New oligo-/poly-meric forms for MX:dpex (1:1) complexes (M = Cu I, AgI; X = (pseudo-)halide; dpex = Ph 2E(CH2)xEPh2, E = (P), As; X = 1, 2)

Article abstract of DOI:10.1016/j.ica.2004.07.026

Single-crystal X-ray structural characterizations of MX:dpam (1:1) ('dpam' = Ph₂AsCH₂AsPh₂) are reported for MX = AgCl, Br; CuI, CN/Cl (all isomorphous) and AgI, AgSCN, CuSCN arrays, all being of the novel form [(μ-X){M(μ-X)(As-dpam-As′)₂M′}] _∞, essentially the familiar M(E-dpem-E′) ₂M′ binuclear array with both 'bridging' and (linking) 'terminal' (pseudo-)halides involved in the polymer. A different arrangement of bridging and linking entities is found with AgX:dpae (1:1) _2(∞|∞), X = Br, NCO, 'dpae' = Ph₂As(CH ₂)₂AsPh₂, now comprising [M(μ-X) ₂(As-dpae-As)M] kernels linked by As-dpae-As′, while in the thiocyanate analogue Ag(_NCS^SCN)Ag units are linked by the dpae ligands into a two-dimensional web. 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.2004.07.026

Inorganica Chimica Acta 358 (2005) 748–762
www.elsevier.com/locate/ica
New oligo-/poly-meric forms for MX:dpex (1:1) complexes
(M = CuI, AgI; X = (pseudo-)halide;
dpex = Ph2E(CH2)xEPh2, E = (P), As; x = 1, 2)
a
a
a,
*
Augusto Cingolani , Corrado Di Nicola , Effendy b,c, Claudio Pettinari
,
c
Brian W. Skelton , Neil Somers , Allan H. White
c
c
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, The University of Western Australia, Crawley, W.A. 6009, Australia
Received 5 July 2004; accepted 23 July 2004
Available online 9 September 2004
Abstract
Single-crystal X-ray structural characterizations of MX:dpam (1:1) (ꢀdpamꢁ = Ph2AsCH2AsPh2) are reported for MX = AgCl,
Br; CuI, CN/Cl (all isomorphous) and AgI, AgSCN, CuSCN arrays, all being of the novel form [(l-X){M(l-X)(As-dpam-
As0)2M0}] , essentially the familiar M(E-dpem-E0)2M0 binuclear array with both ꢀbridgingꢁ and (linking) ꢀterminalꢁ (pseudo-)halides
1
involved in the polymer. A different arrangement of bridging and linking entities is found with AgX:dpae (1:1)2(1|1), X = Br, NCO,
ꢀdpaeꢁ = Ph2As(CH2)2AsPh2, now comprising [M(l-X)2(As-dpae-As)M] kernels linked by As-dpae-As0, while in the thiocyanate ana-
SCN
NCS
logue Agð ÞAg units are linked by the dpae ligands into a two-dimensional web. 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).
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Silver; 31P NMR; ESI MS; X-ray crystal structure; Diphosphine
1. Introduction
which have been structurally characterized beyond
MX:dppe (1:2), these of the form [M(dppe)2]+Xꢀ as
described in [1], and restricted seemingly to only a
handful of complexes of the form MX:dppe (2:3)
(see [3]), or, for dpae, MX:dpae (2:1) [4]; the current
limitations we believe to be a consequence of a signif-
icant tendency on the part of dpee to link metal atoms
in a trans-oid more intractable/often insoluble disposi-
tion in polymeric arrays, a limited selection of AgX:d-
pae (1:1) adducts as defined below being offered which
assist this conjecture. We describe here the spectro-
scopic and structural characterization of an extended
series of adducts of 1:1 stoichiometry MX:dpex to as-
sist our understanding of the Ag(I) species containing
(diphosphine or) diarsine ligands, present both in solid
and solution.
In the preceding pair of papers [1,2], we have de-
scribed the structural definition of adducts of the form
MX:dpem (1:1) (MX = simple coinage metal(I) (Cu,
Ag) salt, dpem ” Ph2E(CH2)EPh2 (E = P, As)) in which
the complex species were discrete. These arrays were lar-
gely exclusive of X = (pseudo-)halide/dpam adducts
(AgCl, NCO excepted); many of the latter systems,
which we have found to present in polymeric form, are
described hereunder.
For dpee ” Ph2E(CH2)2EPh2 ligands, there are, by
comparison, remarkably few derivatives of this type
*
Corresponding author. Fax: +39 737 637345.
E-mail address: claudio.pettinari@unicam.it (C. Pettinari).
0020-1693/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.07.026

