Di-μ-pivalamidato-κ⁴N:O;O:N-bis­[(2,2′-bi­pyridine-κ²N,N′)(sulfato-κO)­platinum(III)] tetrahydrate in a head-to-tail isomerism

The title compound, [Pt₂^III(C₅H₁₀NO)₂(SO₄)₂(C₁₀H₈N₂)₂]·4H₂O, is the first reported example of a complex in which an amidate-bridged Pt(bpy) dimer is stabilized in the oxidation level of Pt^III (bpy is 2,2′-bi­pyridine). The asymmetric unit consists of one half of the formula unit with a twofold axis passing through the center of the dimer. The intradimer Pt^III—Pt^III bond distance [2.5664 (6) Å] is comparable to those reported for α-pyridonate-bridged cis-diammineplatinum(III) dimers [2.5401 (5)–2.5468 (8) Å; Hollis & Lippard (1983). Inorg. Chem. 22, 2605–2614], in spite of the close contact between the bpy planes within the dimeric unit. The axial Pt—O_sulfate distance is 2.144 (7) Å.

S1. Comment

Amidate-bridged cis-diammineplatinum dimers, [Pt^II₂(NH₃)₄(µ-amidato)₂]²⁺ (amidate is α-pyridonate, α-pyrrolidinonate, acetamidate etc.), have been reported to undergo one-step two-electron oxidation to give the corresponding Pt^III₂ dimers with a simultaneous uptake of two axial donors at both ends of the unit, as well as bond formation between the Pt^III centers, resulting in the formation of [Pt^III₂(NH₃)₄(µ-amidato)₂X₂]ⁿ⁺ (X is an axial donor ligand, and n depends on the charge of X). Reversible redox waves corresponding to the Pt^II₂/Pt^III₂ couple have been observed at around 0.4–0.6 V versus. SCE (Hollis & Lippard, 1983; Matsumoto & Matoba, 1986; Sakai et al., 1998). Two geometrical isomers, viz. head-to-head (HH) and head-to-tail (HT) isomers, are possible for this class of dimers, on the basis of the binding directions of the two amidate bridges. On the other hand, the dimers containing Pt(bpy) units instead of cis-Pt(NH₃)₂ units have been shown to exhibit irreversible redox waves corresponding to the Pt^II₂/Pt^III₂ couple; e.g. irreversible oxidation–reduction waves were observed at around 1 V versus. SCE for HT-[Pt^II₂(bpy)₂(µ-α-pyrrolidinonato)₂](ClO₄)₂ (Matsumoto et al., 1992). These suggested that the formation of the Pt^III—Pt^III single bond in the Pt(bpy) dimers is hindered by the repulsive interaction between the two bpy units. We have now found, for the first time, that an 'amidate-bridged Pt^III(bpy) dimer' can be isolated in a stable crystalline form, and we report here the synthesis and crystal structure of HT-[Pt^III₂(bpy)₂(µ-pivalamidato)₂(SO₄)₂]·4H₂O, (I).

The asymmetric unit of (I) consists of one half of the formula unit (Fig. 1). A twofold axis passes through the center of the dimeric unit. There is therefore a crystallographic requirement that this is a head-to-tail isomer. Analysis of the isotropic atomic displacement parameters of the oxygen and nitrogen donors of pivalamidate revealed no evidence for any disorder of the O and NH moieties (see Experimental). The hydrogen-bonding geometry given in Table 3 also supports the validity of our treatment with regard to the binding direction of pivalamidate. To the best of our knowledge, this is the first structurally characterized diplatinum(III) complex capped by two sulfate ions, even though stepwise axial sulfate-ligation equilibria were previously investigated for an α-pyrrolidinonate-bridged cis-diammineplatinum(III) dimer by means of spectrophotometric titration (Sakai, Tsubomura et al., 1993).

The intradimer Pt^III—Pt^III distance in (I) [Pt1—Pt1(-x, y, 1.5 − z) = 2.5664 (6) Å] is unexpectedly short, in spite of the steric hindrance promoted between the bpy planes within the dimeric unit, and is comparable to those reported for the α-pyridonate-bridged cis-diammineplatinum(III) dimers [Pt^III—Pt^III = 2.5401 (5) Å for HH-[Pt^III₂(NH₃)₄(µ-C₅H₄NO)₂(H₂O)(NO₃)](NO₃)₃·2H₂O, and Pt^III—Pt^III = 2.5468 (8) Å for HT-[Pt^III₂(NH₃)₄(µ-C₅H₄NO)₂(NO₃)₂](NO₃)₂^.0.5H₂O (Hollis & Lippard, 1983)]. On the other hand, the Pt^III—Pt^III distance in (I) is ca 0.1 Å shorter than those reported for the α-pyrrolidinonate-bridged cis-diammineplatinum(III) dimers [Pt^III—Pt^III = 2.644 (1) Å for HH-[Pt^III₂(NH₃)₄(µ-C₄H₆NO)₂(NO₂)(NO₃)](NO₃)₂·H₂O (Abe et al., 1991), Pt^III—Pt^III = 2.6366 (7) Å for HH-[Pt^III₂(NH₃)₄(µ-C₄H₆NO)₂(Cl)₂](NO₃)₂ (Sakai et al., 1998) and Pt^III—Pt^III = 2.6239 (9) Å for HH-[Pt^III₂(NH₃)₄(µ-C₄H₆NO)₂(Cl)(NO₃)](NO₃)₂·H₂O (Sakai et al., 1998)] (see also Sakai, Sakamoto et al., 2003; Sakai, Sakai et al., 2004). Thus we realise that a relatively short and strong Pt^III—Pt^III bond is achieved in (I). As shown in Fig. 2 and Table 2, there are some short intramolecular bpy–bpy contacts, N3···N2ⁱ, N3···C6ⁱ and C15···C6ⁱ [symmetry code: (i) −x, y, 1.5 − z].

