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Journal of Molecular Structure 734 (2005) 83–88 <a href=www.elsevier.com/locate/molstruc Synthesis, structural characterisation and solvatochromism of a Ni(II) and a Co(II) compound with 2-aminopyrimidine as a ligand Yufei Song , Chiara Massera , Gerard A. van Albada , Anna Maria Manotti Lanfredi , Jan Reedijk * Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands. Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universita’degli Studi di Parma, Parco Area delle Scienze 17/A, 43100 Parma, Italy Received 7 July 2004; accepted 20 September 2004 Available online 28 October 2004 Abstract Two mononuclear complexes of formula [M(ampym) (SCN) (H O) ] $ 2H O (M Z Ni(II), Co(II); ampym Z 2-aminopyrimidine) have been synthesized and characterized by X-ray diffraction methods, IR and ligand-field spectra. The Ni(II) and Co(II) compounds, which crystallize in the triclinic space group P K 1 , are isostructural, and their solid structures are stabilized by hydrogen bonding and p – p interactions between aminopyrimidine rings. The compounds exhibit solvatochromism as evidenced by a UV/Vis study in different solvents. q 2004 Elsevier B.V. All rights reserved. Keywords: Copper; Solvatochromism; 2-Aminopyrimidine; Thiocyanate 1. Introduction Structure and magnetic studies of metal complexes with 2-aminopyrimidine (abbreviated as ampym) are of con- siderable interest due to the coordination diversity exhibited by the ligand and metal ions [1,2] . With Cu(II), quite a large number of different compounds have been reported and the structures often depend on the nature of the anion and the synthetic method [2,3] . With Ni(II) and Co(II) and ampym as a ligand only a few complexes have been determined by X-ray diffraction methods [4,5] . The investigation of the solvatochromic behavior [6] of mixed-ligand metal complexes has been of importance, because it provides a quantitative approach to recognize the solvent behavior and the role of the solvent in physico- chemical studies [7] ; moreover, it is very helpful for developing environmental sensor materials, which are chromotropic and exhibit color change when exposed to solvent or pollutant molecules [8] . * Corresponding author. Tel.: C 31 71 5274450; fax: C 31 71 5274671. E-mail address: reedijk@chem.leidenuniv.nl (J. Reedijk). 0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2004.09.007 In the present paper, the synthesis and characterization of two mononuclear isostructural thiocyanato compounds with the general formula [M(ampym) (SCN) (H O) ] $ 2H O (M Z Ni(II), Co(II)) will be reported. In addition, the solvatochromism of both compounds has been investigated by UV/vis in different solvents. 2. Experimental section 2.1. General remarks and physical measurements All starting reagents and solvents were purchased from commercial sources and used as received. C, H, N analyses were performed on a Perkin–Elmer 2400 series II analyzer. Infrared spectra were recorded on a Perkin–Elmer Paragon 1000 spectrophotometer equipped with a Golden Gate ATR device, using the diffuse reflectance technique. The UV/vis spectrum of the compound was recorded in the 250–800 nm range with a Cary 50 Varian UV/vis/NIR spectrometer. Electrospray ionization mass spectra (ESI-MS, Positive ion) in MeOH solutions were recorded on a Thermo Finnigan " id="pdf-obj-0-2" src="pdf-obj-0-2.jpg">
Journal of Molecular Structure 734 (2005) 83–88 <a href=www.elsevier.com/locate/molstruc Synthesis, structural characterisation and solvatochromism of a Ni(II) and a Co(II) compound with 2-aminopyrimidine as a ligand Yufei Song , Chiara Massera , Gerard A. van Albada , Anna Maria Manotti Lanfredi , Jan Reedijk * Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands. Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universita’degli Studi di Parma, Parco Area delle Scienze 17/A, 43100 Parma, Italy Received 7 July 2004; accepted 20 September 2004 Available online 28 October 2004 Abstract Two mononuclear complexes of formula [M(ampym) (SCN) (H O) ] $ 2H O (M Z Ni(II), Co(II); ampym Z 2-aminopyrimidine) have been synthesized and characterized by X-ray diffraction methods, IR and ligand-field spectra. The Ni(II) and Co(II) compounds, which crystallize in the triclinic space group P K 1 , are isostructural, and their solid structures are stabilized by hydrogen bonding and p – p interactions between aminopyrimidine rings. The compounds exhibit solvatochromism as evidenced by a UV/Vis study in different solvents. q 2004 Elsevier B.V. All rights reserved. Keywords: Copper; Solvatochromism; 2-Aminopyrimidine; Thiocyanate 1. Introduction Structure and magnetic studies of metal complexes with 2-aminopyrimidine (abbreviated as ampym) are of con- siderable interest due to the coordination diversity exhibited by the ligand and metal ions [1,2] . With Cu(II), quite a large number of different compounds have been reported and the structures often depend on the nature of the anion and the synthetic method [2,3] . With Ni(II) and Co(II) and ampym as a ligand only a few complexes have been determined by X-ray diffraction methods [4,5] . The investigation of the solvatochromic behavior [6] of mixed-ligand metal complexes has been of importance, because it provides a quantitative approach to recognize the solvent behavior and the role of the solvent in physico- chemical studies [7] ; moreover, it is very helpful for developing environmental sensor materials, which are chromotropic and exhibit color change when exposed to solvent or pollutant molecules [8] . * Corresponding author. Tel.: C 31 71 5274450; fax: C 31 71 5274671. E-mail address: reedijk@chem.leidenuniv.nl (J. Reedijk). 0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2004.09.007 In the present paper, the synthesis and characterization of two mononuclear isostructural thiocyanato compounds with the general formula [M(ampym) (SCN) (H O) ] $ 2H O (M Z Ni(II), Co(II)) will be reported. In addition, the solvatochromism of both compounds has been investigated by UV/vis in different solvents. 2. Experimental section 2.1. General remarks and physical measurements All starting reagents and solvents were purchased from commercial sources and used as received. C, H, N analyses were performed on a Perkin–Elmer 2400 series II analyzer. Infrared spectra were recorded on a Perkin–Elmer Paragon 1000 spectrophotometer equipped with a Golden Gate ATR device, using the diffuse reflectance technique. The UV/vis spectrum of the compound was recorded in the 250–800 nm range with a Cary 50 Varian UV/vis/NIR spectrometer. Electrospray ionization mass spectra (ESI-MS, Positive ion) in MeOH solutions were recorded on a Thermo Finnigan " id="pdf-obj-0-4" src="pdf-obj-0-4.jpg">

