Bis­[(2,2-di­methyl-1,3-propane­diamine-[kappa]²N,N')(piperidine-2-car­boxylato-[kappa]²N,O)­platinum(II)] sulfate

The title compound, [Pt(C₆H₁₀NO₂)(C₅H₁₄N₂)]₂(SO₄), crystallizes with two cations in the asymmetric unit. The two complex cations, which have a square-planar Pt^II coordination, are chemically identical but differ slightly in the conformations of their amine groups. A neutral complex, viz. (2,2-di­methyl-1,3-propane­di­amine-[kappa]²N,N')bis(2-piperidine­carb­oxyl­ato-[kappa]N)platinum(II), is shown to form in solution and to change rapidly into the title compound.

S1. Comment

The structural and chemical properties of metal complexes of piperidinecarboxylates have not been studied widely, while those of pyridinecarboxylates have (Gonzales-Vergara et al., 1982; Strearns et al., 1992). Diaminoplatinum(II) complexes of pyridinecarboxylates exhibit significant anticancer activity in vitro (Song et al., 1999 and 2000), even though they do not obey the generally accepted structure–activity relationships (Reedijk,1992) for tumor-active platinum compounds. One molecule of 2-pyridinecarboxylate binds a diaminoplatinum(II) molecule via N,O-coordination, giving a cationic complex, while two molecules of 3- or 4-pyridinecarboxylate bind a diaminoplatinum(II) molecule via N,N-coordination, giving a neutral zwitterionic complex. We investigate here the structure of a Pt^II complex, (I), of a piperidinecarboxylate ligand that has donor N and carboxylate O atoms similar to those found in pyridinecarboxylate complexes.

The reaction of (dmpda-k²N,N')platinum(II) sulfate (where dmpda is 2,2-dimethyl-1,3-propanediamine) and two equivalents of 2-piperidinecarboxylate in D₂O produces a mixture of a neutral complex, [(dmpda-κ²N,N')bis(pip-κN)platinum(II)] (II) (where pip is piperidinecarboxylato), and a cationic complex, [(dmpda-κ²N,N')(pip-κ²N,O)platinum(II)]⁺, in an initial molar ratio of ca 1:0.3 (Scheme 2). This ratio was? assessed by the integration of the ¹H NMR peak at 3.64 p.p.m., corresponding to two methyne protons in the neutral complex, and the peak at 3.90 p.p.m., which is due to the methyne proton in the cationic complex. The signal intensity of the peak at 3.6 p.p.m. decreases, while that at 3.9 p.p.m. increases, so that the molar ratio is reversed in 3 d. This change is faster at higher temperatures, and certainly signifies the transformation of the neutral complex to the cationic complex, accompanied by the loss of one pip ligand. The cationic complex is so stable that its ¹H NMR signals do not change thereafter.

In the crystal structure of (I) there are two chemically identical [(dmpda-κ²N,N')(pip-κ²N,O)Pt]⁺ ions. (Fig. 1). The dmpda ligands in these two molecules are slightly different in their conformations, which reflects the structural flexibility of the dmpda ligand. One pip ligand chelates a Pt atom via a carboxylate O atom and the ring N atom, thus forming a five-membered ring. The sulfate ion is not coordinated to the Pt atom. Pt—N and Pt—O distances (Table 1) fall in the ranges found in other platinum compounds (Goto et al., 1992; Kuroda et al., 1983). The coordination geometries around the Pt atoms are slightly distorted square planar, with the O1—Pt1—N1 [81.50 (17)°] and N4—Pt2—O3 [82.0 (2) °] angles exhibiting maximum deviations for the two Pt complex ions (Table 1). The Pt atom and four coordinated atoms of each Pt complex ion form a well defined least-squares plane, to which the piperidine ring stands almost orthogonal.