A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
749
2. Experimental
[Ag2Cl(dpam)2]+. Anal. Calc. for C65H59Ag2As4Cl2N3:
C, 53.16; H; 4.05; N, 2.86. Found: C, 53.32; H, 4.02;
N, 2.85%. Km (CH2Cl2, 10ꢀ4 M): 0.5 Xꢀ1 mol2 cmꢀ1
.
2.1. Materials and methods
All chemicals were purchased from Aldrich and Lan-
caster and used without further purification. Elemental
analyses (C,H,N,S) were performed in-house with a Fi-
sons Instruments 1108 CHNS-O Elemental Analyser. IR
spectra were recorded from 4000 to 100 cmꢀ1 with a Per-
kin-Elmer System 2000 FT-IR instrument. 1H-, 13C and
31P-NMR spectra were recorded on a VXR-300 Varian
2.2.1.2. AgBr:dpamð1:1Þ ꢁ 112py ð2Þ. Compound 2 has
been obtained as a colorless crystalline solid using a sim-
ilar procedure to that reported for 1, in 70% yield.
Recrystallization from MeCN yields 2. M.p. 250 ꢁC
dec. 1H NMR (CDCl3, 293 K): d 2.75 (s, 2H, CH2dpam),
7.2–7.5 (m, 20H, C6H5), 7.7 (pt, 3H CHpy), 8.6 (m, 4.5H,
CHpy). 13C NMR (CDCl3, 293 K): d 24.53(s, C H2dpam),
128.8, 128.9, 130.9, 136.2 (Carom), 124br, 139.4, 149.9
(Cpy). IR (nujol, cmꢀ1): 3065 (CHarom), 1628w, 1592w,
1581w, 1573w (C'C); 499sh, 480s, 470s, 459m, 449sh,
410w, 325m, 307m, 305w, 275w, 229vw, 203w, 156m,
119sbr, 113sbr, 92sbr. ESI MS (+): 1240 [100] [Ag2Br(d-
pam)2]+. Anal. Calc. for C65H59Ag2As4Br2N3: C, 50.13;
H; 3.82; N, 2.70. Found: C, 49.90; H, 4.01; N, 2.45%. Km
1
spectrometer (300 MHz for H, 75.0 MHz for 13C and
121.4 MHz for 31P). H and C chemical shifts are re-
ported in ppm versus SiMe4, P chemical shift in ppm
versus 85% H3PO4. The electrical conductances of the
acetone, dichloromethane, DMSO and acetonitrile solu-
tions were measured with a Crison CDTM 522 conduc-
timeter at room temperature. Positive and negative
electrospray mass spectra were obtained with a Series
1100 MSI detector HP spectrometer, using an acetonit-
rile mobile phase. Solutions (3 mg/ml) for electrospray
ionization mass spectrometry (ESI-MS) were prepared
using reagent grade acetone or acetonitrile. For the
ESI-MS data, masses and intensities were compared to
those calculated by using the IsoPro Isotopic Abun-
dance Simulator Version 2.1 [5]; peaks containing sil-
ver(I) and copper ions are identified as the centers of
isotopic clusters.
(CH2Cl2, 10ꢀ4 M): 1 Xꢀ1 mol2 cmꢀ1
.
2.2.1.3. AgI :dpamð1:1Þ ꢁ 7=4MeCN ð3Þ. dpam (0.397 g,
1.0 mmol) was added to a MeCN solution of AgI
(0.234 g, 1.0 mmol). The solution was stirred overnight.
A colorless precipitate formed which was stirred for 3 h,
then filtered off and washed with diethyl ether to give a
colorless crystalline solid in 75% yield. M.p. 182–185 ꢁC
1
dec. Recrystallization from MeCN yielded 3. H NMR
(CDCl3, 293 K): d 2.75 (s, 2H, CH2dpam), 7.2–7.5 (m,
20H, C6H5). 13C NMR (CDCl3, 293 K): d 24.53(s,
CH2dpam), 128.8, 128.9, 130.9, 136.2 (Carom). IR (nujol,
cmꢀ1): 1573w (C'C); 588m, 474m, 467m, 458m,
330m, 316m, 265w, 2094w, 196w, 150w, 122w, 90w.
ESI MS (+): 1287 [100] [Ag2I(dpam)2]+. Anal. Calc.
for C25H22AgAs2I (unsolvated) C, 42.47; H; 3.14.
Found: C, 42.13; H, 3.26%. Km (CH2Cl2, 10ꢀ4 M): 1
2.2. Syntheses
2.2.1. Syntheses of the silver and copper complexes
The colorless complexes described were obtained by
crystallization, by slow evaporation, cooling, or interdif-
fusion, of solutions of millimolar stoichiometry of the
metal(I) salt and dpam, dppm or dpae ligand in a few
ml of the specified solvent. Some silver(I) and copper
complexes were amenable to synthesis as pure bulk sam-
ples, analyses and spectral data for which are given
below.
Xꢀ1 mol2 cmꢀ1
.
2.2.1.4. AgSCN:dpam (1:1) (4). Compound 4 has been
obtained as a colorless crystalline solid using a similar
procedure to that reported for 1, with pyridine as sol-
1
vent (82% yield). M.p. >300 ꢁC dec. H NMR (CDCl3,
2.2.1.1. AgCl : dpamð1:1Þ ꢁ 112py ð1Þ. dpam (0.397 g, 1.0
mmol) was added at room temperature to a pyridine
(py) solution (10 ml) of AgCl (0.143 g, 1.0 mmol). The
solution was stirred overnight, then diethyl ether was
added (5 ml). A colorless precipitate formed which
was stirred for 3 h, then filtered off and washed with
diethyl ether to give complex 1 as a colorless crystalline
293 K): d 2.85 (s br, 2H, CH2dpam), 7.2m, 7.4m (m, 20H,
C6H5). 13C NMR (CDCl3, 293 K): d 24.57 (s, CH2dpam),
128.88, 129.12, 133.08, 138.31 (Carom). IR (nujol, cmꢀ1):
3065w (CHarom), 2137, 2084m (SCN), 1592w, 1579w
(C'C); 553w, 474m, 456m, 411w, 372m, 312m, 269w,
202w, 195w, 150w, 119w, 109w, 99w, 89w, 75w. ESI
MS (+):1218 [100] [Ag2(SCN)(dpam)2]+. Anal. Calc.
for C52H44Ag2As4N2S2: C, 48.93; H; 3.47; N, 2.19; S,
5.02. Found: C, 48.71; H, 3.63; N, 2.05; S, 4.77. Km
1
solid in 80% yield. M.p. 246 ꢁC dec. H NMR (CDCl3,
293 K): d 2.83 (s, 2H, CH2dpam), 7.2–7.5 (m, 20H, C6H5),
7.7 (pt, 3H CHpy), 8.7 (m, 4.5H, CHpy). 13C NMR
(CDCl3, 293 K): d 24.30 (s, CH2dpam), 128.95, 128.25,
132.94, 136.2 (Carom), 124br, 138.2, 149.9 (Cpy). IR (nu-
jol, cmꢀ1): 3065w, 3045w (CHarom), 1592w, 1576w,
1560w (C'C); 582m, 552w, 476m, 458m, 410w, 401w,
329m, 310m, 268w, 150br. ESI MS (+): 1195 [100]
(CH2Cl2, 10ꢀ3 M): 1 Xꢀ1 mol2 cmꢀ1
.
2.2.1.5. AgBr:dpae (1:1) Æ MeCN (5). dpae (0.409 g, 1.0
mmol) was added at room temperature to a 1:1 pyri-
dine:MeCN solution 10 ml of AgBr (0.188 g, 1.0 mmol).
The solution was stirred overnight.
A colorless

