(1H-Pyrazole-[kappa]N²)(2,2':6',2''-ter­pyridine-[kappa]³N,N',N'')platinum(II) bis­(perchlorate) nitro­methane monosolvate

The reaction between [PtCl(terpy)]·2H₂O (terpy is 2,2':6',2''-terpyridine) and pyrazole in the presence of two equivalents of AgClO₄ in nitro­methane yields the title compound, [Pt(C₃H₄N₂)(C₁₅H₁₁N₃)](ClO₄)₂·CH₃NO₂, as a yellow crystalline solid. Single-crystal X-ray diffraction shows that the dicationic platinum(II) chelate is square planar with the terpyridine ligand occupying three sites and the pyrazole ligand occupying the fourth. The torsion angle subtended by the pyrazole ring relative to the terpyridine chelate is 62.4 (6)°. Density functional theory calculations at the LANL2DZ/PBE1PBE level of theory show that in vacuo the lowest-energy conformation has the pyrazole ligand in an orientation perpendicular to the terpyridine ligand (i.e. 90°). Seemingly, the stability gained by the formation of hydrogen bonds between the pyrazole NH group and the perchlorate anion in the solid-state structure is sufficient for the chelate to adopt a higher-energy conformation.

S1. Comment

Platinum(II) chelates have been extensively studied since their application as anti-tumour agents was discovered in the 1960s (Jaganyi et al., 2008). Although cis-diaminedichloroplatinum(II) (cisplatin) has been effective in the treatment of particular tumour cell lines, cisplatin resistance in certain cancer cell lines has sparked much research into developing new-generation platinum-based drugs (Thurston, 2007). The substitution kinetics of the title metal chelate have been studied to further develop the understanding of the interactions between the platinum(II) ion and various nucleophiles. This research is critical to the development of new drugs (Jaganyi et al., 2008). The structure of the pyrazole-substituted platinum(II)terpyridine, [Pt(terpy)(pyz)](ClO₄)₂.(CH₃NO₂) (where terpy = 2,2':6',2''-terpyridine and pyz = pyrazole), was elucidated to further develop the understanding of the binding mode of the ancillary ligand, i.e. whether the pyrazole ligand was deprotonated or not.

A search of the Cambridge Structural Database (CSD; Allen, 2002) showed that the title compound is a novel structure. There is, however, a reported µ₂-pyrazolyl structure (Bailey & Gray, 1992). The reported metal chelate was synthesized under basic conditions and, as a result, the pyrazole ligand is deprotonated and a platinum(II)terpyridine cation is bound to each nitrogen atom of the ancillary ligand. The pyrazolyl ligand thus bridges the two chelates.

The title metal chelate crystallized in the monoclinic space group P2₁/c with Z = 4. The cation in the asymmetric unit was associated with two perchlorate anions and a nitromethane solvent molecule in the lattice. In the title compound the pyrazole ligand has bound in a more conventional manner than the previously reported µ₂-pyrazolyl structure, with the nucleophilic ligand displacing the chloride ligand and covalently bonding to the metal centre. The pyrazole ligand occupies the fourth site of the platinum(II) centre, while the terpyridine ligand occupies the other three binding sites, giving a nominally square-planar metal chelate. The Pt1—N1, Pt1—N3 and Pt1—N4 bond lengths are approximately equal at 2.022 (6), 2.018 (6) and 2.011 (6) Å, respectively. The Pt1—N2 bond distance is noticeably shorter at 1.922 (6) Å (refer to Fig. 1 for the numbering scheme). The Pt^II ion is displaced from the least-squares plane defined by the four coordinating N atoms by 0.027 (1) Å. As expected, the N1—Pt1—N4 and N3—Pt1—N4 angles are approximately equal at 98.1 (3) and 99.3 (3)°, respectively. Similarly, the N1—Pt1—N2 and N2—Pt1—N3 angles are similar in magnitude at 80.9 (3) and 81.7 (3)°, respectively. These bond lengths show no noteworthy deviation from those previously reported for similar platinum(II) chelates (Field et al., 2007). It would appear that in the absence of a strong base the pyrazole ligand will preferentially bind through the N atom of the ancillary ligand as opposed to through the deprotonated NH atom.

Insofar as the packing of the metal cation is concerned the metal chelate reported in this work is devoid of any Pt···Pt or π···π interactions as the chelates are not arranged parallel to one another. This is likely due to electrostatic repulsion between the highly charged chelates (dicationic as compared to monocationic species with this ligand architecture) (Field et al., 2003). This repulsion overrides any attractive force from Pt···Pt or π···π interactions.

The structure exhibits a number of hydrogen bonds. The perchlorate anions are hydrogen bonded to both the nitromethane solvent in the lattice and the pyrazole NH group. In addition to this there are numerous aromatic–perchlorate C—H···O interactions. In all cases, the perchlorate O atoms act as hydrogen-bond acceptors and the pyrazole N—H and aromatic C—H hydrogens act as donors. There are additional hydrogen bonds in the lattice between the aromatic C—H groups and the perchlorate anions; however, these intereactions are longer than the sum of the van der Waals radii minus 0.1 Å and are therefore likely to be weak hydrogen bonds and are not discussed. Each methyl group of the nitromethane molecule bridges two perchlorate anions through hydrogen bonding. These perchlorate anions are in turn hydrogen bonded to two adjacent platinum(II) chelates. This combination of hydrogen bonds allows for the formation of an extended three-dimensional supramolecular structure. The hydrogen-bond lengths and angles are summarized in Table 1.

