Inorganica Chimica Acta 384 (2012) 309–317

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Inorganica Chimica Acta

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Fourteen membered hexaaza copper macrocycle: Synthesis, characterization,

crystal structures and the consequence of anion coordination
Ahmad Husain a,1, A. Moheman a, Shahab A.A. Nami b, K.S. Siddiqi a,⇑
a
Department of Chemistry, Aligarh Muslim University, Aligarh 202002, India
b
Department of Kulliyat, Faculty of Unani Medicine, Aligarh Muslim University, Aligarh 202002, India

a r t i c l e i n f o a b s t r a c t

Article history: Fourteen membered hexaaza macrocyclic complexes of the type [CuLX2] (where L = 3,10-bis(ben-
Received 14 October 2010 
zyl)1,3,5,8,10,12-hexaazacyclotetradecane and X ¼ ClO4 , SCN) and [CuL(CH3CN)2](PF6)2(CH3CN)2 have
Received in revised form 10 August 2011 been synthesized by template assisted condensation reaction. They have been characterized by spectral
Accepted 13 December 2011
and X-ray crystallographic techniques. It was of interest to investigate the effect of anions on the gross
Available online 24 December 2011
geometry and chemical properties of Cu(II) ion. The crystal structure of all the complexes show axially
elongated octahedral geometry with weakly coordinated anions. The macrocyclic ring adopts the
Keywords:
trans-III configuration with six- and five-membered chelate rings in chair and gauche conformation,
Crystal structure
Trans-III conformation
respectively. The IR and other spectral properties are consistent with the result of X-ray diffraction. It
Macrocycle was observed that in the solid state the arrangement of the coordination sphere is distorted octahedral
Cu(II) complex whereas in solution, a square-planar structure is predominant. The molar conductivity of the complexes
Axially elongated octahedral indicates that the axially bonded anions are almost entirely dissociated in acetonitrile solution. The EPR
Square-planar spectra of complexes 1–3 are axial and consistent with a dx2 y2 ground state.
Crown Copyright Ó 2011 Published by Elsevier B.V. All rights reserved.

1. Introduction are simple ‘one pot reactions’, inexpensive and high yielding. Metal
template condensation involving amines and formaldehyde have
There is a continuing interest in the chemistry of polyazamacro- been employed in the preparation of various saturated polyazamac-
cycles because of their sturdy chemical and biochemical application. rocyclic complexes containing N–CH2–N linkages [11–14]. Some-
Structural factors, such as ligand rigidity and the electron-donating times, the pendant-arms of the macrocycles can also play an
properties of the nitrogen atoms constituting the polyaza network important role in altering their stereochemistry and thermody-
and their disposition play a significant role in determining the namic parameters, hence affecting their overall physicochemical
binding features towards metal cations [1–7]. Moreover, hexaaza properties [15]. However, the presence of rigid aromatic system
macrocyclic complexes show enhanced thermodynamic and kinetic gives particular coordination properties to the ligands defining dis-
stability as compared to their non-cyclic chelate ligands, and have tinct preorganized binding sites for the metal ions. Copper-contain-
applications in modern chemical techniques such as magnetic ing macrocycles are of considerable interest as low molecular
resonance imaging, imaging with radioisotopes and radiotherapy weight models for biological copper-containing redox proteins [16].
[8,9]. The diverse synthetic utility of hexaaza macrocycles may be In the present study, complexes of 14-membered hexaaza mac-
attributed due to the liberty offered by these systems in terms of rocyclic ligand with Cu(II) containing different anions have been
cavity size, pendant groups and different metal encapsulation characterized by crystallographic studies to investigate the effect
ability. The complexation of hexaaza macrocycles is governed of the anions on the gross geometry and chemical properties of
mainly by the ring size and ionic radii of the metal ions [10]. Cu(II) ion. In order to characterize the [CuLX2] entity structurally
Out of the two well known strategies of synthesis of polyaza- and to assess the consequence of anion coordination, IR, electronic
macrocyclic systems, metal template procedure is considered as spectra and EPR were also recorded and analyzed in this work.
better as it often provides selective routes toward products that
are not obtainable in the absence of metal ions. Such processes
2. Experimental
⇑ Corresponding author. Mobile: +91 9837284930.
2.1. Material and methods
E-mail addresses: [email protected] (A. Husain), kssiddiqi@gmail.
com (K.S. Siddiqi).
1
Present address: Centre for Supramolecular Chemistry Research, Department of Cu(OOCCH3)2H2O, HClO4 (Merck India), ethylenediamine (E.
Chemistry, University of Cape Town, South Africa. Merck), benzylamine and formaldehyde (S.D. Finechem India) were

