Synthesis and crystal structures of p-tert-butylcalix[4]arene 1,3-distal acylhydrazones and macrocyclic nickel complex

ORIGINAL ARTICLE

Synthesis and crystal structures of p-tert-butylcalix[4]arene1,3-distal acylhydrazones and macrocyclic nickel complex

Xin Bi • Jing Sun • Wen-Long Liu •

Chao-Guo Yan

Received: 2 November 2013 / Accepted: 7 January 2014

� Springer Science+Business Media Dordrecht 2014

Abstract A series of the calix[4]arene 1,3-distal diacy-

lhydrazones were successfully prepared by the condensa-

tion of calix[4]arene propylene and butylene bridged

vanillines with 2-hydroxybenzohydrazide or pyridinecar-

bohydrazides. The coordination chemistry of these calixa-

rene diacylhydrazone with transition metal salts was

studied. X-ray single crystal diffraction of nickel complex

shows that a very large metallic macrocycle with 2:2

stoichiometric is formed by two calixarene acylhydrazone

domains act as bidentated planar chelators to coordinate to

two nickel ion in a approximately square-planar geometry.

Keywords Calixarene � Schiff base � Hydrazone �Metallic complex � Crystal structure

Introduction

Calixarenes are a well-known class of polyaromatic mac-

romolecules and have been widely employed as three

dimensional molecular building blocks for the construction

of more elaborate host molecules and functionalized

materials with convergent binding groups and desired

properties in molecular recognition, self-assembly, supra-

molecular chemistry and nano sciences [1–3]. In order to

obtain much better properties and applications, the intro-

duction of various functionalities at its upper and lower rim

has become the most efficient methods [4, 5]. Schiff bases

have been employed widely in the formation of metal

complexes and in the study of inclusion phenomena, owing

to their relatively easy preparation, remarkable stability

and high versatility [6]. The modifications of calixarene

with functionalized Schiff base and other nitrogen-con-

taining derivatives such as amide, urea and pyridines have

become very public [7–12]. A lot of works have demon-

strated the introduction of Schiff base at the lower or upper

rim of calixarenes and used them as cation or anion

receptors and coordination ligands as well as in other wide

applications [13–25]. In the past years, we have designed

several types of calixarene Schiff base ligands and obtained

interesting metal complexes [26–31]. In continuation of our

aim to investigate the coordination environments afforded

by the calixarenes, herein we wish to report the investi-

gation results of synthesis and crystal structures of p-tert-

butylcalix[4]arene 1,3-distal acylhydrazones and macro-

cyclic nickel complex.

Results and discussion

The functionalized calix[4]arene 1,3-disubstituted alde-

hydes (1a–1b) were prepared by our previous reported

alkylation method [27, 29]. The reactions were accom-

plished by alkylation of p-tert-butylcalix[4]arene with 4-(3-

chloropropoxy)-, and 4-(4-chlorobutoxy)-vanillin in the re-

fluxing system of K2CO3/KI/CH3CN for several days. Then

the condensation reactions of calix[4]arene 1,3-disubstituted

aldehydes (1a–1b) with 2-hydroxybenzohydrazide were

carried out in a refluxing mixture of ethanol and chloroform

with acetic acid as acid catalyst for about twenty hours. The

desired calixarene acylhydrazones (2a–2b) were success-

fully obtained in 65 % and 71 % yields, respectively. Under

similar conditions, the reactions of calixarene dialdehydes

(1a–1b) with picolinohydrazide, nicotinohydrazide, and

X. Bi � J. Sun � W.-L. Liu � C.-G. Yan (&)

College of Chemistry & Chemical Engineering, Yangzhou

University, Yangzhou 225002, China

e-mail: [email protected]

123

J Incl Phenom Macrocycl Chem

DOI 10.1007/s10847-014-0382-x

isonicotinohydrazide afforded the corresponding calixarene

diacylhydrazones (3a–3f) in good yields (Scheme 1).

The structures of calix[4]arene 1,3-distal acylhydrazones

2a–2b and 3a–3f were fully characterized by 1H and 13C

NMR, IR spectra. As for an example, the 1H NMR spectra of

2b clearly display two doublets at 4.25 and 3.30 ppm with

germinal coupling J = 12.0 Hz, which are typical signs of

the axial and equatorial protons of bridging methylene

groups in 1,3-disubstituted calixarene in cone conformation

[32]. The 1,3-disubstitution at the lower rim was also con-

firmed by the appearance of two singlets at about 1.28 and

0.97 ppm for the tert-butyl groups on the upper rim. The

formation of the acylhydrazone was further determined by a

singlet at 12.31 ppm for two CONH groups, a singlet at 8.91

for the phenolic hydroxy groups and a singlet at 8.70 ppm for

two CH=N group. A singlet at 3.72 ppm for the two methoxy

groups and three broad singlets at 4.00, 2.26 and 2.15 ppm

for the two bridging OCH2CH2CH2CH2O units clearly

indicate that the two long chains of acylhydrazones exist in

nearly same environments. The other calixarene acylhydra-

zones also show similar 1H NMR spectral features, which are

consistent with the 1,3-distal configuration of p-tert-butyl-

calix[4]arene. The single crystal X-ray analysis of calixarene

acylhydrazone 2a confirmed the 1,3-distal configuration

assigned by means of 1H NMR spectra (Fig. 1). It is clear to

see that the calix[4]arene core remains in cone conformation.