The mean-plane calculations performed for the four-coordinated atoms [N1, N2, N3 and O1(-x, y, 1.5 − z)] reveal that the Pt coordination plane is slightly deformed but is roughly planar, the four-atom r.m.s. deviation being 0.029 Å. Atom Pt1 is displaced from the mean plane defined by atoms N1, N2, N3 and O1(-x, y, 1.5 − z) by 0.024 (3) Å towards atom Pt1(-x, y, 1.5 − z) within the unit. The dihedral angle (τ) between the two Pt coordination planes within the dimeric unit and their mean torsional twist (ω) about the Pt—Pt axis are estimated as τ = 17.1 (3)° and ω = 16.8 (4)° (see Fig. 2; see also torsion angles in Table 1), respectively. The dihedral angle between the two bpy planes within the dimeric unit is estimated as 16.3 (2)°. Thus the bpy plane is nearly coplanar with the Pt coordination plane [they are inclined by 2.7 (3)° to one another].

The axial Pt^III—O(sulfate) distance [2.144 (7) Å] is comparable to those reported thus far for the α-pyridonate-bridged cis-diammineplatinum(III) dimers [Pt^III—O(axial H₂O) = 2.122 (6) Å and Pt^III—O(axial NO₃⁻) = 2.193 (7) Å for HH-[Pt^III₂(NH₃)₄(µ-C₅H₄NO)₂(H₂O)(NO₃)](NO₃)₃·2H₂O, and Pt^III—O(axial NO₃⁻) = 2.17 (1) Å for HT-[Pt^III₂(NH₃)₄(µ-C₅H₄NO)₂(NO₃)₂](NO₃)₂·0.5H₂O (Hollis & Lippard, 1983)].

As shown in Fig. 3, the crystal packing is partly stabilized by relatively weak hydrophobic interactions among the tertiary butyl moieties and the bpy units, where the shortest intermolecular bpy–bpy separation is estimated as 3.69 (1) Å. The dimer–dimer interactions along the c axis are also stabilized by O(sulfate)···O(water)···O(water)···O(sulfate) hydrogen bonds [i.e. O5···O7···O6ⁱ···O3ⁱ], where O5···O7 = 2.750 (12) Å, O7···O6ⁱ = 2.784 (14) Å and O6ⁱ···O3ⁱ = 2.864 (13) Å; symmetry code: (i) x, −y + 2, z − 0.5; see also Table 2). The dimer is also connected to a neighbouring dimer via an inversion center by forming O(sulfate)···O(water)···O(sulfate) hydrogen bonds [i.e. O5···O7···O4(-x + 0.5, −y + 2.5, −z + 2); O7···O4(-x + 0.5, −y + 2.5, −z + 2) = 2.828 (12) Å; see also Table 2].

