On ammonium-bis(dithiocarbamato)-copper(I)-monohydrate and Mono(dithiocarbamato)-copper(I)

Article abstract of DOI:10.1002/zaac.201300321

The title compounds NH₄[Cu(S₂CNH₂) ₂]·H₂O (A) and CuS₂CNH₂ (B) were prepared from aqueous alcoholic solutions by reaction of ammoniumdithiocarbamate with copper sulfate in presence of excess cyanide as reductive. (A) crystallizes in the orthorhombic space group C222₁ (No. 20) with a = 8.9518(6), b = 9.6414(6) and c = 10.6176(8) A, Z = 4. (B) crystallizes in the orthorhombic space group P2₁2 ₁2₁ (No. 19) with a = 5.9533(4), b = 6.6276(4) and c = 9.4834(5) A, Z = 4. In the crystal structure of (A) copper has a tetrahedral surrounding of four monodentate dithiocarbamate ligands. These structural units form 2D nets stacked along [001]. Staggered chains consisting of H₂O and NH₄⁺ penetrate the crystal structure along [001] yielding additional coherence via hydrogen bonds. The crystal structure of (B) comprises a three-dimensional tetrahedral framework of CuS ₄ units exclusively linked by vertices. The arrangement is reminiscent of a filled β-cristobalite structure with the dithiocarbamate ligands extending into the hollow spaces. Thermal decomposition precedes stepwise finally giving Cu₂S in each case.

Full text of DOI:10.1002/zaac.201300321

Job/Unit: Z13321
/KAP1
Date: 05-09-13 13:41:56
Pages: 8
ARTICLE
DOI: 10.1002/zaac.201300321
On Ammonium-bis(dithiocarbamato)-copper(I)-monohydrate and
Mono(dithiocarbamato)-copper(I)
Christoph L. Teske*[a]
Dedicated to Professor Wolfgang Bensch on the Occasion of His 60th Birthday
Keywords: Dithiocarbamates; Copper; Preparation; X-ray diffraction; Thermal decomposition
Abstract. The title compounds NH
CuS CNH (B) were prepared from aqueous alcoholic solutions by consisting of H
reaction of ammoniumdithiocarbamate with copper sulfate in presence yielding additional coherence via hydrogen bonds. The crystal struc-
of excess cyanide as reductive. (A) crystallizes in the orthorhombic ture of (B) comprises a three-dimensional tetrahedral framework of
space group C222 (No. 20) with a = 8.9518(6), b = 9.6414(6) and CuS units exclusively linked by vertices. The arrangement is reminis-
c = 10.6176(8) Å, Z = 4. (B) crystallizes in the orthorhombic space cent of a filled β-cristobalite structure with the dithiocarbamate ligands
group P2 (No. 19) with a = 5.9533(4), b = 6.6276(4) and c = extending into the hollow spaces. Thermal decomposition precedes
.4834(5) Å, Z = 4. In the crystal structure of (A) copper has a tetrahe- stepwise finally giving Cu S in each case.
4
[Cu(S
2
CNH
2
)
2
]·H
2
O (A) and
structural units form 2D nets stacked along [001]. Staggered chains
+
2
2
2 4
O and NH penetrate the crystal structure along [001]
1
4
1 1 1
2 2
9
2
dral surrounding of four monodentate dithiocarbamate ligands. These
inert gas atmosphere and recystallization of the raw product.[10] This
report is on the substituted synthesis of copper(I)- dithocarbamates
using solutions of ammoniumdithiocarbamate in the presence of an
excess of cyanide as reductive.
Introduction
Copper dithiocarbamates exist for all three oxidation states
I–III. Most common are copper(II) complexes Cu(S CNR )
2
2 2
(
R = organic moieties), which have been prepared and crystal-
[1–5]
a) NH
freshly prepared white ammoniumdithiocarbamate (3.3 g, 30 mmol)
in EtOH/H O (60 mL, 1:2) was mixed with a solution of KCN (2.6 g,
0 mmol) in H O (25 mL). While stirring at room temp. a solution of
CuSO ·5H O (2.5 g, 10 mmol) in water (25 mL) was slowly added (ca.
