Syntheses and structures of adducts of stoichiometry MX:dpex (2:1) (n), M = CuI, AgI, X = (pseudo-) halogen, dppx = Ph2E(CH2)xEPh2, E = P, As

Article abstract of DOI:10.1016/j.ica.2005.06.011

Single crystal X-ray studies have defined the structures of a number of adducts of the form MX:dpex (2:1), M = univalent coinage metal (Cu, Ag), X = (pseudo-)halide, dpex = bis(diphenylpnicogeno)alkane, Ph₂E(CH ₂)_xEPh₂, E = P, As, of diverse types, some novel. The adducts of AgCl,Br:dppm and AgNCO:dpem (x = 1) are tetranuclear as is the AgNO₃:dppp (x = 3) array, all derivative of the familiar 'step' structure while the combination CuCN:dppm yields a two-dimensional web of twenty-membered macro/metallacycles. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution ( ¹H, ¹³C, ³¹P NMR, ESI MS) and in the solid state (IR).

Full text of DOI:10.1016/j.ica.2005.06.011

Inorganica Chimica Acta 359 (2006) 53–63
www.elsevier.com/locate/ica
Syntheses and structures of adducts of stoichiometry
MX:dpex (2:1)(n), M = CuI, AgI, X = (pseudo-) halogen,
dppx = Ph2E(CH2)xEPh2, E = P, As
a
a,
c
Corrado Di Nicola , Effendy b,c, Claudio Pettinari *, Brian W. Skelton ,
c
c
Neil Somers , Allan H. White
a
`
Dipartimento di Scienze Chimiche, Universita degli Studi di Camerino, via S. Agostino 1, 62032 Camerino, MC, Italy
b
Jurusan Kimia, FMIPA Universitas Negeri Malang, Jalan Surabaya 6, Malang 65145, Indonesia
c
Chemistry M313, University of Western Australia, Crawley, WA 6009, Australia
Received 20 April 2005; accepted 13 June 2005
Available online 27 October 2005
Abstract
Single crystal X-ray studies have defined the structures of a number of adducts of the form MX:dpex (2:1), M = univalent coin-
age metal (Cu, Ag), X = (pseudo-)halide, dpex = bis(diphenylpnicogeno)alkane, Ph2E(CH2)xEPh2, E = P, As, of diverse types,
some novel. The adducts of AgCl,Br:dppm and AgNCO:dpem (x = 1) are tetranuclear as is the AgNO3:dppp (x = 3) array, all
derivative of the familiar ꢀstepꢁ structure while the combination CuCN:dppm yields a two-dimensional web of twenty-membered
macro/metallacycles. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solu-
tion (1H, 13C, 31P NMR, ESI MS) and in the solid state (IR).
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Silver; 31P NMR; X-ray crystal structure; Diphosphine; Copper; Complexes; Spectroscopy
1. Introduction
clear [M(l-X)2(l-E-dpex-E0)2M0] (AgO2CPh:dppf) [7],
and tetranuclear ꢀstepꢁ structures for dppm (x = 1) with
CuCl [8,9], Br [10–12], I [10,11] and AgCl [13]; there are
also numerous less immediately relevant examples
involving gold(I). Polymeric forms are also evident in
the adducts Cu(ac):dppe (x = 2) [14], Ag(ac):dppm [15]
(ac = acetate) and AgNO3:dpae [16], all complexes
involving bridging oxyanion units.
Previous contributions [1–6] in the present sequence
have described the structural characterization of adducts
of stoichiometry MX:dpex (1:1) [1–5] or (2:3)(n) [6],
M = univalent coinage metal (copper(I), silver(I)),
X = simple anion, usually (pseudo-)halide or, where
possible, oxyanions ClO4, NO3, carboxylate (spanning
a
range of basicities), dpex = Ph2E(CH2)xEPh2,
In the course of our preceding studies, primarily
directed at the definition of arrays of 1:1 MX:dpex stoi-
chiometry, we have found that the crystallization of
solutions of that stoichiometry have, on occasion,
yielded (usually poorly) crystalline materials of other
stoichiometries, a number of those of the augmented
(2:3) stoichiometry being described in the preceding
paper [6]. Herein, we describe a number of adducts we
have encountered, of diminished MX:L stoichiometric
bis(diphenylpnicogeno)-alkane (or, on occasion,
bis(diphenylphosphino)-ferrocene, ꢀdppfꢁ) [5]. Adducts
of these combinations with the stoichiometry 2:1 are
rather rare in the literature, being manifested by binu-
*
Corresponding author. Tel.: +39 0737 402234; fax: +39 0737
637345.
E-mail address: claudio.pettinari@unicam.it (C. Pettinari).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.06.011

54
C. Di Nicola et al. / Inorganica Chimica Acta 359 (2006) 53–63
ratio, normally 2:1, both with copper(I) and silver(I)
salts, with diverse dpex, yielding structures mostly deriv-
ative of the tetranuclear ꢀstepꢁ form.
417 Hz). IR (nujol, cmꢀ1): 3045w, 1583w, 1573w,
1482m, 553m, 520s, 505s, 469s, 443m, 431m, 416m,
363w, 351w, 193w, 177w, 152w, 121w, 107w, 98w, 90w,
78w, 71w. ESI MS (+): 680 [50] [Ag2Br(dppm)]+, 1064
[1 0 0] [Ag2Br(dppm)2]+; Anal. Calc. for C25H22Ag2-
Br2P2: C, 39.51; H, 2.92. Found: C, 39.73; H, 3.01%. Km
(CH2Cl2, 10ꢀ3 M): 12 Xꢀ1 mol2 cmꢀ1. Crystals for the
X-ray work were obtained from 2-mpy.
2. Experimental
2.1. Materials and methods
All syntheses, handling and measurements were car-
ried out as described in the preceding paper [6]. For
the ESI-MS data, masses and intensities were compared
to those calculated by using the IsoPro Isotopic Abun-
dance Simulator Version 2.1 [17]; peaks containing
silver(I) ions are identified as the centres of isotopic
clusters.
2.2.4. AgNCO:dppm (2:1)2 Æ 2MeCN (3)
The dppm (0.38 g, 1.0 mmol) was added at room tem-
perature to an acetonitrile solution (15 ml) of AgNCO
(0.30 g, 2.0 mmol). After the addition, a colorless precip-
itate immediately formed and the suspension was stirred
for 1 h. The precipitate was filtered off and washed with
MeCN to give complex 3 as a pale-brown crystalline
1
solid in 85% yield. M.p. 270 ꢁC dec. H NMR (CDCl3,
2.2. Syntheses
293 K): d 2.0 (s, 3H, CH3CN), 3.4 (pt, 2H, PCH2P),
7.3 (m, 12H, C6H5), 7.5 (m, 8H, C6H5). 31P{1H}
1
2.2.1. Syntheses of the silver complexes
NMR (CDCl3, 293 K): d 9.0 (d, J(31P,Ag) = 658 Hz).
