(N-Methyl-4,4'-bipyridinium)(2,2':6',2''-ter­pyridine)­platinum(II) triperchlorate monohydrate

In the title compound, [Pt(C₁₅H₁₁N₃)(C₁₁H₁₁N₂)](ClO₄)₃·H₂O, the PtN₄ coordination plane is distorted from a planar geometry owing to the relatively strong intermolecular terpy-terpy interactions, giving rise to a bent structure with respect to the terpy moiety (terpy = 2,2':6',2''-ter­pyridine). The coord­inated pyridyl plane of N-methyl-4,4'-bipyridinium (MQ) is inclined by 81.7 (1)° with respect to the Pt coordination plane. The dihedral angle between the two pyridyl planes within MQ is 33.5 (2)°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.008 Å
• H-atom completeness 92%
• Disorder in solvent or counterion
• R factor = 0.033
• wR factor = 0.089
• Data-to-parameter ratio = 16.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.29
         From the CIF: _reflns_number_total               6948
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         7666
         Completeness (_total/calc)             90.63%
          Alert C: < 95% complete

PLAT_302  Alert C Anion/Solvent Disorder .........................      24.00 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:C26 H24 Cl3 N5 O13 Pt1
          Atom count from the _atom_site data:  C26 H22 Cl3 N5 O13 Pt1

CELLZ_01
         From the CIF: _cell_formula_units_Z    2
         From the CIF: _chemical_formula_sum  C26 H24 Cl3 N5 O13 Pt
         TEST: Compare cell contents of formula and atom_site data

         atom    Z*formula  cif sites diff
         C         52.00     52.00    0.00
         H         48.00     44.00    4.00
         Cl         6.00      6.00    0.00
         N         10.00     10.00    0.00
         O         26.00     26.00    0.00
         Pt         2.00      2.00    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

 2 Alert Level C = Please check

---

S1. Comment

We previously reported that amidate-bridge Pt^II dimers with a general formula of [Pt₂(NH₃)₄(µ-amidato)₂]²⁺ (amidate = acetamidate, α-pyrrolidinonate, α-pyridonate, etc.) serve as effective H₂-producing catalysts in a well known photosystem consisting of edta, Ru(bpy)₃²⁺ and methylviologen (Sakai et al., 1993) (methylviologen = N,N'-dimethyl-4,4'-bipyridinium dichloride). Up to now, a large number of mono- and dinuclear Pt^II complexes have been prepared in our laboratory, and their catalytic activity has been evaluated by monitoring the photochemical hydrogen production from water under the visible-light illumination (unpublished results). Consequently, we recently found that mononuclear Pt^II complexes of N-methyl-4,4'-bipyridinium (MQ), such as the title complex, (I), exhibit relatively high catalytic function compared to the common mononuclear Pt^II complexes. Here we report the crystal structure of one of such complexe prepared in our laboratory.

The asymmetric unit of (I) consists of a mononuclear Pt^II complex cation, three perchlorate anions and a water molecule. Although various Pt(terpy) complexes have been reported to possess a planar geometry around the Pt(terpy) moiety (Cini et al., 2001; Lowe et al., 2001; Ross et al., 2001; Yam et al., 2001; Yam et al., 2002), the Pt(terpy) moiety in (I) is found to have a bent structure. The dihedral angles between the planes N1/C1—C5 and N2/C6—C10, and between the planes N2/C6—C10 and N3/C11—C15 are 9.2 (3)° and 5.6 (4)°, respectively. Moreover, the dihedral angle between the planes N1/C1—C5 and N3/C11—C15 is 14.2 (3)°. The N—C—C—N torsion angles (Table 1) indicate that the two pyridyl rings at either end of terpy are twisted toward the same side from the N2/C6—C10 plane. Consequently, the N1 atom shows an exceptional behavior, being shifted out of the Pt1/N2—N4 plane by 0.167 (6) Å, while the four-atom r.m.s. deviation from the mean plane is 0.019 Å. The pyridyl plane of MQ, which is bound to the Pt(II) atom, is canted by 81.7 (1)° with respect to the plane Pt1/N2—N4. The pyridyl planes within MQ are twisted by 33.5 (2)° to each other.

The origin of the bent structure discussed above can be understood by looking at the terpy–terpy interactions in the crystal. As shown in Fig. 2a, there are two different types of π–π stacking interactions between the terpy moieties. It also shows that the terpy moiety has a bent structure because the it is pushed down by the two adjacent cations at either end of the unit (as shown by the arrows in Fig. 2 b). The complexes shown in Fig. 2 are related by an inversion centre, where the plane-to-plane separations are 3.43 (2) Å for the stacking given by the C8—C14 moiety, and 3.46 (1) Å for that given by the C1—C3 unit. The Pt···Pt distances at the former and the latter geometries are 7.6411 (7) Å and 8.1543 (7) Å, respectively, confirming the lack of any metal–metal interaction. Details of the photochemical, electrochemical and catalytic properties of (I) will be reported elsewhere.

S2. Experimental

A solution of [PtCl(terpy)]Cl (0.1 mmol, 0.05 g; Howe-Grant & Lippard, 1980) in water (10 ml) and AgClO₄ (0.2 mmol, 0.042 g) was refluxed in the dark for 2 h. To the solution was added MQ(ClO₄) (0.1 mmol, 0.027 g; Sakai et al., 2003) and the mixture was further refluxed for 4 h. After the precipitated AgCl was removed by filtration, the filtrate was evaporated to a total volume of about 5 ml until a small amount of orange precipitate started to deposit. To the solution was then added 2–3 drops of an aqueous saturated sodium perchlorate solution. Leaving the solution to stand overnight afforded (I) as an orange precipitate. The product was finally recrystallized from hot water to give the final product as orange needles (yield: 51%). Analysis calculated for PtO₁₂N₅Cl₃C₂₆H₂₂ (calculated as an anhydrous form): C, 34.78; H, 2.47; N, 7.80%; found: C, 35.79; H, 2.56; N, 7.48%. ¹HNMR (D₂O, 296 K): δ = 4.36 (s, 3H); 7.54–7.60 (m, 6H); 7.70 (d, 2H, J = 5.44 Hz); 8.24–8.42 (m, 8H); 8.41 (d, 2H, J = 6.93 Hz); 8.90 (d, 2H, J = 6.93 Hz); 9.28 p.p.m. (d, 2H, J = 6.76 Hz).

