research communications
Redetermination of the catena-poly[[[bis(ethylenediamine)platinum(II)]-μ-iodido-[bis(ethylenediamine)platinum(IV)]-μ-iodido] tetrakis(octane-1-sulfonate) dihydrate]
ofaDepartment of Chemistry and Research Center for Smart Molecules, Rikkyo University, Nishi-Ikebukuro 3-34-1, Toshima-ku, 171-8501 Tokyo, Japan
*Correspondence e-mail: cnmatsu@rikkyo.ac.jp
The structure of the title compound, which represents a mixed-valence platinum(II,IV) complex, {[PtIIPtIVI2(C2H8N2)4][CH3(CH2)7SO3]4·2H2O}n, has been redetermined in a different In contrast to the previously reported determination in the P21cn [Matsushita & Taira (1999). Synth. Met. 102, 1787–1788], the current model was refined in the centrosymmetric Pmcn using the original diffraction data. The title compound has a linear chain structure composed of square-planar [Pt(en)2]2+ and elongated octahedral trans-[PtI2(en)2]2+ cations (en is ethylenediamine) stacked alternately, bridged by the I atoms, parallel to the c axis. Inorganic layers aligned parallel to the bc plane, composed of the Pt-complex columns, the –SO3− part of the octane-1-sulfonate anion, and the water molecule of crystallization, are stacked alternately with organic layers composed of the long-chain along the a axis. The Pt and I sites are located on the same mirror plane whereby the I site is equally disordered over two positions. The Pt and I atoms form a slight zigzag ⋯I—PtIV—I⋯PtII⋯ chain, with PtIV—I bond lengths of 2.6888 (17) and 2.7239 (17) Å, PtII⋯I contacts of 3.2065 (17) and 3.1732 (16) Å, and PtIV—I⋯PtII angles of 178.3 (3) and 176.7 (2)°. The mixed-valence state of the Pt site is expressed by the structural parameter δ = (PtIV—I)/(PtII⋯I), with values of 0.839 and 0.858 for the two independent I atoms. In the crystal, N—H⋯O hydrogen bonds involving the cationic chains, the sulfonate groups and water molecules of crystallization, stabilize the columnar structure.
CCDC reference: 1423010
1. Chemical context
The title compound, [Pt(en)2][PtI2(en)2](CH3(CH2)7SO3)4·2H2O (en is ethylenediamine, C2N2H8), (I), is a member of the family of one-dimensional halogen-bridged mixed-valence metal complexes, formulated as [MII(AA)2][MIVX2(AA)2]Y4 [MII/MIV = PtII/PtIV, PdII/PdIV, NiII/NiIV, PdII/PtIV, NiII/PtIV; X = Cl, Br, 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 of Robin & Day (1967), as described in previous reports (Matsushita et al., 1989, 1995; Matsushita, 1993).
The metal–halogen distances in crystals of MX-chain compounds characterize the physical properties based on the mixed-valence state. Compound (I) is one of the first examples of MX-chain structures including a long-chain alkyl group as an organic part. In a previous article (Matsushita & Taira, 1999), we have briefly reported the crystal data of (I), i.e. lattice parameter, reliability indices, and have presented a view of the crystal packing; atomic coordinates and further structure data were not deposited at that time. The reported structure was originally refined in the non-centrosymmetric P21cn. However, close examination of the atomic coordinates strongly suggests that the crystal packing has an inversion center at (1/4, 1/2, 1/2). Therefore, the structure of (I) was redetermined in the centrosymmetric Pmcn and is reported here.
2. Structural comments
As shown in Fig. 1, the structure of (I) is built up of 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, parallel to the c axis. The Pt and I sites lie on the same mirror plane, and form an infinite slight zigzag ⋯I—PtIV—I⋯PtII⋯ chain. The I atoms are not located at the exact midpoint between adjacent Pt atoms and are equally disordered over two sites close to the midpoint. Thus, the Pt site is occupationally disordered by 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 the 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 a number of other MX-chain compounds (Beauchamp et al., 1982; Yamashita et al., 1985; Toriumi et al., 1993; Matsushita et al., 1992; Huckett et al., 1993; Matsushita, 2003, 2006).
