One-dimensional Cu^I and Ag^I ladder-like coordination polymers supported by 2-ethyl-1-(pyridin-3-ylmeth­yl)-1H-benzimidazole

The title complexes, poly[[bis­[[mu]₂-2-ethyl-1-(pyridin-3-ylmeth­yl)-1H-benzimidazole-[kappa]²N¹:N³]copper(I)] tetra­fluoro­borate aceto­nitrile monosolvate], {[Cu(C₁₅H₁₅N₃)₂]BF₄·CH₃CN}_n, (I), and poly[[bis­[[mu]₂-2-ethyl-1-(pyridin-3-ylmeth­yl)-1H-benz­imidazole-[kappa]²N¹:N³]silver(I)] perchlorate methanol monosolvate], {[Ag(C₁₅H₁₅N₃)₂]ClO₄·CH₃OH}_n, (II), are isostructural and exhibit one-dimensional ladder-like structures in which each asymmetric unit contains one metal ion (Cu⁺ or Ag⁺), two 2-ethyl-1-(pyridin-3-ylmeth­yl)-1H-benzimidazole (bep) ligands, one counter-anion (tetra­fluoro­borate or perchlorate) and one interstitial mol­ecule (aceto­nitrile or methanol). Each metal ion exhibits a distorted tetra­hedral coordination geometry consisting of two pyridyl and two benzimidazole N atoms from four distinct ligands. Two metal ions are linked by two bep ligands to form a centrosymmetric 18-membered M₂(bep)₂ metallacycle, while adjacent M₂(bep)₂ metallacycles are further inter­linked by another two bep ligands resulting in a ladder-like array. In the extended structure, four adjacent ladder-like arrays are connected together through C-H...F, O-H...O and C-H...O hydrogen bonds between bep ligands, solvent mol­ecules and counter-anions into a three-dimensional supra­molecular structure.

S1. Introduction

Currently, the rational design and synthesis of inorganic–organic coordination polymers have attracted considerable attention due to the intriguing variety of architectures and topologies, and potential applications in gas storage and separation, ion exchange, magnetism, and luminescence (Hill et al., 2005; Hong et al., 2007; Murray et al., 2009; Zhang, Liu et al., 2010; Zhang, Zhang et al., 2013). Many factors, such as the metal centres (as nodes), organic linkers (as building blocks), solvent molecules, temperature, templates, counter-anions etc., can affect the final architectures (Tong et al., 1998; Ferey et al., 2005; Bradshaw et al., 2005; Uemura et al., 2006; Zhang, Wang et al., 2010). In particular, the structure of the ligand and the coordination mode of the metal ion play key roles in the manipulation of the coordination polymer (Liu et al., 2007; Lee et al., 2008; Zheng et al., 2009).

There has been much inter­est and progress recently in the crystal engineering of supra­molecular architectures organized and sustained by means of bis-heterocyclic chelating or bridging ligands with pyridine, pyrazine, imidazole and diazo­les, and 4,4'-bi­pyridine and its derivatives have been the most frequently used bridging ligands to constructed inter­esting grid or chain-like coordination polymers (Hartshorn et al., 1998; Li et al., 2007; Zhai et al., 2011). Recently, pyridyl/benzimidazolyl-based ligands with a freely rotatable methyl­ene (–CH₂–) juncture between the pyridyl ring and the benzimidazole moiety have attracted considerable attention for two main reasons: (i) they possess flexibility owing to the presence of the methyl­ene (–CH₂–) spacer; (ii) they can act as µ₂-bridging ligands via the pyridyl and benzimidazole N atoms. In previous studies, N-(pyridin-2-yl­methyl)-1H-benzimidazole (2-pb-m), N-(pyridin-3-yl­methyl)-1H-benzimidazole (3-pb-m) and N-(pyridin-4-yl­methyl)-1H-benzimidazole (4-pb-m) have been used to create some one-dimensional double-helical chains and two- and three-dimensional networks with d¹⁰ metals (Wang et al., 2009; Huang et al., 2006).

To extend the study of these types of ligands, an ethyl group was introduced into the 2-position of the benzimidazole system giving a new ligand 2-ethyl-1-(pyridin-3-yl­methyl)-1H-benzimidazole (bep) which is expected to result in inter­esting structures mediated by by steric and electronic effects of the ethyl group. In this study, two isostructural compounds, {[Cu(bep)₂]BF₄.CH₃CN)}_n, (I), and {[Ag(bep)₂]ClO₄.CH₃OH)}_n, (II), were obtained by the reaction of bep and [Cu(CH₃CN)₄]BF₄ or AgClO₄. These two isostructural complexes exhibit one-dimensional ladder-like structures which are different from previously reported complexes.

S2. Experimental

S2.1. Synthesis and crystallization

Bep was synthesized according to the method reported by Huang et al. (2006). For the preparation of (I), a solution of [Cu(CH₃CN)₄]BF₄ (0.05 mmol) in a mixture of CH₃CN (3 ml) and N,N-di­methyl­formamide (DMF, 3 ml) was added to bep (0.1 mmol). A yellow solution formed and was filtered off. Di­ethyl ether was diffused slowly into the solution and, after several days, yellow block-shaped crystals suitable for X-ray diffraction analysis had formed (yield ~60%). Elemental analysis calculated for C₃₂H₃₃BCuF₄N₇: C 57.71, H 4.99, N 14.72%; found: C 57.48, H 5.12, N 14.34%. For the preparation of (II), a solution of AgClO₄ (0.05 mmol) in a mixture of CH₃OH (3 ml) and DMF (3 ml) was added to bep (0.1 mmol). A yellow solution formed and was filtered off. Di­ethyl ether was diffused slowly into the solution and, after several days, yellow block-shaped crystals suitable for X-ray diffraction analysis had formed (yield ~80%). Elemental analysis calculated for C₃₁H₃₄AgClN₆O₅: C 52.15, H 4.80, N 11.77%; found: C 52.01, H 4.96, N 11.46%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. In both structures, all C-bound H atoms were placed in idealized positions, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

In order to make the refinement of the aceto­nitrile solvent molecules in (I) and the methanol solvent molecules in (II) fully anisotropic, all their C, N and O atoms were subjected to a `rigid bond' restraint (DELU instruction in SHELXL97; Sheldrick, 2008), i.e. the components of the (anisotropic) displacement parameters in the direction of the corresponding bonds were restrained to be equal within an effective standard uncertainty of 0.005 Å. In addition, within this same set of atoms, those closer than 1.7 Å were restrained with an effective standard uncertainty of 0.005 Å to have the same U^ij components (SIMU instruction). The refinement of the H atoms of the solvent aceto­nitrile molecules in (II) required the inclusion of some inter­molecular restraints to avoid convergence to unreasonable inter­molecular H···H distances. The H···H inter­molecular shortest contact distances were restrained to 2.30 Å.

S3. Results and discussion

As compounds (I) and (II) are isostructural, only the structure of (I) is described in detail here. The asymmetric unit of (I) contains one Cu^I atom, two coordinated bep ligands, one tetra­fluoro­borate counter-anion and one lattice aceto­nitrile molecule (Fig. 1). The Cu^I centre adopts a distorted tetra­hedral coordination geometry consisting of two pyridyl (py) N atoms [N6ⁱ and N3ⁱⁱ; symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z] and two benzimidazole (Bm) N atoms (N1 and N4), which are from four distinct ligands. The Cu—N_Bm bond lengths [2.018 (2) and 2.041 (2) Å] are distinctly shorter than those of Cu—N_py [2.108 (2) and 2.155 (2) Å] due to the benzimidazole group being more electron-rich, and hence a stronger donor than the pyridyl group. The same results have been observed by others (Su et al., 1999). The bond angles around each Cu^I centre (Table 2) are within the expected range for similar complexes (Su et al., 1999). In (II), the Ag—N_Bm [2.230 (3) and 2.257 (3) Å] and Ag—N_py [2.397 (3) and 2.443 (3) Å] bond lengths are both longer than the Cu—N bonds in (I) due to the Ag⁺ radius being larger than that of Cu⁺ (Huang et al., 2006).

