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Solvent Mediated Hydrogen-bonded Supramolecular Network of a Cu(II)

Complex Involving N2O Donor Ligand and Terephthalate

Research · October 2015

DOI: 10.13140/RG.2.1.2010.4406

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Journal of the Korean Chemical Society
2011, Vol. 55, No. 2
Printed in the Republic of Korea
DOI 10.5012/jkcs.2011.55.2.199

N2O 주개 리간드와 테레프탈레이트를 포함하는 구리(II) 착물의 용매를

매개로 한 수소결합형 초분자 네트워크
Jishnunil Chakraborty*
Department of Basic Science, IERCEM Institute of Information Technology, Banipur, 24 Parganas(N),
743233, West Bengal, India
(접수 2010. 9. 16; 수정 2010. 10. 25; 게재확정 2010. 11. 15)

Solvent Mediated Hydrogen-bonded Supramolecular Network of a Cu(II)

Complex Involving N2O Donor Ligand and Terephthalate
Jishnunil Chakraborty*
Department of Basic Science, IERCEM Institute of Information Technology, Banipur, 24 Parganas(N),
743233, West Bengal, India. *E-mail: [email protected]
(Received September 16, 2010; Revised October 25, 2010; Accepted November 15, 2010)

요 약. 일차원 수소결합형 배위고분자 [CuII(C13H17N3OBr)(C8H5O4)]·2H2O.CH3OH을 합성하여 단결정 X-선 회절 연구로

특성을 규명하였다. 단량체 단위는 사각평면의 중심 CuII를 갖고 있다. 네개의 배위자리 중 세자리는 N2O-주개 세트를 갖
는 Schiff 염기형 리간드 (4-bromo-2-[(2-piperazin-1-yl-ethylimino)-methyl]-phenol)가 차지하고, 네 번째 자리는 옆에 있는 테
레프탈레이트 단위의 산소 원자가 차지한다. 두개의 인접한 중성분자는 분자간 N-H---O 및 O-H---N 수소결합에 의해 연
결되어 이합체 쌍을 형성한다. 각 이합체 쌍은 불연속적인 물 및 메탄올 분자에 의해 수소결합으로 다시 연결되어 일차
원 초분자 네트워크를 형성한다.
주제어: 사각평면 구리(II) 착물, 결정구조, 수소결합, 일차원 초분자 네트워크

ABSTRACT. The title one-dimensional hydrogen-bonded coordination compound [CuII(C13H17N3OBr)(C8H5O4)].2H2O.

CH3OH has been synthesized and characterized by single crystal X-ray diffraction study. The monomeric unit contains a
square-planar CuII centre. The four coordination sites are occupied by a tridentate anionic Schiff base ligand (4-bromo-2-[(2-
piperazin-1-yl-ethylimino)-methyl]-phenol) which furnishes an N2O-donor set, with the fourth position being occupied by the
oxygen atom of an adjacent terephthalate unit. Two adjacent neutral molecules are linked through intermolecular N-H---O and
O-H---N hydrogen bonds and generate a dimeric pair. Each dimeric pair is connected with each other via discrete water and
methanol molecules by hydrogen bonding to form a one-dimensional supramolecular network.
Keywords: Square-planar copper(II) complex, Crystal structure, Hydrogen bonding, One-dimensional supramolecular network

INTRODUCTION pounds of transition metals that can form hydrogen bonded

supramolecular architectures with interesting dimensions
Hydrogen bonds having appreciable degree of direc- and topologies.
tionality, flexibility and suitable strength are very impor- Although the principles for controlling the solid struc-
tant and have been widely studied in physics, chemistry tures of the target products still need to be classified and
and biology.1 Moreover, most reported work on crystal established, many rational synthetic strategies have been
engineering has concentrated on organic supramolecular put forward.11,12 Among them, the selection of appropriate
compounds.2-5 Crystal engineering with coordination bonds ligands as building blocks is undoubtedly a key point in
is a very popular research area because of the stable coor- manipulating the structures. Organic aromatic polycarbox-
dination bonds and versatile coordination modes of the ylates as one of the multidentate O-donor ligands have
metal ions, especially the transition metals. However, tran- been extensively employed in the preparation of multidi-
sition metal coordination compounds assembled by hydro- mensional networks. In this respect, as a rigid and versatile
gen bonding interactions have been less well studied.6-10 In ligand, terephthalate has been studied extensively.13-15 It
this perspective, our aim is to construct coordination com- can not only act as a hydrogen bond donor but also as an

