Straight ⋯I—PtIV—I⋯PtII⋯ chains are observed in the mixed-valent title salt. Extensive hydrogen bonding involving the amino groups, hydrogen sulfate counter-anions and water molecules of crystallization stabilizes the crystal packing.
Keywords: crystal structure; platinum complex; one-dimensional chain complex; iodido-bridged complex; Pt(II,IV) mixed-valence; MX-chain
Abstract
The title compound, catena-poly[[[bis(ethylenediamine-κ2 N,N′)platinum(II)]-μ-iodido-[bis(ethylenediamine-κ2 N,N′)platinum(IV)]-μ-iodido] tetra(hydrogen sulfate) dihydrate], {[PtII(C2H8N2)2][PtIVI2(C2H8N2)2](HSO4)4·2H2O}n, has a linear chain structure comprising alternating platinum cations with mixed-valent oxidation states of +II/IV. Square-planar [Pt(en)2]2+ cations and elongated octahedral trans-[PtI2(en)2]2+ cations (en is ethylenediamine) are stacked alternately parallel to the b axis, and are bridged by the I ligands. The Pt site of the [PtII/IV(en)2] units is located on a twofold rotation axis. The I site, which is located on the same twofold rotation axis, is equally disordered over two positions. The Pt and I sites form a straight ⋯I—PtIV—I⋯PtII⋯ chain, with PtIV—I bond lengths of 2.7202 (6) and 2.6917 (6) Å, and PtII⋯I contacts of 3.2249 (6) and 3.2534 (6) Å. The mixed-valence state of the Pt site is expressed by the structural parameter δ = (PtIV–I)/(PtII⋯I), with values of 0.843 and 0.827 for the two independent I atoms. In the crystal structure, the cationic columnar structure is stabilized by hydrogen bonds of the type N—H⋯O between the amine groups of the Pt complex chains and the disordered hydrogen sulfate counter anions, and between the amine groups and water molecules of crystallization. In addition, O—H⋯O hydrogen bonds between the hydrogen sulfate anions and water molecules of crystallization and between the hydrogen sulfate anions themselves consolidate the crystal packing.
Chemical context
The title mixed-valence compound, [PtII(en)2][PtIVI2(en)2](HSO4)4·2H2O (en is ethylenediamine, C2N2H8), (I), is a member of the family of one-dimensional halogenido-bridged mixed-valence metal complexes, formulated as [M II(AA)2][M IV X 2(AA)2]Y 4 [M II/M IV = PtII/PtIV; PdII/PdIV; NiII/NiIV; PdII/PtIV; NiII/PtIV; X = Cl, Br, I; AA = NH2(CH2)2NH2, etc.; Y = ClO4 −, BF4 −, X −, etc.], which are often referred to as MX-chains and are typical mixed-valence compounds belonging to class II in the classification of Robin & Day (1967 ▸). MX-chains have attracted much interest because of their one-dimensional mixed-valence electron systems, as described in a previous report (Matsushita, 2006 ▸).
The metal–halogen distances in crystals of MX-chains characterize their physical properties based on the mixed-valence electronic state. The X-ray structure determination of (I) was performed to gain structural information for MX-chains and to compare (I) with chlorido- and bromido-bridged PtII/PtIV mixed-valence complexes with a hydrogen sulfate counter-anion, i.e. [PtII(en)2][PtIV
X
2(en)2](HSO4)4 (X = Cl, Br) (Matsushita et al., 1992 ▸; Matsushita, 2003 ▸).
Structural commentary
The structures of the molecular components of (I) are displayed in Fig. 1 ▸. The asymmetric unit of (I) comprises half of a Pt-complex moiety, [PtII(en)2]2+ or [PtIVI2(en)2]2+, one HSO4 − anion, and a half-molecule of water. The Pt and I atoms of the Pt-complex moiety and the O atom of the water molecule are located on twofold rotation axes. The hydrogen sulfate anion lies on a general position. As shown in Fig. 2 ▸, the structure of (I) is built up of columns extending parallel to the b axis, composed of square-planar [Pt(en)2]2+ cations and elongated octahedral trans-[PtI2(en)2]2+ cations stacked alternately and bridged by the I ligands. The Pt and I atoms form an infinite straight ⋯I—PtIV—I⋯PtII⋯ chain. The same straight chains are also observed in [PtII(en)2][PtIV X 2(en)2](HSO4)4 (X = Cl, Br) (Matsushita et al., 1992 ▸; Matsushita, 2003 ▸). The title salt (I) is, however, not isotypic with these hydrogen sulfates of the chlorido- and bromido-bridged complexes whereas the latter structures show isotypism with each other.
