Spectrochimica Acta Part A 65 (2006) 1112–1119

Synthesis, molecular structure and vibrational spectra of a

dimeric complex formed by cobalt and glycine
O. Versiane a , B.L. Rodrigues b , J.M. Ramos c , C.A. Téllez c , J. Felcman a,∗
a Department of Chemistry, Pontifı́cia Universidade Católica do Rio de Janeiro, Rua Marquês de São Vicente, 225, 22451-900, Rio de Janeiro, RJ, Brazil
b Institute of Physics of São Carlos, Universidade de São Paulo, São Carlos, SP, Brazil
c Institute of Chemistry, Department of Inorganic Chemistry, Universidade Federal Fluminense, Rio de Janeiro, RJ, Brazil

Received 8 December 2005; accepted 9 February 2006

Abstract
The structure of [Co(gly)2 (OH)2 ]·1.5(H2 O) was solved by X-ray diffraction. It crystallizes in the space group P-1, with two independent dimmers
in the unit cell. The results for the calculated vibrational spectra are in good agreement with the experimental one. The infrared spectrum and ab
initio calculations are consistent with the crystallographic results.
© 2006 Elsevier B.V. All rights reserved.

Keywords: X-ray diffraction; Infrared spectroscopy; DFT:B3LYP/3-21G calculated spectra; di-␮-Hydroxy-bis diglycinate cobalt(III) complex

1. Introduction 2. Experimental

Glycine is the smallest aminoacid and for this reason it fits
into crowded regions of many peptide chains, being used in
the synthesis of many protein and non-protein compounds. It
is the only ␣-amino acid that is not optically active and is also
a neurotransmitter [1]. Guanidinoacetic acid is an amino acid
characterized by the presence of a guanidine group, which is an
important group in many biological processes. Guanidinoacetic
acid is synthesized in the kidneys [2,3] involving the transamid-
ination of glycine via arginine, catalyzed by glycineaminidino-
transferase. Cobalt is an essential metal for living organisms.
It is important to human nutrition as it is the metal center of
Vitamin B12 .
The present article reports the obtainment, the molecular
structure and the vibrational spectra of a dimeric complex
formed by cobalt and glycine, in a reaction vessel containing
the aminoacids glycine and guanidinoacetic acid. No crystalline
complex containing gaa either alone or in a mixed complex with
glycine appeared in a similar time.
2.1. Synthesis
In an aqueous solution containing 2 mmol of guanidinoacetic
acid (0.2342 g), 2 mmol of glycine (0.1501 g) were added. The
mixture was heated to 50 ◦ C for 3 h and was left to rest for 24 h
at 4 ◦ C. The excess of ligand formed after cooling was dissolved
and 2 mmol of cobalt(II) nitrate were added. The solution was
heated again to 50 ◦ C. After 4 h, the pH was adjusted to 6.0 and
the solution was closed in a glass vessel and stored for 2 months
at 4 ◦ C. After this period small crystals were collected from the
reaction mixture, washed with ethanol and dried at 60 ◦ C for 1 h.
2.2. Crystal structure
The structure of [Co(gly)2 (OH)2 ]·1.5(H2 O) was solved by
X-ray diffraction. Data were collected in a Nonius KappaCCD
diffractometer at T = 293 K. The HKL Denzo and Scalepack pro-
grams [4] were used for cell refinement and data reduction.

2.3. Vibrational analysis

2.3.1. Infrared spectroscopy

∗ Corresponding author. Tel.: +55 21 31141329; fax: +55 21 31141637. The infrared spectra were recorded on a Perkin-Elmer 2000
E-mail address: felcman@rdc.puc-rio.br (J. Felcman). FT-IR spectrometer. Data were collected with 0.5 cm−1 interval