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, as follows: I—PtIV—I; Pt—I1 = 2.6888 (17), Pt—I2 = 2.7239 (17) Å, and I1—PtIV–I2 = 179.1 (3)°. I⋯PtII⋯I; Pt⋯I1 = 3.2065 (17), Pt⋯I2 = 3.1732 (16) Å, and I1⋯PtII⋯I2 = 177.5 (2). Bond angles of the Pt—I chain are Pt—I1⋯Pt = 178.3 (3) and Pt—I2⋯Pt = 176.7 (2)°. Other bond lengths and angles are given in Table 1.
The structural parameters indicating the mixed-valence state of the Pt atom, expressed by δ = (PtIV–I)/(PtII⋯I), are 0.839 and 0.858 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), comparable with that of [Pt(NH3)4][PtI2(NH3)4](HSO4)4·2H2O (0.834; Tanaka et al., 1986), and somewhat larger than that of [Pt(en)2][PtI2(en)2](HPO4)(H2PO4)I·3H2O (0.812 and 0.818; Matsushita, 2006).
3. Supramolecular features
Table 2 lists the N—H⋯O hydrogen bonds which stabilize the columnar structure composed only of cationic complexes, as shown in Fig. 1. A [PtII/IV(en)2] unit is bound to an adjacent Pt-complex unit in the column by the hydrogen-bond linkages, NH⋯counter-anion/(water molecule)⋯HN. The hydrogen-bond linkages are a common structural characteristics of MX-chain compounds.
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As a result of the intercolumnar hydrogen-bond linkages, as shown in Figs. 2 and 3, the columns form in layers parallel to the bc plane. The inorganic layer composed of the Pt-complex columns, –SO3− part of the octane-1-sulfonate ion and the water molecule of crystallization, are stacked alternately with organic layers composed of the long-chain along the direction of the a axis. The layer of the long-alkyl chain adopts an interdigitating structure.
4. Synthesis and crystallization
The title compound was prepared by a procedure previously reported (Matsushita & Taira, 1999). Metallic bronze plate-like crystals were obtained by recrystallization from an aqueous solution on slow evaporation.
5. Refinement
Although the F in the previous report (Matsushita & Taira, 1999), the present on basis of the original diffraction data was performed on F2. For better comparison with the previous model in P21cn, the non-standard setting Pmcn of No. 62 (standard setting Pnma) was chosen. The present model converged with improved reliability factors, and the s.u. values for the bond lengths and angles also decreased.
was performed onThe arrangements of both the Pt-complex cations and the anions with the long-alkyl chain suggest that the repeat unit is half of the c-axis dimension. However, the different orientations of the cations and the anions cause the repeat unit to be the c axis. Therefore, reflections with an index of l = odd are very weak. As the result, a rather low percentage of reflections with [I > 2σ(I)] are observed.
The H atoms were placed in geometrically calculated positions and refined as riding (C—H = 0.97 Å and N—H = 0.90 Å), with the constraint Uiso(H) = 1.5Ueq(C, N). The H atoms of the water molecule were located from a Fourier map and restrained with a distance of O—H = 0.82 (2) Å and Uiso(H) = 1.5Ueq(O). The maximum and minimum electron-density peaks lie within 0.75 Å of the Pt atom.
Crystal data, data collection and structure .
details are summarized in Table 3
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Supporting information
CCDC reference: 1423010
10.1107/S2056989015016801/wm5192sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016801/wm5192Isup2.hkl
The title compound, [Pt(en)2][PtI2(en)2](CH3(CH2)7SO3)4·2H2O (en is ethylenediamine, C2N2H8), (I), is a member of the family of one-dimensional halogen-bridged mixed-valence metal complexes, formulated as [MII(AA)2][MIVX2(AA)2]Y4 [MII/MIV = PtII/PtIV, PdII/PdIV, NiII/NiIV, PdII/PtIV, NiII/PtIV; X = Cl, Br, 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 of Robin & Day (1967), as described in previous reports (Matsushita et al., 1989, 1995; Matsushita, 1993).