Figure 1.
The structures of the molecular components of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level for non-H atoms. Light-blue dashed lines represent N—H⋯O and O—H⋯O hydrogen bonds. Each site of atoms I1 and I2 is half occupied. [Symmetry code: (i) 
− x, y, − z].
Figure 2.
A view of the columnar structure of compound (I), running parallel to the b axis. Displacement ellipsoids are drawn at the 50% probability level for non-H atoms. The violet hollow ellipsoids of I atoms and the violet hollow lines between Pt and I atoms represent the disordered part of the ⋯I—PtIV—I⋯PtII⋯ chain. Light-blue dashed lines represent hydrogen bonds.
The I sites in (I) are not located at the exact midpoint between adjacent Pt sites and thus are equally disordered over two sites close to the midpoint. Consequently, the Pt site is occupationally disordered over the PtII and PtIV atoms. 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 being of a one-dimensionally ordered structure type, with the other two directions being in a disordered state. The structural order–disorder situation of the Pt site in (I) has also been observed in the structures of a number of other MX-chains (Endres et al., 1980 ▸; Beauchamp et al., 1982 ▸; Cannas et al., 1983 ▸; Yamashita et al., 1985 ▸; Matsushita et al., 1992 ▸, 2017 ▸; Toriumi et al., 1993 ▸; Huckett et al., 1993 ▸; Matsushita, 2003 ▸, 2005a ▸,b ▸, 2015 ▸; Matsushita & Taira, 2015 ▸).
With respect to the two sites for the disordered I atoms, the shorter Pt—I distances are assigned to PtIV—I and the longer ones to PtII⋯I contacts, as follows: I—PtIV—I; Pt—I1 = 2.7202 (6) Å, Pt—I2 = 2.6917 (6) Å; I⋯PtII⋯I; Pt⋯I1 = 3.2249 (6) Å, Pt⋯I2 = 3.2534 (6) Å. Other bond lengths and angles are collated in Table 1 ▸.
Table 1. Selected geometric parameters (Å, °).
| Pt—N2 | 2.055 (2) | N2—C2 | 1.492 (4) |
| Pt—N1 | 2.057 (2) | C1—C2 | 1.501 (4) |
| Pt—I2 | 2.6917 (6) | S—O3 | 1.432 (2) |
| Pt—I1 | 2.7202 (6) | S—O1 | 1.448 (2) |
| Pt—I1i | 3.2249 (6) | S—O4 | 1.491 (2) |
| Pt—I2ii | 3.2534 (6) | S—O2 | 1.499 (2) |
| N1—C1 | 1.499 (4) | ||
| N2—Pt—N1 | 83.23 (10) | N2—C2—C1 | 107.3 (2) |
| N2—Pt—I2 | 90.27 (6) | O3—S—O1 | 113.41 (15) |
| N1—Pt—I2 | 89.96 (6) | O3—S—O4 | 111.27 (15) |
| N2—Pt—I1 | 89.73 (6) | O1—S—O4 | 105.28 (14) |
| N1—Pt—I1 | 90.04 (6) | O3—S—O2 | 109.72 (14) |
| C1—N1—Pt | 108.82 (17) | O1—S—O2 | 110.33 (16) |
| C2—N2—Pt | 108.60 (18) | O4—S—O2 | 106.55 (15) |
| N1—C1—C2 | 107.7 (2) |
Symmetry codes: (i) 
; (ii) 
.
