Synthesis and structural characterization of adducts of silver(I) nitrate with ER3 (E = P, As, Sb; R = Ph, cy, o-tolyl, mes) and oligodentate aromatic bases derivative of 2,2′-bipyridyl, L, AgNO3:ER3:L (1:1:1)

Article abstract of DOI:10.1016/j.ica.2006.07.017

Twenty-one adducts of the form AgNO₃:ER₃:L (1:1:1) (E = P, As, Sb; R = Ph, cy, o-tolyl, mes; L = 2,2′-bipyridyl ('bpy')-based ligand), together with AgNO₃:Pcy₃:tpy (2:2:1) and AgNO₃:PPh₃:tpy (1:2:1) ('tpy' ≡ (2,2′:6,2″-terpyridine)), have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, ¹H and ³¹P NMR) and single crystal X-ray diffraction studies. The resulting complexes are predominantly of the form [(R₃ E) AgL]⁺ NO₃^-, with trigonal EAgN₂ coordination environments, the planarity of which is perturbed by the approach of the nitrate anion. The nitrate ion shows uni- or (semi-)bidentate coordination, excepting the complex AgNO₃:P(o-tol)₃:dpca (1:1:1) (dpca = bis(2-picolyl)amine) where the anion is uncoordinated, the donor dpca being a pincer-tridentate. The complex AgNO₃:Pcy₃:tpy (2:2:1), also reported, is dinuclear with a bridging unidentate nitrate and a terpyridine, the latter bridging through its central ring, with the peripheral rings forming chelates to either side, whereas the complex AgNO₃:PPh₃:tpy (1:2:1) is ionic with a five-coordinate silver, bonded to tridentate tpy and two phosphines.

Full text of DOI:10.1016/j.ica.2006.07.017

Inorganica Chimica Acta 360 (2007) 1433–1450
www.elsevier.com/locate/ica
Synthesis and structural characterization of adducts of silver(I)
nitrate with ER3 (E = P, As, Sb; R = Ph, cy, o-tolyl, mes)
and oligodentate aromatic bases derivative
of 2,20-bipyridyl, L, AgNO3:ER3:L (1:1:1)
a
a
a,
*
Corrado Di Nicola , Effendy b,c, Fabio Marchetti , Claudio Pettinari
,
b
b
Brian W. Skelton , Allan H. White
a
`
Dipartimento di Scienze Chimiche, Universita degli Studi di Camerino, Via S. Agostino 1, 62032 Camerino MC, Italy
Chemistry M313, School of Biomedical, Biomolecular and Chemical Sciences, The University of Western Australia, Crawley, WA 6009, Australia
b
c
Jurusan Pendidikan Kimia, FMIPA Universitas Negeri Malang, Jalan Surabaya 6, Malang 65145, Indonesia
Received 29 May 2006; accepted 6 July 2006
Available online 21 July 2006
Abstract
Twenty-one adducts of the form AgNO3:ER3:L (1:1:1) (E = P, As, Sb; R = Ph, cy, o-tolyl, mes; L = 2,20-bipyridyl (‘bpy’)-based
ligand), together with AgNO3:Pcy3:tpy (2:2:1) and AgNO3:PPh3:tpy (1:2:1) (‘tpy’ ” (2,20:6,200-terpyridine)), have been synthesized and
characterized by analytical, spectroscopic (IR, far-IR, 1H and 31P NMR) and single crystal X-ray diffraction studies. The resulting com
plexes are predominantly of the form ½ðR3EÞAgLꢀþNO ꢁ, with trigonal EAgN2 coordination environments, the planarity of which is
3
perturbed by the approach of the nitrate anion. The nitrate ion shows uni- or (semi-)bidentate coordination, excepting the complex
AgNO3:P(o-tol)3:dpca (1:1:1) (dpca = bis(2-picolyl)amine) where the anion is uncoordinated, the donor dpca being a pincer-tridentate.
The complex AgNO3:Pcy3:tpy (2:2:1), also reported, is dinuclear with a bridging unidentate nitrate and a terpyridine, the latter bridging
through its central ring, with the peripheral rings forming chelates to either side, whereas the complex AgNO3:PPh3:tpy (1:2:1) is ionic
with a five-coordinate silver, bonded to tridentate tpy and two phosphines.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Silver nitrate; Phosphine; Aromatic N-bases; Single crystal X-ray studies; NMR
1. Introduction
derivatives with N-donor ligands such as 3,40-dipyridyl-
amine [10] or tris{2-[2-(1-methyl)imidazolyl]-methylimino-
Silver(I) systems containing aromatic nitrogen donor
ligands have potential applications in photography or sil-
ver plating by electrochemical processes [1–4]. Further,
some silver(I) derivatives exhibit antimicrobial and antitu-
mor activity [5–7], and some studies have revealed that
macrocyclic silver(I) complexes undergo very slow acid-
dependent decomplexation [8,9], a feature useful for
111Ag-based radioimmunotherapy. Recently, silver(I)
ethyl}amine [11] have shown in the solid state a
mononuclear and dinuclear nature, respectively, which
interconnect via hydrogen-bonding to afford interesting
supramolecular structures with new topologies, with poten-
tial applications in host–guest chemistry [12–16]. Previous
studies have defined arrays for various AgX/unidentate
N-base/unidentate P-base combinations [17,18], and, con-
currently with the present, we now publish further studies
combining bidentate N- and bidentate E-base forms
[19,20]. In the preceding paper [21], we extended this work
further to encompass the study of the nature of adducts of
*
Corresponding author. Tel.: +390737 402234; fax: +39 0737 637345.
E-mail address: claudio.pettinari@unicam.it (C. Pettinari).
0020-1693/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.07.017

1434
C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
the form AgX:ER3:L (1:1:1), where E could be P (extended
here, and in the following paper [22] to also include As,
Sb), R = Ph, cy (=cyclohexyl), o-tol (=o-tolyl), mes
(=mesityl), L similarly diverse in electronic and steric
characteristics, as an oligo-dentate nitrogen base, here
2,20-bipyridyl (‘bpy’), 1,10-phenanthroline (‘phen’), 2,9-
dimethyl,1,10-phenanthroline (‘dmp’), 2,20-biquinolyl
(‘bq’), bis(2-pyridyl)amine (‘dpa’), bis(2-pyridyl)ketone
(‘dpk’), 2,20:60,200-terpyridyl (‘tpy’), and bis(2-picolyl)-
amine (‘dpca’). In Ref. [21], we addressed the adducts of sil-
ver(I) perchlorate, as the first of a series of studies of arrays
of increasing oxyanion basicity. In this paper, we describe
an array of complexes obtained for X = NO3, a further
array for X = carboxylate being described in the following
paper [22].
846s m(NO3), 524vs, 504s, 493s, 444m, 435m, 417m
m(PPh3). 1H NMR (CDCl3, 293 K): d, 7.45m, 757m
(15H, PC18H15), 7.79dd, 7.92s, 8.41dd, 9.05dd (8H,
CHphen). 31P NMR (CDCl3, 223 K): d, 14.0dbr
(1J(31P–109/107Ag): 674.6 Hz).
2.1.3. Synthesis of AgNO3:PPh3:dmp (1:1:1) (3)
Compound 3 (0.563 g, yield 88%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using a
methanol solution of AgNO3 (0.170 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and dmp (0.208 g, 1.0 mmol). M.p.
250–252 ꢁC. Anal. Calc. for C32H27AgN3O3P: C, 60.01;
H, 4.25; N, 6.56. Found: C, 59.74; H, 4.33; N, 6.35%. Km
(CH3CN, 10ꢁ4 M): 123 Xꢁ1 cm2 molꢁ1
10ꢁ4 M): 38 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1): 1617w,
. . . . . .
. Km (CH2Cl2,
1585w, 1576w, 1511m m(C C, C N), 1455m, 1311m,
•
•
2. Experimental
855s m(NO3), 526vs, 505s, 489s, 444m, 435m, 416m
m(PPh3). 1H NMR (CDCl3, 293 K): d, 2.82s (6H, CH3dmp),
7.42m, 756m (15H, PC18H15), 7.63d, 7.81s, 8.28d (6H,
CHdmp). 31P NMR (CDCl3, 223 K): d, 11.4dd
Experimental procedures follow those recorded in an
accompanying paper [19]; in the majority of cases, crystals
suitable for the X-ray work were readily obtained from a
few milliliters of MeCN solutions of the reagents on a mil-
limolar scale by slow cooling and/or evaporation in
ambience.
1
(1J(31P–109Ag): 534.7 Hz; J(31P–107Ag): 463.7 Hz), 13.8dd
(1J(31P–109Ag): 701.9 Hz; 1J(31P–107Ag): 606.6 Hz). The
compound was modelled in the X-ray study as 3ƽ
MeOH.
2.1. Syntheses
2.1.4. Synthesis of AgNO3:PPh3:bq (1:1:1) (4)
Compound 4 (0.578 g, yield 84%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using
an acetonitrile solution of AgNO3 (0.170 g, 1.0 mmol),
PPh3 (0.262 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol).
M.p. 261–263 ꢁC. Anal. Calc. for C36H27AgN3O3P: C,
62.81; H, 3.95; N, 6.10. Found: C, 62.56; H, 4.11; N,
6.73%. Km (CH3CN, 10ꢁ4 M): 113 Xꢁ1 cm2 molꢁ1. Km
(CH2Cl2, 10ꢁ4 M): 35 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
1747w, 1738w m(NO3), 1617m, 1593s, 1571sh, 1554m,
2.1.1. Synthesis of AgNO3:PPh3:bpy (1:1:1) (1)
A solution containing AgNO3 (0.170 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and bpy (0.156 g, 1.0 mmol) in 5 mL
of CH3CN was stirred with warming for 1 h and then
cooled at room temperature. A colourless crystalline pre-
cipitate was slowly formed, which was filtered off, washed
with CH3CN (5 mL), dried under reduced pressure and
shown to be compound 1 (0.562 g, yield 95%). M.p. 182–
185 ꢁC. Anal. Calc. for C28H23AgN3O3P: C, 57.16; H,
3.94; N, 7.14. Found: C, 57.30; H, 3.90; N, 7.21%. Km
. . .
. . .
1546m, 1504s m(C C,
C
N), 1436s, 1317s, 828s
•
•
(CH3CN, 10ꢁ4 M): 118 Xꢁ1 cm2 molꢁ1
10ꢁ4 M): 37 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1): 1590w,
. . . . . .
. Km (CH2Cl2,
m(NO3), 521vs, 507s, 499s, 487s, 480s, 441m, 433m, 424m,
1
394m m(PPh3). H NMR (CDCl3, 293 K): d, 7.38m, 752m
(15H, PC18H15), 7.64m, 8.14d, 8.28d, 8.32dd (12H, CHbq).
1573w, 1566w m(C C, C N), 1452m, 1313mbr, 834m
•
•
31P NMR (CDCl3, 223 K): d, 13.9dd (1J(31P–109Ag):
m(NO3), 522s, 496vs, 434m, 419m, 409m, 400m m(PPh3).
1H NMR (CDCl3, 293 K): d, 7.50m (15H, PC18H15),
7.56m, 7.96dt, 8.21dd, 8.70dd (8H, CHbpy). 31P NMR
(CDCl3, 223 K): d, 11.6dd (1J(31P–109Ag): 449.2 Hz;
1J(31P–107Ag): 389.3 Hz), 18.8dd (1J(31P–109Ag): 740.6 Hz;
1J(31P–107Ag): 640.9 Hz).
1
695.7 Hz; J(31P–107Ag): 603.0 Hz).
2.1.5. Synthesis of AgNO3:PPh3:dpa (1:1:1) (5)
Compound 5 (0.530 g, yield 88%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of AgNO3 (0.170 g,
1.0 mmol), PPh3 (0.262 g, 1.0 mmol), and dpa (0.171 g,
1.0 mmol). M.p. 230–232 ꢁC. Anal. Calc. for C28H24Ag-
N4O3P: C, 55.74; H, 4.01; N, 9.29. Found: C, 55.38; H,
2.1.2. Synthesis of AgNO3:PPh3:phen (1:1:1) (2)
Compound 2 (0.590 g, yield 96%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using a
methanol solution of AgNO3 (0.170 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and phen (0.180 g, 1.0 mmol). M.p.
149–151 ꢁC. Anal. Calc. for C30H28AgN3O3P: C, 58.84;
H, 3.97; N, 6.86. Found: C, 58.72; H, 3.91; N, 6.74%. Km
4.13; N, 8.98%. Km (CH3CN, 10ꢁ4 M): 98 Xꢁ1 cm2 molꢁ1
.
Km (CH2Cl2, 10ꢁ4 M): 5 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
3300m, 3250m, 3190m m(N–Hdpa), 1742w, 1738w m(NO3),
. . .
. . .
1630s, 1575s, 1526m, m(C C, C N), 1412s, 1338s, 826m
•
•
1
(CH3CN, 10ꢁ4 M): 120 Xꢁ1 cm2 molꢁ1
10ꢁ4 M): 35 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1): 1619w,
. . . . . .
. Km (CH2Cl2,
m(NO3), 520vs, 506s, 493s, 440m, 427m, 407s m(PPh3). H
NMR (CDCl3, 293 K): d, 7.47m (15H, PC18H15), 6.83m,
7.34m, 7.66dd, 8.03dd (8H, CHdpa), 10.10br (1H, NHdpa).
1587w, 1572w, 1510m m(C C, C N), 1454m, 1309m,
•
•

