Bis[tris­(1,10-phenanthroline)nickel(II)] tris­[dicyanidoargentate(I)] nitrate 4.2-hydrate

The title compound, [Ni(C₁₂H₈N₂)₃]₂[Ag(CN)₂]₃(NO₃)·4.2H₂O, crystallizes with two independent [Ni(phen)₃]²⁺ cations (phen is 1,10-phenanthroline; both Ni atoms have threefold symmetry and N₆ donor sets), three near-linear [Ag(CN)₂]⁻ anions, one nitrate anion (N site symmetry 3) and 4.2 water mol­ecules of crystallization, some of which are disordered. The [Ag(CN)₂]⁻ anions are situated within cavities created by the phenanthroline ligands of adjacent [Ni(phen)₃]²⁺ cations. Some short C—H...O and C—H...N inter­actions may help to establish the packing.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• H-atom completeness 86%
• Disorder in solvent or counterion
• R factor = 0.031
• wR factor = 0.086
• Data-to-parameter ratio = 18.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  N6     ..  O1WB    ..       2.86 Ang.

Alert level C
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....      >O1WA
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....      <O1WB
PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........        O2W
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels ..........          2

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C78 H56.4 Ag3 N19 Ni2 O7.2
            Atom count from the _atom_site data:  C78 H48 Ag3 N19 Ni2 O7.2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    6
           From the CIF: _chemical_formula_sum  C78 H56.40 Ag3 N19 Ni2 O7.20
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        468.00    468.00    0.00
           H        338.40    288.00   50.40
           Ag        18.00     18.00    0.00
           N        114.00    114.00    0.00
           Ni        12.00     12.00    0.00
           O         43.20     43.20    0.00
PLAT302_ALERT_4_G Anion/Solvent Disorder .........................      13.00 Perc.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: Prof. Saeed Ahmad states that all of his collaborators are involved in this work. Prof. Stoeckli-Evans states that her student (MA) and herself were involved with the crystal structure analysis.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

S1. Comment

Supramolecular structures based on [Ag(CN)₂]^- anions are of significant interest because of their potential for structural, magnetic and catalytic applications, as witnessed by some recent work in this area (Ahmad et al., 2007; Ren et al., 2005; Shorrock et al., 2002; Zhang et al., 2006). We have begun investigations of the structural and chemical properties of metal(II)—Ag(I) coordination polymers that contain the [Ag(CN)₂]^- anion as a bridging unit (Ahmad et al., 2007). Mixed-ligand metal complexes of 1,10-phenanthroline (phen), and its substituted derivatives, are also interesting because they play an important role in biological systems, such as binding small molecules to DNA (Sastri et al., 2003). A search of the Cambridge Structural Database (CSD V5.29, last update Jan 2008; Allen, 2002) revealed the presence of more than 50 complexes involving the [Ni(phen)₃]²⁺ cation. In the present study we attempted to prepare a coordination polymer consisting of [Ni(phen)₂]²⁺ cations and [Ag(CN)₂]^-, but instead, the title compound, (I), was isolated.

The molecular structure of (I) is shown in Fig. 1. The two independent [Ni(phen)₃]²⁺ cations have 3-fold symmetry and both Ni atoms have octahedral environments formed by six nitrogen atoms from three 1,10-phenanthroline ligands (Table 1) with normal bond distances and angles. The coordination environment of metal in the [Ag(CN)₂]^- anion is close to linear [C—Ag—C = 176.78 (13)°].

In the crystal structure of (I), the [Ag(CN)₂]^- anions are situated within cavities created by the phenanthroline ligands of two [Ni(phen)₃]²⁺ cations (see Fig. 2), hence the silver atoms are isolated from one another. The cationic and anionic units are associated with each other through C—H···O and C—H···N weak interactions (Table 2). The disordered water molecules of crystallization in (I) occupy regions in the vicinity of the 3 symmetry positions (Fig. 3).

The crystal structure of (I) is very similar to that of bis[tris(bipyridine)nickel(II)] tris[dicyanoargentate(I)] chloride nonahydrate, (II), (Černák et al., 1994). Both crystallize in the trigonal space group R3, with a similar disposition in the crystal of the [Ni(phen)₃]²⁺ and [Ag(CN)₂]^- ionic moeties. In (II), however, the secondary anion, Cl^-, is partially distributed over the positions of the water molecules of crystallization (Fig. 4).

