Synthesis and structural characterization of adducts of silver(I) oxyanion salts, AgX (X = ClO4, NO3), with Ph2E(CH2)xEPh2 ('dpex'; E = P, As; x = 1-4) and oligodentate aromatic N-bases derivative of 2,2′-bipyridyl, 'L', AgX:dpex:L (2:1:2)

Inorganica Chimica Acta 360 (2007) 1388–1413

www.elsevier.com/locate/ica

Synthesis and structural characterization of adducts of silver(I)

oxyanion salts, AgX (X = ClO₄, NO₃), with Ph₂E(CH₂)_xEPh₂

(‘dpex’; E = P, As; x = 1–4) and oligodentate aromatic

N-bases derivative of 2,2⁰-bipyridyl, ‘L’, AgX:dpex:L (2:1:2)

c

c,

c

Eﬀendy ^a,b, Fabio Marchetti , Claudio Pettinari ^*, Riccardo Pettinari ,

a

Brian W. Skelton , Allan H. White

a

Chemistry M313, School of Biomedical, Biomolecular and Chemical Sciences, The University of Western Australia, Crawley, WA 6009, Australia

b

Jurusan Pendidikan Kimia, FMIPA Universitas Negeri Malang, Jalan Surabaya 6, Malang 65145, Indonesia

c

`

Dipartimento di Scienze Chimiche, Universita degli Studi di Camerino, via S. Agostino 1, 62032 Camerino MC, Italy

Received 30 May 2006; accepted 6 July 2006

Available online 21 July 2006

Abstract

1

The syntheses and the spectroscopic characterization (IR, H, ¹³C and ³¹P NMR, ESI-MS and conductivity studies) of a number of

adducts of silver(I) perchlorate and nitrate, AgX, with N,N⁰(,N⁰⁰)-oligodentate ligands L, derivative of 2,2⁰-bipyridyl, together with

Ph₂E(CH₂)_xEPh₂(”‘dpex’, x predominantly 1,2 (‘dpem’, ‘dpee’) but also 3,4 (‘dppp’, ‘dppb’), E = P, As) are reported, of stoichiometry

AgX:dpex:L (2:1:2), L = 2,2⁰-bipyridyl (‘bpy’); 1,10-phenanthroline (‘phen’); 2,9-dimethyl, 1,10-phenanthroline (‘dmp’); bis(2-pyr-

idyl)amine (‘dpa’); 2,2⁰-biquinolyl (‘bq’); 2,2⁰:6⁰,2⁰⁰-terpyridyl (‘tpy’). For AgClO₄:dppm:bpy, phen, dmp, tpy; AgClO₄:dpem:phen,

dmp, tpy; AgNO₃:dppm:bpy, bq (2:1:2), the compounds are of the form [LAg(E-dpem-E⁰)AgL]X₂, the pair of Ag–E bonds lying cis/par-

allel about the ECH₂E core, of quasi-C_2vsymmetry; for AgClO₄:dppm:dpa; AgNO₃:dppm:bpy (2:1:2), the Ag–E bonds lie trans, with a

cation symmetry (quasi-)2. In AgNO₃:dppm, dpam:dmp (2:1:2), loosely coordinated nitrate ions approach one of the silver atoms as

unidentate ligands, Ag–E being ‘cis’: [(O₂NO)(dmp)Ag(E-dpem-E⁰)Ag(dpm)](NO₃). The majority of [LAg(E-dpex-E⁰)AgL] (dpex =

dpee, dpeb) arrays (AgClO₄:dppe:bpy, bq, dpa, tmp, tpy; AgClO₄:dpae:bpy, bq; AgClO₄:dpdae:dmp (E = P, E⁰= As); AgClO₄:dppb:dpa,

bq, tpy; AgNO₃:dppb:tpy (2:1:2)) are centrosymmetric and trans-oid with close approaches to the silver atoms by oxyanions or solvent

(MeCN) molecules; AgClO₄:dpae:dmp (2:1:2) is cis-oid, as also are the dppp adducts, AgClO₄:dppp:dmp, bq (2:1:2). A novel bridging

tpy coordination mode is found, whereby pairs of silver atoms are linked g²(r,p) into a single stranded polymer in AgClO₄:dppp:tpy

(2:1:2), thus [. . .Ag(P-dppp-P⁰)Ag((l-N⁰⁰)tpy)₂. . .]_(1|1)

.

Keywords: Silver salts; Oxyanion; 2:1:2 Adducts; N-donor ligands; Complexes; Structures; Diphosphine; Aromatic N-bases; Single crystal X-ray studies;

NMR

1. Introduction

of the possible arrays of complexes formed with simple

coinage metal(I) salts with simple or important group 15

donor bases. Reports thus far have been primarily focussed

on adducts of copper(I) and silver(I) (pseudo-)halide and

oxyanion salts, ﬁrstly with uni- and (oligo-/)bi-dentate

(aromatic (pyridine)) nitrogen bases with varying degrees

of steric hindrance [1,2] with parallel studies of systems

Recent series of publications have approached compre-

hensive and systematic deﬁnition by structural methods

*

Corresponding author. Tel.: +390737 402234; fax: +390737 637345.

E-mail address: claudio.pettinari@unicam.it (C. Pettinari).

doi:10.1016/j.ica.2006.07.016

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1389

with unidentate ER₃(E = P, As, Sb) and bidentate

Ph₂E(CH₂)_xPPh₂(E = P, As) dpex ligands, of diverse stoi-

chiometries. Recent studies of the latter arrays have been

concerned with systems primarily of the form AgX:dpex

of (1:1)_(n)and (2:3)_(n)stoichiometries [3–7]. Studies of

mixed ligand systems have been more limited; the present

report describes the synthesis and structural deﬁnition, of

a quasi-systematic and comprehensive nature, of adducts

of the form AgX (X = oxyanion (NO₃, ClO₄)):dpex

(= ‘dppm’, Ph₂PCH₂PPh₂; ‘dpam’, Ph₂AsCH₂AsPh₂;

‘dppe’, Ph₂P(CH₂)₂PPh₂; ‘dpae’, Ph₂As(CH₂)₂AsPh₂;

‘dpdae’, Ph₂P(CH₂)₂AsPh₂; ‘dppp’, Ph₂P(CH₂)₃PPh₂;

‘dppb’, Ph₂P(CH₂)₄PPh₂):L (= 2,2⁰-bipyridyl, ‘bpy’; 1,10-

phenanthroline, ‘phen’; 2,9-dimethyl, 1,10-phenanthroline,

‘dmp’; 2,2⁰-biquinolyl, ‘bq’; bis(2-pyridyl)amine, ‘dpa’; and

2,2⁰:6⁰,2⁰⁰-terpyridyl, ‘tpy’), deﬁning arrays of 2:1:2 stoichi-

ometry, with diﬀerent novel forms described. Comple-

mentary studies, including unidentate ER₃ligands and

diﬀerent stoichiometries, are oﬀered in accompanying

papers [8–11].

amounts of materials should be prepared, and these should

be handled with great caution.

2.1.1. AgX (=ClO₄):dpex:L (2:1:2) (ÆnS) complexes

2.1.1.1. Synthesis of AgClO₄:dppm:bpy (2:1:2) (1). A solu-

tion containing AgClO₄(0.414 g, 2.0 mmol), dppm

(0.384 g, 1.0 mmol) and bpy (0.312 g, 2.0 mmol) in 10 mL

of CH₃CN was stirred for 12 h at room temperature. The

solution was then evaporated under vacuum and the color-

less residue washed with diethyl ether and shown to be

compound 1 (1.089 g, yield: 98%); m.p. 229–232 ꢁC (dec),

272–273 ꢁC. Anal. Calc. for C₄₅H₃₈Ag₂Cl₂N₄O₈P₂: C,

48.63; H, 3.45; N, 5.04. Found: C, 48.80; H, 3.51; N,

5.13%. IR (nujol, cm^ꢀ1): 1589s, 1567m, 1537sh m(C C,

. . .

•

. . .

C

N), 1100sh, 1088sbr, 625s, 620s, m(ClO₄), 530w,

•

1

505w, 478w, 403w. H NMR (CD₃CN, 293 K): d, 3.96 (t,

2H, CH_2dppm), 7.45 (m, 12H, C₆H_5dppm+ 4H, CH_bpy),

7.70 (m, 8H, C₆H_5dppm), 7.98 (m, 8H, CH_bpy), 8.43 (m,

4H, CH_bpy). ¹³C NMR (CD₃CN, 293 K): d, 26.06 (m,

CH_2dppm), 123.63 (t, C5_bpy), 127.14 (s, C3_bpy), 130.44 (m,

C_dppm), 131.62 (m, C_dppm), 132.65 (s, C_dppm), 134.15 (t,

C_dppm), 140.90 (m, C4_bpy+ C_dppm), 151.85 (s, C6_bpy),

152.00 (s, C2_bpy). ³¹P NMR (CD₃CN, 293 K): d, 12.5 (d,

¹J(³¹P–Ag): 670.9 Hz). ESI MS (+): 189 (35)

[Ag(MeCN)₂]⁺, 304 (45) [Ag(bpy)(MeCN)]⁺, 492 (100)

[Ag₂(dppm)₂]²⁺, 1018 (15) [Ag₂(dppm)₂Cl]⁺, 1082 (25)

[Ag₂(dppm)₂ClO₄]⁺.

2. Experimental

All syntheses and handlings were carried out in the air.

All chemicals were purchased from Aldrich and Lancaster

and used without further puriﬁcation. Elemental analyses

(C, H, N) were performed in-house with a Fisons Instru-

ments 1108 CHNS-O Elemental Analyser. IR spectra

were recorded from 4000 to 100 cm^ꢀ1with a Perkin–

Elmer System 2000 FT-IR instrument. ¹H, ¹³C and ³¹P

NMR spectra were recorded on a Mercury Plus Varian

2.1.1.2. Synthesis of AgClO₄:dppm:phen (2:1:2) (2). AgClO₄

(0.414 g, 2.0 mmol) and dppm (0.384 g, 1 mmol) were

added to an acetonitrile solution (10 mL) containing

0.360 g (2.0 mmol) of phen. A colorless precipitate immedi-

ately formed. The suspension was stirred overnight, then

was ﬁltered oﬀ and the colorless residue washed with

diethyl ether and shown to be compound 2 (0.629 g, yield:

54%). Re-crystallization from MeCN gives the MeCN sol-

vate, 2 Æ MeCN; m.p. 293–294 ꢁC. Anal. Calc. for

C₄₉H₃₈Ag₂Cl₂N₄O₈P₂: C, 50.76; H, 3.30; N, 4.83. Found:

C, 50.93; H, 3.21; N, 4.80%. IR (nujol, cm^ꢀ1): 1620s,

1

400 NMR spectrometer (400 MHz for H, 100 MHz for

¹³C, and 162.1 MHz for ³¹P). H and C chemical shifts

are reported in ppm versus SiMe₄, P chemical shifts in

ppm versus H₃PO₄85%. The electrical conductances of

the acetone, dichloromethane, DMSO and acetonitrile

solutions were measured with a Crison CDTM 522 con-

ductimeter at room temperature. Positive and negative

electrospray mass spectra were obtained with a Series

1100 MSI detector HP spectrometer, using an acetonitrile

mobile phase. Solutions (3 mg/mL) for electrospray ioni-

zation mass spectrometry (ESI-MS) were prepared using

reagent grade acetone or acetonitrile. For the ESI-MS

data, masses and intensities were compared to those cal-

culated by using the IsoPro Isotopic Abundance Simula-

tor, version 2.1 [12]; peaks containing silver(I) ions are

identiﬁed as the centres of isotopic clusters. Unless stated

otherwise, crystals for the X-ray work were obtained from

a few mL of acetonitrile solutions of the reagents on a

millimolar scale by slow cooling and/or evaporation in

ambience, these crystals frequently being solvated forms

of the adducts.

. . .

1589s, 1572s, 1512s m(C C, C N), 1110sh, 1073sbr,

•

625s, 620s m(ClO₄), 520m, 503m, 483m, 470m, 448m,

1

420m, 338w, 273m, 246m. H NMR (CD₃CN, 293 K): d,

4.07 (t, 2H, CH_2dppm), 7.48–7.53 (m, 12H, C₆H_5dppm),

7.73–7.84 (m, 8H, C₆H_5dppm), 7.59–7.55 (m, 4H, CH_phen),

7.69 (s, 4H, CH_phen), 8.23 (dd, 4H, CH_phen), 8.71 (m, 4H,

CH_phen). ¹³C NMR (CD₃CN, 293 K): d, 26.53 (m,

CH_2dppm), 125.80 (s, C_phen), 128.04 (s, C_phen), 129.72 (s,

C_phen), 130.49 (m, C_dppm), 132.68 (s, C_dppm), 132 (m br,

C_dppm), 134.31 (m, C_dppm), 139.93 (s, C_phen), 141.89 (s,

C_phen), 152.23 (s, C_phen). ³¹P NMR (CD₃CN, 293 K): d,

14.9 (m, ¹J(³¹P–Ag): 670.9 Hz). For the material re-crystal-

lized from CH₃CN as 2 Æ MeCN: ESI MS (+): 189 (35)

[Ag(MeCN)₂]⁺, 328 (45) [Ag(phen)(MeCN)]⁺, 467 (85)

[Ag(phen)₂]⁺, 672 (100) [Ag(dppm)(phen)]⁺, 872 (25)

[Ag₂(dppm)(phen)ClO₄]⁺, 1018 (25) [Ag₂(dppm)₂Cl]⁺,

2.1. Syntheses

Safety note. Perchlorate salts of metal complexes with

organic ligands are potentially explosive! Only small

1058

(25)

[Ag₂(dppm)(phen)₂ClO₄]⁺,

1082

(25)

[Ag₂(dppm)₂ClO₄]⁺.

1390

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

2.1.1.3. Synthesis of AgClO₄:dppm:dmp (2:1:2) (3). Com-

pound 3 has been prepared in 34% yield (0.456 g) following

a procedure similar to that reported for 2 by using AgClO₄

(0.414 g, 2.0 mmol), dppm (0.384 g, 1.0 mmol) and dmp

(0.416 g, 2.0 mmol). Re-crystallization from MeCN gives

3. MeCN; m.p. 318–319 ꢁC. Anal. Calc. for C₅₃H₄₆Ag₂Cl_2-

N₄O₈P₂: C, 52.37; H, 3.81; N, 4.61. Found: C, 52.53; H,

3.78; N, 4.48%. IR (nujol, cm^ꢀ1): 1619s, 1589s, 1573sh,

(CD₃CN, 293 K): d, 25.7 (m, CH_2dppm), 114.2, 117.1 (s,

C_dpa), 129.3 (br, C_dppm), 131.0 (br, C_dppm), 131.6 (m,

C_dppm), 133.0 (br, C_dppm), 139.5 (s, C_dpa), 148.2 (s, C_dpa),

154.1 (s, C_dpa). ³¹P NMR (CD₃CN, 293 K): d, 7.4 (d,

¹J(³¹P–Ag): 668.4 Hz). For the material re-crystallized

from MeCN as 5 Æ 1/3H₂O: ESI MS (+): 189 (35)

[Ag(MeCN)₂]⁺, 663 (50) [Ag(dpa)(dppm)]⁺, 868 (25)

[Ag₂(dppm)(dpa)ClO₄]⁺.

. . .

1555s, 1503s m(C C, C N), 1100sh, 1076sbr, 621s

•

m(ClO₄), 550m, 522m, 506m, 478m, 443m, 426m, 403w,

360w, 341w. H NMR (CD₃CN, 293 K): d, 2.69 (s, 12H,

2.1.1.6. Synthesis of AgClO₄:dppm:tpy (2:1:2) (6). Com-

pound 6 (0.266 g, yield: 80%) has been prepared following

a procedure similar to that reported for 1 by using AgClO₄

(0.104 g, 0.5 mmol), dppm (0.096 g, 0.25 mmol) and tpy

(0.116 g, 0.5 mmol); m.p. 295–296 ꢁC. Anal. Calc. for

C₅₅H₄₄Ag₂Cl₂N₆O₈P₂: C, 52.20; H, 3.50; N, 6.64. Found:

C, 52.10; H, 3.60; N, 6.77%. IR (nujol, cm^ꢀ1): 2318m,

1

CH_3dmp), 4.03 (t, 2H, CH_2dppm), 7.38–7.45 (m, 4H,

C₆H_5dppm+ CH_dmp),

7.67–7.80

(m,

4H,

C₆H_5dppm+ CH_dmp), 8.13 (m, 4H, CH_dmp). ¹³C NMR

(CD₃CN, 293 K): d, 25.04 (m, CH_2dppm), 29.47

(s, CH_3dmp), 125.80 (s, C_dmp), 127.07 (s, C_dmp), 128.07 (s,

C_dmp), 130.32 (m, C_dppm), 132.30 (s, C_dmp), 132.62

(s, C_dppm), 133.87 (m, C_dppm), 140.16 (s, C_dmp), 159.61 (s,

. . .

2000w, 1600m, 1573m, 1555m m(C C, C N), 1079sbr,

•

622s m(ClO₄), 473w, 346w, 290w. ¹H NMR (CD₃CN,

293 K): d, 3.76 (t, 2H, CH_2dppm), 7.27–7.54 (m, 20H,

C₆H_5dppm+ 6H, CH_tpy), 7.90 (m, 4H, CH_tpy), 8.06–8.20

(m, 12H, CH_tpy). ¹³C NMR (CD₃CN, 293 K): d, 25.0 (m,

CH_2dppm), 123.88, 124.15 (s, C_tpy), 126.3 (s, C_tpy), 130.23

(br, C_dppm), 132.4 (br, C_dppm), 133.9 (m, C_dppm), 139.8 (s,

C_tpy), 141.3 (s, C_tpy), 151.4 (s, C_tpy), 153.3 (s, C_tpy),

153.8(s, C_tpy). ³¹P NMR (CD₃CN, 293 K): d, 6.4 (d,

¹J(³¹P–Ag): 569.6 Hz).

