close

Вход

Забыли?

вход по аккаунту

?

Synthesis Spectral Properties and Crystal Structure of Aqua-2-N-2-hydroxybenzylideneiminoethane Sulphonic Acid Copper II Monohydrate.

код для вставкиСкачать
31
Aqua-2-(N-2-hydroxybeenzylideneimino)ethane sulphonicacid Cu(I1) Monohydrate
Synthesis, Spectral Properties, and Crystal Structure of
Aqua-2-(N-2-hydroxybenzylideneimino)ethaneSulphonic Acid Copper
(11) Monohydrate
Marja Salo’, Reijo H&ntiliiinena,Urho Turpeinena,and Maire Lehtinen
School of Pharmacy, University of Helsinki, SF-00170 Helsinki, Finland
Inorganic Chemistry, University of Helsinki, SF-00100 Helsinki, Finland
a) Division of
Received February 3,1989
Some properties of the title compound are determined by spectroscopic
examinationand X-ray analysis.
Synthese, Spektroskopische WenSchaFten und KristPUstruktur von
Aqua-2~-Zhydroxybenzyudenimino)ellraoSulfonsilure Kupfer 0
Monohydrat
Eigenschaftenvon kp1a-2-(N-2-hydroxybenzylidenimino)ethanSulfons;iure
Kupfer (11) Monohydrat werden durch spektroskopische Untersuchungen
und Rontgensmkturanalyseder Verbindungbeschrieben.
2-Aminoethane sulphonic acid (taurine), an amino acid with biological
and physiological significance, has become of considerable interest during
the last two decades. Taurine exists unattached especially in brain, nervous
and muscular tissues’). Among its functions, it stabilizes cell membranes in
the retina’), strengthens heart function, and inhibits cardiac arrhythmias3)
and convulsion. Hydrophilic taurine crosses the blood-brain barrier poorly.
Recently, derivatives that are more lipophilic have been synthesized. e.g.
talt~imide~”and N-pivaloyltaurine6),which effectively inhibit convulsions
even when administered intraperitoneally. The mechanism of taurine action
appears to be associated with its complexation with metal ions, e.g. Ca (11)
and Zn (10, though its real character is still undecided’). The primary
amino group in taurine reacts easily with aldehydes and aldehyde derivaP
These imino compounds form complexes
tives yielding S C ~bases&’*’.
with trivalent metal ions in 1:2 ratio and with divalent cations mainly in 1:l
ratio. Formation constants of these complexes lie between lo7and 10’ with
the nature of the cenhlll atom being the main influence on these values.
Moreover, complexes are more stable when formed with aivalent than with
divalent metal cations. The pharmacological activity of the complexes has
not been studied, though copper complexes could conceivably have uses in
drug ~ a t m e n t ’ ~ ) .
ExperimentalPart
Two cm3 salicylaldehyde (Merck) in ethanol were added to a water solution containing 1 g of taurine (Fluka AG). The pH of the mixture was adjusted to 8 with 0.5 M KOH in ethanol. After refluxing of the mixture for
a b u t 15 min, the precipitated Schiff base compound salicylidenetaurine,
was filtered off and dried. The title complex was prepared by dissolving
3.75 mmol of CuClz in 25 cm3 water and adding the above prepared S c h g
base ligand in equimolar ratio. After standing for one day at room temp. the
precipitate was filtered off and dried at 80’C. The precipitate consisted of a
dark green, powder-like component and of larger, lighter-coloured crystals.
The crystals were characterizedby analysis of the copper content.
Information about the collection and of crystal and diffraction data is
summarized in Table 1. The intensities were corrected for Lorentz and polarization effects. The absorption comction was included by empirical Cpscan method. The structure was solved by direct and Fourier methods of the