S2. Experimental

For the synthesis of (II), a suspension of PtCl₂(bpy) (1 mmol, 0.42 g; Morgen & Burstall, 1934), AgNO₃ (2 mmol, 0.34 g) and pivalamide (1.5 mmol, 0.15 g) in water (7 ml) was refluxed for 3 h in the dark, during which the color of the solution turned deep red. The solution was then filtered while it was hot in order to remove the precipitated AgCl. Leaving the filtrate at room temperature overnight afforded (II) as deep-red block-like crystals, which were collected by filtration and air-dried (yield 65%). Complex (II) was purified by recrystallization from hot water [(II) (0.1 g) was dissolved in ca 1 ml of water; about 80% of the product was re-collected]. Analysis calculated for Pt₂O₁₃N₈C₃₀H₄₆: C 32.26, H 4.15, N 10.03%; found: C 32.30, H 3.91, N 9.99%. IR (KBr): 3421 (w, br), 2360 (m), 2341 (w), 1607 (w), 1560 (m), 1489 (w), 1454 (w), 1384 (s), 1188 (w), 1029 (w, br), 769 (m), 722 (m), 650 (m, br), 419 (w) cm⁻¹. UV–vis absorption (in H₂O, 293 K): λ_max = 306 nm (ε = 20400 M⁻¹cm⁻¹), λ_max = 361 nm (ε = 2080 M⁻¹cm⁻¹), λ_max = 475 nm (ε = 2110 M⁻¹cm⁻¹). ¹⁹⁵Pt NMR (D₂O, 296 K, referenced to −1624 p.p.m. of K₂PtCl₄): −2064 p.p.m. (singlet characteristic of HT). Complex (II) was confirmed to be a head-to-tail isomer, part of which was reported by Sakai, Takeshita et al. (1993). For the synthesis of (I), a solution of (II) (0.25 mmol, 0.28 g) and K₂S₂O₈ (0.3 mmol, 0.08 g) in water (15 ml) was stirred at room temperature for 15 min. The solution was filtered to remove impurities and then evaporated to dryness. The yellow powder deposited was redissolved in a minimum amount of water (ca 3 ml). Leaving the solution to stand in air at room temperature for a few days afforded (I) as yellow prisms, which were collected by filtration and air-dried by suction (yield 68%). Analysis calculated for Pt₂S₂O₁₄N₆C₃₀H₄₄: C 30.88, H 3.80, N 7.20%; found: C 30.82, H 3.10, N 7.09%. IR (KBr): 3440 (m, br), 3077 (w, br), 2962 (w), 1606 (m), 1581 (m), 1503 (w), 1454 (m), 1426 (w), 1370 (w), 1313 (w), 1253 (w), 1182 (s), 1117 (versus), 1076 (w), 1051 (w), 1012 (versus), 917 (m), 873 (s), 777 (m), 614 (m), 587 (w) cm⁻¹. The crystals were confirmed to be stable in air at room temperature. A diffraction-quality single-crystal was mounted on a glass fiber and used in the data collection.

S3. Refinement

As recently reported for several different dimers doubly bridged by chain amidate ligands (Sakai, Kurashima et al., 2003; Sakai, Ikuta et al., 2003; Sakai, Shiomi et al., 2003), it is often possible to determine the binding direction of the O– and N-donors of each amidate on the basis of the results of least-squares calculations performed for two possible directions. Moreover, when the U_eq values of Pt atoms are reasonably small, a disorder model based on the mixing of HH and HT isomers is not favored, since the intradimer Pt—Pt distances of the HH and HT isomers are, in general, markedly different from one another (Sakai et al., 1998). In (I), atom Pt1 has a reasonably small U_eq value [0.02294 (15) Ų], indicating that the mixing of the HH and HT isomers is not likely to be promoted in this system. The location of atoms O1 and N1 have been determined rationally from the comparison of two sets of U_eq values, viz. U_eq(O1) = 0.0277 (12) Ų and U_eq(N1) = 0.0273 (15) Ų, and U_eq(N instead of O1) = 0.0152 (12) Ų and U_eq(O instead of N1) = 0.0448 (18) Ų. The former set, corresponding to the reported combination, clearly shows a good balance and was thereby adopted as a reasonable set. As a result, the H atom on atom N1 is located at the idealized position as a riding atom as mentioned below. The tertiary butyl group shows orientational disorder in which two sets of positions (C3A/C4A/C5A and C3B/C4B/C5B) are located around atom C2. The disordered C atoms were assumed to have the same isotropic displacement parameter. Furthermore, all six C(tertiary)—C(methyl) distances and three C(methyl)—C(methyl) distances within each site were respectively restrained as equal. The occupation factors of sites A and B converged at 70.7 (15) and 29.3 (15)%, respectively. All H atoms, except for those of water molecules, were located at their idealized positions as riding atoms [C—H(aromatic) = 0.93 Å, C—H(methyl) = 0.96 Å and N—H = 0.86 Å], and included in the refinement in the riding-motion approximation, with U_iso(H) = 1.2U_eq(carrier atom). Water H atoms were not located. In the final difference Fourier synthesis, 32 residual peaks in the range 1.02–2.78 e Å⁻³ were observed, not only within 1.4 Å of atom Pt1 but also near atoms O2, O3, O4, O5, O6, O7, C2, C11 and C13. The deepest hole was located 0.54 Å from atom Pt1.

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, TEXSAN (Molecular Structure Corporation, 2001), KENX, and ORTEP (Johnson, 1976).

Figures

	Fig. 1. The structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are shown at the 50% probability level. H atoms have been omitted for clarity, and only one orientation is shown for the disordered tert-butyl groups. Dashed lines denote hydrogen bonds.
	Fig. 2. The structure of (I), along the Pt1—Pt1(-x, y, 1.5 − z) vector. H atoms and water molecules have been omitted for clarity; only one orientation is shown for the disordered tert-butyl groups. [Symmetry code: (i) −x, y, 1.5 − z.]
	Fig. 3. A stereoview of the crystal packing of (I). Non-H atoms have been drawn as ideal spheres, and H atoms and hydrogen bonds have been omitted: only one orientation is shown for the disordered tert-butyl groups.