Two metal ions are bridged by two µ₂-bep ligands, forming an 18-membered M₂(bep)₂ metallacycle with an M···M separation of 7.933 (1) Å for (I) and 8.167 (5) Å for (II) (Fig. 2). C—H···π inter­actions between ethyl H atoms of one ligand and the benzimidazole system of another molecule stabilize further the metallacycle [C—H···π(centroid): 3.086 Å for (I) and 3.303 Å for (II)]. Such metallacycles can be viewed as the rungs of the ladder, which are further connected by two bep ligands to form one-dimensional ladder-like arrays with the M···M separations of 9.368 (1) Å for (I) and 9.560 (7) Å for (II).

In contrast with other analogues, the title compounds exhibit one-dimensional ladder-like coordination polymers with metallacycle units, which maybe result of two factors: (i) the ligand possessing flexibility owing to the presence of a methyl­ene (–CH₂–) spacer between the pyridyl ring and the benzimidazole moiety; (ii) the steric and electronic effect of the ethyl group introduced into the 2-position of benzimidazole. Thus, the present work once again emphasizes the important role played by both the metal centres, and organic linkers, on the final structures of coordination complexes.

In the crystal packing, four adjacent ladder-like arrays are connected through C—H···F, O—H···O and C—H···O hydrogen-bonding inter­actions between bep ligands, lattice solvent molecules and counter-anions into a three-dimensional supra­molecular structure. In (I), the tetra­fluoro­borate anion connects four adjacent ladder-like arrays through C19—H19A···F3, C10—H10A···F2 and C10—H10B···F4 hydrogen bonds (Table 2), forming the three-dimensional supermolecular structure (Fig. 3a). In (II), the perchlorate anion acts in the same manner through C10—H10A···O3, C23—H23A···O4, O5—H5B···O1 and C31—H31C···O3 hydrogen bonds (Table 2 and Fig. 3b).

Related literature

For related literature, see: Bradshaw et al. (2005); Ferey et al. (2005); Hartshorn & Steel (1998); Hill et al. (2005); Hong (2007); Huang et al. (2006); Lee et al. (2008); Li et al. (2007); Liu et al. (2007); Murray et al. (2009); Su et al. (1999); Tong et al. (1998); Uemura et al. (2006); Wang et al. (2009); Zhai et al. (2011); Zhang et al. (2013); Zhang, Liu, Kanegawa & Sato (2010); Zhang, Wang, Feng & Li (2010); Zheng et al. (2009).

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).

Figures

Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radii and have been omitted from symmetry-generated atoms for clarity. [Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z.] [Please provide fully labelled ellipsoid plot]

Fig. 2 (a) The one-dimensional ladder-like chain of (I) and (II), (b) the 18-membered M₂(bep)₂ metallacycle and (c) a schematic view of the one-dimensional ladder-like chain. The Cu atom and the organic linear ligands are represented by red balls and the curved line mixed linear ligands act as linkers.

Fig. 3 (a) The three-dimensional network of (I) formed by C—H···F hydrogen-bonding interactions (partial H atoms have been omitted for clarity) and (b) the three-dimensional network of (II) formed by O—H···O and C—H···O hydrogen-bonding interactions (partial H atoms have been omitted for clarity).

(1) Poly[[bis[µ₂-2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole-κ²N¹:N³]copper(I)] tetrafluoroborate acetonitrile monosolvate]