Related literature

For a closely related structure containing 2,2'-bipyridine, see: Černák et al. (1994).

For related literature, see: Ahmad et al. (2007); Allen (2002); Ren et al. (2005); Sastri et al. (2003); Shorrock et al. (2002); Zhang et al. (2006).

S2. Experimental

An aqueous mixture of Ni(NO₃)₂^.6H₂O, 1,10-phenanthroline (phen) and K[Ag(CN)₂], was made up in a molar ratio of 1:1:2. After stirring the mixture for 25–30 min, a pink precipitate appeared. This was filtered off and the colourless filtrate left to evaporate slowly at room temperature. After a few days pink blocks of (I) were obtained, which were washed with methanol.

S3. Refinement

The aromatic H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 Å with U_iso(H) = 1.2U_eq(C). The H atoms of the water molecules could not be located.

Computing details

Data collection: X-AREA (Stoe & Cie, 2006); cell refinement: X-AREA (Stoe & Cie, 2006); data reduction: X-RED32 (Stoe & Cie, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids drawn at the 50% probability level [H atoms and water molecules of crystallization have been omitted for clarity; Symmetry codes: (i) -y + 1, x-y, z; (ii) -x + y+1,-x + 1, z; (iv) -y + 1, x-y + 1, z; (iii) -x + y, -x + 1, z;(v) -y, x-y, z; (vi) -x + y, -x, z]
	Fig. 2. Two views of the [Ag(CN)2]^- anion situated within a cavity created by the phenanthroline ligands of two [Ni(phen)3]^2+ cations.
	Fig. 3. A view along the c axis of the crystal packing of (I) showing the formation of the hexagonally shaped water clusters [The H-atoms have been omitted for clarity; the O···O contacts are shown as blue dotted lines].
	Fig. 4. A view along the c axis of the crystal packing of (II) [The published coordinates have been transformed from rhombohedral to hexagonal axes; the H-atoms have been removed for clarity, and the O···O contacts are shown as blue dotted lines].

Bis[tris(1,10-phenanthroline)nickel(II)] tris[dicyanidoargentate(I)] nitrate 4.2-hydrate

Crystal data

[Ni(C12H8N2)3]2[Ag(CN)2]3(NO3)·4.2H2O	Dx = 1.700 Mg m^−3
Mr = 1816.05	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 29311 reflections
Hall symbol: -R 3	θ = 1.7–29.6°
a = 16.2738 (7) Å	µ = 1.41 mm^−1
c = 46.398 (2) Å	T = 173 K
V = 10641.6 (8) Å^3	Block, pink
Z = 6	0.50 × 0.40 × 0.30 mm
F(000) = 5472

Data collection

Stoe IPDSII diffractometer	6400 independent reflections
Radiation source: fine-focus sealed tube	5514 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 29.2°, θmin = 1.7°
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2003)	h = −21→20
Tmin = 0.454, Tmax = 0.651	k = −19→22
28787 measured reflections	l = −63→63

