Counter-anion role in the formation of two supra­molecular complexes: [Ag₂(DPP)₂](ClO₄)₂·CH₃CN and [Ag₂(DPP)₂(NO₃)₂] {DPP is N-[(di­phenyl­phosphanyl)methyl]pyridin-4-amine}

The title compounds, bis­{μ-N-[(di­phenyl­phosphanyl)methyl]pyridin-4-amine-κ²N¹:P}disilver bis­(perchlorate) aceto­nitrile monosolvate, [Ag₂(C₁₈H₁₇N₂P)₂](ClO₄)₂·CH₃CN, (1), and bis­{μ-N-[(di­phenyl­phosphanyl)methyl]pyridin-4-amine-κ²N¹:P}bis­[(nitrato-κ²O,O)silver], [Ag₂(C₁₈H₁₇N₂P)₂(NO₃)₂], (2), each contain disilver macrocyclic [Ag₂(C₁₈H₁₇N₂P)₂]²⁺ cations lying about inversion centres. The cations are constructed by two N-[(di­phenyl­phosphanyl)methyl]pyridin-4-amine (DPP) ligands linking two Ag⁺ cations in a head-to-tail fashion. In (1), the unique Ag⁺ cation has a near-linear coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands. Two ClO₄⁻ anions doubly bridge two metallomacrocycles through Ag...O and N—H...O weak inter­actions to form a chain extending in the c direction. The half-occupancy aceto­nitrile mol­ecule lies with its methyl C atom on a twofold axis and makes a weak N...Ag contact. In (2), there are two independent [Ag(C₁₈H₁₇N₂P)]⁺ cations. The nitrate anions weakly chelate to each Ag⁺ cation, leading to each Ag⁺ cation having a distorted tetra­hedral coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands, and two chelating nitrate O atoms. Each dinuclear [Ag₂(C₁₈H₁₇N₂P)₂(NO₃)₂] mol­ecule acts as a four-node to bridge four adjacent equivalent mol­ecules through N—H...O inter­actions, forming a two-dimensional sheet parallel to the bc plane. Each sheet contains dinuclear molecules involving just Ag1 or Ag2 and these two types of sheet are stacked in an alternating fashion. The sheets containing Ag1 all lie near x = , , etc, while those containing Ag2 all lie near x = 0, 1, 2 etc. Thus, the two independent sheets are arranged in an alternating sequence at x = 0, , 1, etc. These two different supra­molecular structures result from the different geometric conformations of the templating anions which direct the self-assembly of the cations and anions.

S1. Introduction

The crystal engineering of metallo-supra­molecular architectures involving metallo-organic frameworks as building blocks has been studied extensively due to their structural versatility, unique properties and applications in different areas of science, such as materials and nanotechnology (Li et al., 2012; Liu et al., 2012; Neogi et al., 2013; Ye et al., 2011). Numerous routes have been investigated for supra­molecular architectures, some of which are controlled by the formation of conventional covalent bonds and others by supra­molecular contacts, such as hydrogen bonding, π–π stacking and X—H···π (X = O, N, C) inter­actions etc. (Ji et al., 2010; Wang et al., 2008; Zheng et al., 2010). A variety of molecular architectures, such as multiple helicates, cages, grids, two-dimensional sheets, diamondoid networks and porous frameworks, have been prepared by different inter­actions. Counter-anions sometimes also take a secondary role in directing supra­molecular assembly via weak metal–anion inter­actions and the geometric effects of templating anions, such as NO₃^-, ClO₄^-, CF₃SO₃^-, BF₄^-, PF₆^- and SbF₆^-, and this can result in significant structural variation (Kundu et al., 2010; Audhya et al., 2010; Ni et al., 2010; Raehm et al., 2003). Weak metal–anion inter­actions usually take place between `soft' metals (Ag<sup>I</sup> and Au<sup>I</sup>) and `hard' coordination atoms (O and F), which could tune the linking modes of metal–organic building blocks and endow different properties on the resulting supra­molecular architectures.

We report here the dinuclear macrocycle cation complex [Ag₂(DPP)₂]²⁺ constructed from N-[(di­phenyl­phosphanyl)methyl]­pyridin-4-amine (DPP) and the Ag⁺ cation, which performs as a building block to construct two supra­molecular assemblies with counter-anions of NO₃^- and ClO₄^- (see scheme). Weak metal–oxygen inter­actions and the shape of the anions play a key role in determining the supra­molecular structures. [Ag₂(DPP)₂](ClO₄)₂.CH₃CN, (1), forms a one-dimensional chain but [Ag₂(DPP)₂](NO₃)₂, (2), is a two-dimensional sheet.

S2. Experimental

S2.1. Synthesis and crystallization

For the synthesis of complex (1), AgClO₄ (0.0207 g, 0.1 mmol) was added to a mixture of CH₃CN (2 ml) and CH₃COCH₃ (2 ml) containing DPP (0.0292 g, 0.10 mmol). The resulting solution was diffused with di­ethyl ether after stirring for 1 h at room temperature. After 2d, colourless block-shaped crystals of (1) were obtained. Analysis, calculated for C₃₈H₃₇Ag₂Cl₂N₅O₈P₂: C 43.85, H 3.58, N 6.73%; found: C 43.69, H 3.82, N 6.94%. IR ([Medium?, ν, cm^-1): 1611, 1579, 1528, 1435, 1225, 1089, 824, 751, 696, 623.

For the synthesis of complex (2), AgNO₃ (0.0168 g, 0.1 mmol) was added to a mixture of CH₃CN–C₆H₅CH₃–DMF (DMF is di­methyl­formamide; 5 ml, with a volume ratio of 2:2:1) containing DPP (0.0292 g, 0.10 mmol). The resulting solution was diffused with di­ethyl ether after stirring for 1 h at room temperature. After a week, colourless block-shaped crystals of (2) suitable for X-ray analysis were obtained. Analysis, calculated for C₃₆H₃₄Ag₂N₆O₆P₂: C 46.75, H 3.68, N 9.09%; found: C 47.34, H 3.87, N 8.76%. IR ([Medium?, ν, cm^-1): 1607, 1569, 1524, 1430, 1219, 1060, 820, 758, 692, 623.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were generated geometrically, with C—H = 0.93–0.99 Å, and refined with a riding model, with U_iso(H) = 1.2–1.5U_eq(C). [Please check added text]

S3. Results and discussion

X-ray diffraction analysis for complex (1) establishes that the asymmetric unit contains one DPP ligand, one Ag⁺ cation, one ClO₄^- counter-ion and one half-occupancy aceto­nitrile molecule, lying with its methyl C atom on a twofold axis (Fig. 1). The [Ag₂(DPP)₂]²⁺ dimer lies about an inversion centre. The unique Ag⁺ cation is coordinated by one P atom and one pyridine N atom from two different DPP ligands, exhibiting a nearly linear geometry. There is also a long contact to the aceto­nitrile N atom; see Table 2 for geometric details, which are comparable with those of the reported structures of similar complexes (Wang et al., 2008).

