Complexes of Ag^I with cationic ligands: bis[(pyridylmethyl)ammonio]silver(I) salts

Bis­[(2-pyridyl­methyl)­ammonio]silver(I) trinitrate, [Ag(C₆H₉N₂)₂](NO₃)₃, (I), and bis{bis­[(4-pyridyl­methyl)­ammonio]silver(I)} hexakis­(perchlorate) dihydrate, [Ag(C₆H₉N₂)₂]₂(ClO₄)₆·2H₂O, (II), are rare examples of complexes with cationic ligands. In (I), the Ag⁺ cation has a T-shaped [2+1] coordination involving the pyridine N atoms and a nitrate O atom, while in (II) there are three independent two-coordinate Ag complex cations (two with the Ag atoms on independent inversion centres) and disordered ClO₄^- ions. The crystal structures reveal the role of hydrogen bonding in stabilizing these complexes.

S1. Comment

Cationic ligands are much less common than anionic or neutral ligands. Examples for which structurally characterized metal complexes are known belong to four categories: (i) the well known tropylium cation (Cotton & Wilkinson, 1988), (ii) thiamine-substituted ligands (Louloudi & Hadjiliadis, 1994), (iii) the quaternary ammonium ion, N(CH₂CH₂)₃NH⁺ (Stucky & Ross, 1969) and (iv) the protonated phosphinoalkyl amine, (Ph₂PCH₂CH₂)₃NH⁺ (Cecconi et al., 1984). Protonation of the primary amine side-chain of an N-heterocyclic compound leads to another class of such ligands. Complexes of these ligands are expected to have added stability due to hydrogen bonding with anions. In this paper, we report the crystal structures of two such complexes, (I) and (II). \sch

The asymmetric unit of compound (I) is made up of two protonated ligands bound to Ag with a near-linear geometry [N1—Ag—N3 165.76 (11)°]. A nitrate O atom is also weakly bonded to Ag, leading to a T-shaped AgN₂O coordination, with all four atoms nearly coplanar [r.m.s. deviation for the mean plane 0.041 Å]. All non-H atoms in the two aromatic ligands, except one ammonium N (N2) and the Ag atom, form another mean plane with r.m.s. deviation 0.056 Å. What is remarkable is that the two ligands are in a `syn' configuration, which brings the two –NH₃⁺ groups close together. This seemingly less stable arrangement is stabilized by an array of NO₃^- ions arranged in a semi-circular fashion around the –NH₃⁺ groups, forming numerous hydrogen bonds (Table 2).

The asymmetric unit of compound (II) contains three Ag atoms. Ag1 and Ag3 are situated on inversion centres and are coordinated to two protonated ligands, whereas Ag2 is coordinated to two crystallographically independent protonated ligands, with a linear geometry [N3—Ag2—N5 174.8 (3)°] around Ag2. There are six anions in the unit cell and all were found to be disordered. The disorder was modelled by splitting each perchlorate O atom into two parts, which were refined isotropically. As in the case of (I), all 18 NH₃⁺ H atoms in (II) are involved in hydrogen-bonding interactions with the anions.

In both structures, the number of potential hydrogen-bond acceptor atoms is higher than the number of `acidic' H atoms. This leads to numerous three-centre (bifurcated-donor type) hydrogen-bonds. However, the available number of acceptor atoms is limited by crystal-packing constraints. In (I), six out of nine O atoms, and in (II), nine out of 24 ClO₄^- O atoms and two water O atoms, are able to act as acceptors. In contrast with the usual situation where hydrogen-bonding inhibits positional disorder, all the ClO₄^- ions in (II) are disordered. It appears that this unusual situation is a consequence of the small number of available acceptors.

S2. Experimental

Compound (I) was synthesized by slowly adding, with stirring, a solution of 2-amp [0.2 ml, 1.9 mmol; amp is (aminomethyl)pyridine] in 0.1 N HNO₃ (5 ml) to an aqueous solution of AgNO₃ (5 ml; 0.108 g, 0.64 mmol). Crystals of (I) were obtained by leaving the solution at 277 K for a few days. Identical crystals were also obtained when Ag(2-amp)NO₃ (Swarnabala & Rajasekharan, 1997) was recrystallized from 0.1 N HNO₃. Compound (II) was synthesized by dissolving polymeric Ag(4-amp)ClO₄·0.5H₂O (Sailaja & Rajasekharan, 2000) in 0.1 N HClO₄. Single crystals of (II) were obtained by slow evaporation of the acid solution at 277 K.

S3. Refinement

For compound (I), –NH₃ H atoms were located from difference maps and refined isotropically. Other H atoms were located by geometrical considerations and refined using a riding model with common isotropic displacement parameters, which were refined. For compound (II), H₂O H atoms were located from difference maps and bond length constraints were applied. All other H atoms were located by geometrical considerations and refined using a riding model. U_iso values for –NH₃ H atoms were refined; other H atoms were assigned fixed U_iso values, equal to 1.2U_eq of the parent atom for ring atoms, and 1.5U_eq for –CH₂ and H₂0.

Computing details

For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: Xtal3.5 (Hall et al., 19??); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and ring H atoms have been omitted for clarity. Important hydrogen bonds are shown as broken lines [symmetry codes: (i) -x, 1/2 + y, 1/2 - z; (ii) 1 + x, y, z; (iii) 1 + x, 1/2 - y, 1/2 + z].

Fig. 2. The molecular structures of the three different complex cations in (II) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and ring H atoms have been omitted for clarity. Only one part of each disordered ClO4^- ion is shown, with the disordered O atoms represented by circles. Important hydrogen bonds are shown as broken lines. In (a), symmetry code: (i) - x, 1 - y, 1 - z. In (b), symmetry codes: (i) 1 - x, y - 1, z; (ii) - x, 1 - y, - z; (iii) 1 - x, - y, -z; (iv) x - 1, y, z. In (c), symmetry code: (i) 1 - x, 1 - y, -z.

(I) Bis[(2-pyridylmethyl)ammonio]silver(I) trinitrate

Crystal data

[Ag(C6H9N2)2](NO3)3	F(000) = 1032
Mr = 512.20	Dx = 1.828 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.854 (2) Å	Cell parameters from 25 reflections
b = 19.752 (12) Å	θ = 7.8–13.7°
c = 10.662 (7) Å	µ = 1.15 mm^−1
β = 93.66 (3)°	T = 293 K
V = 1860.7 (16) Å^3	Rhombic, light yellow
Z = 4	0.45 × 0.25 × 0.09 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	2655 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.049
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
ω/2θ scans	h = 0→10
Absorption correction: semi-empirical (using intensity measurements) (North et al., 1968)	k = 0→23
Tmin = 0.831, Tmax = 0.999	l = −12→12
3481 measured reflections	2 standard reflections every 60 min
3259 independent reflections	intensity decay: none

