A head-to-head isomer of bis{bis(μ-5-carboxy-α-pyridonato)­bis­[cis-diammineplatinum(II)]} tetranitrate tetrahydrate

In the title compound, [Pt₂(C₆H₄NO₃)₂(NH₃)₄]₂(NO₃)₄·4H₂O, a head-to-head dimer has an association with another dimer unit through an inversion center to give a tetraplatinum chain structure. The interaction is stabilized not only by a metal–metal interaction but also by four hydrogen bonds formed between the ammines and the O atoms of bridging amidates [N...O = 2.988 (17) and 3.030 (16) Å]. The intra- and interdimer Pt—Pt distances within the tetranuclear cation are 2.9023 (8) and 3.1821 (11) Å, respectively.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.022 Å
• H-atom completeness 76%
• Disorder in solvent or counterion
• R factor = 0.063
• wR factor = 0.197
• Data-to-parameter ratio = 18.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.25
         From the CIF: _reflns_number_total               5608
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         6010
         Completeness (_total/calc)             93.31%
          Alert C: < 95% complete

RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.101

PLAT_302  Alert C Anion/Solvent Disorder .........................      44.00 Perc.

General Notes



FORMU_01  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:C24 H48 N16 O28 Pt4
          Atom count from the _atom_site data:  C24 H36 N16 O28 Pt4

CELLZ_01
         From the CIF: _cell_formula_units_Z    4
         From the CIF: _chemical_formula_sum  C24 H48 N16 O28 Pt4
         TEST: Compare cell contents of formula and atom_site data

         atom    Z*formula  cif sites diff
         C         96.00     96.00    0.00
         H        192.00    144.00   48.00
         N         64.00     64.00    0.00
         O        112.00    112.00    0.00
         Pt        16.00     16.00    0.00
          Difference between formula and atom_site contents detected.
          WARNING: H atoms missing from atom site list. Is this intentional?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

We previously reported that amidate-bridged dinuclear Pt^II complexes [Pt₂(NH₃)₄(µ-amidato)₂]²⁺ (amidate = α-pyrrolidinonate, α-pyridonate, acetamidate, etc.) behave as relatively efficient H₂-evolving catalysts in a well known photosystem consisting of edta, Ru(bpy)₃²⁺ (bpy = 2,2'-bipyridine), and methylviologen (N,N'-dimethyl-4,4'-bipyridinium dichloride) (Sakai & Matsumoto, 1990; Sakai et al., 1993). Since then, one of our interests has concentrated on the development of dinuclear Pt^II complexes tethered to tris(2,2'-bipyridine)ruthenium(II) derivatives. Such hybrid materials may serve as efficient artificial photosynthetic devices which carry out visible-light-induced photocatalytic conversion of water into molecular hydrogen. The title compound, (I), can be regarded as an analog for the α-pyridonate Pt₄^II complex previously reported by Hollis & Lippard (1983) (Note that it is now understood that the tetranuclear structures of this type are only stabilized in the crystal, and immediately cleave into dimers upon dissolution into aqueous media.) The carboxyl unit on the bridging ligand in (I) can be used to make a peptide bond with an amino group in a certain chemical component to be tethered to the diplatinum entity. We now report here on the crystal structure of the title compound, (I). The subsequent studies on its application will appear in future publications.