In the solid-state structure of (1), two adjacent [Ag₂(DPP)₂]²⁺ cations are doubly bridged by two ClO₄^- anions to form a one-dimensional supra­molecular chain through weak Ag···O and N—H···O inter­actions (Fig. 2 and Table 3). Each ClO₄^- anion affords two O atoms to contact with two adjacent cations, one O atom (O3) hydrogen-bonding with atom N2 from a cation, while another O atom (O2) inter­acts weakly with an adjacent Ag1ⁱ cation [O2···Ag1ⁱ = 3.171 (5) Å; symmetry code: (i) x, -y + 1, z - 1/2]. Each [Ag₂(DPP)₂]²⁺ cation bridges four adjacent ClO₄^- anions via two Ag···O and two N—H···O weak inter­actions (Fig. 2). Thus, the weak Ag—O and N—H···O inter­actions are the primary tools in assembling the [Ag₂(DPP)₂]²⁺ cations and ClO₄^- anions into a chain extending in the c direction. Adjacent cations in the chain are located at 62.2 (3)° to each other (defined by their P···P lines). The aceto­nitrile molecule, lying about a twofold axis, helps to link the centrosymmetric dimers, in addition to the linkage provided by the perchlorate group. A weak C4—H4A···O2ⁱⁱ contact [symmetry code: x, -y + 1, z + 1/2] (see Table 3) is also present in the chain of dimers extending in the c direction. There are only simple van der Waals contacts between these chains.

To study further the influence of the anion as a template for supra­molecular self-assembly, complex (2) was prepared using AgNO₃ instead of AgClO₄. X-ray diffraction analysis shows there are two crystallographically independent but structurally very similar [Ag₂(DPP)₂](NO₃)₂ units (Fig. 3), each lying about independent inversion centres. Two Ag⁺ cations are bridged by two DPP ligands in a head-to-tail fashion, constructing a dinuclear [Ag₂(DPP)₂]²⁺ cation similar to that in complex (1), but the coordination environment around the Ag atom is quite different from that in (1). The bond distances (Table 4) are similar to those in (1), but the N—Ag—P angles are much smaller than those in (1), while the Ag···Ag separations [6.497 (2) and 6.262 (2) Å] in the two independent dimers are also much longer than the corresponding value in (1). Furthermore, the Ag···O distances (see Table 4) are much less than the sum of the van der Waals radii of Ag and O atoms (3.27 Å; Winter, 1993). The NO₃^- anions could be considered as being in a chelating mode to coordinate weakly to Ag⁺, and thus the coordination environment of Ag⁺ in (2) could be described as a distorted tetra­hedral geometry constructed by one P atom from one DPP, one N atom from another DPP and two chelating O atoms from one NO₃^- anion.

Such a geometric conformation results in longer Ag···Ag separations and smaller N—Ag—P angles in (2), compared with the corresponding values in (1) where the coordination environment of Ag⁺ is nearly linear. The pyridine ring-centred distances in the cations of (2) are 4.336 (2) and 4.622 (5) Å, similar to that in (1) [4.417 (1) Å].

Each [Ag₂(C₁₈H₁₇N₂P)₂(NO₃)₂] dimer molecule of (2) performs as a four-node to bridge four adjacent equivalent molecules through N—H···O inter­actions, forming a two-dimensional sheet parallel to the bc plane. Adjacent sheets are constructed by dimers with Ag1 and dimers with Ag2, respectively (Fig. 4). The sheets of dimers with Ag1 all lie near a = 1/2, 3/2, 5/2 etc., while the similar sheets with Ag2 dimers all lie near a = 0, 1, 2 etc. There is only one type of contact between these parallel sheets and that is listed as C24—H24A···O3^v in Table 5. Thus, the two independent sheets are arranged in an alternating sequence at a = 0, 1/2, 1, 3/2 etc., with C—H···O contacts and simple van der Waals contacts between the sheets.

In summary, two supra­molecular structures are constructed with different geometric conformations of the anions as template. The tetra­hedrally geometric ClO₄^- anions link the [Ag₂(DPP)₂]²⁺ cations into a one-dimensional chain structure, while trigonal–planar NO₃^- anions bridge the cations into a two-dimensional supra­molecular structure.

Related literature

For related literature, see: Audhya et al. (2010); Ji et al. (2010); Kundu et al. (2010); Li et al. (2012); Liu et al. (2012); Neogi et al. (2013); Ni et al. (2010); Raehm et al. (2003); Wang et al. (2008); Winter (1993); Ye et al. (2011); Zheng et al. (2010).

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. The Ag coordination environment in compound (1), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the ??% probability level [Please complete]. The heavy dashed line indicates the Ag···O interaction and the lighter dashed lines indicate hydrogen bonds. [OK?] [Symmetry codes: (a) x, -y + 1, z + 1/2; (b) -x + 1, -y + 1, -z + 2.]
	Fig. 2. The one-dimensional supramolecular chain of (1), extending along the c axis. H atoms attached to C atoms have been omitted for clarity. Dashed lines indicate hydrogen bonds. [OK?] [Symmetry codes: (A) -x + 1, -y + 1, -z + 2; (C) -x + 1, y, -z + 3/2; (D) x, -y + 1, z + 1/2.]
	Fig. 3. Plots of the two complete independent dimers in compound (2). [Symmetry codes: (a) -x + 1, -y + 1, -z; (b) -x + 2, -y + 2, -z + 2.]
	Fig. 4. The two independent two-dimensional supramolecular sheets in (2), parallel to the bc plane. H atoms attached to C atoms have been omitted for clarity. Dashed lines indicate hydrogen bonds. [OK?] [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 1, y + 1/2, -z + 1/2; (iii) -x + 1, y - 1/2, -z + 1/2; (A) -x + 2, -y + 2, -z + 2; (C) -x + 2, y - 1/2, -z + 3/2; (D) -x + 2, y + 1/2, -z + 3/2.]