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0425P)^2 + 1.9184P] where P = (Fo^2 + 2Fc^2)/3
3259 reflections	(Δ/σ)max = 0.044
288 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.65 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	0.16524 (3)	0.027372 (15)	0.41011 (3)	0.05162 (13)
C1	−0.0620 (5)	0.0200 (2)	0.1803 (4)	0.0582 (11)
H1	−0.0353	−0.0253	0.1904	0.070 (5)*
C2	−0.1724 (5)	0.0364 (2)	0.0903 (4)	0.0690 (13)
H2	−0.2206	0.0029	0.0412	0.070 (5)*
C3	−0.2108 (6)	0.1032 (2)	0.0738 (4)	0.0698 (13)
H3	−0.2849	0.1158	0.0124	0.070 (5)*
C4	−0.1388 (5)	0.1510 (2)	0.1487 (4)	0.0560 (10)
H4	−0.1639	0.1965	0.1386	0.070 (5)*
C5	−0.0290 (4)	0.13172 (19)	0.2391 (3)	0.0426 (8)
C6	0.0601 (4)	0.1810 (2)	0.3210 (4)	0.0536 (10)
H61	0.1069	0.1567	0.3923	0.100 (9)*
H62	0.1407	0.1994	0.2737	0.100 (9)*
N1	0.0102 (4)	0.06633 (15)	0.2551 (3)	0.0459 (7)
N2	−0.0269 (5)	0.2374 (2)	0.3682 (4)	0.0568 (9)
HN21	0.028 (5)	0.262 (2)	0.419 (4)	0.059 (13)*
HN22	−0.106 (7)	0.224 (3)	0.398 (6)	0.10 (2)*
HN23	−0.046 (7)	0.265 (3)	0.293 (6)	0.11 (2)*
C7	0.3756 (5)	−0.0471 (2)	0.6074 (4)	0.0499 (9)
H7	0.3336	−0.0835	0.5622	0.070 (5)*
C8	0.4807 (5)	−0.0600 (2)	0.7042 (4)	0.0566 (10)
H8	0.5080	−0.1043	0.7249	0.070 (5)*
C9	0.5453 (5)	−0.0065 (3)	0.7701 (4)	0.0650 (12)
H9	0.6186	−0.0136	0.8352	0.070 (5)*
C10	0.4980 (5)	0.0586 (2)	0.7370 (4)	0.0578 (10)
H10	0.5392	0.0958	0.7805	0.070 (5)*
C11	0.3910 (4)	0.06781 (18)	0.6405 (3)	0.0422 (8)
C12	0.3300 (4)	0.1356 (2)	0.5964 (4)	0.0533 (10)
H121	0.3414	0.1392	0.5068	0.100 (9)*
H122	0.2225	0.1369	0.6090	0.100 (9)*
N3	0.3305 (3)	0.01547 (14)	0.5747 (3)	0.0423 (7)
N4	0.3997 (7)	0.1939 (2)	0.6569 (5)	0.0676 (12)
HN41	0.349 (5)	0.231 (3)	0.627 (5)	0.075 (15)*
HN42	0.488 (5)	0.190 (2)	0.641 (4)	0.046 (14)*
HN43	0.402 (9)	0.195 (4)	0.739 (8)	0.17 (3)*
N5	0.0842 (3)	−0.12816 (16)	0.3587 (3)	0.0477 (7)
O1	0.0283 (4)	−0.18583 (14)	0.3591 (3)	0.0630 (8)
O2	0.0596 (4)	−0.08920 (16)	0.4471 (3)	0.0742 (9)
O3	0.1592 (4)	−0.10885 (19)	0.2743 (4)	0.0903 (11)
N6	−0.4092 (4)	0.23671 (17)	0.3996 (3)	0.0528 (8)
O4	−0.3367 (4)	0.20896 (16)	0.4883 (3)	0.0740 (9)
O5	−0.5491 (3)	0.2297 (2)	0.3843 (3)	0.0778 (10)
O6	−0.3456 (4)	0.2711 (3)	0.3228 (4)	0.1099 (16)
N7	0.2617 (5)	0.33928 (19)	0.4896 (4)	0.0654 (10)
O7	0.2004 (3)	0.29058 (15)	0.5438 (3)	0.0623 (7)
O8	0.3710 (7)	0.3670 (3)	0.5395 (5)	0.156 (2)
O9	0.2118 (5)	0.3544 (2)	0.3830 (4)	0.0898 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag	0.0532 (2)	0.04857 (19)	0.0504 (2)	0.00171 (14)	−0.01792 (13)	0.00329 (13)
C1	0.069 (3)	0.049 (2)	0.054 (2)	0.0050 (19)	−0.015 (2)	−0.0080 (18)
C2	0.077 (3)	0.063 (3)	0.063 (3)	0.000 (2)	−0.030 (2)	−0.012 (2)
C3	0.074 (3)	0.067 (3)	0.063 (3)	0.001 (2)	−0.036 (2)	0.005 (2)
C4	0.057 (2)	0.050 (2)	0.057 (2)	−0.0014 (19)	−0.020 (2)	0.0105 (19)
C5	0.043 (2)	0.045 (2)	0.0392 (19)	−0.0037 (16)	−0.0034 (15)	0.0041 (16)
C6	0.047 (2)	0.044 (2)	0.068 (3)	0.0006 (17)	−0.0184 (19)	−0.0016 (19)
N1	0.0480 (17)	0.0453 (18)	0.0425 (16)	0.0020 (14)	−0.0112 (13)	0.0009 (13)
N2	0.048 (2)	0.059 (2)	0.063 (2)	−0.0087 (18)	−0.0056 (19)	−0.0089 (19)
C7	0.053 (2)	0.042 (2)	0.053 (2)	0.0025 (17)	−0.0068 (18)	0.0002 (17)
C8	0.065 (3)	0.046 (2)	0.057 (2)	0.0149 (19)	−0.011 (2)	0.0041 (19)
C9	0.064 (3)	0.070 (3)	0.059 (3)	0.017 (2)	−0.021 (2)	0.001 (2)
C10	0.053 (2)	0.054 (2)	0.064 (3)	0.0071 (19)	−0.019 (2)	−0.009 (2)
C11	0.0358 (18)	0.042 (2)	0.048 (2)	0.0011 (15)	−0.0056 (15)	0.0001 (16)
C12	0.050 (2)	0.042 (2)	0.066 (3)	−0.0048 (17)	−0.0090 (19)	0.0009 (18)
N3	0.0409 (16)	0.0410 (17)	0.0439 (17)	0.0003 (13)	−0.0060 (13)	0.0015 (13)
N4	0.094 (4)	0.046 (2)	0.059 (3)	0.009 (2)	−0.024 (2)	−0.0070 (18)
N5	0.0426 (17)	0.0441 (18)	0.055 (2)	0.0016 (14)	−0.0045 (15)	0.0032 (16)
O1	0.077 (2)	0.0378 (15)	0.0721 (19)	−0.0099 (14)	−0.0151 (15)	−0.0010 (13)
O2	0.074 (2)	0.0646 (19)	0.085 (2)	−0.0126 (16)	0.0170 (18)	−0.0297 (18)
O3	0.088 (3)	0.086 (2)	0.101 (3)	0.007 (2)	0.043 (2)	0.021 (2)
N6	0.0470 (19)	0.0443 (18)	0.066 (2)	0.0008 (15)	−0.0022 (16)	0.0073 (16)
O4	0.0638 (19)	0.066 (2)	0.088 (2)	0.0087 (16)	−0.0266 (17)	0.0169 (18)
O5	0.0440 (17)	0.112 (3)	0.077 (2)	0.0048 (17)	0.0005 (15)	0.035 (2)
O6	0.057 (2)	0.153 (4)	0.120 (3)	−0.011 (2)	0.007 (2)	0.067 (3)
N7	0.082 (3)	0.049 (2)	0.063 (2)	−0.0161 (19)	−0.012 (2)	−0.0028 (18)
O7	0.0666 (19)	0.0564 (17)	0.0646 (18)	0.0010 (15)	0.0089 (15)	0.0075 (14)
O8	0.179 (5)	0.143 (4)	0.135 (4)	−0.100 (4)	−0.067 (4)	−0.006 (3)
O9	0.103 (3)	0.083 (3)	0.080 (2)	−0.007 (2)	−0.020 (2)	0.029 (2)

Geometric parameters (Å, º)

