N-Metallation of MS2N2 rings. X-ray crystal structures of [(η5-C5Me5)Ir(S 2N2)Au(PPh3)][ClO4], [{η 5-C5Me5Ir(S2N2)Au} 2 (μ2-dppm)][ClO4]2 and [Au(dppeS-P)Cl]2

Article abstract of DOI:10.1039/b306847a

Bimetallic complexes [(η⁵-C₅R₅) M(S₂N₂)Au(PPh₃)][ClO₄] and tetrametallic species [{(η⁵-C₅R₅) M(S ₂N₂)Au}₂(μ₂-P^P)][ClO ₄]₂ (R = H, M = Co; R = Me, M = Ir; P^P = dppm or dppe) can be prepared by treatment of [(η⁵-C₅R ₅)M(S₂N2)] with gold(I) electrophiles generated by chloride abstraction from [AuCl(PPh₃)] or [(AuCl) ₂(μ₂-P^P)]. X-Ray crystallography of [(η⁵-C ₅Me₅) Ir(S₂N₂)Au(PPh ₃)][ClO₄] and [{(η⁵-C₅Me ₅)Ir(S₂N₂)Au}₂(η ₂-dppm)][ClO₄]₂ confirms auration of the metal-bound nitrogen atom of the MS₂N₂ ring. π-Stacking of theMS₂N₂ rings occurs within both structures.

Full text of DOI:10.1039/b306847a

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N-Metallation of MS2N2 rings. X-ray crystal structures of
[(g5-C5Me5)Ir(S2N2)Au(PPh3)][ClO4], [{(g5-C5Me5)Ir(S2N2)Au}2
(l2-dppm)][ClO4]2 and [Au(dppeS-P)Cl]2
Stephen M. Aucott, Pravat Bhattacharyya, Heather L. Milton, Alexandra M. Z. Slawin and
J. Derek Woollins*
School of Chemistry, University of St Andrews, Fife, Scotland KY16 9ST.
E-mail: jdw3@st-and.ac.uk; Fax: +44-1334-463384; Tel: +44-1334-463861
Received (in London, UK) 16th June 2003, Accepted 1st August 2003
First published as an Advance Article on the web 29th August 2003
Bimetallic complexes [(Z5-C5R5)M(S2N2)Au(PPh3)][ClO4] and tetrametallic species [{(Z5-C5R5)
M(S2N2)Au}2(m2-P^P)][ClO4]2 (R ¼ H, M ¼ Co; R ¼ Me, M ¼ Ir; P^P ¼ dppm or dppe) can
be prepared by treatment of [(Z5-C5R5)M(S2N2)] with gold(I) electrophiles generated by chloride
abstraction from [AuCl(PPh3)] or [(AuCl)2(m2-P^P)]. X-Ray crystallography of [(Z5-C5Me5)
Ir(S2N2)Au(PPh3)][ClO4] and [{(Z5-C5Me5)Ir(S2N2)Au}2(m2-dppm)][ClO4]2 confirms auration of the
metal-bound nitrogen atom of the MS2N2 ring. p-Stacking of theMS2N2 rings occurs within both
structures.
Introduction
The chemistry of sulfur–nitrogen heterocycle and cage systems
has elicited considerable attention from both theoretical and
synthetic standpoints. The general development of this fasci-
nating area has been hampered by the paucity of stable and
easily handled S–N reagents. Thus, despite its renowned explo-
sive tendencies, tetrasulfur tetranitride (S4N4) has been the
most commonly used material for the synthesis of binary S–N
systems,1 organic heterocycles2 and metalla-sulfur–nitrogen
complexes.3,4
We recently reported the preparation of the tin(IV) disulfur-
dinitrido complex [nBu2Sn(S2N2)]2 , which shows great promise
as a metathesis reagent for the synthesis of ES2N2 (E ¼ metal
Fig. 1 Structures of complexes 1–6.