1386-1425/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2006.02.013
 O. Versiane et al. / Spectrochimica Acta Part A 65 (2006) 1112–1119 1113

with a resolution of 4 cm−1 . The scanning speed was 0.2 cm s−1 the programs SHELXS97 [6] and SHELXL97 [7], respectively.
and 120 scans were performed. The samples were measured in The position of the hydrogen atoms bonded to carbon and nitro-
the range of 4000–370 cm−1 as KBr pellets, and in the region of gen was determined geometrically and refined as riding, with
710–30 cm−1 as polyethylene pellets. d[C–H] = 0.97 Å and d(N–H) = 0.90 Å. Water hydrogen atoms
were fixed geometrically. Hydrogen displacement parameters
2.3.2. Computational methods Uiso of all but the isolated water hydrogen atoms were set as
Ab initio calculations were performed with the Gaussian 98 equal to 1.2 times Ueq of the parent atom. Displacement param-
[5] suite of programs within the Windows system, using the eters for water hydrogen atoms were fixed in 0.050 Å.
DFT:B3LYP/3-21G group base. The optimized geometry of the The crystal of [Co(gly)2 (OH)]2 ·1.5(H2 O) crystallizes in the
complex was based on the crystal structure determined by X- space group P-1, with two independent dimmers in the unit cell.
ray diffraction. The harmonic vibrational wavenumbers were Each asymmetric unit has 1.5 water molecules: one of them
calculated from the optimized geometry of the molecule. in the general position with occupation 1.0, and the other dis-
ordered around the inversion center with occupation 0.5. The
3. Results and discussion two cobalt atoms of each dimmer are related by the inversion
center, in such a way that two half dimmers are in the asym-
3.1. Crystal structure metric unit (Fig. 1). Geometric parameters (Table 2) show that
the two cobalt atoms are octahedrally coordinated, with Co N
Data collection parameters and relevant experimental results and Co O bond lengths, as well as N Co O bond angles,
are given in Table 1. The structure was solved and refined using in good agreement with values obtained in previously deter-
mined structures of Co–glycine compounds [8–16] (Table 3).
The closeness between Co N bond lengths, Co O bond lengths
Table 1
Crystal data and structure refinement for Co(gly)2 (OH)]2 ·1.5(H2 O)
and N Co O bond angles indicates that each cobalt atom inter-
acts with similar strength with both glycinates. These inter-
Empirical formula Co2 C8 H21 N4 O11.5 actions are stronger than those observed for Ni–glycine and
Formula weight 475.15
Temperature (K) 293 (2)
Cr–glycine. The crystal structure is stabilized by hydrogen
Wavelength (Å) 0.71073 bonds. Three of these (O10–H10a · · · O22, N11–H11b · · · O22
Crystal system Triclinic and N22–H22d · · · O14) link adjacent glycinates of two neigh-
Space group P-1 boring [Co(gly)2 (OH)] dimmers. The other three hydrogen
Unit cell dimensions (Å) a = 5.3230 (4)  = 83.189 (4)◦ bonds (Table 4) link glycinates through the water non-disordered
b = 12.1800 (10)  = 78.870 (4)◦
molecule.
c = 12.9050 (11)  = 80.451 (5)◦
Volume (Å3 ) 806.33 (11) Complexes of glycine and first-row transition metals (Co,
Z 2 Cr and Ni) are reported in the literature. Metal–glycine coordi-
Density (calculated) 1.957 nation through the nitrogen (N1) and one carboxylate oxygen
(Mg/m3 ) (O1), forming a five-member ring, is commonly found in these
Absorption coefficient 2.127
compounds. The metal coordination presents a slightly distorted
(mm−1 )
F(0 0 0) 486 octahedral geometry. The O1–M–N1 angle varies from around
Crystal size 0.07 mm × 0.05 mm 80◦ in chromium complexes to almost 90◦ in cobalt complexes
× 0.04 mm (Table 4). The closer to 90◦ the value of the O1–M–N1 angle
Theta range for data 3.23–25.00 is, the shorter are the M N1 and M O1 bond lengths (Fig. 2).
collection (◦ )
Therefore, since the atomic radii of Co(1.16 Å), Cr (1.17 Å) and
Index ranges −6 < = h < = 5,
−14 < = k < = 14, Ni (1.15 Å) are close to one another, it seems the closer to 90◦
−15 < = l < = 15 the angle is, the stronger is the metal–glycine interaction.
Reflections collected 5231
Independent reflections 2838 [R(int) = 0.0819] 3.2. Oxidation state of cobalt
Completeness to 99.7
theta = 25.00◦ (%)
Absorption correction None The presence of Co(III) in the complex, determined by the
Max. and min. 0.92 and 0.87 application of charge balance considerations to the structural
transmission model, is at variance with the nature of the Co(II) salt starting
Refinement method Full-matrix material. The same occurred with the complex of cobalt with
least-squares on F2
aspartic acid [17].
Data/restraints/parameters 2838/0/231
Goodness-of-fit on F2 0.925
Final R indices R1 = 0.0515, 3.3. Vibrational spectra
[I > 2sigma(I)] wR2 = 0.1021
R indices (all data) R1 = 0.1171, The experimental FT-IR and calculated DFT: B3LYP/6-
wR2 = 0.1211 31G vibrational spectra (cm−1 ) of di-␮-hydroxy-bis diglycinate
Largest diff. peak and 0.604 and −0.635 e
hole (Å−3 )
cobalt(III) are shown in Table 5 and are in good agreement with
one another.
1114 O. Versiane et al. / Spectrochimica Acta Part A 65 (2006) 1112–1119