Di-µ-pivalamidato-κ⁴N,O- bis[(sulfato)(2,2'-bipyridine-κ²N,N')platinum(III)] tetrahydrate

Crystal data

[Pt2(C5H10NO)2(C10H8N2)2(SO4)2]·4H2O	F(000) = 2264
Mr = 1167.01	? # Insert any comments here.
Monoclinic, C2/c	Dx = 2.085 Mg m^−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 22.535 (2) Å	Cell parameters from 7382 reflections
b = 11.9796 (12) Å	θ = 2.5–27.5°
c = 16.4774 (17) Å	µ = 7.70 mm^−1
β = 123.285 (2)°	T = 296 K
V = 3718.5 (6) Å^3	Prism, yellow
Z = 4	0.18 × 0.11 × 0.08 mm

Data collection

Bruker SMART APEX CCD-detector diffractometer	4288 independent reflections
Radiation source: fine-focus sealed tube	3218 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.145
Detector resolution: 8.366 pixels mm^-1	θmax = 27.5°, θmin = 2.1°
ω scans	h = −29→29
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001a)	k = −15→15
Tmin = 0.147, Tmax = 0.623	l = −21→21
20489 measured reflections

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)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.128	w = 1/[σ^2(Fo^2) + (0.0564P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
4288 reflections	Δρmax = 2.78 e Å^−3
238 parameters	Δρmin = −1.61 e Å^−3
12 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00183 (14)

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.

Mean-plane data from final SHELXL refinement run:-

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

2.1540 (0.0590) x + 1.7782 (0.0275) y + 12.6936 (0.0283) z = 12.5484 (0.0290)

* −0.0287 (0.0031) N1 * −0.0299 (0.0033) N2 * 0.0301 (0.0033) N3 * 0.0285 (0.0031) O1_$1 − 0.0238 (0.0031) Pt1 − 2.5617 (0.0032) Pt1_$1

Rms deviation of fitted atoms = 0.0293

2.1540 (0.0589) x − 1.7782 (0.0274) y + 12.6936 (0.0282) z = 6.4919 (0.0386)

Angle to previous plane (with approximate e.s.d.) = 17.07 (0.34)

* −0.0285 (0.0031) O1 * 0.0287 (0.0032) N1_$1 * 0.0299 (0.0033) N2_$1 * −0.0301 (0.0033) N3_$1 0.0238 (0.0031) Pt1_$1 2.5617 (0.0032) Pt1

Rms deviation of fitted atoms = 0.0293

1.1248 (0.0372) x + 1.7012 (0.0451) y + 13.1660 (0.0182) z = 12.8562 (0.0304)

Angle to previous plane (with approximate e.s.d.) = 16.91 (0.30)

* 0.0011 (0.0065) N2 * 0.0520 (0.0076) C6 * 0.0081 (0.0090) C7 * −0.0494 (0.0073) C8 * −0.0601 (0.0062) N3 * 0.0017 (0.0085) C11 * 0.0251 (0.0088) C12 * 0.0215 (0.0079) C13 − 3.1272 (0.0104) N2_$1 − 3.1936 (0.0128) C6_$1 − 3.4948 (0.0114) C7_$1 − 3.7612 (0.0160) C8_$1 − 2.9529 (0.0115) N3_$1 − 3.3782 (0.0105) C11_$1 − 3.6796 (0.0126) C12_$1 − 3.5779 (0.0110) C13_$1

Rms deviation of fitted atoms = 0.0352

1.1557 (0.3360) x + 1.7605 (0.1783) y + 13.1427 (0.1210) z = 12.9058 (0.1592)

Angle to previous plane (with approximate e.s.d.) = 0.30 (1.28)

* 0.0000 (0.0001) C12 * 0.0000 (0.0001) C13 * 0.0000 (0.0000) C14 3.6923 (0.0124) C12_$2 3.6923 (0.0124) C13_$2 3.6923 (0.0124) C14_$2

Rms deviation of fitted atoms = 0.0000

2.1540 (0.0590) x + 1.7782 (0.0275) y + 12.6936 (0.0283) z = 12.5484 (0.0290)

Angle to previous plane (with approximate e.s.d.) = 2.55 (1.30)

* −0.0287 (0.0031) N1 * −0.0299 (0.0033) N2 * 0.0301 (0.0033) N3 * 0.0285 (0.0031) O1_$1 − 0.0238 (0.0031) Pt1 − 2.5617 (0.0032) Pt1_$1

Rms deviation of fitted atoms = 0.0293

1.1216 (0.0308) x + 1.7019 (0.0353) y + 13.1673 (0.0132) z = 12.8540 (0.0265)

