Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615019877/uk3120sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615019877/uk3120Isup2.hkl |
CCDC reference: 1432418
The title compound, [Pt(en)2][PtCl2(en)2](HOC6H4N═ NC6H4SO3)4.2H2O (en is ethylenediamine), (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 and NiII/PtIV; X = Cl, Br and I; AA = NH2(CH2)2NH2 etc.; Y = ClO4-, HSO4-, X- etc.], hereinafter abbreviated as MX-chain compounds, which are typical mixed-valence compounds belonging to class II in the classification of Robin & Day (1967). MX-chain compounds have attractedmuch interest because of their one-dimensional mixed-valence electron systems, as described in a previous report (Matsushita, 2006).
Compound (I) has been prepared as an MX-chain compound combined with an azobenzene-derived counter-ion. This counter-ion was chosen because it displays photochromic behaviour on the basis of cis-trans isomerization [Reference?]. However, crystals of (I) do not display photochromic behaviour. Since a certain amount of space is necessary for cis–trans isomerization of the azobenzene counter-ion, the photochromic behaviour may be suppressed by packing in the crystal. Spectroscopic changes in a similar MX-chain compound with an amphiphilic azobenzene derivative in aqueous solution and in poly(vinyl alcohol) cast films by photo-irradiation have been reported (Einaga et al., 2005). Structural information on MX-chain compounds having such a bulky azobenzene-derived counter-ion has not been published previously. The present X-ray crystallographic analysis of (I) was performed in order to elucidate the crystal packing and to obtain the metal–halogen distances, which reflect the mixed-valence state, for an MX-chain compound having a bulky azobenzene-derived counter-ion.
The title compound was prepared by a procedure similar to that of Matsushita & Taira (1999). To an aqueous solution containing [Pt(en)2]2+ (0.26 mmol) and trans-[PtCl2(en)2]2+ (0.26 mmol) was added an aqueous solution of sodium 4-hydroxyazobenzene-4'-sulfonate (1.14 mmol, 0.342 g). After removing a white–orange precipitate by filtration, the deep-yellow filtrate was allowed to stand at room temperature for several days. Yellow platelet crystals of (I) suitable for X-ray analysis were obtained after slow evaporation and were collected by filtration (yield 0.326 g, 68%, based on Pt).
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in geometrically calculated positions and refined as riding, with methylene C—H = 0.97 Å, aromatic C—H = 0.93 Å, N—H = 0.90 Å and O—H = 0.82 Å, and with the constraint Uiso(H) = 1.2Ueq(C,N,O).
The molecular structure of (I) is shown in Fig. 1. As shown in Fig. 2, the structure of (I) is built up from columns composed of square-planar [Pt(en)2]2+ and elongated octahedral trans-[PtCl2(en)2]2+ cations stacked alternately, bridged by Cl atoms, along the b axis. The Pt atoms lie on an inversion centre. The Cl atoms are not located at the exact mid-point between adjacent Pt atoms, but are disordered over two general sites, related by an inversion centre, close to the mid-point. The Pt and Cl atoms form an infinite zigzag ···Cl—PtIV—Cl···PtII··· chain, with the shorter Pt—Cl bond length [2.3140 (14) Å] assigned to PtIV—Cl and the longer one [3.5969 (15) Å] to PtII···Cl, and a PtIV—Cl···PtII angle of 170.66 (6)° (Table 2). The PtII···Cl bond length is longer than those of other MX-chain compounds, for example, [Pt(en)2][PtCl2(en)2]Y4 [3.191 (4) Å for Y = PF6 (Matsushita, 2005b), 3.142 (2) Å for Y = HSO4 (Matsushita, 2003), 3.101 (4) Å for Y = ClO4 (Huckett et al., 1993), and 3.052 (3) Å for Y = BF4 (Matsushita, 2005a)]. The Pt···Pt distance of 5.8922 (3) Å is the longest of those of the reported MX-chain compounds, cf. [Pt(en)2][PtCl2(en)2]Y4 [5.518 (2) Å for Y = PF6, 5.465 (1) Å for Y = HSO4, 5.428 (4) Å for Y = ClO4 and 5.372 (2) Å for Y = BF4].
Each Pt site is occupied by a disordered combination of PtII and PtIV atoms. The valence order 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 been observed in a number of other MX-chain compounds (Beauchamp et al., 1982; Yamashita et al., 1985; Matsushita et al.,1992; Toriumi et al., 1993; Huckett et al., 1993; Matsushita, 2003, 2005a,b).