0 min). Spontaneously, a first precipitation started. Nevertheless, a
largely complete precipitation of the bright yellow complex ammo-
nium salt required several hours. A small sample (precipitate plus its
mother liquor) was shortly warmed up until most of the precipitate
4 2 2 2 2
[Cu(S CNH ) ]·H O: In an Erlenmeyer flask a solution of
lographically investigated.
Dithiocarbamates have also
[
16]
III
played a prominent role in the development of Cu chemis-
try.[6,7]
2
Copper(I)-dithiocarbamate can be prepared e.g. by dis-
4
2
proportionation of copper(II) salts together with a co-generated
copper(III) species,[ from the conproportionation reaction of
activated copper powder with Cu salts or by chemical re-
8]
4
2
1
II
[9]
II
duction of Cu species with NH OH·HCl in presence of alkali-
2
dithiocarbamate.[ Meanwhile several Cu -dithiocarbamates
10]
I
have been prepared and some crystal structures were estab- had dissolved again. After cooling down at room temp. and leaving
lished.[
11–15]
However, it is noteworthy that no crystal structure undisturbed for several days, bright yellow transparent single crystals
suitable for X-ray investigations had formed (Figure 1, bottom). The
determination or further advanced investigation of the most
simple copper dithiocarbamate complex with R = H exists.
This article reports on the preparation and crystal structures of
NH [Cu(S CNH ) ]·H O and CuS CNH .
residual microcrystalline product was collected via filtration after two
days, washed with H O, an aqueous solution of two percent NH Cl,
again with H O and subsequently with EtOH and dried in an air current
at ambient temperature. When NH [Cu(S CNH ]·H O was stored at
2
4
2
4
2
2 2
2
2
2
4
2
2
)
2
2
open air at room temp. it decayed slowly becoming more and more
ocher yellow. The percent composition data (standard deviation in
brackets) were determined by combustion analysis on a CHNS-Rapid-
Element-Analyzer (Heraeus GmbH) using thiourea as standard:
Experimental Section
Preparation
–
1
NH
8.46); H 3.03(9) (calcd. 3.55); N 14.4(3) (calcd. 14.78); S 45.0(5)
calcd. 45.17)%.
4 2 2 2 2
[Cu(S CNH ) ]·H O Mw = 283.93 g·mol ; C 8.49(7) (calcd.
Chemical reduction of the royal blue-colored solution of
]2+ with NH
[
Cu(NH OH·HCl (and N ·H O, respectively) in pres-
3
)
4
2
2
H
4
2
(
ence of dithiocarbamates has disadvantages. It affords working under
*
Dr. C. L. Teske
b) CuS
prepare CuS
2
CNH
2
: A similar process as described above was applied to
but at elevated temperature. After the first step,
E-Mail: cteske@ac.uni-kiel.de
2
CNH
2
[
a] Institut für Anorganische Chemie
Christian-Albrechts-Universität Kiel
Max-Eyth-Str. 2
when all of the copper solution was added, the yellow suspension was
boiled. The temperature increased with decreasing content of EtOH.
At about 82 °C all of the initially formed yellow precipitate had dis-
24118 Kiel, Germany
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

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C. L. Teske
ARTICLE
Single Crystal X-ray Investigation
Single crystal X-ray diffraction data were collected with a STOE Im-
aging Plate Diffraction System (IPDS-1) with graphite monochro-
α
matized Mo-K radiation (λ = 0.7107 Å) at 200(2) K. The raw data
were corrected for Lorentz and polarization effects, and an absorption
[
17]
[18]
correction was applied using X-Red and X-Shape. The structures
were solved by Direct Methods employing the SHELXTL program
[
19]
2
package
and the refinement was performed against F . The non-
hydrogen atoms were refined with anisotropic displacement param-
eters. The hydrogen atoms of the amino groups were allowed to ride
on their parent atom with idealized geometry and were refined with
fixed bond length (N–H = 0.86 Å). The isotropic displacement param-
eters were fixed [Uiso(H) = 1.2 Ueq(N)]. For the ammonium ions of
NH
4 2 2 2 2
[Cu(S CNH ) ]·H O, an ideal tetrahedral H–N–H angle was as-
[
20]
sumed where the corresponding H–H distances are 1.486 Å.