1

C_dmp). ³¹P NMR (CD₃CN, 293 K): d, 8.3 (m, J(³¹P–Ag):

642.5 Hz). For the material re-crystallized from MeCN as

3.MeCN: ESI MS (+): 356 (20) [Ag(dmp)(MeCN)]⁺, 525

(100) [Ag(dmp)₂]⁺, 701 (38) [Ag(dppm)(dmp)]⁺, 1018 (5)

[Ag₂(dppm)₂Cl]⁺, 1082 (5) [Ag₂(dppm)₂ClO₄]⁺.

2.1.1.4. Synthesis of AgClO₄:dppm:bq (2:1:2) (4). Com-

pound 4 (0.243 g, yield: 74%) has been prepared following

a procedure similar to that reported for 1 by using AgClO₄

(0.104 g, 0.5 mmol), dppm (0.096 g, 0.25 mmol), and bq

(0.128 g, 0.5 mmol); m.p. 300–301 ꢁC. Anal. Calc. for

C₆₁H₄₆Ag₂Cl₂N₄O₈P₂: C, 55.86; H, 3.53; N, 4.27. Found:

C, 55.03; H, 3.59; N, 4.23%. IR (nujol, cm^ꢀ1): 1618m,

2.1.1.7. Synthesis of AgClO₄:dpam:phen (2:1:2) (7),

AgClO₄:dpam:dmp (2:1:2) (8), and AgClO₄:dpam:tpy

(2:1:2) (9). Complexes 7–9 were obtained by crystalliza-

tion of millimolar stoichiometries of silver perchlorate with

dpam and the appropriate aromatic oligodentate ligand L

from acetonitrile solution, by standing and evaporation

in ambience. Satisfactory bulk sample analyses were

obtained from the following:

7(Æ¼MeCN): AgClO₄:dpam:phen (2:1:2) Æ ¼MeCN.

Anal. Calc. for C_49.5H_38.75Ag₂As₂Cl₂N_4.25O₈: C, 47.28; H,

3.11; N, 4.73. Found: C, 47.50; H, 3.11; N, 4.64%; m.p.

slow decomposition at room temperature.

. . .

1589s, 1556w, 1534w, 1503w m(C C, C N), 1083sbr

•

1

m(ClO₄), 522w, 477m, 267w. H NMR (CD₃CN, 293 K):

d, 4.29 (m, 2H, CH_2dppm), 7.26–7.87 (m, 20H,

C₆H_5dppm+ CH_bq), 8.15 (d, 4H, CH_bq), 8.40 (d, 4H,

CH_bq). ¹³C NMR (CD₃CN, 293 K): d, 30.94 (s, CH_2dppm),

120.63 (s, C3_bq), 129.27, 129.55, 129.69, 130.41, 132.87 (s,

C_bq+ C_dppm), 130.50 (m, C_dppm), 132.61 (s, C_dppm),

134.10 (m, C_dppm), 141.35 (s, C4_bq), 145.94 (s, C10_bq),

152.37 (s, C2_bq). ³¹P NMR (CD₃CN, 293 K): d, 11.6 (d,

¹J(³¹P–Ag): 653.6 Hz).

8(ÆMeCN): AgClO₄:dpam:dmp (2:1:2) Æ MeCN. Anal.

Calc. for C₅₅H₄₉Ag₂As₂Cl₂N₅O₈: C, 49.13; H, 3.67; N,

5.21. Found: C, 49.22; H, 3.72; N, 5.05%.

2.1.1.5. Synthesis of AgClO₄:dppm:dpa (2:1:2) (5). Com-

pound 5 (0.276 g, yield: 97%) has been prepared following

a procedure similar to that reported for 1 by using AgClO₄

(0.104 g, 0.5 mmol), dppm (0.096 g, 0.25 mmol), and dpa

(0.085 g, 0.5 mmol). Re-crystallization from MeCN in

ambience yielded the material modelled in the X-ray study

as 5 Æ 1/3H₂O; m.p. 146–147 ꢁC (dec), >239 ꢁC. Anal. Calc.

for C₄₅H₄₀Ag₂Cl₂N₆O₈P₂: C, 47.35; H, 3.53; N, 7.37.

9: AgClO₄:dpam:tpy (2:1:2). Anal. Calc. for

C₅₅H₄₄Ag₂As₂Cl₂N₆O₈: C, 48.81; H, 3.28; N, 6.21. Found:

C, 48.75; H, 3.27; N, 6.21%; m.p. 262–265 ꢁC.

2.1.1.8. Synthesis of AgClO₄:dppe:bpy (2:1:2) (10). Com-

pound 10 (1.114 g, yield: 99%) has been prepared following

a procedure similar to that reported for 1, by using AgClO₄

(0.414 g, 2 mmol), dppe (0.398 g, 1 mmol), and bpy

(0.312 g, 2 mmol); m.p. 251–252 ꢁC. Anal. Calc. for

C₄₆H₄₀Ag₂Cl₂N₄O₈P₂: C, 49.09; H, 3.58; N, 4.98. Found:

C, 48.95; H, 3.44; N, 4.80%. IR (nujol, cm^ꢀ1): 1590s,

Found: C, 47.10; H, 3.57; N, 7.32%. IR (nujol, cm^ꢀ1):

. . .

3331w m(N–H), 1643s, 1632s, 1573s, 1530s m(C C,

•

. . .

C

N), 1082sbr m(ClO₄), 519m, 505m, 472m, 407m,

•

333w. ¹H NMR (CD₃CN, 293 K): d, 3.80 (s, 2H, CH_2dppm),

6.84 (t, 4H, CH_dpa), 7.19 (d, 4H, CH_dpa), 7.40 (m, 12H,

C₆H_5dppm), 7.61–7.75 (m, 12H, C₆H_5dppm+ 4H, CH_dpa),

7.95 (m, 4H, CH_dpa), 8.21 (sbr, 1H, NH_dpa). ¹³C NMR

1573m, 1567m, 1556w, 1537w, 1504w m(C C, C N),

. . .

•

1093sbr, 621s m(ClO₄), 506w, 490w, 448w, 412w, 329w,

254w. ¹H NMR (CD₃CN, 293 K): d, 2.61 (d, 4H, CH_2dppe),

7.49–7.63 (m, 20H, C₆H_5dppe+ 4H, CH_bpy), 8.06–8.14 (m,

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1391

1

4H, CH_bpy), 8.32 (d, 4H, CH_bpy), 8.61 (d, 4H, CH_bpy). ¹³C

NMR (CD₃CN, 293 K): d, 26.96 (d, CH_2dppe), 123.76 (s,

C5_bpy), 126.94 (s, C3_bpy), 130.40 (d, C_dppe), 132.43 (d,

C_dppe), 133.89 (d, C_dppe), 140.70 (s, C4_bpy), 151.99 (s,

C6_bpy), 152.87 (s, C2_bpy). ³¹P NMR (CD₃CN, 293 K): d,

11.5br. ³¹P NMR (CD₃CN, 233 K): d, 12.6 (d, ¹J(³¹P–

Ag): 686 Hz).

478m, 407m, 331m. H NMR (CD₃CN, 293 K): d, 2.16,

2.19 (s, 8H, CH₃CN + H₂O), 2.39 (br, 4H, CH_2dppe), 6.94

(t, 4H, CH_dpa), 7.36–7.48 (m, 20H, C₆H_5dppe+ 4H, CH_dpa),

7.74 (m, 4H, CH_dpa), 8.19 (m, 4H, CH_dpa). ¹³C NMR

(CD₃CN, 293 K): d, 24.20 (m, CH_2dppe), 114.54, 118.40

(s, C_dpa), 130.42 (m, C_dppe), 132.35 (s, C_dppe), 133.70 (m,

C_dppe) 140.07 (s, C_dpa), 149.30 (s, C_dpa), 155.64 (s, C_dpa).

³¹P NMR (CD₃CN, 293 K): d, 10.4 (d, ¹J(³¹P–Ag):

443.9 Hz). Re-crystallization from MeCN in ambience

yielded a material modelled in the X-ray study as

13 Æ MeCN Æ H₂O.

2.1.1.9. Synthesis of AgClO₄:dppe:dmp (2:1:2) (11). Com-

pound 11 (0.550 g, yield: 79%) has been prepared as

11 Æ 2MeCN following a procedure similar to that reported

for 2 by using AgClO₄(0.207 g, 1 mmol), dppe (0.198 g,

0.5 mmol) and dmp (0.208 g, 1 mmol); m.p. >79 ꢁC, 290–

291 ꢁC. Anal. Calc. for C₆₂H₆₀Ag₂Cl₂N₈O₈P₂: C, 53.43;

H, 4.34; N, 8.04. Found: C, 53.28; H, 4.20; N, 7.89%. IR

2.1.1.12. Synthesis of AgClO₄:dppe:tpy (2:1:2) (14). Com-

pound 14 (0.313 g, yield: 98%) has been obtained following

a procedure similar to that reported for 1 by using AgClO₄

(0.104 g, 0.5 mmol), dppe (0.099 g, 0.25 mmol), and tpy

(0.116 g, 0.5 mmol); m.p. 229 ꢁC. Anal. Calc. for

C₅₆H₄₆Ag₂Cl₂N₆O₈P₂: C, 52.56; H, 3.62; N, 6.57. Found:

C, 52.40; H, 3.70; N, 6.37%. IR (nujol, cm^ꢀ1): 1597m,

(nujol, cm^ꢀ1): 1620s, 1590s, 1556s, 1503s m(C C,

. . .

•

. . .

C

N), 1083sbr, 621s m(ClO₄), 548w, 509w, 478w, 343w.

•

¹H NMR (CD₃CN, 293 K): d, 2.17 (s, 12H, CH₃CN)

2.61 (d, 4H, CH_2dppe), 2.68 (s, 12H, CH_3dmp), 7.44–7.57

(m, 20H, C₆H_5dppe), 7.73 (d, 4H, CH_dmp), 8.46 (d, 4H,

CH_dmp). ¹³C NMR (CD₃CN, 293 K): d, 24.01 (m,

CH_2dppe), 28.40 (s, CH_3dmp), 126.14 (s, C_dmp), 127.19 (s,

C_dmp), 128.54 (s, C_dmp), 130.45 (m, C_dppe), 132.36 (s, C_dppe),

133.73 (m, C_dppe), 140.00 (s, C_dmp), 142.87 (s, C_dmp), 160.06

. . .

1573m, 1555, 1503w m(C C, C N), 1081sbr, 620s

•

1

m(ClO₄), 512w, 349w, 250w. H NMR (CD₃CN, 293 K):

d, 2.08 (d, 4H, CH_2dppe), 7.16–7.53 (m, 20H,

C₆H_5dppe+ 6H, CH_tpy), 7.94 (m, 4H, CH_tpy), 8.22–8.34

(m, 12H, CH_tpy). ¹³C NMR (CD₃CN, 293 K): d, 23.98

(m, CH_2dppe), 123.90, 124.21, 126.40 (s, C_tpy), 130.20 (m,

C_dppe), 132.02 (s, C_dppe), 133.37 (m, C_dppe) 139.77, 141.36

(s, C_tpy), 151.40 (s, C_tpy), 153.45, 154.01 (s, C_tpy). ³¹P

NMR (CD₃CN, 293 K): d, 6.32s br. ³¹P NMR (CD₃CN,

233 K): d, 5.84 (d, ¹J(³¹P–Ag): 631 Hz). Compound 14

was re-crystallized from MeCN as 14 Æ 2MeCN.

(s, C_dmp). ³¹P NMR (CD₃CN, 293 K): d, 8.9 (d, J(³¹P–

1

Ag): 623.9 Hz).

2.1.1.10. Synthesis of AgClO₄:dppe:bq (2:1:2) (12). Com-

pound 12 (0.295 g, yield: 89%) has been synthesised follow-

ing a procedure similar to that reported for 1 by using

AgClO₄(0.104 g, 0.5 mmol), dppe (0.099 g, 0.25 mmol),

and bq (0.128 g, 0.5 mmol); m.p. 305–306 ꢁC. Anal. Calc.

for C₆₂H₄₈Ag₂Cl₂N₄O₈P₂: C, 56.17; H, 3.65; N, 4.23.

Found: C, 56.20; H, 3.61; N, 4.12%. IR (nujol, cm^ꢀ1):

2.1.1.13. Synthesis of AgClO₄:dpae:bpy (2:1:2) (15),

AgClO₄:dpae:dmp (2:1:2) (16), AgClO₄:dpae:bq (2:1:2)

(17) and AgClO₄:dpdae:bq (2:1:2) (18). Complexes 15–18

were obtained by crystallization of millimolar stoichiome-

tries of silver perchlorate with dpam or dpdae and the

appropriate aromatic oligodentate ligand L, from acetoni-

trile solution, by standing and evaporation in ambience.

Satisfactory bulk sample analyses were obtained from the

following:

15: AgClO₄:dpae:bpy (2:1:2). Anal. Calc. for

C₄₆H₄₀Ag₂As₂Cl₂N₄O₈: C, 45.54; H, 3.32; N, 4.62. Found:

C, 45.45; H, 3.47; N, 4.72%; m.p. 208–211 ꢁC (dec).

16(ÆH₂O): AgClO₄:dpae:dmp (2:1:2) Æ H₂O. Anal. Calc.

for C₅₄H₅₀Ag₂As₂Cl₂N₄O₉: C, 48.83; H, 3.72; N, 4.26.

Found: C, 48.42; H, 3.64; N, 4.31%; m.p. >144 ꢁC (dec).

17(Æ2MeCN): AgClO₄:dpae:bq (2:1:2) Æ 2MeCN. Anal.

Calc. for C₆₆H₅₄Ag₂As₂Cl₂N₆O₈: C, 53.00; H, 3.64; N,

5.62. Found: C, 52.92; H, 4.08; N, 5.15%; m.p. >78 ꢁC

(dec).

. . .

1620s, 1591m, 1555m, 1537w, 1503w m(C C, C N),

•

1091sbr, 620br m(ClO₄), 510w, 483w, 449w, 334w. ¹H

NMR (CD₃CN, 293 K): d, 2.73 (d, 4H, CH_2dppe), 7.44–

7.59 (m, 20H, C₆H_5dppe+ 8H, CH_bq), 7.86 (d, 4H, CH_bq),

8.00 (d, 4H, CH_bq), 8.44 (d, 4H, CH_bq), 8.57 (d, 4H, CH_bq).

¹³C NMR (CD₃CN, 293 K): d, 23.26 (m, CH_2dppe), 121.15

(s, C3_bq), 129.43, 129.64, 130.14, 130.46, 132.15 (s, C_bq),

130.67 (m, C_dppe), 132.97 (s, C_dppe), 133.70 (m, C_dppe

)

141.11 (s, C4_bq), 146.91 (s, C10_bq), 153.41 (s, C2_bq). ³¹P

1

NMR (CD₃CN, 293 K): d, 8.8 (d, J(³¹P–Ag): 601.7 Hz).

Compound 12 was re-crystallized from MeCN as

12 Æ 2MeCN.

2.1.1.11. Synthesis of AgClO₄:dppe:dpa (2:1:2) (13). Com-

pound 13 (0.307 g, yield: 98%) has been synthesised as

13 Æ 2MeCN Æ H₂O following a procedure similar to that

reported for 1 by using AgClO₄(0.104 g, 0.5 mmol), dppe

(0.099 g, 0.25 mmol), and dpa (0.085 g, 0.5 mmol); m.p.

211–212 ꢁC. Anal. Calc. for C₄₆H₄₂Ag₂Cl₂N₆O₈P₂: C,

47.83; H, 4.01; N, 8.92. Found: C, 47.59; H, 3.86; N,

9.11%. IR (nujol, cm^ꢀ1): 3338m, 3240w, 3218m, 3180m,

m(N–H) + m(O–H), 2197 (CN) 1632s, 1578s, 1529s

18(Æ2MeCN): AgClO₄:dpdae:bq (2:1:2) Æ 2MeCN. Anal.

Calc. for C₆₆H₅₄Ag₂AsCl₂N₆O₈P: C, 54.61; H, 3.75; N,

5.75. Found: C, 54.49; H, 3.90; N, 5.62%.

2.1.1.14. Synthesis of AgClO₄:dppp:bq (2:1:2) (19). Com-

pound 19 (0.096 g, yield: 29%) has been synthesised follow-

ing a procedure similar to that reported for 1 by using

. . .

m(C C, C N), 1094sbr, 639s, 621s m(ClO₄), 507m,

•

1392

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

AgClO₄(0.104 g, 0.5 mmol), dppp (0.103 g, 0.25 mmol),

and bq (0.128 g, 0.5 mmol); m.p. 285–286 ꢁC. Anal. Calc.

for C₆₃H₅₀Ag₂Cl₂N₄O₈P₂: C, 56.48; H, 3.76; N, 4.18.

Found: C, 56.20; H, 3.81; N, 4.06%. IR (nujol, cm^ꢀ1):

N, 4.86. Found: C, 50.11; H, 3.64; N, 4.78%. IR (nujol,

. . . . . .

cm^ꢀ1): 1667m, 1630s, 1589s, 1565s m(C C, C N),

•

1090sbr, 630s, 618 s m(ClO₄), 521m, 485m, 466w, 419m,

398w, 350w, 311m. ¹H NMR (CD₃CN, 293 K): d, 1.77

(m, 4H, CH_2dppb), 2.48 (d, 4H, CH_2dppb), 7.45–7.71 (m,

20H, C₆H_5dppb+ 4H, CH_bpy), 8.06–8.15 (m, 4H, CH_bpy),

8.35 (m, 4H, CH_bpy), 8.68 (m, 4H, CH_bpy). ¹³C NMR

(CD₃CN, 293 K): d, 26.96 (d, CH_2dppb), 28.00 (m,

CH_2dppb), 123.72 (s, C5_bpy), 126.97 (s, C3_bpy), 130.23 (d,

C_dppb), 132.17 (s, C_dppb), 133.00 (d, C_dppb), 133.85 (d,

C_dppb), 140.71 (s, C4_bpy), 152.05 (s, C3_bpy), 152.89 (s,

C2_bpy). ³¹P NMR (CD₃CN, 293 K): d, 10.1 (d, ¹J(³¹P–

Ag): 681.2 Hz). Compound 22 was re-crystallized from

MeCN as 22 Æ 2MeCN.

