(6,7-Dimethyl-2,3-di-2-pyridyl­quinoxaline)bis­(3-methyl­pyridine)­platinum(II) bis­(hexa­fluoro­phosphate) acetone solvate 0.5-hydrate

The crystal structure of the title compound, [Pt(C₆H₇N)₂(C₂₀H₁₆N₄)](PF₆)₂·C₃H₆O·0.5H₂O, is composed of a bivalent square-planar platinum(II) complex, two PF₆^- counter-ions and solvent mol­ecules. The di-2-pyridylquinoxaline ligands are known to confer an `L shape' on square-planar platinum(II) complexes, which also display inter­calating properties. The structural characterization reported here is a contribution to a wide-ranging study focused on structural and dynamical analyses of these substrates, which may provide better insight into their biological mechanisms and activities. The expected `L-shaped' skeleton of the metallic complex combined with the antiparallel orientation of substituted pyridines (anti conformation) generates chiral objects, found in the solid state as a racemic mixture.

S1. Comment

Many platinum complexes show biological properties related to their reactivity toward duplex DNA (Sundquist & Lippard, 1990). Beyond cisDDP (cisplatinum) activity (Harder & Rosenberg, 1970) due to the formation of covalent DNA complexes, some aromatic species were found to react with DNA through intercalation (Lerman, 1961). The intercalation was demonstrated to occur also for Pt coordination complexes bearing wide, flat aromatic groups (Barton & Lippard, 1979). The great interest in these substrates led to careful characterizations of metal complexes with extended flat moieties both by NMR and by X-ray crystallography; beyond the solid-state structure, the solution dynamic behavior is, of course, also related to their activity (Rotondo et al., 2003). Among the wide variety of complexes obtained using substituted pyridyls as ligands, those containing 6,7-dimethyl-2,3-bis-2-pyridylquinoxaline (DMeDPQ) were found to coordinate Pt^II as a symmetrical seven-membered bis(pyridyl)metal chelate ring (Escuer et al., 1989). The resulting `L-shaped' complexes possess intercalating properties (Cusumano et al., 2004). Moreover, the L-shaped skeleton is prochiral, so that the combination with non-symmetrical ancillary ligands gives optically active complexes. For the [Pt(DMeDPQ)(3-Mepy)₂]²⁺ cation, 3-methylpyridyl (3-Mepy) ligands are roughly perpendicular to the coordination plane. When the methyl groups of the 3-Mepy ligands are on the same side of the coordination plane, two Cs symmetric conformations will be generated (syn-up and syn-down); alternatively, the methyl groups can be placed on opposite sides, resulting in the loss of the mirror plane and the consequent development of two chiral C₁ enantiomeric conformers, anti-C and anti-A (see scheme).

Because the free 3-Mepy rotation is observed in solution, all of the four conformers give rise to an averaged NMR signal (Rotondo et al., 2004). In the solid state only the chiral conformers (perhaps because they are thermodynamically favoured) are detected, and since the space group is centrosymmetric, the crystal contains a racemic mixture. The asymmetric unit of the title compound, (I), is occupied by one Pt^II cation complex, two hexafluorophosphate ions, an acetone molecule and a water molecule with 50% occupancy. The metal is bound to four pyridyl N atoms (Table 1 and Fig. 1). The four coordinating N atoms are positioned around platinum(II) in the typical square-planar geometry, the maximum deviation from the mean plane being 0.028?(5) Å (for N1). All the pyridyl rings are almost perfectly planar, as is the fused quinoline system. The angle between the metal coordination plane and the plane of the fused quinoline system is 75.8?(2)°, leading to the known L-shaped arrangement (Fig. 1). Even though all four pyridyl rings tend to flip away from the coordination plane, the strained DMeDPQ pyridyl rings are less tilted than free pyridyl ligands [the angles of the mean planes with respect to the coordination plane are 71.4?(3) and 70.2 ?(3)° versus 81.3?(3) and 83.1?(3)°, respectively]. This configuration confirms the previous hypothesis of Rotondo et al. (2004) regarding the stiffness of the DMeDPQ ligand often affecting partner ligands.

The crystal packing of (I) is mainly stabilized by conventional and unconventional intermolecular hydrogen interactions of types O—H···F, O—H···N and C—H···F (Table 2 and Fig. 2). The close proximity between an F atom and the metal centre should be noted [Pt1···F4 = 3.503?(1) Å, and the angle between the vector Pt1···F4 and the normal to the coordination plane is 8.1?(2)°]. This interaction characterizes many Pt complexes devoid of steric hindrance in the apical position; F4 is indeed located on the side opposite the cumbersome quinoline system. As is the case with most cationic complexes, the cations of (I) are held together mainly through interactions with anion and solvent groups (Fig. 2).

S2. Experimental

The title complex was prepared as described by Rotondo et al. (2004); colorless crystals suitable for X-ray analysis were obtained by slow evaporation from acetone.