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.086	w = 1/[σ^2(Fo^2) + (0.0528P)^2 + 11.6906P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
6400 reflections	Δρmax = 0.89 e Å^−3
353 parameters	Δρmin = −0.80 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00026 (3)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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)
Ni1	0.66667	0.33333	0.09760 (1)	0.0219 (1)
N1	0.55774 (12)	0.22921 (12)	0.12273 (3)	0.0263 (4)
N2	0.54772 (11)	0.30552 (11)	0.07265 (3)	0.0236 (4)
C1	0.56354 (16)	0.19654 (16)	0.14863 (4)	0.0331 (6)
C2	0.48349 (18)	0.13805 (16)	0.16522 (5)	0.0366 (6)
C3	0.39524 (17)	0.10971 (15)	0.15449 (5)	0.0343 (6)
C4	0.38610 (15)	0.13989 (14)	0.12682 (4)	0.0293 (5)
C5	0.29696 (16)	0.11155 (16)	0.11340 (5)	0.0359 (6)
C6	0.29168 (15)	0.14076 (16)	0.08686 (5)	0.0358 (6)
C7	0.37639 (14)	0.20643 (14)	0.07144 (4)	0.0284 (5)
C8	0.37537 (15)	0.24171 (16)	0.04399 (5)	0.0338 (6)
C9	0.45898 (16)	0.30945 (17)	0.03200 (4)	0.0339 (6)
C10	0.54358 (15)	0.34083 (15)	0.04711 (4)	0.0290 (5)
C11	0.46468 (13)	0.23886 (13)	0.08459 (4)	0.0235 (5)
C12	0.47022 (14)	0.20149 (13)	0.11212 (4)	0.0242 (5)
Ni2	0.33333	0.66667	0.08188 (1)	0.0186 (1)
N3	0.23944 (10)	0.54770 (11)	0.10601 (3)	0.0211 (4)
N4	0.33131 (11)	0.55851 (11)	0.05706 (3)	0.0211 (4)
C13	0.19556 (13)	0.54382 (14)	0.13060 (4)	0.0254 (5)
C14	0.13796 (14)	0.45900 (15)	0.14521 (4)	0.0294 (5)
C15	0.12376 (14)	0.37531 (14)	0.13348 (4)	0.0285 (5)
C16	0.16541 (13)	0.37618 (14)	0.10678 (4)	0.0253 (5)
C17	0.14959 (15)	0.29206 (14)	0.09207 (4)	0.0302 (6)
C18	0.18904 (15)	0.29717 (14)	0.06616 (4)	0.0298 (5)
C19	0.25180 (14)	0.38706 (13)	0.05303 (4)	0.0253 (5)
C20	0.29664 (16)	0.39689 (15)	0.02637 (4)	0.0297 (6)
C21	0.35881 (16)	0.48563 (15)	0.01624 (4)	0.0307 (6)
C22	0.37553 (14)	0.56505 (14)	0.03227 (4)	0.0269 (5)
C23	0.27092 (12)	0.47077 (12)	0.06744 (4)	0.0205 (4)
C24	0.22410 (12)	0.46493 (12)	0.09427 (4)	0.0207 (4)
O2W	0.043 (2)	0.0466 (16)	0.0515 (3)	0.128 (12)	0.200