750
A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
precipitate formed which was stirred for 3h, then filtered
off and washed with diethyl ether to give a colorless crys-
talline solid in 89% yield. Slow recrystallization from
3.35. Found: C, 45.52; H, 3.45. Km (CH2Cl2, 10ꢀ3 M):
2 Xꢀ1 mol2 cmꢀ1
.
1
MeCN yields 5. M.p. 205 ꢁC dec. H NMR (CDCl3,
2.2.1.9. CuSCN:dppm (1:1) Æ 3MeCN (9). Compound 9
has been obtained as a colorless crystalline solid using a
similar procedure to that reported for 1, but with MeCN
as solvent (92% yield). Slow recrystallization from MeCN
yield 9. M.p. 222–226 ꢁC dec. 1H NMR ((CD3)2CO, 293
K): d 2.85 (s br, 2H, CH2dppm), 7.2m, 7.5m (m, 20H,
C6H5). 13C NMR ((CD3)2CO, 293 K): d 24.61 (s,
CH2dppm), 129.32s, 133.75 (Carom). 31P{1H} NMR
((CD3)2CO, 295K). 31P{1H} NMR (CDCl3, 218K): d
ꢀ28.2, ꢀ27.6, ꢀ27.4, ꢀ21.5, ꢀ12.9, ꢀ9.9, ꢀ5.0, ꢀ4.8 (s
br). IR (nujol, cmꢀ1): 3072w, 3045w (CHarom), 2098s,
2072 (SCN), 1582w (C'C); 552w, 518m, 509s, 440m,
418m, 360w, 318w, 200br, 171w, 141w, 99w, 71w. ESI
MS (+): 922 [35] [Cu2(CN)(dppm)2]+; 954 [100]
[Cu2(SCN)(dppm)2]+; 1436 [40] [Cu3(SCN)2(dppm)3]+.
Anal. Calc. for C52H44Cu2N2P4S2 (unsolvated) C, 61.71;
H; 4.38; N, 2.77; S, 6.34. Found: C, 61.82; H, 4.52; N,
293 K): d 2.28 (s, 4H, CH2dpae), 7.2–7.5 (m, 20H,
C6H5). 13C NMR (CDCl3, 293 K): d 23.87 (s, CH2dpae),
128.9, 129.0, 133.2, 138.4 (Carom). IR (nujol, cmꢀ1): 3065
(CHarom), 1651w, 1589w, 1579w, 1539w, 1505w, 619w,
592w, 480m, 464m, 448w, 411w, 346w, 333w, 316m,
302w, 288w, 280m, 264w, 222w, 203w. ESI MS (+):
1080 [100] [Ag(dpae)2]+. Anal. Calc. for C26H24A-
gAs2Br: C, 46.33; H; 3.59. Found: C, 46.12; H, 3.75%.
Km (CH2Cl2, 10ꢀ3 M): 1 Xꢀ1 mol2 cmꢀ1
.
2.2.1.6. AgSCN:dpae (1:1) (6). Compound 6 has been
obtained as a colorless crystalline solid using a similar
procedure to that reported for 1, but with MeCN as sol-
1
vent (79% yield). M.p. 210 ꢁC dec. H NMR (CDCl3,
293 K): d 2.17 (s, 4H, CH2dpae), 7.2–7.3 (m, 20H,
C6H5). 13C NMR (CDCl3, 293 K): d 23.7 (s, CH2dpam),
129.4, 129.9, 132.9, 135.2 (Carom). IR (nujol, cmꢀ1):
3071w, 3045w (CHarom), 2143w, 2093s, 2085s, 1579w,
1539w, 617w, 584m, 574w, 480s, 456m, 329m, 316m,
310m, 288m, 279m, 240w, 222w, 203m. ESI MS
(+):1080 [100] [Ag(dpae)2]+. Anal. Calc. for C27H24A-
gAs2NS: C, 49.72; H; 3.71; N, 2.15; S, 4.92. Found: C,
49.58; H, 3.91; N, 2.22; S, 4.67%. Km (CH2Cl2, 10ꢀ4
2.083; S, 5.97. Km (CH2Cl2, 10ꢀ3 M): 6 Xꢀ1 mol2 cmꢀ1
m (MeCN, 10ꢀ3 M): 46 Xꢀ1 mol2 cmꢀ1
;
K
.
2.2.1.10. CuCN:CuCl:dpam (1:1:2) Æ 3MeCN (10). A
specimen of CuCN:CuCl:dpam (1:1:2) Æ 3MeCN (10)
was obtained adventitiously on one occasion, presuma-
bly a consequence of salt/solvent interaction and has
not been susceptible of rational synthesis, its character-
ization resting solely on the structure determination.
M): 0.1 Xꢀ1 mol2 cmꢀ1
.
2.2.1.7. Synthesis of AgCNO:dpae (1:1) (7). Compound
7 has been obtained as a colorless crystalline solid using
a similar procedure to that reported for 1, but with
MeCN as solvent (84% yield). M.p. 209 ꢁC dec. 1H
NMR (CDCl3, 293 K): d 2.43 (s, 4H, CH2dpae), 7.2–
7.4 (m, 20H, C6H5).13C NMR (CDCl3, 293 K): d 23.9
(s, CH2dpae), 128.9, 129.1, 133.1, 138.3 (Carom). IR (nu-
jol, cmꢀ1): 3071w, 3052w (CHarom), 2138s, 1575w,
1557w, 1540w, 1506w. 636s, 622m, 612m, 586m, 548br,
478s, 470s, 464s 387w, 324m, 314m, 302m, 280m,
266w, 256w, 251w, 239w, 223w, 203m. ESI MS (+):
1080 [100] [Ag(dpae)2]+. Anal. Calc. for C27H24AgAs2-
NO: C, 50.97; H; 3.80; N, 2.20. Found: C, 50.76; H,
2.3. Structure determinations
General procedural details are outlined in a preceding
paper [1]. Full cif. depositions reside with the Cambridge
Crystallographic Data Center, #242137–242146. Specific
details are as follows (individual variations in procedure
(difficulties, anomalies, etc.) are cited as ꢀvariataꢁ).
2.3.1. Crystal/refinement data
2.3.1.1. AgCl:dpam (1:1)2(1|1) Æ 3py (1). C65H59A-
g2As4Cl2N3, M = 1468.6. Monoclinic, space group,
5
˚
˚
P21/c (C2h, No.14), a = 14.18(1) A, b = 16.39(2) A,
3
3.84; N, 2.12%. Km (CH2Cl2, 10ꢀ3 M): 4 Xꢀ1 mol2 cmꢀ1
.
c = 28.268(9) A, b = 114.05(5)ꢁ, V = 6000 A . Dc
(Z = 4 f.u.) = 1.626 g cmꢀ3. lMo = 28 cmꢀ1; specimen:
0.47 · 0.22 · 0.16 mm; Tmin/max = 0.81 (analytical cor-
rection). 2hmax = 50ꢁ; N = 9127, No = 4642; R = 0.051,
˚
˚
2.2.1.8. Synthesis of CuI:dpam (1:1) Æ 3MeCN (8).
Compound 8 has been obtained as a colorless crystalline
solid using a similar procedure to that reported for 1,
but with MeCN as solvent (64% yield). M.p. 141–144
Rw = 0.050. |Dqmax| = 0.9 e Aꢀ3. Single-counter instru-
˚
ment, T ca. 295 K.
1
ꢁC dec. H NMR (CDCl3, 293 K): d 2.92 (s br, 2H,
Variata. Isotropic thermal parameter forms were re-
fined for the non-hydrogen atoms of the pyridine solvent
molecules; assignment of the nitrogen atoms in the pyri-
dine should be regarded as no better than tentative.
CH2dpam), 7.0–7.4 (m, 20H, C6H5). 13C NMR (CDCl3,
293 K): d 24.80 (s, CH2dpam), 128.67, 129.03, 133.13,
137.86 (Carom). IR (nujol, cmꢀ1): 3070w, 3052 (CHarom),
1583w, (C'C), 554m, 473m, 460m, 290w, 262m, 192w,
135w, 72w. ESI MS (+): 977 [100] [Na(dpam)2]; ]1197 [5]
[Cu2(I)(dpam)2]+; 1861 [40] [Cu3(I)2(dpam)3]+. Anal.
Calc. for C25H22CuAs2I (unsolvated): C, 45.31; H;
2.3.1.2. AgBr:dpam (1:1)2(1|1) Æ 3py (2). C65H59Ag2-
As4Br2N3, M = 1557.5. Monoclinic, space group, P21/c
5
˚
˚
(C2h, No.14), a = 14.330(2) A, b = 16.56(2) A, c =