S3. Refinement

The space group of (I) was hypothesized to be centrosymmetric during the data-reduction procedure and finally confirmed by subsequent evaluation (Orpen et al., 1992). All H atoms were treated as riding, with methyl C—H distances of 0.96 Å and aromatic C—H distances of 0.93 Å. The U_iso(H) values were fixed by the `riding-model' technique, being 1.2U_eq(C) for aromatic and 1.5U_eq(C) for methyl H atoms. The water molecule was located in a Fourier difference analysis and refined as a rigid group, while its occupancy factor was calculated by linking it to a free variable; the value found after ten least-squares cycles was fixed in order to reduce the number of parameters.

Computing details

Data collection: XSCANS (Siemens, 1993); cell refinement: XSCANS; data reduction: XPREPW (Bruker, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (Bruker, 1997); software used to prepare material for publication: PARST97 (Nardelli, 1995) and WinGX-PC (Version 1.6.4.05; Farrugia, 1999).

Figures

	Fig. 1. The cation of (I), showing the L-shaped scaffold with the atom-labeling scheme. Displacements ellipsoids are drawn at the 30% probability level for all non-H atoms.
	Fig. 2. The crystal packing of (I), with intermolecular interactions drawn as dotted lines; several atoms have been labeled for ease of correlation with Table 2. H atoms not involved in intermolecular interactions have been omitted for clarity. The atom marked with an asterisk (*) is at the symmetry position (1/2 - x, 1/2 + y, 3/2 - z).

(6,7-Dimethyl-2,3-di-2-pyridylquinoxaline)bis(3-methylpyridine)platinum(II) bis(hexafluorophosphate) acetone solvate 0.5-hydrate

Crystal data

[Pt(C20H16N4)(C6H7N)2](PF6)2·C3H6O·0.5H2O	F(000) = 2068
Mr = 1050.74	Dx = 1.705 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 26 reflections
a = 9.815 (3) Å	θ = 3.9–12.5°
b = 13.105 (3) Å	µ = 3.60 mm^−1
c = 32.039 (7) Å	T = 298 K
β = 96.620 (15)°	Prism, colourless
V = 4093.6 (18) Å^3	0.22 × 0.18 × 0.08 mm
Z = 4

Data collection

Bruker P4 diffractometer	Rint = 0.065
ω scans	θmax = 25°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) (North et al., 1968)	h = −1→11
Tmin = 0.506, Tmax = 0.757	k = −1→15
9390 measured reflections	l = −38→38
7214 independent reflections	3 standard reflections every 196 reflections
3904 reflections with I > 2σ(I)	intensity decay: 6.8%