Crystal data

[Cu(C15H15N3)2]BF4·C2H3N	V = 1486.42 (12) Å^3
Mr = 666.00	Z = 2
Triclinic, P1	F(000) = 688
Hall symbol: -P 1	Dx = 1.488 Mg m^−3
a = 9.3674 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.5367 (6) Å	θ = 2.2–25.0°
c = 13.3150 (7) Å	µ = 0.80 mm^−1
α = 89.912 (2)°	T = 298 K
β = 72.786 (2)°	Block, yellow
γ = 84.599 (1)°	0.68 × 0.21 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer	6748 independent reflections
Radiation source: fine-focus sealed tube	6004 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→12
Tmin = 0.614, Tmax = 0.890	k = −16→16
14603 measured reflections	l = −17→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0762P)^2 + 1.632P] where P = (Fo^2 + 2Fc^2)/3
6748 reflections	(Δ/σ)max = 0.001
408 parameters	Δρmax = 2.17 e Å^−3
20 restraints	Δρmin = −0.91 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
Cu1	0.42937 (3)	0.24036 (2)	0.32103 (2)	0.02427 (12)
N1	0.2425 (2)	0.25010 (17)	0.27419 (17)	0.0219 (4)
N2	0.0736 (2)	0.30988 (17)	0.19341 (17)	0.0224 (4)
N3	−0.4284 (2)	0.36926 (18)	0.28324 (19)	0.0264 (5)
N4	0.4437 (2)	0.20740 (18)	0.46810 (17)	0.0236 (4)
N5	0.3778 (2)	0.18863 (17)	0.64224 (17)	0.0219 (4)
C1	0.1811 (3)	0.1626 (2)	0.24431 (19)	0.0203 (5)
C2	0.2104 (3)	0.0532 (2)	0.2570 (2)	0.0237 (5)
H2A	0.2781	0.0279	0.2925	0.028*
C3	0.1360 (3)	−0.0165 (2)	0.2153 (2)	0.0262 (5)
H3A	0.1537	−0.0898	0.2231	0.031*
C4	0.0341 (3)	0.0211 (2)	0.1613 (2)	0.0258 (5)
H4A	−0.0128	−0.0281	0.1330	0.031*
C5	0.0017 (3)	0.1294 (2)	0.1492 (2)	0.0242 (5)
H5A	−0.0664	0.1545	0.1140	0.029*
C6	0.0762 (3)	0.1991 (2)	0.19250 (19)	0.0211 (5)
C7	0.1748 (3)	0.3359 (2)	0.2426 (2)	0.0218 (5)
C8	0.2027 (3)	0.4474 (2)	0.2649 (2)	0.0287 (6)
H8A	0.1613	0.4969	0.2223	0.034*
H8B	0.3099	0.4527	0.2463	0.034*
C9	0.1310 (4)	0.4775 (3)	0.3803 (3)	0.0410 (7)
H9A	0.1551	0.5477	0.3942	0.061*
H9B	0.1685	0.4265	0.4225	0.061*
H9C	0.0240	0.4775	0.3974	0.061*
C10	−0.0160 (3)	0.3819 (2)	0.1425 (2)	0.0258 (5)
H10A	−0.0228	0.3466	0.0795	0.031*
H10B	0.0344	0.4461	0.1214	0.031*
C11	−0.1724 (3)	0.4132 (2)	0.2146 (2)	0.0246 (5)
C12	−0.2054 (3)	0.5024 (2)	0.2813 (3)	0.0348 (6)
H12A	−0.1317	0.5475	0.2806	0.042*
C13	−0.3498 (3)	0.5242 (2)	0.3495 (3)	0.0390 (7)
H13A	−0.3742	0.5842	0.3945	0.047*
C14	−0.4565 (3)	0.4553 (2)	0.3491 (3)	0.0334 (6)
H14A	−0.5519	0.4690	0.3966	0.040*
C15	−0.2892 (3)	0.3507 (2)	0.2169 (2)	0.0241 (5)
H15A	−0.2691	0.2927	0.1696	0.029*
C16	0.5692 (3)	0.2153 (2)	0.5031 (2)	0.0224 (5)
C17	0.7172 (3)	0.2302 (2)	0.4468 (2)	0.0292 (6)
H17A	0.7471	0.2342	0.3739	0.035*
C18	0.8175 (3)	0.2389 (2)	0.5038 (2)	0.0316 (6)
H18A	0.9167	0.2490	0.4684	0.038*
C19	0.7736 (3)	0.2327 (2)	0.6133 (2)	0.0305 (6)
H19A	0.8437	0.2408	0.6490	0.037*
C20	0.6278 (3)	0.2147 (2)	0.6704 (2)	0.0265 (5)
H20A	0.5986	0.2093	0.7432	0.032*
C21	0.5286 (3)	0.20541 (19)	0.6119 (2)	0.0213 (5)
C22	0.3333 (3)	0.1911 (2)	0.5532 (2)	0.0225 (5)
C23	0.1791 (3)	0.1729 (2)	0.5521 (2)	0.0287 (6)
H23A	0.1614	0.2033	0.4893	0.034*
H23B	0.1065	0.2095	0.6127	0.034*
C24	0.1566 (3)	0.0542 (3)	0.5543 (2)	0.0361 (7)
H24A	0.0574	0.0454	0.5509	0.054*
H24B	0.1687	0.0248	0.6182	0.054*
H24C	0.2294	0.0176	0.4951	0.054*
C25	0.2879 (3)	0.1741 (2)	0.7503 (2)	0.0268 (5)
H25A	0.1835	0.1739	0.7525	0.032*
H25B	0.2950	0.2345	0.7934	0.032*
C26	0.3357 (3)	0.0720 (2)	0.7968 (2)	0.0230 (5)
C27	0.3125 (3)	0.0668 (2)	0.9045 (2)	0.0325 (6)
H27A	0.2703	0.1267	0.9480	0.039*
C28	0.3528 (4)	−0.0283 (3)	0.9463 (2)	0.0364 (7)
H28A	0.3378	−0.0334	1.0183	0.044*
N7	0.6571 (12)	0.7019 (7)	−0.0088 (9)	0.223 (5)
C31	0.6053 (9)	0.6234 (8)	0.0375 (6)	0.163 (4)
C32	0.5185 (11)	0.5398 (8)	0.0993 (5)	0.329 (9)
H32A	0.4936	0.5576	0.1729	0.493*
H32B	0.5777	0.4718	0.0846	0.493*
H32C	0.4279	0.5360	0.0802	0.493*
B1	0.1334 (4)	0.7004 (3)	0.1088 (3)	0.0328 (7)
F1	0.2692 (3)	0.7337 (2)	0.1087 (2)	0.0653 (7)
F2	0.0565 (4)	0.77528 (18)	0.06303 (19)	0.0726 (8)
F3	0.0482 (2)	0.69078 (16)	0.21312 (14)	0.0425 (4)
F4	0.1548 (2)	0.60215 (14)	0.05601 (14)	0.0417 (4)
C29	0.4154 (3)	−0.1153 (2)	0.8800 (2)	0.0294 (6)
H29A	0.4434	−0.1786	0.9088	0.035*
N6	0.4381 (2)	−0.11307 (18)	0.77614 (17)	0.0240 (4)
C30	0.3979 (3)	−0.0203 (2)	0.73583 (19)	0.0216 (5)
H30A	0.4125	−0.0179	0.6637	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01949 (17)	0.02608 (18)	0.03104 (19)	0.00154 (12)	−0.01450 (13)	−0.00219 (12)
N1	0.0167 (9)	0.0234 (10)	0.0271 (10)	0.0003 (8)	−0.0096 (8)	−0.0004 (8)
N2	0.0161 (9)	0.0239 (10)	0.0299 (11)	−0.0011 (8)	−0.0115 (8)	0.0022 (8)
N3	0.0185 (10)	0.0249 (11)	0.0380 (12)	−0.0013 (8)	−0.0121 (9)	0.0007 (9)
N4	0.0146 (9)	0.0292 (11)	0.0289 (11)	−0.0011 (8)	−0.0099 (8)	−0.0011 (8)
N5	0.0154 (9)	0.0236 (10)	0.0273 (11)	0.0013 (8)	−0.0083 (8)	−0.0017 (8)
C1	0.0152 (10)	0.0244 (12)	0.0219 (11)	−0.0006 (9)	−0.0070 (9)	−0.0017 (9)
C2	0.0184 (11)	0.0272 (12)	0.0265 (12)	0.0003 (9)	−0.0091 (9)	0.0022 (9)
C3	0.0225 (12)	0.0240 (12)	0.0313 (13)	−0.0022 (10)	−0.0068 (10)	0.0008 (10)
C4	0.0201 (11)	0.0290 (13)	0.0295 (13)	−0.0060 (10)	−0.0081 (10)	−0.0028 (10)
C5	0.0171 (11)	0.0315 (13)	0.0255 (12)	−0.0018 (10)	−0.0087 (9)	0.0004 (10)
C6	0.0149 (10)	0.0244 (12)	0.0237 (11)	0.0000 (9)	−0.0059 (9)	0.0017 (9)
C7	0.0141 (10)	0.0242 (12)	0.0277 (12)	0.0008 (9)	−0.0080 (9)	−0.0012 (9)
C8	0.0227 (12)	0.0249 (13)	0.0428 (15)	−0.0024 (10)	−0.0161 (11)	0.0018 (11)
C9	0.0428 (17)	0.0322 (15)	0.0492 (18)	0.0005 (13)	−0.0168 (15)	−0.0122 (13)
C10	0.0187 (11)	0.0287 (13)	0.0336 (13)	−0.0021 (10)	−0.0133 (10)	0.0078 (10)
C11	0.0188 (11)	0.0204 (11)	0.0391 (14)	−0.0017 (9)	−0.0155 (10)	0.0074 (10)
C12	0.0233 (13)	0.0239 (13)	0.062 (2)	−0.0019 (10)	−0.0206 (13)	−0.0026 (12)
C13	0.0274 (14)	0.0240 (13)	0.067 (2)	0.0042 (11)	−0.0185 (14)	−0.0142 (13)
C14	0.0201 (12)	0.0294 (14)	0.0506 (17)	0.0054 (10)	−0.0128 (12)	−0.0085 (12)
C15	0.0188 (11)	0.0237 (12)	0.0334 (13)	−0.0006 (9)	−0.0136 (10)	0.0010 (10)
C16	0.0166 (11)	0.0251 (12)	0.0291 (12)	−0.0006 (9)	−0.0128 (10)	0.0006 (9)
C17	0.0182 (12)	0.0389 (15)	0.0330 (14)	−0.0041 (11)	−0.0112 (10)	0.0081 (11)
C18	0.0182 (12)	0.0370 (15)	0.0450 (16)	−0.0076 (11)	−0.0161 (11)	0.0117 (12)
C19	0.0247 (13)	0.0316 (14)	0.0442 (16)	−0.0055 (11)	−0.0232 (12)	0.0062 (11)
C20	0.0260 (13)	0.0272 (13)	0.0311 (13)	−0.0010 (10)	−0.0163 (11)	0.0007 (10)
C21	0.0165 (11)	0.0188 (11)	0.0300 (12)	−0.0003 (9)	−0.0097 (9)	−0.0012 (9)
C22	0.0162 (11)	0.0235 (12)	0.0287 (12)	0.0022 (9)	−0.0095 (9)	−0.0034 (9)
C23	0.0129 (11)	0.0407 (15)	0.0341 (14)	−0.0028 (10)	−0.0092 (10)	−0.0014 (11)
C24	0.0277 (14)	0.0476 (18)	0.0373 (15)	−0.0150 (13)	−0.0130 (12)	−0.0007 (13)
C25	0.0204 (12)	0.0294 (13)	0.0271 (13)	0.0046 (10)	−0.0037 (10)	−0.0032 (10)
C26	0.0146 (10)	0.0285 (12)	0.0242 (12)	−0.0004 (9)	−0.0037 (9)	−0.0021 (9)
C27	0.0305 (14)	0.0385 (15)	0.0249 (13)	0.0033 (12)	−0.0046 (11)	−0.0073 (11)
C28	0.0381 (16)	0.0488 (18)	0.0200 (12)	−0.0009 (13)	−0.0061 (11)	0.0009 (11)
N7	0.185 (8)	0.191 (9)	0.219 (10)	−0.045 (7)	0.062 (7)	−0.061 (7)
C31	0.110 (6)	0.216 (9)	0.097 (5)	0.067 (5)	0.046 (4)	0.071 (5)
C32	0.142 (9)	0.268 (14)	0.457 (17)	0.053 (9)	0.071 (12)	0.198 (13)
B1	0.0459 (19)	0.0272 (15)	0.0255 (15)	−0.0008 (14)	−0.0120 (13)	0.0028 (11)
F1	0.0552 (14)	0.0650 (15)	0.0721 (16)	−0.0250 (12)	−0.0073 (12)	−0.0162 (12)
F2	0.136 (2)	0.0401 (11)	0.0522 (13)	0.0193 (13)	−0.0523 (15)	0.0049 (9)
F3	0.0422 (10)	0.0499 (11)	0.0315 (9)	0.0071 (8)	−0.0087 (8)	0.0014 (8)
F4	0.0626 (12)	0.0299 (9)	0.0356 (9)	−0.0032 (8)	−0.0194 (9)	−0.0026 (7)
C29	0.0270 (13)	0.0358 (14)	0.0267 (13)	−0.0018 (11)	−0.0103 (11)	0.0065 (11)
N6	0.0182 (10)	0.0277 (11)	0.0269 (11)	−0.0001 (8)	−0.0087 (8)	−0.0009 (8)
C30	0.0173 (11)	0.0269 (12)	0.0212 (11)	0.0005 (9)	−0.0072 (9)	−0.0011 (9)