A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
751
3
˚
˚
28.227(6) A, b = 114.72(2)ꢁ, V = 6086 A . Dc (Z = 4
f.u.) = 1.700
0.40 · 0.34 · 0.51 mm; Tmin/max = 0.76 (analytical cor-
rection). 2hmax = 50ꢁ; N = 4433, No = 3639; R = 0.035,
g . l ; specimen:
cmꢀ3 Mo = 40 cmꢀ1
Rw = 0.040. |Dqmax| = 1.0 e Aꢀ3. Single-counter instru-
˚
0.10 · 0.49 · 0.78 mm; Tmin/max = 0.23 (analytical cor-
rection). 2hmax = 50ꢁ; N = 8909, No = 4416; R = 0.056,
ment, T ca. 295 K.
Rw = 0.059. |Dqmax| = 1.1 e Aꢀ3. Single-counter instru-
Variata. The thiocyanate is disordered over two
approximately centrosymmetrically (within the anion)
related sites, i.e., end-for-end, site occupancies refining
to 0.596(2) and complement.
˚
ment, T ca. 295 K.
2.3.1.3. AgI :dpamð1:1Þ2ð1j1Þ ꢁ 7=4MeCN ð3Þ. C50H44A-
g2As4I2 Æ 7/2MeCN, M = 1557.8. Triclinic, space group
1
ꢀ
˚
˚
P1 ðCi ; No: 2Þ, a = 24.399(6) A, b = 17.283(7) A,
2.3.1.7. AgNCO:dpae (1:1)(1|1) (7). C27H24AgAs2-
NO, M = 636.2. Monoclinic, space group C2/c (C62h,
˚
c = 14.052(8) A, a = 91.14(5), b = 92.03(4), c = 93.44(3)ꢁ,
V = 5910 A . Dc (Z = 4 f.u.) = 1.751 g cmꢀ3. lMo = 38
3
˚
˚
No.15), a = 21.236(2) A, b = 13.859(1) A, c = 19.503(2)
˚
cmꢀ1; specimen: 0.14 · 0.65 · 0.18 mm; Tmin/max = 0.71
A, b = 120.607(1)ꢁ, V = 4940 A . Dc (Z = 8
f.u.) = 1.711 specimen:
cmꢀ3 Mo = 35 cmꢀ1
0.22 · 0.10 · 0.08 mm; Tmin/max = 0.76. 2hmax = 58ꢁ;
3
˚
˚
(analytical
correction).
2hmax = 45ꢁ;
N = 15431,
ꢀ3
g
.
l
;
˚
No = 7114; R = 0.067, Rw = 0.067. |Dqmax| = 1.7 e A
Single-counter instrument, T ca. 295 K.
.
Nt = 29230,
N = 6214 (Rint = 0.045),
No = 4265;
R = 0.035, Rw = 0.036. |Dqmax| = 0.98(9) e Aꢀ3. CCD
instrument, T ca. 153 K.
˚
Variata. The central methylene group of ligand 4 was
modelled as disordered over a pair of sites of equal occu-
pancy. Non-hydrogen atoms of the acetonitriles 3–7
were modelled with isotropic thermal parameter forms;
solvent nitrogen atom assignments must be regarded
as tentative.
Variata. Phenyl ring 11 and the cyanate group were
both modelled as disordered over pairs of sites, occu-
pancies set at 0.5 after trial refinement.
2.3.1.8. CuI:dpam (1:1)2(1|1) Æ 3MeCN (8). C56H53-
As4Cu2I2N3, M = 1448.7. Monoclinic, space group
2.3.1.4. AgSCN:dpam (1:1)2(1|1) (4). C52H44A-
g2As4N2S2, M = 1276.5. Monoclinic, space group P21/
˚
P21/c, a = 13.948(3) A, b = 16.531(4) A, c = 26.679(5)
˚
3
5
˚
˚
˚
n (C2h, No.14; variant)), a = 13.32(1) A, b = 23.59(1)
A, b = 112.782(4)ꢁ, V = 5671 A . Dc (Z = 4
3
cmꢀ3 Mo = 42 cmꢀ1
.
l
;
˚
˚
˚
A, c = 15.632(8) A, b = 94.39(5)ꢁ, V = 4898 A . Dc
(Z = 4 f.u.) = 1.698 g cmꢀ3. lMo = 35 cmꢀ1; specimen:
0.23 · 0.42 · 0.21 mm; Tmin/max = 0.87 (analytical cor-
rection). 2hmax = 50ꢁ; N = 8432, No = 3608; R = 0.045,
f.u.) = 1.696 specimen:
g
0.55 · 0.22 · 0.12 mm; Tmin/max = 0.60. 2hmax = 58ꢁ;
Nt = 62239, N = 13987 (Rint = 0.036), No = 9123;
R = 0.036, Rw = 0.038. |Dqmax| = 1.2(3) e Aꢀ3. CCD
˚
Rw = 0.038. |Dqmax| = 0.6 e Aꢀ3. Single-counter instru-
instrument, T ca. 298 K.
Variata. The complex is similar to but not isomor-
phous with its Ag/Cl,Br analogues (1, 2) as above.
˚
ment, T ca. 295 K.
Variata. Phenyl ring 122 was modelled as disordered
over two sets of sites of equal occupancy.
2.3.1.9. CuSCN:dppm (1:1)2(1|1) Æ 3MeCN (9). C58-
H53Cu2N5P4S2, M = 1135.2. Triclinic, space group P1
2.3.1.5. AgBr:dpae (1:1)2(1|1) Æ MeCN (5). C54H51A-
g2As4Br2N, M = 1389.3. Triclinic, space group P1,
(C11, No.1), a = 12.788(2) A, b = 13.370(2) A,
˚
˚
ꢀ
˚
˚
˚
a = 19.16(1) A, b = 12.391(8) A, c = 12.312(8) A,
˚
A,
c = 18.480(2)
a = 87.563(2)ꢁ,
b = 81.393(2)ꢁ,
3
˚
a = 110.33(5), b = 102.66(5), c = 99.16(4)ꢁ, V = 2584
c = 67.574(2)ꢁ, V = 2887 A . Dc (Z = 2 f.u.) = 1.304
g
A . Dc (Z = 2 f.u.) = 1.785 g cmꢀ3. lMo = 59 cmꢀ1; spec-
cmꢀ3. lMo = 9.6 cmꢀ1; specimen: 0.3 · 0.2 · 0.2 mm;
Tmin/max = 0.74. 2hmax = 58ꢁ; Nt = 31856, N = 13308
(Rint = 0.036), No = 9774; R = 0.041, Rw = 0.045.
3
˚
imen: 0.22 · 0.20 · 0.08 mm; Tmin/max = 0.54 (analytical
correction).
2hmax = 46ꢁ;
N = 7188,
No = 2423;
R = 0.11, Rw = 0.11. |Dqmax| = 1.7 e Aꢀ3. Single-counter
instrument, T ca. 153 K.
|Dqmax| = 0.46(9) e Aꢀ3. CCD instrument, T ca. 295 K.
˚
˚
Variata. ꢀFriedelꢁ data were preserved distinctly, xabs
refining to ꢀ0.002(15).
Variata. Weak and limited data would support mean-
ingful anisotropic displacement parameter refinement
for Ag, Br, and As only. Phenyl ring 42n was modelled
as disordered over two sets of sites, occupancies set at
0.5 after trial refinement; the nitrogen atom of the aceto-
nitrile was not distinguishable.
2.3.1.10. CuCN:CuCl:dpam (1:1:2)(1|1) Æ 3MeCN
(10). C57H53As4ClCu2N4, M = 1256.3. a = 13.574(3)
˚
˚
˚
A, b = 16.430(4) A, c = 25.937(6) A, b = 112.743(4)ꢁ,
V = 5335 A . Dc (Z = 4 f.u.) = 1.564 g cmꢀ3. lMo = 34
3
˚
cmꢀ1; specimen: 0.8 · 0.1 · 0.1 mm; Tmin/max = 0.75.
2hmax = 58ꢁ; Nt = 53787, N = 13707 (Rint = 0.090),
No = 8239; R = 0.051, Rw = 0.051. |Dqmax| = 1.7(4)
2.3.1.6. AgSCN:dpae (1:1)(1|1) (6). C27H24AgAs2NS,
˚
ꢀ
M = 652.3. Triclinic, space group P1, a = 12.271(5) A,
˚
˚
˚
b = 12.212(3) A, c = 10.098(3) A, a = 69.84(2),
e Aꢀ3. CCD instrument, T ca. 153 K.
3
˚
b = 82.08(3), c = 62.93(3)ꢁ, V = 1265 A . Dc (Z = 2
Variata. This complex is isomorphous with the CuI
array (8) and was refined in a similar cell and coordinate
f.u.) = 1.713
g
cmꢀ3
.
l
Mo = 33 cmꢀ1
;
specimen:

