A one-dimensional iodine-bridged Pt^II/Pt^IV mixed-valence complex, catena-poly[[[bis­(ethyl­ene­diamine)­platinum(II)]-[mu]-iodo-[bis­(ethyl­ene­di­amine)platinum(IV)]-[mu]-iodo] hydrogenphosphate dihydrogenphosphate iodide trihydrate]

The title compound, {[Pt^IIPt^IVI₂(C₂H₈N₂)₄](HPO₄)(H₂PO₄)I·3H₂O}_n, has a chain structure composed of square-planar [Pt(en)₂]²⁺ and elongated octa­hedral trans-[PtI₂(en)₂]²⁺ cations (en is ethyl­ene­diamine) stacked alternately along the c axis and bridged by the I atoms; a three-dimensionally valence-ordered system exists with respect to the Pt sites. The title compound also has a unique cyclic tetra­mer structure composed of two hydrogenphosphate and two dihydrogenphosphate ions connected by strong hydrogen bonds [O...O = 2.522 (10), 2.567 (10) and 2.569 (11) Å]. The Pt and I atoms form a zigzag ...I-Pt^IV-I...Pt^II... chain, with Pt^IV-I bond distances of 2.6997 (7) and 2.6921 (7) Å, inter­atomic Pt^II...I distances of 3.3239 (8) and 3.2902 (7) Å, and Pt^IV-I...Pt^II angles of 154.52 (3) and 163.64 (3)°. The structural parameters indicating the mixed-valence state of platinum, expressed by [delta] = (Pt^IV-I)/(Pt^II-I), are 0.812 and 0.818 for the two independent I atoms.

S1. Comment

The title compound, (I), is a member of the family of one-dimensional halogen-bridged mixed-valence metal complexes, formulated as [M^II(AA)₂][M^IVX₂(AA)₂]Y₄ [M^II/M^IV = Pt^II/Pt^IV, Pd^II/Pd^IV, Ni^II/Ni^IV, Pd^II/Pt^IV and Ni^II/Pt^IV; X = Cl, Br and I; AA = NH₂(CH₂)₂NH₂ etc.; Y = ClO₄⁻, HSO₄⁻, X⁻ etc.], hereafter abbreviated as MX-chain compounds, which are typical mixed-valence compounds belonging to class II in the classification by Robin & Day (1967). MX-chain compounds have been attracting much interest as a result of the one-dimensional mixed-valence electron system. Unusual physical properties, such as a remarkably dichroic intense absorption band attributed to an intervalence charge-transfer (IVCT) transition from M^II to M^IV in the mixed-valence state, progressive Raman scattering in resonance with the IVCT band, and photoinduced mid-gap absorption bands due to soliton and polaron formation, are characteristics of the one-dimensional mixed-valence system.

The metal–halogen distances in crystals of MX-chain compounds characterize these physical properties on the basis of the mixed-valence state. The valence ordering of the metal site in the mixed-valence state is also structurally interesting because of the relation to the soliton and polaron formation as a mismatch of the valence alternation. The present X-ray crystallographic analysis of the title compound, (I), [Pt(en)₂][PtI₂(en)₂](HPO₄)(H₂PO₄)I·3H₂O (en is ethylenediamine), has been performed in order to gather further structural information on these MX-chain compounds.

As shown in Fig. 1, the structure of (I) is built up from columns composed of square-planar [Pt(en)₂]²⁺ and elongated octahedral trans-[PtI₂(en)₂]²⁺ cations stacked alternately, bridged by the I atoms, along the c axis. Pt1 and Pt2 sites are assigned to Pt^IV and Pt^II, respectively. The Pt and I atoms are occupied at general sites in the unit cell, and form an infinite zigzag ···I–Pt^IV–I···Pt^II··· chain, with Pt^IV–I distances of 2.6997 (7) and 2.6921 (7) Å, Pt^II···I distances of 3.3239 (8) and 3.2902 (7) Å (Table 1).