The colourless complexes described were obtained by
crystallization, by slow evaporation and/or cooling, of
solutions of millimolar stoichiometry of AgX or CuCN
with dpex in a few ml of the specified solvent.
IR (nujol, cmꢀ1): 3052w, 2170s (CNO), 2143 (CN),
1589w, 1569w, 1481m, 552w, 519s, 505m, 480s, 474s,
449m, 439s, 420m, 335m, 317m, 255m, 209w, 151m,
109m, 96w, 85w, 71w. ESI MS (+): 492 [30]
[Ag(dppm)]+, 642 [5] [Ag2(CNO)(dppm)]+, 1026 [75]
[Ag2(CNO)(dppm)2]+; 1544 [1 0 0] [Ag3(CNO)(CN)-
(dppm)3]+. Anal. Calc. for C29H25Ag2N3O2P2: C,
48.03; H, 3.47; N, 5.79. Found: C, 47.73; H, 3.53; N,
2.2.2. AgCl:dppm (2:1)2 (1)
The dppm (0.38 g, 1.0 mmol) was added at room tem-
perature to a pyridine solution (10 ml) of AgCl (0.29 g,
2.0 mmol). After the addition, a colorless precipitate
immediately formed and the suspension was stirred for
2 h. The precipitate was filtered off and washed with
MeCN to give complex 1 as a colourless crystalline solid
5.42%. Km (CH2Cl2, 10ꢀ3 M): 1.3 Xꢀ1 mol2 cmꢀ1
.
2.2.5. AgNCO:dpam (2:1)2 (4)
The dpam (0.47 g, 1.0 mmol) was added at room tem-
perature to an ethanol solution (15 ml) of AgNCO
(0.30 g, 2.0 mmol). After the addition, a colorless precip-
itate immediately formed and the suspension was stirred
for 1 h. The precipitate was filtered off and washed with
MeCN to give complex 4 as a colorless crystalline solid
in 60% yield. M.p. 300 ꢁC dec. 1H NMR (CDCl3,
293 K): d 2.8 (s, 2H, AsCH2As), 7.3 (m, 12H, C6H5),
7.5 (m, 8H, C6H5). IR (nujol, cmꢀ1): 3052w, 2170s
(CNO), 1592w, 1579w, 553w, 474m, 456m, 411w,
372m, 312m, 269w, 202w, 195w, 150w, 119w, 109w,
99w, 89w, 75w. ESI MS (+): 730 [10+ [Ag2(CNO)
(dpam)]+, 1202 [75] [Ag2(CNO)(dpam)2]+; 1544 [1 0 0]
[Ag3(CNO)2(dpam)3]+. Anal. Calc. for C27H22Ag2N2-
O2As2: C, 42.00; H, 2.87; N, 3.63. Found: C, 41.86; H,
1
in 95% yield. M.p. 319–324 ꢁC dec. H NMR (CDCl3,
293 K): d 3.4 (br, 2H, PCH2P), 7.2–7.7 (2m br, 20H,
C6H5). 31P{1H} NMR (CDCl3, 293 K): d 4.6 (d br,
1
1J(31P,Ag) = 637 Hz) ꢀ2.8 (d br, J(31P,Ag) = 446 Hz).
IR (nujol, cmꢀ1): 3071w, 3046w, 1586w, 1481m, 552m,
521s, 505s, 482s, 474s, 448s, 438m, 423w, 384w, 313w,
179w, 149w, 126w, 106w, 96w, 89w, 74w. ESI MS (+):
635 [50] [Ag2Cl(dppm)]+; 1019 [1 0 0] [Ag2Cl(dppm)2]+;
1163 [40] [Ag3Cl2(dppm)2]+, 1548 [5] [Ag3Cl2(dppm)3]+.
Anal. Calc. for C25H22Ag2Cl2P2: C, 44.75; H, 3.30.
Found: C, 44.45; H, 3.15%. Km (CH2Cl2, 10ꢀ3 M):
11.2 Xꢀ1 mol2 cmꢀ1. Crystals for the X-ray work were
obtained from 2-methylpyridine (2-mpy).
2.2.3. AgBr:dppm (2:1)2 (2)
2.93; N, 3.53%. Km (CH2Cl2, 10ꢀ3 M): 1.1 Xꢀ1 mol2 cmꢀ1
.
The dppm (0.38 g, 1.0 mmol) was added at room tem-
perature to a pyridine solution (10 ml) of AgBr (0.38 g,
2.0 mmol). The solution was stirred for 48 h and then
slowly evaporated until a colourless precipitate formed
which was washed with Et2O to give compound 2 as a col-
ourless solid in 75% yield. M.p. 346–348 ꢁC dec. 1H NMR
(CDCl3, 293 K): d 3.4 (br, 2H, PCH2P), 7.0–7.8 (4m br,
20H, C6H5). 31P{1H} NMR (CDCl3, 293 K): d 1.4 (d
br, 1J(31P,Ag) = 595 Hz) ꢀ4.8 (d br, 1J(31P,Ag) =
Crystals for the X-ray work were obtained from 2-mpy.
2.2.6. AgNO3:dppp (2:1)2 (5)
The dppp (0.47 g, 1.0 mmol) was added at room tem-
perature to a methanol solution (15 ml) of AgNO3
(0.30 g, 2.0 mmol). After the addition, a colorless precip-
itate immediately formed and the suspension was stirred
for 12 h. The precipitate was filtered off and washed with
MeOH to give complex 5 as a colorless crystalline solid

C. Di Nicola et al. / Inorganica Chimica Acta 359 (2006) 53–63
55
1
in 70% yield. M.p. 282–287 ꢁC dec. H NMR (CDCl3,
293 K): d 1.96 (m, 2H, CH2CH2CH2), 2.4 (m, 4H,
CH2CH2CH2), 7.4 (m, 12H, C6H5), 7.5 (m, 8H, C6H5).
31P{1H} NMR (CDCl3, 293 K): d 11.0 (br). 31P{1H}
NMR (CDCl3, 223 K): d 10.97 (dd 1J(31P,107Ag) =
728 Hz, 1J(31P,109Ag) = 836 Hz). IR (nujol, cmꢀ1):
3071w, 2046w, 1586m, 1481m, 1436s, 1299s (NO3),
552m, 521s, 505s, 482s, 474s, 448s, 438m, 423w, 384w,
313w, 179w, 149w, 126w, 106w, 96w, 89w, 74w. ESI
MS (+): 690 [10] [Ag(NO3)(dppp)]+; 1102 [1 0 0]
[Ag2NO3(dppp)2]+. Anal. Calc. for C27H22Ag2N2O6P2:
C, 43.11; H, 3.48; N, 3.72. Found: C, 42.81; H, 3.69;
(Rint = 0.042), Noꢀ=3 5091; R = 0.038, Rw = 0.049.
