Bis[1-hydroxypyridine-2(1H)-thionato-S,O]copper(II)

Article abstract of DOI:10.1107/S0108270101012306

Synchrotron radiation was used to determine the crystal structure of copper pyrithione from a microcrystalline fragment. The Cu complex was prepared by the combination of aqueous solution of CuCl₂ and Na(PT) at room temperature. The resulting g

Full text of DOI:10.1107/S0108270101012306

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Compound (I) adopts a trans-square-planar arrangement,
with Cu1 situated at a centre of inversion in the space group
P1 (Fig. 1). The Cu1ÐS1 and Cu1ÐO1 bond distances
ISSN 0108-2701
Bis[1-hydroxypyridine-2(1H)-thion-
ato-S,O]copper(II)
Andrew D. Bond,a* Neil Feeder,a² Simon J. Teatb and
William Jonesa
aDepartment of Chemistry, University of Cambridge, Lensfield Road, Cambridge
CB2 1EW, England, and bCLRC Daresbury Laboratory, Daresbury, Warrington
WA4 4AD, England
Figure 1
The molecular unit in (I), showing displacement ellipsoids at the 50%
probability level and H atoms as small spheres of arbitrary radii
[symmetry code: (i) x, y, z].
Correspondence e-mail: adb29@cam.ac.uk
Received 16 July 2001
Accepted 19 July 2001
(Table 1) are shorter than those in zinc pyrithione [average
Ê
The crystal structure of the widely used title fungicidal
material, [Cu(C5H4NOS)2], has been determined at 150 (2) K
from a microcrystalline fragment using synchrotron radiation.
The molecule adopts a trans-square-planar con®guration, with
the Cu atom sited at a crystallographic centre of inversion.
2.308 (3) and 2.115 (6) A, respectively]. Molecules of (I) are
linked into chains by CÐHÁ Á ÁO interactions, forming an R22(8)
ii
ii
Ê
hydrogen-bond motif [H5Á Á ÁO1 2.41 A and C5ÐH5Á Á ÁO1
164ꢀ; symmetry code: (ii) x,
1
y, z] (Fig. 2). The same
motif exists in the divalent Ni complex of pyrithione (Chen et
al., 1991), in which a cis-square-planar geometry leads to the
formation of discrete dimers rather than extended chains.
Comment
Cyclic thiohydroxamic acids, such as 1-hydroxypyridine-
2(1H)-thione (pyrithione), ®nd extensive use as fungicides
(Paulus, 1993). In particular, complexes of pyrithione with Zn
and Cu are highly active broad-spectrum antimicrobial agents.
Zinc pyrithione is the active ingredient in most antidandruff
shampoos (Arch Chemicals, 2000a). Copper pyrithione is sold
extensively (outside the USA) as a marine antifouling
product; marine paints containing copper pyrithione are easy
to formulate and show excellent stability even when subjected
to extreme thermal conditions (Arch Chemicals, 2000b). The
crystal structure of zinc pyrithione has been known for almost
25 years (Barnett et al., 1977), and a considerable number of
pyrithione complexes have been prepared and their crystal
Figure 2
The projection onto (100) showing chains of (I) linked via CÐHÁ Á ÁO
interactions.
structures determined (Chen et al., 1991; Hu et al., 1991; Xu et
al., 1995; Wen et al., 1996). Despite this extensive research, the
crystal structure of copper pyrithione has remained elusive.
This may undoubtedly be attributed to the fact that copper
pyrithione does not readily form large single crystals suitable
for diffraction analysis with laboratory instruments. We report
here the crystal structure of copper pyrithione, (I), determined
from a microcrystalline fragment using the additional bright-
ness of the Synchrotron Radiation Source at Daresbury,
England (Cernik et al., 1997).
Molecules of (I) in adjacent chains are stacked such that S1
in one molecule lies directly above Cu1 in an adjacent mol-
ecule, with Cu1Á Á ÁS1iii = 3.4447 (13) A [symmetry code: (iii)
Ê
1
x, y, z]. The same arrangement exists below Cu1
1
[Cu1Á Á ÁS1iv; symmetry code: (iv)
x, y, z], such that
the coordination geometry around it may be considered to be
a tetragonally distorted octahedron (Fig. 3), i.e. a Jahn±Teller-
distorted octahedral geometry about CuII (d9). Molecules of
(I), therefore, form extended stacks containing edge-sharing
octahedra along the [100] direction. Within these stacks,
pyrithione rings of adjacent molecules are coplanar, with
² Present address: P®zer Global R&D, Ramsgate Road, Sandwich, Kent
CT13 9NJ, England.
Ê
interplanar separations of 3.25 A.
ꢁ
Acta Cryst. (2001). C57, 1157±1158
# 2001 International Union of Crystallography
Printed in Great Britain ± all rights reserved 1157