Also
fixed isotropic displacement parameters [Uiso(H) = 1.5Ueq(N)] were
used. In the early stages of the refinement of the structure model for
NH
NH
4
[Cu(S
2
CNH
2 2 2
) ]·H O, the calculation was carried out only with 8
+
4
which is not consistent with the empirical formula. To satisfy
the analytically confirmed composition in the final refinement, the po-
sition (8c) was occupied (50:50) by N(2) and O respectively, and the
+
occupancy factors of the hydrogen atoms of NH
4
became sof = 0.75.
More technical details of the data acquisition and some selected results
of the refinement are summarized in Table 1. The final atomic coordi-
nates as well as the equivalent isotropic displacement parameters are
Table 1. Crystal data and structure refinement for (A)
NH
4
[Cu(S
2
CNH
2
)
2
]·H
2
2 2
O and (B) CuS CNH .
Figure 1. SEM images of the copper dithiocarbamate crystals prepared
from aqueous alcohol solutions (NH [Cu(S CNH ]·H O bottom and
CuS CNH top).
A
B
4
2
2
)
2
2
2
2
Empirical formula
Formula weight
Temperature /K
C
2
H10CuN
OS
4
2 2
CH CuNS
3
283.91
200(2)
0.71073
155.70
200(2)
0.71073
solved again. The heating was continued while stirring and the initially
yellow solution became light orange. In the temperature range of T ≈ Wavelength /Å
9
1
0–95 °C an ocher, crystalline precipitate appeared. After additional
5 min of heating, hot suspension was quickly sucked off, washed with Space group
Crystal system
orthorhombic
C222
orthorhombic
P2
1
1 1 1
2 2
hot EtOH/H
with EtOH and dried under vacuum. Honey-colored, transparent crys-
tals of CuS CNH had formed (Figure 1, top). Analysis: CuS CNH
2
Mw = 155.71 g·mol ; C 7.77(5) (calcd. 7.71); H 1.21(1) (calcd. 1.29);
N 8.87(3) (calcd. 8.99); S 41.72(15) (calcd. 41.19)%.
2
O (1:2) and later with cold NH
4
Cl solution and finally a /Å
8.9518(6)
9.6414(6)
10.6176(8)
916.38(11)
4
2.058
3.243
576
5.9533(4)
6.6276(4)
9.4834(5)
374.18(4)
4
2.764
6.709
304
b /Å
c /Å
Volume /Å
Z
2
2
2
3
–1
–
3
ρ (calcd.) /g·cm
–
1
μ /mm
F(000)
Differential Thermal Analysis (DTA-TG-MS)
Crystal size /mm
0.09 ϫ 0.06 ϫ
.03
yellow
3.11 to 27.97.
7254
1102
0.09 ϫ 0.08 ϫ
0.04
honey-colored
3.75 to 27.94
3660
891
0.0363
99.5
For thermal analysis a STA-409CD instrument from Netzsch, which
was connected to a quadrupole mass spectrometer (Balzers) via Skim-
mer coupling was used. The DTA-TG investigations were carried out
0
Color
θ range /°
Reflections collected
Independent reflections
2
in a N atmosphere (purity: 5.0 / at heating rates of 1, 4 and
–
1
8
K·min ). Analogue scan modes were applied for the MS measure-
–
1
ments in a dynamic He atmosphere at heating rates of 8 K·min . All
Rint
0.1161
99.2
–
1
measurements were performed at a flow rate of 75 mL·min in the Completeness /%
temperature range T = 25–800 °C (crucible: sintered Al
2
O
3
). The resi-
Absorption correction
Max. /min. transmission
numerical
0.6756 / 0.4451
numerical
0.4304 / 0.2925
891 / 0 / 47
1.058
0.0239
0.0576
dues and some intermediates were isolated for X-ray powder diffrac-
tion. Corrections for buoyancy and current effects were applied during
data evaluation. The instrument is calibrated with standard reference
samples from Netzsch.