(1) Bis{µ-N-[(diphenylphosphanyl)methyl]pyridin-4-amine-κ²N¹:P}disilver bis(perchlorate) acetonitrile monosolvate

Crystal data

[Ag2(C18H17N2P)2](ClO4)2·C2H3N	Z = 4
Mr = 1040.31	F(000) = 2088
Monoclinic, C2/c	Dx = 1.675 Mg m^−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 11.928 (2) Å	θ = 2.5–28.0°
b = 18.192 (3) Å	µ = 1.21 mm^−1
c = 19.026 (3) Å	T = 293 K
β = 91.988 (3)°	Block, colourless
V = 4126.0 (12) Å^3	0.46 × 0.34 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4447 independent reflections
Radiation source: fine-focus sealed tube	2995 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→15
Tmin = 0.605, Tmax = 0.751	k = −23→21
10757 measured reflections	l = −21→24

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0727P)^2 + 4.9016P] where P = (Fo^2 + 2Fc^2)/3
4447 reflections	(Δ/σ)max = 0.002
267 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.

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	Occ. (<1)
Ag1	0.65542 (3)	0.38326 (2)	1.00024 (2)	0.07792 (19)
P1	0.81927 (8)	0.36619 (5)	0.93652 (5)	0.0436 (2)
N1	0.4939 (3)	0.58932 (18)	0.94507 (18)	0.0519 (8)
N2	0.7689 (2)	0.48847 (17)	0.85624 (16)	0.0474 (7)
H2B	0.7698	0.4865	0.8111	0.057*
C1	0.4963 (3)	0.5728 (2)	0.8764 (2)	0.0566 (10)
H1A	0.4333	0.5839	0.8483	0.068*
C2	0.5848 (3)	0.5409 (2)	0.8454 (2)	0.0505 (9)
H2A	0.5814	0.5309	0.7975	0.061*
C3	0.6811 (3)	0.52304 (19)	0.88594 (18)	0.0417 (8)
C4	0.6814 (3)	0.5428 (2)	0.95672 (19)	0.0471 (8)
H4A	0.7444	0.5342	0.9857	0.057*
C5	0.5877 (3)	0.5750 (2)	0.9832 (2)	0.0538 (10)
H5A	0.5895	0.5876	1.0306	0.065*
C6	0.8610 (3)	0.4551 (2)	0.8964 (2)	0.0483 (9)
H6A	0.8864	0.4886	0.9333	0.058*
H6B	0.9231	0.4467	0.8658	0.058*
C7	0.8056 (3)	0.3006 (2)	0.86509 (19)	0.0457 (8)
C8	0.7345 (4)	0.2411 (2)	0.8741 (2)	0.0604 (10)
H8A	0.6939	0.2375	0.9148	0.072*
C9	0.7234 (4)	0.1870 (3)	0.8229 (3)	0.0715 (13)
H9A	0.6776	0.1466	0.8301	0.086*
C10	0.7799 (4)	0.1933 (3)	0.7619 (3)	0.0737 (13)
H10A	0.7719	0.1576	0.7272	0.088*
C11	0.8486 (5)	0.2527 (3)	0.7522 (3)	0.0792 (14)
H11A	0.8866	0.2571	0.7105	0.095*
C12	0.8622 (4)	0.3064 (3)	0.8038 (2)	0.0661 (12)
H12A	0.9096	0.3461	0.7967	0.079*
C13	0.9436 (3)	0.3394 (2)	0.9874 (2)	0.0453 (8)
C14	1.0117 (3)	0.2812 (2)	0.9685 (2)	0.0570 (10)
H14A	0.9967	0.2556	0.9269	0.068*
C15	1.1023 (4)	0.2616 (3)	1.0123 (3)	0.0736 (13)
H15A	1.1488	0.2232	0.9993	0.088*
C16	1.1240 (4)	0.2972 (3)	1.0735 (3)	0.0756 (14)
H16A	1.1840	0.2823	1.1026	0.091*
C17	1.0581 (4)	0.3558 (3)	1.0933 (3)	0.0695 (12)
H17A	1.0739	0.3805	1.1352	0.083*
C18	0.9684 (4)	0.3770 (2)	1.0499 (2)	0.0586 (10)
H18A	0.9243	0.4167	1.0625	0.070*
N3	0.5292 (8)	0.3627 (6)	0.8715 (5)	0.083 (2)	0.50
C19	0.5133 (7)	0.3485 (6)	0.8148 (7)	0.068 (2)	0.50
C20	0.5000	0.3286 (7)	0.7500	0.126 (4)
H20A	0.4356	0.3522	0.7285	0.189*	0.50
H20B	0.5656	0.3415	0.7249	0.189*	0.50
H20C	0.4898	0.2763	0.7486	0.189*	0.50
Cl1	0.79174 (11)	0.45084 (8)	0.65833 (6)	0.0758 (4)
O1	0.7781 (10)	0.3831 (4)	0.6219 (3)	0.223 (5)
O2	0.7745 (4)	0.5080 (3)	0.6096 (2)	0.1155 (16)
O3	0.7095 (4)	0.4532 (3)	0.7074 (2)	0.1212 (17)
O4	0.8910 (4)	0.4521 (6)	0.6947 (3)	0.233 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0604 (2)	0.0745 (3)	0.1018 (3)	0.01911 (17)	0.0444 (2)	0.0175 (2)
P1	0.0351 (5)	0.0460 (5)	0.0503 (5)	0.0053 (4)	0.0116 (4)	0.0046 (4)
N1	0.0451 (18)	0.0481 (18)	0.063 (2)	0.0104 (14)	0.0149 (15)	0.0058 (15)
N2	0.0455 (16)	0.0538 (19)	0.0433 (17)	0.0104 (14)	0.0074 (13)	0.0037 (14)
C1	0.044 (2)	0.065 (3)	0.062 (3)	0.0078 (18)	0.0047 (18)	0.011 (2)
C2	0.050 (2)	0.057 (2)	0.045 (2)	0.0070 (17)	0.0053 (17)	0.0057 (18)
C3	0.0417 (18)	0.0377 (18)	0.0461 (19)	0.0025 (14)	0.0085 (15)	0.0059 (15)
C4	0.046 (2)	0.051 (2)	0.045 (2)	0.0056 (16)	0.0054 (16)	0.0034 (16)
C5	0.060 (2)	0.054 (2)	0.048 (2)	0.0042 (18)	0.0113 (18)	0.0023 (18)
C6	0.0372 (18)	0.049 (2)	0.059 (2)	0.0056 (15)	0.0123 (16)	0.0068 (17)
C7	0.0392 (18)	0.048 (2)	0.050 (2)	0.0039 (15)	0.0048 (15)	0.0059 (16)
C8	0.062 (3)	0.062 (3)	0.057 (2)	−0.004 (2)	0.0051 (19)	0.006 (2)
C9	0.075 (3)	0.060 (3)	0.080 (3)	−0.009 (2)	0.000 (3)	0.005 (2)
C10	0.080 (3)	0.067 (3)	0.074 (3)	0.010 (3)	−0.009 (3)	−0.013 (2)
C11	0.083 (4)	0.093 (4)	0.062 (3)	−0.001 (3)	0.020 (2)	−0.010 (3)
C12	0.062 (3)	0.073 (3)	0.064 (3)	−0.012 (2)	0.022 (2)	−0.007 (2)
C13	0.0403 (18)	0.043 (2)	0.053 (2)	−0.0003 (15)	0.0099 (16)	0.0077 (16)
C14	0.045 (2)	0.053 (2)	0.073 (3)	0.0095 (17)	0.0005 (19)	−0.007 (2)
C15	0.050 (3)	0.058 (3)	0.112 (4)	0.007 (2)	−0.010 (2)	−0.002 (3)
C16	0.057 (3)	0.072 (3)	0.096 (4)	−0.004 (2)	−0.021 (3)	0.012 (3)
C17	0.073 (3)	0.070 (3)	0.064 (3)	−0.014 (2)	−0.011 (2)	0.004 (2)
C18	0.056 (2)	0.056 (3)	0.065 (3)	−0.0001 (18)	0.006 (2)	−0.004 (2)
N3	0.069 (6)	0.102 (7)	0.077 (6)	0.013 (5)	−0.004 (5)	−0.006 (5)
C19	0.047 (5)	0.066 (6)	0.090 (8)	0.000 (4)	0.000 (5)	−0.010 (5)
C20	0.103 (8)	0.149 (10)	0.127 (9)	0.000	0.000 (7)	0.000
Cl1	0.0710 (7)	0.1063 (10)	0.0511 (6)	0.0160 (6)	0.0155 (5)	0.0151 (6)
O1	0.422 (15)	0.126 (5)	0.123 (5)	0.102 (7)	0.026 (7)	−0.017 (4)
O2	0.161 (4)	0.110 (3)	0.074 (2)	−0.030 (3)	−0.016 (3)	0.026 (2)
O3	0.096 (3)	0.194 (5)	0.075 (2)	0.001 (3)	0.027 (2)	0.004 (3)
O4	0.065 (3)	0.489 (15)	0.145 (5)	−0.020 (5)	−0.012 (3)	0.125 (7)