The metal–halogen distances in crystals of MX-chain compounds characterize the physical properties based on the mixed-valence state. Compound (I) is one of the first examples of MX-chain structures including a long-chain alkyl group as an organic part. In a previous article (Matsushita & Taira, 1999), we have briefly reported the crystal data of (I), i.e. lattice parameter,
reliability indices, and have presented a view of the crystal packing; atomic coordinates and further structure data were not deposited at that time. The reported structure was originally refined in the non-centrosymmetric P21cn. However, close examination of the atomic coordinates strongly suggests that the crystal packing has an inversion center at (1/4, 1/2, 1/2). Therefore, the structure of (I) was redetermined in the centrosymmetric Pmcn and is reported here.As shown in Fig. 1, the structure of (I) is built up of 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, parallel to the c axis. The Pt and I sites lie on the same mirror plane, and form an infinite slight zigzag ···I—PtIV—I···PtII··· chain. The I atoms are not located at the exact midpoint between adjacent Pt atoms and are equally disordered over two sites close to the midpoint. Thus, the Pt site is occupationally disordered by 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 the 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 a number of other MX-chain compounds (Beauchamp et al., 1982; Yamashita et al., 1985; Toriumi et al., 1986, 1993; Matsushita et al., 1992; Huckett et al., 1993; Matsushita, 2003, 2006).
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, as follows: I—PtIV—I; Pt—I1 = 2.6888 (17) Å, Pt—I2 = 2.7239 (17) Å, and I1—PtIV–I2 = 179.1 (3) °. I···PtII···I; Pt···I1 = 3.2065 (17) Å, Pt···I2 = 3.1732 (16) Å, and I1···PtII···I2 = 177.5 (2). Bond angles of the Pt—I chain are Pt—I1···Pt = 178.3 (3) ° and Pt—I2···Pt = 176.7 (2)°. Other bond lengths and angles are given in Table 1.
The structural parameters indicating the mixed-valence state of the Pt atom, expressed by δ = (PtIV–I)/(PtII···I), are 0.839 and 0.858 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)], comparable with that of [Pt(NH3)4][PtI2(NH3)4](HSO4)4·2H2O [0.834; Tanaka et al., 1986)], and somewhat larger than that of [Pt(en)2][PtI2(en)2](HPO4)(H2PO4)I·3H2O [0.812 and 0.818; Matsushita, 2006)].
Table 2 lists the N—H···O hydrogen bonds which stabilize the columnar structure composed only of cationic complexes, as shown in Fig. 1. A [PtII/IV(en)2] unit is bound to an adjacent Pt-complex unit in the column by the hydrogen-bond linkages, NH···counter-anion/(water molecule)···HN. The hydrogen-bond linkages are a common structural characteristics of MX-chain compounds.
As a result of the intercolumnar hydrogen-bond linkages, as shown in Figs. 2 and 3, the columns form in layers parallel to the bc plane. The inorganic layer composed of the Pt-complex columns, –SO3- part of the octane-1-sulfonate ion and the water molecule of crystallization, are stacked alternately with organic layers composed of the long-chain
along the direction of the a axis. The layer of the long-alkyl chain adopts an interdigitating structure.The title compound was prepared by a procedure previously reported (Matsushita & Taira, 1999). Metallic bronze plate-like crystals were obtained by recrystallization from an aqueous solution on slow evaporation.
Although the
was performed on F in the previous report (Matsushita & Taira, 1999), the present on basis of the original diffraction data was performed on F2. For better comparison with the previous model in P21cn, the non-standard setting Pmcn of No. 62 (standard setting Pnma) was chosen. The present model converged with improved reliability factors, and the s.u. values for the bond lengths and angles also decreased.The arrangements of both the Pt-complex cations and the anions with the long-alkyl chain suggest that the repeat unit is half of the c-axis dimension. However, the different orientations of the cations and the anions cause the repeat unit to be the c axis. Therefore, reflections with an index of l = odd are very weak. As the result, a rather low percentage of reflections with [I > 2σ(I)] are observed.
The H atoms were placed in geometrically calculated positions and refined as riding (C—H = 0.97 Å and N—H = 0.90 Å), with the constraint Uiso(H) = 1.5Ueq(C, N). The H atoms of the water molecule were located from a Fourier map and restrained with a distance of O—H = 0.82 (2) Å and Uiso(H) = 1.5Ueq(O). The maximum and minimum electron-density peaks lie within 0.75 Å of the Pt atom.