Data / restraints / parameters 1102 / 10 / 64
2
GOOF (F )
(F Ͼ 4σ(F
(F Ͼ 4σ(F
(all data)
(all data)
1.088
R
wR
1
o
o
))
o
0.0297
0.0757
0.0316
0.0771
2
o
))
R
1
0.0253
0.0582
X-ray Powder Diffraction (XRPD)
wR
2
Absolute structure parameter 0.013(19)
0.021(19)
0.011(3)
0.557 / –0.349
XRPD experiments were performed using a STOE Transmission Pow-
der Diffraction System STADI P (Cu-Kα1 radiation; λ = 1.54056 Å)
equipped with a MYTHEN 1K detector from DECTRIS.
Extinction coefficient
0.0034(7)
–
3
δF /e·Å
0.516 / –0.445
2
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

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Date: 05-09-13 13:41:56
Pages: 8
Ammonium-bis(dithiocarbamato)-copper(I)-monohydrate and Mono(dithiocarbamato)-copper(I)
listed in Table 2. Table 3 shows a list of the shortest interatomic dis-
tances and some selected bonding angles as well as the hydrogen bond-
data for CuS
2 2
CNH are listed in Table 4. Further details of the crystal
structure investigations may be obtained from the Fachinformations-
ing geometry for NH
4
[Cu(S
2
CNH
2
)
2
]·H
2
O. The corresponding zentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany (Fax:
49-7247-808-666; E-Mail: crysdata@fiz-karlsruhe.de, http://
www.fiz-karlsruhe.de/request for deposited data.html) on quoting the
depository numbers CSD-426584 for NH [Cu(S CNH ]·H O and
CSD-426583 for CuS CNH
+
4
Table 2. Atomic coordinates (ϫ10 ) and equivalent isotropic displace-
2
3
4
2
2
)
2
2
ment parameters (Å ϫ 10 ) (standard deviations in parenthesis). Ueq
is defined as one third of the trace of the orthogonalized Uij tensor.
2
2
.
NH
4
[Cu(S
2
2 2 2
CNH ) ]·H O
Results and Discussion
x
y
z
U
eq
Cu
0
9903(1)
11302(1)
8632(1)
7283(3)
7012(3)
9232(3)
2500
25(1)
27(1)
25(1)
23(1)
35(1)
43(1)
a) Crystal Structures
S
S
(1)
1391(1)
1480(1)
2306(2)
1954(2)
4510(2)
3862(1)
1137(1)
1928(3)
3098(2)
3856(2)
(2)
1
) NH [Cu(S CNH ) ]·H O
4 2 2 2 2
C
N
N
(1)
(2)/O
In the crystal structure, the copper atoms are coordinated by
four monodentate dithiocarbamate ligands in tetrahedral align-
ment (Figure 2). Tetrahedral and trigonal geometries are the
Calculated coordinates of hydrogen atoms (ϫ 104)
1
I [21]
norm for d °Cu .
