Bis{4-[N,N-bis(2-cyano­ethyl)­amino]­pyridine-[kappa]N¹}silver(I) perchlorate, with the perchlorate anion located in the cation cavity

The title complex, bis­[3,3'-(pyridine-4-imino-[kappa]N¹)­di­propane­nitrile]silver(I) perchlorate, [Ag(CEAP)₂]ClO₄ {CEAP is 4-[N,N-bis(2-cyano­ethyl)­amino]­pyridine, C₁₁H₁₂N₄}, has been prepared and characterized. The unit cell consists of two crystallographically non-equivalent mol­ecules. Cation cavities are constructed by [Ag(CEAP)₂]⁺ cations through hydrogen bonds, and the ClO₄^- anions are incorporated into the cavities in [mu]₄- and [mu]₂-ClO₄^- bridging modes through C-H...O hydrogen bonds.

S1. Comment

Recently, a series of compounds with zeolite-like molecular-sized channels, pores and cavities have been attracting considerable attention (Bowes et al., 1996; Kitazawa et al., 1992; Martin et al., 1998). These compounds can bind many molecules into their cavities, which gives them unique properties as catalysts, as ion-exchangers, for molecular separation sorption, etc. (Behrens et al., 1997; Fujita et al., 1994; Hoelderich et al., 1988). The cavities are constructed by organic components as well as by coordination polymers. Clearly, molecular recognition and self-organization are important factors in the sorbing of the guest (Ducharme et al., 1988; Endo et al., 1995; Geib et al., 1991). It has been found that hydrogen-bonding interactions are very important for molecular recognition in a wide variety of crystal-packing configurations (Bishop et al., 1993; Hunter, 1994; Smith, 1998; Zaworotko, 1994). Silver is an important element, with abundant catalytic properties. Absorbed oxygen on the silver surface is well known in the catalysis of epoxide fomation and oxidative coupling of methane (Epling et al., 1997; Minahan et al., 1996; Serafin et al., 1998). Silver complexes have also been well documented as catalysts in many reactions, such as enantioselective alkylation of imino easter (Ferraris et al., 2002) and the hetero-Diels-Alder reaction (Hague et al., 2001). In this paper, we report the synthesis of the title compound, (I), which shows a two-dimensional layer structure.

The unit cell of (I) consists of two types of basic units that have the same chemical composition but crystallographically non-equivalent conformation. Each unit contains an Ag(CEAP)₂⁺ cation and a ClO₄⁻ anion, and they form a vaulted structure. In the cation, each Ag atom is coordinated by two N atoms in the pyridine rings of two ligands, with Ag—N distances in the range 2.138 (3)–2.142 (3) Å and N—Ag—N angles of 179.1 (1)° in unit (a) and 177.1 (1)° in unit (b). The bond distances and angles are all within the range typically observed in Ag complexes (Furuta et al., 1999; Ozutsumi et al., 1997; Smith et al., 1999). The Cl—O distances in the two units are 1.396 (3)–1.460 (3) Å, which are also within the typical range (Riera et al., 1998). The dramatic difference between units (a) and (b) is the dihedral angle of the ligands. In unit (a), which consists of the Ag1 complex and Cl1 perchlorate, the angle between the planes of the two pyridine rings of the ligand is 45.8 (2)°. But in unit (b), which consists of the Ag2 complex and Cl2 perchlorate, the two pyridine rings are nearly coplanar and the angle between their planes is 16.7 (2)°. The complex packing consists of parallel layers. In one layer, all arc-centers of the vaulted cations have the same positions, and they stack above or below the plane. The two adjacent layers form a zip-like structure, and they are connected via? C—H···N hydrogen bonds (C4—H4···N4ⁱ, C40—H40A···N4, C35—H35···N16^v; Table 2). We also found that neighboring layers slide laterally with respect to each other. The sliding of the layers and the vaulted structure of the Ag(CEAP)₂⁺ cations make hydrogen-bond formation easy. In each layer, there are many chains composed of alternate? basic units, and the unit–unit distance (see Fig. 2 l_u-u) in the chain is 8.893 (3) Å. All chains in the layer are parallel, with a chain–chain distance (see Fig. 2 l_c-c) of 19.020 (2) Å. Neighboring chains also slide over each other, and they are connected? by C—H···N hydrogen bonds, with a C10···N11(1 − x, 1 − y, 2 − z) distance of 3.362 (6) Å. In a chain, the supramolecular cavites of the host are composed of adjacent units assembled through C—H···N hydrogen bonds. The length (see Fig. 2 l_c) and width (see Fig.2 l_u-u) of the cavity are 11.274 (2) and 8.893 (3) Å, respectively. All ClO₄⁻ anions are located as guests in the cavities and are connected to? the Ag(CEAP)₂⁺ cations through C—H···O interactions. In unit (a), the ClO₄⁻ anion bridges three Ag(CEAP)₂⁺ in the two layers to form a zip-like structure through C38—H38···O2, C10—H10B···O3 and C29—H29A···O4 (1 − x, 1 − y, 2 − z) hydrogen bonds. This anion also connects an adjacent zip structure, through the C32—H32B···O4 hydrogen bond. Therefore, the ClO₄⁻ anion in unit (a) bridges four Ag(CEAP)₂⁺ cations to form a µ₄-ClO₄⁻ bridging mode. In unit (b), the ClO₄⁻ anion bridges two Ag(CEAP)₂⁺ cations with a µ₂-ClO₄⁻ bridging mode (see Fig.3) to form a zip structure through C17—H17A···O7(1 + x, y, −1 + z) and C34—H34···O7(1 + x, y, z) hydrogen bonds. The O···H distances are in the range 2.51–2.59 Å, with C···O distances in the range 3.279 (5)–3.446 (5) Å, falling into the normal range of C—H···O separations (Desiraju, 1991; Steiner et al., 1998).