Geometric parameters (Å, º)

Ag1—N1^i	2.152 (3)	C9—H9A	0.9300
Ag1—P1	2.3560 (10)	C10—C11	1.373 (7)
Ag1—N3	2.855 (10)	C10—H10A	0.9300
Ag1—O2^ii	3.171 (5)	C11—C12	1.389 (7)
P1—C13	1.809 (4)	C11—H11A	0.9300
P1—C7	1.811 (4)	C12—H12A	0.9300
P1—C6	1.863 (4)	C13—C14	1.390 (5)
N1—C5	1.338 (5)	C13—C18	1.395 (6)
N1—C1	1.342 (5)	C14—C15	1.388 (6)
N1—Ag1^i	2.152 (3)	C14—H14A	0.9300
N2—C3	1.361 (4)	C15—C16	1.349 (7)
N2—C6	1.450 (5)	C15—H15A	0.9300
N2—H2B	0.8600	C16—C17	1.384 (7)
C1—C2	1.357 (6)	C16—H16A	0.9300
C1—H1A	0.9300	C17—C18	1.383 (6)
C2—C3	1.399 (5)	C17—H17A	0.9300
C2—H2A	0.9300	C18—H18A	0.9300
C3—C4	1.393 (5)	N3—C19	1.120 (13)
C4—C5	1.373 (5)	C19—C20	1.289 (13)
C4—H4A	0.9300	C20—C19^iii	1.289 (13)
C5—H5A	0.9300	C20—H20A	0.9600
C6—H6A	0.9700	C20—H20B	0.9600
C6—H6B	0.9700	C20—H20C	0.9599
C7—C12	1.372 (6)	Cl1—O4	1.351 (5)
C7—C8	1.389 (6)	Cl1—O3	1.377 (4)
C8—C9	1.387 (6)	Cl1—O2	1.404 (4)
C8—H8A	0.9300	Cl1—O1	1.421 (7)
C9—C10	1.367 (7)
N1^i—Ag1—P1	174.00 (9)	C9—C10—H10A	120.2
C13—P1—C7	105.95 (17)	C11—C10—H10A	120.2
C13—P1—C6	103.12 (17)	C10—C11—C12	120.9 (5)
C7—P1—C6	106.42 (18)	C10—C11—H11A	119.5
C13—P1—Ag1	116.05 (12)	C12—C11—H11A	119.5
C7—P1—Ag1	114.73 (12)	C7—C12—C11	119.9 (4)
C6—P1—Ag1	109.56 (12)	C7—C12—H12A	120.1
C5—N1—C1	116.0 (3)	C11—C12—H12A	120.1
C5—N1—Ag1^i	118.3 (3)	C14—C13—C18	119.0 (4)
C1—N1—Ag1^i	124.7 (3)	C14—C13—P1	122.9 (3)
C3—N2—C6	123.7 (3)	C18—C13—P1	118.1 (3)
C3—N2—H2B	118.1	C15—C14—C13	119.4 (4)
C6—N2—H2B	118.3	C15—C14—H14A	120.3
N1—C1—C2	124.2 (4)	C13—C14—H14A	120.3
N1—C1—H1A	117.9	C16—C15—C14	121.1 (4)
C2—C1—H1A	117.9	C16—C15—H15A	119.5
C1—C2—C3	119.7 (4)	C14—C15—H15A	119.5
C1—C2—H2A	120.1	C15—C16—C17	120.7 (4)
C3—C2—H2A	120.1	C15—C16—H16A	119.6
N2—C3—C4	123.0 (3)	C17—C16—H16A	119.6
N2—C3—C2	120.5 (3)	C18—C17—C16	119.2 (5)
C4—C3—C2	116.6 (3)	C18—C17—H17A	120.4
C5—C4—C3	119.3 (3)	C16—C17—H17A	120.4
C5—C4—H4A	120.3	C17—C18—C13	120.6 (4)
C3—C4—H4A	120.3	C17—C18—H18A	119.7
N1—C5—C4	124.1 (4)	C13—C18—H18A	119.7
N1—C5—H5A	118.0	N3—C19—C20	176.1 (11)
C4—C5—H5A	118.0	C19^iii—C20—C19	147.4 (15)
N2—C6—P1	111.8 (3)	C19^iii—C20—H20A	52.8
N2—C6—H6A	109.3	C19—C20—H20A	110.6
P1—C6—H6A	109.3	C19^iii—C20—H20B	62.1
N2—C6—H6B	109.3	C19—C20—H20B	109.3
P1—C6—H6B	109.3	H20A—C20—H20B	109.5
H6A—C6—H6B	107.9	C19^iii—C20—H20C	103.9
C12—C7—C8	119.0 (4)	C19—C20—H20C	108.5
C12—C7—P1	123.6 (3)	H20A—C20—H20C	109.5
C8—C7—P1	117.4 (3)	H20B—C20—H20C	109.5
C9—C8—C7	120.7 (4)	O4—Cl1—O3	106.5 (3)
C9—C8—H8A	119.7	O4—Cl1—O2	115.6 (4)
C7—C8—H8A	119.7	O3—Cl1—O2	109.4 (3)
C10—C9—C8	119.9 (5)	O4—Cl1—O1	110.3 (6)
C10—C9—H9A	120.0	O3—Cl1—O1	106.6 (5)
C8—C9—H9A	120.0	O2—Cl1—O1	108.0 (3)
C9—C10—C11	119.6 (5)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+1, z+1/2; (iii) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3	0.86	2.16	2.966 (5)	155
C4—H4A···O2^ii	0.93	2.49	3.213 (5)	134

