Synthesis, structures of novel zinc and copper compounds based on pyridazino[3,2-c]1,2,4-triazole derivatives

Article abstract of DOI:10.1016/j.molstruc.2008.11.030

Ligands 6-phenyl-3-(4′-pyridinyl) pyridazino[3,2-c]1,2,4-triazole (L¹), 6-phenyl-3-(3′-pyridinyl) pyridazino[3,2-c]1,2,4-triazole (L²) and 3,6-diphenyl pyridazino[3,2-c]1,2,4-triazole (L³) have been designed and synthesize

Full text of DOI:10.1016/j.molstruc.2008.11.030

Journal of Molecular Structure 920 (2009) 342–349
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis, structures of novel zinc and copper compounds based
on pyridazino[3,2-c]1,2,4-triazole derivatives
Dun Chen a, Duo-Zhi Wang a, Jian-Bin Zhang b, Ling-Hua Cao a,
*
a College of Chemistry and Chemical Engineering, Xinjiang University, 14 ShengLi road, Urumqi 830046, PR China
b Physics and Chemistry Test Center of Xinjiang University, Urumqi 830046, PR China
a r t i c l e i n f o
a b s t r a c t
Ligands 6-phenyl-3-(40-pyridinyl) pyridazino[3,2-c]1,2,4-triazole (L1), 6-phenyl-3-(30-pyridinyl) pyridaz-
ino[3,2-c]1,2,4-triazole (L2) and 3,6-diphenyl pyridazino[3,2-c]1,2,4-triazole (L3) have been designed and
synthesized. Reactions of these ligands with CuII, CuI and ZnII, five new metal–organic coordination com-
plexes were obtained. X-ray diffraction analyses show that complexes 1, 3 and 4 are mononuclear struc-
ture, 5 is trinuclear complex, while 2 possess 1D chain structure. Complexes 1, 3, 4 and 5 were further
assembled into infinite 1D structure by weak interactions, while 2 possesses noticeable weak interaction
between two CuI atoms bridged by iodine [CuIꢀ ꢀ ꢀCuI = 2.6616(13) Å] and was extended into 2D sheet by
Article history:
Received 27 September 2008
Received in revised form 11 November 2008
Accepted 13 November 2008
Available online 24 November 2008
Keywords:
Pyridazino[3,2-c]1,2,4-triazole
CuII/CuI/ZnII complex
Crystal structure
p p stacking interaction between adjacent chains. In addition, the steric hindrances of substituent prob-
ꢀ ꢀ ꢀ
ably weaken the coordination abilities of the pyridazine or triazole N donors.
Ó 2008 Elsevier B.V. All rights reserved.
1. Introduction
be a series of promising organic connectors in crystal engineering of
coordination complex due to the existence of reliable pyridyl groups
as well as triazole ring with rich coordination modes. Herein, we re-
port five new coordination complexes with the three ligands, which
display different crystal structures. [Cu(L1)(ClO4)Cl] (1), {[Cu(L2)I]}n
(2), [Cu(L3)(CH3OH)2(ClO4)2] (3), [Zn(L3)Cl2] (4), [Cu3(L3)Cl6] (5).
Complexes 1, 3 and 4 are mononuclear structure, 5 is trinuclear com-
plex, while 2 possess 1D chain structure and noticeable weak inter-
Over the past decades, the rational design and synthesis of me-
tal–organic supramolecular architectures are interesting and
important in producing new functional materials with desired
magnetic, catalytic, electric and fluorescent properties as well as
potential applications in ion exchange and gas storage [1–3]. Pre-
paring new promising materials by reaction of organic ligands
(as building blocks) with different metal ions (or metal clusters)
is one of the challenges in this area. The skillful selections of organ-
ic ligands and metal ions are pivotal role for designing reasonable
complexes [4].
action between CuI and CuI [2.6616(13) Å].
A systematic
investigation of the role of ligand conformation has also been carried
out based on this series of complexes (Chart 1).
In general, the coordination conformation of metal complexes
containing flexible ligands was less predictable due to the possible
occurrence of molecular isomerism involving the adoption of
different ligand conformations [5–8]. Therefore, to further extend
the attractive research, we prepared three new rigid ligands,
6-phenyl-3-(40-pyridinyl) pyridazino[3,2-c]1,2,4-triazole (L1), 6-
phenyl-3-(30-pyridinyl) pyridazino[3,2-c]1,2,4-triazole (L2) and
3,6-diphenyl pyridazino[3,2-c]1,2,4-triazole (L3), anticipating that
the rigidity of ligand may introduce additional structural constraint
in controlling the assembly of metal–organic complexes. We also
hope to reveal some structural factors of the ligands for dominating
the self-assembly, and the result may provide new information of
the spacer effect that such ligands exert on their coordination pref-
erences. In this context, three new ligands have also been proven to
2. Experimental
2.1. Materials and general methods
Solvents and starting materials for synthesis were purchased
commercially and used as received. 3-Phenyl-6-chloropyridazine
and L3 were prepared according to reported procedures [9]. IR
spectra were measured on a Brucker Equinox 55 FT-IR spectrome-
ter with KBr Pellets in the range of 4000–400 cmꢁ1. Elemental
analyses were performed on a Thermo Flash EA-1112 analyzer.