These hydrogen-bond lengths are all shorter than the sum of the van der Waals radii minus 0.2 Å. Although hydrogen-bond length does not necessarily correlate linearly with bond strength because of packing constraints in the lattice, it is probable that these bonds are moderate in strength as the bond lengths are considerably shorter than the van der Waals radii of the atoms. The strongly electron-withdrawing nitro group of the solvent will result in a more polar C—H bond than usual and as such could increase the strength of this hydrogen bond, based on simple electrostatic arguments.

The pyrazole ligand is neither coplanar nor perpendicular to the terpyridine ligand; the N1—Pt—N4—N5 torsion angle is 62.4 (6)°. The structure of the metal chelate in vacuo was calculated using density functional theory (DFT) methods at the PBE1PBE/LANL2DZ level of theory. PBE1PBE (Perdew et al., 1997) is a gradient-corrected functional. The LANL2DZ (Hay & Dunning, 1976; Hay & Wadt, 1985a,b,c) basis set makes use of effective core potentials to deal with atoms in the second row of the periodic table and beyond. The DFT calculations were all performed with GAUSSIAN03W (Frisch et al., 2004) with no symmetry constraints imposed on any of the calculations. The X-ray structure coordinates were used for the input structure for a full geometry optimization.

The geometry-optimized cation shows that in vacuo the pyrazole ligand in the lowest-energy conformation is perpendicular to the terpyridine ligand (i.e. 90°). This conformation would lead to minimal non-bonded repulsion between the pyridine hydrogen atoms and the pyrazole ligand and as such is a low-energy structure. This orientation would also allow for π-interaction between the pyrazole ligand and the d_xy orbital of the Pt^II, which is non-bonding with respect to the terpyridine ligand. In the solid-state structure the pyrazole ligand is orientated at an angle of 62.4 (6)° relative to the terpyridine ligand. This deviation from the lowest-energy conformation is seemingly due to hydrogen bonding between the pyrazole NH and the perchlorate anion in the lattice. It would appear that the stability gained through the hydrogen bonding is sufficient for the molecule to adopt a higher-energy conformation.

Aside from the torsion angle of the pyrazole ligand the calculated and experimental structures are very similar, with minimal differences in geometry about the platinum(II) centre and the terpyridine ligand. The Pt—N bond lengths of the calculated and experimental structures are essentially equivalent (within 3σ). These bond lengths are summarized in Table 2. An overlay of the two structures has been calculated using Mercury 2.3 (Fig. 2) and shows that the solid-state structure deviates only slightly from the calculated, lowest energy conformation. This minimal deviation is indicated by the relatively small r.m.s. deviation value of 0.202 Å.

Related literature

For related literature, see: Allen (2002); Bailey & Gray (1992); Field et al. (2003, 2007); Frisch et al. (2004); Hay & Dunning (1976); Hay & Wadt (1985a,b,c); Jaganyi et al. (2008); Perdew et al. (1997); Pitteri et al. (1995); Thurston (2007).

S2. Experimental

The complex, chloro(2,2':6',2"-terpyridine)platinum(II)chloride dihydrate, [Pt(terpy)C1]C1.2H₂O was synthesized as described by literature methods (Pitteri et al., 1995). AgClO₄ (54 mg, 0.26 mmol) was added to [Pt(terpy)C1]C1.2H₂O (70 mg, 0.13 mmol) dissolved in nitromethane (4 ml) and stirred at approximately 323 K for 1 h. The solution turned pale yellow and a white precipitate, AgCl(s), formed. This precipitate was filtered off. Pyrazole (9 mg, 0.13 mmol) was added to the solution which immediately turned dark yellow in colour. Yellow crystals of [Pt(terpy)(pyz)](ClO₄)₂(CH₃NO₂) were grown via vapour diffusion of diethylether into a concentrated nitromethane solution of the platinum(II) terpyridine (yield 69%).

S3. Refinement

The positions of all hydrogen atoms were calculated using the standard riding model of SHELXL97. with C—H(aromatic) distances of 0.93 Å and Uiso = 1.2 Ueq. The only exception is the pyrazole hydrogen atom which was located in the difference Fourier map and allowed to refine isotropically. The perchorlate oxygen atoms were treated with a static disorder model with isotropic oxygen atoms. This method lead to a smaller range of Cl—O bond lengrhs and improved s.u.'s when compared to a dynamic model. Each perchlorate anion shows orientational disorder. Around Cl1 there are two sets of possible positions defined by O1A/O2A/O3A/O4A and O1B/O2B/O3B/O4B, while around Cl2 there are O5A/O6A/O7A/O8A and O5B/O6B/O7B/O8B. The Cl—O distances were restrained to 1.43 (2) Å. The occupancies for the sites A and B around Cl1 converged to 52.1 (5) and 47.9 (5)%, respectively, while around Cl2 the occupancies converged to 63.2 (5) and 36.8 (5)%, respectively.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. Fully labelled displacement ellipsoid plot (30% probability level) of the title compound.
	Fig. 2. Least-squares fit of the non-H atoms of the DFT calculated (dark; blue in the electronic version of the paper) and X-ray crystal structures (light; yellow) of [Pt(terpy)(pyz)]^2+, showing the similar coordination geometry of the platinum(II)–terpyridine unit and the difference in torsion angle of the pyrazole ligand. The r.m.s. deviation of the fit is 0.202 Å.