.3136(7), Cu–S(2) = 2ϫ 2.3370(8) (Table 3a), Cu–Saverage
2.3255(8)) are consistent with average Cu–S distances from
The four distances Cu–S (Cu–S(1) = 2ϫ
x
y
z
U
eq
2
=
H
(1)
H
(2)
H
(3)
H
(4)
H
(5)
H
(6)
1286
2385
3488(11)
4910(40)
4770(40)
4740(30)
7525
6318
9120(40)
8374(18)
9610(40)
9780(30)
3489
3494
3870(30)
3970(30)
3117(19)
4520(20)
42
42
64
64
64
64
[
14]
literature (e.g. 2.285(2) and 2.286(2) Å {[Cu(S CMe )] } ,
2
2–[22]
2 2 n
+
2
.33 Å, [Cu(Me NC(S)SC(S)Me ) ] SO4
and 2.322 Å
2
2 2 2
I
in the tetrahedral surrounding of Cu in the crystal structure of
covellite (CuS)[ ). Every dithiocarbamate ligand connects
23]
two CuS units forming a two-dimensional framework (Fig-
4
CuS
2 2
CNH
ure 3 and Figure 4), where every sulfur atom has only one next
copper neighbor. The layers are stacked along [001] and the
coherence among the layers is firstly given by weak to medium
x
y
z
U
eq
Cu
9147(1)
5952(1)
8542(1)
4195(5)
4982(5)
2410(1)
4058(1)
282(1)
4440(4)
4179(5)
8693(1)
9414(1)
6775(1)
7994(3)
6711(3)
20(1)
18(1)
18(1)
17(1)
24(1)
S
S
(1)
strong hydrogen bonds N–H···S (Table 3a). A staggered chain
(2)
+
consisting of H O and NH which is incorporated among the
C
N
2
4
layers running along [001] (Figure 4 left) provides for ad-
Calculated coordinates of hydrogen atoms (ϫ 104)
ditional hydrogen bonds ([N/O]–H···N and [N/O]–H···S)
(Table 3). During the refinement of the crystal structure model,
x
y
z
U
eq
the O and N(2) atoms were assigned statistically to the same
position (vide supra). Actually, no differentiation is possible,
but significant differences among the hydrogen bonds are no-
H
H
(1)
6389
4101
3815
4370
6586
5978
28
28
(2)
4 2 2 2 2
Table 3. Selected bond lengths /Å and angles /° and hydrogen bonding geometry for NH [Cu(S CNH ) ]·H O (standard deviations in parenthe-
sis).
(
Cu–S(1)
Cu–S(1)(
Cu–S(2)(
Cu–S(2)
S
S
2.3370(8)
2.3370(8)
2.3136(7)
2.3136(7)
1.720(3)
1.716(3)
1.308(4)
1.720(3)
S
S
S
S
S
S
C
(2) i)–Cu–S(2)
116.04(4)
102.93(3)
112.80(3)
112.80(3)
102.93(3)
109.51(4)
112.14(11)
110.01(11)
N
N
(1)–C–S(2)
(1)–C–S(1)
120.8(2)
121.1(2)
118.06(19)
120.0
120.0
120.0
H
H
H
H
(4)–[N(2)/O]–H(5) 112(2)
(3)–[N(2)/O]–H(6) 106.3(19)
i)
i)
(i)
(iii)
(iii)
(2) –Cu–S(1)
(2)–Cu–S(1)
S(2)–C–S(1)
(4)–[
N(2)/O]–H(6)
110(2)
(
i)
(i)
(2) –Cu–S(1)
C–N(1)–H(1)
C–N(1)–H(2)
(5)–[N(2)/O]–H(6) 112(2)
(1)–C(
(2)–C
ii)
(2)–Cu–S(1)
(i)
(
i)
(1)–Cu–S(1)
H
H
H
(1)–N(1)–H(2)
(3)–[N(2)/O]–H(4) 106.2(19)
(3)–[N(2)/O]–H(5) 109(2)
(
ii)
C–N(1)(
–S(1)–Cu
iii)
C–S(1)
C–S(2)–Cu
D–H···A
D–H
H···A
D···A
Ͻ D–H···A
(1)–H(1)–S(2)(
(1)–H(1)–S(1)(
(1)–H(2)–S(2)(
(1)–H(2)–S(2)(
i)
0.88
0.88
0.88
0.88
0.92
0.92
0.92
0.92
0.90
0.90
2.726
3.032
2.809
2.984
2.586
2.819
3.080
2.403
2.221
1.983
3.543
3.648
3.639
3.572
3.234
3.432
3.732
3.289
3.010
2.846
154.96
128.76
157.95
125.89
127.87
125.01
129.34
165.33
146.76
159.24
N
N
N
N
iv)
v)
vi)
[
[
[
[
[
[
N
(2)/O]–H(3)–N(1)
(2)/O]–H(3)–S(1)
(2)/O]–H(3)–S(1)
(2)/O]–H(4)–S(1)
(2)/O]–H(5) [N(2)/O]
(2)/O]–H(6) [N(2)/O]
N
N
N
N
N
(
iv)
(
vii)
(
(
viii)
iv)
Symmetry transformations used to generate equivalent atoms: (i) –x, y, –z+1/2; (ii) –x+1/2, y+1/2, –z+1/2; (iii) –x+1/2, y–1/2, –z+1/2; (iv) x, –
y+2, –z+1; (v) –x+1/2, y–1/2, –z+1/2; (vi) –x+1/2, –y+3/2, z+1/2; (vii) x+1/2, y–1/2, z; (viii) –x+1, y, –z+1/2.
