Manganese(II), Iron(II), Cobalt(II) and Nickel(II) complexes of methanesulfonic acid hydrazide. Crystal structure of trans-dichlorotetrakis(methanesulfonic acid hydrazide-N2)cobalt(II) and trans-dichlorotetrakis(methanesulfonic acid hydrazide-N2)nickel(II)

Article abstract of DOI:10.1515/znb-2002-1016

The complexes [M(MSH)₄Cl₂] (MSH = CH₃SO₂NHNH₂; M = Mn (1), Fe (2), Co (3) and Ni (4)) were synthesized and characterized by elemental analysis, molar electric conductivity, IR and d-d electronic spectra. The X-ray single crystal analysis revealed for 3 (triclinic, P1?, a = 8.077(2), b = 8.622(2), c = 8.742(2) ?, α = 71.98(3), β = 75.30(3), γ = 64.11(3)°, V = 515.8(2) ?³, Z = 1) and 4 (triclinic, P1?, a = 8.050(2), b = 8.588(2), c = 8.686(2) ?, α = 73.35(3), β = 75.76(3), γ = 63.94(3)°, V = 511.8(2) ?³, Z = 1) that MSH is coordinated via the amino N atom, the donor atoms and the metal are coplanar, and the Cl ligands are in trans-configuration. On the basis of IR data a similar structure is suggested for 1 and 2. The electronic spectra of 3 and 4 are interpreted by the Angular Overlap Model and bonding parameters are derived: e_σ(N) = 3384(15), e_σ(Cl) = 2788(25), e_π(Cl) = 150(21) cm^-1 for 3, and e_σ(N) = 3668(21), e_σ(Cl) = 2602(150), e_π(Cl) = -21(128) cm^-1 for 4.

Full text of DOI:10.1515/znb-2002-1016

Manganese(II), Iron(II), Cobalt(II) and Nickel(II) Complexes of
Methanesulfonic Acid Hydrazide. Crystal Structure of
2
trans-Dichlorotetrakis(methanesulfonic Acid Hydrazide-N )cobalt(II)
2
and trans-Dichlorotetrakis(methanesulfonic Acid Hydrazide-N )nickel(II)
a
b
b
Nicolay I. Dodoff , Maria Kubiak , and Janina Kuduk-Jaworska
a
Institute of Molecular Biology, Bulgarian Academy of Sciences, Acad. G. Bonchev Street,
Block 21, 1113 Sofia, Bulgaria
Faculty of Chemistry, Wrocław University, 14 F. Joliot Curie Street, 50Ð383 Wrocław, Poland
b
Reprint requests to Dr. N. I. Dodoff. E-mail: dodoff@bas.bg
Z. Naturforsch. 57b, 1174Ð1183 (2002); received May 18, 2002
Methanesulfonic Acid Hydrazide, Metal Complexes, X-Ray Structure
4 2 3 2 2
The complexes [M(MSH) Cl ] (MSH = CH SO NHNH ; M = Mn (1), Fe (2), Co (3) and
Ni (4)) were synthesized and characterized by elemental analysis, molar electric conductivity,
¯
IR and d-d electronic spectra. The X-ray single crystal analysis revealed for 3 (triclinic, P1,
˚
a = 8.077(2), b = 8.622(2), c = 8.742(2) A, α = 71.98(3), ꢀ = 75.30(3), γ = 64.11(3)∞, V =
˚
3
¯
˚
5
ꢀ
15.8(2) A , Z = 1) and 4 (triclinic, P1, a = 8.050(2), b = 8.588(2), c = 8.686(2) A, α = 73.35(3),
˚
3
= 75.76(3), γ = 63.94(3)∞, V = 511.8(2) A , Z = 1) that MSH is coordinated via the amino
N atom, the donor atoms and the metal are coplanar, and the Cl ligands are in trans-configu-
ration. On the basis of IR data a similar structure is suggested for 1 and 2. The electronic
spectra of 3 and 4 are interpreted by the Angular Overlap Model and bonding parameters
Ð1
are derived: e
σ σ π σ
(N) = 3384(15), e (Cl) = 2788(25), e (Cl) = 150(21) cm for 3, and e (N) =
Ð1
3
668(21), e (Cl) = 2602(150), e (Cl) = Ð21(128) cm for 4.
σ
π
Introduction
structure analysis of [Zn(MSH) Cl ], which re-
2 2
vealed that the coordination of zinc is pseudo-
tetrahedral and the ligand is bound to it via the
Sulfonamide [1Ð3], and hydrazine [4] deriva-
tives, as well as compounds containing both frag-
ments in the same molecule [5] exhibit versatile
pharmacological activity, and in particular, a cyto-
static effect. Transition metal complexes of hy-
drazides and sulfonamides also find application in
chemotherapy [6]. Complexes of aromatic sulfon-
amides and sulfonylhydrazines have been inten-
sively studied as carbonic anhydrase inhibitors [7].