Ag—N1	2.217 (3)	C9—C10	1.390 (7)
Ag—N3	2.224 (3)	C10—C11	1.366 (5)
Ag—O2	2.526 (3)	C11—N3	1.342 (5)
C1—N1	1.349 (5)	C11—C12	1.508 (5)
C1—C2	1.364 (6)	C12—N4	1.439 (5)
C2—C3	1.371 (6)	N5—O3	1.214 (4)
C3—C4	1.368 (6)	N5—O1	1.242 (4)
C4—C5	1.378 (5)	N5—O2	1.247 (4)
C5—N1	1.346 (5)	N6—O6	1.229 (5)
C5—C6	1.499 (5)	N6—O4	1.236 (4)
C6—N2	1.460 (5)	N6—O5	1.247 (4)
C7—N3	1.338 (5)	N7—O8	1.206 (5)
C7—C8	1.369 (6)	N7—O9	1.229 (5)
C8—C9	1.375 (6)	N7—O7	1.263 (5)
N1—Ag—N3	165.76 (11)	N3—C11—C10	121.8 (3)
N1—Ag—O2	102.41 (12)	N3—C11—C12	113.4 (3)
N3—Ag—O2	90.70 (11)	C10—C11—C12	124.8 (3)
N1—C1—C2	123.1 (4)	N4—C12—C11	115.8 (3)
C1—C2—C3	118.7 (4)	C7—N3—C11	118.2 (3)
C4—C3—C2	119.1 (4)	C7—N3—Ag	118.3 (2)
C3—C4—C5	119.9 (4)	C11—N3—Ag	123.5 (2)
N1—C5—C4	121.3 (3)	O3—N5—O1	121.9 (4)
N1—C5—C6	115.3 (3)	O3—N5—O2	119.8 (4)
C4—C5—C6	123.3 (4)	O1—N5—O2	118.3 (3)
N2—C6—C5	115.3 (3)	N5—O2—Ag	111.1 (2)
C5—N1—C1	117.9 (3)	O6—N6—O4	121.1 (4)
C5—N1—Ag	124.8 (2)	O6—N6—O5	117.9 (4)
C1—N1—Ag	116.9 (3)	O4—N6—O5	121.0 (4)
N3—C7—C8	123.1 (4)	O8—N7—O9	122.0 (5)
C7—C8—C9	118.8 (4)	O8—N7—O7	120.0 (4)
C8—C9—C10	118.3 (4)	O9—N7—O7	117.9 (4)
C11—C10—C9	119.8 (4)
N3—C11—C12—N4	−175.2 (4)	O7—N2—C6—C12	29.3 (2)
N1—C5—C6—N2	−141.8 (4)	O7—N4—C12—C6	14.5 (3)
N2—C6—C12—N4	−44.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN21···O7	0.86 (5)	2.04 (5)	2.860 (5)	160 (4)
N2—HN21···O9	0.86 (5)	2.49 (5)	3.129 (6)	132 (4)
N2—HN22···O4	0.83 (6)	2.33 (6)	3.151 (6)	168 (6)
N2—HN22···O6	0.83 (6)	2.40 (6)	2.910 (6)	120 (5)
N2—HN23···O1^i	0.97 (7)	1.91 (7)	2.858 (6)	165 (5)
N4—HN41···O7	0.90 (6)	1.94 (6)	2.818 (6)	163 (5)
N4—HN42···O4^ii	0.82 (4)	2.35 (4)	3.051 (8)	145 (4)
N4—HN43···O5^iii	0.88 (9)	2.17 (9)	2.867 (5)	137 (7)
N4—HN43···O9^iv	0.88 (9)	2.55 (8)	3.162 (8)	128 (7)

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

(II) Bis{bis[(2-pyridylmethyl)ammonio]silver(I)} hexakis(perchlorate) dihydrate, [Ag(C₆H₉N₂)₂]₂(ClO₄)₆·2H₂O

Crystal data

[Ag(C6H9N2)2]2(ClO4)6·2H2O	Z = 2
Mr = 1285.08	F(000) = 1288
Triclinic, P1	Dx = 1.886 Mg m^−3
a = 11.3358 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.5436 (10) Å	Cell parameters from 25 reflections
c = 14.6015 (17) Å	θ = 15.0–17.6°
α = 77.700 (8)°	µ = 1.32 mm^−1
β = 89.519 (6)°	T = 293 K
γ = 74.421 (6)°	Rectangular, colourless
V = 2262.5 (3) Å^3	0.44 × 0.44 × 0.32 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	5117 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.009
Graphite monochromator	θmax = 25.0°, θmin = 1.8°
ω/2θ scans	h = −4→13
Absorption correction: semi-empirical (using intensity measurements) (North et al., 1968)	k = −16→17
Tmin = 0.915, Tmax = 0.982	l = −17→17
8138 measured reflections	3 standard reflections every 90 min
7939 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)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.181	w = 1/[σ^2(Fo^2) + (0.1016P)^2 + 1.328P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.021
7939 reflections	Δρmax = 0.78 e Å^−3
605 parameters	Δρmin = −0.58 e Å^−3
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0067 (7)