˚
|Dqmax| = 1.4(1) e A
.
Variata. The above chloride and bromide are not
isomorphous; the latter, also, is not isomorphous with
the other crystallographically defined orthorhombic
form of the chloride (Pbca, a = 15.945, b = 17.400,
c = 17.666 Aꢀ3) [13], although derivative of it. (Note
˚
that the potential centre of symmetry in the present tet-
ramer is violated by the orientations of the phenyl rings
on P(1,3)).
2.3.3. AgNCO:dppm (2:1)2 Æ 2MeCN, 3
N, 3.77%. Km (CH2Cl2, 10ꢀ3 M): 15 Xꢀ1 mol2 cmꢀ1
.
C58H50Ag4N6O4P4, M = 1450.4. Monoclinic, space
group P21/n (C52h, No. 14; variant), a = 11.256(2),
˚
2.2.7. CuCN:dppm (2:1)(1|1) (6)
b = 13.709(2), c = 17.678(2) A, b = 92.794(2), V =
3
2724 A . Dc (Z = 2 tetramers) = 1.768 g cmꢀ3. lMo
=
˚
The dppm (0.38 g, 1.0 mmol) was added at room tem-
perature to an acetonitrile solution (15 ml) of CuCN
(0.18 g, 2.0 mmol). After the addition, a colorless precip-
itate immediately formed and the suspension was stirred
for 12 h. The precipitate was filtered off and washed with
MeOH to give complex 6 as a colorless crystalline solid
15.9 cmꢀ1
;
specimen:
0.15 · 0.12 · 0.10
mm;
Tmin/max = 0.86. 2hmax = 58ꢁ; Nt = 31345, N = 6946
(Rint = 0.033), No = 5510; R = 0.026, Rw = 0.026.
|Dqmax| = 0.77(9) e Aꢀ3. (x,y,z,Uiso H
)
refined.
˚
Variata. NCO(2) was modelled as disordered over
two sites, pivoted about N, C, O being assigned site
occupancies of 0.5 after trial refinement, the nitrogen
seemingly the coordinated atom in both orientations.
The possibility that ꢀNCO(2)ꢁ is actually MeCN was
considered and rejected. (Note that lattice acetonitrile
hydrogen atoms were refinable in (x,y,z,Uiso).)
1
in 56% yield. M.p. 227–234 ꢁC dec. H NMR (CDCl3,
293 K): d 3.0 (br, 2H, PCH2P), 6.4–7.8 (m br, 20H,
C6H5). 31P{1H} NMR (CDCl3, 293 K): d ꢀ16.4,
ꢀ14.7, ꢀ13.1 (s). 31P{1H} NMR (CDCl3, 223 K): d
ꢀ14.0 (br). IR (nujol, cmꢀ1): 3052m, 2124m, 2071w,
1586w, 1573w, 1482s, 553w, 531m, 518s, 507s, 476s,
471s, 452m, 421s, 409s, 389m, 357m, 324m, 217w,
208w, 181w, 171w, 157w, 137w, 128w, 106w, 86m,
80m. Anal. Calc. for C27H22Cu2N2P2: C, 57.55; H,
3.83; N, 4.97. Found: C, 57.64; H, 3.81; N, 4.82%. Km
2.3.4. AgNCO:dpam (2:1)2, 4
C54H44Ag4As4N4O4, M = 1544.1. Monoclinic, space
group P21/n, a = 11.3915(9), b = 16.234(1), c =
(CH2Cl2, 10ꢀ3 M): 0.5 Xꢀ1 mol2 cmꢀ1
.
14.609(1) A, b = 109.266(1)ꢁ, V = 2550 A . Dc (Z = 2
3
˚
˚
tetramers) = 2.010 g cmꢀ3
. l ; specimen:
Mo = 41 cmꢀ1
2.3. Structure determinations
cuboid, 0.1 mm; Tmin/max = 0.88. 2hmax = 58ꢁ; Nt =
29886, N = 6294 (Rint = 0.024), No = 5017; R = 0.024,
Rw = 0.022. |Dqmax| = 0.7(1) e Aꢀ3. (x,y,z,Uiso H
)
refined.
˚
General procedural details are outlined in the preced-
ing paper [6], CCD data obtained at ca. 153 K being
used in all cases; specific details are as follows (CCDC
depositions: 249378–249383):
2.3.5. AgNO3:dppp (2:1)2, 5
C54H52Ag4N4O12P4, M = 1504.4. Monoclinic, space
group P21/c (C52h, No. 14), a = 15.239(2), b = 14.002(2),
3
˚
˚
2.3.1. AgCl:dppm (2:1)2, 1
C50H44Ag4Cl4P4, M = 1342.1. Triclinic, space group
c = 26.304(4) A, b = 94.562(4)ꢁ, V = 5595 A . Dc (Z =
4 tetramers) = 1.786 g cmꢀ3. lMo = 18.6 cmꢀ1; speci-
1
ꢀ
P1 (Ci , No. 2), a = 13.3759(9), b = 13.7304(9), c =
men: 0.29 · 0.25 · 0.18 mm; Tmin,max = 0.80. 2hmax =
˚
16.2990(11) A, a = 86.335(2)ꢁ, b = 66.207(2)ꢁ, c =
50ꢁ; Nt = 114237, N = 9860 (Rint = 0.058), No = 8198;
3
ꢀ3
˚
˚
66.536(2)ꢁ, V = 2496 A . Dc (Z = 1 tetramer) =
1.786 g cmꢀ3. lMo = 19.2 cmꢀ1; specimen: 0.20 · 0.18 ·
0.18 mm; Tmin/max = 0.81. 2hmax = 65ꢁ; Nt = 36026,
N = 17739 (Rint = 0.046), No = 11408; R = 0.048,
R = 0.051, Rw = 0.069. |Dqmax| = 2.82(4) e A
.
2.3.6. CuCN:dppm (2:1)(1|1), 6
C27H22Cu12N2P2, M = 563.5. Monoclinic, space
ꢀ3
group C2 (C3 ;2, No. 5), a = 16.943(2), b = 8.2744(8),
˚
Rw = 0.056. |Dqmax| = 1.7(1) e A
.