Journal of Molecular Structure 734 (2005) 83–88

Journal of Molecular Structure 734 (2005) 83–88 <a href=www.elsevier.com/locate/molstruc Synthesis, structural characterisation and solvatochromism of a Ni(II) and a Co(II) compound with 2-aminopyrimidine as a ligand Yufei Song , Chiara Massera , Gerard A. van Albada , Anna Maria Manotti Lanfredi , Jan Reedijk * Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands. Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universita’degli Studi di Parma, Parco Area delle Scienze 17/A, 43100 Parma, Italy Received 7 July 2004; accepted 20 September 2004 Available online 28 October 2004 Abstract Two mononuclear complexes of formula [M(ampym) (SCN) (H O) ] $ 2H O (M Z Ni(II), Co(II); ampym Z 2-aminopyrimidine) have been synthesized and characterized by X-ray diffraction methods, IR and ligand-field spectra. The Ni(II) and Co(II) compounds, which crystallize in the triclinic space group P K 1 , are isostructural, and their solid structures are stabilized by hydrogen bonding and p – p interactions between aminopyrimidine rings. The compounds exhibit solvatochromism as evidenced by a UV/Vis study in different solvents. q 2004 Elsevier B.V. All rights reserved. Keywords: Copper; Solvatochromism; 2-Aminopyrimidine; Thiocyanate 1. Introduction Structure and magnetic studies of metal complexes with 2-aminopyrimidine (abbreviated as ampym) are of con- siderable interest due to the coordination diversity exhibited by the ligand and metal ions [1,2] . With Cu(II), quite a large number of different compounds have been reported and the structures often depend on the nature of the anion and the synthetic method [2,3] . With Ni(II) and Co(II) and ampym as a ligand only a few complexes have been determined by X-ray diffraction methods [4,5] . The investigation of the solvatochromic behavior [6] of mixed-ligand metal complexes has been of importance, because it provides a quantitative approach to recognize the solvent behavior and the role of the solvent in physico- chemical studies [7] ; moreover, it is very helpful for developing environmental sensor materials, which are chromotropic and exhibit color change when exposed to solvent or pollutant molecules [8] . * Corresponding author. Tel.: C 31 71 5274450; fax: C 31 71 5274671. E-mail address: reedijk@chem.leidenuniv.nl (J. Reedijk). 0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2004.09.007 In the present paper, the synthesis and characterization of two mononuclear isostructural thiocyanato compounds with the general formula [M(ampym) (SCN) (H O) ] $ 2H O (M Z Ni(II), Co(II)) will be reported. In addition, the solvatochromism of both compounds has been investigated by UV/vis in different solvents. 2. Experimental section 2.1. General remarks and physical measurements All starting reagents and solvents were purchased from commercial sources and used as received. C, H, N analyses were performed on a Perkin–Elmer 2400 series II analyzer. Infrared spectra were recorded on a Perkin–Elmer Paragon 1000 spectrophotometer equipped with a Golden Gate ATR device, using the diffuse reflectance technique. The UV/vis spectrum of the compound was recorded in the 250–800 nm range with a Cary 50 Varian UV/vis/NIR spectrometer. Electrospray ionization mass spectra (ESI-MS, Positive ion) in MeOH solutions were recorded on a Thermo Finnigan " id="pdf-obj-0-8" src="pdf-obj-0-8.jpg">