Angle to previous plane (with approximate e.s.d.) = 2.66 (0.32)

* 0.0050 (0.0068) N2 * 0.0561 (0.0080) C6 * 0.0122 (0.0093) C7 * −0.0455 (0.0098) C8 * −0.0260 (0.0096) C9 * 0.0073 (0.0086) C10 * −0.0565 (0.0067) N3 * 0.0052 (0.0088) C11 * 0.0284 (0.0092) C12 * 0.0246 (0.0092) C13 * 0.0176 (0.0088) C14 * −0.0284 (0.0079) C15

Rms deviation of fitted atoms = 0.0314

1.1216 (0.0307) x − 1.7019 (0.0353) y + 13.1673 (0.0132) z = 6.8969 (0.0304)

Angle to previous plane (with approximate e.s.d.) = 16.34 (0.17)

* −0.0050 (0.0068) N2_$1 * −0.0561 (0.0080) C6_$1 * −0.0122 (0.0093) C7_$1 * 0.0455 (0.0098) C8_$1 * 0.0260 (0.0095) C9_$1 * −0.0073 (0.0086) C10_$1 * 0.0565 (0.0067) N3_$1 * −0.0052 (0.0088) C11_$1 * −0.0284 (0.0092) C12_$1 * −0.0246 (0.0092) C13_$1 * −0.0176 (0.0088) C14_$1 * 0.0284 (0.0079) C15_$1