2.2. Preparation of ligands
2.2.1. Synthesis of L1 {6-phenyl-3-(40-pyridinyl) pyridazino[3,2-
c]1,2,4-triazole}
3-Phenyl-6-chloropyridazine (0.6 g, 0.003 mol) was dissolved in
1-butanol (15 mL), and isoniazide (0.42 g, 0.003 mol) was added to
* Corresponding author. Tel.: +86 991 8582809.
E-mail address: clhxj@xju.edu.cn (L.-H. Cao).
0022-2860/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2008.11.030

D. Chen et al. / Journal of Molecular Structure 920 (2009) 342–349
343
N
N
N
N
N
N
N
N
N
N
N
N
N
N
L1
L2
L3
Chart 1.
the above solution. The resulting solution was heated to refluxing
for 12 h, and then cooled to room temperature, filtered. A yellow
residue was obtained. The pure yellow product of L1 was separated
tion of L1 (7 mg, 0.025 mmol) in CHCl3 (8 mL). The system was left
for about 1 month at room temperature, and blue crystals were ob-
tained. Yield: 26.5%. Anal. Calcd for C64H44CuCl2N20O8: C, 56.70; H,
3.27; N, 20.66%. Found: C, 56.60; H, 3.24; N, 20.69%. IR (cmꢁ1, KBr
pellets): 3458vs, 3091s, 2704w, 2471w, 1636vs, 1558s, 1546vs,
1471s, 1457vs, 1336vs, 1286s, 1266m, 1222m, 1207m, 1163m,
1085vs, 999vs, 942w, 839vs, 774vs, 756vs, 744vs, 695vs, 668s,
624s, 593w.
isoniazid
L1
Cl
2.3.2. {[Cu(L2)I]}n (2)
N
N
A solution of CuI (19 mg, 0.10 mmol) in CH3CN (8 mL) was
added into a solution of L2 (6.8 mg, 0.025 mmol) in CHCl3 (8 mL).
The system was left for about 2 months at room temperature,
and yellow crystals were obtained. Yield: 19.3%. Anal. Calcd for
C16H11CuIN5: C, 41.44; H, 2.39; N, 15.10%. Found: C, 41.31; H,
2.41; N, 14.96%. IR (cmꢁ1, KBr pellets): 3595s, 3112m, 3049w,
2735s, 2659m, 1615s, 1589m, 1476m, 1356s, 1286m, 1056s,
965m, 900s, 820m, 756m, 723m, 650m.
nicotinic hydrazide
L2
(3-phenyl-6-chloropyridazine)
Chart 2.
by column chromatography on silica gel (EtOH/CH2Cl2). Yield:
48.3% (Chart 2).
2.2.2. Synthesis of L2 {6-phenyl-3-(30-pyridinyl) pyridazino[3,2-
c]1,2,4-triazole}
2.3.3. [Cu(L3)(CH3OH)2(ClO4)2] (3)
A solution of Cu(ClO4)2ꢀ6H2O (37 mg, 0.10 mmol) in CH3OH
(8 mL) was added into a solution of L3 (6.8 mg, 0.025 mmol) in
CH3OH (8 mL). The system was left for about 2 weeks at room tem-
perature, and blue crystals were obtained. Yield: 31%. Anal. Calcd
for C70H56CuCl2N16O10: C, 59.39; H, 3.99; N, 15.83%. Found: C,
59.43; H, 3.97; N, 15.79%. IR (cmꢁ1, KBr pellets): 3431s, 3121w,
3071w, 2986w, 1600m, 1554s, 1525m, 1469vs, 1454s, 1394m,
1368m, 1351vs, 1293m, 1095vs, 1011s, 950m, 821m, 769vs,
687vs, 622s, 569m, 485w.
The pure yellow product of L2 was obtained in the same way as
for L1 by using nicotinic hydrazide instead of isoniazide. Yield: 57%.
2.3. Synthesis of complexes 1–5
2.3.1. [Cu(L1)(ClO4)Cl] (1)
A solution of CuCl2ꢀ2H2O (17 mg, 0.10 mmol) and Cu(ClO4)2ꢀ
6H2O (37 mg, 0.10 mmol) in CH3OH (8 mL) was added into a solu-
Table 1
Crystallographic data and structure refinement summary for complexes 1–5.