Synthesis, structural characterisation and solvatochromism of a Ni(II) and a Co(II) compound with 2-aminopyrimidine as a ligand

Yufei Song a , Chiara Massera b , Gerard A. van Albada a , Anna Maria Manotti Lanfredi b , Jan Reedijk a, *

a Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands. b Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universita’degli Studi di Parma, Parco Area delle Scienze 17/A, 43100 Parma, Italy

Received 7 July 2004; accepted 20 September 2004 Available online 28 October 2004

Abstract

Two mononuclear complexes of formula [M(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O (MZNi(II), Co(II); ampymZ2-aminopyrimidine) have been synthesized and characterized by X-ray diffraction methods, IR and ligand-field spectra. The Ni(II) and Co(II) compounds, which crystallize in the triclinic space group PK1, are isostructural, and their solid structures are stabilized by hydrogen bonding and pp interactions between aminopyrimidine rings. The compounds exhibit solvatochromism as evidenced by a UV/Vis study in different solvents. q 2004 Elsevier B.V. All rights reserved.

Keywords: Copper; Solvatochromism; 2-Aminopyrimidine; Thiocyanate

1. Introduction

Structure and magnetic studies of metal complexes with 2-aminopyrimidine (abbreviated as ampym) are of con- siderable interest due to the coordination diversity exhibited by the ligand and metal ions [1,2]. With Cu(II), quite a large number of different compounds have been reported and the structures often depend on the nature of the anion and the synthetic method [2,3]. With Ni(II) and Co(II) and ampym as a ligand only a few complexes have been determined by X-ray diffraction methods [4,5]. The investigation of the solvatochromic behavior [6] of mixed-ligand metal complexes has been of importance, because it provides a quantitative approach to recognize the solvent behavior and the role of the solvent in physico- chemical studies [7]; moreover, it is very helpful for developing environmental sensor materials, which are chromotropic and exhibit color change when exposed to solvent or pollutant molecules [8].

* Corresponding author. Tel.: C31 71 5274450; fax: C31 71 5274671. E-mail address: reedijk@chem.leidenuniv.nl (J. Reedijk).

0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved.

doi:10.1016/j.molstruc.2004.09.007

In the present paper, the synthesis and characterization of two mononuclear isostructural thiocyanato compounds with the general formula [M(ampym) 2 (SCN) 2 (H 2 O) 2 ]$ 2H 2 O (MZNi(II), Co(II)) will be reported. In addition, the solvatochromism of both compounds has been investigated by UV/vis in different solvents.

2. Experimental section

2.1. General remarks and physical measurements

All starting reagents and solvents were purchased from commercial sources and used as received. C, H, N analyses were performed on a Perkin–Elmer 2400 series II analyzer. Infrared spectra were recorded on a Perkin–Elmer Paragon 1000 spectrophotometer equipped with a Golden Gate ATR device, using the diffuse reflectance technique. The UV/vis spectrum of the compound was recorded in the 250–800 nm range with a Cary 50 Varian UV/vis/NIR spectrometer. Electrospray ionization mass spectra (ESI-MS, Positive ion) in MeOH solutions were recorded on a Thermo Finnigan

  • 84 Y. Song et al. / Journal of Molecular Structure 734 (2005) 83–88

AQA apparatus. The ligand-field spectra of the solid samples were recorded in the 200–2000 nm range on a Perkin–Elmer Lambda 900 UV/Vis/NIR spectrometer in the diffuse reflectance mode with MgO as a reference. The conductivity measurement was performed with a Philips PW 9526 digital conductivity meter and PW 9551/60 measuring cell with a 1 mM solution of the complexes in MeOH, H 2 O and MeCN.