A dimer cation found in the asymmetric unit of (I) has an association to the neighbouring dimer unit through an inversion center to give a tetranuclear structure, as observed for the α-pyridonate analog ([Pt₂(NH₃)₄(µ-α-pyridonato)₂]₂(NO₃)₄) (Hollis & Lippard, 1983). The dimer–dimer association is stabilized with four hydrogen bonds formed between the ammine ligands and the O atoms of amidate bridges (see Fig. 1 and Table 2). Both the intra- and interdimer Pt—Pt distances within the tetranuclear cation in (I) [Pt—Pt(intradimer) = Pt1—Pt2 = 2.9023 (8) Å; Pt—Pt(interdimer) = Pt2—Pt2ⁱ = 3.1821 (11) Å) are slightly longer than those reported for the α-pyridonate analog (Pt—Pt(intradimer) = 2.8767 (7) Å and Pt—Pt(interdimer) = 3.1294 (4) Å] (Hollis & Lippard, 1983). It is obvious that introduction of carboxyl unit onto the α-pyridonate ligand results in elongation in each Pt—Pt distance. Such a tendency has already been observed in our previous studies. For instance, [Pt^II₂(NH₃)₄(µ-glycolato)₂]²⁺ has a longer Pt—Pt(intradimer) distance compared to that of [Pt^II₂(NH₃)₄(µ-acetato)₂]²⁺ (Sakai & Takeshita et al., 1998), where the hydroxyl group of glycolate serves as an electron-withdrawing group. Thus, there has been a clear tendency that the decrease in electron density at the Pt^II centers results in elongation of Pt—Pt distances in this class of diplatinum complexes. Perhaps, a dative bond formed by use of a filled Pt 5d_z2 orbital and a vacant Pt 6p orbital must be weakened by the decrease in electron density at the metal centers. On the other hand, two Pt atoms within the dimer unit are shifted out of their individual Pt coordination planes in such a manner that they have an attractive interaction toward one another. Atoms Pt1 and Pt2 are respectively shifted by 0.055 (6) and 0.088 (6) Å, where the four-atom r.m.s. deviations in the best-plane calculations are 0.013 and 0.012 Å, respectively. Structural features of this type of dimers have also been evaluated by use of two structural parameters. One is a dihedral angle between the two Pt coordination planes within the dimeric unit (τ), and the other is an average torsional twist of them about the Pt—Pt axis (ω). The value of τ = 30.5 (4)° in (I) is quite comparable to the value of τ = 30.0° reported for the α-pyridonate analog (Hollis & Lippard, 1983). On the other hand, the ω value is effectively smaller in (I) [ω = 10.7° in (I); ω = 20.3° in the α-pyridonate analog], which must be due to the fact that the carboxyl units play a considerable role in the stabilization of intertetramer associations described below.

An intriguing feature due to the presence of carboxyl units in (I) is that the tetrameric units are strongly correlated to each other to afford a one-dimensional network (Fig. 2). A twofold axis, which is parallel to the b axis, is located at the mid-point of a geometry where the intertetramer interaction is achieved. The interactions are not only stabilized with hydrogen bonds formed between the ammine ligands and the O atoms of carboxyl units [N2···O2(-x, y, 1.5 − z) = 2.818 (17) Å], but also stabilized with π–π-stacking interactions achieved between the carboxyl units. The plane-to-plane separation is estimated as 3.36 Å, and the shortest contact is 3.47 (2) Å given by O5···C8(-x, y, 1.5 − z). However, the intertetramer Pt—Pt distance [6.4394 (12) Å, see also Table 1] indicates the lack of any metal–metal interaction between the tetramers. It must be also noted that both carboxyl units have a relatively short contact with a water molecule [O3···O13 = 2.60 (2) Å and O5···O14 = 2.61 (3) Å], which is indicative of strong hydrogen bonds formed between these moieties.

S2. Experimental

To an aqueous solution of cis-[Pt(NH₃)₂(OH₂)₂](NO₃)₂ (0.5 mmol/3.5 ml H₂O), prepared as previously described (Sakai, Takeshita et al., 1998; Sakai, Tanaka et al., 1998), was added 5-carboxy-α-pyridone (6-hydroxynicotinic acid) (0.5 mmol). The solution was heated at 353 K for 4 h followed by filtration if necessary. Leaving of the resulting green solution at 278 K for a few days afforded the title compound (I) as dark-green prisms, which were collected by filtration and air-dried (yield: 7%). Analysis calculated for C₂₄H₄₈N₁₆O₂₈Pt₄: C 16.11, H 2.70, N 12.53%; found: C 16.34, H 2.56, N 12.28%.