3
˚
˚
c = 9.2263(9) A, b = 107.671(2)ꢁ, V = 1232 A . Dc
(Z = 2 f.u.) = 1.518 g cmꢀ3. lMo = 18.7 cmꢀ1; specimen:
0.24 · 0.16 · 0.09 mm; Tmin,max = 0.91. 2hmax = 68ꢁ;
Nt = 9246, N = 2300 (Rint = 0.016), No = 2163; R =
2.3.2. AgBr:dppm (2:1)2, 2
C50H44Ag4Br4P4, M = 1519.9. Orthorhombic, space
group Pca21 (C52v, No. 29), a = 16.671(2), b = 17.210(2),
3
ꢀ3
˚
˚
˚
c = 17.367(2) A, V = 4983 A . Dc (Z = 4) = 2.026
g cmꢀ3. lMo = 49 cmꢀ1; specimen: 0.13 · 0.13 · 0.12
mm; Tmin/max = 0.77. 2hmax = 58ꢁ; Nt = 46707, N = 6484
0.023, Rw = 0.028. |Dqmax| = 0.45(6) e A .
Variata. Refinement behaviour suggests a preferred
orientation for the CN group.

56
C. Di Nicola et al. / Inorganica Chimica Acta 359 (2006) 53–63
3. Results and discussion
When the reaction between dppm and CuCN was
carried out in the presence of a large excess of the copper
salt, the 2:1 CuCN:dppm adduct 6 formed (Fig. 2). This
compound shows a lower solubility relative to the com-
plexes 1–5, which prevents full characterization in solu-
tion; its poor solubility in ionizing solvents is in
accordance with the polymeric nature defined in the
solid state (see below).
3.1. Syntheses
The reaction in solution at room temperature of two
equivalents of AgX (X = NCO, Cl, Br) with one equiv-
alent of bis(diphenylphosphino)methane (dppm) has
given rise to tetra-nuclear 2:1 adducts AgX:dppm 1–3
(Fig. 1). The adducts AgNCO:dpam (2:1) 4 and
AgNO3:dppp (2:1) 5 have been prepared similarly by
reaction of the silver salt with corresponding di-arsine
or di-phosphine donor (Fig. 1). The ligand to metal ratio
employed is important for the syntheses of the com-
pounds, different species being generally formed when
equimolar quantities, or donor excesses were employed.
For example, when the reaction between dppm and
AgNCO was carried out in an equimolar ratio, the pre-
viously reported trinuclear [Ag3(dppm)3(NCO)3] species
formed. The choice of the solvent is also important: the
adducts 1 and 2 can be obtained only in pyridine-type
solvents, whereas in MeCN from the same reactions
adducts of stoichiometries 1:1 were formed.
Compounds 1–5 are generally air-stable, colorless
materials, moderately soluble not only in strongly ioniz-
ing solvents such as DMSO, dimethylformamide and
acetone, but also in chlorinated solvents such as CH2Cl2
or CHCl3. Solid samples of 3 and 4 show sensitivity to
light, whereas all the other species are essentially stable
in the solid state. Conductivity measurements, as
expected, indicated that 1–5 are non-electrolytes or
partly ionized in dichloromethane, Km being always in
the range 1–15 Xꢀ1 cm2 molꢀ1. This suggest a strong
interaction between Ag and the halide, pseudohalide
or nitrate counterion also in solution.
3.2. Spectroscopy
The infrared spectra of 1–6 (see Section 2) are consis-
tent with the formulations proposed, showing all of the
bands required by the presence of the counter-ion and of
the phosphorus or arsenic donor [18], the bands due to
the phosphine and arsine ligands being only slightly
shifted with respect to those of the free donors. In the
far-IR spectra of derivatives 1–6 the broad absorptions
near 500 cmꢀ1 and those at 450–400 cmꢀ1 are probably
due to Whiffenꢁs y and t vibrations, respectively. The
absorptions in the region 2140–2040 due to CN, and
NCO groups are in accordance with those reported in
the literature for bridging pseudohalide groups [19,20].
No band has been detected at low frequencies that can
be assigned unequivocally to any M-halide stretching
vibration, as expected for strongly bonded bridging
halide groups.
In the 1H NMR spectra of 1–5 in CDCl3 (see Section
2), the signals due to the diphosphine and diarsine
ligands show different patterns with respect to those
found for the free donors, confirming the existence of
complexes in solution. The bridging methylene reso-
nances in 1–5 appear as a broad singlet or resolved
multiplet between 2.50 and 3.30 ppm generally down-
X
M
X
OCN
M
M
P
M
NCO
X
M
OCN
M
M
Cu
N
C
N
C
M
X
NCO
C
N
C
H2C
N
N
Cu
P
Cu
P
1: X = Cl
3
2: X = Br
4: X = NCO
CH2
Ph
O
Ph
O
N
O
P
P
Ph
Ph
P
P
P
Ag
Ag
O
Cu
Cu
O
N
N
C
C
O
O
N
O
O
C
N
C
N
Cu
P
Ag
Ag
O
P
O
N
Ph
Ph
Ph
Ph
O
5
Fig. 1. Structures of the compounds 1–5.
Fig. 2. Polymeric structure of compound 6.

C. Di Nicola et al. / Inorganica Chimica Acta 359 (2006) 53–63
57
field shifted with respect to those found in the free
donors.
(X = Cl, Br, I) combinations with unidentate group 15
ligands; in this form central and peripheral pairs of M
and of X atoms may be defined. The central M and X
atoms are normally regarded as three-coordinate, leav-
ing the M atom with the potential to coordinate a fourth
unidentate ligand, while the peripheral M and X are
two-coordinate, leaving the M atom potentially capable
of coordinating up to two further donors. This possibil-
ity may be fully realized in rare MX:L (unidentate) [1]
(4:6) adducts, e.g., CuI: 2-methylpyridine, the pair of
peripheral adducts occupying both ꢀaxialꢁ and ꢀequato-
rialꢁ sites [22]; usually such adducts are of 4:4 stoichiom-
etry, in which case the peripheral substituent is normally
ꢀaxialꢁ, in contrast to the infinite polymeric ꢀstairꢁ struc-
ture where all substituents are ꢀequatorialꢁ, the ꢀaxialꢁ
sites being occupied by polymer-extending linkages. In
the simple MX:unidentate L (4:4) examples of the chair
[23], the peripheral metal atoms are normally three-
coordinate, leaving a fourth potential coordination site
more or less exposed and remaining thus in the course
of crystallization with excess of coordinating ligand or
solvent, presumably, in the common examples because
The 31P NMR room temperature spectra of com-
pounds 1–3 (CDCl3 solution) exhibit two broad dou-
blets, shifted downfield with respect to the signal of
the free donor. This suggests that in this case rapid
exchange equilibrium between the coordinated and the
free dppm is not occurring. The relative intensities of
the two doublets are concentration dependent. The mag-
nitudes of the J(31P,Ag) coupling constants (ꢁ600 Hz)
in the first doublet are in accordance with the presence
of silver centres coordinated by a single phosphorus
atom, whereas the second doublets, characterized by
1J(31P,Ag) coupling constants of ca. 400 Hz, are typical
of trinuclear [Ag3X2(dppm)3]+ and dinuclear [Ag2X2-
(dppm)2] [1–5] species containing AgP2 components.