The two bulky bisphenol units with substituents of acylhy-

drazones at lower rim [dihedral angle: 8.15(0.49)] exist more

perpendicular to other two bisphenol units without substit-

uents [dihedral angle: 79.46(0.25)]. The two long connecting

acylhydrazonyl chains stretch equivalently outside and exist

in a parallel arrangement to one direction. The adjacent

molecules are linked together through both intermolecular

hydrogen bonds (O12-H12��O7, 2.545(14)) and C–H��p

Table 1 Crystal data of compounds 2a and 2a–Ni

Phase 2a 2a–Ni

Empirical formula C83H99Cl3N4O13 C164H188N8Ni2O24

Formula weight 1467.01 2772.64

Temperature 293(2) K 293(2) K

Wavelength 0.71073 A 0.71073 A

Crystal system Monoclinic Monoclinic

Space group P 21/c C 2/c

Unit cell dimensions a = 24.736(10) A, a = 90� a = 31.825(4) A, a = 90�.

b = 17.502(7) A, b = 114.160(5)� b = 17.301(2) A, b = 99.789(2)�c = 20.469(8) A, c = 90� c = 34.465(4) A, c = 90�

Volume 8085(6) A3 18700(4) A3

Z 4 4

Density (calculated) 1.205 Mg m-3 0.985 Mg m-3

Absorption coefficient 0.176 mm-1 0.258 mm-1

F(000) 3,120 5,904

Crystal size 0.28 9 0.26 9 0.24 mm3 0.32 9 0.26 9 0.20 mm3

Theta range for data collection 1.47–27.73�. 1.52–25.00�Index ranges -32 \=h \=31, -22 \=k \=22, -26 \=l \=21 -34 \=h \=37, -20 \=k \=20, -40 \=l \=40

Reflections collected 70,749 66,956

Independent reflections 18,999 [R(int) = 0.1993] 16,483 [R(int) = 0.0826]

Completeness to theta = 27.73� 97.3 % 99.9 %

Absorption correction Semi-empirical from equivalents Semi-empirical from equivalents

Max. and min. transmission 0.959 and 0.952 0.950 and 0.923

Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2

Data/restraints/parameters 18,491/2,755/950 16,470/133/946

Goodness-of-fit on F2 0.977 1.173

Final R indices [I [ 2sigma(I)] R1 = 0.1,256, wR2 = 0.3094 R1 = 0.0766, wR2 = 0.1785

R indices (all data) R1 = 0.3297, wR2 = 0.4357 R1 = 0.1290, wR2 = 0.1921

Extinction coefficient 0.0018(6)

Largest diff. peak and hole 0.651 and -0.653 e.A-3 0.817 and -0.578 e.A-3


123

interactions between methoxy carbon atoms of the phenyl

rings [C72–Cg 3.628(1), Cg stands for the center of C75–

C80 phenyl ring] (Fig. 2) to give a 3D supramolecular net-

work (Table 3).

The coordination reactions of the above prepared calixa-

renes were carried out by refluxing ethanol solution of

ligands 2a–2b and 3a–3b with several transition metal ace-

tate or nitrate for some times. The transition metal complexes

are easily obtained in high yields by filtration of the resulting

precipitates. But it is very difficult to get the single crystal

with high quality for X-ray diffraction. After trying many

times, we have successfully determined the single crystal

structure of the complex 2a–Ni by X-ray diffraction method

(Fig. 3). The complex 2a–Ni crystallizes in the monoclinic

C 2/c space group. The asymmetric unit of 2a–Ni consists of

two half Ni2? ions and one 2a ligand, and symmetry

expansion reveals a Ni(II) dimeric complex of two.

Ni(II) ions connecting two doubly deprotonated ligands.