(1H-Pyrazole-κN²)(2,2':6',2''-terpyridine- κ³N,N',N'')platinum(II) bis(perchlorate) nitromethane monosolvate

Crystal data

[Pt(C15H11N3)(C3H4N2)](ClO4)2·CH3NO2	F(000) = 1464
Mr = 756.38	Dx = 2.032 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4879 reflections
a = 16.351 (5) Å	θ = 2.9–26°
b = 11.534 (4) Å	µ = 5.96 mm^−1
c = 14.075 (5) Å	T = 296 K
β = 111.311 (5)°	Needle, yellow
V = 2472.9 (14) Å^3	0.60 × 0.40 × 0.20 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur2 CCD diffractometer	4877 independent reflections
Radiation source: fine-focus sealed tube	3848 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ω scans at fixed θ angles	θmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan (Blessing, 1995)	h = −20→19
Tmin = 0.124, Tmax = 0.382	k = −14→14
16387 measured reflections	l = −11→17

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)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.091P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.004
4877 reflections	Δρmax = 2.24 e Å^−3
339 parameters	Δρmin = −1.68 e Å^−3
49 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: 0.0028 (3)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.771959 (17)	0.29071 (2)	0.081761 (19)	0.04125 (15)
C1	0.6910 (5)	0.1477 (8)	0.2054 (7)	0.061 (2)
H1	0.6725	0.2169	0.2248	0.073*
C2	0.6705 (6)	0.0482 (9)	0.2401 (7)	0.073 (3)
H2	0.6385	0.0498	0.2829	0.088*
C3	0.6957 (6)	−0.0543 (9)	0.2140 (8)	0.077 (3)
H3	0.6805	−0.1236	0.2369	0.092*
C4	0.7438 (6)	−0.0538 (8)	0.1534 (7)	0.071 (3)
H4	0.7631	−0.1232	0.1353	0.085*
C5	0.7637 (5)	0.0490 (6)	0.1191 (6)	0.0480 (16)
C6	0.8144 (5)	0.0607 (7)	0.0508 (6)	0.0512 (18)
C7	0.8485 (5)	−0.0262 (7)	0.0087 (7)	0.062 (2)
H7	0.8425	−0.1034	0.0240	0.074*
C8	0.8902 (6)	0.0013 (9)	−0.0541 (8)	0.074 (3)
H8	0.9122	−0.0573	−0.0834	0.089*
C9	0.9013 (5)	0.1188 (8)	−0.0766 (6)	0.058 (2)
H9	0.9309	0.1385	−0.1196	0.070*
C11	0.8689 (5)	0.3284 (7)	−0.0477 (6)	0.0513 (18)
C12	0.9104 (5)	0.3813 (7)	−0.1045 (6)	0.059 (2)
H12	0.9396	0.3374	−0.1377	0.071*
C13	0.9087 (6)	0.4989 (8)	−0.1119 (7)	0.068 (2)
H13	0.9366	0.5360	−0.1504	0.082*
C14	0.8650 (6)	0.5631 (8)	−0.0615 (7)	0.064 (2)
H14	0.8636	0.6436	−0.0655	0.076*
C15	0.8238 (6)	0.5059 (7)	−0.0059 (6)	0.0547 (19)
H15	0.7933	0.5488	0.0265	0.066*
C16	0.5985 (7)	0.5049 (9)	0.1483 (8)	0.077 (3)
H16	0.5411	0.5218	0.1419	0.093*
C17	0.6674 (9)	0.5637 (9)	0.2017 (8)	0.090 (4)
H17	0.6693	0.6312	0.2386	0.107*
C10	0.8673 (5)	0.2010 (6)	−0.0333 (6)	0.0480 (18)
C18	0.7394 (7)	0.5028 (7)	0.1920 (7)	0.069 (3)
H18	0.7982	0.5227	0.2237	0.083*
N1	0.7359 (4)	0.1519 (6)	0.1452 (5)	0.0483 (15)
N2	0.8252 (4)	0.1701 (5)	0.0295 (5)	0.0434 (13)
N3	0.8260 (4)	0.3913 (5)	0.0030 (4)	0.0464 (14)
N4	0.7095 (4)	0.4136 (6)	0.1309 (5)	0.0512 (15)
N5	0.6227 (4)	0.4176 (6)	0.1043 (5)	0.0633 (17)
H5	0.5870	0.3691	0.0635	0.076*
Cl1	0.55827 (15)	0.30650 (19)	0.37359 (16)	0.0602 (5)
O1A	0.4833 (8)	0.3207 (17)	0.2852 (10)	0.127 (8)*	0.52 (2)
O2A	0.5643 (12)	0.1910 (9)	0.4103 (15)	0.122 (8)*	0.52 (2)
O3A	0.6361 (7)	0.3313 (14)	0.3532 (11)	0.083 (5)*	0.52 (2)
O4A	0.5575 (10)	0.3835 (14)	0.4524 (10)	0.122 (8)*	0.52 (2)