S3. Refinement

Two nitrate ions are both treated as being disordered over two sites. One of two nitrate anions shows orientational disorder in which two sets of positions of (O7A, O8A and O9A) and (O7B, O8B and O9B) are located around atom N7. For each disordered nitrate ion, the disordered O atoms were supposed to have the same isotropic displacement parameter. Furthermore, the N—O distances were restrained at 1.22 Å, three O···O distances within each nitrate ion were restrained as equal, and each nitrate ion was restrained to be planar. In each case, two sites are judged to be equally populated and therefore the occupation factors for all the disordered atoms were assumed as 50%. Aromatic and ammine H atoms were located at idealized positions as riding atoms (C—H = 0.93 Å and N—H = 0.89 Å), while those of carboxyl groups and water molecules were not located. In the final difference Fourier synthesis, relatively large four residual peaks in the range 4.03–5.48 e Å⁻³ were observed within 1.03 Å from Pt atoms. Other 12 peaks in the range 1.00–1.84 e Å⁻³ were located near either Pt atoms or disordered nitrate ions.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: KENX (Sakai, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997), TEXSAN (Molecular Structure Corporation, 2001), KENX (Sakai, 2002) and ORTEPII (Johnson, 1976).

Figures

	Fig. 1. The structure of the tetranuclear Pt^II4 complex cation in (I), showing the atom-labeling scheme. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. A view down the b axis, showing the intertetramer interactions leading to a one-dimensional network, where hydrogen bonds formed between the tetramers are drawn by blue dotted lines and π–π interactions achieved between the carboxyl units are indicated by pink lines. Hydrogen bonds formed within the basic tetrameric unts are omitted for clarity.

cis-Diammine(L-pyrolglutamato)platinum(II)

Crystal data

[Pt2(C6H4NO3)2(NH3)4]2(NO3)4·4H2O	F(000) = 3360
Mr = 1789.14	Dx = 2.443 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.648 (4) Å	Cell parameters from 8766 reflections
b = 13.3574 (16) Å	θ = 2.3–28.0°
c = 15.5128 (19) Å	µ = 11.57 mm^−1
β = 96.998 (3)°	T = 296 K
V = 4863.6 (11) Å^3	Prism, dark green
Z = 4	0.25 × 0.10 × 0.05 mm

Data collection

Bruker SMART APEX CCD-detector diffractometer	5608 independent reflections
Radiation source: fine-focus sealed tube	3623 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.101
Detector resolution: 8.366 pixels mm^-1	θmax = 28.3°, θmin = 2.7°
ω scans	h = −31→30
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001)	k = −17→17
Tmin = 0.115, Tmax = 0.325	l = −20→20
20325 measured reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.197	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1051P)^2 + 48.6026P] where P = (Fo^2 + 2Fc^2)/3
5608 reflections	(Δ/σ)max = 0.001
298 parameters	Δρmax = 5.48 e Å^−3
28 restraints	Δρmin = −1.62 e Å^−3

Special details

Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

22.0816 (0.0354) x + 3.8252 (0.0564) y − 5.0698 (0.0610) z = 2.4416 (0.0389)

* −0.0114 (0.0057) O1 * 0.0114 (0.0057) O4 * 0.0116 (0.0058) N3 * −0.0116 (0.0058) N4 − 2.8313 (0.0063) Pt1 − 0.0876 (0.0058) Pt2

Rms deviation of fitted atoms = 0.0115

−19.0744 (0.0603) x + 0.8137 (0.0524) y + 10.5773 (0.0488) z = 4.9654 (0.0377)

Angle to previous plane (with approximate e.s.d.) = 30.47 (0.35)

* 0.0131 (0.0058) N1 * −0.0129 (0.0057) N2 * −0.0133 (0.0059) N5 * 0.0132 (0.0058) N6 − 2.8990 (0.0056) Pt2 − 0.0553 (0.0057) Pt1