By contrast, at room temperature the CDCl3 NMR
spectrum of 5 exhibits a broad signal which becomes a
double doublet at low temperature, consistent with the
abundances and gyromagnetic ratios for 107Ag and
109Ag. The coupling constant values for this compound
are the highest hitherto observed for silver(I) diphosph-
ino complexes, suggesting not only a strong interaction
in solution between donors and the acceptors but also
confirming that only one P atom of each donor is coor-
dinated to each silver centre [21].
`
of the relative bulk of the extant substituent vis-a-vis
any second ligand or coordinating solvent capable of
coordinating further. With bidentate dpex, here, nota-
bly, dppm, the ligand usually spans peripheral and cen-
tral metal atoms, the archetypical forms previously
described in the CuX (X = Cl, Br, I):dppm (4:2) [7–12]
and AgCl:dppm (4:2) [13] adducts, the latter, here,
recorded in a new polymorph, together with its bromide
counterpart (Fig. 3(a)), the ligands spanning and coordi-
nating at central and peripheral sites; as with the uniden-
tate 4:4 complexes this does not necessarily pre-empt
polymer formation, but nevertheless presumably hinders
it, similarly, with access only possible in some circum-
stances to additional strongly coordinating ligands of
small steric profile, such as acetonitrile. Topologically,
the ꢀstepꢁ structure may be regarded as a ꢀcubeꢁ structure,
severed along the centre of one face and unfolded; per-
haps unsurprisingly, with relatively minor perturbations
in respect of any or all of M, X, L or, even, lattice forces,
it appears readily susceptible of ꢁdistortionꢁ to other
conformations. Thus, with the ligand dppNH =
P2PNH-PPh2, the 4:2 AgBr adduct takes a form [(l2-Br)-
(l3-Ag)2(l4-Br)2(l3-Ag)2(l2-Br)] with an ꢀoctahedralꢁ
core, the four equatorial silver atoms spanned pairwise
to either side by the l2-bromines, and on the other equa-
torial edges by the dppNH ligands [24], while at a more
fundamental level, one phase of CuCl:dppm (4:2) has
very long Mꢂ ꢂ ꢂX distances within the central M2X2
rhomb [9] (see below).
The positive electrospray mass spectra of 1–5 (the
most relevant data are reported in Section 2) suggest
the non-existence of the tetranuclear species in acetoni-
trile solution, i.e., considerable dissociation in that sol-
vent. It is noteworthy that the major peaks in the
positive spectra of all species always arise from the cat-
ionic species [M2(dpex)2X]+, consequent upon the
breaking of bridging bonds, and the loss of X counter-
ions. In some cases peaks due to dinuclear species
[M2(dpax)X]+ have been detected; [M3(dpex)3X2]+ and
[M3(dpex)2X2]+ have been also observed. Molecular
weight data of 1 in both CHCl3 (930) and CH2Cl2
(925) suggested substantial dissociation in solution.
As reported in the previous papers [1–5] the negative
electrospray spectra are always dominated byꢀthe pres-
ence of molecular peaks due to Xꢀ and AgX2
.
3.3. Single crystal X-ray studies
A number of adducts of simple silver(I) salts MX have
been crystallized with various L = dpex ligands, of gross
stoichiometry MX:L (2:1), their structures defined by sin-
gle crystal X-ray methods, in a diversity of oligo- and
poly-meric forms. The oligomers are, in fact all tetra-
mers, all more or less derivative of the familiar ꢀchairꢁ
or ꢀstepꢁ structure, and we discuss them first in order of
increasing complexity, with a final description of a cop-
per(I) adduct which adopts a different (polymeric) form.
Archetypical examples of the ꢀstepꢁ tetramer have
been described for a considerable variety of M/X
Cyanate (NCO) has been little explored as a pseudo-
halide X in MX:L adducts of the present or any related
or derivative form, and in the present work, a pair of
(centrosymmetric) adducts of this stoichiometry have
been defined with silver for both dppm and dpam, these

58
C. Di Nicola et al. / Inorganica Chimica Acta 359 (2006) 53–63
Fig. 3. (a) Projection of tetranuclear AgBr:dppm (4:2), 2. (b) Projection of tetranuclear AgNCO:dpam (4:2), 4. (c) Projection of the tetranuclear
AgNCO:dppm (4:2), 3, showing the approaches of the associated pair of acetonitrile solvent molecules. NCO(2) is disordered over two sets of sites of
equal occupancy.
being AgNCO:dpem (4:2); 3, 4 the dpam adduct is
unsolvated and more obviously (derivative) of the step
form, the dppm adduct being solvated by acetonitrile
which interacts weakly with the substrate. The two
adducts are depicted in Fig. 3(b,c), their geometries
being presented comparatively in Table 1. They provide
a focus of particular interest in displaying the break-
down/buildup relationship between the ꢀstepꢁ structure
and a more open array, and the possible role of solvent
interactions in such a process. Interestingly, it is the cen-
tral plane which is preserved at the expense of the
peripheral, the geometries within indicative of tighter
binding; the disruption is associated with enhanced
Ag–E interaction in the dppm adduct, with the periphe-
ral silver atom environment becoming quasi-linear.
Complete linearity presumably is not found because of
residual interactions within the cluster, and, in the case
of the dppm adduct, solvation by acetonitrile, the sol-
vating molecules approaching and perturbing the geom-
˚
etry: Ag(2)ꢂ ꢂ ꢂN(31) 3.140(3) A.

C. Di Nicola et al. / Inorganica Chimica Acta 359 (2006) 53–63
59
The adduct AgNO3:dppp (4:2), devoid of crystallo-
graphic symmetry, with one full tetranuclear aggregate
comprising the asymmetric unit of the structure, is a fur-
ther interesting variation on this theme, the first (deriv-
ative) of this type recorded with L other than dpem.