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.067	w = 1/[σ^2(Fo^2) + (0.023P)^2 + 10.6011P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.122	(Δ/σ)max = 0.002
S = 1.02	Δρmax = 0.83 e Å^−3
7214 reflections	Δρmin = −0.71 e Å^−3
532 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt1	0.49093 (5)	0.20441 (4)	0.615543 (15)	0.03917 (14)
N1	0.4041 (10)	0.3138 (8)	0.6480 (3)	0.048 (3)
C2	0.4703 (14)	0.3991 (10)	0.6602 (4)	0.055 (4)
H2	0.5591	0.4076	0.6534	0.066*
C3	0.4153 (15)	0.4741 (11)	0.6820 (5)	0.066 (4)
H3	0.465	0.5325	0.6904	0.079*
C4	0.2847 (17)	0.4608 (11)	0.6910 (5)	0.075 (5)
H4	0.2436	0.5115	0.7056	0.09*
C5	0.2115 (14)	0.3735 (10)	0.6791 (4)	0.059 (4)
H5	0.1234	0.3638	0.6864	0.071*
C6	0.2721 (13)	0.3012 (11)	0.6560 (3)	0.048 (3)
C7	0.2009 (10)	0.2047 (11)	0.6419 (3)	0.042 (3)
N8	0.1467 (10)	0.1542 (8)	0.6711 (3)	0.048 (3)
C9	0.0776 (13)	0.0685 (10)	0.6601 (4)	0.048 (3)
C10	0.0251 (13)	0.0056 (11)	0.6899 (4)	0.060 (4)
H10	0.0385	0.0244	0.7181	0.072*
C11	−0.0441 (14)	−0.0809 (11)	0.6792 (5)	0.060 (4)
C12	−0.0674 (13)	−0.1143 (10)	0.6357 (5)	0.061 (4)
C13	−0.0168 (15)	−0.0515 (10)	0.6063 (5)	0.066 (4)
H13	−0.0309	−0.0704	0.5782	0.079*
C14	0.0542 (11)	0.0385 (9)	0.6170 (4)	0.040 (3)
N15	0.1067 (10)	0.0959 (8)	0.5869 (3)	0.047 (3)
C16	0.1777 (11)	0.1770 (9)	0.5983 (3)	0.038 (3)
C17	0.2267 (12)	0.2365 (8)	0.5637 (3)	0.037 (3)
C18	0.1371 (12)	0.2734 (9)	0.5310 (4)	0.047 (3)
H18	0.0433	0.2622	0.5302	0.056*
C19	0.1891 (14)	0.3272 (9)	0.4992 (4)	0.060 (4)
H19	0.1292	0.355	0.4776	0.073*
C20	0.3281 (14)	0.3401 (10)	0.4993 (4)	0.062 (4)
H20	0.3644	0.3738	0.4775	0.074*
C21	0.4110 (12)	0.3008 (11)	0.5331 (4)	0.054 (3)
H21	0.5054	0.309	0.5338	0.065*
N22	0.3634 (9)	0.2512 (7)	0.5652 (3)	0.043 (3)
C23	−0.0992 (16)	−0.1473 (11)	0.7129 (4)	0.093 (6)
H23A	−0.0792	−0.1152	0.7399	0.14*
H23B	−0.0562	−0.2131	0.7135	0.14*
H23C	−0.1966	−0.155	0.7065	0.14*
C24	−0.1449 (14)	−0.2096 (12)	0.6238 (4)	0.091 (5)
H24A	−0.0956	−0.2672	0.6363	0.137*
H24B	−0.1554	−0.2168	0.5937	0.137*
H24C	−0.2337	−0.2061	0.6335	0.137*
N25	0.5684 (9)	0.0925 (7)	0.5818 (3)	0.039 (2)
C26	0.5179 (14)	−0.0012 (10)	0.5833 (4)	0.060 (4)
H26	0.4515	−0.0157	0.6009	0.072*
C27	0.5639 (17)	−0.0766 (11)	0.5587 (5)	0.080 (5)
H27	0.53	−0.1425	0.5606	0.096*
C28	0.6566 (15)	−0.0576 (12)	0.5320 (5)	0.075 (5)
H28	0.6858	−0.1092	0.5153	0.09*
C29	0.7076 (13)	0.0403 (11)	0.5300 (4)	0.054 (4)
C30	0.6614 (13)	0.1125 (10)	0.5557 (4)	0.050 (3)
H30	0.6962	0.1784	0.555	0.06*
C31	0.8129 (13)	0.0666 (11)	0.5005 (4)	0.080 (5)
H31A	0.7719	0.1106	0.4786	0.12*
H31B	0.844	0.0052	0.4884	0.12*
H31C	0.8893	0.1008	0.516	0.12*
N32	0.6133 (10)	0.1672 (7)	0.6678 (3)	0.044 (3)
C33	0.7379 (13)	0.2082 (12)	0.6750 (4)	0.060 (4)
H33	0.7711	0.2451	0.6535	0.072*
C34	0.8197 (14)	0.1987 (13)	0.7125 (5)	0.075 (4)
