Co-ordination chemistry of 1,1′-bis(diphenylthiophosphoryl)ferrocene (dptpf) towards silver(I). Crystal structure of the polymeric complex [Ag2(μ-dptpf){(SPPh2)2CH2} 2]n[ClO4]2n

Article abstract of DOI:10.1039/a708959g

The ligand 1,1′-bis(diphenylthiophosphoryl)ferrocene, dptpf, reacted with various silver complexes to afford two-, three- or four-co-ordinate species. Thus the reaction of dptpf with [Ag(OClO₃)(PPh₃)] in 1:1 or 1:2 molar ratio gave the three-co-ordinate [Ag(dptpf)(PPh₃)]ClO₄ or the linear [Ag₂(dptpf)(PPh₃)₂][ClO₄] ₂ derivatives. Similarly, the treatment of dptpf with AgClO₄ in 2:1 or 1:1 molar ratio afforded the homoleptic compounds [Ag(dptpf)₂]ClO₄ or [Ag(dptpf)]ClO₄; in the latter dptpf acts as a trans-chelating ligand. The complex [Ag(dptpf)]ClO₄ can react further with bidentate ligands such as 2,2′-bipyridine (bipy) or bis(diphenylthiophosphoryl)methane, (SPPh₂)₂CH₂, leading to the four-co-ordinate [Ag(dptpf)(bipy)]ClO₄ or the four-co-ordinate polymeric species [Ag₂(μ-dptpf){(SPPh₂)₂CH₂} ₂]_n[ClO₄]_2n, which was characterised by X-ray diffraction.

Full text of DOI:10.1039/a708959g

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Co-ordination chemistry of 1,1Ј-bis(diphenylthiophosphoryl)ferrocene
(dptpf) towards silver(I). Crystal structure of the polymeric complex
[Ag2(ì-dptpf){(SPPh2)2CH2}2]n[ClO4]2n ‡
M. Concepción Gimeno,a Peter G. Jones,b Antonio Laguna*,†,a and Cristina Sarrocaa
a Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
b Institut für Anorganische und Analytische Chemie der Technischen Universität, Postfach 3329,
D-38023 Braunschweig, Germany
The ligand 1,1Ј-bis(diphenylthiophosphoryl)ferrocene, dptpf, reacted with various silver complexes to afford two-,
three- or four-co-ordinate species. Thus the reaction of dptpf with [Ag(OClO3)(PPh3)] in 1:1 or 1:2 molar ratio
gave the three-co-ordinate [Ag(dptpf)(PPh3)]ClO4 or the linear [Ag2(dptpf)(PPh3)2][ClO4]2 derivatives. Similarly,
the treatment of dptpf with AgClO4 in 2:1 or 1:1 molar ratio afforded the homoleptic compounds [Ag(dptpf)2]-
ClO4 or [Ag(dptpf)]ClO4; in the latter dptpf acts as a trans-chelating ligand. The complex [Ag(dptpf)]ClO4 can
react further with bidentate ligands such as 2,2Ј-bipyridine (bipy) or bis(diphenylthiophosphoryl)methane,
(SPPh2)2CH2, leading to the four-co-ordinate [Ag(dptpf)(bipy)]ClO4 or the four-co-ordinate polymeric species
[Ag2(µ-dptpf){(SPPh2)2CH2}2]n[ClO4]2n, which was characterised by X-ray diffraction.
1
The diphosphine 1,1Ј-bis(diphenylphosphine)ferrocene (dppf),
although synthesised more than two decades ago,1 has recently
received much attention in view of its chemical uniqueness and
industrial importance. The ability of this ligand to confer the
qualities of the ferrocenyl group on the resultant complexes
without disturbing the inherent characteristics of the latter has
widened the scope of metal complexes in the design of catalysts,
drugs and materials.2 One of the more important features of
dppf is its flexibility; it can modify its steric bite in order to
adapt to different geometric requirements of the metal centres.