The calixarene acylhydrazone ligand in 2a–Ni acts as a

duple negatively charged tetradentate ligand to connect

with two Ni atoms via carbonyl oxygen and imino nitrogen

atoms from two acylhydrazone. Each Ni(II) ion in the

dimeric complex is coordinated by two imino nitrogen

atoms and two amide oxygen atoms of the two acylhyd-

razone groups from two ligands to give a approximately

square-planar geometry. The Ni–O distances are 1.835(3)

and 1.794(3) A, and the Ni–N distances are 1.859 (3) and

1.873 (3) A, respectively. Close inspection shows that two

calixarenes core still exist in cone conformation with two

bisphenol units without substituents (dihedral angle:

78.49(0.14)) is much inclined than the other two bisphenol

units (dihedral angle: 13.21(0.19)) as that in the ligand 2a,

the 2:2 stoichiometric complex was constituted by linkage

of two Ni ions and two calixarene acylhydrazone ligands,

therefore a very large metallocyclic framework containing

seventy-six atoms is also formed with a closest intermo-

lecular Ni��Ni distance of 3.2505(12) A.

Experimental section

Material and apparatus

p-tert-Butylcalix[4]arene [33], and its 1,3-disubstituted

aldehydes [27, 29] were prepared according to the

Table 2 Selected Bond lengths [A] and angles [�] for 2a-Ni

Ni(1)–O(10)#1 1.835(3)

Ni(1)–O(10) 1.835(3)

Ni(1)–N(2)#1 1.859(3)

Ni(2)–O(12) 1.794(3)

Ni(2)–O(12)#1 1.794(3)

Ni(2)–N(4)#1 1.873(3)

O(10)#1–Ni(1)–O(10) 179.38(19)

O(10)#1–Ni(1)–N(2)#1 84.84(14)

O(10)–Ni(1)–N(2)#1 95.15(14)

O(10)#1–Ni(1)–N(2) 95.15(14)

O(10)–Ni(1)–N(2) 84.83(14)

N(2)#1–Ni(1)–N(2) 177.2(2)

O(12)–Ni(2)–O(12)#1 176.88(19)

O(12)–Ni(2)–N(4)#1 96.05(13)

O(12)#1–Ni(2)–N(4)#1 83.88(13)

O(12)–Ni(2)–N(4) 83.88(13)

O(12)#1–Ni(2)–N(4) 96.05(13)

N(4)#1–Ni(2)–N(4) 177.7(2)

Symmetry transformations used to generate equivalent atoms: #1 –x

? 1, y, -z ? 5/2

OHOH OO

nO

CHO

nO

CHO

OMe OMe

NH

ONH2

EtOH/CHCl3

OHOH OO

nO

nO

OMe OMe

NNHO

N

NNHO

N

N

OHOH OO

nO

nO

OMe OMe

NNHO

NNHO

OH OH

NH

NH2

O

OH

EtOH/CHCl3

2a-2b 1a-1b (n = 3, 4) 3a-3f

Scheme 1 Synthesis of calixarene 1,3-distal acylhydrazones 2a–2b and 3a–3f


123

published method. Solvents were purified by standard

techniques. All reactions were monitored by TLC. Melting

points were taken on a hot-plate microscope apparatus. IR

spectra were obtained on a Bruker Tensor 27 spectrometer

(KBr disc). NMR spectra were recorded with a Bruker AV-

600 spectrometer with DMSO-d6 as solvent and TMS as

internal standard (600 and 150 MHz for 1H and 13C NMR

spectra, respectively). X-ray data were collected on a

Bruker Smart APEX-2 diffractometer.

X-ray crystallography

Single-crystal X-ray diffraction analyses were carried out

on a Bruker SMART APEX II CCD diffractometer with

graphite-monochromated Mo–Ka radiation (k = 0.71073

A) at 296(2) K. Empirical absorption corrections were

applied by using the SADABS program [34]. The struc-

tures were solved by direct methods and refined by the full

matrix least-squares based on F2 using SHELXTL

Fig. 1 Molecular structure of

compound 2a

Fig. 2 The hydrogen bonds and C–H��p interactions between molecules


123

programme package [35]. All non-hydrogen atoms were

refined anisotropically. The hydrogen atoms attached to

ligands were generated geometrically. Further details of the

data determination, crystal data and structure refinement

parameters are summarized in Table 1. Selected bond

lengths and angles are presented in Table 2. The Hydrogen

bonds for crystals 2a and 2a-Ni are listed in Table 3.

General procedure of reaction of calixarene 1,3-

disubstituted aldehydes with acylhydrazine

A mixture of calixarene 1,3-disubstituted aldehydes

(1.0 mmol), 2-hydroxybenzohydrazide (2.0 mmol, 0.304 g)

and acetic acid (1.0 mL) in ethanol (10.0 mL) and chloro-

form (20.0 mL) was refluxed for about 20 h. After cooling,

the resulting precipitates were collected by filtration and

washed several times with cold ethanol to give white solid.