S2. Experimental

The synthesis of the title compound, (I), was performed in the dark. A solution of AgNO₃ (170 mg, 1 mmol) in 10 ml CH₃OH was added to a stired solution of 4-[N,N-bis(2-cyanoethyl)amino]pyridine (400 mg, 2 mmol) in CH₃OH (20 ml) at room temperature, the reaction mixture was stired for 1 h and filtered. A solution of NaClO₄ (122.5 mg, 1 mmol) in CH₃OH (5 ml) was added to the clear filtrate and stired for 15 min. The reaction mixture was filtered again, and colorless single crystals of (I) suitable for X-ray analysis were obtained after several days by slow evaporation of the filtrate.

Analysis calculated for AgC₂₂H₂₄N₈O₄Cl: C 43.47, H 3.98, N 18.44; found: C 43.35, H 4.01, N 18.40.

S3. Refinement

The positions of all H atoms were fixed geometrically, and distances to H atoms were set by the program SHELXTL (Bruker, 2000)?.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids shown at the 50% probability level.
	Fig. 2. Supramolecular cavites in a molecular layer. H atoms have been omitted for clarity.
	Fig. 3. (a) A view of the µ2-ClO4^− bridge mode in the basic unit (b), involving atoms Ag2 and Cl2. (b) A view of the µ4-ClO4^− bridge mode in the basic unit (a), involving atoms Ag1 and Cl1.

4-[N,N-bis(2-cyanoethyl)amino]pyridine silver(I) perchlorate

Crystal data

[Ag(C11H12N4)2](ClO4)	Z = 4
Mr = 607.81	F(000) = 1232
Triclinic, P1	Dx = 1.574 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.221 (2) Å	Cell parameters from 2238 reflections
b = 14.457 (2) Å	θ = 2.7–22.3°
c = 19.897 (2) Å	µ = 0.94 mm^−1
α = 76.39 (1)°	T = 293 K
β = 84.20 (1)°	Block, colorless
γ = 88.06 (1)°	0.3 × 0.3 × 0.2 mm
V = 2564.6 (7) Å^3

Data collection

Bruker Smart Apex CCD area detector diffractometer	8825 independent reflections
Radiation source: sealed tube	6422 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ϕ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: empirical (using intensity measurements) SADABS; Bruker, 2000	h = −11→11
Tmin = 0.762, Tmax = 0.827	k = −17→11
13111 measured reflections	l = −24→23

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0418P)^2 + 1.1404P] where P = (Fo^2 + 2Fc^2)/3
8825 reflections	(Δ/σ)max < 0.001
601 parameters	Δρmax = 0.83 e Å^−3
0 restraints	Δρmin = −0.98 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

8.5985 (0.0057) x − 4.7604 (0.0222) y + 0.0151 (0.0294) z = 0.4068 (0.0268)

* 0.0077 (0.0026) N1 * −0.0066 (0.0029) C1 * 0.0000 (0.0029) C2 * 0.0053 (0.0028) C3 * −0.0042 (0.0028) C4 * −0.0022 (0.0027) C5

Rms deviation of fitted atoms = 0.0051

− 3.6847 (0.0133) x + 12.8624 (0.0107) y + 0.4139 (0.0281) z = 9.2453 (0.0179)

Angle to previous plane (with approximate e.s.d.) = 45.78 (0.15)

* −0.0122 (0.0025) N5 * −0.0014 (0.0026) C12 * 0.0137 (0.0026) C13 * −0.0128 (0.0025) C14 * 0.0000 (0.0026) C15 * 0.0128 (0.0027) C16

Rms deviation of fitted atoms = 0.0105

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

7.8487 (0.0079) x − 6.1431 (0.0213) y + 4.6860 (0.0290) z = 7.7192 (0.0368)

* −0.0085 (0.0027) N9 * 0.0104 (0.0029) C23 * 0.0021 (0.0028) C24 * −0.0157 (0.0027) C25 * 0.0179 (0.0027) C26 * −0.0062 (0.0027) C27

Rms deviation of fitted atoms = 0.0115

8.5003 (0.0066) x − 5.1466 (0.0239) y − 0.1481 (0.0314) z = 4.9497 (0.0338)

Angle to previous plane (with approximate e.s.d.) = 16.74 (0.17)

* −0.0201 (0.0028) N13 * 0.0189 (0.0030) C34 * −0.0056 (0.0030) C35 * −0.0057 (0.0029) C36 * 0.0042 (0.0030) C37 * 0.0081 (0.0031) C38