NH group.
2
Here we report the synthesis, spectroscopic and
structural characterization of Mn(II), Fe(II),
Co(II), and Ni(II) complexes of MSH.
Results and Discussion
The new complexes, all of the type
Methanesulfonic acid hydrazide (MSH), [M(MSH) Cl ], were prepared from MSH and
4
2
CH SO NHNH , is the prototype of the com- metal chlorides in organic solvents (see Experi-
3
2
2
pounds combining the two pharmacophoric mental). Analytical results and some physical
groups, sulfonamide and hydrazine residue. Pre- properties of the compounds are listed in Table 1.
viously we studied the crystal structure and vibra- The complex 1 is hygroscopic and should be han-
tional spectra of MSH [8], and synthesized and dled and stored in a dry atmosphere. On exposure
characterized its azomethine derivatives [9, 10]. to air, 2 slowly turns to yellow, because of oxida-
The parent compound and its azomethine deriva- tion to Fe(III), and should be stored in a sealed
tives exhibit antibacterial and cytostatic activity ampule. Compounds 3 and 4 are stable under
[9]. MSH is apparently a potential ligand, and its usual conditions. All the complexes are soluble in
metal complexes could also be of interest for phar- water, methanol and ethanol; 1, 2 and 3 are also
macology. However, the coordination chemistry of soluble in acetonitrile, and 1 in tetrahydrofuran.
MSH has not been explored. Recently we re-
The attempts to isolate Pd(II) and Pt(II) com-
ported [11] the preparation and X-ray crystal plexes of MSH were unsuccessful. Upon mixing
0
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D
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N. I. Dodoff et al. · Manganese(II), Iron(II), Cobalt(II) and Nickel(II) Complexes
1175
Table 1. Elemental analyses and physical properties of MSH complexes.
Complex
Formula
Analysis: found (calcd) [%]
Colour Melting
Λ
m
b, ΩÐ1 molÐ1 cm2
a
No.
1
C
H
N
O
S
Metal
range [∞C] MeOH
EtOH
[Mn(MSH) Cl
[Fe(MSH) Cl
[Co(MSH) Cl
[Ni(MSH) Cl
4
2
]
8.78 4.85 19.89 22.64 23.18 10.20 white
8.48) (4.27) (19.79) (22.60) (22.64) (9.70)
98Ð100
115
130
115
112
29
(
(
(
(
2
4
2
]
8.70 4.44 19.15 22.86 22.21 10.22 yellow- 137Ð139
37
8.47) (4.26) (19.75) (22.56) (22.61) (9.85) ish-white
3
4
2
]
8.68 4.31 19.51 22.10 22.74 10.61 pink
8.42) (4.24) (19.65) (22.44) (22.48) (10.33)
157Ð160
27
4
4
2
]
8.97 4.81 19.27 22.96 22.23 10.44 sky-blue 186Ð190
33
8.43) (4.24) (19.65) (22.45) (22.49) (10.29)
a
With decomposition; b molar electric conductivity of 1 ¥ 10Ð3 M solutions of the complexes in methanol and ethanol.
water solutions of MSH, and of K PdCl , K PtCl
4
Crystal structure of 3 and 4
2
4
2
and K PtI , respectively, yellow precipitates are
2
4
formed initially, which rapidly decompose at am-
Although the crystal structure of metal coordi-
bient temperature. The ligand is oxidized with re- nation compounds of hydrazine and its derivatives
lease of gaseous product, probably N , and deposi- has been extensively studied by Braibanti et al.
2
tion of metallic Pd and Pt, respectively. Oxidation [13], and by other workers [14Ð16], it seems that
of MSH was also observed by Fe(III), Cu(II), and there are few examples of structurally charac-
Ag(I) salts.
terized coordinated sulfonylhydrazines [11, 17].
Complexes 3 and 4 are isostructural; the molec-
The molar electric conductivity (Λ ) values of
m
the complexes (Table 1) are much higher than the ular structure of 3 is presented in Fig. 1. Selected
expected for non-electrolytes, and reach the geometric parameters for 3 and 4 are listed in
ranges characteristic for the 1:1 electrolyte type, in Table 2. The ligand MSH is bound to the metal
both methanol and ethanol [12]. This shows that atom by the NH groups. The sulfonyl oxygens do
2
partial dissociation of the chloride ligands takes not participate in the coordination, and this is not
place in these solvents.
surprising since the examples of coordinated sulfo-
nyl groups are very rare [18]. The four N donor
˚
Table 2. Selected bond lengths (A)
Parameter
3, M = Co
n = 1 n = 2
4, M = Ni
n = 1 n = 2
and angles (deg) for complexes 3
and 4. Atom labelling according to
Fig. 1.