0020-1693/$ - see front matter Crown Copyright Ó 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.12.019
310 A. Husain et al. / Inorganica Chimica Acta 384 (2012) 309–317

used as received. Elemental analysis was done with a FLASH EA 2.4. Synthesis of [CuL(CH3CN)2](PF6)2(CH3CN)2 (3)
1112 SERIES CHNS analyzer. IR spectra (4000–400 cm1) were re-
corded with a Spectrolab Interspec FT/IR-2020 spectrometer as To an acetonitrile (20 mL) solution of [CuL(ClO4)2] (1) (1 mM,
KBr disc. The conductivity measurements were carried out with a 0.645 g) was added an excess of potassium hexafluorophosphate
CM–82T Elico conductivity bridge in acetonitrile. The electronic and filtered to remove solid KClO4. The red filtrate was allowed
spectra were recorded with a Perkin Elmer Lambda–35 UV–Vis to stand for a few days at 4 °C to give red crystals. Yield: 94%
spectrophotometer in CH3CN. Magnetic susceptibility measure- (0.606 g). M.p.: 297 °C. Km: 275 X1 cm2 M1. Anal. Calc. for
ments in powdered samples were performed at 25 °C by Faraday C22H34CuF12N6P2 (3): C, 40.03; H, 5.15; N, 15.56. Found: C, 40.23;
method with a Sherwood Scientific magnetic susceptibility balance, H, 5.28; N, 15.45% IR (KBr, cm1): 3269, 3173, 2916, 2885, 2294,
calibrated against Hg[Co(SCN)4]. EPR spectra were recorded in the 2259, 1466, 1435, 1379, 1334, 1273, 1188, 1159, 1080, 1057,
solid state and in frozen CH3CN with a JEOL FE3X EPR spectrometer 999, 823, 738, 702, 638, 557, 445.
at X-band microwave frequency. Powder XRD pattern of all samples
were recorded on a Bruker-Axs, D8 Advance diffractometer using 2.5. X-ray crystal structure determination and refinements
Cu Ka X-radiation at 35 kV and 25 mA. Diffraction patterns were
collected over 2h range of 5–50° at scan rate of 1°/min. Single crystals suitable for X-ray crystallographic analysis were
Caution! Although our samples never exploded during handling, obtained by slow evaporation of the solvent from the acetonitrile
perchlorate metal complexes are potentially explosive: they should solution of 1 at room temperature and that of 3 at 4 °C. Crystals
be handled with care. of 2 were grown by slow evaporation of a 1:1 mixture of acetonitrile
and DMF and a few drops of water. X-ray data for 1 were collected
2.2. Synthesis of [CuL(ClO4)2] (1) [(L = 3,10-bis(benzyl)1,3,5,8,10,12- using graphite-monochromated Mo Ka radiation (K = 0.71073 Å)
hexaazacyclotetradecane)] on ‘‘Bruker SMART APEX CCD Diffractometer’’ at 100(2) K. The pro-
gram SMART [17] was used for collecting frames of data, indexing
To an ethanolic (50 mL) solution of Cu(OOCCH3)2H2O (5 mM, reflections, and determining lattice parameters for 1. The data inte-
0.998 g) were slowly added ethylenediamine (10 mM, 0.669 mL), gration and reduction were processed with SAINT [17] software. An
40% formaldehyde (20 mM, 1.600 mL) and benzylamine (10 mM, empirical absorption correction was applied to the collected reflec-
1.092 mL) with constant stirring. After refluxing this mixture for tions with SADABS [18] using XPREP [19]. X-ray data for 2 and 3 were
48 h, the red-violet solution was cooled to room temperature and collected on Oxford Diffraction Gemini CCD equipped diffractome-
filtered to remove any insoluble solid. To this filtrate an excess of ter at 298(2) K using graphite-monochromated Mo Ka radiation
70% perchloric acid was added with continuous stirring which (K = 0.71073 Å). The strategy for the data collection was evaluated
yielded pink colored precipitate (Scheme 1). It was filtered and by the CRYSALISPRO CCD software and collected by the standard
washed with ethanol and dried over P2O5. The complex was recrys- ‘phi-omega scan’ techniques, scaled and reduced using CRYSALISPRO
tallized from acetonitrile. Red crystals were obtained after 7 days. RED software [20]. The linear absorption coefficients, scattering
Yield: 80% (2.58 g). M.p.: 255 °C. Km: 247 X1 cm2 M1. Anal. factors for the atoms and the anomalous dispersion corrections
Calc. for C22H34Cl2CuN6O8 (1): C, 40.97; H, 5.31; N, 13.03. Found: were taken from the International Tables for X-ray Crystallography
C, 40.81; H, 5.41; N, 13.15%. IR (KBr, cm1): 3243, 3173, 2924, [21]. The structures were solved by direct method using SHELXS-97
2879, 1449, 1421, 1377, 1335, 1275, 1114, 1073, 997, 830, 896, program [22] and were refined on F2 by full-matrix least-square
855, 750, 703, 624, 437. technique using the SHELXL-97 [22] program. Figures were drawn
using ORTEP-3.2 [23] and MERCURY-2.3 [24]. All non-hydrogen atoms
were refined with anisotropic displacement parameters. H atoms
2.3. Synthesis of [CuL(SCN)2] (2)
were refined isotropically. The pertinent crystal data and refine-
ment parameters for compounds 1, 2 and 3 are compiled in Table 1.
To a solution of [CuL(ClO4)2] (1) (1 mM, 0.645 g) in acetonitrile
(20 mL) was added an excess of potassium thiocyanate and stirred
for 1 h. It was filtered to remove solid KClO4 and the solvent was evap- 3. Results and discussion
orated to dryness to give purple blue powder. It was dissolved in ace-
tonitrile-DMF mixture with a few drops of water and left to stand at 3.1. Crystal structure description of [CuL(ClO4)2] (1)
room temperature. Violet crystals thus obtained after 1 month were
filtered and washed with ethanol. Yield: 95% (0.612 g). M.p.: The molecular structure and the atomic numbering scheme of 1 is
228 °C. Km: 254 X1 cm2 M1. Anal. Calc. for C24H34CuN8S2 (2): C, shown in Fig. 1. Crystallographic data, selected bond lengths and bond
51.27; H, 6.10; N, 19.93. Found: C, 50.87; H, 5.99; N, 19.73%. IR (KBr, angles are listed in Tables 1 and 2. It was crystallizes in triclinic system
cm1): 3194, 2897, 2868, 2049, 1459, 1418, 1269, 1188, 1147, 1060, with P1 space group. The asymmetric units comprise of half a mole-
1012, 951, 856, 742, 698, 640, 592, 480, 418. cule and the other half of the molecules are generated through a

