Preparation and crystal structure of copper(I) carbonyl hydrogensulfate, obtained by carbonylation in sulphuric acid

Article abstract of DOI:10.1002/1521-3749(200208)628:8<1868::AID-ZAAC1868>3.0.CO;2-R

The hydrogensulfato-carbonyl derivative [Cu(CO)(SO₄H)]_n, as obtained from the Cu₂O/ H₂SO₄/CO system and recrystallized from H₂SO₄/(CH₃O)₂SO₂ has been shown to possess a crystal structure organised in infinite chains built up by corner sharing of {CuO₃(CO)} and {S(OH)O₃} tetrahedra. The chains are connected by hydrogen bonds in layers, with CO groups leaning out on both sides. The absorption of CO by CuSO₄/Cu or by Cu₂O in sulfuric acid was quantified as a function of concentration. The CuSO₄/Cu system in water absorbs carbon monoxide (CO/Cu molar ratio = 1.0).

Full text of DOI:10.1002/1521-3749(200208)628:8<1868::AID-ZAAC1868>3.0.CO;2-R

Preparation and Crystal Structure of Copper(I) Carbonyl Hydrogensulfate,
obtained by Carbonylation in Sulphuric Acid
Daniela Belli Dell’Amico, Fausto Calderazzo, Luca Labella, Fabio Lorenzini and Fabio Marchetti*
`
Pisa / Italy, Dipartimento di Chimica e Chimica Industriale, Universita di Pisa
Received February 21st, 2002.
Dedicated to Professor Joachim Strähle on the Occasion of his 65th Birthday
Abstract. The hydrogensulfato-carbonyl derivative [Cu(CO)-
(SO4H)]n, as obtained from the Cu2O/ H2SO4/CO system and
recrystallized from H2SO4/(CH3O)2SO2 has been shown to possess
a crystal structure organised in infinite chains built up by corner
sharing of {CuO3(CO)} and {S(OH)O3} tetrahedra. The chains are
connected by hydrogen bonds in layers, with CO groups leaning
out on both sides. The absorption of CO by CuSO4/Cu or by Cu2O
in sulfuric acid was quantified as a function of concentration. The
CuSO4/Cu system in water absorbs carbon monoxide (CO/Cu mo-
lar ratio ϭ 1.0).
Keywords: Copper; Copper(I) carbonyls; Metal hydrogensulfates
Darstellung von Kupfer(I)-carbonyl-hydrogensulfat durch Carbonylierung in
Schwefelsäure und die Kristallstruktur
Inhaltsübersicht. Das Hydrogensufato-carbonyl-Derivat [Cu(CO)-
(SO4H)]n wurde aus dem Gemisch Cu2O/H2SO4/CO erhalten und
aus H2SO4/(CH3O)2SO2 umkristallisiert. Es hat eine Kristallstruk-
tur, die aus unendlichen Ketten von über Ecken verbrückten
{CuO3(CO)}- und {S(OH)O3}-Tetraedern aufgebaut ist. Die Ket-
ten sind über Wasserstoffbrückenbindungen zu Schichten mit an
beiden Seiten herausragenden CO-Gruppen verbunden. Die Ab-
sorption von CO durch CuSO4/Cu oder Cu2O in der Schwefelsäure
wurde als Funktion der Konzentration bestimmt. Das CuSO4/Cu-
System in Wasser absorbiert CO (CO/Cu Molverhältnis ϭ 1,0)
1 Introduction
copper(I) for carbon monoxide was anticipated to be much
higher than that of silver(I). These considerations suggested
that copper(I) could be a good candidate for the isolation
of the corresponding hydrogensulfato complex, with or
without coordinated carbon monoxide, thus adding a new
member to the series of the still limited family of hydro-
gensulfato metal complexes [4]. Further interest in this field
was anticipated by the observation that the number of carb-
onyl complexes of copper(I) with oxygen donor ligands is
still limited [5]. As the result of the reversible carbon mon-
oxide absorption by Cu(ClO4)2/Cu in water, compounds
analytically characterised as Cu(ClO4)(CO)(H2O)x have
been reported [6]. Work from these Laboratories has shown
that trifluoro- and trichloroacetato carbonyl derivatives are
obtained by syn-proportionation between copper(II) tri-
haloacetate and copper in the presence of CO [7]. More-
over, carbon monoxide was found to be absorbed by sus-
pensions of Cu2O in Et2O in the presence of sulfonic acids
(added molecular sieves take care of the water formed in
the reaction), giving carbonyl derivatives of formula
[Cu(SO3R)(CO)]n (with R ϭ CH3, C2H5, CF3 or p-
CH3C6H4) [8]. The crystal structure of the ethyl derivative
has been determined, vide infra.