-199-
200 Jishnunil Chakraborty

Scheme 1. Schematic representation for the preparation of the complex.

acceptor due to the existence of protonated and/or depro- refluxed for 1 hour. A solid mass of the Schiff base was
tonated carboxyl groups. Therefore, terephthalate is regarded collected after slow evaporation of the solvent and dried
as an excellent candidate for the construction of multidi- under vacuum. Yield: 95%. Anal. calc. for C13H18N3OBr
mensional hydrogen-bonded frameworks. However, the (%): C, 50.08; H, 5.78; N, 13.48. Found: C, 50.11; H, 5.82;
introduction of another kind of both N- and O- donor N, 13.46. Characteristic IR data (cm-1): 3340 (b, νO-H),
chelating ligands such as the tridentate Schiff bases in the 3250 (m, νN-H), 1650 (s, νC=N). 1H NMR (CDCl3): δ 7.35
{M/terephthalate} (M=transitional metal) system may (d, 1H, Ar-H), 6.57 (d, 1H, Ar-H), 7.54 (s, 1H, Ar-H), 9.80
induce new structural evolution. The introduction of the (s, 1H, OH), 8.20 (s, 1H, HC=N), 3.58 (t, 2H, CH2), 2.33 (t,
N-donor chelating ligands into the metal sites may not only 2H, CH2), 2.46 (t, 4H, piperazin CH2), 2.65 (t, 4H, pip-
inhibit the expansion of polymeric frameworks but also act erazin CH2), 2.14 (s, 1H, NH).
as active sites for hydrogen bonding. The synthesis and
crystal structure of a mixed-ligand CuII complex 1 (Scheme Preparation of [CuII(C13H17N3OBr)(C8H5O4)].2H2O.
1), using a tridentate Schiff base 4-bromo-2-[(2-piperazin- CH3OH
1-yl-ethylimino)-methyl]-phenol and terephthalate, con- A solution of 4-bromo-2-[(2-piperazin-1-yl-ethylimino)-
structing a one-dimensional hydrogen-bonded network are methyl]-phenol (0.311 g, 1.0 mmol) in 10 mL of methanol
reported herein. was added to a methanolic solution (10 mL) of copper(II)
perchlorate (0.370 g, 1.0 mmol) with constant stirring. The
EXPERIMENTAL color of the solution turned deep green. An aqueous solu-
tion (10 mL) terephthalic acid (0.166 g, 1.0 mmol) was
Materials then added to this mixture along with 2.0 mmol (0.202 g)
5-bromosalicylaldehyde and 1-(2-aminoethyl)pipera- of triethylamine. The resulting solution was stirred for 10
zine of AR grade were purchased from Aldrich and used as minutes and then filtered off. Deep green crystals suitable
received. Terephthalic acid was of analytical reagent grade for X-ray diffraction were obtained after 5 days. Anal. calc.
(Fluka). Copper(II) perchlorate was prepared by reaction for C22H30N3O8BrCu (%): C, 43.43; H, 4.93; N, 6.90. Found:
of Cu2(OH)2CO3 with perchloric acid in water. Methanol, C, 43.41; H, 4.86; N, 6.94. Characteristic IR data (cm-1):
ethanol and triethylamine were of reagent grade and were 1637-1645 (s, νC=N), 1695 (s, νC=O), 1570 (m, νas(COO)),
used without further purification. Double distilled water 1367 (m, νs(COO)).
was used throughout.
IR spectroscopy
Preparation of 4-bromo-2-[(2-piperazin-1-yl-eth- In the IR spectrum of 1 the strong band in the range
ylimino)-methyl]-phenol 1637-1645 cm-1 can be assigned to νC=N, which suggests
For the preparation of the title compound, the ligand 4- coordination of the Schiff base ligand to the metal center
bromo-2-[(2-piperazin-1-yl-ethylimino)-methyl]-phenol through the imine nitrogen atom. The presence of the
was prepared by mixing 5-bromosalicylaldehyde (25 mmol) broad band in the range 2900-2400 cm-1 is indicative of
and 1-(2-aminoethyl)piperazine (25 mmol) in 50 ml of eth- hydrogen bond between the N-H group of piperazine and
anol. The reaction mixture was stirred for 30 min at room the carboxylate oxygen of terephthalate as well as solvent
temperature to give a light yellow solution, and then it was methanol molecule. A strong νC=O stretching band at 1695