The structural parameter indicating the mixed-valence state of the Pt atom, expressed by δ = (PtIV—Cl)/(PtII···Cl), is 0.643. This value is much smaller than those of [Pt(en)2][PtCl2(en)2]Y4 [0.729 for Y = PF6 (Matsushita, 2005b), 0.739 for Y = HSO4 (Matsushita, 2003), 0.750 for Y = ClO4 (Huckett et al., 1993) and 0.760 for Y = BF4 (Matsushita, 2005a)]. The very small δ value of (I) is produced by the above-mentioned very long PtII···Cl distance. The δ parameter, which correlates well with the energy position of the inter-valence charge-transfer absorption band (Matsushita, 1993), depends on the size of the counter-anion, as described previously (Matsushita et al., 1995). The obviously long PtII···Cl distance and the obviously small δ value of (I) suggest that the bulky azobenzene-derived counter-ion tends to prevent and weaken the formation of the mixed-valence ···Cl—PtIV—Cl···PtII··· chain.
Hydrogen bonds in (I) (Table 3) 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, namely the N1—H1A···O2···H5A—O5···H1B—N1 and N2—H2A···O1···H4A—O4···H2B—N2 linkages, and their symmetry-related counterparts. In addition, the donor N2—H2B group is also hydrogen-bonded to atom O3, and forms a three-centre bond. The crystal packing is further stabilized by intercolumnar hydrogen-bond linkages, as shown in Fig. 3. The presence of the inter-counter-ion hydrogen bond between hydroxy atom O4 and sulfonate atom O1 is unique compared with other MX-chain compounds.
Data collection: RAPID-AUTO (Rigaku, 2006); cell refinement: RAPID-AUTO (Rigaku, 2006); data reduction: RAPID-AUTO (Rigaku, 2006); 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) and publCIF (Westrip, 2010).
[Pt2Cl2(C2H8N2)4](C12H9N2O4S)4·2H2O | F(000) = 918 |
Mr = 1846.62 | Dx = 1.822 Mg m−3 |
Monoclinic, P2/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yc | Cell parameters from 19956 reflections |
a = 18.0782 (7) Å | θ = 3.3–32.1° |
b = 5.8922 (3) Å | µ = 4.44 mm−1 |
c = 15.8365 (3) Å | T = 296 K |
β = 93.7245 (7)° | Platelet, yellow |
V = 1683.35 (11) Å3 | 0.18 × 0.09 × 0.02 mm |
Z = 1 |
Rigaku R-AXIS RAPID imaging-plate diffractometer | 5847 independent reflections |
Radiation source: X-ray sealed tube | 4097 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 10.00 pixels mm-1 | θmax = 32.0°, θmin = 3.3° |
ω scans | h = −26→26 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −8→8 |
Tmin = 0.616, Tmax = 0.915 | l = −23→23 |
36062 measured reflections |
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)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0201P)2 + 1.4401P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
5847 reflections | Δρmax = 0.50 e Å−3 |