2a

White solid; 0.845 g; yield: 65 %, m.p. 168–169 �C; 1H

NMR (600 MHz, DMSO-d6) d: 11.93 (s, 2H, OH), 11.72

(s, 2H, NH), 8.58 (s, 2H, CH=N), 8.36 (s, 2H, ArH), 7.89

(d, J = 7.6 Hz, 2H, ArH), 7.42 (t, J = 7.6 Hz, 2H, ArH),

7.37 (s, 2H, OH), 7.24 (d, J = 8.0 Hz, 2H, ArH), 7.13 (t,

J = 13.2 Hz, 10H, ArH), 6.97–6.92 (m, 4H, ArH), 4.52 (t,

J = 5.6 Hz, 4H, ArCH2Ar), 4.17 (d, J = 5.6 Hz, 4H,

OCH2), 4.09 (s, 4H, OCH2), 3.82 (s, 6H, OCH3), 3.46–3.41

(m, 4H, ArCH2Ar), 2.37 (s, 4H, CH2), 1.18 (s, 18H, CH3),

1.13 (s, 18H, CH3); 13C NMR (150 MHz, CDCl3) d: 164.6,

159.1, 150.1, 150.0, 149.4, 149.3, 148.9, 147.2, 141.4,

133.7, 133.2, 128.4, 127.4, 126.9, 125.7, 125.3, 122.2,

118.8, 117.2, 115.7, 112.4, 108.6, 72.6, 64.7, 55.6, 34.0,

33.6, 31.3, 31.1, 30.9, 29.4; IR (KBr) t: 3427, 2959, 2870,

1643, 1601, 1557, 1511, 1486, 1464, 1422, 1362, 1306,

1269, 1222, 1172, 1141, 1101, 1055, 1036, 979, 871,

632 cm-1.

2b

White solid, 0.944 g; yield: 71 %, m.p. 157–158 �C; 1H

NMR (600 MHz, CDCl3) d: 12.31 (s, 2H, NH), 8.91 (s, 4H,

OH), 8.70 (s, 2H, CH=N), 8.30 (s, 4H, ArH), 7.64 (s, 2H,

ArH), 7.17 (s, 2H, ArH), 7.04 (s, 4H, ArH), 6.93 (s, 2H,

ArH), 6.85–6.81 (m, 6H, ArH), 6.53 (d, J = 7.2 Hz, 2H,

ArH), 4.25 (d, J = 12.0 Hz, 4H, ArCH2Ar), 4.00 (s, 8H,

OCH2), 3.72 (s, 6H, OCH3), 3.30 (d, J = 12.0 Hz, 4H,

ArCH2Ar), 2.26 (s, 4H, CH2), 2.15 (s, 4H, CH2), 1.28 (s,

18H, CH3), 0.97 (s, 18H, CH3); 13C NMR (150 MHz,

Table 3 Hydrogen bonds for crystals 2a and 2a–Ni [A and �]

D-H��A d(D-H) d(H��A) d(D��A) \(DHA)

2a

O(13)-H(13)��O(8) 0.82 2.14 2.663(14) 122.0

O(12)-H(12)��O(7)#1 0.82 1.73 2.544(13) 169.9

O(8)-H(8)��O(13) 0.82 1.86 2.663(14) 166.0

O(4)-H(4)��O(1) 0.82 2.54 3.175(9) 135.7

O(2)-H(2)��O(1) 0.82 2.10 2.864(9) 155.4

N(21)-H(21A)��O(12) 0.86 1.92 2.611(15) 136.1

N(12)-H(12D)��O(8) 0.86 2.04 2.707(17) 133.8

2a_Ni

O(1)-H(1)��O(2) 0.82 2.16 2.959(4) 164.4

O(3)-H(3A)��O(2) 0.82 2.14 2.889(4) 151.7

O(9)-H(9)��N(1) 0.82 1.86 2.581(5) 146.0

Symmetry transformations used to generate equivalent atoms: for 2a:

#1 -x ? 1, -y, -z ? 2 for 2a-Ni: #1 -x ? 1 , y, -z ? 5/2

Fig. 3 Molecular structure of compound 2a–Ni


123

CDCl3) d: 166.2, 151.0, 150.6, 150.3, 149.7, 149.6, 147.1,

141.7, 134.5, 132.8, 127.8, 126.2, 125.6, 125.2, 123.2,

119.4, 118.1, 114.2, 111.9, 108.7, 76.0, 68.6, 60.5, 58.4,

55.8, 34.0, 33.8, 31.9, 31.7, 31.1, 26.9, 26.1, 20.7; IR (KBr)

t: 3423, 2957, 2869, 1643, 1600, 1551, 1511, 1486, 1421,

1361, 1304, 1269, 1225, 1173, 1141, 1036, 975, 903,

635 cm-1.