752
A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
setting. The occurrence of mixed (pseudo-)halide com-
ponents was unexpected; both species refine credibly
and unscrambled, although the cyanide, as is often the
case, is best modelled with C/N composites.
tion) = 0.81.
R = 0.046, Rw = 0.050. |Dqmax| = 0.76(4)
(x,y,z,Uiso)H
295 K.
2hmax = 50ꢁ;
N = 2571,
No = 1873;
e
ꢀ3
˚
A .
refined. Single counter instrument, T ca.
For reference purposes, the structure of ꢀdpaeꢁ (and
dpape ” (Ph2P(CH2)2AsPh2)), crystallized from acetonit-
rile, has also been determined; the structure of dppe have
been previously defined for two polymorphs, both mono-
clinic P21/n, Z = 2 [6]. dpae and dpape as defined here are
isomorphous with one of these (Form II of [6a]).
˚
2.3.1.12. dpape. C26H24AsP, M = 442.4. a = 9.088(2) A,
˚
˚
b = 5.778(2) A, c = 21.684(4) A, b = 103.73(1)ꢁ,
V = 1106 A . Dc = 1.328 g cmꢀ3. lMo = 15.5 cmꢀ1; spec-
3
˚
imen: 0.14 · 0.61 · 0.16 mm; Tmin/max (gaussian correc-
tion) = 0.90.
2hmax = 60ꢁ;
N = 3226,
No = 1575;
e
ꢀ3
˚
A .
R = 0.046, Rw = 0.046. |Dqmax| = 0.49(4)
(x,y,z,Uiso H refined.
˚
2.3.1.11. dpae. C26H24As2, M = 486.3. a = 9.104(5) A,
)
˚
˚
b = 5.803(6) A, c = 21.83(1) A, b = 103.86(4)ꢁ,
Comment. In both of these structures, as in the parent
dppe, the molecules lie disposed about crystallographic
inversion centers, entailing in dpape scrambling of the
P and As components. These were not resolvable in
refinement, nor any disorder consequent in their pen-
dant substituents, refinement proceeding otherwise
smoothly. The molecules are necessarily ꢀtrans-oidꢁ, as
found in many of their structures in which they occur
in bridging mode, and as is also the case in the structure
of dppe [6].
V = 1120 A . Dc = 1.442 g cmꢀ3. lMo = 30 cmꢀ1; speci-
men: 0.20 · 0.84 · 0.24 mm; Tmin/max (analytical correc-
3
˚
Ph
As
M
Ph
As
M
Ph
As
M
Ph
As
M
Ph
Ph
Ph
Ph
Ph
Ph
X
X
X
X
As
Ph
As
Ph
As
Ph
As
Ph
Ph
Ph
Ph
Ph
1: M = Ag, X = Cl;
2: M = Ag, X = Br;
3: M = Ag, X = I;
8: M = Cu, X = I
Ph
Ph
Ph
Ph
As
Br
Br
As
Ag
As
Ag
Ag
As
Ag
As
Br
Br
Ph
Ph
Ph
Ph
As
Ph
E
Ph
E
Ph
E
Ph
E
Ph
Ph
Ph
Ph
Ph
Ph
N
5
Ph
Ph
As
S
C
N
C
S
M
M
M
M
S
N
S
C
Ph
Ph
E
E
E
E
As
Ph
As
As
Ph
Ph
Ph
Ph
Ph
Ph
Ph
S
C
N
S
N
Ph
Ph
Ag
Ph
Ph
Ph
Ph
Ag
N
C
As
Ph
As
As
Ph
4: M = Ag, X = As
9: M = Cu, X = P
Ph
Ph
As
Ph
As
Cu
As
Ph
Ph
Ph
As
Ph
Ph
Ph
6
Ph
Ph
Ph
Ph
O
C
As
Cu
As
Ph
As
Cu
As
Ph
Ph
Ph
O
C
N
Ph
Ph
Ph
Ph
As
N
Cu
As
Ph
N
C
C
N
As
Ag
As
Ag
Ag
As
Ag
As
Cl
Cl
N
C
O
Ph
Ph
Ph
Ph
As
Ph
Ph
Ph
Ph
N
Ph
C
O
Ph
10
7
Chart 1.
Chart 2.

A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
753
3. Results and discussion
all the other species are essentially stable in the solid
state. Conductivity measurements, as expected, indi-
cated that 1–9 are non-electrolytes in dichloromethane,
The reaction of MX (X = CN, CNO or SCN) with an
equimolar quantity of bis(diphenylarsino)-methane
(dpam) or -ethane (dpae) at room temperature has given
rise to polynuclear 1:1 adducts dpex:MX 1–8 (Charts 1
and 2). The adduct dppm: CuSCN (1:1) 9 has been pre-
pared similarly in MeCN by reaction of equimolar
quantities of CuSCN and bis(diphenylphosphino)meth-
ane (dppm); the choice of the solvent may be a determi-
nant both for the obtaining of the compounds and the
aggregation into a polynuclear structure, as, e.g., with
AgCl:dpam which is also obtained as a trinuclear form
of the same (unsolvated) gross stoichiometry from
acetonitrile solution. When MeCN or pyridine or a mix-
ture was employed, as in the present work, polymeric
species were obtained, whereas in the presence of piperi-
dine as solvent, trinuclear compounds have been
obtained [1].
the values being always in the range 1–4 Xꢀ1 cm2 molꢀ1
.
This suggests a strong interaction between Ag and the
halide or pseudo-halide counterion also in solution.
The conductivity values found for 1, 2, 4, 7 and 9 in
acetonitrile suggest some partial ionic dissociation in
solution in accordance with the occurrence of the fol-
lowing dissociative equilibria also supported from the
ESI MS data (see below).
½MðdpaxÞðXÞꢂ ꢀ n=2½M2ðdpaxÞ Xꢂþ þ Xꢀ
ð1Þ
ð2Þ
n
2
½MðdpaxÞðXÞꢂ ꢀ n=3½M3ðdpaxÞ X2ꢂþ þ Xꢀ
n
3
3.1. Spectroscopy
The infrared spectra of 1–9 (see Section 2) are con-
sistent with the formulations proposed, showing all of
the bands required by the presence of the counter-ion
and of the phosphorus or arsenic donor [7], the bands
due to the phosphine and arsine ligands being only
slightly shifted with respect to those of the free
Compounds 1–9 are generally air-stable, colorless
materials, poorly soluble not only in chlorinated sol-
vents such as CH2Cl2 or CHCl3, but also in strongly ion-
izing solvents such as DMSO, dimethylformamide and
acetone, in accordance with their polymeric nature. So-
lid samples of 1 and 2 show sensitivity to light, whereas
Fig. 1. 31P NMR (low temperature) spectrum (CDCl3 solution) of compound 9.

754
A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
donors. In the far-IR spectra of derivatives 1–4, the
broad absorptions near 500 cmꢀ1 and those at 450–
400 cmꢀ1 are likely due to Whiffenꢁs y and t vibra-
tions, respectively. The absorptions in the region
2140–2040 cmꢀ1 due to CN, SCN and CNO groups
are in accordance with those reported in the literature
for bridging pseudo-halide groups [8,9]. 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.
Fig. 2. ESI MS (ion positive mode) spectra of compounds 5 (a) and 9 (b).