MÐCl
2.425(1)
2.447(1)
MÐN(n2)
2.186(2)
2.177(2)
1.438(1)
1.443(1)
1.659(2)
1.752(2)
1.434(2)
89.34(5)
2.122(2)
2.123(2)
1.440(2)
1.462(2)
1.655(2)
1.751(2)
1.440(2)
88.74(5)
S(n)ÐO(n1)
1.435(1)
1.440(1)
1.665(2)
1.756(2)
1.436(2)
89.32(5)
1.442(2)
1.462(2)
1.657(2)
1.758(2)
1.445(2)
89.06(6)
S(n)ÐO(n2)
S(n)ÐN(n1)
S(n)ÐC(n)
N(n1)ÐN(n2)
ClÐMÐN(n2)
N(12)ÐMÐN(22)
N(n1)ÐN(n2)ÐM
O(n1)Ð S(n)ÐO(n2)
O(n1)ÐS(n)ÐN(n1)
O(n2)ÐS(n)ÐN(n1)
O(n1)ÐS(n)ÐC(n)
O(n2)ÐS(n)ÐC(n)
N(n2)ÐN(n1)ÐS(n)
N(n1)ÐS(n)ÐC(n)
N(n2)ÐN(n1)ÐS(n)ÐC(n)
H(n4)ÐN(n1)ÐS(n)ÐC(n)
H(n5)ÐN(n2)ÐN(n1)ÐH(n4)
91.85(6)
91.32(7)
110.8(1)
118.7(1)
110.7(1)
104.8(1)
108.8(1)
109.6(1)
116.6(1)
103.1(1)
-93.6(1)
144(2)
109.8(1)
118.7(1)
110.5(1)
104.3(1)
108.8(1)
109.8(1)
117.9(1)
103.6(1)
95.9(1)
110.4(1)
119.0(1)
110.6(1)
104.7(1)
108.4(1)
110.1(1)
116.4(1)
102.8(1)
-92.7(2)
144(2)
109.9(1)
119.1(1)
110.7(1)
104.1(1)
107.9(1)
110.6(1)
118.0(1)
103.3(1)
94.4(2)
-137(2)
-137(2)
82(3)
-84(3)
158(3)
79(3)
-83(3)
162(3)
H(n6)ÐN(n2)ÐN(n1)ÐH(n4) -163(3)
-162(3)
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176
N. I. Dodoff et al. · Manganese(II), Iron(II), Cobalt(II) and Nickel(II) Complexes
4 2
Fig. 1. ORTEP drawing for [Co(MSH) Cl ] (3). Ellipsoids are at the 50% probability level.
atoms and the metal are coplanar and the two Cl cantly in the three cases. In the Zn(II) complex,
ligands are in trans-position to each other. The co- the amino group is in gauche-orientation with re-
ordination polyhedron MN Cl approaches almost spect to SÐC and one of the SÐO bonds, and the
4
2
D4h symmetry. The MÐN bond lengths in 3 and 4 hydrogen atom at the sulfonamide nitrogen and
have the usual values for a coordinated hydrazine the other oxygen are almost eclipsed. In the dimer
group [13]. The CoÐN bonds are longer (average of the MSH, both the NH group and the H atom
2
˚
by ca. 0.06 A) as compared to the NiÐN bonds, at the sulfonamide nitrogen are gauche-oriented
whereas the CoÐCl bonds are somewhat shorter with respect to the SÐC and SÐO bonds. In com-
˚
(
by ca. 0.02 A) with respect to the NiÐCl bonds. plexes 3 and 4, however, the NH group is gauche-
2
Thus the tetragonal deformation is more pro- oriented toward the SÐC and SÐO bonds, but the
nounced in 4 than in 3. The symmetry of the com- H atom is gauche-positioned toward the two SÐO
plex molecule is near to C , although the true bonds. The bond lengths and bond angles do not
2h
point group is Ci.
It is interesting to compare the conformation of
vary considerably in the three regarded cases.
Fig. 2 shows the crystal packing and hydrogen
the ligand in 3 and 4, with that in [Zn(MSH) Cl ] bonding geometry for 3; for 4 they are analogous.