(The above appears to be the first with dpam). Indeed,
the most closely related array appears to be the
AgBr:dppNH (4:2) [24] adduct mentioned above,
the expansion of the cluster along the axis between the
peripheral anions permitted by the substitution of
the multidentate nitrate allowing accommodation of
the more extended dppp ligand. (Note that the dppp
ligands are in extended ꢀantiꢁ forms.) Although the core
of the present molecule (Fig. 4, Table 2) is tabulated as if
the core were centrosymmetric, there are substantial
divergences between ꢀequivalentꢁ parameters, and, in
fact, inspection shows that although the (PAgNO3)4
array has quasi-i symmetry, the relationship between
the ligand hydrocarbon strings is mm (normal to the
page of Fig. 4, through C(12,120)). The nitrates which bind
the core are of two different types – the bis-chelate form
of nitrates 1, 10, the two chelates with a common atom,
and the O,O0-chelate/O0-unidentate of nitrates 2, 20. We
finally note records of other AgNO3:dpex adducts in
the form of AgNO3:dppm (1:1)2, essentially [(O2NOAg)-
(P-dppm-P0)2(AgONO2)] with an eight-membered
macrocycle, and AgNO3:AgPF6:dppm (1:1:2), essentially
[(dppm)2Ag2(O Æ NO Æ O)2Ag2dppm2](PF6)2 [25], relevant
to the present. Related complexes have recently been
reported with modified ligand types, viz. Agtfa:-
cy2PCH2Pcy2 (2:1) (discrete) [26] and Agtfa:cis-
Ph2PCH:CHPPh2 (2:1) (polymeric) [27].
1
Fig. 4. Projection of tetranuclear AgNO3:dppp (4:2) normal to the Ag4
plane.
Table 1
Selected geometries, AgNCO:dpem (4:2), 4, 3
Atoms
Parameter
Atoms
Parameter
˚
Distances (A)
Ag(1)–E(1)
Ag(1)–N(1)
2.5030(4), 2.3682(7)
2.639(2), 2.379(2)
2.374(2), 2.296(2)
2.294(3), 2.508(2)
3.284(3), 3.134(3)
3.372(3), 3.312(3)
3.2994(4), 3.0372(9)
3.8282(3), 3.4706(5)
3.2120(4), 3.0823(4)
2.294(3)
Ag(2)–E(2)
Ag(2)–N(1)
Ag(2)–N(21)
Ag(2)ꢂ ꢂ ꢂN(1)
N(1)–C(1)
C(1)–O(1)
N(2)–C(2)
C(2)–O(2)
Ag(1)ꢂ ꢂ ꢂAg(2)
2.4502(4), 2.3555(6)
2.351(3), 3.150(2)
2.238(2), 2.108(2)
3.678(3), 3.175(2)
1.167(3), 1.175(3)
1.204(3), 1.204(3)
1.181(4), 1.18(1)a
1.195(4), 1.14(2)a
3.2857(4), 3.4084(4)
Ag(1)–N(1)
Ag(1)–N(2)
N(1)ꢂ ꢂ ꢂN(1)
N(1)ꢂ ꢂ ꢂN(2)
E(1)ꢂ ꢂ ꢂE(2)
Ag(1)ꢂ ꢂ ꢂAg(1)
Ag(1)ꢂ ꢂ ꢂAg(2)
Ag(1)ꢂ ꢂ ꢂN(2)
Angles (ꢁ)
E(1)–Ag(1)–N(1)
E(1)–Ag(1)–N(1)
E(1)–Ag(1)–N(2)
N(1)–Ag(1)–N(1)
N(1)–Ag(1)–N(2)
N(1)–Ag(1)–N(2)
Ag(2)–N(2)–Ag(1)
Ag(2)–N(2)–C(2)
Ag(1)–N(2)–C(2)
N(1)–C(1)–O(1)
E(1)–C(0)–E(2)
130.18(7), 135.53(5)
116.61(5), 128.93(5)
127.46(6), 114.71(5)
80.57(7), 84.16(7)
98.50(9), 85.27(7)
85.92(8), 95.60(7)
92.91(8), 94.78(8)
114.7(2), 140.3(8)a
152.2(2), 109.1(7)
177.7(4), 177.5(3)
114.5(1), 111.3(1)
E(2)–Ag(2)–N(1)
E(2)–Ag(2)–N(2)
N(1)–Ag(2)–N(2)
Ag(1)–N(1)–Ag(1)
Ag(1)–N(1)–Ag(2)
Ag(1)–N(1)–Ag(2)
C(1)–N(1)–Ag(1)
C(1)–N(1)–Ag(2)
C(1)–N(1)–Ag(1)
N(21)–C(2)–O(2)
124.49(5)
139.68(6), 165.03(6)
94.52(8)
99.43(7), 95.84(7)
85.64(7)
82.12(6)
127.5(2), 113.0(2)
116.5(2)
127.5(2), 144.5(2)
179.0(3), 176(1)
The value for the E = As adduct precedes that of its E = P counterpart. Italicized atoms are centrosymmetrically related.
a
0
0
0
0
0
0
˚
For the second component C(2 )–N(2 ,0 ) are 1.14(2), 1.29(2) A; Ag(2)–N(2)–C(2 ), N(2)–C(2 )–O(2 ) 146.3(9)ꢁ, 172.(2)ꢁ. In the dpam adduct the
dihedral angle between the central and peripheral Ag2N2 planes is 82.50(8)ꢁ. In the two adducts, the central NCO ligands make dihedral angles of
71.74(5)ꢁ, 71.89(6)ꢁ with their central Ag2N2 planes. The angle between the two NCO(2,20) lines is 19.0(1)ꢁ.