Strong hydrogen bonds are observed not only between a platinum complex ion and the sulfate anion but also between complex cations. All N atoms serve as hydrogen-bond donors. Sulfate O atoms (O5, O6 and O7), and carboxylate O atoms (O1 and O3) coordinated with Pt atoms, serve as hydrogen-bond acceptors. Such a net of hydrogen bonds helps construct a layer whose orientation includes the a direction and the bc diagonal. Short interatomic distances that might accommodate hydrogen-bonding interactions are listed in Table 2.

It is noticeable that the distance across the platinum coordination plane in (I), between a methyl group in the amine and methylene groups in the pip ligand, is 5–6 Å. It is unlikely that significant steric hindrance occurs in this distance, even though the thermal motion of the dmpda ligand is considered. However, the steric hindrance is expected to increase severely in the case of the N,N-coordinated complex, (II), between a methyl group of the dmpda ligand and the carboxylate group of a pip ligand across the platinum coordination plane (Scheme 1). This steric hindrance is possibly an important reason for the transformation of (II) to (I). This transformation would diminish remarkably the steric hindrance occurring across the platinum coordination plane of the N,N-coordinated complex. This study on the crystal structure of (I) suggests that the transformation of the neutral complex to the cationic complex may be induced by the steric interaction between the amine and piperidinecarboxylate ligands.

S2. Experimental

To a suspension of (dmpda)PtI₂ (1.17 g, 2.0 mmol) in water (35 ml) was added silver sulfate (0.62 g, 2.0 mmol) in water (65 ml). The reaction mixture was stirred for 6 h, with protection from light. After the precipitate AgI had been filtered off, Ba[pip]₂ (0.78 g, 2.0 mmol) was added to the filtrate. The reaction mixture was stirred for 3 d, at which point the precipitated BaSO₄ was filtered off and the filtrate was evaporated to dryness under reduced pressure. The product was finally recrystallized from methanol and ether. Crystals suitable for X-ray analysis were obtained by slow evaporation of the methanol solution at room temperature over a period of 1 week. After filtration, the crystals were washed with ether. Analysis calculated for C₂₂H₄₈N₆O₈Pt₂S: C 27.88, H 5.07, N 8.87%; found: C 27.78, H 5.02, N 8.75%. ¹H NMR (D₂O): δ 3.90 (t, 1H, CH), 2.94 (m, 2H, CH₂), 2.42 (m, 4H, CH₂-dmpda), 2.25 (m, 1H, CH₂), 2.10 (m, 1H, CH₂), 1.89 (m, 1H, CH₂), 1.60 (m, 3H,CH₂), 0.96 (d, 6H, CH₃-dmpda).

S3. Refinement

The locations of all the H atoms were constrained to ideal positions an refined using a riding model.

Computing details

Data collection: CD4CA0 (Enraf–Nonius, 1989); cell refinement: CD4CA0; data reduction: CADDAT (Enraf-Nonius, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for window (Farrugia, 1998); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of [(dmpda-κ^2N,N')(pip-κ^2N,O)Pt(II)]2SO4. Displacement ellipsoids are shown at the 50% probability level.

Bis[(2,2-Dimethyl-1,3-propanediamine-κ²N,N')(piperidine-2-carboxylato- κ²N,O)platinum(II)] sulfate

Crystal data

[Pt(C5H14N2)(C6H10NO2)]2SO4	Z = 2
Mr = 946.90	F(000) = 916
Triclinic, P1	Dx = 2.049 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0043 (13) Å	Cell parameters from 25 reflections
b = 11.0480 (18) Å	θ = 10.5–14.3°
c = 23.763 (3) Å	µ = 9.22 mm^−1
α = 101.882 (14)°	T = 293 K
β = 91.135 (13)°	Block, pale yellow
γ = 95.216 (12)°	0.25 × 0.2 × 0.12 mm
V = 1535.0 (5) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	4241 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 25.0°, θmin = 0.9°
ω/2θ scans	h = 0→7
Absorption correction: empirical (using intensity measurements) (CADDAT; Enraf–Nonius, 1989)	k = −13→13
Tmin = 0.12, Tmax = 0.33	l = −28→28
5955 measured reflections	3 standard reflections every 3600 min
5387 independent reflections	intensity decay: none

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0187P)^2 + 2.3696P] where P = (Fo^2 + 2Fc^2)/3
5387 reflections	(Δ/σ)max = 0.001
352 parameters	Δρmax = 0.74 e Å^−3
0 restraints	Δρmin = −0.73 e Å^−3

Special details

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.