2
2
[11], as well as in the non-coordinated MSH where The parameters of the hydrogen bonds for 3 and
in the solid state two molecules of MSH dimerize 4 are collected in Table 3. All types of hydrogen
through hydrogen bonds between the NH and atoms, even those of the methyl groups (one
2
NH groups [8]. In the Zn(II) complex the sulfon- H atom per CH group), are involved in a system
3
amide nitrogen is completely planarized, in dis- of hydrogen bonds. The hydrogen atom of the NH
tinct with the MSH dimer where the sum of the groups has short contacts with the Cl ligands, and
bond angles at this atom is 347 ∞. In 3 and 4 the those of the NH groups with the sulfonyl oxygen
2
sulfonamide nitrogen is less planarized as evi- atoms. The NH groups participate in intramolecu-
denced by the sum of the bond angles (334Ð lar hydrogen bonds, whereas the NH and CH3
2
3
39 ∞). The conformations of MSH with respect to groups are involved in both intra- and intermolec-
the rotation around the SÐN bond differ signifi- ular bonds.
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N. I. Dodoff et al. · Manganese(II), Iron(II), Cobalt(II) and Nickel(II) Complexes
1177
NH group, the spectrum of partially deuterated
2
specimen of complex 4 was examined (Fig. 3,
Table 4). An alternative assignment concerning
the NH rocking vibrations could not be ruled out,
2
Ð1
the bands in the interval of 585Ð623 cm to be
ascribed to them. In such a case the band at 470
cm in the spectrum of the deuterated complex 4
would correspond to that at 623 cm
Ð1
Ð1
for the
non-deuterated complex (isotopic ratio 1.33). If
this is so, all the three bands in the range of 490Ð
Ð1
5
35 cm should be attributed to SO bending
2
vibrations.
Among the five IR-active normal vibrations of
the D4h coordination polyhedron MN Cl , [30] we
could tentatively point out the A2u metal-chlorine
4
2
4 2
Fig. 2. The crystal packing of [Co(MSH) Cl ] (3). Hy-
drogen bonds are indicated by dashed lines.
stretching, ascribing to it the bands in the interval
Ð1
of 243Ð255 cm (Table 4). These are the most
Infrared spectra
intensive bands in the far IR region and their posi-
tion conforms with the data for complexes with
relevant structure [30Ð33].
Previously, [8] an entire interpretation of the vi-
brational spectra of MSH, supported by normal
coordinate analysis, has been done which helped
the full assignment of IR bands of the coordinated
MSH. The assignments are based on the literature
data for molecules containing appropriate frag-
d-d Electronic spectra
The Angular Overlap Model (AOM) is an appro-
ments, a sulfonyl group [19Ð22] and a hydrazine priate tool for interpreting d-d electronic spectra of
residue [23, 24] (an expanded reference list can be complexes with symmetry lower than cubic, and has
found in [8]), as well as for metal complexes of been successfully applied to tetragonal complexes
hydrazine derivatives [11, 25Ð29], including sulfo- with the MN Hal chromophores [30, 34, 35]. Fig. 4
4
2
nylhydrazines [7c, d]. There is a close correspond- shows the diffuse-reflectance electronic spectra of 3
ence between the spectra of the four coordination and 4, along with the assignment of the d-d transi-
Ð1
compounds studied which suggest all they should tions. The bands in the range of 5900Ð6700 cm
,
Ð1
be of the same structural type. Selected IR spec- and the shoulders at 7350 cm appear in the
troscopic data for MSH and its complexes are pre- spectra of all the four complexes and should be
sented in Table 4. For better assignment of the ascribed to overtone and combination vibrational
bands of the hydrazine residue, and in particular, transitions of the ligand. The d-d spectra of 3 and 4
the wagging, twisting and rocking modes of the were analysed by AOM (D4h symmetry of the
Table 3. Hydrogen bonding geometry for complexes 3 and 4a.
˚
˚
4
˚
4
DH···A
DÐH, A
H···A, A
D···A, A
< (DHA), deg
3
4
3
3
3
4
N(21)H(24)···Cl(
i)
0.86(2) 0.83(3)
0.89(2) 0.86(3)
0.85(2) 0.87(3)
0.84(2) 0.86(3)
0.91(2) 0.91(3)
0.81(2) 0.85(3)
0.95(3) 0.91(4)
0.96(2) 0.95(3)
2.39(2) 2.41(3)
2.39(2) 2.43(3)
2.35(2) 2.34(3)
2.31(2) 2.34(3)
2.49(2) 2.52(3)
2.45(2) 2.39(3)
2.81(3) 2.86(4)
2.76(2) 2.75(3)
3.105(2) 3.080(2)
3.060(2) 3.051(2)
3.009(2) 3.040(2)
3.041(2) 3.071(2)
3.178(2) 3.190(2)
3.114(2) 3.066(2)
3.698(2) 3.702(2)
3.573(2) 3.569(2)
140(2)
132(2)
135(2)
146(2)
133(2)
140(2)
156(2)
142(2)
138(2)
130(3)
138(2)
143(2)
131(2)
137(2)
154(3)
145(2)
N(22)H(25)···O(21) (
N(22)H(26)···O(12) (
N(12)H(16)···O(22) (
ii)
iii)
iv)
ii)
(
N(12)H(15)···O(21)
(i)
N(11)H(14)···Cl
C(1)H(13)···Cl(
C(2)H(23)···Cl(
v)
vi)
a
(i)
Ðx, Ðy, Ðz; (ii) Ðx + 1, Ðy, Ðz; (iii) x, y + 1, z;
Symmetry transformations used to generate equivalent atoms:
(
iv)
(v)
(vi)
x, y, z Ð 1;
x, y Ð 1, z;
x, y, z + 1.