or non-metal) rings.5,6 For example [(Z5-C5Me5)Ir(S2N2)],
only the second crystallographically characterised metal
cyclopentadienyl S2N2 complex, is accessible from [(Z5-
C5Me5)IrCl2(PPh3)] or [(Z5-C5Me5)IrCl(m-Cl)]2 .6 Moreover
[(Z5-C5Me5)Ir(S2N2)] undergoes metallation at the non metal-
bound nitrogen atom by [(Z5-C5Me5)IrCl(PPh3)]+ to give [(Z5-
C5Me5)2Ir2(S2N2)Cl(PPh3)]+. Conversely, the metal-bound
nitrogen atom is the site of protonation in metal–[S2N2H]ꢀ
complexes7,8 and of metallation in [M(S2N2)(PPh3)]2 (M ¼ Pt
or Pd),9 [R2Sn(S2N2)]2 (R ¼ nBu, Me ortBu)6,10,11 and
[Ph4P]2[Ni3(S2N2)2],12 which contain M2(m2-N)2 cores.
The air- and moisture- stable complexes are soluble in dichloro-
methane, thf and acetone. The X-ray crystal structures of
[(Z5-C5Me5)Ir(S2N2)Au(PPh3)][ClO4] and [{(Z5-C5Me5)Ir(S2-
N2)Au}2(m2-dppm)][ClO4]2 (see below) confirm that metalla-
tion occurs, as expected, at the more electron-rich metal-bound
nitrogen atom. An attempt to metallate both nitrogen centres
of [(Z5-C5H5)Co(S2N2)] with two equivalents of [Au(PPh3)]+
in dichloromethane led to an intractable mixture of products.
FAB+ MS for 1 and 2 contained peaks for [(arene)M(S2-
N2)Au(PPh3)]+ at m/z 879 and 675 respectively, but the dica-
tionic complexes 3–6 were less straightforward. Peaks at m/z
813 for 3, 4 and m/z 827 for 5, 6 corresponded to
[Au2(P^P)Cl]+, with higher mass peaks of weaker intensity
for 3–5 assigned to [(P^P)Au2Cl(S2N2)M(arene)]+ (m/z 1233,
1030 and 1246 respectively). Since elemental analyses and
NMR spectroscopy have indisputably established the purity
of 1–6, we cannot explain the peculiar mass spectrometric data
for 3–6. The IR spectra of the complexes are dominated by
bands arising from the phosphine co-ligands and the perchlo-
rate anions (ca. 1100, 625 cmꢀ1), bands from the S2N2 groups
could not be assigned with certainty.
Auration of MS2N2 rings by gold(I) electrophiles has not
been previously reported. In this paper we describe the N-
metallation of [(Z5-C5H5)Co(S2N2)] and [(Z5-C5Me5)Ir(S2N2)]
by cations generated by halide abstraction from gold(I)-chlo-
ride precursors, including representative X-ray crystal structures.
Results and discussion
Chloride abstraction from [AuCl(PPh3)] and [(AuCl)2(m2-P^P)]
(P^P ¼ dppm or dppe) with silver(I) perchlorate in dichloro-
methane, followed by addition of stoichiometric quantities of
[(Z5-C5H5)Co(S2N2)] or [(Z5-C5Me5)Ir(S2N2)] generated the
heterometallic complexes 1–6 (Fig. 1) in 24–68% yields, the
The crystal structure of 1 (Fig. 2) confirms metallation of
the metal-bound nitrogen atom N(1). The IrS2N2 ring retains
its planarity,6 the N(1)–Au(1)–P(1) axis is approximately linear
dppe complexes 5,
6 being isolated in lowest yields.