229 parameters | Δρmin = −0.67 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: heavy-atom method | Extinction coefficient: 0.00058 (13) |
[Pt2Cl2(C2H8N2)4](C12H9N2O4S)4·2H2O | V = 1683.35 (11) Å3 |
Mr = 1846.62 | Z = 1 |
Monoclinic, P2/c | Mo Kα radiation |
a = 18.0782 (7) Å | µ = 4.44 mm−1 |
b = 5.8922 (3) Å | T = 296 K |
c = 15.8365 (3) Å | 0.18 × 0.09 × 0.02 mm |
β = 93.7245 (7)° |
Rigaku R-AXIS RAPID imaging-plate diffractometer | 5847 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 4097 reflections with I > 2σ(I) |
Tmin = 0.616, Tmax = 0.915 | Rint = 0.037 |
36062 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.50 e Å−3 |
5847 reflections | Δρmin = −0.67 e Å−3 |
229 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 > σ(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) | |
Pt1 | 0.0000 | 0.0000 | 0.0000 | 0.04019 (5) | |
Cl1 | −0.00984 (9) | 0.3908 (2) | −0.00989 (10) | 0.0556 (4) | 0.50 |
S1 | 0.16616 (4) | 0.50242 (12) | 0.16451 (5) | 0.04404 (14) | |
O1 | 0.18520 (13) | 0.4493 (4) | 0.07845 (15) | 0.0612 (6) | |
O2 | 0.10469 (11) | 0.3626 (4) | 0.18888 (15) | 0.0560 (5) | |
O3 | 0.15447 (13) | 0.7423 (4) | 0.17749 (16) | 0.0611 (6) | |
O4 | 0.74058 (13) | −0.2157 (4) | 0.49739 (16) | 0.0676 (6) | |
H4A | 0.7509 | −0.3441 | 0.4820 | 0.081* | |
O5 | 0.0000 | 0.6731 (6) | 0.2500 | 0.0734 (10) | |
H5A | 0.0297 | 0.5778 | 0.2354 | 0.088* | |
N1 | 0.01072 (16) | −0.0377 (5) | −0.12646 (16) | 0.0583 (7) | |
H1A | −0.0161 | −0.1576 | −0.1460 | 0.070* | |
H1B | −0.0062 | 0.0870 | −0.1543 | 0.070* | |
N2 | 0.11222 (14) | 0.0477 (5) | 0.00391 (17) | 0.0560 (7) | |
H2A | 0.1249 | 0.1687 | 0.0364 | 0.067* | |
H2B | 0.1357 | −0.0751 | 0.0264 | 0.067* | |
N3 | 0.44572 (14) | 0.2412 (4) | 0.36021 (17) | 0.0519 (6) | |
N4 | 0.46564 (14) | 0.0389 (4) | 0.35194 (18) | 0.0532 (6) | |
C1 | 0.0905 (2) | −0.0733 (7) | −0.1410 (2) | 0.0739 (10) | |
H1C | 0.0996 | −0.0415 | −0.1995 | 0.089* | |
H1D | 0.1046 | −0.2291 | −0.1286 | 0.089* | |
C2 | 0.1342 (2) | 0.0853 (8) | −0.0835 (2) | 0.0693 (9) | |
H2C | 0.1868 | 0.0567 | −0.0865 | 0.083* | |
H2D | 0.1242 | 0.2412 | −0.1003 | 0.083* | |
C3 | 0.24454 (15) | 0.4195 (5) | 0.22970 (18) | 0.0425 (6) | |
C4 | 0.28121 (17) | 0.5698 (5) | 0.2843 (2) | 0.0518 (7) | |
H4 | 0.2620 | 0.7141 | 0.2920 | 0.062* | |
C5 | 0.34708 (16) | 0.5050 (5) | 0.3280 (2) | 0.0523 (7) | |
H5 | 0.3719 | 0.6062 | 0.3649 | 0.063* | |
C6 | 0.37564 (15) | 0.2905 (5) | 0.31658 (19) | 0.0451 (6) | |
C7 | 0.33796 (17) | 0.1380 (5) | 0.2625 (2) | 0.0538 (7) | |
H7 | 0.3568 | −0.0070 | 0.2553 | 0.065* | |
C8 | 0.27236 (17) | 0.2025 (5) | 0.2195 (2) | 0.0533 (7) | |
H8 | 0.2468 | 0.1001 | 0.1837 | 0.064* | |
C9 | 0.53538 (15) | −0.0153 (5) | 0.3925 (2) | 0.0471 (6) | |
C10 | 0.56194 (17) | −0.2302 (5) | 0.3751 (2) | 0.0565 (8) | |