Earlier some of us have used sulfuric acid to prepare and
characterise silver hydrogensulfate Ag(SO4H)) [1a]. On the
track of our long-standing interest in carbonyl chemistry of
late transition metals, which profited considerably from a
lasting scientific collaboration with Strähle and his cowork-
ers [1bϪe], we measured the CO uptake by sulfuric acid
solutions of Agϩ at atmospheric pressure. In agreement
with some earlier data [2], we observed a limited absorption
of carbon monoxide corresponding to a CO/Ag molar ratio
of 0.3. Furthermore, no solid compound different from
Ag(SO4H) could be isolated from the solution [1].
Copper(I) sulfate which has been prepared and structur-
ally characterized, was reported to be metastable [3]. The
hypothesis that Cu(SO4H) might be stable had to be taken
into consideration, as the single charge on the HSO4Ϫ anion
could drastically modify the thermodynamics of the system
with respect to Cu2SO4. On the other hand, carbon mon-
oxide can stabilise copper(I) derivatives, and the affinity of
* Prof. Fabio Marchetti
Dip. di Chimica e Chimica Industriale
Universita di Pisa
Via Risorgimento. 35
I-56126 Pisa / Italy
In this paper we report the study of the system Cu2O/
H2SO4 in the absence and in the presence of CO and the
successful isolation and structural determination of
[Cu(SO4H)(CO]n.
`
FAX (ϩ39) 050 20237, e-mail: fama@dcci.unipi.it
1868
 WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044Ϫ2313/02/628/1868Ϫ1872 $ 20.00ϩ.50/0 Z. Anorg. Allg. Chem. 2002, 628, 1868Ϫ1872

Copper(I) Carbonyl Hydrogensulfate
graphic Data Centre, CCDC reference number 176512. 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. codeϩ(1223)336-033; e-mail: teched@chemcrys.cam.ac.uk].
2 Experimental
All preparations were carried out in standard Schlenk tubes under
dinitrogen or carbon monoxide, as indicated. Elemental analyses
were performed in the house by standard procedures. IR spectra
were measured with a Perkin-Elmer FT-IR mod.1725X spectro-
photometer. Commercial H2SO4 96 % (J. T. Baker), Cu2O (Janssen)
and (CH3O)2SO2 (Aldrich) have been used as received.
Table 1 Crystal data and structure refinement.
Empirical formula
M
CHCuO5S
188.62
Colour
Colourless
1.40 ϫ 0.34 ϫ 0.18
monoclinic
P21/c (No. 14)
8.5900(7)
4.8980(6)
12.027(1)
95.193(9)
4
2.486
4.672
503.96(9)
368
Crystal size / mm
Crystal system
Space group
Preparation of [Cu(SO4H)(CO)]n
˚
a / A
Copper(I) oxide Cu2O (7.50 g, 52.4 mmol) was gradually added to
concentrated H2SO4 (20 mL) under CO at room temperature. After
10 d the grey suspension was filtered and the solid was washed with
dimethylsulfate (2 ϫ 25 mL), dried in vacuo (P ϭ 10Ϫ2 Torr) at
25 °C for 22 h and stored under CO in sealed vials (0.972 g).
Elemental analysis, found (calc.): Cu, 32.4 (33.7). From the filtrate,
further product precipitated out at Ϫ18 °C as colourless leaflets,
which were filtered, washed with dimethylsulfate and dried in vacuo
(0.592 g). A third crop of the product (0.178 g) was similarly ob-
tained from the previous mother liquor maintained at Ϫ18 °C.
Crystals from the third crop were used for the X-ray diffractometric
experiment. The total yield of the product was 9 %. IR spectrum
˚
b / A
˚
c / A
β / °
Z
Dc / (g · cmϪ3
µ / mmϪ1
)
3
˚
V / A
F(000)
θ range / °
2.38 Ϫ 31.99
0.1535, 0.0744
2461
1753
0.0148
Max., min. transmission
No. reflections collected
No. independent reflections
Rint
No. observed reflections, I > 2σ
Data / restraints / parameters
Extinction coefficient
ρmin, ρmax / (e · A
Completeness to θ ϭ 31.99°
R1 ϭ ΣʈFoΗϪΗFcʈ / ΣΗFoΗ, I > 2σ(I)
wR2 ϭ {Σ[w(Fo2ϪFc2)2] / Σ[w(Fo2)2]}1/2
Goodness-of-fit, GooF ϭ S ϭ
{Σ[w(Fo2ϪFc2)2] / (n Ϫ p}1/2
1271
(Nujol): νCO 2120 cmϪ1
.