1466
New J. Chem., 2003, 27, 1466–1469
DOI: 10.1039/b306847a
This journal is # The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2003

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Fig. 2 X-Ray crystal structure of 1 (C–H bonds and perchlorate
˚
counterion omitted for clarity). Selected bond lengths (A) and angles
(ꢁ) (esd’s in parentheses): Au(1)–N(1) 2.059(4), Au(1)–P(1)
2.2400(15), N(1)–S(1) 1.584(4), N(1)–Ir(1) 2.984(4), S(1)–N(2)
1.568(5), N(2)–S(2) 1.664(5), S(2)–Ir(1) 2.2060(15), N(1)–Au(1)–P(1)
173.71(12), S(1)–N(1)–Ir(1) 120.0(3), S(1)–N(1)–Au(1) 115.4(2), Ir(1)–
N(1)–Au(1) 124.6(2), N(2)–S(1)–N(1) 110.5(2), S(1)–N(2)–S(2)
116.2(3), N(2)–S(2)–Ir(1) 107.42(18), N(1)–Ir(1)–S(2) 85.81(13).
Fig. 3 X-Ray crystal structure of 3ꢂCH2Cl2 (C–H bonds, solvent
molecule and perchlorate counterions omitted for clarity).
ligands from a metal centre;5,6 we were intrigued as to whether
the gold(I) centres of [(AuCl)2(m2-P^P)] (P^P ¼ dppm or dppe)
could be linked with an [S2N2]2ꢀ unit to give nine- or ten-mem-
bered rings. To this end, [nBu2Sn(S2N2)]2 and [(AuCl)2(m2-
P^P)] (1 : 1 molar ratio) were refluxed together in thf for four
hours. 31P{1H} NMR spectra of crude reaction mixtures con-
tained one major component, characterised by two doublets
(JPP 16 Hz for dppm, 63 Hz for dppe) and several weaker sing-
lets. Gelpermeation chromatography(BiobeadsSX-8, dichloro-
methane eluant) enabled purification of the mixtures,
monitored by 31P{1H} NMR spectroscopy of 1 cm3 fractions
collected prior to, and including, the yellow eluate. Fractions
whose 31P{1H} NMR spectra did not contain doublets were
not studied further. For the dppe complex, colourless crystals
were grown from dichloromethane–hexane by solvent diffu-
sion. X-Ray crystallography revealed, unexpectedly, a dimeric
structure [Au(dppeS-P)Cl]2 (Fig. 4) i.e. one AuCl unit had
been abstracted from [(AuCl)2(m2-dppe)] and the uncoordi-
nated phosphorus(III) centre converted into the phosphorus(V)
sulfide by reaction with [S2N2]2ꢀ, two such [Au(dppeS-P)Cl]
units being linked by an Au–Au interaction. The structure of
[Au(dppeS-P)Cl]2 contains approximately linear P–Au–Cl
units [P(1)–Au(1)–Cl(1) 174.93(8)ꢁ, P(3)–Au(2)–Cl(2) 172.69(8)ꢁ]
whose axes are gauche to one another [P(1)–Au(1)–Au(2)–
Cl(2) ꢀ58ꢁ, P(3)–Au(2)–Au(1)–Cl(1) ꢀ62ꢁ]. The Au(1)–Au(2)
[173.71(12)ꢁ] with Au(1)–N(1) and Au(1)–P(1) distances of
˚
2.059(4) and 2.2400(15) A respectively. The IrS2N2 rings are
˚
stacked [interplanar separation ca. 3.4 A] in the manner
of other MS2N2 structures,7,13 but intermolecular Auꢂ ꢂ ꢂAu
interactions or close cation–anion contacts are absent.
A comparison of metallacycle bond lengths for [(Z5-
C5Me5)Ir(S2N2)], 1 and [(Z5-C5Me5)2Ir2(S2N2)Cl(PPh3)][PF6]
(Table 1), indicates that metallation appears to change the
IrS2N2 bond lengths and angles in a similar fashion to proto-
nation.8 The Ir–S(2) distances in 1 is 0.02 A longer than in
˚
5
˚
[(Z -C5Me5)Ir(S2N2)], with N(1)–S(1) ca. 0.05–0.07 A longer
in the bimetallic complexes compared to [(Z5-C5Me5)Ir(S2N2)].