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. Disorder of the six perchlorate ions was modelled by splitting each oxygen into two parts and their site occupations were tied to FVAR which were refined.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ag1	0.0000	0.5000	0.5000	0.0853 (4)
N1	−0.1868 (5)	0.5931 (4)	0.4932 (3)	0.0513 (14)
N2	−0.5952 (5)	0.7920 (4)	0.3451 (4)	0.0539 (14)
HN21	−0.6695	0.8304	0.3356	0.08 (3)*
HN22	−0.5943	0.7353	0.3340	0.14 (4)*
HN23	−0.5468	0.8177	0.3078	0.07 (2)*
C1	−0.2098 (6)	0.6888 (5)	0.4779 (5)	0.0535 (17)
H1	−0.1442	0.7158	0.4773	0.064*
C2	−0.3247 (6)	0.7497 (5)	0.4629 (5)	0.0523 (16)
H2	−0.3359	0.8169	0.4518	0.063*
C3	−0.4253 (5)	0.7137 (4)	0.4639 (4)	0.0409 (14)
C4	−0.4002 (6)	0.6134 (5)	0.4860 (5)	0.0535 (17)
H4	−0.4651	0.5851	0.4917	0.064*
C5	−0.2846 (7)	0.5551 (5)	0.4995 (5)	0.0544 (17)
H5	−0.2714	0.4876	0.5134	0.065*
C6	−0.5534 (6)	0.7794 (6)	0.4425 (5)	0.067 (2)
H61	−0.6086	0.7519	0.4839	0.101*
H62	−0.5563	0.8429	0.4549	0.101*
Ag2	0.38167 (6)	0.33395 (5)	0.28575 (5)	0.0844 (3)
N3	0.1989 (5)	0.4269 (5)	0.2766 (4)	0.0572 (15)
N4	−0.2177 (5)	0.6323 (4)	0.1630 (4)	0.0505 (13)
HN41	−0.2920	0.6706	0.1587	0.06 (2)*
HN42	−0.2191	0.5774	0.1490	0.12 (4)*
HN43	−0.1725	0.6604	0.1243	0.06 (2)*
N5	0.5591 (5)	0.2322 (4)	0.3040 (4)	0.0582 (15)
N6	0.9544 (5)	−0.0253 (4)	0.2973 (4)	0.0522 (14)
HN61	1.0266	−0.0656	0.3137	0.15 (5)*
HN62	0.9588	0.0173	0.2465	0.06 (2)*
HN63	0.9034	−0.0577	0.2869	0.044 (19)*
C7	0.1759 (6)	0.5237 (5)	0.2594 (5)	0.0599 (18)
H7	0.2419	0.5506	0.2501	0.072*
C8	0.0618 (6)	0.5853 (5)	0.2549 (5)	0.0487 (15)
H8	0.0505	0.6526	0.2428	0.058*
C9	−0.0380 (5)	0.5469 (4)	0.2685 (4)	0.0400 (13)
C10	−0.0150 (6)	0.4466 (5)	0.2891 (5)	0.0552 (17)
H10	−0.0794	0.4180	0.3013	0.066*
C11	0.1018 (7)	0.3896 (5)	0.2913 (5)	0.065 (2)
H11	0.1155	0.3220	0.3035	0.077*
C12	−0.1657 (5)	0.6129 (5)	0.2604 (4)	0.0512 (16)
H121	−0.2164	0.5823	0.3038	0.077*
H122	−0.1647	0.6740	0.2765	0.077*
C13	0.5707 (6)	0.1377 (6)	0.3386 (6)	0.067 (2)
H13	0.5001	0.1167	0.3472	0.081*
C14	0.6818 (7)	0.0703 (5)	0.3619 (5)	0.0613 (19)
H14	0.6850	0.0053	0.3870	0.074*
C15	0.7883 (5)	0.0972 (5)	0.3490 (4)	0.0438 (14)
C16	0.7738 (6)	0.1949 (5)	0.3101 (6)	0.064 (2)
H16	0.8431	0.2171	0.2974	0.077*
C17	0.6616 (7)	0.2595 (5)	0.2898 (6)	0.072 (2)
H17	0.6562	0.3251	0.2652	0.087*
C18	0.9100 (6)	0.0267 (6)	0.3747 (5)	0.0619 (19)
H181	0.9052	−0.0209	0.4313	0.093*
H182	0.9683	0.0610	0.3877	0.093*
Ag3	0.5000	0.5000	0.0000	0.0757 (3)
N7	0.5531 (5)	0.6334 (4)	−0.0334 (4)	0.0532 (14)
N8	0.7872 (7)	0.8923 (5)	−0.1006 (6)	0.085 (2)
HN81	0.7997	0.9500	−0.1110	0.14 (4)*
HN82	0.8109	0.8654	−0.1479	0.10 (4)*
HN83	0.8289	0.8560	−0.0498	0.10 (3)*
C19	0.6617 (7)	0.6359 (5)	−0.0657 (4)	0.0552 (17)
H19	0.7146	0.5781	−0.0754	0.066*
C20	0.7009 (6)	0.7200 (5)	−0.0859 (4)	0.0494 (16)
H20	0.7778	0.7185	−0.1092	0.059*
C21	0.6243 (6)	0.8057 (4)	−0.0709 (4)	0.0443 (14)
C22	0.5100 (7)	0.8036 (5)	−0.0383 (5)	0.0611 (18)
H22	0.4547	0.8605	−0.0289	0.073*
C23	0.4787 (7)	0.7166 (5)	−0.0199 (5)	0.0621 (19)
H23	0.4021	0.7159	0.0031	0.075*
C24	0.6569 (7)	0.9014 (5)	−0.0892 (5)	0.065 (2)
H241	0.6113	0.9435	−0.1455	0.098*
H242	0.6312	0.9330	−0.0374	0.098*
Cl1	0.11807 (16)	0.74027 (13)	0.44975 (15)	0.0648 (5)
O1A	0.1423 (7)	0.8316 (6)	0.4499 (7)	0.066 (2)*	0.660 (10)
O1B	0.1549 (17)	0.8186 (14)	0.4023 (15)	0.085 (6)*	0.340 (10)
O2A	0.0151 (8)	0.7624 (6)	0.3788 (6)	0.072 (3)*	0.660 (10)
O2B	0.069 (2)	0.6773 (17)	0.4190 (15)	0.111 (8)*	0.340 (10)
O3A	0.2209 (9)	0.6831 (7)	0.4053 (7)	0.094 (3)*	0.660 (10)
O3B	0.234 (2)	0.6772 (16)	0.5149 (16)	0.116 (8)*	0.340 (10)
O4A	0.0955 (9)	0.6849 (8)	0.5284 (7)	0.098 (4)*	0.660 (10)
O4B	0.035 (2)	0.7767 (18)	0.5284 (16)	0.120 (8)*	0.340 (10)
Cl2	−0.48567 (16)	0.55174 (14)	0.26079 (13)	0.0602 (5)
O5A	−0.5775 (7)	0.5832 (7)	0.3268 (5)	0.057 (3)*	0.70 (2)
O5B	−0.544 (3)	0.526 (3)	0.338 (2)	0.118 (10)*	0.30 (2)
O6A	−0.4644 (9)	0.6384 (7)	0.2055 (9)	0.079 (3)*	0.70 (2)
O6B	−0.4642 (15)	0.6479 (12)	0.2401 (15)	0.049 (5)*	0.30 (2)
O7A	−0.5288 (9)	0.4995 (8)	0.2023 (6)	0.067 (3)*	0.70 (2)
O7B	−0.5575 (19)	0.5392 (19)	0.1814 (15)	0.065 (6)*	0.30 (2)
O8A	−0.3802 (9)	0.4848 (7)	0.3188 (9)	0.082 (3)*	0.70 (2)
O8B	−0.3573 (17)	0.4942 (13)	0.2721 (17)	0.067 (6)*	0.30 (2)
Cl3	0.24140 (18)	0.08189 (13)	0.35830 (14)	0.0624 (5)
O9A	0.2700 (7)	0.1593 (6)	0.2968 (6)	0.070 (3)*	0.646 (9)
O9B	0.1389 (15)	0.1261 (12)	0.2779 (11)	0.078 (5)*	0.354 (9)
O10A	0.1606 (10)	0.1171 (7)	0.4278 (7)	0.096 (3)*	0.646 (9)
O10B	0.341 (2)	0.0149 (16)	0.3227 (16)	0.119 (8)*	0.354 (9)
O11A	0.2130 (12)	0.0141 (9)	0.3247 (10)	0.122 (4)*	0.646 (9)
O11B	0.274 (2)	0.1311 (18)	0.4056 (17)	0.126 (8)*	0.354 (9)
O12A	0.3546 (13)	0.0339 (11)	0.4199 (10)	0.139 (5)*	0.646 (9)
O12B	0.207 (2)	−0.0032 (16)	0.4044 (16)	0.112 (7)*	0.354 (9)
Cl4	0.16913 (16)	0.85940 (12)	0.13061 (12)	0.0545 (4)