O3W	0.1111 (11)	0.0799 (8)	0.0346 (3)	0.080 (5)	0.200
Ag1	−0.00155 (1)	0.47423 (1)	0.08079 (1)	0.0352 (1)
N5	−0.0135 (2)	0.6044 (2)	0.12942 (5)	0.0638 (10)
N6	0.02865 (18)	0.34982 (19)	0.03319 (4)	0.0486 (7)
C25	−0.01043 (19)	0.5588 (2)	0.11172 (5)	0.0432 (8)
C26	0.01549 (17)	0.39317 (18)	0.05002 (5)	0.0370 (7)
O1	0.0012 (2)	0.07445 (19)	0.12175 (8)	0.0961 (13)
N7	0.00000	0.00000	0.12009 (8)	0.0415 (8)
O1WA	0.0227 (2)	0.1884 (2)	0.00412 (7)	0.0713 (11)	0.850
O1WB	−0.0212 (12)	0.1577 (12)	0.0217 (4)	0.067 (6)	0.150
H1	0.62440	0.21370	0.15610	0.0400*
H2	0.49050	0.11820	0.18390	0.0440*
H3	0.34040	0.07000	0.16560	0.0410*
H5	0.24010	0.07100	0.12350	0.0430*
H6	0.23140	0.11800	0.07810	0.0430*
H8	0.31730	0.21890	0.03380	0.0410*
H9	0.45930	0.33490	0.01350	0.0410*
H10	0.60070	0.38950	0.03880	0.0350*
H13	0.20380	0.60120	0.13860	0.0300*
H14	0.10900	0.45910	0.16300	0.0350*
H15	0.08600	0.31710	0.14330	0.0340*
H17	0.11070	0.23180	0.10070	0.0360*
H18	0.17510	0.24030	0.05640	0.0360*
H20	0.28390	0.34230	0.01550	0.0360*
H21	0.39040	0.49320	−0.00160	0.0370*
H22	0.42020	0.62620	0.02520	0.0320*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0225 (1)	0.0225 (1)	0.0209 (2)	0.0112 (1)	0.0000	0.0000
N1	0.0292 (8)	0.0251 (8)	0.0245 (7)	0.0136 (7)	0.0020 (6)	0.0044 (6)
N2	0.0236 (7)	0.0254 (8)	0.0236 (7)	0.0137 (6)	0.0016 (5)	0.0029 (6)
C1	0.0390 (11)	0.0333 (10)	0.0280 (9)	0.0189 (9)	0.0005 (8)	0.0072 (8)
C2	0.0499 (13)	0.0318 (11)	0.0277 (9)	0.0201 (10)	0.0074 (9)	0.0085 (8)
C3	0.0430 (12)	0.0235 (9)	0.0329 (9)	0.0139 (9)	0.0131 (8)	0.0057 (7)
C4	0.0311 (10)	0.0218 (9)	0.0335 (9)	0.0120 (8)	0.0091 (7)	0.0034 (7)
C5	0.0267 (10)	0.0268 (10)	0.0492 (12)	0.0096 (8)	0.0100 (9)	0.0042 (9)
C6	0.0234 (9)	0.0317 (11)	0.0500 (12)	0.0120 (9)	0.0012 (8)	0.0028 (9)
C7	0.0254 (9)	0.0265 (9)	0.0345 (9)	0.0139 (8)	−0.0007 (7)	−0.0012 (7)
C8	0.0294 (10)	0.0387 (11)	0.0374 (10)	0.0201 (9)	−0.0070 (8)	−0.0022 (8)
C9	0.0357 (11)	0.0455 (12)	0.0287 (9)	0.0265 (10)	−0.0011 (8)	0.0059 (8)
C10	0.0298 (10)	0.0331 (10)	0.0271 (8)	0.0180 (8)	0.0034 (7)	0.0072 (7)