C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
1435
31P NMR (CDCl3, 223 K): d, 17.4dd (1J(31P–109Ag):
C, 59.04; H, 3.72; N, 5.74. Found: C, 59.18; H, 3.92; N,
5.73%. Km (CH3CN, 10ꢁ4 M): 135 Xꢁ1 cm2 molꢁ1. Km
(CH2Cl2, 10ꢁ4 M): 23 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
1
744.7 Hz; J(31P–107Ag): 645.8 Hz).
. . .
. . .
2.1.6. Synthesis of AgNO3:PPh3:dpk (1:1:1) (6)
1622m, 1591s, 1524m, 1503s m(C C, C N), 1434s,
•
•
Compound 6 (0.573 g, yield 93%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using
an acetonitrile solution of AgNO3 (0.170 g, 1.0 mmol),
PPh3 (0.262 g, 1.0 mmol), and dpk (0.184 g, 1.0 mmol).
M.p. 141–143 ꢁC. Anal. Calc. for C29H23AgN3O4P: C,
56.51; H, 3.76; N, 6.82. Found: C, 57.82; H, 3.82; N,
6.64%. Km (CH3CN, 10ꢁ4 M): 124 Xꢁ1 cm2 molꢁ1. Km
(CH2Cl2, 10ꢁ4 M): 56 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
1750w, 1738w m(NO3), 1654s, 1611w, 1590m, 1567m
1310s, 828vs m(NO3), 502m, 481s, 470vs, 462s, 397m,
377m m(AsPh3), 347s, 322s, 316s. 1H NMR (CDCl3,
293 K): d, 7.29m, 7.38m (15H, AsC18H15), 7.50dt, 7.60dt,
7.73dd, 8.14d, 8.26d, 8.39d (12H, CHbq). The compound
was modelled in the X-ray study as 9ÆMeCN.
2.1.10. Synthesis of AgNO3:SbPh3:dpa (1:1:1) (10)
Compound 10 (0.646 g, yield 95%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of AgNO3 (0.170 g,
1.0 mmol), SbPh3 (0.353 g, 1.0 mmol), and dpa (0.171 g,
1.0 mmol). M.p. 168–170 ꢁC. Anal. Calc. for C28H24Ag-
N3O3Sb: C, 48.45; H, 3.49; N, 8.07. Found: C, 48.42; H,
. . .
. . .
m(C C, C N), 1434s, 1315s, 833s, 821s m(NO3), 513s,
•
•
504vs, 458w, 4425m, 414m, 403w m(PPh3), 386m, 304w,
280w, 262m, 247w, 228w, 221w. 1H NMR (CDCl3,
293 K): d, 7.32m (15H, PC18H15), 7.59dt, 7.94dt, 8.09dd,
8.86dd (8H, CHdpk). 31P NMR (CDCl3, 223K): d, 11.4dd
3.61; N, 8.16%. Km (CH3CN, 10ꢁ4 M): 144 Xꢁ1 cm2 molꢁ1
.
1
(1J(31P–109Ag): 535.9 Hz; J(31P–107Ag): 466.2 Hz), 13.7dd
Km (CH2Cl2, 10ꢁ4 M): 3 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
3335m, 3240m, 3180m m(NHdpa), 1744w, 1736w m(NO3),
1
(1J(31P–109Ag): 749.5 Hz; J(31P–107Ag): 649.4 Hz).
. . .
. . .
1627s, 1578s, 1575s, 1527s, m(C C, C N), 1432s,
•
•
2.1.7. Synthesis of AgNO3:AsPh3:bpy (1:1:1) (7)
1339s, 825m m(NO3), 525m, 460s, 453s, 442m, 406m,
345w, 328w m(SbPh3), 283s, 265vs. 1H NMR (CDCl3,
293 K): d, 7.46m (15H, SbC18H15), 6.74m, 7.35m, 7.55m,
8.11dd (8H, CHdpa), 9.35br (1H, NHdpa).
Compound 7 (0.575 g, yield 91%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using
an acetonitrile solution of AgNO3 (0.170 g, 1.0 mmol),
AsPh3 (0.306 g, 1.0 mmol), and bpy (0.156 g, 1.0 mmol).
M.p. 174–176 ꢁC. Anal. Calc. for C28H23AgAsN3O3: C,
53.19; H, 3.67; N, 6.65. Found: C, 53.44; H, 3.80; N,
6.47%. Km (CH3CN, 10ꢁ4 M): 137 Xꢁ1 cm2 molꢁ1. Km
(CH2Cl2, 10ꢁ4 M): 23 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
2.1.11. Synthesis of AgNO3:SbPh3:bq (1:1:1) (11)
Compound 11 (0.670 g, yield 86%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using an
acetonitrile/ethanol solution of AgNO3 (0.170 g, 1.0 mmol),
SbPh3 (0.353 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol). M.p.
238–240 ꢁC. Anal. Calc. for C36H27AgN3O3Sb: C, 55.49; H,
3.49; N, 5.39. Found: C, 55.72; H, 3.58; N, 5.26%. Km
. . .
. . .
1587m, 1574m, 1523w, m(C C, C N), 1461s, 1305s,
•
•
824m m(NO3), 470vs, 408m m(AsPh3), 333m, 321s. 1H
NMR (CDCl3, 293 K): d, 7.40m (15H, AsC18H15), 7.50m,
7.89dd, 8.15dd, 8.71dd (8H, CHbpy).
(CH3CN, 10ꢁ4 M): 135 Xꢁ1 cm2 molꢁ1
10ꢁ4 M): 24 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1): 1617m,
. . . . . .
. Km (CH2Cl2,
2.1.8. Synthesis of AgNO3:AsPh3:dpa (1:1:1) (8)
1594m, 1575w, 1556w, 1546w, 1503s m(C C, C N),
• •
Compound 8 (0.556 g, yield 86%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using
an acetonitrile solution of AgNO3 (0.170 g, 1.0 mmol),
AsPh3 (0.306 g, 1.0 mmol), and dpa (0.171 g, 1.0 mmol).
M.p. 205–207 ꢁC. Anal. Calc. for C28H24AgAsN4O3: C,
51.96; H, 3.74; N, 8.66. Found: C, 52.12; H, 3.90; N,
8.62%. Km (CH3CN, 10ꢁ4 M): 110 Xꢁ1 cm2 molꢁ1. Km
(CH2Cl2, 10ꢁ4 M): 3 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
3310m, 3240m, 3190m m(N–Hdpa), 1742w, 1738w m(NO3),
1432s, 1402m, 1334s, 819s m(NO3), 501m, 488m, 482m,
1
456vs, 426w, 399w, m(SbPh3), 279m, 267s, 224m. H NMR
(CDCl3, 293 K): d, 7.30m, 7.45m (15H, SbC18H15), 7.49dt,
7.58dt, 7.63dt, 8.11d, 8.24d, 8.50d (12H, CHbq). The com-
pound was modelled in the X-ray study as 11Æ1½EtOH.
2.1.12. Synthesis of AgNO3:Pcy3:bpy (1:1:1) (12)
Compound 12 (0.466 g, yield 77%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of AgNO3 (0.170 g,
1.0 mmol), Pcy3 (0.280 g, 1.0 mmol), and bpy (0.156 g,
1.0 mmol). M.p. 144–146 ꢁC. Anal. Calc. for C28H41Ag-
N3O3P: C, 55.45; H, 6.93; N, 6.93. Found: C, 55.41; H,
. . .
. . .
1626s, 1575s, 1526m, m(C C, C N), 1412s, 1340s,
•
•
825m m(NO3), 525m, 478s, 471vs, 458s, 406s m(AsPh3),
339m, 325s, 317s. 1H NMR (CDCl3, 293 K): d, 7.43m
(15H, AsC18H15), 6.83m, 7.32m, 7.62m, 8.10m (8H,
CHdpa), 9.50br (1H, NHdpa).
6.88; N, 7.12%. Km (CH3CN, 10ꢁ4 M): 134 Xꢁ1 cm2 molꢁ1
.
Km (CH2Cl2, 10ꢁ4 M): 35 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
. . .
2.1.9. Synthesis of AgNO3:AsPh3:bq (1:1:1) (9)
1745w, 1736w m(NO3), 1614m, 1594s, 1572m m(C C,
•
. . .
Compound 9 (0.688 g, yield 94%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using
an acetonitrile solution of AgNO3 (0.170 g, 1.0 mmol),
AsPh3 (0.306 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol).
M.p. >220 ꢁC (dec.). Anal. Calc. for C36H27AgAsN3O3:
C
N), 1454s, 1310vs, 823m m(NO3), 515vs, 471m, 460m,
•
1
410s, 391m, 383m m(Pcy3). H NMR (CDCl3, 293 K): d,
1.36m, 1.91m (33H, PC18H33), 7.57dt, 8.07dt, 8.42dd,
8.66dd (8H, CHbpy). 31P NMR (CDCl3, 223 K): d, 46.2dd
(1J(31P–109Ag): 723.8 Hz; 1J(31P–107Ag): 627.3 Hz). The