O13A	0.1958 (10)	0.9045 (6)	0.2057 (7)	0.055 (3)*	0.65 (3)
O13B	0.236 (3)	0.8980 (17)	0.1824 (19)	0.098 (8)*	0.35 (3)
O14A	0.0371 (10)	0.8758 (10)	0.1312 (10)	0.078 (3)*	0.65 (3)
O14B	0.0533 (18)	0.8461 (18)	0.1625 (17)	0.075 (6)*	0.35 (3)
O15A	0.1989 (13)	0.9086 (9)	0.0439 (7)	0.081 (4)*	0.65 (3)
O15B	0.144 (2)	0.9420 (17)	0.0438 (13)	0.081 (7)*	0.35 (3)
O16A	0.2415 (12)	0.7583 (9)	0.1533 (12)	0.099 (4)*	0.65 (3)
O16B	0.210 (2)	0.7689 (15)	0.107 (2)	0.091 (8)*	0.35 (3)
Cl5	0.33778 (17)	0.10203 (12)	−0.20008 (13)	0.0598 (5)
O17A	0.2343 (11)	0.1343 (8)	−0.2700 (10)	0.074 (4)*	0.57 (2)
O17B	0.2172 (14)	0.1398 (11)	−0.2371 (13)	0.069 (5)*	0.43 (2)
O18A	0.4351 (17)	0.0537 (15)	−0.2508 (13)	0.119 (7)*	0.57 (2)
O18B	0.4369 (17)	0.0883 (16)	−0.2595 (13)	0.085 (6)*	0.43 (2)
O19A	0.3304 (12)	0.0112 (11)	−0.1447 (10)	0.104 (5)*	0.57 (2)
O19B	0.3476 (18)	0.0452 (16)	−0.1109 (16)	0.116 (7)*	0.43 (2)
O20A	0.3497 (12)	0.1681 (9)	−0.1455 (10)	0.098 (5)*	0.57 (2)
O20B	0.3881 (15)	0.1868 (11)	−0.2026 (13)	0.091 (6)*	0.43 (2)
Cl6	0.1358 (3)	0.61935 (17)	−0.07344 (17)	0.0965 (8)
O21A	0.0198 (16)	0.6839 (12)	−0.1196 (12)	0.116 (6)*	0.572 (15)
O21B	0.060 (3)	0.547 (2)	−0.0540 (18)	0.174 (11)*	0.428 (15)
O22A	0.2212 (12)	0.5595 (9)	−0.1234 (8)	0.087 (4)*	0.572 (15)
O22B	0.163 (3)	0.5299 (16)	−0.0944 (16)	0.131 (8)*	0.428 (15)
O23A	0.1120 (15)	0.6023 (11)	0.0224 (11)	0.125 (6)*	0.572 (15)
O23B	0.183 (2)	0.6254 (16)	0.0114 (16)	0.136 (8)*	0.428 (15)
O24A	0.2194 (16)	0.6876 (13)	−0.0824 (12)	0.159 (7)*	0.572 (15)
O24B	0.0593 (19)	0.6965 (14)	−0.1439 (14)	0.097 (6)*	0.428 (15)
OW1	0.9206 (5)	0.7545 (5)	0.0596 (4)	0.0734 (15)
HW11	0.996 (6)	0.735 (6)	0.034 (6)	0.110*
HW12	0.922 (8)	0.803 (6)	0.094 (6)	0.110*
OW2	0.9463 (5)	0.1054 (4)	0.1235 (4)	0.0751 (15)
HW21	0.883 (7)	0.077 (6)	0.124 (7)	0.113*
HW22	0.918 (8)	0.169 (4)	0.119 (7)	0.113*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0490 (5)	0.1119 (8)	0.0594 (5)	0.0345 (5)	−0.0098 (4)	−0.0142 (5)
N1	0.042 (3)	0.055 (4)	0.042 (3)	0.006 (3)	−0.005 (2)	−0.004 (3)
N2	0.033 (3)	0.055 (4)	0.064 (4)	−0.004 (3)	−0.009 (3)	−0.001 (3)
C1	0.033 (3)	0.062 (5)	0.063 (4)	−0.019 (3)	−0.006 (3)	0.001 (3)
C2	0.051 (4)	0.040 (3)	0.066 (4)	−0.017 (3)	−0.001 (3)	−0.005 (3)
C3	0.033 (3)	0.045 (4)	0.043 (3)	−0.009 (3)	0.001 (3)	−0.009 (3)
C4	0.048 (4)	0.052 (4)	0.070 (5)	−0.027 (3)	0.001 (3)	−0.016 (3)
C5	0.062 (5)	0.037 (3)	0.057 (4)	−0.006 (3)	−0.004 (3)	−0.003 (3)
C6	0.041 (4)	0.077 (5)	0.073 (5)	0.006 (4)	−0.008 (3)	−0.022 (4)
Ag2	0.0542 (4)	0.1013 (5)	0.0712 (4)	0.0328 (3)	−0.0094 (3)	−0.0303 (4)
N3	0.045 (3)	0.069 (4)	0.050 (3)	0.003 (3)	−0.007 (3)	−0.019 (3)
N4	0.037 (3)	0.056 (4)	0.052 (3)	−0.007 (3)	−0.007 (3)	−0.004 (3)
N5	0.038 (3)	0.063 (4)	0.065 (4)	0.006 (3)	0.001 (3)	−0.021 (3)
N6	0.040 (3)	0.043 (3)	0.064 (4)	0.001 (3)	0.011 (3)	−0.006 (3)
C7	0.041 (4)	0.062 (5)	0.072 (5)	−0.008 (3)	−0.003 (3)	−0.012 (4)
C8	0.044 (4)	0.037 (3)	0.064 (4)	−0.010 (3)	−0.008 (3)	−0.010 (3)
C9	0.035 (3)	0.045 (3)	0.039 (3)	−0.008 (3)	−0.003 (2)	−0.012 (3)
C10	0.049 (4)	0.050 (4)	0.065 (4)	−0.016 (3)	−0.011 (3)	−0.005 (3)
C11	0.074 (5)	0.049 (4)	0.067 (5)	−0.003 (4)	−0.021 (4)	−0.022 (4)
C12	0.035 (3)	0.068 (4)	0.044 (4)	−0.008 (3)	0.001 (3)	−0.007 (3)
C13	0.036 (4)	0.074 (5)	0.097 (6)	−0.021 (4)	0.003 (4)	−0.022 (5)
C14	0.057 (5)	0.046 (4)	0.080 (5)	−0.015 (3)	0.002 (4)	−0.010 (4)
C15	0.037 (3)	0.052 (4)	0.041 (3)	−0.003 (3)	0.000 (3)	−0.017 (3)
C16	0.043 (4)	0.057 (5)	0.099 (6)	−0.019 (3)	0.017 (4)	−0.026 (4)
C17	0.064 (5)	0.044 (4)	0.096 (6)	0.003 (4)	0.015 (4)	−0.011 (4)
C18	0.045 (4)	0.075 (5)	0.055 (4)	0.005 (3)	−0.002 (3)	−0.017 (4)
Ag3	0.1165 (8)	0.0621 (5)	0.0694 (6)	−0.0586 (5)	0.0158 (5)	−0.0159 (4)
N7	0.069 (4)	0.057 (4)	0.047 (3)	−0.034 (3)	0.010 (3)	−0.017 (3)
N8	0.103 (6)	0.066 (4)	0.091 (6)	−0.055 (4)	−0.017 (5)	0.014 (5)
C19	0.078 (5)	0.049 (4)	0.047 (4)	−0.025 (4)	0.004 (4)	−0.017 (3)
C20	0.056 (4)	0.052 (4)	0.046 (4)	−0.026 (3)	0.006 (3)	−0.009 (3)
C21	0.051 (4)	0.042 (4)	0.038 (3)	−0.014 (3)	−0.003 (3)	−0.005 (3)
C22	0.061 (5)	0.051 (4)	0.072 (5)	−0.014 (3)	0.005 (4)	−0.015 (4)
C23	0.050 (4)	0.066 (5)	0.078 (5)	−0.027 (4)	0.013 (4)	−0.020 (4)
C24	0.079 (5)	0.055 (4)	0.068 (5)	−0.031 (4)	0.006 (4)	−0.007 (4)
Cl1	0.0496 (10)	0.0449 (9)	0.0963 (14)	−0.0165 (8)	0.0110 (10)	−0.0030 (9)
Cl2	0.0482 (10)	0.0652 (11)	0.0717 (12)	−0.0223 (8)	0.0042 (9)	−0.0159 (9)
Cl3	0.0673 (12)	0.0554 (10)	0.0731 (12)	−0.0305 (9)	0.0173 (10)	−0.0154 (9)
Cl4	0.0602 (11)	0.0492 (9)	0.0587 (10)	−0.0185 (8)	0.0029 (8)	−0.0171 (8)
Cl5	0.0692 (12)	0.0404 (9)	0.0630 (11)	−0.0066 (8)	−0.0030 (9)	−0.0074 (8)
Cl6	0.135 (2)	0.0684 (14)	0.0808 (16)	−0.0074 (15)	−0.0044 (15)	−0.0307 (12)
OW1	0.071 (4)	0.093 (4)	0.063 (3)	−0.036 (3)	0.007 (3)	−0.013 (3)
OW2	0.101 (4)	0.050 (3)	0.068 (3)	−0.018 (3)	−0.007 (3)	−0.003 (3)