H10 | 0.5335 | −0.3278 | 0.3402 | 0.068* | |
C11 | 0.63043 (18) | −0.3001 (5) | 0.4094 (2) | 0.0563 (8) | |
H11 | 0.6482 | −0.4437 | 0.3972 | 0.068* | |
C12 | 0.67241 (17) | −0.1553 (6) | 0.4619 (2) | 0.0529 (7) | |
C13 | 0.64535 (19) | 0.0571 (6) | 0.4808 (2) | 0.0570 (8) | |
H13 | 0.6733 | 0.1530 | 0.5168 | 0.068* | |
C14 | 0.57760 (17) | 0.1269 (5) | 0.4466 (2) | 0.0519 (7) | |
H14 | 0.5598 | 0.2699 | 0.4597 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.04710 (8) | 0.03326 (7) | 0.03823 (8) | −0.00365 (7) | −0.01231 (5) | −0.00233 (6) |
Cl1 | 0.0687 (10) | 0.0353 (7) | 0.0609 (9) | 0.0027 (6) | −0.0122 (7) | 0.0001 (6) |
S1 | 0.0393 (3) | 0.0380 (3) | 0.0542 (4) | −0.0049 (3) | −0.0014 (3) | −0.0007 (3) |
O1 | 0.0568 (13) | 0.0728 (16) | 0.0537 (13) | −0.0120 (11) | 0.0008 (10) | −0.0027 (10) |
O2 | 0.0430 (11) | 0.0545 (13) | 0.0701 (14) | −0.0077 (10) | −0.0005 (10) | 0.0059 (11) |
O3 | 0.0563 (13) | 0.0442 (12) | 0.0813 (16) | 0.0002 (10) | −0.0071 (11) | −0.0016 (11) |
O4 | 0.0557 (13) | 0.0708 (16) | 0.0749 (16) | 0.0146 (12) | −0.0055 (12) | −0.0087 (13) |
O5 | 0.059 (2) | 0.072 (2) | 0.091 (3) | 0.000 | 0.0227 (19) | 0.000 |
N1 | 0.0737 (18) | 0.0621 (18) | 0.0377 (12) | −0.0179 (13) | −0.0075 (12) | −0.0073 (11) |
N2 | 0.0487 (14) | 0.0630 (18) | 0.0543 (15) | −0.0060 (11) | −0.0130 (12) | −0.0023 (12) |
N3 | 0.0430 (13) | 0.0467 (14) | 0.0656 (16) | −0.0001 (11) | 0.0003 (12) | −0.0036 (12) |
N4 | 0.0410 (12) | 0.0519 (17) | 0.0667 (16) | 0.0010 (10) | 0.0041 (11) | −0.0029 (12) |
C1 | 0.087 (3) | 0.076 (2) | 0.059 (2) | −0.003 (2) | 0.011 (2) | −0.0150 (18) |
C2 | 0.056 (2) | 0.085 (2) | 0.067 (2) | −0.0059 (19) | 0.0018 (17) | −0.0009 (19) |
C3 | 0.0375 (13) | 0.0381 (12) | 0.0519 (16) | −0.0035 (11) | 0.0020 (12) | −0.0032 (11) |
C4 | 0.0480 (16) | 0.0420 (14) | 0.0646 (19) | 0.0046 (12) | −0.0018 (14) | −0.0149 (13) |
C5 | 0.0489 (14) | 0.0445 (14) | 0.0621 (17) | −0.0013 (14) | −0.0065 (13) | −0.0146 (15) |
C6 | 0.0378 (14) | 0.0444 (15) | 0.0531 (16) | −0.0029 (11) | 0.0037 (12) | −0.0036 (12) |
C7 | 0.0476 (16) | 0.0376 (14) | 0.076 (2) | 0.0020 (12) | 0.0009 (15) | −0.0110 (14) |
C8 | 0.0471 (16) | 0.0424 (15) | 0.069 (2) | −0.0045 (12) | −0.0031 (14) | −0.0137 (14) |
C9 | 0.0398 (13) | 0.0435 (14) | 0.0589 (16) | −0.0006 (13) | 0.0095 (12) | 0.0021 (14) |
C10 | 0.0475 (17) | 0.0444 (16) | 0.078 (2) | −0.0043 (13) | 0.0034 (15) | −0.0059 (15) |
C11 | 0.0493 (17) | 0.0428 (16) | 0.077 (2) | 0.0040 (13) | 0.0095 (16) | 0.0010 (15) |
C12 | 0.0454 (16) | 0.0578 (19) | 0.0564 (18) | 0.0029 (14) | 0.0092 (14) | 0.0043 (14) |
C13 | 0.0519 (17) | 0.059 (2) | 0.0601 (19) | 0.0048 (14) | 0.0010 (15) | −0.0089 (14) |
C14 | 0.0510 (17) | 0.0438 (16) | 0.0612 (19) | 0.0044 (13) | 0.0059 (14) | −0.0030 (14) |