1753 / 0 / 78
0.010(3)
Ϫ1.294, 0.775
100.0 %
0.0436
0.1248
In a comparative experiment carried out in the absence of carbon
monoxide, the deep red Cu2O (11.60 g, 81.1 mmol) was added to
concentrated H2SO4 (50 mL) under N2 at room temperature and
stirred for two days at room temperature. The resulting brown
solid, filtered and washed with two portions of dimethylsulfate
(2 ϫ 20 mL) was dried in vacuo at T ϭ 60 °C (14.31 g). An X-ray
powder diffraction diagram showed peaks due to metallic copper,
CuSO4 and CuSO4·5 H2O (presumably originated from exposure
to moisture during data collection).
Ϫ3
˚
)
1.042
Reaction of copper(I) with H2SO4 under CO.
Gasvolumetric measurements
In a series of experiments carried out under CO (T ϭ 26 °C; P
756Ϭ770 Torr) and monitored gas-volumetrically, Cu2O was pro-
gressively added to 10 mL of concentrated H2SO4 (96 %): the ex-
perimental CO/Cu molar ratio was 1.3 with 5.55 mmol of Cu2O,
and decreased to 1.0 when further Cu2O (17.5 mmol) was intro-
duced. The addition of Cu2O to H2SO4 corresponds to a dilution
of the acid (from 96 % to 86 % with 5.55 mmol of Cu2O, and to
58 % with 23.05 mmol of Cu2O).
Structure determination
A plate of [Cu(SO4H)(CO)]n was sealed under a CO atmosphere in
a glass capillary, together with a drop of its mother liquor and
mounted on a Bruker-AXS P4 four-circle diffractometer. Diffrac-
tion data were collected at 293(2) K with graphite-monochromated
Mo-Kα radiation operating at 50 kV and 40 mA. The cell para-
meters listed in Table 1 have been calculated using the XSCANS
program [9] from the setting angles of 26 strong reflections with θ
ranging between 11.34° and 14.96°. Due to the difficult sample
handling, the very long specimen could not be cut and its longer
edge (1.4 mm) overcame the diameter of the incident beam colli-
mator (1.0 mm), thus introducing systematic errors in intensity
evaluation which could not be completely corrected by the ψ-scan
procedure. Data reduction was performed by SHELXTL [10]. The
structure was solved by the direct method and difference Fourier
map using SHELXS-97 [11] and refined on F2 by full matrix least-
squares techniques using SHELXL-97 [11]. The hydrogen atom was
located in the difference Fourier map and was refined without con-
straints.
In another experiment carried out in 50 % H2SO4, 0.04 g of Cu2O
(0.28 mmol) absorbed CO (T ϭ 26 °C; P ϭ 752 Torr) up to a CO/
Cu molar ratio of 1.0. Comparable results were obtained in experi-
ments [12] where the CO uptake by the system CuSO4/Cu/H2SO4
was measured. In a typical experiment CuSO4 ·5 H2O (0.260 g,
1.04 mmol) and a slight excess of Cu (0.070 g, 1.10 mmol ) were
individually introduced in sealed glass ampoules and then con-
tacted with concentrated H2SO4 (96 %, 10 ml) under CO at 26 °C
and P ϭ 766 Torr. A volume of carbon monoxide corresponding
to a CO/Cu molar ratio of 1.3 was found to be absorbed in 2.5 h.
The system was treated in vacuo for 1 h and then supplied again
with CO: the absorption of CO, after appropriate correction for
the known volume of the reactor, corresponded to a CO/Cu molar
The crystal data and the main reliability parameters of the struc-
ture refinement are listed in Table 1. The largest difference Fourier
ratio of 0.3. IR: νCO 2182, 2144 cmϪ1
.