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
3

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C. L. Teske
2 2
Table 4. Selected bond lengths /Å and angles /° and hydrogen bonding geometry for CuS CNH (standard deviations in parenthesis).
ARTICLE
Cu–S(1)
Cu–S(1)(
Cu–S(2)(
Cu–S(2)
2.2973(9)
2.3074(8)
2.3300(8)
2.3900(9)
1.723(3)
1.737(3)
1.315(4)
1.737(3)
S
S
S
S
S
S
(1)–Cu–S(1)(i)
(1)–Cu–S(2)
110.77(2)
113.09(3)
115.09(3)
98.82(3)
102.25(3)
115.21(2)
109.86(11)
112.77(11)
Cu–S(1)–Cu(iii)
114.62(3)
103.95(11)
107.92(10)
122.56(3)
119.2(3)
119.5(3)
121.21(18)
120.0
C–N–H(2)
H(1)–N–H(2)
120.0
120.0
i)
(iV)
(iV)
C
C
–S(2)–Cu
–S(2)–Cu
(
i)
(v)
(1) –Cu–S(2)
ii)
(ii)
(v)
(1)–Cu–S(2)
Cu–S(2)–Cu
N–C–S(1)
N–C–S(2)
(
i)
(ii)
S
S
(1)–C
(1) –Cu–S(2)
(2)–C(
iV)
(2)–Cu–S(2)
(ii)
(vi)
(
vi)
C–N
C–S(1)–Cu
C–S(1)–Cu
S
(1)–C–S(2)
C–S(2)(
vi)
(iii)
C–N–H(1)
D–H···A
D–H
H···A
D···A
Ͻ D–H···A
N–H1–S(2)(
N–H1–S(1)
N–H2–S(2)(
0.880
0.880
0.880
2.675
2.956
2.642
3.342
3.460
3.434
133.43
118.22
150.28
vii)
viii)
Symmetry transformations used to generate equivalent atoms: (i) x+1/2, –y+1/2, –z+2; (ii) –x+2, y+1/2, –z+3/2; (iii) x–1/2, –y+1/2, –z+2;
iv) –x+1, y–1/2, –z+3/2; (v) –x+2, y–1/2, –z+3/2; (vi) –x+1, y+1/2, –z+3/2; (vii) –x+3/2, –y+1, z–1/2; (viii) x–1/2, –y+1/2, –z+1.
(
ticeable, though. An alternative (enlarged) view of the stag-
gered chain is given in the ultimate left part of Figure 4 were
+
an arbitrarily alternating arrangement of H O and NH4 is il-
2
lustrated. An appropriate reallocation of the hydrogen atoms
demonstrates a plausible alignment of the hydrogen bonds (O–
H···N and N–H···O = 1.983 Å, respectively and N–H···O =
2
.221 Å).
Figure 3. Partial view of the three-dimensional crystal structure of
NH [Cu(S CNH ]·H O (viewing direction along [001], for better
4
2
2
)
2
2
clarity only one Cu-dithocarbamate layer is depicted).
Figure 2. Tetrahedral surrounding of copper in NH
4 2 2 2
[Cu(S CNH ) ]·
H
2
O. For symmetry transformations and distances see Table 3. Hydro-
gen atoms are drawn as circles of arbitrary radii. The displacement
ellipsoids of the heavy atoms are drawn at the 80% probability.