N(2)–S(2) is also lengthened in the binuclear complexes.
The crystal structure of 3ꢂCH2Cl2 shows two [(Z5-
C5Me5)Ir(S2N2)] units linked by [Au2(m2-dppm)]2+ (Fig. 3),
selected bond lengths and angles appearing in Table 2. The
two N–Au–P axes [N(1)–P(1)–Au(1) 172.1(3)ꢁ, N(3)–Au(3)–
P(3) 174.9(2)ꢁ] are parallel, the IrS2N2 rings adopting a head-
to-tail stacking arrangement with respect to one another.
˚
The Au(1)–Au(3) distance [3.1931(9) A] is slightly longer than
generally found for digold(I) complexes containing a bridging
14–22
˚
diphosphine ligand [2.576–3.173 A].
The molecular con-
formation enforced by the Auꢂ ꢂ ꢂAu interaction results in a
˚
separation [3.2626(5) A] is at the upper limit of the range
rare intramolecular example of MS2N2 ring p-stacking, the
observed for unsupported (i.e. without bridging ligands)
24–31
˚
N(1)ꢂ ꢂ ꢂN(3) and S(2)ꢂ ꢂ ꢂS(4) distances being 3.56 and 3.90 A
FAB+ MS
˚
Au(I)–Au(I) contacts [3.031(1)–3.264(2) A].
respectively, additionally the face-to-face phenyl rings have
˚
for the dppm and dppe complexes contained strong peaks
at m/z 613 and 627 respectively for [Au(P^PS)]+.
an interplanar separation of 3.77 A. There is one short Auꢂ ꢂ ꢂO
˚
interaction with a perchlorate anion [Au(1)ꢂ ꢂ ꢂO(2) 3.31 A], but
In conclusion, metallation of [(Z5-C5H5)Co(S2N2)] and
[(Z5-C5Me5)Ir(S2N2)] by gold(I) electrophiles takes place at
the more electron-rich metal-bound nitrogen atom; we have
obtained bimetallic and tetrametallic complexes. X-Ray crys-
tallography reveals that the metallacycle experiences some dis-
tortion upon N-metallation but planarity of the MS2N2 ring
is retained. Furthermore, intramolecular p-stacking of the
MS2N2 rings occurs in the tetrametallic systems.
no significant intercation contacts. Compound 3 represents an
interesting oligomer or building subunit for polymeric M–S–N
organometallic chains.
We have demonstrated that [nBu2Sn(S2N2)]2 can form
MS2N2 chelate rings by metathetical exchange of cis-chloride
Table
C5Me5)Ir(S2N2)], 1 and [(Z5-C5Me5)2Ir2(S2N2)Cl(PPh3)][PF6].a
1 A
comparison of metallacycle bond lengths in [(Z5-
[(Z5-C5Me5)2Ir2
[(Z5-C5Me5)Ir(S2N2)]
1
(S2N2)Cl(PPh3)]+
Experimental
Ir–N(1)
Ir–S(2)
1.962(6)
2.175(2)
1.509(7)
1.563(9)
1.632(8)
1.983(4)
2.206(1)
1.584(4)
1.568(4)
1.664(4)
1.961(1)
2.179(2)
1.558(10)
1.531(9)
1.685(9)
Reactions were conducted under dinitrogen, subsequent proce-
dures were performed in air. Dichloromethane was dried and
distilled from calcium hydride prior to use, all other solvents
and reagents were used as received. [(Z5-C5Me5)Ir(S2N2)] and
[(Z5-C5H5)Co(S2N2)] were prepared by literature methods,6,23
chlorogold(I)–phosphine complexes were prepared by treating
N(1)–S(1)
S(1)–N(2)
N(2)–S(2)
a
N(1) and S(2) are the metal-bound atoms of the [S2N2]2ꢀ chain
New J. Chem., 2003, 27, 1466–1469
1467

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ꢁ
˚
Table 2 Selected bond lengths (A) and angles ( ) for 3.CH2Cl2 (esd’s
in parentheses)
into this solution afforded 54 mg (59%) of 3 as red crystals.