Scheme 1. Synthesis of [CuL(ClO4)2] (1).

 A. Husain et al. / Inorganica Chimica Acta 384 (2012) 309–317 311

Table 1
Crystallographic data and structure refinement parameters for 1, 2 and 3.

Complex [CuL(ClO4)2] (1) [CuL(SCN)2] (2) [CuL(CH3CN)2](PF6)22CH3CN (3)

Empirical formula C22H34Cl2CuN6O8 C24H34CuN8S2 C30H46CuF12N10P2
Formula weight 644.99 562.25 900.25
T (K) 100(2) 298(2) 298(2)
0
0.71073 0.71073 0.71073
k (Å
A)
Crystal system Triclinic Rhombohedral Monoclinic
Space group 
P1 
R3 P2(1)/c
a (Å) 10.156(3) 29.766(6) 12.5103(9)
b (Å) 11.433(3) 29.766(6) 16.0648(11)
c (Å) 11.965(3) 7.9265(11) 20.8753(15)
a (°) 86.679(5) 90 90
b (°) 75.765(4) 90 99.8510(10)
c (°) 87.829(5) 120 90
V (Å3) 1344.0(6) 6082.2(19) 4133.6(5)
Z, qcalc (g cm3) 2, 1.594 9, 1.382 4, 1.447
Absorption coefficient (mm1) 1.070 0.991 0.696
F(0 0 0) 670 2655 1852
Crystal size (mm) 0.28  0.20  0.20 0.40  0.20  0.10 0.25  0.20  0.20
h Range for data collection (°) 2.07–25.00 2.74–24.99 1.61–25.00
Limiting indices 12 6 h 6 10, 12 6 k 6 13, 35 6 h 6 27, 23 6 k 6 34, 14 6 h 6 14, 19 6 k 6 19,
14 6 l 6 14 9 6 l 6 9 24 6 l 6 24
Reflections collected/unique 6855/4664 [Rint = 0.0245] 8105/2381 [Rint = 0.0628] 39 271/7278 [Rint = 0.0400]
Maximum and minimum 0.8145 and 0.7539 0.9074 and 0.6926 0.8734 and 0.8453
transmission
Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data/restraints/parameters 4664/4/371 2381/3/168 7278/2/516
Goodness-of-fit on F2 1.066 0.957 1.039
Final R indices [I > 2r(I)] R1 = 0.0475, wR2 = 0.1336 R1 = 0.0506, wR2 = 0.1226 R1 = 0.0699, wR2 = 0.1953
R indices (all data) R1 = 0.0528, wR2 = 0.1396 R1 = 0.0787, wR2 = 0.1308 R1 = 0.0864, wR2 = 0.2098
Largest diff. peak and hole (e Å3) 1.160 and 0.815 0.573 and 0.360 1.021 and 0.426
Completeness to h = 25.00 (%) 98.5 99.9 100.0

Table 2
Selected bond lengths (Å) and bond angles (°) for [CuL(ClO4)2] (1).

