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ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1155-1158

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]

CROSSMARK_Color_square_no_text.svg

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, {[PtIIPtIVI2(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[Matsushita, N. & Taira, A. (1999). Synth. Met. 102, 1787-1788.]). 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—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.

1. Chemical context

The title compound, [Pt(en)2][PtI2(en)2](CH3(CH2)7SO3)4·2H2O (en is ethyl­enedi­amine, C2N2H8), (I)[link], 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[Robin, M. B. & Day, P. (1967). Advances Inorganic Chemistry and Radiochemistry, edited by H. J. Emeléus & A. G. Sharpe, Vol. 10, pp. 247-422. New York: Academic Press.]), as described in previous reports (Matsushita et al., 1989[Matsushita, N., Kojima, N., Ban, T. & Tsujikawa, I. (1989). Bull. Chem. Soc. Jpn, 62, 1785-1790.], 1995[Matsushita, N., Kitagawa, H. & Mitani, T. (1995). Synth. Met. 71, 1933-1934.]; Matsushita, 1993[Matsushita, N. (1993). Synth. Met. 56, 3401-3406.]).

The metal–halogen distances in crystals of MX-chain compounds characterize the physical properties based on the mixed-valence state. Compound (I)[link] 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[Matsushita, N. & Taira, A. (1999). Synth. Met. 102, 1787-1788.]), we have briefly reported the crystal data of (I)[link], 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)[link] was redetermined in the centrosymmetric space group Pmcn and is reported here.

[Scheme 1]

2. Structural comments

As shown in Fig. 1[link], the structure of (I)[link] 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)[link] belongs to one of three different classes of the order–disorder problem pointed out by Keller (1982[Keller, H. J. (1982). Extended Linear Chain Compounds, edited by J. S. Miller, pp. 357-407. New York: Plenum.]). The structure of (I)[link] 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)[link] has also been observed in a number of other MX-chain compounds (Beauchamp et al., 1982[Beauchamp, A. L., Layek, D. & Theophanides, T. (1982). Acta Cryst. B38, 1158-1164.]; Yamashita et al., 1985[Yamashita, M., Toriumi, K. & Ito, T. (1985). Acta Cryst. C41, 876-878.]; Toriumi et al., 1993[Toriumi, K., Yamashita, M., Kurita, S., Murase, I. & Ito, T. (1993). Acta Cryst. B49, 497-506.]; Matsushita et al., 1992[Matsushita, N., Taga, T. & Tsujikawa, I. (1992). Acta Cryst. C48, 1936-1939.]; Huckett et al., 1993[Huckett, S. C., Scott, B., Love, S. P., Donohoe, R. J., Burns, C. J., Garcia, E., Frankcom, T. & Swanson, B. I. (1993). Inorg. Chem. 32, 2137-2144.]; Matsushita, 2003[Matsushita, N. (2003). Acta Cryst. E59, m26-m28.], 2006[Matsushita, N. (2006). Acta Cryst. C62, m33-m36.]).

[Figure 1]
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 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[link].

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 = (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[Breer, H., Endres, H., Keller, H. J. & Martin, R. (1978). Acta Cryst. B34, 2295-2297.]); [Pt(pn)2][PtI2(pn)2]I4 (0.940; Endres et al., 1980[Endres, H., Keller, H. J., Martin, R., Traeger, U. & Novotny, M. (1980). Acta Cryst. B36, 35-39.]); [Pt(tn)2][PtI2(tn)2](ClO4)4 (tn is 1,3-di­amino­propane) (0.95; Cannas et al., 1984[Cannas, M., Marongiu, G., Keller, H. J., Müller, B. & Martin, R. (1984). Z. Naturforsch. Teil B, 39, 197-200.]); [Pt(en)2][PtI2(en)2](ClO4)4 (0.919; Endres et al., 1979[Endres, H., Keller, H. J., Martin, R., Hae Nam Gung, & Traeger, J. (1979). Acta Cryst. B35, 1885-1887.]), comparable with that of [Pt(NH3)4][PtI2(NH3)4](HSO4)4·2H2O (0.834; Tanaka et al., 1986[Tanaka, M., Tsujikawa, I., Toriumi, K. & Ito, T. (1986). Acta Cryst. C42, 1105-1109.]), and somewhat larger than that of [Pt(en)2][PtI2(en)2](HPO4)(H2PO4)I·3H2O (0.812 and 0.818; Matsushita, 2006[Matsushita, N. (2006). Acta Cryst. C62, m33-m36.]).