Complexes 5, 6 were crystallised from dichloromethane–
diethyl ether by solvent diffusion.
N(1)–S(1)
N(1)–Ir(1)
1.584(9)
1.983(8)
2.066(7)
2.184(3)
1.664(9)
1.561(9)
2.252(3)
N(3)–S(3)
N(3)–Ir(3)
1.608(8)
1.984(8)
2.057(7)
2.203(3)
1.668(9)
1.563(8)
2.249(3)
1 Red crystals, yield 34%. Found (calc. for C28H30AuClIr-
N2O4PS2): C 34.2 (34.3), H 2.7 (3.1), N 2.7 (2.9)%. dP : 31.7
(s). dH : 7.70–7.57 (m, 18H, Ph), 1.51 (s, 15H, C5Me5). FAB+
MS: m/z 879, [M+ ꢀ ClO4].
N(1)–Au(1)
Ir(1)–S(2)
N(3)–Au(3)
Ir(3)–S(4)
S(2)–N(2)
N(2)–S(1)
Au(1)–P(1)
N(4)–S(4)
N(4)–S(3)
Au(3)–P(3)
2 Purple crystals, yield 68%. Found (calc. for C23H20AuCl-
CoN2O4PS2): C 35.8 (35.6), H 2.45 (2.6), N 3.6 (3.6)%. dP :
30.0 (s). dH : 7.80–7.61 (m, 18H, Ph), 6.01 (s, 5H, C5H5).
FAB+ MS: m/z 675, [M+ ꢀ ClO4].
S(1)–N(1)–Ir(1)
S(1)–N(1)–Au(1)
Ir(1)–N(1)–Au(1)
N(1)–Ir(1)–S(2)
N(2)–S(2)–Ir(1)
S(1)–N(2)–S(2)
N(2)–S(1)–N(1)
N(1)–Au(1)–P(1)
N(1)–Au(1)–Au(3)
P(1)–Au(1)–Au(3)
119.8(4)
S(3)–N(3)–Ir(3)
S(3)–N(3)–Au(3)
Ir(3)–N(3)–Au(3)
N(3)–Ir(3)–S(4)
N(4)–S(4)–Ir(3)
S(3)–N(4)–S(4)
N(4)–S(3)–N(3)
N(3)–Au(3)–P(3)
N(3)–Au(3)–N(1)
Au(3)–Au(1)–P(1)
119.7(4)
115.4(4)
124.8(4)
86.1(2)
110.8(4)
129.3(4)
85.8(2)
3 Red crystals, yield 59%. Found (calc. for C45H52Au2Cl2Ir2-
N4O8P2S4): C 29.8 (29.8), H 2.5 (2.9), N 2.8 (3.1)%. dP : 26.8
(s). dH : 7.70–7.44 (m, 20H, Ph), 4.43 (t, 2H, J ¼ 15 Hz,
CH2), 2.04 (s, 30H, C5Me5). FAB+ MS: m/z, 813
[Au2(dppm)Cl]+, 1233 [Au2(dppm)Cl(S2N2)Ir(C5Me5)]+.
4 Purple crystals, yield 60%. Found (calc. for C35H32Au2Cl2-
Co2N4O8P2S4): C 29.8 (29.8), H 2.2 (2.3), N 3.7 (4.0)%. dP :
26.4 (s). dH : 7.90 (m, 8H, Ph), 7.51 (m, 12H, Ph), 5.86 (s,
1H, C5H5), 4.50 (t, 2H, J ¼ 13 Hz, CH2). FAB+ MS: m/z
813 [Au2(dppm)Cl]+, 1030 [Au2(dppm)Cl(S2N2)Co(C5H5)]+.