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
Cu1ÐO1
Cu1ÐS1
S1ÐC1
O1ÐN1
N1ÐC5
1.939 (3)
2.2445 (11)
1.703 (4)
1.354 (5)
1.362 (6)
N1ÐC1
C1ÐC2
C2ÐC3
C3ÐC4
C4ÐC5
1.366 (6)
1.405 (6)
1.365 (6)
1.405 (7)
1.356 (7)
O1iÐCu1ÐS1i
O1ÐCu1ÐS1i
O1iÐCu1ÐS1
O1ÐCu1ÐS1
87.96 (9)
92.04 (9)
92.04 (9)
87.96 (9)
C1ÐS1ÐCu1
N1ÐO1ÐCu1
O1ÐN1ÐC5
O1ÐN1ÐC1
95.67 (15)
115.7 (3)
116.6 (4)
120.6 (4)
Symmetry code: (i) x; y; z.
Figure 3
The coordination geometry around Cu1 illustrating the axial Jahn±Teller
distortion.
Ê
quent re®nement, with a CÐH distance of 0.95 A and an isotropic
displacement parameter ®xed at 1.2 times Ueq of the C atom to which
they were attached. For subsequent discussion of the structure, the
H-atom positions derived from the X-ray results were normalized to
standard neutron-derived values (Allen et al., 1987) along the CÐH
vector.
Experimental
1-Hydroxypyridine-2(1H)-thione (HPT) was obtained as the hy-
drated sodium salt, Na(PT)ÁxH2O, from Aldrich. The CuII complex
was prepared by the combination of aqueous solutions of CuCl2 and
Na(PT) in a 1:2 molar ratio at room temperature. The resulting green
precipitate was removed by ®ltration under gravity and dried in air at
room temperature. Attempts to prepare single crystals of (I) suitable
for X-ray diffraction using laboratory instruments were unsuccessful,
since the material consistently crystallized as ¯orets of ®ne needles.
Data were therefore collected at Station 9.8, Daresbury SRS,
England, from a needle cut from a ¯oret grown by slow evaporation
of a solution of (I) in dimethyl sulfoxide.
Data collection: SMART (Bruker, 1998); cell re®nement: LSCELL
(Clegg, 1997); data reduction: SAINT (Bruker, 1998); program(s)
used to solve structure: SHELXS97 (Sheldrick, 1997); program(s)
used to re®ne structure: SHELXL97; molecular graphics: XP in
SHELXTL (Siemens, 1996) and CAMERON (Watkin et al., 1996).
We thank the EPSRC and Avecia Ltd for funding to ADB
via a CASE studentship.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GD1171). Services for accessing these data are
described at the back of the journal.
Crystal data
3
[Cu(C5H4NOS)2]
Mr = 315.84
Triclinic, P1
a = 4.0545 (7) A
b = 7.5723 (12) A
Dx = 1.917 Mg m
Synchrotron radiation
ꢃ = 0.6884 A
Ê
Ê
Cell parameters from 1797
re¯ections
Ê
Ê
References
c = 9.0629 (14) A
ꢄ = 3.2±29.1ꢀ
ꢅ = 2.37 mm
T = 150 (2) K
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1±19.
Arch Chemicals Inc. (2000a). For details see http://www.olinbiocides.com/
Products/ZincOmadine.asp
Arch Chemicals Inc. (2000b). For details see http://www.olinbiocides.com/
Products/Copper.asp
1
ꢀ = 81.096 (4)ꢀ
ꢁ = 86.190 (4)ꢀ
ꢂ = 85.197 (4)ꢀ
Needle, green
0.04 Â 0.02 Â 0.01 mm
3
Ê
V = 273.53 (8) A
Z = 1
Barnett, B. L., Kretschmar, H. C. & Hartman, F. A. (1977). Inorg. Chem. 16,
1834±1838.
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Cernik, R. J., Clegg, W., Catlow, C. R. A., Bushnell-Wye, G., Flaherty, J. V.,
Greaves, G. N., Burrows, I., Taylor, D. J., Teat, S. J. & Hamichi, M. (1997). J.
Synchrotron Rad. 4, 279±286.
Chen, X.-T., Hu, Y.-H., Wu, D.-X., Weng, L.-H. & Kang, B.-S. (1991). Poly-
hedron, 10, 1651±1657.
Clegg, W. (1997). LSCELL. University of Newcastle-upon-Tyne, England.
Hu, Y.-H., Weng, L.-H., Huang, L.-R., Chen, X.-T., Wu, D.-X. & Kang, B.-S.
(1991). Acta Cryst. C47, 2655±2656.
Paulus, W. (1993). Microbicides for the Protection of Materials: A Handbook.
London: Chapman & Hall.
Sheldrick, G. M. (1997). SHELXL97, SHELXS97 and SADABS. University of
Data collection
Bruker SMART CCD diffrac-
tometer
Thin-slice ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
Tmin = 0.911, Tmax = 0.977
2505 measured re¯ections
1430 independent re¯ections
1074 re¯ections with I > 2ꢆ(I)
Rint = 0.044
ꢄ
max = 29.2ꢀ
h = 5 ! 5
k = 10 ! 10
l = 12 ! 12
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.061
wR(F2) = 0.161
S = 1.01
1430 re¯ections
79 parameters
H-atom parameters constrained
w = 1/[ꢆ2(Fo2) + (0.1051P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢆ)max = 0.011
3
Ê
Áꢇmax = 1.29 e A
È
Gottingen, Germany.
3
Ê
1.04 e A
Áꢇmin
=
Siemens (1996). XP in SHELXTL. Version 5.06. Siemens Analytical X-ray
Instruments Inc., Madison, Wisconsin, USA.
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical
Crystallography Laboratory, University of Oxford, England.
Wen, T.-B., Shi, J.-C., Liu, Q.-T., Kang, B.-S., Wu, B.-M. & Mak, T. C. W. (1996).
Acta Cryst. C52, 1204±1206.
Xu, Y.-J., Kang, B.-S., Chen. X.-T. & Huang, L.-R. (1995). Acta Cryst. C51,
370±374.
Note that the transmission factors of the absorption correction are
not real since they include corrections for beam decay and possibly
crystal decay (the two cannot be distinguished). The numbers listed in
the CIF are those calculated by SHELXL97 (Sheldrick, 1997). H
atoms were placed geometrically and allowed to ride during subse-
ꢁ
1158 Andrew D. Bond et al.
[Cu(C5H4NOS)2]
Acta Cryst. (2001). C57, 1157±1158