. . .

1617s, 1591s, 1555m, 1503w, m(C C, C N), 1088sbr,

•

621s m(ClO₄), 522m, 513m, 480s, 448m, 395w, 318w,

274w. ¹H NMR (CD₃CN, 293 K): d, 2.60 (sbr, 2H,

CH_2dppp), 2.82 (sbr, 4H, CH_2dppp), 7.40–7.59 (m, 20H,

C₆H_5dppp+ 8H, CH_bq), 7.83 (m, 8H, CH_bq), 8.37 (d, 4H,

CH_bq), 8.51 (d, 4H, CH_bq). ¹³C NMR (CD₃CN, 293 K):

d, 23.26, 28.40 (m, CH_2dppp), 121.05 (s, C_bq), 129.35,

129.45, 129.99, 130.64, 132.25 (s, C_bq), 130.40 (d, C_dppp),

132.51 (s, C_dppp), 133.70 (d, C_dppp) 141.07 (s, C_bq), 146.64

(s, C_bq), 153.13 (s, C_bq). ³¹P NMR (CD₃CN, 293 K): d,

7.9 (d, ¹J(³¹P–Ag): 630.0 Hz). Compound 19 was re-crystal-

lized from MeCN as 19 Æ 2MeCN.

2.1.1.18. Synthesis of AgClO₄:dppb:bq (2:1:2) (23). Com-

pound 23 (0.140 g, yield: 41%) has been prepared following

a procedure similar to that reported for 1 by using AgClO₄

(0.104 g, 0.5 mmol), dppb (0.106 g, 0. 25 mmol), and bq

(0.128 g, 0.5 mmol); m.p. 298–299 ꢁC. Anal. Calc. for

C₆₄H₅₂Ag₂Cl₂N₄O₈P₂: C, 56.78; H, 3.87; N, 4.14. Found:

C, 56.50; H, 3.77; N, 4.01%. IR (nujol, cm^ꢀ1): 1614s,

2.1.1.15. Synthesis of AgClO₄:dppp:dpa (2:1:2) (20). Com-

pound 20 (0.287 g, yield: 98%) has been prepared follow-

ing a procedure similar to that reported for 1 by using

AgClO₄(0.104 g, 0.5 mmol), dppp (0.099 g, 0.25 mmol),

and dpa (0.085 g, 0.5 mmol); m.p. 115–116 ꢁC. Anal. Calc.

for C₄₈H₄₆Ag₂Cl₂N₆O₈P₂: C, 48.27; H, 3.79; N, 7.19.

. . .

1591s, 1555m, 1503s, m(C C, C N), 1094sbr, 622s

•

Found: C, 48.29; H, 3.66; N, 7.10%. IR (nujol, cm^ꢀ1):

m(ClO₄), 514s, 486s, 461w, 398w. ¹H NMR (CD₃CN,

293 K): d, 1.88 (sbr, 4H, CH_2dppb), 2.58 (sbr, 4H, CH_2dppb),

7.40–7.55 (m, 20H, C₆H_5dppb+ 8H, CH_bq), 7.87 (m, 8H,

CH_bq), 8.40 (d, 4H, CH_bq), 8.53 (d, 4H, CH_bq). ¹³C

NMR (CD₃CN, 293 K): d, 26.96 (d, CH_2dppb), 28.00 (q,

CH_2dppb), 121.04 (s, C_bq), 129.36, 129.55, 130.05, 130.78,

132.14 (s, C_bq), 130.35 (d, C_dppb), 132.54 (s, C_dppb),

133.85 (d, C_dppb) 140.98 (s, C_bq), 147.02 (s, C_bq), 153.59

(s, C_bq). ³¹P NMR (CD₃CN, 293 K): d, 5.9 (d, ¹J(³¹P–

Ag): 683.3 Hz). Compound 23 was re-crystallized from

MeCN/EtOH as 23 Æ 2MeCN Æ EtOH. ESI MS (+): 404

(20) [Ag(bq)(MeCN)]⁺, 532 (50) [Ag(dppb)]⁺, 576 (20)

. . .

3339m m(N–H), 1640sbr, 1573sbr, 1530sbr m(C C,

•

. . .

C

N), 1080sbr, 639s, 620s m(ClO₄), 514m, 484m, 452w,

•

407w, 332m. ¹H NMR (CD₃CN, 293 K): d, 1.70 (sbr,

2H, CH_2dppp), 2.57 (sbr, 4H, CH_2dppp), 6.85 (t, 4H,

CH_dpa), 7.28 (d, 4H, CH_dpa), 7.50 (m, 20H, C₆H_5dppp),

7.73 (t, 4H, CH_dpa), 8.08 (d, 4H, CH_dpa). ¹³C NMR

(CD₃CN, 293 K): d, 23.77, 28.58 (m, CH_2dppp), 114.86,

118.10 (s, C_dpa), 130.35 (d, C_dppp), 132.14 (s, C_dppp),

133.60 (d, C_dppp) 140.21 (s, C_dpa), 149.53 (s, C_dpa),

155.60 (s, C_dpa). ³¹P NMR (CD₃CN, 293 K): d, 7.2 (d,

¹J(³¹P–Ag): 655.9 Hz).

[Ag₂(dppb)(bq)₂]²⁺

[Ag(dppb)(bq)]⁺.

,

620 (100) [Ag(bq)₂]⁺, 791 (45)

2.1.1.16. Synthesis of AgClO₄:dppp:tpy (2:1:2) (21). Com-

pound 21 (0.316 g, yield: 98%) has been prepared follow-

ing a procedure similar to that reported for 1 by using

AgClO₄(0.104 g, 0.5 mmol), dppp (0.099 g, 0.25 mmol),

and tpy (0.116 g, 0.5 mmol); m.p. 217–218 ꢁC. Anal. Calc.

for C₅₇H₄₈Ag₂Cl₂N₆O₈P₂: C, 52.92; H, 3.74; N, 6.50.

Found: C, 52.89; H, 3.66; N, 6.48%. IR (nujol, cm^ꢀ1):

2.1.1.19. Synthesis of AgClO₄:dppb:tpy (2:1:2) (24). Com-

pound 24 (0.227 g, yield: 69%) has been prepared following

a procedure similar to that reported for 1 by using AgClO₄

(0.104 g, 0.5 mmol), dppb (0.109 g, 0.25 mmol), and tpy

(0.116 g, 0.5 mmol); m.p. 104–105 ꢁC. Anal. Calc. for

C₅₈H₅₀Ag₂Cl₂N₆O₈P₂: C, 53.27; H, 3.85; N, 6.43. Found:

C, 53.30; H, 3.70; N, 6.40%. IR (nujol, cm^ꢀ1): 1570sbr,

. . .

1586sbr, 1514w m(C C, C N), 1100sh, 1071sbr, 621s

•

m(ClO₄), 514w, 474w, 322w, 292w. ¹H NMR (CD₃CN,

293 K): d, 1.43 (sbr, 2H, CH_2dppp), 2.16 (sbr, 4H,

CH_2dppp), 7.35 (m, 20H, C₆H_5dppp), 7.42 (m, 4H, CH_tpy),

7.88 (m, 4H, CH_tpy), 8.17 (m, 8H, CH_tpy), 8.28 (m, 4H,

. . .

1537sbr, 1503sbr m(C C, C N), 1083sbr, 621s m(ClO₄),

•

1

515w, 482w, 406w, 306w. H NMR (CD₃CN, 293 K): d,

1.43 (sbr, 4H, CH_2dppb), 2.18 (sbr, 4H, CH_2dppb), 7.35 (m,

20H, C₆H_5dppb), 7.91 (m, 4H, CH_tpy), 8.17–8.27 (m, 14H,

CH_tpy), 8.37 (m, 4H, CH_tpy). ¹³C NMR (CD₃CN, 293 K):

d, 26.70 (m, CH_2dppb), 27.49 (m, CH_2dppb), 123.80,

124.12, 126.32 (s, C_tpy), 130.12 (m, C_dppb), 131.67 (s,

C_dppb), 133.60 (m, C_dppb) 139.64, 141.20 (s, C_tpy), 151.43

(s, C_tpy), 153.67, 154.11 (s, C_tpy). ³¹P NMR (CD₃CN,

293 K): d, 4.1 (d, ¹J(³¹P–Ag): 548.6 Hz). Compound 24

has been re-crystallized from ethanol as 24 Æ EtOH Æ ESI

MS (+): 340 (70) [Ag(tpy)]⁺, 533 (100) [Ag(dppb)]⁺, 766

CH_tpy). ³¹P NMR (CD₃CN, 293 K): d, 3.5 (d br, J(³¹P–

1

Ag): 506.9 Hz).

2.1.1.17. Synthesis of AgClO₄:dppb:bpy (2:1:2) (22). Com-

pound 22 (0.565 g, yield: 98%) has been synthesised fol-

lowing a procedure similar to that reported for 1 by

using AgClO₄(0.207 g, 1 mmol), dppb (0.197 g,

0.5 mmol), and bpy (0.156 g, 1 mmol); m.p. 195–196 ꢁC.

Anal. Calc. for C₄₈H₄₄Ag₂Cl₂N₄O₈P₂: C, 49.98; H, 3.84;

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1393

(20) [Ag₂(dppb)(tpy)]⁺, 1102 (45) [Ag₂(dppb)₂(Cl)]⁺, 1168

(45) [Ag₂(dppb)₂(ClO₄)]⁺.

C, 59.13; H, 3.69; N, 6.78%. IR (nujol, cm^ꢀ1): 1615m,

. . . . . .

1590s, 1556w, 1534w, 1503s m(C C, C N), 1434m,

•

1

1375s, 824s (NO₃), 521m, 507w, 477m, 269m. H NMR

(CD₃CN, 293 K): d, 4.30 (t, 2H, CH_2dppm), 7.34 (m, 4H,

CH_bq), 7.46 (m, 12H, C₆H_5dppm), 7.55 (m, 4H, CH_bq),

7.82 (m, 8H, C₆H_5dppm+ 8H, CH_bq), 8.22 (m, 4H, CH_bq),

8.37 (m, 4H, CH_bq). ¹³C NMR (CD₃CN, 293 K): d, 26.0

(br, CH_2dppm), 120.68 (s, C_bq), 129.25, 129.49, 129.74,

129.96, 130.50 (m, C_dppm), 130.6 (s, C_bq), 132.0 (br,

2.1.2. AgX (=NO₃):dpex:L (2:1:2) (ÆnS) complexes

2.1.2.1. Synthesis of AgNO₃:dppm:bpy (2:1:2) (25). Com-

pound 25 (0.484 g, yield: 93%) has been prepared following

a procedure similar to that reported for 2 by using AgNO₃

(0.169 g, 1.0 mmol), dppm (0.192 g, 0.5 mmol) and bpy

(0.156 g, 1.0 mmol); m.p. 181–182 ꢁC. Anal. Calc. for

C₄₅H₃₈Ag₂N₆O₆P₂: C, 52.15; H, 3.70; N, 8.11. Found: C,

52.08; H, 3.61; N, 8.13%. IR (nujol, cm^ꢀ1): 1587s, 1555s,

C_dppm), 132.5, 132.8 (s, C_dppm+ C_bq) 134.12 (m, C_dppm

)

141.13 (s, C_bq), 146.24 (s, C_bq), 152.8 (br, C_bq). ³¹P

NMR (CD₃CN, 293 K): d, 11.3 (dbr, ¹J(³¹P–Ag):

616.6 Hz). Compound 27 was re-crystallized from MeCN

in ambience as 27 Æ 2MeCN Æ ½H₂O. ESI MS (+): 621

(100) [Ag(bq)₂]⁺, 1018 (10) [Ag₂(dppm)₂Cl]⁺, 1046 (5)

[Ag₂(dppm)₂NO₃]⁺.

. . .

1537s, 1504s, 1503m, 1464m, m(C C, C N), 1446m,

•

1375s, 828s (NO₃), 519w, 481w, 447w, 211s. ¹H NMR

(CD₃CN, 293 K): d, 4.01 (t, 2H, CH_2dppm), 7.43 (m, 12H,

C₆H_5dppm+ 4H, CH_bpy), 7.71 (m, 8H, C₆H_5dppm), 7.96

(m, 4H, CH_bpy), 8.08 (m, 4H, CH_bpy), 8.47 (m, 4H, CH_bpy).

¹³C NMR (CD₃CN, 293 K): d, 26.06 (m, CH_2dppm), 123.51

(m, C_dppm), 126.96 (s, C_bpy), 130.44 (m, C_dppm), 131.9 (m,

C_dppm), 132.65 (s, C_bpy), 134.18 (m, C_dppm), 140.7 (t, C_bpy),

151.9 (s, C_bpy), 152.06 (s, C_bpy), 152.26 (s, C_bpy). ³¹P NMR

2.1.2.4. Synthesis of AgNO₃:dpam:dmp (2:1:2) (28). Com-

plex 28 ðꢁ1½MeCN ꢁ H₂OÞ was obtained by crystallization

of millimolar stoichiometries of the silver nitrate with

dpam and dmp from acetonitrile solution by standing

1

(CD₃CN, 293 K): d, 12.0 (d, J(³¹P–Ag): 668.6 Hz). Com-

pound 25 was re-crystallized from MeCN/EtOH/CHCl₃

in ambience as 25 Æ H₂O. ESI MS (+): 189 (20)

[Ag(MeCN)₂]⁺, 263 (25) [Ag(bpy)]⁺, 304 (70) [Ag(bpy)-

and evaporation in ambience. Anal. Calc. for C₅₆H_54.5-

Ag₂As₂N_7.5O₈: C, 50.72; H, 4.19; N, 7.92. Found: C,

51.12; H, 4.18; N, 7.89%; m.p. >137 ꢁC (dec).

(MeCN)]⁺,

419

(100)

[Ag(bpy)₂]⁺,

647

(10)

[Ag(dppm)(bpy)]⁺, 1018 (25) [Ag₂(dppm)₂Cl]⁺, 1046 (25)

[Ag₂(dppm)₂NO₃]⁺.

2.1.2.5. Synthesis of AgNO₃:dppp:dmp (2:1:2) (29). Com-

pound 29 (0.393 g, yield: 67%) has been prepared following

a procedure similar to that reported for 2 by using AgNO₃

(0.169 g, 1 mmol), dppp (0.206 g, 0.5 mmol) and dmp

(0.208 g, 1 mmol); m.p. 266–267 ꢁC. Anal. Calc. for

C₅₅H₅₀Ag₂N₆O₆P₂: C, 56.62; H, 4.15; N, 7.20. Found: C,

56.50; H, 4.09; N, 7.16%. IR (nujol, cm^ꢀ1): 1619s, 1594s,

2.1.2.2. Synthesis of AgNO₃:dppm:dmp (2:1:2) (26). Com-

pound 26 (0.295 g, yield: 52%) has been prepared following

a procedure similar to that reported for 2 by using AgNO₃

(0.169 g, 1 mmol), dppm (0.192 g, 0.5 mmol) and dmp

(0.208 g, 1 mmol); m.p. 258–259 ꢁC. Anal. Calc. for

C₅₃H₄₆Ag₂N₆O₆P₂: C, 55.81; H, 4.06; N, 7.37. Found: C,

55.68; H, 4.04; N, 7.29%. IR (nujol, cm^ꢀ1): 1621s, 1590s,

. . .

1557s, 1503m m(C C, C N), 1435m, 1420sh, 1376s,

•

1300sh, 1030m, 855s, 827m, 737m, 727m (NO₃), 549s,

522s, 480s, 461w, 442w, 433w, 401w, 318w. ¹H NMR

(CD₃CN, 293 K): d, 2.62 (s, 12H, CH_3dmp), 2.78 (br, 6H,

CH_2dppp), 7.39–7.46 (m, 4H, CH_dmp+ 12H, C₆H_5dppm),

7.59 (mbr, 8H, C₆H_5dppp), 7.90 (s, 4H, CH_dmp), 8.37 (d,

4H, CH_dmp). ¹³C NMR (CD₃CN, 293 K): d, 24.70 (m,

CH_2dppp), 29.31 (s, CH_3dmp), 126.02 (s, C_dmp), 127.12 (s,

C_dmp), 128.44 (s, C_dmp), 130.20 (m, C_dppp), 132.07 (s, C_dmp),

132.74 (s, C_dppp), 133.60 (m, C_dppp), 139.87 (s, C_dmp),

159.99 (s, C_dmp). ³¹P NMR (CD₃CN, 293 K): d, 6.7 (d,

¹J(³¹P–Ag): 658.5 Hz). Compound 29 was re-crystallized

from MeCN as 29 Æ ½MeCN.

. . .

1573m, 1556s, 1503m m(C C, C N), 1410m, 1370s,

•

1250sh, 1095m, 860s, 838m, 827m, 741m, 728m, (NO₃),

549m, 523m, 510m, 475m, 447w, 431w, 355w. H NMR

1

(CD₃CN, 293 K): d, 2.69 (s, 12H, CH_3dmp), 4.04 (t, 2H,

CH_2dppm), 7.28–7.48 (m, 4H, CH_dmp+ 12H, C₆H_5dppm),

7.72–7.83 (m, 4H, CH_dmp+ 8H, C₆H_5dppm), 8.15 (mbr,

4H, CH_dmp). ¹³C NMR (CD₃CN, 293 K): d, 24.79 (t,

CH_2dppm), 29.28 (s, CH_3dmp), 125.87 (s, C_dmp), 127.07 (s,

C_dmp), 128.11 (s, C_dmp), 130.31 (m, C_dppm), 132.13

(s, C_dmp), 132.57 (s, C_dppm), 133.92 (m, C_dppm), 140.16 (s,

C_dmp), 159.71 (s, C_dmp). ³¹P NMR (CD₃CN, 293 K): d,

8.2 (d, ¹J(³¹P–Ag): 643.8 Hz). Compound 26 was re-crystal-

lized from MeCN in ambience as 26 Æ 3/2MeCN Æ ½H₂O.

ESI MS (+): 356 (10) [Ag(dmp)(MeCN)]⁺, 523 (100)

[Ag(dmp)₂]⁺, 701 (20) [Ag(dppm)(dmp)]⁺.