Bond lengths Bond angles

N(1B)–Cu(1B) 2.002(2) N(1B)–Cu(1B)–N(2B)#1 93.92(10)
N(2B)–Cu(1B) 2.015(2) N(1B)–Cu(1B)–N(2B) 86.08(10)
N(1A)–Cu(1A) 1.994(3) N(1A)–Cu(1A)–N(2A) 86.11(10)
N(2A)–Cu(1A) 2.020(3) N(1A)–Cu(1A)–N(2A)#2 93.89(10)

Symmetry transformations used to generate equivalent atoms: #1 x + 1, y + 1,

z + 1 #2 x + 1, y, z.

and (Cu(1B)–N(1B) = 2.002(2) Å, Cu(1B)–N(2B) = 2.015(2) Å] occupy-

ing equatorial plane in an essentially square-planar arrangement and
two weakly coordinated perchlorate anions at the axial position. The
two independent molecules in the asymmetric unit show slightly 0
dif-
ferent Cu–O (perchlorate) interactions [Cu(1A)–O(4A) = 2.474 ÅA and
Cu(1B)–O(1B) = 2.651 Å]. The overall coordination geometry around
Cu(II) may therefore, be described as an elongated octahedron which
is expected from the Jahn–Teller distortion.
The six-membered chelate rings adopt a chair conformation,
whereas five-membered rings assume a gauche conformation.
The chelate angles were N(1A)–Cu(1A)–N(2A) = 86.11(10)°,
N(1A)–Cu(1A)–N(2A)#2 = 93.89(10)° and N(1B)–Cu(1B)–N(2B) =
86.08(10)°, N(1B)–Cu(1B)–N(2B)#1 = 93.92(10)° for five- and six-
membered rings in unit A and B, respectively. The Cu–N and Cu–O
bond lengths are similar to other Cu(II) complexes with cyclam-
Fig. 1. Molecular structure (ORTEP diagram with 50% thermal ellipsoids) of 1, along
with the atomic numbering scheme. Hydrogen atoms have been omitted for clarity. derived ligands where perchlorate is axially coordinated [25,26].
The trans-III configuration of N-donors enables the hexaaza ring to
adopt least strained conformation, i.e. an eclipsed pair of gauche
center of symmetry. There are two metal atoms in the asymmetric five-membered chelate rings and two chair six-membered rings.
unit sitting on inversion centers. The two resulting molecules have The perchlorate ion indicates a lengthening of the Cl–O bond
equivalent geometries (Table 2). The coordination environment of involving O(4A) and O(1B), which were weakly coordinated to
the Cu(II) ion is (N4O2) coordinated with four secondary amine nitro- the Cu atom. The Cl(1A)–O(4A) and Cl(1B)–O(1B) bond length were
gen atoms [Cu(1A)–N(1A = 1.994(3) Å, Cu(1A)–N(2A) = 2.020(3) Å) 1.452(2) and 1.437(2) Å, which were significantly longer than the
312 A. Husain et al. / Inorganica Chimica Acta 384 (2012) 309–317

Fig. 2. Depicting intermolecular hydrogen bonded 1D polymeric array along a axis for complex 1. Hydrogen atoms except those involved in H-bonding have been omitted for
clarity.

Table 4
Table 3
Selected bond lengths (Å) and bond angles (°) for [CuL(SCN)2] (2).
Intramolecular and intermolecular hydrogen bonds of the N–H  O and C–H  O type
in complex [CuL(ClO4)2] (1). Bond lengths Bond angles

D–H  A d(D  A) d(H  A) (D–H  A) (°) Cu(1)–N(1) 2.035(3) N(2)–Cu(1)–N(1) 94.14(11)
(Å) (Å) Cu(1)–N(2) 2.011(3) N(2)#1–Cu(1)–N(1) 85.86(11)
Cu(1)–N(4) 2.528(3) C(11)–N(1)–C(9) 113.6(3)
N(1A)– 2.939 2.187 145.3 (x, y  1, z)
S(2)–C(12) 1.562(5) C(8)–N(3)–C(9) 115.1(3)
H(N1A)  O(3B)
C(12)–N(4) 1.192(5) C(8)–N(3)–C(7) 114.8(3)
N(1B)– 2.976 2.214 147.07 (x + 1, y, z + 1)
C(9)–N(3)–C(7) 115.7(3)
H(N1B)  O(1A)
N(1)–Cu(1)–N(4) 89.93(12)
N(1B)– 3.131 2.639 117.33 (x + 1, y + 1,
N(1)–Cu(1)–N(4)#1 90.07(12)
H(N1B)  O(1B) z + 1)
N(2)–Cu(1)–N(4) 87.59(13)
N(2A)– 3.104 2.293 156.66 (x + 1, y, z)
N(2)–Cu(1)–N(4)#1 92.40(13)
H(N2A)  O(3A)
N(2B)– 2.994 2.159 161.01 Symmetry transformations used to generate equivalent atoms: #1 x + 1, y,
H(N2B)  O(2B) z + 1.