The structural parameters indicating the mixed-valence state of the Pt site, expressed by δ = (PtIV–I)/(PtII⋯I), are 0.843 and 0.827 for I1 and I2, respectively. These values are smaller than those of [Pt(pn)2][PtI2(pn)2](ClO4)4 (pn is 1,2-diaminopropane) (0.937; 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 (tn is 1,3-diaminopropane) (0.95; Cannas et al., 1984 ▸), [Pt(en)2][PtI2(en)2](ClO4)4 (0.919; Endres et al., 1979 ▸), but are comparable with those of [Pt(NH3)4][PtI2(NH3)4](HSO4)4·2H2O (0.834; Tanaka et al., 1986 ▸), [Pt(en)2][PtI2(en)2](C8H17SO3)4·2H2O (0.839 and 0.858; Matsushita, 2015 ▸), and somewhat larger than those of [Pt(en)2][PtI2(en)2](HPO4)(H2PO4)I·3H2O (0.812 and 0.818; Matsushita, 2006 ▸).
Supramolecular features
Hydrogen bonds in (I) (Table 2 ▸) stabilize the columnar structure composed only of cationic complexes, as shown in Fig. 2 ▸. A [PtII/IV(en)2] unit is bound to an adjacent Pt-complex unit in the column by four hydrogen-bond linkages as follows: two linkages N1—H1A⋯O1—S—O3⋯H1B—N1 and two linkages N2—H2A⋯O5—H5⋯O1⋯H2B—N2. In addition, the donor group O5—H5 is hydrogen-bonded to atom O3, and forms a three-centre hydrogen-bond. Such hydrogen-bonded linkages are common structural motifs of MX-chains (Matsushita, 2003 ▸, 2005a ▸,b ▸, 2006 ▸, 2015 ▸; Matsushita et al., 1992 ▸, 2017 ▸; Matsushita & Taira, 2015 ▸).
Table 2. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N1—H1A⋯O1 | 0.89 | 2.01 | 2.895 (3) | 173 |
| N1—H1B⋯O3ii | 0.89 | 2.29 | 3.057 (3) | 145 |
| N2—H2A⋯O5iii | 0.89 | 2.03 | 2.905 (3) | 169 |
| N2—H2B⋯O1iv | 0.89 | 2.39 | 3.132 (3) | 141 |
| O5—H5⋯O1v | 0.82 | 2.28 | 3.032 (4) | 152 |
| O5—H5⋯O3v | 0.82 | 2.36 | 2.936 (3) | 128 |
| O2—H2⋯O2vi | 0.82 | 1.92 | 2.595 (5) | 139 |
| O4—H4⋯O4vii | 0.82 | 1.83 | 2.560 (5) | 148 |
Symmetry codes: (ii) ; (iii) 
; (iv) 
; (v) 
; (vi) 
; (vii) 
.
As a result of the intercolumnar hydrogen-bond linkages, N1—H1A⋯O1⋯H2B—N2 between the Pt-complex columns and hydrogen sulfate ions, and N2—H2A⋯O5⋯H2A—N2 between the Pt-complex columns and the water molecule of crystallization, represented by light-blue dashed lines in Fig. 3 ▸, the columns are organized in layers parallel to the ab plane.
Figure 3.
The crystal packing of compound (I), projected on the ac plane. Magenta dashed lines represent hydrogen bonds between the hydrogen sulfate ions. Light-blue dashed lines represent the other hydrogen bonds. Solid orange lines indicate the unit cell.