2.1.2.6. Synthesis of AgNO₃:dppb:tpy (2:1:2) (30). Com-

pound 30 (0.209 g, yield: 67%) has been obtained following

a procedure similar to that reported for 1 by using AgNO₃

(0.085 g, 0.5 mmol), dppb (0.109 g, 0.25 mmol), and tpy

(0.116 g, 0.5 mmol); m.p. 229–230 ꢁC. Anal. Calc. for

C₅₈H₅₀Ag₂N₈O₆P₂: C, 56.51; H, 4.09; N, 9.09. Found: C,

56.44; H, 4.06; N, 9.00%. IR (nujol, cm^ꢀ1): 1587s, 1576s,

2.1.2.3. Synthesis of AgNO₃:dppm:bq (2:1:2) (27). Com-

pound 27 (0.187 g, 60%) has been prepared following a

procedure similar to that reported for 1 by using AgNO₃

(0.084 g, 0.5 mmol), dppm (0.096 g, 0.25 mmol), and bq

(0.128 g, 0.5 mmol); m.p. 238–239 ꢁC. Anal. Calc. for

C₆₁H₄₆Ag₂N₆O₆P₂: C, 59.24; H, 3.75; N, 6.80. Found:

. . .

1567s m(C C, C N), 1450s, 1420s, 1380br, 1290sh,

•

1096s, 1000m, 848m, 824m, 737s, 719s (NO₃) 516s, 479s,

457w, 423s, 304w. ¹H NMR (CD₃CN, 293 K): d, 1.48

(sbr, 4H, CH_2dppb), 2.72 (sbr, 4H, CH_2dppb), 7.38 (m,

1394

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

20H, C₆H_5dppb+ 4H, CH_tpy), 7.93 (m, 4H, CH_tpy), 8.15 (t,

2H, CH_tpy), 8.30 (m, 8H, CH_tpy), 8.52 (d, 4H, CH_tpy). ¹³C

NMR (CD₃CN, 293 K): d, 23.6 (m, CH_2dppb), 28.3 (m,

CH_2dppb), 123.87, 124.22, 126.34 (s, C_tpy), 130.30 (d, C_dppb),

131.89 (s, C_dppb), 133.50 (d, C_dppb) 139.72, 141.32 (s, C_tpy),

151.36 (s, C_tpy), 153.67, 154.14 (s, C_tpy). ³¹P NMR

(CD₃CN, 293 K): d, 1.75 br. ³¹P NMR (CD₃CN,

morphous with its dpam analogue (see 7 below) and was

reﬁned in the same cell and coordinate setting.

2.2.1.1.3. AgClO₄:dppm:dmp (2:1:2) Æ MeCN (3 Æ MeCN).

C₅₅H₄₉Ag₂Cl₂N₅O₈P₂, M = 1256.7. Triclinic, space group

1

˚

P1 (C_i, No. 2), a = 13.158(1) A, b = 13.814(1) A, c =

˚

14.447(1) A, a = 98.506(2)ꢁ, b = 100.208(2)ꢁ, c = 94.028(2)ꢁ,

V = 2543 A . D_calc(Z = 2) = 1.64₁g cm^ꢀ3

.

l_Mo= 1.00

3

˚

223 K): d, 2.24 (dd, J(³¹P–¹⁰⁹Ag): 689 Hz; J(³¹P–¹⁰⁷Ag):

mm^ꢀ1; specimen: 0.26 · 0.18 · 0.13 mm; ‘T_min/max’ = 0.75.

2h_max= 70ꢁ; N_t= 50806, N = 22084 (R_int= 0.051), N_o=

13969; R = 0.050, R_w= 0.057.

1

599 Hz).

Variata. This complex is isomorphous with its dpam

analogue (see below, 8) and was reﬁned in the same cell

and coordinate setting.

2.2. Structure determinations

Full spheres of ‘low’-temperature CCD area-detector

diﬀractometer data were measured (Bruker AXS instru-

ment, x-scans, monochromatic Mo Ka radiation,

2.2.1.1.4. AgClO₄:dppm:dpa (2:1:2) Æ 1/3H₂O (5 Æ 1/3

H₂O). C₄₅H_40.67Ag₂Cl₂N₆O_8.33P₂, M = 1147.5. Ortho-

15

rhombic, space group Pbca (D , No. 61), a =

2h

˚

k = 0.7107₃A; T ca. 153 K), yielding N_t(otal)reﬂections,

˚

22.886(3) A, b = 41.453(4) A, c = 14.168(2) A, V = 13441

these merging to N unique after ‘empirical’/multiscan

absorption correction (proprietary software), N_owith

F > 4r(F) being considered ‘observed’ and used in the large

block/full matrix least square reﬁnements, reﬁning aniso-

tropic displacement parameters forms for the non-hydrogen

A . D_calc(Z = 12) = 1.70₁g cm^ꢀ3. l_Mo= 1.13 mm^ꢀ1; spec-

3

˚

imen: 0.26 · 0.20 · 0.10 mm; ‘T_min/max’ = 0.80. 2h_max

=

50ꢁ; N_t= 124713, N = 12169 (R_int= 0.10), N_o= 8557;

R = 0.074, R_w= 0.12.

2.2.1.1.5. AgClO₄:dppm:tpy (2:1:2) (6). C₅₅H₄₄Ag₂Cl_2-

N₆O₈P₂, M = 1265.6. Monoclinic, space group P2₁/c

atoms, (x,y,z,U_{iso H}being included, constrained at esti-

)

mates where possible. Conventional residuals R, R_won |F|

at convergence are cited (reﬂection weights: (r²(F) +

0.0004F²)^ꢀ1). Neutral atom complex scattering factors were

employed within the ^XTAL3.7 program system [13]. Perti-

nent results are given below and in the tables and ﬁgures,

the latter showing 50% probability displacement amplitudes

for the non-hydrogen atoms, hydrogen atoms having arbi-

5

˚

(C_2h, No. 14), a = 14.338(2) A, b = 13.137(2) A, c =

3

˚

27.856(3) A, b = 96.657(2)ꢁ, V = 5212 A . D_calc(Z = 4) =

1.61₃g cm^ꢀ3. l_Mo= 0.98 mm^ꢀ1; specimen: 0.28 · 0.26 ·

0.22 mm; ‘T_min/max’ = 0.90. 2h_max= 58ꢁ; N_t= 49784, N =

12904 (R_int= 0.025), N_o= 9432; R = 0.043, R_w= 0.058.

Variata. This complex is isomorphous with its dpam

analogue (see below, 9) and was reﬁned in the same cell

and coordinate setting. T was 298 K for this study.

˚

trary radii of 0.1 A; carbon atoms, if labelled, may be

denoted by number only, for economy of space. Individual

divergences/variations in procedure are cited as ‘variata’.

2.2.1.1.6.

AgClO₄:dpam:phen

(2:1:2) Æ ¼MeCN

(7 Æ ¼MeCN). C_49.5H_38.75Ag₂As₂Cl₂N_4.25O₈, M = 1257.7.

˚

Monoclinic, space group P2₁/n, a = 13.468(2) A, b =

˚

2.2.1. Crystal/reﬁnement data

2.2.1.1. AgX (=ClO₄):dpex:L (2:1:2) (ÆnS) complexes.

2.2.1.1.1. AgClO₄:dppm:bpy (2:1:2) (1). C₄₅H₃₈Ag₂Cl₂-

12.612(2) A,

c = 28.014(5) A,

b = 91.987(3)ꢁ,

V =

4756 A . D_calc(Z = 4) = 1.75₆g cm^ꢀ3. l_Mo= 2.38 mm^ꢀ1

;

3

˚

specimen:

0.11 · 0.10 · 0.03 mm;

‘T_min/max’ = 0.81.

N₄O₈P₂, M = 1111.4. Orthorhombic, space group Pna2₁

2h_max= 50ꢁ; N_t= 38272, N = 8331 (R_int= 0.080), N_o=

5816; R = 0.061, R_w= 0.080.

9

˚

(C_2v, No. 33), a = 25.472(4) A, b = 13.630(4) A, c =

3

25.248(2) A, V = 8770 A . D_calc(Z = 8) = 1.68₃g cm^ꢀ3

_Mo= 1.15 mm^ꢀ1

specimen: 0.42 · 0.37 · 0.36 mm;

‘T_min/max’ = 0.72. 2h_max= 58ꢁ; N_t= 80239, N = 11181

(R_int0.052), N_o= 9317; R = 0.045, R_w= 0.062;

.

Variata. This complex is isomorphous with its dppm

analogue (see above, 2), albeit only obtained as much smal-

ler crystals. The acetonitrile site occupancy was constrained

at 0.25 after trial reﬁnement.

˚

l

;

=

x_abs= 0.14(3).

2.2.1.1.7. AgClO₄:dpam:dmp (2:1:2) Æ MeCN (8 Æ MeCN).

C₅₅H₄₉Ag₂As₂Cl₂N₅O₈, M = 1344.6. Triclinic, space group

2.2.1.1.2. AgClO₄:dppm:phen (2:1:2) Æ MeCN (2 Æ

MeCN). C₅₁H₄₁Ag₂Cl₂N₅O₈P₂, M = 1200.5. Monoclinic,

space group P2₁/n (C⁵_2h, No. 14 (variant)), a =

˚

P1, a = 13.198(1) A, b = 14.256(1) A, c = 14.440(1) A, a =

3

˚

97.050(2)ꢁ, b = 99.389(2)ꢁ, c = 95.210(2)ꢁ, V = 2643 A .

13.689(1) A, b = 12.563(1) A, c = 27.945(3) A, b =

D_calc(Z = 2) = 1.69₈g cm^ꢀ3. l_Mo= 2.1 mm^ꢀ1; specimen:

0.17 · 0.14 · 0.09 mm; ‘T_min/max’ = 0.82. 2h_max= 58ꢁ;

N_t= 32321, N = 14138 (R_int= 0.026), N_o= 9556; R =

0.041, R_w= 0.054.

˚

92.057(2)ꢁ, V = 4803 A . D_calc(Z = 4) = 1.66₀g cm^ꢀ3

.

3

˚

l

_Mo= 1.05 mm^ꢀ1

;

specimen:

0.35 · 0.29 · 0.18 mm;

‘T_min/max’ = 0.87. 2h_max= 65ꢁ; N_t= 85367, N = 17362

(R_int= 0.044), N_o= 13219; R = 0.043, R_w= 0.060.

Variata. The compound is isomorphous with its dppm

analogue (see above, 3). T was 298 K for this study.

2.2.1.1.8. AgClO₄:dpam:tpy (2:1:2) (9). C₅₅H₄₄Ag₂-

As₂Cl₂N₆O₈, M = 1353.5. Monoclinic, space group P2₁/c,

Variata. Phenyl ring 12· was modelled as disordered

over two sets of sites, site occupancies set at 0.5 after trial

reﬁnement, with rigid body constraints. Acetonitrile atom

assignments, here and below, were conﬁrmed by reﬁnement

behaviour and location of the hydrogen atoms. It is iso-

˚

a = 14.058(1) A, b = 13.249(1) A, c = 27.604(2) A, b =

98.058(2)ꢁ, V = 5091 A . D_calc(Z = 4) = 1.76₆g cm^ꢀ3

.

3

˚

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1395

l

_Mo= 2.2 mm^ꢀ1

;

specimen:

0.25 · 0.22 · 0.16 mm;

2.2.1.1.14. AgClO₄:dpae:bpy (2:1:2) (15). C₄₆H₄₀Ag₂As₂-

Cl₂N₄O₈, M = 1213.3. Triclinic, space group P1, a =

‘T_min/max’ = 0.81. 2h_max= 70ꢁ; N_t= 100806, N = 22433

(R_int= 0.051), N_o= 15229; R = 0.041, R_w= 0.050.

Variata. The compound is isomorphous with its dppm

analogue (see above, 6).

2.2.1.1.9. AgClO₄:dppe:bpy (2:1:2) (10). C₄₆H₄₀Ag₂-

Cl₂N₄O₈P₂, M = 1125.4. Triclinic, space group P1,

˚

8.6503(5) A,

b = 11.2273(7) A,

c = 12.4476(8) A,

3

˚

a = 70.019(1)ꢁ, b = 83.360(1)ꢁ, c = 84.229(1)ꢁ, V = 1126 A .

D_calc(Z = 1) = 1.78₉cm^ꢀ3. l_Mo= 2.50 mm^ꢀ1; specimen:

0.24 · 0.14 · 0.12 mm; ‘T_min/max’ = 0.76. 2h_max= 75ꢁ; N_t=

23397, N = 11604 (R_int= 0.026), N_o= 8084; R = 0.034,

R_w= 0.037.

˚

a = 9.5497(7) A, b = 10.5432(8) A, c = 12.816(1) A, a =

3

˚

68.672(2)ꢁ, b = 70.046(2)ꢁ, c = 73.058(2)ꢁ, V = 1109 A .

2.2.1.1.15. AgClO₄:dpae:dmp (2:1:2) Æ H₂O (16 Æ H₂O).

C₅₄H₅₀Ag₂As₂Cl₂N₄O₉, M = 1335.6. Triclinic, space group

D_calc(Z = 1) = 1.68₅g cm^ꢀ3. l_Mo= 1.1 mm^ꢀ1; specimen:

0.25 · 0.17 · 0.12 mm; ‘T_min/max’ = 0.78. 2h_max= 75ꢁ;

N_t= 21288, N = 10819 (R_int= 0.016), N_o= 9392; R =

0.027, R_w= 0.034.

˚

P1, a = 13.734(1) A, b = 14.487(1) A, c = 16.455(1) A,

a = 100.305(2)ꢁ, b = 105.108(2)ꢁ, c = 114.202(2)ꢁ, V =

2727 A . D_calc(Z = 2) = 1.62₆g cm^ꢀ3. l_Mo= 2.08 mm^ꢀ1

;

3

˚

2.2.1.1.10. AgClO₄:dppe:dmp:MeCN (2:1:2:2) Æ 2MeCN

(11 Æ 2MeCN). C₆₂H₆₀Ag₂Cl₂N₈O₈P₂, M = 1393.8. Tri-

specimen:

0.11 · 0.08 · 0.07 mm;

‘T_min/max’ = 0.82.

2h_max= 60ꢁ; N_t= 53870, N = 15817 (R_int= 0.035), N_o=

11533; R = 0.054, R_w= 0.080.

˚

clinic, space group P1, a = 11.0425(5) A, b = 12.0947(6)

˚

A, c = 12.7527(6) A, a = 94.988(1)ꢁ, b = 100.749(1)ꢁ, c =

Variata. Perchlorates 1 and 3 were modelled as disor-

dered over pairs of sites, occupancies set at 0.5 after trial

reﬁnement; the oxygen atoms of perchlorate 2 were mod-

elled as disordered about Cl(2), set at an inversion centre.

2.2.1.1.16. AgClO₄:dpae:bq (2:1:2) Æ 2MeCN (17). C₆₆-

H₅₄Ag₂As₂Cl₂N₆O₈, M = 1495.7. Triclinic, space group

111.323(1)ꢁ, V = 1536 A . D_calc(Z = 1) = 1.50₆g cm^ꢀ3

.

3

˚

l

_Mo= 0.84 mm^ꢀ1

;

specimen:

0.30 · 0.20 · 0.15 mm;

‘T_min/max’ = 0.86. 2h_max= 75ꢁ; N_t= 28987, N = 14863

(R_int= 0.021), N_o= 12181; R = 0.032, R_w= 0.038.

2.2.1.1.11. AgClO₄:dppe:bq (2:1:2) Æ 2MeCN (12 Æ 2MeCN).

C₆₆H₅₄Ag₂Cl₂N₆O₈P₂, M = 1407.8. Triclinic, space group

˚

P1, a = 10.8068(7) A, b = 10.8429(7) A, c = 14.3374(9) A,

a = 105.823(1)ꢁ, b = 102.818(1)ꢁ, c = 104.812(1)ꢁ, V =

˚

P1, a = 10.7328(8) A, b = 10.8086(8) A, c = 14.470(1) A,

a = 107.208(2)ꢁ, b = 103.093(2)ꢁ, c = 104.661(2)ꢁ, V =

3

1484 A . D_calc(Z = 1) = 1.67₃g cm^ꢀ3. l_Mo= 1.92 mm^ꢀ1

;

˚

1466 A . D_calc(Z = 1) = 1.59₄g cm^ꢀ3. l_Mo= 0.88 mm^ꢀ1

;

specimen:

0.38 · 0.32 · 0.23 mm;

‘T_min/max’ = 0.72.

3

˚

specimen:

0.25 · 0.20 · 0.10 mm;

‘T_min/max’ = 0.80.

2h_max= 75ꢁ; N_t= 30166, N = 15134 (R_int= 0.023), N_o=

11502; R = 0.032, R_w= 0.038.

Variata. The compound is isomorphous with its dppe

(see above, 12) and dpdae (see next, 18) analogues.

2.2.1.1.17. AgClO₄:dpdae:bq (2:1:2) Æ 2MeCN (18 Æ

2MeCN). C₆₆H₅₄Ag₂AsCl₂N₆O₈P, M = 1451.7. Triclinic,

2h_max= 65ꢁ; N_t= 22433, N = 10538 (R_int= 0.033), N_o=

8017; R = 0.044, R_w= 0.048.

Variata. The compound is isomorphous with its P/As

and As₂counterparts (see below, 17, 18) and was reﬁned

in the same cell and coordinate setting.

˚

2.2.1.1.12. AgClO₄:dppe:dpa:MeCN:H₂O (2:1:2:2:1)

(13 Æ 2MeCN Æ H₂O). C₅₀H₅₀Ag₂Cl₂N₈O₉P₂, M = 1255.6.

space group P1, a = 10.7696(6) A, b = 10.8373(7) A,

c = 14.4036(9) A,

˚

a = 106.731(1)ꢁ,

b = 102.924(1)ꢁ,

3

˚

Triclinic, space group P1, a = 10.824(1) A, b = 11.220(1)

c = 104.717(1)ꢁ, V = 1475 A . D_calc(Z = 1) = 1.63₄

g cm^ꢀ3. l_Mo= 1.40 mm^ꢀ1; specimen: 0.38 · 0.24 · 0.12

mm; ‘T_min/max’ = 0.74. 2h_max= 75ꢁ; N_t= 30032, N =

15059 (R_int= 0.022), N_o= 11623; R = 0.030, R_w= 0.037.