Symmetry code: (ii) x, −y+1, z+1/2.

(2) bis{µ-N-[(diphenylphosphanyl)methyl]pyridin-4-amine-κ²N¹:P}bis[(nitrato-κ²O,O)silver]

Crystal data

[Ag2(C18H17N2P)2(NO3)2]	Z = 4
Mr = 924.37	F(000) = 1856
Monoclinic, P21/c	Dx = 1.644 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.448 (5) Å	θ = 2.6–28.1°
b = 17.498 (6) Å	µ = 1.19 mm^−1
c = 16.006 (5) Å	T = 296 K
β = 97.475 (4)°	Block, colourless
V = 3734 (2) Å^3	0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	8472 independent reflections
Radiation source: fine-focus sealed tube	6592 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 27.6°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→17
Tmin = 0.797, Tmax = 0.891	k = −22→22
24006 measured reflections	l = −20→20

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0434P)^2] where P = (Fo^2 + 2Fc^2)/3
8472 reflections	(Δ/σ)max = 0.004
469 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.89 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	0.530647 (15)	0.509563 (10)	0.204426 (12)	0.04690 (7)
P1	0.51910 (4)	0.39222 (3)	0.27560 (3)	0.03469 (13)
N1	0.49043 (16)	0.41706 (11)	−0.09121 (12)	0.0444 (5)
N2	0.49198 (15)	0.29787 (11)	0.13468 (11)	0.0429 (5)
H2B	0.4475	0.2625	0.1339	0.052*
C1	0.49460 (17)	0.33701 (11)	0.06218 (14)	0.0373 (5)
C2	0.4189 (2)	0.32552 (13)	−0.00539 (15)	0.0472 (6)
H2A	0.3680	0.2905	−0.0006	0.057*
C3	0.4199 (2)	0.36564 (14)	−0.07810 (15)	0.0485 (6)
H3A	0.3683	0.3569	−0.1216	0.058*
C4	0.56390 (19)	0.42666 (13)	−0.02697 (15)	0.0450 (6)
H4A	0.6147	0.4611	−0.0345	0.054*
C5	0.56990 (17)	0.38968 (13)	0.04888 (14)	0.0398 (5)
H5A	0.6229	0.3992	0.0909	0.048*
C6	0.55601 (18)	0.30921 (13)	0.21275 (14)	0.0402 (5)
H6A	0.6242	0.3169	0.2008	0.048*
H6B	0.5553	0.2632	0.2465	0.048*
C7	0.59728 (16)	0.38149 (13)	0.37663 (14)	0.0374 (5)
C8	0.60856 (17)	0.31144 (13)	0.41723 (14)	0.0421 (5)
H8A	0.5804	0.2680	0.3902	0.051*
C9	0.66056 (19)	0.30513 (16)	0.49659 (15)	0.0510 (6)
H9A	0.6685	0.2576	0.5225	0.061*
C10	0.7008 (2)	0.36917 (19)	0.53764 (17)	0.0634 (8)
H10A	0.7351	0.3651	0.5918	0.076*
C11	0.6905 (3)	0.4384 (2)	0.4991 (2)	0.0771 (9)
H11A	0.7180	0.4816	0.5270	0.092*
C12	0.6391 (2)	0.44519 (16)	0.41825 (18)	0.0631 (8)
H12A	0.6329	0.4928	0.3922	0.076*
C13	0.39427 (16)	0.36832 (11)	0.30128 (14)	0.0355 (5)
C14	0.37305 (18)	0.36469 (14)	0.38424 (15)	0.0472 (6)
H14A	0.4245	0.3719	0.4283	0.057*
C15	0.2770 (2)	0.35061 (15)	0.40192 (17)	0.0540 (7)
H15A	0.2643	0.3482	0.4576	0.065*
C16	0.1998 (2)	0.34013 (14)	0.33739 (18)	0.0527 (7)
H16A	0.1351	0.3308	0.3494	0.063*
C17	0.2187 (2)	0.34360 (15)	0.25528 (18)	0.0576 (7)
H17A	0.1669	0.3362	0.2116	0.069*
C18	0.31548 (18)	0.35813 (15)	0.23730 (15)	0.0490 (6)
H18A	0.3274	0.3610	0.1814	0.059*
N5	0.64176 (16)	0.63684 (11)	0.31203 (13)	0.0457 (5)
O1	0.68227 (15)	0.68426 (11)	0.36233 (14)	0.0714 (6)
O2	0.54888 (15)	0.63702 (12)	0.29282 (15)	0.0744 (6)
O3	0.69176 (14)	0.58799 (10)	0.27911 (13)	0.0599 (5)
Ag2	0.948112 (16)	1.031511 (11)	0.806690 (12)	0.05028 (7)
P2	0.96514 (5)	0.92081 (3)	0.72632 (3)	0.03697 (13)
N3	1.01525 (15)	0.90435 (10)	1.07593 (12)	0.0414 (4)
N4	0.97578 (15)	0.80084 (11)	0.83938 (11)	0.0435 (5)
H4B	1.0090	0.7596	0.8339	0.052*
C19	0.98394 (17)	0.83311 (12)	0.91674 (13)	0.0357 (5)
C20	1.06046 (19)	0.80921 (13)	0.97965 (14)	0.0451 (6)
H20A	1.1018	0.7685	0.9697	0.054*
C21	1.07377 (19)	0.84648 (13)	1.05596 (15)	0.0453 (6)
H21A	1.1261	0.8308	1.0960	0.054*
C22	0.93888 (18)	0.92384 (13)	1.01702 (14)	0.0414 (5)
H22A	0.8961	0.9626	1.0301	0.050*
C23	0.91964 (17)	0.89065 (13)	0.93906 (14)	0.0386 (5)
H23A	0.8647	0.9060	0.9014	0.046*
C24	0.91577 (18)	0.83046 (13)	0.76570 (14)	0.0428 (5)
H24A	0.8482	0.8393	0.7787	0.051*
H24B	0.9120	0.7924	0.7213	0.051*
C25	0.90645 (18)	0.92720 (14)	0.61701 (14)	0.0439 (5)
C26	0.8839 (3)	0.86482 (18)	0.56470 (17)	0.0724 (9)
H26A	0.8946	0.8157	0.5861	0.087*
C27	0.8462 (3)	0.8747 (2)	0.48184 (19)	0.0935 (12)
H27A	0.8309	0.8322	0.4477	0.112*
C28	0.8310 (3)	0.9455 (2)	0.44909 (19)	0.0823 (10)
H28A	0.8064	0.9515	0.3924	0.099*
C29	0.8515 (3)	1.0079 (2)	0.4988 (2)	0.0848 (11)
H29A	0.8398	1.0567	0.4766	0.102*
C30	0.8900 (3)	0.99846 (17)	0.58287 (18)	0.0667 (8)
H30A	0.9049	1.0413	0.6166	0.080*
C31	1.09599 (17)	0.89874 (12)	0.71842 (14)	0.0375 (5)
C32	1.1251 (2)	0.83544 (15)	0.6761 (2)	0.0653 (8)
H32A	1.0767	0.8015	0.6514	0.078*
C33	1.2243 (2)	0.82208 (18)	0.6701 (2)	0.0790 (10)
H33A	1.2425	0.7793	0.6411	0.095*