S3. Refinement

One of the three ClO₄⁻ anions shows orientational disorder. Around the Cl2 atom there are two sets of possible positions of (O5A, O6A, O7A, O8A) and (O5B, O6B, O7B, O8B). It was assumed that these disordered O atoms have the same isotropic displacement parameter. Furthermore, Cl—O distances were restrained to 1.43 Å and six O—O distances within each perchlorate ion were restrained to be equal. The site occupation factors for A and B converged at 41.9 (5) and 58.1 (5)%, respectively. A water molecule is also assumed to be disordered over two sites (O13A and O13B). These are assumed to have the same isotropic displacement parameter. The occupation factors of sites A and B converged at 33 (2) and 67 (2)%, respectively. All the H atoms except for those of the water molecule were located at idealized positions as riding atoms (C—H(methyl)=0.96 Å, C—H(aromatic)=0.93 Å). Water H atoms were not located. In the final difference Fourier synthesis, 8 residual peaks in the range 1.1–1.61 e Å⁻³ were observed within 0.99 Å of the Pt atom.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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. Structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. (a) Top view and (b) side view of the intermolecular interactions leading to a bent structure of the terpy moiety. Hydrogen atoms are omitted for clarity.

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

Crystal data

[Pt(C15H11N3)(C11H11N2)](ClO4)3·H2O	F(000) = 896
Mr = 915.94	? # Insert any comments here.
Triclinic, P1	Dx = 1.974 Mg m^−3
a = 10.2302 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.4229 (11) Å	Cell parameters from 5125 reflections
c = 13.6086 (11) Å	θ = 2.3–28.2°
α = 62.287 (1)°	µ = 4.89 mm^−1
β = 83.403 (1)°	T = 296 K
γ = 68.990 (1)°	Needls, orange
V = 1541.3 (2) Å^3	0.2 × 0.09 × 0.03 mm
Z = 2

Data collection

Bruker SMART APEX CCD-detector diffractometer	6948 independent reflections
Radiation source: fine-focus sealed tube	6193 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
Detector resolution: 8.366 pixels mm^-1	θmax = 28.3°, θmin = 1.8°
ω scans	h = −13→13
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001)	k = −17→17
Tmin = 0.337, Tmax = 0.659	l = −17→18
13736 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0448P)^2] where P = (Fo^2 + 2Fc^2)/3
6948 reflections	(Δ/σ)max = 0.002
423 parameters	Δρmax = 1.40 e Å^−3
38 restraints	Δρmin = −1.21 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.

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)

− 5.3674 (0.0126) x + 7.3962 (0.0159) y + 7.8329 (0.0163) z = 7.2121 (0.0241)

* −0.0488 (0.0017) N1 * 0.0578 (0.0020) N2 * −0.0486 (0.0017) N3 * 0.0396 (0.0014) N4 0.0033 (0.0017) Pt1

Rms deviation of fitted atoms = 0.0491

− 5.3053 (0.0180) x + 8.0009 (0.0218) y + 6.4249 (0.0264) z = 6.8310 (0.0391)

Angle to previous plane (with approximate e.s.d.) = 8.54 (0.30)

* 0.0092 (0.0036) C1 * −0.0044 (0.0040) C2 * −0.0054 (0.0041) C3 * 0.0106 (0.0037) C4 * −0.0062 (0.0033) C5 * −0.0038 (0.0032) N1 3.4502 (0.0075) C1_$5 3.4638 (0.0080) C2_$5 3.4647 (0.0075) C3_$5

Rms deviation of fitted atoms = 0.0070

− 6.1161 (0.0159) x + 6.5315 (0.0225) y + 7.0797 (0.0233) z = 5.6155 (0.0386)

Angle to previous plane (with approximate e.s.d.) = 9.21 (1/3)

* −0.0066 (0.0032) C6 * −0.0033 (0.0036) C7 * 0.0087 (0.0037) C8 * −0.0046 (0.0035) C9 * −0.0052 (0.0032) C10 * 0.0110 (0.0030) N2

Rms deviation of fitted atoms = 0.0070

− 6.0816 (0.0176) x + 6.0830 (0.0250) y + 7.9334 (0.0240) z = 6.2250 (0.0352)

Angle to previous plane (with approximate e.s.d.) = 5.56 (0.36)

* −0.0065 (0.0033) C11 * 0.0110 (0.0037) C12 * −0.0044 (0.0040) C13 * −0.0067 (0.0039) C14 * 0.0116 (0.0034) C15 * −0.0049 (0.0030) N3

Rms deviation of fitted atoms = 0.0080

− 5.3053 (0.0180) x + 8.0009 (0.0218) y + 6.4249 (0.0264) z = 6.8310 (0.0391)

Angle to previous plane (with approximate e.s.d.) = 14.15 (1/3)

* 0.0092 (0.0036) C1 * −0.0044 (0.0040) C2 * −0.0054 (0.0041) C3 * 0.0106 (0.0037) C4 * −0.0062 (0.0033) C5 * −0.0038 (0.0032) N1