Variata. This compound is isomorphous with the

analogue preceding (18); P, As were modelled as

composites.

˚

A, c = 12.175(1) A, a = 107.778(2)ꢁ, b = 97.072(2)ꢁ,

3

˚

c = 105.826(2)ꢁ, V = 1320 A . D_calc(Z = 1) = 1.58₀

g cm^ꢀ3

.

l

_Mo= 0.97 mm^ꢀ1

;

specimen:

0.22 · 0.17 ·

0.12 mm; ‘T_min/max’ = 0.81. 2h_max= 75ꢁ; N_t= 25315,

N = 12878 (R_int= 0.027), N_o= 9620; R = 0.046, R_w=

0.053.

Variata. The perchlorate was modelled as rotationally

disordered over two sets of sites about one of the Cl–O

bonds, site occupancies of the relevant atoms set at 0.5

after trial reﬁnement. ‘Water molecule oxygen’ hydrogen

atoms were not located.

2.2.1.1.18. AgClO₄:dppp:bq (2:1:2) Æ 2MeCN (19 Æ

2MeCN). C₆₇H₅₆Ag₂Cl₂N₆O₈P₂, M = 1421.8. Monoclinic,

˚

space group P2₁/n, a = 13.8061(8) A, b = 30.128(2) A,

3

˚

c = 14.5565(9) A, b = 97.959(1)ꢁ, V = 5997 A . D_calc

(Z = 4) = 1.57₅g cm^ꢀ3_Mo= 0.86 mm^ꢀ1

.

l

;

specimen:

2.2.1.1.13. AgClO₄:dppe:tpy (2:1:2) Æ 2MeCN (14 Æ

2MeCN). C₆₀H₅₂Ag₂Cl₂N₈O₈P₂, M = 1361.7. Triclinic,

0.56 · 0.24 · 0.13 mm; ‘T_min/max’ = 0.69. 2h_max= 67ꢁ;

N_t= 85786, N = 22008 (R_int= 0.037), N_o= 17059; R =

0.036, R_w= 0.042.

2.2.1.1.19. AgClO₄:dppp:dpa (2:1:2) (20). C₄₈H₄₆Ag₂-

Cl₂N₆O₈P₂, M = 1183.5. Triclinic, space group P1, a =

˚

space group P1, a = 10.5276(5) A, b = 11.1687(5) A,

˚

c = 13.1763(7) A,

a = 73.337(1)ꢁ,

b = 81.449(1)ꢁ,

c = 75.880(1)ꢁ, V = 1434 A . D_calc(Z = 1) = 1.57₆cm^ꢀ3

.

3

˚

_Mo= 0.90 mm^ꢀ1

;

specimen:

0.17 · 0.14 · 0.10 mm;

10.424(1) A, b = 11.628(2) A, c = 12.236(1) A, a =

˚

l

3

˚

‘T_min/max’ = 0.92. 2h_max= 75ꢁ; N_t= 28793, N = 13461

(R_int= 0.017), N_o= 10583; R = 0.033, R_w= 0.039.

Variata. The CN component of the acetonitrile was

modelled as disordered over two sets of sites, occupancies

reﬁning to 0.726(5) and complement.

64.999(2)ꢁ, b = 71.941(2)ꢁ, c = 86.992(2)ꢁ, V = 1273 A .

D_calc(Z = 1) = 1.54₄g cm^ꢀ3. l_Mo= 0.99 mm^ꢀ1; specimen:

0.47 · 0.42 · 0.32 mm; ‘T_min/max’ = 0.72. 2h_max= 58ꢁ;

N_t= 26126, N = 6765 (R_int= 0.028), N_o= 5248; R =

0.044, R_w= 0.051.

1396

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

Variata. The material underwent a phase transforma-

tion at low temperature, and data were acquired at ca.

298 K.

2.2.1.1.20. AgClO₄:dppp:tpy (2:1:2) (21). C₅₇H₄₈Ag₂-

Cl₂N₆O₈P₂, M = 1293.6. Monoclinic, space group P2₁/c,

Variata. Phenyl ring 21 and anion and solvent compo-

nents were modelled as disordered over pairs of sites, occu-

pancies set at 0.5 after trial reﬁnement. Water molecule

hydrogen atoms were not located.

2.2.1.2.2. AgNO₃:dppm:dmp (2:1:2) Æ MeCN Æ ½H₂O

(26 Æ MeCN Æ ½H₂O). C₅₅H₅₀Ag₂N₇O_6.5P₂, M = 1190.7.

˚

a = 10.8782(6) A, b = 22.379(1) A, c = 22.258(1) A, b =

102.804(1)ꢁ, V = 5284 A . D_calc= 1.62₆g cm^ꢀ3. l_Mo= 0.97

Triclinic, space group P1, a = 13.453(1) A, b = 14.047(1)

3

˚

mm^ꢀ1; specimen: 0.60 · 0.18 · 0.14 mm; ‘T_min/max’ = 0.84.

2h_max= 75ꢁ; N_t= 108356, N = 27658 (R_int= 0.048),

N_o= 16802; R = 0.039, R_w= 0.040.

A, c = 14.553(2) A, a = 67.164(3)ꢁ, b = 86.515(3)ꢁ, c =

˚

79.838(3)ꢁ, V = 2495 A . D_calc(Z = 2) = 1.58₅g cm^ꢀ3

l

.

3

˚

_Mo= 0.91 mm^ꢀ1

;

specimen:

0.35 · 0.20 · 0.03 mm;

2.2.1.1.21. AgClO₄:dppb:bpy (2:1:2) Æ 2MeCN (22 Æ

2MeCN). C₅₂H₅₀Ag₂Cl₂N₆O₈P₂, M = 1235.6. Monoclinic,

space group P2₁/c, a = 20.819(2) A, b = 17.471(1) A, c =

‘T_min/max’ = 0.75. 2h_max= 58ꢁ; N_t= 42804, N = 20249

(R_int= 0.055), N_o= 12371; R = 0.047, R_w= 0.048.

Variata. The ‘water molecule oxygen’ residue (no associ-

ated hydrogen atoms were located) was assigned a site

occupancy of 0.5 after trial reﬁnement.

˚

3

˚

14.853(1) A, b = 106.156(2)ꢁ, V = 5189 A . D_calc(Z =

! 4) = 1.58₁g cm^ꢀ3. l_Mo= 0.98 mm^ꢀ1; specimen: 0.32 ·

0.25 · 0.30 mm; ‘T_min/max’ = 0.80. 2h_max= 65ꢁ; N_t= 92967,

N = 18334 (R_int= 0.047), N_o= 12404; R = 0.035, R_w=

0.038.

2.2.1.2.3. AgNO₃:dppm:bq (2:1:2) Æ 2MeCN Æ ½H₂O

(27 Æ 2MeCN Æ ½H₂O). C₆₅H₅₃Ag₂N₈O_6.5P₂, M = 1327.9.

˚

Monoclinic, space group P2₁/c, a = 14.951(2) A, b =

3

˚

Variata. Perchlorate group 1 was modelled with a ClO₂

component disordered over two sets of sites, in concert

with perchlorate 2, rotationally disordered about a Cl–O

bond, site occupancies of the two components of each

reﬁning to 0.791(4) and complement.

12.750(2) A, c = 30.237(4) A, b = 98.105(4)ꢁ, V = 5706 A .

D_calc(Z = 4) = 1.54₅g cm^ꢀ3. l_Mo= 0.81 mm^ꢀ1; specimen:

0.16 · 0.10 · 0.05 mm; ‘T_min/max’ = 0.74. 2h_max= 58ꢁ; N_t=

118513, N = 15175 (R_int= 0.11), N_o= 11177; R = 0.042,

R_w= 0.047.

2.2.1.1.22. AgClO₄:dppb:bq (2:1:2) Æ 2MeCN Æ EtOH

(23 Æ 2MeCN Æ EtOH). C₇₀H₆₄Ag₂Cl₂N₆O₉P₂, M = 1481.9.

Triclinic, space group P1, a = 11.3309(8) A, b =

Variata. The ‘water molecule oxygen’ was modelled sim-

ilarly to the previous compound.

˚

2.2.1.2.4.

H₂O ð28 ꢁ 1½MeCN ꢁ H₂OÞ. C₅₆H_54.5Ag₂As₂N_7.5O₈, M =

AgNO₃: dpam : dmp ð2 : 1 : 2Þ ꢁ 1½MeCNꢁ

˚

12.0313(9) A, c = 13.854(1) A, a = 96.510(2)ꢁ, b = 99.706

3

˚

(2)ꢁ, c = 117.470(2)ꢁ, V = 1612 A . D_calc(Z = 1) =

1326.2. Monoclinic, space group P2₁/c, a = 18.6310(11)

1.52₇g cm^ꢀ3. l_Mo= 0.80 mm^ꢀ1; specimen: 0.18 · 0.16 ·

0.09 mm; ‘T_min/max’ = 0.86. 2h_max= 75ꢁ; N_t= 33028,

N = 16475 (R_int= 0.026), N_o= 11896; R = 0.040, R_w=

0.044.

A, b = 11.0495(7) A, c = 25.7580(15) A, b = 95.872(1)ꢁ,

˚

V = 5275 A . D_calc(Z = 4) = 1.67₀g cm^ꢀ3

. l_Mo= 2.05

3

˚

mm^ꢀ1; specimen: 0.26 · 0.25 · 0.23 mm; ‘T_min/max’ = 0.82.

2h_max= 70ꢁ; N_t= 96917, N = 23180 (R_int= 0.047), N_o=

16849; R = 0.041, R_w= 0.055.

Variata. Diﬀerence map residues were modelled as

EtOH disordered about a centre of symmetry, the oxygen

further disordered over two sites whose occupancies were

set at 0.25.

2.2.1.1.23. AgClO₄:dppb:tpy (2:1:2) Æ EtOH (24 Æ EtOH).

C₆₀H₅₆Ag₂Cl₂N₆O₉P₂, M = 1353.7. Triclinic, space group

Variata. Diﬀerence map residues were modelled in terms

of a second acetonitrile and a water molecule oxygen, both

disordered, with site occupancies set at 0.5 after trial

reﬁnement.

2.2.1.2.5. AgNO₃:dppp:dmp (2:1:2) Æ ½MeCN (29 Æ

½MeCN). C₅₆H_51.5Ag₂N_6.5O₆P₂, M = 1182.2. Mono-

˚

P1, a = 9.950(1) A, b = 11.414(1) A, c = 14.582(2) A, a =

3

˚

102.349(3)ꢁ, b = 104.173(3)ꢁ, c = 109.482(3)ꢁ, V = 1433 A .

clinic, space group P2₁/c, a = 10.726(1) A, b = 20.375(3)

D_calc(Z = 1) = 1.56₉g cm^ꢀ3. l_Mo= 0.90 mm^ꢀ1; specimen:

0.28 · 0.22 · 0.16 mm; ‘T_min/max’ = 0.80. 2h_max= 75ꢁ; N_t=

28999, N = 14594 (R_int= 0.023), N_o= 12558; R = 0.032,

R_w= 0.041.

A, c = 23.891(3) A, b = 102.790(2)ꢁ, V = 5092 A . D_calc

(Z = 4) = 1.55₁g cm^ꢀ3. l_Mo= 0.89 mm^ꢀ1; specimen: 0.16 ·

0.13 · 0.11 mm; ‘T_min/max’ = 0.91. 2h_max= 58ꢁ; N_t=

47074, N = 12805 (R_int= 0.046), N_o= 9203; R = 0.049,

R_w= 0.061.

3

˚

Variata. As in the previous case the oxygen atom of the

ethanol, disposed about an inversion centre, was modelled

as disordered over two sites, occupancies set at 0.25.

Variata. Nitrate 1 was modelled as disordered over two

sets of sites, occupancies set at 0.5 with constrained geom-

etries, and isotropic displacement parameter forms. Aceto-

nitrile (non-disordered) was reﬁned similarly.

2.2.1.2. AgX (=NO₃):dpex:L (2:1:2) (ÆnS) complexes.

2.2.1.2.1. AgNO₃:dppm:bpy (2:1:2) Æ H₂O (25 Æ H₂O).

2.2.1.2.6. AgNO₃:dppb:tpy (2:1:2) (30). C₅₈H₅₀Ag₂-

C₄₅H₄₀Ag₂N₆O₇P₂, M = 1054.5. Monoclinic, space group

N₈O₆P₂, M = 1232.8. Triclinic, space group P1, a =

6

˚

C2/c (C_2h, No. 15), a = 31.733(3) A, b = 17.302(2) A, c =

9.8410(6) A, b = 10.7735(7) A, c = 12.9754(8) A, a =

3

˚

16.953(2) A, b = 114.243(2)ꢁ, V = 8487 A . D_calc(Z = 8) =

1.65₀g cm^ꢀ3. l_Mo= 1.06 mm^ꢀ1; specimen: 0.15 · 0.13 ·

0.10 mm; ‘T_min/max’ = 0.78. 2h_max= 58ꢁ; N_t= 88831,

N = 11270 (R_int= 0.062), N_o= 8175; R = 0.040, R_w=

0.046.

102.995(1)ꢁ, b = 104.253(1)ꢁ, c = 94.987(1)ꢁ, V = 1284 A .

D_calc(Z = 1) = 1.59₄g cm^ꢀ3. l_Mo= 0.89 mm^ꢀ1; specimen:

0.43 · 0.22 · 0.21 mm; ‘T_min/max’ = 0.85. 2h_max= 70ꢁ;

N_t= 25532, N = 11209 (R_int= 0.021), N_o= 9769; R =

0.032, R_w= 0.043.

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1397

3. Results and discussion

of the derivatives. In addition, compounds containing

weakly coordinated ClO₄or NO₃undergo complete ionic

dissociation, not only in acetonitrile but also in non-ioniz-

ing solvents such as dichloromethane, values in the former

3.1. Syntheses

A number of adducts of general formula AgX:dpex:L

(2:1:2) (Charts 1–8) have been synthesised by the reaction

of two equivalents of N,N⁰-bidentate (bpy, phen, dmp,

bq, dpa) or N,N⁰,N⁰⁰-tridentate (tpy) aromatic ligands, L,

derivative of 2,2⁰-bipyridyl, with two equivalents of sil-

ver(I) perchlorate or nitrate and one equivalent of an

E,E⁰-bidentate dpex ligand according to

solvent being in the range 40–50 X^ꢀ1cm²mol^ꢀ1

.

3.2. Spectroscopy

The infrared spectra (Section 2) are consistent with the

formulations proposed, showing all of the bands required

by the presence of the organic N,N⁰-donor, and the biden-

tate phosphine or arsine ligands [14]. In the far-IR spectra

of all phosphino derivatives we assigned, on the basis of

previous reports, the broad absorptions near 500 cm^ꢀ1

and those at 480–400 cm^ꢀ1to Whiﬀen’s y and t vibrations

[15].

2AgX þ 1dpex þ 2L þ yH₂O

S

! AgX : dpex : Lð: xS : yH₂OÞð2 : 1 : 2ðx : yÞÞ

ð1Þ

When less than two equivalents of the ligand L were used,

some unreacted starting material was often recovered from

the reaction. On the other hand, when more than one

equivalent of E,E⁰-bidentate dpex was employed, the dpex:

AgX (2:1) adducts were the predominant species obtained,

no adducts containing N,N⁰-donor ligands being isolated.

All the compounds, air-stable, colorless materials, are

insoluble in diethyl ether and ethanol and soluble in ace-

tone, acetonitrile, and DMSO. The nitrato derivatives

25–30 are moderately soluble also in chlorinated solvents.

The conductivity measurements are in accordance with

the ionic formulations found in the solid state for most

The IR spectra of the perchlorato silver complexes 1–9,

11, 13–19, and 21–23 always showed two absorptions char-

acteristic of ionic perchlorate groups: a strong broad band

in the range 1110–1080 cm^ꢀ1(m₃) and a sharp medium or

strong band at ca. 625 cm^ꢀ1(m₄) [16]. They are indicative

ꢀ

of uncomplexed ionic or weakly interacting ClO₄groups

in accordance with the structures found in the solid state,

and with the behaviour shown by these complexes in solu-

tion. The absorptions are very similar to those found for

the ionic [(PPh₃)₄Cu]ClO₄and diﬀerent from those found

in the strongly distorted trigonal planar [(cy₃P)₂CuOClO₃]

N

Ag

Ph₂P

N

Ag

Ph₂P

N

Ag

PPh₂

-

PPh₂

2 ClO₄

CH₂

-

2 ClO₄

1

2

N

Ag

N

Ag

Ph₂P

Ag

Ph₂P

PPh₂

CH₂

-

2 ClO₄

-

2 ClO₄

CH₂

4

3

H

N

NH

N

Ag

Ph₂P

N

Ag

Ph₂P

N

Ag

N

PPh₂

-

2 ClO₄

PPh₂

CH₂

5

-

2 ClO₄

6

Chart 1.

1398

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

N

Ag

-

2 ClO₄

Ph As

Ph

As Ph

Ph

Ph As

Ph

As Ph

Ph

CH₂

8

CH₂

7

N

Ag

N

-

2 ClO₄

As

Ph

As

Ph

CH₂

9

Ph

Chart 2.

-

2ClO₄

Ph

Me

O

Me

Ph

O

P

Cl

O

NCMe

Ag

P

H₂C

CH₂

N

O

N

H₂C

CH₂

Ag

N

P

Ag

MeCN

P

N

Ph

N

O

Ph

Me

O

N

Ph

N

Ph

Me

Cl

O

11

10

Ph

O

MeCN

OH₂

Ph

P

Ph

O

Cl

H₂C

CH₂

O

N

P

N

O

Ag

OH₂

H₂C

CH₂

N

P

N

Ag

NH

N

Ph

HN

P

MeCN

O

N

Ph

O

N

Ph

N

Ph

Cl

O

-

2ClO₄

12

13

Chart 3.

containing a unidentate perchlorate group [17,18]. The IR

spectrum of 20 exhibits three strong absorptions at ca.