3. Supra­molecular features

Table 2[link] lists the N—H⋯O hydrogen bonds which stabilize the columnar structure composed only of cationic complexes, as shown in Fig. 1[link]. 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.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯O2iii 0.90 2.16 2.983 (11) 152
N1—H1B⋯O4iv 0.90 2.27 3.103 (11) 154
N2—H2A⋯O1v 0.90 2.21 2.975 (10) 142
N2—H2B⋯O2vi 0.90 2.19 2.971 (11) 145
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-{\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[link] and 3[link], 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]
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]
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[Matsushita, N. & Taira, A. (1999). Synth. Met. 102, 1787-1788.]). 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[Matsushita, N. & Taira, A. (1999). Synth. Met. 102, 1787-1788.]), 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 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 refinement details are summarized in Table 3[link].

Table 3
Experimental details

Crystal data
Chemical formula [Pt(C2H8N2)4][PtI2(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)
V3) 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[Coppens, P., Leiserowitz, L. & Rabinovich, D. (1965). Acta Cryst. 18, 1035-1038.])
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−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[Molecular Structure Corporation (1988). MSC/AFC Diffractometer Control Software. MSC, The Woodlands, Texas, USA.]), local program F2-AFC (Matsushita, 1998[Matsushita, N. (1998). F2-AFC. University of Tokyo, Japan.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]).

Supporting information


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 [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, 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.

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—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)].

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

Synthesis and crystallization top

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.