Crystal data, data collection and structure
details are summarized in Table 3.Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell
MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); data reduction: local program F2-AFC (Matsushita, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. A view of the columnar structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 40% probability level for non-H atoms. The violet-line ellipsoids and dashed-line bonds represent the disordered part of the Pt—I chain. Blue dashed lines represent the hydrogen bonds. | |
Fig. 2. The crystal packing of the title compound, viewed along the c axis. Blue dashed lines represent the hydrogen bonds. Orange solid lines indicate the unit cell. | |
Fig. 3. The crystal packing of the title compound viewed along the b axis. Blue dashed lines represent the hydrogen bonds. Orange solid lines indicate the unit cell. |
[Pt2I2(C2H8N2)4](C8H17SO3)4·2H2O | F(000) = 1676 |
Mr = 1693.53 | Dx = 1.812 Mg m−3 |
Orthorhombic, Pmcn | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2n 2a | Cell parameters from 25 reflections |
a = 36.997 (3) Å | θ = 10.0–14.0° |
b = 7.118 (2) Å | µ = 5.69 mm−1 |
c = 11.788 (3) Å | T = 301 K |
V = 3104.3 (11) Å3 | Plate, metallic bronze |
Z = 2 | 0.17 × 0.15 × 0.05 mm |
Rigaku AFC-5S diffractometer | 2039 reflections with I > 2σ(I) |
Radiation source: X-ray sealed tube | Rint = 0.006 |
Graphite monochromator | θmax = 32.5°, θmin = 2.9° |
ω scans | h = 0→55 |
Absorption correction: gaussian (Coppens et al., 1965) | k = 0→10 |
Tmin = 0.467, Tmax = 0.757 | l = 0→17 |
5883 measured reflections | 3 standard reflections every 100 reflections |
5688 independent reflections | intensity decay: none |
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)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.0247P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.92 | (Δ/σ)max < 0.001 |
5688 reflections | Δρmax = 1.66 e Å−3 |
174 parameters | Δρmin = −2.12 e Å−3 |
2 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: heavy-atom method | Extinction coefficient: 0.00020 (3) |
[Pt2I2(C2H8N2)4](C8H17SO3)4·2H2O | V = 3104.3 (11) Å3 |
Mr = 1693.53 | Z = 2 |
Orthorhombic, Pmcn | Mo Kα radiation |
a = 36.997 (3) Å | µ = 5.69 mm−1 |
b = 7.118 (2) Å | T = 301 K |
c = 11.788 (3) Å | 0.17 × 0.15 × 0.05 mm |
Rigaku AFC-5S diffractometer | 2039 reflections with I > 2σ(I) |
Absorption correction: gaussian (Coppens et al., 1965) | Rint = 0.006 |
Tmin = 0.467, Tmax = 0.757 | 3 standard reflections every 100 reflections |
5883 measured reflections | intensity decay: none |