1
2
3
4
5
Chemical formula
Formula weight
Crystal system
Space group
C64H44CuCl2N20O8
1355.63
Tetragonal
P4/n
C16H11CuIN5
463.7
C70H56CuCl2N16O10
1415.75
Monoclinic
P2(1)/c
C34H24ZnCl2N8
680.88
C68H48Cu3Cl6N16
1492.54
Triclinic
Triclinic
Triclinic
ꢀ
ꢀ
ꢀ
P1
P1
P1
T/K
293(2)
293(2)
293(2)
293(2)
293(2)
a/Å
b/Å
c/Å
17.023(2)
17.023(2)
11.384(2)
90
3298.7(9)
2
9.1024(18)
9.5071(19)
10.351(2)
72.00(3)
775.1(3)
2
10.1994(3)
15.2497(4)
20.3126(5)
100.4940(10)
3106.53(14)
2
10.256(2)
11.027(2)
13.684(3)
81.03(3)
1499.2(5)
2
11.936(2)
12.399(3)
12.949(3)
65.93(3)
1696.4(6)
1
b/°
V/Å3
Z
D/g cmꢁ3
1.365
0.482
1.987
3.406
1.514
0.516
1.508
1.038
1.461
1.222
l
/mmꢁ1
F(000)
1390
448
1462
696
757
Total/unique/Rint
24410/2915/0.0541
0.0732/0.2364
7678/3521/0.0389
0.0382/0.1271
24877/5778/0.0263
0.0443/0.1125
14401/6623/0.0284
0.0332/0.0961
16666/7630/0.0306
0.0631/0.2741
Ra/wRb
a
R =
wR = [
R
(||Fo| ꢁ |Fc||)/
R|Fo|.
b
R
w(|Fo|2 ꢁ |Fc|2)2/
R .
w(Fo2)]1/2

344
D. Chen et al. / Journal of Molecular Structure 920 (2009) 342–349
Table 2
C34H24ZnCl2N8: C, 59.98; H, 3.55; N, 16.46%. Found: C, 60.02; H,
3.53; N, 16.51%. IR (cmꢁ1, KBr pellets): 3606s, 3265m, 3001m,
2765w, 2224m, 1976m, 1653s, 1526s, 1456m, 1309m, 1228w,
1156vs, 1087s, 964m, 867m, 777m, 654s.
Selected bond lengths (Å) and angles (°) for complexes 1–5.
Complex 1
Cl(2)ACu(1)
N(5)ACu(1)ACl(2)
N(5)#2ACu(1)AN(5)#3
2.390(3)
98.56(10)
88.73(3)
Cu(1)AN(5)#2
N(5)ACu(1)AN(5)#2
2.042(3)
162.9(2)
2.3.5. [Cu3(L3)Cl6] (5)
Complex 2
Blue crystals of 5 suitable for X-ray analysis were obtained by
the similar method described for 3, except for using CuCl2ꢀ2H2O in-
stead of Cu(ClO4)2ꢀ6H2O. Yield: 33%. Anal. Calcd for
C68H48Cu3Cl6N16: C, 54.72; H, 3.24; N, 15.01%. Found: C, 54.79; H,
3.26; N, 15.06%. IR (cmꢁ1, KBr pellets): 3442s, 3079m, 1698w,
1533s, 1474vs, 1454s, 1360s, 1297s, 1178m, 1126m, 1074m,
1008m, 826m, 772vs, 691vs, 635m, 565m, 486w, 434w.
Cu(2)ꢀ ꢀ ꢀCu(2)#2
2.6616(13)
2.7085(13)
2.074(4)
109.51(15)
109.78(12)
I(1)ACu(2)
Cu(2)AN(1)
2.6115(13)
2.058(4)
I(1)ACu(2)#2
Cu(2)AN(5)#1
N(1)ACu(2)AN(5)#1
N(5)#1ACu(2)AI(1)
N(1)ACu(2)AI(1)
I(1)ACu(2)AI(1)#2
110.19(11)
119.99(3)
Complex 3
Cu(1)AN(3)
Cu(1)AO(5)
1.9958(18)
2.451(2)
Cu(1)AN(8)
2.0742(18)
N(3)#1ACu(1)AN(3)
O(5)ACu(1)AO(5)
N(3)ACu(1)AO(5)
180.00(12)
180.00(10)
85.83(7)
N(8)#1ACu(1)AN(8)
N(3)#1ACu(1)AN(8)
N(8)ACu(1)AO(5)
180.00(10)
91.02(7)
91.65(5)
2.4. X-ray crystallography
Single-crystal X-ray diffraction measurements for complexes
Complex 4
1–5 were carried out on
a R-AXIS SPIDER diffractometer
Zn(1)AN(1)
Zn(1)ACl(2)
N(5)AZn(1)ACl(2)
N(5)AZn(1)AN(1)
Cl(2)AZn(1)ACl(3)
2.0276(17)
2.2366(10)
110.58(5)
104.84(7)
114.67(3)
Zn(1)AN(5)
Zn(1)ACl(3)
N(5)AZn(1)ACl(3)
N(1)AZn(1)ACl(3)
2.0674(17)
2.2254(10)
100.78(5)
118.10(6)
equipped with a graphite crystal monochromator situated in
the incident beam for data collection at 293(2) K. The determina-
tions of unit cell parameters and data collections were performed
with MoKa radiation (k = 0.71073 Å) and unit cell dimensions
Complex 5
were obtained with least-squares refinements. The program
SAINT [10] was used for integration of the diffraction profiles.
All structures were solved by direct methods using the SHELXS
program of the SHELXTL package and refined with SHELXL [11].