C11	0.0242 (8)	0.0217 (8)	0.0260 (8)	0.0126 (7)	0.0019 (6)	0.0002 (6)
C12	0.0263 (9)	0.0196 (8)	0.0265 (8)	0.0113 (7)	0.0043 (7)	0.0018 (6)
Ni2	0.0182 (1)	0.0182 (1)	0.0196 (2)	0.0091 (1)	0.0000	0.0000
N3	0.0191 (7)	0.0209 (7)	0.0215 (6)	0.0087 (6)	0.0010 (5)	0.0000 (5)
N4	0.0224 (7)	0.0215 (7)	0.0212 (6)	0.0124 (6)	0.0011 (5)	0.0001 (5)
C13	0.0230 (8)	0.0282 (9)	0.0238 (8)	0.0120 (7)	0.0024 (6)	−0.0005 (7)
C14	0.0242 (9)	0.0344 (10)	0.0256 (8)	0.0116 (8)	0.0046 (7)	0.0041 (7)
C15	0.0230 (9)	0.0284 (9)	0.0291 (9)	0.0091 (7)	0.0033 (7)	0.0081 (7)
C16	0.0207 (8)	0.0235 (9)	0.0294 (8)	0.0094 (7)	−0.0012 (7)	0.0027 (7)
C17	0.0297 (10)	0.0208 (9)	0.0359 (10)	0.0095 (8)	−0.0002 (8)	0.0037 (7)
C18	0.0335 (10)	0.0189 (8)	0.0370 (10)	0.0131 (8)	−0.0022 (8)	−0.0029 (7)
C19	0.0280 (9)	0.0227 (8)	0.0283 (8)	0.0151 (7)	−0.0022 (7)	−0.0018 (7)
C20	0.0387 (11)	0.0288 (9)	0.0280 (9)	0.0217 (9)	−0.0017 (8)	−0.0046 (7)
C21	0.0397 (11)	0.0328 (10)	0.0258 (8)	0.0228 (9)	0.0059 (8)	−0.0004 (7)
C22	0.0302 (9)	0.0268 (9)	0.0265 (8)	0.0164 (8)	0.0067 (7)	0.0036 (7)
C23	0.0204 (8)	0.0205 (8)	0.0226 (7)	0.0117 (7)	−0.0004 (6)	0.0007 (6)
C24	0.0182 (7)	0.0218 (8)	0.0217 (7)	0.0096 (7)	−0.0012 (6)	0.0011 (6)
O2W	0.17 (3)	0.13 (2)	0.070 (8)	0.064 (14)	0.029 (11)	0.057 (10)
O3W	0.103 (10)	0.047 (6)	0.096 (9)	0.042 (7)	−0.066 (8)	−0.042 (6)
Ag1	0.0301 (1)	0.0415 (1)	0.0319 (1)	0.0163 (1)	−0.0012 (1)	−0.0025 (1)
N5	0.084 (2)	0.088 (2)	0.0441 (12)	0.0616 (18)	−0.0165 (12)	−0.0209 (13)
N6	0.0533 (13)	0.0660 (15)	0.0356 (10)	0.0366 (12)	−0.0068 (9)	−0.0062 (10)
C25	0.0431 (13)	0.0557 (15)	0.0367 (11)	0.0292 (12)	−0.0066 (9)	−0.0044 (10)
C26	0.0337 (11)	0.0452 (13)	0.0316 (10)	0.0194 (10)	−0.0034 (8)	0.0003 (9)
O1	0.095 (2)	0.0522 (14)	0.154 (3)	0.0465 (15)	0.0142 (19)	0.0261 (16)
N7	0.0363 (11)	0.0363 (11)	0.052 (2)	0.0182 (5)	0.0000	0.0000
O1WA	0.077 (2)	0.0626 (17)	0.0815 (19)	0.0403 (16)	0.0047 (17)	0.0071 (15)
O1WB	0.060 (9)	0.066 (10)	0.070 (10)	0.027 (8)	−0.005 (8)	−0.023 (8)