Fig. 1. Ortep drawing of (a) one of the [Co(gly)2 (OH)]2 independent dimmers and (b) two neighboring dimmers showing the interdimeric hydrogen bonds. Ellipsoids
at 20% probability level.

Fig. 2. Comparison between (a) d[M–N] and <(N–M–O); (b) d[M–O] and <(N–M–O) for M–glycine compounds.
 O. Versiane et al. / Spectrochimica Acta Part A 65 (2006) 1112–1119 1115

Table 2
Selected geometric parameters(Å,◦ ) for [Co(gly)2 (OH)]2 ·1.5(H2 O)
Co1–Co1a 2.8761 (18) Co1–N12 1.919 (5) Co2–N22 1.928 (5)
Co1–O10 1.937 (4) C13–O13 1.289 (8) O21–C21 1.287 (7)
Co1–O10a 1.898 (4) C13–C14 1.500 (9) C21–C22 1.525 (9)
Co1–O11 1.906 (4) N12–C14 1.480 (8) N21–C22 1.486 (8)
Co1–N11 1.922 (5) C13–O14 1.235 (7) C21–O22 1.224 (8)
Co1–N12 1.919 (5) Co2–Co2b 2.8733 (18) Co2–O23 1.898 (4)
O11–C11 1.295 (8) Co2–O20 1.920 (4) Co2–N22 1.928 (5)
C11–C12 1.494 (8) Co2–O20b 1.896 (4) C23–O23 1.302 (7)
N11–C12 1.479 (7) Co2–O21 1.889 (4) C23–C24 1.487 (9)
C11–O12 1.235 (8) Co2–N21 1.929 (5) N22–C24 1.464 (7)
Co1–O13 1.903 (4) C23–O24 1.219 (7)

O10a –Co1–O10 82.77 (18) O20b –Co2–O20 82.31 (17)

O11–Co1–O10 92.64 (18) O21–Co2–O20 92.13 (17)
O13–Co1–O10 88.58 (18) O23–Co2–O20 88.79 17)
N11–Co1–O10 93.5 (2) N21–Co2–O20 93.25 (19)
N12–Co1–O10 172.7 (2) N22–Co2–O20 173.2 (2)
O10a –Co1–O11 174.08 (19) O20b –Co2–O21 173.61 (18)
O13–Co1–O11 91.05 (18) O23–Co2–O21 90.67 (19)
N11–Co1–O11 85.49 (19) N21–Co2–O21 85.9 (2)
N12–Co1–O11 91.6 (2) N22–Co2–O21 91.6 (2)
O10a –Co1–O13 92.57 (18) O20b –Co2–O23 92.35 (18)
N11–Co1–O13 176.0 (2) N21–Co2–O23 176.1 (2)
N12–Co1–O13 85.46 (19) N22–Co2–O23 85.46 (19)
O10a –Co1–N11 91.04 (19) O20b –Co2–N21 91.2 (2)
N12–Co1–N11 92.7 (2) N22–Co2–N21 92.7 (2)
O10a –Co1–N12 93.33 (19) O20b –Co2–N22 94.25 (19)
Co1a –O10–Co1 97.43 (18) Co2b –O20–Co2 98.13 (17)
a Symmetry code: 2−x, 1−y, 1−z.
b Symmetry code: 2−x, −y, 2−z.

