectra were recorded on a Bruker DPX-400 spectrometer. Thermogravi-

metry and differential scanning calorimetry were measured on a NETZSCH STA

409 PC system in static air at a scanning rate of 10 �C min-1. All reagents were

purchased from commercial sources.

Synthesis of 4-Amino-3,5-Dipentyl-4H-1,2,4-Triazole (4-NH2-3,5-(C5H11)2tz)

n-Hexanoic acid (0.02 mol, 2.5 mL) and 80% hydrazine (0.024 mol, 1.5 mL) were

sealed in a Teflon-lined autoclave and heated in an oven at 180 �C for 72 h. The

resulted waxy solid was dissolved in water and the mixture was neutralized with

diluted HCl until pH = 7. After filtered, the residue was washed with Et2O and the

resulted solid was recrystallized from CH2Cl2 to afford colorless sheets in 43%

yield. M.p. 156–158 �C. Anal. Calcd. for C12H24N4: C, 64.24; H, 10.78; N, 24.97%.

Found: C, 64.71; H, 11.19; N, 25.82%. IR (KBr pellet, cm-1): 3240(s), 3112(s),

2956(s), 1656(m), 1523(s), 1466(s), 1379(m), 1340(w), 1310(w), 1115(m), 980(m),

728(m). 1H NMR (ppm, CDCl3): d = 0.92 (t, 6H, –CH3e), 1.34 (m, 8H, –CH2

c– and

–CH2d–), 1.76 (m, 4H, –CH2

b–), 2.75 (t, 4H, –CH2a–), 4.54 (s, 2H, –NH2). For the

assignment of 1H-NMR resonances see Fig. S1.

Synthesis of 3,5-Dipentyl-1H-1,2,4-Triazole (3,5-(C5H11)2tzH)

To a stirred solution of 4-NH2-3,5-(C5H11)2tz (0.015 mol, 3.36 g) in 30%

hypophosphorous acid (75 mL), an aqueous solution (15 mL) of sodium nitrite

(0.075 mol, 5.19 g) was added slowly with the temperature being maintained at

20 �C. During this process vigorous N2 evolution was observed and the mixture was

stirred for one more hour at the same temperature until the bubbles ceased to form.

Then the pH of the obtained solution was adjusted to ca 7 by a diluted solution of

NaOH, white precipitate formed. After filtration, the residue was recrystallized from

MeOH-H2O (1:1). Yield: 83%. M.p. 61–63 �C. Anal. Calcd. for C12H23N3: C,

68.85; H, 11.07; N, 20.07%. Found: C, 68.57; H, 11.29; N, 19.91%. IR (KBr, cm-1):

3143(m), 2954(s), 1865(m), 1571(s), 1508(s), 1464(s), 1333(m), 1293(m), 1193(w),

1067(s), 954(m), 729(m). 1H NMR (ppm, CDCl3): d = 0.88 (t, 6H, –CH3e), 1.34

(t, 8H, –CH2c– a nd –CH2

d–), 1.75 (m, 4H, –CH2b–), 2.74 (t, 4H, –CH2

a–). For the

assignment of 1H-NMR resonances see Fig. S2.

{Ag4[4-NH2-3,5-(C5H11)2tz]6}(BF4)4 (1)

An ethanol solution (2 mL) of 4-NH2-3,5-(C5H11)2tz (0.05 mmol, 0.0112 g) was

layered on the surface of an aqueous solution of AgBF4 (0.05 mmol, 0.0097 g) in a

test tube. Colorless prismatic crystals of 1 were obtained within several days. Yield:

42%. Anal. Calcd. for C72H144N24Ag4B4F16: C, 40.70; H, 6.83; N, 15.82%. Found:

C,40.54; H, 6.90; N, 15.76%. IR (KBr pellet, cm-1): 3243(m), 3113(w), 2956(s),

Synthesis and Structures of Silver(I) 417

123

2931(s), 1536(w), 1524(m), 1466(m), 1083(s), 733(w), 533(m), 522(m). 1H NMR

(ppm, DMSO-d6): d = 0.87 (t, 6H, –CH3e), 1.31 (m, 8H, –CH2

c– and –CH2d–), 1.678

(m, 4H, –CH2b–), 2.740 (t, 4H, –CH2

a–), 5.97 (s, 2H, –NH2).