Geometric parameters (Å, º)

Ag1—C25	2.043 (3)	C6—C7	1.443 (3)
Ag1—C26	2.055 (3)	C7—C8	1.401 (3)
Ni1—N1^i	2.090 (2)	C7—C11	1.399 (3)
Ni1—N2^i	2.101 (2)	C8—C9	1.370 (4)
Ni1—N1^ii	2.0903 (19)	C9—C10	1.395 (4)
Ni1—N2^ii	2.1014 (16)	C11—C12	1.437 (3)
Ni1—N1	2.0903 (17)	C1—H1	0.9500
Ni1—N2	2.1014 (18)	C2—H2	0.9500
Ni2—N4^iii	2.090 (2)	C3—H3	0.9500
Ni2—N4	2.0898 (16)	C5—H5	0.9500
Ni2—N4^iv	2.090 (2)	C6—H6	0.9500
Ni2—N3	2.0925 (15)	C8—H8	0.9500
Ni2—N3^iii	2.0925 (19)	C9—H9	0.9500
Ni2—N3^iv	2.092 (2)	C10—H10	0.9500
O2W—O2W^v	1.27 (5)	C13—C14	1.396 (3)
O2W—O2W^vi	1.27 (4)	C14—C15	1.375 (3)
O2W—O3W	1.24 (3)	C15—C16	1.409 (3)
O1—N7	1.204 (3)	C16—C17	1.433 (3)
N1—C1	1.336 (3)	C16—C24	1.399 (3)
N1—C12	1.354 (3)	C17—C18	1.346 (3)
N2—C11	1.358 (3)	C18—C19	1.435 (3)
N2—C10	1.333 (2)	C19—C20	1.404 (3)
N3—C24	1.355 (2)	C19—C23	1.406 (3)
N3—C13	1.331 (3)	C20—C21	1.367 (3)
N4—C23	1.354 (2)	C21—C22	1.395 (3)
N4—C22	1.333 (3)	C23—C24	1.438 (3)
N5—C25	1.125 (4)	C13—H13	0.9500
N6—C26	1.142 (4)	C14—H14	0.9500
C1—C2	1.398 (4)	C15—H15	0.9500
C2—C3	1.364 (4)	C17—H17	0.9500
C3—C4	1.409 (3)	C18—H18	0.9500
C4—C5	1.427 (4)	C20—H20	0.9500
C4—C12	1.404 (3)	C21—H21	0.9500
C5—C6	1.338 (3)	C22—H22	0.9500
Ag1···Ni2	4.7375 (3)	O1WA···N6	2.911 (4)
Ag1···Ni1^v	4.7580 (3)	O1WA···O1WA^viii	2.924 (5)
Ag1···Ni2	4.7375 (3)	O1WB···N6	2.860 (18)
Ag1···Ni2	4.7375 (3)	O2W···N7	3.265 (15)
Ni1···Ag1^vii	4.7580 (3)	O2W···N7	3.265 (15)
Ni1···Ag1^iv	4.7580 (3)	O2W···N7	3.265 (15)
Ni1···Ag1^vi	4.7580 (3)	O2W···O3W^vi	2.36 (3)
Ni2···Ag1^iii	4.7375 (2)	O3W···O3W^v	2.80 (3)
Ni2···Ag1^iv	4.7375 (3)	O3W···O3W^vi	2.80 (2)
Ni2···Ag1	4.7375 (3)
C25—Ag1—C26	176.78 (13)	N2—C10—C9	122.9 (2)
N1—Ni1—N2	79.41 (7)	N2—C11—C12	116.93 (19)
N1—Ni1—N2^i	97.46 (7)	N2—C11—C7	123.20 (17)
N1—Ni1—N1^ii	91.91 (7)	C7—C11—C12	119.87 (19)
N1—Ni1—N2^ii	167.39 (9)	C4—C12—C11	119.3 (2)
N1^i—Ni1—N2	167.39 (8)	N1—C12—C11	117.42 (18)
N2—Ni1—N2^i	92.56 (7)	N1—C12—C4	123.30 (18)
N1^ii—Ni1—N2	97.46 (9)	C2—C1—H1	119.00
N1—Ni1—N1^i	91.91 (8)	N1—C1—H1	119.00
N1^i—Ni1—N2^i	79.41 (8)	C3—C2—H2	120.00
N1^i—Ni1—N1^ii	91.91 (9)	C1—C2—H2	120.00
N1^i—Ni1—N2^ii	97.46 (9)	C2—C3—H3	120.00
N1^ii—Ni1—N2^i	167.39 (10)	C4—C3—H3	120.00
N2^i—Ni1—N2^ii	92.56 (8)	C6—C5—H5	119.00
N1^ii—Ni1—N2^ii	79.41 (7)	C4—C5—H5	119.00
N2—Ni1—N2^ii	92.56 (8)	C7—C6—H6	120.00
N3—Ni2—N4^iii	94.73 (7)	C5—C6—H6	120.00
N4—Ni2—N4^iv	92.55 (7)	C9—C8—H8	120.00
N3^iii—Ni2—N4	169.48 (8)	C7—C8—H8	120.00