This fact has allowed the synthesis of a great variety of com-
plexes with uncommon geometries, e.g. trigonal planar or
tetrahedral gold() derivatives,3 and is likely to play a role in the
activity of various dppf-based metalloorganic catalysts.4
The oxidation of dppf with sulfur to give the bis(diphenyl-
thiophosphoryl)ferrocene (dptpf) ligand provides a new deriv-
ative with a longer and more flexible backbone. We have previ-
ously demonstrated the bonding ability of dptpf towards AuI
or AgI by preparing the species [M(dptpf)]ϩ with dptpf acting
as a trans-chelating ligand,5 and recently the analogous copper
derivative has been obtained.6 Here we report on the co-
ordination chemistry of dptpf with silver() complexes. The use
of [Ag(dptpf)]ϩ as starting material has allowed not only the
increase in the co-ordination number of the silver centre but
the synthesis of the novel polymeric species [Ag2(µ-dptpf)-
{(SPPh2)2CH2}2]n[ClO4]2n.
anion at 1100vs (br) and 620s cmϪ1. In the H NMR spectra
three multiplets appear in the ratio 4:4:35 or 4:4:50, corres-
ponding to the α and β protons of the cyclopentadienyl ring
and to those in the phenyl groups. The 31P-{1H} NMR spectra
at room temperature show a sharp resonance for the phos-
phorus of the dptpf and a broad signal for the PPh3. At Ϫ55 ЊC
a singlet (dptpf) and two doublets (PPh3) are observed with an
approximate ratio of 2:1 or 1:1 for complexes 1 or 2, respect-
ively (see Experimental). The two doublets arise from the
coupling of the phosphorus with the two silver nuclei, 107Ag
and 109Ag. In the positive-ion liquid secondary ion mass spectra
(LSIMS) for complexes 1 or 2 the cation molecular peak
appears only for the monocationic species [Ag(dptpf)(PPh3)]ϩ
at m/z = 987 (1%). The most intense peak in both spectra is the
fragment [Ag(dptpf)]ϩ, which appears at m/z = 727.
The treatment of dptpf with AgClO4 in molar ratio 2:1 or
1:1 gives the homoleptic derivatives [Ag(dptpf)2]ClO4 3 or
[Ag(dptpf)]ClO4 4. Compound 3 is probably tetrahedral while 4,
which we have previously reported,5 has a silver centre linearly
co-ordinated by the dptpf as a trans-chelating ligand, represent-
ing the first example of this type of complex for silver.
Compound 3 is a yellow air- and moisture-stable solid that
behaves as a 1:1 electrolyte in acetone solutions. The 1H NMR
spectrum shows the resonances for the cyclopentadienyl and
phenyl ring in the appropriate ratio. The 31P-{1H} spectrum is a
singlet because of the equivalence of the phosphorus atoms. In
the positive-ion LSIMS the cation molecular peak appears at
m/z = 1345 (4%), although the most intense peak corresponds
to the fragment [Ag(dptpf)]ϩ at m/z = 727.
Results and Discussion
The reaction of dptpf with [Ag(OClO3)(PPh3)] in dichloro-
methane allows the synthesis of the three-co-ordinate [Ag-
(dptpf)(PPh3)]ClO4 1 or the linear [Ag2(µ-dptpf)(PPh3)2][ClO4]2
2 derivatives in high yield (Scheme 1). Complexes 1 and 2 are
air- and moisture-stable solids that behave as 1:1 or 1:2 electro-
lytes, respectively, in acetone solutions.
Taking into account the linear co-ordination of the silver
centre in complex 4, we surmised that this could easily react
with further ligands, increasing the co-ordination number of
the silver atom. Indeed, the reaction with bipy (2,2Ј-bipyridine)
leads to the four-co-ordinate species [Ag(dptpf)(bipy)]ClO4.