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
Pt1	0.18372 (4)	0.098463 (19)	0.101509 (9)	0.02370 (7)
Pt2	0.20426 (4)	0.41393 (2)	0.399760 (10)	0.03048 (8)
N1	0.3085 (8)	0.2795 (4)	0.1227 (2)	0.0262 (11)
H1D	0.3543	0.2977	0.1605	0.031*
N2	0.0822 (9)	0.0971 (4)	0.1822 (2)	0.0292 (11)
H2D	0.1895	0.1416	0.2069	0.035*
H2E	−0.0408	0.1383	0.1871	0.035*
N3	0.0665 (9)	−0.0819 (4)	0.0676 (2)	0.0318 (12)
H3D	−0.0576	−0.0801	0.0461	0.038*
H3E	0.1691	−0.1142	0.0433	0.038*
N4	−0.0457 (9)	0.2747 (5)	0.3934 (2)	0.0329 (12)
H4D	−0.1626	0.2916	0.3723	0.039*
N5	0.1344 (9)	0.4512 (5)	0.3224 (2)	0.0357 (13)
H5D	0.2420	0.4239	0.2985	0.043*
H5E	0.0046	0.4071	0.3083	0.043*
N6	0.4705 (9)	0.5449 (5)	0.4073 (2)	0.0373 (13)
H6D	0.5340	0.5556	0.4428	0.045*
H6E	0.5723	0.5159	0.3819	0.045*
O1	0.3039 (7)	0.1158 (4)	0.02385 (17)	0.0330 (10)
O2	0.5715 (9)	0.2254 (4)	−0.0124 (2)	0.0481 (13)
O3	0.2574 (8)	0.3715 (5)	0.4781 (2)	0.0453 (12)
O4	0.0935 (10)	0.2682 (5)	0.5393 (2)	0.0595 (15)
C1	0.4596 (11)	0.2075 (5)	0.0277 (3)	0.0305 (14)
C2	0.5075 (10)	0.2902 (5)	0.0873 (3)	0.0308 (14)
H2	0.6280	0.2556	0.1054	0.037*
C3	0.5917 (12)	0.4244 (6)	0.0863 (3)	0.0399 (16)
H3A	0.6640	0.4635	0.1232	0.048*
H3B	0.7024	0.4247	0.0571	0.048*
C4	0.4042 (13)	0.4989 (6)	0.0737 (3)	0.0474 (19)
H4A	0.4629	0.5843	0.0753	0.057*
H4B	0.3400	0.4647	0.0354	0.057*
C5	0.2263 (12)	0.4953 (6)	0.1170 (3)	0.0434 (17)
H5A	0.1074	0.5439	0.1090	0.052*
H5B	0.2895	0.5313	0.1554	0.052*
C6	0.1314 (11)	0.3609 (6)	0.1143 (3)	0.0349 (15)
H6A	0.0223	0.3593	0.1438	0.042*
H6B	0.0549	0.3285	0.0772	0.042*
C7	0.0304 (12)	−0.0214 (6)	0.1998 (3)	0.0346 (15)
H7A	−0.0430	−0.0055	0.2363	0.041*
H7B	0.1700	−0.0552	0.2063	0.041*
C8	−0.1165 (12)	−0.1186 (6)	0.1576 (3)	0.0390 (16)
C9	−0.3288 (12)	−0.0673 (8)	0.1410 (4)	0.062 (2)
H9A	−0.4056	−0.0352	0.1751	0.093*
H9B	−0.4241	−0.1325	0.1166	0.093*
H9C	−0.2910	−0.0019	0.1208	0.093*
C10	−0.1765 (19)	−0.2271 (7)	0.1879 (4)	0.080 (3)
H10A	−0.2598	−0.1986	0.2213	0.120*
H10B	−0.0417	−0.2577	0.1993	0.120*
H10C	−0.2655	−0.2927	0.1620	0.120*
C11	0.0107 (12)	−0.1712 (5)	0.1049 (3)	0.0349 (15)