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178
N. I. Dodoff et al. · Manganese(II), Iron(II), Cobalt(II) and Nickel(II) Complexes
Table 4. Selected IR bands ( ν˜ , cmÐ1) for MSH and its complexes in CsI.
Compound No.
Assignment
MSH
1
2
3
4
4-deuterated
c
3
3
3
3
354sha
317 m
277 m
136 m
3323 m
3322 m
3320 m
3316 m
2479 m (1.34)b
ν
a
(NH
2
) ,
3262 m
3220sh
3266 m
3228sh
3202 m
3262 m
3228sh
3190 m
3259 m
3220sh
3184sh
3168 m
1619 m
1605sh
1435 m
1339s
2450w (1.33)
2406w (1.34)
2368 m (1.34)
ν(NH)
ν (NH )
s 2
3
195 m
3181 m
1
617 m
1620 m
1620 m
1610sh
1433sh
1336s
1619 m
1607sh
1434sh
1336s
1192 m (1.36)
δ(NH
2
)
1
607sh
1
1
1
1
395sh
1434sh
1334s
1082 m (1.33)
1332s (1.01)
δ(NH)
335s
δ
s
(CH
(SO
τ(NH
3
),
318s
1317sh
1202 m
ν
a
2
)
2
)
295sh
1207 m
1187 m
1142s
1212 m
1189 m
1142s
1217 m
1195 m
1143s
892w (1.36)
882sh (1.35)
1151s (0.99)
1035w (1.00)
1
170sh
1
1
158s
1141s
ν
s
(SO
2
)
130sh
1020sh
1
1020sh
1009w
1272 m
907 m
756 m
746 m
627 m
598 m
529 m
510 m
494 m
456 m
396w
1027sh
1016w
1272 m
909 m
757 m
746 m
642sh
611 m
532 m
510 m
498 m
458 m
397w
1032sh
1022w
1274 m
912 m
758 m
747 m
657sh
623 m
535 m
512 m
501 m
461 m
397w
ν(NN)
005w
937 m
850 m
764 m
1273 m
905 m
756 m
1082 m (1.18)
850 m (1.07)
730w (1.04)
719w (1.04)
558 m (1.18)
ω(NH
ν(SN)
ν(CS)
2
)
7
44 m
6
50 m
29s
625 m
δ(NH)
δ(SO
5
85 m
5
Ð
527 m
510sh
528 m (1.01)
443 m (1.14)
2
)
ρ(NH
2
)d
4
90 m
4
4
3
45 m
454 m
391w
340w
255 m
470 m (0.98)
395w (1.01)
345w (1.00)
243 m (1.00)
ω(SO
2
)
09w
44 m
ρ(SO
τ(SO
ν(MCl
2
)
341w
254 m
342w
244 m
345w
243 m
2
)
Ð
2
), A2u
a
b
, in parentheses; c nota-
Abbreviations: m Ð medium, s Ð strong, sh Ð shoulder, w Ð weak; isotopic ratio, ν˜
/ν˜
H D
d
tions: a Ð asymmetric, s Ð symmetric, δ Ð bending, ν Ð stretching, ρ Ð rocking, τ Ð twisting, ω Ð wagging; see
the text for another possible assignment of ρ(NH ) modes.