The layers are connected along the direction of the c axis by two very short hydrogen bonds (Table 2 ▸) between hydrogen sulfate ions as follows: O2—H2⋯O2vi and O4—H4⋯O4vii, represented by magenta dashed lines in Fig. 3 ▸. Atom pairs O2 and O2vi and O4 and O4vii both are related by inversion centers. Thus, atoms H2 and H4 are equally disordered over two sites between atoms O2 and between atoms O4, respectively. One-dimensional hydrogen-bonded chains of hydrogen sulfate anions run along the a-axis direction. Similar hydrogen-bonded chains of hydrogen sulfate anions are observed in [PtII(en)2][PtIV X 2(en)2](HSO4)4 (X = Cl, Br) (Matsushita et al., 1992 ▸; Matsushita, 2003 ▸). In the hydrogen sulfate ion, the lengths of the S—O(H) bonds [S—O2 = 1.499 (2) Å, S—O4 = 1.491 (2) Å] are longer than those of the S—O bonds [S—O1 = 1.448 (2) Å, S—O3 = 1.432 (2) Å]. This difference in the S—O bond lengths supports the fact that both O2 and O4 are bonded to a hydrogen atom, however in a disordered manner. A similar difference in the lengths of the S—O and S—O(H) bonds is also observed in [PtII(en)2][PtIV X 2(en)2](HSO4)4 (X = Cl, Br) (Matsushita et al., 1992 ▸; Matsushita, 2003 ▸). In these hydrogen sulfates, however, the hydrogen atoms of the hydrogen sulfate anions, which also hydrogen-bond to neighbouring hydrogen sulfate anions, are not disordered. The lengths of the S—O(H) bond and the S—O bond for the acceptor O atom are 1.494 (10) and 1.420 (8) Å, respectively, for the chlorido-bridged complex and 1.45 (2) and 1.35 (3) Å for the bromido-bridged complex. These longer and shorter lengths for the S—O bonds indicate that the hydrogen atoms of the hydrogen sulfate ions are not disordered.
The intracolumnar, intercolumnar and interlayer hydrogen-bonds, as discussed above, stabilize the crystal packing in (I).
Synthesis and crystallization
A preparation procedure for the title salt was previously reported (Matsushita et al., 1989 ▸). In the literature, the obtained salt was originally reported as a tetrahydrate. The present X-ray crystallographic study, however, reveals the salt to be a dihydrate. Probably, the amount of water molecules of the salt was overestimated at that time due to the hygroscopic nature of the polycrystalline sample because the salt was obtained from a concentrated sulfuric acid solution. The powder X-ray diffraction pattern simulated on the basis of the present single-crystal data is in good agreement with the experimental data reported previously for the powder sample.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. Atoms I1, I2 and H2 and H4 are each disordered over two positions and were modelled with an occupancy factor of 0.5. Hydrogen atoms were placed in geometrically calculated positions and refined as riding, with C—H = 0.97 Å, N—H = 0.89 Å, and O—H = 0.82 Å, and with U iso(H) = 1.2U eq(C,N) and 1.5U eq(O). Hydrogen atoms bonded to O atoms were calculated by the HFIX 147 command of SHELXL (Sheldrick, 2015b ▸). Evaluation of the S—O2 bond length for atom H2, the S—O4 bond length for atom H4, and the O3⋯O5 and O1⋯O5 hydrogen bonds together with other hydrogen-bonding interactions showed the expected behaviour, and therefore the localization of these H atoms was considered to be correct. The maximum and minimum electron density peaks are located 0.67 and 0.17 Å, respectively, from atom Pt.