60
C. Di Nicola et al. / Inorganica Chimica Acta 359 (2006) 53–63
Table 2
Selected geometries, AgNO3 : dppp (4:2), 5
Atoms
Parameter
Atoms
Parameter
˚
Distances (A)
Ag(1)–P(1)
2.357(2), 2.348(1)
2.405(4), 2.329(4)
3.216(5), 3.050(7)
2.901(5), 3.159(5)
2.320(4), 2.364(5)
2.603(4), 2.638(5)
1.297(6), 1.269(9)
1.241(7), 1.26(1)
1.232(7), 1.220(8)
4.1296(8), 4.1034(8)
Ag(2)–P(2)
2.347(2), 2.358(1)
2.193(4), 2.293(4)
2.854(8), 2.567(5)
2.695(4), 2.525(5)
3.094(7)
1.236(7), 1.231(7)
1.262(7), 1.261(7)
1.257(7), 1.256(6)
2.882(7)
Ag(1)–O(11)
Ag(1)–O(13)
Ag(1)–O(220)
Ag(1)–O(230)
Ag(1)–O(21)
N(1)–O(11)
N(1)–O(12)
N(1)–O(13)
Ag(1). . .Ag(20)
Ag(2)–O(110)
Ag(2)–O(120)
Ag(2)–O(220)
N(2). . .N(20)
N(10)–O(21)
N(10)–O(22)
N(1)–O(23)
O(23). . .O(110)
Ag(1). . .Ag(2)
5.133(1), 5.167(1)
Angles (ꢁ)
P(1)–Ag(1)–O(11)
P(1)–Ag(1)–O(13)
P(1)–Ag(1)–O(220)
P(1)–Ag(1)–O(230)
P(1)–Ag(1)–O(21)
O(11)–Ag(1)–O(13)
O(11)–Ag(1)–O(220)
O(11)–Ag(1)–O(230)
O(11)–Ag(1)–O(21)
O(13)–Ag(1)–O(220)
O(13)–Ag(1)–O(230)
O(13)–Ag(1)–O(21)
O(220)–Ag(1)–O(230)
O(220)–Ag(1)–O(21)
O(11)–N(1)–O(12)
O(11)–N(1)–O(13)
O(12)–N(1)–O(13)
129.6(1), 137.5(1)
91.43(9), 98.9(1)
106.5(1), 102.32(9)
146.1(1), 142.2(1)
121.9(1), 113.8(1)
43.0(1), 44.6(2)
123.7(1), 118.8(1)
78.8(3), 75.8(2)
73.8(1), 85.3(2)
155.3(1), 134.3(2)
120.8(1), 99.3(2)
75.2(1), 126.5(2)
47.2(1), 43.4(1)
80.9(1), 79.7(1)
117.1(5), 115.3(7)
120.3(5), 119.1(6)
122.6(5), 124.4(8)
P(2)–Ag(2)–O(110)
P(2)–Ag(2)–O(120)
P(2)–Ag(2)–O(220)
O(110)–Ag(2)–O(120)
O(110)Ag(1)–O(220)
O(120)–Ag(2)–O(220)
Ag(1)–O(220)–Ag(2)
Ag(1)–O(11)–Ag(20)
O(21)–N(2)–O(22)
O(21)–N(2)–O(23)
O(22)–N(2)–O(23)
Ag(1)–O(21)–N(2)
Ag(10)–O(22)–N(2)
Ag(10)–O(23)–N(2)
Ag(1)–O(11)–N(1)
Ag(1)–O(110)–N(1)
Ag(2)–O(11)–N(1)
Ag(20)–O(12)–N(1)
Ag(20)–O(22)–N(2)
167.1(1), 154.8(1)
119.5(1), 133.3(1)
102.1(1), 109.2(1)
47.8(2), 52.5(1)
90.7(2), 93.5(1)
138.3(2), 93.3(2)
133.0(2), 130.4(2)
123.0(2), 130.3(2)
121.1(5), 121.6(5)
119.9(5), 120.5(5)
119.0(5), 117.9(5)
116.7(3), 113.2(4)
77.7(3), 82.5(3)
117.1(4), 111.0(4)
110.9(3), 115.6(4)
74.1(3), 80.7(5)
100.8(3), 113.1(4)
89.4(3), 81.0(5)
122.8(4), 129.2(4)
˚
Ag out-of-plane deviations (dA)
NO3(1)
dAg(1)
dAg(20)
NO3(2)
dAg(1)
dAg(10)
dAg(20)
dAg(2)
1.544(8), 0.392(1)
0.202(9), ꢀ0.16(2)
2.315(7), 2.386(7)
0.72(1), 0.493(9)
1.24(1), 0.99(1)
1.74(1), 1.94(1)
The second value in each entry is associated with the atom complement related by the quasi-inversion centre within the array.
Torsions in the dppp ligands (carbons denoted by number only): Ag–P(1)–1–12 ꢀ53.6(5), ꢀ46.6(4); P(1)–1–12–2 161.0(4), 174.3(4); Ag–P(2)–2–12
59.7(5), 45.4(4); P(2)–2–12–2 ꢀ178.2(4), 176.4(4)ꢁ. The dihedral angles of the NO3 planes (1,2,1020) to the central Ag4 plane (v2 497) are 63.7(2)ꢁ,
18.4(2)ꢁ, 25.4(2)ꢁ, 23.4(2)ꢁ.
ꢀUnsolvatedꢁ MX:dpem (4:2) (X = Cl, Br, I) ꢀstepꢁ
structures thus far are predominantly structurally
described for M = Cu, there being only one example
for M = Ag (Cl/dppm), in contrast to the MX:PPh3
(4:4) arrays which, although not numerous, are described
for both M = Cu, Ag [23]. Interestingly, in these
MX:PPh3 adducts, the peripheral trigonal metal atom
(M = Cu or Ag) has an essentially planar environment
(R(angles) = 358.0 ꢀ 359.8ꢁ for the examples listed in
[23]), a state of affairs carrying over less rigorously to
the present: for the examples of Table 3, the sums are
351.4 (P/Ag/Cl), >358.3 (P/Cu/Cl,Br), 349.9ꢁ (P/Cu/I),
suggesting that perhaps for some of these arrays (those
with the largest M or X?) steric effects due to incorpora-
tion of the E ·2 into a chelate may introduce strain.
The remaining adduct of gross MX:dpex (2:1) stoichi-
ometry is polymeric with (E-dpex-E0)M motifs linked
diversely by anionic motifs to make a two-dimensional
polymer comprised of twenty-membered macrocycles;
in the CuCN:dppm (2:1)(1|1) adduct, depicted in
Fig. 5, the asymmetric unit is CuCN:0.5 dppm, a crystal-
lographic 2-axis passing through the central carbon of
the dppm ligand. The cyanide is tentatively assigned as
ordered on the basis of refinement behaviour. The cop-
per atom is three-coordinate, Cu–P, C, N (3/2 ꢀ x,
˚
1/2 + y, ꢀz) being 2.2339(7), 1.921(3), 1.959(3) A, with
P–Cu–C, N 132.55(9), 111.28(8), C–Cu–N 115.1(1), R
0
˚
358.9ꢁ; C–N is 1.156(4) A, with Cu–C–N, Cu –N–C
170.0(3), 164.2(2)ꢁ. A further structurally characterized