O1B	0.4887 (9)	0.3697 (17)	0.3023 (15)	0.138 (9)*	0.48 (2)
O2B	0.5630 (17)	0.1906 (11)	0.343 (2)	0.150 (10)*	0.48 (2)
O3B	0.6372 (8)	0.3682 (17)	0.3837 (16)	0.113 (7)*	0.48 (2)
O4B	0.5511 (14)	0.2894 (16)	0.4654 (16)	0.107 (8)*	0.48 (2)
Cl2	0.94052 (15)	0.71134 (14)	0.24900 (17)	0.0531 (5)
O5A	1.0162 (16)	0.7872 (15)	0.2902 (19)	0.142 (8)*	0.632 (18)
O6A	0.8914 (9)	0.7249 (10)	0.1425 (10)	0.093 (5)*	0.632 (18)
O7A	0.9620 (11)	0.5924 (12)	0.2502 (11)	0.089 (4)*	0.632 (18)
O8A	0.8889 (10)	0.7330 (10)	0.3095 (11)	0.080 (4)*	0.632 (18)
O5B	0.992 (2)	0.803 (2)	0.232 (3)	0.109 (10)*	0.368 (18)
O6B	0.8541 (17)	0.7254 (17)	0.261 (2)	0.080 (7)*	0.368 (18)
O7B	0.9970 (14)	0.6104 (16)	0.2836 (15)	0.066 (5)*	0.368 (18)
O8B	0.9714 (19)	0.736 (2)	0.356 (2)	0.111 (9)*	0.368 (18)
C1S	0.4259 (8)	0.1564 (13)	0.0890 (9)	0.107 (4)
H1S1	0.3858	0.0922	0.0733	0.160*
H1S2	0.4646	0.1518	0.1591	0.160*
H1S3	0.4598	0.1539	0.0458	0.160*
N1S	0.3770 (7)	0.2641 (9)	0.0722 (7)	0.081 (2)
O1S	0.3053 (8)	0.2563 (10)	0.0784 (9)	0.126 (3)
O2S	0.4083 (8)	0.3523 (10)	0.0574 (8)	0.156 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.0349 (2)	0.0406 (2)	0.0461 (2)	0.00298 (10)	0.01213 (13)	−0.00055 (11)
C1	0.052 (5)	0.068 (6)	0.069 (5)	0.017 (4)	0.030 (4)	0.021 (4)
C2	0.050 (5)	0.089 (7)	0.081 (6)	−0.004 (5)	0.025 (5)	0.031 (5)
C3	0.073 (6)	0.065 (6)	0.095 (7)	0.000 (5)	0.034 (5)	0.032 (5)
C4	0.056 (5)	0.049 (5)	0.094 (7)	0.001 (4)	0.011 (5)	0.014 (5)
C5	0.040 (4)	0.042 (4)	0.054 (4)	0.003 (3)	0.008 (3)	0.005 (3)
C6	0.044 (4)	0.050 (4)	0.052 (4)	0.008 (3)	0.008 (3)	−0.002 (3)
C7	0.062 (5)	0.043 (4)	0.075 (5)	0.007 (4)	0.019 (4)	−0.011 (4)
C8	0.061 (6)	0.074 (6)	0.080 (6)	0.018 (5)	0.018 (5)	−0.021 (5)
C9	0.049 (5)	0.064 (5)	0.065 (5)	0.013 (4)	0.024 (4)	0.002 (4)
C11	0.035 (4)	0.061 (4)	0.050 (4)	−0.005 (3)	0.006 (3)	−0.001 (4)
C12	0.048 (5)	0.063 (5)	0.067 (5)	0.015 (4)	0.022 (4)	0.009 (4)
C13	0.057 (5)	0.077 (6)	0.069 (5)	−0.008 (4)	0.021 (4)	0.012 (5)
C14	0.064 (5)	0.057 (5)	0.072 (5)	0.005 (4)	0.027 (4)	0.012 (4)
C15	0.061 (5)	0.045 (4)	0.059 (5)	0.002 (3)	0.022 (4)	0.003 (3)
C16	0.078 (7)	0.077 (6)	0.089 (7)	0.024 (5)	0.045 (6)	0.000 (5)
C17	0.156 (12)	0.059 (6)	0.083 (7)	0.020 (7)	0.080 (8)	−0.003 (5)
C10	0.030 (4)	0.055 (5)	0.050 (4)	0.006 (3)	0.004 (3)	0.002 (3)
C18	0.100 (8)	0.048 (5)	0.067 (5)	−0.014 (5)	0.040 (5)	−0.013 (4)
N1	0.028 (3)	0.052 (4)	0.058 (4)	−0.001 (3)	0.008 (3)	0.006 (3)
N2	0.031 (3)	0.044 (3)	0.051 (3)	0.007 (2)	0.010 (3)	−0.003 (3)
N3	0.045 (3)	0.044 (3)	0.051 (3)	0.002 (3)	0.019 (3)	−0.002 (3)
N4	0.054 (4)	0.048 (4)	0.056 (4)	0.005 (3)	0.024 (3)	0.002 (3)
N5	0.050 (4)	0.067 (4)	0.075 (4)	0.018 (3)	0.025 (3)	0.005 (3)
Cl1	0.0514 (12)	0.0708 (13)	0.0538 (11)	0.0038 (9)	0.0137 (9)	0.0015 (9)
Cl2	0.0609 (13)	0.0431 (10)	0.0621 (12)	0.0059 (8)	0.0304 (10)	0.0033 (8)
C1S	0.087 (8)	0.138 (12)	0.090 (8)	0.014 (8)	0.027 (7)	−0.010 (8)
N1S	0.077 (7)	0.090 (7)	0.070 (6)	−0.002 (5)	0.021 (5)	0.001 (5)
O1S	0.092 (7)	0.119 (6)	0.161 (10)	0.027 (7)	0.040 (6)	0.009 (7)
O2S	0.197 (11)	0.130 (9)	0.121 (8)	−0.041 (9)	0.035 (7)	0.030 (7)

Geometric parameters (Å, º)