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | [Pt(C2H8N2)2][PtI2(C2H8N2)2](HSO4)4·2H2O |
| M r | 1308.70 |
| Crystal system, space group | Monoclinic, P2/n |
| Temperature (K) | 296 |
| a, b, c (Å) | 7.2964 (2), 5.9451 (2), 18.2253 (7) |
| β (°) | 92.318 (1) |
| V (Å3) | 789.93 (5) |
| Z | 1 |
| Radiation type | Mo Kα |
| μ (mm−1) | 11.15 |
| Crystal size (mm) | 0.50 × 0.40 × 0.35 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID imaging plate |
| Absorption correction | Multi-scan (ABSCOR; Rigaku, 1995 ▸) |
| T min, T max | 0.010, 0.020 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 16218, 2733, 2541 |
| R int | 0.048 |
| (sin θ/λ)max (Å−1) | 0.746 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.024, 0.046, 1.21 |
| No. of reflections | 2733 |
| No. of parameters | 106 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 2.12, −1.69 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018016158/wm5469sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018016158/wm5469Isup2.hkl
CCDC reference: 1878955
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| [Pt(C2H8N2)2][PtI2(C2H8N2)2](HSO4)4·2H2O | F(000) = 614 |
| Mr = 1308.70 | Dx = 2.751 Mg m−3 |
| Monoclinic, P2/n | Mo Kα radiation, λ = 0.71075 Å |
| a = 7.2964 (2) Å | Cell parameters from 14539 reflections |
| b = 5.9451 (2) Å | θ = 3.1–32.1° |
| c = 18.2253 (7) Å | µ = 11.15 mm−1 |
| β = 92.318 (1)° | T = 296 K |
| V = 789.93 (5) Å3 | Block, gold |
| Z = 1 | 0.50 × 0.40 × 0.35 mm |
Data collection
| Rigaku R-AXIS RAPID imaging plate diffractometer | 2733 independent reflections |
| Radiation source: X-ray sealed tube | 2541 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.048 |
| Detector resolution: 10.00 pixels mm-1 | θmax = 32.0°, θmin = 3.1° |
| ω scans | h = −10→10 |
| Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) | k = −8→8 |
| Tmin = 0.010, Tmax = 0.020 | l = −27→27 |
| 16218 measured reflections |
Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
| wR(F2) = 0.046 | w = 1/[σ2(Fo2) + 0.4688P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.21 | (Δ/σ)max < 0.001 |
| 2733 reflections | Δρmax = 2.12 e Å−3 |
| 106 parameters | Δρmin = −1.68 e Å−3 |
| 0 restraints | Extinction correction: SHELXL-2014/7 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: dual | Extinction coefficient: 0.0149 (4) |
Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Pt | 0.2500 | 0.98097 (2) | 0.2500 | 0.01577 (6) | |
| I1 | 0.2500 | 1.43852 (10) | 0.2500 | 0.02522 (15) | 0.5 |
| I2 | 0.2500 | 0.52821 (9) | 0.2500 | 0.02578 (15) | 0.5 |
| N1 | 0.4066 (3) | 0.9807 (3) | 0.34641 (14) | 0.0247 (5) | |
| H1A | 0.4946 | 0.8775 | 0.3443 | 0.030* | |
| H1B | 0.4593 | 1.1145 | 0.3533 | 0.030* | |