Complex 5 is an air- and moisture-stable yellow solid that
behaves as a 1:1 electrolyte in acetone solutions. Its IR spec-
trum presents, apart from the bands arising from dptpf and the
Their IR spectra are very similar and show bands arising
from the PPh3 and dptpf ligands and those of the perchlorate
anion ClO4Ϫ, the vibrations ν(C᎐N) at 1655m and 1687m cmϪ1
᎐
from the bipy ligand. The 1H NMR spectrum shows two multi-
plets for the Cp protons and four resonances, two doublets and
two virtual triplets, for the bipy protons. The positive-ion
† E-Mail: alaguna@posta.unizar.es
‡ Dedicated to Professor Pascual Royo on the occasion of his 60th
birthday.
J. Chem. Soc., Dalton Trans., 1998, Pages 1277–1280
1277

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Ph2
P
Ph2
P
Ph2
P
Ph2
P
S
S
S
S
S
S
S
(i )
(iii )
Ag
PPh3
ClO4
Fe
Fe
Ag
ClO4
Fe
Fe
P
S
P
P
P
Ph2
Ph2
Ph2
Ph2
1
3
(ii )
(iv )
Ph2
P
Ph2
P
S
S
Ag PPh3
Ag
ClO4
Fe
[ClO4]2
Fe
P
S
Ph3P Ag
S
P
Ph2
Ph2
(v)
(vi )
2
4
Ph2
P
S
2+
N
N
S
Ag
Fe
ClO4
S
S
S
P
S
Ph2
S
P
Ag
Ag
Fe
Ph2
S
[ClO4]2n + dptpf
P
Ph2
S
5
6
S
S = (SPPh2)2CH2
Scheme 1 (i) [Ag(OClO3)(PPh3)]; (ii) 2 [Ag(OClO3)(PPh3)]; (iii) ¹ AgClO4; (iv) AgClO4; (v) bipy; (vi) (SPPh2)2CH2
¯
²
LSIMS shows the cationic peak, [Ag(dptpf)(bipy)]ϩ, at
m/z = 982 (1%). Again the most intense peak corresponds to the
fragment [Ag(dptpf)]ϩ.
We have also carried out the reaction of [Ag(dptpf)]ClO4
with (SPPh2)2CH2. However, in contrast to the reaction men-
tioned above we obtained a complex of stoichiometry [Ag2-
(dptpf){(SPPh2)2CH2}2][ClO4]2 6 and the free ligand dptpf. The
1H NMR spectrum of 6 shows a triplet for the methylene pro-
tons of (SPPh2)2CH2, two multiplets for the cyclopentadienyl
protons and a multiplet for phenyl protons. The ratio is
1:1:1:15 which agrees with the proposed formula. The 31P-
{1H} NMR spectrum presents two singlets for the equivalent
phosphorus atoms of dptpf and (SPPh2)2CH2, respectively,
with an approximate ratio of 1:2. The positive-ion LSIMS
shows neither the molecular peak, [Ag2(dptpf){(SPPh2)2CH2}2]-
[ClO4]2, nor the [M]2ϩ peak as expected for dicationic species.
However some fragmentation peaks are present at m/z = 1281
(6%, [Ag2(dptpf){(SPPh2)2CH2}]ϩ), 1173 (7%, [Ag(dptpf)-
{(SPPh2)2CH2}]ϩ), 1111 (10%, [Ag2{(SPPh2)2CH2}2]ϩ) and 727
(100%, [Ag(dptpf)]ϩ).
With these spectroscopic data we imagined a dinuclear struc-
ture with two chelating (SPPh2)2CH2 and one bridging dptpf
ligand. However, when we solved the crystal structure of com-
plex 6 by X-ray diffraction, it turned out to be the polymeric
species shown in Fig. 1. It is possible that in solution complex
6 is monomeric, because it is very soluble in common
organic solvents and no higher peaks appear in the positive-ion
FAB mass spectrum. In the solid state the polymeric chain
arises through the connection of the [Ag2(dptpf){(SPPh2)2-
CH2}2]2ϩ units through one of the sulfur atoms of the
(SPPh2)2CH2 ligand (see Fig. 2).