There is no disorder of the bridging halogen atoms in (I), although the other MX-chain compounds have disordered structures. The I atoms are not located at the exact mid-point between the two adjacent Pt atoms but at a position displaced somewhat from the mid-point to the Pt1 site. The valence ordering of the Pt site in (I) belongs to one of three different classes of the order–disorder problem pointed out by Keller (1982); the structure of (I) can be regarded as a three-dimensionally valence-ordered structure. This type of valence ordering of the Pt site is rare. Five compounds belonging to this type were described in the review of Keller (1982). After published the review, the re-refinements and re-analyses for these five compounds have shown that they belong to another class, that is, one-dimensionally valence-ordered structures with the other two directions in a disordered state; these compounds are [Pt(tn)₂][PtX₂(tn)₂](BF₄)₄ (tn is 1,3-propanediamine and X = Cl and Br) and [Pt(tn)₂][PtBr₂(tn)₂](ClO₄)₄, re-analyzed by Cannas et al. (1983), and [Pt(en)₂][PtX₂(en)₂](ClO₄)₄ (X = Cl and Br), re-analyzed by Huckett et al. (1993) and Toriumi et al. (1993). The valence ordering of the Pt site in a majority of the MX-chain compounds belongs to this one-dimensionally valence ordered structure. So far, on the other hand, a few MX-chain compounds, [Pt(tn)₂][PtI₂(tn)₂](ClO₄)₄ (Cannas et al., 1984) and [Pt(NH₃)₄][PtI₂(NH₃)₄](HSO₄)₄·2H₂O (Tanaka et al., 1986), have been reported anew as belonging to the three-dimensionally valence-ordered system to which (I) belongs.

The structural parameter indicating the mixed-valence state of the Pt atom, expressed by δ = (Pt^IV–I)/(Pt^II···I), is 0.812 and 0.818 for atoms I1 and I2, respectively. These values are much smaller than those of [Pt(pn)₂][PtI₂(pn)₂](ClO₄)₄ (0.937; pn is 1,2-propanediamine; Breer et al., 1978), [Pt(pn)₂][PtI₂(pn)₂]I₄ (0.940; Endres et al., 1980), [Pt(tn)₂][PtI₂(tn)₂](ClO₄)₄ (0.95; Cannas et al., 1984) and [Pt(en)₂][PtI₂(en)₂](ClO₄)₄ (0.919; Endres et al., 1979), and somewhat smaller than that of [Pt(NH₃)₄][PtI₂(NH₃)₄](HSO₄)₄·2H₂O (0.834; Tanaka et al., 1986).

The hydrogen bonds, listed in Table 2, stabilize the columnar structure composed only of cationic complexes, as shown in Fig. 1. A [Pt^II/IV(en)₂] unit is bound to an adjacent Pt complex unit in the column by four hydrogen-bond linkages, NH···counter-anion(+ water molecule)···HN. There are two sets of four hydrogen-bond linkages; one is composed of N11–H···O11–P1–O13···H–N22, N12–H···O22–P2–O21···H–O31···H–N21, N13–H···O14···H–N23 and N14–H···I3···H–O32···H–N24, and the other is composed of N21–H···O12···H–N12, N22–H···I3···H–O32···H–N11, N23–H···O23–P2–O21···H–O31···H–N13 and N24–H···O11–P1–O13···H–N14. The crystal packing is further stabilized by intercolumnar hydrogen-bond linkages, as shown in Fig. 2.

As shown in Fig. 3, a cyclic tetramer structure composed of two hydrogenphosphate ions and two dihydrogenphosphate ions is formed by strong O–H···O hydrogen bonds [2.522 (10), 2.567 (10) and 2.569 (11) Å]; the O···O distances are comparable to the average values in hydrogenphosphates (2.597 Å) and dihydrogenphosphates (2.574 Å; Ferraris & Ivaldi, 1984). An MX-chain compound containing dimerized anions has already been reported; this is [Pt(NH₃)₄][PtBr₂(NH₃)₄](HSO₄)₄ (Tanaka et al., 1982), which also has strong O–H···O hydrogen bonds [2.582 (9) Å] in the dimer. The present tetramer structure of the counter-anion is the first observation in the MX-chain compounds in our best knowledge. In addition, the tetramers form a chain structure parallel to the Pt–I chain, connected by hydrogen bonds with the water molecules (O31).