Rms deviation of fitted atoms = 0.0123

Refinement. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses. 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
Ag1	0.53776 (4)	0.84897 (3)	0.247521 (16)	0.05426 (12)
Ag2	0.97604 (4)	0.65100 (3)	0.774192 (16)	0.05707 (13)
C1	0.5323 (4)	0.8787 (3)	0.3968 (2)	0.0434 (10)
H1	0.5641	0.9392	0.3733	0.052*
C2	0.5211 (4)	0.8573 (3)	0.4688 (2)	0.0434 (10)
H2	0.5461	0.9023	0.4922	0.052*
C3	0.4709 (4)	0.7656 (3)	0.5069 (2)	0.0394 (10)
C4	0.4347 (4)	0.7021 (3)	0.4671 (2)	0.0395 (9)
H4	0.4003	0.6417	0.4891	0.047*
C5	0.4507 (4)	0.7303 (3)	0.3947 (2)	0.0407 (10)
H5	0.4262	0.6872	0.3697	0.049*
C12	0.4846 (4)	0.8544 (3)	0.09566 (19)	0.0364 (9)
H12	0.3959	0.8281	0.1167	0.044*
C13	0.5121 (4)	0.8657 (3)	0.02576 (19)	0.0372 (9)
H13	0.4413	0.8484	0.0010	0.045*
C14	0.6454 (4)	0.9030 (3)	−0.01036 (19)	0.0337 (9)
C15	0.7442 (4)	0.9309 (3)	0.03290 (19)	0.0388 (9)
H15	0.8340	0.9572	0.0137	0.047*
C16	0.7037 (4)	0.9181 (3)	0.1031 (2)	0.0411 (10)
H16	0.7688	0.9381	0.1295	0.049*
C6	0.4963 (5)	0.8115 (3)	0.6195 (2)	0.0479 (11)
H6A	0.4459	0.7937	0.6658	0.057*
H6B	0.4617	0.8741	0.5970	0.057*
C7	0.6614 (5)	0.8144 (3)	0.6246 (2)	0.0573 (12)
H7A	0.6961	0.7519	0.6473	0.069*
H7B	0.7121	0.8319	0.5783	0.069*
C8	0.6925 (5)	0.8844 (4)	0.6644 (3)	0.0612 (13)
C9	0.4085 (5)	0.6463 (3)	0.6176 (2)	0.0460 (11)
H9A	0.3163	0.6322	0.6041	0.055*
H9B	0.4004	0.6413	0.6668	0.055*
C10	0.5249 (5)	0.5706 (3)	0.6391 (2)	0.0479 (11)
H10A	0.5910	0.5950	0.6657	0.058*
H10B	0.4779	0.5152	0.6696	0.058*
C11	0.6119 (5)	0.5400 (3)	0.5813 (2)	0.0486 (11)
C17	0.8345 (4)	0.9317 (3)	−0.1133 (2)	0.0428 (10)
H17A	0.8550	0.8924	−0.1466	0.051*
H17B	0.9014	0.9125	−0.0778	0.051*
C18	0.8635 (5)	1.0385 (3)	−0.1513 (2)	0.0515 (11)
H18A	0.9492	1.0417	−0.1843	0.062*
H18B	0.7814	1.0633	−0.1772	0.062*
C19	0.8861 (5)	1.0996 (3)	−0.1025 (2)	0.0492 (11)
C20	0.5745 (4)	0.8995 (3)	−0.1267 (2)	0.0420 (10)
H20A	0.5912	0.9461	−0.1705	0.050*
H20B	0.4778	0.9114	−0.1061	0.050*
C21	0.5787 (5)	0.7987 (3)	−0.1413 (2)	0.0496 (11)
H21A	0.5256	0.8005	−0.1812	0.059*
H21B	0.6792	0.7821	−0.1533	0.059*
C22	0.5168 (6)	0.7235 (3)	−0.0828 (2)	0.0560 (12)
C23	0.9650 (5)	0.6777 (3)	0.9217 (2)	0.0461 (11)
H23	1.0219	0.7297	0.8988	0.055*
C24	0.9167 (4)	0.6712 (3)	0.99213 (19)	0.0391 (9)
H24	0.9403	0.7174	1.0146	0.047*
C25	0.8291 (4)	0.5898 (3)	1.02835 (19)	0.0375 (9)
C26	0.8037 (4)	0.5221 (3)	0.9895 (2)	0.0382 (9)
H26	0.7526	0.4669	1.0107	0.046*
C27	0.8551 (4)	0.5389 (3)	0.9203 (2)	0.0421 (10)
H27	0.8328	0.4945	0.8959	0.051*
C34	1.0597 (5)	0.7668 (3)	0.6260 (2)	0.0459 (11)
H34	1.0911	0.8087	0.6503	0.055*
C35	1.0734 (4)	0.7962 (3)	0.5533 (2)	0.0427 (10)
H35	1.1077	0.8566	0.5313	0.051*
C36	1.0339 (4)	0.7321 (3)	0.51331 (19)	0.0403 (10)
C37	0.9803 (5)	0.6406 (3)	0.5548 (2)	0.0455 (10)
H37	0.9524	0.5944	0.5332	0.055*
C38	0.9713 (5)	0.6228 (3)	0.6263 (2)	0.0498 (11)
H38	0.9385	0.5633	0.6512	0.060*
C28	0.6938 (5)	0.4972 (3)	1.1372 (2)	0.0460 (11)
H28A	0.7035	0.4905	1.1862	0.055*
H28B	0.7347	0.4405	1.1241	0.055*
C29	0.5302 (5)	0.5065 (3)	1.1247 (2)	0.0471 (11)
H29A	0.4942	0.5690	1.1286	0.056*
H29B	0.5189	0.5003	1.0780	0.056*
C30	0.4438 (5)	0.4327 (3)	1.1755 (2)	0.0505 (12)
C31	0.7726 (4)	0.6607 (3)	1.1305 (2)	0.0428 (10)
H31A	0.6855	0.6563	1.1628	0.051*
H31B	0.7672	0.7201	1.0959	0.051*
C32	0.9082 (5)	0.6623 (3)	1.1706 (2)	0.0504 (11)
H32A	0.9199	0.6007	1.2021	0.060*
H32B	0.9948	0.6740	1.1379	0.060*
C33	0.8936 (5)	0.7356 (3)	1.2098 (2)	0.0496 (11)