General procedure of reaction of calixarene 1,3-

disubstituted aldehydes with acylhydrazine

A mixture of calixarene 1,3-disubstituted aldehydes

(1.0 mmol), pyridinecarbohydrazide (2.0 mmol, 0.274 g)

and acetic acid (1.0 mL) in ethanol (10.0 mL) and chlo-

roform (20.0 mL) was refluxed for about 20 h. After

cooling, the resulting precipitates were collected by filtra-

tion and washed several times with cold ethanol to give

white solid.

3a (n = 3, picolinohydrazide)

White solid; 0.686 g. Yield: 54 %, m.p. 150–152 �C; 1H

NMR (600 MHz, CDCl3) d: 10.84 (s, 2H, NH), 8.24–8.07

(m, 6H, ArH), 7.90 (s, 2H, OH), 7.56–7.50 (m, 4H, ArH),

7.08–6.98 (m, 10H, ArH), 6.82 (s, 4H, ArH), 4.42 (s, 4H,

OCH2), 4.27 (d, J = 10.2 Hz, 4H, ArCH2 Ar), 4.14 (s, 4H,

OCH2), 3.91 (s, 6H, OCH3), 3.34 (d, J = 10.2 Hz, 4H,

ArCH2Ar), 2.44 (s, 4H, CH2), 1.31 (s, 18H, CH3), 0.90 (s,

18H, CH3); 13C NMR (150 MHz, CDCl3) d: 159.9, 150.9,

150.8, 149.7, 149.4, 149.2, 149.0, 148.0, 147.1, 137.4,

132.7, 127.6, 126.6, 126.5, 125.6, 125.2, 123.5, 122.6,

112.2, 108.6, 72.8, 65.7, 56.1, 33.9, 31.9, 31.8, 30.9, 29.9;

IR (KBr) t: 3435, 2957, 2870, 1600, 1507, 1426, 1387,

1270, 1233, 1202, 1136, 1041, 872, 812, 749, 624 cm-1.

3b (n = 4, picolinohydrazide)



CH = N), 8.23 (d, J = 6.6 Hz, 2H, ArH), 8.19 (s, 2H,

ArH), 7.81 (s, 2H, ArH), 7.70 (s, 2H, ArH), 7.51 (s, 2H,

OH), 7.07–7.03 (m, 8H, ArH), 6.83 (s, 4H, ArH), 6.78 (d,

J = 6.6 Hz, 2H, ArH), 4.30 (d, J = 12.6 Hz, 4H,

ArCH2Ar), 4.15 (s, 4H, OCH2), 4.06 (s, 4H, OCH2), 3.90

(s, 6H, OCH3), 3.34 (d, J = 12.6 Hz, 4H, ArCH2Ar), 2.29

(s, 4H, CH2), 2.22 (s, 4H, CH2), 1.30 (s, 18H, CH3), 0.95

(s, 18H, CH3); 13C NMR (150 MHz, CDCl3) d (ppm):

160.0, 150.9, 150.8, 149.8, 149.7, 149.4, 149.1, 147.9,

146.9, 141.5, 137.4, 132.6, 127.7, 126.6, 126.5, 125.9,

125.5, 125.2, 123.1, 122.7, 112.0, 108.8, 76.0, 68.6, 56.0,

33.7, 31.9, 31.7, 31.4, 30.9, 26.9, 26.0, 18.4; IR (KBr) t:

3384, 2957, 2870, 1598, 1506, 1363, 1270, 1234, 1202,

1138, 1035, 1003, 872, 812, 749, 701, 626 cm-1.

3c (n = 3, nicotinohydrazide)



CH=N), 8.68–8.60 (m, 2H, ArH), 8.37 (s, 2H, ArH), 8.22

(d, J = 6.0 Hz, 2H, ArH), 7.67 (s, 2H, ArH), 7.31 (s, 2H,

OH), 7.03 (s, 6H, ArH), 6.85–6.81 (m, 6H, ArH), 6.72 (d,

J = 7.2 Hz, 2H, ArH), 4.36 (s, 4H, OCH2), 4.23 (d,

J = 11.4 Hz, 4H, ArCH2Ar), 4.10 (s, 4H, OCH2), 3.75 (s,

6H, OCH3), 3.30 (d, J = 11.4 Hz, 4H, ArCH2Ar), 2.41 (s,

4H, CH2), 1.26 (s, 18H, CH3), 1.00 (s, 18H, CH3); 13C

NMR (150 MHz, CDCl3) d (ppm): 162.7, 151.7, 150.9,

150.8, 150.6, 149.8, 149.4, 148.2, 147.1, 141.6, 136.5,

132.7, 129.3, 127.7, 126.4, 125.9, 125.6, 125.1, 123.7,

123.4, 112.4, 108.5, 72.6, 65.8, 55.9, 34.0, 33.8, 31.7, 31.4,

31.0, 29.9, 18.4; IR (KBr) t: 3433, 2958, 2872, 1602, 1512,

1479, 1420, 1372, 1271, 1234, 1202, 1135, 1038, 955, 872,

814, 708, 628 cm-1.