3.3.1. O–H, N–H and C–H stretching
For the di-␮-hydoxy-bis diglycinate cobalt(III) the vibra-
tional analysis must be centered on some special spectral fea-
tures. One of them concerns the presence of the absorption bands
of the two hydroxyl groups which act, as a bridge connect-
ing the two central cobalt atoms of the complex. There were
doubts about whether the -␮- position must be occupied by
two water molecules or by two hydroxyl groups. The Fourier
transform infrared spectrum in the high-energy region presents
a very broad band which includes the absorption of the –NH2
and –CH2 groups. In the region of 3600–2800 cm−1 the vibra-
tional representation predicts 18 vibrational modes (there are
four –CH2 groups and four –NH2 groups and two –OH groups)
that can be subdivided as Γ NH = 8 A (IR, R), Γ CH = 8 A (IR,
R) and Γ OH = 2 A (IR, R). In this region we can find a very
broad and asymmetrical band centered at 3300 cm−1 giving the
position of the fundamentals pertaining to the –OH, –NH2 and
–CH2 groups joint to bands of combinations. With the intention
of fixing the position of the overlapped bands we have calcu-
lated the second derivative and performed the deconvolution
band analysis. Overlapped bands were found at: 3449, 3427,
3381, 3317, 3289, 3258, 3230, 3161, 3121, 2973, 2937, 2924,
2891 and 2852 cm−1 .
The Gaussian fit was calculated and converged with a reduced
Chi-square = 116.3613 and with a correlation (R2 ) = 0.9992785,
the standard error being equal to 3.68 × 10−3 , and giving in the
region of 3700–2750 cm−1 the position of bands with nearly
the same wavenumber as the second derivate has pointed out.
Concerning the observed bands in the above-mentioned region,
two of them at 3450 and at 3427 cm−1 can be assigned as ν(OH)
of the hydroxyl groups.
In the structural framework of the bis-diglycinate-␮-hydroxy
cobalt(III) complex four NH2 groups we found with a total
of eight N–H stretchings. The bands found at 3381 and at
3317 cm−1 and at 3230 and 3161 cm−1 can be assigned indu-
bitably to the ν(NH) vibrational modes of the –NH2 groups.
These wavenumbers follows the Bellamy–Williams [18] amino
group wavenumber relation νs (a ) = 345.53 + 0.87νas (a ) with an
error of ca. 0.3. The DFT:B3LYP/3-21G calculations also reflect
these trends.
Concerning the four –CH2 groups that are in the framework
structure of the Co(III) glycinate complex, we expected eight
C H stretchings in the region below 3000 cm−1 . In the broad
band between 3600 and 2700 cm−1 we were able to observe by
means of the second derivative only five overlapped bands at
2974, 2938, 2924, 2891 and at 2852 cm−1 , bands which were
indubitably assigned to the C H stretching. The remaining C H
stretching vibrational modes are of very weak intensity and they
were not observed.
3.3.2. ν(C O) stretching
In the complex structure there are four carboxylate groups
providing a total of four ν(C O) normal modes. In the FT-IR
spectrum we could find a very intensive band with a broad profile
centered at 1638 cm−1 . The calculated second derivative shows
the presence of four bands at: 1684, 1655, 1637 and 1605 cm−1
1116 O. Versiane et al. / Spectrochimica Acta Part A 65 (2006) 1112–1119