N4—Ni2—N4^iii	92.55 (7)	C8—C9—H9	120.00
N3^iv—Ni2—N4^iv	79.56 (7)	C10—C9—H9	120.00
N3^iv—Ni2—N3^iii	94.05 (8)	C9—C10—H10	118.00
N3^iv—Ni2—N4^iii	169.48 (7)	N2—C10—H10	119.00
N3^iv—Ni2—N4	94.73 (7)	N3—C13—C14	122.84 (18)
N4^iv—Ni2—N4^iii	92.55 (7)	C13—C14—C15	118.97 (19)
N3^iii—Ni2—N4^iii	79.56 (8)	C14—C15—C16	119.77 (18)
N3—Ni2—N4	79.56 (6)	C15—C16—C17	123.61 (18)
N3—Ni2—N3^iv	94.05 (7)	C15—C16—C24	116.88 (18)
N3—Ni2—N4^iv	169.48 (8)	C17—C16—C24	119.51 (18)
N3—Ni2—N3^iii	94.05 (6)	C16—C17—C18	120.94 (18)
N3^iii—Ni2—N4^iv	94.73 (7)	C17—C18—C19	121.10 (18)
O2W^v—O2W—O2W^vi	60 (3)	C20—C19—C23	117.26 (17)
O2W^v—O2W—O3W	140.5 (17)	C18—C19—C23	119.06 (18)
O2W^vi—O2W—O3W	109 (3)	C18—C19—C20	123.68 (18)
Ni1—N1—C1	128.62 (17)	C19—C20—C21	119.42 (19)
C1—N1—C12	117.80 (19)	C20—C21—C22	119.6 (2)
Ni1—N1—C12	113.07 (12)	N4—C22—C21	122.61 (18)
Ni1—N2—C10	129.53 (16)	N4—C23—C24	117.32 (16)
Ni1—N2—C11	112.89 (12)	C19—C23—C24	119.65 (16)
C10—N2—C11	117.54 (19)	N4—C23—C19	123.03 (18)
Ni2—N3—C24	113.01 (12)	N3—C24—C23	117.01 (15)
C13—N3—C24	118.01 (16)	N3—C24—C16	123.43 (18)
Ni2—N3—C13	128.98 (13)	C16—C24—C23	119.56 (16)
C22—N4—C23	118.00 (16)	N3—C13—H13	119.00
Ni2—N4—C23	112.93 (12)	C14—C13—H13	118.00
Ni2—N4—C22	128.90 (13)	C15—C14—H14	120.00
O1^v—N7—O1^vi	119.6 (2)	C13—C14—H14	121.00
O1—N7—O1^vi	119.6 (2)	C14—C15—H15	120.00
O1—N7—O1^v	119.6 (3)	C16—C15—H15	120.00
N1—C1—C2	122.6 (2)	C16—C17—H17	120.00
C1—C2—C3	119.6 (2)	C18—C17—H17	119.00
C2—C3—C4	119.4 (2)	C19—C18—H18	119.00
C3—C4—C12	117.2 (2)	C17—C18—H18	119.00
C3—C4—C5	123.5 (2)	C21—C20—H20	120.00
C5—C4—C12	119.31 (19)	C19—C20—H20	120.00
C4—C5—C6	121.5 (2)	C22—C21—H21	120.00
C5—C6—C7	120.8 (2)	C20—C21—H21	120.00
C6—C7—C8	123.5 (2)	N4—C22—H22	119.00
C8—C7—C11	117.5 (2)	C21—C22—H22	119.00
C6—C7—C11	118.95 (18)	Ag1—C25—N5	177.4 (3)
C7—C8—C9	119.3 (2)	Ag1—C26—N6	177.3 (3)
C8—C9—C10	119.5 (2)
N2—Ni1—N1—C1	−175.0 (2)	Ni2—N4—C23—C19	174.54 (17)
N2—Ni1—N1—C12	−3.53 (14)	Ni2—N4—C23—C24	−4.6 (2)
N1^i—Ni1—N1—C1	14.2 (2)	C22—N4—C23—C24	179.7 (2)
N1^i—Ni1—N1—C12	−174.32 (15)	N1—C1—C2—C3	2.4 (4)
N2^i—Ni1—N1—C1	93.8 (2)	C1—C2—C3—C4	0.0 (4)
N2^i—Ni1—N1—C12	−94.76 (15)	C2—C3—C4—C5	177.9 (2)
N1^ii—Ni1—N1—C1	−77.8 (2)	C2—C3—C4—C12	−2.4 (3)
N1^ii—Ni1—N1—C12	93.70 (15)	C3—C4—C12—N1	2.8 (3)
N1—Ni1—N2—C10	−176.73 (19)	C3—C4—C12—C11	−176.24 (19)
N1—Ni1—N2—C11	0.57 (13)	C5—C4—C12—N1	−177.5 (2)
N2^i—Ni1—N2—C10	−79.62 (19)	C3—C4—C5—C6	−178.9 (2)