C39	1.0031 (5)	0.6828 (3)	0.4051 (2)	0.0499 (11)
H39A	1.0382	0.6203	0.4274	0.060*
H39B	1.0494	0.6992	0.3579	0.060*
C40	0.8382 (5)	0.6796 (3)	0.4032 (2)	0.0544 (12)
H40A	0.7916	0.6634	0.4503	0.065*
H40B	0.8029	0.7420	0.3806	0.065*
C41	0.7976 (6)	0.6071 (4)	0.3645 (3)	0.0628 (13)
C42	1.1048 (5)	0.8455 (3)	0.4003 (2)	0.0470 (11)
H42A	1.1700	0.8330	0.3620	0.056*
H42B	1.1622	0.8728	0.4289	0.056*
C43	0.9903 (5)	0.9193 (3)	0.3707 (2)	0.0538 (12)
H43A	1.0396	0.9741	0.3404	0.065*
H43B	0.9309	0.8920	0.3429	0.065*
C44	0.8975 (5)	0.9502 (3)	0.4238 (3)	0.0543 (12)
N1	0.5002 (4)	0.8175 (2)	0.35835 (16)	0.0399 (8)
N2	0.4633 (4)	0.7409 (2)	0.57875 (16)	0.0446 (8)
N3	0.7106 (6)	0.9386 (4)	0.6962 (2)	0.0874 (15)
N4	0.6766 (5)	0.5155 (3)	0.5373 (2)	0.0657 (11)
N5	0.5785 (4)	0.8792 (2)	0.13680 (16)	0.0412 (8)
N6	0.6825 (3)	0.9137 (2)	−0.08030 (16)	0.0369 (8)
N7	0.9059 (4)	1.1438 (3)	−0.0644 (2)	0.0590 (10)
N8	0.4748 (6)	0.6645 (3)	−0.0383 (2)	0.0814 (14)
N9	0.9354 (4)	0.6149 (2)	0.88488 (17)	0.0468 (9)
N10	0.7759 (4)	0.5817 (2)	1.09634 (16)	0.0421 (8)
N11	0.3764 (5)	0.3743 (3)	1.21703 (19)	0.0634 (11)
N12	0.8767 (4)	0.7938 (3)	1.2410 (2)	0.0597 (11)
N13	1.0061 (4)	0.6847 (2)	0.66301 (16)	0.0452 (9)
N14	1.0443 (4)	0.7527 (2)	0.44280 (16)	0.0425 (8)
N15	0.7727 (5)	0.5546 (3)	0.3337 (2)	0.0711 (13)
N16	0.8238 (5)	0.9759 (3)	0.4662 (3)	0.0760 (13)
Cl2	0.20629 (14)	0.86994 (10)	0.77829 (7)	0.0678 (3)
O5	0.2578 (3)	0.7736 (2)	0.77718 (16)	0.0678 (3)
O6	0.2955 (4)	0.9367 (2)	0.73160 (17)	0.0678 (3)
O7	0.0561 (4)	0.8739 (2)	0.76139 (17)	0.0678 (3)
O8	0.2031 (3)	0.8823 (2)	0.84745 (17)	0.0678 (3)
Cl1	0.71035 (12)	0.34676 (8)	0.76277 (6)	0.0525 (2)
O1	0.7497 (3)	0.2514 (2)	0.75398 (15)	0.0525 (2)
O2	0.7961 (3)	0.4156 (2)	0.71250 (15)	0.0525 (2)
O3	0.5571 (3)	0.3632 (2)	0.75459 (15)	0.0525 (2)
O4	0.7356 (3)	0.3526 (2)	0.83252 (15)	0.0525 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0691 (3)	0.0643 (2)	0.02670 (18)	0.00383 (18)	−0.00010 (16)	−0.00761 (15)
Ag2	0.0653 (3)	0.0747 (3)	0.02777 (19)	0.00534 (19)	0.00058 (16)	−0.00810 (16)
C1	0.055 (3)	0.037 (2)	0.034 (2)	−0.004 (2)	0.003 (2)	−0.0028 (19)
C2	0.056 (3)	0.041 (2)	0.035 (2)	−0.008 (2)	−0.005 (2)	−0.0090 (18)
C3	0.045 (2)	0.040 (2)	0.035 (2)	−0.0058 (19)	−0.0027 (19)	−0.0123 (18)
C4	0.043 (2)	0.036 (2)	0.042 (2)	−0.0013 (18)	−0.0033 (19)	−0.0132 (18)
C5	0.047 (3)	0.040 (2)	0.040 (2)	0.0013 (19)	−0.0037 (19)	−0.0184 (19)
C12	0.036 (2)	0.038 (2)	0.035 (2)	−0.0001 (17)	−0.0004 (18)	−0.0074 (18)
C13	0.042 (2)	0.036 (2)	0.035 (2)	0.0013 (18)	−0.0041 (18)	−0.0098 (17)
C14	0.039 (2)	0.033 (2)	0.031 (2)	−0.0012 (17)	−0.0029 (18)	−0.0109 (17)
C15	0.043 (2)	0.039 (2)	0.035 (2)	−0.0095 (18)	−0.0067 (18)	−0.0053 (18)
C16	0.048 (3)	0.039 (2)	0.036 (2)	−0.0060 (19)	−0.0075 (19)	−0.0047 (18)
C6	0.054 (3)	0.053 (3)	0.037 (2)	−0.009 (2)	−0.001 (2)	−0.011 (2)
C7	0.057 (3)	0.065 (3)	0.047 (3)	−0.011 (2)	−0.001 (2)	−0.007 (2)
C8	0.065 (3)	0.066 (3)	0.053 (3)	−0.017 (3)	−0.007 (3)	−0.011 (3)
C9	0.055 (3)	0.047 (3)	0.034 (2)	−0.008 (2)	−0.005 (2)	−0.0024 (19)
C10	0.060 (3)	0.045 (3)	0.039 (2)	−0.012 (2)	−0.004 (2)	−0.008 (2)
C11	0.059 (3)	0.039 (3)	0.047 (3)	−0.014 (2)	−0.004 (2)	−0.006 (2)
C17	0.040 (2)	0.044 (3)	0.042 (2)	−0.0062 (19)	0.0083 (19)	−0.0073 (19)
C18	0.047 (3)	0.053 (3)	0.046 (3)	−0.008 (2)	0.010 (2)	0.000 (2)
C19	0.041 (3)	0.046 (3)	0.052 (3)	−0.004 (2)	0.006 (2)	0.002 (2)
C20	0.047 (3)	0.042 (2)	0.038 (2)	0.0036 (19)	−0.0032 (19)	−0.0125 (19)