Geometric parameters (Å, º)

Cu1—N1	2.018 (2)	C14—H14A	0.9300
Cu1—N4	2.041 (2)	C15—H15A	0.9300
Cu1—N6^i	2.108 (2)	C16—C21	1.394 (4)
Cu1—N3^ii	2.155 (2)	C16—C17	1.397 (4)
N1—C7	1.328 (3)	C17—C18	1.383 (4)
N1—C1	1.396 (3)	C17—H17A	0.9300
N2—C7	1.364 (3)	C18—C19	1.396 (4)
N2—C6	1.386 (3)	C18—H18A	0.9300
N2—C10	1.474 (3)	C19—C20	1.392 (4)
N3—C15	1.341 (3)	C19—H19A	0.9300
N3—C14	1.348 (4)	C20—C21	1.390 (3)
N3—Cu1^iii	2.155 (2)	C20—H20A	0.9300
N4—C22	1.320 (3)	C22—C23	1.487 (3)
N4—C16	1.398 (3)	C23—C24	1.522 (4)
N5—C22	1.368 (3)	C23—H23A	0.9700
N5—C21	1.386 (3)	C23—H23B	0.9700
N5—C25	1.458 (3)	C24—H24A	0.9600
C1—C2	1.393 (3)	C24—H24B	0.9600
C1—C6	1.402 (3)	C24—H24C	0.9600
C2—C3	1.380 (4)	C25—C26	1.509 (4)
C2—H2A	0.9300	C25—H25A	0.9700
C3—C4	1.403 (4)	C25—H25B	0.9700
C3—H3A	0.9300	C26—C27	1.387 (4)
C4—C5	1.384 (4)	C26—C30	1.390 (3)
C4—H4A	0.9300	C27—C28	1.383 (4)
C5—C6	1.392 (4)	C27—H27A	0.9300
C5—H5A	0.9300	C28—C29	1.374 (4)
C7—C8	1.492 (4)	C28—H28A	0.9300
C8—C9	1.517 (4)	N7—C31	1.223 (5)
C8—H8A	0.9700	C31—C32	1.482 (5)
C8—H8B	0.9700	C32—H32A	0.9600
C9—H9A	0.9600	C32—H32B	0.9600
C9—H9B	0.9600	C32—H32C	0.9600
C9—H9C	0.9600	B1—F1	1.375 (4)
C10—C11	1.511 (4)	B1—F2	1.379 (4)
C10—H10A	0.9700	B1—F4	1.387 (4)
C10—H10B	0.9700	B1—F3	1.394 (4)
C11—C12	1.383 (4)	C29—N6	1.337 (3)
C11—C15	1.398 (3)	C29—H29A	0.9300
C12—C13	1.390 (4)	N6—C30	1.348 (3)
C12—H12A	0.9300	N6—Cu1^i	2.108 (2)
C13—C14	1.382 (4)	C30—H30A	0.9300
C13—H13A	0.9300
N1—Cu1—N4	126.94 (9)	N3—C15—H15A	118.1
N1—Cu1—N6^i	101.41 (8)	C11—C15—H15A	118.1
N4—Cu1—N6^i	104.97 (9)	C21—C16—C17	120.2 (2)
N1—Cu1—N3^ii	118.24 (8)	C21—C16—N4	109.5 (2)
N4—Cu1—N3^ii	99.80 (9)	C17—C16—N4	130.3 (2)
N6^i—Cu1—N3^ii	102.48 (9)	C18—C17—C16	117.4 (3)
C7—N1—C1	105.5 (2)	C18—C17—H17A	121.3
C7—N1—Cu1	128.08 (17)	C16—C17—H17A	121.3
C1—N1—Cu1	124.81 (16)	C17—C18—C19	121.7 (2)
C7—N2—C6	107.2 (2)	C17—C18—H18A	119.2
C7—N2—C10	128.2 (2)	C19—C18—H18A	119.2
C6—N2—C10	124.4 (2)	C20—C19—C18	121.8 (2)
C15—N3—C14	117.2 (2)	C20—C19—H19A	119.1
C15—N3—Cu1^iii	119.66 (18)	C18—C19—H19A	119.1
C14—N3—Cu1^iii	119.59 (19)	C21—C20—C19	115.9 (2)
C22—N4—C16	105.4 (2)	C21—C20—H20A	122.1
C22—N4—Cu1	127.69 (17)	C19—C20—H20A	122.1
C16—N4—Cu1	126.17 (17)	N5—C21—C20	131.3 (2)
C22—N5—C21	107.0 (2)	N5—C21—C16	105.6 (2)
C22—N5—C25	128.4 (2)	C20—C21—C16	123.0 (2)
C21—N5—C25	124.6 (2)	N4—C22—N5	112.5 (2)
C2—C1—N1	130.6 (2)	N4—C22—C23	123.8 (2)
C2—C1—C6	120.1 (2)	N5—C22—C23	123.7 (2)
N1—C1—C6	109.3 (2)	C22—C23—C24	111.8 (2)
C3—C2—C1	117.9 (2)	C22—C23—H23A	109.3
C3—C2—H2A	121.0	C24—C23—H23A	109.3
C1—C2—H2A	121.0	C22—C23—H23B	109.3
C2—C3—C4	121.4 (2)	C24—C23—H23B	109.3
C2—C3—H3A	119.3	H23A—C23—H23B	107.9
C4—C3—H3A	119.3	C23—C24—H24A	109.5
C5—C4—C3	121.6 (2)	C23—C24—H24B	109.5
C5—C4—H4A	119.2	H24A—C24—H24B	109.5
C3—C4—H4A	119.2	C23—C24—H24C	109.5
C4—C5—C6	116.6 (2)	H24A—C24—H24C	109.5
C4—C5—H5A	121.7	H24B—C24—H24C	109.5
C6—C5—H5A	121.7	N5—C25—C26	113.4 (2)
N2—C6—C5	132.0 (2)	N5—C25—H25A	108.9
N2—C6—C1	105.6 (2)	C26—C25—H25A	108.9
C5—C6—C1	122.4 (2)	N5—C25—H25B	108.9
N1—C7—N2	112.4 (2)	C26—C25—H25B	108.9
N1—C7—C8	122.6 (2)	H25A—C25—H25B	107.7
N2—C7—C8	124.9 (2)	C27—C26—C30	117.8 (2)
C7—C8—C9	110.5 (2)	C27—C26—C25	119.9 (2)
C7—C8—H8A	109.6	C30—C26—C25	122.3 (2)
C9—C8—H8A	109.6	C28—C27—C26	119.2 (3)
C7—C8—H8B	109.6	C28—C27—H27A	120.4
C9—C8—H8B	109.6	C26—C27—H27A	120.4
H8A—C8—H8B	108.1	C29—C28—C27	119.1 (3)
C8—C9—H9A	109.5	C29—C28—H28A	120.4
C8—C9—H9B	109.5	C27—C28—H28A	120.4