Table 3 ing. Also in the tetraaqua serine aluminum(III) cation com-

Bond lengths (Å) and angles (◦ ) form M–glycine interactions of previously plex: [20] [Al(Ser)(H2 O)4 ]2+ , the ν(C O) stretching mode was
determined structures
assigned at 1618 cm−1 . The wavenumbers (cm−1 ) calculated
Compound M–N (Å) M–O (Å) O–M–N (◦ ) by the DFT:B3LYP/3-21G procedure agree with the observed
[Co(gly)3 ]a 1.922 (7) 1.905 (6) 86.7 (3) and overlapped bands for which we can provide the correlation:
[Co(gly)3 ]a 1.948 (7) 1.919 (6) 85.2 (3) 1677(calc.) ⇔ 1684 cm−1 (obs.), 1671 (calc.) ⇔ 1655 (obs.),
[Co(gly)3 ]a 1.940 (7) 1.881 (6) 85.9 (3) 1667(calc.) ⇔ 1637 (obs.), 1666 (calc.) ⇔ 1605 (obs.).
[Co(gly)3 ]a 1.922 (7) 1.898 (6) 86.5 (3)
[Co(gly)3 ]a 1.943 (7) 1.913 (6) 87.0 (3)
[Co(gly)3 ]a 1.945 (7) 1.897 (6) 87.1 (3)
3.3.3. H–C–H bending
[Co(gly)3 ]·2H2 Ob 1.926 (4) 1.899 (4) 86.2 (2) Four methylene groups are present in the Co(III) bisgly-
[Co(gly)3 ]·2H2 Ob 1.935 (5) 1.896 (3) 86.3 (2) cinate complex, which must result in twelve HCH bending.
[Co(gly)3 ]·2H2 Ob 1.936 (4) 1.876 (3) 87.0 (2) Due to the higher overlapped degree we were not able to
[Co(gly)3 ]·2H2 Ob 1.929 (4) 1.885 (3) 86.7 (2) assign all these HCH bendings [21], but since they are con-
[Co(gly)3 ]·2H2 Ob 1.929 (5) 1.897 (4) 86.6 (2)
sidered as characteristic frequencies of the –CH2 groups, a
[Co(gly)3 ]·2H2 Ob 1.932 (4) 1.911 (4) 85.9 (2)
[Co(gly)2 (H2 O)]2 ·(H2 O)2 c 1.923 (5) 1.905 (4) 85.4 (2) tentative and comparative assignment was done, including also
[Co(gly)2 (H2 O)]2 ·(H2 O)2 c 1.919 (5) 1.902 (4) 85.5 (2) the wavenumber prediction for these HCH bending modes of the
[Co(gly)2 (H2 O)]2 ·(H2 O)2 c 1.927 (5) 1.890 (4) 85.9 (2) DFT:B3LYP/3-21G calculations. The –CH2 groups are bonding
[Co(gly)2 (H2 O)]2 ·(H2 O)2 c 1.930 (5) 1.897 (4) 85.6 (2) to their neighboring carbon atoms forming a pseudo-tetrahedral
␮-Cr(gly)2 (OH)2 d 2.067 (6) 1.977 (4) 00.00
structure, as usual we can differentiate scissoring, wagging,
␮-Cr(gly)2 (OH)2 d 2.061 (5) 1.970 (4) 00.00
[Cr(gly)(edda)]e 2.053 (6) 1.961 (6) 83.5 (2) twisting ande rocking vibrations. The following comparison
[Na[Ni(gly)3 ]ClO4 ·D2 Of 2.091 (3) 2.044 (2) 82.1 (1) between the vibrational spectra of bis-diglycinate-␮-hydroxy-
[Na[Ni(gly)3 ]ClO4 ·D2 Of 2.088 (2) 2.047 (2) 81.3 (1) cobalt(III), [Ni(Asp)(OH)(H2 O)], aspartic acid, propanoic acid
[Na[Ni(gly)3 ]ClO4 ·D2 Of 2.095 (3) 2.060 (2) 81.0 (1) and propane provides a good correlation for the HCH bending
[Ni(bipi)(gly)2 ]·3H2 Og 2.089 (3) 2.086 (3) 80.6 (1)
(Table 6). The calculated DFT:B3LYP/3-21G values are given
[Ni(bipi)(gly)2 ]·3H2 Og 2.093 (3) 2.072 (3) 80.7 (1)
[Ni(phen)(gly)2 ]·3H2 Og 2.085 (3) 2.073 (3) 80.7 (1) in parenthesis, and according to the visual description given by