Fig. 1 Part of the polymeric chain of the cation of complex 6 in the
crystal showing the atom numbering scheme, radii are arbitrary; H
atoms are omitted for clarity
S
S
Ag
S
S
S
S
S
S
Ag
S
Ag
S
S
Ag
S
S
S = (SPPh2)2CH2,
S
S = dptpf
Fig. 2 Formation of the polymeric complex 6 in the solid state
‘Ag2(µ-dptpf){(SPPh2)2CH2}2’ unit that repeats to form a poly-
meric chain, although the asymmetric unit is only half the for-
mula because the iron atom lies on an inversion centre. The
single independent silver atom displays a distorted tetrahedral
geometry; it is co-ordinated by a chelating (SPPh2)2CH2 ligand
The structure of the cation of 6 consists of a monomeric
1278
J. Chem. Soc., Dalton Trans., 1998, Pages 1277–1280

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were recorded on a Varian Unity 300 spectrometer and a
Bruker ARX 300 spectrometer in CDCl3. Chemical shifts are
cited relative to SiMe4 (1H, external) and 85% H3PO4 (31P,
external). The starting materials dptpf,1b [Ag(OClO3)(PPh3)]11
and (SPPh2)2CH2 12 were prepared by published procedures. All
other chemicals used were commercially available and used
without further purification. CAUTION: perchlorate salts with
organic cations may be explosive.
Table 1 Selected bond lengths (Å) and angles (Њ) for complex 6
Ag᎐S3#
Ag᎐S1
2.514(2)
2.534(2)
1.780(7)
1.817(7)
1.800(7)
1.840(7)
1.809(7)
1.822(7)
Ag᎐S2
Ag᎐S2#
P1᎐C21
P1᎐S1
2.530(2)
2.801(2)
1.804(7)
1.982(2)
1.806(7)
1.997(2)
1.816(7)
1.972(2)
P1᎐C11
P1᎐C31
P2᎐C41
P2᎐C1
P3᎐C61
P3᎐C1
P2᎐C51
P2᎐S2
P3᎐C71
P3᎐S3
Syntheses
S3#᎐Ag᎐S2
S2᎐Ag᎐S1
129.81(6)
120.23(6)
96.57(6)
106.8(3)
107.1(3)
110.6(2)
105.8(3)
107.7(3)
110.5(2)
106.3(3)
105.1(3)
111.6(2)
106.01(9)
103.95(9)
107.74(9)
S3#᎐Ag᎐S1
S3#᎐Ag᎐S2#
S1᎐Ag᎐S2#
C11᎐P1᎐C31
C11᎐P1᎐S1
C31᎐P1᎐S1
C41᎐P2᎐C1
C41᎐P2᎐S2
C1᎐P2᎐S2
C61᎐P3᎐C1
C61᎐P3᎐S3
C1᎐P3᎐S3
P2᎐S2᎐Ag
Ag᎐S2᎐Ag#
P3᎐C1᎐P2
104.99(6)
96.93(6)
98.81(6)
104.7(3)
112.9(2)
114.3(2)
109.1(3)
110.6(2)
112.8(2)
106.5(3)
111.5(2)
115.2(2)
106.91(9)
83.43(6)
117.7(4)
[Ag(dptpf)(PPh3)]ClO4 1. To a solution of [Ag(OClO3)-
(PPh3)] (0.047 g, 0.1 mmol) in dichloromethane (20 cm3) was
added dptpf (0.062 g, 0.1 mmol) and the mixture stirred for 1 h.
Concentration of the solution to ca. 5 cm3 and addition of
diethyl ether (10 cm3) gave 1 as an orange solid. Yield 80%. ΛM
142 ΩϪ1 cm2 molϪ1 (Found: C, 56.15; H, 3.96; S, 6.06. Calc. for
C52H43AgClFeO4P3S2: C, 57.40; H, 3.98; S, 5.89%). NMR data,
1H: δ 4.40 (m, 4 H, C5H4), 4.61 (m, 4 H, C5H4), 7.1–7.8 (m, 35
H, Ph); 31P-{1H}: δ 44.9 (s, dptpf), 8.1 [dd, PPh3, J(109AgP)
543.0, J(107AgP) 447.1 Hz].