H34	0.9065	0.2282	0.7162	0.09*
C35	0.7717 (15)	0.1449 (11)	0.7447 (4)	0.066 (4)
H35	0.8232	0.1408	0.7709	0.079*
C36	0.6470 (16)	0.0976 (11)	0.7375 (4)	0.062 (4)
C37	0.5671 (14)	0.1115 (10)	0.6993 (4)	0.061 (4)
H37	0.4803	0.0822	0.6951	0.073*
C38	0.5895 (19)	0.0333 (14)	0.7703 (5)	0.123 (7)
H38A	0.6606	−0.0095	0.7839	0.184*
H38B	0.5164	−0.0084	0.7572	0.184*
H38C	0.555	0.0769	0.7908	0.184*
P1	0.8492 (5)	0.4298 (3)	0.58960 (14)	0.0694 (12)
F1	0.9960 (14)	0.4519 (14)	0.5992 (5)	0.246 (9)
F2	0.8824 (15)	0.3148 (8)	0.5899 (4)	0.181 (6)
F3	0.8115 (16)	0.5435 (8)	0.5889 (4)	0.172 (6)
F4	0.7015 (11)	0.3964 (12)	0.5819 (4)	0.200 (6)
F5	0.8687 (15)	0.4354 (10)	0.5433 (3)	0.178 (6)
F6	0.8313 (15)	0.4253 (8)	0.6364 (3)	0.162 (5)
P2	0.1088 (6)	0.3141 (4)	0.82095 (17)	0.0943 (16)
F7	−0.0379 (11)	0.3664 (9)	0.8178 (4)	0.165 (5)
F8	0.2520 (11)	0.2630 (10)	0.8264 (4)	0.174 (6)
F9	0.0507 (15)	0.2211 (11)	0.7999 (7)	0.259 (9)
F10	0.131 (2)	0.3544 (13)	0.7791 (4)	0.252 (9)
F11	0.0813 (17)	0.2771 (16)	0.8635 (5)	0.269 (10)
F12	0.1619 (13)	0.4114 (12)	0.8392 (6)	0.227 (8)
C39	0.632 (3)	0.4384 (16)	0.4268 (7)	0.202 (13)
H39A	0.6939	0.4691	0.4092	0.303*
H39B	0.6128	0.4862	0.448	0.303*
H39C	0.5488	0.4198	0.41	0.303*
C40	0.8350 (17)	0.3230 (16)	0.4351 (6)	0.144 (9)
H40A	0.8966	0.3778	0.4439	0.216*
H40B	0.8297	0.315	0.4052	0.216*
H40C	0.8682	0.2609	0.4486	0.216*
C41	0.697 (2)	0.3465 (14)	0.4470 (5)	0.091 (6)
O42	0.6383 (12)	0.2900 (10)	0.4682 (4)	0.109 (4)
O43	0.325 (2)	0.172 (2)	0.7534 (8)	0.122 (9)	0.5
H43A	0.2505	0.198	0.7689	0.183*	0.5
H43B	0.2843	0.1174	0.7343	0.183*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.0421 (2)	0.0388 (2)	0.0369 (2)	0.0005 (4)	0.00563 (18)	0.0011 (3)
N1	0.050 (7)	0.055 (8)	0.035 (5)	−0.003 (7)	−0.005 (5)	0.003 (6)
C2	0.059 (10)	0.053 (9)	0.056 (9)	0.003 (8)	0.021 (8)	0.001 (8)
C3	0.063 (11)	0.046 (9)	0.088 (12)	−0.005 (9)	0.006 (9)	−0.017 (9)
C4	0.084 (12)	0.054 (10)	0.087 (12)	0.020 (10)	0.007 (10)	−0.040 (9)
C5	0.059 (9)	0.055 (9)	0.066 (10)	−0.005 (8)	0.013 (8)	−0.018 (8)
C6	0.056 (8)	0.046 (8)	0.038 (7)	0.006 (9)	−0.004 (6)	−0.005 (8)
C7	0.027 (6)	0.064 (8)	0.036 (6)	0.001 (8)	0.009 (5)	−0.003 (8)
N8	0.056 (7)	0.051 (7)	0.041 (6)	−0.007 (6)	0.022 (6)	−0.016 (5)
C9	0.050 (9)	0.043 (8)	0.054 (9)	0.009 (7)	0.016 (7)	−0.003 (7)
C10	0.065 (10)	0.066 (10)	0.050 (9)	0.005 (9)	0.011 (8)	0.009 (8)
C11	0.056 (9)	0.062 (10)	0.062 (10)	−0.009 (8)	−0.002 (8)	0.019 (8)
C12	0.047 (9)	0.046 (9)	0.088 (12)	−0.005 (8)	−0.007 (8)	0.017 (9)
C13	0.064 (10)	0.057 (9)	0.071 (11)	−0.008 (9)	−0.011 (9)	−0.011 (8)
C14	0.033 (7)	0.039 (7)	0.046 (8)	−0.003 (6)	−0.004 (6)	0.003 (7)
N15	0.062 (7)	0.041 (6)	0.043 (6)	−0.006 (6)	0.018 (6)	−0.001 (5)
C16	0.038 (7)	0.045 (9)	0.033 (7)	0.005 (6)	0.006 (6)	−0.002 (6)