SHELXS-86 and XTAL-83 program ~ystems’~’’~).
H atoms were located
Arch. Pharm. (Weinheim) 323.31-33 (1990)
Tab. 1: Data for X-ray diffraction study of [Cu (GHgN04S) HzOIH20
M,
326.83
6.971 (2)
9.317 (1)
10.447 (2)
108.86 (2)
101.27 (2)
105.69 (1)
2
1.83
1.847
18
9.67-25.23
0.71069
Pi
334
&A
b
C
a,deg
B
7
2
D,, g cm-3
D C
orientation mns
range (28). deg
radiation (MoKa)
space group
F (000)
method
20-range, deg
scan speed, deglmin
unique re8
observed rcfl
(Fo >WFo))
R
Rw [Ew (IF01- IFel)’ / Ew lF01~1”’
diffractometer
monochromator
W-SCan
5-55
2-25
2689
2324
0.027
0.026
Nicolet P3
PPhite
from the difference Fourier map. Refinement with non-hydrogen atoms
anisotmpically and H atoms isotropically converged to R4.027 and
R 4 . 0 2 6 . Scamring factors for neutral atoms and anomalous dispersion
The molecular figure
corrections for Cu and S atoms were incl~ded’~’~).
was drawn using the ORW pgram’”. AU calculations were performed
on the VAX 8650 computer system.
Spectmmetric studies, W and visible region: Beckman DK-2A spectm
photometer, salicylidenetaurine in water 4 lo4 M (2W360 nm) and
2 . lo4 M (350-1000 nm); concentration of the copper (11) complex in dimethylsulphoxide 0.002% (320-1000 nm). - IR specera: Nicolet 2OSXC
FT-IR spectrometer,KBr, powder and crystals.
OVCH Verlagsgesellschaft mbH, D-6940 Weinheim. 1990
-
0365-6233/90/0101-01$02.50x)
32
Salo and coworkers
Tab. 2: Atomic coordinates (x 104) and isotropic thermal paramters 8.;
10461(1)
11777(1)
12073(3)
13241(3)
11806(3)
9182(3)
12516(3)
1283l(5)
88840)
9226(4)
90334)
7826(4
74434)
6319(4)
5858(4)
6458(4)
7545(4)
8095(4)
3346 (1)
3792 (1)
43132)
3024(2)
5112(2)
2822(2)
5262(2)
4939(4)
1200(2)
2278(3)
OW3)
-0026(3)
-0050(3)
-1558(3)
- 16%(3)
-0291(3)
1205(3)
13633)
2524 (1)
5729 (1)
45640)
6070(2)
6940(2)
0586(2)
2467(2)
-0124(3)
2442(2)
5023(2)
3729(3)
1263(3)
-0157(2)
- 1304(3)
-2682(3)
-2943(3)
-1853(3)
-0427(2)
1.66
1.52
2.11
2.39
2.31
2.38
2.16
5.55
1.48
1.64
1.71
1.61
1.54
1.91
2.15
2.06
2.00
1.65
Discussion
Table 2 lists the atomic positional and equivalent isotropic
thermal parameters (Bq).Table 3 gives the interatomic distances and angles. Figure 1 shows a view of the discrete
complex molecule. The environment at the fivecoordinated
Cu @) ion is a square pyramid, where the basal plane consists of tridentate salicylidenetaurine ligand and one mrdinated water molecule. The interatomic distances in the basal
plane vary from 1.885 (2) to 1.991 (2) A. The less strongly
joined 0 (sulph) atom of the adjacent com lex unit occupies
an apical site with a distance of 2.436 (2) .
H
Tab. 3: Interatomic distances (A)and angles ("). (i = equivalent position
-x+2, -y+l, -z+l)
1.973(2)
2.436(2)
1.885(2)
1.991(2)
1.%9(2)
1.479(2)
1.448(2)
1.443(2)
1.776(2)
1.476(4)
1.282(2)
1.5133)
1.447(4)
1.405(3)
1A1l(4)
1.367(4)
1.394(4)
1.370(3)
1.412(4)
1.3 18(2)
Fig. 1. Molecular view and numbering scheme.
C(4)-C(9)-C(8)
%.93(8)
94.18(8)
166.53(9)
168.88(8)
84.08(8)
85.28(8)
131.1400)
122.w 11)
122.50(20)
127.5O( 19)
111.21(13)
111.08(12)
104.88(11)
113.89(11)
111.83(19)
112.69(22)
127.43(24)
115.16(21)
117.55(24)
123.03(18)
121.69(26)
118.75(20)
121.33(26)
120.71(27)
123.24(23)
118.06(19)
Fig. 2. Stereoviewof the unit cell packing.
Arch. Phurm. (Weinheim) 323.31 -33 (1990)
33
Aqua-2-(N-2-hydroxybeenzylideneimino)ethanesulphonic acid Cu(I1) Monohydrate
powder-like and crystal complexes lies in the absorption of
the hydroxyl group; there is a hydroxyl absorption at 3350