5 Red blocks, yield 24%. Found (calc. for C46H52Au2Cl2Ir2-
N4O8P2S4): C 31.05 (30.18), H 2.40 (2.97), N 2.89 (3.06)%. dP :
27.5 (s). dH : 7.73–7.47 (m, 20H, Ph), 3.22 (d, 4H, J ¼ 6 Hz,
CH2), 2.01 (s, 30H, C5Me5). FAB+ MS: m/z 827 [Au2(dp-
pe)Cl]+, 1246 [Au2(dppe)Cl(S2N2)Ir(C5Me5)]+.
107.6(3)
116.3(5)
110.2(4)
172.1(2)
97.2(2)
107.9(3)
116.1(5)
110.4(5)
174.9(2)
92.9(2)
88.45(7)
88.13(7)
[AuCl(tht)] (tht ¼ tetrahydrothiophen) with stoichiometric
quantities of the phosphine in dichloromethane. 31P{1H} and
1H NMR spectra (109.4 and 270.0 MHz respectively, d2-
dichloromethane) were recorded on a JEOL GSX 270 spectro-
meter, FAB+ mass spectra (3-nitrobenzyl alcohol matrix) were
carried out by the EPSRC National Mass Spectrometry
Service Centre (Swansea).
6 Purple crystals, yield 24%. Found (calc. for C36H34Au2Cl2-
Co2N4O8P2S4): C 30.24 (30.38), H 2.32 (2.41), N 3.43 (3.94)%.
dP : 28.7 (s). dH : 7.86 (m, 8H, Ph), 7.54 (m, 12H, Ph), 6.04 (s,
10H, C5H5), 3.29 (s, 4H, CH2). FAB+ MS: m/z 827 [Au2(dp-
pe)Cl]+.
CAUTION! Perchlorate salts are potentially explosive and
should be handled with care.
The general procedure employed is illustrated for 3.
To [(AuCl)2(m2-dppm)] (41 mg, 0.05 mmol) in dichloro-
methane (5 cm3) was added silver(I) perchlorate (21 mg, 0.1
mmol) and the solution stirred in the dark for 1.5 h. [(Z5-
C5Me5)Ir(S2N2)] (42 mg, 0.1 mmol) was added as a solid in
one portion and the mixture stirred for 18 h in the dark. The
grey-black mixture was filtered through Celite, which was
washed further with dichloromethane (20 cm3). The filtrate
was concentrated to ca. 1 cm3, vapour diffusion of diethyl ether
Reaction between [(AuCl)2(m2-P^P)] and [nBu2Sn-
(S2N2)]2 ; [(AuCl)2(m2-P^P)] (0.17 mmol) and [nBu2Sn(S2N2)]2
(0.17 mmol) were refluxed in thf (8 cm3) for four hours. The
solvent was evaporated in vacuo, the products extracted into
dichloromethane (2 cm3) and purified by gel permeation chro-
matography (Biobeads SX-8, dichloromethane eluant), 1 cm3
fractions collected prior to, and including, the yellow eluate
were monitored by 31P(1H} NMR spectroscopy. Fractions giv-
ing singlets in their 31P{1H} NMR spectra were discarded,
those containing a pair of doublets were combined. From the
reaction using [(AuCl)2(m2-dppe)], colourless needles of
[Au(dppeS-P)Cl]2 were grown by layering dichloromethane
solutions of the appropriate fractions with hexane.
[Au(dppmS-P)Cl]2 dP : 36.7 (d, J ¼ 16), 16.9 (d, J ¼ 16 Hz).
FAB+ MS: m/z 613, [Au(dppmS)]+.
[Au(dppeS-P)Cl]2 dP : 43.9 (d, J ¼ 63), 32.5 (d, J ¼ 63 Hz).
FAB+ MS: m/z 627, [Au(dppeS)]+.