Pt1—N1 | 2.037 (2) | C4—C5 | 1.391 (4) |
Pt1—N2 | 2.045 (3) | C4—H4 | 0.9300 |
Pt1—Cl1 | 2.3140 (14) | C5—C6 | 1.381 (4) |
Pt1—Cl1i | 2.3140 (14) | C5—H5 | 0.9300 |
Pt1—Cl1ii | 3.5969 (15) | C6—C7 | 1.389 (4) |
Cl1—Cl1ii | 1.366 (3) | C6—N3 | 1.433 (4) |
Cl1—Pt1iii | 3.5969 (15) | C7—C8 | 1.382 (4) |
N1—C1 | 1.489 (5) | C7—H7 | 0.9300 |
N1—H1A | 0.9000 | C8—H8 | 0.9300 |
N1—H1B | 0.9000 | N3—N4 | 1.255 (3) |
N2—C2 | 1.481 (5) | N4—C9 | 1.414 (4) |
N2—H2A | 0.9000 | C9—C10 | 1.388 (4) |
N2—H2B | 0.9000 | C9—C14 | 1.391 (4) |
C1—C2 | 1.495 (5) | C10—C11 | 1.382 (4) |
C1—H1C | 0.9700 | C10—H10 | 0.9300 |
C1—H1D | 0.9700 | C11—C12 | 1.383 (5) |
C2—H2C | 0.9700 | C11—H11 | 0.9300 |
C2—H2D | 0.9700 | C12—O4 | 1.368 (4) |
S1—O1 | 1.461 (2) | C12—C13 | 1.383 (5) |
S1—O2 | 1.455 (2) | C13—C14 | 1.370 (4) |
S1—O3 | 1.446 (2) | C13—H13 | 0.9300 |
S1—C3 | 1.767 (3) | C14—H14 | 0.9300 |
C3—C4 | 1.377 (4) | O4—H4A | 0.8200 |
C3—C8 | 1.387 (4) | O5—H5A | 0.8200 |
N1—Pt1—N1i | 180.0 (2) | O3—S1—O1 | 112.80 (15) |
N1—Pt1—N2i | 96.47 (11) | O2—S1—O1 | 110.87 (14) |
N1i—Pt1—N2i | 83.53 (11) | O3—S1—C3 | 107.84 (13) |
N1—Pt1—N2 | 83.53 (11) | O2—S1—C3 | 106.60 (13) |
N1i—Pt1—N2 | 96.47 (11) | O1—S1—C3 | 104.90 (14) |
N2i—Pt1—N2 | 180.00 (2) | C4—C3—C8 | 120.1 (3) |
N1—Pt1—Cl1i | 86.91 (9) | C4—C3—S1 | 121.6 (2) |
N1i—Pt1—Cl1i | 93.09 (9) | C8—C3—S1 | 118.0 (2) |
N2i—Pt1—Cl1i | 86.39 (9) | C3—C4—C5 | 119.8 (3) |
N2—Pt1—Cl1i | 93.61 (9) | C3—C4—H4 | 120.1 |
N1—Pt1—Cl1 | 93.09 (9) | C5—C4—H4 | 120.1 |
N1i—Pt1—Cl1 | 86.91 (9) | C6—C5—C4 | 120.1 (3) |
N2i—Pt1—Cl1 | 93.61 (9) | C6—C5—H5 | 120.0 |
N2—Pt1—Cl1 | 86.39 (9) | C4—C5—H5 | 120.0 |
Cl1i—Pt1—Cl1 | 180.00 (10) | C5—C6—C7 | 120.0 (3) |
N1—Pt1—Cl1ii | 98.29 (8) | C5—C6—N3 | 116.7 (3) |
N1i—Pt1—Cl1ii | 81.71 (8) | C7—C6—N3 | 123.3 (3) |
N2i—Pt1—Cl1ii | 100.64 (8) | C8—C7—C6 | 119.8 (3) |
N2—Pt1—Cl1ii | 79.36 (8) | C8—C7—H7 | 120.1 |
Pt1—Cl1—Pt1iii | 170.66 (6) | C6—C7—H7 | 120.1 |
C1—N1—Pt1 | 108.8 (2) | C7—C8—C3 | 120.1 (3) |
C1—N1—H1A | 109.9 | C7—C8—H8 | 119.9 |
Pt1—N1—H1A | 109.9 | C3—C8—H8 | 119.9 |
C1—N1—H1B | 109.9 | N4—N3—C6 | 113.1 (2) |
Pt1—N1—H1B | 109.9 | N3—N4—C9 | 114.9 (3) |
H1A—N1—H1B | 108.3 | C10—C9—C14 | 119.3 (3) |
C2—N2—Pt1 | 108.5 (2) | C10—C9—N4 | 115.2 (3) |
C2—N2—H2A | 110.0 | C14—C9—N4 | 125.5 (3) |
Pt1—N2—H2A | 110.0 | C11—C10—C9 | 120.4 (3) |
C2—N2—H2B | 110.0 | C11—C10—H10 | 119.8 |
Pt1—N2—H2B | 110.0 | C9—C10—H10 | 119.8 |
H2A—N2—H2B | 108.4 | C10—C11—C12 | 119.7 (3) |
N1—C1—C2 | 107.3 (3) | C10—C11—H11 | 120.2 |
N1—C1—H1C | 110.3 | C12—C11—H11 | 120.2 |
C2—C1—H1C | 110.3 | O4—C12—C11 | 122.1 (3) |
N1—C1—H1D | 110.3 | O4—C12—C13 | 117.9 (3) |
C2—C1—H1D | 110.3 | C11—C12—C13 | 120.0 (3) |
H1C—C1—H1D | 108.5 | C14—C13—C12 | 120.4 (3) |