1160, 1120 and 1080 cm^ꢀ1, respectively, typical of m₈, m₆

and m₁, and two absorptions at ca. 639 and 620 cm^ꢀ1pre-

sumably due to m₃and m₇, all indicative of a bidentate per-

chlorate group as found in the solid state. The IR spectra

of 10, 12 and 24 (for which the single crystal X-ray studies

In the spectra of derivatives 25 and 26, the m₂, m₃and m₄

modes of vibration of ionic NO₃groups (D_3hsymmetry)

ꢀ

and a unique weak m₁+ m₄combination band in the over-

tone region 1700–1800 cm^ꢀ1have been detected throughout

in accordance with their ionic structures [19]. In the spectra

of complexes 29 and 30, the separation between m₁and m₄is

ca. 40 cm^ꢀ1, consistent with a unidentate nitrato ligand

m₁+ m₄[20]. The weak interactions between the silver(I) cat-

ions and the nitrate groups in 29 and 30 are reﬂected in the

small magnitudes of the splittings of the asymmetric N–O

stretching modes [21]. The presence of two diﬀerent absorp-

tions due to m_asymat 1420 and 1370 cm^ꢀ1and to out-of

ꢀ

indicated unidentate ClO₄groups) exhibit in the regions

1100–1000 and 640–600 cm^ꢀ1analogous bands to those

found for the ionic complexes 1–9, 11, 13–19, and 21–23,

ꢀ

suggesting very weak interactions between the ClO₄ions

and the silver centres.

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1399

N

-

2 ClO₄

O

Ph

N

Ph

O

N

Cl

Ag

O

As

H₂C

CH₂

Ph

H₂

C

N

P

Ag

N

P

C

As

Ph

O

H₂

Ph

O

N

Ph

Ag

N

Cl

N

O

14

15

Ph

Me

P

H₂C

CH₂

N

-

N

2 ClO₄

Ag

P

N

Ph

N

Ph

Me

16

O

Ph

O

Cl

Ph

O

P

Cl

O

N

H₂C

CH₂

As

O

N

H₂C

CH₂

N

Ag

As

Ph

N

Ag

O

N

As

Ph

O

Ph

O

N

Cl

O

Ph

N

Cl

O

18

17

Chart 4.

-

2 ClO₄

N

Ph

O

Ph

Cl

O

Ag

P

N

O

H₂C

CH₂

Ph

N

H₂C

CH₂

Ag

N

O

P

Ag

O

NH

Cl

N

Ph

HN

Ph

N

O

19

20

Chart 5.

plane deformation at ca. 840 and 820 cm^ꢀ1in the spectrum

of derivative 28 is consistent with the presence of both ionic

and unidentate NO₃groups (see below). The decrease in

energy of the out-of-plane deformation mode, m₂, in passing

from derivative 26–30 is consistent with increasing coordi-

nation of the nitrate oxygens [21].

1400

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

N

P

Ph

P

Ag

N

Ag

N

H₂

C

Ag

P

N

H₂

C

N

CH₂

H₂

N

Ag

P

Ag

Ph

-

Ph

2ClO₄

H₂

C

N

P

C

Ph

H₂

H

₂Ph

Ph

22

21

N

O

Ph

N

O

Ag

Cl

Ag

P

O

Ph

H₂

C

H₂

C

N

Ph

H₂C

O

Cl

C

O

Cl

O

H₂

O

Ph

P

O

N

P

H₂

C

O

N

H₂

P

Ag

CH₂

O

Ph

Ag

O

Ph

O

N

Cl

O

N

24

23

Chart 6.

N

O

N

Ag

P

Ag

N

Ag

O

Ph

P

Ph

-

2 NO₃

CH₂

P

-

Ph

NO₃

Ph

CH₂

26

Ph

25

N

O

N

Ag

N

Ag

O

Ag

O

P

As

Ph

As

Ph

P

CH₂

28

-

Ph

2 NO₃

NO₃

CH₂

27

Ph

Chart 7.

1

In the ¹H and ¹³C NMR spectra (see Section 2), the sig-

nals due to the diphosphine and N,N⁰-donor ligands show

diﬀerent patterns with respect to those found for the free

donors, conﬁrming the existence of the complexes in solu-

tion. For example, in the H NMR spectra the bridging

methylene resonances appear as broad singlets or multi-

plets between 1.40 and 4.33 ppm downﬁeld shifted with

respect to those found in the free donors. The chemical

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1401

N

Ag

O

N

O

N

P

Ph

P

Ph

O

CH₂

Ph

P

CH₃

CH₂

CH₃

Ph

CH₂

O

N

Ph

CH₂

Ph

Ag

P

Ag

N

Ph

N

Ag

N

CH₃

N

O

CH₃

N

O

29

30

Chart 8.

shifts depend on the ancillary N,N⁰-donor ligands, the

greater d being found in the case of the bq derivatives,

the lower in the case of the tpy complexes.

The ³¹P NMR data (chemical shifts, Ag–³¹P coupling

constants) in CD₃CN solution of all complexes conﬁrm

their stability in this solvent. The room temperature ³¹P

NMR spectra of complexes 10, 14, and 30 consist of broad

singlets, presumably in consequence of exchange equilibria

that are reasonably fast in relation to the NMR time scale.

Exchange is quenched at low temperature (233 K), and one

and/or two unresolved doublets or resolved pairs of dou-

blets, arising from coupling between the phosphorus and

silver atoms, are observed in the accessible temperature

range. In particular, in the spectrum of derivative 30, typ-

ical pairs of doublets, due to ¹J(³¹P–¹⁰⁷Ag) and

¹J(³¹P–¹⁰⁹Ag) coupling, are resolved at 233 K and the

observed ¹J(³¹P–¹⁰⁷Ag)/¹J(³¹P–¹⁰⁹Ag) ratio is in good

agreement with that calculated from the gyromagnetic

ratio of the Ag nuclei c(¹⁰⁷Ag)/c(¹⁰⁹Ag) [22]. For all the

other derivatives broad doublets were also observed at

room temperature, suggesting that rapid exchange equilib-

ria are not operative in these compounds.

Fig. 1. ³¹P NMR spectrum of compound 2.

perturbed by the presence of weakly bonded counter-ions

or solvent molecules. The coupling constant value deter-

mined for compound 13 (443 Hz) is representative of an

AgP₂N₂coordination environment and indicates a dissoci-

ation of the complex in solution in accordance with the

following equilibrium:

The ³¹P NMR spectra of compounds 2 (Fig. 1) and 3

exhibit at room temperature an AA⁰XXA⁰A pattern [23]

because of the non-equivalence of the phosphorus atoms

(consistent with the X-ray data) resulting from the large

²J(P–P), for the three possible combinations of the two sil-

ver isotopes. It is interesting to note that the pattern is sim-

ilar to that found by us also for [Ag₂(dppm)₂(X)₂] [24]

species. Muetterties and Alegranti [25] and Goel and Pilon

[26] indicated that the spin–spin constant (J) between phos-

phorus and silver is dependant on the number of coordi-

nated phosphorus atoms in the silver complex, and that it

is possible to determine the number of the latter from mea-

surement of the J values in the ³¹P NMR spectra. On the

basis of the detected values, AgPN₃coordination environ-

ments are probable in solution for compounds 6, 21 and

24, cf. AgPN₂coordination environments for compounds

1–5, 22, 23, 25, 27, 29 and 30, consistent with the structures

found in the solid state.

½ðdpaÞAgðH₂OÞðP-dppe-PÞðMeCNÞAgðdpaÞꢂðClO₄Þ₂

! ½ðdppeÞAgðdpaÞꢂðClO₄Þ þ ½AgðdpaÞðClO₄Þꢂ

ð2Þ

It should be noted that the signals for every free diphos-

phine appear upﬁeld of those of the corresponding silver(I)

complexes. Dd(³¹P) = d(³¹P_complex) ꢀ d(³¹P_ligand); the diﬀer-

ences in shift between each free diphosphine and the corre-

sponding silver(I) derivatives are of the order of 28–34 ppm

for dppm, 18–23.5 ppm for dppe, 20.3–24.7 for dppp and

ﬁnally 17.2–25.6 for dppb. The shifts are a function of

the chain length in the P-donor and the nature of the ancil-

lary N,N⁰-donor ligands, but do not depend on the nature

of the counter-ions, the perchlorate complex d values being

close to those found for the analogous nitrate species and

suggesting the absence of any interaction between silver

and the counter-ions also in solution. The shift is greater

in the case of the bidentate N,N⁰-donors bpy and phen

and decreases with increasing basicity of the N,N⁰-donor.

As expected d strongly diminishes with increasing number

The coupling constant values found for 11, 12, 19 and 26

are in accordance with AgPN₂coordination environments

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Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

Fig. 2. Projection of the [LAg(E-dpem-E)AgL]²⁺aggregates of the 2:1:2 AgX:dpem:L complexes. Internal crystallographic symmetry is noted. (a) Species

with ‘cis’-dispositions of the pair of

L , in 1 (cation 1; cation 2 is similar) (perchlorate salt); (ii)

ligands: (i) [(bpy)Ag(dppm)Ag(bpy)]²⁺

[(phen)Ag(dpam)Ag(phen)]²⁺, in 7 Æ ¼MeCN (the E = P analogue (2) is isomorphous) (perchlorate salt); (iii) [(dmp)Ag(dppm)Ag(dmp)]²⁺, in 3 Æ MeCN

(the E = As analogue (8) is isomorphous) (perchlorate salt); (iv) [(tpy)Ag(dppm)Ag(tpy)]²⁺, in 6 (the E = As analogue (9) is isomorphous) (perchlorate salt);

(v) [(bq)Ag(dppm)Ag(bq)]²⁺, in 27 Æ 2MeCN Æ ½H₂O (nitrate salt). (b) Species with ‘trans’-dispositions of the pair of L ligands: (i) [(dpa)Ag(dpp-

m)Ag(dpa)]²⁺, in 5 Æ /3 H₂O (cation 1; cations 2, 3 are similar, all cations being disposed on crystallographic 2-axes); (ii) [(bpy)Ag(dppm)Ag(bpy)]

,

2+

1

in 25 Æ H₂O. (c) Species with additional coordinative interactions from anion (or solvent (none)). (i) [(O₂NO)(dmp)Ag(dppm)Ag(dmp)]⁺, in

26 Æ MeCN Æ ½H₂O; (ii) [(O₂NO)(dmp)Ag(dpam)Ag(dmp)]⁺, in 28 ꢁ 1½MeCN ꢁ H₂O.

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1403

of N donor atoms, the lower d always being found in the

tpy derivatives.

and [Ag(dpex)(L)]⁺, consequent upon the breaking of

bridging bonds due to the diphosphine ligand. In some

cases, peaks due to dinuclear species [Ag₂(dpex)X]⁺have

been detected. The negative electrospray spectra are always

dominated by the presence of molecular peaks due to X

The positive electrospray mass spectra of selected deriv-

atives (the most relevant data are reported in Section 2)

suggest, under our experimental conditions, not only the

existence in acetonitrile solution of [Ag₂(dpex)(L)₂]²⁺spe-

cies in acetonitrile solution, but also large dissociation

towards mononuclear fragments such as [Ag(dpex)(L)]⁺,

[Ag(L)₂]⁺[Ag(dpex)₂]⁺and [Ag(dpex)(solvent)]⁺. It is

noteworthy that the major peak in the positive spectra of

all species is always due to the cationic species [Ag(L)]⁺

ꢀ

and AgX₂

.

3.3. Single crystal X-ray studies

The twenty-nine compounds described here are of

(x:y:z) = AgX:dpex:L (2:1:2) stoichiometry, incorporating

Fig. 3. Unit cell contents of: (a) [(bpy)Ag(dppm)Ag(bpy)](ClO₄)₂, 1, projected down b; (b) [(phen)Ag(dpam)Ag(phen)](ClO₄)₂Æ ¼MeCN, 7 Æ ¼MeCN,

1

projected down b; (c) [(dmp)Ag(dppm)Ag(dmp)](ClO₄)₂Æ MeCN, 3 Æ MeCN, projected down a; (d) [(dpa)Ag(dppm)Ag(dpa)](ClO₄)₂Æ /3 H₂O, 5 Æ /3 H₂O,

projected down c; (e) [(tpy)Ag(dppm)Ag(tpy)](ClO₄)₂, 6, projected down b; (f) [(bpy)Ag(dppm)Ag(bpy)](NO₃)₂Æ H₂O, 25 Æ H₂O, projected down c; (g)

[(dmp)(O₂NO)Ag(dppm)Ag(dmp)](NO₃) Æ MeCN Æ ½H₂O, 26 Æ MeCN Æ ½H₂O, projected down a; (h) [(bq)Ag(dppm)Ag(bq)](NO₃)₂Æ 2MeCN Æ ½H₂O,

27 Æ 2MeCN Æ ½H₂O, projected down b. (i) ½ðdmpÞðO₂NOÞAgðdpamÞAgðdmpÞꢂðNO₃Þ ꢁ 1½MeCN ꢁ ½H₂O, 28 ꢁ 1½MeCN ꢁ ½H₂O, projected down b.

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Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

all forms of dpex ligands employed. All but one of these

(AgClO₄:dppp:tpy (2:1:2), 21) contain binuclear species,

predominantly of the form [LAg(E-dpex-E⁰)AgL]²⁺(X^ꢀ)₂,

containing three-coordinate (four in the L = tpy com-

plexes) (N,N⁰(,N⁰⁰)-L)AgE environments, simply that in

the case of most of the dpem adducts, but in the cases of

the dpee, dppp, dppb adducts, subject to augmentation

by interactions of diverse strengths with unidentate solvent

(usually MeCN) or uni- or (semi-)bidentate O(,O⁰)-anions,

the latter phenomenon presumably consequent on the more

spacious disposition of the binuclear arrays permitted by

expansion of the polymethylene dpex string, and in some

cases the more spacious and less powerful donor character-

istics of E = As dpex ligands; e.g. with dpam and the more

basic nitrate, such interactions may also be found. Insofar

as the N,N⁰-bidentate ligands are concerned, all these

behave as chelates (bpy, bq, dpa always in their ‘cis’-forms)

with similar ‘bite’ angles and Ag–N distances, dpa excepted

where the chelate ring is six-membered rather than ﬁve;

bpy, bq and dpa ligands are essentially planar although

the interplanar dihedral angle between the pair of aromatic

components may be as great as 22ꢁ (Table 2). With these

Fig. 4. Projections of the [LAg(E-dpee-E⁰)AgL] units (with associated solvents or anions) of: (a) [(bpy)(O₃ClO)Ag(dppe)Ag(O₃ClO) (bpy)], 10

(centrosymmetric); (b) [(dmp)(MeCN)Ag(dppe)Ag(NCMe)(dmp)]²⁺, in 11 Æ 2MeCN (centrosymmetric); (c) [(bq)(O₃ClO)Ag(dppe)Ag(OClO₃)(bq)], in

12 Æ 2MeCN (centrosymmetric; the P/As (18) and As₂(17) analogues are isomorphous); (d) [(dpa)(MeCN)(H₂O)Ag(dppe)Ag(OH₂)(NCMe)(dpa)]²⁺, in

13 Æ 2MeCN Æ H₂O (centrosymmetric); (e) [(tpy)Ag(dppe)Ag(tpy)]²⁺, in 14 Æ 2MeCN (centrosymmetric); (f) [(bpy)(O₂ClO₂)Ag(dpAe)Ag(O₂ClO₂)(bpy)], 15

(centrosymmetric); (g) [(dmp)Ag(dpae)Ag(dmp)]²⁺, in 16 Æ H₂O.

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1405

rather general comments in mind, we discuss the individual

arrays, representative depictions being given in Figs. 1–7,

with geometries and conformational descriptors being sum-

marised in Tables 1–4. In a number of cases, the planar

arrays of the N,N⁰-base ligands, in particular, lead to inter-

esting stackings, also portrayed in the ﬁgures.

Fig. 5. Unit cell contents of: (a) [(bpy)(O₃ClO)Ag(dppe)Ag(OClO₃)(bpy)], 10, projected down a; (b) [(dmp)(MeCN)Ag(dppe)Ag(NCMe)(dmp)]-

(ClO₄)₂Æ 2MeCN, 11 Æ 2MeCN, projected down a; (c) [(bq)(O₃ClO)Ag(dppe)Ag(OClO₃)(bq)] Æ 2MeCN, 12 Æ 2MeCN, projected down a; (d) [(dpa)-

(MeCN)(H₂O)Ag(dppe)Ag(OH₂)(NCMe)(dpa)](ClO₄)₂Æ MeCN Æ H₂O, 13 Æ MeCN Æ H₂O, projected down a; (e) [(tpy)Ag(dppe)Ag(tpy)](ClO₄) Æ 2MeCN,

14 Æ 2MeCN, projected down a; (f) [(bpy)(O₂ClO₂)Ag(dpae)Ag(O₂ClO₂)(bpy)], 15, projected down a.

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Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

Fig. 6. Projections of the binuclear [LAg(P-dppx-P⁰)AgL] units of: (a) [(bq)Ag(dppp)Ag(bq)]²⁺, in 19 Æ 2MeCN; (b) [(dpa)(O₂ClO₂)Ag(dppp)Ag

(O₂ClO₂)(dpa)], 20; (c) ½. . . AgðtpyÞ₂AgðdpppÞ . . .ꢂ_ð1j1Þ^2þ, in 21; (d) [(bpy)Ag(dppb)Ag(bpy)]²⁺, in 22 Æ 2MeCN; (e) [(bq)(O₃ClO)Ag(dppb)Ag(O₃ClO)(bq)]

in 23 Æ 2MeCN Æ EtOH (centrosymmetric); (f) [(tpy)(O₃ClO)Ag(dppb)Ag(OClO₃)(tpy)], in 24 Æ EtOH (centrosymmetric); (g) [(dmp)(O₂NO)Ag(dppp)Ag

(ONO₂)(dmp)], 29; (h) [(tpy)(O₂NO)Ag(dppb)Ag(ONO₂)(tpy)], in 30 (centrosymmetric).