Geometric parameters (Å, º)

Ag1—N1^i	2.175 (5)	Cl1—O4B	1.57 (2)
Ag1—N1	2.175 (5)	O1A—O1B	0.760 (19)
N1—C1	1.314 (8)	O2A—O2B	1.24 (2)
N1—C5	1.360 (9)	O2B—O4A	1.66 (2)
N2—C6	1.461 (9)	O2B—O3A	1.75 (2)
N2—HN21	0.8700	O3A—O3B	1.59 (2)
N2—HN22	0.8700	O3B—O4A	1.55 (2)
N2—HN23	0.8700	O4A—O4B	1.33 (2)
C1—C2	1.353 (9)	Cl2—O5B	1.34 (3)
C1—H1	0.9300	Cl2—O6A	1.423 (10)
C2—C3	1.374 (8)	Cl2—O7A	1.425 (9)
C2—H2	0.9300	Cl2—O6B	1.452 (17)
C3—C4	1.375 (9)	Cl2—O8A	1.461 (10)
C3—C6	1.502 (8)	Cl2—O8B	1.462 (18)
C4—C5	1.346 (9)	Cl2—O5A	1.462 (8)
C4—H4	0.9300	Cl2—O7B	1.49 (2)
C5—H5	0.9300	O5A—O5B	0.80 (3)
C6—H61	0.9700	O6A—O6B	0.550 (19)
C6—H62	0.9700	O7A—O7B	0.60 (2)
Ag2—N5	2.133 (5)	O8A—O8B	0.726 (19)
Ag2—N3	2.136 (5)	Cl3—O11B	1.22 (3)
N3—C7	1.328 (9)	Cl3—O11A	1.302 (13)
N3—C11	1.349 (9)	Cl3—O9A	1.393 (8)
N4—C12	1.484 (8)	Cl3—O12B	1.43 (2)
N4—HN41	0.8700	Cl3—O10A	1.444 (10)
N4—HN42	0.8700	Cl3—O10B	1.45 (2)
N4—HN43	0.8700	Cl3—O12A	1.488 (15)
N5—C17	1.327 (9)	Cl3—O9B	1.563 (16)
N5—C13	1.329 (9)	O9A—O11B	1.55 (2)
N6—C18	1.499 (8)	O9A—O9B	1.723 (18)
N6—HN61	0.8700	O9B—O11A	1.621 (19)
N6—HN62	0.8700	O10A—O11B	1.37 (2)
N6—HN63	0.8700	O10A—O12B	1.79 (2)
C7—C8	1.355 (9)	O10B—O11A	1.45 (2)
C7—H7	0.9300	O10B—O12A	1.52 (2)
C8—C9	1.385 (8)	O11A—O12B	1.14 (2)
C8—H8	0.9300	O11B—O12A	1.44 (3)
C9—C10	1.378 (9)	Cl4—O13B	1.37 (2)
C9—C12	1.495 (8)	Cl4—O16B	1.39 (2)
C10—C11	1.357 (10)	Cl4—O15A	1.402 (10)
C10—H10	0.9300	Cl4—O14B	1.437 (19)
C11—H11	0.9300	Cl4—O16A	1.447 (12)
C12—H121	0.9700	Cl4—O14A	1.451 (11)
C12—H122	0.9700	Cl4—O13A	1.463 (9)
C13—C14	1.366 (10)	Cl4—O15B	1.52 (2)
C13—H13	0.9300	O13A—O13B	0.57 (3)
C14—C15	1.365 (9)	O14A—O14B	0.55 (2)
C14—H14	0.9300	O15A—O15B	0.68 (2)
C15—C16	1.378 (9)	O16A—O16B	0.74 (2)
C15—C18	1.477 (8)	Cl5—O19B	1.37 (2)
C16—C17	1.354 (10)	Cl5—O17B	1.395 (15)
C16—H16	0.9300	Cl5—O20A	1.406 (12)
C17—H17	0.9300	Cl5—O18B	1.411 (19)
C18—H181	0.9700	Cl5—O19A	1.418 (14)
C18—H182	0.9700	Cl5—O18A	1.433 (18)
Ag3—N7	2.142 (5)	Cl5—O17A	1.469 (12)
Ag3—N7^ii	2.142 (5)	Cl5—O20B	1.485 (16)
N7—C19	1.321 (9)	O17A—O17B	0.530 (18)
N7—C23	1.328 (9)	O18B—O20B	1.77 (3)
N8—C24	1.459 (10)	O19A—O19B	0.83 (2)
N8—HN81	0.8700	O19B—O20A	1.76 (2)
N8—HN82	0.8700	O20A—O20B	0.960 (16)
N8—HN83	0.8700	Cl6—O22B	1.35 (2)
C19—C20	1.384 (9)	Cl6—O23B	1.38 (2)
C19—H19	0.9300	Cl6—O23A	1.406 (16)
C20—C21	1.373 (9)	Cl6—O22A	1.426 (12)
C20—H20	0.9300	Cl6—O24B	1.438 (19)
C21—C22	1.383 (9)	Cl6—O21A	1.465 (17)
C21—C24	1.504 (9)	Cl6—O21B	1.51 (3)
C22—C23	1.377 (9)	Cl6—O24A	1.532 (18)
C22—H22	0.9300	O21A—O24B	0.61 (2)
C23—H23	0.9300	O21B—O22B	1.29 (3)
C24—H241	0.9700	O21B—O23A	1.70 (3)
C24—H242	0.9700	O22A—O22B	0.93 (2)
Cl1—O4A	1.320 (10)	O23A—O23B	0.95 (2)
Cl1—O2B	1.34 (2)	O23B—O24A	1.59 (3)
Cl1—O1B	1.366 (19)	OW1—HW11	0.93 (5)
Cl1—O1A	1.427 (9)	OW1—HW12	0.95 (5)
Cl1—O3A	1.472 (10)	OW2—HW21	0.91 (5)
Cl1—O2A	1.488 (8)	OW2—HW22	0.88 (5)
Cl1—O3B	1.57 (2)
N1^i—Ag1—N1	180.0	O6A—Cl2—O7B	91.5 (9)
C1—N1—C5	117.3 (5)	O7A—Cl2—O7B	23.5 (8)
C1—N1—Ag1	121.3 (5)	O6B—Cl2—O7B	110.4 (11)
C5—N1—Ag1	121.3 (4)	O8A—Cl2—O7B	131.1 (10)
C6—N2—HN21	109.5	O8B—Cl2—O7B	115.2 (11)
C6—N2—HN22	109.5	O5A—Cl2—O7B	104.6 (8)
HN21—N2—HN22	109.5	O5B—O5A—Cl2	66 (2)
C6—N2—HN23	109.5	O5A—O5B—Cl2	82 (3)
HN21—N2—HN23	109.5	O6B—O6A—Cl2	82 (2)
HN22—N2—HN23	109.5	O6A—O6B—Cl2	76 (2)
N1—C1—C2	123.0 (6)	O7B—O7A—Cl2	85 (2)
N1—C1—H1	118.5	O7A—O7B—Cl2	72 (2)
C2—C1—H1	118.5	O8B—O8A—Cl2	75.7 (18)
C1—C2—C3	121.0 (6)	O8A—O8B—Cl2	75.5 (19)
C1—C2—H2	119.5	O11B—Cl3—O11A	167.2 (13)
C3—C2—H2	119.5	O11B—Cl3—O9A	72.7 (11)
C2—C3—C4	115.3 (6)	O11A—Cl3—O9A	119.2 (7)
C2—C3—C6	122.3 (6)	O11B—Cl3—O12B	118.9 (14)
C4—C3—C6	122.4 (6)	O11A—Cl3—O12B	49.2 (9)
C5—C4—C3	121.9 (6)	O9A—Cl3—O12B	168.4 (10)
C5—C4—H4	119.0	O11B—Cl3—O10A	61.5 (11)
C3—C4—H4	119.0	O11A—Cl3—O10A	114.4 (7)
C4—C5—N1	121.2 (6)	O9A—Cl3—O10A	110.6 (5)
C4—C5—H5	119.4	O12B—Cl3—O10A	77.2 (10)
N1—C5—H5	119.4	O11B—Cl3—O10B	114.8 (15)
N2—C6—C3	112.3 (6)	O11A—Cl3—O10B	63.4 (10)
N2—C6—H61	109.2	O9A—Cl3—O10B	88.7 (9)
C3—C6—H61	109.2	O12B—Cl3—O10B	86.0 (13)
N2—C6—H62	109.2	O10A—Cl3—O10B	156.3 (10)
C3—C6—H62	109.2	O11B—Cl3—O12A	63.3 (12)
H61—C6—H62	107.9	O11A—Cl3—O12A	107.1 (8)
N5—Ag2—N3	175.0 (2)	O9A—Cl3—O12A	104.2 (6)
C7—N3—C11	117.0 (6)	O12B—Cl3—O12A	82.5 (10)
C7—N3—Ag2	121.7 (5)	O10A—Cl3—O12A	98.6 (7)
C11—N3—Ag2	121.2 (5)	O10B—Cl3—O12A	62.2 (10)
C12—N4—HN41	109.5	O11B—Cl3—O9B	122.8 (13)
C12—N4—HN42	109.5	O11A—Cl3—O9B	68.2 (8)
HN41—N4—HN42	109.5	O9A—Cl3—O9B	71.0 (7)
C12—N4—HN43	109.5	O12B—Cl3—O9B	100.6 (11)
HN41—N4—HN43	109.5	O10A—Cl3—O9B	92.7 (7)