H11A	0.1483	−0.1991	0.1175	0.042*
H11B	−0.0785	−0.2432	0.0825	0.042*
C12	0.0892 (12)	0.3028 (7)	0.4939 (3)	0.0406 (16)
C13	−0.1169 (12)	0.2758 (6)	0.4531 (3)	0.0381 (16)
H13	−0.2070	0.3461	0.4638	0.046*
C14	−0.2655 (14)	0.1594 (7)	0.4580 (3)	0.056 (2)
H14A	−0.2783	0.1569	0.4984	0.068*
H14B	−0.4142	0.1646	0.4425	0.068*
C15	−0.1799 (17)	0.0399 (7)	0.4270 (4)	0.066 (3)
H15A	−0.0420	0.0274	0.4460	0.079*
H15B	−0.2890	−0.0296	0.4285	0.079*
C16	−0.1383 (16)	0.0447 (7)	0.3654 (3)	0.057 (2)
H16A	−0.2769	0.0536	0.3456	0.068*
H16B	−0.0808	−0.0316	0.3460	0.068*
C17	0.0322 (13)	0.1558 (6)	0.3644 (3)	0.0461 (18)
H17A	0.1714	0.1442	0.3831	0.055*
H17B	0.0621	0.1591	0.3247	0.055*
C18	0.1153 (11)	0.5830 (6)	0.3210 (3)	0.0396 (16)
H18A	0.0019	0.6135	0.3473	0.048*
H18B	0.0647	0.5880	0.2826	0.048*
C19	0.3333 (11)	0.6683 (6)	0.3370 (3)	0.0393 (16)
C20	0.5131 (13)	0.6364 (7)	0.2942 (3)	0.053 (2)
H20A	0.4563	0.6372	0.2563	0.079*
H20B	0.5560	0.5553	0.2952	0.079*
H20C	0.6410	0.6965	0.3040	0.079*
C21	0.2748 (17)	0.8020 (7)	0.3389 (5)	0.076 (3)
H21A	0.1599	0.8213	0.3659	0.115*
H21B	0.2223	0.8088	0.3014	0.115*
H21C	0.4057	0.8590	0.3505	0.115*
C22	0.4177 (12)	0.6674 (6)	0.3976 (3)	0.0453 (18)
H22A	0.5514	0.7251	0.4066	0.054*
H22B	0.3053	0.6977	0.4243	0.054*
S	−0.3998 (3)	0.27077 (16)	0.25816 (7)	0.0342 (4)
O5	−0.3262 (8)	0.3495 (4)	0.3148 (2)	0.0450 (12)
O6	−0.2283 (10)	0.2803 (6)	0.2166 (3)	0.0690 (17)
O7	−0.6049 (9)	0.3157 (6)	0.2391 (2)	0.0621 (16)
O8	−0.4530 (13)	0.1439 (5)	0.2624 (3)	0.083 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.02617 (13)	0.02439 (12)	0.01915 (12)	−0.00031 (9)	0.00118 (9)	0.00249 (9)
Pt2	0.02765 (15)	0.03900 (15)	0.02299 (14)	−0.00007 (11)	−0.00266 (11)	0.00408 (11)
N1	0.031 (3)	0.033 (3)	0.015 (2)	0.001 (2)	0.001 (2)	0.005 (2)
N2	0.034 (3)	0.028 (3)	0.021 (3)	−0.002 (2)	0.004 (2)	−0.003 (2)
N3	0.036 (3)	0.033 (3)	0.024 (3)	0.000 (2)	0.002 (2)	0.000 (2)
N4	0.034 (3)	0.033 (3)	0.028 (3)	0.001 (2)	−0.006 (2)	0.002 (2)
N5	0.033 (3)	0.045 (3)	0.027 (3)	−0.001 (3)	0.003 (2)	0.005 (2)
