Structure and characterization of tris(4-morpholinedithiocarbamato-S, S′)cobalt(·)-acetonitrile solvate complex:[Co(S2CNC4H8O)3]·CH3CN

Article abstract of DOI:10.1023/A:1014318410461

The crystal and molecular structure of the complex [Co(S₂CNC₄H₈O)₃]·CH₃CN has been determined by X-ray crystallography. The compound crystallizes in the triclinic system, space group P1, with lattice parameters a = 10.561(2), b = 11.114(2), c = 13.011(3) A, α = 103.88(3), β= 101.58(3), γ = 114.91(1)°, and Z = 2. X-ray analysis reveals that the cobalt(III) atom is located at the apparent intersection of D₃ symmetry. 'Despite the apparent presence of the rotational axes, all of the atoms in the structure were found to be unique; there are no symmetry-related atoms. The central cobalt atom is octahedrally coordinated by an arrangement of six S atoms. The octahedron is distorted as a result of the forced configuration of the four-membered chelate ring. The average Co-S distance is 2.273 A. The FT-IR spectra clearly show there are acetonitrile molecules in the crystal lattice.

Full text of DOI:10.1023/A:1014318410461

C
Journal of Chemical Crystallography, Vol. 31, No. 5, May 2001 ( 2002)
Structure and characterization
of tris(4-morpholinedithiocarbamato-S,S0)cobalt( )-
acetonitrile solvate complex: [Co(S2CNC4H8O)3] CH3CN
Jiangrun Zhang,(1) Fangfang Jian,(1) Lude Lu,(1) Xujie Yang,(1) and Xin Wang(1)*
Received January 28, 2001
The crystal and molecular structure of the complex [Co(S2CNC4H8O)3] CH3CN has been
determined by X-ray crystallography. The compound crystallizes in the triclinic system,
¯
˚
space group P1, with lattice parameters a = 10.561(2), b = 11.114(2), c = 13.011(3) A,
= 103.88(3), = 101.58(3), = 114.91(1) , and Z = 2. X-ray analysis reveals that
the cobalt(III) atom is located at the apparent intersection of D symmetry. Despite the
3
apparent presence of the rotational axes, all of the atoms in the structure were found to
be unique; there are no symmetry-related atoms. The central cobalt atom is octahedrally
coordinated by an arrangement of six S atoms. The octahedron is distorted as a result of
the forced configuration of the four-membered chelate ring. The average Co S distance
˚
is 2.273 A. The FT-IR spectra clearly show there are acetonitrile molecules in the crystal
lattice.
KEY WORDS: Cobalt complex; dialkyldithiocarbamate; octahedron.
Introduction
makes them further attractive for the deter-
mination of metals by gas chromatography.7
The dialkyldithiocarbamate anion, S2CNR2
Morpholine-N-carbodithioate has been suggested
as a possible analytical reagent in the spec-
trophotometric and volumetric determination of
some 34 elements.8 Recently, it has been uti-
lized in the gravimertic determination of tel-
lurium, copper, bismuth, cobalt, palladium, and
nickel.9 The reagent was used in the thin layer
and paper chromatographic separation of metal
complexes.10 We also know that the tris-chelated
cobalt(III) complexes of N,N-disubstituted dithio-
carbamates which are noncharged species and
kinetically inert should be resolvable into opti-
cal enantiomers.11 In this paper, we reported the
crystal structure of the title compound. Also, IR
and TG spectra of the title compound have been
determined.
(dtc), and its derivatives are used extensively
in inorganic and organic chemistry, and as ac-
tive agents in pharmacology, medicine, and
biochemistry.1 The ability of dtc to bind to metals
has been known for many years.2 It forms chelate
complexes with virtually all transition elements.3
Water soluble dialkyldithiocarbamate complexes
are known to have been tested in various medical
applications.4,5 Their good performance in liquid–
liquid extraction and other analytical procedures6
(1) Materials Chemistry Laboratory, Nanjing University of Science
and Technology, Nanjing, 210094, People’s Republic of China.
*To whom correspondence should be addressed; e-mail: wxin@
public1.ptt.js.cn.
251
C
1074-1542/01/0500-0251/0 2002 Plenum Publishing Corporation