H9A—C9—H9B	109.5	N7—C31—C32	170.4 (9)
C8—C9—H9C	109.5	C31—C32—H32A	109.5
H9A—C9—H9C	109.5	C31—C32—H32B	109.5
H9B—C9—H9C	109.5	H32A—C32—H32B	109.5
N2—C10—C11	112.0 (2)	C31—C32—H32C	109.5
N2—C10—H10A	109.2	H32A—C32—H32C	109.5
C11—C10—H10A	109.2	H32B—C32—H32C	109.5
N2—C10—H10B	109.2	F1—B1—F2	110.7 (3)
C11—C10—H10B	109.2	F1—B1—F4	110.3 (3)
H10A—C10—H10B	107.9	F2—B1—F4	110.1 (3)
C12—C11—C15	117.6 (2)	F1—B1—F3	107.9 (3)
C12—C11—C10	122.0 (2)	F2—B1—F3	108.1 (3)
C15—C11—C10	120.4 (2)	F4—B1—F3	109.7 (2)
C11—C12—C13	119.4 (3)	N6—C29—C28	123.0 (3)
C11—C12—H12A	120.3	N6—C29—H29A	118.5
C13—C12—H12A	120.3	C28—C29—H29A	118.5
C14—C13—C12	118.9 (3)	C29—N6—C30	117.6 (2)
C14—C13—H13A	120.6	C29—N6—Cu1^i	119.65 (18)
C12—C13—H13A	120.6	C30—N6—Cu1^i	121.62 (17)
N3—C14—C13	123.0 (3)	N6—C30—C26	123.2 (2)
N3—C14—H14A	118.5	N6—C30—H30A	118.4
C13—C14—H14A	118.5	C26—C30—H30A	118.4
N3—C15—C11	123.9 (2)
N4—Cu1—N1—C7	113.9 (2)	Cu1^iii—N3—C14—C13	159.6 (3)
N6^i—Cu1—N1—C7	−127.3 (2)	C12—C13—C14—N3	−2.2 (5)
N3^ii—Cu1—N1—C7	−16.3 (2)	C14—N3—C15—C11	1.8 (4)
N4—Cu1—N1—C1	−82.9 (2)	Cu1^iii—N3—C15—C11	−156.8 (2)
N6^i—Cu1—N1—C1	35.9 (2)	C12—C11—C15—N3	−3.4 (4)
N3^ii—Cu1—N1—C1	146.89 (19)	C10—C11—C15—N3	175.6 (2)
N1—Cu1—N4—C22	−2.2 (3)	C22—N4—C16—C21	−1.3 (3)
N6^i—Cu1—N4—C22	−119.4 (2)	Cu1—N4—C16—C21	169.25 (17)
N3^ii—Cu1—N4—C22	134.8 (2)	C22—N4—C16—C17	178.6 (3)
N1—Cu1—N4—C16	−170.63 (19)	Cu1—N4—C16—C17	−10.9 (4)
N6^i—Cu1—N4—C16	72.2 (2)	C21—C16—C17—C18	−2.5 (4)
N3^ii—Cu1—N4—C16	−33.7 (2)	N4—C16—C17—C18	177.7 (3)
C7—N1—C1—C2	179.8 (3)	C16—C17—C18—C19	0.2 (4)
Cu1—N1—C1—C2	13.4 (4)	C17—C18—C19—C20	1.7 (5)
C7—N1—C1—C6	0.9 (3)	C18—C19—C20—C21	−1.2 (4)
Cu1—N1—C1—C6	−165.47 (16)	C22—N5—C21—C20	177.2 (3)
N1—C1—C2—C3	−177.4 (2)	C25—N5—C21—C20	−1.4 (4)
C6—C1—C2—C3	1.4 (4)	C22—N5—C21—C16	−1.2 (3)
C1—C2—C3—C4	0.2 (4)	C25—N5—C21—C16	−179.9 (2)
C2—C3—C4—C5	−1.2 (4)	C19—C20—C21—N5	−179.4 (3)
C3—C4—C5—C6	0.5 (4)	C19—C20—C21—C16	−1.2 (4)
C7—N2—C6—C5	−176.9 (3)	C17—C16—C21—N5	−178.3 (2)
C10—N2—C6—C5	−0.9 (4)	N4—C16—C21—N5	1.6 (3)
C7—N2—C6—C1	0.8 (3)	C17—C16—C21—C20	3.1 (4)
C10—N2—C6—C1	176.8 (2)	N4—C16—C21—C20	−177.0 (2)
C4—C5—C6—N2	178.5 (3)	C16—N4—C22—N5	0.5 (3)
C4—C5—C6—C1	1.1 (4)	Cu1—N4—C22—N5	−169.83 (16)
C2—C1—C6—N2	179.9 (2)	C16—N4—C22—C23	−177.1 (2)
N1—C1—C6—N2	−1.1 (3)	Cu1—N4—C22—C23	12.5 (4)
C2—C1—C6—C5	−2.1 (4)	C21—N5—C22—N4	0.4 (3)
N1—C1—C6—C5	176.9 (2)	C25—N5—C22—N4	179.0 (2)
C1—N1—C7—N2	−0.4 (3)	C21—N5—C22—C23	178.1 (2)
Cu1—N1—C7—N2	165.38 (17)	C25—N5—C22—C23	−3.3 (4)
C1—N1—C7—C8	176.5 (2)	N4—C22—C23—C24	97.7 (3)
Cu1—N1—C7—C8	−17.7 (4)	N5—C22—C23—C24	−79.7 (3)
C6—N2—C7—N1	−0.3 (3)	C22—N5—C25—C26	115.1 (3)
C10—N2—C7—N1	−176.0 (2)	C21—N5—C25—C26	−66.5 (3)
C6—N2—C7—C8	−177.1 (2)	N5—C25—C26—C27	151.7 (2)
C10—N2—C7—C8	7.1 (4)	N5—C25—C26—C30	−30.9 (3)
N1—C7—C8—C9	−72.1 (3)	C30—C26—C27—C28	0.5 (4)
N2—C7—C8—C9	104.4 (3)	C25—C26—C27—C28	178.1 (3)
C7—N2—C10—C11	−96.8 (3)	C26—C27—C28—C29	0.3 (5)
C6—N2—C10—C11	88.1 (3)	C27—C28—C29—N6	−0.8 (5)
N2—C10—C11—C12	89.6 (3)	C28—C29—N6—C30	0.5 (4)
N2—C10—C11—C15	−89.3 (3)	C28—C29—N6—Cu1^i	168.6 (2)
C15—C11—C12—C13	2.1 (4)	C29—N6—C30—C26	0.4 (4)
C10—C11—C12—C13	−176.9 (3)	Cu1^i—N6—C30—C26	−167.46 (18)
C11—C12—C13—C14	0.5 (5)	C27—C26—C30—N6	−0.9 (4)
C15—N3—C14—C13	1.0 (4)	C25—C26—C30—N6	−178.4 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···F2^iv	0.97	2.55	3.505 (4)	169
C10—H10B···F4	0.97	2.39	3.353 (3)	175
C19—H19A···F3^v	0.93	2.53	3.412 (3)	158