C34	1.2968 (2)	0.87061 (17)	0.7062 (2)	0.0651 (8)
H34A	1.3639	0.8613	0.7015	0.078*
C35	1.2700 (2)	0.93291 (17)	0.74934 (19)	0.0627 (8)
H35A	1.3192	0.9658	0.7749	0.075*
C36	1.1702 (2)	0.94759 (14)	0.75541 (16)	0.0510 (6)
H36A	1.1527	0.9905	0.7845	0.061*
O4	0.79309 (14)	1.11428 (11)	0.74249 (13)	0.0657 (5)
O5	0.80158 (17)	1.20439 (13)	0.65210 (14)	0.0805 (7)
O6	0.93558 (15)	1.16341 (10)	0.72664 (13)	0.0633 (5)
N6	0.84259 (17)	1.16112 (11)	0.70640 (13)	0.0491 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.05831 (14)	0.03519 (10)	0.04811 (12)	−0.00184 (8)	0.01032 (9)	0.00993 (7)
P1	0.0373 (3)	0.0311 (3)	0.0351 (3)	−0.0013 (2)	0.0027 (2)	0.0041 (2)
N1	0.0577 (13)	0.0366 (10)	0.0397 (11)	−0.0034 (9)	0.0091 (10)	0.0045 (8)
N2	0.0566 (12)	0.0355 (10)	0.0369 (10)	−0.0108 (9)	0.0071 (9)	0.0011 (8)
C1	0.0471 (14)	0.0276 (10)	0.0387 (12)	0.0007 (9)	0.0114 (10)	−0.0014 (9)
C2	0.0543 (15)	0.0431 (13)	0.0442 (13)	−0.0147 (11)	0.0061 (12)	0.0017 (10)
C3	0.0578 (16)	0.0465 (14)	0.0392 (13)	−0.0078 (12)	−0.0010 (12)	0.0005 (10)
C4	0.0482 (15)	0.0386 (12)	0.0501 (14)	−0.0045 (11)	0.0134 (12)	0.0030 (10)
C5	0.0403 (13)	0.0385 (12)	0.0409 (12)	−0.0020 (10)	0.0066 (10)	−0.0008 (9)
C6	0.0482 (14)	0.0338 (12)	0.0389 (12)	0.0031 (10)	0.0062 (10)	0.0037 (9)
C7	0.0356 (12)	0.0386 (12)	0.0370 (11)	−0.0026 (10)	0.0015 (10)	0.0032 (9)
C8	0.0396 (13)	0.0428 (13)	0.0430 (13)	−0.0021 (11)	0.0018 (10)	0.0030 (10)
C9	0.0505 (15)	0.0582 (16)	0.0432 (14)	0.0058 (13)	0.0017 (12)	0.0107 (12)
C10	0.0639 (19)	0.077 (2)	0.0447 (15)	0.0014 (16)	−0.0083 (14)	0.0008 (14)
C11	0.087 (2)	0.068 (2)	0.069 (2)	−0.0174 (18)	−0.0184 (18)	−0.0148 (17)
C12	0.076 (2)	0.0456 (15)	0.0625 (18)	−0.0130 (14)	−0.0107 (15)	0.0013 (13)
C13	0.0378 (12)	0.0271 (10)	0.0414 (12)	0.0011 (9)	0.0047 (10)	0.0028 (9)
C14	0.0436 (14)	0.0559 (15)	0.0420 (13)	0.0070 (12)	0.0053 (11)	0.0023 (11)
C15	0.0569 (17)	0.0577 (16)	0.0513 (15)	0.0070 (13)	0.0216 (13)	0.0025 (12)
C16	0.0458 (15)	0.0426 (14)	0.0736 (18)	−0.0047 (11)	0.0220 (14)	−0.0042 (12)
C17	0.0432 (15)	0.0631 (17)	0.0648 (18)	−0.0096 (13)	0.0006 (13)	−0.0091 (14)
C18	0.0435 (14)	0.0618 (16)	0.0414 (13)	−0.0065 (12)	0.0042 (11)	−0.0008 (11)
N5	0.0490 (13)	0.0349 (10)	0.0524 (12)	−0.0002 (9)	0.0035 (10)	0.0004 (9)
O1	0.0670 (13)	0.0566 (12)	0.0860 (15)	−0.0006 (10)	−0.0077 (11)	−0.0247 (11)
O2	0.0462 (12)	0.0701 (13)	0.1033 (17)	0.0098 (10)	−0.0036 (11)	−0.0253 (12)
O3	0.0554 (11)	0.0468 (10)	0.0789 (13)	0.0029 (9)	0.0145 (10)	−0.0116 (9)
Ag2	0.06975 (15)	0.03882 (11)	0.04263 (11)	0.00932 (9)	0.00868 (10)	−0.00563 (7)
P2	0.0415 (3)	0.0350 (3)	0.0331 (3)	0.0060 (2)	0.0000 (2)	−0.0023 (2)
N3	0.0518 (12)	0.0370 (10)	0.0359 (10)	0.0055 (9)	0.0080 (9)	−0.0002 (8)
N4	0.0549 (12)	0.0373 (10)	0.0375 (10)	0.0090 (9)	0.0035 (9)	−0.0009 (8)
C19	0.0414 (13)	0.0319 (11)	0.0351 (11)	−0.0040 (9)	0.0094 (10)	0.0015 (8)
C20	0.0528 (15)	0.0391 (12)	0.0435 (13)	0.0118 (11)	0.0069 (11)	−0.0017 (10)
C21	0.0531 (15)	0.0416 (13)	0.0399 (13)	0.0102 (11)	0.0011 (11)	0.0028 (10)
C22	0.0446 (14)	0.0408 (12)	0.0413 (12)	0.0059 (10)	0.0153 (11)	0.0006 (10)
C23	0.0339 (12)	0.0446 (13)	0.0382 (12)	0.0041 (10)	0.0080 (10)	0.0057 (9)
C24	0.0429 (14)	0.0450 (13)	0.0404 (12)	−0.0036 (11)	0.0050 (11)	−0.0047 (10)
C25	0.0397 (13)	0.0559 (15)	0.0355 (12)	0.0068 (11)	0.0029 (10)	0.0023 (10)
C26	0.106 (3)	0.0630 (18)	0.0417 (15)	−0.0123 (18)	−0.0143 (16)	0.0013 (13)
C27	0.131 (3)	0.095 (3)	0.0457 (18)	−0.024 (2)	−0.022 (2)	−0.0008 (18)
C28	0.086 (2)	0.116 (3)	0.0387 (16)	−0.011 (2)	−0.0148 (16)	0.0131 (18)
C29	0.109 (3)	0.084 (2)	0.059 (2)	0.021 (2)	−0.003 (2)	0.0264 (18)
C30	0.088 (2)	0.0589 (18)	0.0502 (16)	0.0185 (16)	−0.0011 (16)	0.0041 (13)
C31	0.0379 (12)	0.0339 (11)	0.0391 (12)	0.0012 (9)	−0.0007 (10)	0.0031 (9)
C32	0.0450 (16)	0.0501 (16)	0.101 (2)	−0.0025 (12)	0.0124 (15)	−0.0291 (15)
C33	0.0511 (18)	0.0581 (18)	0.131 (3)	0.0046 (15)	0.0245 (19)	−0.0241 (19)
C34	0.0396 (15)	0.0589 (18)	0.098 (2)	0.0030 (13)	0.0137 (15)	0.0223 (17)
C35	0.0469 (16)	0.0601 (17)	0.077 (2)	−0.0155 (14)	−0.0066 (14)	0.0088 (15)
C36	0.0521 (16)	0.0412 (13)	0.0574 (15)	−0.0056 (12)	−0.0013 (12)	−0.0035 (11)
O4	0.0570 (12)	0.0579 (11)	0.0846 (14)	0.0015 (9)	0.0180 (10)	0.0247 (10)
O5	0.0800 (15)	0.0818 (15)	0.0767 (14)	0.0109 (12)	−0.0008 (11)	0.0417 (12)
O6	0.0508 (12)	0.0524 (11)	0.0853 (14)	−0.0042 (9)	0.0028 (10)	0.0144 (10)
N6	0.0558 (14)	0.0401 (11)	0.0516 (12)	0.0052 (10)	0.0084 (11)	0.0075 (9)