3d (n = 4, nicotinohydrazide)


NMR (600 MHz, CDCl3) d: 12.88 (s, 2H, NH), 10.70 (s,

2H, CH=N), 9.31 (d, J = 7.8 Hz, 2H, ArH), 8.97 (s, 2H,

ArH), 8.79 (d, J = 5.4 Hz, 2H, ArH), 8.12 (t, J = 6.0 Hz,

2H, ArH), 7.79 (s, 2H, ArH), 7.60 (s, 2H, OH), 7.07 (s, 4H,

ArH), 6.91 (d, J = 6.6 Hz, 2H, ArH), 6.85 (s, 4H, ArH),

6.63 (d, J = 8.4 Hz, 2H, ArH), 4.29 (d, J = 13.2 Hz, 4H,

ArCH2Ar), 4.16 (t, J = 5.4 Hz, 4H, OCH2), 4.07 (t,

J = 5.4 Hz, 4H, OCH2), 3.91(s, 6H, OCH3), 3.34 (d,

J = 12.6 Hz, 4H, ArCH2Ar), 2.45–2.40 (m, 4H, CH2),

2.26–2.22 (m, 4H, CH2), 1.29 (s, 18H, CH3), 0.99 (s, 18H,

CH3); 13C NMR (150 MHz, CDCl3) d: 150.8, 150.7, 149.7,

149.6, 149.4, 147.1, 146.7, 141.6, 132.8, 132.7, 127.7,

125.9, 125.6, 125.5, 125.2, 111.6, 75.9, 68.7, 56.2, 55.9,

34.0, 33.9, 33.8, 33.7, 32.6, 31.7, 31.4, 31.0, 27.1, 26.3; IR

(KBr) t: 3422, 2958, 2869, 1600, 1513, 1477, 1424, 1365,

1272, 1202, 1135, 1036, 970, 871, 813, 679, 625 cm-1.

3e (n = 3, isonicotinohydrazide)



ArH), 8.52 (s, 2H, CH=N), 8.02–7.83 (m, 4H, ArH), 7.42

(d, J = 13.2 Hz, 2H, ArH), 7.03 (s, 6H, ArH), 6.94 (s, 2H,

ArH), 6.80–6.77 (m, 6H, ArH), 4.36 (s, 4H, OCH2), 4.22

(d, J = 11.4 Hz, 4H, ArCH2Ar), 4.10 (s, 4H, OCH2), 3.74

(s, 6H, OCH3), 3.28 (d, J = 11.4 Hz, 4H, ArCH2Ar), 2.40

(s, 4H, CH2), 1.26 (s, 18H, CH3), 0.95 (s, 18H, CH3); 13C

NMR (150 MHz, CDCl3) d: 161.5, 152.1, 151.3, 150.6,

149.8, 149.4, 147.1, 141.7, 132.7, 127.8, 126.2, 125.9,

125.6, 125.1, 123.5, 123.4, 112.4, 109.1, 72.7, 65.8, 65.0,

34.0, 33.8, 31.7, 31.4, 31.0, 29.9; IR (KBr) t: 3422, 2959,


123

2872, 1603, 1510, 1479, 1418, 1366, 1272, 1235, 1203,

1136, 1046, 955, 872, 813, 752, 684 cm-1.

3f (n = 4, isonicotinohydrazide)

white solid; 0.623 g; yield: 48 %, m.p. 174–175 �C; 1H


ArH), 8.57 (s, 2H, CH=N), 8.20 (s, 4H, ArH), 7.71 (s, 2H,

OH), 7.16 (s, 2H, ArH), 7.02 (s, 4H, ArH), 6.81 (s, 6H, ArH),

6.46 (s, 2H, ArH), 4.45 (s, 4H, OCH2), 4.23 (s, 4H, OCH2),

3.95 (d, J = 17.4 Hz, 4H, ArCH2Ar), 3.69 (s, 6H, OCH3),

3.29 (s, 4H, ArCH2Ar), 2.21 (s, 4H, CH2), 2.10 (s, 4H, CH2),

1.26 (s, 18H, CH3), 0.97 (s, 18H, CH3); 13C NMR (150 MHz,

CDCl3) d (ppm): 151.5, 150.7, 149.6, 146.9, 145.8, 141.5,

137.5, 132.7, 127.7, 125.9, 125.5, 125.1, 124.4, 124.3, 123.4,

111.9, 109.1, 76.0, 68.8, 55.9, 34.0, 33.8, 31.7, 31.0, 27.0,

26.4; IR (KBr) t: 3423, 2957, 2870, 1603, 1509, 1419, 1366,

1270, 1203, 1136, 1032, 871, 751, 630 cm-1.

