Silver(I) complexes of 2-(2-amino­eth­yl)pyridine: nitrate and perchlorate salts of bis­[μ-2-(2-amino­eth­yl)pyridine-κ²N:N′]disilver(I)

2-(2-Amino­eth­yl)pyridine (2-aep, C₇H₁₀N₂) acts as a bridging ligand in bis­[μ-2-(2-amino­eth­yl)pyridine-κ²N:N′]disilver(I) dinitrate, [Ag₂(2-aep)₂](NO₃)₂, and bis­[μ-2-(2-amino­eth­yl)­pyridine-κ²N:N′]disilver(I) diperchlorate, [Ag₂(2-aep)₂](ClO₄)₂. Both salts contain the dinuclear [Ag₂(2-aep)₂]²⁺ cation, which possesses a crystallographic inversion center. The Ag...Ag distance is 3.1163 (5) Å for the nitrate and 3.0923 (3) Å for the perchlorate salt, and may indicate a weak d¹⁰–d¹⁰ inter­action in each case. Essentially linear coordination of the Ag^I atom is perturbed by weak coordination to the anionic O atoms. These latter inter­actions organize the dinuclear cations into one-dimensional polymeric chains in the crystals of the two salts.

S1. Comment

The design of coordination polymers requires knowledge of geometrical and ligand atom preferences of the metal ion as well as the structural features of the ligand (Khlobystov et al., 2001). Ag^I, well known for its preference for linear coordination, can bind with bidentate ligands to form one-dimensional polymeric chains as well as ligand bridged dinuclear complexes. The observed stereochemistry and crystal structures are influenced by several factors: (i) metal–metal interaction indicated by an Ag···Ag distance in the range 2.8–3.4 Å; (ii) coordination shell expansion leading to coordination number 3 or higher, which may be accomplished through the coordination of an additional ligand or anions; (iii) non-covalent interactions with anions; (iv) π–π stacking interaction between aromatic groups.

We recently reported some Ag^I complexes with various isomers of aminomethylpyridines (amp; Sailaja & Rajasekharan, 2003; Sailaja & Rajasekharan, 2000), which illustrate the above factors. To study further the effect of anions on the structures through self-assembly processes, we have synthesized two complexes of Ag^I with 2-(2'-aminoethyl)pyridine (2-aep) and with NO₃⁻ and ClO₄⁻ as anions, viz. [Ag₂(2-aep)₂](NO₃)₂, (I), and [Ag₂(2-aep)₂](ClO₄)₂, (II). Even though 2-aep is the next higher homologue of 2-amp, the structures of the present Ag^I complexes are entirely different.

In both (I) and (II), the cationic part consists of a 12-membered ring with an inversion center, made up of two Ag atoms bridged by two 2-aep ligands in a head-to-tail fashion (Figs. 1 and 2). The Ag atoms are coordinated to the pyridine and amine groups from two different ligands in a nearly linear mode. The conformation of the 12-membered ring is such that there is a close contact between the two Ag atoms [3.1163 (5) Å for (I) and 3.0923 (3) Å for (II)]. There are additional weak interactions with two anionic O atoms [Ag–O = 2.7091 (18) and 2.8290 (19) Å for (I), and 2.8476 (15) and 2.9529 (15) Å for (II)]. These interactions, coming from two different anions, lead to the formation of anion-bridged one-dimensional chains of the dinuclear cations (Figs. 3 and 4). The chains are linked by a hydrogen bond between one H atom of the NH₂ group and a free O atom of the anions [N2···O3(1 + x, y, 1 + z) = 3.124 (3) Å and 146 (2)° for (I); N2···O3(1 − x, 1 − y, −z) = 3.162 (2) Å and 134 (2)° for (II)], the other H atom being hydrogen bonded to another free O atom of the anion within the chain itself [N2···O3(−x, 1 − y, 2 − z) = 3.195 (3) Å and 158 (2)° for (I); N2···O4 = 3.099 (2) Å and 164 (3)° for (II)]. With regard to the formation of the chains, (I) and (II) are exactly analogous to the structure of [Ag₂(8-aminoquinoline)₂](NO₃)₂, (III) (Schmidbaur et al., 1991), which contains a ten-membered cation ring [Ag–Ag = 3.035 (1) Å, Ag–O = 2.435 (2) Å and 2.728 (1) Å, and N—Ag—N = 152.6 (1)°].