Pt1—N2	1.922 (6)	C17—H17	0.9300
Pt1—N4	2.011 (6)	C10—N2	1.352 (10)
Pt1—N3	2.018 (6)	C18—N4	1.315 (10)
Pt1—N1	2.022 (6)	C18—H18	0.9300
C1—N1	1.308 (10)	N4—N5	1.331 (8)
C1—C2	1.337 (12)	N5—H5	0.8600
C1—H1	0.9300	Cl1—O4B	1.35 (2)
C2—C3	1.346 (14)	Cl1—O1A	1.403 (8)
C2—H2	0.9300	Cl1—O1B	1.415 (8)
C3—C4	1.353 (13)	Cl1—O2B	1.415 (9)
C3—H3	0.9300	Cl1—O2A	1.420 (9)
C4—C5	1.364 (11)	Cl1—O4A	1.425 (9)
C4—H4	0.9300	Cl1—O3A	1.432 (8)
C5—N1	1.368 (10)	Cl1—O3B	1.434 (8)
C5—C6	1.486 (11)	O1A—O1B	0.61 (3)
C6—N2	1.324 (10)	O2A—O2B	0.94 (3)
C6—C7	1.381 (10)	O2A—O4B	1.43 (2)
C7—C8	1.336 (13)	O3A—O3B	0.60 (2)
C7—H7	0.9300	O4A—O4B	1.112 (18)
C8—C9	1.418 (13)	Cl2—O7A	1.414 (13)
C8—H8	0.9300	Cl2—O5B	1.42 (3)
C9—C10	1.351 (11)	Cl2—O8A	1.422 (13)
C9—H9	0.9300	Cl2—O6A	1.428 (13)
C11—C12	1.366 (11)	Cl2—O8B	1.43 (3)
C11—N3	1.375 (10)	Cl2—O5A	1.45 (2)
C11—C10	1.485 (11)	Cl2—O7B	1.455 (18)
C12—C13	1.360 (12)	Cl2—O6B	1.49 (2)
C12—H12	0.9300	O5A—O5B	0.79 (3)
C13—C14	1.389 (12)	O5A—O8B	1.49 (3)
C13—H13	0.9300	O7A—O7B	0.63 (2)
C14—C15	1.373 (11)	O8A—O6B	0.72 (2)
C14—H14	0.9300	O8A—O8B	1.27 (3)
C15—N3	1.326 (9)	C1S—N1S	1.449 (16)
C15—H15	0.9300	C1S—H1S1	0.9600
C16—C17	1.295 (15)	C1S—H1S2	0.9600
C16—N5	1.316 (10)	C1S—H1S3	0.9600
C16—H16	0.9300	N1S—O2S	1.191 (13)
C17—C18	1.420 (14)	N1S—O1S	1.210 (14)
N2—Pt1—N4	176.7 (2)	O1B—Cl1—O2A	132.3 (11)
N2—Pt1—N3	81.7 (3)	O2B—Cl1—O2A	38.8 (11)
N4—Pt1—N3	99.3 (3)	O4B—Cl1—O4A	47.1 (8)
N2—Pt1—N1	80.9 (3)	O1A—Cl1—O4A	111.4 (8)
N4—Pt1—N1	98.1 (3)	O1B—Cl1—O4A	89.9 (11)
N3—Pt1—N1	162.6 (3)	O2B—Cl1—O4A	147.5 (12)
N1—C1—C2	122.9 (9)	O2A—Cl1—O4A	108.7 (8)
N1—C1—H1	118.6	O4B—Cl1—O3A	127.8 (11)
C2—C1—H1	118.6	O1A—Cl1—O3A	110.7 (8)
C1—C2—C3	120.7 (9)	O1B—Cl1—O3A	107.4 (12)
C1—C2—H2	119.6	O2B—Cl1—O3A	88.6 (13)
C3—C2—H2	119.6	O2A—Cl1—O3A	108.1 (8)
C2—C3—C4	118.3 (8)	O4A—Cl1—O3A	106.9 (7)
C2—C3—H3	120.8	O4B—Cl1—O3B	111.4 (12)
C4—C3—H3	120.8	O1A—Cl1—O3B	119.6 (11)
C3—C4—C5	119.7 (9)	O1B—Cl1—O3B	106.1 (9)
C3—C4—H4	120.2	O2B—Cl1—O3B	110.6 (14)
C5—C4—H4	120.2	O2A—Cl1—O3B	119.2 (11)
C4—C5—N1	120.9 (8)	O4A—Cl1—O3B	82.9 (10)
C4—C5—C6	124.7 (7)	O3A—Cl1—O3B	24.2 (9)
N1—C5—C6	114.4 (6)	O1B—O1A—Cl1	78.6 (11)
N2—C6—C7	119.1 (7)	O2B—O2A—Cl1	70.3 (7)
N2—C6—C5	112.6 (6)	O2B—O2A—O4B	126.5 (12)
C7—C6—C5	128.3 (7)	Cl1—O2A—O4B	56.6 (9)
C8—C7—C6	119.6 (8)	O3B—O3A—Cl1	78.2 (10)
C8—C7—H7	120.2	O4B—O4A—Cl1	63.1 (12)
C6—C7—H7	120.2	O1A—O1B—Cl1	76.4 (10)
C7—C8—C9	120.8 (8)	O2A—O2B—Cl1	70.9 (8)
C7—C8—H8	119.6	O3A—O3B—Cl1	77.7 (10)
C9—C8—H8	119.6	O4A—O4B—Cl1	69.8 (12)
C10—C9—C8	117.5 (8)	O4A—O4B—O2A	129.9 (19)