Metal atoms in each complex were located from the E-maps
and other non-hydrogen atoms were located in successive differ-
ence Fourier syntheses and refined with anisotropic thermal
parameters on F2. Hydrogen atoms of carbon were included in
calculated positions and refined with fixed thermal parameters
riding on their parent atoms. The hydrogen atoms of part of
water were located from Fourier difference maps with suitable
restraint, and those of the remaining part could not be located
in the difference map. Crystallographic data and experimental de-
tails for structural analyses are summarized in Table 1.
Cu(2)AN(5)
Cu(2)ACl(3)
Cu(2)ACl(4)
N(2)ACu(1)
Cl(4)ACu(2)AN(1)
Cl(4)ACu(2)ACl(3)
N(2)ACu(1)ACl(4)
N(2)#1ACu(1)ACl(4)#1
1.991(4)
Cu(2)AN(1)
Cu(2)ACl(5)
Cl(4)ACu(1)
2.046(4)
2.3223(19)
2.2711(15)
2.2715(19)
2.5651(15)
1.998(4)
87.81(12)
102.52(7)
88.41(12)
88.41(12)
Cl(4)ACu(2)AN(5)
Cl(4)ACu(2)ACl(5)
N(2)#1ACu(1)ACl(4)
N(2)ACu(1)ACl(4)#1
99.55(15)
94.08(7)
91.59(12)
91.59(12)
Symmetry code for 1: #1 ꢁy + 1/2, x, z; #2 ꢁx + 1/2, ꢁy + 1/2, z; #3 y, ꢁx + 1/2, z; for
2: #1 ꢁx + 1, ꢁy + 2, ꢁz + 1; #2 ꢁx + 1, ꢁy + 2, ꢁz; for 3: #1 ꢁx + 2, ꢁy + 1, ꢁz; for 5:
#1 ꢁx, ꢁy, ꢁz + 1.
2.3.4. [Zn(L3)Cl2] (4)
Colorless crystals of 4 suitable for X-ray analysis were obtained
by the similar method described for 3, except for using ZnCl2ꢀ2H2O
instead of Cu(ClO4)2ꢀ6H2O. Yield: ꢂ27.8%. Anal. Calcd for
CCDC reference numbers 690056 (for 1), 684730 (for 2), 683208
(for 3), 684729 (for 4), 684731 (for 5). For crystallographic data in
Fig. 1. (a) Coordination environment of CuII center in 1, (b) the 1D polymeric chain through the C(2)AH(2A)ꢀ ꢀ ꢀO(4) weak interactions (H atoms omitted for clarity).

D. Chen et al. / Journal of Molecular Structure 920 (2009) 342–349
345
Fig. 2. (a) Coordination environment of CuI center in 2, view of (b) the 1D polymeric chain in 2, and (c) the 2D sheet through the adjacent chains
atoms omitted for clarity).
pꢀ ꢀ ꢀ
p
stacking interactions (H
CIF or other electronic format see http://www.ccdc.cam.ac.uk/
deposit.
3.2. Description of the crystal structure
3.2.1. [Cu(L1)(ClO4)Cl] complex (1)
3. Results and discussion
The single crystal X-ray analysis revealed that complex 1 crys-
tallizes in the tetragonal space group P4/n and the selected bond
distances and angles were listed in Table 2, the CuII center is
five-coordinated with square-pyramidal configuration, with four
N atoms from four distinct L1 ligands [CuAN = 2.042(3) Å] defining
the basal plane, and the Cl atom occupying the axial position
[CuACl = 2.390(3) Å] (see Fig. 1a). The angle of Cl(2)ACu(1)
AN(5) is 98.56(10)° while N(5)ACu(1)AN(5) angles are 88.73(3)°
and 162.9(2)°, respectively. Four N(5) atoms coordinated to CuII
center are coplanar with a square arrangement [length of side,
N(5)AN(5) = 2.856 Å]. The Cl atom and the CuII center lie on the
axis of the square. All atoms of L1 ligand are nearly planar and
the dihedral angles between the two distinct ligands are 66.7°,
78°, 113.3°, respectively. It is worth noting that Complex 1 consist
3.1. Synthesis and general characterization
All ligands were prepared as yellow powder by the reaction of
3-phenyl-6-chloropyridazine with different hydrazines. The infra-
red spectra of ligands exhibit characteristic absorptions of C@N
bond on the triazole ring at about 1410 cmꢁ1, whereas the corre-
sponding C@N bond absorption of complexes 1–5 appear at about
1450–1500 cmꢁ1 due to coordinate. In infrared spectra of 1–5, the
stretching vibration of the CH bond on the pyridazine ring appears
in the region of 3400–3650 cmꢁ1 as strong sharp bands compared
with 3100–3300 cmꢁ1 of the free ligands due to coordinate. In the
IR spectra of 1 and 3, there are characteristic bands of the ClO4ꢁ an-
ions at 930–1080 cmꢁ1
.