Journal of the Korean Chemical Society

 N2O 주개 리간드와 테레프탈레이트를 포함하는 구리(II) 착물의 용매를 매개로 한 수소결합형 초분자 네트워크 201

cm-1 in the spectrum of the complex confirms that one of Table 2. Selected bond lengths (Å) and angles (°) for the complex
the carboxylate groups of terephthalate is present in a pro- Bond Lengths (Å)
tonated form. The spectrum also shows typical chelating Cu1–O1 1.913(4) Cu1–N1 1.934(5)
carboxylate antisymmetric and symmetric stretching bands Cu1–O2 1.948(4) Cu1–N2 2.099(4)
at 1570 and 1367 cm-1 for 1. Bond Angles (°)
O1–Cu1–O2 91.80(17) O1–Cu1–N2 176.55(15)
Physical measurements O1–Cu1–N1 92.56(19) O2–Cu1–N1 174.25(18)
Microanalysis (CHN) was performed in a Perkin-Elmer O2–Cu1–N2 91.17(16) N1–Cu1–N2 84.60(18)
240C elemental analyzer. FT-IR spectra were obtained on a
Nicolet MAGNA-IR 750 spectrometer with samples pre- Table 3. Hydrogen bond distances (Å) and bond angles (°)
pared as KBr pellets in the 4000-400 cm-1 region. The 1H- D–H---A D---A H---A ∠D–H---A
NMR spectra were recorded on a 300 MHz Bruker Avance N3–H3---O6 2.836(7) 2.3500 116.00
DPX 300 machine, Switzerland in CDCl3 with TMS as the N3–H3---O4 2.840(8) 2.3100 120.00
O4–H4O---N3 2.840(8) 2.0700 160.00
internal standard at room temperature.
O6–H6---O7 2.738(9) 2.0000 150.00

Crystal structure determination and structural

refinement of 1 gram was applied, which resulted in transmission coefficients
The diffraction data for 1 were collected at 150 K on a ranging from 0.682 to 0.729. The structure was solved by
Bruker SMART CCD area-detector diffractometer, using direct methods and refined by full-matrix least-squares
monochromated Mo-Kα radiation (λ=0.71073Å). Data based on F2 with anisotropic thermal parameters for non-
reduction and cell refinement were performed using the hydrogen atoms using SHELXS-9717 (structure solution)
programs Bruker SAINT and Bruker SMART. An empir- and SHELXL-9718 (structure refinement). The software used
ical absorption correction by using the SADABS16 pro- to prepare material for publication was WINGX V1.80.03.
The crystallographic data for the complex are summarized
Table 1. Crystal data for the complex in Table 1. Selected bond lengths and angles are given in
Formula C22H28BrN3O8Cu Table 2. Hydrogen bonds are listed in Table 3.
Formula Weight 605.92
Crystal System Monoclinic RESULTS AND DISCUSSION
Space group P21/n (No. 14)
a/Å 10.0259(13) Structural description
b/Å 17.823(2) The molecular structure of the title complex is shown in
c/Å 13.9051(18) Fig. 1, with selected bond lengths and angles are listed in
β/° 102.102(4) Table 2. The crystal structure of the complex shows that the
V / Å3 2429.5(5) asymmetric unit contains a mononuclear molecule of the
Z 4
Dcalc (g/cm3) 1.657
µ (mm-1) 2.596
F(000) 1236
Temperature (K) 150
λ/Å 0.71073 (Mo-Kα)
θMin-Max / ° 4.3-25.9
Reflections collected 28305
Independent reflections 4686
Observed data [I > 2σ(I)] 3639
Data / restraints / parameters 4686 / 0 / 326
Goodness-of-fit on F2 1.082
Final R indices [I > 2σ(I)] R1 = 0.0592
wR2 = 0.1670 Fig. 1. ORTEP drawing of 1. Thermal ellipsoids are at 30% prob-
R indices (all data) R1 = 0.0776 ability level. All hydrogen atoms and solvent molecules have been
wR2 = 0.1801 omitted for clarity.