Symmetry codes: (iv) −x, −y+1, −z; (v) −x+1, −y+1, −z+1.

(2) Poly[[bis[µ₂-2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole-κ²N¹:N³]silver(I)] perchlorate methanol monosolvate]

Crystal data

[Ag(C15H15N3)2]ClO4·CH4O	V = 1614 (2) Å^3
Mr = 713.96	Z = 2
Triclinic, P1	F(000) = 732
Hall symbol: -P 1	Dx = 1.469 Mg m^−3
a = 9.560 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.946 (10) Å	θ = 2.2–27.1°
c = 13.849 (11) Å	µ = 0.76 mm^−1
α = 90.163 (10)°	T = 298 K
β = 108.773 (9)°	Block, yellow
γ = 95.518 (9)°	0.60 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer	7140 independent reflections
Radiation source: fine-focus sealed tube	5396 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 28.4°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
Tmin = 0.850, Tmax = 0.860	k = −17→16
10939 measured reflections	l = −10→17

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) = 0.118	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0557P)^2 + 1.1704P] where P = (Fo^2 + 2Fc^2)/3
7140 reflections	(Δ/σ)max < 0.001
400 parameters	Δρmax = 0.78 e Å^−3
9 restraints	Δρmin = −0.51 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
Ag1	0.09029 (3)	0.24459 (2)	0.33648 (2)	0.05197 (11)
N1	0.2835 (3)	0.2553 (2)	0.2788 (2)	0.0438 (6)
N2	0.4372 (3)	0.3144 (2)	0.1958 (2)	0.0428 (6)
N3	0.9311 (3)	0.3858 (2)	0.2933 (3)	0.0551 (8)
N4	0.0594 (3)	0.2031 (2)	0.4870 (2)	0.0469 (7)
N5	0.1199 (3)	0.1824 (2)	0.6552 (2)	0.0446 (6)
N6	0.0661 (3)	−0.1111 (2)	0.7796 (2)	0.0518 (7)
C1	0.3400 (3)	0.1709 (3)	0.2472 (2)	0.0416 (7)
C2	0.3108 (4)	0.0648 (3)	0.2578 (3)	0.0501 (8)
H2A	0.2469	0.0398	0.2927	0.060*
C3	0.3800 (4)	−0.0015 (3)	0.2145 (3)	0.0575 (9)
H3A	0.3626	−0.0727	0.2207	0.069*
C4	0.4753 (4)	0.0351 (3)	0.1619 (3)	0.0585 (10)
H4A	0.5196	−0.0122	0.1336	0.070*
C5	0.5057 (4)	0.1397 (3)	0.1506 (3)	0.0520 (9)
H5A	0.5696	0.1640	0.1155	0.062*
C6	0.4363 (3)	0.2073 (3)	0.1943 (2)	0.0395 (7)
C7	0.3426 (4)	0.3380 (3)	0.2465 (3)	0.0435 (7)
C8	0.3099 (5)	0.4448 (3)	0.2645 (3)	0.0608 (10)
H8A	0.2032	0.4471	0.2429	0.073*
H8B	0.3497	0.4925	0.2236	0.073*
C9	0.3757 (7)	0.4793 (4)	0.3750 (4)	0.0968 (17)
H9A	0.3511	0.5481	0.3839	0.145*
H9B	0.4817	0.4794	0.3960	0.145*
H9C	0.3363	0.4325	0.4157	0.145*
C10	0.5223 (4)	0.3859 (3)	0.1479 (3)	0.0511 (9)
H10A	0.4692	0.4463	0.1259	0.061*
H10B	0.5309	0.3516	0.0880	0.061*
C11	0.6758 (4)	0.4204 (3)	0.2204 (3)	0.0461 (8)
C12	0.7055 (5)	0.5094 (3)	0.2813 (4)	0.0722 (13)
H12A	0.6309	0.5521	0.2769	0.087*
C13	0.8473 (5)	0.5351 (3)	0.3493 (4)	0.0796 (14)
H13A	0.8686	0.5943	0.3918	0.096*
C14	0.9555 (5)	0.4717 (3)	0.3527 (4)	0.0665 (11)
H14A	1.0503	0.4892	0.3985	0.080*
C15	0.7942 (4)	0.3627 (3)	0.2289 (3)	0.0494 (8)
H15A	0.7765	0.3036	0.1866	0.059*
C16	−0.0661 (4)	0.2120 (3)	0.5159 (3)	0.0427 (7)
C17	−0.2091 (4)	0.2305 (3)	0.4579 (3)	0.0568 (9)
H17A	−0.2350	0.2378	0.3877	0.068*
C18	−0.3115 (4)	0.2377 (3)	0.5084 (4)	0.0667 (11)
H18A	−0.4084	0.2493	0.4715	0.080*
C19	−0.2722 (5)	0.2277 (3)	0.6133 (4)	0.0676 (11)
H19A	−0.3432	0.2345	0.6451	0.081*
C20	−0.1319 (4)	0.2082 (3)	0.6716 (3)	0.0560 (9)
H20A	−0.1066	0.2007	0.7418	0.067*
C21	−0.0300 (4)	0.2003 (2)	0.6208 (3)	0.0424 (7)
C22	0.1662 (4)	0.1848 (3)	0.5719 (3)	0.0445 (7)
C23	0.3188 (4)	0.1660 (3)	0.5739 (3)	0.0632 (10)
H23A	0.3887	0.1872	0.6406	0.076*
H23B	0.3457	0.2087	0.5239	0.076*
C24	0.3314 (5)	0.0544 (4)	0.5517 (4)	0.0851 (15)
H24A	0.4281	0.0477	0.5469	0.128*
H24B	0.2569	0.0314	0.4884	0.128*
H24C	0.3173	0.0128	0.6057	0.128*
C25	0.2061 (4)	0.1685 (3)	0.7615 (3)	0.0561 (9)
H25A	0.1954	0.2261	0.8027	0.067*
H25B	0.3103	0.1708	0.7673	0.067*
C26	0.1611 (4)	0.0682 (3)	0.8038 (3)	0.0452 (8)
C27	0.1843 (5)	0.0609 (3)	0.9076 (3)	0.0657 (11)
H27A	0.2250	0.1186	0.9513	0.079*
C28	0.1472 (6)	−0.0313 (4)	0.9453 (3)	0.0785 (14)
H28A	0.1616	−0.0371	1.0147	0.094*
C29	0.0884 (5)	−0.1154 (3)	0.8793 (3)	0.0620 (10)
H29A	0.0631	−0.1779	0.9054	0.074*
C30	0.1028 (4)	−0.0205 (3)	0.7438 (3)	0.0464 (8)
H30A	0.0880	−0.0171	0.6742	0.056*
C31	0.9220 (17)	0.5758 (11)	0.0796 (13)	0.298 (8)
H31A	0.9462	0.5905	0.1515	0.446*
H31B	1.0083	0.5566	0.0656	0.446*
H31C	0.8441	0.5197	0.0587	0.446*
Cl1	0.36635 (11)	0.70352 (7)	0.10573 (7)	0.0550 (2)
O1	0.2294 (5)	0.7397 (4)	0.1060 (5)	0.152 (2)
O2	0.4377 (5)	0.7825 (3)	0.0640 (3)	0.1128 (14)
O3	0.3390 (6)	0.6084 (3)	0.0533 (3)	0.1209 (16)
O4	0.4470 (5)	0.6944 (3)	0.2100 (2)	0.0987 (12)
O5	0.8712 (11)	0.6702 (9)	0.0222 (8)	0.264 (5)
H5B	0.9534	0.7072	0.0322	0.316*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.04669 (17)	0.05521 (17)	0.0643 (2)	0.00097 (11)	0.03339 (14)	−0.00017 (13)
N1	0.0379 (14)	0.0469 (15)	0.0549 (17)	0.0046 (11)	0.0264 (13)	0.0051 (13)
N2	0.0336 (14)	0.0499 (15)	0.0512 (16)	0.0056 (11)	0.0220 (12)	0.0090 (13)
N3	0.0404 (16)	0.0481 (17)	0.079 (2)	0.0061 (13)	0.0221 (16)	0.0025 (15)
N4	0.0366 (15)	0.0595 (17)	0.0514 (17)	0.0064 (12)	0.0230 (13)	0.0051 (14)
N5	0.0391 (15)	0.0459 (15)	0.0494 (16)	−0.0010 (12)	0.0164 (13)	0.0036 (12)
N6	0.0517 (17)	0.0526 (17)	0.0507 (18)	−0.0004 (13)	0.0179 (14)	0.0016 (14)
C1	0.0349 (16)	0.0498 (18)	0.0422 (18)	0.0062 (13)	0.0148 (14)	0.0045 (14)
C2	0.0435 (19)	0.0508 (19)	0.059 (2)	0.0038 (15)	0.0214 (17)	0.0076 (16)
C3	0.052 (2)	0.049 (2)	0.071 (3)	0.0085 (16)	0.0176 (19)	0.0019 (18)
C4	0.050 (2)	0.059 (2)	0.068 (3)	0.0137 (17)	0.0198 (19)	−0.0086 (19)
C5	0.0397 (18)	0.070 (2)	0.052 (2)	0.0120 (16)	0.0214 (16)	0.0019 (18)
C6	0.0309 (15)	0.0493 (18)	0.0405 (17)	0.0061 (13)	0.0141 (13)	0.0053 (14)
C7	0.0373 (17)	0.0483 (18)	0.0509 (19)	0.0069 (14)	0.0218 (15)	0.0063 (15)
C8	0.057 (2)	0.048 (2)	0.090 (3)	0.0095 (17)	0.041 (2)	0.008 (2)
C9	0.120 (5)	0.064 (3)	0.117 (5)	−0.004 (3)	0.059 (4)	−0.024 (3)
C10	0.0435 (19)	0.058 (2)	0.061 (2)	0.0123 (16)	0.0272 (17)	0.0223 (17)
C11	0.0417 (18)	0.0424 (17)	0.063 (2)	0.0064 (14)	0.0290 (17)	0.0165 (16)
C12	0.052 (2)	0.047 (2)	0.127 (4)	0.0122 (18)	0.040 (3)	0.002 (2)
C13	0.066 (3)	0.047 (2)	0.130 (4)	0.0022 (19)	0.038 (3)	−0.019 (2)
C14	0.046 (2)	0.059 (2)	0.092 (3)	−0.0006 (18)	0.021 (2)	−0.007 (2)
C15	0.046 (2)	0.0446 (18)	0.066 (2)	0.0075 (15)	0.0290 (18)	0.0054 (16)
C16	0.0358 (16)	0.0482 (18)	0.0496 (19)	0.0030 (13)	0.0217 (15)	0.0072 (15)
C17	0.045 (2)	0.073 (2)	0.059 (2)	0.0131 (18)	0.0241 (18)	0.0215 (19)
C18	0.037 (2)	0.081 (3)	0.090 (3)	0.0152 (19)	0.031 (2)	0.022 (2)
C19	0.055 (2)	0.079 (3)	0.090 (3)	0.014 (2)	0.050 (2)	0.011 (2)
C20	0.056 (2)	0.063 (2)	0.060 (2)	0.0002 (18)	0.0351 (19)	0.0018 (18)
C21	0.0379 (17)	0.0430 (17)	0.0512 (19)	−0.0002 (13)	0.0224 (15)	0.0011 (14)
C22	0.0335 (16)	0.0481 (18)	0.054 (2)	0.0011 (13)	0.0184 (15)	−0.0011 (15)
C23	0.039 (2)	0.082 (3)	0.071 (3)	0.0078 (18)	0.0210 (19)	0.000 (2)
C24	0.063 (3)	0.101 (4)	0.101 (4)	0.032 (3)	0.034 (3)	−0.005 (3)
C25	0.049 (2)	0.061 (2)	0.049 (2)	−0.0087 (17)	0.0069 (17)	−0.0020 (17)
C26	0.0343 (17)	0.055 (2)	0.0421 (18)	0.0031 (14)	0.0070 (14)	−0.0008 (15)
C27	0.077 (3)	0.067 (3)	0.042 (2)	0.003 (2)	0.007 (2)	−0.0080 (19)
C28	0.103 (4)	0.087 (3)	0.039 (2)	0.004 (3)	0.015 (2)	0.009 (2)
C29	0.066 (3)	0.066 (2)	0.050 (2)	0.005 (2)	0.0150 (19)	0.0163 (19)
C30	0.0445 (19)	0.056 (2)	0.0379 (17)	−0.0030 (15)	0.0152 (15)	−0.0010 (15)
C31	0.287 (15)	0.270 (15)	0.306 (17)	−0.150 (12)	0.106 (13)	−0.048 (12)
Cl1	0.0654 (6)	0.0501 (5)	0.0498 (5)	0.0014 (4)	0.0204 (4)	0.0048 (4)
O1	0.091 (3)	0.167 (5)	0.205 (6)	0.039 (3)	0.050 (3)	0.004 (4)
O2	0.166 (4)	0.083 (2)	0.103 (3)	−0.015 (2)	0.071 (3)	0.025 (2)
O3	0.198 (5)	0.077 (2)	0.094 (3)	−0.017 (3)	0.067 (3)	−0.025 (2)
O4	0.120 (3)	0.108 (3)	0.059 (2)	−0.006 (2)	0.020 (2)	0.0110 (18)
O5	0.216 (8)	0.297 (13)	0.263 (12)	−0.041 (9)	0.077 (8)	−0.088 (9)