S2. Experimental

Compound (I) was prepared using a procedure similar to that of Matsushita (1993). Golden plate-like crystals were obtained by recrystallization from an aqueous solution on slow evaporation.

S3. Refinement

A PLATON (Spek, 2003) analysis of (I) pointed out the possible presence of two additional symmetry axes, viz. a mirror plane perpendicular to the a axis and an n-glide plane perpendicular to the c axis, and suggested a proposed space group, Pmnn (No. 58). A detailed check of the reflections observed, however, indicates that the Laue class is still 2/m. The R_int value was 0.152 if the Laue class mmm was assumed. A refinement in the space group Pmnn could not be performed successfully. H atoms attached to C and N atoms were placed in geometrically calculated positions. H atoms of the phosphate ions were located at positions calculated on the basis of whether the P—O distances were long or short. As the result, the H atoms were attached to atoms O14, O23 and O24, which have longer P—O distances than the others. H atoms attached to atoms O31 and O32 of the water molecules were placed in positions satisfying their hydrogen-bonding geometry. Atom H33A of the other water molecule (O33) was also placed in a position based on the hydrogen bond between atoms O33 and O11. Atom H33B was placed in a position generated using an HFIX instruction, because the O33/H33B group does not have a hydrogen-bond acceptor. All H atoms were refined as riding (C—H = 0.97 Å, N—H = 0.90 Å and O—H = 0.82 Å), with the constraint U_iso(H) = 1.5U_eq(C,N,O). The highest peak in the difference map is located 0.94 Å from atom Pt2 and the deepest hole is located 0.86 Å from atom Pt1.

Computing details

Data collection: AFC Diffractometer Control Software (Rigaku, 1987); cell refinement: AFC Diffractometer Control Software; data reduction: AFC Diffractometer Control Software and local program F2-AFC (Matsushita, 1998); program(s) used to solve structure: SHELX76 (Sheldrick, 1976); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the columnar structure of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines represent hydrogen bonds. [Symmetry code: (i) x, y, z + 1.]
	Fig. 2. The crystal packing of (I), viewed along the c axis. Dashed lines indicate hydrogen bonds.
	Fig. 3. A view of the cyclic tetramer structure composed of two hydrogenphosphate and two dihydrogenphosphate ions, togather with neighboring water molecules of crystallization and iodide ions. Displacement ellipsoids are drawn at the 50% probability level. Dash lines represent hydrogen bonds. Symmetry codes: (i) x, y, z + 1; (vi) −x + 1, −y, −z + 1; (viii) or (vii)? −x + 1, −y + 1, − z + 1.]

catena-poly[[[bis(ethylenediamine)platinum(II)]-µ-iodo- [bis(ethylenediamine)platinum(IV)]-µ-iodo] hydrogenphosphate dihydrogenphosphate iodide trihydrate]

Crystal data

[Pt2I2(C2H8N2)4](HPO4)(H2PO4)I·3H2O	F(000) = 2312
Mr = 1258.29	Dx = 2.913 Mg m^−3
Monoclinic, P21/n	Melting point: not measured K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71069 Å
a = 14.808 (1) Å	Cell parameters from 50 reflections
b = 16.478 (2) Å	θ = 10.0–15.0°
c = 11.758 (1) Å	µ = 13.14 mm^−1
β = 90.84 (1)°	T = 295 K
V = 2868.7 (5) Å^3	Plate, gold
Z = 4	0.20 × 0.20 × 0.06 mm

Data collection

Rigaku AFC-5S diffractometer	4431 reflections with I > 2σ(I)
Radiation source: X-ray sealed tube	Rint = 0.018
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
θ/2θ scans	h = −19→19
Absorption correction: gaussian (Coppens et al., 1965)	k = 0→21
Tmin = 0.127, Tmax = 0.501	l = 0→15
7883 measured reflections	3 standard reflections every 100 reflections
6603 independent reflections	intensity decay: none

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)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 18.1327P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
4491 reflections	Δρmax = 2.91 e Å^−3
314 parameters	Δρmin = −2.02 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: heavy-atom method	Extinction coefficient: 0.00064 (4)