C21	0.066 (3)	0.041 (3)	0.042 (2)	−0.002 (2)	−0.008 (2)	−0.011 (2)
C22	0.081 (4)	0.038 (3)	0.050 (3)	−0.005 (2)	−0.005 (3)	−0.014 (2)
C23	0.052 (3)	0.048 (3)	0.035 (2)	−0.010 (2)	−0.001 (2)	−0.003 (2)
C24	0.043 (2)	0.040 (2)	0.034 (2)	−0.0046 (19)	−0.0011 (18)	−0.0088 (18)
C25	0.040 (2)	0.042 (2)	0.032 (2)	−0.0042 (18)	−0.0008 (18)	−0.0124 (18)
C26	0.038 (2)	0.038 (2)	0.040 (2)	−0.0015 (18)	−0.0015 (18)	−0.0113 (18)
C27	0.043 (2)	0.046 (3)	0.037 (2)	0.000 (2)	−0.0040 (19)	−0.0093 (19)
C34	0.058 (3)	0.049 (3)	0.037 (2)	−0.010 (2)	−0.008 (2)	−0.019 (2)
C35	0.055 (3)	0.041 (2)	0.033 (2)	−0.010 (2)	−0.0046 (19)	−0.0090 (18)
C36	0.051 (3)	0.042 (2)	0.029 (2)	−0.0074 (19)	−0.0050 (19)	−0.0094 (18)
C37	0.059 (3)	0.042 (3)	0.034 (2)	−0.008 (2)	−0.004 (2)	−0.0063 (19)
C38	0.063 (3)	0.047 (3)	0.036 (2)	−0.006 (2)	−0.009 (2)	0.000 (2)
C28	0.055 (3)	0.044 (3)	0.039 (2)	−0.013 (2)	0.007 (2)	−0.0134 (19)
C29	0.056 (3)	0.045 (3)	0.044 (3)	−0.016 (2)	0.011 (2)	−0.022 (2)
C30	0.064 (3)	0.058 (3)	0.037 (2)	−0.019 (2)	0.009 (2)	−0.029 (2)
C31	0.046 (3)	0.044 (2)	0.039 (2)	−0.0022 (19)	0.002 (2)	−0.0154 (19)
C32	0.053 (3)	0.051 (3)	0.047 (3)	−0.002 (2)	−0.001 (2)	−0.012 (2)
C33	0.054 (3)	0.052 (3)	0.044 (3)	−0.011 (2)	−0.010 (2)	−0.011 (2)
C39	0.061 (3)	0.054 (3)	0.036 (2)	−0.007 (2)	−0.003 (2)	−0.013 (2)
C40	0.057 (3)	0.062 (3)	0.043 (3)	−0.004 (2)	0.000 (2)	−0.013 (2)
C41	0.065 (3)	0.065 (4)	0.055 (3)	−0.015 (3)	−0.009 (3)	−0.004 (3)
C42	0.054 (3)	0.046 (3)	0.037 (2)	−0.012 (2)	0.005 (2)	−0.0058 (19)
C43	0.057 (3)	0.050 (3)	0.050 (3)	−0.019 (2)	−0.004 (2)	−0.001 (2)
C44	0.050 (3)	0.051 (3)	0.058 (3)	−0.017 (2)	−0.002 (3)	−0.003 (2)
N1	0.047 (2)	0.046 (2)	0.0271 (17)	−0.0007 (16)	0.0005 (15)	−0.0118 (15)
N2	0.052 (2)	0.048 (2)	0.0338 (19)	−0.0103 (17)	−0.0022 (16)	−0.0103 (16)
N3	0.105 (4)	0.093 (4)	0.078 (3)	−0.027 (3)	−0.011 (3)	−0.041 (3)
N4	0.075 (3)	0.051 (3)	0.068 (3)	−0.007 (2)	0.003 (2)	−0.011 (2)
N5	0.048 (2)	0.042 (2)	0.0318 (18)	−0.0006 (16)	−0.0010 (16)	−0.0070 (15)
N6	0.0386 (19)	0.0396 (19)	0.0330 (18)	−0.0042 (15)	−0.0003 (15)	−0.0103 (14)
N7	0.055 (3)	0.052 (3)	0.068 (3)	−0.0058 (19)	−0.003 (2)	−0.013 (2)
N8	0.126 (4)	0.053 (3)	0.068 (3)	−0.012 (3)	0.006 (3)	−0.024 (2)
N9	0.055 (2)	0.052 (2)	0.0335 (19)	−0.0009 (18)	−0.0027 (17)	−0.0099 (17)
N10	0.050 (2)	0.043 (2)	0.0343 (19)	−0.0096 (16)	0.0042 (16)	−0.0137 (15)
N11	0.079 (3)	0.070 (3)	0.042 (2)	−0.027 (2)	0.015 (2)	−0.020 (2)
N12	0.073 (3)	0.061 (3)	0.046 (2)	−0.022 (2)	−0.009 (2)	−0.011 (2)
N13	0.057 (2)	0.049 (2)	0.0305 (19)	−0.0063 (18)	−0.0016 (17)	−0.0100 (17)
N14	0.056 (2)	0.044 (2)	0.0281 (18)	−0.0104 (16)	−0.0011 (16)	−0.0094 (15)
N15	0.092 (3)	0.059 (3)	0.066 (3)	−0.030 (2)	−0.020 (2)	−0.012 (2)
N16	0.071 (3)	0.069 (3)	0.087 (4)	−0.031 (2)	0.009 (3)	−0.018 (3)
Cl2	0.0657 (7)	0.0775 (7)	0.0603 (6)	−0.0101 (5)	0.0057 (5)	−0.0196 (5)
O5	0.0657 (7)	0.0775 (7)	0.0603 (6)	−0.0101 (5)	0.0057 (5)	−0.0196 (5)
O6	0.0657 (7)	0.0775 (7)	0.0603 (6)	−0.0101 (5)	0.0057 (5)	−0.0196 (5)
O7	0.0657 (7)	0.0775 (7)	0.0603 (6)	−0.0101 (5)	0.0057 (5)	−0.0196 (5)
O8	0.0657 (7)	0.0775 (7)	0.0603 (6)	−0.0101 (5)	0.0057 (5)	−0.0196 (5)
Cl1	0.0508 (5)	0.0519 (5)	0.0518 (5)	0.0007 (4)	0.0035 (4)	−0.0094 (4)
O1	0.0508 (5)	0.0519 (5)	0.0518 (5)	0.0007 (4)	0.0035 (4)	−0.0094 (4)
O2	0.0508 (5)	0.0519 (5)	0.0518 (5)	0.0007 (4)	0.0035 (4)	−0.0094 (4)
O3	0.0508 (5)	0.0519 (5)	0.0518 (5)	0.0007 (4)	0.0035 (4)	−0.0094 (4)
O4	0.0508 (5)	0.0519 (5)	0.0518 (5)	0.0007 (4)	0.0035 (4)	−0.0094 (4)