It is instructive to compare the present structure with those of Ag^I complexes of the lower homologues of 2-aep, viz. 2-(aminomethyl)pyridine (2-amp) and 2-aminopyridine (2-apy). Both Ag(2-amp)NO₃, (IV) (Swarnabala & Rajasekharan, 1997), and Ag(2-amp)ClO₄, (V) (Sailaja & Rajasekharan, 2000), form one-dimensional ligand bridged chains. Weak coordination with the anion is observed in the structures but there is no Ag–Ag bonding. In the case of 2-apy, complexes with Ag^I carboxylates have been characterized (You & Zhu, 2004). Generally, the aromatic amine group does not coordinate because of its low basicity. However, the structure of [Ag₂(2-apy)₂](CF₃COO)₂, (VI), contains an eight-membered dication ring with three-coordinate Ag and a close Ag···Ag contact. An important feature of two-coordinate Ag^I complexes in the solid state is coordination to anions. The range of interaction extends from weak non-covalent to covalent character as seen from the following data for the above-mentioned compounds: Ag—O (Å) and N—Ag—N (°) for (I): 2.709 (2) and 167.92 (6); (II): 2.848 (2) and 171.48 (6); (III): 2.435 (2) and 152.6 (1); (IV): 2.72 (3) and 164.9 (2); (V): 2.732 (3) and 171.0 (1); (VI): 2.384 (3) and 134.0 (1). The deviation of the N—Ag—N group from linearity correlates with the strength of the Ag–O interaction. In (VI), where the Ag–O bond is the strongest, the coordination geometry is close to trigonal planar.

The nature of d¹⁰–d¹⁰ interactions in AgI complexes has been reviewed elsewhere (Sailaja & Rajasekharan, 2003). Even though there is no need to propose an Ag–Ag bond in dibridged structures, the interaction between two Ag⁺ complex ions at distances less than two times of the van der Waals radius of Ag (1.72 Å; Bondi, 1964) is, no doubt, an attractive one.

S2. Experimental

For the preparation of [Ag₂(2-aep)₂](NO₃)₂, to an acetonitrile solution (5 ml) of AgNO₃ (0.169 g, 1.00 mmol), 2-aep (0.12 ml, 1.0 mmol) was added slowly with constant stirring. The white precipitate formed was filtered off and dried. It was re-dissolved in acetonitrile, and the solution was allowed to evaporate at low temperature (288 K) to yield colorless crystals suitable for X-ray data collection. Yield 0.18 g (0.62 mmol, 62%). Analysis calculated for C₁₄H₂₀Ag₂N₆O₆ (584.10): C 28.78, H 3.45, N 14.48%; found: C 29.37, H 3.53, N 13.99%. IR (KBr disk, cm⁻¹): 3258, 1595, 1477, 1375, 1035, 991, 825, 765, 588. For the preparation of [Ag₂(2-aep)₂](ClO₄)₂, to an aqueous solution (10 ml) of AgClO₄·H₂O (0.225 g, 1.00 mmol), 2-aep (0.12 ml, 1.0 mmol) was added slowly with constant stirring. The white precipitate formed was filtered off and dried. It was re-dissolved in acetonitrile, and the solution was allowed to evaporate at low temperature (288 K) to produce colorless crystals suitable for X-ray data collection. Yield 0.20 g (0.60 mmol, 60%). Analysis calculated for C₁₄H₂₀Ag₂Cl₂N₄O₈ (658.98): C 25.52, H 3.06, N 8.50%; found: C 24.76, H 2.98, N 7.95%. IR (KBr disk, cm⁻¹): 3308, 1595, 1477, 1437, 1392, 1305, 1039, 765, 520.

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989) for (I); SMART (Bruker, 2000) for (II). Cell refinement: CAD-4 Software for (I); SMART for (II). Data reduction: Xtal3.5 (Hall et al., 1995) for (I); SAINT (Bruker, 2000) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. An ORTEP-3 view (Farrugia, 1997) of [Ag2(2-aep)2](NO3)2. Displacement ellipsoids are shown at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 2 − z.]
	Fig. 2. An ORTEP-3 view (Farrugia, 1997) of [Ag2(2-aep)2](ClO4)2. Displacement ellipsoids are shown at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 1 − z.]
	Fig. 3. The polymeric chain in (I), showing weak contacts between [Ag2(2-aep)2]^2+ and NO3^− units. Atoms are shown as circles of increasing size in the order C, N, O, Ag. H atoms have been omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 2 − z.]
	Fig. 4. A polymeric chain in (II), showing weak contacts between [Ag2(2-aep)2]^2+ and ClO4^− units. Atoms are shown as circles of increasing size in the order C, N, O, Cl, Ag. H atoms have been omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 1 − z.]