Geometric parameters (Å, º)

Ag1—N1^i	2.2089 (19)	Ag2—N3^ii	2.1889 (19)
Ag1—P1	2.3630 (8)	Ag2—P2	2.3528 (8)
Ag1—O2	2.636 (2)	Ag2—O4	2.635 (2)
Ag1—O3	2.708 (2)	Ag2—O6	2.634 (2)
P1—C7	1.820 (2)	P2—C31	1.822 (2)
P1—C13	1.828 (2)	P2—C25	1.827 (2)
P1—C6	1.870 (2)	P2—C24	1.856 (2)
N1—C4	1.341 (3)	N3—C22	1.345 (3)
N1—C3	1.343 (3)	N3—C21	1.346 (3)
N1—Ag1^i	2.2089 (19)	N3—Ag2^ii	2.1889 (19)
N2—C1	1.352 (3)	N4—C19	1.352 (3)
N2—C6	1.436 (3)	N4—C24	1.436 (3)
N2—H2B	0.8601	N4—H4B	0.8591
C1—C2	1.400 (3)	C19—C23	1.403 (3)
C1—C5	1.406 (3)	C19—C20	1.406 (3)
C2—C3	1.361 (3)	C20—C21	1.376 (3)
C2—H2A	0.9300	C20—H20A	0.9300
C3—H3A	0.9300	C21—H21A	0.9300
C4—C5	1.369 (3)	C22—C23	1.370 (3)
C4—H4A	0.9300	C22—H22A	0.9300
C5—H5A	0.9300	C23—H23A	0.9300
C6—H6A	0.9700	C24—H24A	0.9700
C6—H6B	0.9700	C24—H24B	0.9700
C7—C12	1.380 (3)	C25—C30	1.368 (4)
C7—C8	1.386 (3)	C25—C26	1.385 (4)
C8—C9	1.372 (3)	C26—C27	1.368 (4)
C8—H8A	0.9300	C26—H26A	0.9300
C9—C10	1.374 (4)	C27—C28	1.350 (5)
C9—H9A	0.9300	C27—H27A	0.9300
C10—C11	1.358 (4)	C28—C29	1.359 (5)
C10—H10A	0.9300	C28—H28A	0.9300
C11—C12	1.391 (4)	C29—C30	1.388 (4)
C11—H11A	0.9300	C29—H29A	0.9300
C12—H12A	0.9300	C30—H30A	0.9300
C13—C18	1.386 (3)	C31—C32	1.381 (3)
C13—C14	1.395 (3)	C31—C36	1.387 (3)
C14—C15	1.380 (3)	C32—C33	1.371 (4)
C14—H14A	0.9300	C32—H32A	0.9300
C15—C16	1.378 (4)	C33—C34	1.363 (4)
C15—H15A	0.9300	C33—H33A	0.9300
C16—C17	1.372 (4)	C34—C35	1.364 (4)
C16—H16A	0.9300	C34—H34A	0.9300
C17—C18	1.392 (4)	C35—C36	1.381 (4)
C17—H17A	0.9300	C35—H35A	0.9300
C18—H18A	0.9300	C36—H36A	0.9300
N5—O1	1.233 (3)	O4—N6	1.244 (3)
N5—O3	1.246 (2)	O5—N6	1.228 (3)
N5—O2	1.247 (3)	O6—N6	1.251 (3)
N1^i—Ag1—P1	153.01 (5)	N3^ii—Ag2—P2	149.81 (5)
C7—P1—C13	102.59 (10)	C31—P2—C25	104.32 (10)
C7—P1—C6	103.57 (10)	C31—P2—C24	103.55 (10)
C13—P1—C6	105.01 (10)	C25—P2—C24	104.37 (11)
C7—P1—Ag1	116.83 (7)	C31—P2—Ag2	112.09 (7)
C13—P1—Ag1	115.28 (7)	C25—P2—Ag2	114.37 (8)
C6—P1—Ag1	112.13 (8)	C24—P2—Ag2	116.81 (8)
C4—N1—C3	115.4 (2)	C22—N3—C21	116.2 (2)
C4—N1—Ag1^i	124.02 (16)	C22—N3—Ag2^ii	122.55 (15)
C3—N1—Ag1^i	119.98 (17)	C21—N3—Ag2^ii	121.07 (16)
C1—N2—C6	126.68 (19)	C19—N4—C24	124.83 (19)
C1—N2—H2B	116.7	C19—N4—H4B	117.6
C6—N2—H2B	116.7	C24—N4—H4B	117.6
N2—C1—C2	119.5 (2)	N4—C19—C23	123.6 (2)
N2—C1—C5	124.2 (2)	N4—C19—C20	119.7 (2)
C2—C1—C5	116.3 (2)	C23—C19—C20	116.7 (2)
C3—C2—C1	120.0 (2)	C21—C20—C19	119.6 (2)
C3—C2—H2A	120.0	C21—C20—H20A	120.2
C1—C2—H2A	120.0	C19—C20—H20A	120.2