Rms deviation of fitted atoms = 0.0131

7.4317 (0.1951) x + 3.5686 (0.1198) y + 13.4324 (0.0729) z = 10.1917 (0.0569)

Angle to previous plane (with approximate e.s.d.) = 72.64 (0.47)

* 0.0007 (0.0146) C12 * −0.0003 (0.0052) O5 * −0.0003 (0.0054) O6 * −0.0002 (0.0041) C8 3.6072 (0.0215) C12_$3 3.1792 (0.0264) O5_$3 4.2449 (0.0187) O6_$3 3.3034 (0.0255) C8_$3

Rms deviation of fitted atoms = 0.0004

7.4317 (0.1948) x − 3.5686 (0.1197) y + 13.4324 (0.0728) z = 9.9569 (0.1113)

Angle to previous plane (with approximate e.s.d.) = 30.99 (0.73)

* −0.0007 (0.0146) C12_$3 * 0.0003 (0.0051) O5_$3 * 0.0003 (0.0054) O6_$3 * 0.0002 (0.0041) C8_$3 − 3.6072 (0.0214) C12 − 3.1792 (0.0264) O5 − 4.2449 (0.0186) O6 − 3.3034 (0.0254) C8

Rms deviation of fitted atoms = 0.0004

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)
Pt1	0.08681 (2)	0.19941 (4)	0.60542 (3)	0.04542 (19)
Pt2	0.18727 (2)	0.21857 (5)	0.51626 (4)	0.0517 (2)
O1	0.2235 (4)	0.1938 (8)	0.6402 (7)	0.062 (3)
O2	0.0794 (5)	0.2426 (13)	0.9455 (9)	0.094 (4)
O3	0.1653 (6)	0.2243 (13)	1.0190 (8)	0.109 (5)
O4	0.1713 (5)	0.3664 (7)	0.5386 (7)	0.068 (3)
O5	−0.0592 (6)	0.4783 (12)	0.6644 (9)	0.101 (5)
O6	−0.0403 (6)	0.6276 (11)	0.6143 (9)	0.103 (5)
O7A	0.0253 (7)	−0.0437 (18)	0.3203 (14)	0.190 (7)*	0.50
O7B	0.0453 (10)	−0.0307 (19)	0.2921 (10)	0.190 (7)*	0.50
O8A	0.1091 (9)	0.014 (3)	0.3322 (18)	0.190 (7)*	0.50
O8B	0.1186 (6)	0.003 (3)	0.3792 (18)	0.190 (7)*	0.50
O9A	0.0682 (13)	−0.009 (3)	0.4443 (9)	0.190 (7)*	0.50
O9B	0.0386 (10)	−0.011 (3)	0.4256 (13)	0.190 (7)*	0.50
O10A	0.2200 (11)	−0.0443 (19)	0.6708 (12)	0.172 (6)*	0.50
O10B	0.2281 (8)	−0.0368 (19)	0.6396 (16)	0.172 (6)*	0.50
O11A	0.2593 (9)	−0.056 (4)	0.8002 (15)	0.172 (6)*	0.50
O11B	0.3150 (9)	0.004 (3)	0.655 (2)	0.172 (6)*	0.50
O12A	0.1704 (8)	−0.076 (3)	0.7720 (19)	0.172 (6)*	0.50