S2᎐Ag᎐S2#
C11᎐P1᎐C21
C21᎐P1᎐C31
C21᎐P1᎐S1
C41᎐P2᎐C51
C51᎐P2᎐C1
C51᎐P2᎐S2
C61᎐P3᎐C71
C71᎐P3᎐C1
C71᎐P3᎐S3
P1᎐S1᎐Ag
P2᎐S2᎐Ag#
P3᎐S3᎐Ag#
[Ag2(ì-dptpf)(PPh3)2][ClO4]2 2. To a solution of [Ag(O-
ClO3)(PPh3)] (0.094 g, 0.2 mmol) in dichloromethane (20 cm3)
was added dptpf (0.062 g, 0.1 mmol) and the mixture stirred for
1 h. Concentration of the solution of ca. 5 cm3 and addition of
diethyl ether (10 cm3) gave 2 as an orange solid. Yield 89%. ΛM
253 ΩϪ1 cm2 molϪ1 (Found: C, 52.75; H, 3.67; S, 4.42. Calc. for
C70H58Ag2Cl2FeO8P4S2: C, 52.91; H, 3.71; S, 4.00%). NMR
data, 1H: δ 4.36 (m, 4 H, C5H4), 4.63 (m, 4 H, C5H4), 7.1–8.0 (m,
50 H, Ph); 31P-{1H}: δ 50.9 (s, dptpf), 17.1 [dd, PPh3, J(109AgP)
566.8, J(107AgP) 493.6 Hz].
1
–
Symmetry transformation used to generate equivalent atoms: # Ϫx ϩ 2,
3
–
Ϫy ϩ 2, Ϫz.
(atoms S2 and S3), whereby one sulfur atom (S2) also forms a
bridge to an adjacent silver atom, leading to four-membered
Ag2S2 rings with inversion symmetry. This type of co-
ordination for the (SPPh2)2CH2 ligand has not been previously
reported. A search of the Cambridge Database revealed no
other cases where one sulfur atom of the ligand co-ordinates
one, and the other two, metal atoms.7 The fourth co-ordination
site is occupied by one sulfur atom (S1) of the dptpf ligand,
which then links (via its second symmetry-related S1) the
monomeric units to form the polymer. Table 1 lists bond
lengths and angles for complex 6; three of the Ag᎐S distances
are similar Ag᎐S1 2.534(2), Ag᎐S2 2.530(2) and Ag᎐S3#
2.514(2) Å. These distances are slightly shorter than in other
tetrahedral silver complexes such as [AgBr([18]aneS6)]8 ([18]-
[Ag(dptpf)2]ClO4 3. To a dichloromethane solution (20 cm3)
of AgClO4 (0.021 g, 0.1 mmol) was added dptpf (0.124 g, 0.2
mmol) and the mixture stirred for 1 h. Evaporation of the sol-
vent to ca. 5 cm3 and addition of diethyl ether (10 cm3) gave 3 as
a yellow solid. Yield 62%. ΛM 129 ΩϪ1 cm2 molϪ1 (Found: C,
54.48; H, 4.13; S, 7.58. Calc. for C44H56AgClFe2O4P4S4: C,
54.97; H, 3.95; S, 8.38%). NMR data, 1H: δ 4.38 (m, 8 H, C5H4),
4.53 (m, 8 H, C5H4), 7.4–7.8 (m, 40 H, Ph); 31P-{1H}: δ 46.1 (s,
dptpf).