Rms deviation of fitted atoms = 0.0070

− 6.0816 (0.0176) x + 6.0830 (0.0250) y + 7.9334 (0.0240) z = 6.2250 (0.0352)

Angle to previous plane (with approximate e.s.d.) = 14.15 (1/3)

* −0.0065 (0.0033) C11 * 0.0110 (0.0037) C12 * −0.0044 (0.0040) C13 * −0.0067 (0.0039) C14 * 0.0116 (0.0034) C15 * −0.0049 (0.0030) N3

Rms deviation of fitted atoms = 0.0080

− 5.6135 (0.0153) x + 6.9539 (0.0229) y + 7.9081 (0.0163) z = 6.8763 (0.0276)

Angle to previous plane (with approximate e.s.d.) = 4.44 (0.35)

* 0.0148 (0.0007) N4 * −0.0303 (0.0015) Pt1 * 0.0155 (0.0008) N2 * 0.0001 (0.0000) N3 − 0.1674 (0.0060) N1

Rms deviation of fitted atoms = 0.0185

− 6.1161 (0.0159) x + 6.5315 (0.0225) y + 7.0797 (0.0233) z = 5.6155 (0.0386)

Angle to previous plane (with approximate e.s.d.) = 4.31 (0.34)

* −0.0066 (0.0032) C6 * −0.0033 (0.0036) C7 * 0.0087 (0.0037) C8 * −0.0046 (0.0035) C9 * −0.0052 (0.0032) C10 * 0.0110 (0.0030) N2

Rms deviation of fitted atoms = 0.0070

− 5.6135 (0.0153) x + 6.9539 (0.0229) y + 7.9081 (0.0163) z = 6.8763 (0.0276)

Angle to previous plane (with approximate e.s.d.) = 4.31 (0.34)

* 0.0148 (0.0007) N4 * −0.0303 (0.0015) Pt1 * 0.0155 (0.0008) N2 * 0.0001 (0.0000) N3 − 0.1674 (0.0060) N1

Rms deviation of fitted atoms = 0.0185

− 6.1161 (0.0159) x + 6.5315 (0.0225) y + 7.0797 (0.0233) z = 5.6155 (0.0386)

Angle to previous plane (with approximate e.s.d.) = 4.31 (0.34)

* −0.0066 (0.0032) C6 * −0.0033 (0.0036) C7 * 0.0087 (0.0037) C8 * −0.0046 (0.0035) C9 * −0.0052 (0.0032) C10 * 0.0110 (0.0030) N2

Rms deviation of fitted atoms = 0.0070

− 5.6135 (0.0153) x + 6.9539 (0.0229) y + 7.9081 (0.0163) z = 6.8763 (0.0276)

Angle to previous plane (with approximate e.s.d.) = 4.31 (0.34)

* 0.0148 (0.0007) N4 * −0.0303 (0.0015) Pt1 * 0.0155 (0.0008) N2 * 0.0001 (0.0000) N3 − 0.1674 (0.0060) N1

Rms deviation of fitted atoms = 0.0185

− 6.0816 (0.0176) x + 6.0830 (0.0250) y + 7.9334 (0.0240) z = 6.2250 (0.0352)

Angle to previous plane (with approximate e.s.d.) = 4.44 (0.35)

* −0.0065 (0.0033) C11 * 0.0110 (0.0037) C12 * −0.0044 (0.0040) C13 * −0.0067 (0.0039) C14 * 0.0116 (0.0034) C15 * −0.0049 (0.0030) N3

Rms deviation of fitted atoms = 0.0080

− 5.6135 (0.0153) x + 6.9539 (0.0229) y + 7.9081 (0.0163) z = 6.8763 (0.0276)

Angle to previous plane (with approximate e.s.d.) = 4.44 (0.35)

* 0.0148 (0.0007) N4 * −0.0303 (0.0015) Pt1 * 0.0155 (0.0008) N2 * 0.0001 (0.0000) N3 − 0.1674 (0.0060) N1 0.0454 (0.0069) C6 0.1519 (0.0086) C7 0.2147 (0.0090) C8 0.1518 (0.0078) C9 0.0472 (0.0061) C10 − 0.0058 (0.0066) C11 − 0.0826 (0.0090) C12 − 0.1887 (0.0107) C13 − 0.1857 (0.0100) C14 − 0.0720 (0.0075) C15

Rms deviation of fitted atoms = 0.0185

− 6.0316 (0.0063) x + 6.4222 (0.0082) y + 7.5647 (0.0153) z = 6.0473 (0.0174)

Angle to previous plane (with approximate e.s.d.) = 2.85 (0.26)

* −0.0724 (0.0037) C6 * −0.0201 (0.0044) C7 * 0.0533 (0.0044) C8 * 0.0536 (0.0043) C9 * 0.0025 (0.0042) C10 * −0.0413 (0.0034) N2 * 0.0203 (0.0044) C11 * −0.0317 (0.0046) C12 * −0.0698 (0.0047) C13 * −0.0247 (0.0047) C14 * 0.0624 (0.0039) C15 * 0.0681 (0.0035) N3

Rms deviation of fitted atoms = 0.0487

− 5.6135 (0.0153) x + 6.9539 (0.0229) y + 7.9081 (0.0163) z = 6.8763 (0.0276)

Angle to previous plane (with approximate e.s.d.) = 2.85 (0.26)

* 0.0148 (0.0007) N4 * −0.0303 (0.0015) Pt1 * 0.0155 (0.0008) N2 * 0.0001 (0.0000) N3 − 0.1674 (0.0060) N1

Rms deviation of fitted atoms = 0.0185

4.2032 (0.0195) x + 11.0567 (0.0165) y − 1.5336 (0.0284) z = 8.4017 (0.0261)

Angle to previous plane (with approximate e.s.d.) = 81.74 (0.14)