| N2 | 0.0356 (3) | 0.9826 (3) | 0.31975 (14) | 0.0254 (5) | |
| H2A | −0.0501 | 1.0791 | 0.3036 | 0.030* | |
| H2B | −0.0144 | 0.8463 | 0.3215 | 0.030* | |
| C1 | 0.2853 (4) | 0.9293 (5) | 0.40872 (16) | 0.0317 (6) | |
| H1C | 0.3428 | 0.9795 | 0.4548 | 0.038* | |
| H1D | 0.2643 | 0.7685 | 0.4118 | 0.038* | |
| C2 | 0.1070 (4) | 1.0503 (5) | 0.39440 (17) | 0.0313 (6) | |
| H2C | 0.0201 | 1.0094 | 0.4310 | 0.038* | |
| H2D | 0.1260 | 1.2117 | 0.3965 | 0.038* | |
| S | 0.73971 (11) | 0.53489 (12) | 0.41680 (4) | 0.02863 (16) | |
| O1 | 0.7066 (3) | 0.6617 (4) | 0.34976 (13) | 0.0463 (6) | |
| O2 | 0.6291 (3) | 0.6293 (4) | 0.47713 (14) | 0.0474 (6) | |
| H2 | 0.5242 | 0.5798 | 0.4734 | 0.071* | 0.5 |
| O3 | 0.7028 (4) | 0.2994 (4) | 0.40865 (14) | 0.0431 (6) | |
| O4 | 0.9361 (3) | 0.5761 (4) | 0.43844 (13) | 0.0422 (5) | |
| H4 | 0.9504 | 0.5661 | 0.4832 | 0.063* | 0.5 |
| O5 | 0.7500 | 0.2587 (5) | 0.2500 | 0.0321 (7) | |
| H5 | 0.7954 | 0.3426 | 0.2200 | 0.048* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Pt | 0.01352 (8) | 0.01268 (8) | 0.02104 (8) | 0.000 | −0.00028 (5) | 0.000 |
| I1 | 0.0248 (3) | 0.0168 (3) | 0.0340 (3) | 0.000 | 0.0010 (2) | 0.000 |
| I2 | 0.0292 (3) | 0.0151 (3) | 0.0328 (3) | 0.000 | −0.0006 (2) | 0.000 |
| N1 | 0.0218 (12) | 0.0239 (11) | 0.0277 (12) | 0.0006 (8) | −0.0072 (10) | −0.0011 (8) |
| N2 | 0.0208 (12) | 0.0247 (11) | 0.0309 (13) | 0.0010 (8) | 0.0061 (10) | 0.0030 (9) |
| C1 | 0.0394 (18) | 0.0325 (15) | 0.0231 (14) | 0.0034 (13) | −0.0013 (13) | 0.0019 (11) |
| C2 | 0.0362 (18) | 0.0317 (14) | 0.0264 (15) | 0.0053 (12) | 0.0074 (13) | −0.0005 (11) |
| S | 0.0268 (4) | 0.0302 (4) | 0.0288 (4) | 0.0001 (3) | −0.0014 (3) | −0.0002 (3) |
| O1 | 0.0403 (14) | 0.0602 (15) | 0.0382 (14) | 0.0105 (12) | −0.0009 (11) | 0.0158 (12) |
| O2 | 0.0473 (15) | 0.0433 (14) | 0.0533 (16) | −0.0060 (11) | 0.0242 (12) | −0.0156 (11) |
| O3 | 0.0501 (15) | 0.0326 (12) | 0.0471 (16) | −0.0032 (10) | 0.0096 (12) | −0.0097 (10) |
| O4 | 0.0283 (12) | 0.0560 (14) | 0.0419 (14) | −0.0073 (10) | −0.0041 (10) | 0.0105 (12) |
| O5 | 0.0262 (17) | 0.0400 (18) | 0.0300 (19) | 0.000 | 0.0011 (14) | 0.000 |
Geometric parameters (Å, º)
| Pt—N2 | 2.055 (2) | N2—H2A | 0.8900 |
| Pt—N2i | 2.055 (2) | N2—H2B | 0.8900 |
| Pt—N1i | 2.057 (2) | C1—C2 | 1.501 (4) |
| Pt—N1 | 2.057 (2) | C1—H1C | 0.9700 |
| Pt—I2 | 2.6917 (6) | C1—H1D | 0.9700 |
| Pt—I1 | 2.7202 (6) | C2—H2C | 0.9700 |
| Pt—I1ii | 3.2249 (6) | C2—H2D | 0.9700 |
| Pt—I2iii | 3.2534 (6) | S—O3 | 1.432 (2) |
| I1—I2iii | 0.5332 (6) | S—O1 | 1.448 (2) |
| I1—Ptiii | 3.2249 (6) | S—O4 | 1.491 (2) |
| I2—I1ii | 0.5332 (6) | S—O2 | 1.499 (2) |
| I2—Ptii | 3.2534 (6) | O2—H2 | 0.8200 |
| N1—C1 | 1.499 (4) | O4—H4 | 0.8200 |