HN42—N4—HN43	109.5	O10B—Cl3—O9B	106.9 (11)
C17—N5—C13	117.2 (6)	O12A—Cl3—O9B	168.7 (8)
C17—N5—Ag2	122.8 (5)	Cl3—O9A—O11B	48.4 (10)
C13—N5—Ag2	119.8 (5)	Cl3—O9A—O9B	59.1 (6)
C18—N6—HN61	109.5	O11B—O9A—O9B	96.5 (12)
C18—N6—HN62	109.5	Cl3—O9B—O11A	48.3 (7)
HN61—N6—HN62	109.5	Cl3—O9B—O9A	49.9 (6)
C18—N6—HN63	109.5	O11A—O9B—O9A	88.1 (10)
HN61—N6—HN63	109.5	O11B—O10A—Cl3	51.0 (11)
HN62—N6—HN63	109.5	O11B—O10A—O12B	91.2 (14)
N3—C7—C8	123.7 (7)	Cl3—O10A—O12B	51.0 (8)
N3—C7—H7	118.1	Cl3—O10B—O11A	53.2 (10)
C8—C7—H7	118.1	Cl3—O10B—O12A	60.0 (11)
C7—C8—C9	119.2 (6)	O11A—O10B—O12A	98.1 (16)
C7—C8—H8	120.4	O12B—O11A—Cl3	71.2 (14)
C9—C8—H8	120.4	O12B—O11A—O10B	97.7 (18)
C10—C9—C8	117.6 (6)	Cl3—O11A—O10B	63.3 (11)
C10—C9—C12	121.7 (6)	O12B—O11A—O9B	111.8 (16)
C8—C9—C12	120.7 (6)	Cl3—O11A—O9B	63.5 (8)
C11—C10—C9	119.7 (7)	O10B—O11A—O9B	103.9 (13)
C11—C10—H10	120.1	Cl3—O11B—O10A	67.5 (13)
C9—C10—H10	120.1	Cl3—O11B—O12A	67.6 (14)
N3—C11—C10	122.7 (7)	O10A—O11B—O12A	104.4 (18)
N3—C11—H11	118.7	Cl3—O11B—O9A	58.9 (11)
C10—C11—H11	118.7	O10A—O11B—O9A	105.6 (17)
N4—C12—C9	109.8 (5)	O12A—O11B—O9A	98.9 (16)
N4—C12—H121	109.7	O11B—O12A—Cl3	49.1 (11)
C9—C12—H121	109.7	O11B—O12A—O10B	99.2 (16)
N4—C12—H122	109.7	Cl3—O12A—O10B	57.8 (10)
C9—C12—H122	109.7	O11A—O12B—Cl3	59.6 (13)
H121—C12—H122	108.2	O11A—O12B—O10A	101.4 (17)
N5—C13—C14	122.9 (6)	Cl3—O12B—O10A	51.8 (8)
N5—C13—H13	118.6	O13B—Cl4—O16B	125.4 (13)
C14—C13—H13	118.6	O13B—Cl4—O15A	94.3 (12)
C15—C14—C13	120.8 (7)	O16B—Cl4—O15A	92.2 (10)
C15—C14—H14	119.6	O13B—Cl4—O14B	119.5 (15)
C13—C14—H14	119.6	O16B—Cl4—O14B	95.4 (12)
C14—C15—C16	115.1 (6)	O15A—Cl4—O14B	130.3 (10)
C14—C15—C18	122.4 (6)	O13B—Cl4—O16A	99.2 (11)
C16—C15—C18	122.5 (6)	O16B—Cl4—O16A	30.2 (9)
C17—C16—C15	122.0 (7)	O15A—Cl4—O16A	111.2 (7)
C17—C16—H16	119.0	O14B—Cl4—O16A	98.9 (11)
C15—C16—H16	119.0	O13B—Cl4—O14A	125.0 (14)
N5—C17—C16	122.0 (7)	O16B—Cl4—O14A	103.3 (11)
N5—C17—H17	119.0	O15A—Cl4—O14A	108.9 (6)
C16—C17—H17	119.0	O14B—Cl4—O14A	22.0 (9)
C15—C18—N6	111.2 (5)	O16A—Cl4—O14A	116.0 (8)
C15—C18—H181	109.4	O13B—Cl4—O13A	22.7 (12)
N6—C18—H181	109.4	O16B—Cl4—O13A	136.9 (12)
C15—C18—H182	109.4	O15A—Cl4—O13A	110.2 (6)
N6—C18—H182	109.4	O14B—Cl4—O13A	96.9 (8)
H181—C18—H182	108.0	O16A—Cl4—O13A	106.9 (7)
N7—Ag3—N7^ii	180.0	O14A—Cl4—O13A	103.3 (6)
C19—N7—C23	117.5 (6)	O13B—Cl4—O15B	97.3 (12)
C19—N7—Ag3	121.6 (5)	O16B—Cl4—O15B	111.0 (12)
C23—N7—Ag3	120.9 (5)	O15A—Cl4—O15B	26.5 (8)
C24—N8—HN81	109.5	O14B—Cl4—O15B	108.0 (11)
C24—N8—HN82	109.5	O16A—Cl4—O15B	135.7 (9)
HN81—N8—HN82	109.5	O14A—Cl4—O15B	86.0 (9)
C24—N8—HN83	109.5	O13A—Cl4—O15B	104.1 (8)
HN81—N8—HN83	109.5	O13B—O13A—Cl4	70 (3)
HN82—N8—HN83	109.5	O13A—O13B—Cl4	88 (3)
N7—C19—C20	123.5 (7)	O14B—O14A—Cl4	78 (3)
N7—C19—H19	118.3	O14A—O14B—Cl4	80 (3)
C20—C19—H19	118.3	O15B—O15A—Cl4	86 (2)
C21—C20—C19	118.9 (6)	O15A—O15B—Cl4	67 (2)
C21—C20—H20	120.5	O16B—O16A—Cl4	71 (2)
C19—C20—H20	120.5	O16A—O16B—Cl4	79 (2)
C20—C21—C22	117.7 (6)	O19B—Cl5—O17B	113.3 (10)
C20—C21—C24	123.9 (6)	O19B—Cl5—O20A	78.4 (11)
C22—C21—C24	118.4 (6)	O17B—Cl5—O20A	103.2 (9)
C23—C22—C21	119.4 (7)	O19B—Cl5—O18B	120.6 (12)
C23—C22—H22	120.3	O17B—Cl5—O18B	120.9 (11)
C21—C22—H22	120.3	O20A—Cl5—O18B	109.3 (11)
N7—C23—C22	122.9 (7)	O19B—Cl5—O19A	34.5 (9)
N7—C23—H23	118.5	O17B—Cl5—O19A	99.8 (8)
C22—C23—H23	118.5	O20A—Cl5—O19A	112.6 (8)
N8—C24—C21	114.2 (6)	O18B—Cl5—O19A	110.7 (11)
N8—C24—H241	108.7	O19B—Cl5—O18A	107.2 (12)
C21—C24—H241	108.7	O17B—Cl5—O18A	122.6 (11)
N8—C24—H242	108.7	O20A—Cl5—O18A	123.9 (10)
C21—C24—H242	108.7	O18B—Cl5—O18A	20.1 (10)
H241—C24—H242	107.6	O19A—Cl5—O18A	91.2 (11)
O4A—Cl1—O2B	77.2 (10)	O19B—Cl5—O17A	129.3 (10)
O4A—Cl1—O1B	151.4 (11)	O17B—Cl5—O17A	21.1 (7)
O2B—Cl1—O1B	131.2 (13)	O20A—Cl5—O17A	117.3 (7)
O4A—Cl1—O1A	120.6 (6)	O18B—Cl5—O17A	100.1 (9)
O2B—Cl1—O1A	157.1 (11)	O19A—Cl5—O17A	106.2 (8)
O1B—Cl1—O1A	31.5 (8)	O18A—Cl5—O17A	101.8 (9)
O4A—Cl1—O3A	109.5 (6)	O19B—Cl5—O20B	111.2 (11)
O2B—Cl1—O3A	76.8 (10)	O17B—Cl5—O20B	106.8 (8)
O1B—Cl1—O3A	84.1 (9)	O20A—Cl5—O20B	38.7 (6)
O1A—Cl1—O3A	107.1 (5)	O18B—Cl5—O20B	75.1 (12)
O4A—Cl1—O2A	110.0 (6)	O19A—Cl5—O20B	144.3 (9)
O2B—Cl1—O2A	51.8 (10)	O18A—Cl5—O20B	93.9 (12)
O1B—Cl1—O2A	90.6 (9)	O17A—Cl5—O20B	107.2 (8)
O1A—Cl1—O2A	105.9 (5)	O17B—O17A—Cl5	72 (3)
O3A—Cl1—O2A	102.1 (5)	O17A—O17B—Cl5	87 (3)
O4A—Cl1—O3B	64.3 (9)	Cl5—O18B—O20B	54.3 (9)
O2B—Cl1—O3B	106.7 (13)	O19B—O19A—Cl5	69.8 (18)
O1B—Cl1—O3B	103.4 (12)	O19A—O19B—Cl5	76 (2)
O1A—Cl1—O3B	94.8 (9)	O19A—O19B—O20A	127 (2)
O3A—Cl1—O3B	62.9 (9)	Cl5—O19B—O20A	51.6 (8)
O2A—Cl1—O3B	157.7 (9)	O20B—O20A—Cl5	75.1 (13)