2.2. General synthesis of the complexes

Ni(NO 3 ) 2 $6H 2 O (10 mmol, 2.9 g) dissolved in water (10 mL) was added to a solution of NH 4 SCN (20 mmol, 1.5 g) in water (30 mL), and the 2-aminopyrimidine (20 mmol, 1.9 g) in 20 mL of methanol was added to the well stirred aqueous solution. The resulting solution was filtered and left to evaporate at room temperature. Blue crystals were collected after 1 week. Yield 62%. For the Ni(II) Compound (1): ESI-MS: m/zZ438.2; Elemental analysis [found(calc.)] for C 10 H 18 NiN 8 O 4 S 2 : C 27.5 (27.4); H 4.3 (4.1); N 25.7 (25.6); S 14.5 (14.6). IR (cm K 1 ):

3460.3 (w), 3330.4 (m), 2084.7 (s), 1629.0 (s), 1569.7 (s), 1489.4 (s), 1360.0 (s), 1195.8 (s), 787.0 (s), 660.2 (s), 523.7 (s). (w, m and s represent the intensity of the absorption peaks as weak, medium and strong, respectively).

The Co(II) compound (2) was synthesized in the similar way, and blue crystals were collected after about 1 week.

Yield 60%. ESI-MS: m / zZ 438.4. Elemental analysis [found(calc.)] for C 10 H 18 CoN 8 O 4 S 2 : C 27.5 (27.4); H 4.2 (4.1); N 25.7 (25.6); S 14.5 (14.6). IR (cm K 1 ): 3462.0 (w),

  • 3332.0 (m), 2075.7 (s), 1627.9 (s), 1569.9 (s), 1486.0 (s),

  • 1358.8 (m), 787.4 (m), 659.7 (m), 522.0 (m).

2.3. X-ray crystallographic study

The molecular structure of both [M(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O (MZNi(II) and Co(II)) was determined by single-crystal X-ray diffraction methods. Crystallographic and experimental details for the two structures are summar- ized in Table 1. Intensity data and cell parameters were recorded at room temperature (25 8C) on a Bruker AXS Smart 1000 single-crystal diffractometer (Mo Ka radiation) equipped with a CCD area detector. The data reduction was performed using the SAINT and SADABS programs [9]. The structure was solved by Direct Methods using the SIR97 program [10] and refined on F 0 by full-matrix least- squares procedures, using the SHELXL-97 program [11]. All non-hydrogen atoms were refined with anisotropic atomic displacements. The hydrogen atoms were located in the difference Fourier map with the exception of the hydrogen atoms of the water molecules of

2

Table 1

Crystallographic data for [M(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O (MZNi(II) and Co(II))

 

Compound

[Ni(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O

[Co(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O

Empirical formula

C 10 H 18 N 8 NiO 4 S 2

C 10 H 18 CoN 8 O 4 S 2

Formula weight

437.15

437.37

Crystal system

Triclinic

Triclinic

Space group

PK1 (no. 2)

PK1 (no. 2)

a (A ˚ )

7.259(5)

9.145(3)

b (A ˚ )

7.895(5)

7.943(3)

c (A ˚ )

9.065(5)

7.328(3)

a (8)

67.578(5)

103.311(5)

b (8)

72.511(5)

107.381(5)

g (8)

76.860(5)

67.378(5)

V (A ˚ 3 )

454.3(5)

464.9(3)

Z

1

1

D calcd (g/cm 3 )

1.598

1.562

m(mm K 1 )

1.331

1.180

Crystal size (mm)

0.13!0.16!0.20

0.16!0.18!0.24

F(000)

226

225

T (K)

293(2)

293(2)

Radiation (A ˚ )

0.71069

0.71069

Reflections collected

5109

3884

Indipendent reflections

2050 [R(int)Z0.0340]

1926 [R(int)Z0.0169]

Observed reflections [IO2s(I)]

1467

1839

Data/restraints/parameters

2050/7/143

1926/0/143

q range for data collection (8)