* −0.0018 (0.0035) C16 * −0.0042 (0.0035) C17 * 0.0111 (0.0035) C18 * −0.0123 (0.0041) C19 * 0.0064 (0.0041) C20 * 0.0008 (0.0034) N4

Rms deviation of fitted atoms = 0.0075

0.6563 (0.0215) x + 12.6263 (0.0088) y + 4.1061 (0.0260) z = 10.9862 (0.0114)

Angle to previous plane (with approximate e.s.d.) = 33.51 (0.18)

* −0.0065 (0.0038) C21 * 0.0029 (0.0038) C22 * 0.0019 (0.0033) C23 * −0.0032 (0.0034) C24 * −0.0003 (0.0034) C25 * 0.0053 (0.0033) N5

Rms deviation of fitted atoms = 0.0039

− 5.7297 (0.0121) x + 7.2711 (0.0151) y + 6.8246 (0.0120) z = 6.1259 (0.0269)

Angle to previous plane (with approximate e.s.d.) = 45.08 (0.14)

* 0.0284 (0.0042) C1 * −0.0930 (0.0049) C2 * −0.1118 (0.0047) C3 * −0.0039 (0.0045) C4 * 0.0874 (0.0044) C5 * 0.0827 (0.0043) C6 * 0.0845 (0.0045) C7 * 0.0038 (0.0045) C8 * −0.0999 (0.0042) C9 * −0.0963 (0.0037) C10 * 0.1060 (0.0036) N1 * 0.0121 (0.0035) N2

Rms deviation of fitted atoms = 0.0787

− 6.0316 (0.0063) x + 6.4222 (0.0082) y + 7.5647 (0.0153) z = 6.0473 (0.0174)

Angle to previous plane (with approximate e.s.d.) = 6.53 (0.19)

* −0.0725 (0.0037) C6 * −0.0201 (0.0044) C7 * 0.0533 (0.0044) C8 * 0.0536 (0.0043) C9 * 0.0025 (0.0042) C10 * 0.0203 (0.0044) C11 * −0.0317 (0.0046) C12 * −0.0698 (0.0047) C13 * −0.0247 (0.0047) C14 * 0.0624 (0.0039) C15 * −0.0413 (0.0034) N2 * 0.0681 (0.0035) N3

Rms deviation of fitted atoms = 0.0487

− 6.0823 (0.0056) x + 6.7543 (0.0065) y + 6.6993 (0.0092) z = 5.3936 (0.0139)

Angle to previous plane (with approximate e.s.d.) = 5.20 (0.12)

* 0.0421 (0.0046) C1 * −0.1384 (0.0049) C2 * −0.2005 (0.0051) C3 * −0.0744 (0.0048) C4 * 0.0776 (0.0043) C5 * 0.0975 (0.0043) C6 * 0.0683 (0.0046) C7 * 0.0202 (0.0046) C8 * −0.0213 (0.0044) C9 * 0.0121 (0.0042) C10 * 0.0096 (0.0043) C11 * −0.1563 (0.0048) C12 * −0.2052 (0.0051) C13 * −0.0567 (0.0048) C14 * 0.1415 (0.0043) C15 * 0.1382 (0.0038) N1 * 0.0873 (0.0036) N2 * 0.1582 (0.0036) N3

Rms deviation of fitted atoms = 0.1129

− 6.1342 (0.0100) x + 6.1695 (0.0160) y + 7.6621 (0.0359) z = 5.9661 (0.0360)

Angle to previous plane (with approximate e.s.d.) = 6.48 (1/5)

* −0.0040 (0.0036) C8 * 0.0256 (0.0041) C9 * −0.0302 (0.0037) C10 * 0.0139 (0.0040) C11 * −0.0025 (0.0043) C12 * −0.0175 (0.0039) C13 * 0.0147 (0.0035) C14 3.4313 (0.0056) C8_$4 3.4017 (0.0055) C9_$4 3.4575 (0.0053) C10_$4 3.4134 (0.0054) C11_$4 3.4298 (0.0056) C12_$4 3.4448 (0.0056) C13_$4 3.4126 (0.0053) C14_$4

Rms deviation of fitted atoms = 0.0182

− 5.6135 (0.0153) x + 6.9539 (0.0229) y + 7.9081 (0.0163) z = 6.8763 (0.0276)

Angle to previous plane (with approximate e.s.d.) = 3.85 (0.31)

* 0.0148 (0.0007) N4 * −0.0303 (0.0015) Pt1 * 0.0155 (0.0008) N2 * 0.0001 (0.0000) N3 − 0.1674 (0.0060) N1

Rms deviation of fitted atoms = 0.0185

4.2032 (0.0195) x + 11.0567 (0.0165) y − 1.5336 (0.0284) z = 8.4017 (0.0261)

Angle to previous plane (with approximate e.s.d.) = 81.74 (0.14)

* −0.0018 (0.0035) C16 * −0.0042 (0.0035) C17 * 0.0111 (0.0035) C18 * −0.0123 (0.0041) C19 * 0.0064 (0.0041) C20 * 0.0008 (0.0034) N4