C10—C9—H9	121.2	Cl1—O4B—O2A	61.1 (10)
C8—C9—H9	121.2	O7A—Cl2—O5B	124.3 (13)
C12—C11—N3	121.5 (8)	O7A—Cl2—O8A	111.2 (7)
C12—C11—C10	124.0 (8)	O5B—Cl2—O8A	119.0 (13)
N3—C11—C10	114.5 (7)	O7A—Cl2—O6A	99.3 (8)
C13—C12—C11	119.3 (9)	O5B—Cl2—O6A	83.3 (15)
C13—C12—H12	120.3	O8A—Cl2—O6A	112.3 (8)
C11—C12—H12	120.3	O7A—Cl2—O8B	101.0 (12)
C12—C13—C14	119.5 (8)	O5B—Cl2—O8B	91.3 (17)
C12—C13—H13	120.2	O8A—Cl2—O8B	52.8 (11)
C14—C13—H13	120.2	O6A—Cl2—O8B	158.4 (12)
C15—C14—C13	119.0 (8)	O7A—Cl2—O5A	114.1 (10)
C15—C14—H14	120.5	O5B—Cl2—O5A	31.9 (13)
C13—C14—H14	120.5	O8A—Cl2—O5A	105.1 (11)
N3—C15—C14	122.0 (8)	O6A—Cl2—O5A	115.2 (11)
N3—C15—H15	119.0	O8B—Cl2—O5A	62.3 (13)
C14—C15—H15	119.0	O7A—Cl2—O7B	25.3 (8)
C17—C16—N5	109.1 (9)	O5B—Cl2—O7B	107.9 (15)
C17—C16—H16	125.5	O8A—Cl2—O7B	112.5 (9)
N5—C16—H16	125.5	O6A—Cl2—O7B	119.0 (9)
C16—C17—C18	105.2 (9)	O8B—Cl2—O7B	82.6 (13)
C16—C17—H17	127.4	O5A—Cl2—O7B	90.2 (12)
C18—C17—H17	127.4	O7A—Cl2—O6B	110.2 (10)
C9—C10—N2	120.1 (7)	O5B—Cl2—O6B	125.4 (14)
C9—C10—C11	127.0 (8)	O8A—Cl2—O6B	28.4 (9)
N2—C10—C11	112.8 (7)	O6A—Cl2—O6B	84.9 (12)
N4—C18—C17	109.0 (10)	O8B—Cl2—O6B	81.2 (14)
N4—C18—H18	125.5	O5A—Cl2—O6B	126.4 (12)
C17—C18—H18	125.5	O7B—Cl2—O6B	124.2 (11)
C1—N1—C5	117.5 (7)	O5B—O5A—Cl2	72 (3)
C1—N1—Pt1	129.6 (6)	O5B—O5A—O8B	124 (4)
C5—N1—Pt1	112.9 (5)	Cl2—O5A—O8B	58.1 (13)
C6—N2—C10	122.7 (6)	O7B—O7A—Cl2	81 (2)
C6—N2—Pt1	119.1 (5)	O6B—O8A—O8B	145 (3)
C10—N2—Pt1	118.0 (5)	O6B—O8A—Cl2	81 (2)
C15—N3—C11	118.6 (7)	O8B—O8A—Cl2	63.9 (13)
C15—N3—Pt1	128.5 (6)	O5A—O5B—Cl2	76 (3)
C11—N3—Pt1	112.9 (5)	O8A—O6B—Cl2	70 (2)
C18—N4—N5	105.2 (7)	O7A—O7B—Cl2	74 (2)
C18—N4—Pt1	131.4 (7)	O8A—O8B—Cl2	63.3 (13)
N5—N4—Pt1	123.4 (5)	O8A—O8B—O5A	111 (2)
C16—N5—N4	111.5 (8)	Cl2—O8B—O5A	59.6 (14)
C16—N5—H5	124.3	N1S—C1S—H1S1	109.5
N4—N5—H5	124.3	N1S—C1S—H1S2	109.5
O4B—Cl1—O1A	120.8 (12)	H1S1—C1S—H1S2	109.5
O4B—Cl1—O1B	115.2 (13)	N1S—C1S—H1S3	109.5
O1A—Cl1—O1B	24.9 (11)	H1S1—C1S—H1S3	109.5
O4B—Cl1—O2B	100.8 (13)	H1S2—C1S—H1S3	109.5
O1A—Cl1—O2B	88.1 (12)	O2S—N1S—O1S	124.4 (13)
O1B—Cl1—O2B	112.9 (10)	O2S—N1S—C1S	121.0 (13)
O4B—Cl1—O2A	62.3 (9)	O1S—N1S—C1S	114.6 (11)
O1A—Cl1—O2A	110.8 (8)
N1—C1—C2—C3	−0.1 (14)	O2B—Cl1—O1B—O1A	6 (4)
C1—C2—C3—C4	1.4 (15)	O2A—Cl1—O1B—O1A	−35 (4)
C2—C3—C4—C5	−1.4 (14)	O4A—Cl1—O1B—O1A	−150 (3)
C3—C4—C5—N1	0.1 (12)	O3A—Cl1—O1B—O1A	102 (3)
C3—C4—C5—C6	−178.8 (8)	O3B—Cl1—O1B—O1A	127 (3)
C4—C5—C6—N2	−179.5 (7)	O4B—O2A—O2B—Cl1	7 (3)
N1—C5—C6—N2	1.6 (10)	O4B—Cl1—O2B—O2A	−6 (2)
C4—C5—C6—C7	1.3 (13)	O1A—Cl1—O2B—O2A	−127.5 (19)