residual peak (0.775 e · AϪ3) is placed in the middle of the SϪO(2)
˚
bond and is probably due to some inefficiency of the model in
Reaction of copper(II) sulfate and metallic copper
with CO in H2O
describing the electron density of the sulfur atom. The largest nega-
Ϫ3
˚
˚
tive one (Ϫ1.294 e · A ) placed at 0.86 A from Cu may be attri-
buted to a similar reason. Further details of the crystal structure
investigation have been deposited with the Cambridge Crystallo-
Gas-volumetric experiment. Two sealed fragile ampoules individu-
ally containing CuSO4·5 H2O (0.070 g, 0.28 mmol) and an excess
Z. Anorg. Allg. Chem. 2002, 628, 1868Ϫ1872
1869

D. Belli Dell’Amico, F. Calderazzo, L. Labella, F. Lorenzini, F. Marchetti
to what observed for Cu(SO3C2H5)(CO) at 2117 cmϪ1 [8]
and for Cu(ClO4)(CO)(H2O)2 at 2130 cmϪ1 [6]. On the
other hand, in concentrated sulfuric acid, i. e. under con-
ditions of CO absorption corresponding to a CO/Cu molar
ratio of 1.3, a weak band at 2182 cmϪ1 and a rather intense
one at 2144 cmϪ1 were observed. We suggest that the band
at 2144 cmϪ1 is due to a monocarbonyl-copper derivative,
while the band at 2182 cmϪ1 is related to a dicarbonyl de-
rivative, by analogy with similar compounds described in
the literature, namely Cu[1-EtϪCB11F11](CO)2 (νCO: 2184,
of Cu (0.070 g, 1.10 mmol) were introduced into a reactor together
with deionized H2O (10 mL) under CO at 26 °C and P ϭ 751 Torr.
After breakage of the ampoules, a CO uptake corresponding to a
CO/Cu molar ratio of 1.0 was measured. IR: νCO 2111 cmϪ1. The
addition of an excess of Na(BPh4) caused the complete evolution
of CO.
Solid Cu2O or suspensions of Cu2O in water did not absorb CO.
Formation of Cu[BPh4]
Copper sulfate CuSO4·5 H2O (1.43 g, 5.72 mmol) and an excess of
Cu (3.092 g, 48.66 mmol) were introduced in a reactor containing
deionized H2O (30 mL) under CO at room temperature. The mix-
ture was stirred until the CO uptake ceased (about 4 h). The sus-
pension was filtered and the filtrate was treated with a solution of
Na(BPh4) (3.840 g, 11.22 mmol) in water (60 mL). An immediate
gas evolution was observed and a colourless solid precipitated out.
The suspension was filtered and the solid was washed with two
portions of deionized water (2 x 20 mL) and dried in vacuo (2.790 g,
65 % yield). Elemental analysis, found (calc.): Cu, 16.6 (16.6). IR
spectrum (PCTFE, most intense bands): 3044, 1574, 1556, 1475,
2166 cmϪ1
,
OCϪCuϪCO 124.1°) [13a] and Cu-
[N(SO2CF3)2](CO)2 (νCO: 2184, 2158 cmϪ1, OCϪCuϪCO
122.0°) [13b]. The second band expected for a dicarbonyl
derivative having a bent OC-Cu-CO group could be respon-
sible for the observed broadening (at about 2150 cmϪ1) of
the most intense absorption. In agreement with the litera-
ture [14], the equilibrium (see eq. 2) between the two species
in solution is displaced to the left under a reduced partial
pressure of CO, while the monocarbonyl complex is stable.
As already observed by Souma et al. [2], we found that the
position of the band attributed to the monocarbonyl species
depends on the sulfuric acid concentration (2144 or
2120 cmϪ1 in 96 % or 50 % H2SO4, respectively). In ad-
dition, when the sulfuric acid concentration decreases, the
band at high energy (2182 cmϪ1) disappears. The solvent
may influence both the equilibrium between the dicarbonyl-
and the monocarbonyl-copper complexes (see eq. 2), and
the degree of solvation of the monocarbonyl-copper species.
In less concentrated sulfuric acid, the greater availability of
the solvent for complexation to the copper atom causes the
CϵO stretching to shift to lower wavenumbers. In aqueous
solution hydrated species such as [Cu(CO)(H2O)m(SO4H)]n
may exist, the degree of complexity n and the number of
co-ordinated H2O groups depending on the concentration
of the acid medium. As a matter of fact, the CO/Cu molar
ratio established gas-volumetrically corresponds to about
1.3 in 96 % H2SO4, decreases by dilution of the acid and
reaches 1.0 in about 60 % H2SO4, while further dilution
does not affect this value.
1423 cmϪ1
.
Reaction of copper(II) sulfate and metallic copper
with CO in CH3OH
Copper sulfate CuSO4·5 H2O (0.110 g, 0.44 mmol) and an excess of
Cu (0.510 g, 8.03 mmol) were introduced into a reactor containing
CH3OH (9.2 mL) under CO at 27.2 °C. The CO uptake corres-
ponded to a CO/Cu molar ratio of 1.0. IR spectrum of the solution:
νCO 2101 cmϪ1
.