N2—C2—C1 | 108.2 (3) | C14—C13—H13 | 119.8 |
N2—C2—H2C | 110.0 | C12—C13—H13 | 119.8 |
C1—C2—H2C | 110.0 | C13—C14—C9 | 120.2 (3) |
N2—C2—H2D | 110.0 | C13—C14—H14 | 119.9 |
C1—C2—H2D | 110.0 | C9—C14—H14 | 119.9 |
H2C—C2—H2D | 108.4 | C12—O4—H4A | 109.5 |
O3—S1—O2 | 113.23 (14) | N1ii—O5—H5A | 109.5 |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z; (iii) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.90 | 2.08 | 2.954 (3) | 162 |
N1—H1B···O5ii | 0.90 | 2.08 | 2.904 (4) | 151 |
N2—H2A···O1 | 0.90 | 2.07 | 2.920 (3) | 158 |
N2—H2B···O4iv | 0.90 | 2.44 | 3.082 (4) | 129 |
N2—H2B···O3v | 0.90 | 2.63 | 3.332 (4) | 136 |
O4—H4A···O1vi | 0.82 | 1.97 | 2.711 (3) | 150 |
O5—H5A···O2 | 0.82 | 2.03 | 2.847 (3) | 174 |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z; (iv) −x+1, y, −z+1/2; (v) x, y−1, z; (vi) −x+1, y−1, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Pt2Cl2(C2H8N2)4](C12H9N2O4S)4·2H2O |
Mr | 1846.62 |
Crystal system, space group | Monoclinic, P2/c |
Temperature (K) | 296 |
a, b, c (Å) | 18.0782 (7), 5.8922 (3), 15.8365 (3) |
β (°) | 93.7245 (7) |
V (Å3) | 1683.35 (11) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 4.44 |
Crystal size (mm) | 0.18 × 0.09 × 0.02 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID imaging-plate diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.616, 0.915 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36062, 5847, 4097 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.746 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.062, 1.04 |
No. of reflections | 5847 |
No. of parameters | 229 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.67 |
Computer programs: RAPID-AUTO (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
Pt1—N1 | 2.037 (2) | C1—C2 | 1.495 (5) |
Pt1—N2 | 2.045 (3) | S1—O1 | 1.461 (2) |
Pt1—Cl1 | 2.3140 (14) | S1—O2 | 1.455 (2) |
Pt1—Cl1i | 3.5969 (15) | S1—O3 | 1.446 (2) |
N1—C1 | 1.489 (5) | S1—C3 | 1.767 (3) |
N2—C2 | 1.481 (5) | ||
N1—Pt1—N2 | 83.53 (11) | O3—S1—O2 | 113.23 (14) |
N1—Pt1—Cl1 | 93.09 (9) | O3—S1—O1 | 112.80 (15) |
N2—Pt1—Cl1 | 86.39 (9) | O2—S1—O1 | 110.87 (14) |
Pt1—Cl1—Pt1ii | 170.66 (6) | O3—S1—C3 | 107.84 (13) |
C1—N1—Pt1 | 108.8 (2) | O2—S1—C3 | 106.60 (13) |
C2—N2—Pt1 | 108.5 (2) | O1—S1—C3 | 104.90 (14) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2iii | 0.90 | 2.08 | 2.954 (3) | 162 |
N1—H1B···O5i | 0.90 | 2.08 | 2.904 (4) | 151 |
N2—H2A···O1 | 0.90 | 2.07 | 2.920 (3) | 158 |
N2—H2B···O4iv | 0.90 | 2.44 | 3.082 (4) | 129 |
N2—H2B···O3v | 0.90 | 2.63 | 3.332 (4) | 136 |
O4—H4A···O1vi | 0.82 | 1.97 | 2.711 (3) | 150 |
O5—H5A···O2 | 0.82 | 2.03 | 2.847 (3) | 174 |
Symmetry codes: (i) −x, −y+1, −z; (iii) −x, −y, −z; (iv) −x+1, y, −z+1/2; (v) x, y−1, z; (vi) −x+1, y−1, −z+1/2. |