2.5–28.0

2.5–27.6

Index ranges

K9%h%9; K9 %k%10;K11%l%11

K11%h%11; K9%k%10; K9%l%9

Goodness-of-fit on F 2 a

0.921

1.08

Final R indices (obs. data) b

R1Z0.0384, wR2Z0.0840

R1Z0.0288, wR2Z0.0864

R indices (all data) b

R1Z0.0613, wR2Z0.0890

R1Z0.0301, wR2Z0.0876

Largest diff. peak and hole (e/A ˚ K 3 )

0.422 and K0.423

0.500 and K0.345

a Goodness-of-fit S Z P W ðF o K F c Þ 2 ðn K pÞ 1=2 , where n is the number of reflections and p the number of parameters.

b

R 1 Z P sF o j K F c s P jF o j;

wR 2 Z

P W ðF o K F c Þ 2 P WF o

1=2

.

Y. Song et al. / Journal of Molecular Structure 734 (2005) 83–88

85

Y. Song et al. / Journal of Molecular Structure 734 (2005) 83–88 85 Fig. 1. An

Fig. 1. An ortep view (20% probability) of [Ni(ampym) 2 (SCN) 2 (H 2 O) 2 ]$

2H 2 O with the used atomic numbering scheme.

crystallizations. The weighting scheme used in the last

cycle of refinement was w Z 1½=s 2 F

2

0

  • C ð0:0456PÞ 2 and w Z

1=½s 2 F

2

0

C ð0:0582PÞ 2 C 0:1432P (where P Z ðF

2

0

2

C 2F

c

Þ=3)

for (1) and (2), respectively.

Table 2

Molecular geometry calculations were carried out using

the PARST97 program [12]. Drawings were obtained by

ORTEP3 in the WinGX suite [13]. All calculations were

carried out on a DIGITAL Alpha Station 255 computer.

3. Results and discussion

3.1. Description of the structure

[M(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 0 (MZNi(II) and Co(II))

The Ni(II) and Co(II) compounds are isostructural with

the metal ion lying on an inversion center; an ORTEP view

of the Ni(II) compound is depicted in Fig. 1. Selected bond

distances and angles for both complexes are reported in

Table 2.

A slightly distorted octahedral coordination is observed

around both metal ions: four short in-plane bonds involve

two trans oxygens from the water molecules [Ni–O1Z

2.072(2) A ˚ ,Co–O1Z2.093(2) A ˚ ] and two trans nitrogen

atoms

from

the

thiocyanate

groups [Ni–N4 Z

2.058(3) A ˚ ,Co–N4Z2.107(2) A ˚ ]. The axial positions are

occupied by the N1 endocyclic nitrogen from two trans-

oriented ampym ligands [Ni–N1Z2.147(2) A ˚ ,Co–N1Z

2.217(2) A ˚ ]. The S1–C5–N4 thiocyanate groups are nearly

linear with angles of 178.0(3)8 and 177.9(2)8 for the Ni(II)

and Co(II) compounds, respectively. The thiocyanate groups

are not linear coordinated to the metal ions (angles M–N–C

are 153 and 1548 for MZCo, and Ni, respectively), and the

origin from the deviation of 1808 appears to be related to

the hydrogen bonding in the lattice. The dihedral angles that

the least-square plane through NI–N2–C1–C2–C3–C4 forms

Selected bond lengths (A ˚ ), angles (8) and hydrogen bonding parameters for [M(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O (MZNi(II) and Co(II))

[Ni(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O

Bond lengths: Ni1–O1 2.072(2); Ni1– N4 2.058(3); Ni1–N1 2.147(2)

Bond angles: O1–Ni1–N1 89.38(8); N4–Ni1–O1 91.71(10); N4–Ni1–N1 92.04(10); S1–C5–N4 178.0(3); Ni1-N4–C5 153.7(2)

Hydrogen bonds

D–H/A

H/A(A ˚ )

D/A (A ˚ )

D–H/A(8)

N3–H1N/O1

2.23(4)

2.934(2)

134(2)

N3–H1N/N4

2.48(3)

3.073(4)

124(2)

N3–H2N/S1 (1Kx, Ky, 2Kz)

2.62(2)

3.499(3)

164(1)

O1–H2S/O1S

1.88(3)

2.768(3)

169(3)

O1–H1S/O1S (Kx, 1Ky, 1Kz)

1.90(3)

2.771(4)

164(2)