cm-' in the spectrum of the crystals.
Further details concerning the crystal structure can be obtained from Fachinformationszentrum Karlsruhe, Gesellschaft fiir wissenschaftlich-technischeInformation mbH,
D-7514 Eggenstein-Leopoldshafen2, quoting the Journal,
the author and the No. CSD-53714.
0
3600
2800
2000 1600 1200 8 0 0 4 0 0
WAVENUHBER
References
1
2
3
4
5
6
a
3600
2800
2000 1600 1200 800
400
WAVENUMBER
7
8
9
Flg. 3. The infrared specm of salicylidenetaurine (A) and its copper (11)
complex (B) (crystalline component).
10
11
12
The crystal structure is stabilized by a hydrogen bond between the coordinated water oxygen O(5) atom and the lattice water oxygen O(6) atom. The distance 0(5)..0(6) is
2.685 (4) A, the H..O value is 1.93 (4) A, and the angle
0(5)-H(10)..0(6) is 179'. A weaker hydrogen bonding interaction, through the lattice water oxygen 0(6), may be
expected with the O(4) atom of the salicylidene group. The
O..O distance is 2.919 (5) A and the H..O value 2.40 (3) A.
The IR spectrum of salicylidenetaurine (Fig. 3) shows absorptions at 1640 cm" (vC=N) and at 1205 and 1190 cm"
(6s-0),and additionally a weak v0-H absorption at 3440
vcp-'. ~n
the spectrum of the Cu @) complex, the bands of
vC=N and 6s-0are shifted to lower wave numbers (1620
and 1150 cm-'). The difference between the spectra of the
Arch. Pharm. (Weinhim) 323.31-33(1990)
13
14
15
16
17
18
19
J.A. Sturman, R.C. Moretz. J:H. French, and H.M. Wisniewski, Pmgress in Clinical and Biolocical Research 179.43 (1985).
M.Neuringer. J.A. Sturman, G.Y. Wen, and H.M. Wisniewski. ibid.
53.
J. Azuma, K. Takhra, N. Awata. A. Sawamura. H. Ohta, T.T.Y. Hamaguchi. K. Fukuda, and S. Kishimoto. ibid.. 195.
P. Kontro, I.-B. LindCn, G. Goth6ni. S.S. Oja, Sulfur Amino Acids:
Biochemical and Clinical Aspects, p. 21 1, (1983).
K. Nakagawa, and RJ.Huxtable, N e w h e m . Int. 7,819 (1985).
L. Ahtee, H. Auvinen. A.-R. Miienpiiii M-L.Vahala, M.Lehtinen, and
J. Halmekoski. Acta PharmacoL'et Toxicol. 57.96 (1985).
R.J. Huxtable, Adv. Exp. Med Biol. 139. I (1982).
K.G. Mehta, K.G. Sharma, and R.K. Mehta, Ind. J. Chem. 21A. 86
(1982).
C.P. Gupta, N.K. Sankhla, and R.K. Mehta. J. Prakt. Chem. 321.691
(1979).
M.R. Mali.andR.K. Mehta, Chem. Anal. (Wamaw)21,1261(1976).
P. Mehta, S. Bhatia, and R.K. Mehta, J. Prakt.Chem. 326.689 (1984).
B.R. Singhvi, P.K. Kanungo. and R.K. Mehta, Curr. Sci. 46. 222
(1977).
J.R.J. Sorenson.Chem.Br.20.1110(1984).
G.M. Sheldrick, SHELXS-86 for the Solution of Crystal Structuns
from Diffraction Data, Univ. of Glittingen (1986).
Weiter Einzelheiten zur Kristallsrmltturuntersuchungklinnen beim
Fachinformationszentrum Energie, Physik. Mathematik D-7514 Eggenstcin-leopoldshafen 2. unter Angabe der Hintedegungsnummer.
des Autors und des Zeitschriftenzitates angefordert werden.
J.M. Stewart and S.R. Hall, The XTAL System of Crystallographic
Programs, Tech. Rep. 'IR-1364. Computer Science Center, Univ. of
Maryland, College Park, Maryland (1983).
D.T. Cromer and J.B. Mann. ActaCrystallogr. A24 321 (1968).
R.F. Stewart, E.R. Davidson. and W.T. Simpson, J. Chem. Phys. 42.
3175(1965).
W.C. Hamilton. Acta Crystallogr. 12,609(1959).
C.K. Johnson,ORTEP (1963, Report ORNL-3794. Oak Ridge National Laboratory, Tennessee, U.S.A.
[m331
Документ
Категория
Без категории
Просмотров
0
Размер файла
228 Кб
Теги
acid, crystals, hydroxybenzylideneiminoethane, structure, synthesis, properties, sulphonic, aqua, monohydrate, coppel, spectral
1/--страниц
Пожаловаться на содержимое документа