[Ni(phen)(gly)2 ]·3H2 Og 2.073 (3) 2.071 (3) 80.7 (1) the Gaussian program [8] these vibrational modes could not be
[Ni(gly)2 (H2 O)2 ]h 2.077 (2) 2.067 (2) 81.3 (1) considered as pure vibrational modes.
[Ni(gly)2 (H2 O)2 ]i 2.08 2.06 81.1
[Ni(gly)2 (ImH)2 ]j 2.102 (4) 2.071 (3) 80.4 (2)
3.3.4. HNH bending
[Ni(gly)2 (ImH)2 ]j 2.104 (4) 2.108 (3) 79.6 (1)
The DFT:B3LYP/3-21G calculations predict for the infrared
a [8].
b
spectrum of the Co(III) bis-glycinate complex two HNH bend-
[9].
c ings at higher values than the C O stretching absorption. Instead
Present work.
d [10]. of the profile of the intensive C O band it shows an asymmetry
e [11]. and the second derivative shows many peaks in the beginning
f [12]. of the band but none of them could be assigned as pertaining
g [13].
h
to HNH bending modes because they are as weak in intensity
[14].
i as the noise intensity. We did a comparative and approximate
[15].
j [16]. assignment following previous HNH bending assignments of
amino acid complexes supported by the DFT calculated spec-
trum (Table 7).
which can be assigned to the ν(C O) stretching modes. Our
assignment agrees with the previous C O assignment of the 3.3.5. Framework metal-ligand stretching and bending
Cd cysteine dichloride ammin complex [19] in which the band The assignment that involved the two Co atoms coordi-
observed at 1604 cm−1 was attributed to the C O stretch- nated in a pseudo-octahedral fashion is based strictly in the
DFT:B3LYP/3-21G calculations. The ν(Co–OH) vibrational
Table 4 mode was assigned at 604 cm−1 (IR) being the calculated and
Hydrogen bond parameters for [Co(gly)2 (OH)]2 ·1.5(H2 O) scaled value 543 cm−1 . The ν(Co–NH2 ) vibrational mode was
A–H · · · B A–H (Å) H · · · B (Å) A · · · B (Å) A–H · · · B (◦ )
assigned at 563 cm−1 (513 calculated value) coinciding with the
double oscillator O–Ni–N explicit (H2 O–Ni–NH2 ) assignment
N21–H21B · · · O1 0.90 2.57 3.186 (5) 126.5 at 463 cm−1 found in the [Ni(asp)(OH)(H2 O)] complex [21].
O1–H11 · · · O12a 0.85 2.477 (6) 3.273 (6) 156.31 (12)
O1–H12 · · · O12b 0.85 1.890 (5) 2.726 (5) 167.67 (19)
The coupled mode ν(CoN + CoO) or ν(O–Co–N) was assigned at
O10–H10A · · · O22 1.018 (4) 1.877 (5) 2.758 (6) 142.9 (3) 495 cm−1 (517 cm−1 calculated value). The stretchings ν(CoO)
N11–H11B · · · O22 0.90 2.27 2.945 (7) 131.5 and ν(COM) which appears without a considerable mixture were
N22–H22D · · · O14c 0.90 2.04 2.911 (7) 162.6 assigned at 445 and at 422 cm−1 , respectively. Bending modes
a Symmetry code: −x + 1, −y + 1, −z + 2. such as δ(OCoO) and δ(CoOC) were assigned tentatively at
b Symmetry code: −x + 2, −y + 1, −z + 2. 410, 405 and at 338 cm−1 . The wavenumber found at 318 cm−1 ,
c Symmetry code: −x + 2, −y + 1, −z + 1. according to the DFT:B3LYP/3-21G calculations appears to be
 O. Versiane et al. / Spectrochimica Acta Part A 65 (2006) 1112–1119 1117