N1—C3—C2	124.4 (2)	N3—C21—C20	123.7 (2)
N1—C3—H3A	117.8	N3—C21—H21A	118.2
C2—C3—H3A	117.8	C20—C21—H21A	118.2
N1—C4—C5	125.0 (2)	N3—C22—C23	124.6 (2)
N1—C4—H4A	117.5	N3—C22—H22A	117.7
C5—C4—H4A	117.5	C23—C22—H22A	117.7
C4—C5—C1	118.9 (2)	C22—C23—C19	119.1 (2)
C4—C5—H5A	120.5	C22—C23—H23A	120.5
C1—C5—H5A	120.5	C19—C23—H23A	120.5
N2—C6—P1	113.85 (16)	N4—C24—P2	113.48 (16)
N2—C6—H6A	108.8	N4—C24—H24A	108.9
P1—C6—H6A	108.8	P2—C24—H24A	108.9
N2—C6—H6B	108.8	N4—C24—H24B	108.9
P1—C6—H6B	108.8	P2—C24—H24B	108.9
H6A—C6—H6B	107.7	H24A—C24—H24B	107.7
C12—C7—C8	118.3 (2)	C30—C25—C26	117.8 (2)
C12—C7—P1	119.84 (19)	C30—C25—P2	117.8 (2)
C8—C7—P1	121.53 (17)	C26—C25—P2	124.3 (2)
C9—C8—C7	121.1 (2)	C27—C26—C25	120.7 (3)
C9—C8—H8A	119.5	C27—C26—H26A	119.6
C7—C8—H8A	119.5	C25—C26—H26A	119.6
C8—C9—C10	119.9 (3)	C28—C27—C26	120.7 (3)
C8—C9—H9A	120.0	C28—C27—H27A	119.6
C10—C9—H9A	120.0	C26—C27—H27A	119.6
C11—C10—C9	120.0 (3)	C27—C28—C29	120.1 (3)
C11—C10—H10A	120.0	C27—C28—H28A	120.0
C9—C10—H10A	120.0	C29—C28—H28A	120.0
C10—C11—C12	120.5 (3)	C28—C29—C30	119.6 (3)
C10—C11—H11A	119.7	C28—C29—H29A	120.2
C12—C11—H11A	119.7	C30—C29—H29A	120.2
C7—C12—C11	120.1 (3)	C25—C30—C29	121.1 (3)
C7—C12—H12A	119.9	C25—C30—H30A	119.4
C11—C12—H12A	119.9	C29—C30—H30A	119.4
C18—C13—C14	117.8 (2)	C32—C31—C36	118.0 (2)
C18—C13—P1	119.97 (17)	C32—C31—P2	122.79 (19)
C14—C13—P1	122.13 (18)	C36—C31—P2	119.20 (18)
C15—C14—C13	121.1 (2)	C33—C32—C31	120.8 (3)
C15—C14—H14A	119.5	C33—C32—H32A	119.6
C13—C14—H14A	119.5	C31—C32—H32A	119.6
C16—C15—C14	120.3 (2)	C34—C33—C32	120.9 (3)
C16—C15—H15A	119.9	C34—C33—H33A	119.6
C14—C15—H15A	119.9	C32—C33—H33A	119.6
C17—C16—C15	119.7 (2)	C33—C34—C35	119.4 (3)
C17—C16—H16A	120.1	C33—C34—H34A	120.3
C15—C16—H16A	120.1	C35—C34—H34A	120.3
C16—C17—C18	120.1 (3)	C34—C35—C36	120.5 (3)
C16—C17—H17A	120.0	C34—C35—H35A	119.8
C18—C17—H17A	120.0	C36—C35—H35A	119.8
C13—C18—C17	121.1 (2)	C35—C36—C31	120.5 (2)
C13—C18—H18A	119.5	C35—C36—H36A	119.8
C17—C18—H18A	119.5	C31—C36—H36A	119.8
O1—N5—O3	121.4 (2)	O5—N6—O4	121.1 (2)
O1—N5—O2	120.2 (2)	O5—N6—O6	120.4 (2)
O3—N5—O2	118.4 (2)	O4—N6—O6	118.6 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1^iii	0.86	2.22	3.078 (3)	172
N2—H2B···O2^iii	0.86	2.49	3.120 (3)	131
N4—H4B···O6^iv	0.86	2.12	2.941 (3)	158
C24—H24A···O3^v	0.97	2.46	3.365 (3)	155

Symmetry codes: (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y−1/2, −z+3/2; (v) x, −y+3/2, z+1/2.