Synthesis of transition metal complexes

A mixtrue of calixarene acylhydrazone 2a (0.2 mmol) and

Ni(OAc)2�4H2O (0.20 mmol) in ethanol (15 mL) was

refluxed overnight. After cooling, the resulting precipitates

were collected by filtration and washed with water and eth-

anol to give the red solid 2a–Ni. Yield: 83 %, m.p.[300 �C,

IR(KBr): 3423, 2958, 2871, 1626, 1592, 1488, 1367, 1272,

1202, 1150, 1098, 1046, 983, 948, 872, 787, 754, 694,

629 cm-1.

Supporting information

Single crystal data for compound 2a (CCDC 948656) and

2a–Ni (CCDC 948657) have been deposited in the Cam-

bridge Crystallographic Data Center. These data can be

obtained free of charge via http://www.ccdc.ac.ck./

data_request/cif.

Acknowledgments This work was financially supported by the

National Natural Science Foundation of China (Grant Nos. 20972132,

21372192) and the Priority Academic Program Development of Ji-

angsu Higher Education Institutions.

References

1. Bohmer, B.: Calixarenes, macrocycles with (almost) unlimited

possibilities. Angew. Chem. Int. Ed. Engl. 34, 713–745 (1995)

2. Mokhtari, B., Pourabdollah, K., Dalali, N.: Analytical applica-

tions of calixarenes from 2005 up-to-date. J. Incl. Phenom.

Macrocycl. Chem. 69, 1–55 (2011)

3. Borisova, N.E., Reshetova, M.D., Ustynyuk, Y.A.: Metal-free

methods in the synthesis of macrocyclic schiff bases. Chem. Rev.

107, 46–79 (2007)

4. Homden, D.M., Redshaw, C.: The use of calixarenes in metal-

based catalysis. Chem. Rev. 108, 5086–5130 (2008)

5. Pluth, M.D., Raymond, K.N.: Reversible guest exchange in

supramolecular host–guest assemblies. Chem. Soc. Rev. 36,

161–171 (2007)

6. Bazzicalupi, C., Bencini, A., Bianchi, A., Danesi, A., Faggi, E.,

Giorgi, C., Santarelli, S., Valtancoli, B.: Coordination properties

of polyamine-macrocycles containing terpyridine units. Coord.

Chem. Rev. 252, 1052–1068 (2008)

7. Wieser, C., Dielman, C., Matt, D.: Calixarene and resorcinarene

ligands in transition metal chemistry. Coord. Chem. Rev. 165,

93–161 (1997)

8. Vigato, P.A., Tamburini, S., Bertolo, L.: The development of

compartmental macrocyclic Schiff bases and related polyamine

derivatives. Coord. Chem. Rev. 251, 1311–1492 (2007)

9. Creaven, B.S., Donlon, D.F., McGinley, J.: Coordination chem-

istry of calix[4]arene derivatives with lower rim functionalisation

and their applications. Coord. Chem. Rev. 253, 893–962 (2009)

10. Cummings, S.D.: Platinum complexes of terpyridine: interaction

and reactivity with biomolecules. Coord. Chem. Rev. 253,

1495–1516 (2009)

11. Yilmaz, A., Memon, S., Yilmaz, M.: Synthesis and study of

allosteric effects on extraction behavior of novel calixarene-based

dichromate anion receptors. Tetrahedron 58, 7735–7740 (2002)

12. Halouani, H., Dumazet-Bonnamour, I., Perrin, M., Lamartine, R.:

First Synthesis and Structure of b-Ketoimine Calix[4]arenes:

complexation and extraction studies. J. Org. Chem. 69,

6521–6527 (2004)

13. Singh, N., Lee, G.W., Jang, D.O.: p-tert-Butylcalix[4]arene-based

fluororeceptor for the recognition of dicarboxylates. Tetrahedron

64, 1482–1486 (2008)

14. Ceborska, M., Tarnowska, A., Ziach, K., Jurczak, J.: Dynamic

combinatorial libraries of macrocycles derived from phthalic

aldehydes and a, x-diamines. Tetrahedron 66, 9532–9537 (2010)

15. Yang, F.F., Zhao, X., Guo, H.Y., Lin, J.R., Liu, Z.H.: Syntheses

and extraction properties of novel biscalixarene and thiaca-

lix[4]arene hydrazone derivatives. J. Incl. Phenom. Macrocycl.