mean of the other three Cl–O bonds [27]. The mononuclear units lengths and bond angles are given in Tables 1 and 4. It was crystal-
are held together by intermolecular hydrogen bonds to form an lizes in rhombohedral system with R3  space group with nine for-
infinite one-dimensional polymeric array along a axis (Fig. 2). mula units per unit cell (Fig. 4). The asymmetric unit is made up
The hydrogen bonding parameters are collected in Table 3. of half a molecule, the other half of the molecule is generated
through a center of symmetry. The crystallographic asymmetric
3.2. Crystal structure description of [CuL(SCN)2] (2) unit of 2 consists of [CuL]2+ cation and two thiocyanate anions in
isothiocyanate binding mode. The thiocyanate ion is known to form
The molecular structure of 2 along with the atomic numbering both thiocyanato (M–SCN) and isothiocyanato (M–NCS) complexes,
scheme is shown in Fig. 3. Crystallographic data, selected bond depending on the nature of metal ion [28]. Pearson [29] suggests

Fig. 3. Molecular structure (ORTEP diagram with 50% thermal ellipsoids) of complex 2, along with the atomic numbering scheme. Hydrogen atoms have been omitted for
clarity.
 A. Husain et al. / Inorganica Chimica Acta 384 (2012) 309–317 313

that S in SCN is soft and will prefer to coordinate with soft acids
whereas N in SCN is hard and coordinates with hard acids. The
copper atom is in an axially distorted octahedral (N4 + N2) environ-
ment with four secondary amine nitrogen atoms occupying the
equatorial plane, similar to 1 and two isothiocyanate groups at
the axial positions. Two cross bond angles N(1)–Cu(1)–N(1)#1
and N(2)–Cu(1)–N(2)#1 in equatorial plane show that the Cu(II)
ion is located in a square plane without any axial displacement.
The large Cu(1)–N(4) bond length of 2.528(3) Å in trans configura-
tion, are similar to those found for weakly coordinated axial SCN
in hexa-coordinate (N4N2) copper complexes such as trans-[Cu
(Me2en)2(NCS)2] [30], trans-[Cu(amepy)2(NCS)2] and [Cu(a-
L)(NCS)2] [31–33]. The thiocyanate groups show small distortions
[N(4)–(C12)–S(2) = 177.74(4)°] from linearity as is usually ob-
served [34]. The Cu–N–C angles related to the thiocyanate anion
are Cu(1)–N(4)–C(12) [119.9(6)°]. Therefore, the overall geometry
of Cu(II) may be described as an elongated octahedron similar to
1. The chelate angles N(1)–Cu(1)–N(2), N(1)–Cu(1)–N(2)#1 were
94.14(11)°, 85.86(11)° for six-membered and five-membered rings,
respectively. Analysis of the crystal packing reveals that mononu-
Fig. 4. Unit cell diagram of complex 2. Hydrogen atoms have been omitted for clear units are held together by intermolecular hydrogen bonds
clarity. involving the N(2)–H(2A) protons and S(2) with d(D  A) = 3.615Å,

Fig. 5. Depicting intermolecular hydrogen bonded 1D polymeric array along a axis in complex 2. Hydrogen atoms except those involved in H-bonding have been omitted for
clarity.

Fig. 6. Molecular structure (ORTEP diagram with 50% thermal ellipsoids) of complex 3, along with the atomic numbering scheme. Hydrogen atoms have been omitted for
clarity.
314 A. Husain et al. / Inorganica Chimica Acta 384 (2012) 309–317

Table 5
Selected bond lengths (Å) and bond angles (°) for [CuL(CH3CN)2](PF6)22CH3CN (3).