252
Zhang, Jian, Lu, Yang, and Wang
Experimental
A summary of the key crystallographic in-
formation is given in Table 1. The crystal was
mounted on a four-circle CAD4 diffractometer.
Reflection data and reflections for the unit cell
All chemicals were obtained from a commer-
cial source and used without further purification.
determination were measured at 20 C using Mo
˚
K
radiation ( = 0.71073 A) with a graphite
Synthesis of the C4H8ONCS2Na
monochromator. The technique used was ω-scan
with limits 1.72 < < 24.98 . Empirical ab-
sorption correction were carried out by using the
SADABS13 program.
To a stirred solution of morpholine (1.00 g,
11.5 mmol) in CH3CN (100 mL) was added at be-
low 4 C, carbon disulfide (0.874 g, 11.5 mmol)
and sodium hydroxide (50% aqueous solution,
11.5 mmol). After stirring for 4–5 h, the solution
was left to evaparate at room temperature. The
pure C4H8ONCS2Na was obtained by recrystal-
lization from the solution of CH3CN. Yield: 92%.
The structure of the title compound was
solved by direct methods and refined by least
squares on F2 by using the SHELXTL14 software
package. All non-H atoms were anisotropically
refined. The hydrogen atoms were located
by difference synthesis and refined isotropically.
The final conventional R(F) = 0.0368 and
wR(F2) = 0.1126 for I > 2 (I) with weighting
scheme, w = 1/[ 2(F2) + (0.0662P)2 +
Synthesis of the Co(III)(C4H8ONCS2)3
To
a
heated aqueous solution of
1.4057P], where
The molecular graphics were plotted using
P
=
(F2
+
2Fc2)/3.
C4H8ONCS2Na (0.15 mol) was added an
aqueous solution of Co(CH3COO)3, (0.05 mol)
with stirring. A green precipitate was deposited
and collected by filtration. The precipitate was
washed with water and dried over P4O10. Single
crystals suitable for X-ray analysis were obtained
by recrystalization from CH3CN. The C, H, and
N contents were determined by elemental analy-
sis (Found: C, 34.47; H, 4.24; N, 9.42%. Calcd
for C17H27N4NCoO3S6: C, 34.77; H, 4.60; N,
9.54%).
Table 1. Summary of Crystallographic Results for
[Co(S2CNC4H8O)3] CH3CN
Empirical formula
Formula weight
Crystal system
Space group
Unit cell dimensions
CoC17H27N4O3S6
586.72
Triclinic
¯
P1
˚
˚
˚
a = 10.561(2) A
b = 11.114(2) A
c = 13.011(3) A
= 103.88(3)
= 101.58(3)
= 114.91(3)
1263.2(4)
2
The IR spectrum (KBr pellets) showed vC
stretching bands at 1483, 2963, and 2849 cm
N
1
3
˚
Volume, A
for the morpholine ring. The absence of vC at
S
Z
1600 cm 1 in the IR spectrum of Co(III) complex
suggests that the cobalt atom is chelated with both
Density (calculated), Mg/m3
Absorption coefficient, mm
F(000)
1.543
1.202
608
1
the sulfur atoms of CS2.12 The existence of vC
N
˚
at 2080 cm 1 suggests the presence of CH3CN.
Thermal analysis of the title compound show
that the complex first decomposes at a tempera-
ture of 144 C. The lost weight is 7.4%, which
indicates the evaporation of the CH3CN solvent
(Calcd 7.0%). At 347.8 C, the complex decom-
poses quickly, until at 395.2 C the weight loss is
82.0%, suggesting that the residue is Co2S3 (Calcd
81.8%).
Radiation, A
Mo K ( = 0.71073)
Temperature, K
range, deg
293(2)
1.72–24.98
Limiting indices
0
h
15
12, 13
15
k
11,
l
Independent reflections
R [I > 2 (I)]
4698/4434 [R = 0.0242]
int
R1 = 0.0368, wR2 = 0.1126
R1 = 0.0525, wR2 = 0.1291
1.133
R(all data)
Goodness of fit on F2
Largest diffraction peak and
0.809 and 0.466
3
˚
hole e/A