C4–H4/N4 (1Kx, 1Ky, 1Kz)

2.69(4)

3.077(5)

105(2)

C4–H4/O1 (1Kx, 1Ky, 1Kz)

2.66(3)

3.130(4)

111(2)

[Co(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O

Bond lengths: Co1–O1 2.093(2); Co1–N4 2.107(2); Co1–N1 2.217(2)

 

Bond angles: O1–Co1–N4 88.71(7); O1–Co1–N1 91.06(6); N4–Co1–N1 92.29(6); N4–C5–S1 177.9(2); Co1–N4–C5 151.0(2)

 

Hydrogen bonds

D–H/A

H/A(A ˚ )

D/A (A ˚ )

D–H/A(8)

N3–H2N/O1 (2Kx, 1Ky, Kz)

2.29(4)

2.983(3)

134(4)

N3–H2N/N4

2.49(3)

3.123(3)

128(3)

N3–H1N/S1 (1Kx, 2Ky, Kz)

2.67(3)

3.522(3)

170(3)

O1–H2S/O1S (2Kx, 1Ky, 1Kz)

1.97(3)

2.768(2)

170(4)

O1–H1S/O1S

2.06(4)

2.773(3)

167(3)

C4–H4/N4 (2Kx, 1Ky, Kz)

2.78(4)

3.135(3)

107(2)

C4–H4/O1

2.78(3)

3.220(3)

107(2)

  • 86 Y. Song et al. / Journal of Molecular Structure 734 (2005) 83–88

with the equatorial plane, with the N1–M–O1 and with

N1–M–N4 moieties are 87.4(1), 43.8(1) and 47.9(1)8 in the

Ni(II) compound and 87.0(1), 44.4(1) and 46.9(1)8 in the

Co(II) complex.

To the best of our knowledge, the only related Ni(II) or

Co(II) complexes containing two ampym and two water

molecules in an octahedral arrangement around the metal

ion is the polymeric compound [Ni(SO 4 )(C 4 H 5 N 3 ) 2

(H 2 O) 2 ]$C 6 H 5 N 3 [5]. In this complex, the sulfate ion acts

as a bridging moiety between the metal atoms which

present, in the equatorial plane, two mutually cis nitrogen

atoms from ampym and two mutually cis oxygen atoms

from the water molecules.

The configuration of the present complexes, with the

ampym ligands almost orthogonal to the equatorial plane

and nearly bisecting the O1–M–N4 bond angles, is

correlated to the bifurcated intramolecular hydrogen bonds

that a N–H group from the ampym NH 2 moieties forms with

the oxygen and nitrogen atoms of the adjacent water and

thiocyanate

ligands

[N3 / O1 Z 2.934(4) A ˚ ,N3 / N4 Z

3.073(4) A ˚

for the Ni(II) complex; N3/O1Z2.983(3) A ˚ ,

N3/N4Z3.123(2) A ˚

for the Co(II) compound; see also

Table 2].

The structure is further stabilized by intermolecular

interactions between the other hydrogen atom of the NH 2

groups and sulfur atoms from neighboring complexes

[N3/S1Z3.499(3) A ˚

in Ni II compound and N3/S1Z

3.522(2) A ˚ in Co II complex] and by intermolecular hydro-

gen bonds that the coordinated water molecules form, as

hydrogen donors, with the solvate ones [O1/O1SZ

2.768(3) and 2.771(4) A ˚ for the Ni(II) complex; O1/O1S

and O1/O1SZ2.768(2) A ˚

also Table 3].

for the Co(II) compound; see

86 Y. Song et al. / Journal of Molecular Structure 734 (2005) 83–88 with the equatorial

Fig. 2. Crystal packing of the [M(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O complex

(MZNi(II) and Co(II)) showing the pp interactions between the aromatic

rings of neighboring molecules.

compounds, respectively (see Fig. 2). Also these inter-

actions contribute to the stability of the complexes.