Chem. 61, 139–145 (2008)

16. Nimse, S.B., Kim, J., Ta, V.T., Kim, S.H., Song, K.S., Jung, C.Y.,

Nguyen, V.T., Kim, T.: New water-soluble iminecalix[4]arene

with a deep hydrophobic cavity. Tetrahedron Lett. 50, 7346–7350

(2009)

17. Ali, A., Joseph, R., Mahieu, B., Rao, C.P.: Synthesis and char-

acterization of a (1?1) cyclic Schiff base of a lower rim 1,3-

diderivative of p-tert-butylcalix[4]arene and its complexes of

VO2?, UO22?, Fe3?, Ni2?, Cu2? and Zn2?. Polyhedron 29,

1035–1040 (2010)

18. McGinley, J., McKee, V., Walsh, J.: Synthesis, characterisation

and metal complexation reactions of two calix[4]arene deriva-

tives functionalised with pendant benzamide arms. Inorg. Chim.

Acta 375, 57–62 (2011)

19. Erdemir, S., Deveci, P., Taner, B., Kocyigit, O.: Synthesis and

electrochemical properties of calix[4]arene derivatives containing

ferrocene units in the cone and 1,3-alternate conformation. Tet-

rahedron 68, 642–646 (2012)

20. Sap, A., Tabakci, B., Yilmaz, A.: Calix[4]arene-based Mannich

and Schiff bases as versatile receptors for dichromate anion

extraction: synthesis and comparative studies. Tetrahedron 68,

8739–8745 (2012)

21. Shaabani, B., Shaghaghi, Z.: Synthesis, characterization and

electrochemical properties of two new calix[4]arene derivatives

bearing two ferrocene imine or ferrocene amine units at the upper

rim. Tetrahedron 66, 3259–3264 (2010)

22. Shaabani, B., Shaghaghi, Z., Khandar, A.: Optical spectroscopy

studies of the complexation of bis(azophenol)calix[4]arene pos-

sessing chromogenic donors with Ni2?, Co2?, Cu2?, Pb2? and


123

Hg2?. Spectrochim. Acta. A. Mol. Biomol. Spectrosc. 98, 81–85

(2012)

23. Chawla, H.M., Gupta, T.: New chromogenic bis(isatin hydrazo-

nyl)calix[4]arenes for dual recognition of fluoride and silver ions.

Tetrahedron Lett. 54, 1794–1797 (2013)

24. Chawla, H.A., Goel, P., Shukla, R.: New calix[4]arene based

oxalylamido receptors for recognition of copper(II). Tetrahedron

Lett 54, 2766–2769 (2013)

25. Ward, J.P., White, J.M., Young, C.G.: Synthesis, characterization

and metal ion complexation and extraction capabilities of

calix[4]arene Schiff base compounds. Tetrahedron 69,

8824–8830 (2013)

26. Yan, C.G., Li, L., Liu, W.L.: Metallic macrocycle with a 1,3-

alternate calix[4]arene salicylideneamine ligand. J. Coord. Chem.

62, 2118–2124 (2009)

27. Sun, J., Liu, D.M., Wang, J.X., Yan, C.G.: Transition metal

complexes of bidentate p-tert-butylcalix[4]arene S-alkyldithioc-

arbazate Schiff bases. J. Coord. Chem. 62, 2337–2346 (2009)

28. Sun, J., Liu, D.M., Wang, J.X., Yan, C.G.: Regioselective syn-

thesis of calix[4]arene 1,3-diand monosubstituted sulfur-con-

taining Schiff bases. J. Incl. Phenom. Macrocycl. Chem. 64,

317–324 (2009)

29. Sun, J., Liu, D.M., Wang, J.X., Yan, C.G.: Syntheses and Crystal

Structures of Calix[4]arene Dithiocarbazate Schiff Bases. Chem.

Res. Chin. Univ. 26, 572–577 (2010)

30. Li, L., Gu, W.W., Yan, C.G.: Syntheses, Crystal Structures and

Complexing Properties of 1,3-Distal Calix[4]arene Schiff Bases.

Chem. Res. Chin. Univ. 26, 38–45 (2010)

31. Bi, X., Sun, J., Yan, C.G.: Efficient Construction and Structure

Determination of Novel Macrocycles with Calixarene Bishyd-

razones. J. Chin. Chem. 30, 1539–1542 (2012)

32. Mahon, M.F., McGinley, J., Rooney, A.D., Walsh, J.: Calix[4]-

arene Schiff bases—potential ligands for fluorescent studies.

Tetrahedron 64, 11058–11066 (2008)

33. Gutsche, C.D., Dhawan, B., Leonis, M., Stewart, H.: p-tert-

Butylcalix[4]arene. Org. Synth. 68, 238–246 (1990)

34. Sheldrick, G.M.: SADABS, Program for Empirical Absorption

Correction of Area Detector Data. University of Gottingen,

Germany (2002)

35. Sheldrick, G. M.: SHELXTL, Version 6.10, Reference Manual,

Bruker-AXS, 5465 E. Cheryl, Parkway, Madison, 53711–5373

(2000)


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Synthesis and crystal structures of p-tert-butylcalix[4]arene 1,3-distal acylhydrazones and macrocyclic nickel complex