3 Results and Discussion
At the onset of this work the preparation of Cu(SO4H) was
attempted by the route successfully applied for Ag(SO4H)
[1]. The addition of Cu2O to sulfuric acid in a dinitrogen
atmosphere at room temperature results in a brown suspen-
sion of metal copper and copper(II) sulfate. On the other
hand, Cu2O was reported [2] to absorb CO in concentrated
sulfuric acid forming solutions of copper(I) carbonyl com-
plexes, [Cu(CO)n]ϩ (n ϭ 1Ϭ3, depending on temperature,
sulfuric acid concentration and CO pressure).
[Cu(CO)]ϩ ϩ CO q [Cu (CO)2]ϩ
(2)
Analogous results were obtained starting from equimolar
mixtures of copper(II) sulfate and metallic copper under
CO. A syn-proportionation reaction was observed ac-
companied by CO uptake with CO/Cu molar ratios de-
pending on sulfuric acid concentration, similar to the re-
sults obtained with Cu2O. In water the reaction proceeds
up to CO/Cu molar ratio of 1.0, the IR spectrum of the
solution showing a band at 2111 cmϪ1, a value to be com-
pared with the previous ones, recorded in 96 % and 50 %
H2SO4, which confirms the tendency of νCO’s to shift
towards lower values with increasing donating power of the
solvent. The aqueous solution thus obtained was treated
with Na(BPh4) in an attempt to precipitate the hypothetical
Cu(CO)(H2O)m(BPh4) arising from the cationic complex in
solution. However, complete evolution of CO was observed
with formation of the colourless sparingly soluble
In our hands, Cu2O in concentrated sulfuric acid (96 %,
initial concentration) under CO gave a colourless solution
or a suspension of a light grey solid, depending on the rela-
tive amounts of Cu2O and sulfuric acid. The solid analyses
as Cu(SO4H)(CO), but the structure of the product could
only be established by X-ray crystallography, vide infra. The
nature of the carbonylated species in solution depends on
the final sulfuric acid concentration. Other species beside
Cu(SO4H)(CO) may be present in solution, since carbon
monoxide was absorbed up to a CO/Cu molar ratio of 1.3,
observed at concentrations of H2SO4 as high as 86 %.
1/2 Cu2O ϩ H2SO4 ϩ CO Ǟ 1/n [Cu(SO4H)(CO]n ϩ 1/2 H2O (1)
The solid of composition Cu(SO4H)(CO), as a dispersion
in Nujol, shows a strong absorption at 2120 cmϪ1, similar
1870
Z. Anorg. Allg. Chem. 2002, 628, 1868Ϫ1872

Copper(I) Carbonyl Hydrogensulfate
Cu(BPh4), whereby presumably an aromatic ring of the
anion displaces carbon monoxide from the coordination
sphere of the metal through its πϪelectron density. Al-
though Cu(BPh4) is known, its structure has not been re-
ported. It was prepared from CuBr2 and Li(BPh4) [15a], or
by acidification of Cu(BPh4)py4 [15b], or from CuPh and
BPh3 in diethylether [15c].
Hydrogensulfato groups show their usual tetrahedral struc-
˚
ture [4] with a marked lengthening of the SϪOH (1.555 A)
˚
bond with respect to the SϪO ones (mean value 1.453 A).
Each hydrogensulfato anion uses its non-protonated oxy-
gens to bonding three different copper centres. A list of the
bond distances and angles is shown in Table 2. The Cu-CO
˚
and CϪO bond distances of 1.807 and 1.104 A, respec-
The carbonyl species of copper(I) obtained in H2SO4 are
well soluble in sulfuric acid and copper(I) concentrations
up to 5 M can be obtained. A solution prepared from
Cu2O, CO and initially 96 % H2SO4, after addition of di-
methylsulfate, was stored at low temperature (Ϫ18 °C) giv-
ing colourless plates of [Cu(SO4H)(CO]n, very sensitive to
moisture, which were used for the X-ray diffraction study.
The structure of [Cu(SO4H)(CO]n is shown in Fig. 1, where
the atoms of the asymmetric unit together with those di-
rectly connected to it are labelled. In the structure may be
distinguished chains, growing along b, made by the conden-
sation of eight-membered rings {Cu2O4S2}. Two types of
rings, both possessing an inversion centre are present, and,
although crystallographically distinct, they are very similar.