C17	0.037 (7)	0.037 (7)	0.039 (7)	−0.005 (6)	0.011 (6)	−0.009 (6)
C18	0.032 (7)	0.048 (9)	0.059 (8)	−0.001 (6)	0.000 (6)	0.003 (7)
C19	0.070 (10)	0.046 (9)	0.064 (9)	−0.003 (8)	0.005 (8)	0.023 (7)
C20	0.058 (9)	0.070 (10)	0.057 (9)	−0.012 (8)	0.002 (8)	0.023 (8)
C21	0.051 (8)	0.057 (8)	0.054 (8)	0.004 (9)	0.009 (7)	0.008 (9)
N22	0.040 (6)	0.045 (6)	0.045 (6)	−0.001 (5)	0.012 (5)	0.005 (5)
C23	0.118 (14)	0.090 (12)	0.078 (11)	−0.028 (11)	0.036 (11)	0.020 (10)
C24	0.095 (12)	0.077 (11)	0.107 (12)	−0.021 (12)	0.031 (10)	−0.008 (12)
N25	0.033 (6)	0.043 (7)	0.040 (6)	0.008 (5)	0.002 (5)	−0.003 (5)
C26	0.070 (10)	0.035 (8)	0.076 (11)	0.001 (8)	0.013 (8)	0.011 (8)
C27	0.106 (14)	0.048 (10)	0.092 (13)	0.028 (10)	0.034 (11)	−0.001 (9)
C28	0.073 (12)	0.079 (13)	0.076 (12)	0.021 (10)	0.022 (10)	−0.025 (10)
C29	0.047 (9)	0.060 (10)	0.056 (9)	0.018 (8)	0.011 (7)	0.001 (8)
C30	0.053 (9)	0.037 (8)	0.060 (9)	−0.010 (7)	0.005 (7)	−0.014 (7)
C31	0.070 (10)	0.095 (12)	0.079 (11)	0.017 (10)	0.031 (9)	−0.024 (10)
N32	0.038 (6)	0.037 (6)	0.058 (7)	0.007 (5)	0.011 (5)	−0.003 (5)
C33	0.053 (8)	0.070 (9)	0.055 (8)	−0.002 (10)	0.003 (7)	0.002 (10)
C34	0.052 (9)	0.081 (11)	0.089 (11)	0.011 (11)	−0.006 (9)	−0.002 (12)
C35	0.062 (10)	0.080 (11)	0.052 (9)	−0.001 (9)	−0.014 (8)	0.000 (9)
C36	0.080 (11)	0.060 (10)	0.044 (9)	0.006 (9)	0.001 (9)	0.010 (8)
C37	0.063 (10)	0.061 (9)	0.061 (9)	−0.011 (8)	0.014 (8)	0.012 (8)
C38	0.142 (18)	0.131 (17)	0.092 (14)	−0.033 (15)	−0.008 (13)	0.035 (13)
P1	0.071 (3)	0.065 (3)	0.073 (3)	−0.017 (3)	0.014 (2)	0.005 (2)
F1	0.111 (11)	0.33 (2)	0.28 (2)	−0.094 (14)	−0.052 (12)	0.059 (16)
F2	0.264 (16)	0.092 (9)	0.212 (13)	0.034 (10)	0.135 (12)	0.031 (9)
F3	0.290 (18)	0.078 (8)	0.164 (11)	0.026 (10)	0.094 (12)	0.015 (7)
F4	0.077 (8)	0.274 (18)	0.242 (16)	−0.031 (11)	−0.014 (9)	−0.069 (14)
F5	0.277 (16)	0.182 (12)	0.089 (8)	0.057 (12)	0.077 (10)	0.033 (8)
F6	0.290 (16)	0.127 (9)	0.075 (7)	−0.035 (11)	0.039 (9)	−0.009 (7)
P2	0.098 (4)	0.081 (4)	0.098 (4)	−0.010 (3)	−0.014 (3)	0.008 (3)
F7	0.097 (9)	0.142 (10)	0.251 (15)	0.002 (8)	0.004 (9)	0.019 (10)
F8	0.127 (9)	0.207 (15)	0.176 (11)	0.069 (10)	−0.027 (8)	−0.043 (10)
F9	0.210 (15)	0.118 (11)	0.42 (3)	−0.029 (12)	−0.096 (16)	−0.102 (16)
F10	0.41 (3)	0.242 (18)	0.118 (10)	0.120 (19)	0.095 (14)	0.069 (12)
F11	0.243 (17)	0.38 (3)	0.200 (14)	0.070 (18)	0.085 (13)	0.185 (17)
F12	0.137 (11)	0.191 (15)	0.36 (2)	−0.066 (11)	0.051 (13)	−0.153 (16)
C39	0.29 (3)	0.125 (19)	0.21 (3)	0.09 (2)	0.08 (2)	0.064 (19)
C40	0.087 (14)	0.20 (3)	0.152 (19)	−0.032 (16)	0.048 (13)	0.046 (18)
C41	0.124 (17)	0.096 (15)	0.051 (10)	−0.015 (13)	0.008 (11)	0.010 (10)
O42	0.129 (10)	0.104 (9)	0.100 (9)	−0.013 (10)	0.035 (8)	0.000 (9)
O43	0.12 (2)	0.14 (3)	0.10 (2)	0.007 (19)	−0.003 (16)	0.003 (16)