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 4491 reflections with F²>0. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F. 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
Pt1	0.24608 (2)	0.23848 (2)	0.11758 (3)	0.01726 (10)
I1	0.26218 (4)	0.21541 (5)	−0.10854 (5)	0.02966 (16)
I2	0.22630 (4)	0.27170 (4)	0.34001 (5)	0.02638 (15)
N11	0.3684 (5)	0.2964 (6)	0.1216 (7)	0.0279 (19)
H11A	0.4018	0.2787	0.1811	0.042*
H11B	0.3987	0.2858	0.0574	0.042*
N12	0.1970 (5)	0.3517 (5)	0.0769 (7)	0.0226 (17)
H12A	0.1610	0.3485	0.0147	0.034*
H12B	0.1641	0.3710	0.1347	0.034*
N13	0.2978 (5)	0.1253 (5)	0.1581 (7)	0.0279 (19)
H13A	0.3297	0.1060	0.0995	0.042*
H13B	0.3349	0.1292	0.2191	0.042*
N14	0.1240 (5)	0.1767 (5)	0.1140 (7)	0.0289 (19)
H14A	0.0941	0.1850	0.1790	0.043*
H14B	0.0893	0.1940	0.0554	0.043*
C11	0.3527 (6)	0.3847 (6)	0.1319 (9)	0.030 (2)
H11C	0.4063	0.4143	0.1100	0.045*
H11D	0.3391	0.3985	0.2101	0.045*
C12	0.2742 (7)	0.4070 (6)	0.0548 (9)	0.030 (2)
H12C	0.2564	0.4628	0.0688	0.045*
H12D	0.2920	0.4025	−0.0240	0.045*
C13	0.2220 (7)	0.0690 (7)	0.1835 (10)	0.035 (3)
H13C	0.2024	0.0764	0.2611	0.053*
H13D	0.2411	0.0131	0.1742	0.053*
C14	0.1456 (7)	0.0888 (7)	0.1005 (9)	0.033 (2)
H14C	0.1639	0.0777	0.0231	0.050*
H14D	0.0929	0.0560	0.1168	0.050*
Pt2	0.24131 (2)	0.26796 (2)	0.61942 (3)	0.01899 (10)
N21	0.1901 (6)	0.3801 (5)	0.6555 (7)	0.0291 (19)
H21A	0.1552	0.3974	0.5970	0.044*
H21B	0.1556	0.3772	0.7177	0.044*
N22	0.3599 (5)	0.3307 (6)	0.6089 (7)	0.030 (2)
H22A	0.3932	0.3236	0.6727	0.045*
H22B	0.3920	0.3128	0.5494	0.045*
N23	0.2920 (5)	0.1555 (5)	0.5836 (7)	0.0266 (18)
H23A	0.3254	0.1578	0.5204	0.040*
H23B	0.3276	0.1384	0.6415	0.040*
N24	0.1214 (5)	0.2084 (6)	0.6294 (7)	0.029 (2)
H24A	0.0907	0.2264	0.6899	0.044*
H24B	0.0879	0.2180	0.5664	0.044*
C21	0.2658 (7)	0.4388 (7)	0.6758 (9)	0.035 (2)
H21C	0.2455	0.4940	0.6626	0.052*
H21D	0.2884	0.4345	0.7534	0.052*
C22	0.3376 (7)	0.4165 (7)	0.5940 (9)	0.035 (3)
H22C	0.3164	0.4262	0.5168	0.053*
H22D	0.3909	0.4495	0.6078	0.053*
C23	0.2150 (7)	0.0978 (7)	0.5663 (9)	0.036 (3)
H23C	0.1953	0.0990	0.4873	0.054*
H23D	0.2347	0.0431	0.5841	0.054*
C24	0.1381 (7)	0.1205 (7)	0.6409 (9)	0.033 (2)
H24C	0.0844	0.0904	0.6185	0.050*
H24D	0.1527	0.1073	0.7195	0.050*
P1	0.49573 (14)	0.17724 (16)	0.3806 (2)	0.0210 (5)
O11	0.4898 (5)	0.2423 (5)	0.2894 (6)	0.0313 (17)
O12	0.5800 (4)	0.1235 (4)	0.3707 (6)	0.0269 (15)
O13	0.4934 (5)	0.2164 (5)	0.4980 (6)	0.0304 (16)
O14	0.4097 (4)	0.1208 (5)	0.3699 (7)	0.0321 (17)
H14	0.4256	0.0740	0.3575	0.048*
P2	0.49812 (16)	0.06835 (17)	0.7320 (2)	0.0257 (5)
O21	0.4966 (5)	0.0655 (5)	0.8595 (6)	0.042 (2)
O22	0.5831 (4)	0.0303 (5)	0.6829 (7)	0.0353 (18)
O23	0.4124 (4)	0.0282 (5)	0.6784 (8)	0.0378 (19)
H23	0.4214	−0.0206	0.6701	0.057*
O24	0.4909 (5)	0.1598 (4)	0.6972 (6)	0.0348 (17)