aneS6 = 1,4,7,10,13,16-hexathiacyclooctadecane)
2.636(1) Å], [Ag{(SPPh2)2CH2}{(PPh2)2C2B10H10}]ClO4
[2.514(1)–
9
[2.540(2), 2.588(2) Å], [Ag2{S2C2(CN)2}(PPh3)4]10 [2.568(7),
2.653(7) Å for the silver atom in a tetrahedral geometry]. The
other distance Ag᎐S2# is longer, 2.801(2) Å, and corresponds
to the three-co-ordinate sulfur atom; this agrees with our
proposed pathway for polymer formation. A search of the
Cambridge Database revealed 426 Ag᎐S bonds involving four-
co-ordinate silver; the bond lengths ranged from 2.360–3.008
Å. The Ag᎐S2# distance of 2.801(2) Å can thus reasonably be
regarded as a bonding interaction. Within the four-membered
ring, the independent angles are 96.57(6)Њ at Ag and 83.43(6)Њ at
S2, the Ag᎐Ag# distance is 3.554(1) Å, too long to be con-
sidered an interaction. The angles at silver vary between
96.57(6) (as above) and 129.81(6)Њ [S2᎐Ag᎐S3#]; the bite angle
of the (SPPh2)2CH2 ligand is 96.93(6)Њ. Owing to the imposed
symmetry, the cyclopentadienyl rings ideally stagger and the
phosphorus atoms are antiperiplanar.
[Ag(dptpf)(bipy)]ClO4 5. To a dichloromethane solution (20
cm3) of [Ag(dptpf)]ClO4 (0.081 g, 0.1 mmol) was added bipy
(0.011 g, 0.1 mmol) and the mixture stirred for 2 h. Evaporation
of the solvent to ca. 5 cm3 and addition of diethyl ether (10 cm3)
gave 5 as a yellow solid. Yield 78%. ΛM 133 ΩϪ1 cm2 molϪ1
(Found: C, 53.52; H, 3.78; N, 2.76; S, 6.75. Calc. for C44H26-
AgClFeN2O4P2S2: C, 53.76; H, 3.66; N, 2.85; S, 6.51%). NMR
1
data, H: δ 4.38 (m, 4 H, C5H4), 4.61 (m, 4 H, C5H4), 7.37 (t,
2 H, bipy), 7.4–7.7 (m, 20 H, Ph), 7.94 (t, 2 H, bipy), 8.27 (d,
2 H, bipy), 8.41 (d, 2 H, bipy), 31P-{1H}: δ 44.8 (s, dptpf).
[Ag2(ì-dptpf){(SPPh2)2CH2}2]n[ClO4]2n 6. To a dichloro-
methane solution (20 cm3) of [Ag(dptpf)]ClO4 (0.081 g, 0.1
mmol) was added (SPPh2)2CH2 (0.045 g, 0.1 mmol) and the
mixture stirred for 30 min. Evaporation of the solvent to ca. 5
cm3 and addition of diethyl ether (10 cm3) gave 6 as a yellow
solid. Yield 72%. ΛM 133 ΩϪ1 cm2 molϪ1 (Found: C, 52.03; H,
3.51; S, 10.01. Calc. for C84H72Ag2Cl2FeO8P6S6 (monomeric
Experimental
1
unit): C, 52.27; H, 3.76; S, 9.96%). NMR data, H: δ 4.03 (t,
Infrared spectra were recorded in the range 4000–200 cmϪ1 on a
Perkin-Elmer 883 spectrophotometer using Nujol mulls
between polyethylene sheets. Conductivities were measured in
ca. 5 x 10Ϫ4 mol dmϪ3 solutions with a Philips 9509 conduct-
imeter, C and H analyses were carried out with a Perkin-Elmer
2400 microanalyzer. Mass spectra were recorded on a VG
Autospec, with the liquid secondary-ion mass spectra (LSIMS)
technique, using nitrobenzyl alcohol as matrix, NMR spectra
4 H, CH2), 4.43 (m, 4 H, C5H4), 4.47 (m, 4 H, C5H4), 7.4–7.9
(m, 60 H, Ph); 31P-{1H}: δ 40.6 (s, dptpf), 34.2 [s, (SPPh2)2CH2].