Table 5
Experimental FT-IR and calculated DFT: B3LYP/6-31G vibrational spectrum (cm−1 ) of di-␮-hydroxy-bis-diglycinate cobalt(III).
DFT:B3LYP/6-31G Scaled wavenumbers FT-IR observed Second Approximate
(x 0.9613) wavenumbers derivative assignment

3744 3599 3449 ν(OH)

3641 3500 3429 3427 ν(OH)
3561 2429 3386 3381 ν(NH)
3556 3418 3312 3317 ν(NH)
3519 3383 3289 3289 ν(NH)
3508 3372 3258 3258 ν(NH)
3464 3330 3234 3230 ν(NH)
3463 3329 3160 3161 ν(CH)
3232 3107 3123 6121 ν(CH)
3171 3048 2974 2973 ν(CH)
3170 3047 2936 2937 ν(CH)
3167 3044 2924 ν(CH)
3150 2891 ν(CH) + ν(NH)
3124 3003 2855 2852 ν(CH)
3108 2988 ν(CH)
2107 2987 ν(CH)
3106 2986 ν(CH)
3092 2972 ν(CH)
1763 1695 δ(HNH)
1740 1673 δ(HNH) + δ(HCH)
1733 1666 1689 1683 ν(C O)
1727 1660 1655 1656 ν(C O)
1723 1656 1637 1634 ν(C O) + δ(HNH)
1722 1655 1605 1605 ν(C O)
1703 1637 δ(HNH)
1696 1630 1585 1581 δ(HNH)
1525 1466 δ(HCH)
1509 1451 1564 1564 δ(HCH)
1508 1450 1546 1543 δ(HCH)
1506 1447 δ(HCH)
1421 1366 1517 1519 δ(HNH)
1420 1365 1507 1501 δ(HCH) + δ(HNH)
1418 1363 δ(HCH)
1402 1348 δ(HCH) + δ(HNH)
1352 1300 δ(HCH) + δ(HNH)
1349 1297 1466 1463 δ(HCH)
1338 1286 δ(HCH)
1334 1282 δ(HCH) + δ(HNH)
1334 1282 δ(HCH) + δ(HNH)
1328 1277 δ(HCH) + δ(HNH)
1289 1239 1428 1427 ν(C C) + ν(C O) + ν(O C C)
1283 1197 1374 1380 δ(C O)
1257 1208 1338 δ(C O)
1249 1201 1310 1306 ρ(CH3 ) + ρ(NH2 )
1210 1163 1267 ρ(CH3 ) + ρ(NH2 )
1207 1160 1228 1226 ρ(CH3 ) + ρ(NH2 )
1201 1155 1198 1198 ρ(CH3 ) + ρ(NH2 )
1189 1143 1160 1160 ν(C N)
1170 1125 1121 1118 δ(HCH) wagg.
1168 1123 1071 1066 δ(HNH) wagg.
1029 989 1047 1042 δ(HNH) wagg. + ν(C N)
1022 982 ρ(OH)
1014 975 1020 ρ(OH)
1007 968 ρ(OH)
1003 964 990 998 Bending coupled modes
999 960 ρ(CH3 )
982 944 ρ(NH2 )
975 937 975 965 ρ(CH3 ) + ρ(NH2 )
972 934 ρ(CH3 ) + ρ(NH2 )
969 931 952 951 ρ(CH3 ) + ρ(NH2 )
920 884 920 919 ρ(NH2 ) + ␯(C N)
911 876 ν(C C) + ν(C O)
1118 O. Versiane et al. / Spectrochimica Acta Part A 65 (2006) 1112–1119

Table 5 (Continued )
DFT:B3LYP/6-31G Scaled wavenumbers FT-IR observed Second Approximate
(x 0.9613) wavenumbers derivative assignment

908 873 ν(C C) + ν(C O)