Bond lengths Bond angles

Cu(1)–N(1) 2.006(4) N(2)–Cu(1)–N(1) 86.26(14)
Cu(1)–N(2) 2.002(3) N(2)–Cu(1)–N(3) 92.96(13)
Cu(1)–N(3) 2.011(3) N(3)–Cu(1)–N(4) 86.57(13)
Cu(1)–N(4) 2.010(3) N(1)–Cu(1)–N(4) 94.03(14)
Cu(1)–N(7) 2.747(4) N(2)–Cu(1)–N(9) 93.22(15)
Cu(1)–N(9) 2.432(4) N(1)–Cu(1)–N(9) 89.96(15)
N(7)–C(27) 1.118(7) N(3)–Cu(1)–N(9) 93.77(15)
N(8)–C(29) 1.127(8) N(4)–Cu(1)–N(9) 89.59(15)
N(9)–C(23) 1.120(5) N(1)–Cu(1)–N(3) 176.23(15)
N(10)–C(25) 1.118(7) N(2)–Cu(1)–N(4) 177.18(15)
C(27)–N(7)–Cu(1) 143.13(4)
C(23)–N(9)–Cu(1) 158.2(4)
N(1)–Cu(1)–N(7) 89.33(17)
N(2)–Cu(1)–N(7) 85.93(15)
N(3)–Cu(1)–N(7) 86.93(16)
N(1)–Cu(1)–N(9) 89.96(14)
Fig. 7. Unit cell diagram of complex 3. Hydrogen atoms have been omitted for
N(2)–Cu(1)–N(9) 93.23(15)
clarity.
N(3)–Cu(1)–N(9) 93.77(14)
N(4)–Cu(1)–N(7) 91.25(15)
N(4)–Cu(1)–N(9) 89.60(15)

Fig. 8. Solvent-anion interaction for complex 3. Arrangement of PF6 nd two solvent molecules due to F  H bonding in unit cell. Hydrogen atoms have been omitted for
clarity.
 A. Husain et al. / Inorganica Chimica Acta 384 (2012) 309–317 315