2
MN Cl chromophore) with fitting the calculated to trans-[MN Cl ] (M = Co, Ni) chromophores [30,
4
2
4
2
the experimental wave numbers [36]. The parame- 34, 40] and is more pronounced for the Ni(II) com-
ters are presented in Table 5. The e parameters of plex as compared to the Co(II) analogue. The data
π
the nitrogen ligands were assumed equal to zero of Lever et al. [34b, c] on such complexes with
[34] in these calculations. For 4, the number of sym-diethylethylenediamine show that dσ parame-
bands permitted all the three AOM parameters ter (negative) is larger in absolute value for the
plus the Rakah B and C parameters to be opti- Ni(II) complex than for the Co(II) one. The values
mized, and only the spin-orbit coupling parameter of the e parameters of 3 and 4, which are a meas-
σ
Ð1
ꢁ
was fixed to 550 cm (0.87 ꢁNi(II)(free ion)) [37]. ure of the tetragonal deformation (the e parame-
π
The ratio between the optimized values of C and ters are small), correlate with the MÐN and
B is 3.84. In the case of 3, fixed values were used MÐCl bond lengths (Table 2): the NiÐN bonds are
for both C and ꢁ; C was taken equal to 3.84 B shorter than CoÐN, and the NiÐCl bonds are
(
like for 4), and ꢁ was assumed 450 cmÐ1 [38]. The longer than CoÐCl. The values of the average split-
McClure parameters dσ and dπ [39a] derived for ting parameter Dq [39a] for 3 and 4 are 936 and
3
they are Ð799 and Ð21 cm , respectively. As evi-
denced by the AOM and McClure parameters, the exhibits a broad band with a maximum at ca.
ave
Ð1
Ð1
are Ð447 and 150 cm , respectively; and for 4 997 cm , respectively.
Ð1
The diffuse reflectance spectrum of complex 2
Ð1
tetragonal deformation in complexes 3 and 4 is rel- 10000 cm . This band is poorly resolved and no
atively weak with respect to other complexes with conclusions regarding the tetragonal deformation
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N. I. Dodoff et al. · Manganese(II), Iron(II), Cobalt(II) and Nickel(II) Complexes
1179
4 2
Fig. 3. IR spectra of non-deuterated and partially deuterated [Ni(MSH) Cl ] (4) in CsI disks.
Table 5. AOM parameters (cmÐ1) for complexes 3 and 4.
a
Experimental
Starting compounds
Parameter
3
4
3384(15)b
Hydrated metal chlorides and other chemicals
were commercial products (purum or pro analysi).
When necessary, metal chlorides were dehydrated
with 2,2-dimethoxypropane [41] and the solvents
were purified by the routine procedures [42]. MSH
was prepared by the procedure of Powell and
Whiting [43], with some modifications [8].
e
e
e
e
B
C
ꢁ
σ
(N)
πc(N), eπs(N)
(Cl)
πc(Cl), eπs(Cl)
3668(21)
c
c
0
0
σ
2788(25)
150(21)
802(2)
2602(150)
Ð21(128)
832(5)
c
3079c
3197(31)
450
550c
a
b
For definition of the parameters see [39]; standard
deviations in parentheses; c fixed values are used in cal- Preparation of the complexes
culations.
[
Mn(MSH) Cl ] (1). 0.25 g (1.99 mmol) of
4 2
MnCl was dissolved in a mixture of ethanol and
2
could be done. The position of the band corres- acetonitrile (0.5 and 1.2 ml, respectively), and a so-
5
lution of 0.91 g (8.26 mmol) of MSH in acetonitrile
(2 ml) was added. The reaction mixture was
heated at 40 ∞C for 10 min, then it was cooled to
room temperature, diethyl ether (1 ml) was added
and the solution was left in a freezer at Ð30 ∞C
overnight. The hygroscopic colourless crystals
were filtered, washed with acetonitrileÐdiethyl
ether mixture (1:1, 10 ml), than with diethyl ether
ponds to the only spin-allowed transition T
5
2
g
5
E in high-spin Fe(II) complexes with effective
g
octahedral symmetry, and gives the value of the
averaged 10 Dqave parameter [39a], which is sim-
ilar to that of complexes 3 and 4.
It is known [39a] that d-d bands of hexacoordi-
nated high-spin Mn(II) complexes have extremely
low intensity and in the presence of organic li- and petroleum ether. These manipulations were
gands they could rarely be detected. This is also carried out avoiding the access of moisture (CaCl2
the case with complex 1. Nevertheless, the two tube). The product was dried in vacuo over P O .
2 5
Yield: 0.41 g (36%). Because of hygroscopicity the
compound was stored in a glass ampule.
weak absorptions observed in the diffuse reflec-
Ð1
tance spectrum of 1, at ca. 15700 and 24100 cm
,
[
Fe(MSH) Cl ] (2). 0.25 g (1.26 mmol) of freshly
4 2
could tentatively be ascribed to the transitions
recrystallized (H O/HCl) FeCl ·4H O was dis-
6
4
6
4
4
2
2
2
A1g 5 T and A 5 A , E (G), respec-
1g
1g
1g
g
solved in methanol (2.5 ml) under a layer of petro-
leum ether (to prevent the oxidation by air). The
methanol used was previously deaerated by boil-
tively [39a].