5688 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 2 restraints |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | Δρmax = 1.66 e Å−3 |
5688 reflections | Δρmin = −2.12 e Å−3 |
174 parameters |
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 > 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pt | 0.2500 | 0.25626 (11) | 0.18219 (3) | 0.02517 (11) | |
I1 | 0.2500 | 0.2445 (9) | 0.41018 (13) | 0.0337 (5) | 0.50 |
I2 | 0.2500 | 0.2378 (9) | 0.45114 (13) | 0.0344 (6) | 0.50 |
N1 | 0.2915 (2) | 0.0656 (11) | 0.1722 (6) | 0.036 (2) | |
H1A | 0.2941 | 0.0071 | 0.2394 | 0.053* | |
H1B | 0.2862 | −0.0217 | 0.1194 | 0.053* | |
N2 | 0.2918 (3) | 0.4454 (12) | 0.1908 (7) | 0.043 (3) | |
H2A | 0.2934 | 0.5098 | 0.1253 | 0.064* | |
H2B | 0.2878 | 0.5277 | 0.2474 | 0.064* | |
C1 | 0.3255 (3) | 0.1620 (14) | 0.1418 (8) | 0.050 (3) | |
H1C | 0.3260 | 0.1911 | 0.0614 | 0.075* | |
H1D | 0.3462 | 0.0836 | 0.1598 | 0.075* | |
C2 | 0.3261 (3) | 0.3405 (14) | 0.2118 (8) | 0.048 (3) | |
H2C | 0.3283 | 0.3100 | 0.2917 | 0.072* | |
H2D | 0.3467 | 0.4173 | 0.1903 | 0.072* | |
O4 | 0.2500 | 0.7653 (16) | 0.0327 (9) | 0.073 (3) | |
H4 | 0.2677 (5) | 0.718 (13) | 0.000 (7) | 0.109* | |
S1 | 0.66363 (7) | 0.3288 (3) | 0.07740 (19) | 0.0466 (6) | |
O1 | 0.6733 (2) | 0.2765 (13) | −0.0376 (5) | 0.080 (2) | |
O2 | 0.69019 (16) | 0.2676 (13) | 0.1594 (4) | 0.0525 (16) | |
O3 | 0.65542 (19) | 0.5260 (9) | 0.0862 (6) | 0.068 (2) | |
C11 | 0.6225 (3) | 0.2054 (12) | 0.1073 (7) | 0.053 (3) | |
H11A | 0.6059 | 0.2242 | 0.0448 | 0.079* | |
H11B | 0.6277 | 0.0721 | 0.1119 | 0.079* | |
C12 | 0.6044 (2) | 0.2663 (17) | 0.2159 (7) | 0.048 (2) | |
H12A | 0.6020 | 0.4020 | 0.2165 | 0.072* | |
H12B | 0.6192 | 0.2303 | 0.2801 | 0.072* | |
C13 | 0.5670 (3) | 0.1764 (14) | 0.2275 (8) | 0.058 (3) | |
H13A | 0.5534 | 0.1998 | 0.1585 | 0.087* | |
H13B | 0.5699 | 0.0416 | 0.2349 | 0.087* | |
C14 | 0.5457 (2) | 0.246 (2) | 0.3255 (7) | 0.056 (2) | |
H14A | 0.5445 | 0.3824 | 0.3212 | 0.084* | |
H14B | 0.5585 | 0.2144 | 0.3947 | 0.084* | |
C15 | 0.5077 (3) | 0.1697 (15) | 0.3330 (7) | 0.056 (3) | |
H15A | 0.5091 | 0.0344 | 0.3419 | 0.084* | |
H15B | 0.4955 | 0.1945 | 0.2617 | 0.084* | |
C16 | 0.4847 (2) | 0.2488 (16) | 0.4288 (7) | 0.058 (2) | |
H16A | 0.4968 | 0.2239 | 0.5002 | 0.087* | |
H16B | 0.4832 | 0.3840 | 0.4198 | 0.087* | |
C17 | 0.4468 (3) | 0.1704 (13) | 0.4350 (9) | 0.060 (3) | |
H17A | 0.4344 | 0.1988 | 0.3645 | 0.090* | |
H17B | 0.4483 | 0.0347 | 0.4414 | 0.090* | |
C18 | 0.4244 (3) | 0.244 (2) | 0.5322 (8) | 0.078 (3) | |