903 868 848 849 ν(C C) + ν(C O)
868 834 δ(HNH) wagg.
850 817 805 808 δ(HNH) wagg.
794 763 δ(HNH) wagg.
788 758 δ(HNH) wagg.
751 722 749 759 ρ(NH2 )
748 719 720 718 δ(NCCo) ring
732 704 ρ(CH2 ) + ρ(NH2 )
724 696 δ(ring bending)
720 692 678 673 δ(OH)
614 590 655 649 ρ(C O)
611 587 ρ(C O)
602 579 Ring torsion
597 574 δ(NCC)
596 573 δ(NCC + NcoO)
565 543 604 598 ν(Co OH)
534 513 563 564 ν(Co NH2 )
521 501 531 529 Coupled skeletal stretching
517 497 495 496 ν(Co N + CoO) or ν(O Co N)
506 486 Coupled mode
496 477 445 445 ν(CoO)
488 469 422 421 ν(CoN)
483 464 ν(CoO)
467 449 Skeletal stretching
464 446 ν(Co OH)
462 444 Coupled mode
447 430 ν(CoO) + coupled modes
427 410 δ(OCoO)
421 405 δ(OCoO)
404 388 391 395 δ(CoOC)
384 369 384 386 Torsion
383 359 381 Torsion
349 335 ρ(OH)
331 318 377 377 ν(CoO) + ν(CoN)
322 310 325 325 Torsion
311 299 303 303 ρ(OH)
281 270 279 279 δ(OH) wagg. or ρ(OH)
265 255 Torsional modes
252 242 250 250 Torsional modes
242 233 Torsional modes
225 216 224 224 Torsional modes
216 208 Torsional modes
200 192 203 203 Torsional modes
176 169 176 176 Torsional modes
170 163 Torsional modes
169 162 150 150 Torsional modes
142 137 Torsional modes
137 132 131 131 Torsional modes
116 111 Torsional modes
106 102 Torsional modes
102 98 Torsional modes
85 82 85 Torsional modes
71 68 Torsional modes
56 Torsional modes
58
45 43 41 Torsional modes
38 37 Torsional modes
 O. Versiane et al. / Spectrochimica Acta Part A 65 (2006) 1112–1119 1119

Table 6
Comparative experimental assignment for the δ (HCH) vibrational modes: [Co(gly)2 (OH)2 ]·1.5(H2 O), [Ni(Asp)(OH)(H2 O)4 ], aspartic acid, propanoic acid and
propane
Co(III) Ni(II) Aspartic acid Propanoic acid Propane Assignment

1425 (1427) 1416 (1422) 1464 1452 δ(HCH) sciss.

1373 (1372) 1354 (1308) 1399 (1369) 1420 1390 δ(HCH) wagg.
1230 (1241) 1228 (1160) 1254 (1216) 1258 1278 δ(HCH) twist.
1045 (996) 1097 (1000) 1073 (1029) 1083 1052 ν(CC) + δ(HCH) wagg.
850 857 (738) 852 867 ν(CC)

Data from Ref. [21].

Table 7
Comparative assignment for the δ (HNH) vibrational modes for amino acid complexes supported by DFT calculations
Co(II) (gly)2 [Al(Ser)(H2 O)4 ]2+ [Ni(Asp)(OH)(H2 O)] [Cd(cys)Cl2 ]− Serine Approximate assignment

1695, 1673, 1637 1727 [δ(HCH) or ν(C O)] 1619 δ(HCH)

1581, 1522, 1507 1560 1592 δ(HNH) sciss.
1409 1409 δ(HNH) + ν(CC)
1348 1354, 1331 δ(HNH) + δ(HCH)CH2
1290, 1245 1273 1303 δ(HNH) twist
1119 1118 1177 1195, 1124 δ(HNH) wagg.
1071, 1047 1082 1048 δ(HNH) wagg. + δ(HCH) twist.
805 808 868 965, 913, 873 850 δ(NH2 ) wagg. or ρ(NH2 )
749 766 ρ(NH2 )

Data from Refs. [19], [20] and [21].

a mixture of the ν(CoO) + ν(COM) vibrational modes. Torsional C. Gonzalez, M. Head-Gordon, E.S. Replogle, J.A. Pople, Gaussian 98,
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