Rms deviation of fitted atoms = 0.0075

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	0.550368 (15)	0.646105 (14)	0.688224 (13)	0.03936 (7)
Cl1	0.10301 (12)	0.88258 (10)	0.78862 (10)	0.0510 (3)
Cl2	0.44157 (15)	0.96172 (14)	0.19842 (13)	0.0689 (4)
Cl3	1.06173 (15)	0.51272 (12)	0.71701 (12)	0.0598 (3)
O1	0.2375 (5)	0.8271 (5)	0.7600 (4)	0.1009 (18)
O2	0.0516 (6)	0.7918 (5)	0.8633 (6)	0.127 (2)
O3	0.1190 (7)	0.9404 (4)	0.8469 (5)	0.1076 (18)
O4	0.0145 (5)	0.9636 (5)	0.6910 (4)	0.0960 (15)
O5A	0.3246 (11)	0.9568 (13)	0.2581 (11)	0.1195 (14)*	0.419 (5)
O5B	0.3737 (10)	0.9435 (10)	0.3006 (7)	0.1195 (14)*	0.581 (5)
O6A	0.4343 (14)	1.0002 (13)	0.0827 (7)	0.1195 (14)*	0.419 (5)
O6B	0.4107 (10)	0.9064 (9)	0.1428 (8)	0.1195 (14)*	0.581 (5)
O7A	0.4950 (14)	1.0423 (11)	0.2121 (12)	0.1195 (14)*	0.419 (5)
O7B	0.3655 (10)	1.0902 (7)	0.1223 (8)	0.1195 (14)*	0.581 (5)
O8A	0.5558 (11)	0.8464 (9)	0.2469 (11)	0.1195 (14)*	0.419 (5)
O8B	0.5755 (8)	0.9592 (10)	0.2064 (9)	0.1195 (14)*	0.581 (5)
O9	0.9693 (6)	0.5924 (5)	0.6208 (4)	0.1035 (17)
O10	1.1830 (5)	0.4397 (5)	0.6923 (6)	0.1098 (19)
O11	0.9898 (6)	0.4407 (5)	0.8013 (5)	0.0963 (15)
O12	1.1000 (6)	0.5833 (4)	0.7541 (4)	0.0888 (14)
O13A	0.7821 (19)	0.594 (3)	0.494 (2)	0.105 (2)*	0.327 (18)
O13B	0.7882 (9)	0.5310 (13)	0.5341 (10)	0.105 (2)*	0.673 (18)
N1	0.6237 (4)	0.7830 (3)	0.6026 (3)	0.0447 (8)
N2	0.6717 (4)	0.6183 (4)	0.8046 (3)	0.0437 (8)
N3	0.5273 (4)	0.4936 (3)	0.8098 (3)	0.0454 (9)
N4	0.4159 (4)	0.6806 (3)	0.5681 (3)	0.0421 (8)
N5	−0.0659 (4)	0.8239 (3)	0.1539 (3)	0.0481 (9)
C1	0.6037 (6)	0.8590 (5)	0.4934 (5)	0.0562 (12)
H1	0.5426	0.8553	0.4505	0.067*
C2	0.6689 (6)	0.9411 (5)	0.4429 (6)	0.0686 (16)
H2	0.6541	0.9914	0.3667	0.082*
C3	0.7579 (6)	0.9488 (5)	0.5067 (6)	0.0752 (19)
H3	0.8039	1.0040	0.4741	0.090*
C4	0.7769 (5)	0.8732 (5)	0.6190 (6)	0.0621 (14)
H4	0.8344	0.8785	0.6633	0.075*
C5	0.7109 (5)	0.7894 (4)	0.6662 (5)	0.0502 (11)
C6	0.7345 (5)	0.6973 (5)	0.7835 (4)	0.0489 (11)
C7	0.8147 (5)	0.6822 (6)	0.8672 (5)	0.0633 (15)
H7	0.8589	0.7364	0.8546	0.076*
C8	0.8280 (6)	0.5854 (6)	0.9697 (5)	0.0670 (16)
H8	0.8807	0.5753	1.0271	0.080*
C9	0.7654 (5)	0.5028 (5)	0.9900 (5)	0.0598 (14)
H9	0.7768	0.4368	1.0595	0.072*
C10	0.6851 (5)	0.5208 (4)	0.9039 (4)	0.0481 (11)
C11	0.6065 (5)	0.4490 (4)	0.9045 (4)	0.0495 (11)
C12	0.6119 (6)	0.3404 (5)	0.9941 (5)	0.0629 (14)
H12	0.6643	0.3114	1.0593	0.076*
C13	0.5386 (7)	0.2754 (5)	0.9858 (6)	0.0745 (18)
H13	0.5430	0.2015	1.0447	0.089*
C14	0.4587 (6)	0.3216 (5)	0.8888 (6)	0.0656 (16)
H14	0.4091	0.2789	0.8818	0.079*
C15	0.4534 (5)	0.4315 (5)	0.8029 (5)	0.0539 (12)
H15	0.3976	0.4635	0.7386	0.065*
C16	0.2769 (5)	0.7337 (4)	0.5716 (4)	0.0490 (11)
H16	0.2449	0.7538	0.6290	0.059*
C17	0.1811 (5)	0.7590 (4)	0.4928 (4)	0.0467 (10)
H17	0.0859	0.7948	0.4980	0.056*
C18	0.2257 (4)	0.7314 (4)	0.4059 (4)	0.0415 (9)
C19	0.3674 (5)	0.6752 (5)	0.4041 (5)	0.0547 (12)
H19	0.4008	0.6522	0.3486	0.066*
C20	0.4603 (5)	0.6526 (5)	0.4841 (5)	0.0569 (13)
H20	0.5559	0.6172	0.4799	0.068*
C21	0.0649 (5)	0.8244 (5)	0.1287 (4)	0.0548 (12)
H21	0.0905	0.8456	0.0557	0.066*
C22	0.1602 (5)	0.7942 (5)	0.2085 (4)	0.0540 (12)
H22	0.2498	0.7962	0.1896	0.065*
C23	0.1244 (5)	0.7604 (4)	0.3178 (4)	0.0435 (10)
C24	−0.0106 (5)	0.7592 (4)	0.3419 (4)	0.0477 (10)