1436
C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
compound was modelled in the X-ray study as 12Æ3/
8MeCN.
2.1.17. Synthesis of AgNO3:P(o-tol)3:bpy (1:1:1) (17)
Compound 17 (0.580 g, yield 92%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of AgNO3 (0.170 g,
1.0 mmol), P(o-tol)3 (0.304 g, 1.0 mmol), and bpy
(0.156 g, 1.0 mmol). M.p. 212–214ꢁC. Anal. Calc. for
C31H29AgN3O3P: C, 59.06; H, 4.64; N, 6.67. Found: C,
58.78; H, 4.77; N, 6.83%. Km (CH3CN, 10ꢁ4 M):
132 Xꢁ1 cm2 molꢁ1. Km (CH2Cl2, 10ꢁ4 M): 40 Xꢁ1 cm2
molꢁ1. IR (nujol, cmꢁ1): 1747w, 1738w, 1732w m(NO3),
2.1.13. Synthesis of AgNO3:Pcy3:phen (1:1:1) (13)
Compound 13 (0.523 g, yield 83%) has been prepared
following a procedure similar to that reported for 1 by
using a methanol solution of AgNO3 (0.170 g, 1.0 mmol),
Pcy3 (0.280 g, 1.0 mmol), and phen (0.180 g, 1.0 mmol).
M.p. 237–239 ꢁC. Anal. Calc. for C30H41AgN3O3P: C,
57.15; H, 6.55; N, 6.66. Found: C, 57.41; H, 6.52; N,
6.53%. Km (CH3CN, 10ꢁ4 M): 111 Xꢁ1 cm2 molꢁ1. Km
(CH2Cl2, 10ꢁ4 M): 57 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
1741w m(NO3), 1617m, 1590m, 1570m, 1512s, 1500m
. . .
. . .
1633w, 1587m, 1573w, 1564w m(C C, C N), 1439m,
•
•
1392m, 1302s br, 822s, 802s m(NO3), 564s, 557sh, 519m,
511m, 468vs, 461vs, 440w, 411m m(P(o-tol)3), 279m,
267m, 227m, 205m. 1H NMR (CDCl3, 293 K): d, 2.54s
(9H, P(C6H4-ortho-CH3)3), 6.91dd, 7.21t, 7.38m (12H,
P(C6H4-ortho-CH3)3), 7.45dt, 8.02dt, 8.34d, 8.44dd (8H,
CHbpy). 31P NMR (CDCl3, 223 K): d, ꢁ18.4d br
(1J(31P–109/107Ag): 672.5 Hz). The compound was modelled
in the X-ray study as 17ƽMeCN.
. . .
. . .
m(C C, C N), 1425s, 1307s, 844vs m(NO3), 520vs, 471s,
•
•
458m, 416m, 392w, 380w m(Pcy3). 1H NMR (CDCl3,
293 K): d, 1.38m, 1.94m (33H, PC18H33), 7.95dd, 8.07s,
8.56dd, 9.04dd (8H, CHphen). 31P NMR (CDCl3, 223 K):
d, 46.3dd (1J(31P–109Ag): 725.1 Hz; 1J(31P–107Ag):
627.3 Hz), 33.0dd (1J(31P–109Ag): 529.7 Hz; J(31P–107Ag):
1
458.9 Hz).
2.1.18. Synthesis of AgNO3:P(o-tol)3:bq (1:1:1) (18)
Compound 18 (0.613 g, yield 84%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of AgNO3 (0.170 g,
1.0 mmol), P(o-tol)3 (0.304 g, 1.0 mmol), and bq (0.256 g,
1.0 mmol). M.p. 255–257 ꢁC. Anal. Calc. for C39H33Ag-
N3O3P: C, 64.12 H, 4.55; N, 5.75. Found: C, 64.40; H,
2.1.14. Synthesis of AgNO3:Pcy3:bq (1:1:1) (14)
Compound 14 (0.649 g, yield 92%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using a
methanol solution of AgNO3 (0.170 g, 1.0 mmol), Pcy3
(0.280 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol). M.p. 184–
186 ꢁC. Anal. Calc. for C36H45AgN3O3P: C, 61.19; H, 6.42;
N, 5.95. Found: C, 61.33; H, 6.48; N, 5.90%. Km (CH3CN,
4.71; N, 5.85%. Km (CH3CN, 10ꢁ4 M): 129 Xꢁ1 cm2 molꢁ1
.
10ꢁ4 M): 115 Xꢁ1 cm2 molꢁ1
52 Xꢁ1 cm2 molꢁ1 IR (nujol, cmꢁ1): 1732w, 1718w
m(NO3), 1618m, 1593s, 1555m, 1549m, 1535w, 1504s
. . . . . .
.
Km (CH2Cl2, 10ꢁ4 M):
Km (CH2Cl2, 10ꢁ4 M): 41 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
.
1619m, 1594s, 1574m, 1564m, 1554m, 1546m, 1504s
. . .
. . .
m(C C, C N), 1455s, 1433m, 1417w, 1338m, 1307s br,
•
•
m(C C, C N), 1446s, 1420w, 1309s, 828s m(NO3), 564w,
833s, 822m m(NO3), 564vs, 521m, 514m, 488s, 473vs,
468vs, 461vs, 440m m(P(o-tol)3), 399m, 278m, 272m. 1H
NMR (CDCl3, 293 K): d, 2.39s (9H, P(C6H4-ortho-
CH3)3), 7.08m, 7.45m (12H, P(C6H4-ortho-CH3)3), 7.63dt,
7.75dt, 7.92m, 8.53d, 8.71d (12H, CHbq). 31P NMR
(CDCl3, 223 K): d, ꢁ8.6 br.
•
•
547m, 533w, 514m, 501w, 484s, 472w, 443w, 420w, 399m
1
m(Pcy3), 280m, 224m. H NMR (CDCl3, 293 K): d, 1.24m,
1.83m (33H, PC18H33), 7.62dt, 7.74dt, 7.82dt, 8.33d, 8.38d,
8.62d (12H, CHbq). 31P NMR (CDCl3, 223 K): d, 37.3dd
1
(1J(31P–109Ag): 701.9 Hz; J(31P–107Ag): 609.2 Hz), 32.9dd
(1J(31P–109Ag): 528.6 Hz; 1J(31P–107Ag): 457.8 Hz).
2.1.19. Synthesis of AgNO3:P(o-tol)3:dpa (1:1:1) (19)
Compound 19 (0.567 g, yield 88%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of AgNO3 (0.170 g,
1.0 mmol), P(o-tol)3 (0.304 g, 1.0 mmol), and dpa
(0.171 g, 1.0 mmol). M.p. 171–173 ꢁC. Anal. Calc. for
C31H30AgN4O3P: C, 57.69; H, 4.68; N, 8.68. Found: C,
57.55; H, 4.60; N, 8.34%. Km (CH3CN, 10ꢁ4 M):
105 Xꢁ1 cm2 molꢁ1. Km (CH2Cl2, 10ꢁ4 M): 4 Xꢁ1 cm2
2.1.15. Synthesis of AgNO3:Pcy3:dpa (1:1:1) (15)
Compound 15 (0.540, yield 87%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using a
methanol solution of AgNO3 (0.170 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and dpa (0.171 g, 1.0 mmol). M.p.
190ꢁC (dec.). Anal. Calc. for C28H42AgN3O3P: C, 54.11;
H, 6.81; N, 9.01. Found: C, 53.78; H, 6.71; N, 8.83%. Km
(CH3CN, 10ꢁ4 M): 102 Xꢁ1 cm2 molꢁ1
10ꢁ4 M): 3 Xꢁ1 cm2 molꢁ1
. Km (CH2Cl2,
.
molꢁ1. IR (nujol, cmꢁ1): 1740w, 1733w, 1698w m(NO3),
. . .
1638s, 1588s, 1578s, 1547w, 1531s, 1514w m(C C,
•
. . .
2.1.16. Synthesis of AgNO3:Ascy3:bq (1:1:1) (16)
C
N), 1440s, 1413s mas(NO3), 1290s, 824m, 803s ms(NO3),
•
Complex 16 was obtained by crystallization of millimo-
lar stoichiometries of AgNO3 with Ascy3 and bq, from ace-
tonitrile solution by standing and evaporation in ambience.
M.p. 187–90 ꢁC. Anal. Calc. for C36H45AgAsN3O3: C,
57.61; H, 6.04; N, 5.60. Found: C, 57.54; H, 6.01; N,
5.52%. Km (CH3CN, 10ꢁ4 M): 122 Xꢁ1 cm2 molꢁ1. Km
565s, 558sh, 519s, 469vs, 460vs, 440w, 405m m(P(o-tol)3),
326m, 279m, 226m. 1H NMR (CDCl3, 293 K): d, 2.43s
(9H, P(C6H4-ortho-CH3)3), 6.91dd, 7.21t, 7.40m (12H,
P(C6H4-ortho-CH3)3), 6.76m, 7.35m, 7.62dd, 7.80dd (8H,
CHdpa), 9.80br (1H, NHdpa). 31P NMR (CDCl3, 223 K):
d, ꢁ17.3d (1J(31P–109/107Ag): 673.8 Hz). The compound
was modelled in the X-ray study as 19ƽEtOH.
(CH2Cl2, 10ꢁ4 M): 48 Xꢁ1 cm2 molꢁ1
.

C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
1437
2.1.20. Synthesis of AgNO3:P(o-tol)3:dpca:H2O (1:1:1:1)
(20)
8.00dt, 8.18dt, 8.27dd, 8.70d (11H, CHtpy). 31P NMR
(CDCl3, 223 K): d, 33.1dd (1J(31P–109Ag): 528.6 Hz;
1J(31P–107Ag): 457.8 Hz), 42.7dd (1J(31P–109Ag): 740.9 Hz;
1J(31P–107Ag): 647.1 Hz).
Compound 20 (0.641 g, yield 93%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of AgNO3 (0.170 g,
1.0 mmol), P(o-tol)3 (0.304 g, 1.0 mmol) and dpca
(0.199 g, 1.0 mmol). M.p. 195–197 ꢁC. Anal. Calc. for
C33H34AgN4O4P: C, 57.49; H, 4.97; N,8.13. Found: C,
57.60; H, 5.06; N, 8.14%. Km (CH3CN, 10ꢁ4 M):
139 Xꢁ1 cm2 molꢁ1. Km (CH2Cl2, 10ꢁ4 M): 56 Xꢁ1 cm2
molꢁ1. IR (nujol, cmꢁ1): 3360v br m(N–Hdpca + H2O),
2.1.23. Synthesis of AgNO3:PPh3:tpy (1:2:1) (23)
Compound 23 (0.834 g, yield 90%) has been prepared
following a procedure similar to that reported for 1 by
using a methanol solution of AgNO3 (0.170 g, 1.0 mmol),
PPh3 (0.524 g, 2.0 mmol), and tpy (0.233 g, 1.0 mmol).
M.p. 180ꢁC (dec.). Anal. Calc. for C51H41AgN4O3P2: C,
66.03; H, 4.45; N, 6.04. Found: C, 65.78; H, 4.47; N,
5.80%. Km (CH3CN, 10ꢁ4 M): 165 Xꢁ1 cm2 molꢁ1. Km
. . .
. . .
1644m d(H2O), 1590s, 1567m m(C C, C N), 1441s
•
•
mas(NO3), 1313s br, 828m, 799m ms(NO3), 564s, 557sh,
521s, 504s, 464vs, 440m, 409m, 402m m(P(o-tol)3), 303m,
268vs. H NMR (CDCl3, 293 K): d, 2.39s (9H, P(C6H4-
(CH2Cl2, 10ꢁ4 M): 23 Xꢁ1 cm2 molꢁ1
.
1
2.2. Structure determinations
ortho-CH3)3), 4.07s (4H, CH2dpac), 4.80br (2H, H2O),
7.17t, 7.28m, 7.40dt (12H, P(C6H4-ortho-CH3)3), 6.87t,
7.03dt, 7.64dt, 7.72d (8H, CHdpca), NHdpca not observed.
31P NMR (CDCl3, 223 K): d, ꢁ17.5d br (1J(31P–109/
107Ag): 640.8 Hz). The compound was modelled in the X-
ray study as 20ƽH2O.
General procedures are described in an accompanying
paper [19]; specific details are as follows. For 1, 2, T was
ca. 300 K. CCDC Nos. 605475–605497.
2.2.1. Crystal/refinement data
2.2.1.1. AgNO3:PPh3:bpy (1:1:1) (1). C28H23AgN3O3P,
2.1.21. Synthesis of AgNO3:PPhmes2:tpy (1:1:1) (21)
Compound 21 (0.630 g, yield 84%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of AgNO3 (0.170 g,
1.0 mmol), PPhmes2 (0.346 g, 1.0 mmol), and tpy
(0.233 g, 1.0 mmol). M.p. 205–208 ꢁC. Anal. Calc. for
C39H38AgN4O3P: C, 62.49; H, 5.11; N, 7.47. Found: C,
62.62; H, 5.10; N, 7.32%. Km (CH3CN, 10ꢁ4 M):
116 Xꢁ1 cm2 molꢁ1. Km (CH2Cl2, 10ꢁ4 M): 45 Xꢁ1 cm2
M = 588.4. Triclinic, space group P1 ðC1i ; No: 2Þ,
ꢀ
˚
a = 18.267(2), b = 9.689(1), c = 8.139(1) A, a = 112.496
3
˚
(2)ꢁ, b = 96.410(2)ꢁ, c = 100.032(2)ꢁ, V = 1285 A . Dcalc
(Z = 2) = 1.520 g cmꢁ3. lMo = 8.8 cmꢁ1; specimen: 0.62 ·
0.28 · 0.12 mm; ‘T’min/max = 0.85. 2hmax = 58ꢁ; Nt =
14338; N = 6259 (Rint = 0.022), No = 4401; R = 0.031,
Rw = 0.035. (x,y,z,Uiso)H refined.
molꢁ1. IR (nujol, cmꢁ1): 1603s, 1589s, 1578s m(C C,
2.2.1.2. AgNO3:PPh3:phen (1:1:1) (2). C30H23AgN3O3P,
M = 612.4. Monoclinic, space group P21/c ðC52h; No: 14Þ,
. . .
•
. . .
C
N), 1445s mas(NO3), 1328s br, 828m, 800m ms(NO3),
•
˚
a = 17.192(2), b = 8.913(1), c = 17.994(2) A, b = 105.726(2)ꢁ,
570m, 560vs, 543m, 524m, 512w, 482s, 447vs, 430vs,
410m, 401m m(PPhmes2), 303m, 268vs. H NMR (CDCl3,
3
V = 2654 A . Dcalc (Z = 4) = 1.532 g cmꢁ3. lMo = 8.6 cmꢁ1
;
˚
1
specimen: 0.20 · 0.15 · 0.10 mm; ‘T’min/max = 0.67. 2hmax
=
293 K): d, 1.90s, 2.26s (18H, P(C6H5)(C6H2-2,4,6-
(CH3)3)2), 6.76s, 6.77s (4H, P(C6H5)(C6H2-2,4,6-
(CH3)3)2), 7.23t, 7.27t, 7.41d (5H, P(C6H5)(C6H2-2,4,6-
(CH3)3)2), 7.45br, 7.91t, 8.08sbr, 8.18t, 8.30dd (11H,
CHtpy). 31P NMR (CDCl3, 298 K): d, ꢁ11.2s. 31P NMR
(CDCl3, 223 K): d, ꢁ12.1dd (1J(31P–109Ag): 710.3 Hz;
1J(31P–107Ag): 615.3 Hz).
58ꢁ; Nt = 29634, N = 6707 (Rint = 0.028), No = 3613; R =
0.036, Rw = 0.037. (x,y,z,Uiso)H refined.
2.2.1.3. AgNO3:PPh3:dmp (1:1:1) Æ ½MeOH (3 Æ ½
MeOH). C32H27AgN3O3P Æ ½CH3OH, M = 656.4. Mono-
clinic, space group C2/c ðC62h; No: 15Þ, a =48.535(3),
˚
b = 8.3275(5), c = 37.678(2) A, b = 129.604(1)ꢁ, V =
3
11733 A . Dcalc (Z = 16) = 1.486 g cmꢁ3. lMo = 7.8 cmꢁ1
;
˚
2.1.22. Synthesis of AgNO3:Pcy3:tpy (2:2:1) (22)
specimen: 0.35 · 0.27 · 0.20 mm; ‘T’min/max = 0.80. 2hmax
=
Compound 22 (0.499 g, yield 88%) has been prepared
following a procedure similar to that reported for 1 by
using a methanol solution of AgNO3 (0.170 g, 1.0 mmol),
Pcy3 (0.280 g, 1.0 mmol), and tpy (0.233 g, 1.0 mmol).
M.p. 174–176 ꢁC. Anal. Calc. for C51H77Ag2N5O6P2: C,
54.03; H, 6.84; N, 6.18. Found: C, 53.84; H, 6.75; N,
6.37%. Km (CH3CN, 10ꢁ4 M): 250 Xꢁ1 cm2 molꢁ1. Km
(CH2Cl2, 10ꢁ4 M): 32 Xꢁ1 cm2 molꢁ1. IR (nujol, cmꢁ1):
1741w, 1733w m(NO3), 1592s, 1573m, 1567m, 1560m
58ꢁ; Nt = 64761, N = 14878 (Rint = 0.025), No = 9403;
R = 0.037, Rw = 0.042. (x,y,z,Uiso)H refined.
Variata. Solvent difference map residues were modelled
as 0.5MeOH.
2.2.1.4. AgNO3:PPh3:bq (1:1:1) (4). C36H27AgN3O3P,
M = 688.5. Triclinic, space group P1, a = 16.673(2),
˚
b = 10.488(1),
c = 10.040(2) A,
a = 63.65(1)ꢁ,
b =
3
˚
. . .
. . .
86.19(1)ꢁ, c = 86.843(1)ꢁ, V = 1569 A . Dcalc (Z = 2) =
m(C C, C N), 1438vs, 1406s, 1353vs, 1290vs, 850s,
•
•
1.457 g cmꢁ3
. l ; specimen: 0.08 · 0.38 ·
Mo = 7.3 cmꢁ1
830m, 818m m(NO3), 542w, 515vs, 487m, 471m, 459w,
1
0.79 mm; ‘T’min/max = 0.82. 2hmax = 50ꢁ; N = 5506,
No = 3586; R = 0.047, Rw = 0.046.
450w, 416s, 392m, 383m m(Pcy3), 351w, 288m. H NMR
(CDCl3, 293 K): d, 1.18m, 1.70m (33H, PC18H33), 7.45dd,