Refinement top

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 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 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
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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)4·2H2OF(000) = 1676
Mr = 1693.53Dx = 1.812 Mg m3
Orthorhombic, PmcnMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2n 2aCell parameters from 25 reflections
a = 36.997 (3) Åθ = 10.0–14.0°
b = 7.118 (2) ŵ = 5.69 mm1
c = 11.788 (3) ÅT = 301 K
V = 3104.3 (11) Å3Plate, metallic bronze
Z = 20.17 × 0.15 × 0.05 mm
Data collection top
Rigaku AFC-5S
diffractometer
2039 reflections with I > 2σ(I)
Radiation source: X-ray sealed tubeRint = 0.006
Graphite monochromatorθmax = 32.5°, θmin = 2.9°
ω scansh = 055
Absorption correction: gaussian
(Coppens et al., 1965)
k = 010
Tmin = 0.467, Tmax = 0.757l = 017
5883 measured reflections3 standard reflections every 100 reflections
5688 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H 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 reflectionsΔρmax = 1.66 e Å3
174 parametersΔρmin = 2.12 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: heavy-atom methodExtinction coefficient: 0.00020 (3)
Crystal data top
[Pt2I2(C2H8N2)4](C8H17SO3)4·2H2OV = 3104.3 (11) Å3
Mr = 1693.53Z = 2
Orthorhombic, PmcnMo Kα radiation
a = 36.997 (3) ŵ = 5.69 mm1
b = 7.118 (2) ÅT = 301 K
c = 11.788 (3) Å0.17 × 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)
Rint = 0.006
Tmin = 0.467, Tmax = 0.7573 standard reflections every 100 reflections
5883 measured reflections intensity decay: none
5688 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0442 restraints
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 0.92Δρmax = 1.66 e Å3
5688 reflectionsΔρmin = 2.12 e Å3
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
xyzUiso*/UeqOcc. (<1)
Pt0.25000.25626 (11)0.18219 (3)0.02517 (11)
I10.25000.2445 (9)0.41018 (13)0.0337 (5)0.50
I20.25000.2378 (9)0.45114 (13)0.0344 (6)0.50
N10.2915 (2)0.0656 (11)0.1722 (6)0.036 (2)
H1A0.29410.00710.23940.053*
H1B0.28620.02170.11940.053*
N20.2918 (3)0.4454 (12)0.1908 (7)0.043 (3)
H2A0.29340.50980.12530.064*
H2B0.28780.52770.24740.064*
C10.3255 (3)0.1620 (14)0.1418 (8)0.050 (3)
H1C0.32600.19110.06140.075*
H1D0.34620.08360.15980.075*
C20.3261 (3)0.3405 (14)0.2118 (8)0.048 (3)
H2C0.32830.31000.29170.072*
H2D0.34670.41730.19030.072*
O40.25000.7653 (16)0.0327 (9)0.073 (3)
H40.2677 (5)0.718 (13)0.000 (7)0.109*
S10.66363 (7)0.3288 (3)0.07740 (19)0.0466 (6)
O10.6733 (2)0.2765 (13)0.0376 (5)0.080 (2)
O20.69019 (16)0.2676 (13)0.1594 (4)0.0525 (16)
O30.65542 (19)0.5260 (9)0.0862 (6)0.068 (2)
C110.6225 (3)0.2054 (12)0.1073 (7)0.053 (3)
H11A0.60590.22420.04480.079*
H11B0.62770.07210.11190.079*
C120.6044 (2)0.2663 (17)0.2159 (7)0.048 (2)
H12A0.60200.40200.21650.072*
H12B0.61920.23030.28010.072*
C130.5670 (3)0.1764 (14)0.2275 (8)0.058 (3)
H13A0.55340.19980.15850.087*
H13B0.56990.04160.23490.087*
C140.5457 (2)0.246 (2)0.3255 (7)0.056 (2)
H14A0.54450.38240.32120.084*