O12B	0.2767 (15)	−0.048 (4)	0.7629 (15)	0.172 (6)*	0.50
O13	0.1200 (8)	0.2153 (13)	1.1635 (14)	0.134 (6)*
O14	−0.1506 (11)	0.557 (2)	0.7153 (17)	0.090 (7)*	0.50
O15	−0.0014 (18)	0.168 (3)	0.288 (2)	0.139 (13)*	0.50
N1	0.0868 (5)	0.0475 (9)	0.6236 (8)	0.066 (3)
H1A	0.1211	0.0280	0.6479	0.099*
H1B	0.0785	0.0171	0.5726	0.099*
H1C	0.0609	0.0314	0.6583	0.099*
N2	0.0259 (6)	0.1885 (10)	0.5004 (8)	0.066 (3)
H2A	−0.0085	0.1890	0.5183	0.100*
H2B	0.0306	0.1316	0.4723	0.100*
H2C	0.0290	0.2401	0.4650	0.100*
N3	0.2101 (6)	0.0763 (10)	0.4887 (10)	0.078 (4)
H3A	0.2180	0.0421	0.5379	0.117*
H3B	0.2407	0.0779	0.4606	0.117*
H3C	0.1815	0.0468	0.4555	0.117*
N4	0.1570 (6)	0.2453 (12)	0.3897 (9)	0.072 (4)
H4A	0.1805	0.2868	0.3666	0.108*
H4B	0.1226	0.2729	0.3867	0.108*
H4C	0.1547	0.1878	0.3604	0.108*
N5	0.1444 (4)	0.2120 (8)	0.7123 (7)	0.045 (3)
N6	0.0834 (4)	0.3521 (7)	0.5940 (7)	0.042 (2)
N7	0.0675 (5)	−0.0130 (9)	0.3656 (9)	0.190 (7)*
N8A	0.2166 (7)	−0.0586 (17)	0.7477 (12)	0.172 (6)*	0.50
N8B	0.2733 (8)	−0.0267 (16)	0.6859 (14)	0.172 (6)*	0.50
C1	0.1233 (6)	0.2243 (11)	0.7891 (10)	0.056 (4)
H1	0.0843	0.2334	0.7890	0.068*
C2	0.1580 (6)	0.2239 (11)	0.8672 (9)	0.055 (3)
C3	0.2159 (6)	0.2139 (13)	0.8664 (11)	0.069 (5)
H3D	0.2407	0.2155	0.9178	0.083*
C4	0.2358 (6)	0.2018 (13)	0.7893 (12)	0.070 (5)
H4	0.2747	0.1919	0.7890	0.084*
C5	0.2012 (6)	0.2033 (10)	0.7106 (9)	0.051 (3)
C6	0.1303 (7)	0.2316 (13)	0.9473 (10)	0.065 (4)
C7	0.0360 (6)	0.3970 (12)	0.6156 (8)	0.056 (4)
H7	0.0076	0.3571	0.6342	0.067*
C8	0.0279 (7)	0.4957 (12)	0.6116 (9)	0.061 (4)
C9	0.0704 (8)	0.5560 (13)	0.5827 (10)	0.071 (4)
H9	0.0660	0.6252	0.5795	0.085*
C10	0.1185 (8)	0.5113 (13)	0.5590 (12)	0.080 (5)
H10	0.1471	0.5504	0.5400	0.096*
C11	0.1247 (7)	0.4041 (12)	0.5634 (9)	0.060 (4)