N6	0.030 (3)	0.048 (3)	0.033 (3)	−0.006 (3)	−0.006 (2)	0.012 (3)
O1	0.039 (3)	0.037 (2)	0.021 (2)	−0.001 (2)	0.0055 (19)	0.0018 (18)
O2	0.061 (3)	0.044 (3)	0.038 (3)	−0.002 (2)	0.022 (3)	0.006 (2)
O3	0.042 (3)	0.062 (3)	0.030 (3)	−0.010 (2)	−0.008 (2)	0.011 (2)
O4	0.065 (4)	0.074 (4)	0.040 (3)	−0.010 (3)	−0.008 (3)	0.020 (3)
C1	0.034 (4)	0.031 (3)	0.027 (3)	0.005 (3)	0.003 (3)	0.006 (3)
C2	0.026 (3)	0.031 (3)	0.037 (4)	−0.001 (3)	0.001 (3)	0.010 (3)
C3	0.039 (4)	0.035 (3)	0.044 (4)	−0.009 (3)	0.000 (3)	0.009 (3)
C4	0.058 (5)	0.030 (3)	0.056 (5)	−0.004 (3)	0.004 (4)	0.018 (3)
C5	0.045 (4)	0.031 (3)	0.056 (5)	0.010 (3)	0.015 (4)	0.010 (3)
C6	0.029 (3)	0.035 (3)	0.041 (4)	0.007 (3)	0.005 (3)	0.006 (3)
C7	0.045 (4)	0.038 (3)	0.020 (3)	0.000 (3)	0.008 (3)	0.006 (3)
C8	0.046 (4)	0.038 (4)	0.031 (4)	−0.004 (3)	0.008 (3)	0.006 (3)
C9	0.028 (4)	0.075 (5)	0.065 (6)	−0.005 (4)	0.011 (4)	−0.022 (4)
C10	0.135 (10)	0.048 (5)	0.048 (5)	−0.036 (5)	0.026 (6)	0.008 (4)
C11	0.042 (4)	0.022 (3)	0.039 (4)	0.001 (3)	0.005 (3)	0.005 (3)
C12	0.041 (4)	0.052 (4)	0.028 (4)	−0.006 (3)	−0.007 (3)	0.011 (3)
C13	0.039 (4)	0.040 (4)	0.033 (4)	0.002 (3)	0.004 (3)	0.002 (3)
C14	0.059 (5)	0.060 (5)	0.043 (5)	−0.022 (4)	0.001 (4)	0.008 (4)
C15	0.095 (7)	0.044 (4)	0.054 (5)	−0.014 (4)	−0.023 (5)	0.014 (4)
C16	0.084 (6)	0.042 (4)	0.040 (4)	0.002 (4)	−0.001 (4)	−0.001 (3)
C17	0.061 (5)	0.046 (4)	0.027 (4)	0.007 (4)	0.001 (3)	−0.003 (3)
C18	0.030 (4)	0.047 (4)	0.042 (4)	0.004 (3)	−0.005 (3)	0.010 (3)
C19	0.032 (4)	0.037 (4)	0.047 (4)	0.002 (3)	−0.008 (3)	0.007 (3)
C20	0.048 (5)	0.063 (5)	0.049 (5)	−0.003 (4)	0.008 (4)	0.017 (4)
C21	0.081 (7)	0.046 (5)	0.099 (8)	0.006 (5)	−0.036 (6)	0.010 (5)
C22	0.034 (4)	0.040 (4)	0.057 (5)	−0.007 (3)	−0.008 (3)	0.003 (3)
S	0.0296 (8)	0.0421 (8)	0.0278 (8)	0.0047 (7)	−0.0027 (7)	−0.0004 (7)
O5	0.042 (3)	0.050 (3)	0.037 (3)	0.009 (2)	−0.019 (2)	−0.004 (2)
O6	0.059 (4)	0.085 (4)	0.065 (4)	0.016 (3)	0.032 (3)	0.013 (3)
O7	0.040 (3)	0.104 (4)	0.033 (3)	0.030 (3)	−0.010 (2)	−0.015 (3)
O8	0.119 (6)	0.047 (3)	0.077 (5)	−0.012 (4)	−0.004 (4)	0.006 (3)