N1—C5—C6—C7	−177.7 (7)	O1B—Cl1—O2B—O2A	−130 (2)
N2—C6—C7—C8	−1.3 (12)	O4A—Cl1—O2B—O2A	2 (3)
C5—C6—C7—C8	177.9 (8)	O3A—Cl1—O2B—O2A	121.8 (19)
C6—C7—C8—C9	1.2 (14)	O3B—Cl1—O2B—O2A	111 (2)
C7—C8—C9—C10	−0.8 (14)	O4B—Cl1—O3B—O3A	137 (2)
N3—C11—C12—C13	−0.6 (12)	O1A—Cl1—O3B—O3A	−74 (3)
C10—C11—C12—C13	−179.3 (8)	O1B—Cl1—O3B—O3A	−97 (3)
C11—C12—C13—C14	0.1 (13)	O2B—Cl1—O3B—O3A	26 (3)
C12—C13—C14—C15	−0.5 (13)	O2A—Cl1—O3B—O3A	68 (3)
C13—C14—C15—N3	1.5 (13)	O4A—Cl1—O3B—O3A	175 (3)
N5—C16—C17—C18	−2.6 (11)	Cl1—O4A—O4B—O2A	12 (2)
C8—C9—C10—N2	0.5 (12)	O1A—Cl1—O4B—O4A	−91.5 (15)
C8—C9—C10—C11	−178.3 (8)	O1B—Cl1—O4B—O4A	−64.0 (17)
C12—C11—C10—C9	−3.7 (13)	O2B—Cl1—O4B—O4A	174.2 (16)
N3—C11—C10—C9	177.6 (7)	O2A—Cl1—O4B—O4A	169.6 (19)
C12—C11—C10—N2	177.4 (7)	O3A—Cl1—O4B—O4A	77.5 (16)
N3—C11—C10—N2	−1.4 (9)	O3B—Cl1—O4B—O4A	56.9 (17)
C16—C17—C18—N4	2.0 (11)	O1A—Cl1—O4B—O2A	98.8 (12)
C2—C1—N1—C5	−1.1 (12)	O1B—Cl1—O4B—O2A	126.4 (13)
C2—C1—N1—Pt1	178.7 (6)	O2B—Cl1—O4B—O2A	4.6 (15)
C4—C5—N1—C1	1.1 (11)	O4A—Cl1—O4B—O2A	−169.6 (19)
C6—C5—N1—C1	−179.9 (7)	O3A—Cl1—O4B—O2A	−92.1 (12)
C4—C5—N1—Pt1	−178.7 (6)	O3B—Cl1—O4B—O2A	−112.7 (13)
C6—C5—N1—Pt1	0.3 (8)	O2B—O2A—O4B—O4A	−21 (5)
N2—Pt1—N1—C1	178.9 (7)	Cl1—O2A—O4B—O4A	−13 (2)
N4—Pt1—N1—C1	−4.3 (7)	O2B—O2A—O4B—Cl1	−8 (3)
N3—Pt1—N1—C1	177.0 (7)	O7A—Cl2—O5A—O5B	117 (3)
N2—Pt1—N1—C5	−1.3 (5)	O8A—Cl2—O5A—O5B	−121 (3)
N4—Pt1—N1—C5	175.5 (5)	O6A—Cl2—O5A—O5B	3 (3)
N3—Pt1—N1—C5	−3.2 (11)	O8B—Cl2—O5A—O5B	−153 (3)
C7—C6—N2—C10	1.0 (11)	O7B—Cl2—O5A—O5B	125 (3)
C5—C6—N2—C10	−178.3 (6)	O6B—Cl2—O5A—O5B	−100 (3)
C7—C6—N2—Pt1	176.5 (6)	O7A—Cl2—O5A—O8B	−90.1 (15)
C5—C6—N2—Pt1	−2.8 (9)	O5B—Cl2—O5A—O8B	153 (3)
C9—C10—N2—C6	−0.7 (12)	O8A—Cl2—O5A—O8B	31.9 (14)
C11—C10—N2—C6	178.3 (6)	O6A—Cl2—O5A—O8B	156.0 (14)
C9—C10—N2—Pt1	−176.2 (6)	O7B—Cl2—O5A—O8B	−81.5 (15)
C11—C10—N2—Pt1	2.9 (8)	O6B—Cl2—O5A—O8B	53.0 (19)
N3—Pt1—N2—C6	−178.2 (6)	O5B—Cl2—O7A—O7B	55 (3)
N1—Pt1—N2—C6	2.4 (5)	O8A—Cl2—O7A—O7B	−98 (2)
N3—Pt1—N2—C10	−2.5 (6)	O6A—Cl2—O7A—O7B	144 (2)
N1—Pt1—N2—C10	178.0 (6)	O8B—Cl2—O7A—O7B	−44 (3)
C14—C15—N3—C11	−2.0 (12)	O5A—Cl2—O7A—O7B	21 (3)
C14—C15—N3—Pt1	179.1 (6)	O6B—Cl2—O7A—O7B	−128 (3)
C12—C11—N3—C15	1.6 (11)	O7A—Cl2—O8A—O6B	−93 (2)
C10—C11—N3—C15	−179.7 (7)	O5B—Cl2—O8A—O6B	112 (3)
C12—C11—N3—Pt1	−179.4 (6)	O6A—Cl2—O8A—O6B	17 (2)
C10—C11—N3—Pt1	−0.6 (8)	O8B—Cl2—O8A—O6B	179 (3)
N2—Pt1—N3—C15	−179.4 (7)	O5A—Cl2—O8A—O6B	143 (2)
N4—Pt1—N3—C15	3.8 (7)	O7B—Cl2—O8A—O6B	−121 (2)
N1—Pt1—N3—C15	−177.5 (7)	O7A—Cl2—O8A—O8B	87.9 (16)
N2—Pt1—N3—C11	1.6 (5)	O5B—Cl2—O8A—O8B	−67 (2)