A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
755
Table 1
(a) Selected polymer geometries, AgX:dpam (1:1); the asymmetric unit in each case is as follows except for the iodide where a sequence of two units is
Ph(a)
Ph(a)
C(2)
Ph(b)
Ph(b)
As(22)
Ag(2)
As(21)
Ag(1)
(X(2'))
X(2)
X(1)
C(1)
Ph(b)
As(11)
Ph(a)
Ph(b)
As(12)
Ph(a)
Cl (1)
Br (2)
I (3)
SCN (4)
˚
Distances (A)
X(1)–Ag(n)
2.591(4), 2.579(3)
2.656(4), 2.642(4)
3.709(4), 5.175(5)
2.594(2), 2.570(3)
2.605(2), 2.607(3)
3.307(4), 3.255(4)
2.693(3), 2.670(2)
2.756(3), 2.743(4)
3.650(4), 5.335(5)
2.596(2), 2.573(3)
2.596(2), 2.602(3)
3.305(4), 3.252(4)
2.827(3), 2.788(3)
2.895(3), 2.906(3)
3.492(2), 5.490(3)
2.595(4), 2.608(4)
2.567(4), 2.599(3)
3.237(4), 3.291(4)
2.834(3), 2.786(3)
2.894(3), 2.882(3)
3.629(3), 5.552(3)
2.572(4), 2.597(3)
2.616(4), 2.619(3)
3.276(4), 3.283(4)
2.653(3), 2.638(4)
2.640(4), 2.29(1)
3.820(2), 6.898(3)
2.571(2), 2.551(2)
2.609(2), 2.604(2)
3.252(2), 3.280(2)
X(2)–Ag(n(0))
Ag(1)ꢁ ꢁ ꢁAg(2,20)
Ag(1)–As(n1)
Ag(2)–As(n2)
As(n1)ꢁ ꢁ ꢁAs(n2)
Angles (ꢁ)
Ag(1)–X(1)–Ag(2)
Ag(10)–X(2)–Ag(2)
X(1)–Ag(1,2)–X(20,2)
As(1n)–Ag(n)–As(2n)
X(1)–Ag(1)–As(n1)
X(1)–Ag(2)–As(n2)
X(2)–Ag(1)–As(n1)
X(2)–Ag(2)–As(n2)
As(n1)–C(n)–As(n2)
91.7(1)
155.2(1)
112.9(1), 105.8(1)
85.77(8)
151.96(8)
76.91(8)
143.7(1)
80.43(3)
146.4(1)
92.39(9)
a
107.88(9), 104.39(7)
123.39(7), 113.16(6)
105.78(7), 106.23(7)
111.39(8), 111.48(7)
106.25(7), 106.56(7)
109.60(6), 106.30(9)
115.2(5), 115.0(8)
103.56(9), 110.63(9)
119.8(1), 114.6(1)
111.1(1), 111.3(1)
112.3(1), 114.4(1)
110.0(1), 99.3(1)
102.3(1), 101.3(1)
112(1), 111(1)
103.65(9), 116.41(9)
118.6(1), 116.3(1)
110.0(1), 110.3(1)
110.0(1), 111.6(1)
105.8(1), 107.3(1)
103.1(1), 99.07(9)
114(1), 101(2)/127(2)
105.8(1), 110.2(3)
119.53(6), 120.94(6)
104.61(9), 107.88(9)
102.96(9), 104.63(9)
107.1(1), 110.9(1)
112.5(3), 105.1(3)
112.7(5)
121.60(6), 111.09(6)
103.9(1), 105.9(1)
109.7(1), 110.6(1)
107.1(1), 105.7(1)
111.7(1), 107.7(1)
115.8(6), 112.6(6)
(b) Copper(I) analogues
E/X
As/I (8)
As/Cl,CNb (10)
P/SCNc (9)
˚
Distances (A)
X(1)–Cu(n)
2.6338(8), 2.6044(7)
2.7149(7), 2.7011(9)
3.722(1), 5.191(1)
2.3724(9), 2.363(1)
2.386(1), 2.391(1)
3.3010(9)
2.384(2), 2.392(1)
1.959(5), 1.956(5)
3.824(1), 4.998(1)
2.378(1), 2.369(1)
2.397(1), 2.384(1)
3.291(1), 3.239(1)
2.367(2), 2.395(2)
2.022(7), 2.422(2)
3.257(1), 6.406(2)
2.267(2), 2.271(2)
2.253(2), 2.274(3)
3.073(3), 3.096(3)
2.383(2), 2.392(2)
2.026(7), 2.410(2)
3.248(2), 6.414(2)
2.270(3), 2.278(3)
2.262(3), 2.272(2)
3.102(3), 3.073(3)
X(2)–Cu(n(0))
Cu(1)ꢁ ꢁ ꢁCu(2,20)
Cu(1)–E(n1)
Cu(2)–E(n2)
E(n1)ꢁ ꢁ ꢁE(n2)
Angles (ꢁ)
Cu(1)–X(1)–Cu(2)
Cu(1)–X(2)–Cu(20)
X(1)–Cu(1,2)–X(20,200)
E(1n)–Cu(n)–E(2n)
X(1)–Cu(1)–E(n1)
X(1)–Cu(2)–E(n2)
X(20)–Cu(1)–E(n1)
X(2)–Cu(2)–E(n2)
E(n1)–C(n)–E(n2)
90.54(2)
146.83(2)
106.41(6)
b
86.30(7)
c
85.75(7)
c
108.23(2), 110.44(2)
117.91(3), 110.60(3)
109.52(3), 104.29(3)
110.36(3), 109.32(3)
105.32(3), 111.31(3)
108.04(3), 108.04(3)
116.5(2), 114.8(2)
121.6(1), 112.7(1)
111.98(3), 105.79(3)
104.92(5), 100.99(5)
106.29(5), 104.53(5)
106.7(2), 110.5(2)
111.3(2), 115.5(2)
114.0(2), 111.1(2)
105.9(2), 89.84(8)
112.90(7), 114.55(8)
104.54(8), 118.20(7)
108.05(9), 115.8(1)
105.2(2), 109.1(2)
107.5(1), 118.19(9)
112.7(3), 115.2(4)
104.6(2), 91.29(8)
117.17(8), 113.12(8)
114.9(1), 105.16(9)
118.66(9), 107.1(1)
107.9(3), 106.1(3)
116.8(1), 107.4(1)
114.8(4), 113.4(3)
a
Ag(1)–S–C 118.1(4)ꢁ; also: S–C–N(1,2) are 178(2)ꢁ, 172(1)ꢁ; Ag(2)–N–C 174(1)ꢁ (entries involving N atoms are italicized in the table). For
˚
thiocyanate 1, Ag(1,2)–S–C are 105.5(5)ꢁ, 100.4(5)ꢁ. Within the two thiocyanates, S–C are 1.67(2), 1.67(1) and C–N 1.12(2), 1.13(2) A.
b
˚
C–N is 1.168(7)A; Cu(1,2)–N–C are 172.9(5)ꢁ, 163.0(4)ꢁ.
For the l-SCN, S–C are 1.66(1), 1.67(1); C–N are 1.15(1), 1.15(1) A; Cu,Cu –S–C are 112.9(4)ꢁ, 109.4(3)ꢁ, 112.9(4)ꢁ, 109.6(3)ꢁ and S–C–N
c
0
˚
˚
171(1)ꢁ, 170(1)ꢁ; for the ambidentate S–C–N, S–C are 1.659(8)ꢁ, 1.651(8)ꢁ; C–N 1.14(1), 1.15(1) A; Cu–S–C are 113.8(3)ꢁ, 114.0(3)ꢁ, Cu–N–C
155.7(6)ꢁ, 155.3(5)ꢁ and S–C–N 177.5(7)ꢁ, 176.6(7)ꢁ.

756
A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
In the 1H NMR spectra of 1–9 in CDCl3 (see Section
have been detected in accordance with the results pre-
viously reported [1] and conductivity studies. The
major peak present in the spectra of the dpae species
is due to a 2:1 adduct [Ag(dpae)2], which suggests che-
lation of the As2-donor in solution.
2), the signals due to the diphosphine and diarsine lig-
ands show a different pattern with respect to those
found for the free donors, confirming the existence of
complexes in solution. The bridging methylene reso-
nances in 1–5 and 9 appear as a broad singlet or re-
solved multiplet between 2.50 and 3.30 ppm generally
downfield shifted with respect to those found in the free
donors.
As reported in the previous papers [1,2], the negative
electrospray spectra are always dominated bꢀy the pres-
ence of molecular peaks due to X and AgX2
.
The 31P NMR room temperature spectrum of com-
pound 9 (acetone solution) exhibits a single sharp signal,
downfield shifted with respect to the free donor, this
suggesting the occurrence of a rapid exchange equilib-
rium between the coordinated and the free dppm or
the formation of a unique oligo- nuclear species contain-
ing equivalent P atoms. By contrast, at low temperature
the CDCl3 NMR spectrum of 9 exhibits eight broad sig-
nals in accordance with the existence of a number of dif-
ferent species in solution, presumably consequent upon
disruption of the polynuclear structure (Fig. 1).
The positive electrospray mass spectra of 1–9 (the
most relevant data are reported in Section 2, with
two typical spectra reported in Fig. 2) further confirm
the existence of the free ligand and of dinuclear and
trinuclear species in acetonitrile solution, the isotopic
distribution being always in accordance with the cal-
culated composition. It is noteworthy that the major
peak in the positive spectra of all species is always
due to a dicationic species [M2(dpex)2X]+ consequent
upon the breaking of bridging bonds, with loss of X
counter-ions, the data being in good accordance with
those derived from conductivity studies. In some
cases, peaks due to trinuclear species [M3(dpax)3X2]+
4. Single-crystal X-ray studies
The results of room temperature single-crystal X-
ray studies on crystalline adducts of the various
silver(I) salts AgX, X = Cl, Br, I, SCN, with dpam ob-
tained from pyridine or acetonitrile, are consistent
with their formulation in terms of stoichiometry and
connectivity as 1:1 AgX:dpam complexes, variously
solvated as above. For the chloride, the complex is
obtained in two distinct isomeric forms; that from
acetonitrile, ꢀaꢁ, is ionic [Cl2Ag3(dpam)]+Cl, with a cat-
ion closely resembling that found in the dppm ana-
logue, and is recorded in an accompanying paper
[1]. As the latter compound is a member of a family
of X = Cl, Br, and I arrays, and the present arsenic
analogue an isolated occurrence for that ligand, we
have included the details of its geometry in that report
for comparative purposes; it is not isomorphous with
any members of that family.
The ꢀbꢁ-form is a one-dimensional polymer with the
X = Br, I, and SCN counterparts being similar in form
(Table 1, Fig. 3); the chloride and bromide are isomor-
phous. In all except the iodide, one 2:2 formula unit of
Fig. 3. (a) Projection of the polymer of AgCl:dpam (1:1)2(1|1) (1) (the bromide (2) is isomorphous and the two iodides 3, 8 similar), normal to the
polymer axis. (b) (i,ii) Projections of the polymers of MSCN:dpem (1:1)2(1|1) (M,E = Cu,P(9); Ag,As(6)), normal to the polymer axis. (c) Projection
of the polymer of CuCl:CuCN:dppm (1:1:2)(1|1), normal to the polymer axis.