1438
C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
2.2.1.5. AgNO3:PPh3:dpa (1:1:1) (5). C28H24AgN4O3P,
M = 603.4. Monoclinic, space group P21/n ðC52h; No:
2.2.1.11. AgNO3:SbPh3:bq (1:1:1) Æ 1½EtOH (11 Æ 1½EtOH).
C39H36AgN3O4.5Sb, M = 848.4. Triclinic, space group P1, a =
˚
14 ðvariantÞÞ, a = 17.189(2), b = 9.171(1), c = 18.013(2)
9.571(1), b = 11.690(1), c = 16.826(2) A, a = 70.283(2)ꢁ,
3
3
˚
˚
˚
A, b = 113.618(2)ꢁ, V = 2602 A . Dcalc (Z = 4) = 1.540 g
cmꢁ3. lMo = 8.7 cmꢁ1; specimen: 0.38 · 0.16 · 0.11 mm;
‘T’min/max = 0.87. 2hmax = 58ꢁ; Nt = 30216, N = 6553
b = 82.962(2)ꢁ, c = 75.957(2)ꢁ, V = 1717 A . Dcalc (Z =
2) = 1.640 g cmꢁ3. lMo = 14.0 cmꢁ1; specimen: 0.25 · 0.15 ·
0.13 mm; ‘T’min/max = 0.83. 2hmax = 58ꢁ; Nt = 9513 (hemi-
sphere), N = 7321 (Rint = 0.013), No = 6331; R = 0.024,
Rw = 0.027.
(Rint = 0.028),
No = 5685;
R = 0.023,
Rw = 0.019.
(x,y,z,Uiso H refined.
)
Variata. One of the solvent molecules was modelled as
disordered about a crystallographic inversion centre.
2.2.1.6. AgNO3:PPh3:dpk (1:1:1) (6). C29H23AgN3O4P,
M = 616.4. Triclinic, space group P1, a = 13.283(5),
˚
b = 10.902(2),
c = 9.542(3) A,
a = 90.14(2)ꢁ,
b =
2.2.1.12. AgNO3:Pcy3:bpy (1:1:1) Æ 3/8MeCN (12 Æ 3/
8MeCN). C28H41AgN3O3P Æ 3/8MeCN, M = 621.9. Tri-
clinic, space group P1, a = 19.917(3), b = 15.407(2),
3
˚
108.07(3)ꢁ, c = 90.34(2)ꢁ, V = 1313 A . Dcalc (Z = 2) =
1.558 g cmꢁ3
. l ; specimen: 0.04 · 0.36 ·
Mo = 8.7 cmꢁ1
˚
0.52 mm; ‘T’min/max = 0.78. 2hmax = 50ꢁ; N = 4612, No =
3145; R = 0.042 Rw = 0.041.
c = 10.024(2) A, a = 82.91(2)ꢁ, b = 78.04(2)ꢁ, c = 82.45
3
(1)ꢁ, V = 2968 A . Dcalc (Z = 4) = 1.392 g cmꢁ3. lMo
=
=
˚
7.7 cmꢁ1; specimen: 0.30 · 0.42 · 0.08 mm; ‘T’min/max
0.85. 2hmax = 55ꢁ; N = 10406, No = 5863; R = 0.054,
Rw = 0.054.
Variata. Difference map residues were modelled (rigid
body) as MeCN, site occupancy set at 0.75 after trial
refinement.
2.2.1.7. AgNO3:AsPh3:bpy (1:1:1) (7). C28H23AgAsN3O3,
M = 632.3. Triclinic, space group P1, a = 18.325(2),
˚
b = 9.629(1), c = 8.0710(9) A, a = 112.056(2)ꢁ, b =
3
˚
95.443(2)ꢁ, c = 100.402(2)ꢁ, V = 1277 A . Dcalc (Z = 2) =
1.644 g cmꢁ3
.
l
Mo = 21 cmꢁ1
;
specimen: 0.40 · 0.20 ·
0.20 mm; ‘T’min/max = 0.75. 2hmax = 58ꢁ; Nt = 14426,
N = 6093 (Rint = 0.018), No = 5355; R = 0.022, Rw =
2.2.1.13. AgNO3:Pcy3:phen (1:1:1) (13). C30H41Ag-
0.030. (x,y,z,Uiso H
)
refined.
N3O3P, M = 630.5. Monoclinic, space group P21/c,
˚
a = 8.7447(4),
b = 37.064(2),
c = 9.5248(5) A,
3
b = 110.944(1)ꢁ, V = 2883 A . Dcalc (Z = 4) = 1.452 g cmꢁ3
.
˚
2.2.1.8. AgNO3:AsPh3:dpa (1:1:1) (8). C28H24AgAsN4O3,
M = 647.3. Monoclinic, space group P21/n, a = 17.313(1),
l
Mo = 7.9 cmꢁ1
;
specimen:
0.43 · 0.20 · 0.05 mm;
˚
‘T’min/max = 0.79. 2hmax = 58ꢁ; Nt = 32904, N = 7302
(Rint = 0.029), No = 4587; R = 0.040 Rw = 0.041. (x,y,z,
Uiso)H refined.
b = 9.2056(1),
c = 18.049(2) A,
b = 112.842(1)ꢁ,
3
V = 2651 A . Dcalc (Z = 4) = 1.622 g cmꢁ3. lMo = 20 cmꢁ1
;
˚
specimen:
2hmax = 58ꢁ; Nt = 30469, N = 6565 (Rint = 0.018), No =
5961; R = 0.018, Rw = 0.028. (x,y,z,Uiso H refined.
0.42 · 0.22 · 0.12 mm;
‘T’min/max = 0.76.
)
2.2.1.14. AgNO3:Pcy3:bq (1:1:1) (14). C36H45AgN3O3P,
ꢀ
Variata. This complex is isomorphous with its E = Sb
counterpart, 10 (see below), and was refined in the same
cell and coordinate setting.
M = 706.6. Triclinic, space group P1, a = 9.5088(9),
˚
b = 10.977(1), c = 16.861(2) A, a = 78.393(1)ꢁ, b = 78.604
3
˚
(1)ꢁ, c = 80.926(1)ꢁ, V = 1677 A . Dcalc (Z = 2) = 1.399
g cmꢁ3. lMo = 6.9 cmꢁ1; specimen: 0.38 · 0.28 · 0.18 mm;
‘T’min/max = 0.90. 2hmax = 58ꢁ; Nt = 18634; N = 8155
2.2.1.9. AgNO3:AsPh3:bq (1:1:1) Æ MeCN (9 Æ MeCN). C38-
H30AgAsN4O3, M = 773.5. Monoclinic, space group P21/c,
(Rint = 0.012),
No = 7379;
R = 0.022,
Rw = 0.031.
˚
(x,y,z,Uiso H refined.
)
a = 8.957(2),
b = 17.989(1),
c = 20.910(4) A,
b = 100.872(3)ꢁ, V = 3309 A . Dcalc (Z = 4) =1.553 g cmꢁ3
.
3
˚
l
Mo = 16.5 cmꢁ1
;
specimen: 0.10 mm (cuboid); ‘T’min/
2.2.1.15. AgNO3:Pcy3:dpa (1:1:1) (15). C28H42AgN4O3P3,
ꢀ
max = 0.85. 2hmax = 58ꢁ; Nt = 38846, N = 8420 (Rint
0.028), No = 6897; R = 0.029, Rw = 0.037. (x,y,z,Uiso)H
refined.
=
M = 621.5. Triclinic, space group P1, a = 9.974(2),
˚
b = 15.841(3), c = 19.483(4) A, a = 111.332(2)ꢁ, b =
3
˚
90.440(2)ꢁ, c = 91.133(3)ꢁ, V = 2866 A . Dcalc (Z = 4) =
1.440 g cmꢁ3
. l ; specimen: 0.56 · 0.32 ·
Mo = 8.0 cmꢁ1
2.2.1.10. AgNO3:SbPh3:dpa (1:1:1) (10). C28H24Ag-
N3O3Sb, M = 694.1. Monoclinic, space group P21/n,
0.13 mm; ‘T’min/max = 0.86. 2hmax = 58ꢁ; Nt = 32796;
N = 13828 (Rint = 0.016), No = 12593; R = 0.023,
Rw = 0.035. (x,y,z,Uiso H refined.
˚
a = 17.562(2),
b = 9.2343(8),
c = 18.079(2) A,
b =
)
111.307(1)ꢁ, V = 2732 A . Dcalc (Z = 4) = 1.688 g cmꢁ3
.
3
˚
l
Mo = 17.4 cmꢁ1
;
specimen:
0.55 · 0.24 · 0.10 mm;
2.2.1.16. AgNO3:Ascy3:bq (1:1:1) (16). C36H45AgAsN3O3,
ꢀ
‘T’min/max = 0.77. 2hmax = 58ꢁ; Nt = 31309, N = 6846
(Rint = 0.026), No = 6499; R = 0.033, Rw = 0.038.
Variata. This complex is isomorphous with its E = As
counterpart (see above) and was refined in the same cell
and coordinate setting.
M = 750.6. Triclinic, space group P1, a = 9.459(1),
˚
b = 10.914(1),
c = 16.823(2) A,
a = 79.261(2)ꢁ,
b =
3
˚
79.000(2)ꢁ, c = 81.039(2)ꢁ, V = 1662 A . Dcalc (Z = 2) =
1.500 g cmꢁ3
.
l
Mo = 16.3 cmꢁ1
; specimen: 0.35 · 0.15 ·
0.13 mm; ‘T’min/max
=
0.79. 2hmax = 58ꢁ; Nt = 19272;