Geometric parameters (Å, º)

Ag1—N1	2.139 (3)	C23—H23	0.9300
Ag1—N5	2.139 (3)	C24—C25	1.451 (5)
Ag2—N9	2.138 (3)	C24—H24	0.9300
Ag2—N13	2.142 (3)	C25—N10	1.371 (5)
C1—N1	1.356 (5)	C25—C26	1.420 (5)
C1—C2	1.387 (5)	C26—C27	1.379 (5)
C1—H1	0.9300	C26—H26	0.9300
C2—C3	1.430 (5)	C27—N9	1.356 (5)
C2—H2	0.9300	C27—H27	0.9300
C3—N2	1.384 (5)	C34—N13	1.323 (5)
C3—C4	1.415 (5)	C34—C35	1.402 (5)
C4—C5	1.396 (5)	C34—H34	0.9300
C4—H4	0.9300	C35—C36	1.433 (5)
C5—N1	1.365 (5)	C35—H35	0.9300
C5—H5	0.9300	C36—N14	1.358 (5)
C12—N5	1.360 (5)	C36—C37	1.458 (5)
C12—C13	1.360 (5)	C37—C38	1.380 (5)
C12—H12	0.9300	C37—H37	0.9300
C13—C14	1.416 (5)	C38—N13	1.345 (5)
C13—H13	0.9300	C38—H38	0.9300
C14—N6	1.372 (5)	C28—N10	1.482 (5)
C14—C15	1.442 (5)	C28—C29	1.550 (6)
C15—C16	1.380 (5)	C28—H28A	0.9700
C15—H15	0.9300	C28—H28B	0.9700
C16—N5	1.345 (5)	C29—C30	1.478 (6)
C16—H16	0.9300	C29—H29A	0.9700
C6—N2	1.501 (5)	C29—H29B	0.9700
C6—C7	1.539 (6)	C30—N11	1.177 (5)
C6—H6A	0.9700	C31—N10	1.459 (5)
C6—H6B	0.9700	C31—C32	1.553 (6)
C7—C8	1.476 (7)	C31—H31A	0.9700
C7—H7A	0.9700	C31—H31B	0.9700
C7—H7B	0.9700	C32—C33	1.452 (6)
C8—N3	1.141 (6)	C32—H32A	0.9700
C9—N2	1.481 (5)	C32—H32B	0.9700
C9—C10	1.525 (6)	C33—N12	1.155 (5)
C9—H9A	0.9600	C39—N14	1.473 (5)
C9—H9B	0.9601	C39—C40	1.526 (6)
C10—C11	1.481 (6)	C39—H39A	0.9700
C10—H10A	0.9700	C39—H39B	0.9700
C10—H10B	0.9700	C40—C41	1.517 (7)
C11—N4	1.128 (5)	C40—H40A	0.9700
C17—N6	1.490 (5)	C40—H40B	0.9700
C17—C18	1.570 (5)	C41—N15	1.123 (6)
C17—H17A	0.9700	C42—N14	1.499 (5)
C17—H17B	0.9700	C42—C43	1.533 (6)
C18—C19	1.492 (7)	C42—H42A	0.9700
C18—H18A	0.9700	C42—H42B	0.9700
C18—H18B	0.9700	C43—C44	1.436 (7)
C19—N7	1.131 (6)	C43—H43A	0.9700
C20—N6	1.475 (5)	C43—H43B	0.9700
C20—C21	1.550 (5)	C44—N16	1.152 (6)
C20—H20A	0.9700	Cl2—O6	1.396 (3)
C20—H20B	0.9700	Cl2—O8	1.426 (3)
C21—C22	1.475 (6)	Cl2—O7	1.454 (4)
C21—H21A	0.9700	Cl2—O5	1.460 (3)
C21—H21B	0.9700	Cl1—O2	1.429 (3)
C22—N8	1.122 (5)	Cl1—O3	1.444 (3)
C23—N9	1.343 (5)	Cl1—O4	1.452 (3)
C23—C24	1.409 (5)	Cl1—O1	1.460 (3)
N1—Ag1—N5	179.10 (13)	C35—C34—H34	117.1
N9—Ag2—N13	177.12 (13)	C34—C35—C36	119.2 (4)
N1—C1—C2	124.4 (4)	C34—C35—H35	120.4
N1—C1—H1	117.8	C36—C35—H35	120.4
C2—C1—H1	117.8	N14—C36—C35	124.2 (4)
C1—C2—C3	119.5 (4)	N14—C36—C37	121.5 (3)
C1—C2—H2	120.2	C35—C36—C37	114.3 (3)
C3—C2—H2	120.2	C38—C37—C36	119.5 (4)
N2—C3—C4	122.7 (4)	C38—C37—H37	120.2
N2—C3—C2	120.9 (3)	C36—C37—H37	120.2
C4—C3—C2	116.3 (4)	N13—C38—C37	125.3 (4)
C5—C4—C3	119.7 (4)	N13—C38—H38	117.3
C5—C4—H4	120.1	C37—C38—H38	117.3
C3—C4—H4	120.1	N10—C28—C29	111.1 (3)
N1—C5—C4	123.9 (4)	N10—C28—H28A	109.4
N1—C5—H5	118.1	C29—C28—H28A	109.4
C4—C5—H5	118.1	N10—C28—H28B	109.4
N5—C12—C13	124.2 (4)	C29—C28—H28B	109.4
N5—C12—H12	117.9	H28A—C28—H28B	108.0
C13—C12—H12	117.9	C30—C29—C28	110.9 (4)
C12—C13—C14	121.8 (4)	C30—C29—H29A	109.5
C12—C13—H13	119.1	C28—C29—H29A	109.5