(I) bis[µ-2-(2-aminoethyl)pyridine-κ²N:N']disilver(I) dinitrate

Crystal data

[Ag2(C7H10N2)2](NO3)2	Z = 1
Mr = 584.10	F(000) = 288
Triclinic, P1	Dx = 2.133 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5983 (9) Å	Cell parameters from 25 reflections
b = 7.8834 (10) Å	θ = 9.0–10.7°
c = 8.2843 (10) Å	µ = 2.20 mm^−1
α = 96.126 (10)°	T = 298 K
β = 108.37 (1)°	Needle, colorless
γ = 101.011 (10)°	0.60 × 0.24 × 0.24 mm
V = 454.80 (10) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	1945 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
Tmin = 0.545, Tmax = 0.590	l = −10→10
2109 measured reflections	3 standard reflections every 250 reflections
2070 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.047	w = 1/[σ^2(Fo^2) + (0.0239P)^2 + 0.2512P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2070 reflections	Δρmax = 0.45 e Å^−3
136 parameters	Δρmin = −0.30 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0382 (15)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ag	0.34583 (2)	0.60123 (2)	0.92022 (2)	0.04171 (8)
C1	0.2589 (3)	0.8861 (3)	1.1364 (3)	0.0376 (4)
H1	0.1369	0.8173	1.0749	0.045*
C2	0.2780 (3)	1.0387 (3)	1.2435 (3)	0.0406 (4)
H2	0.1706	1.0732	1.2527	0.049*
C3	0.4578 (3)	1.1401 (3)	1.3371 (3)	0.0414 (5)
H3	0.4743	1.2442	1.4104	0.050*
C4	0.6125 (3)	1.0844 (3)	1.3199 (3)	0.0378 (4)
H4	0.7355	1.1504	1.3828	0.045*
C5	0.5857 (3)	0.9295 (2)	1.2087 (2)	0.0305 (4)
C6	0.7521 (3)	0.8646 (3)	1.1898 (3)	0.0381 (4)
H6A	0.8526	0.9643	1.1960	0.046*
H6B	0.7129	0.7916	1.0767	0.046*
C7	0.8310 (3)	0.7596 (3)	1.3272 (3)	0.0396 (4)
H7A	0.9509	0.7391	1.3212	0.048*
H7B	0.8566	0.8273	1.4404	0.048*
N1	0.4094 (2)	0.8320 (2)	1.1167 (2)	0.0321 (3)
N2	0.6977 (3)	0.5891 (2)	1.3062 (2)	0.0359 (4)
N3	−0.1563 (2)	0.5617 (2)	0.7599 (2)	0.0350 (3)
O1	−0.0192 (2)	0.6394 (3)	0.7243 (2)	0.0575 (5)
O2	−0.1627 (3)	0.5971 (2)	0.9067 (2)	0.0651 (6)
O3	−0.2896 (3)	0.4538 (3)	0.6497 (2)	0.0710 (6)
H8A	0.592 (4)	0.607 (3)	1.312 (3)	0.037 (6)*
H8B	0.748 (4)	0.546 (4)	1.398 (4)	0.045 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag	0.04567 (11)	0.03604 (11)	0.03496 (10)	0.00979 (7)	0.00622 (7)	−0.00590 (6)
C1	0.0293 (9)	0.0366 (10)	0.0410 (11)	0.0019 (8)	0.0086 (8)	0.0033 (8)
C2	0.0385 (11)	0.0396 (11)	0.0462 (12)	0.0112 (9)	0.0178 (9)	0.0048 (9)
C3	0.0494 (12)	0.0306 (10)	0.0392 (11)	0.0056 (9)	0.0135 (9)	−0.0027 (8)
C4	0.0362 (10)	0.0321 (10)	0.0353 (10)	−0.0016 (8)	0.0064 (8)	−0.0001 (8)
C5	0.0317 (9)	0.0301 (9)	0.0279 (9)	0.0031 (7)	0.0096 (7)	0.0076 (7)
C6	0.0341 (10)	0.0394 (11)	0.0421 (11)	0.0050 (8)	0.0172 (8)	0.0065 (9)
C7	0.0319 (10)	0.0407 (11)	0.0382 (10)	0.0077 (8)	0.0047 (8)	−0.0020 (8)
N1	0.0340 (8)	0.0276 (7)	0.0299 (8)	0.0020 (6)	0.0088 (6)	0.0017 (6)
N2	0.0403 (9)	0.0380 (9)	0.0290 (8)	0.0118 (7)	0.0105 (7)	0.0043 (7)
N3	0.0331 (8)	0.0346 (8)	0.0355 (8)	0.0090 (7)	0.0089 (7)	0.0058 (7)
O1	0.0402 (9)	0.0774 (13)	0.0589 (11)	0.0088 (8)	0.0239 (8)	0.0177 (9)
O2	0.0835 (14)	0.0602 (12)	0.0480 (10)	−0.0062 (10)	0.0358 (10)	−0.0038 (9)
O3	0.0676 (12)	0.0726 (13)	0.0433 (10)	−0.0194 (10)	0.0032 (9)	0.0001 (9)