C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
1439
N = 8106 (Rint = 0.021), No = 7237; R = 0.024, Rw = 0.033.
(x,y,z,Uiso H refined.
l
Mo = 8.5 cmꢁ1
;
specimen:
0.23 · 0.15 · 0.05 mm;
)
‘T’min/max = 0.78. 2hmax = 58ꢁ; Nt = 56354, N = 13355
(Rint = 0.029), No = 8134; R = 0.033, Rw = 0.033.
Variata. The two nitrate groups were modelled as
disordered over pairs of sites, site occupancies refining to
0.875(9) (NO3(1)) and 0.5 (NO3(2)) (major components)
and complements.
2.2.1.17. AgNO3:P(o-tol)3:bpy (1:1:1) Æ ½MeCN (17 Æ ½
MeCN). C32H30.5AgN3.5O3P, M = 651.0. Triclinic, space
˚
group P1, a = 10.013(2), b = 10.384(2), c = 15.545(2) A,
a = 89.801(2)ꢁ,
b = 84.765(2)ꢁ,
c = 63.480(2)ꢁ,
3
V = 1438 A . Dcalc (Z = 2) = 1.502 g cmꢁ3. lMo = 8.0
˚
cmꢁ1; specimen: 0.20 · 0.16 · 0.12 mm; ‘T’min/max = 0.86.
2hmax = 58ꢁ; Nt = 16888; N = 7064 (Rint
No = 6460; R = 0.025, Rw = 0.032. (x,y,z,Uiso H
(solvent excepted).
2.2.1.23. AgNO3:PPh3:tpy (1:2:1) (23). C51H41Ag-
N4O3P2, M = 927.7. Triclinic, space group P1,
a = 9.6945(4), b = 14.6436(6), c = 15.0975(6) A, a =
ꢀ
=
0.018),
refined
˚
)
3
˚
90.893(1)ꢁ, b = 90.704(1)ꢁ, c = 99.229(1)ꢁ, V = 2115 A .
Variata. The acetonitrile was modelled as disordered
about a centre of symmetry.
Dcalc (Z = 2) = 1.457 g cmꢁ3. lMo = 6.0 cmꢁ1; specimen:
0.30 · 0.25 · 0.20 mm; ‘T’min/max = 0.91. 2hmax = 75ꢁ;
Nt = 43272, N = 21695 (Rint = 0.024), No = 17950;
R = 0.031, Rw = 0.037.
2.2.1.18. AgNO3:P(o-tol)3:bq (1:1:1) (18). C39H33Ag-
ꢀ
N3O3P, M = 730.6. Triclinic, space group P1, a =
Variata. The complex is isomorphous with its perchlo-
rate analogue [23] and was refined in the same cell and
coordinate setting.
˚
10.635(1), b = 10.756(2), c = 16.712(3) A, a = 89.123(2)ꢁ,
3
˚
b = 74.927(2)ꢁ, c = 62.177(2)ꢁ, V = 1620 A . Dcalc
(Z = 2) = 1.498 g cmꢁ3. lMo = 7.2 cmꢁ1; specimen: 0.40 ·
0.22 · 0.13 mm; ‘T’min/max = 0.89. 2hmax = 58ꢁ; Nt =
18297; N = 7862 (Rint = 0.023), No = 6635; R = 0.030,
3. Results and discussion
Rw = 0.037. (x,y,z,Uiso)H refined.
3.1. Syntheses
2.2.1.19. AgNO3:P(o-tol)3:dpa (1:1:1) Æ ½EtOH (19 Æ
½EtOH). C32H33AgN4O3.5P, M = 668.5. Triclinic, space
The adducts 1–21 (Chart 1), of general formula
AgNO3:ER3:L (1:1:1), have been synthesized by the reac-
tion of one equivalent of N,N0-bidentate aromatic ligand,
L, derivative of 2,20-bipyridyl, with one equivalent of sil-
ver(I) nitrate and one equivalent of unidentate ER3,
according to the following equation:
ꢀ
˚
group P1, a = 10.116(1), b = 10.470(1), c = 15.687(2) A,
a = 87.157(2)ꢁ, b = 83.252(2)ꢁ, c = 64.256(2)ꢁ, V =
3
1486 A . Dcalc (Z = 2) = 1.494 g cmꢁ3. lMo = 7.7 cmꢁ1
;
˚
specimen: 0.10 · 0.08 · 0.06 mm; ‘T’min/max = 0.87.2hmax
=
58ꢁ; N = 14783; N = 7280 (Rint = 0.030), No = 5649;
t
R = 0.036, Rw = 0.038.
S
Variata. The solvent molecule was modelled as disor-
dered about a centre of symmetry.
AgNO3 þ ER3 þ L ! AgNO3 : ER3 : L ð1 : 1 : 1Þ
ð1Þ
(E = P, As or Sb; R = Ph, cy, o-tolyl or mes; L = bpy,
phen, dmp, bq, dpa, dpk, dpca or tpy; S = acetonitrile or
methanol).
2.2.1.20. AgNO3:P(o-tol)3:dpca (1:1:1) Æ ½H2O (20 Æ
½H2O). C33H35AgN4O3.5P, M = 682.5. Monoclinic, space
˚
Adduct 22 (Chart 1) also has been synthesized by mixing
AgNO3, Pcy3 and tpy in 1:1:1 molar ratio, but its formula
is AgNO3:Pcy3:tpy (2:2:1). Adduct 23 was obtained simi-
larly, by the use of AgNO3:PPh3:tpy (1:2:1) in that ratio.
All the compounds, air-stable, colourless materials, are
insoluble in diethyl ether and alcohols but soluble in chlori-
nated solvents, acetone, acetonitrile and DMSO. The con-
ductivity measurements are in accordance with the ionic
formulation found in the solid state for the derivatives 20,
22 and 23. In addition the compounds 1–4, 6, 7, 9, 11–17
and 21, containing the weakly coordinated NO3, undergo
complete ionic dissociation, not only in acetonitrile but also
in non-ionizing solvents such as dichloromethane, Km being
in the range 120–160 in the former solvent and in the latter
40–50 Xꢁ1 cm2 molꢁ1 [24]. Moreover, derivatives 5, 8, 10,
15 and 19, containing the dpa ligand, which forms hydro-
gen-bonding networks in the solid state involving interac-
tion of its N–H component with the nitrate group (see
crystallographic studies below), are 1:1 electrolytes in aceto-
nitrile but non-electrolytes in dichloromethane [24].
group C2/c, a = 35.272(6), b = 10.311(2), c = 18.735(3) A,
3
b = 116.493(2)ꢁ, V = 6098 A . Dcalc (Z = 8) = 1.487 g cmꢁ3
.
=
˚
l
Mo =7.6cmꢁ1; specimen: 0.20·0.13·0.13mm; ‘T’min/max
0.85. 2hmax = 56ꢁ; Nt = 30272, N = 7738 (Rint = 0.030),
No = 6138; R = 0.034, Rw = 0.041. (x,y,z,Uiso H refined.
)
2.2.1.21. AgNO3:PPhmes2:tpy (1:1:1) (21). C39H38Ag-
N4O3P, M = 749.6. Monoclinic, space group P21/c, a =
˚
18.540(2), b = 11.552(1), c = 16.494(2) A, b = 102.425(2)ꢁ,
3
V = 3450 A . Dcalc (Z = 4) = 1.443 g cmꢁ3
.
lMo = 6.8
˚
cmꢁ1; specimen: 0.27 · 0.23 · 0.13 mm; ‘T’min/max = 0.85.
2hmax = 75ꢁ; Nt = 71239, N = 18132 (Rint = 0.049), No =
10849; R = 0.040, Rw = 0.040.
The following pairs of tpy adducts, of less usual stoichi-
ometries, are also recorded:
2.2.1.22. AgNO3:Pcy3:tpy (2:2:1) (22). C51H77Ag2-
N5O6P2, M = 1133.9. Monoclinic, space group P21/n,
˚
a = 15.1339(8), b = 9.8940(5), c = 36.136(2) A, b =
3
102.072(1)ꢁ, V = 5291 A . Dcalc (Z = 4) = 1.423 g cmꢁ3
.
˚

1440
C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
O
O
N
O
O
N
O
N
N
N
O
O
O
O
O
O
O
O
O
O
Me
N
N
N
Ag
Ag
Ag
N
N
Ag
Ag
1
Ph3P
Ph3P
Ph3P
Ph3P
N
N
5
Ph3P
N
N
N
H
N
Me
2
3
4
O
O
O
O
O
N
N
N
O
N
O
O
N
O
O
O
O
O
O
O
N
Ag
O
N
Ag
Ag
N
Ag
Ph3As
C
N
Ph3Sb
N
Ph3P
Ag
N
N
Ph3As
N
Ph3As
N
N
H
N
H
N
10
9
8
7
6
O
O
O
O
O
N
N
N
O
O
O
N
N
O
O
O
O
O
O
O
N
N
Ag
Ag
N
Ag
N
Ag
11
N
Ag
cy3P
cy3P
cy3P
N
N
cy3P
Ph3Sb
N
H
N
N
N
12
13
15
14
O
O
N
O
O
N
N
O
O
N
O
O
O
O
O
O
N
Ag
N
N
Ag
Ag
cy3As
N
N
N
H
Ag
(o-tol)3P
(o-tol)3P
N
(o-tol)3P
N
N
16
17
18
19
O
N
O
O
N
O
O
N
Pcy3
Ag
Ag
Pcy3
NO3
P(o-tol)3
N
PPh3
O
N
N
N
Ag
NO3
N
Ag
N
H
Ag
NO3
N
N
N
N
PPh3
PPhmes3
N
20
21
23
22
Chart 1.

C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
1441
3.2. Spectroscopy
The low temperature 31P NMR spectrum of derivative 20
shows a broad doublet with a J(Ag–P) value of 640 Hz, in
accordance with a AgN3P coordination environment in
solution, as found in the crystal structure (see below). Fi-
nally, in the low temperature 31P NMR spectrum of deriv-
ative 22 two pairs of doublets have been detected, one at
42.7 ppm (J(Ag–P) of 740.9 and 647.1 Hz) and the other at
33.1 ppm (J(Ag–P) of 528.6 and 457.8 Hz). This behaviour
could be explained by the existence in solution of three dif-
ferent Ag-containing species such as those arising from a
dissociation equilibrium like the following:
The infrared spectra (Section 2) are consistent with the
formulations proposed, showing all of the bands required
by the presence of the organic N-donors and bidentate
phosphine or arsine ligands [25]. In the far-IR spectra of
all phosphino derivatives we assigned, on the basis of pre-
vious reports, the broad absorptions near 500 cmꢁ1 and
those at 480–400 cmꢁ1 to Whiffen’s y and t vibrations [26].
In the spectra of derivatives 20 and 22, the m2, m3 and m4
ꢁ
modes of vibration of ionic NO3 groups (D3h symmetry)
and a unique weak m1 + m4 combination band in the over-
tone region 1700–1800 cmꢁ1 have been detected through-
out in accordance with their ionic structures [27]. In the
spectra of complexes 1–12, 16–18 and 21, the separation
between m1 and m4 is ca. 40 cmꢁ1 in accordance with a unid-
entate nitrato ligand m1 + m4 [28]. The weak interactions
between the silver(I) cation and the nitrate group in 13,
14 and 16 are reflected in the small magnitude of the split-
tings of the asymmetric N–O stretching modes [29]. The
presence of several different absorptions due to m(NO3) in
the spectrum of derivative 22 is consistent with the presence
of both ionic and unidentate NO3 groups (see below). The
IR spectra of the dpa-containing derivatives 5, 8, 10 and 19
exhibit broad bands over 3100 cmꢁ1 due to N–Hꢂ ꢂ ꢂO–NO2
H-bonding, observed also in their crystal structures.
2[Ag2(Pcy3)2(L)NO3]NO3 ¡[Ag(Pcy3)2(NO3)]+[Ag(L)NO3]
ð3Þ
where the resonance with higher J(Ag–P) is related to the
dinuclear species [Ag2(Pcy3)2(L)NO3]NO3 containing two
AgNOP coordination environments, and that with lower
J(Ag–P) is clearly related to the species [Ag(Pcy3)2(NO3)],
previously reported and investigated both in the solid state
and in solution [32].
3.3. Single crystal X-ray studies
The stoichiometries, connectivities and stereochemist-
ries of complexes 1–23, variously solvated, have also been
established by single crystal X-ray diffraction studies.
Except for derivative 22, the complexes are mononuclear,
based on a quasi-planar three-coordinate EAgN2 coordi-
nation environment in an [(R3E)AgL] complex, with
complementary counterion and, on occasion, accompany-
ing solvent. The usual symmetry of the ER3 arrays is 3
(or very rarely m) (or less), and that of the ligand is
2 mm (or less), these being normally incompatible, so
that it is unsurprising that the asymmetric unit of the
structures is never less than one formula unit (thus,
devoid of symmetry); in only three cases (3, 12, 15) does
it rise to two. Although the symmetry of the coordination
sphere itself can be as high as 2 mm, there is usually a
significant asymmetry in the pair of E–Ag–N angles, con-
sequent on the presence of an unsymmetrical disposition
of the ER3 group or other less internal effects. Any
potential symmetry of the array may be degraded further
by interaction of the (thus far) cationic [(R3E)AgL]+ spe-
cies with the counterion or nearby solvent or ‘impurity’
(H2O). Solvent or impurity approaches, given the nature
of the species employed, should be unidentate; in fact, no
close solvent approaches are observed at all, despite the
naked aspect of the silver atom within its planar environ-
ment, a situation perhaps exploitable in catalysis. Interac-
tions with nitrate anions are widespread and diverse in
their nature and strength: all are capable of bidentate
approaches, and the species observed may range from
O,O0-bidentate to O,O0-semibidentate, one oxygen being
more strongly bound than the other, to O-unidentate,
to unbound, with a number of interactions lying between
the latter pair in strength. In general, the EAgN2 in-plane
1
The H NMR spectra of derivatives 1–14 and 17–22
show the signals due to the phosphine and N-donor
ligands, shifted with respect to those found for the free
donors, thus indicating the existence of complexes also in
chlorinated solvent solution.
At room temperature, the 31P NMR spectra of complexes
1–6, 12–14 and 17–22 show a unique broad resonance, pre-
sumably in consequence of exchange equilibria that are rea-
sonably fast in relation to the NMR time scale. However, the
exchange is quenched at low temperature (223 K), and one
unresolved doublet or resolved pairs of doublets, arising
from coupling between the phosphorus and silver atoms,
are observed in the accessible temperature range.
Based on the previous work of Muetterties and Alegr-
anti [30] and Goel and Pilon [31], that showed the spin–spin
constant (J) between phosphorus and silver to be depen-
dant on the number of coordinated phosphorus atoms in
the silver complex, and that it is possible to determine
the number of the latter from measurement of the J values
in the 31P NMR spectra, we can assign AgPN2 coordina-
tion environments in solution for all derivatives 1–6,
12–14 and 17–19, as their J(Ag–P) fall in the range
600–750 Hz. In the low temperature 31P NMR spectra of
derivatives 1, 3, 6, 13 and 16, however, a minor doublet
or pair of doublets has been detected, with J(Ag–P) in the
range 380–540 Hz, in accordance with the presence in solu-
tion of additional AgP2-containing species, presumably
formed from dissociation equilibria such as the following:
2[Ag(PR3)(L)]NO3 ¡ [Ag(PR3)2(NO3)] + [Ag(L)2]NO3
ð2Þ