3.3.1. The AgX:dpem:L (2:1:2) complexes (1–3; 5–9)

(X = ClO₄); 25–28 (X = NO₃) (ÆnS)

which we call ‘cis’, the torsion Ag–P. . .P–Ag is close to zero

(Fig. 2; Table 2), compounds of this cis-type being exempli-

ﬁed by the (2:1:2) adducts: AgClO₄:dppm:bpy, phen, dmp,

tpy (1–3, 6); AgClO₄:dpam:phen, dmp, tpy (7–9) (the three

latter compounds being isomorphous with their dppm

counterparts); AgNO₃:dppm:bpy, bq (25, 27). The putative

symmetry of the core of this array is mm2/C_2v, but this is

diminished (a), by the deviation of the methylene group

from the Ag₂E₂plane, (b), by diﬀerences in torsions of

the phenyl rings, which may be accommodating (c) torsions

The ‘simple’ [LAg(dppm)AgL]X₂salts, found for both

X = ClO₄, NO₃, are the most numerous and fall into two

forms. The disposition of the substituents of the E atom

are ‘staggered’ with respect to the hydrogens of the central

methylene group, such that one pair of substituents, X,

form a quasi-planar array XPCPX, the other two substitu-

ents pendant to either side of that plane. In the majority of

cases, the coplanar ‘X’ substituents are Ag; in a situation

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1407

Fig. 7. Unit cell contents of: (a) [(bq)Ag(dppp)Ag(bq)](ClO₄)₂Æ 2MeCN, 19 Æ 2MeCN, projected down a; (b) [(dpa)(O₂ClO₂)Ag(dppp)Ag(O₂ClO₂)(dpa)],

20, projected down a; (c) [(bpy)Ag(dppb)Ag(bpy)](ClO₄)₂Æ 2MeCN, 22 Æ 2MeCN, projected down c; (d) [(bq)(O₃ClO)Ag(dppb)Ag(OClO₂)(bq)] Æ 2MeCN Æ

EtOH, 23 Æ 2MeCN Æ EtOH, projected down a; (e) [(tpy)(O₃ClO)Ag(dppb)Ag(OClO₃)(tpy)] Æ EtOH, 24 Æ EtOH, projected down a; (f) [(dmp)-

(O₂NO)Ag(dppp)Ag(ONO₂)(dmp)], 29 Æ EtOH, projected down a; (g) [(tpy)(O₂NO)Ag(dppb)Ag(ONO₂)(tpy)], 30, projected down a.

of the AgN₂ligand planes. The driver of the latter may be

‘packing’ forces (a) within the lattices (see Fig. 3) or (b)

within the cation, arising from interligand overlaps. There

are substantial deviations in some cases from equivalence

of the pair of E-Ag-N,N⁰angles, with, sometimes, counter-

part diﬀerences in Ag-N,N⁰. Deviations of the silver

atoms from the ligand planes may be considerable, most

notably so in bpy, bq, and dpa adducts where the pyridyl

rings containing the donor atoms are not fused, as in phen,

dmp. In all of these cases, one formula unit, devoid of

Table 1

Geometrical descriptors of dpem complexes: 1–3, 5–9 (X = ClO₄); 25–28 (X = NO₃)

˚

X/dpem/L

Ag

Ag–E (A)

Ag–N (A)

Ag. . .Ag (A)

E–Ag–N (ꢁ)

N–Ag–N (ꢁ)

Ag–E–C (ꢁ)

E–C–E (ꢁ)

Adducts of 2:1:2 stoichiometry: binuclear [LAg(dpem)AgL]²⁺arrays

(ClO₄/)dppm/bpy (1)

Ag(1)

Ag(2)

Ag(3)

Ag(4)

2.363(3)

2.337(3)

2.366(3)

2.344(3)

2.277(8), 2.360(8)

2.311(9), 2.251(8)

2.279(9), 2.352(8)

2.244(9), 2.366(3)

3.073(1)

3.113(1)

145.5(2), 141.2(2)

130.6(2), 155.2(2)

147.0(2), 140.5(2)

151.0(2), 134.3(2)

71.6(3)

74.1(2)

72.2(3)

73.7(3)

119.1(3)

110.1(3)

115.4(3)

112.6(3)

112.7(5)

113.0(5)

phen (2)

dmp (3)

dpa (5)

Ag(1)

Ag(2)

2.3347(7)

2.3489(7)

2.250(2), 2.318(2)

2.282(2), 2.314(2)

3.0946(4)

3.5057(4)

154.43(6), 130.14(6)

145.92(6), 140.88(6)

73.89(8)

73.06(8)

117.51(7)

111.35(9)

112.6(1)

116.8(2)

Ag(1)

Ag(2)

2.3483(7)

2.3669(7)

2.258(3), 2.319(2)

2.318(3), 2.296(2)

147.06(7), 139.11(7)

145.68(7), 141.34(7)

73.8(1)

72.99(9)

113.99(9)

114.7(1)

Ag(1)

Ag(2)

Ag(3)

2.340(3)

2.335(3)

2.355(3)

2.249(9), 2.284(8)

2.237(9), 2.292(8)

2.260(9), 2.292(8)

145.6(2), 131.6(2)

146.6(2), 129.2(2)

140.3(2), 135.1(2)

82.8(3)

84.1(3)

84.5(8)

112.4(2)

113.5(2)

110.1(2)

112.6(2)

114.4(7)

114.2(8)

tpy (6)

Ag(1)

Ag(2)

2.3825(9)

2.414(1)

2.389(3), 2.324(3), 2.674(4)

2.460(4), 2.388(4), 2.492(4)

3.4057(6)

115.98(8), 172.36(8), 106.32(8)

110.0(1), 177.37(9), 115.4(1)

131.1(1), 69.6(1), 66.5(1)

134.5(1), 67.4(1), 67.2(1)

118.0(1)

111.6(1)

114.2(2)

(NO₃/)dppm/bpy (25)

dmp^a(26)

Ag(1)

Ag(2)

2.3308(9)

2.336(1)

2.272(3), 2.287(3)

2.263(3), 2.285(5)

147.91(8), 139.49(7)

151.2(1), 135.2(1)

72.6(1)

73.1(1)

110.7(1)

112.3(1)

112.7(1)

115.0(2)

113.2(1)

Ag(1)

Ag(2)

2.377(1)

2.3457(9)

2.300(2), 2.383(3)

2.278(3), 2.298(3)

3.4180(5)

3.3507(6)

153.00(8), 129.35(7)

147.55(9), 136.53(7)

72.08(9)

74.0(1)

119.31(9)

110.9(1)

bq (27)

Ag(1)

Ag(2)

2.361(1)

2.384(1)

2.289(3), 2.307(3)

2.294(3), 2.337(3)

145.40(8), 142.01(7)

153.89(8), 134.43(7)

72.5(1)

71.7(1)

111.7(1)

116.7(1)

(ClO₄/)dpam/phen (7)

dmp (8)

Ag(1)

Ag(2)

2.449(1)

2.431(1)

2.317(8), 2.290(8)

2.324(8), 2.246(8)

3.125(1)

3.7380(6)

3.5799(5)

141.7(2), 144.9(2)

130.3(2), 154.3(2)

73.1(3)

74.2(3)

113.1(3)

118.4(3)

109.5(4)

114.9(2)

112.1(1)

Ag(1)

Ag(2)

2.440(5)

2.4486(5)

2.259(4), 2.314(3)

2.290(4), 2.278(3)

148.1(1), 138.03(9)

144.7(1), 141.29(9)

73.9(1)

116.6(1)

115.8(1)

tpy (9)

Ag(1)

Ag(2)

2.4829(3)

2.5059(4)

2.395(2), 2.333(2), 2.532(3)

2.433(3), 2.381(3), 2.447(3)

133.33(6), 177.63(6), 109.83(6)

110.01(7), 175.92(6), 112.49(7)

133.10(8), 69.04(8), 67.94(8)

136.4(1), 68.2(1), 68.3(1)

121.85(8)

113.33(8)

(NO₃/)dpam/dmp^a(28)

Ag(1)

Ag(2)

2.4586(3)

2.4457(3)

2.272(2), 2.369(2)

2.269(2), 2.298(2)

3.4624(3)

153.61(6), 130.21(6)

149.59(6), 135.35(6)

72.82(8)

73.87(8)

119.91(8)

111.25(8)

110.9(1)

a

˚

In these two adducts, signiﬁcant interactions between anion and Ag(1) are found, Ag–O 2.630(3), 2.593(2) A.

Table 2

Conformational descriptors of dpem complexes: 1–3, 5–9 (X = ClO₄); 25–28 (X = NO₃)

X/dpem/L

Ag

L¹/L²

(ꢁ)

(py/py; bq/bq)

(ꢁ)

dAg

(A)

C–E–Ag–N

(ꢁ)

E–C–E–Ag

(ꢁ)

E–C–P–C(11,21)

(ꢁ)

Ag–E–C(1n1)–C–(1nx)

(ꢁ)

Ag–E. . .E–Ag

(ꢁ)

˚

Adducts of 2:1:2 stoichiometry: binuclear [LAg(dpem)AgL]²⁺arrays

(ClO₄/)dppm/bpy (1)

Ag(1)

Ag(2)

Ag(3)

Ag(4)

12.2(4)^a

11.3(4)

17.8(4)

3.8(4)

0.34(1), 0.27(1)

0.21(1), 0.64(1)

0.06(2), 0.24(2)

0.27(2), 0.66(2)

83.3(5), ꢀ119.9(5)

115.8(4), ꢀ71.3(6)

ꢀ73.5(5), 115.1(5)

76.2(5), ꢀ121.3(4)

53.4(6)

ꢀ39.4(6)

ꢀ53.7(5)

43.8(5)

ꢀ70.7(6), 178.0(5)

84.9(6), ꢀ164.4(5)

69.1(6), ꢀ179.2(5)

ꢀ82.0(1), 167.5(5)

ꢀ13.4(9), 66.3(8)

ꢀ33.44(1), ꢀ67.8(9)

17.4(10), ꢀ77.6(8)

29.9(10), 57.5(8)

8.13(9)

2.8(4)

ꢀ7.08(9)

18.2(4)

phen (2)

Ag(1)

Ag(2)

9.39(5)

2.69(4)

0.116(2)

0.017(2)

ꢀ54.5(2), 148.4(1)

ꢀ50.9(2)

77.5(2), ꢀ169.7(3)/

22.1(3), 81.5(5)

27.4(3), 32.4(3)

ꢀ1.15(3)

ꢀ175.1(3)

90.9(1), ꢀ95.5(1)

ꢀ92.4(2), 92.3(2)

144.9(2), ꢀ34.7(2)

ꢀ106.8(4), 73.2(5)

ꢀ107.5(5), 76.3(5)

107.1(5), ꢀ79.4(5)

46.4(2)

ꢀ77.7(2), 170.7(2)

dmp (3)

dpa (5)

Ag(1)

Ag(2)

0.019(3)

0.322(3)

56.1(2)

ꢀ54.8(2)

65.2(2)

ꢀ63.1(2)

ꢀ73.9(2), 176.1(2)

10.4(3), 86.6(3)

21.5(3), 79.0(2)

1.32(3)

76.2(2), ꢀ176.9(2)

Ag(1)

Ag(2)

Ag(3)

17.1(4)

16.6(4)

22.2(4)

0.77(2), 0.05(2)

0.80(1), 0.07(2)

0.68(2), 0.35(2)

ꢀ66.6(4), ꢀ175.1(3)

ꢀ66.1(4), ꢀ177.3(4)

172.9(4), 63.9(4)

6.8(10), 63.3(8)

4.4(1), 64.3(9)

3.0(9), ꢀ21.2(9)

ꢀ16.8(4), ꢀ56.4(3)

117.68(9)

114.2(1)

ꢀ114.06(9)

ꢀ5.75(3)

tpy (6)

Ag(1)

Ag(2)

4.3(2)^a

26.3(2)(p/p⁰⁰), 4.1(2),

30.4(2)(p/c)

0.140(7), 1.599(7),

0.023(7)(c)

0.35(1), 0.22(1),

0.20(1)

45.7(2), ꢀ178.4(5),

52.5(2)

ꢀ84.0(2), 167.9(2)

ꢀ159.6(1)

6.8(3), 3.6(3), 7.9(3)

ꢀ91.7(2), ꢀ94(2),

91.9(2)

ꢀ56.1(2)

69.4(1), 175.4(2)

ꢀ19.4(4), ꢀ82.9(4)

(NO₃/)dppm/bpy (25)

Ag(1)

Ag(2)

20.04(8)^a

2.8(1)

12.6(2)

0.053(5), 0.072(5)

0.382(6), 0.212(7)

117.0(2), ꢀ64.3(2)

106.2(2), ꢀ85.9(2)

ꢀ63.6(2)

ꢀ59.9(2)

64.66(2), 173.1(2)

59.2(5)/73.1(5),

177.4(2)

ꢀ18.3(3), ꢀ80.0(3)

ꢀ110.41(3)

0.5(11)/2.5(8), 33.7(3)

dmp (26)

bq (27)

Ag(1)

Ag(2)

1.03(4)

0.084(3)

0.165(3)

48.0(2), ꢀ89.1(1)

ꢀ164.6(2), 39.7(2)

ꢀ48.3(2)

79.2(2), ꢀ172.3(2)

ꢀ78.2(2), 175.3(2)

17.8(3), 65.0(3)

ꢀ9.4, ꢀ62.4(3)

10.31(3)

15.18(3)

56.3(2)

Ag(1)

Ag(2)

3.80(9)^a

4.42(9)

1.08(7)

0.099(5), 0.244(5)

0.382(5), 0.467(4)

ꢀ165.4(2), 20.5(2)

61.5(2)

ꢀ45.7(2)

ꢀ70.3(2), ꢀ177.0(2)

10.6(4), ꢀ83.9(3)

66.5(2), ꢀ112.0(2)

82.9(2), ꢀ168.8(2)

15.6(3), 77.8(3)

(ClO₄/)dpam/phen (7)

dmp (8)

Ag(1)

Ag(2)

8.3(2)

0.014(7)

0.061(7)

97.0(4), ꢀ91.6(4)

ꢀ144.3(4), 54.8(6)

ꢀ43.1(5)

82.7(5), ꢀ169.3(5)

ꢀ78.9(5), 172.4(5)

ꢀ29.0(9), ꢀ33.1(9)

ꢀ20.7(9), 87.7(9)

5.7(4), 82.7(4)

22.2(4), 77.9(4)

0.85(4)

1.54(2)

46.8(5)

Ag(1)

Ag(2)

3.06(6)

6.8(1)^a

0.020(4)

0.269(4)

ꢀ90.9(2), 92.3(2)

55.8(2)

ꢀ53.4(2)

ꢀ76.1(2), 176.9(2)

144.2(2), ꢀ29.8(2)

77.8(2), ꢀ176.4(2)

tpy (9)

Ag(1)

Ag(2)

20.5(1)(p/p), 6.0(1),

26.4(1)(p/c)

6.8(2)(p/p), 5.4(2),

6.0(2)(p/c)

0.162(4), 1.318(4),

0.073(4)

0.309(7), 0.199(7),

0.111(6)

41.7(1), ꢀ137(1),

ꢀ157.1(1)

47.8(2)

ꢀ90.8(1), 164.4(1)

ꢀ12.6(3), ꢀ55.7(2)

ꢀ22.9(3), ꢀ73.5(3)

ꢀ7.34(1)

ꢀ93.1(1), ꢀ171(1),

89.6(1)

ꢀ52.4(1)

69.6(2), 174.1(1)

(NO₃/)dpam/dmp (28)

Ag(1)

Ag(2)

0.28(4)

0.089(3)

0.042(3)

63.8(2), 82.6(1)

ꢀ157.7(1), 41.6(1)

ꢀ51.1(2)

83.6(2), ꢀ172.4(1)

ꢀ79.3(2), 175.7(1)

ꢀ3.4(3), 59.8(2)

6.80(1)

54.7(1)

ꢀ31.8(3), ꢀ68.7(2)

a

The angle between the planes of the ‘inner’/overlapping py rings of the bpy or bq or the central rings of the tpy is given.