A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
757
Fig. 3 (continued)
each comprises the asymmetric unit of the structure. In
each case, the complex is a one-dimensional polymer,
comprising a zig-zag spine of alternating silver and
(pseudo-) halide moieties, there being two distinct types
of each: ꢁ ꢁ ꢁX(20)Ag(1)X(1)Ag(2)X(2)Ag(10)ꢁ ꢁ ꢁ. The
dpam ligands span successive pairs of silver atoms,

758
A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
Fig. 3 (continued)
one of each type, pairwise, so that one of the halide
entities, X(1), is encapsulated by them and the other
not;
chloride within the capsules and the cyanide linking
them.
Room-temperature single crystal studies have been
carried out on adducts formed between dpae and vari-
ous silver(I) salts with results also consistent with their
formulation as polymeric complexes of 1:1 AgX:dpax
stoichiometry (Table 2, Figs. 4 and 5). Unlike our at-
tempts to produce usefully crystalline analogues with
the phosphorus counterpart ligand, we find the present
species to present as nicely formed crystals with alacrity,
reflected in the precision accessible in their structure
determinations in all cases except one, that one (AgBr:
dpae (1:1)) being the only complex in the present array
which is solvated. Within the 1:1 complexes of various
silver(I) salts with the various dppx ligands, those form-
ing bulk, nicely crystalline adducts, optimum for diffrac-
tion studies, in which the species are polymeric tend to
be rare, the only examples recorded in the accompany-
ing papers being those of the chloride (b-form) and thi-
ocyanate with dppn (Ph2P(CH2)5PPh2) [3]. Polymeric
species may well occur with dppe, but thus far we have
been unable to obtain them pure and sufficiently crystal-
line to be amenable to single crystal studies. The present
bromide, albeit of uncongenial crystalline form, yielding
an imprecise structure, nevertheless is of considerable
interest in displaying yet another new form of polymer.
In it, and in the 1:1 cyanate and thiocyanate adducts,
also polymeric, the silver atom is four-coordinated with
(l-X)2AgAs2 environments, the two As atoms drawn
from different ligands. In the bromide, 5, we find the
(l-X)2Ag component of the coordination sphere satis-
fied by the formation of the common Ag(l-X2)2Ag ar-
ray, X = Br; such entities form ꢀkernelsꢁ in the ꢀparcelꢁ
compounds discussed in a subsequent paper, as well as
in polymers such as that found in the b-form of the
˚
with a pair of ꢀcapsulesꢁ spanning an approximately 14 A
unit cell dimension in each case, the second capsule here
being related to the first by a twofold screw axis in
monoclinic space group P21/c, in the bromide and io-
dide, the thiocyanate generator being the glide plane.
In the iodide, a pair of such capsules similarly span
the unit cell, but the pair in total now make up the
ꢀ
(4:4) asymmetric unit in triclinic space group P1. The
thiocyanate is remarkable in exhibiting two types of thi-
ocyanate entities, that within the capsule S-bridging the
pair of silver atoms, whereas that linking successive cap-
sules links ambidentately, SCN, one silver to either end.
Of particular interest in this structure is the skewing of
the bridging thiocyanate group towards ligand 1, per-
haps in response to a number of close contacts from
adjacent strands.
A less extensive but similar array has been structur-
ally characterized for copper(I), for CuI with dpam, sim-
ilar to the AgCl,Br/dpam counterparts, although from a
different solvent, and for CuSCN with dppm, the only
example for either metal with that ligand; the latter is
not isomorphous with its silver(I):dpam counterpart.
An interesting adventitious form, whose synthesis we
have as yet been unable to reproduce, has been credibly
defined with mixed anions, namely chloride and cyanide,
which stoichiometrically occupy the two distinct types of
available sites, thus CuCl:CuCN:dpam (1:1:2)(1|1), the

A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
759
Fig. 4. (a) Projection of the polymer of AgBr:dpae (1:1)2(1|1) (10) normal to the polymer axis. (b) Projection of the polymer of AgNCO:dpae
(1:1)2(1|1) (7) normal to the polymer axis.
1:1 AgCl:dppn adduct [3]. We found that formation of
the ꢀparcelꢁ compound type in 2:2 AgX:dppx adducts
was common with Ph2P(CH2)xPPh2 for x P 4; for
x = 3 dimer formation occurred with a pair of bidentate
ligands bridging the two silver atoms as in the parcel
compound type, but with steric strain apparently such
as to inhibit Ag(l-X)2Ag kernel formation in all cases
except one (the acetate) with the most basic ligand. Here
with the dpae ligand, we find an intact Ag(l-Br)2Ag ker-
nel retaining its integrity when bridged by one dpae lig-
and, clearly, however, in a situation of considerable
strain, the Ag(l-Br)2 Ag array folding across the Brꢁ ꢁ ꢁBr
line. Such an arrangement precludes a second dpae lig-
and bridging similarly, and so we find those compo-
nents, one half of each of two independent
centrosymmetric ligands, linking successive kernels into
a single stranded polymer. The geometry of the folded
Ag(l-Br)2Ag kernel is compared with those of planar
analogues drawn from various AgBr:dppx studies re-
corded in accompanying papers in Table 3. The Ag(l-
Br)2Ag unit, bridged by one of the bidentate ligands to
form a capsule, and with the other bidentate ligand link-
ing the capsules into an infinite one-dimensional poly-
mer with (l-X)2AgE2 nodes in the context of 1:1
AgX:dpex stoichiometry, forms an interesting contrast
with the ꢀisomericꢁ form involving halide linked Ag(l-