Rms deviation of fitted atoms = 0.0314

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	0.042947 (15)	0.97604 (3)	0.84268 (2)	0.02294 (15)
S1	0.17203 (12)	1.0678 (2)	1.04836 (15)	0.0321 (5)
O1	0.0266 (3)	1.0789 (5)	0.6558 (4)	0.0277 (12)
O2	0.1070 (4)	0.9944 (5)	0.9975 (5)	0.0368 (15)
O3	0.1935 (4)	1.0660 (7)	1.1483 (5)	0.0482 (18)
O4	0.1524 (4)	1.1804 (6)	1.0073 (5)	0.0453 (18)
O5	0.2241 (4)	1.0229 (6)	1.0330 (6)	0.0501 (19)
O6	0.3198 (6)	0.9972 (8)	1.3260 (9)	0.082 (3)
O7	0.3136 (7)	1.0901 (8)	0.9778 (8)	0.096 (4)
N1	0.0821 (4)	1.1106 (6)	0.8168 (5)	0.0273 (15)
H1	0.1094	1.1540	0.8648	0.033*
N2	0.0069 (4)	0.8339 (6)	0.8682 (5)	0.0272 (15)
N3	0.1139 (4)	0.8672 (6)	0.8501 (5)	0.0273 (15)
C1	0.0688 (4)	1.1369 (7)	0.7317 (6)	0.0287 (18)
C2	0.1000 (5)	1.2387 (7)	0.7169 (6)	0.039 (2)
C3A	0.0335 (8)	1.3099 (16)	0.6498 (12)	0.077 (3)*	0.707 (15)
H3A1	0.0117	1.3309	0.6837	0.093*	0.707 (15)
H3A2	0.0005	1.2674	0.5932	0.093*	0.707 (15)
H3A3	0.0470	1.3758	0.6305	0.093*	0.707 (15)
C3B	0.068 (2)	1.347 (2)	0.723 (3)	0.077 (3)*	0.293 (15)
H3B1	0.0717	1.3500	0.7840	0.093*	0.293 (15)
H3B2	0.0186	1.3496	0.6709	0.093*	0.293 (15)
H3B3	0.0925	1.4087	0.7180	0.093*	0.293 (15)
C4A	0.1468 (9)	1.3054 (15)	0.8088 (10)	0.077 (3)*	0.707 (15)
H4A1	0.1208	1.3233	0.8377	0.093*	0.707 (15)
H4A2	0.1614	1.3731	0.7934	0.093*	0.707 (15)
H4A3	0.1880	1.2622	0.8537	0.093*	0.707 (15)
C4B	0.1784 (9)	1.237 (4)	0.800 (2)	0.077 (3)*	0.293 (15)
H4B1	0.1994	1.1678	0.7985	0.093*	0.293 (15)
H4B2	0.1824	1.2435	0.8609	0.093*	0.293 (15)
H4B3	0.2026	1.2981	0.7927	0.093*	0.293 (15)
C5A	0.1351 (9)	1.2080 (18)	0.6651 (13)	0.077 (3)*	0.707 (15)
H5A1	0.1022	1.1676	0.6070	0.093*	0.707 (15)
H5A2	0.1758	1.1620	0.7065	0.093*	0.707 (15)
H5A3	0.1499	1.2746	0.6486	0.093*	0.707 (15)
C5B	0.095 (2)	1.233 (4)	0.6217 (17)	0.077 (3)*	0.293 (15)
H5B1	0.1145	1.1630	0.6179	0.093*	0.293 (15)
H5B2	0.1215	1.2932	0.6181	0.093*	0.293 (15)
H5B3	0.0463	1.2379	0.5688	0.093*	0.293 (15)
C6	−0.0488 (5)	0.8294 (8)	0.8774 (7)	0.035 (2)
H6	−0.0716	0.8948	0.8759	0.042*
C7	−0.0720 (6)	0.7280 (9)	0.8892 (8)	0.047 (3)
H7	−0.1113	0.7243	0.8937	0.057*
C8	−0.0367 (7)	0.6327 (9)	0.8941 (9)	0.054 (3)
H8	−0.0527	0.5638	0.9004	0.065*
C9	0.0229 (6)	0.6386 (8)	0.8897 (8)	0.045 (3)
H9	0.0480	0.5743	0.8952	0.054*
C10	0.0447 (5)	0.7411 (8)	0.8772 (6)	0.032 (2)
C11	0.1057 (5)	0.7604 (7)	0.8693 (7)	0.0324 (19)
C12	0.1520 (6)	0.6786 (8)	0.8777 (8)	0.045 (2)
H12	0.1457	0.6049	0.8891	0.053*
C13	0.2076 (5)	0.7075 (11)	0.8690 (8)	0.051 (3)
H13	0.2387	0.6531	0.8735	0.061*
C14	0.2164 (5)	0.8164 (9)	0.8536 (8)	0.044 (2)
H14	0.2545	0.8370	0.8497	0.053*
C15	0.1686 (5)	0.8961 (9)	0.8439 (7)	0.038 (2)
H15	0.1745	0.9702	0.8329	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.02148 (19)	0.0219 (2)	0.02608 (19)	0.00053 (13)	0.01349 (14)	0.00201 (13)
S1	0.0292 (11)	0.0346 (12)	0.0289 (10)	−0.0025 (10)	0.0137 (9)	0.0008 (10)
O1	0.030 (3)	0.029 (3)	0.026 (3)	−0.005 (3)	0.017 (3)	−0.002 (3)
O2	0.040 (4)	0.034 (4)	0.039 (4)	−0.011 (3)	0.023 (3)	−0.002 (3)
O3	0.047 (4)	0.055 (4)	0.028 (3)	−0.009 (4)	0.011 (3)	0.000 (3)
O4	0.057 (5)	0.032 (4)	0.040 (4)	−0.003 (3)	0.022 (4)	0.000 (3)
O5	0.034 (4)	0.053 (5)	0.066 (5)	0.003 (3)	0.029 (4)	−0.007 (4)
O6	0.064 (6)	0.089 (7)	0.099 (9)	0.016 (5)	0.049 (6)	0.034 (6)
O7	0.152 (11)	0.070 (7)	0.125 (9)	−0.037 (7)	0.113 (9)	−0.037 (6)
N1	0.027 (4)	0.021 (4)	0.031 (4)	−0.005 (3)	0.014 (3)	−0.002 (3)
N2	0.030 (4)	0.021 (4)	0.032 (4)	−0.002 (3)	0.019 (3)	0.003 (3)
N3	0.022 (3)	0.031 (4)	0.028 (3)	0.001 (3)	0.013 (3)	0.003 (3)
C1	0.025 (4)	0.024 (4)	0.040 (5)	0.005 (4)	0.020 (4)	−0.002 (4)
C2	0.053 (6)	0.027 (5)	0.043 (5)	−0.012 (4)	0.031 (5)	−0.001 (4)
C6	0.032 (5)	0.037 (5)	0.041 (5)	0.000 (4)	0.023 (4)	0.004 (4)
C7	0.041 (6)	0.047 (6)	0.063 (7)	−0.010 (5)	0.035 (6)	−0.001 (5)
C8	0.078 (8)	0.031 (6)	0.076 (8)	−0.013 (6)	0.057 (7)	−0.001 (5)
C9	0.057 (7)	0.027 (5)	0.059 (7)	0.003 (5)	0.036 (6)	0.003 (5)
C10	0.038 (5)	0.029 (5)	0.033 (4)	0.000 (4)	0.023 (4)	0.004 (4)
C11	0.035 (5)	0.027 (5)	0.038 (5)	0.006 (4)	0.021 (4)	0.005 (4)
C12	0.054 (6)	0.025 (5)	0.058 (7)	0.006 (5)	0.033 (6)	0.005 (5)
C13	0.039 (6)	0.066 (8)	0.056 (7)	0.018 (5)	0.031 (5)	0.005 (6)
C14	0.031 (5)	0.052 (7)	0.052 (6)	0.005 (5)	0.025 (5)	0.002 (5)
C15	0.027 (4)	0.041 (6)	0.048 (6)	0.002 (4)	0.022 (4)	0.003 (4)

Geometric parameters (Å, º)