Structure and characterization of tris
253
SHELXTL.14 Atomic scattering factors and
anomalousdispersioncorrectionsweretakenfrom
International Tables for X-ray Crystallography.15
The final position parameters of non-H atoms are
given in Table 2.
Results and discussions
Figure 1 shows a perspective view of the title
compound with atomic numbering scheme. Se-
lected bond lengths and angles are presented in
Table 3.
The crystal structure contains two tris (4-
morpholinedithiocarbamato-S,S0) cobalt(III) ace-
Fig. 1. The molecular structure of [Co(S2CNC4H8O)3]
CH3CN showing the atom labeling scheme. Atoms are rep-
resented as thermal ellipsoids at 30% level.
Table 2. Atomic Coordinates(104) and Equivalent Isotropic
3
2
˚
tonitrile solvate molecules, [Co(S2CNC4H8O)3]
CH3CN. X-ray analysis reveals that the cobalt(III)
Displacement Parameters (10 A )
a
X
Y
Z
Ueq
atom is located at the apparent intersection of D
3
symmetry. Despitetheapparentpresenceofthero-
tational axes, all of the atoms in the structure were
found to be unique; there are no symmetry-related
Co
7293(1)
5053(1)
6049(1)
6620(1)
7983(1)
9494(1)
8480(1)
372(4)
7426(4)
14021(3)
3276(4)
7261(4)
11117(3)
8874(7)
4579(4)
2090(5)
607(6)
1457(6)
2988(6)
7296(4)
6485(7)
7204(7)
8311(8)
7684(7)
9885(4)
12203(5)
13733(5)
13061(5)
11425(4)
7893(7)
6634(8)
4756(1)
4583(1)
4101(1)
2480(1)
4882(1)
5211(1)
7144(1)
2379(5)
524(3)
10226(3)
3679(4)
2256(4)
7978(3)
8673(8)
4062(4)
3807(6)
2566(7)
2099(7)
3309(6)
3085(4)
694(5)
2313(1)
1542(1)
3487(1)
1340(1)
768(1)
3469(1)
3302(1)
2815(4)
2436(3)
6108(3)
2740(3)
567(3)
35(1)
46(1)
44(1)
41(1)
44(1)
41(1)
41(1)
84(1)
67(1)
59(1)
51(1)
53(1)
41(1)
120(2)
43(1)
66(1)
78(2)
77(2)
71(2)
40(1)
73(2)
74(2)
84(2)
73(2)
35(1)
51(1)
60(1)
52(1)
47(1)
75(2)
96(2)
S(1)
S(2)
S(3)
S(4)
S(5)
S(6)
O(1)
O(2)
O(3)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(1)
C(1)
C(1)
C(1)
C(1)
C(1)
C(1)
C(1)
˚
Table 3. Selected Bond Lengths (A) and Bond Angles (deg) of the
Compound
Bond lengths
Co S(3)
Co S(2)
Co S(5)
Co S(6)
Co S(1)
Co S(4)
S(1) C(1)
O(1) C(3)
N(1) C(1)
N(1) C(2)
2.257(1)
2.263(1)
2.273(1)
2.277(2)
2.282(1)
2.287(1)
1.708(4)
1.416(7)
1.321(5)
1.465(6)
4824(3)
699(6)
2605(3)
2055(5)
1817(5)
3376(5)
3709(4)
369(3)
922(5)
Bond angles
72(5)
1506(5)
2031(5)
1455(5)
3997(3)
5495(4)
5627(5)
5375(4)
5233(4)
968(5)
S(3) Co S(6)
S(5) Co S(1)
S(2) Co S(4)
S(5) Co S(6)
S(2) Co S(1)
S(3) Co S(4)
C(3) O(1) C(4)
C(9) O(2) C(8)
C(14) O(3) C(13)
C(2) N(1) C(5)
C(7) N(2) C(10)
C(15) N(3) C(12)
167.37(4)
166.33(5)
164.42(5)
76.20(6)
76.12(5)
76.41(5)
109.4(4)
109.4(4)
109.2(3)
113.8(4)
113.5(4)
113.7(3)
2012(6)
2767(5)
6941(4)
7727(5)
8793(5)
10447(5)
9451(4)
8562(6)
8390(9)
1322(5)
aUeq is defined as one third of the trace of the orthogonalized
Ui j tensor.