H24	−0.0383	0.7367	0.4144	0.057*
C25	−0.1033 (5)	0.7916 (4)	0.2577 (4)	0.0505 (11)
H25	−0.1939	0.7909	0.2739	0.061*
C26	−0.1682 (6)	0.8616 (6)	0.0630 (5)	0.0666 (15)
H26A	−0.1187	0.8462	0.0044	0.100*
H26B	−0.2209	0.9457	0.0345	0.100*
H26C	−0.2309	0.8170	0.0916	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.03931 (10)	0.04587 (11)	0.03541 (11)	−0.01474 (7)	−0.00305 (6)	−0.01939 (8)
Cl1	0.0555 (6)	0.0493 (6)	0.0505 (7)	−0.0212 (5)	−0.0006 (5)	−0.0215 (5)
Cl2	0.0690 (8)	0.0795 (9)	0.0614 (9)	−0.0298 (7)	0.0009 (7)	−0.0310 (7)
Cl3	0.0681 (8)	0.0620 (7)	0.0511 (7)	−0.0208 (6)	−0.0014 (6)	−0.0275 (6)
O1	0.076 (3)	0.140 (5)	0.066 (3)	−0.004 (3)	0.005 (2)	−0.056 (3)
O2	0.114 (4)	0.105 (4)	0.142 (6)	−0.075 (4)	−0.001 (4)	−0.011 (4)
O3	0.173 (5)	0.073 (3)	0.086 (4)	−0.036 (3)	−0.020 (4)	−0.043 (3)
O4	0.086 (3)	0.102 (4)	0.075 (3)	−0.018 (3)	−0.026 (2)	−0.025 (3)
O9	0.119 (4)	0.103 (4)	0.067 (3)	−0.033 (3)	−0.026 (3)	−0.019 (3)
O10	0.078 (3)	0.120 (4)	0.168 (6)	−0.028 (3)	0.012 (3)	−0.100 (4)
O11	0.129 (4)	0.085 (3)	0.086 (4)	−0.058 (3)	0.017 (3)	−0.035 (3)
O12	0.123 (4)	0.094 (3)	0.082 (3)	−0.059 (3)	0.015 (3)	−0.052 (3)
N1	0.0456 (19)	0.0450 (19)	0.045 (2)	−0.0176 (16)	0.0011 (16)	−0.0199 (17)
N2	0.0384 (18)	0.057 (2)	0.038 (2)	−0.0132 (16)	−0.0026 (15)	−0.0257 (18)
N3	0.0433 (19)	0.046 (2)	0.046 (2)	−0.0142 (16)	0.0054 (16)	−0.0216 (17)
N4	0.0470 (19)	0.0442 (19)	0.036 (2)	−0.0129 (16)	−0.0051 (15)	−0.0194 (16)
N5	0.050 (2)	0.051 (2)	0.045 (2)	−0.0136 (17)	−0.0112 (17)	−0.0236 (18)
C1	0.061 (3)	0.057 (3)	0.048 (3)	−0.021 (2)	0.003 (2)	−0.021 (2)
C2	0.076 (4)	0.056 (3)	0.066 (4)	−0.025 (3)	0.019 (3)	−0.023 (3)
C3	0.073 (4)	0.062 (3)	0.101 (6)	−0.035 (3)	0.032 (4)	−0.043 (4)
C4	0.053 (3)	0.069 (3)	0.087 (4)	−0.031 (3)	0.014 (3)	−0.048 (3)
C5	0.049 (2)	0.054 (3)	0.060 (3)	−0.020 (2)	0.008 (2)	−0.036 (2)
C6	0.040 (2)	0.067 (3)	0.053 (3)	−0.019 (2)	0.003 (2)	−0.038 (2)
C7	0.044 (3)	0.101 (4)	0.068 (4)	−0.023 (3)	0.001 (2)	−0.058 (4)
C8	0.049 (3)	0.103 (5)	0.060 (4)	−0.013 (3)	−0.007 (2)	−0.054 (4)
C9	0.047 (3)	0.080 (4)	0.045 (3)	−0.005 (2)	−0.007 (2)	−0.033 (3)
C10	0.042 (2)	0.058 (3)	0.038 (2)	−0.006 (2)	−0.0015 (18)	−0.025 (2)
C11	0.043 (2)	0.055 (3)	0.042 (3)	−0.008 (2)	0.0004 (19)	−0.021 (2)
C12	0.058 (3)	0.055 (3)	0.052 (3)	−0.010 (2)	0.006 (2)	−0.014 (2)
C13	0.072 (4)	0.054 (3)	0.075 (4)	−0.019 (3)	0.022 (3)	−0.017 (3)
C14	0.064 (3)	0.053 (3)	0.082 (5)	−0.030 (3)	0.021 (3)	−0.030 (3)
C15	0.051 (3)	0.062 (3)	0.061 (3)	−0.023 (2)	0.010 (2)	−0.036 (3)
C16	0.044 (2)	0.060 (3)	0.046 (3)	−0.013 (2)	−0.0032 (19)	−0.029 (2)
C17	0.041 (2)	0.062 (3)	0.039 (2)	−0.013 (2)	−0.0021 (18)	−0.027 (2)
C18	0.042 (2)	0.046 (2)	0.036 (2)	−0.0158 (18)	−0.0036 (17)	−0.0168 (19)
C19	0.050 (3)	0.075 (3)	0.048 (3)	−0.011 (2)	0.000 (2)	−0.042 (3)
C20	0.041 (2)	0.080 (4)	0.061 (3)	−0.012 (2)	0.000 (2)	−0.047 (3)
C21	0.061 (3)	0.069 (3)	0.037 (3)	−0.021 (3)	0.000 (2)	−0.026 (2)
C22	0.047 (2)	0.075 (3)	0.043 (3)	−0.021 (2)	0.001 (2)	−0.029 (2)
C23	0.049 (2)	0.046 (2)	0.039 (2)	−0.0141 (19)	−0.0056 (18)	−0.0209 (19)
C24	0.050 (2)	0.054 (3)	0.040 (3)	−0.022 (2)	0.0001 (19)	−0.019 (2)
C25	0.047 (2)	0.055 (3)	0.048 (3)	−0.020 (2)	−0.004 (2)	−0.019 (2)
C26	0.061 (3)	0.087 (4)	0.052 (3)	−0.019 (3)	−0.019 (2)	−0.033 (3)