Each ring shares three atoms: Cu, O, S, with the preceding
one and three with the following one in the chain.
tively, compare well with the corresponding distances ob-
served in metal carbonyl derivatives of copper(I) with oxy-
gen donor ligands [5].
˚
Table 2 Bond lengths/A and angles/° for Cu(CO)HSO4.
CuϪC
1.807(3)
2.062(2)
2.070(2)
2.145(2)
1.104(4)
SϪO(4)
SϪO(3)
SϪO(5)
SϪO(2)
1.446(2)
1.448(2)
1.464(2)
1.555(2)
CuϪO(3Ј)
CuϪO(4Љ)
CuϪO(5)
CϪO(1)
CϪCuϪO(3Ј)
CϪCuϪO(4Љ)
CϪCuϪO(5)
O(3)ϪCuϪO(4Љ)
O(3Ј)ϪCuϪO(5)
O(4Ј)ϪCuϪO(5)
O(1)ϪCϪCu
125.5(1)
122.2(1)
116.7(1)
94.32(8)
93.76(9)
97.54(8)
175.8(4)
113.2(1)
O(4)ϪSϪO(5)
O(3)ϪSϪO(5)
O(4)ϪSϪO(2)
O(3)ϪSϪO(2)
O(5)ϪSϪO(2)
SϪO(3)ϪCuЈ
SϪO(4)ϪCuЉ
SϪO(5)ϪCu
111.5(1)
113.2(1)
107.6(1)
104.1(1)
106.5(1)
130.9(1)
127.5(1)
128.4(1)
O(4)ϪSϪO(3)
Symmetry transformations used to generate equivalent atoms: Ј ϭ Ϫx, Ϫy
ϩ 1, Ϫz ; Љ ϭ Ϫx, Ϫy, Ϫz
As it can be seen in Fig. 1, the CO groups are almost paral-
lel, leaning out of the chain in two opposite directions, up
and down; on the other hand, the OH groups stick out
also in two opposite directions, forward and backward. The
structure of the chain and the positions of the carbonyl
groups are reminiscent of those found in [Cu(SO3Et)(CO)]n,
where the ethyl and the carbonyl groups are bent approxi-
mately in the same direction [8]. In the structure of
[Cu(SO3Et)(CO)]n the chains are held together by van der
Fig. 1 View of a chain present in the structure of Cu(CO)HSO4
projected down c. Primed atoms are related to unprimed ones by
the symmetry operations given in Table 1. The b translation and
the inversion operators are also drawn.
The copper atom presents a pseudo-tetrahedral coordi-
nation, being connected to one carbonyl group and to three
oxygens, belonging to three different hydrogensulfato li-
gands. The distortion from the ideal tetrahedral geometry
is due, beside the difference in length between CuϪO and
CuϪC bonds, to the wide CϪCuϪO angles (mean value
121.5°) with respect to the OϪCuϪOЈ ones (mean value
95.2°). Such an angular difference is normally observed in
Cu(I) carbonyl derivatives with O-ancillary ligands and is
consistent with the greater CuϪO distance and the greater
electronegativity of oxygen which removes negative charge
from the copper allowing the OϪCuϪOЈ angles to close.
Fig. 2 Projection down a of a layer of hydrogen bonded chains
with the screw helix 21 relating two neighbouring ones.
Z. Anorg. Allg. Chem. 2002, 628, 1868Ϫ1872
1871

D. Belli Dell’Amico, F. Calderazzo, L. Labella, F. Lorenzini, F. Marchetti
Waals interactions. Further stabilisation of the solid-state
structure of our compound may arise from the fact that the
OH groups can behave as donors towards the O(5) atoms,
establishing a network of hydrogen bonds, which organize
the chains in layers spreading in the yz plane. A section of
one of these planes is shown in Fig. 2.
The layers have both faces covered by CO groups lodging
within the corresponding CO’s of neighbouring ones. The
joining of two adjacent layers is shown in Fig. 3 together
with the symmetry operators relating the layers.
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The carbonyl derivative [Cu(SO4H)(CO)] is the first
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`
Acknowledgements. We thank the Ministero dell’ Universita
e della Ricerca Scientifica e Tecnologica (MURST),
Progetti di Rilevante Interesse Nazionale 2000-2001, for fin-
ancial support. The authors also wish to thank the COST
Action D17/003 of the European Community for promot-
ing the scientific activity.
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1872
Z. Anorg. Allg. Chem. 2002, 628, 1868Ϫ1872