H24	0.5039	0.1648	0.6301	0.052*
O31	0.3738 (5)	0.0072 (5)	0.0100 (7)	0.0376 (18)
H31A	0.4158	−0.0160	0.0428	0.056*
H31B	0.4028	0.0301	−0.0394	0.056*
O32	0.4986 (5)	0.2135 (7)	−0.0319 (7)	0.053 (3)
H32A	0.5082	0.1645	−0.0326	0.080*
H32B	0.4981	0.2389	−0.0919	0.080*
O33	0.5110 (7)	0.6022 (7)	0.6098 (9)	0.072 (3)
H33A	0.5337	0.6451	0.6310	0.108*
H33B	0.4604	0.5923	0.6335	0.108*
I3	0.49447 (5)	0.40902 (5)	0.85113 (7)	0.0405 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.01723 (16)	0.0197 (2)	0.01485 (16)	0.00014 (13)	−0.00006 (11)	0.00041 (15)
I1	0.0309 (3)	0.0406 (4)	0.0174 (3)	0.0016 (3)	0.0000 (2)	−0.0048 (3)
I2	0.0305 (3)	0.0313 (4)	0.0175 (3)	0.0009 (3)	0.0041 (2)	−0.0011 (3)
N11	0.020 (4)	0.042 (6)	0.021 (4)	−0.010 (4)	−0.002 (3)	0.000 (4)
N12	0.021 (3)	0.022 (4)	0.025 (4)	0.006 (3)	0.003 (3)	0.001 (4)
N13	0.037 (4)	0.021 (5)	0.026 (4)	0.005 (4)	−0.008 (3)	0.004 (4)
N14	0.029 (4)	0.031 (5)	0.027 (4)	−0.005 (4)	−0.005 (3)	0.007 (4)
C11	0.032 (5)	0.025 (6)	0.033 (5)	−0.014 (4)	0.003 (4)	0.005 (5)
C12	0.045 (6)	0.012 (5)	0.035 (6)	0.000 (4)	0.001 (5)	0.002 (4)
C13	0.048 (6)	0.018 (6)	0.040 (6)	0.004 (5)	−0.004 (5)	0.006 (5)
C14	0.044 (6)	0.024 (6)	0.033 (6)	−0.016 (5)	0.003 (5)	0.006 (5)
Pt2	0.01904 (16)	0.0209 (2)	0.01713 (17)	0.00175 (14)	0.00182 (12)	−0.00117 (16)
N21	0.040 (5)	0.022 (5)	0.026 (4)	0.004 (4)	0.006 (4)	0.005 (4)
N22	0.024 (4)	0.033 (5)	0.033 (5)	−0.006 (4)	−0.001 (3)	−0.005 (4)
N23	0.034 (4)	0.024 (5)	0.022 (4)	0.003 (4)	0.005 (3)	0.001 (4)
N24	0.017 (3)	0.041 (6)	0.030 (4)	0.001 (4)	0.000 (3)	0.000 (4)
C21	0.047 (6)	0.023 (6)	0.034 (6)	−0.007 (5)	0.006 (5)	−0.005 (5)
C22	0.044 (6)	0.030 (6)	0.032 (6)	−0.016 (5)	−0.002 (5)	0.001 (5)
C23	0.043 (6)	0.030 (6)	0.034 (6)	−0.003 (5)	0.007 (5)	−0.017 (5)
C24	0.041 (6)	0.035 (7)	0.025 (5)	−0.014 (5)	0.010 (4)	0.000 (5)
P1	0.0211 (10)	0.0214 (13)	0.0204 (11)	−0.0012 (9)	−0.0006 (9)	0.0018 (10)
O11	0.037 (4)	0.037 (5)	0.020 (3)	−0.006 (3)	−0.002 (3)	0.010 (3)
O12	0.017 (3)	0.026 (4)	0.038 (4)	0.003 (3)	0.002 (3)	0.000 (3)
O13	0.039 (4)	0.033 (4)	0.020 (3)	−0.003 (3)	−0.001 (3)	−0.006 (3)
O14	0.019 (3)	0.030 (4)	0.048 (5)	−0.001 (3)	−0.003 (3)	−0.005 (4)
P2	0.0275 (12)	0.0224 (14)	0.0273 (13)	0.0001 (10)	0.0025 (10)	0.0052 (11)
O21	0.044 (4)	0.046 (5)	0.035 (4)	0.007 (4)	0.002 (3)	0.018 (4)
O22	0.029 (3)	0.033 (4)	0.044 (4)	−0.002 (3)	0.013 (3)	−0.009 (4)
O23	0.028 (3)	0.020 (4)	0.065 (5)	0.000 (3)	−0.005 (3)	0.001 (4)
O24	0.063 (5)	0.018 (4)	0.024 (4)	−0.001 (4)	0.001 (3)	0.003 (3)
O31	0.036 (4)	0.042 (5)	0.035 (4)	0.005 (4)	0.006 (3)	0.005 (4)
O32	0.044 (4)	0.072 (7)	0.044 (5)	0.003 (5)	0.003 (4)	−0.021 (5)
O33	0.076 (7)	0.058 (7)	0.082 (8)	−0.004 (6)	0.006 (6)	−0.021 (6)
I3	0.0349 (4)	0.0438 (5)	0.0427 (4)	0.0020 (3)	0.0010 (3)	−0.0134 (4)