Pt1—O1^i	2.004 (6)	C13—C14	1.365 (16)
Pt1—O2	2.144 (7)	C14—C15	1.380 (13)
Pt1—N1	1.993 (7)	N1—H1	0.8600
Pt1—N2	2.027 (7)	C3A—H3A1	0.9600
Pt1—N3	2.015 (7)	C3A—H3A2	0.9600
Pt1—Pt1^i	2.5664 (6)	C3A—H3A3	0.9600
O1—C1	1.282 (10)	C3B—H3B1	0.9600
N1—C1	1.302 (11)	C3B—H3B2	0.9600
C1—C2	1.492 (12)	C3B—H3B3	0.9600
S1—O5	1.433 (7)	C4A—H4A1	0.9600
S1—O3	1.439 (7)	C4A—H4A2	0.9600
S1—O4	1.466 (7)	C4A—H4A3	0.9600
S1—O2	1.508 (7)	C4B—H4B1	0.9600
N2—C6	1.346 (11)	C4B—H4B2	0.9600
N2—C10	1.359 (11)	C4B—H4B3	0.9600
N3—C15	1.337 (11)	C5A—H5A1	0.9600
N3—C11	1.355 (11)	C5A—H5A2	0.9600
C2—C5A	1.494 (9)	C5A—H5A3	0.9600
C2—C3B	1.513 (10)	C5B—H5B1	0.9600
C2—C5B	1.513 (10)	C5B—H5B2	0.9600
C2—C4A	1.514 (9)	C5B—H5B3	0.9600
C2—C4B	1.530 (10)	C6—H6	0.9300
C2—C3A	1.542 (9)	C7—H7	0.9300
C6—C7	1.378 (14)	C8—H8	0.9300
C7—C8	1.368 (16)	C9—H9	0.9300
C8—C9	1.386 (15)	C12—H12	0.9300
C9—C10	1.378 (13)	C13—H13	0.9300
C10—C11	1.469 (12)	C14—H14	0.9300
C11—C12	1.380 (13)	C15—H15	0.9300
C12—C13	1.382 (15)
O3···O6	2.864 (13)	C15···C6^i	3.228 (13)
O5···O7	2.750 (12)	N2···C5B^iv	3.59 (3)
O7···O4^ii	2.828 (12)	C6···C5B^iv	3.60 (4)
O7···O6^iii	2.784 (14)	C7···C5B^iv	3.64 (4)
N3···N2^i	3.125 (10)	C8···C5B^iv	3.64 (4)
N3···C6^i	3.221 (12)	C9···C5B^iv	3.58 (3)
C10···C10^i	3.515 (18)	C10···C5B^iv	3.549 (18)
C11···N2^i	3.411 (12)	C7···C3A^iv	3.62 (2)
C11···C10^i	3.595 (13)	C8···C3A^iv	3.66 (2)
C13···C7^i	3.636 (16)	C14···C12^v	3.741 (15)
C14···C6^i	3.605 (14)
N1—Pt1—N3	96.1 (3)	C13—C14—C15	120.0 (10)
N1—Pt1—N2	176.8 (3)	N3—C15—C14	120.3 (9)
N3—Pt1—N2	80.7 (3)	C1—N1—H1	118.0
N1—Pt1—O2	94.8 (3)	Pt1—N1—H1	118.0
N3—Pt1—O2	90.0 (3)	C2—C3A—H3A1	109.5
N2—Pt1—O2	85.7 (3)	C2—C3A—H3A2	109.5
N1—Pt1—O1^i	86.9 (3)	H3A1—C3A—H3A2	109.5
O1^i—Pt1—N3	175.7 (2)	C2—C3A—H3A3	109.5
O1^i—Pt1—N2	96.3 (3)	H3A1—C3A—H3A3	109.5
O1^i—Pt1—O2	86.7 (2)	H3A2—C3A—H3A3	109.5
N1—Pt1—Pt1^i	83.0 (2)	C2—C3B—H3B1	109.5
O1^i—Pt1—Pt1^i	86.02 (16)	C2—C3B—H3B2	109.5
N3—Pt1—Pt1^i	97.3 (2)	H3B1—C3B—H3B2	109.5
N2—Pt1—Pt1^i	96.9 (2)	C2—C3B—H3B3	109.5
O2—Pt1—Pt1^i	172.53 (19)	H3B1—C3B—H3B3	109.5
O5—S1—O3	113.7 (5)	H3B2—C3B—H3B3	109.5
O5—S1—O4	109.4 (5)	C2—C4A—H4A1	109.5
O3—S1—O4	111.7 (5)	C2—C4A—H4A2	109.5
O5—S1—O2	108.8 (4)	H4A1—C4A—H4A2	109.5
O3—S1—O2	104.0 (4)	C2—C4A—H4A3	109.5
O4—S1—O2	109.0 (4)	H4A1—C4A—H4A3	109.5
C1—O1—Pt1^i	119.2 (5)	H4A2—C4A—H4A3	109.5
S1—O2—Pt1	122.4 (4)	C2—C4B—H4B1	109.5