Although the two structures are very similar, slight

differences are visible. In the Ni(II) complex, the nearest

atom to the metal center is the equatorial nitrogen N4, while

in the Co(II) compound, it is the equatorial oxygen O1 from

the coordinated water molecule. This slight distortion from

octahedral could be induced by the hydrogen bond network,

which involves, besides the above cited hydrogen

bonds, also the intramolecular bifurcated interactions

C–H/N(NCS) and C–H/O(coordinated H 2 O) involving

The inversion-related aromatic rings show a slipped

the

ampym

C4–H4

group

[C4 / N4 Z 3.077(5) A ˚ ,

C4

stacking to form chains running along the [001] (Ni) and

/O1Z3.130(4) A ˚

for

the

Ni(II)

complex;

C4/N4Z

[100] (Co) directions with the shortest ring–ring distance of

3.135(3) A ˚ ,

C4

/ O1 Z 3.220(3) A ˚

for the Co(II)

3.324(4)

and

3.342(4) A ˚

in the Ni(II) and Co(II)

compound].

Table 3

UV/vis absorption of the two complexes in different solvents

Complexes/

l (nm) and 3 (l mol K 1 cm K 1 )

solvents/color

[Ni(ampym) 2 (SCN) 2

(H 2 O) 2 ]$2H 2 O

383 (72.6); 625 (23.1);

light blue

400 (272); 664 (35);

737

(26); light green

L402 (182); 679 (42);

737

(26); light green

Green (weak solubility)

397 (25.2); 666 (11.0);

737

(10.0); light blue

Green (weak solubility)

[Co(ampym) 2 (SCN) 2

(H 2 O) 2 ]$2H 2 O

563

(200.4); 630 (562);

blue

480

(33.2); 524 (46.8);

556

(44.2); 620 (57.1);

blue purple

485

(45.6); 587 (202);

625

(346); blue

635

(240.6); skyblue

519

(42.4); 480 (30.2);

pink

774

(9.6); deep blue

563 (104.6); 610 (214.6);

537 (214.0); 632 (449.2);

MeCN

EtOH

DMF

Ether

MeOH

Aceton

3.2. Infrared spectroscopy

The position of the bands of the thiocyanate group related

to the stretching frequency of the CN moiety can be used to

characterize the coordination mode of this ligand to the

metal ions. The CN stretching of a bridging thiocyanate is

usually found to be above 2100 cm K 1 [14]. In the case of the

nickel(II) complex, the stretching frequency of the thiocya-

nate occurs at 2084 cm K 1 , which indicates normal end-on

NCS coordination. The bands corresponding to the stretch-

ing frequency of CS and NCS appear at 787 and 463 cm K 1 ,

which is in good agreement with an end-on NCS

coordination. For the Co(II) complex, the typical stretching

frequency for the thiocyanate group can be observed at

2075 cm K 1 , while the band belonging to CS and the

deformation frequency NCS occur at 787 and 459 cm K 1 ,

respectively.

Y. Song et al. / Journal of Molecular Structure 734 (2005) 83–88

87

3.3. Ligand-field spectroscopy

The diffuse reflectance spectra of the solid Ni(II)

compound shows three strong bands at 9.8!10 3 cm K 1

(s 1 ; 3 A 2g 3 T 2g ), 15.8! 10 3 cm K 1 (s 2 ; 3 A 2g 3 T 1g (F)) and

25.7! 10 3 cm K 1 (s 3 ; 3 A 2g 3 T 1g (P)), which are the typical

absorption bands for an octahedral Ni(II) complex[15]. Two

strong bands at 30.3! 10 3 and 33.3!10 3 cm K 1 are also

visible, which are attributable to the LMCT from the ligands

to the Ni(II) atom. The value calculated by semi-empirical

equation[15] for the D q (the crystal-field parameter), B

(Racah parameter) and D q /B are 980, 806 and 1.21 cm K 1 ,

respectively.

The ligand-field spectrum of the solid Co(II) compound

shows a strong band at 30.7!10 3 cm K 1 corresponding to

the ligand to metal charge transfer (LMCT) band, while

the bands at 19.9!10 3 cm K 1 (s 3 ; 4 T 1g (P)– 4 T 1g (F)) and

8.9!10 3 cm K 1 (s 1 ; 4 T 2g 4 T 1g ) are typical for octahedrally

coordinated Co(II) with this chromophore[16]. However, the

band for the transition from 4 A 2g 4 A 1g (s 2 ) is not observed in

the spectrum. The value calculated for the D q , B and D q /B [16]

are 890, 811 and 1.10 cm K 1 , respectively.