Geometric parameters (Å, º)

Ag—N2^i	2.1671 (18)	C5—N1	1.343 (2)
Ag—N1	2.1747 (17)	C5—C6	1.497 (3)
Ag—O2^ii	2.7091 (18)	C6—C7	1.517 (3)
Ag—O1	2.8290 (19)	C6—H6A	0.9700
Ag—Ag^i	3.1163 (5)	C6—H6B	0.9700
C1—N1	1.343 (3)	C7—N2	1.477 (3)
C1—C2	1.371 (3)	C7—H7A	0.9700
C1—H1	0.9300	C7—H7B	0.9700
C2—C3	1.374 (3)	N2—Ag^i	2.1671 (18)
C2—H2	0.9300	N2—H8A	0.85 (3)
C3—C4	1.373 (3)	N2—H8B	0.88 (3)
C3—H3	0.9300	N3—O3	1.227 (2)
C4—C5	1.388 (3)	N3—O2	1.237 (2)
C4—H4	0.9300	N3—O1	1.240 (2)
N2^i—Ag—N1	167.92 (6)	C5—C6—C7	112.98 (17)
N2^i—Ag—O2^ii	101.16 (6)	C5—C6—H6A	109.0
N1—Ag—O2^ii	90.65 (6)	C7—C6—H6A	109.0
N2^i—Ag—O1	83.20 (7)	C5—C6—H6B	109.0
N1—Ag—O1	95.26 (6)	C7—C6—H6B	109.0
O2^ii—Ag—O1	85.98 (6)	H6A—C6—H6B	107.8
N2^i—Ag—Ag^i	80.41 (5)	N2—C7—C6	112.17 (17)
N1—Ag—Ag^i	104.28 (5)	N2—C7—H7A	109.2
O2^ii—Ag—Ag^i	80.51 (5)	C6—C7—H7A	109.2
O1—Ag—Ag^i	156.25 (4)	N2—C7—H7B	109.2
N1—C1—C2	122.65 (19)	C6—C7—H7B	109.2
N1—C1—H1	118.7	H7A—C7—H7B	107.9
C2—C1—H1	118.7	C5—N1—C1	118.58 (17)
C1—C2—C3	119.2 (2)	C5—N1—Ag	124.74 (13)
C1—C2—H2	120.4	C1—N1—Ag	116.49 (13)
C3—C2—H2	120.4	C7—N2—Ag^i	115.73 (13)
C4—C3—C2	118.56 (19)	C7—N2—H8A	109.3 (17)
C4—C3—H3	120.7	Ag^i—N2—H8A	112.0 (17)
C2—C3—H3	120.7	C7—N2—H8B	105.2 (19)
C3—C4—C5	120.08 (19)	Ag^i—N2—H8B	108.3 (18)
C3—C4—H4	120.0	H8A—N2—H8B	106 (2)
C5—C4—H4	120.0	O3—N3—O2	119.23 (19)
N1—C5—C4	120.94 (18)	O3—N3—O1	120.9 (2)
N1—C5—C6	117.98 (17)	O2—N3—O1	119.84 (19)
C4—C5—C6	121.07 (18)	N3—O1—Ag	116.62 (14)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H8B···O3^iii	0.88 (3)	2.36 (3)	3.124 (3)	146 (2)
N2—H8A···O3^ii	0.86 (3)	2.38 (3)	3.195 (3)	158 (2)

Symmetry codes: (ii) −x, −y+1, −z+2; (iii) x+1, y, z+1.