Geometric parameters (Å, º)

Pt1—N2	2.025 (5)	C7—H7A	0.9700
Pt1—N1	2.028 (5)	C7—H7B	0.9700
Pt1—O1	2.034 (4)	C8—C11	1.518 (9)
Pt1—N3	2.044 (5)	C8—C9	1.519 (11)
Pt2—N5	2.010 (5)	C8—C10	1.541 (9)
Pt2—N4	2.029 (5)	C9—H9A	0.9600
Pt2—N6	2.035 (5)	C9—H9B	0.9600
Pt2—O3	2.038 (5)	C9—H9C	0.9600
N1—C2	1.485 (8)	C10—H10A	0.9600
N1—C6	1.489 (8)	C10—H10B	0.9600
N1—H1D	0.9100	C10—H10C	0.9600
N2—C7	1.465 (7)	C11—H11A	0.9700
N2—H2D	0.9000	C11—H11B	0.9700
N2—H2E	0.9000	C12—C13	1.525 (9)
N3—C11	1.478 (7)	C13—C14	1.523 (9)
N3—H3D	0.9000	C13—H13	0.9800
N3—H3E	0.9000	C14—C15	1.513 (12)
N4—C17	1.473 (8)	C14—H14A	0.9700
N4—C13	1.489 (8)	C14—H14B	0.9700
N4—H4D	0.9100	C15—C16	1.501 (11)
N5—C18	1.478 (8)	C15—H15A	0.9700
N5—H5D	0.9000	C15—H15B	0.9700
N5—H5E	0.9000	C16—C17	1.530 (10)
N6—C22	1.479 (8)	C16—H16A	0.9700
N6—H6D	0.9000	C16—H16B	0.9700
N6—H6E	0.9000	C17—H17A	0.9700
O1—C1	1.302 (7)	C17—H17B	0.9700
O2—C1	1.215 (7)	C18—C19	1.535 (9)
O3—C12	1.315 (8)	C18—H18A	0.9700
O4—C12	1.216 (8)	C18—H18B	0.9700
C1—C2	1.526 (8)	C19—C20	1.513 (10)
C2—C3	1.528 (8)	C19—C22	1.518 (10)
C2—H2	0.9800	C19—C21	1.540 (10)
C3—C4	1.513 (10)	C20—H20A	0.9600
C3—H3A	0.9700	C20—H20B	0.9600
C3—H3B	0.9700	C20—H20C	0.9600
C4—C5	1.501 (10)	C21—H21A	0.9600
C4—H4A	0.9700	C21—H21B	0.9600
C4—H4B	0.9700	C21—H21C	0.9600
C5—C6	1.529 (8)	C22—H22A	0.9700
C5—H5A	0.9700	C22—H22B	0.9700
C5—H5B	0.9700	S—O8	1.433 (6)
C6—H6A	0.9700	S—O6	1.453 (6)
C6—H6B	0.9700	S—O7	1.466 (5)
C7—C8	1.513 (9)	S—O5	1.479 (5)
N2—Pt1—N1	93.06 (19)	C11—C8—C9	111.5 (6)
N2—Pt1—O1	174.38 (17)	C7—C8—C10	106.6 (6)
N1—Pt1—O1	81.50 (17)	C11—C8—C10	106.4 (6)
N2—Pt1—N3	95.47 (19)	C9—C8—C10	109.7 (7)
N1—Pt1—N3	171.36 (19)	C8—C9—H9A	109.5
O1—Pt1—N3	90.01 (18)	C8—C9—H9B	109.5
N5—Pt2—N4	95.0 (2)	H9A—C9—H9B	109.5
N5—Pt2—N6	87.4 (2)	C8—C9—H9C	109.5
