Redetermination of the crystal structure of catena-poly[[[bis­(ethyl­enedi­amine)­platinum(II)]-μ-iodido-[bis­(ethyl­enedi­amine)­platinum(IV)]-μ-iodido] tetra­kis­(octane-1-sulfonate) dihydrate]

Matsushita, N.

doi:10.1107/S2056989015016801

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Volume 71| Part 10| October 2015| Pages 1155-1158

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Redetermination of the crystal structure of catena-poly[[[bis(ethylenediamine)platinum(II)]-μ-iodido-[bis(ethylenediamine)platinum(IV)]-μ-iodido] tetrakis(octane-1-sulfonate) dihydrate]

Nobuyuki Matsushita ^a ^*

^aDepartment 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

Edited by M. Weil, Vienna University of Technology, Austria (Received 25 July 2015; accepted 8 September 2015; online 12 September 2015)

The structure of the title compound, which represents a mixed-valence platinum(II,IV) complex, {[Pt^IIPt^IVI₂(C₂H₈N₂)₄][CH₃(CH₂)₇SO₃]₄·2H₂O}_n, has been redetermined in a different space group. In contrast to the previously reported determination in the space group P2₁cn [Matsushita & Taira (1999 ). Synth. Met. 102, 1787–1788], the current model was refined in the centrosymmetric space group 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 alkyl groups 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—Pt^IV—I⋯Pt^II⋯ chain, with Pt^IV—I bond lengths of 2.6888 (17) and 2.7239 (17) Å, Pt^II⋯I contacts of 3.2065 (17) and 3.1732 (16) Å, and Pt^IV—I⋯Pt^II angles of 178.3 (3) and 176.7 (2)°. The mixed-valence state of the Pt site is expressed by the structural parameter δ = (Pt^IV—I)/(Pt^II⋯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.

Keywords: crystal structure; redetermination; MX-chain structure; Pt^II/Pt^IV mixed-valence.

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 [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, Ni^II/Pt^IV; 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, space group, 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 space group 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 space group 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—Pt^IV—I⋯Pt^II⋯ 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 Pt^II and Pt^IV 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 ).

Figure 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.

With respect to the two sites for the disordered I atoms, the shorter Pt—I distances are assigned to Pt^IV—I and the longer ones to Pt^II⋯I, as follows: I—Pt^IV—I; Pt—I1 = 2.6888 (17), Pt—I2 = 2.7239 (17) Å, and I1—Pt^IV–I2 = 179.1 (3)°. I⋯Pt^II⋯I; Pt⋯I1 = 3.2065 (17), Pt⋯I2 = 3.1732 (16) Å, and I1⋯Pt^II⋯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.

Table 1
Selected geometric parameters (Å, °)

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) $[-x+{\script{1\over 2}}, y, z]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

The structural parameters indicating the mixed-valence state of the Pt atom, expressed by δ = (Pt^IV–I)/(Pt^II⋯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 [Pt^II/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.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱⁱⁱ	0.90	2.16	2.983 (11)	152
N1—H1B⋯O4^iv	0.90	2.27	3.103 (11)	154
N2—H2A⋯O1^v	0.90	2.21	2.975 (10)	142
N2—H2B⋯O2^vi	0.90	2.19	2.971 (11)	145
O4—H4⋯O1^v	0.83 (2)	2.23 (3)	2.853 (8)	132 (4)
O4—H4⋯O2^v	0.83 (2)	2.44 (7)	3.175 (9)	148 (11)
Symmetry codes: (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x, y-1, z; (v) -x+1, -y+1, -z; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 alkyl groups along the direction of the a axis. The layer of the long-alkyl chain adopts an interdigitating structure.

Figure 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.

Figure 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.

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 refinement was performed on F in the previous report (Matsushita & Taira, 1999), the present refinement on basis of the original diffraction data was performed on F². For better comparison with the previous model in space group P2₁cn, the non-standard setting Pmcn of space group 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 U_iso(H) = 1.5U_eq(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 U_iso(H) = 1.5U_eq(O). The maximum and minimum electron-density peaks lie within 0.75 Å of the Pt atom.

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	[Pt(C₂H₈N₂)₄][PtI₂(C₂H₈N₂)₄](C₈H₁₇SO₃)₄·2H₂O
M_r	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
Absorption correction	Gaussian (Coppens et al., 1965 )
T_min, T_max	0.467, 0.757
No. of measured, independent and observed [I > 2σ(I)] reflections	5883, 5688, 2039
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	1.66, −2.12
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988 $[Molecular Structure Corporation (1988). MSC/AFC Diffractometer Control Software. MSC, The Woodlands, Texas, USA.]$ ), local program F2-AFC (Matsushita, 1998 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and DIAMOND (Brandenburg, 2006 ).