Table 1
Silver atom environments, AgNO3:ER3:L(:S) (1:1:1(:1))
P
a
0
˚
˚
˚
ER3:L(:S/NO3)
Ag–NO3(/S) (A)
Ag–E (A)
Ag–N,N (A)
(S/NO3)–Ag–E (ꢁ)
(S/NO3)–Ag–N,N0 (ꢁ)
E–Ag–N,N0 (ꢁ)
N–Ag–N0 (ꢁ)
(ꢁ)
ꢀ
2:603ð3Þ;
(1) PPh3:bpy:O2NO
2.3528(8)
2.304(2), 2.359(2)
113.02(5)
96.51(7)
108.78(8)
103.3(1)
96.2(1)
85.58(8), 91.34(8)
81.08(9), 131.20(9)
100.2(1), 103.5(1)
103.3(1), 79.8(1)
112.0(1), 85.3(1)
103.2(2), 86.8(2)
95.4(2), 126.0(2)
83.61(2), 100.87(6)
89.4(2), 98.8(2)
90.9(2), 104.6(2)
87.81(6), 94.60(6)
80.63(6), 134.14(6)
85.22(5), 101.88(4)
121.58(4), 80.78(5)
90.56(6), 97.45(6)
135.21(6), 99.02(6)
87.23(7), 99.50(8)
127.52(8), 83.94(9)
102.00(7), 79.24(7)
98.76(7), 121.06(7)
81.7(2), 91.7(2)
151.86(6), 126.21(6)
71.34(7)
349.4
2:798ð3Þ
(2) PPh3:phen:O(,ONO)
2.466(3)(,3.320(4))
2.678(3)(,3.008(3))
2.354(1)
2.382(1)
2.382(1)
2.363(2)
2.315(3), 2.334(3)
2.339(4), 2.352(3)
2.313(4), 2.355(3)
2.326(5), 2.328(5)
132.66(9), 131.76(8)
139.20(6), 143.67(8)
138.08(6), 143.17(8)
133.1(2), 138.0(1)
72.6(1)
71.7(1)
72.2(1)
70.7(2)
337.0
354.6
353.5
341.8
(3) PPh3:dmp:O(,ONO) (mol. 1)
(3) PPh3:dmp:O(,ONO) (mol. 2)
(4) PPh3:bq:O2NO
2.721(5)(,3.012(6))
ꢀ
2:512ð6Þ;
112.6(1)
89.9(2)
2:813ð6Þ
(5) PPh3:dpa:O(,ONO)
(6) PPh3:dpk:O2NO
2.452(2)(,3.020(2))
2.466(4)
2.3465(6)
2.363(2)
2.280(2), 2.364(2)
2.273(5)
2.700(5)(O)
119.92(5)
119.1(1)
104.6(1)
110.10(3)
95.93(4)
121.02(3)
102.45(3)
108.09(4)
77.96(4)
123.24(5)
98.09(6)
112.50(5)
87.43(4)
106.4(1)
108.2(3)
113.52(7)
114.10(3)
95.09(3)
96.94(3)
112.28(3)
134.44(4)
119.95(4)
105.38(5)
136.03(5)
102.27(6)
166.72(6)
115.53(4)
139.28(4)
106.71(8)
120.3(1)
135.90(5), 125.24(5)
151.1(1), 110.9(1)
79.20(8)
65.4(1)
340.3
327.4
2.790(5)
ꢀ
(7) AsPh3:bpy:O2NO
(8) AsPh3:dpa:O2NO
(9) AsPh3:bq:O2NO
(10) SbPh3:dpa:O2NO
(11) SbPh3:bq:O2NO
2.4495(3)
2.4427(2)
2.4482(5)
2.5733(3)
2.6069(3)
2.306(1), 2.348(1)
151.11(4), 125.41(4)
133.79(3), 123.66(4)
137.72(5), 138.86(5)
132.26(5), 122.43(7)
135.75(4), 140.27(5)
71.84(5)
79.87(5)
71.36(7)
80.50(9)
71.32(6)
348.4
337.3
347.9
335.2
347.3
2:541ð2Þ;
2:789ð2Þ
ꢀ
2.279(6), 2.354(1)
2.305(2), 2.318(2)
2.282(2), 2.336(2)
2.334(3), 2.339(2)
2:458ð1Þ;
2:898ð2Þ
ꢀ
2:514ð2Þ;
2:928ð2Þ
ꢀ
2:438ð2Þ;
2:883ð2Þ
ꢀ
2:519ð2Þ;
2:982ð3Þ
(12) Pcy3:bpy:O(,ONO) (mol. 1)
(12) Pcy3:bpy:O(,ONO) (mol. 2)
(13) Pcy3:phen:ONO2
2.657(8)(,3.145(7))
2.357(2)
2.347(2)
2.328(7), 2.332(6)
2.294(8), 2.319(6)
2.409(3), 2.290(3)
2.343(1), 2.358(1)
2.256(1), 2.376(2)
2.256(1), 2.337(2)
2.319(2), 2.335(1)
2.333(1), 2.418(4)
147.6(2), 137.8(2)
149.9(2), 134.5(2)
71.3(2)
71.8(2)
71.3(1)
69.73(4)
80.47(5)
80.64(5)
70.23(5)
69.80(6)
356.7
356.2
342.8
342.9
357.6
360.0
342.3
313.8
2.561(10)
2.564(2)
84.6(3), 86.2(3)
2.3557(8)
2.3732(4)
2.3639(5)
2.3617(5)
2.4535(3)
2.3835(8)
104.86(9), 85.34(9)
90.02(4), 95.26(4)
91.51(5), 97.94(4)
78.05(4), 99.18(4)
92.56(5), 97.45(5)
95.13(5), 89.98(5)
78.88(5), 123.92(5)
112.92(6), 86.82(6)
89.62(8), 84.67(8)
94.48(9), 131.15(8)
71.33(8), 71.89(7)
77.77(5), 93.81(5)
67.83(5), 67.34(5)
99.7(1), 80.7(1)
119.62(7), 151.90(7)
137.25(3), 135.93(3)
157.18(4), 119.99(4)
158.37(4), 120.98(4)
137.73(4), 134.36(4)
127.96(4), 116.03(4)
(14) Pcy3:bq:ONO2
2.508(2)
(15) Pcy3:dpa:ONO2 (mol. 1)
(15) Pcy3:dpa:ONO2 (mol. 2)
(16) Ascy3:bq:O(,ONO)
2.662(1)
2.877(1)
2.475(2)(,3.133(2))
2.418(1)
(17) P(o-tol)3:bpy:O2NO
2.850(2)
(18) P(o-tol)3:bq:O(,ONO)
(19) P(o-tol)3:dpa:O2NO
2.461(1)(,3.020(2))
2.4199(6)
2.3973(7)
2.349(2), 2.416(2)
2.318(3), 2.378(3)
132.92(5), 140.06(5)
128.32(8), 118.63(6)
69.93(7)
81.0(1)
342.9
328.0
ꢀ
2:519ð2Þ;
2:839ð2Þ
(20) P(o-tol)3:dpca:(NO3)
(21) PPhmes2:tpy:ONO2
2.342(2)(N(c))
2.618(2)
2.3956(8)
2.4348(5)
2.417(2), 2.618(2)
2.419(2), 2.457(1)
119.90(6), 108.03(5)
110.61(3), 116.76(4)
109.68(8)
130.52(5)
337.6
357.9
2.378(2)(N(c))
2.696(5)
2.545(2)b
(22) Pcy3:tpy:ONO2 (Ag(1))
2.3695(9)
2.3850(9)
2.563(2), 2.258(3)
2.645(2), 2.366(3)
139.11(6), 145.2(6)
119.70(6), 126.34(6)
68.89(8)
66.21(8)
352.2
312.3
(Ag(2))
101.6(1), 108.4(1)
a
˚
Contacts in parentheses lie between 3 and 3.5 A.
b
0
0
0
00
˚
˚
Ag(2)–O(12) is 2.649(4) A; O(0 12)–Ag(2)–P(2),N(1,1 ),O(11) are 112.38(8)ꢁ, 127.98(9)ꢁ, 83.5(1)ꢁ, 48.1(1)ꢁ; O(11 )–Ag(1,2) are 2.82(2), 2.25(2) A; O(11 )–Ag(1)–P(1),N(1,1 ),O(11) are 95.4(5)ꢁ,
0
˚
92.1(4)ꢁ, 105.0(5)ꢁ, 30.0(5)ꢁ, O(11 )–Ag(2)–P(2),N(1,1 ),O(11,12) are 134.7(6)ꢁ, 104.6(6)ꢁ, 78.6(6)ꢁ, 34.1(7)ꢁ, 25.1(6)ꢁ. Ag(1)ꢂ ꢂ ꢂAg(2) is 3.2765(6) A.