(II) bis[µ-2-(2-aminoethyl)pyridine-κ²N:N']disilver(I) diperchlorate

Crystal data

[Ag2(C7H10N2)2](ClO4)2	Z = 1
Mr = 658.98	F(000) = 324
Triclinic, P1	Dx = 2.199 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9933 (5) Å	Cell parameters from 5208 reflections
b = 8.0990 (5) Å	θ = 2.5–28.3°
c = 8.4726 (5) Å	µ = 2.29 mm^−1
α = 98.294 (1)°	T = 100 K
β = 97.990 (1)°	Needle, colorless
γ = 110.495 (1)°	0.30 × 0.27 × 0.18 mm
V = 497.67 (5) Å^3

Data collection

Bruker SMART CCD area detector diffractometer	2336 independent reflections
Radiation source: sealed tube	2304 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ϕ and ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.514, Tmax = 0.662	k = −10→10
5743 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0257P)^2 + 0.2891P] where P = (Fo^2 + 2Fc^2)/3
2336 reflections	(Δ/σ)max = 0.002
144 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.69 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ag	0.61995 (2)	0.41385 (2)	0.58872 (2)	0.01498 (6)
C1	0.7366 (2)	0.1531 (2)	0.3848 (2)	0.0158 (3)
H1	0.8516	0.2350	0.4475	0.019*
C2	0.7303 (3)	0.0035 (2)	0.2801 (2)	0.0168 (3)
H2	0.8382	−0.0191	0.2730	0.020*
C3	0.5627 (3)	−0.1139 (2)	0.1848 (2)	0.0168 (3)
H3	0.5544	−0.2178	0.1108	0.020*
C4	0.4080 (3)	−0.0772 (2)	0.1993 (2)	0.0152 (3)
H4	0.2928	−0.1550	0.1341	0.018*
C5	0.4228 (2)	0.0745 (2)	0.3100 (2)	0.0126 (3)
C6	0.2573 (2)	0.1177 (2)	0.3280 (2)	0.0144 (3)
H6A	0.2830	0.2013	0.4338	0.017*
H6B	0.1543	0.0056	0.3284	0.017*
C7	0.2024 (2)	0.2030 (2)	0.1913 (2)	0.0147 (3)
H7A	0.1874	0.1245	0.0851	0.018*
H7B	0.0836	0.2127	0.1987	0.018*
N1	0.5861 (2)	0.1884 (2)	0.40234 (18)	0.0133 (3)
N2	0.3407 (2)	0.3847 (2)	0.19942 (19)	0.0135 (3)
Cl	0.87035 (5)	0.56783 (5)	0.21678 (5)	0.01297 (9)
O1	0.8184 (2)	0.6206 (2)	0.36711 (17)	0.0250 (3)
O2	1.0143 (2)	0.5031 (2)	0.2502 (2)	0.0279 (3)
O3	0.9306 (2)	0.72075 (19)	0.14083 (17)	0.0225 (3)
O4	0.71336 (18)	0.42709 (19)	0.10729 (17)	0.0211 (3)
H8A	0.441 (4)	0.383 (4)	0.189 (3)	0.029 (7)*
H8B	0.305 (4)	0.424 (4)	0.113 (4)	0.029 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag	0.01605 (9)	0.01257 (8)	0.01472 (8)	0.00599 (6)	0.00019 (5)	−0.00072 (5)
C1	0.0133 (8)	0.0163 (8)	0.0168 (8)	0.0053 (7)	0.0009 (6)	0.0036 (7)
C2	0.0143 (8)	0.0175 (8)	0.0203 (9)	0.0073 (7)	0.0046 (7)	0.0046 (7)
C3	0.0193 (9)	0.0144 (8)	0.0166 (8)	0.0071 (7)	0.0042 (7)	0.0006 (7)
C4	0.0150 (8)	0.0141 (8)	0.0153 (8)	0.0048 (7)	0.0021 (6)	0.0016 (6)
C5	0.0127 (8)	0.0126 (8)	0.0131 (8)	0.0048 (6)	0.0025 (6)	0.0046 (6)
C6	0.0135 (8)	0.0132 (8)	0.0170 (8)	0.0057 (6)	0.0040 (6)	0.0028 (6)
C7	0.0125 (8)	0.0130 (8)	0.0170 (8)	0.0047 (6)	0.0004 (6)	0.0007 (6)
N1	0.0137 (7)	0.0115 (7)	0.0134 (7)	0.0044 (6)	0.0016 (5)	0.0014 (5)
N2	0.0121 (7)	0.0132 (7)	0.0144 (7)	0.0045 (6)	0.0021 (6)	0.0018 (6)
Cl	0.01122 (19)	0.01351 (19)	0.01329 (19)	0.00509 (15)	0.00084 (14)	0.00058 (15)
O1	0.0300 (8)	0.0270 (8)	0.0166 (7)	0.0094 (6)	0.0094 (6)	−0.0009 (6)
O2	0.0208 (7)	0.0290 (8)	0.0371 (9)	0.0175 (6)	−0.0012 (6)	0.0034 (7)
O3	0.0251 (7)	0.0169 (7)	0.0228 (7)	0.0040 (6)	0.0040 (6)	0.0069 (6)
O4	0.0148 (6)	0.0194 (7)	0.0200 (7)	0.0002 (5)	−0.0013 (5)	−0.0028 (5)