Geometric parameters (Å, º)

Pt1—I1	2.6997 (7)	N22—C22	1.462 (14)
Pt1—I2	2.6921 (7)	N22—H22A	0.9000
Pt1—N11	2.048 (7)	N22—H22B	0.9000
Pt1—N12	2.055 (8)	N23—C23	1.496 (13)
Pt1—N13	2.069 (8)	N23—H23A	0.9000
Pt1—N14	2.075 (8)	N23—H23B	0.9000
Pt2—N21	2.044 (8)	N24—C24	1.475 (14)
Pt2—N22	2.043 (8)	N24—H24A	0.9000
Pt2—N23	2.045 (8)	N24—H24B	0.9000
Pt2—N24	2.034 (8)	C21—C22	1.490 (14)
Pt2—I1^i	3.3239 (8)	C21—H21C	0.9700
Pt2—I2	3.2902 (7)	C21—H21D	0.9700
N11—C11	1.478 (13)	C22—H22C	0.9700
N11—H11A	0.9000	C22—H22D	0.9700
N11—H11B	0.9000	C23—C24	1.496 (14)
N12—C12	1.490 (12)	C23—H23C	0.9700
N12—H12A	0.9000	C23—H23D	0.9700
N12—H12B	0.9000	C24—H24C	0.9700
N13—C13	1.489 (13)	C24—H24D	0.9700
N13—H13A	0.9000	P1—O11	1.518 (7)
N13—H13B	0.9000	P1—O12	1.537 (6)
N14—C14	1.492 (14)	P1—O13	1.524 (7)
N14—H14A	0.9000	P1—O14	1.582 (7)
N14—H14B	0.9000	O14—H14	0.8200
C11—C12	1.509 (13)	P2—O21	1.500 (8)
C11—H11C	0.9700	P2—O22	1.527 (7)
C11—H11D	0.9700	P2—O23	1.556 (7)
C12—H12C	0.9700	P2—O24	1.565 (8)
C12—H12D	0.9700	O23—H23	0.8200
C13—C14	1.520 (14)	O24—H24	0.8200
C13—H13C	0.9700	O31—H31B	0.8200
C13—H13D	0.9700	O31—H31A	0.8201
C14—H14C	0.9700	O32—H32B	0.8200
C14—H14D	0.9700	O32—H32A	0.8205
N21—C21	1.497 (13)	O33—H33B	0.8200
N21—H21A	0.9000	O33—H33A	0.8201
N21—H21B	0.9000
N11—Pt1—N12	83.8 (3)	N14—C14—H14C	110.2
N11—Pt1—N13	95.2 (3)	C13—C14—H14C	110.2
N11—Pt1—N14	178.4 (3)	N14—C14—H14D	110.2
N12—Pt1—N13	179.0 (3)	C13—C14—H14D	110.2
N12—Pt1—N14	97.8 (3)	H14C—C14—H14D	108.5
N13—Pt1—N14	83.2 (3)	C21—N21—Pt2	109.7 (6)
N11—Pt1—I1	89.9 (2)	C21—N21—H21A	109.7
N12—Pt1—I1	86.3 (2)	Pt2—N21—H21A	109.7
N13—Pt1—I1	93.6 (2)	C21—N21—H21B	109.7
N14—Pt1—I1	90.0 (2)	Pt2—N21—H21B	109.7
N11—Pt1—I2	89.5 (2)	H21A—N21—H21B	108.2
N12—Pt1—I2	89.9 (2)	C22—N22—Pt2	107.6 (6)
N13—Pt1—I2	90.3 (2)	C22—N22—H22A	110.2
N14—Pt1—I2	90.7 (2)	Pt2—N22—H22A	110.2
I1—Pt1—I2	176.16 (3)	C22—N22—H22B	110.2
Pt1—I1—Pt2^ii	154.52 (3)	Pt2—N22—H22B	110.2
Pt1—I2—Pt2	163.64 (3)	H22A—N22—H22B	108.5
I2—Pt2—I1^i	165.88 (2)	C23—N23—Pt2	108.8 (6)
N21—Pt2—N22	83.0 (3)	C23—N23—H23A	109.9