N4—Pt2—N6	175.9 (2)	H9A—C9—H9C	109.5
N5—Pt2—O3	176.8 (2)	H9B—C9—H9C	109.5
N4—Pt2—O3	82.0 (2)	C8—C10—H10A	109.5
N6—Pt2—O3	95.6 (2)	C8—C10—H10B	109.5
C2—N1—C6	115.0 (5)	H10A—C10—H10B	109.5
C2—N1—Pt1	105.7 (3)	C8—C10—H10C	109.5
C6—N1—Pt1	110.1 (4)	H10A—C10—H10C	109.5
C2—N1—H1D	108.6	H10B—C10—H10C	109.5
C6—N1—H1D	108.6	N3—C11—C8	114.0 (5)
Pt1—N1—H1D	108.6	N3—C11—H11A	108.8
C7—N2—Pt1	119.9 (4)	C8—C11—H11A	108.8
C7—N2—H2D	107.4	N3—C11—H11B	108.8
Pt1—N2—H2D	107.4	C8—C11—H11B	108.8
C7—N2—H2E	107.4	H11A—C11—H11B	107.7
Pt1—N2—H2E	107.4	O4—C12—O3	122.3 (6)
H2D—N2—H2E	106.9	O4—C12—C13	122.2 (6)
C11—N3—Pt1	121.3 (4)	O3—C12—C13	115.5 (6)
C11—N3—H3D	107.0	N4—C13—C14	112.9 (5)
Pt1—N3—H3D	107.0	N4—C13—C12	109.1 (5)
C11—N3—H3E	107.0	C14—C13—C12	113.9 (6)
Pt1—N3—H3E	107.0	N4—C13—H13	106.8
H3D—N3—H3E	106.7	C14—C13—H13	106.8
C17—N4—C13	113.6 (5)	C12—C13—H13	106.8
C17—N4—Pt2	110.2 (4)	C15—C14—C13	113.7 (7)
C13—N4—Pt2	106.1 (4)	C15—C14—H14A	108.8
C17—N4—H4D	108.9	C13—C14—H14A	108.8
C13—N4—H4D	108.9	C15—C14—H14B	108.8
Pt2—N4—H4D	108.9	C13—C14—H14B	108.8
C18—N5—Pt2	116.3 (4)	H14A—C14—H14B	107.7
C18—N5—H5D	108.2	C16—C15—C14	110.5 (7)
Pt2—N5—H5D	108.2	C16—C15—H15A	109.5
C18—N5—H5E	108.2	C14—C15—H15A	109.5
Pt2—N5—H5E	108.2	C16—C15—H15B	109.5
H5D—N5—H5E	107.4	C14—C15—H15B	109.5
C22—N6—Pt2	115.2 (4)	H15A—C15—H15B	108.1
C22—N6—H6D	108.5	C15—C16—C17	108.4 (6)
Pt2—N6—H6D	108.5	C15—C16—H16A	110.0
C22—N6—H6E	108.5	C17—C16—H16A	110.0
Pt2—N6—H6E	108.5	C15—C16—H16B	110.0
H6D—N6—H6E	107.5	C17—C16—H16B	110.0
C1—O1—Pt1	112.9 (4)	H16A—C16—H16B	108.4
C12—O3—Pt2	113.6 (4)	N4—C17—C16	112.6 (6)
O2—C1—O1	123.6 (6)	N4—C17—H17A	109.1
O2—C1—C2	120.0 (6)	C16—C17—H17A	109.1
O1—C1—C2	116.3 (5)	N4—C17—H17B	109.1
N1—C2—C1	109.3 (5)	C16—C17—H17B	109.1
N1—C2—C3	113.3 (5)	H17A—C17—H17B	107.8