C12	−0.0280 (9)	0.5384 (14)	0.6312 (10)	0.074 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.0364 (3)	0.0572 (4)	0.0420 (3)	0.0004 (2)	0.0026 (2)	0.0029 (2)
Pt2	0.0415 (3)	0.0682 (4)	0.0464 (3)	−0.0001 (2)	0.0096 (2)	0.0052 (2)
O1	0.043 (5)	0.095 (8)	0.050 (6)	0.006 (5)	0.014 (4)	0.002 (5)
O2	0.056 (8)	0.157 (13)	0.074 (8)	−0.008 (8)	0.024 (6)	−0.012 (8)
O3	0.079 (9)	0.209 (18)	0.039 (6)	−0.012 (9)	0.006 (6)	0.002 (8)
O4	0.075 (7)	0.047 (6)	0.083 (8)	0.004 (5)	0.016 (6)	−0.001 (5)
O5	0.098 (10)	0.122 (12)	0.091 (9)	0.050 (9)	0.042 (8)	0.032 (8)
O6	0.129 (12)	0.091 (10)	0.092 (10)	0.047 (9)	0.022 (8)	0.006 (8)
N1	0.063 (8)	0.057 (8)	0.075 (9)	−0.004 (6)	−0.003 (7)	0.014 (6)
N2	0.068 (9)	0.075 (9)	0.057 (8)	0.007 (7)	0.011 (6)	−0.002 (6)
N3	0.072 (9)	0.070 (9)	0.096 (11)	0.003 (7)	0.030 (8)	0.000 (8)
N4	0.060 (8)	0.091 (10)	0.070 (9)	0.017 (7)	0.025 (7)	0.021 (8)
N5	0.033 (5)	0.063 (7)	0.040 (6)	0.002 (4)	0.002 (4)	0.008 (5)
N6	0.046 (6)	0.031 (5)	0.051 (6)	0.004 (4)	0.016 (5)	0.010 (4)
C1	0.034 (7)	0.074 (10)	0.062 (9)	−0.003 (6)	0.010 (6)	0.012 (7)
C2	0.042 (7)	0.075 (10)	0.047 (8)	−0.010 (6)	0.004 (6)	−0.003 (7)
C3	0.039 (8)	0.116 (15)	0.051 (8)	−0.005 (8)	−0.003 (6)	−0.010 (8)
C4	0.037 (8)	0.100 (13)	0.071 (11)	−0.006 (7)	0.001 (7)	−0.004 (9)
C5	0.040 (7)	0.059 (9)	0.055 (8)	−0.001 (6)	0.008 (6)	0.003 (6)
C6	0.059 (10)	0.093 (12)	0.044 (8)	−0.017 (8)	0.009 (7)	−0.011 (7)
C7	0.054 (8)	0.072 (10)	0.041 (7)	0.014 (7)	0.008 (6)	0.009 (6)
C8	0.072 (10)	0.065 (10)	0.046 (8)	0.007 (8)	0.005 (7)	−0.003 (7)
C9	0.090 (12)	0.061 (10)	0.063 (10)	0.007 (9)	0.012 (9)	0.004 (8)
C10	0.086 (12)	0.058 (10)	0.098 (14)	−0.007 (9)	0.020 (10)	−0.001 (9)
C11	0.067 (9)	0.060 (9)	0.055 (8)	0.017 (7)	0.010 (7)	0.004 (7)
C12	0.104 (14)	0.075 (12)	0.043 (8)	0.046 (10)	0.004 (8)	0.007 (8)