H18A | 0.4356 | 0.2109 | 0.6028 | 0.117* | |
H18B | 0.4006 | 0.1902 | 0.5290 | 0.117* | |
H18C | 0.4226 | 0.3784 | 0.5268 | 0.117* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.0375 (2) | 0.02157 (17) | 0.01644 (15) | 0.000 | 0.000 | 0.0004 (3) |
I1 | 0.0448 (11) | 0.0391 (9) | 0.0173 (7) | 0.000 | 0.000 | 0.002 (2) |
I2 | 0.0552 (12) | 0.0308 (11) | 0.0173 (8) | 0.000 | 0.000 | −0.0001 (18) |
N1 | 0.035 (6) | 0.036 (5) | 0.036 (5) | 0.007 (4) | 0.012 (4) | 0.000 (3) |
N2 | 0.068 (9) | 0.034 (5) | 0.026 (4) | −0.020 (5) | 0.006 (4) | 0.003 (3) |
C1 | 0.044 (7) | 0.069 (7) | 0.037 (5) | 0.015 (5) | 0.010 (5) | 0.002 (5) |
C2 | 0.041 (6) | 0.055 (6) | 0.048 (5) | −0.009 (5) | −0.005 (5) | 0.013 (5) |
O4 | 0.100 (8) | 0.036 (5) | 0.081 (7) | 0.000 | 0.000 | −0.023 (6) |
S1 | 0.0548 (15) | 0.0516 (13) | 0.0334 (11) | −0.0170 (11) | −0.0039 (12) | 0.0021 (10) |
O1 | 0.099 (6) | 0.099 (6) | 0.041 (3) | −0.040 (6) | 0.009 (4) | 0.002 (5) |
O2 | 0.048 (3) | 0.064 (4) | 0.045 (3) | −0.009 (5) | −0.004 (3) | 0.008 (4) |
O3 | 0.064 (5) | 0.048 (4) | 0.091 (5) | −0.019 (3) | −0.016 (4) | 0.014 (4) |
C11 | 0.058 (6) | 0.050 (6) | 0.049 (5) | −0.017 (5) | −0.003 (5) | 0.012 (4) |
C12 | 0.045 (5) | 0.052 (6) | 0.048 (4) | −0.023 (6) | −0.019 (4) | 0.003 (6) |
C13 | 0.055 (7) | 0.062 (6) | 0.057 (6) | −0.010 (5) | 0.007 (6) | 0.012 (5) |
C14 | 0.056 (5) | 0.055 (5) | 0.058 (5) | −0.022 (8) | −0.007 (5) | 0.000 (7) |
C15 | 0.042 (6) | 0.063 (6) | 0.064 (7) | −0.014 (5) | 0.006 (5) | 0.017 (5) |
C16 | 0.053 (5) | 0.056 (5) | 0.064 (5) | −0.017 (7) | −0.005 (5) | 0.021 (9) |
C17 | 0.045 (6) | 0.054 (5) | 0.081 (7) | −0.008 (5) | 0.014 (7) | 0.015 (6) |
C18 | 0.066 (7) | 0.086 (7) | 0.083 (7) | −0.004 (10) | 0.005 (6) | −0.009 (10) |
Pt—N1i | 2.052 (8) | C11—C12 | 1.509 (11) |
Pt—N1 | 2.052 (8) | C11—H11A | 0.9700 |
Pt—N2i | 2.052 (8) | C11—H11B | 0.9700 |
Pt—N2 | 2.052 (8) | C12—C13 | 1.531 (12) |
Pt—I1 | 2.6888 (17) | C12—H12A | 0.9700 |
Pt—I2ii | 2.7239 (17) | C12—H12B | 0.9700 |
Pt—I2 | 3.1732 (16) | C13—C14 | 1.483 (12) |
Pt—I1iii | 3.2065 (17) | C13—H13A | 0.9700 |
N1—C1 | 1.479 (11) | C13—H13B | 0.9700 |
N1—H1A | 0.9000 | C14—C15 | 1.513 (12) |
N1—H1B | 0.9000 | C14—H14A | 0.9700 |
N2—C2 | 1.495 (12) | C14—H14B | 0.9700 |
N2—H2A | 0.9000 | C15—C16 | 1.522 (12) |
N2—H2B | 0.9000 | C15—H15A | 0.9700 |
C1—C2 | 1.515 (12) | C15—H15B | 0.9700 |
C1—H1C | 0.9700 | C16—C17 | 1.511 (12) |
C1—H1D | 0.9700 | C16—H16A | 0.9700 |
C2—H2C | 0.9700 | C16—H16B | 0.9700 |
C2—H2D | 0.9700 | C17—C18 | 1.510 (12) |
O4—H4 | 0.83 (2) | C17—H17A | 0.9700 |