adduct of CuCN with a simple phosphine ligand giving

Table 3
Selected geometries, MX:dppm (4:4) (X = halide) (following the nomenclature of ref. [23] (see footnote))
E/M/X/solvent (phase)[Ref]
Tetramer core geometries
˚
Distances (A)
a
b
c
d
e
f
g
h
i
j
k
l
m
n
P/Ag/Cla (ꢀaꢁ)
2.665(3)
2.622(1)
2.635(2)
2.764(2)
2.742(2)
2.603(2)
2.689(1)
2.663(1)
2.721(2)
2.734(2)
2.665(3)
2.591(2)
2.679(1)
2.747(4)
2.735(2)
2.754(2)
2.679(1)
2.769(1)
2.771(2)
2.846(2)
2.415(3)
2.458(1)
2.418(2)
2.554(2)
2.535(2)
2.380(3)
2.379(1)
2.395(1)
2.396(3)
2.402(3)
2.364(3)
2.377(1)
2.363(1)
2.383(3)
2.380(4)
3. 635(3)
3.5143(6)
3.8112(6)
3.650(1)
3.814(2)
3.983(2)
3.679(2)
4.116(2)
3.374(3)
3.5957(5)
3.4525(6)
3.348(2)
3.346(1)
3.748(3)
3.633(2)
3.798(1)
4.042(2)
3.988(2)
4.112(3)
3.795(2)
3.802(2)
4.232(3)
4.181(3)
3.254(3)
3.1266(7)
3.0630(7)
3.154(1)
3.307(2)
3.880(3)
4.157(2)
3.625(2)
4.019(2)
3.859(2)
P/Ag/Clb (ꢀbꢁ mol. 1), 1
(ꢀbꢁ mol. 2)
P/Ag/Brb, 2
P/Cu/Cl/(C2H4Cl2;C2/c)c
2.312(7)
2.368(3)
2.575(2)
2.785
2.740(5)
2.697(3)
2.579(2)
2.729
2.324(7)
2.358(3)
2.523(2)
2.634
2.357(6)
2.387(3)
2.552(2)
2.711
2.272(5)
2.252(2)
2.338(2)
2.510
2.196(5)
2.203(3)
2.214(4)
2.230
2.194(5)
2.185(3)
2.184(4)
2.216
3.468(5)
3.628(2)
3.449(2)
3.671
3.699(8)
3.548(2)
3.830(2)
4.116
2.914(4)
2.992(2)
2.944(2)
2.684
3.610(7)
3.580(2)
3.832(2)
4.284
3.750(9)
3.723(3)
4.022(2)
4.174
2.905(4)
2.958(2)
3.180(2)
3.108
3.494(7)
3.423(2)
3.695(2)
3.349
d
ꢀ
(Me2CO; P1)
Bre
If
Angles (ꢁ)
a
b
c
d
e
f
g
h
i
k
k
l
t
n
s
P/Ag/Cla (ꢀaꢁ)
P/Ag/Clb (ꢀbꢁ mol. 1), 1
(ꢀbꢁ mol. 2)
92.76(8) 87.24(7)
97.15(4) 82.85(4)
87.98(4) 92.09(5)
97.27(5) 83.87(5)
96.29(6) 82.28(5)
90.72(9) 56.18(6) 114.90(9) 117.77(9) 58.60(5) 83.09(9)
86.96(4) 84.11(3) 125.27(4) 128.73(6) 72.27(3) 90.80(6)
90.65(4) 78.91(3) 122.54(4) 122.01(5) 69.01(3) 85.12(4)
93.69(5) 74.13(4) 116.44(8) 114.17(8) 69.46(5) 78.49(5)
77.75(7) 121.83(8) 151.8(1)
89.91(4) 151.40(5) 118.59(5)
93.92(4) 150.54(5) 114.07(4)
98.67(6) 144.58(9) 115.05(9)
100.97(9) 80.65(6) 114.5(4)
93.43(4) 81.56(4) 112.6(3)
91.37(5) 78.81(4) 112.1(2)
98.67(5) 94.37(5) 113.9(6)
101.20(6) 97.98(5) 113.9(6)
1
ꢀ
ꢀ
1
ꢀ
1
P/Ag/Brc, 2
1
94.15(5) 73.84(5) 115.00(9) 121.3(1)
72.53(5) 78.46(6)
95.49(6) 150.6(1)
109.6(1)
P/Cu/Cl/(CH2Cl2;C2/c)c 93.7(2)
88.3(2)
90.6(2) 69.3(1) 129.6(2) 114.8(2)
89.93(5) 71.83(5) 130.79(4) 118.11(6) 76.96(5) 80.90(6) 101.00(5) 136.45(4) 121.98(6) 103.94(6) 88.42(4) 113.44(5)
77.0(2) 78.7(2)
102.5(2) 130.0(2)
127.5(2)
108.0(2)
80.67(8) 110.4(10)
1
ꢀ
c,d
ꢀ
ꢀ
(Me2CO; P1)
88.70(6) 91.30(6)
95.98(6) 84.02(6)
1
Bre
If
97.36(6) 70.03(6) 113.2(1)
116.1(1)
115.9
76.68(6) 74.45(6) 103.13(7) 142.5(1)
112.7(1)
109.0
104.18(7) 89.20(5) 114.32(6)
100.7
1
ꢀ
ꢀ
96.5
83.5
106.0
59.0
112.6
68.8
62.9
110.1
130.8
80.0
113.9
1
a M1–X01
b M1–X1
c M1–X2
d M2–X1
e M2–X2
f M1–E1
k X1ꢂ ꢂ ꢂX2
a X1–M1–X01
b M1–X1 ꢀ M01
c X1–M1–X2
d M1–X1–M2
e E–M1–X01
f E1–M1–X2
g M2–X1–M01
h M1–X2–M2
i X1–M2–X02
k E02–M2–X2
k E02–M2–X1
l X01–M1–X2
e
g M02–E2
l X1 ꢂ ꢂ ꢂ X02
m M1 ꢂ ꢂ ꢂ M02
n X1 ꢂ ꢂ ꢂ M02
X
M
X
2
2
E
h M1 ꢂ ꢂ ꢂ M01
i X1 ꢂ ꢂ ꢂ X01
j M1ꢂ ꢂ ꢂM2
d
c
f
a
b
E
M
1
1
1
X
M
s is the crystallographic symmetry of the complex
N.B. There is a slight change in the
definition of ꢀ, n, l, cf. [16]. t is the M2X2
(central) (obligate planar, if
E
E
M
X
2
g
centrosymmetric)/M2X2(peripheral)
(usually appreciably non-planar) dihedral
angle. n is the E–C–E angle.
a
Ref. [13].
This work.
Ref. [9].
Ref. [8].
b
c
d
e
Ref. [12]; note that [10,11] records a similar (unsolvated) earlier determination in space group P21/c.
Ref. [10,11] (no s.u.ꢁs available).
f

62
C. Di Nicola et al. / Inorganica Chimica Acta 359 (2006) 53–63
Fig. 5. Projection of CuCN:dppm (2:1)(1|1), 6 (a) down b, showing the sheet disposition in the ab face of the cell; (b) down c*, a vertical, b horizontal
in the page, showing the two-dimensional web.
rise to a two-dimensional web of linked macrocycles is
noted in CuCN:PPh3 (1:2)6, in which the macrocycles
are comprised of eighteen-membered (CuCN)6 rings,
with the PPh3 ligands pendant from four-coordinate
(N/C)2CuP2 units [28].
Acknowledgements
Support from the Australian Research Council, the
University of Camerino and Fondazione CARIMA is
gratefully acknowledged.

C. Di Nicola et al. / Inorganica Chimica Acta 359 (2006) 53–63
63
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