N4—Pt1—N3—C11	−175.2 (5)	O6A—Cl2—O8A—O8B	−161.9 (14)
N1—Pt1—N3—C11	3.5 (11)	O5A—Cl2—O8A—O8B	−36.0 (16)
C17—C18—N4—N5	−0.7 (9)	O7B—Cl2—O8A—O8B	60.6 (17)
C17—C18—N4—Pt1	179.7 (6)	O6B—Cl2—O8A—O8B	−179 (3)
N3—Pt1—N4—C18	−63.5 (7)	O8B—O5A—O5B—Cl2	−27 (3)
N1—Pt1—N4—C18	116.9 (7)	O7A—Cl2—O5B—O5A	−81 (3)
N3—Pt1—N4—N5	116.9 (6)	O8A—Cl2—O5B—O5A	71 (3)
N1—Pt1—N4—N5	−62.7 (6)	O6A—Cl2—O5B—O5A	−177 (3)
C17—C16—N5—N4	2.4 (11)	O8B—Cl2—O5B—O5A	24 (3)
C18—N4—N5—C16	−1.0 (9)	O7B—Cl2—O5B—O5A	−59 (3)
Pt1—N4—N5—C16	178.7 (6)	O6B—Cl2—O5B—O5A	104 (3)
O4B—Cl1—O1A—O1B	84 (3)	O8B—O8A—O6B—Cl2	2 (4)
O2B—Cl1—O1A—O1B	−175 (3)	O7A—Cl2—O6B—O8A	97 (2)
O2A—Cl1—O1A—O1B	153 (3)	O5B—Cl2—O6B—O8A	−86 (3)
O4A—Cl1—O1A—O1B	32 (3)	O6A—Cl2—O6B—O8A	−164 (2)
O3A—Cl1—O1A—O1B	−87 (3)	O8B—Cl2—O6B—O8A	−1 (2)
O3B—Cl1—O1A—O1B	−62 (3)	O5A—Cl2—O6B—O8A	−47 (3)
O4B—Cl1—O2A—O2B	173 (2)	O7B—Cl2—O6B—O8A	74 (2)
O1A—Cl1—O2A—O2B	58 (2)	O5B—Cl2—O7B—O7A	−134 (3)
O1B—Cl1—O2A—O2B	73 (2)	O8A—Cl2—O7B—O7A	92 (2)
O4A—Cl1—O2A—O2B	−179 (2)	O6A—Cl2—O7B—O7A	−42 (3)
O3A—Cl1—O2A—O2B	−63 (2)	O8B—Cl2—O7B—O7A	137 (3)
O3B—Cl1—O2A—O2B	−87 (2)	O5A—Cl2—O7B—O7A	−161 (2)
O1A—Cl1—O2A—O4B	−114.8 (14)	O6B—Cl2—O7B—O7A	63 (3)
O1B—Cl1—O2A—O4B	−99.9 (17)	O6B—O8A—O8B—Cl2	−2 (5)
O2B—Cl1—O2A—O4B	−173 (2)	O6B—O8A—O8B—O5A	34 (6)
O4A—Cl1—O2A—O4B	8.0 (15)	Cl2—O8A—O8B—O5A	36.4 (15)
O3A—Cl1—O2A—O4B	123.8 (13)	O7A—Cl2—O8B—O8A	−108.4 (12)
O3B—Cl1—O2A—O4B	100.2 (15)	O5B—Cl2—O8B—O8A	126.3 (15)
O4B—Cl1—O3A—O3B	−53 (3)	O6A—Cl2—O8B—O8A	51 (4)
O1A—Cl1—O3A—O3B	117 (3)	O5A—Cl2—O8B—O8A	140.1 (17)
O1B—Cl1—O3A—O3B	91 (3)	O7B—Cl2—O8B—O8A	−125.7 (14)
O2B—Cl1—O3A—O3B	−156 (3)	O6B—Cl2—O8B—O8A	0.6 (13)
O2A—Cl1—O3A—O3B	−122 (3)	O7A—Cl2—O8B—O5A	111.5 (12)
O4A—Cl1—O3A—O3B	−5 (3)	O5B—Cl2—O8B—O5A	−13.8 (17)
O1A—Cl1—O4A—O4B	112.7 (16)	O8A—Cl2—O8B—O5A	−140.1 (17)
O1B—Cl1—O4A—O4B	125.6 (16)	O6A—Cl2—O8B—O5A	−89 (4)
O2B—Cl1—O4A—O4B	−11 (3)	O7B—Cl2—O8B—O5A	94.2 (14)
O2A—Cl1—O4A—O4B	−9.7 (18)	O6B—Cl2—O8B—O5A	−139.5 (14)
O3A—Cl1—O4A—O4B	−126.2 (15)	O5B—O5A—O8B—O8A	−7 (5)
O3B—Cl1—O4A—O4B	−128.2 (17)	Cl2—O5A—O8B—O8A	−38.0 (15)
O4B—Cl1—O1B—O1A	−109 (3)	O5B—O5A—O8B—Cl2	31 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O2A^i	0.86	2.16	2.85 (2)	134 (1)
C1—H1···O3A	0.93	2.47	3.31 (2)	149 (1)
C1S—H1S2···O1A	0.96	2.58	3.20 (2)	123 (1)
C1S—H1S3···O4A^i	0.96	2.46	3.40 (2)	170 (1)
C7—H7···O6A^ii	0.93	2.52	3.36 (2)	150 (1)
C8—H8···O8A^i	0.93	2.47	3.31 (2)	150 (1)
C14—H14···O8A^iii	0.93	2.41	3.08 (2)	128 (1)
C16—H16···O2A^iv	0.93	2.52	3.28 (2)	139 (1)

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