S1—O3 | 1.440 (7) | C17—H17B | 0.9700 |
S1—O2 | 1.446 (6) | C18—H18A | 0.9600 |
S1—O1 | 1.451 (7) | C18—H18B | 0.9600 |
S1—C11 | 1.791 (9) | C18—H18C | 0.9600 |
N1i—Pt—N1 | 96.8 (5) | O3—S1—O2 | 112.9 (5) |
N1i—Pt—N2i | 82.7 (2) | O3—S1—O1 | 111.7 (5) |
N1—Pt—N2i | 179.4 (4) | O2—S1—O1 | 112.3 (4) |
N1i—Pt—N2 | 179.4 (4) | O3—S1—C11 | 106.5 (5) |
N1—Pt—N2 | 82.7 (2) | O2—S1—C11 | 107.3 (4) |
N2i—Pt—N2 | 97.7 (5) | O1—S1—C11 | 105.5 (4) |
N1i—Pt—I1 | 92.1 (2) | C12—C11—S1 | 113.8 (6) |
N1—Pt—I1 | 92.1 (2) | C12—C11—H11A | 108.8 |
N2i—Pt—I1 | 88.3 (3) | S1—C11—H11A | 108.8 |
N2—Pt—I1 | 88.3 (3) | C12—C11—H11B | 108.8 |
N1i—Pt—I2ii | 87.3 (2) | S1—C11—H11B | 108.8 |
N1—Pt—I2ii | 87.3 (2) | H11A—C11—H11B | 107.7 |
N2i—Pt—I2ii | 92.2 (3) | C11—C12—C13 | 111.0 (8) |
N2—Pt—I2ii | 92.2 (3) | C11—C12—H12A | 109.4 |
I1—Pt—I2ii | 179.1 (3) | C13—C12—H12A | 109.4 |
N1i—Pt—I2 | 91.7 (2) | C11—C12—H12B | 109.4 |
N1—Pt—I2 | 91.7 (2) | C13—C12—H12B | 109.4 |
N2i—Pt—I2 | 88.7 (2) | H12A—C12—H12B | 108.0 |
N2—Pt—I2 | 88.7 (2) | C14—C13—C12 | 114.1 (8) |
I1—Pt—I2 | 0.6 (2) | C14—C13—H13A | 108.7 |
I2ii—Pt—I2 | 178.52 (4) | C12—C13—H13A | 108.7 |
N1i—Pt—I1iii | 86.6 (2) | C14—C13—H13B | 108.7 |
N1—Pt—I1iii | 86.6 (2) | C12—C13—H13B | 108.7 |
N2i—Pt—I1iii | 92.9 (2) | H13A—C13—H13B | 107.6 |
N2—Pt—I1iii | 92.9 (2) | C13—C14—C15 | 114.6 (9) |
I1—Pt—I1iii | 178.12 (4) | C13—C14—H14A | 108.6 |
I2ii—Pt—I1iii | 1.0 (2) | C15—C14—H14A | 108.6 |
I2—Pt—I1iii | 177.5 (2) | C13—C14—H14B | 108.6 |
Pt—I1—Ptiv | 178.3 (3) | C15—C14—H14B | 108.6 |
Ptiv—I2—Pt | 176.7 (2) | H14A—C14—H14B | 107.6 |
C1—N1—Pt | 110.1 (6) | C14—C15—C16 | 115.5 (8) |
C1—N1—H1A | 109.6 | C14—C15—H15A | 108.4 |
Pt—N1—H1A | 109.6 | C16—C15—H15A | 108.4 |
C1—N1—H1B | 109.6 | C14—C15—H15B | 108.4 |
Pt—N1—H1B | 109.6 | C16—C15—H15B | 108.4 |
H1A—N1—H1B | 108.1 | H15A—C15—H15B | 107.5 |
C2—N2—Pt | 108.7 (6) | C17—C16—C15 | 114.7 (9) |
C2—N2—H2A | 109.9 | C17—C16—H16A | 108.6 |
Pt—N2—H2A | 109.9 | C15—C16—H16A | 108.6 |
C2—N2—H2B | 109.9 | C17—C16—H16B | 108.6 |
Pt—N2—H2B | 109.9 | C15—C16—H16B | 108.6 |
H2A—N2—H2B | 108.3 | H16A—C16—H16B | 107.6 |
N1—C1—C2 | 105.7 (8) | C18—C17—C16 | 114.7 (9) |
N1—C1—H1C | 110.6 | C18—C17—H17A | 108.6 |
C2—C1—H1C | 110.6 | C16—C17—H17A | 108.6 |
N1—C1—H1D | 110.6 | C18—C17—H17B | 108.6 |
C2—C1—H1D | 110.6 | C16—C17—H17B | 108.6 |
H1C—C1—H1D | 108.7 | H17A—C17—H17B | 107.6 |
N2—C2—C1 | 108.4 (8) | C17—C18—H18A | 109.5 |
N2—C2—H2C | 110.0 | C17—C18—H18B | 109.5 |
C1—C2—H2C | 110.0 | H18A—C18—H18B | 109.5 |
N2—C2—H2D | 110.0 | C17—C18—H18C | 109.5 |