N21—Pt2—N23	179.7 (3)	Pt2—N23—H23A	109.9
N21—Pt2—N24	95.6 (3)	C23—N23—H23B	109.9
N22—Pt2—N23	97.3 (3)	Pt2—N23—H23B	109.9
N22—Pt2—N24	178.5 (3)	H23A—N23—H23B	108.3
N23—Pt2—N24	84.1 (3)	C24—N24—Pt2	109.5 (6)
N24—Pt2—I1^i	83.5 (2)	C24—N24—H24A	109.8
N22—Pt2—I1^i	97.0 (2)	Pt2—N24—H24A	109.8
N21—Pt2—I1^i	93.8 (2)	C24—N24—H24B	109.8
N23—Pt2—I1^i	86.2 (2)	Pt2—N24—H24B	109.8
C11—N11—Pt1	108.7 (6)	H24A—N24—H24B	108.2
C11—N11—H11A	109.9	C22—C21—N21	106.1 (8)
Pt1—N11—H11A	110.0	C22—C21—H21C	110.5
C11—N11—H11B	110.0	N21—C21—H21C	110.5
Pt1—N11—H11B	109.9	C22—C21—H21D	110.5
H11A—N11—H11B	108.3	N21—C21—H21D	110.5
C12—N12—Pt1	109.0 (5)	H21C—C21—H21D	108.7
C12—N12—H12A	109.9	N22—C22—C21	108.9 (9)
Pt1—N12—H12A	109.9	N22—C22—H22C	109.9
C12—N12—H12B	109.9	C21—C22—H22C	109.9
Pt1—N12—H12B	109.9	N22—C22—H22D	109.9
H12A—N12—H12B	108.3	C21—C22—H22D	109.9
C13—N13—Pt1	109.3 (6)	H22C—C22—H22D	108.3
C13—N13—H13A	109.8	C24—C23—N23	110.3 (8)
Pt1—N13—H13A	109.8	C24—C23—H23C	109.6
C13—N13—H13B	109.8	N23—C23—H23C	109.6
Pt1—N13—H13B	109.8	C24—C23—H23D	109.6
H13A—N13—H13B	108.3	N23—C23—H23D	109.6
C14—N14—Pt1	106.9 (6)	H23C—C23—H23D	108.1
C14—N14—H14A	110.3	N24—C24—C23	108.6 (9)
Pt1—N14—H14A	110.3	N24—C24—H24C	110.0
C14—N14—H14B	110.3	C23—C24—H24C	110.0
Pt1—N14—H14B	110.3	N24—C24—H24D	110.0
H14A—N14—H14B	108.6	C23—C24—H24D	110.0
N11—C11—C12	108.1 (8)	H24C—C24—H24D	108.3
N11—C11—H11C	110.1	O11—P1—O13	109.8 (4)
C12—C11—H11C	110.1	O11—P1—O12	113.1 (4)
N11—C11—H11D	110.1	O13—P1—O12	110.0 (4)
C12—C11—H11D	110.1	O11—P1—O14	108.7 (4)
H11C—C11—H11D	108.4	O13—P1—O14	107.0 (4)
N12—C12—C11	109.4 (8)	O12—P1—O14	108.0 (4)
N12—C12—H12C	109.8	P1—O14—H14	109.5
C11—C12—H12C	109.8	O21—P2—O22	112.9 (4)
N12—C12—H12D	109.8	O21—P2—O23	111.6 (5)
C11—C12—H12D	109.8	O22—P2—O23	110.1 (4)
H12C—C12—H12D	108.2	O21—P2—O24	106.8 (5)
N13—C13—C14	107.1 (8)	O22—P2—O24	110.5 (5)
N13—C13—H13C	110.3	O23—P2—O24	104.6 (4)
C14—C13—H13C	110.3	P2—O23—H23	109.5
N13—C13—H13D	110.3	P2—O24—H24	109.5
C14—C13—H13D	110.3	H31B—O31—H31A	98.4
H13C—C13—H13D	108.5	H32B—O32—H32A	119.6
N14—C14—C13	107.4 (8)	H33B—O33—H33A	116.1