Table 6 3.4. IR Spectral studies

Hydrogen bonds of the N–H  F and N–H  N type between the macrocycle and PF6
and CH3CN in complex [CuL(CH3CN)2](PF6)22CH3CN (3).
IR spectra of 1–3 (Fig. S1, Supporting information) show common
D–H  A d(D  A) d(H  A) (D–H  A) (°) absorption bands, characteristic of the tetraaza macrocyclic ligand
(Å) (Å) in the region 3269–3194 cm1, indicating the presence of NH groups
N(1)– 3.031(7) 2.30(5) 154(5) (x, 1/2  y, 1/ in the complexes. Complex 1 shows two splitted peaks at 1111 and
H(1N)  N(10) 2 + z) 1074 cm1 (m3-antisymmetric stretching) assigned to perchlorate
N(2)– 3.210(7) 2.41(5) 153(4) (1 + x, y, z)
H(2N)  F(10)
ions [35]. This splitting clearly explains the presence of coordinated
N(3)–H(3N)  N(8) 2.999(7) 2.27(5) 147(4) (1 + x, y, z) perchlorate ion [36]. The band at 999 cm1 (m2-symmetric stretch-
C(26)– 3.347(8) 2.52 145 ing) further supports that perchlorate ions are coordinated in the
H(26A)  F(2) complex [37]. The peak around 621 cm1 (m4-antisymmetric bend-
C(28)– 3.310(10) 2.41 157 (1 + x, y, z)
ing) belongs to a perchlorate bending vibration.
H(28B)  F(4)
The m(CN) stretching frequency of the thiocyanate group can be
used for characterization of the coordination mode to the metal ion
[38,39]. The stretching frequency m(CN) of thiocyanate are lower in
d(H  A) = 2.882 Å and (D–H  A) = 143° to form an infinite one- N-bonded (near 2050 cm1) than S-bonded complexes (near
dimensional polymeric chain along the b axis (Fig. 5). 2100 cm1). The m(CN) observed at 2050 cm1 in 2 suggests that
the pseudo-halide is coordinated to copper through the nitrogen
atom (terminal N-bonded) [40].
3.3. Crystal structure description of [CuL(CH3CN)2](PF6)22CH3CN (3)
The spectrum of 3 displays broad and intense bands at 845 and
555 cm1 consistent with the characteristic m3(Flu) IR-active modes
The molecular structure of the complex 3 along with the atomic
of the PF6 anions [38]. It showed two bands at 2341 and
numbering scheme is shown in Fig. 6. Crystallographic data, selected
2313 cm1 due to the asymmetric and symmetric m(C„N) of the coor-
bond lengths and bond angles are given in Tables 1 and 5. It was crys-
dinated acetonitrile [41]. A band at 2250 cm1 is indicative of uncoor-
tallizes in the space group P2(1)/c of the monoclinic system. The unit
dinated lattice acetonitrile [42]. When IR spectrum of 3 was taken
cell was shown in Fig. 7. The crystal structure of 3 contains a mono-
after drying at 80 °C for 30 min, (Fig. S1, Supporting information)
meric [CuL(CH3CN)2]2+ cation, two hexafluorophosphate anions and
two lattice acetonitrile molecules. The Cu(1) atom is (N4 + N2) coordi-
nated in a distorted elongated octahedron with four secondary amine
nitrogen atoms [Cu(1)–N(1) = 2.006(4) Å, Cu(1)–N(2) = 2.002(3) Å,
Cu(1)–N(3) = 2.011(3) Å and Cu(1)–N(4) = 2.010(3) Å] occupying
the equatorial plane in an square planar arrangement and coordi-
nated by two nitrogen atoms from0
two acetonitrile at the axial posi-
tions (Cu(1)–N(9) = 2.432(4) Å A and Cu(1)–N(7) = 2.747(4) Å). The
two trans bond angles in equatorial plane (N(1)–Cu(1)–N(3) and
N(2)–Cu(1)–N(4) deviate from 180° indicating that the Cu(II) ion is
slightly out of equatorial plane with some axial displacement. The
copper ion is 0.057 Å above the basal plane constituted via N(1),
N(2), N(3), N(4) atoms, towards the N(9) of CH3CN. The two coordi-
nated CH3CN are located at trans positions to each other and are not
exactly at the axial sites of Cu(II) as evident from the bond angle
(N(7)–Cu(1)–N(9) = 178.93°). While in most transition metal com-
plexes of acetonitrile the coordination is approximately linear, it
deviates slightly from linearity. The bond angles N(1)–Cu(1)–N(9),
N(4)–Cu(1)–N(9), N(2)–Cu(1)–N(9), and N(3)–Cu(1)–N(9) are
89.96(15)°, 89.59(15)°, 93.22(15)° and 93.77(15)°, respectively,
suggested that the Cu(1)–N(7) and Cu(1)–N(9) linkages are slightly
bent off the perpendicular to the N(1)–Cu(1)–N(4) and N(2)–Cu(1)–
N(3) plane. The angle between the planes of the two benzene rings
is 23.32° which is possibly due to intramolecular hydrogen.
0
The P–F bond length ranges from 1.454(5) to 1.571(5) Å A with an
0
average of 1.528(5) ÅA. [CuL(CH3CN)2]2+ cation is linked by intramo-
lecular N–H  F hydrogen bonds through uncoordinated PF6 an-
ions and N–H  NNCMe through two lattice acetonitrile molecules,
which are further linked by C–H  F hydrogen bonds. In the crystal
packing four PF6 anions and two lattices CH3CN were arranged in
a square manner by H  F bonding forming to a 2D network (Fig. 8).
Pertinent structural parameters of the hydrogen-bonded contacts
are collated in Table 6.
During the solving crystal structure, it was suggested that some
F atoms were disordered and multiple splitting was suggested for
single F atoms. The fluorine atoms of PF6 counter ions have a high
thermal parameter since data was collected at room temperature.
We tried refining those atoms in two positions with reduced occu- Fig. 9. (a) EPR spectra of 1, 2 and 3 determined at RT on polycrystalline powder
pancy but there was no decrease in R value and, therefore, we con- sample. (b) EPR spectra of 1, 2 and 3 determined at 140 K on a frozen CH3CN–
sider that our original refinement is the best. C6H5CH3 (1:1, v/v) glass.
316 A. Husain et al. / Inorganica Chimica Acta 384 (2012) 309–317

Table 7
EPR parameters of the complexes 1–3.

Complex Temperature g|| g\ giso G A||

[CuL(ClO4)2] (1) RT 2.180 2.043 2.088 4.366 –
LNT 2.095 2.025 2.048 4.083 96
[CuL(SCN)2] (2) RT 2.177 2.045 2.089 4.091 –
LNT 2.067 2.019 2.035 3.874 170.6
[CuL(CH3CN)2](PF6)22CH3CN (3) RT 2.225 2.056 2.112 4.147 –
LNT 2.176 2.050 2.092 3.64 214