Geometric parameters (Å, º)

Pt1—N32	2.005 (10)	C26—C27	1.371 (17)
Pt1—N1	2.017 (10)	C26—H26	0.93
Pt1—N22	2.019 (9)	C27—C28	1.342 (18)
Pt1—N25	2.022 (9)	C27—H27	0.93
N1—C2	1.328 (15)	C28—C29	1.382 (18)
N1—C6	1.360 (14)	C28—H28	0.93
C2—C3	1.354 (16)	C29—C30	1.366 (16)
C2—H2	0.93	C29—C31	1.517 (17)
C3—C4	1.359 (18)	C30—H30	0.93
C3—H3	0.93	C31—H31A	0.96
C4—C5	1.381 (17)	C31—H31B	0.96
C4—H4	0.93	C31—H31C	0.96
C5—C6	1.377 (16)	N32—C33	1.331 (14)
C5—H5	0.93	N32—C37	1.365 (14)
C6—C7	1.491 (18)	C33—C34	1.373 (16)
C7—N8	1.308 (13)	C33—H33	0.93
C7—C16	1.436 (14)	C34—C35	1.377 (18)
N8—C9	1.338 (14)	C34—H34	0.93
C9—C10	1.404 (16)	C35—C36	1.368 (18)
C9—C14	1.429 (16)	C35—H35	0.93
C10—C11	1.345 (17)	C36—C37	1.388 (16)
C10—H10	0.93	C36—C38	1.507 (19)
C11—C12	1.452 (18)	C37—H37	0.93
C11—C23	1.534 (16)	C38—H38A	0.96
C12—C13	1.385 (17)	C38—H38B	0.96
C12—C24	1.489 (17)	C38—H38C	0.96
C13—C14	1.393 (16)	P1—F1	1.468 (13)
C13—H13	0.93	P1—F4	1.506 (11)
C14—N15	1.371 (14)	P1—F5	1.518 (10)
N15—C16	1.300 (13)	P1—F6	1.530 (10)
C16—C17	1.478 (14)	P1—F3	1.535 (11)
C17—N22	1.351 (13)	P1—F2	1.542 (11)
C17—C18	1.376 (14)	P2—F12	1.472 (13)
C18—C19	1.382 (15)	P2—F9	1.475 (13)
C18—H18	0.93	P2—F10	1.479 (13)
C19—C20	1.375 (16)	P2—F11	1.499 (13)
C19—H19	0.93	P2—F8	1.549 (11)
C20—C21	1.378 (15)	P2—F7	1.587 (12)
C20—H20	0.93	C39—C41	1.48 (2)
C21—N22	1.345 (13)	C39—H39A	0.96
C21—H21	0.93	C39—H39B	0.96
C23—H23A	0.96	C39—H39C	0.96
C23—H23B	0.96	C40—C41	1.48 (2)
C23—H23C	0.96	C40—H40A	0.96
C24—H24A	0.96	C40—H40B	0.96
C24—H24B	0.96	C40—H40C	0.96
C24—H24C	0.96	C41—O42	1.195 (17)
N25—C26	1.327 (14)	O43—H43A	0.9919
N25—C30	1.332 (13)	O43—H43B	0.992
N32—Pt1—N1	89.4 (4)	C28—C27—H27	119.2
N32—Pt1—N22	175.7 (4)	C26—C27—H27	119.2
N1—Pt1—N22	86.3 (4)	C27—C28—C29	118.6 (14)
N32—Pt1—N25	92.5 (4)	C27—C28—H28	120.7
N1—Pt1—N25	177.1 (4)	C29—C28—H28	120.7
N22—Pt1—N25	91.7 (4)	C30—C29—C28	117.9 (13)
C2—N1—C6	119.4 (12)	C30—C29—C31	121.0 (14)
C2—N1—Pt1	121.8 (9)	C28—C29—C31	121.1 (13)
C6—N1—Pt1	118.7 (9)	N25—C30—C29	122.7 (12)
N1—C2—C3	123.5 (13)	N25—C30—H30	118.6
N1—C2—H2	118.2	C29—C30—H30	118.6
C3—C2—H2	118.2	C29—C31—H31A	109.5
C2—C3—C4	117.3 (14)	C29—C31—H31B	109.5
C2—C3—H3	121.3	H31A—C31—H31B	109.5
C4—C3—H3	121.3	C29—C31—H31C	109.5
C3—C4—C5	121.3 (14)	H31A—C31—H31C	109.5
C3—C4—H4	119.3	H31B—C31—H31C	109.5
C5—C4—H4	119.3	C33—N32—C37	117.8 (11)
C6—C5—C4	118.4 (13)	C33—N32—Pt1	119.7 (9)
C6—C5—H5	120.8	C37—N32—Pt1	122.0 (9)
C4—C5—H5	120.8	N32—C33—C34	123.2 (14)
N1—C6—C5	119.8 (13)	N32—C33—H33	118.4
N1—C6—C7	118.0 (12)	C34—C33—H33	118.4
C5—C6—C7	122.1 (12)	C33—C34—C35	119.1 (14)
N8—C7—C16	122.5 (12)	C33—C34—H34	120.4