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O11	0.90	1.91	2.796 (10)	170
N11—H11B···O32	0.90	2.18	2.990 (12)	149
N12—H12A···O12^iii	0.90	2.11	2.987 (10)	164
N12—H12B···O22^iii	0.90	2.10	2.870 (11)	143
N13—H13A···O31	0.90	2.05	2.854 (12)	148
N13—H13B···O14	0.90	2.08	2.972 (10)	170
N14—H14A···I3^iii	0.90	2.96	3.689 (8)	139
N14—H14B···O13^iii	0.90	2.15	2.937 (11)	146
N21—H21A···O31^iv	0.90	2.24	3.002 (11)	142
N21—H21B···O12^v	0.90	2.13	3.030 (11)	176
N22—H22A···I3	0.90	2.92	3.686 (8)	144
N22—H22B···O13	0.90	2.27	3.038 (11)	143
N23—H23A···O14	0.90	2.26	3.132 (11)	162
N23—H23B···O23	0.90	2.25	2.962 (11)	136
N24—H24A···O11^v	0.90	1.98	2.846 (11)	161
N24—H24B···O32^v	0.90	2.08	2.909 (11)	153
O14—H14···O22^vi	0.82	1.79	2.569 (11)	159
O23—H23···O12^vi	0.82	1.76	2.567 (10)	167
O24—H24···O13	0.82	1.77	2.522 (10)	151
O31—H31B···O21^ii	0.82	1.93	2.731 (10)	165
O31—H31A···O21^vi	0.82	1.90	2.717 (10)	171
O32—H32B···I3^ii	0.82	2.88	3.502 (12)	134
O32—H32A···O21^ii	0.82	2.07	2.753 (13)	140
O33—H33A···O11^vii	0.82	2.11	2.824 (13)	145

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