acetonitrile bands disappear indicating the complete loss of acetoni- [(g||  2.0023)/(g\  2.0023)] > 4 (Table 7) thus, the extent of inter-
trile molecules. action between Cu(II) centers is negligible, indicating an essentially
mononuclear structure [52].
3.5. Electronic spectra and magnetic moment The frozen solution spectra of the complexes are axial with
g|| > g\ > 2.0 and G = 3.6–4.1, confirm the square based geometries
The electronic spectra of 1–3 complexes were measured in ace- of the complexes, as observed in the X-ray crystal structures of 1–
tonitrile solutions. All complexes exhibit very intense bands in the 3. Frozen spectrum of 1 is well resolved with a quartet hyperfine
250–275 nm region assignable to p ? p⁄ intraligand charge-trans- structure (Cu, I = 3/2) while those of 2 and 3 are partially resolved.
fer bands. The appearance of a single broad d–d band in the visible A square-based CuN4 chromophore is expected to show g|| value of
spectrum of square-planar or tetragonally distorted octahedral about 2.200 and an A|| value of 180–220 G. The nuclear hyperfine
complexes containing neutral macrocyclic diimine ligands is com- coupling for 2 and 3 is observed in the g|| signal with three of the
mon [43]. In the present study, the spectra display one broad d–d four components clearly resolved, the last one being obscured by
band at Kmax 497, 532 and 498 nm for complex 1, 2 and 3, respec- the g\ component. Accordingly, the orbital ground state of the
tively, contributed from the CuN4 square-based planar coordination Cu(II) would be basically dx2  dy2 and the polyhedra could be sta-
environment which indicates that the M–X (where X = ClO4, SCN tistically distorted [53].
and NCCH3) bonds are entirely dissociated [44]. Similar behavior
has also been reported by Kang et al. [45]. This can be adequately 3.7. PXRD studies
explained as a d–d transition of Cu(II) ion in the complex with a
D4h symmetry [46]. The phase purity of all Cu(II) complexes was confirmed by
Tetragonal distortions involving elongation of the axial bonds PXRD. The experimental PXRD patterns of 1 and 2 are consistent
that remove the degeneracy are very common, especially with r- with the simulated ones, as determined from the single-crystal
bonding ligands such as 1,2-diamines [47]. This fact suggests that X-ray diffraction data (Fig. S2, Supporting information). Difference
in tetragonally distorted octahedral Cu(II) complexes involving in intensities and peak positions between the PXRD patterns of the
unidentate ligands, the axially coordinated groups are weakly two sets of compound 3 is due to the loss of solvent molecules dur-
bonded and not positioned by lattice packing factors. This is indic- ing grinding. Intensity of the experimental XRD patterns is a little
ative of a reduction of the coordination number of the examined weak, due to the preferred orientation of the powder samples and
complex to form a square planar CuN4 chromophore after solva- the instrumental limitations.
tion. The molar conductivity of perchlorate, thiocyanate and hexa-
fluorophosphate salts of Cu(II) complexes measured in acetonitrile 4. Conclusion
solution was found to be in the range of 283–375 X1 cm2 M1
corresponding to a 1:2 electrolyte [48]. The contradiction between Cu(II) complexes have been synthesized by one-pot template
the crystal structure of Cu(II) complex and the conductivity data reaction. It may be proposed that in the solid state, most probably
indicate that the perchlorate and hexafluorophosphate anions are due to crystal packing effects, the arrangement of the coordination
coordinated to the Cu(II) ion in solid state and are labile in solution. sphere is distorted octahedral whereas in solution, the square-pla-
The magnetic moment at room temperature for 1–3 was in the nar one is prevalent. Further, oxygen from perchlorate molecule
range 1.9–1.8 B.M. and these values are within the usual range. and nitrogen from thiocyanate and acetonitrile is semi-coordi-
nated to copper, stabilizing an octahedral geometry in the solid
3.6. EPR studies state. The molar conductivity determination reflects that the axi-
ally bonded groups are almost entirely dissociated in acetonitrile
The X-band EPR spectra of polycrystalline powder of 1, 2 and 3 solution.
were recorded at room temperature and in frozen acetonitrile–tol-
uene (1:1) mixture (Fig. 9). EPR spectral parameters for complexes Acknowledgements
1–3 are summarized in Table 7. The powder spectra at RT were
typical for axial-type Cu(II) complexes with two g values and We are indebted to the Department of Chemistry, IIT Kanpur
g|| > g\ > 2.03, suggesting a dx2 y2 ground state which is consistent and School of Chemistry, University of Hyderabad, for providing
with a tetragonally distorted octahedral stereochemistry [49]. single crystal X-ray facilities. Dr. Suneel P. Singh, Department of
The broadening of the spectrum of 2 and 3 is probably due to spin Chemistry, University of Guelph Ontario, Canada is gratefully
relaxation. The absence of any half field signal suggests the pres- acknowledged for his valuable discussion. We are grateful to the
ence of only one transition metal ion. The g|| < 2.3 indicate a con- Council of Scientific and Industrial Research, New Delhi (Research
siderable covalent character [50]. The smaller g|| value indicates Scheme No. 21(0685)/07 EMR-II) for the financial support. One of
increased delocalization of the unpaired electron away from the us (SAAN) thanks Department of Science and Technology for finan-
metal nucleus and has been often interpreted in terms of increased cial assistance under SERC FAST Scheme, No. SR/FT/CS-031/2008,
covalency in the metal-ligand bond [51]. The calculated G value NewDelhi, India.
 A. Husain et al. / Inorganica Chimica Acta 384 (2012) 309–317 317

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