C14—C13—H13	119.1	C30—C29—H29B	109.5
N6—C14—C13	125.1 (3)	C28—C29—H29B	109.5
N6—C14—C15	120.8 (3)	H29A—C29—H29B	108.1
C13—C14—C15	114.1 (3)	N11—C30—C29	178.7 (4)
C16—C15—C14	119.2 (4)	N10—C31—C32	112.9 (3)
C16—C15—H15	120.4	N10—C31—H31A	109.0
C14—C15—H15	120.4	C32—C31—H31A	109.0
N5—C16—C15	125.7 (4)	N10—C31—H31B	109.0
N5—C16—H16	117.2	C32—C31—H31B	109.0
C15—C16—H16	117.2	H31A—C31—H31B	107.8
N2—C6—C7	110.3 (3)	C33—C32—C31	111.1 (4)
N2—C6—H6A	109.6	C33—C32—H32A	109.4
C7—C6—H6A	109.6	C31—C32—H32A	109.4
N2—C6—H6B	109.6	C33—C32—H32B	109.4
C7—C6—H6B	109.6	C31—C32—H32B	109.4
H6A—C6—H6B	108.1	H32A—C32—H32B	108.0
C8—C7—C6	109.8 (4)	N12—C33—C32	177.6 (5)
C8—C7—H7A	109.7	N14—C39—C40	111.9 (4)
C6—C7—H7A	109.7	N14—C39—H39A	109.2
C8—C7—H7B	109.7	C40—C39—H39A	109.2
C6—C7—H7B	109.7	N14—C39—H39B	109.2
H7A—C7—H7B	108.2	C40—C39—H39B	109.2
N3—C8—C7	177.1 (6)	H39A—C39—H39B	107.9
N2—C9—C10	115.7 (3)	C41—C40—C39	111.3 (4)
N2—C9—H9A	112.2	C41—C40—H40A	109.4
C10—C9—H9A	123.1	C39—C40—H40A	109.4
N2—C9—H9B	111.2	C41—C40—H40B	109.4
C10—C9—H9B	79.8	C39—C40—H40B	109.4
H9A—C9—H9B	109.5	H40A—C40—H40B	108.0
C11—C10—C9	115.4 (4)	N15—C41—C40	176.9 (6)
C11—C10—H10A	108.4	N14—C42—C43	115.0 (3)
C9—C10—H10A	108.4	N14—C42—H42A	108.5
C11—C10—H10B	108.4	C43—C42—H42A	108.5
C9—C10—H10B	108.4	N14—C42—H42B	108.5
H10A—C10—H10B	107.5	C43—C42—H42B	108.5
N4—C11—C10	178.9 (5)	H42A—C42—H42B	107.5
N6—C17—C18	113.7 (3)	C44—C43—C42	112.8 (4)
N6—C17—H17A	108.8	C44—C43—H43A	109.0
C18—C17—H17A	108.8	C42—C43—H43A	109.0
N6—C17—H17B	108.8	C44—C43—H43B	109.0
C18—C17—H17B	108.8	C42—C43—H43B	109.0
H17A—C17—H17B	107.7	H43A—C43—H43B	107.8
C19—C18—C17	112.8 (4)	N16—C44—C43	179.2 (5)
C19—C18—H18A	109.0	C1—N1—C5	116.1 (3)
C17—C18—H18A	109.0	C1—N1—Ag1	123.1 (3)
C19—C18—H18B	109.0	C5—N1—Ag1	120.7 (3)
C17—C18—H18B	109.0	C3—N2—C9	120.4 (3)
H18A—C18—H18B	107.8	C3—N2—C6	121.3 (3)
N7—C19—C18	177.8 (5)	C9—N2—C6	118.1 (3)
N6—C20—C21	114.1 (3)	C16—N5—C12	115.0 (3)
N6—C20—H20A	108.7	C16—N5—Ag1	122.3 (3)
C21—C20—H20A	108.7	C12—N5—Ag1	122.6 (3)
N6—C20—H20B	108.7	C14—N6—C20	121.2 (3)
C21—C20—H20B	108.7	C14—N6—C17	123.0 (3)
H20A—C20—H20B	107.6	C20—N6—C17	115.7 (3)
C22—C21—C20	114.5 (4)	C23—N9—C27	115.7 (3)
C22—C21—H21A	108.6	C23—N9—Ag2	120.0 (3)
C20—C21—H21A	108.6	C27—N9—Ag2	123.1 (3)
C22—C21—H21B	108.6	C25—N10—C31	123.0 (3)
C20—C21—H21B	108.6	C25—N10—C28	122.2 (3)
H21A—C21—H21B	107.6	C31—N10—C28	114.0 (3)
N8—C22—C21	177.3 (6)	C34—N13—C38	115.7 (3)
N9—C23—C24	125.3 (4)	C34—N13—Ag2	122.7 (3)
N9—C23—H23	117.3	C38—N13—Ag2	121.6 (3)
C24—C23—H23	117.3	C36—N14—C39	121.2 (3)
C23—C24—C25	117.7 (4)	C36—N14—C42	121.4 (3)
C23—C24—H24	121.2	C39—N14—C42	117.3 (3)
C25—C24—H24	121.2	O6—Cl2—O8	111.7 (2)
N10—C25—C26	123.8 (4)	O6—Cl2—O7	113.3 (2)
N10—C25—C24	119.9 (3)	O8—Cl2—O7	107.0 (2)
C26—C25—C24	116.3 (3)	O6—Cl2—O5	110.2 (2)
C27—C26—C25	119.6 (4)	O8—Cl2—O5	108.9 (2)
C27—C26—H26	120.2	O7—Cl2—O5	105.5 (2)