{Ag[3,5-(C5H11)2tz]}n (2)

A solution of AgNO3 (0.01 mmol, 0.0017 g) in 2 mL of 25% aqueous ammonia was

mixed with a methanol solution (2 mL) of 3,5-(C5H11)2-tzH (0.01 mmol, 0.0021 g).

The resulting solution was allowed to evaporate slowly to produce colorless blocks

of 2 in 62% yield within a couple of days, suitable for X-ray work. Anal. Calcd. for

C12H22N3Ag: C, 45.58; H, 7.01; N, 13.29%. Found: C, 45.52; H, 7.14; N, 13.00%.

IR (KBr pellet, cm-1): 2928(s), 1493(s), 1360(s), 1262(w), 1232(w), 1184(w),

1081(m), 969(m), 812(m), 726(m).

{Cu2[3,5-(C5H11)2tz]Br}n (3)

3,5-(C5H11)2-tzH (0.05 mmol, 0.0104 g) and CuBr2 (0.05 mmol, 0.0111 g) were

dissolved in 4 mL of water. The mixture was sealed in a Teflon-lined autoclave and

heated in an oven at 180 �C for 72 h and then slowly cooled to room temperature.

Colorless crystals of 3 were obtained in 39% yield. Anal. Calcd. for

C12H22N3Cu2Br: C, 34.70; H, 5.34; N, 10.12%. Found: C, 34.76; H, 5.41; N,

10.13%. IR (KBr pellet, cm-1): 2956(s), 2926(s), 2854(s), 1509(s), 1464(m),

1375(m), 1083(w), 727(w).

X-ray Structure Determination

Diffraction intensities were collected on a Rigaku Saturn 724 diffractometer (for 1),

Rigaku RAXIS IV imaging plate diffractometer (for 2) and Bruker SMART APEX

II diffractometer (for 3), with graphite-monochromated Mo-Ka radiation

(0.71073 A). Absorption corrections were applied by using the multiscan program.

The structures were solved by direct methods and refined by least square techniques

using the SHELXS-97 and SHELXL-97 programs [23]. All non-hydrogen atoms

were refined with anisotropic displacement parameters; hydrogen atoms were

generated geometrically.

Owing to the poor quality of crystal data of 1, only a preliminary structure

analysis was carried out. However, the stoichiometry and heavy atom positions were

unequivocally determined. For 1: C72H144N24Ag4B4F16, Orthorhombic, Pna21,

a = 26.492(5), b = 21.231(4), c = 53.854(1) A, V = 30290(10) A3, S = 1.460,

R1 = 0.2254 for 64297 reflections with I [ 2r(I) and 1361 parameters. The

crystallographic data of 2 and 3 are listed in Table 1.

CCDC 849696 and 849697 contain the supplementary crystallographic data for 2and 3. These data can be obtained free of charge from The Cambridge

Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

418 W.-H. Zhang et al.

123

Acknowledgments This work has been supported by the NSF of China (No. 21071126 and

No. J0830412) and a research grant for undergraduate students of Zhengzhou University.

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Table 1 Crystal data for 2 and

32 3

Formula C12H22N3Ag C12H22BrCu2N3

Mr 316.20 415.32

Crystal size (mm3) 0.18 9 0.17 9 0.16 0.14 9 0.13 9 0.11

Crystal system Tetragonal Tetragonal

Space group I41/a I41/a

a, A 19.029(3) 17.723(3)

b, A 19.029(3) 17.723(3)

c, A 16.790(3) 20.014(4)

a, deg 90 90

b, deg 90 90

c, deg 90 90

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Z 16 16

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l, mm-1 1.308 5.235

F (000), e 2592 3328

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-17 B k B 22 -22 B k B 22

-19 B l B 16 -26 B l B 19

Refl. coll./unique/Rint 9139/2663/0.0536 20438/3905/0.0923

Param. refined 146 165

Final R1/wR2

[I C 2 r (I)]0.0608/0.1395 0.0650/0.1719

GoF (F2) 1.190 0.956

Dqfin (max/min), eA-3 0.428/-0.398 0.605/-0.540

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