Table 3

Geometrical descriptors of dpex (¼dpem) complexes: 10–24, 29, 30

˚

X,S/dpex/L

Ag

Ag/X,S (A)

Ag–E (A)

Ag–N (A)

X,S–Ag–E (ꢁ)

X,S–Ag–N (ꢁ)

E–Ag–N (ꢁ)

N–Ag–N (ꢁ)

R (ꢁ)

Adducts of 2:1:2 stoichiometry: binuclear [(X/S)LAg(dpex)AgL(X/S)]ⁿ⁺arrays

O₃ClO/dppe/bpy (10)

MeCN/dppe/dmp(ClO₄) (11)

O₃ClO/dppe/bq (12)

Ag(1)

2.539(2)

3.164(2)

2.758(4)

3.020(4)

2.3675(3)

2.3432(4)

2.3594(5)

2.317(1), 2.340(1)

2.301(1), 2.270(1)

2.304(3), 2.305(2)

108.78(4)

99.00(4)

105.30(6)

82.46(8)

98.64(5), 108.38(5)

86.12(5), 70.02(5)

85.1(1), 108.62(9)

95.81(9), 79.4(1)

129.93(3), 132.39(4)

134.14(3), 150.61(3)

139.67(6), 135.72(7)

71.20(4)

70.02(5)

71.59(9)

333.4₂

354.7₇

346.9₈

MeCN/dppe/dpa(ClO₄) (13)

/dppe/tpy(ClO₄) (14)

Ag(1)

2.3337(6)

2.4055(5)

2.279(2), 2.265(2)

2.464(1), 2.443(1)(p),

2.405(1)(c)

136.22(7), 138.65(5)

109.74(4), 106.89(4)(p),

141.56(3)(c)

82.67(8)

67.48(5), 68.00(5),

135.35(5)

357.5₄

352.1₁

O₃ClO/dpae/bpy (15)

/dpae/dmp(ClO₄) (16)

Ag(1)

Ag(2)

2.683(2)

2.4676(2)

2.4348(6)

2.4386(8)

2.316(2), 2.340(1)

2.254(4), 2.337(6)

2.306(7), 2.251(5)

119.33(4)

92.16(6), 89.30(6)

135.50(4), 133.28(4)

156.8(1), 128.5(1)

140.7(1), 145.4(2)

71.70(6)

73.9(2)

73.7(2)

340.4₈

359.₂

359.₈

O₃ClO/dpae/bq (17)

Ag(1)

2.818(2),

2.980(3)

2.4487(2)

2.294(2), 2.290(1)

99.16(3),

109.29(4)

86.31(6), 113.09(5),

104.69(6), 77.91(6)

138.13(4), 138.35(5)

72.08(6)

348.5₆

O₃ClO/dpdae/bq (18)

O₂NO/dppp/dmp (29)

Ag(1)

2.787(2)

2.4006(2)

2.298(1), 2.301(1)

102.26(3)

86.01(5), 111.03(4)

139.12(3), 136.69(3)

71.75(5)

347.5₆

Ag(1)

Ag(2)

Ag(1)

Ag(2)

Ag(1)

2.605(9)

2.878(4)

2.346(1)

2.354(1)

2.3442(6)

2.3638(6)

2.3840(5)

2.292(4), 2.308(4)

2.294(3), 2.310(4)

2.277(2), 2.288(2)

2.287(2), 2.320(1)

2.466(2), 2.505(2),

2.401(2)(c)

2.333(2), 3.168(2),

2.295(2)(c)

2.262(2), 2.306(2)

2.276(2), 2.313(2)

106.8(2)

94.91(9)

80.2(2), 90.0(2)

81.8(1), 100.9(1)

143.9(1), 140.2(1)

142.0(1), 143.53(8)

147.48(4), 138.90(4)

149.09(4), 138.90(4)

113.32(4), 100.71(4),

119.57(4)(c)

131.11(5), 99.55(3),

146.34(4)(c)

146.45(5), 139.18(5)

144.38(5), 140.35(4)

73.3(1)

72.99(6)

71.99(5)

67.76(6), 67.05(6),

132.63(6)(p/p⁰⁰)

72.10(6), 62.24(5),

129.31(5)(p/p⁰⁰)

72.68(7)

357.₄

358.₈

359.3₇

359.9₈

373.8₈

/dppp/bq(ClO₄) (19)

/dppp/tpy (ClO₄) (21)

(Note: ‘S’ is the p-tpy N

approach)

2.391(2)

2.989(2)

124.47(5)

122.05(4)

92.09(6), 94.84(6),

115.63(6)(c)

80.98(6), 71.64(5),

81.01(5)(c)

Ag(2)

2.3531(5)

365.0₀

/dppb/bpy(ClO₄) (22)

Ag(1)

Ag(2)

2.3372(6)

2.3441(6)

358.3₁

357.2₄

72.51(6)

O₃ClO/dppb/bq (23)

O₃ClO/dppb/dpa (20)

O₃ClO/dppb/tpy (24)

Ag(1)

3.043(2)

2.930(7)

2.587(1)

2.3687(6)

2.346(1)

2.3875(4)

2.278(2), 2.344(2)

2.263(4), 2.297(3)

83.01(6)

106.5(1)

111.43(4)

95.31(7), 126.15(7)

74.6(2), 99.9(2)

150.10(5), 132.51(5)

141.10(8), 134.5(2)

71.67(6)

81.3(2)

354.2₈

356.₉

2.469(1), 2.488(2),

2.369(1)(c)

100.49(6), 77.36(6),

110.88(5)

111.64(4), 115.11(5),

136.97(3)

67.49(5), 67.51(5),

130.37(6)

361.6₆

O₂NO/dppb/tpy (30)

Ag(1)

2.416(1)

2.3736(5)

2.401(1), 2.598(1),

2.438(1)

136.58(3)

78.44(5), 91.05(4),

96.55(5)

129.67(3), 91.05(4),

123.11(4)

67.97(4), 64.51(4),

129.61(5)

353.₂

Table 4

Conformational descriptors of dpex (¼dpem) adducts: 10–24, 29, 30

X,S/dpex/L

Ag

(py/py; bq/bq)^ꢀ

(ꢁ)

dAg

(A)

C–E–Ag–N

(ꢁ)

C–C–E–Ag

(ꢁ)

C–C–E–C(11,21)

(ꢁ)

E,C–C–C–E

(ꢁ)

˚

Adducts of 2:1:2 stoichiometry: binuclear [(X/S)LAg(dpex)AgL(X/S)]ⁿ⁺arrays

O₃ClO/dppe/bpy (10)

Ag(1)

2.25(6)

0.531(3), 0.657(2)

0.301(2), 0.376(2)

0.359(4), 0.118(4)

ꢀ122.85(7), 136.00(6)

31.42(5), ꢀ126.87(7)

81.3(2), ꢀ158.3(2)

64.45(8)

50.1(1)

ꢀ59.77(9), ꢀ170.74(7)

ꢀ74.3(1), 176.6(1)

71.7(2), ꢀ178.9(2)

180(ꢀ)

MeCN/dppe/dmp (ClO₄) (11)

O₃ClO/dppe/bq (12)

4.85(1)

ꢀ52.4(2)

MeCN/dppe/dpa (ClO₄) (13)

/dppe/tpy (ClO₄) (14)

Ag(1)

5.18(9)

0.654(4), 0.596(4)

0.366(9), 0.294(3), 0.420(3)

ꢀ34.3(1), 120.7(1)

61.5(2)

56.6(1)

ꢀ67.4(2), ꢀ175.2(2)

180(ꢀ)

14.94(6), 12.51(6), 11.61(6)(p/p⁰⁰)

ꢀ77.91(6), 76.10(6), 0.42(8)

ꢀ68.9(1), ꢀ177.3(1)

180(ꢀ)

O₃ClO/dpae/bpy (15)

/dpae/dmp (ClO₄) (16)

Ag(1)

Ag(2)

9.46(6) (3.1(1))

0.062(4), 0.471(3)

0.043(4)

0.051(6)

ꢀ111.8(1), 138.2(1)

ꢀ7.4(4), 154.8(3)

166.2(3), ꢀ20.1(3)

65.6(2)

35.0(4)

173.7(3)

ꢀ58.9(2), ꢀ167.4(1)

154.9(3), ꢀ97.6(4)

48.1(4), ꢀ58.8(4)

180(ꢀ)

167.1(2)

O₃ClO/dpae/bq (17)

O₃ClO/dpdae/bq (18)

O₂NO/dppp/dmp (29)

Ag(1)

5.88(5)

0.315(3), 0.064(3)

0.329(2), 0.088(2)

76.9(1), ꢀ159.0(1)

79.80(9), ꢀ158.35(8)

ꢀ49.3(2)

ꢀ50.4(1)

ꢀ77.1(3)

ꢀ51.0(3)

62.0(2)

76.5(2), ꢀ176.7(1)

74.8(1), ꢀ177.1(1)

51.7(3), 159.7(3)

76.5(3), ꢀ174.7(3)

ꢀ61.7(2), ꢀ171.2(1)

57.9(2), 168.1(1)

ꢀ74.4(2), 176.0(2)

75.6(2), ꢀ175.5(2)

71.6(2), 179.4(1)

180(ꢀ)

175.5(3)

170.4(3)

5.39(4)

Ag(1)

Ag(2)

Ag(1)

Ag(2)

Ag(1)

Ag(2)

Ag(1)

(67.67(7))

0.004(4)

0.195(3)

29.8(2), ꢀ177.9(2)

ꢀ112.8(2), 86.0(2)

ꢀ1.5(1), ꢀ167.5(1)

72.1(1), ꢀ110.0(1)

152.3(1), ꢀ50.5(1)

ꢀ157.9(1), 51.0(1)

64.42(8), ꢀ149.26(8),

141.17(8)(c)

46.5(1), 171.6(1), ꢀ135.2(1)

ꢀ63.6(1), 158.9(1)

ꢀ112.8(2), 95.8(2)

/dppp/bq (ClO₄) (19)

/dppb/bpy/(ClO₄) (22)

/dppp/tpy (ClO₄) (21)

5.90(5) (1.57(4))

5.58(5)

16.2(1) (13.4(1))

16.9(1)

3.82(7), 2.16(8), 2.79(8)(p/p⁰⁰)

0.028(2), 0.258(2)

0.158(2), 0.069(3)

0.566(4), 0.285(5)

0.764(4), 0.114(4)

0.422(3), 0.589(4), 0.610(3)(c)

ꢀ176.4(1)

ꢀ67.5(1)

176.4(2)

43.5(2)

178.3(2)^a

ꢀ173.1(2)

ꢀ174.6(1)

ꢀ44.0(2)

ꢀ58.7(2)

Ag(2)

Ag(1)

7.25(9), 46.80(8), 51.26(9)(p/p⁰⁰)

0.66(4), 1.353(3), 0.325(3)(c)

0.173(3), 0.147(3)

ꢀ55.7(2)

51.1(2)

64.3(2)

45.3(1)

65.4(2), 174.9(1)

ꢀ167.2(1)

177.1(1)^a

O₃ClO/dppb/bq (23)

O₃ClO/dppb/dpa (20)

O₃ClO/dppb/tpy (24)

1.56(1)

ꢀ72.8(2), 177.6(2)

ꢀ64.5(3), ꢀ175.2(2)

ꢀ77.0(1), 176.0(1)

3.6(3)

0.41(1), 0.65(1)

ꢀ168.7(2)^a

ꢀ177.8(1)^a

6.33(7), 20.29(7), 23.50(7)(p/p⁰⁰)

0.940(3), 0.384(3), 0.613(3)

126.06(8), ꢀ71.06(7),

ꢀ154.34(7)(c)

O₂NO/dppb/tpy (30)

Ag(1)

19.41(6), 4.25(6), 19.08(6)(p/p⁰⁰)

0.319(3), 0.896(3), 0.652(3)(c)

111.54(7), ꢀ36.00(6),

ꢀ54.0(1)

72.6(1), 180.0(1)

169.7(1)^a

23.88(6)(c)

a

C–C–C–C is 178.2(2)ꢁ for 22 and (obligate) 180ꢁ for 20, 23, 24, 30.

intraligand values; interligand values in parentheses.

ꢀ

1412

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

crystallographic symmetry, sometimes inclusive of solvent,

comprises the asymmetric unit of the structure (exception:

AgClO₄:dppm:bpy (2:1:2) (1) where two formula units are

required).

these approaches concomitant with perturbations of the

EAgN₂(L) array from planarity broadly consistent with

the closeness of the interaction (Table 3). The only repre-

sentative in which the full cation is devoid of symmetry,

comprising with the anion the asymmetric unit, is

AgClO₄:dpae:dmp (2:1:2) Æ H₂O, (16), in which, despite

a trans conformation of the central bond of the ligand,

one of the C–C–As–Ag strings is also, unusually, trans,

so that the disposition of the two dmp ligands is cis-

oid. The dmp ligand planes are essentially parallel (inter-

planar dihedral angle 3.1(1)ꢁ), with their methyl substitu-

ents confronting, but beyond the van der Waals’

distance; despite the As (rather than P) E donors, there

are no close anion approaches to the silver atoms.

The trends described for AgClO₄:dppe:L (2:1:2) are car-

ried over into the more limited range of 3.3.3.

The alternative form found (among the other possibili-

ties) is ‘trans’, where the two silver atoms lie in the opposite

sides of the (now) CECEC plane, a situation of potentially

2-symmetry, realized in the AgClO₄:dppm:dpa (2:1:2)

adduct (5), where each of the three independent cations lies

with the central carbon disposed on a crystallographic 2-

axis. The AgNO₃:dppm:bpy (2:1:2) analogue (25),

although of this disposition, has one independent formula

unit in the asymmetric unit of the cell. In both forms,

exchange of P for As in the dpem ligand has little eﬀect

on associated Ag–N distances, despite the substantial

increases in Ag–E. Ag–N(tpy) are rather more irregular

than in the other complexes, with no necessary equivalence

between the outer (peripheral = ‘p’) distances for any one

ligand, although Ag–N (central = ‘c’) is always the shortest

of the three, sometimes only by a very small margin.

Although they are not isomorphous, the two dmp/NO₃

adducts AgNO₃:dppm, dpam:dmp (2:1:2) (26, 28) are

intriguing in that a signiﬁcant, albeit long interaction, with

one of the silver atoms with an anion, in each case a unid-

entate nitrate, is found, so that the binuclear component

may be considered an ion pair: [(O₂NO)(dpm)-

Ag(dpem)Ag(dpm)]⁺.

3.3.3. The AgX:dppb:L (2:1:2) complexes (22–24) (ÆnS)

Here again centrosymmetric forms predominate, being

found in AgClO₄:dppb:bq, tpy (ÆS) (23, 24) and

AgNO₃:dppb:tpy (2:1:2) (30). In all of these ‘trans’ binu-

clear arrays, inclusive of the tpy adducts, the silver atoms

are approached by anion oxygen atoms; a trans-oid array,

devoid of crystallographic symmetry and any close anion

or solvent approach, is also found in AgClO₄:dppb:bpy

(2:1:2) Æ 2MeCN (22). More subtle are the forms found in

3.3.4. The AgX:dppp:L (2:1:2) complexes (19–21) (ÆnS)

Here with the inability of the ligand to adopt any (quasi-)

centrosymmetric conformation (as is also the case with

dpem), a diversity of forms is found (Fig. 6; Table 3). Both

AgClO₄:dppp:dpa, bq (2:1:2) (19, 20) are cis-oid with one

formula unit in the asymmetric unit of each structure,

whereas in the bq adduct the two silver atoms lie on the

one side of the CPCCCPC ligand spine ‘plane’, in such a

way that the extended quinolyls oriented oblique to the

spine can overlap intramolecularly, the dpa adduct has

the silver atoms disposed to either side and no intramolec-

ular ligand overlap is found. Close anion-silver approaches

are only found in the latter, presumably precluded by over-

laps, both intra- and inter-molecular, in the former.

3.3.2. The AgClO₄:dpee:L (2:1:2) complexes (10–18)

(ÆnS)

Expansion of the polymethylene chain from one to

two units between the pair of E atoms of the now dpee

ligands is accompanied by transformation of the [LAg-

(dpex)AgL] array from the tightly constrained cis array

predominant in the dpem complexes, to a form with a

more ﬂexible E(CH₂)₂E string and a less favourable

arrangement for the close intermolecular approach of

parallel aromatic L planes. The predominant form of

[LAg(dpee)AgL] observed is one in which one half of a

centrosymmetric entity comprises the asymmetric unit

of the structure, the centre of symmetry lying at the

mid point of the dpee ligand, the central C–C bond of

which exhibits a torsion necessarily 180ꢁ; the pair of L

ligands are well-removed from each other, their planes

stacking parallel to those of other inversion related mol-

ecules. Such is the situation with AgClO₄:dppe:bpy, bq,

dpa, dmp, tpy (10–14); AgClO₄:dpae:bpy, bq, (15, 17),

and the adduct of the mixed P/As dpdae ligand

Ph₂P(CH₂)₂AsPh₂in which, as usual, the E sites are

modelled as scrambled in AgClO₄:dpdae:dmp (2:1:2),

(18). In all of these except the tpy adduct, in which the

coordination number of the silver is elevated by the tri-

dentate ligand, the Ag coordination environment is aug-

mented by approaches of perchlorate anions, uni- or

semi-bidentate (Figs. 4 and 5; Table 3) or acetonitrile

(the latter accompanied in one case by a very distant

water molecule oxygen (dppe/dpa) (13 Æ 2MeCN Æ H₂O)),

The bridging role of tpy noted above is manifest in the

ﬁnal (2:1:2) example, unique of its type, in (AgClO₄:dppp:

tpy) (2:1:2)_(1|1), 21, in which, unlike the pair of (2:1:2)

NO₃/dpem adducts described above, in which the tpy

bridge a pair of silver atoms in intradimer mode, successive

Ag(P-dppp-P)Ag units are linked by pairs of bridging tpy

(Fig. 3; Table 3). Of further interest is the fact that, rather

than the central pyridyl of the tpy bridging in ‘crevice’

g²(p)-mode, one of the peripheral pyridyl nitrogens bridges

in g²(r,p) mode, pairs of silver atoms being linked by

pairs of such interactions: [. . .Ag(P-dppp-P)Ag((l-N⁰⁰)-

tpy)₂. . .]_(1|1)to form a single stranded polymer (the prop-

agator of which is the a translation), the silver atoms lying

cis-oid about the dppp string. In the AgN₂Ag ring Ag. . .Ag

are 4.1199(2), N. . .N 3.606(3), Ag–N (bridging) 2.505(2),

˚

3.168(2) (r); 2.391(2), 2.989(2) A.

Eﬀendy et al. / Inorganica Chimica Acta 360 (2007) 1388–1413

1413

[10] C. Di Nicola, Eﬀendy, F. Marchetti, C. Pettinari, B.W. Skelton,

A.H. White, Inorg. Chim. Acta 360 (2007) 1433.

4. Supplementary data

[11] Eﬀendy, F. Marchetti, C. Pettinari, R. Pettinari, B.W. Skelton, A.H.

White, Inorg. Chim. Acta 360 (2007) 1451.

[12] M.W. Senko, IsoPro Isotopic Abundance Simulator, v. 2.1; National

High Magnetic Field Laboratory, Los Alamos National Laboratory,

Los Alamos, NM.

Full .cif depositions, excluding structure factor ampli-

tudes, reside with the Cambridge Crystallographic Data

Centre, CCDC 295744–295772.

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Acknowledgement

Thanks are due to the University of Camerino for ﬁnan-

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Article Doi

Synthesis and structural characterization of adducts of silver(I) oxyanion salts, AgX (X = ClO4, NO3), with Ph2E(CH2)xEPh2 ('dpex'; E = P, As; x = 1-4) and oligodentate aromatic N-bases derivative of 2,2′-bipyridyl, 'L', AgX:dpex:L (2:1:2)

DOI: 10.1016/j.ica.2006.07.016

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Full text of DOI:10.1016/j.ica.2006.07.016

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