N2^i—Ni1—N2—C11	97.68 (14)	C12—C4—C5—C6	1.4 (3)
N1^ii—Ni1—N2—C10	92.71 (18)	C5—C4—C12—C11	3.5 (3)
N1^ii—Ni1—N2—C11	−89.99 (14)	C4—C5—C6—C7	−3.4 (4)
N2^ii—Ni1—N2—C10	13.06 (19)	C5—C6—C7—C8	−178.1 (2)
N2^ii—Ni1—N2—C11	−169.63 (14)	C5—C6—C7—C11	0.4 (3)
N3—Ni2—N4—C23	2.76 (14)	C11—C7—C8—C9	−3.6 (3)
N3^iv—Ni2—N4—C22	−88.9 (2)	C6—C7—C11—N2	−175.3 (2)
N3^iv—Ni2—N4—C23	96.01 (15)	C6—C7—C8—C9	174.9 (2)
N4^iv—Ni2—N4—C22	−9.1 (2)	C6—C7—C11—C12	4.5 (3)
N4^iv—Ni2—N4—C23	175.74 (15)	C8—C7—C11—N2	3.3 (3)
N4^iii—Ni2—N4—C22	83.6 (2)	C8—C7—C11—C12	−176.9 (2)
N4—Ni2—N3—C13	178.8 (2)	C7—C8—C9—C10	1.1 (4)
N4—Ni2—N3—C24	−0.55 (14)	C8—C9—C10—N2	2.3 (4)
N3^iv—Ni2—N3—C13	84.70 (19)	C7—C11—C12—N1	174.50 (19)
N3^iv—Ni2—N3—C24	−94.62 (15)	C7—C11—C12—C4	−6.4 (3)
N3^iii—Ni2—N3—C13	−9.7 (2)	N2—C11—C12—C4	173.41 (18)
N3^iii—Ni2—N3—C24	171.03 (15)	N2—C11—C12—N1	−5.7 (3)
N4^iii—Ni2—N3—C13	−89.50 (19)	N3—C13—C14—C15	−1.6 (4)
N4^iii—Ni2—N3—C24	91.19 (15)	C13—C14—C15—C16	−1.5 (4)
N3—Ni2—N4—C22	177.9 (2)	C14—C15—C16—C17	−175.9 (2)
N4^iii—Ni2—N4—C23	−91.59 (15)	C14—C15—C16—C24	3.3 (3)
C12—N1—C1—C2	−2.1 (3)	C15—C16—C17—C18	177.9 (2)
Ni1—N1—C12—C4	−173.11 (16)	C24—C16—C17—C18	−1.2 (4)
Ni1—N1—C1—C2	169.10 (17)	C15—C16—C24—N3	−2.3 (3)
C1—N1—C12—C4	−0.6 (3)	C15—C16—C24—C23	178.2 (2)
C1—N1—C12—C11	178.46 (19)	C17—C16—C24—N3	176.9 (2)
Ni1—N1—C12—C11	6.0 (2)	C17—C16—C24—C23	−2.6 (3)
Ni1—N2—C10—C9	174.54 (17)	C16—C17—C18—C19	3.0 (4)
C11—N2—C10—C9	−2.7 (3)	C17—C18—C19—C20	178.6 (3)
Ni1—N2—C11—C7	−177.83 (16)	C17—C18—C19—C23	−0.9 (4)
Ni1—N2—C11—C12	2.4 (2)	C18—C19—C20—C21	−176.9 (2)
C10—N2—C11—C7	−0.2 (3)	C23—C19—C20—C21	2.6 (4)
C10—N2—C11—C12	−179.97 (18)	C18—C19—C23—N4	178.0 (2)
C13—N3—C24—C23	178.91 (19)	C18—C19—C23—C24	−2.9 (3)
Ni2—N3—C24—C16	178.82 (17)	C20—C19—C23—N4	−1.5 (3)
Ni2—N3—C13—C14	−176.67 (17)	C20—C19—C23—C24	177.6 (2)
C24—N3—C13—C14	2.6 (3)	C19—C20—C21—C22	−1.1 (4)
Ni2—N3—C24—C23	−1.7 (2)	C20—C21—C22—N4	−1.7 (4)
C13—N3—C24—C16	−0.6 (3)	N4—C23—C24—N3	4.3 (3)
C23—N4—C22—C21	2.8 (3)	N4—C23—C24—C16	−176.2 (2)
Ni2—N4—C22—C21	−172.11 (18)	C19—C23—C24—N3	−174.9 (2)
C22—N4—C23—C19	−1.2 (3)	C19—C23—C24—C16	4.7 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N5^ix	0.95	2.45	3.284 (4)	147
C5—H5···O1^vi	0.95	2.36	3.176 (5)	144
C8—H8···O1WA^viii	0.95	2.54	3.465 (4)	166
C17—H17···O1	0.95	2.47	3.423 (4)	177
C20—H20···N6^viii	0.95	2.60	3.312 (3)	132

Symmetry codes: (vi) −x+y, −x, z; (viii) y, −x+y, −z; (ix) y−1/3, −x+y−2/3, −z+1/3.