Geometric parameters (Å, º)

Ag—N1	2.1458 (15)	C5—C6	1.503 (2)
Ag—N2^i	2.1498 (16)	C6—C7	1.521 (2)
Ag—O2^ii	2.8476 (15)	C6—H6A	0.9900
Ag—O1	2.9529 (15)	C6—H6B	0.9900
Ag—Ag^i	3.0923 (3)	C7—N2	1.485 (2)
C1—N1	1.353 (2)	C7—H7A	0.9900
C1—C2	1.375 (3)	C7—H7B	0.9900
C1—H1	0.9500	N2—Ag^i	2.1498 (15)
C2—C3	1.392 (3)	N2—H8A	0.83 (3)
C2—H2	0.9500	N2—H8B	0.89 (3)
C3—C4	1.386 (3)	Cl—O2	1.4336 (14)
C3—H3	0.9500	Cl—O3	1.4416 (14)
C4—C5	1.393 (2)	Cl—O1	1.4465 (14)
C4—H4	0.9500	Cl—O4	1.4506 (13)
C5—N1	1.353 (2)
N1—Ag—N2^i	171.48 (6)	C7—C6—H6A	109.2
N1—Ag—O2^ii	99.77 (5)	C5—C6—H6B	109.2
N2^i—Ag—O2^ii	76.42 (5)	C7—C6—H6B	109.2
N1—Ag—O1	82.61 (5)	H6A—C6—H6B	107.9
N2^i—Ag—O1	104.00 (5)	N2—C7—C6	111.63 (14)
O2^ii—Ag—O1	80.22 (5)	N2—C7—H7A	109.3
N1—Ag—Ag^i	101.34 (4)	C6—C7—H7A	109.3
N2^i—Ag—Ag^i	86.09 (4)	N2—C7—H7B	109.3
O2^ii—Ag—Ag^i	141.05 (3)	C6—C7—H7B	109.3
O1—Ag—Ag^i	70.56 (3)	H7A—C7—H7B	108.0
N1—C1—C2	122.80 (17)	C1—N1—C5	118.77 (15)
N1—C1—H1	118.6	C1—N1—Ag	117.23 (12)
C2—C1—H1	118.6	C5—N1—Ag	123.86 (12)
C1—C2—C3	118.64 (17)	C7—N2—Ag^i	116.08 (11)
C1—C2—H2	120.7	C7—N2—H8A	113.2 (19)
C3—C2—H2	120.7	Ag^i—N2—H8A	108.3 (19)
C4—C3—C2	119.09 (17)	C7—N2—H8B	107.5 (18)
C4—C3—H3	120.5	Ag^i—N2—H8B	106.9 (18)
C2—C3—H3	120.5	H8A—N2—H8B	104 (3)
C3—C4—C5	119.54 (17)	O2—Cl—O3	109.92 (9)
C3—C4—H4	120.2	O2—Cl—O1	109.69 (10)
C5—C4—H4	120.2	O3—Cl—O1	109.39 (9)
N1—C5—C4	121.13 (16)	O2—Cl—O4	109.85 (9)
N1—C5—C6	118.21 (15)	O3—Cl—O4	108.77 (9)
C4—C5—C6	120.65 (16)	O1—Cl—O4	109.20 (9)
C5—C6—C7	112.02 (14)	Cl—O1—Ag	132.94 (9)
C5—C6—H6A	109.2

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H8B···O3^iii	0.89 (3)	2.48 (3)	3.162 (2)	134 (2)
N2—H8A···O4	0.83 (3)	2.30 (3)	3.099 (2)	164 (3)

Symmetry code: (iii) −x+1, −y+1, −z.