C1—C2—C3	113.9 (5)	N5—C18—C19	114.5 (5)
N1—C2—H2	106.6	N5—C18—H18A	108.6
C1—C2—H2	106.6	C19—C18—H18A	108.6
C3—C2—H2	106.6	N5—C18—H18B	108.6
C4—C3—C2	112.1 (5)	C19—C18—H18B	108.6
C4—C3—H3A	109.2	H18A—C18—H18B	107.6
C2—C3—H3A	109.2	C20—C19—C22	110.8 (6)
C4—C3—H3B	109.2	C20—C19—C18	112.4 (6)
C2—C3—H3B	109.2	C22—C19—C18	111.1 (6)
H3A—C3—H3B	107.9	C20—C19—C21	110.0 (7)
C5—C4—C3	110.1 (6)	C22—C19—C21	105.6 (6)
C5—C4—H4A	109.6	C18—C19—C21	106.7 (6)
C3—C4—H4A	109.6	C19—C20—H20A	109.5
C5—C4—H4B	109.6	C19—C20—H20B	109.5
C3—C4—H4B	109.6	H20A—C20—H20B	109.5
H4A—C4—H4B	108.2	C19—C20—H20C	109.5
C4—C5—C6	109.8 (5)	H20A—C20—H20C	109.5
C4—C5—H5A	109.7	H20B—C20—H20C	109.5
C6—C5—H5A	109.7	C19—C21—H21A	109.5
C4—C5—H5B	109.7	C19—C21—H21B	109.5
C6—C5—H5B	109.7	H21A—C21—H21B	109.5
H5A—C5—H5B	108.2	C19—C21—H21C	109.5
N1—C6—C5	112.3 (5)	H21A—C21—H21C	109.5
N1—C6—H6A	109.1	H21B—C21—H21C	109.5
C5—C6—H6A	109.1	N6—C22—C19	115.3 (6)
N1—C6—H6B	109.1	N6—C22—H22A	108.4
C5—C6—H6B	109.1	C19—C22—H22A	108.4
H6A—C6—H6B	107.9	N6—C22—H22B	108.4
N2—C7—C8	115.3 (5)	C19—C22—H22B	108.4
N2—C7—H7A	108.5	H22A—C22—H22B	107.5
C8—C7—H7A	108.5	O8—S—O6	110.7 (4)
N2—C7—H7B	108.5	O8—S—O7	107.5 (4)
C8—C7—H7B	108.5	O6—S—O7	109.4 (4)
H7A—C7—H7B	107.5	O8—S—O5	111.1 (4)
C7—C8—C11	111.2 (6)	O6—S—O5	110.2 (4)
C7—C8—C9	111.2 (6)	O7—S—O5	107.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O7^i	0.91	1.85	2.745 (7)	169
N2—H2D···O7^i	0.90	2.18	2.987 (7)	150
N2—H2E···O6	0.90	2.03	2.882 (8)	158
N3—H3D···O1^ii	0.90	2.15	3.022 (7)	163
N3—H3E···O2^iii	0.90	2.12	2.974 (7)	158
N4—H4D···O5	0.91	1.91	2.787 (7)	161
N5—H5D···O7^i	0.90	1.95	2.817 (7)	160
N5—H5E···O5	0.90	2.05	2.877 (7)	152
N6—H6D···O3^iv	0.90	2.20	3.074 (7)	163
N6—H6E···O5^i	0.90	2.31	3.100 (8)	147

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