Crystallography
The crystal was mounted in inert oil on a glass fibre and trans-
ferred to the cold gas stream of a Siemens P4 diffractometer
equipped with an LT-2 low temperature attachment. Data were
J. Chem. Soc., Dalton Trans., 1998, Pages 1277–1280
1279

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symmetry was used. The major features of residual density are
associated with one of the solvent molecules, which may be
disordered. Further details of the data collection and structure
refinement are given in Table 2.
CCDC reference number 186/911.
See http://www.rsc.org/suppdata/dt/1998/1277/ for crystallo-
graphic files in .cif format.
Table 2 Details of data collection and structure refinement for
complex 6
Compound
6ؒ3CH2Cl2
Chemical Formula
M
Crystal habit
Crystal size/mm
Crystal system
Space group
C84H72Ag2Cl2FeO8P6S6ؒ3CH2Cl2
2184.86
Orange tablet
0.75 × 0.40 × 0.12
Monoclinic
C2/c
Acknowledgements
a/Å
b/Å
c/Å
26.933(4)
11.2087(12)
31.404(3)
105.737(8)
9125(2)
4
We thank the Dirección General de Investigación Científica y
Técnica (No. PB94-0079) and the Fonds der Chemischen
Industrie for financial support.
β/Њ
U/Å3
Za
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F(000)
T/ЊC
2θmax/Њ
4424
Ϫ100
50
1.113
8146
8001
0.034
0.059
0.156
7996
526
425
0.866
2.5
µ(Mo-Kα)/mmϪ1
No. of reflections measured
No. of unique reflections
Rint
Rb [F, F > 4σ(F)]
wRc (F2, all reflections)
No. of reflections used
No. of parameters
No. of restraints
Sd
Maximum ∆ρ/e ÅϪ3
a Based on formula with one Fe atom. b R (F) = Σ||Fo| Ϫ |Fc||/Σ|Fo|. c wR
¹
(F2 ) = [Σw(Fo2 Ϫ Fc2)2/Σw(Fo )2]²;
w
Ϫ1 = σ2(Fo ) ϩ (aP)2 ϩ bP, where
2
2
7 F. H. Allen and O. Kennard, Chem. Des. Autom. News, 1993, 8, 37;
Cambridge Database, October 1997.
8 P. J. Blower, J. A. Clackson, S. C. Rawle, J. R. Hartman, R. E. Wolf,
R. Yagbasan, S. G. Bott and S. R. Cooper, Inorg. Chem., 1989, 28,
4040.
P = [Fo2 ϩ 2Fc2]/3 and a and b are constants adjusted by the program.
¹
d S = [Σw(Fo2 Ϫ Fc2)2/(n Ϫ p)]², where n is the number of data and p the
number of parameters.
9 E. Bembenek, O. Crespo, M. C. Gimeno, P. G. Jones and
A. Laguna, Chem. Ber., 1994, 127, 835.
10 D. D. Heinrich, J. P. Fackler and P. Lahuerta, Inorg. Chim. Acta,
1986, 116, 15.
11 F. A. Cotton, L. R. Falvello, R. Usón, J. Forniés, M. Tomás,
J. M. Casas and I. Ara, Inorg. Chem., 1987, 26, 1366.
12 A. B. P. Lever, E. Montavani and B. S. Ramaswany, Can. J. Chem.,
1971, 49, 1957.
13 G. M. Sheldrick, SHELXL 93, Program for Crystal Structure
Refinement, University of Göttingen, 1993.
collected using monochromated Mo-Kα radiation (λ = 0.710 73
Å), scan type ω. Cell constants were refined from setting angles
of 58 reflections in the range 2θ 7–25Њ; ψ scans displayed no
significant intensity variations, therefore no absorption correc-
tion could be applied. The structure was solved by direct
methods and refined on F2 using the program SHELXL 93.13
All non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were included using a riding model. Special refinement
details: because of the rather weak data, an effect attributable
to the dichloromethane of solvation, a system of restraints to
light-atom displacement-factor components and local ring
Received 12th December 1997; Paper 7/08959G
1280
J. Chem. Soc., Dalton Trans., 1998, Pages 1277–1280