2
) CuS CNH
2 2
In the crystal structure, the copper atoms have also tetrahe-
dral coordination spheres with four monodentate dithiocarbam-
ate ligands. This copper surrounding is more irregular as in the
crystal structure of the ammonium salt described above be-
cause of four different Cu–S distances (Table 4), but the
Figure 4. Partial view of the three-dimensional crystal structure of
4 2 2 2 2
NH [Cu(S CNH ) ]·H O (viewing direction along [010]). In the left
part, the alternating alignment of N(2) and O has been arbitrarily ideal-
average distance Cu–S = 2.3312(9) Å is similar. Furthermore, ized for the interpretation of the different hydrogen bonds (O–H···N
and N–H···O = 1.983 Å, respectively and N–H···O = 2.221 Å).
each sulfur atom has two next copper neighbors. Therefore,
each sulfur atom is a common vertex of two “tetrahedra”. The
three-dimensional arrangement (via common vertices) with dron is alternately pointing either upwards or downwards out
six-membered rings (Figure 5) is reminiscent of a filled β-cris- of the plane of projection. The irregular Cu–S distances reflect
tobalite structure[ where the fourth vertex of each tetrahe- the strongly distorted six-membered rings with tilted tetrahe-
24]
4
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Ammonium-bis(dithiocarbamato)-copper(I)-monohydrate and Mono(dithiocarbamato)-copper(I)
dra. The basal planes of the tetrahedra are not parallel and the
apical vertices (marked as globes in Figure 5) do not point to
the same opposite directions. The dithiocarbamate ligands ex-
tend into the hollow spaces of the three-dimensional tetrahe-
dral framework providing medium strong and weak hydrogen
bonds (N–H···S, Table 4).
4 2 2
Figure 5. CuS tetrahedra in the crystal structure of CuS CNH show-
ing the 3D linkage by common vertices (see text).
Figure 6.
NH [Cu(S
Thermogram
(DTA,
TG,
DTG
curves)
for
–
1
4
2
CNH ]·H O (heating rate: 1 K·min ).
2
)
2
2
b) Thermal Decomposition Reactions
Thermal decomposition of aliphatic metal dithiocarbamates
is supposed to take place via thiocyanate intermediates.[ Be-
fore entering upon further considerations, it must be noted that
in each case the mass steps in the TG curves are not very well
separated (Figure 6 and Figure 7). Nevertheless, some of the
events, observable while heating up, will be assigned tenta-
tively to plausible mass losses with the aid of stoichiometric
calculations and XRPDs of the recovered intermediates and
residues.
25]
NH [Cu(S CNH ) ]·H O
4
2
2 2
2
The thermal decomposition of NH [Cu(S CNH ) ]·H O is a
4
2
2 2
2
complex endothermic process. On heating the thermal decom-
position starts early in the range of T ≈ 33–95 °C depending
on the heating rate. The process proceeds in several steps over-
lapping in the temperature range from RT to T ≈ 350 °C (Fig-
ure 6) and ending up at T ≈ 800 °C (Δm(exp) = 69.9%). The
theoretical mass loss for the formation of Cu S is Δ
=
2
m(theo)
7
1.96%. During the analogue scans (MS measurements) the
following characteristic gaseous decomposition products were
detected: NH m/z = 17, H O m/z = 18, HCN m/z = 27, H S
3
2
2
–
m/z = 34, H CNS m/z = 60, S m/z = 64 and CS = 76. On
2
2
2
heating, a particular sharp endothermic peak on the DTA curve
is observed at Tp = 170.9 °C which coincides with an inflec-
tion point on the TG curve. The experimental mass loss of Δm
Figure 7. Thermogram (DTA, TG, DTG curves) for CuS
2
CNH
2
(heat-
5
–
1
=
51.2% is in perfect accordance with a calculated loss of ing rate: 1 K·min ).
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Pages: 8
C. L. Teske
ARTICLE
Δm(theo) = 51.16% for the release of NH , CS , H O and H S lines of Cu S[ and Cu1.81S,[29] which partly coincide are def-
28]
3
2
2
2
2
(
ratio: 2:1:1:0.5). Technically this corresponds to the decay of initely observable.
one mol NH S CNH and the total loss of all water of
4
2
2
crystallization. However, the additional emergence of H S is
an evidence for at least partial formation of CuSCN. The
2
Conclusions
I
XRPD of an intermediate taken from the temperature range T
It was shown that the preparation of Cu -dithiocarbamates
[26]
≈
180 to 200 °C shows the lines of β-CuSCN.