X-ray crystallography
Single crystal diffraction studies on 1, 3ꢂCH2Cl2 and
[Au(dppeS-P)Cl]2 were performed on a Bruker SMART
CCD diffractometer at 125 K with graphite monochromated
˚
Mo-Ka radiation (l ¼ 0.71073 A). Details of data collections
and structural refinements are given in Table 3. The structures
were solved by direct methods, non-hydrogen atoms were
refined with anisotropic displacement parameters, hydrogen
atoms bound to carbon were idealised and fixed (C–H 0.95
˚
A). Structural refinements were by the full-matrix least-squares
method on F2 using the program SHELXTL.32 Crystallo-
graphic data (excluding structure factors) for the structures
reported in this paper have been deposited with the Cambridge
Crystallographic Database Centre.y
Fig. 4 X-Ray crystal structure of [Au(dppeS-P)Cl]2(C–H bonds
ꢁ
˚
omitted for clarity). Selected bond lengths (A) and angles ( ) (esd’s
in parentheses): Au(1)–P(1) 2.245(2), Au(1)–Cl(1) 2.292(2), Au(1)–
Au(2) 3.2626(5), S(2)–P(2) 1.958(3), Au(2)–P(3) 2.2359(19), Au(2)–
Cl(2) 2.2974(17), S(4)–P(4) 1.961(3), P(1)–Au(1)–Cl(1) 174.93(8),
P(1)–Au(1)–Au(2) 108.71(6), Cl(1)–Au(1)–Au(2) 75.86(6), P(3)–Au(2)–
Cl(2) 172.69(8), P(3)–Au(2)–Au(1) 110.80(5), Cl(2)–Au(2)–Au(1)
76.11(5).
y CCDC reference numbers 213795–213798. See http://www.rsc.org/
suppdata/nj/b3/b306847a/ for crystallographic data in .cif or other
electronic format.
1468
New J. Chem., 2003, 27, 1466–1469

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Table 3 Details of X-ray data collections and structural refinements for 1, 3.CH2Cl2 and [Au(dppeS-P)Cl]2
1
3.CH2Cl2
[Au(dppeS-P)Cl]2
Empirical Formula
M
C28H30AuClIrN2O4PS2
978.25
125(2)
C46H54Au2Cl4Ir2N4O8P2S4
1901.24
125(2)
C52H48Au2Cl2P4S2
1325.74
125(2)
T/K
˚
l/A
Crystal system
0.71073
Monoclinic
P2(1)/c
0.71073
Orthorhombic
Pca2(1)
0.71073
Triclinic
¯
P1
Space group
˚
a/A
˚
13.0057(17)
11.2301(15)
21.098(3)
90
32.363(8)
10.367(3)
16.838(4)
90
11.0993(8)
13.0681(10)
19.3948(14)
84.735(1)
76.483(1)
64.900(1)
2476.9(3), 2
1.778
b/A
˚
c/A
a/ꢁ
b/ꢁ
g/ꢁ
98.213(2)
90
90
90
3
˚
U/A , Z
3049.9(7), 4
2.130
9.477
5649(3), 4
2.235
10.321
Dc/Mg mꢀ3
m/mmꢀ1
F(000)
6.273
1288
1856
3584
Crystal size/mm
y range/ꢁ
Reflections collected
Independent reflections (Rint
Goodness-of-fit on F2
R1, wR2
0.1 ꢃ 0.1 ꢃ 0.1
1.58–23.29
14 834
0.25 ꢃ 0.15 ꢃ 0.06
1.96–23.33
23 332
0.18 ꢃ 0.1 ꢃ 0.1
2.02–23.36
12 636
)
4361 (0.0470)
0.955
0.0233, 0.0464
7349 (0.0473)
0.952
0.0259, 0.0632
7038 (0.0410)
0.900
0.0364, 0.0713
15 R. Uson, A. Laguna, M. Laguna, M. N. Fraile, P. G. Jones and
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Acknowledgements
We are grateful to the EPSRC (S. M. A., P. B.) and the
University of St. Andrews (H. L. M.) for funding.
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