2011, Vol. 55, No. 2

202 Jishnunil Chakraborty

type [CuII(C13H17N3OBr)(C8H5O4)] along with two water

and one methanol molecules as solvent of crystallization.
The coordination environment for the copper center is best
described by an approximately square-planar geometry.
The Schiff base 4-bromo-2-[(2-piperazin-1-yl-ethylimino)-
methyl]-phenol binds to the metal centre through two
nitrogen atoms and one phenolate oxygen atom. Obvi-
ously, the Schiff base coordinates in a tridentate fashion to
the Cu2+ ion. The C=N bond formed by the condensation
reaction of length 1.285(8)Å is within the normal double
bond range of 1.28-1.30Å. The other coordination site of Fig. 2. View along the crystallographic c-axis of the one-dimen-
sional structure of the title complex.
the metal ion is occupied by an oxygen atom of tereph-
thalate (O2) while the other carboxylate unit of terephtha-
late does not lose its H atom. Since there is a difference
between two C-O bond distances of the free CO2 group
(1.234(10) and 1.267(10)Å), so it should be considered as
an acidic type of -CO2H. This fact is in good agreement
with the IR data. The Cu1-O1 distance of 1.913(4)Å is
considerably shorter than the Cu1-O2 distance of 1.948(4)
Å, indicating that more negative charge is localized on the
phenolic O1 atom than on the carboxylate O2 atom.19 The
O3 atom of terephthalate seems to coordinate to the Cu(II)
ion in the apical position with a bond distance of 2.727(5)Å.
This distance is too long to be considered as a normal Cu1-
O3 distance. The central copper atom is slightly above the
square plane (0.016Å). By coordination to the metal atom,
the tridentate Schiff base ligand forms six- and five-mem-
bered chelate rings. The dihedral angles between the mean
planes phenyl and six-membered ring, phenyl and five-
membered ring and six- and five-membered rings are 2.83, Fig. 3. A view of the hydrogen-bonded dimeric structure of the
14.34 and 11.50o, respectively. Also, the phenyl ring of the complex.
Schiff base forms a dihedral angle of 63.62o with that of the
terephthalate. These informations suggest that the mole- oxygen atom (O3) through appreciable degree of interac-
cule is deviated from planarity. tion (O3---O7 = 2.722Å). This value is in good agreement
Owing to the presence of solvent CH3OH and H2O mol- to that of the previously reported compound.20 It is obvi-
ecules and considerable degree of hydrogen donation by ous that the solvent molecules play a crucial role (i.e., act-
the tridentate Schiff base and monoprotonated terephtha- ing like mediator) in constructing the supramolecular
late, the crystal structure is stabilized by extensive hydro- network. It is noteworthy that the piperazine N-H group
gen bonding. The complex unit forms hydrogen bond with undergoes hydrogen bonding in a ‘bifurcated’ fashion
solvent molecules and other adjacent complex units, thereby (N3-H3---O4 and N3–H3---O6) to construct the dimeric
facilitates the formation of a one-dimensional network pair as well as the network (Fig. 4). The Cu---Cu separa-
along the crystallographic c-axis as shown in Fig. 2. Two tion within a dimeric pair is 13.212Å while that within two
adjacent neutral [CuII(C13H17N3OBr)(C8H5O4)] molecules adjacent dimers is 10.026Å. The greater degree of Cu---Cu
are held together via N3-H3---O4 and O4-H4O---N3 inter- separation within a dimeric pair reveals the fact that the
molecular hydrogen bonds, leading to a dimeric pair (Fig. two molecules are at their opposite orientation to facilitate
3). There are two discrete CH3OH (O6) and H2O (O7) mol- hydrogen bonding. In addition, the two carboxyl groups of
ecules that actually bridge the dimeric pairs through N3- terephthalate are slightly twisted, i.e., they are not in the
H3---O6 and O6-H6---O7 hydrogen bonds. In addition, same plane and make an angle of 34.60o favoring the for-
the water molecule connects its neighboring terephthalate mation of the network. The phenyl rings of the adjacent