Table 2
Ligand and anion descriptors, AgX:ER3:L(:S) (1:1:1(:1))
bq=bq
ðꢃÞ
dAg (A)
dAgNO ðAÞ
0.552(6)
Ag–O(,O0)-Y (ꢁ)
Ag–E–C(n1)–C(n2(6)) (ꢁ)
E–Ag–O–N (ꢁ)
O–N–O (ꢁ)
˚
˚
ER3:L(:S/X)
h
py=py
3
ꢁ
101:7ð2Þ;
(1) PPh3:bpy:O2NO
12.7(1)
0.361(4), 0.267(5)
42.2(3), 34.8(3), 46.8(2)
ꢁ83.5(2)
123.0(2)
ꢁ175.1(2)
ꢁ122.8(1)
148.7(4)
70.2(4)
ꢁ128.7(5)
ꢁ82.5(1)
81.4(4)
118.4(3)
92:2ð2Þ
121.5(2)
100.5(2)
(2) PPh3:phen:O(,ONO)
0.343(3)
0.008(3)
0.039(4)
0.023(9), 0.103(9)
0.352(7)
1.593(7)
2.190(7)
0.52(1)
ꢁ40.8(4), ꢁ44.3(3), ꢁ53.9(3)
ꢁ34.6(3), ꢁ44.4(3), ꢁ64.5(4)
28.6(4), 46.9(3), 74.2(4)
119.7(4)
119.2(3)
110.9(6)
116.9(8)
(3) PPh3:dmp:O(,ONO) (mol. 1)
(3) PPh3:dmp:O(,ONO) (mol. 2)
(4) PPh3:bq:O2NO
107.5(6)
ꢁ
105:5ð5Þ;
4.6(2)
13.1(6), 32.0(6), 71.2(5)
92:1ð4Þ
(5) PPh3:dpa:O(,ONO)
(6) PPh3:dpk:O2NO
25.04(8)
41.1(3)
0.166(4), 1.345(4)
0.221(9)
0.100(5)
0.14(1)
111.3(2)
12.0(2), 42.1(3), 44.9(2)
14.7(5), 22.2(4), 28.1(5)
120.4(2)
118.4(4)
ꢁ
104:6ð4Þ;
89:2ð3Þ
ꢁ114.4(4)
ꢁ
102:3ð1Þ;
(7) AsPh3:bpy:O2NO
(8) AsPh3:dpa:O2NO
(9) AsPh3:bq:O2NO
(10) SbPh3:dpa:O2NO
(11) SbPh3:bq:O2NO
13.06(7)
24.42(5)
5.67(5)
0.437(3), 0.206(3)
0.134(2), 1.274(2)
0.356(3), 0.213(3)
0.125(4), 1.149(4)
0.137(3), 0.130(3)
0.035(1)
0.142(3)
0.875(4)
0.190(4)
0.332(5)
42.0(2), 33.5(2), 47.2(1)
8.4(1), 42.0(2), 43.4(1)
7.9(2), 25.7(2), 47.7(2)
2.4(2), 42.3(2), 41.2(2)
45.4(2), 51.2(2), 54.3(2)
ꢁ84.5(1)
118.5(1)
120.1(1)
119.7(2)
120.0(2)
120.0(3)
119.2(9)
90:6ð1Þ
ꢁ
107:4ð1Þ;
ꢁ78.53(9)
ꢁ62.6(1)
ꢁ69.7(1)
ꢁ64.9(2)
ꢁ68.4(5)
86:0ð1Þ
ꢁ
105:0ð1Þ;
85:6ð1Þ
ꢁ
107:1ð2Þ;
23.00(8)
1.58(5)
85:4ð2Þ
ꢁ
108:5ð2Þ;
86:0ð2Þ
(12) Pcy3:bpy:O(,ONO) (mol. 1)
(12) Pcy3:bpy:O(,ONO) (mol. 2)
(13) Pcy3:phen:ONO2
6.4(3)
11.0(3)
0.19(1), 0.12(1)
0.06(1), 0.51(1)
0.018(4)
0.487(2), 0.517(2)
0.048(3), 1.008(2)
0.212(2), 0.825(2)
0.405(2), 0.498(2)
0.331(4), 0.071(3)
0.36(2)
0.76(2)
110.7(6)
135.1(9)
115.0(2)
109.3(1)
124.02(9)
132.13(8)
108.3(1)
106.7(1)
86.2(1)
ꢁ55.4(6), 48.5(7), 20.5(5)
ꢁ57.9(5), 49.1(6), 25.6(5)
ꢁ53.4(5), ꢁ30.2(3), 61.2(3)
64.9(1), ꢁ63.0(2), 33.5(1)
ꢁ28.2(1), ꢁ43.2(1), 52.4(1)
59.7(1), ꢁ45.2(1), ꢁ28.2(1)
66.4(1), ꢁ62.1(4), 33.2(1)
ꢁ45.5(1), ꢁ44.0(2), ꢁ54.7(2)
1.579(7)
1.419(3)
2.082(3)
1.833(3)
1.465(3)
0.510(4)
105.9(2)
ꢁ73.4(1)
ꢁ49.2(1)
ꢁ6.3(1)
120.2(4)
119.5(2)
118.4(2)
119.1(1)
119.8(2)
118.7(2)
(14) Pcy3:bq:ONO2
8.11(3)
(15) Pcy3:dpa:O(,ONO) (mol. 1)
(15) Pcy3:dpa:O(,ONO) (mol. 2)
(16) Ascy3:bq:O(,ONO)
18.065(5)
10.73(5)
7.90(4)
ꢁ73.2(1)
ꢁ98.8(1)
(17) P(o-tol)3:bpy:O2NO
8.11(8)
(18) P(o-tol)3:bq:O(ONO)
(19) P(o-tol)3:dpa:O2NO
23.51(6)
7.3(1)
0.152(3), 0.961(3)
0.144(6), 0.125(5)
0.282(5)
0.343(7)
112.0(2)
45.5(2), 46.2(2), 59.0(2)
ꢁ53.2(2), ꢁ40.8(3), ꢁ51.8(3)
ꢁ117.5(2)
ꢁ57.9(2)
145.9(2)
118.7(2)
118.6(2)
ꢁ
105:0ð2Þ;
89:7ð2Þ
(20) P(o-tol)3:dpca:(NO3)
(21) PPhmes2:tpy:ONO2
27.98(9)
3.45(7), 7.27(7)
0.128(4), 1.535(4)
0.615(3), 0.285(3)(p,p)
ꢁ55.3(2), ꢁ30.5(3), ꢁ53.4(2)
1.610(4)
127.2(1)
12.7(2), 73.2(1), 30.0(1)
100.3(2)
0.483(3)(c)
a
a
a
a
(22) Pcy3:tpy:ONO2
9.16(7)
42.3(3), ꢁ59.7(3), ꢁ70.4(2)
116.8(4)
28.7(3), 50.8(3), 56.2(3)
a
0
˚
Deviations of Ag(1,2) out of the two component planes: ꢁ2.288(9), 0.12(1); ꢁ1.30(7), 1.74(5) A; Ag(1,2)–O(11,11 )–N(01) for the two components are 120.9(3)ꢁ, 100.4(3)ꢁ; 116(1)ꢁ, 121(2)ꢁ; Ag(2)–
O(12)–N(01) 94.6(3)ꢁ; P(1,2)–Ag(1,2)–O(11)–N(01) (two components) are 39.4(3)ꢁ, ꢁ91.6(3)ꢁ; ꢁ82(2)ꢁ, 35(2)ꢁ.

1444
C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
angle sum, 360ꢁ for a completely planar array, dimin-
ishes, as expected, broadly in parallel with the strength
of the interaction with the approaching species, asymme-
try in the E–Ag–N,N0 angles broadly correlating in the
manner expected with the Ag–N distances; for a given
anion, the strength of interaction tends to be greater in
E = As, Sb complexes, cf. the counterpart E = P arrays,
as expected, and in keeping with the diminished base
strength of ER3, with concomitant change in the Ag–N
distances.
The ligands L offer a range of ‘bites’, those of bpy, phen,
dmp, and bq being similar, while dpa, with a six- cf. a five-
membered chelate ring, has a greater ‘bite’, also true of
dpk, dpca and tpy – but here, with a further O or N donor
atom introduced between the peripheral pair of rings, the
ligand is potentially tridentate. The ligands generally are
extended planar arrays, although in those cases (bpy, bq,
and dpa) where there is no central aromatic ring fusing
the two donor rings, there may be an appreciable dihedral
angle between the latter. The ligand planes, in general, are
a dominant determinant of crystal packing. Core and
ligand geometries for all of the species are summarized in
Tables 1 and 2, with individual species depicted in the fig-
ure. We comment individually on the various structures as
follows.
ters on anion 2 are high and may be a foil for unresolved
disorder. (The deviation of the silver atom from the nitrate
plane (Table 2) is a useful indicator of its inclination to the
coordination plane.) The dmp ligand is more highly hin-
dered than its parents phen or bpy, but this appears to have
little impact on the overall coordination environment of
the metal.
3.3.4. AgNO3:PPh3:bq (1:1:1) (4)
Here, despite the electronic similarity between bpy and
bq, the nitrate approach is less symmetrical than in the
above bpy counterpart.
3.3.5. AgNO3:PPh3:dpa (1:1:1) (5)
Here, given some tendency of dpa to bind in unidentate
mode in some complexes (e.g. Ref. [22]), it is of interest to
observe that, compared to (e.g.) its bq counterpart (above),
the geometries in the coordination sphere are similar, the
only substantial change concerning the ‘bite’ of the dpa
ligand, which exhibits a substantial dihedral angle between
the pair of aromatic ring planes. Interspecies hydrogen-
bonding is observed from the (uncoordinated) central
N,H of the ligand to the nitrate (O(3)ꢂ ꢂ ꢂH,N 2.12(3) (x,
˚
y ꢁ 1, z), 2.851(3) A). In this and the other dpa (and
dpk) complexes studied, the EAgN2(N,O) angle sums are
6340ꢁ, perhaps a consequence of the enlarged chelate ring
3.3.1. AgNO3:PPh3:bpy (1:1:1) (1)
˚
in these complexes; Ag–O(NO3) are short, 62.5 A.
The nitrate approach to the silver atom here is that of a
somewhat unsymmetrical chelate (Fig. 1(a)), the asymme-
try and skewing of the approach perhaps a concomitant
of short intra-molecular contacts O(1)ꢂ ꢂ ꢂH(32), 2.87(3)
3.3.6. AgNO3:PPh3:dpk (1:1:1) (6)
Here the possible coordination of the second pyridyl
ring is pre-empted by the semi-bidentate chelation of the
anion, coupled with coordination by the linker unit to form
a five- rather than six-membered chelate. The Ag–O inter-
action is weak; P–Ag–N,O are concomitantly unsymmetri-
cal, P–Ag–N being larger.
0
˚
and O(2)ꢂ ꢂ ꢂH(6) 2.80(3) A, with angles P–Ag–N,N (bpy)
being very unsymmetrical (151.86(6)ꢁ, 121.21(6)ꢁ). As in
most of the other EPh3 (and P(o-tol)3) arrays presented
here, the EPh3 disposition is quasi-3.
With the weaker donors E = As, Sb displacing P in the
EPh3 component, it might be expected that the remaining
ligands might interact more strongly, perhaps with con-
comitant change in the nature of the complex. Changes
in Ag–N,O distances of a qualitative nature are found,
as expected, but they are not large, and seem to impact
little on the form of the complex in the less extensive
arrays studied, the nitrate ions interacting in semi-biden-
tate mode.
3.3.2. AgNO3:PPh3:phen (1:1:1) (2)
This complex in juxtaposition with the above bpy coun-
terpart enhances the dilemma concerning the mode of
interaction of the anion, whereas in semi-bidentate mode
in the bpy complex, the longer Agꢂ ꢂ ꢂO interaction is direc-
ted nearer the PPh3 ligand; here we find the nitrate to lie
quasi-coplanar with the phosphorus atom with the more
weakly interacting oxygen lying over the phen ligand, gen-
erally reflecting the rather arbitrary nitrate dispositions
throughout the array of complexes. Although the phen is
quasi-coplanar with one of the PPh3 phenyl rings, the P–
Ag–N angles are essentially equal.
3.3.7. AgNO3:AsPh3:bpy (1:1:1) (7)
This compound is remarkable for the disparity in the
pair of E–Ag–N angles, a feature not observed in the other
pair of AsPh3 complexes studied, presumably to be attrib-
uted to ‘lattice effects’ in the absence of any more satisfac-
tory ‘intramolecular’ hypothesis.
3.3.3. AgNO3:PPh3:dmp (1:1:1) Æ ½MeOH
(3 Æ ½MeOH)
In this array, two independent molecules are found in
the asymmetric unit, with one methanol solvent; the latter,
not disordered, nevertheless appears not to interact closely
with any anion components. In both molecules, the anions
are effectively semi-bidentate, but differ somewhat in their
orientations vis-a-vis the substrate; displacement parame-
3.3.8. AgNO3:AsPh3:dpa (1:1:1) (8)
Again, intermolecular dpa-NHꢂ ꢂ ꢂO(NO3) interactions
are found, O(3)ꢂ ꢂ ꢂH,N(central) (x, y ꢁ 1, z) being 2.00(2),
˚
2.854(2) A.

C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
1445
Fig. 1. Projections of the complex aggregates of the following (R3P)Ag(N,N0-aromatic base)/NO3 systems: (a) [(Ph3P)Ag(N,N0-bpy)(O,O0-NO3)] (1); (b)
[(Ph3P)Ag(N,N0-phen)(O-NO3)] (2); (c) [(Ph3P)Ag(N,N0-dmp)(O-NO3)] (two molecules), in 3 Æ ½MeOH; (d) [(Ph3P)Ag(N,N0-bq)(O,O0-NO3)] (4); (e)
[(Ph3P)Ag(N,N0-dpa)(O-NO3)] (5); (f) [(Ph3P)Ag(N,O0-dpk)(O,O0-NO3)] (6); (g) [(Ph3As)Ag(N,N0-bpy)(O-NO3)] (7); (h) [(Ph3As)Ag(N,N0-dpa)(O-NO3)]
(8) (the E = Sb counterpart, 10, is isomorphous); (i) [(Ph3As)Ag(N,N0-bq)(O-NO3)], in 9 Æ MeCN; (j) [(Ph3Sb)Ag(N,N0-bq)(O-NO3)], in 11 Æ 1½EtOH; (k)
[(cy3P)Ag(N,N0-bpy)(O-NO3)] (two molecules), in 12 Æ 3/8MeCN; (l) [(cy3P)Ag(N,N0-phen)(O-NO3)] (13); (m) [(cy3P)Ag(N,N0-bq)(O-NO3)] (14); (n)
[(cy3P)Ag(N,N0-dpa)(O-NO3)] (two molecules) (15); (o) [(cy3As)Ag(N,N0-bq)(O-NO3)] (16); (p) [{(o-tol)3P}Ag(N,N0-bpy)(O2-NO3)], in 17 Æ ½MeCN; (q)
[{(o-tol)3P}Ag(N,N0-bq)(O-NO3)] (18); (r) [{(o-tol)3P}Ag(N,N0-dpa)(O2-NO3)], in 19 Æ ½EtOH; (s) [{(o-tol)3P}Ag(N,N,0N00-dpca)](NO3), in 20 Æ ½H2O; (t)
[(mes2PhP)Ag(N,N0,N00-tpy)(O-NO3)] (21); (u) [{(cy3P)Ag}2(N,N0,l-N0-tpy)(O,l-O0-NO3)](NO3) (22); (v) [(Ph3P)2Ag(N,N0,N00-tpy)](NO3) (23).