O4A—Cl1—O4B	53.9 (9)	O20B—O20A—O19B	117.6 (17)
O2B—Cl1—O4B	106.6 (13)	Cl5—O20A—O19B	50.0 (8)
O1B—Cl1—O4B	106.4 (12)	O20A—O20B—Cl5	66.2 (13)
O1A—Cl1—O4B	77.7 (9)	O20A—O20B—O18B	111.3 (16)
O3A—Cl1—O4B	159.9 (9)	Cl5—O20B—O18B	50.5 (8)
O2A—Cl1—O4B	95.0 (9)	O22B—Cl6—O23B	117.2 (13)
O3B—Cl1—O4B	97.6 (12)	O22B—Cl6—O23A	104.7 (12)
O1B—O1A—Cl1	69.8 (17)	O23B—Cl6—O23A	39.8 (9)
O1A—O1B—Cl1	78.7 (18)	O22B—Cl6—O22A	39.1 (10)
O2B—O2A—Cl1	58.0 (11)	O23B—Cl6—O22A	114.1 (11)
O2A—O2B—Cl1	70.2 (13)	O23A—Cl6—O22A	129.5 (8)
O2A—O2B—O4A	104.1 (16)	O22B—Cl6—O24B	114.4 (11)
Cl1—O2B—O4A	50.9 (8)	O23B—Cl6—O24B	128.4 (12)
O2A—O2B—O3A	99.2 (15)	O23A—Cl6—O24B	123.9 (11)
Cl1—O2B—O3A	55.0 (9)	O22A—Cl6—O24B	105.8 (9)
O4A—O2B—O3A	83.9 (11)	O22B—Cl6—O21A	112.4 (12)
Cl1—O3A—O3B	61.5 (9)	O23B—Cl6—O21A	124.0 (11)
Cl1—O3A—O2B	48.2 (8)	O23A—Cl6—O21A	104.1 (10)
O3B—O3A—O2B	88.8 (12)	O22A—Cl6—O21A	120.7 (8)
O4A—O3B—Cl1	50.1 (8)	O24B—Cl6—O21A	24.3 (9)
O4A—O3B—O3A	93.2 (13)	O22B—Cl6—O21B	53.2 (13)
Cl1—O3B—O3A	55.6 (9)	O23B—Cl6—O21B	108.1 (14)
Cl1—O4A—O4B	72.7 (12)	O23A—Cl6—O21B	71.2 (11)
Cl1—O4A—O3B	65.7 (9)	O22A—Cl6—O21B	92.0 (11)
O4B—O4A—O3B	109.9 (15)	O24B—Cl6—O21B	101.7 (13)
Cl1—O4A—O2B	52.0 (9)	O21A—Cl6—O21B	81.8 (12)
O4B—O4A—O2B	102.5 (15)	O22B—Cl6—O24A	126.7 (15)
O3B—O4A—O2B	93.4 (13)	O23B—Cl6—O24A	66.0 (11)
O4A—O4B—Cl1	53.4 (10)	O23A—Cl6—O24A	103.6 (9)
O5B—Cl2—O6A	138.2 (15)	O22A—Cl6—O24A	88.7 (9)
O5B—Cl2—O7A	98.5 (13)	O24B—Cl6—O24A	84.1 (10)
O6A—Cl2—O7A	110.2 (6)	O21A—Cl6—O24A	103.1 (10)
O5B—Cl2—O6B	118.9 (15)	O21B—Cl6—O24A	173.7 (12)
O6A—Cl2—O6B	22.0 (7)	O24B—O21A—Cl6	75 (3)
O7A—Cl2—O6B	131.2 (9)	O22B—O21B—Cl6	57.1 (15)
O5B—Cl2—O8A	81.5 (14)	O22B—O21B—O23A	93 (2)
O6A—Cl2—O8A	115.4 (6)	Cl6—O21B—O23A	51.5 (10)
O7A—Cl2—O8A	108.4 (6)	O22B—O22A—Cl6	66.3 (16)
O6B—Cl2—O8A	107.2 (8)	O22A—O22B—O21B	143 (3)
O5B—Cl2—O8B	109.7 (15)	O22A—O22B—Cl6	74.6 (18)
O6A—Cl2—O8B	96.1 (9)	O21B—O22B—Cl6	69.7 (17)
O7A—Cl2—O8B	98.0 (8)	O23B—O23A—Cl6	68.7 (18)
O6B—Cl2—O8B	97.4 (10)	O23B—O23A—O21B	122 (2)
O8A—Cl2—O8B	28.8 (8)	Cl6—O23A—O21B	57.3 (11)
O5B—Cl2—O5A	32.9 (15)	O23A—O23B—Cl6	71.5 (19)
O6A—Cl2—O5A	106.3 (5)	O23A—O23B—O24A	129 (3)
O7A—Cl2—O5A	111.0 (5)	Cl6—O23B—O24A	61.6 (11)
O6B—Cl2—O5A	90.1 (8)	Cl6—O24A—O23B	52.4 (11)
O8A—Cl2—O5A	105.5 (5)	O21A—O24B—Cl6	80 (3)
O8B—Cl2—O5A	133.5 (10)	HW11—OW1—HW12	109 (6)
O5B—Cl2—O7B	105.6 (14)	HW21—OW2—HW22	111 (6)
N2—C6—C3—C4	−82.8 (8)	N6—C18—C15—C16	−94.9 (8)
N2—C6—C3—C2	97.3 (8)	N6—C18—C15—C14	85.0 (8)
N4—C12—C9—C8	92.3 (7)	N8—C24—C21—C20	−15.3 (10)
N4—C12—C9—C10	−87.3 (7)	N8—C24—C21—C22	165.6 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN21···O1B^iii	0.87	2.24	2.89 (2)	132
N2—HN21···O13A^iii	0.87	2.32	3.002 (10)	135
N2—HN21···O13B^iii	0.87	2.38	2.93 (2)	122
N2—HN21···O11A^iv	0.87	2.62	3.328 (14)	140
N2—HN22···O5A	0.87	2.19	3.058 (11)	171
N2—HN22···O6B	0.87	2.32	2.93 (2)	128
N2—HN23···O18B^v	0.87	2.10	2.92 (2)	157
N2—HN23···O20B^v	0.87	2.35	3.16 (2)	154
N2—HN23···O18A^v	0.87	2.53	3.33 (2)	153
N4—HN41···O6A	0.87	2.20	2.842 (11)	130
N4—HN41···O20A^v	0.87	2.23	2.844 (13)	128
N4—HN41···O20B^v	0.87	2.29	2.981 (17)	137
N4—HN41···O6B	0.87	2.34	2.973 (18)	130
N4—HN42···O22B^v	0.87	1.86	2.68 (2)	155
N4—HN42···O22A^v	0.87	2.11	2.978 (14)	177
N4—HN43···OW1^iii	0.87	2.02	2.865 (8)	163
N6—HN61···O1B^vi	0.87	2.10	2.91 (2)	155
N6—HN61···O1A^vi	0.87	2.37	3.091 (10)	140
N6—HN61···O13A^vi	0.87	2.48	3.057 (13)	124
N6—HN61···O2A^vi	0.87	2.52	2.954 (10)	112
N6—HN62···OW2	0.87	1.95	2.814 (8)	170
N6—HN63···O17A^vii	0.87	2.19	3.058 (13)	175
N6—HN63···O17B^vii	0.87	2.26	3.118 (16)	171
N8—HN81···O13B^viii	0.87	2.16	2.97 (2)	154
N8—HN81···O15B^viii	0.87	2.25	3.00 (2)	144
N8—HN81···O13A^viii	0.87	2.28	3.081 (11)	153
N8—HN81···O15A^viii	0.87	2.46	3.219 (14)	146
N8—HN82···O9B^ii	0.87	1.96	2.758 (18)	151
N8—HN82···O9A^ii	0.87	2.50	3.225 (12)	142
N8—HN83···OW1	0.87	2.00	2.866 (9)	171
OW1—HW11···O23A^ix	0.93 (5)	2.07 (7)	2.796 (17)	134 (8)
OW1—HW11···O23B^ix	0.93 (5)	2.35 (6)	3.22 (2)	156 (8)
OW1—HW11···O21A^ix	0.93 (5)	2.50 (8)	3.105 (18)	123 (7)
OW1—HW12···O14A^ix	0.95 (5)	2.03 (7)	2.830 (12)	141 (7)
OW1—HW12···O14B^ix	0.95 (5)	2.10 (8)	2.87 (2)	138 (7)
OW2—HW21···O15A^ii	0.91 (5)	2.58 (10)	3.031 (12)	111 (7)
OW2—HW22···O24B^ii	0.88 (5)	2.14 (6)	2.942 (19)	151 (8)
OW2—HW22···O24A^ii	0.88 (5)	2.20 (7)	3.026 (19)	155 (8)
OW2—HW22···O21A^ii	0.88 (5)	2.42 (6)	3.178 (17)	144 (7)

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x−1, y+1, z; (v) −x, −y+1, −z; (vi) x+1, y−1, z; (vii) −x+1, −y, −z; (viii) −x+1, −y+2, −z; (ix) x+1, y, z.