H14B0.55850.21440.39470.084*
C150.5077 (3)0.1697 (15)0.3330 (7)0.056 (3)
H15A0.50910.03440.34190.084*
H15B0.49550.19450.26170.084*
C160.4847 (2)0.2488 (16)0.4288 (7)0.058 (2)
H16A0.49680.22390.50020.087*
H16B0.48320.38400.41980.087*
C170.4468 (3)0.1704 (13)0.4350 (9)0.060 (3)
H17A0.43440.19880.36450.090*
H17B0.44830.03470.44140.090*
C180.4244 (3)0.244 (2)0.5322 (8)0.078 (3)
H18A0.43560.21090.60280.117*
H18B0.40060.19020.52900.117*
H18C0.42260.37840.52680.117*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt0.0375 (2)0.02157 (17)0.01644 (15)0.0000.0000.0004 (3)
I10.0448 (11)0.0391 (9)0.0173 (7)0.0000.0000.002 (2)
I20.0552 (12)0.0308 (11)0.0173 (8)0.0000.0000.0001 (18)
N10.035 (6)0.036 (5)0.036 (5)0.007 (4)0.012 (4)0.000 (3)
N20.068 (9)0.034 (5)0.026 (4)0.020 (5)0.006 (4)0.003 (3)
C10.044 (7)0.069 (7)0.037 (5)0.015 (5)0.010 (5)0.002 (5)
C20.041 (6)0.055 (6)0.048 (5)0.009 (5)0.005 (5)0.013 (5)
O40.100 (8)0.036 (5)0.081 (7)0.0000.0000.023 (6)
S10.0548 (15)0.0516 (13)0.0334 (11)0.0170 (11)0.0039 (12)0.0021 (10)
O10.099 (6)0.099 (6)0.041 (3)0.040 (6)0.009 (4)0.002 (5)
O20.048 (3)0.064 (4)0.045 (3)0.009 (5)0.004 (3)0.008 (4)
O30.064 (5)0.048 (4)0.091 (5)0.019 (3)0.016 (4)0.014 (4)
C110.058 (6)0.050 (6)0.049 (5)0.017 (5)0.003 (5)0.012 (4)
C120.045 (5)0.052 (6)0.048 (4)0.023 (6)0.019 (4)0.003 (6)
C130.055 (7)0.062 (6)0.057 (6)0.010 (5)0.007 (6)0.012 (5)
C140.056 (5)0.055 (5)0.058 (5)0.022 (8)0.007 (5)0.000 (7)
C150.042 (6)0.063 (6)0.064 (7)0.014 (5)0.006 (5)0.017 (5)
C160.053 (5)0.056 (5)0.064 (5)0.017 (7)0.005 (5)0.021 (9)
C170.045 (6)0.054 (5)0.081 (7)0.008 (5)0.014 (7)0.015 (6)
C180.066 (7)0.086 (7)0.083 (7)0.004 (10)0.005 (6)0.009 (10)
Geometric parameters (Å, º) top
Pt—N1i2.052 (8)C11—C121.509 (11)
Pt—N12.052 (8)C11—H11A0.9700
Pt—N2i2.052 (8)C11—H11B0.9700
Pt—N22.052 (8)C12—C131.531 (12)
Pt—I12.6888 (17)C12—H12A0.9700
Pt—I2ii2.7239 (17)C12—H12B0.9700
Pt—I23.1732 (16)C13—C141.483 (12)
Pt—I1iii3.2065 (17)C13—H13A0.9700
N1—C11.479 (11)C13—H13B0.9700
N1—H1A0.9000C14—C151.513 (12)
N1—H1B0.9000C14—H14A0.9700
N2—C21.495 (12)C14—H14B0.9700
N2—H2A0.9000C15—C161.522 (12)
N2—H2B0.9000C15—H15A0.9700
C1—C21.515 (12)C15—H15B0.9700
C1—H1C0.9700C16—C171.511 (12)
C1—H1D0.9700C16—H16A0.9700
C2—H2C0.9700C16—H16B0.9700
C2—H2D0.9700C17—C181.510 (12)
O4—H40.83 (2)C17—H17A0.9700
S1—O31.440 (7)C17—H17B0.9700
S1—O21.446 (6)C18—H18A0.9600
S1—O11.451 (7)C18—H18B0.9600
S1—C111.791 (9)C18—H18C0.9600
N1i—Pt—N196.8 (5)O3—S1—O2112.9 (5)
N1i—Pt—N2i82.7 (2)O3—S1—O1111.7 (5)
N1—Pt—N2i179.4 (4)O2—S1—O1112.3 (4)
N1i—Pt—N2179.4 (4)O3—S1—C11106.5 (5)
N1—Pt—N282.7 (2)O2—S1—C11107.3 (4)
N2i—Pt—N297.7 (5)O1—S1—C11105.5 (4)
N1i—Pt—I192.1 (2)C12—C11—S1113.8 (6)
N1—Pt—I192.1 (2)C12—C11—H11A108.8
N2i—Pt—I188.3 (3)S1—C11—H11A108.8
N2—Pt—I188.3 (3)C12—C11—H11B108.8
N1i—Pt—I2ii87.3 (2)S1—C11—H11B108.8
N1—Pt—I2ii87.3 (2)H11A—C11—H11B107.7
N2i—Pt—I2ii92.2 (3)C11—C12—C13111.0 (8)
N2—Pt—I2ii92.2 (3)C11—C12—H12A109.4
I1—Pt—I2ii179.1 (3)C13—C12—H12A109.4
N1i—Pt—I291.7 (2)C11—C12—H12B109.4
N1—Pt—I291.7 (2)C13—C12—H12B109.4
N2i—Pt—I288.7 (2)H12A—C12—H12B108.0