of a [Cu(L1)4Cl]+ cation and a ClO4 in mononuclear basic unit. In
ꢁ

346
D. Chen et al. / Journal of Molecular Structure 920 (2009) 342–349
Fig. 3. (a) Coordination environment of CuII center in 3, (b) the 1D polymeric layer through the O(5)AH(5)ꢀ ꢀ ꢀO(2) and C(8)AH(8A)ꢀ ꢀ ꢀO(2) weak interactions (H atoms omitted
for clarity).
general, the effect of anions on the frameworks of complexes can
be explained as their differences in sizes and coordination ability
[12]. In this complex, the Clꢁ anion is both counteranion and donor,
coordinate to CuII center due to its relatively strong coordination
ability than that of ClO4 [13], while the ClO4 anion is used as
counteranion and weakly bridge two adjacent 1 molecules to
assemble into an infinite 1D supramolecular chain by the
C(2)AH(2A)ꢀ ꢀ ꢀO(4) [the distance of O(4)ꢀ ꢀ ꢀH(2A) is 2.468 Å] weak
interactions (Fig. 1b). It is interesting to note that although every
L1 ligand has a few reasonable coordination sites, only N from pyr-
idine bond to the CuII center, which may be attributed to steric hin-
drance of the substituents.
around each CuI center. It should be pointed out that the intramolec-
ular CuIꢀ ꢀ ꢀCuI distance [CuIꢀ ꢀ ꢀCuI = 2.6616(13) Å] found in the com-
plex is shorter than the sum of the van der Waals’ radii of copper
(2.8 Å) [14], indicating there exists CuIꢀ ꢀ ꢀCuI weak interaction.
In 2, each L2 ligand bridges two adjacent CuI centers in bidentate
coordination fashion, adjacent CuI centers and L2 ligands generate a
1D chain containing two types of metallacyclic rings (A and B) with
different sizes. In A ring, two L2 jointly coordinate to two CuI centers
by using one pyridyl N atom and one triazole N atom of each ligand
to form a 14-membered unit. The centrosymmetric unit is con-
structed in which a pair of ligand-bridged CuIꢀ ꢀ ꢀCuI distance is
7.805 Å. In B ring, two CuI centers are linked by two bridging I atoms
to form the parallelogram. All L2 ligands are almost parallel to each
other in the complex. Besides, these 1D chains were further ex-
ꢁ
ꢁ
3.2.2. {[Cu(L2)I]}n complex (2)
ꢀ
Complex 2 crystallizes in triclinic space group P1 and the selected
tended into 2D supramolecular sheet by inter-sheet
interactions between the phenyl ring and pyridazino ring from adja-
p p stacking
ꢀ ꢀ ꢀ
bond distances and angles were listed in Table 2. The X-ray diffrac-
tion analysis shows that 2 has a 1D chain structure and all the CuI
centers and L2 are equivalent. Each CuI center coordinates to two
bridging iodine atoms [CuAI lengths are 2.7085(13) Å and
2.6115(13) Å, respectively] and one N atom of pyridine from one L2
ligand and one N atom of triazole from another L2 ligand (Fig. 2a).
The Cu(2)AN(5) bond distance is 2.074(4) Å, whereas the
Cu(2)AN(1) bond distance is 2.058(4) Å. The bond angles
[N(1)ACu(2)AN(5) = 109.51(15)°, N(5)ACu(2)AI(1) = 109.78(12)°,
N(1)ACu(2)AI(1) = 110.19(11)° and I(1)ACu(2)AI(1) = 119.99(3)°]
indicate a nearly regular tetrahedral coordination environment
cent chains (Fig. 2c). The centroid–centroid separation is 3.238 Å.
3.2.3. [Cu(L3)(CH3OH)2(ClO4)2] complex (3)
Complex 3 crystallizes in the monoclinic space group P2 (1)/c
and the selected bond distances and angles were listed in Table
2. The X-ray diffraction analysis shows that the mononuclear basic
unit (see Fig. 3a) contains one CuII ion, two coordinated methanol
molecules (two solvated methanol molecules), four L3 ligands, and
ꢁ
two uncoordinated ClO4 groups. Thus, the slightly distorted octa-
hedral coordination geometry CuN4O2 is formed by two oxygen

D. Chen et al. / Journal of Molecular Structure 920 (2009) 342–349
347
Fig. 4. (a) Coordination environment of ZnII center in 4, (b) the 1D polymeric chain through the C(23)AH(23A)ꢀ ꢀ ꢀCl(2) weak interactions (H atoms omitted for clarity).
atoms [CuAO = 2.451(2) Å] from two independent methanol mole-
cules and four N atoms from four independent L3 ligands [the dis-
tances of the CuAN are 1.9958(18) Å and 2.0742(18) Å,
respectively]. The CuII center is coordinated by the nitrogen atom
from triazole of L3 ligand, whereas the nitrogen atoms from pyrid-
azine of L3 ligand do not take part in coordination, probably due to
the steric hindrance. The CuII center is located at an inversion cen-
ter. The bond angles around the CuII center are close to the orthog-
respectively, confirms a nearly regular tetrahedral environment
around the ZnII center. In L3 ligand, the central triazole is nearly
coplanar with the adjacent pyridazine ring with a dihedral angle
of 1.5°. Two L3 ligands are not equivalent in 4. In one L3 ligand,
two phenyl rings are twisted with respect to the central reference
plane (the central trizole and the pyridazine ring), having the dihe-
dral angle of 158.9° and 137.3°, two phenyl rings make a dihedral
angle of 56.5°. For another ligand, it is interesting to note that two
phenyl rings are almost coplanar with respect to the central refer-
ence plane, having the dihedral angle of 25.1° and 2.5°. Two phenyl
rings make a dihedral angle of 27.1°.