N8—C7—C6	115.2 (10)	C35—C34—H34	120.4
C16—C7—C6	121.8 (11)	C36—C35—C34	118.9 (14)
C7—N8—C9	118.1 (11)	C36—C35—H35	120.6
N8—C9—C10	121.9 (13)	C34—C35—H35	120.6
N8—C9—C14	120.3 (12)	C35—C36—C37	119.6 (14)
C10—C9—C14	117.7 (12)	C35—C36—C38	122.4 (14)
C11—C10—C9	122.3 (13)	C37—C36—C38	118.0 (15)
C11—C10—H10	118.8	N32—C37—C36	121.3 (13)
C9—C10—H10	118.8	N32—C37—H37	119.3
C10—C11—C12	121.2 (13)	C36—C37—H37	119.3
C10—C11—C23	120.4 (14)	C36—C38—H38A	109.5
C12—C11—C23	118.4 (13)	C36—C38—H38B	109.5
C13—C12—C11	116.4 (13)	H38A—C38—H38B	109.5
C13—C12—C24	122.4 (14)	C36—C38—H38C	109.5
C11—C12—C24	121.3 (13)	H38A—C38—H38C	109.5
C12—C13—C14	123.0 (13)	H38B—C38—H38C	109.5
C12—C13—H13	118.5	F1—P1—F4	174.1 (10)
C14—C13—H13	118.5	F1—P1—F5	88.0 (9)
N15—C14—C13	120.7 (12)	F4—P1—F5	94.6 (8)
N15—C14—C9	119.9 (11)	F1—P1—F6	91.3 (9)
C13—C14—C9	119.4 (12)	F4—P1—F6	86.2 (8)
C16—N15—C14	118.9 (10)	F5—P1—F6	179.1 (9)
N15—C16—C7	120.0 (11)	F1—P1—F3	92.3 (9)
N15—C16—C17	115.5 (10)	F4—P1—F3	93.1 (9)
C7—C16—C17	124.5 (11)	F5—P1—F3	89.8 (7)
N22—C17—C18	121.4 (11)	F6—P1—F3	89.8 (7)
N22—C17—C16	117.1 (11)	F1—P1—F2	89.5 (9)
C18—C17—C16	121.5 (11)	F4—P1—F2	85.2 (8)
C17—C18—C19	118.9 (11)	F5—P1—F2	90.2 (7)
C17—C18—H18	120.6	F6—P1—F2	90.3 (7)
C19—C18—H18	120.6	F3—P1—F2	178.3 (9)
C20—C19—C18	120.8 (13)	F12—P2—F9	175.7 (11)
C20—C19—H19	119.6	F12—P2—F10	88.3 (11)
C18—C19—H19	119.6	F9—P2—F10	88.3 (11)
C19—C20—C21	116.8 (12)	F12—P2—F11	90.6 (11)
C19—C20—H20	121.6	F9—P2—F11	92.7 (11)
C21—C20—H20	121.6	F10—P2—F11	177.3 (10)
N22—C21—C20	123.8 (12)	F12—P2—F8	93.1 (8)
N22—C21—H21	118.1	F9—P2—F8	89.6 (8)
C20—C21—H21	118.1	F10—P2—F8	91.8 (9)
C21—N22—C17	118.3 (10)	F11—P2—F8	90.7 (8)
C21—N22—Pt1	121.3 (8)	F12—P2—F7	85.9 (8)
C17—N22—Pt1	120.4 (8)	F9—P2—F7	91.6 (8)
C11—C23—H23A	109.5	F10—P2—F7	90.9 (8)
C11—C23—H23B	109.5	F11—P2—F7	86.6 (8)
H23A—C23—H23B	109.5	F8—P2—F7	177.1 (8)
C11—C23—H23C	109.5	C41—C39—H39A	109.5
H23A—C23—H23C	109.5	C41—C39—H39B	109.5
H23B—C23—H23C	109.5	H39A—C39—H39B	109.5
C12—C24—H24A	109.5	C41—C39—H39C	109.5
C12—C24—H24B	109.5	H39A—C39—H39C	109.5
H24A—C24—H24B	109.5	H39B—C39—H39C	109.5
C12—C24—H24C	109.5	C41—C40—H40A	109.5
H24A—C24—H24C	109.5	C41—C40—H40B	109.5
H24B—C24—H24C	109.5	H40A—C40—H40B	109.5
C26—N25—C30	119.4 (11)	C41—C40—H40C	109.5
C26—N25—Pt1	119.2 (9)	H40A—C40—H40C	109.5
C30—N25—Pt1	121.3 (9)	H40B—C40—H40C	109.5
N25—C26—C27	119.8 (13)	O42—C41—C39	123 (2)
N25—C26—H26	120.1	O42—C41—C40	122.1 (19)
C27—C26—H26	120.1	C39—C41—C40	114.5 (18)
C28—C27—C26	121.6 (15)	H43A—O43—H43B	107
N32—Pt1—N1—C2	72.1 (10)	N15—C16—C17—N22	−122.2 (11)
N22—Pt1—N1—C2	−107.1 (9)	C7—C16—C17—N22	59.4 (15)