C1—C2—H2D | 110.0 | H18A—C18—H18C | 109.5 |
H2C—C2—H2D | 108.4 | H18B—C18—H18C | 109.5 |
Symmetry codes: (i) −x+1/2, y, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1/2, −y+1/2, z−1/2; (iv) x, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2v | 0.90 | 2.16 | 2.983 (11) | 152 |
N1—H1B···O4vi | 0.90 | 2.27 | 3.103 (11) | 154 |
N2—H2A···O1vii | 0.90 | 2.21 | 2.975 (10) | 142 |
N2—H2B···O2viii | 0.90 | 2.19 | 2.971 (11) | 145 |
O4—H4···O1vii | 0.83 (2) | 2.23 (3) | 2.853 (8) | 132 (4) |
O4—H4···O2vii | 0.83 (2) | 2.44 (7) | 3.175 (9) | 148 (11) |
Symmetry codes: (v) −x+1, y−1/2, −z+1/2; (vi) x, y−1, z; (vii) −x+1, −y+1, −z; (viii) −x+1, y+1/2, −z+1/2. |
Pt—N1 | 2.052 (8) | Pt—N2 | 2.052 (8) |
N1i—Pt—N1 | 96.8 (5) | N1—Pt—I1 | 92.1 (2) |
N1i—Pt—N2 | 179.4 (4) | N2—Pt—I1 | 88.3 (3) |
N1—Pt—N2 | 82.7 (2) | N1—Pt—I2ii | 87.3 (2) |
N2i—Pt—N2 | 97.7 (5) | N2—Pt—I2ii | 92.2 (3) |
Symmetry codes: (i) −x+1/2, y, z; (ii) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2iii | 0.90 | 2.16 | 2.983 (11) | 151.6 |
N1—H1B···O4iv | 0.90 | 2.27 | 3.103 (11) | 154.2 |
N2—H2A···O1v | 0.90 | 2.21 | 2.975 (10) | 141.9 |
N2—H2B···O2vi | 0.90 | 2.19 | 2.971 (11) | 145.1 |
O4—H4···O1v | 0.83 (2) | 2.23 (3) | 2.853 (8) | 132 (4) |
O4—H4···O2v | 0.83 (2) | 2.44 (7) | 3.175 (9) | 148 (11) |
Symmetry codes: (iii) −x+1, y−1/2, −z+1/2; (iv) x, y−1, z; (v) −x+1, −y+1, −z; (vi) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Pt2I2(C2H8N2)4](C8H17SO3)4·2H2O |
Mr | 1693.53 |
Crystal system, space group | Orthorhombic, Pmcn |
Temperature (K) | 301 |
a, b, c (Å) | 36.997 (3), 7.118 (2), 11.788 (3) |
V (Å3) | 3104.3 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 5.69 |
Crystal size (mm) | 0.17 × 0.15 × 0.05 |
Data collection | |
Diffractometer | Rigaku AFC-5S diffractometer |
Absorption correction | Gaussian (Coppens et al., 1965) |
Tmin, Tmax | 0.467, 0.757 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5883, 5688, 2039 |
Rint | 0.006 |
(sin θ/λ)max (Å−1) | 0.756 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.112, 0.92 |
No. of reflections | 5688 |
No. of parameters | 174 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.66, −2.12 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), local program F2-AFC (Matsushita, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).
Acknowledgements
This work was partly supported by a MEXT-Supported Program for the Strategic Research Foundation at Private Universities (project No. S1311027) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.
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