Journal of the Korean Chemical Society

 N2O 주개 리간드와 테레프탈레이트를 포함하는 구리(II) 착물의 용매를 매개로 한 수소결합형 초분자 네트워크 203

REFERENCES

1. Beatty, A. M. Coord. Chem. Rev. 2003, 246, 131.

2. Rambaran, V. H.; Balof, S.; Moody, L.; VanDerveer, D.;
Holder, A. Cryst. Eng. Commun. 2009, 11, 580.
3. Koshima, H.; Nagano, M.; Asahi, T. J. Am. Chem. Soc.
2005, 127, 2455.
4. Childs, S. L.; Hardcastle, K. I. Cryst. Eng. Commun. 2007,
9, 364.
5. Aakeröy, C. B.; Hussain, I.; Forbes, S.; Desper, J. Cryst. Eng.
Commun. 2007, 9, 46.
Fig. 4. Bifurcated hydrogen bonding that constructs the dimeric 6. Liu, C. S.; Wang, J. J.; Yan, L. F.; Chang, Z.; Bu, X. H.;
pair and the network. Carolina Sañudo, E.; Ribas, J. Inorg. Chem. 2007, 46, 6299.
7. Beatty, A. M. Cryst. Eng. Commun. 2001, 3, 243.
8. Larsson, K.; Öhrström, L. Cryst. Eng. Commun. 2003, 5,
terephthalate units within a dimeric pair are parallel but are 222.
too far apart (4.578Å) for any normal π–π interaction. 9. Aakeröy, C. B.; Beatty, A. M.; Leinen, D. S. J. Am. Chem.
Thus, it is evident that the intermolecular hydrogen bond- Soc. 1998, 120, 7383.
ing is the only factor for the formation of the network. 10. Aakeröy, C. B.; Desper, J.; Valdés-Martínez, J. Cryst. Eng.
Commun. 2004, 6, 413.
SUMMARY 11. Dong, Y.-B.; Jiang, Y.-Y.; Li, J.; Ma, J.-P.; Liu, F.-L.;
Tang, B.; Huang, R.-Q.; Batten, S. R. J. Am. Chem. Soc.
2007, 129, 4520.
It is evident from this discussion that the discrete meth- 12. Zhang, Q.; Ma, J.-P.; Wang, P.; Shi, Z.-Q.; Dong, Y.-B.;
anol and water molecules actively participate in construct- Huang, R.-Q. Cryst. Growth Des. 2008, 8, 2581.
ing a supramolecular network by expanding the dimensionality 13. Chakraborty, J.; Nandi, M.; Mayer-Figge, H.; Sheldrick,
of the structure from zero to one via intermolecular hydro- W. S.; Sorace, L.; Bhaumik, A.; Banerjee, P. Eur. J. Inorg.
gen boding. Chem. 2007, 5033.
14. Li, H.; Eddaoudi, M.; Yaghi, O. M. Nature 1999, 402,
276.
Supporting information 15. Hong, C. S.; Do, Y. Inorg. Chem. 1998, 37, 4470.
CCDC 779516 contains the supplementary crystallo- 16. Sheldrick, G. M.; SADABS, Program for Empirical Absorp-
graphic data for this paper. These data can be obtained free tion Correction of Area Detector Data, University of Göt-
of charge from The Cambridge Crystallographic Data Cen- tingen: Göttingen, Germany, 1996.
tre via www.ccdc.cam.ac.uk/data_request/cif. 17. Sheldrick, G. M. Acta Crystallogr. Sect A 1990, 46, 467.
18. Sheldrick, G. M.; SHELXL-97: Program for Crystal Struc-
ture Refinement, University of Göttingen: Göttingen, Ger-
Acknowledgements. The author would like to thank
many, 1997.
the Department of Inorganic Chemistry, Indian Associ- 19. Langer, V.; Gyepesová, D.; Kohútová, M.; Valent, A. Acta
ation for the Cultivation of Science, Jadavpur, Kolkata- Cryst. 2009, C65, m208.
700032, India, for assistance in collecting X-ray crys- 20. Chakraborty, J.; Saha, M. K.; Banerjee, P. Inorg. Chem.
tallographic data. Commun. 2007, 10, 671.

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