| N1—H1A | 0.8900 | O5—N2iv | 2.905 (3) |
| N1—H1B | 0.8900 | O5—H5 | 0.8200 |
| N2—C2 | 1.492 (4) | ||
| N2—Pt—N2i | 179.45 (11) | C1—N1—Pt | 108.82 (17) |
| N2—Pt—N1i | 96.77 (10) | C1—N1—H1A | 109.9 |
| N2i—Pt—N1i | 83.23 (10) | Pt—N1—H1A | 109.9 |
| N2—Pt—N1 | 83.23 (10) | C1—N1—H1B | 109.9 |
| N2i—Pt—N1 | 96.77 (10) | Pt—N1—H1B | 109.9 |
| N1i—Pt—N1 | 179.92 (11) | H1A—N1—H1B | 108.3 |
| N2—Pt—I2 | 90.27 (6) | C2—N2—Pt | 108.60 (18) |
| N2i—Pt—I2 | 90.27 (6) | C2—N2—H2A | 110.0 |
| N1i—Pt—I2 | 89.96 (6) | Pt—N2—H2A | 110.0 |
| N1—Pt—I2 | 89.96 (6) | C2—N2—H2B | 110.0 |
| N2—Pt—I1 | 89.73 (6) | Pt—N2—H2B | 110.0 |
| N2i—Pt—I1 | 89.73 (6) | H2A—N2—H2B | 108.4 |
| N1i—Pt—I1 | 90.04 (6) | N1—C1—C2 | 107.7 (2) |
| N1—Pt—I1 | 90.04 (6) | N1—C1—H1C | 110.2 |
| I2—Pt—I1 | 180.0 | C2—C1—H1C | 110.2 |
| N2—Pt—I1ii | 90.27 (6) | N1—C1—H1D | 110.2 |
| N2i—Pt—I1ii | 90.27 (6) | C2—C1—H1D | 110.2 |
| N1i—Pt—I1ii | 89.96 (6) | H1C—C1—H1D | 108.5 |
| N1—Pt—I1ii | 89.96 (6) | N2—C2—C1 | 107.3 (2) |
| I2—Pt—I1ii | 0.0 | N2—C2—H2C | 110.3 |
| I1—Pt—I1ii | 180.0 | C1—C2—H2C | 110.3 |
| N2—Pt—I2iii | 89.73 (6) | N2—C2—H2D | 110.3 |
| N2i—Pt—I2iii | 89.73 (6) | C1—C2—H2D | 110.3 |
| N1i—Pt—I2iii | 90.04 (6) | H2C—C2—H2D | 108.5 |
| N1—Pt—I2iii | 90.04 (6) | O3—S—O1 | 113.41 (15) |
| I2—Pt—I2iii | 180.0 | O3—S—O4 | 111.27 (15) |
| I1—Pt—I2iii | 0.0 | O1—S—O4 | 105.28 (14) |
| I1ii—Pt—I2iii | 180.0 | O3—S—O2 | 109.72 (14) |
| I2iii—I1—Pt | 180.0 | O1—S—O2 | 110.33 (16) |
| I2iii—I1—Ptiii | 0.000 (1) | O4—S—O2 | 106.55 (15) |
| Pt—I1—Ptiii | 180.0 | S—O2—H2 | 109.5 |
| I1ii—I2—Pt | 180.0 | S—O4—H4 | 109.5 |
| I1ii—I2—Ptii | 0.0 | N2iv—O5—H5 | 109.5 |
| Pt—I2—Ptii | 180.0 |
Symmetry codes: (i) −x+1/2, y, −z+1/2; (ii) x, y−1, z; (iii) x, y+1, z; (iv) x+1, y−1, z.
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1 | 0.89 | 2.01 | 2.895 (3) | 173 |
| N1—H1B···O3iii | 0.89 | 2.29 | 3.057 (3) | 145 |
| N2—H2A···O5v | 0.89 | 2.03 | 2.905 (3) | 169 |
| N2—H2B···O1vi | 0.89 | 2.39 | 3.132 (3) | 141 |
| O5—H5···O1vii | 0.82 | 2.28 | 3.032 (4) | 152 |
| O5—H5···O3vii | 0.82 | 2.36 | 2.936 (3) | 128 |
| O2—H2···O2viii | 0.82 | 1.92 | 2.595 (5) | 139 |
| O4—H4···O4ix | 0.82 | 1.83 | 2.560 (5) | 148 |
Symmetry codes: (iii) x, y+1, z; (v) x−1, y+1, z; (vi) x−1, y, z; (vii) −x+3/2, y, −z+1/2; (viii) −x+1, −y+1, −z+1; (ix) −x+2, −y+1, −z+1.
Funding Statement
This work was funded by Japan Society for the Promotion of Science grant JP16H06509.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018016158/wm5469sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018016158/wm5469Isup2.hkl
CCDC reference: 1878955
Additional supporting information: crystallographic information; 3D view; checkCIF report