N2—Pt—I288.7 (2)C14—C13—C12114.1 (8)
I1—Pt—I20.6 (2)C14—C13—H13A108.7
I2ii—Pt—I2178.52 (4)C12—C13—H13A108.7
N1i—Pt—I1iii86.6 (2)C14—C13—H13B108.7
N1—Pt—I1iii86.6 (2)C12—C13—H13B108.7
N2i—Pt—I1iii92.9 (2)H13A—C13—H13B107.6
N2—Pt—I1iii92.9 (2)C13—C14—C15114.6 (9)
I1—Pt—I1iii178.12 (4)C13—C14—H14A108.6
I2ii—Pt—I1iii1.0 (2)C15—C14—H14A108.6
I2—Pt—I1iii177.5 (2)C13—C14—H14B108.6
Pt—I1—Ptiv178.3 (3)C15—C14—H14B108.6
Ptiv—I2—Pt176.7 (2)H14A—C14—H14B107.6
C1—N1—Pt110.1 (6)C14—C15—C16115.5 (8)
C1—N1—H1A109.6C14—C15—H15A108.4
Pt—N1—H1A109.6C16—C15—H15A108.4
C1—N1—H1B109.6C14—C15—H15B108.4
Pt—N1—H1B109.6C16—C15—H15B108.4
H1A—N1—H1B108.1H15A—C15—H15B107.5
C2—N2—Pt108.7 (6)C17—C16—C15114.7 (9)
C2—N2—H2A109.9C17—C16—H16A108.6
Pt—N2—H2A109.9C15—C16—H16A108.6
C2—N2—H2B109.9C17—C16—H16B108.6
Pt—N2—H2B109.9C15—C16—H16B108.6
H2A—N2—H2B108.3H16A—C16—H16B107.6
N1—C1—C2105.7 (8)C18—C17—C16114.7 (9)
N1—C1—H1C110.6C18—C17—H17A108.6
C2—C1—H1C110.6C16—C17—H17A108.6
N1—C1—H1D110.6C18—C17—H17B108.6
C2—C1—H1D110.6C16—C17—H17B108.6
H1C—C1—H1D108.7H17A—C17—H17B107.6
N2—C2—C1108.4 (8)C17—C18—H18A109.5
N2—C2—H2C110.0C17—C18—H18B109.5
C1—C2—H2C110.0H18A—C18—H18B109.5
N2—C2—H2D110.0C17—C18—H18C109.5
C1—C2—H2D110.0H18A—C18—H18C109.5
H2C—C2—H2D108.4H18B—C18—H18C109.5
Symmetry codes: (i) x+1/2, y, z; (ii) x, y+1/2, z1/2; (iii) x+1/2, y+1/2, z1/2; (iv) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2v0.902.162.983 (11)152
N1—H1B···O4vi0.902.273.103 (11)154
N2—H2A···O1vii0.902.212.975 (10)142
N2—H2B···O2viii0.902.192.971 (11)145
O4—H4···O1vii0.83 (2)2.23 (3)2.853 (8)132 (4)
O4—H4···O2vii0.83 (2)2.44 (7)3.175 (9)148 (11)
Symmetry codes: (v) x+1, y1/2, z+1/2; (vi) x, y1, z; (vii) x+1, y+1, z; (viii) x+1, y+1/2, z+1/2.
Selected geometric parameters (Å, º) top
Pt—N12.052 (8)Pt—N22.052 (8)
N1i—Pt—N196.8 (5)N1—Pt—I192.1 (2)
N1i—Pt—N2179.4 (4)N2—Pt—I188.3 (3)
N1—Pt—N282.7 (2)N1—Pt—I2ii87.3 (2)
N2i—Pt—N297.7 (5)N2—Pt—I2ii92.2 (3)
Symmetry codes: (i) x+1/2, y, z; (ii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2iii0.902.162.983 (11)151.6
N1—H1B···O4iv0.902.273.103 (11)154.2
N2—H2A···O1v0.902.212.975 (10)141.9
N2—H2B···O2vi0.902.192.971 (11)145.1
O4—H4···O1v0.83 (2)2.23 (3)2.853 (8)132 (4)
O4—H4···O2v0.83 (2)2.44 (7)3.175 (9)148 (11)
Symmetry codes: (iii) x+1, y1/2, z+1/2; (iv) x, y1, 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
Mr1693.53
Crystal system, space groupOrthorhombic, Pmcn
Temperature (K)301
a, b, c (Å)36.997 (3), 7.118 (2), 11.788 (3)
V3)3104.3 (11)
Z2
Radiation typeMo Kα
µ (mm1)5.69
Crystal size (mm)0.17 × 0.15 × 0.05
Data collection
DiffractometerRigaku AFC-5S
diffractometer
Absorption correctionGaussian
(Coppens et al., 1965)
Tmin, Tmax0.467, 0.757
No. of measured, independent and
observed [I > 2σ(I)] reflections
5883, 5688, 2039
Rint0.006
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.112, 0.92
No. of reflections5688
No. of parameters174
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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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