In 4, only N atom from triazole bond to the metal ion, the coor-
dinated mode is same as that of complex 3. Two Cl atoms in the
metal salt are also bound to the zinc ion. In addition, the
C(23)AH(23A)ꢀ ꢀ ꢀCl(2) [Cl(2)ꢀ ꢀ ꢀꢀH(23A) = 2.896 Å] weak interac-
tions were observed between adjacent molecules. Therefore, such
molecules were further assembled into an infinite 1D supramolec-
ular chain by the C(23)AH(23A)ꢀ ꢀ ꢀCl(2) weak interactions between
adjacent molecules (Fig. 4b).
onal
requirement
[the
angles
of
N(3)ACu(1)AN(8),
N(3)ACu(1)AO(5) and N(8)ACu(1)AO(5) are 91.02(7)°, 85.83(7)°
and 91.65(5)°, respectively]. It should be pointed out that all atoms
of L3 are nearly planar, and two adjacent L3 planes are nearly per-
pendicular to each other, whereas two distant L3 planes are almost
ꢁ
parallel to each other in 3. In addition, the ClO4 anions weakly
bridge two adjacent 3 molecules, and the distances of Oꢀ ꢀ ꢀH are
2.603 and 2.262 Å, respectively, the O atoms are well located.
Therefore, such molecules were further assembled into an infinite
1D supramolecular layer by the O(5)AH(5)ꢀ ꢀ ꢀO(2) and
C(8)AH(8A)ꢀ ꢀ ꢀO(2) weak interactions between adjacent molecules
(Fig. 3b).
3.2.5. [Cu3(L3)Cl6] complex (5)
3.2.4. [Zn(L3)Cl2] complex (4)
Complex 5 crystallizes in the triclinic space group P1 and the se-
ꢀ
The X-ray structural analysis reveals that the structure of com-
plex 4 is a mononuclear unit composed of one ZnII ion, two L3 li-
gands and two chlorine atoms. As shown in Fig. 4a, the ZnII
center with a slightly distorted tetrahedral coordination environ-
ment is surrounded by two N atoms from two distinct L3 ligands
and two Cl atoms. The Zn(1)AN(1), Zn(1)AN(5), Zn(1)ACl(2),
Zn(1)ACl(3) bond lengths are 2.0276(17) Å, 2.0674(17) Å,
2.2366(10) Å and 2.2254(10) Å, respectively, within the normal
range of ZnAN and ZnACl lengths in analogous zinc configuration
[15]. The angles of N(5)AZn(1)ACl(2), N(5)AZn(1)ACl(3),
N(5)AZn(1)AN(1), N(1)AZn(1)ACl(3) and Cl(2)AZn(1)ACl(3) are
110.58(5)°, 100.78(5)°, 104.84(7)°, 118.10(6)° and 114.67(3)°,
lected bond distances and angles were listed in Table 2. The X-ray
diffraction analysis shows that 5 which consist of three coppers, six
Cl atoms and four L3 ligands is centrosymmetric with the inversion
center being located at the Cu(1) atom. Three CuII atoms are in one
line [Cu(2)ACu(1)ACu(2) = 180°] and Cu(1) atom is situated nicely
at the middle of two Cu(2) atoms (see Fig. 5a). The nonbonding dis-
tance is 3.330 Å between two adjacent copper atoms. The four L3
ligands are nearly parallel with a Z-shaped, containing two types
of coordination modes.
The conformations of the outer two coppers are identical. Each
Cu(2) has a distorted square-pyramidal geometry and they are
five-coordinate with N2Cl3 donor set. The basal plane, which the

348
D. Chen et al. / Journal of Molecular Structure 920 (2009) 342–349
Fig. 5. (a) The trinuclear structure of 5 showing coordination environments of the CuII ions, (b) the 1D polymeric chain through the C(4)AH(4A)ꢀ ꢀ ꢀCl(5) weak interactions (H
atoms omitted for clarity).
mean deviation is ca. 0.1019 Å, consists of two N atoms from two
distinct L3 ligands and two Cl atoms. The Cu(2)AN(5), Cu(2)AN(1),
Cu(2)ACl(3), Cu(2)ACl(5) bond lengths are 1.991(4) Å, 2.046 (4) Å,
2.2715(19) Å and 2.3223(19) Å, respectively. The apical position is
occupied by bridging Cl(4) atom with a distance of [2.5651(15) Å].
may to influence N atom coordination ability. We obtain complex
[Cu(L1)(Cl)(ClO4)] (1) and know by analyzing the conformation of
1 that Clꢁ is both donor and counteranion while the ClO4ꢁ is count-
eranion and weakly bridge two adjacent 1 molecules to assemble
into an infinite 1D supramolecular chain. Furthermore, in 2, it
should be pointed out that the intramolecular CuIꢀ ꢀ ꢀCuI distance
[CuIꢀ ꢀ ꢀCuI = 2.6616(13) Å] is shorter than the sum of the van der
Waal’s radii of copper (2.8 Å), indicating there exists CuIꢀ ꢀ ꢀCuI weak
interaction. 3 and 4 are mononuclear structure, 5 is trinuclear
complex.