3.4. UV/vis spectra in solution

The two compounds exhibit solvatochromism (Table 3

and Fig. 3), and in the case of the Co(II) complex, the color

changes from light pink (in H 2 O), to pink (in MeOH), blue

purple (in EtOH) and sky blue (in diethyl ether) to deep blue

(in DMF, Aceton, MeCN). The d–d bands of the Co(II)

compound can be found around 456, 506 nm in water and

478, 510 nm in MeOH, respectively. In ethanol, 3 d–d bands

can be seen clearly in the UV/vis spectrum at 470 nm,

520 m and 604 nm. When the solvent used is MeCN, the

d–d bands shift significantly to around 561 and 627 nm,

which indicates the change of the coordination geometry

around Co(II). The charge transfer band which is a shoulder

Y. Song et al. / Journal of Molecular Structure 734 (2005) 83–88 87 3.3. Ligand-field spectroscopy

Fig. 3. UV/Vis spectra of [Co(ampym) 2 (SCN) 2 (H 2 O) 2 ]$2H 2 O in MeCN

(8.1!10 K 4 m),

Acetone (9.2!10 K 4 M), Diethyl Ether (3.1!10 K 3 M),

DMF (7.0!10 K 4 M), EtOH (3.1!10 K 3 M) and MeOH (3.3!10 K 3 M).

peak at around 320–340 nm is overlapped by a very strong

band around 290 nm in different solvents. So we believe that

tetrahedral Co(II) or 5-coordinate Co(II) is present in the

aprotic solvents.

For the Ni(II) complex, the color changes are not so

strong, from light blue (MeOH, H 2 O), to light green (EtOH)

and to green (Ether, Aceton). The UV absorption bands can

be found in the region of 388–395 nm for the LMCT and

two d–d bands (one is in the range of 645–654 and another

one is in the range of 708–720 nm, see Table 3) in water,

methanol, EtOH and DMF. In Ether and MeCN, the charge

transfer band shifts to 379 and 374 nm, and only one d–d

band in the visible range can be observed at 623 and

619 nm, respectively.

The solvatochromism is caused by the different coordi-

nation of the solvents to the metal centers and the resulting

change of the coordination environment around the metal

ions. For the Co(II) complex, the blue color in several

different solvents indicates that the geometry around

the metal must be distorted to tetrahedral or square

pyramidal. When the coordinated water molecules in

[Co(II)(ampym) 2 (SCN) 2 (H 2 O) 2 ] $ 2H 2 O are replaced by

other solvents like aceton or acetonitrile, the coordination

around Co(II) may change from octahedral to a tetra- or

penta- coordination. For the Ni(II) complex, the color

change is not so evident, which may indicate that the

octahedral geometry around Ni(II) is maintained by

replacing the water molecules with different solvents.

The conductivities of these two complexes have been

studied in MeOH, water and MeCN. The obtained values are

quite small in MeOH and H 2 O, which is logical because the

complexes are crystallized from the mixture of MeOH and

water, and no dissociation occurs. In MeCN, the conduc-

tivities of these two compounds are still below 40 cm 2 U K 1

mol K 1 , confirming that the thiocyanate groups are not

dissociated from the metal ions too. Therefore, though the

geometry around the metal ions may change in different

solvents, the thiocyanate groups are still kept in the

coordination surrounding around the metal ions.

4. Conclusions

In the present paper, two mononuclear isostructural

Ni(II) and Co(II) complexes have been obtained, which

show an octahedral geometry around the metal ions. Their

crystal structures are stabilized by hydrogen bonding and

pp interactions between 2-aminopyrimidine rings from

different molecules. Both the compounds show solvatochro-

ism which is due to the substitution of the water molecules

arranged in an octahedral geometry around Ni(II) and Co(II)

by other solvents. The change of the geometry and

coordination environment around the metal centers leads

to the color change and the shift of the charge transfer and

d–d bands in different solvents.

  • 88 Y. Song et al. / Journal of Molecular Structure 734 (2005) 83–88

5. Supplementary material

Crystallographic data (excluding structure factors) for

the structures reported have been deposited with the

Cambridge Crystallographic Data Center as supplementary

publication no. CCDC-242651 and 242652 for compounds

(1) and (2), respectively, and can be obtained free of charge

on application to the CCDC, 12 Union Road, Cambridge

CB2 1EZ, UK. [Fax: (Internet.) C 44-1223/336-033;

Acknowledgements

The work described here has been supported by the

Leiden University Study group WFMO (Werkgroep Fun-

damenteel Materialen-Onderzoek). Support from the NRSC

Catalysis (a Research School Combination of HRSMC and

NIOK) is kindly acknowledged.

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