The next applying cyanide as reductive is a convenient method. The new
distinct mass loss occurs at T ≈ 425 °C (Δm = 15.6%). An compounds NH
[Cu(S CNH ) ]·H O (A) and CuS CNH (B)
4
2 2 2 2 2 2
emission of HCN and S (ratio: 2:1) corresponds to a theoretical were obtained. (A) is the first example comprising of the anion
–
–
loss of Δm(theo) = 15.5%. Both steps add up to Δm = 66.8%. [Cu(S
CNH ) ] which is known as [Cu(S CNR ) ] (R = or-
2 2 2 2 2
2
The calculated Δm = 66.4% applies to the formation of CuS. ganic moiety) from electrochemical investigations of transition
[30]
(
This applies also for a decomposition via NH ,CS , H O and metal dithiocarbamates.
Obviously, this anion has never
In both crystal structures of (A) and
3
2
2
–
[31]
H CNS ; ratio: 2:1:1:1). The trends of the TG curves of both been isolated before.
2
dithiocarbamates in the temperature region above T Ͼ 400 °C (B) copper has a tetrahedral surrounding of its next sulfur
are very similar (Figure 6 and Figure 7). That is why this re- neighbors (from monodentate dithiocarbamate ligands) which
I
gion was not further investigated assuming that the final for- is a characteristic feature for Cu . Both new compounds de-
mation of Cu S (vide infra) would most likely proceed simi- compose at elevated temperatures in the course of complex
2
larly in both cases.
endothermic processes finally giving Cu S.
2
Acknowledgments
CuS CNH
2
2
The thermal decomposition of CuS CNH is also a complex The author is grateful to the institutions Bundesministerium für
2
2
endothermic process. It starts at T ≈ 170 °C and is completed Bildung und Forschung, Deutsche Forschungsgemeinschaft and Baye-
risches Staatministerium für Wissenschaft, Forschung und Kunst for
covering the costs of the Electronic Journals Library and electronic
databases at CAU Kiel. Special thanks go to Prof. Christian Näther
and Inke Jess for their support and the measurements (TG-DTA-MS,
single crystal data) as well as to all colleagues who measured the
XRPDs.
at T ≈ 800 °C (Figure 7). The overall experimental mass loss
is Δm = 48.7% which corresponds perfectly to a calculated
loss of Δm = 48.9% for the formation of Cu S. During the
2
first the large step, at least two strongly overlapping decompo-
sitions occur. At best, one can assume that at T ≈ 434 °C (onset
of an endothermic effect Figure 7) a first partial decomposition
might be completed before the start of the next reaction. The
associated experimental loss Δm = 43.8% corresponds to a References
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[
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8
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[
comprises
(
basically
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5
the
reflections
of
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23]
[27]
(Figure 8). The XRPD from the end
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Figure 8. X-ray powder diagram of an intermediate taken at T ≈
4
00 °C from the decomposition of CuS
2
CNH
2
(arrows indicate the [17] X-RED, Data Reduction Program, Version 1.11, Stoe & Cie
9 5
S ). GmbH, 1998.
lines of covellite, circles indicate the lines of Cu
6
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/KAP1
Date: 05-09-13 13:41:56
Pages: 8
Ammonium-bis(dithiocarbamato)-copper(I)-monohydrate and Mono(dithiocarbamato)-copper(I)
[
[
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1
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[
[
[
Received: June 30, 2013
[
25] A. K. Sharma, Thermochim. Acta 1986, 104, 339–372.
Published Online: ᭿
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7

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C. L. Teske
ARTICLE
C. L. Teske* ....................................................................... 1–8
On Ammonium-bis(dithiocarbamato)-copper(I)-monohydrate
and Mono(dithiocarbamato)-copper(I)
8
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