The
angles
of
Cl(4)ACu(2)AN(1),
Cl(4)ACu(2)AN(5),
Cl(4)ACu(2)ACl(3) and Cl(4)ACu(2)ACl(5) are 87.81(12)°,
99.55(15)°, 102.52(7)° and 94.08(7)°, respectively. Additionally,
Cl(3) and Cl(5) in the metal salt are also bound to the Cu(2) ion,
the distances of Cl(4)ACl(4) and Cl(3)ACl(5) are both 4.542(8) Å.
The environment of central copper atom is nearly regular
square-planar geometry, being coordinated by two N donors from
two distinct ligands and two bridging Cl(4) atoms. The distances of
CuAN and CuACl are 1.998(4) Å and 2.2711(15) Å, respectively.
The sum (value of 360.0°) of the angles Cl(4)ACu(1)AN(2)
[91.59(12)°, 88.41(12)°, 91.59(12)° and 88.41(12)°] Confirms a pla-
nar and nearly orthogonal environment around the Cu(1) center. In
addition, the C(4)AH(4A)ꢀ ꢀ ꢀCl(5) [Cl(5)ꢀ ꢀ ꢀH(4A) = 2.841 Å] weak
interactions were observed between adjacent molecules. There-
fore, such molecules were further assembled into an infinite 1D
supramolecular chain by the C(4)AH(4A)ꢀ ꢀ ꢀCl(5) weak interactions
between adjacent molecules (Fig. 5b).
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (Grant No. 20462006) and Xinjiang Key Laboratory
of Plant Resources & Natural Products Chemistry.
References
[1] (a) Y.-F. Wang, L.-Y. Wang, L.-F. Ma, J. Mol. Struct. 877 (2008) 138;
(b) R.E.P. Winpenny, Chem. Soc. Rev. 27 (1998) 447;
(c) D.L. Caulder, K.N. Raymond, Acc. Chem. Res. 32 (1999) 975;
(d) S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853;
(e) B.J. Holliday, C.A. Mirkin, Angew. Chem. Int. Ed. 40 (2001) 2022;
(f) S.R. Seidel, P.J. Stang, Acc. Chem. Res. 35 (2002) 972;
4. Conclusion
(g) S.C. Manna, E. Zangrando, N.R. Chaudhuri, J. Mol. Struct. 877 (2008) 145;
(h) S. Kitagawa, S. Masaoka, Coord. Chem. Rev. 246 (2003) 73;
(i) S.R. Batten, R. Robson, Angew. Chem. Int. Ed. 37 (1998) 1460;
(j) A.J. Blake, N.R. Champness, P. Hubberstey, W.S. Li, M.A. Withersby, M.
Schröder, Coord. Chem. Rev. 183 (1999) 117;
In order to try to know the function of structural constraint in
controlling the assembly of metal–organic networks, we design
three rigid ligands. We find steric hindrance of the substituents

D. Chen et al. / Journal of Molecular Structure 920 (2009) 342–349
349
(k) P.J. Hagrman, D. Hagrman, J. Zubieta, Angew. Chem. Int. Ed. 38 (1999) 2639;
(l) M.J. Zaworotko, Angew. Chem. Int. Ed. 39 (2000) 3052;
(m) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629;
(n) R. Robson, J. Chem. Soc., Dalton Trans. (2000) 3735.
[2] (a) S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem. Int. Ed. 43 (2004) 2334;
(b) D. Bradshaw, T.J. Prior, E.J. Cussen, J.B. Claridge, M.J. Rosseinsky, J. Am.
Chem. Soc. 126 (2004) 6106;
(b) L. Carlucci, G. Ciani, D.M. Proserpio, S. Rizzato, Chem. Commun. (2000)
1319.
[7] (a) M.B. Zaman, M.D. Smith, H.-C. Loye, Chem. Commun. (2001) 2256;
(b) B. Moulton, E.B. Rather, M.J. Zaworotko, Cryst. Eng. 4 (2001) 309;
(c) M. Du, X.-H. Bu, Y.-M. Guo, H. Liu, S.R. Batten, J. Ribas, T.C.W. Mak, Inorg.
Chem. 41 (2002) 4904;
(d) M.-L. Tong, Y.-M. Wu, J. Ru, X.-M. Chen, H.-C. Chang, S. Kitagawa, Inorg.