1446
C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
Fig. 1 (continued)
3.3.9. AgNO3:AsPh3:bq (1:1:1) Æ MeCN (9 Æ MeCN)
3.3.11. AgNO3:SbPh3:bq (1:1:1) Æ ½EtOH
(11 Æ 1½EtOH)
The acetonitrile plays no role in coordination.
One of the solvent components is disordered (about an
inversion centre), albeit it lies in the proximity of the nitrate
3.3.10. AgNO3:SbPh3:dpa (1:1:1) (10)
Again, we find intermolecular dpa-NHꢂ ꢂ ꢂO(NO3)
˚
(O(3)ꢂ ꢂ ꢂH,O 1.7 (est.), 2.871(5) A); the other solvent mole-
hydrogen-bonding, N,H(central)ꢂ ꢂ ꢂO(3) (x, 1 + y, z)
cule, more well-defined, also is hydrogen-bonded to the
˚
˚
being 2.869(3), 1.98(3) A.
nitrate (O(3)ꢂ ꢂ ꢂH,O 2.29(3), 2.95(2) A).

C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
1447
Fig. 1 (continued)
Ligands of the form Ecy3 normally exhibit a more
bulky steric profile than their EPh3 counterparts, as mea-
sured by the ‘cone angle’ [33]; their conformations in
projections down the M-P coordinate bond may vary
in a manner discussed elsewhere [34], here parametrized
by the Ag–E-C–C torsion angle set (Table 1). In general,
given the essentially three-coordinate nature of the metal
coordination environments, the change has little impact
thereon, except to note that the anion approaches in
the relatively limited range of compounds studied are

1448
C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
Fig. 1 (continued)
as unidentates or weak semi-bidentate ligands. In a num-
ber, the E–Ag–N,N0 angle pairs are again quite dispa-
rate, but in others essentially equal.
3.3.12. AgNO3:Pcy3:bpy (1:1:1) Æ 3/8MeCN (12 Æ 3/8MeCN)
The solvent seemingly does not interact closely with
either of the pair of independent substrate molecules which

C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
1449
are found in the asymmetric unit. The two molecules differ
somewhat in the orientation of their nitrate planes,
although both are similarly semi-bidentate, weakly so, with
the EAgN2 angle sums close to 360ꢁ.
3.3.21. AgNO3:PPhmes2:tpy (1:1:1) (21)
Here the anion approach is genuinely unidentate, per-
haps a consequence of the increased coordination number,
coupled with the increased substituent bulk of the phos-
phine ligand; the phenyl substituent lies nearest to the
anion, so that the mes2 array occupies the void ‘behind’
the tpy, opposed to the nitrate, one of the associated
3.3.13. AgNO3:Pcy3:phen (1:1:1) (13)
Here we find for the first time a genuinely unidentate
˚
˚
Agꢂ ꢂ ꢂH being 2.78(3) A.
nitrate approach, Agꢂ ꢂ ꢂO(2) being 3.385(4) A.
3.3.22. AgNO3:Pcy3:tpy (2:2:1) (22)
3.3.14. AgNO3:Pcy3:bq (1:1:1) (14)
This complex, like the phen counterpart, 13, above,
exhibits a less emphatically unidentate nitrate, Agꢂ ꢂ ꢂO(2)
It is of interest to note that the preceding complexes are
all mononuclear as is the following 23 in which coordina-
tion of a pair of PPh3 ligands is no impediment to coordi-
nation of a tridentate tpy in that cation, obtained with both
perchlorate and nitrate counterions. Nevertheless, in the
present array, it may be that the bulk of the Pcy3 hinders
the coordination of a tridentate tpy coplanar with it (even
though the bulky PPhmes2 ligand in the previous com-
pound 21 appears to offer no such obstacle). Whatever
the cause, the formation of a binuclear complex, in which
the tpy ligand rather than being tridentate, behaves as an
obliquely coordinated bidentate ligand, to each of a pair
of silver atoms, with the central nitrogen atom shared
between both (as described elsewhere [35]) is found, the sil-
ver atoms also being bridged by one of the nitrate groups,
the other being freely ionic. The role of the nitrate group is
interesting; it has its oxygen atoms disordered over two sets
of sites of unequal occupancy. In the major, unprimed
O(11,12) chelate Ag(2) is reasonably symmetrical, with
˚
being 3.158(2) A.
3.3.15. AgNO3:Pcy3:dpa (1:1:1) (15)
Here, in contrast to the other dpa complexes, the PAgN2
angle sums in both of the two independent molecules are
close to 360ꢁ, the nitrate approaches differing markedly in
their dispositions.
3.3.16. AgNO3:Ascy3:bq (1:1:1) (16)
In this complex the nitrate is semi-bidentate.
Throughout all adducts of P(o-tol)3, the ligand confor-
mation has close to 3-symmetry about the Ag–P bond,
the 2-methyl substituents directed toward the metal rather
than within the ligand core. Ag–P are generally slightly
longer than in the PPh3/Pcy3 counterparts, anion coordina-
tion modes being similar.
˚
Ag(2) being only 0.12(1) A out of the plane. Ag(1) lies well
3.3.17. AgNO3:P(o-tol)3:bpy (1:1:1) Æ ½MeCN
(17 Æ ½MeCN)
Here the anion is unsymmetrically bidentate. In this
complex the EAgN2 array is well-removed from planarity,
with Ag–O being correspondingly short.
˚
out of the plane (2.288(9) A) and is contacted only by
˚
O(11) at a distance of 2.696(5) A. The PAgN2 angle sum
about Ag(1) is 353.2ꢁ, in keeping with the nitrate approach
constituting a minor perturbation on what is a possibly
awkward planar environment; the PAgN2 counterpart
environment is well removed from planarity in keeping
with the strong and symmetrical nitrate chelate approach.
In the alternative, minor component, disposition, O(110)
is the only oxygen component to contact either silver atom,
3.3.18. AgNO3:P(o-tol)3:bq (1:1:1) (18)
In this complex semi-bidentate anion interaction is
found, Ag–P being unusually long.
˚
and is well-removed from Ag(1) (2.82(2) A), but strongly
3.3.19. AgNO3:P(o-tol)3:dpa (1:1:1) Æ ½EtOH
(19 Æ ½EtOH)
˚
bound to Ag(2) (2.25(2) A), maintaining the role of a
strong, but now unidentate, donor to the latter, and a neg-
ligible one to Ag(1). In this role, the Ag(1,2) out-of-plane
The anion is semi-bidentate; the solvent again is
disordered about a crystallographic inversion centre, but
with the hydroxylic hydrogen in proximity to the anion,
although seemingly without strong hydrogen-bonding
interaction. Interestingly, the oxygen atom associated with
the shorter Ag–O bond is hydrogen-bonded to the dpa NH
˚
deviations are ꢁ1.30(7), 1.74(5) A.
3.3.23. AgNO3:PPh3:tpy (2:1:1) (23)
The complex is mononuclear [(tpy-N,N0,N00)Ag(PPh3)2]-
(NO3), unsolvated, and isomorphous with its perchlorate
analogue, which is discussed at length in Ref. [23]. Ag–P
˚
group (O(1)..H,N(7) (1 ꢁ x, 1 ꢁ y, z) 2.24(3), 3.034(6) A).
0
are 2.4918(3), 2.5085(3) and Ag–Nc 2.467(1) and Ag–Np,p
0
˚
3.3.20. AgNO3:P(o-tol)3:dpca (1:1:1) Æ ½H2O
(20 Æ ½H2O)
are 2.5602(9), 2.6377(10) A. P–Ag–P is 121.79(1)ꢁ.
This complex is ionic, neither anion nor solvent moieties
interacting with the metal, and the N3Ag set of chelate
rings unsymmetrical relative to each other, perhaps because
of their dispositions relative to the phosphine ligand
substituent.
References
[1] S. Maki, Y. Takaya, Pat. Jpn. Kokai Tokkyo Koho (1994) JP
06295042 A2 (Chem. Abstr. 122 (1997) 11878).
[2] G. Xue, J. Dong, Y. Sun, Langmuir 10 (1994) 1477.

1450
C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 1433–1450
[3] S. Hirabayashi, Y. Kaneko, I. Sakata, Pat. Jpn. Kokai Tokkyo Koho
(1991) JP 03148649 (Chem. Abstr. 116 (1997) 48795).
[4] K. Morimoto, Pat. Jpn. Kokai Tokkyo Koho (1997) JP 09114063
(Chem. Abstr. 127 (1998) 42124).
Corrigendum Effendy, L.M. Engelhardt, P.C. Healy, B.W. Skelton,
A.H. White, Aust. J. Chem. 44 (1991) 1585.
[19] Effendy, F. Marchetti, C. Pettinari, R. Pettinari, B.W. Skelton, A.H.
White, Inorg.Chim. Acta 360 (2007) 1388.
[5] S.J. Berners-Price, P.J. Sadler, Coord. Chem. Rev. 151 (1996) 1.
[6] S.J. Berners-Price, R.K. Johnson, A.J. Giovenella, L.F. Faucette,
C.K. Mirabelli, P.J. Sadler, J. Inorg. Biochem. 33 (1988) 285.
[7] S.J. Berners-Price, D.C. Collier, M.A. Mazid, P.J. Sadler, R.E. Sue,
D. Wilke, Met.-Based Drugs 2 (1995) 111.
[8] A.S. Craig, R. Kataky, D. Parker, H. Adams, N. Bailey, H.
Schneider, J. Chem. Soc., Chem. Commun. (1989) 1870.
[9] A.S. Craig, R. Kataky, R.C. Matthews, D. Parker, G. Ferguson, A.
Lough, H. Adams, N. Bailey, H. Schneider, J. Chem. Soc., Perkin
Trans. 2 (1990) 1523.
[10] C.-H. Zhou, H.-Y. Zhu, Y.-Y. Wang, P. Liu, L.-J. Zhou, D.-S. Li,
Q.-Z. Shi, J. Mol. Struct. 779 (2005) 61.
[11] S.-P. Yang, H.-L. Zhu, X.-H. Yin, X.-M. Chen, L.-N. Ji, Polyhedron
19 (2000) 2237.
[12] S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853.
[13] J.-S. Seo, D. Whang, H. Lee, I. Jun, J. Oh, Y.-J. Jeon, K. Kim,
Nature 404 (2000) 982.
[14] J.W.-F. Yeuning, W.-L. Man, W.-Y. Wong, T.-C. Lau, S. Gao,
Angew. Chem., Int. Ed. 40 (2001) 3032.
[20] Effendy, F. Marchetti, C. Pettinari, R. Pettinari, B.W. Skelton, A.H.
White, Inorg. Chim. Acta 360 (2007) 1414.
[21] Effendy, F. Marchetti, C. Pettinari, B.W. Skelton, A.H. White,
Inorg. Chim. Acta 360 (2007) 1424.
[22] Effendy, F. Marchetti, C. Pettinari, R. Pettinari, B.W. Skelton, A.H.
White, Inorg. Chim. Acta 360 (2007) 1451.
[23] E.W. Ainscough, A.M. Brodie, S.L. Ingham, J.M. Waters, J. Chem.
Soc., Dalton Trans. (1994) 215.
[24] W.J. Geary, Coord. Chem. Rev. 7 (1971) 81.
[25] K. Shobatake, C. Postmus, J.R. Ferraro, K. Nakamoto, Appl.
Spectrosc. 23 (1969) 12.
[26] J. Bradbury, K.P. Forest, R.H. Nuttall, D.W.A. Sharp, Spectrochim.
Acta 23 (1967) 2701.
[27] A.B.P. Lever, E. Mantovani, B.S. Ramaswamy, Can. J. Chem. 49
(1971) 1957.
[28] P.F. Barron, J.C. Dyason, P.C. Healy, L.M. Engelhardt, B.W.
Skelton, A.H. White, J. Chem. Soc., Dalton Trans. (1986)
1965.
[29] P.C. Healy, A.H. White, Spectrochim. Acta A 29 (1973) 1191.
[30] E.L. Muetterties, C.W. Alegranti, J. Am. Chem. Soc. 94 (1972) 6386.
[31] R.G. Goel, P. Pilon, Inorg. Chem. 17 (1978) 2876.
[32] M. Camalli, F. Caruso, Inorg. Chim. Acta 144 (1988) 205.
[33] C.A. Tolman, Chem. Rev. 77 (1977) 313.
[15] J. Pang, E.J.-P. Marcotte, C. Seward, R.S. Brown, S.-N. Wang,
Angew. Chem., Int. Ed. Engl. 40 (2001) 4042.
[16] Q.-D. Liu, J.-R. Li, S. Gao, B.-Q. Ma, H.-Z. Kou, K.-B. Yu, Eur. J.
Inorg. Chem. 42 (2003) 731.
[17] A. Cingolani, Effendy, F. Marchetti, C. Pettinari, B.W. Skelton,
A.H. White, J. Chem. Soc., Dalton Trans. (1999) 4047.
[18] L.M. Engelhardt, P.C. Healy, J.D. Kildea, A.H. White, Aust. J.
Chem. 42 (1989) 895, and subsequent papers;
[34] G.A. Bowmaker, C.L. Brown, R.D. Hart, P.C. Healy, C.E.F.
Rickard, A.H. White, J. Chem. Soc., Dalton Trans. (1999) 881.
[35] S. Bin Silong, J.D. Kildea, W.C. Patalinghug, B.W. Skelton, A.H.
White, Aust. J. Chem. 47 (1994) 1545.