N32—Pt1—N1—C6	−110.7 (9)	N15—C16—C17—C18	56.3 (15)
N22—Pt1—N1—C6	70.1 (9)	C7—C16—C17—C18	−122.1 (13)
C6—N1—C2—C3	2.8 (19)	N22—C17—C18—C19	−0.6 (17)
Pt1—N1—C2—C3	179.9 (10)	C16—C17—C18—C19	−179.0 (11)
N1—C2—C3—C4	−1 (2)	C17—C18—C19—C20	2.8 (19)
C2—C3—C4—C5	1 (2)	C18—C19—C20—C21	−3 (2)
C3—C4—C5—C6	−3 (2)	C19—C20—C21—N22	0 (2)
C2—N1—C6—C5	−4.4 (18)	C20—C21—N22—C17	1.9 (19)
Pt1—N1—C6—C5	178.4 (9)	C20—C21—N22—Pt1	−175.7 (10)
C2—N1—C6—C7	179.9 (10)	C18—C17—N22—C21	−1.7 (17)
Pt1—N1—C6—C7	2.6 (14)	C16—C17—N22—C21	176.8 (10)
C4—C5—C6—N1	4.3 (19)	C18—C17—N22—Pt1	175.9 (8)
C4—C5—C6—C7	179.8 (12)	C16—C17—N22—Pt1	−5.5 (13)
N1—C6—C7—N8	126.1 (12)	N1—Pt1—N22—C21	109.8 (10)
C5—C6—C7—N8	−49.5 (16)	N25—Pt1—N22—C21	−72.3 (10)
N1—C6—C7—C16	−62.0 (15)	N1—Pt1—N22—C17	−67.8 (9)
C5—C6—C7—C16	122.4 (13)	N25—Pt1—N22—C17	110.1 (9)
C16—C7—N8—C9	6.1 (17)	N32—Pt1—N25—C26	84.4 (9)
C6—C7—N8—C9	177.9 (10)	N22—Pt1—N25—C26	−96.2 (9)
C7—N8—C9—C10	175.2 (11)	N32—Pt1—N25—C30	−100.9 (9)
C7—N8—C9—C14	−5.3 (17)	N22—Pt1—N25—C30	78.5 (9)
N8—C9—C10—C11	−179.8 (12)	C30—N25—C26—C27	1.4 (19)
C14—C9—C10—C11	0.8 (19)	Pt1—N25—C26—C27	176.3 (10)
C9—C10—C11—C12	0 (2)	N25—C26—C27—C28	−2 (2)
C9—C10—C11—C23	179.8 (12)	C26—C27—C28—C29	1 (2)
C10—C11—C12—C13	−1 (2)	C27—C28—C29—C30	1 (2)
C23—C11—C12—C13	179.5 (13)	C27—C28—C29—C31	179.8 (13)
C10—C11—C12—C24	−179.5 (13)	C26—N25—C30—C29	0.1 (18)
C23—C11—C12—C24	1 (2)	Pt1—N25—C30—C29	−174.6 (9)
C11—C12—C13—C14	1 (2)	C28—C29—C30—N25	−1 (2)
C24—C12—C13—C14	179.1 (12)	C31—C29—C30—N25	179.6 (11)
C12—C13—C14—N15	177.4 (12)	N1—Pt1—N32—C33	−94.2 (10)
C12—C13—C14—C9	0 (2)	N25—Pt1—N32—C33	87.9 (10)
N8—C9—C14—N15	2.3 (18)	N1—Pt1—N32—C37	76.9 (10)
C10—C9—C14—N15	−178.2 (11)	N25—Pt1—N32—C37	−100.9 (10)
N8—C9—C14—C13	179.4 (11)	C37—N32—C33—C34	−1 (2)
C10—C9—C14—C13	−1.1 (18)	Pt1—N32—C33—C34	170.1 (12)
C13—C14—N15—C16	−176.9 (11)	N32—C33—C34—C35	0 (2)
C9—C14—N15—C16	0.1 (17)	C33—C34—C35—C36	4 (2)
C14—N15—C16—C7	0.5 (16)	C34—C35—C36—C37	−5 (2)
C14—N15—C16—C17	−178.0 (10)	C34—C35—C36—C38	177.2 (15)
N8—C7—C16—N15	−3.8 (18)	C33—N32—C37—C36	−0.1 (19)
C6—C7—C16—N15	−175.1 (11)	Pt1—N32—C37—C36	−171.4 (10)
N8—C7—C16—C17	174.6 (11)	C35—C36—C37—N32	3 (2)
C6—C7—C16—C17	3.3 (17)	C38—C36—C37—N32	−178.8 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O43—H43A···F8	0.99	2.03	2.79 (3)	132
O43—H43A···F9	0.99	2.32	3.29 (3)	166
O43—H43A···F10	0.99	2.4	3.23 (3)	140
O43—H43B···N8	0.99	2.35	3.00 (3)	122
C3—H3···F9^i	0.93	2.5	3.30 (2)	144
C35—H35···F9^ii	0.93	2.55	3.241 (19)	132
C26—H26···F12^iii	0.93	2.51	3.41 (2)	161
C33—H33···F6	0.93	2.51	3.275 (19)	140

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