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1
180
N. I. Dodoff et al. · Manganese(II), Iron(II), Cobalt(II) and Nickel(II) Complexes
Fig. 4. Diffuse reflectance spectra of [Co(MSH)
transitions in D4h MN Cl chromophores. The schemes show the correlation between the experimental band maxima
and the AOM calculated wave numbers (cm ) of the transitions, the symmetry of the excited states in D4h and in
4 2 4 2
Cl ] (3) and [Ni(MSH) Cl ] (4) with assignments of d-d electronic
4
2
Ð1
4
3
O
h
(in parentheses) and the spin-orbit splitting. The ground states are E
g
4 2
(T1g) for [Co(MSH) Cl ], and B1g(A2g)
for [Ni(MSH) Cl
4
2
]; their energies are taken as zero. The AOM parameters are given in Table 5.
ing. The solution of FeCl ·4H O was mixed with
[Co(MSH) Cl ] (3). A solution of 0.25 g
2
2
4
2
a solution of 0.57 g (5.18 mmol) of MSH in meth- (1.93 mmol) of CoCl in methanol (2.5 ml) was
2
anol (2.5 ml), the reaction mixture was heated at mixed with a solution of 0.89 g (8.08 mmol) of
4
0 ∞C for 5 min and left in a freezer at Ð30 ∞C for MSH in the same solvent (4 ml). The mixture was
2
h. The off-white crystalline precipitate was fil- heated at 40 ∞C for 5 min and left in an ice bath
tered and washed with diethyl ether (peroxide- for 3 h. The pink crystals were filtered and washed
free) under nitrogen. Yield: 0.48 g (67%). For with methanol (1 ml) and diethyl ether. Yield:
recrystallization, the crude product was dissolved 0.72 g (65%). The product was recrystallized from
in hot deaerated methanol (7 ml) under a layer boiling methanol (16 ml). The crystals were fil-
of petroleum ether. The solution was filtered and tered, washed with methanol Ð diethyl ether (1:3,
diethyl ether (2 ml) and petroleum ether (2 ml) 4 ml) and dried as above. Yield: 0.57 g (79% of the
were added. The solution was left at Ð30 ∞C over- crude product). Crystal specimens suitable for X-
night and the crystals Ð white, with a slight yellow ray diffraction analysis were obtained as follows. 3
tan Ð were filtered, washed with diethyl ether and (ca. 0.05 g) was dissolved in boiling methanol
petroleum ether under nitrogen. The product was (1 ml), the solution was filtered and the filter
dried in vacuo over P O . Yield of recrystallized washed with methanol (0.5 ml). This solution was
2
5
complex: 0.25 g (52% of the crude product). To carefully layered over carbon tetrachloride (ca.
prevent the oxidation on air, the compound was 5 ml) poured into a short tube. The tube was stop-
stored in a glass ampule.
pered without shaking and left in a refrigerator
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N. I. Dodoff et al. · Manganese(II), Iron(II), Cobalt(II) and Nickel(II) Complexes
1181
(
0 ∞C). The two-layer system thus formed slowly meter with graphite-monochromated MoÐK radi-
α
homogenizes upon standing. After two weeks the ation. Crystals were positioned at 65 mm from the
pink crystals deposited were collected on a filter, KM4CCD camera. 612 Frames were measured at
washed and dried as above.
Ni(MSH) Cl ] (4).
0.75∞ intervals with a counting time of 20 sec. The
[
A
solution of 0.25 g data were corrected for Lorentz and polarization
4
2
(
1.93 mmol) of NiCl2 in methanol (3 ml) was effects. No absorption corrections were performed
mixed with a solution of 0.89 g (8.08 mmol) of for the intensity data. Data reduction and analysis
MSH in the same solvent (4 ml) and it was pro- were carried out with the Kuma Diffraction (Wroc-
ceeded as above. Yield: 0.75 g (68%). The sky-blue ław) programs. The structure was solved by direct
product was recrystallized from boiling methanol methods [44] (programme SHELXS97) and refined
(
50 ml) and the crystals were filtered, washed and by the full-matrix least-squares method on all F2
dried as above. Yield: 0.62 g (83% of the crude data using the SHELXL97 programmes [45]. All
product). Crystals suitable for X-ray diffraction hydrogen atoms were found in a ∆F map. Crystal
analysis were prepared by dissolving 4 (ca. 0.05 g) data and the details of data collection and the re-
in boiling methanol (2.5 ml) and then proceeding finement procedure are collected in Table 6*.
as described for 3. A partially deuterated speci-
men was prepared by dissolving 4 (ca. 0.015 g) in Analyses, spectra and calculations
boiling methanol-d (1.5 ml) and evaporation of
4
Melting points (uncorrected) were determined
the solvent in vacuo. The residue was treated in
with a Boetius heating-plate microscope; the hy-
this way further 3 times. Finally the product was
groscopic complex 1 being in a sealed capillary.
dried in vacuo over P O .