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A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
Table 2
ꢀMolecularꢁ core geometries, AgX:dpae (1:1)
1
˚
Distance (A)
Atoms
Atoms
Angle (ꢁ)
(a) AgBr:dpae (1:1)a (5)
Ag(1)–Br(1)
Ag(1)–Br(2)
2.767(8)
2.712(8)
2.561(7)
2.585(6)
2.713(9)
2.733(8)
2.569(7)
2.584(8)
3.130(6)
4.18(1)
Br(1)–Ag(1)–Br(2)
Br(1)–Ag(1)–As(1)
Br(1)–Ag(1)–As(3)
Br(2)–Ag(1)–As(1)
Br(2)–Ag(1)–As(3)
As(1)–Ag(1)–As(3)
Br(1)–Ag(2)–Br(2)
Br(1)–Ag(2)–As(2)
Br(1)–Ag(2)–As(4)
Br(2)–Ag(2)–As(2)
Br(2)–Ag(2)–As(4)
As(2)–Ag(2)–As(4)
Ag(1)–Br(1)–Ag(2)
Ag(1)–Br(2)–Ag(2)
99.6(3)
104.0(2)
111.3(3)
122.4(3)
100.3(3)
117.8(3)
100.4(2)
113.0(3)
105.4(3)
107.8(3)
105.5(3)
122.3(2)
69.7(2)
Ag(1)–As(1)
Ag(1)–As(3)
Ag(2)–Br(1)
Ag(2)–Br(2)
Ag(2)–As(2)
Ag(2)–As(4)
Ag(1)ꢁ ꢁ ꢁAg(2)
Br(1)ꢁ ꢁ ꢁBr(2)
70.2(2)
(b) AgNCO:dpae (1:1) (7) (atoms i are related by the 2-axis)b
Ag–N
2.281(5)
2.457(3)
N–Ag–Ni
94.5(1)
110.20(9)
Ag–Ni
Ag–As(1)
Ag–As(2)
N–C
N–Ag–As(1)
N–Ag–As(2)
Ni–Ag–As(1)
Ni–Ag–As(2)
As(1)–Ag–As(2)
Ag–N–Agi
Ag–N–C
2.5368(5)
2.5455(3)
113.20(9)
107.31(9)
1.13(2)/1.19(2)
1.22(2)/1.20(2)
3.0565(5)
102.02(9)
124.53(2)
80.3(1)
C–O
Agꢁ ꢁ ꢁAgi
148(1)/150.5(7)
117.2(7)/129.2(8)
173(1)/172(1)
Agi–N–C
N–C–O
(c) AgSCN:dpae (1:1)c (6)
Ag–S(a)
2.662(4)
2.224(6)
2.835(3)
2.21(1)
As(1)–Ag–S(a),N(b)
As(2)–Ag–S(a),N(b)
As(1)–Ag–N(a0),S(b0)
As(2)–Ag–N(a0),S(b0)
As(1)–Ag–As(2)
S(a)–Ag–N(a0)
99.31(6), 107.7(3)
113.40(6), 117.3(3)
112.4(2), 117.9(9)
108.2(2), 91.34(7)
120.36(3)
Ag–N(a0)
Ag–S(b0)
Ag–N(b)
Ag–As(1)
Ag–As(2)
S(a)–C(a)
2.6094(8)
2.5584(9)
1.651(8)
1.106(9)
1.64(1)
101.4(3)
99.8(2)
N(b)–Ag–S(b0)
C(a)–N(a)
S(b)–C(b)
C(b)–N(b)
Ag–S(a)–C(a)
99.5(4)
176.4(8)
S(a)–C(a)–N(a)
Ag–N(a0)–C(a0)
Ag–N(b)–C(b)
1.15(2)
156.3(8)
139(1)
N(b)–C(b)–S(b)
Ag–S(b0)–C(b0)
176.8(8)
99.0(3)
a
The AgBr2/Br2Ag dihedral angle is 53.9(3)ꢁ. Ag–As(1,2,3,4)-C–C torsions are ꢀ59(5)ꢁ, ꢀ77(4)ꢁ, ꢀ23(5)ꢁ, 49(5)ꢁ; torsions in the central C–C
bonds of the two ligands are 86(5)ꢁ, 180(ꢀ)ꢁ.
b
Torsions in the central C–C bonds of the two ligands are 180(ꢀ)ꢁ and ꢀ79.1(5)ꢁ.
c
Torsions in the central bonds of the two ligands are both 180ꢁ.
X)1Ag units bridged by a pair of bidentate ligands; i.e.,
, also of the same stoichiometry. The
the two metal atoms bridged by a pair of bidentate E-
dpex-E0 ligands and a bridging anion with a further anion
as the linker, or the two metal atoms bridged by a pair of
anions and one E-dpex-E0 ligand, the linker now being
the other E-dpex-E0 ligand. Further possibilities might
be envisaged where the metal atoms are bridged by one
halide, one dpex ligand, with a similar pair of linkers,
not realized, or another where a pair of metal atoms are
linked by a pair of anions, such binuclear units are linked
by a pair of ligands. This also is not realized as a linear
polymer here (although AgCl:dppn (1:1) [3] is found as
form of the cyanate analogue, 7, is similar to the
present bromide, the cyanate N-bridging, but
disordered.
In the above forms, we find the stoichiometry of
MX:dpex (1:1) satisfied within the context of an infinite
polymer with arrays containing four-coordinate metal(I)
atoms, wherein binuclear units are strung together by
appropriate linkers. The binuclear unit may comprise

A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
761
Fig. 5. Projection of the macrocyclic polymeric web found in AgSCN:dpae (1:1)2(1|1) (6), normal to the plane of the polymer (a) with and (b)
without phenyl appendages.
one such), the other 1:1 complex, the thiocyanate, which
is a polymer of a more familiar type, comprising
As2Ag(SCN)2AgAs2 kernels, with the familiar eight-
membered ring, a pair of disordered (concerted?) thio-
cyanate groups linking a pair of silver atoms, the ker-
nels acting as nodes for linkage by the bidentate

762
A. Cingolani et al. / Inorganica Chimica Acta 358 (2005) 748–762
Table 3
Comparative (E2)Ag(l-Br)2Ag(E2) kernel geometries
Compound
Ag–Br
Agꢁ ꢁ ꢁAg0
3.719(2)
Brꢁ ꢁ ꢁBr0
4.018(2)
Br–Ag–Br0
94.43(5)
Ag–Br–Ag0
Ref.
[11]
AgBr:PPh3 (2:4)
2.742(1)
2.734(1)
85.43(5)
85.72(1)
AgBr:dppb (2:2)
AgBr:dppn (2:2)
AgBr:dpph (2:2)
AgBr:dpae (2:2)
AgBr:dppp (2:2)
2.801(2)
2.817(1)
3.557(1)
3.814(1)
4.0341(8)
3.130(6)
4.155(2)
4.348(2)
4.040(1)
3.913(1)
4.18(1)
101.42(4)
93.30(2)
88.24(3)
78.58(4)
86.70(2)
91.76(3)
[3]
2.759(1)
2.797(1)
[3]
2.7129(9)
2.904(1)
[3]
2.712(8)
99.6(3)
100.4(2)
69.7(2)
70.2(2)
This work
[3]
ꢀ2.767(8)
2.704(3)
(3.428(2))
4.567(2)
[2] Effendy, C. Di Nicola, M. Nitiatmodjo, C. Pettinari, B.W.
Skelton, A.H. White, Inorg. Chim. Acta, doi:10.1016/
j.ica.2004.07032.
ligands into a polymer, two dimensional here, as a
web of 30-membered macrocyclic units (Fig. 5). An
unexpected form of the one-dimensional array is
found in AgNO3:dppe in which AgX2Ag units are
linked by one ligand with another unidentate pendant
[10].
[3] Effendy, C. Di Nicola, C. Pettinari, B.W. Skelton, N. Somers,
A.H. White, Inorg. Chim. Acta, in preparation.
[4] Effendy, G.A. Koutsantonis, C. Di Nicola, C. Pettinari, B.W.
Skelton, N. Somers, A.H. White, Inorg. Chim. Acta, in
preparation.
[5] Senko, M.W. IsoPro Isotopic Abundance Simulator, v.2.1;
National High Magnetic Field Laboratory, Los Alamos National
Laboratory, Los Alamos, NM.
Acknowledgments
[6] (a) C. Pelizzi, G. Pelizzi, Acta Crystallogr., Sect. B 35 (1979)
1785;
Support from the Australian Research Council, the
University of Camerino and Fondazione CARIMA,
and Proyek RUT VI BPPT LIPI, Indonesia, is gratefully
acknowledged.
(b) E.R.T. Tiekink, Z. Krist.–New Cryst. Struct. 216 (2000)
69.
[7] K. Shobatake, C. Postmus, J.F. Ferraro, K. Nakamoto, Appl.
Spectrosc. 23 (1969) 12.
[8] J.S. Thayer, R. West, Adv. Organomet. Chem. 5 (1967) 169.
[9] J.S. Thayer, D.P. Strommen, J. Organomet. Chem. 5 (1966) 383.
[10] M.S. Huang, P. Zhang, Y. Zhang, H. Yang, L. Zheng, Wuli
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