C25—C26—H26	120.2	O2—Cl1—O3	110.53 (18)
N9—C27—C26	125.2 (4)	O2—Cl1—O4	110.23 (18)
N9—C27—H27	117.4	O3—Cl1—O4	108.47 (17)
C26—C27—H27	117.4	O2—Cl1—O1	109.70 (17)
N13—C34—C35	125.8 (4)	O3—Cl1—O1	108.84 (18)
N13—C34—H34	117.1	O4—Cl1—O1	109.04 (17)
N1—C1—C2—C3	−0.8 (7)	C10—C9—N2—C3	97.1 (5)
C1—C2—C3—N2	177.7 (4)	C10—C9—N2—C6	−88.6 (4)
C1—C2—C3—C4	−0.3 (6)	C7—C6—N2—C3	−84.7 (5)
N2—C3—C4—C5	−177.3 (4)	C7—C6—N2—C9	101.0 (4)
C2—C3—C4—C5	0.7 (6)	C15—C16—N5—C12	−2.4 (6)
C3—C4—C5—N1	0.0 (6)	C15—C16—N5—Ag1	173.1 (3)
N5—C12—C13—C14	1.5 (6)	C13—C12—N5—C16	0.9 (5)
C12—C13—C14—N6	177.9 (4)	C13—C12—N5—Ag1	−174.6 (3)
C12—C13—C14—C15	−2.4 (5)	C13—C14—N6—C20	9.2 (6)
N6—C14—C15—C16	−179.3 (3)	C15—C14—N6—C20	−170.4 (3)
C13—C14—C15—C16	1.1 (5)	C13—C14—N6—C17	−165.4 (3)
C14—C15—C16—N5	1.4 (6)	C15—C14—N6—C17	15.0 (5)
N2—C6—C7—C8	179.7 (4)	C21—C20—N6—C14	−96.1 (4)
N2—C9—C10—C11	−66.3 (5)	C21—C20—N6—C17	78.8 (4)
N6—C17—C18—C19	78.6 (5)	C18—C17—N6—C14	−101.7 (4)
N6—C20—C21—C22	74.1 (5)	C18—C17—N6—C20	83.5 (4)
N9—C23—C24—C25	0.6 (6)	C24—C23—N9—C27	−1.5 (6)
C23—C24—C25—N10	−178.0 (4)	C24—C23—N9—Ag2	166.3 (3)
C23—C24—C25—C26	1.9 (5)	C26—C27—N9—C23	−0.2 (6)
N10—C25—C26—C27	176.5 (4)	C26—C27—N9—Ag2	−167.6 (3)
C24—C25—C26—C27	−3.4 (6)	C26—C25—N10—C31	−165.0 (4)
C25—C26—C27—N9	2.7 (6)	C24—C25—N10—C31	14.9 (6)
N13—C34—C35—C36	−3.4 (7)	C26—C25—N10—C28	4.0 (6)
C34—C35—C36—N14	−179.2 (4)	C24—C25—N10—C28	−176.1 (4)
C34—C35—C36—C37	0.7 (6)	C32—C31—N10—C25	−94.3 (5)
N14—C36—C37—C38	−179.9 (4)	C32—C31—N10—C28	95.9 (4)
C35—C36—C37—C38	0.2 (6)	C29—C28—N10—C25	−84.5 (4)
C36—C37—C38—N13	1.2 (7)	C29—C28—N10—C31	85.4 (4)
N10—C28—C29—C30	−168.5 (3)	C35—C34—N13—C38	4.6 (7)
N10—C31—C32—C33	−173.9 (3)	C35—C34—N13—Ag2	−175.5 (3)
N14—C39—C40—C41	−179.8 (4)	C37—C38—N13—C34	−3.5 (7)
N14—C42—C43—C44	64.4 (5)	C37—C38—N13—Ag2	176.6 (3)
C2—C1—N1—C5	1.5 (6)	C35—C36—N14—C39	179.3 (4)
C2—C1—N1—Ag1	−174.1 (3)	C37—C36—N14—C39	−0.6 (6)
C4—C5—N1—C1	−1.1 (6)	C35—C36—N14—C42	2.3 (6)
C4—C5—N1—Ag1	174.7 (3)	C37—C36—N14—C42	−177.6 (4)
C4—C3—N2—C9	−3.2 (6)	C40—C39—N14—C36	79.6 (5)
C2—C3—N2—C9	178.9 (4)	C40—C39—N14—C42	−103.2 (4)
C4—C3—N2—C6	−177.3 (4)	C43—C42—N14—C36	−101.7 (5)
C2—C3—N2—C6	4.8 (6)	C43—C42—N14—C39	81.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N4^i	0.93	2.59	3.365 (6)	142
C10—H10A···N11^ii	0.97	2.52	3.362 (6)	145
C10—H10B···O3	0.97	2.57	3.346 (5)	137
C10—H10B···N15^i	0.97	2.57	3.267 (6)	129
C17—H17A···O7^iii	0.97	2.52	3.305 (5)	138
C29—H29A···O4^ii	0.97	2.51	3.307 (5)	140
C29—H29B···N8^i	0.97	2.68	3.329 (6)	125
C32—H32B···O4^iv	0.97	2.61	3.279 (5)	127
C32—H32B···N7^v	0.97	2.83	3.474 (6)	125
C34—H34···O7^vi	0.93	2.59	3.405 (5)	147
C35—H35···N16^v	0.93	2.54	3.382 (6)	151
C38—H38···O2	0.93	2.53	3.446 (5)	168
C40—H40A···N4	0.97	2.59	3.380 (6)	138
C43—H43A···N3^v	0.97	2.62	3.457 (7)	145

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