Geometric parameters (Å, º)

Ag1—N1	2.230 (3)	C12—H12A	0.9300
Ag1—N4	2.257 (3)	C13—C14	1.369 (6)
Ag1—N6^i	2.397 (3)	C13—H13A	0.9300
Ag1—N3^ii	2.443 (3)	C14—H14A	0.9300
N1—C7	1.309 (4)	C15—H15A	0.9300
N1—C1	1.393 (4)	C16—C17	1.388 (5)
N2—C7	1.365 (4)	C16—C21	1.393 (5)
N2—C6	1.386 (4)	C17—C18	1.384 (5)
N2—C10	1.471 (4)	C17—H17A	0.9300
N3—C15	1.330 (5)	C18—C19	1.388 (6)
N3—C14	1.339 (5)	C18—H18A	0.9300
N3—Ag1^iii	2.443 (3)	C19—C20	1.373 (6)
N4—C22	1.325 (4)	C19—H19A	0.9300
N4—C16	1.397 (4)	C20—C21	1.384 (5)
N5—C22	1.362 (4)	C20—H20A	0.9300
N5—C21	1.400 (4)	C22—C23	1.494 (5)
N5—C25	1.458 (5)	C23—C24	1.501 (6)
N6—C29	1.330 (5)	C23—H23A	0.9700
N6—C30	1.334 (5)	C23—H23B	0.9700
N6—Ag1^i	2.397 (3)	C24—H24A	0.9600
C1—C2	1.392 (5)	C24—H24B	0.9600
C1—C6	1.399 (4)	C24—H24C	0.9600
C2—C3	1.377 (5)	C25—C26	1.509 (5)
C2—H2A	0.9300	C25—H25A	0.9700
C3—C4	1.390 (6)	C25—H25B	0.9700
C3—H3A	0.9300	C26—C30	1.376 (5)
C4—C5	1.377 (5)	C26—C27	1.387 (5)
C4—H4A	0.9300	C27—C28	1.366 (6)
C5—C6	1.393 (5)	C27—H27A	0.9300
C5—H5A	0.9300	C28—C29	1.371 (6)
C7—C8	1.485 (5)	C28—H28A	0.9300
C8—C9	1.503 (7)	C29—H29A	0.9300
C8—H8A	0.9700	C30—H30A	0.9300
C8—H8B	0.9700	C31—O5	1.494 (9)
C9—H9A	0.9600	C31—H31A	0.9600
C9—H9B	0.9600	C31—H31B	0.9600
C9—H9C	0.9600	C31—H31C	0.9600
C10—C11	1.511 (5)	Cl1—O3	1.386 (4)
C10—H10A	0.9700	Cl1—O2	1.402 (3)
C10—H10B	0.9700	Cl1—O4	1.412 (4)
C11—C12	1.378 (6)	Cl1—O1	1.434 (5)
C11—C15	1.390 (5)	O5—H5B	0.8500
C12—C13	1.388 (6)
N1—Ag1—N4	134.12 (10)	N3—C14—H14A	118.4
N1—Ag1—N6^i	98.85 (11)	C13—C14—H14A	118.4
N4—Ag1—N6^i	103.37 (11)	N3—C15—C11	124.7 (3)
N1—Ag1—N3^ii	116.32 (11)	N3—C15—H15A	117.7
N4—Ag1—N3^ii	98.91 (11)	C11—C15—H15A	117.7
N6^i—Ag1—N3^ii	99.63 (12)	C17—C16—C21	120.3 (3)
C7—N1—C1	106.2 (3)	C17—C16—N4	130.3 (3)
C7—N1—Ag1	127.2 (2)	C21—C16—N4	109.3 (3)
C1—N1—Ag1	125.0 (2)	C18—C17—C16	117.5 (4)
C7—N2—C6	106.9 (3)	C18—C17—H17A	121.3
C7—N2—C10	128.2 (3)	C16—C17—H17A	121.3
C6—N2—C10	124.9 (3)	C17—C18—C19	121.2 (4)
C15—N3—C14	117.0 (3)	C17—C18—H18A	119.4
C15—N3—Ag1^iii	117.1 (2)	C19—C18—H18A	119.4
C14—N3—Ag1^iii	122.5 (3)	C20—C19—C18	122.1 (3)
C22—N4—C16	105.6 (3)	C20—C19—H19A	119.0
C22—N4—Ag1	125.9 (2)	C18—C19—H19A	119.0
C16—N4—Ag1	127.3 (2)	C19—C20—C21	116.6 (4)
C22—N5—C21	106.6 (3)	C19—C20—H20A	121.7
C22—N5—C25	128.6 (3)	C21—C20—H20A	121.7
C21—N5—C25	124.8 (3)	C20—C21—C16	122.3 (3)
C29—N6—C30	117.7 (3)	C20—C21—N5	131.9 (3)
C29—N6—Ag1^i	120.8 (3)	C16—C21—N5	105.8 (3)
C30—N6—Ag1^i	119.6 (2)	N4—C22—N5	112.7 (3)
C2—C1—N1	130.6 (3)	N4—C22—C23	123.0 (3)
C2—C1—C6	120.5 (3)	N5—C22—C23	124.4 (3)
N1—C1—C6	108.9 (3)	C22—C23—C24	112.8 (3)
C3—C2—C1	117.5 (3)	C22—C23—H23A	109.0
C3—C2—H2A	121.3	C24—C23—H23A	109.0
C1—C2—H2A	121.3	C22—C23—H23B	109.0
C2—C3—C4	121.7 (4)	C24—C23—H23B	109.0
C2—C3—H3A	119.2	H23A—C23—H23B	107.8
C4—C3—H3A	119.2	C23—C24—H24A	109.5
C5—C4—C3	121.8 (3)	C23—C24—H24B	109.5
C5—C4—H4A	119.1	H24A—C24—H24B	109.5
C3—C4—H4A	119.1	C23—C24—H24C	109.5
C4—C5—C6	116.9 (3)	H24A—C24—H24C	109.5
C4—C5—H5A	121.6	H24B—C24—H24C	109.5
C6—C5—H5A	121.6	N5—C25—C26	113.9 (3)
N2—C6—C5	132.7 (3)	N5—C25—H25A	108.8
N2—C6—C1	105.6 (3)	C26—C25—H25A	108.8
C5—C6—C1	121.7 (3)	N5—C25—H25B	108.8
N1—C7—N2	112.4 (3)	C26—C25—H25B	108.8
N1—C7—C8	123.0 (3)	H25A—C25—H25B	107.7
N2—C7—C8	124.5 (3)	C30—C26—C27	117.1 (3)
C7—C8—C9	111.8 (4)	C30—C26—C25	122.5 (3)
C7—C8—H8A	109.3	C27—C26—C25	120.3 (3)
C9—C8—H8A	109.3	C28—C27—C26	119.7 (4)
C7—C8—H8B	109.3	C28—C27—H27A	120.2
C9—C8—H8B	109.3	C26—C27—H27A	120.2