Geometric parameters (Å, º)

Pt1—N5	2.021 (11)	O15—O15^v	1.18 (6)
Pt1—N2	2.044 (13)	N5—C5	1.351 (16)
Pt1—N6	2.049 (10)	N5—C1	1.356 (18)
Pt1—N1	2.049 (12)	N6—C11	1.333 (18)
Pt2—O1	2.033 (11)	N6—C7	1.350 (16)
Pt2—N3	2.035 (13)	N8A—N8B	1.79 (3)
Pt2—N4	2.038 (14)	C1—C2	1.38 (2)
Pt2—O4	2.048 (10)	C2—C3	1.378 (19)
Pt1—Pt2	2.9023 (8)	C2—C6	1.48 (2)
Pt2—Pt2^i	3.1821 (11)	C3—C4	1.35 (2)
Pt1—Pt1^ii	6.4394 (12)	C4—C5	1.38 (2)
O5—C8^ii	3.47 (2)	C7—C8	1.33 (2)
O3—O13	2.60 (2)	C8—C9	1.40 (2)
O5—O14	2.61 (3)	C8—C12	1.50 (2)
O1—C5	1.276 (17)	C9—C10	1.37 (2)
O2—C6	1.208 (19)	C10—C11	1.44 (2)
O3—C6	1.31 (2)	N1—H1A	0.8900
O4—C11	1.310 (17)	N1—H1B	0.8900
O5—C12	1.24 (2)	N1—H1C	0.8900
O6—C12	1.25 (2)	N2—H2A	0.8900
O7A—N7	1.2201 (10)	N2—H2B	0.8900
O7B—N7	1.2200 (10)	N2—H2C	0.8900
O8A—N7	1.2201 (10)	N3—H3A	0.8900
O8B—N7	1.2200 (10)	N3—H3B	0.8900
O9A—N7	1.2199 (10)	N3—H3C	0.8900
O9B—N7	1.2201 (10)	N4—H4A	0.8900
O10A—N8A	1.2199 (10)	N4—H4B	0.8900
O10B—N8B	1.2200 (10)	N4—H4C	0.8900
O11A—N8A	1.2198 (10)	C1—H1	0.9300
O11B—N8B	1.2200 (10)	C3—H3D	0.9300
O11B—O14^iii	1.36 (4)	C4—H4	0.9300
O12A—N8A	1.2199 (10)	C7—H7	0.9300
O12B—N8B	1.2200 (10)	C9—H9	0.9300
O14—O11B^iv	1.36 (4)	C10—H10	0.9300
N5—Pt1—N2	177.6 (5)	O1—C5—N5	122.7 (13)
N5—Pt1—N6	90.2 (4)	O1—C5—C4	119.6 (13)
N2—Pt1—N6	89.2 (5)	N5—C5—C4	117.7 (13)
N5—Pt1—N1	88.9 (5)	O2—C6—O3	123.6 (15)
N2—Pt1—N1	91.6 (5)	O2—C6—C2	122.1 (15)
N6—Pt1—N1	176.1 (5)	O3—C6—C2	114.3 (14)
O1—Pt2—N3	87.4 (5)	C8—C7—N6	123.2 (14)
O1—Pt2—N4	175.7 (4)	C7—C8—C9	118.5 (15)
N3—Pt2—N4	91.8 (6)	C7—C8—C12	119.4 (16)
O1—Pt2—O4	93.5 (4)	C9—C8—C12	121.9 (16)
N3—Pt2—O4	174.3 (5)	C10—C9—C8	119.0 (16)
N4—Pt2—O4	86.8 (5)	C9—C10—C11	120.1 (17)
Pt1—Pt2—Pt2^i	158.74 (3)	O4—C11—N6	125.7 (14)
Pt2—Pt1—Pt1^ii	163.81 (2)	O4—C11—C10	116.9 (15)
N5—Pt1—Pt2	82.8 (3)	N6—C11—C10	117.4 (14)
N2—Pt1—Pt2	99.5 (4)	O5—C12—O6	124.8 (18)
N6—Pt1—Pt2	84.1 (3)	O5—C12—C8	114.8 (15)
N1—Pt1—Pt2	99.6 (4)	O6—C12—C8	120.5 (19)
N5—Pt1—Pt1^ii	81.5 (3)	N5—C1—H1	119.0
N2—Pt1—Pt1^ii	96.2 (4)	C2—C1—H1	119.0
N6—Pt1—Pt1^ii	92.2 (3)	C4—C3—H3D	120.8
N1—Pt1—Pt1^ii	83.9 (4)	C2—C3—H3D	120.8
O1—Pt2—Pt1	79.0 (3)	C3—C4—H4	118.3