Geometric parameters (Å, º)

Pt1—N2	1.938 (4)	C7—C8	1.373 (9)
Pt1—N3	2.022 (4)	C8—C9	1.378 (9)
Pt1—N1	2.024 (4)	C9—C10	1.386 (7)
Pt1—N4	2.033 (4)	C10—C11	1.457 (7)
Pt1—Pt1^i	7.6411 (7)	C11—C12	1.385 (7)
Pt1—Pt1^ii	8.1543 (7)	C12—C13	1.384 (9)
Cl1—O3	1.397 (5)	C13—C14	1.385 (10)
Cl1—O2	1.407 (5)	C14—C15	1.378 (8)
Cl1—O4	1.412 (5)	C16—C17	1.375 (6)
Cl1—O1	1.418 (5)	C17—C18	1.381 (6)
Cl2—O5A	1.370 (8)	C18—C19	1.377 (7)
Cl2—O8B	1.374 (7)	C18—C23	1.490 (6)
Cl2—O6B	1.404 (7)	C19—C20	1.381 (7)
Cl2—O6A	1.413 (8)	C21—C22	1.358 (7)
Cl2—O5B	1.435 (7)	C22—C23	1.386 (7)
Cl2—O8A	1.458 (8)	C23—C24	1.387 (6)
Cl2—O7A	1.462 (8)	C24—C25	1.375 (7)
Cl2—O7B	1.488 (7)	C1—H1	0.9300
Cl3—O10	1.397 (5)	C2—H2	0.9300
Cl3—O9	1.418 (5)	C3—H3	0.9300
Cl3—O12	1.436 (5)	C4—H4	0.9300
Cl3—O11	1.441 (5)	C7—H7	0.9300
N1—C1	1.341 (6)	C8—H8	0.9300
N1—C5	1.362 (6)	C9—H9	0.9300
N2—C6	1.336 (6)	C12—H12	0.9300
N2—C10	1.351 (6)	C13—H13	0.9300
N3—C15	1.348 (6)	C14—H14	0.9300
N3—C11	1.361 (6)	C15—H15	0.9300
N4—C20	1.346 (6)	C16—H16	0.9300
N4—C16	1.350 (6)	C17—H17	0.9300
N5—C25	1.325 (6)	C19—H19	0.9300
N5—C21	1.344 (6)	C20—H20	0.9300
N5—C26	1.488 (6)	C21—H21	0.9300
C1—C2	1.361 (8)	C22—H22	0.9300
C2—C3	1.388 (10)	C24—H24	0.9300
C3—C4	1.374 (9)	C25—H25	0.9300
C4—C5	1.381 (7)	C26—H26A	0.9600
C5—C6	1.474 (7)	C26—H26B	0.9600
C6—C7	1.375 (7)	C26—H26C	0.9600
N2—Pt1—N3	81.05 (17)	N3—C11—C12	120.7 (5)
N2—Pt1—N1	80.58 (17)	N3—C11—C10	116.0 (4)
N3—Pt1—N1	161.30 (17)	C12—C11—C10	123.3 (5)
N2—Pt1—N4	177.35 (13)	C13—C12—C11	119.5 (6)
N3—Pt1—N4	99.26 (16)	C12—C13—C14	119.2 (5)
N1—Pt1—N4	99.25 (16)	C15—C14—C13	119.3 (6)
N2—Pt1—Pt1^i	54.13 (12)	N3—C15—C14	121.6 (5)
N3—Pt1—Pt1^i	39.78 (12)	N4—C16—C17	122.0 (5)
N1—Pt1—Pt1^i	127.25 (12)	C16—C17—C18	120.2 (4)
N4—Pt1—Pt1^i	124.70 (11)	C19—C18—C17	117.4 (4)
O3—Cl1—O2	106.4 (4)	C19—C18—C23	121.3 (4)
O3—Cl1—O4	111.7 (3)	C17—C18—C23	121.4 (4)
O2—Cl1—O4	112.7 (3)	C18—C19—C20	120.6 (5)
O3—Cl1—O1	108.2 (4)	N4—C20—C19	121.6 (4)
O2—Cl1—O1	108.1 (4)	N5—C21—C22	120.7 (5)
O4—Cl1—O1	109.4 (3)	C21—C22—C23	120.3 (5)
O8B—Cl2—O6B	121.2 (6)	C22—C23—C24	117.8 (4)
O5A—Cl2—O6A	120.8 (7)	C22—C23—C18	121.1 (4)
O8B—Cl2—O5B	111.6 (6)	C24—C23—C18	121.0 (4)
O6B—Cl2—O5B	114.2 (6)	C25—C24—C23	119.5 (5)
O5A—Cl2—O8A	110.8 (7)	N5—C25—C24	121.2 (4)
O6A—Cl2—O8A	106.7 (7)	N1—C1—H1	118.6
O5A—Cl2—O7A	108.1 (7)	C2—C1—H1	118.6
O6A—Cl2—O7A	105.5 (7)	C1—C2—H2	120.5
O8A—Cl2—O7A	103.5 (7)	C3—C2—H2	120.5
O8B—Cl2—O7B	102.7 (6)	C4—C3—H3	120.6
O6B—Cl2—O7B	100.6 (6)	C2—C3—H3	120.6
O5B—Cl2—O7B	103.3 (6)	C3—C4—H4	119.9
O10—Cl3—O9	110.5 (4)	C5—C4—H4	119.9
O10—Cl3—O12	108.9 (3)	C8—C7—H7	120.7
O9—Cl3—O12	108.0 (3)	C6—C7—H7	120.7
O10—Cl3—O11	110.4 (3)	C7—C8—H8	119.1