2
5
X-ray crystallography
*
Crystallographic data for the structures have been de-
posited with the Cambridge Crystallographic Data
Centre, CCDC-185160 and CCDC-185161. Copies of
the data can be obtained free of charge on application
to the Director, CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK (Fax: int. code +(1223)336-033; e-mail
for inquiry: fileserv@ccdc.cam.ac.uk.
The crystals of 3 and 4 (vide supra) were mounted
on glass fiber and then flash-frozen to 100 K (Ox-
ford Cryosystem-Cryostream Cooler). Preliminary
examination and intensity data collections were
carried out on a Kuma KM4 CCD κ-axis diffracto-
Table 6. Experimental data for the X-ray diffraction studies of complexes 3 and 4.
Item
3
4
Empirical formula
M
C
4
H
24Cl
2
N
8
CoO
8
S
4
4 2 8 8 4
C H24Cl N NiO S
570.38
570.16
Crystal system
Space group symbol
triclinic
P1
triclinic
¯
¯
P1
˚
a [A]
8.077(2)
8.622(2)
8.742(2)
71.98(3)
75.30(3)
64.11(3)
515.8(2)
100(1)
1
8.050(2)
8.588(2)
8.686(2)
73.35(3)
75.76(3)
63.94(3)
511.8(2)
100(1)
1
˚
b [A]
˚
c [A]
α [deg]
ꢀ
[deg]
γ [deg]
˚
3
V [A ]
T [K]
Z
Calculated density [Mg mÐ3]
1.836
1.546
1.850
1.667
Ð1
µ [mm
]
Crystal dimensions [mm]
θ Range [deg]
0.1 ¥ 0.1 ¥ 0.1
0.1 ¥ 0.1 ¥ 0.1
3.49 to 28.27
4.02 to 28.30
Limiting indices
Ð6 Յ h Յ 10, Ð11 Յ k Յ 11,
Ð10 Յ h Յ 7, Ð11 Յ k Յ 10,
Ð11 Յ l Յ 11
Ð11 Յ l Յ 11
3493
Number of reflections measured
Number of independent reflections
Final R indices [I > 2σ(I)]
R Indices (all data)
3579
2272
2236
1
a
= 0.0571b
a
b
b
R
R
1
= 0.0227 , wR
= 0.0261 , wR
2
2
R
R
= 0.0367 , wR
2
2
= 0.0966
= 0.0976
a
b
a
1
= 0.0589
1
= 0.0374 , wR
a
|; b wR
2
2)2]/Σ[w(F ) ]}1/2.
2 2
R(F) = Σ||F
o
| Ð |F
c
||/Σ|F
o
2
= {Σ[w(F
o
Ð F
c
o
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1
182
N. I. Dodoff et al. · Manganese(II), Iron(II), Cobalt(II) and Nickel(II) Complexes
Electric conductivities were measured at 25 ∞C 5270 spectrophotometer using BaSO as a refer-
4
Ð6
Ð1
Ð1
in methanol (Λ = 2.1 ¥ 10
Ω
cm ) and etha- ence. Ð All spectral measurements were per-
Ð7
Ð1
cmÐ1) using a Hydromat formed at room temperature. All sampling manip-
nol (Λ = 5.8 ¥ 10
Ω
conductivity meter. Ð The elemental analyses ulations with the hygroscopic complex 1 were
were performed according to standard microana- carried out in a dry box.
lytical procedures; the metal content was deter-
The electronic spectra were interpreted by
´
mined by atomic absorption spectrometry (TÜBI- means of the Angular Overlap Model [39] using
TAK Laboratories, Ankara, Turkey). Ð Infrared the AOMX programme of Adamsky [36].
Ð1
spectra (4000Ð150 cm ) were recorded in the
solid state as CsI and KBr disks and as nujol mulls Acknowlegements
on a Bruker IFS 113 spectrophotometer. The dif-
ferent modes of sampling gave practically identical
spectra. Ð The diffuse reflectance electronic Dr. Heribert Adamsky for placing the AOMX
spectra (250Ð2000 nm) were taken on a Beckman programme to our disposal.
´
Thanks are due to TÜBITAK (Turkey) and
UNESCO MCBN for financial support, and to
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