Supporting information

CCDC reference: 1423010

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015016801/wm5192sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016801/wm5192Isup2.hkl

checkCIF report

Chemical context top

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 [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, Ni^II/Pt^IV; 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).

Structural comments top

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—Pt^IV—I···Pt^II··· 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 Pt^II and Pt^IV 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 Pt^IV—I and the longer ones to Pt^II···I, as follows: I—Pt^IV—I; Pt—I1 = 2.6888 (17) Å, Pt—I2 = 2.7239 (17) Å, and I1—Pt^IV–I2 = 179.1 (3) °. I···Pt^II···I; Pt···I1 = 3.2065 (17) Å, Pt···I2 = 3.1732 (16) Å, and I1···Pt^II···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 = (Pt^IV–I)/(Pt^II···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)].

Supramolecular features top

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 [Pt^II/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 alkyl groups along the direction of the a axis. The layer of the long-alkyl chain adopts an interdigitating structure.

Synthesis and crystallization top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: 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).

Figures top

	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.

catena-Poly[[[bis(ethylenediamine)platinum(II)]-µ-iodido-[bis(ethylenediamine)platinum(IV)]-µ-iodido] tetrakis(octane-1-sulfonate) dihydrate] top

Crystal data top

[Pt₂I₂(C₂H₈N₂)₄](C₈H₁₇SO₃)₄·2H₂O	F(000) = 1676
M_r = 1693.53	D_x = 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

Data collection top

Rigaku AFC-5S diffractometer	2039 reflections with I > 2σ(I)
Radiation source: X-ray sealed tube	R_int = 0.006
Graphite monochromator	θ_max = 32.5°, θ_min = 2.9°
ω scans	h = 0→55
Absorption correction: gaussian (Coppens et al., 1965)	k = 0→10
T_min = 0.467, T_max = 0.757	l = 0→17
5883 measured reflections	3 standard reflections every 100 reflections
5688 independent reflections	intensity decay: none

Refinement top

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(F_o²) + (0.0247P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max < 0.001
5688 reflections	Δρ_max = 1.66 e Å⁻³
174 parameters	Δρ_min = −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)

Crystal data top

[Pt₂I₂(C₂H₈N₂)₄](C₈H₁₇SO₃)₄·2H₂O	V = 3104.3 (11) Å³
M_r = 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

Data collection top

Rigaku AFC-5S diffractometer	2039 reflections with I > 2σ(I)
Absorption correction: gaussian (Coppens et al., 1965)	R_int = 0.006
T_min = 0.467, T_max = 0.757	3 standard reflections every 100 reflections
5883 measured reflections	intensity decay: none
5688 independent reflections

Refinement top

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	Δρ_max = 1.66 e Å⁻³
5688 reflections	Δρ_min = −2.12 e Å⁻³
174 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—Pt^iv	178.3 (3)	C15—C14—H14B	108.6
Pt^iv—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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^v	0.90	2.16	2.983 (11)	152
N1—H1B···O4^vi	0.90	2.27	3.103 (11)	154
N2—H2A···O1^vii	0.90	2.21	2.975 (10)	142
N2—H2B···O2^viii	0.90	2.19	2.971 (11)	145
O4—H4···O1^vii	0.83 (2)	2.23 (3)	2.853 (8)	132 (4)
O4—H4···O2^vii	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.

Selected geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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···O4^iv	0.90	2.27	3.103 (11)	154.2
N2—H2A···O1^v	0.90	2.21	2.975 (10)	141.9
N2—H2B···O2^vi	0.90	2.19	2.971 (11)	145.1
O4—H4···O1^v	0.83 (2)	2.23 (3)	2.853 (8)	132 (4)
O4—H4···O2^v	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
M_r	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)
T_min, T_max	0.467, 0.757
No. of measured, independent and observed [I > 2σ(I)] reflections	5883, 5688, 2039
R_int	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
Δρ_max, Δρ_min (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.

References

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Volume 71| Part 10| October 2015| Pages 1155-1158

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Redetermination of the crystal structure of catena-poly[[[bis­­(ethyl­enedi­amine)­platinum(II)]-μ-iodido-[bis­­(ethyl­enedi­amine)­platinum(IV)]-μ-iodido] tetra­kis­(octane-1-sulfonate) dihydrate]

1. Chemical context

2. Structural comments

3. Supra­molecular features

4. Synthesis and crystallization

5. Refinement

Supporting information

Acknowledgements

References

research communications

Redetermination of the crystal structure of catena-poly[[[bis(ethylenediamine)platinum(II)]-μ-iodido-[bis(ethylenediamine)platinum(IV)]-μ-iodido] tetrakis(octane-1-sulfonate) dihydrate]

3. Supramolecular features