Chem. 41 (2002) 4846;
(e) Z.-Y. Fu, X.-T. Wu, J.-C. Dai, S.-M. Hu, W.-X. Du, New J. Chem. 26 (2002)
978;
(c) D.-X. Xue, W.-X. Zhang, X.-M. Chen, J. Mol. Struct. 877 (2008) 36;
(d) T.L. Hennigar, D.C. MacQuarrie, P. Losier, R.D. Rogers, M.J. Zaworotko,
Angew. Chem. Int. Ed. Engl. 36 (1997) 972;
(e) O.M. Yaghi, M. O’Keeffe, N.W. Ockwig, H.K. Chae, M. Eddaoudi, J. Kim,
Nature 423 (2003) 705.
(f) M.J. Plater, M.R. Foreman, J. Stang, T. Gelbrich, M.B. Hursthouse, J. Chem.
Soc., Dalton Trans. (2000) 1995.
[3] (a) M.E. Davis, Nature 417 (2002) 813;
[8] (a) M.J. Plater, M.R. St. J. Foreman, T. Gelbrich, S.J. Coles, M.B. Hursthouse, J.
Chem. Soc., Dalton Trans. (2000) 3065;
(b) L. Carlucci, G. Ciani, D.M. Proserpio, F. Porta, Angew. Chem. Int. Ed. 42
(2003) 317;
(c) J.L.C. Rowsell, A.R. Millward, K.S. Park, O.M. Yaghi, J. Am. Chem. Soc. 126
(2004) 5666;
(d) M. Padmanabham, J.C. Joseph, X.-Y. Huang, J. Li, J. Mol. Struct. 855 (2008)
36;
(e) O.R. Evans, W. Lin, Acc. Chem. Res. 35 (2002) 511;
(f) S.R. Batten, K.S. Murray, Coord. Chem. Rev. 246 (2003) 103;
(g) B. Kesanli, W. Lin, Coord. Chem. Rev. 246 (2003) 305;
(h) B. Kesanli, Y. Cui, M.R. Smith, E.W. Bittner, B.C. Bockrath, W. Lin, Angew.
Chem. Int. Ed. 44 (2005) 72;
(i) T.-T. Luo, H.-L. Tsai, S.-L. Yang, Y.-H. Liu, R.D. Yaday, C.-C. Su, C.-H. Ueng, L.-
G. Lin, K.-L. Lu, Angew. Chem. Int. Ed. 44 (2005) 6063;
(j) X.-C. Huang, Y.-Y. Lin, J.-P. Zhang, X.-M. Chen, Angew. Chem. Int. Ed. 45
(2006) 1557;
(b) M. Fujita, Y.J. Kwon, M. Miyazawa, K. Ogure, J. Chem. Soc., Chem. Commun.
(1994) 1977;
(c) M. Fujita, Y.J. Kwon, O. Sasaki, K. Yamaguchi, K. Ogura, J. Am. Chem. Soc. 117
(1995) 7287;
(d) X.-C. Su, S.-R. Zhu, H.-K. Lin, X.-B. Leng, Y.-T. Chen, J. Chem. Soc., Dalton
Trans. (2001) 3163;
(e) M.O. Awaleh, A. Badia, F. Brisse, Inorg. Chem. 44 (2005) 7833;
(f) M.O. Awaleh, A. Badia, F. Brisse, Cryst. Growth Des. 5 (2005) 1897;
(g) M. Du, C.-P. Li, X.-J. Zhao, Cryst. Growth Des. 6 (2006) 335.
[9] L.-H. Cao, C.-F. Wang, J. Tao, Chin. J. Org. Chem. 26 (2006) 1686.
[10] SAINT, Software for Data Extraction and Reduction, Version 6.02, Bruker AXS,
Inc., Madison, WI 2002.
[11] G. M. Sheldrick, SHELXTL NT Version 5.1, Program for Solution and Refinement
of Crystal Structure, University of Göttingen, Germany, 1997.
[12] T.-L. Hu, J.-R. Li, Y.-B. Xie, X.-H. Bu, Cryst. Growth Des. 6 (2006) 648.
[13] J.-H. Yu, K. Mereiter, N. Hassan, C. Feldgitscher, W. Linert, Cryst. Growth Des. 8
(2008) 1535.
(k) B.F. Abrahams, D.J. Price, R. Robson, Angew. Chem. Int. Ed. 45 (2006) 806.
[4] D.-Z. Wang, C.-S. Liu, J.-R. Li, L. Li, Y.-F. Zeng, X.-H. Bu, CrystEngComm 9 (2007)
289.
[5] S. Muthu, J.H.K. Yip, J.J. Vittal, J. Chem. Soc., Dalton Trans. (2002) 4561.
[6] (a) T. Hennigar, D.C. MacQuarrie, P. Loiser, R.D. Rogers, M.J. Zaworotko, Angew.
Chem. Int. Ed. Engl. 36 (1997) 972;
[14] A. Bondi, J. Phys. Chem. 68 (1964) 441.
[15] K.-J. Wei, Y.-S. Xie, J. Ni, M. Zhang, Q.-L. Liu, Cryst. Growth Des. 6 (2006)
1341.