H8A—C8—H8B	107.9	C27—C28—C29	119.0 (4)
C8—C9—H9A	109.5	C27—C28—H28A	120.5
C8—C9—H9B	109.5	C29—C28—H28A	120.5
H9A—C9—H9B	109.5	N6—C29—C28	122.7 (4)
C8—C9—H9C	109.5	N6—C29—H29A	118.7
H9A—C9—H9C	109.5	C28—C29—H29A	118.7
H9B—C9—H9C	109.5	N6—C30—C26	123.9 (3)
N2—C10—C11	111.8 (3)	N6—C30—H30A	118.1
N2—C10—H10A	109.3	C26—C30—H30A	118.1
C11—C10—H10A	109.3	O5—C31—H31A	109.5
N2—C10—H10B	109.3	O5—C31—H31B	109.5
C11—C10—H10B	109.3	H31A—C31—H31B	109.5
H10A—C10—H10B	107.9	O5—C31—H31C	109.5
C12—C11—C15	116.8 (3)	H31A—C31—H31C	109.5
C12—C11—C10	122.2 (3)	H31B—C31—H31C	109.5
C15—C11—C10	121.0 (3)	O3—Cl1—O2	114.3 (3)
C11—C12—C13	119.6 (4)	O3—Cl1—O4	111.3 (3)
C11—C12—H12A	120.2	O2—Cl1—O4	109.9 (2)
C13—C12—H12A	120.2	O3—Cl1—O1	110.2 (3)
C14—C13—C12	118.8 (4)	O2—Cl1—O1	106.2 (3)
C14—C13—H13A	120.6	O4—Cl1—O1	104.4 (3)
C12—C13—H13A	120.6	C31—O5—H5B	101.2
N3—C14—C13	123.1 (4)
N4—Ag1—N1—C7	−118.2 (3)	Ag1^iii—N3—C14—C13	−158.6 (4)
N6^i—Ag1—N1—C7	123.3 (3)	C12—C13—C14—N3	0.1 (8)
N3^ii—Ag1—N1—C7	17.9 (3)	C14—N3—C15—C11	−0.9 (6)
N4—Ag1—N1—C1	78.5 (3)	Ag1^iii—N3—C15—C11	158.6 (3)
N6^i—Ag1—N1—C1	−40.0 (3)	C12—C11—C15—N3	2.1 (5)
N3^ii—Ag1—N1—C1	−145.4 (3)	C10—C11—C15—N3	−177.5 (3)
N1—Ag1—N4—C22	5.6 (3)	C22—N4—C16—C17	−179.7 (4)
N6^i—Ag1—N4—C22	122.4 (3)	Ag1—N4—C16—C17	12.2 (5)
N3^ii—Ag1—N4—C22	−135.4 (3)	C22—N4—C16—C21	1.1 (4)
N1—Ag1—N4—C16	171.5 (2)	Ag1—N4—C16—C21	−167.1 (2)
N6^i—Ag1—N4—C16	−71.7 (3)	C21—C16—C17—C18	0.6 (6)
N3^ii—Ag1—N4—C16	30.5 (3)	N4—C16—C17—C18	−178.6 (4)
C7—N1—C1—C2	−177.5 (4)	C16—C17—C18—C19	0.6 (6)
Ag1—N1—C1—C2	−11.3 (5)	C17—C18—C19—C20	−1.4 (7)
C7—N1—C1—C6	0.1 (4)	C18—C19—C20—C21	0.9 (6)
Ag1—N1—C1—C6	166.3 (2)	C19—C20—C21—C16	0.4 (5)
N1—C1—C2—C3	177.4 (3)	C19—C20—C21—N5	179.3 (4)
C6—C1—C2—C3	0.1 (5)	C17—C16—C21—C20	−1.2 (5)
C1—C2—C3—C4	−0.2 (6)	N4—C16—C21—C20	178.2 (3)
C2—C3—C4—C5	0.2 (6)	C17—C16—C21—N5	179.7 (3)
C3—C4—C5—C6	−0.1 (6)	N4—C16—C21—N5	−0.9 (4)
C7—N2—C6—C5	177.2 (4)	C22—N5—C21—C20	−178.6 (4)
C10—N2—C6—C5	−1.1 (6)	C25—N5—C21—C20	−0.8 (6)
C7—N2—C6—C1	−0.9 (3)	C22—N5—C21—C16	0.4 (3)
C10—N2—C6—C1	−179.2 (3)	C25—N5—C21—C16	178.2 (3)
C4—C5—C6—N2	−177.9 (3)	C16—N4—C22—N5	−0.8 (4)
C4—C5—C6—C1	0.0 (5)	Ag1—N4—C22—N5	167.6 (2)
C2—C1—C6—N2	178.4 (3)	C16—N4—C22—C23	177.5 (3)
N1—C1—C6—N2	0.5 (4)	Ag1—N4—C22—C23	−14.1 (5)
C2—C1—C6—C5	0.1 (5)	C21—N5—C22—N4	0.2 (4)
N1—C1—C6—C5	−177.8 (3)	C25—N5—C22—N4	−177.4 (3)
C1—N1—C7—N2	−0.7 (4)	C21—N5—C22—C23	−178.0 (3)
Ag1—N1—C7—N2	−166.5 (2)	C25—N5—C22—C23	4.3 (5)
C1—N1—C7—C8	179.8 (3)	N4—C22—C23—C24	−85.9 (5)
Ag1—N1—C7—C8	14.0 (5)	N5—C22—C23—C24	92.2 (5)
C6—N2—C7—N1	1.0 (4)	C22—N5—C25—C26	−113.3 (4)
C10—N2—C7—N1	179.2 (3)	C21—N5—C25—C26	69.5 (4)
C6—N2—C7—C8	−179.4 (3)	N5—C25—C26—C30	29.7 (5)
C10—N2—C7—C8	−1.3 (6)	N5—C25—C26—C27	−153.4 (4)
N1—C7—C8—C9	69.7 (5)	C30—C26—C27—C28	−1.0 (6)
N2—C7—C8—C9	−109.8 (4)	C25—C26—C27—C28	−178.0 (4)
C7—N2—C10—C11	92.2 (4)	C26—C27—C28—C29	0.5 (7)
C6—N2—C10—C11	−89.9 (4)	C30—N6—C29—C28	−0.2 (6)
N2—C10—C11—C12	−92.2 (4)	Ag1^i—N6—C29—C28	−164.5 (4)
N2—C10—C11—C15	87.4 (4)	C27—C28—C29—N6	0.2 (8)
C15—C11—C12—C13	−2.1 (6)	C29—N6—C30—C26	−0.4 (5)
C10—C11—C12—C13	177.5 (4)	Ag1^i—N6—C30—C26	164.1 (3)
C11—C12—C13—C14	1.1 (7)	C27—C26—C30—N6	1.0 (5)
C15—N3—C14—C13	−0.3 (6)	C25—C26—C30—N6	177.9 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O1^iii	0.85	2.50	3.275 (13)	153
C10—H10A···O3	0.97	2.58	3.550 (7)	174
C23—H23A···O4^iv	0.97	2.55	3.481 (6)	160
C31—H31C···O3^v	0.96	2.43	3.343 (17)	159

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