O9—Cl3—O11	108.5 (3)	C9—C8—H8	119.1
O12—Cl3—O11	110.5 (3)	C8—C9—H9	120.9
C1—N1—C5	118.9 (4)	C10—C9—H9	120.9
C1—N1—Pt1	127.9 (4)	C13—C12—H12	120.3
C5—N1—Pt1	113.0 (3)	C11—C12—H12	120.3
C6—N2—C10	123.6 (4)	C12—C13—H13	120.4
C6—N2—Pt1	118.6 (3)	C14—C13—H13	120.4
C10—N2—Pt1	117.7 (3)	C15—C14—H14	120.4
C15—N3—C11	119.7 (4)	C13—C14—H14	120.4
C15—N3—Pt1	127.6 (4)	N3—C15—H15	119.2
C11—N3—Pt1	112.6 (3)	C14—C15—H15	119.2
C20—N4—C16	118.1 (4)	N4—C16—H16	119.0
C20—N4—Pt1	122.4 (3)	C17—C16—H16	119.0
C16—N4—Pt1	119.5 (3)	C16—C17—H17	119.9
C25—N5—C21	120.5 (4)	C18—C17—H17	119.9
C25—N5—C26	120.7 (4)	C18—C19—H19	119.7
C21—N5—C26	118.9 (4)	C20—C19—H19	119.7
N1—C1—C2	122.7 (6)	N4—C20—H20	119.2
C1—C2—C3	119.0 (6)	C19—C20—H20	119.2
C4—C3—C2	118.8 (5)	N5—C21—H21	119.6
C3—C4—C5	120.1 (6)	C22—C21—H21	119.6
N1—C5—C4	120.4 (5)	C21—C22—H22	119.8
N1—C5—C6	115.3 (4)	C23—C22—H22	119.8
C4—C5—C6	124.2 (5)	C25—C24—H24	120.3
N2—C6—C7	119.2 (5)	C23—C24—H24	120.3
N2—C6—C5	112.2 (4)	N5—C25—H25	119.4
C7—C6—C5	128.5 (5)	C24—C25—H25	119.4
C8—C7—C6	118.5 (6)	N5—C26—H26A	109.5
C7—C8—C9	121.9 (5)	N5—C26—H26B	109.5
C8—C9—C10	118.1 (5)	H26A—C26—H26B	109.5
N2—C10—C9	118.6 (5)	N5—C26—H26C	109.5
N2—C10—C11	112.6 (4)	H26A—C26—H26C	109.5
C9—C10—C11	128.8 (5)	H26B—C26—H26C	109.5
C5—N1—C1—C2	1.2 (8)	N3—C11—C12—C13	1.7 (8)
N1—C1—C2—C3	−1.3 (9)	C10—C11—C12—C13	−177.2 (5)
C1—C2—C3—C4	−0.1 (9)	C11—C12—C13—C14	−1.4 (8)
C2—C3—C4—C5	1.6 (9)	C12—C13—C14—C15	−0.2 (9)
C1—N1—C5—C4	0.3 (7)	C11—N3—C15—C14	−1.6 (7)
C1—N1—C5—C6	−175.9 (4)	C13—C14—C15—N3	1.8 (8)
C3—C4—C5—N1	−1.7 (8)	C20—N4—C16—C17	0.3 (7)
C3—C4—C5—C6	174.2 (5)	N4—C16—C17—C18	−0.7 (8)
C10—N2—C6—C7	−1.9 (7)	C16—C17—C18—C19	1.9 (7)
C10—N2—C6—C5	175.4 (4)	C16—C17—C18—C23	−178.5 (4)
N1—C5—C6—N2	4.0 (6)	C17—C18—C19—C20	−2.7 (8)
C4—C5—C6—N2	−172.1 (4)	C23—C18—C19—C20	177.7 (5)
N1—C5—C6—C7	−179.0 (5)	C16—N4—C20—C19	−1.1 (8)
C4—C5—C6—C7	4.9 (8)	C18—C19—C20—N4	2.3 (9)
N2—C6—C7—C8	0.4 (7)	C25—N5—C21—C22	−1.3 (8)
C5—C6—C7—C8	−176.4 (5)	C26—N5—C21—C22	178.0 (5)
C6—C7—C8—C9	1.1 (8)	N5—C21—C22—C23	1.1 (8)
C7—C8—C9—C10	−1.2 (8)	C21—C22—C23—C24	−0.3 (8)
C6—N2—C10—C9	1.8 (7)	C21—C22—C23—C18	−177.7 (5)
C6—N2—C10—C11	−179.6 (4)	C19—C18—C23—C22	−35.2 (7)
C8—C9—C10—N2	−0.2 (7)	C17—C18—C23—C22	145.2 (5)
C8—C9—C10—C11	−178.5 (5)	C19—C18—C23—C24	147.4 (5)
C15—N3—C11—C12	−0.1 (7)	C17—C18—C23—C24	−32.1 (7)
C15—N3—C11—C10	178.8 (4)	C22—C23—C24—C25	−0.3 (7)
N2—C10—C11—N3	−3.6 (6)	C18—C23—C24—C25	177.1 (4)
C9—C10—C11—N3	174.8 (5)	C21—N5—C25—C24	0.7 (7)
N2—C10—C11—C12	175.2 (4)	C26—N5—C25—C24	−178.6 (5)
C9—C10—C11—C12	−6.3 (8)	C23—C24—C25—N5	0.1 (7)

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