254
Zhang, Jian, Lu, Yang, and Wang
atoms. The central cobalt atom is octahedrally co-
ordinated by an arrangement of six S atoms. The
octahedron is distorted as a result of the forced
configuration of the four-membered chelate ring.
coplanar. Three planes are mostly perpendicular
to one another, with the dihedral angles of 85.53,
84.09, and 81.73 , respectively.
The solvent molecules are orientated to min-
imize electrostatic repulsions with the complex.
However, no strong hydrogen bonding interac-
tions exist.18
˚
The average Co S distance is 2.273A. The cobalt
atom lies on a twofold axis, which bisects one of
the two dithiocarbamate ligands. The atoms in a
second dithiocarbamate ligand all lie in general
positions, but in turn they generate a third dithio-
carbamate ligand by the action of the twofold
axis. It is easy to see in Fig. 1 that the geometry of
the six S atoms surrounding the cobalt are quite
distorted from that of a regular octahedron, as
demonstrated by the S1 Co S5, S2 Co S4 and
S3 Co S6 angles of 166.33(5), 164.42(5), and
167.37(4) . This distortion from a perfect octahe-
dron is due primarily to the constraint imposed on
the geometry of the molecule by the rigid nature of
the dithiocarbamate ligands and by the size of the
“bite” angles at the metal, which in this case are
S1 Co S2= 76.12(5), S3 Co S4 = 76.41(5),
and S5 Co S6= 76.20(6) . The distorted octahe-
dral configuration of the title complex is also seen
in other derivatives in this series [Co(S2CNR2)3]:
[R = Et, i-Pr, CH2Ph].16,17 The bond lengths
of Co S are in the range of 2.257(1)–2.287(1)
References
1. Thorn, G.D.; Ludwig, R.A. The Dithiocarbamates and Related
Compounds; Elsevier: New York, 1962, p. 1.
2. Gimeno, M.C.; Jambrina, E.; Laguna, A.; Laguna, M.; Murray,
H.H.; Terroba, R. Inorg. Chim. Acta 1996, 249, 69.
3. Allen, F.H.; Kennard, O. Chem. Des. Autom. News 1993, 8, 31.
4. Baldas, J.; Bonnyman, J. Nucl. Med. Biol. 1992, 19, 741.
5. Xie, J.; Funakoshi, T.; Shimada, H.; Kojima, S. Res. Commun.
Mol. Pathol. Pharmacol. 1994, 86(2), 245.
6. Thorn, G.D.; Ludwig, R.A. The Dithiocarbamates and Related
Compounds; Elsevier: Amsterdam, 1962.
7. Riekkola, M.L.; Pakkanen, T.; Niinisto, L. Acta Chemica Scand.
1983, A37, 807.
8. Sakla, A.B.; Helmy, A.A.; Beyer, W.; Harhash, F.E. Talanta.
1979, 26, 519.
9. Kumar, R.; Singh, N.; Singh, H. J. Indian Chem. Soc. 1979, 56,
838.
10. Singh, N.; Kumar, R.; Kansal, B.D. Chromatographia 1978, 11,
408.
11. Gahan, L.R.; Hughes, J.G.; O’Connor, M.J.; Oliver, P.J. J. Inorg.
Chem. 1979, 18, 933.
12. O’Connor, C.; Gilbert, J.D.; Wilkinson, G. J. Chem. Soc. (A)
1969, 84.
13. Sheldrick, G.M. SADABS, Program for Empirical Absorption
Correction of Area Dotector Data, University of Gottingen:
Germany, 1996.
14. Sheldrick, G.M. SHELXTL, Version 5 Reference Manual;
Siemens Analytical X-ray Sysytems: Madison, WI, 1996.
15. Wilson, A.J.C. International Table for X-ray Crystallography;
Kluwer Academic Pulishers: Dordrecht, 1992; Vol. C, Tables
6.1.1.4 (pp. 500–502) and 4.2.6.8 (pp. 219–222) respectively.
16. Brennan, T.; Bernal, I. J. Phys. Chem. 1968, 73, 433.
17. Healy, P.C.; Connor, J.W.; Skelton, B.W.; White, A.H. Aust. J.
Chem. 1990, 43, 1083.
˚
˚
A. The N1 C1 bond distance [1.321(5) A]
is shorter than the other N C bond distance,
which are indicative of considerable double-bond
character.
Three morpholine rings all form the chair
conformation. The maximum atom deviations
˚
from planes of each ring are 2.54, 2.66, 2.68A,
respectively. The chelate rings with the car-
bon atoms of the conjunct morpholine ring are
18. Ricci, Jr., J.S.; Eggars, C.A.; Bernal, I. Inorg. Chim. Acta 1972,
6, 97.