C1—N1—Pt1	124.0 (6)	C2—C4B—H4B2	109.5
C6—N2—C10	121.4 (8)	H4B1—C4B—H4B2	109.5
C6—N2—Pt1	124.2 (6)	C2—C4B—H4B3	109.5
C10—N2—Pt1	114.3 (6)	H4B1—C4B—H4B3	109.5
C15—N3—C11	120.8 (8)	H4B2—C4B—H4B3	109.5
C15—N3—Pt1	124.2 (6)	C2—C5A—H5A1	109.5
C11—N3—Pt1	114.8 (6)	C2—C5A—H5A2	109.5
O1—C1—N1	121.9 (8)	H5A1—C5A—H5A2	109.5
O1—C1—C2	116.6 (8)	C2—C5A—H5A3	109.5
N1—C1—C2	121.5 (8)	H5A1—C5A—H5A3	109.5
C1—C2—C5A	109.7 (11)	H5A2—C5A—H5A3	109.5
C1—C2—C3B	114 (2)	C2—C5B—H5B1	109.5
C1—C2—C5B	111 (2)	C2—C5B—H5B2	109.5
C3B—C2—C5B	110.2 (16)	H5B1—C5B—H5B2	109.5
C1—C2—C4A	113.6 (11)	C2—C5B—H5B3	109.5
C5A—C2—C4A	113.9 (10)	H5B1—C5B—H5B3	109.5
C1—C2—C4B	105 (2)	H5B2—C5B—H5B3	109.5
C3B—C2—C4B	108.3 (16)	N2—C6—H6	119.9
C5B—C2—C4B	108.5 (15)	C7—C6—H6	119.9
C1—C2—C3A	102.1 (10)	C8—C7—H7	120.4
C5A—C2—C3A	109.7 (9)	C6—C7—H7	120.4
C4A—C2—C3A	107.2 (9)	C7—C8—H8	119.9
N2—C6—C7	120.1 (9)	C9—C8—H8	119.9
C8—C7—C6	119.3 (10)	C10—C9—H9	120.4
C7—C8—C9	120.3 (10)	C8—C9—H9	120.4
C10—C9—C8	119.2 (10)	C11—C12—H12	120.3
N2—C10—C9	119.5 (9)	C13—C12—H12	120.3
N2—C10—C11	115.0 (8)	C14—C13—H13	120.3
C9—C10—C11	125.5 (9)	C12—C13—H13	120.3
N3—C11—C12	120.1 (9)	C13—C14—H14	120.0
N3—C11—C10	115.1 (8)	C15—C14—H14	120.0
C12—C11—C10	124.8 (9)	N3—C15—H15	119.8
C11—C12—C13	119.4 (10)	C14—C15—H15	119.8
C14—C13—C12	119.4 (10)
N1—Pt1—Pt1^i—O1	16.5 (3)	C7—C8—C9—C10	−2.1 (18)
N3—Pt1—Pt1^i—N2^i	17.0 (3)	C6—N2—C10—C9	4.2 (14)
O1—C1—C2—C5A	−53.7 (11)	C6—N2—C10—C11	−177.5 (8)
N1—C1—C2—C5A	128.5 (10)	C8—C9—C10—N2	−0.7 (16)
O1—C1—C2—C3B	105.7 (17)	C8—C9—C10—C11	−178.8 (10)
N1—C1—C2—C3B	−72.1 (18)	C15—N3—C11—C12	−3.4 (14)
O1—C1—C2—C5B	−19.1 (18)	C15—N3—C11—C10	178.2 (8)
N1—C1—C2—C5B	163.0 (17)	N2—C10—C11—N3	−2.7 (12)
O1—C1—C2—C4A	177.6 (10)	C9—C10—C11—N3	175.4 (9)
N1—C1—C2—C4A	−0.2 (13)	N2—C10—C11—C12	178.9 (9)
O1—C1—C2—C4B	−136.1 (16)	C9—C10—C11—C12	−3.0 (16)
N1—C1—C2—C4B	46.0 (17)	N3—C11—C12—C13	1.7 (15)
O1—C1—C2—C3A	62.6 (10)	C10—C11—C12—C13	−180.0 (10)
N1—C1—C2—C3A	−115.3 (10)	C11—C12—C13—C14	0.9 (17)
C10—N2—C6—C7	−4.8 (14)	C12—C13—C14—C15	−2.0 (17)
N2—C6—C7—C8	1.8 (16)	C11—N3—C15—C14	2.3 (14)
C6—C7—C8—C9	1.6 (18)	C13—C14—C15—N3	0.5 (16)

Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1/2, −y+5/2, −z+2; (iii) x, −y+2, z−1/2; (iv) x, −y+2, z+1/2; (v) −x+1/2, −y+3/2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.86	2.01	2.757 (10)	144