N3—Pt2—Pt1	105.7 (4)	C5—C4—H4	118.3
N4—Pt2—Pt1	105.2 (4)	C8—C7—H7	118.4
O4—Pt2—Pt1	80.0 (3)	N6—C7—H7	118.4
O1—Pt2—Pt2^i	84.2 (3)	C10—C9—H9	120.5
N3—Pt2—Pt2^i	86.4 (4)	C8—C9—H9	120.5
N4—Pt2—Pt2^i	91.5 (4)	C9—C10—H10	119.9
O4—Pt2—Pt2^i	88.1 (3)	C11—C10—H10	119.9
C5—O1—Pt2	128.6 (9)	Pt1—N1—H1A	109.5
C11—O4—Pt2	126.9 (10)	Pt1—N1—H1B	109.5
C5—N5—C1	120.0 (12)	H1A—N1—H1B	109.5
C5—N5—Pt1	123.3 (9)	Pt1—N1—H1C	109.5
C1—N5—Pt1	116.6 (9)	H1A—N1—H1C	109.5
C11—N6—C7	121.7 (12)	H1B—N1—H1C	109.5
C11—N6—Pt1	121.8 (9)	Pt1—N2—H2A	109.5
C7—N6—Pt1	116.5 (9)	Pt1—N2—H2B	109.5
O7B—N7—O8B	120.01 (9)	H2A—N2—H2B	109.5
O8B—N7—O9B	119.99 (9)	Pt1—N2—H2C	109.5
O9A—N7—O7A	120.01 (9)	H2A—N2—H2C	109.5
O9A—N7—O8A	120.01 (9)	H2B—N2—H2C	109.5
O7A—N7—O8A	119.98 (9)	Pt2—N3—H3A	109.5
O11A—N8A—O12A	120.00 (9)	Pt2—N3—H3B	109.5
O11A—N8A—O10A	120.00 (9)	H3A—N3—H3B	109.5
O12A—N8A—O10A	120.00 (9)	Pt2—N3—H3C	109.5
O10B—N8B—O11B	120.01 (9)	H3A—N3—H3C	109.5
O10B—N8B—O12B	120.00 (9)	H3B—N3—H3C	109.5
O11B—N8B—O12B	120.00 (9)	Pt2—N4—H4A	109.5
N5—C1—C2	122.0 (12)	Pt2—N4—H4B	109.5
C1—C2—C3	118.5 (13)	H4A—N4—H4B	109.5
C1—C2—C6	117.5 (13)	Pt2—N4—H4C	109.5
C3—C2—C6	123.9 (14)	H4A—N4—H4C	109.5
C4—C3—C2	118.3 (15)	H4B—N4—H4C	109.5
C3—C4—C5	123.3 (14)
N5—Pt1—Pt2—O1	12.8 (4)	C1—C2—C6—O3	175.8 (15)
N1—Pt1—Pt2—N3	9.3 (6)	C3—C2—C6—O3	−2 (3)
N2—Pt1—Pt2—N4	12.4 (6)	C11—N6—C7—C8	−3 (2)
N6—Pt1—Pt2—O4	8.1 (4)	N6—C7—C8—C9	1 (2)
C5—N5—C1—C2	−3 (2)	N6—C7—C8—C12	175.9 (12)
N5—C1—C2—C3	2 (2)	C7—C8—C9—C10	0 (2)
N5—C1—C2—C6	−176.2 (14)	C12—C8—C9—C10	−174.7 (15)
C1—C2—C3—C4	−2 (2)	C8—C9—C10—C11	0 (3)
C6—C2—C3—C4	176.2 (16)	C7—N6—C11—O4	−178.0 (13)
C2—C3—C4—C5	3 (3)	C7—N6—C11—C10	3 (2)
C1—N5—C5—O1	−178.4 (13)	C9—C10—C11—O4	179.0 (15)
C1—N5—C5—C4	4 (2)	C9—C10—C11—N6	−2 (2)
C3—C4—C5—O1	178.2 (16)	C7—C8—C12—O5	12 (2)
C3—C4—C5—N5	−4 (2)	C9—C8—C12—O5	−173.2 (16)
C1—C2—C6—O2	−3 (3)	C7—C8—C12—O6	−168.1 (16)
C3—C2—C6—O2	178.3 (18)	C9—C8—C12—O6	7 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O4^i	0.89	2.21	2.988 (17)	146
N4—H4A···O1^i	0.89	2.30	3.030 (16)	139
N2—H2A···O2^ii	0.89	1.97	2.818 (17)	159

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