Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113000541/wq3023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113000541/wq3023Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113000541/wq3023IIsup3.hkl | |
Chemdraw file https://doi.org/10.1107/S0108270113000541/wq3023Isup4.cdx | |
Chemdraw file https://doi.org/10.1107/S0108270113000541/wq3023IIsup5.cdx |
CCDC references: 925760; 925761
For related literature, see: Basolo et al. (1950); Buckton (1855); Endres et al. (1979); Keller (1982); Matsushita et al. (1992); Meyer et al. (1982); Okamoto, Mitani, Toriumi & Yamashita (1992); Okamoto, Toriumi, Mitani & Yamashita (1992); Toriumi et al. (1993).
The following reagents were prepared according to literature procedures: [Pt(en)2]Cl2 (Basolo et al., 1950) and K2Pt(NCS)4 (Buckton, 1855). Commercially available ethane-1,2-diamine (Wako) and K2PtCl4 (Inuisho) were used as received.
For the preparation of [Pt(en)2](NCS)2, liquid ethane-1,2-diamine (0.83 g, 13.8 mmol) was added to a solution of K2Pt(NCS)4 (1.10 g, 2.0 mmol) in water (20 ml) and the mixture heated to boiling. After cooling to room temperature, another equimolar solution of K2Pt(NCS)4 in water (10 ml) was added to give a bright-yellow precipitate. The solid was filtered off, washed with water and then suspended in water. Ethane-1,2-diamine (2.00 g) was added and the solution warmed to give a clear pale-yellow solution. The mixture was filtered and allowed to evaporate until a yellow crystalline solid appeared. After addition of ethanol, the precipitate was filtered off, washed with ethanol and diethyl ether, and dried under vacuum (yield 1.08 g, 61.1%). Analysis calculated for C6H16N6S2Pt: C 16.70, H 3.74, N 19.48%; found: C 16.79, H 3.58, N 19.67%.
For the preparation of [PtIV(OH)2(en)2](ClO4)2, Pt(en)2Cl2 (1.00 g, 2.59 mmol) was dissolved in H2O (5 ml) and an aqueous solution (5 ml) of AgClO4 (1.18 g, 5.69 mmol) was added. The mixture was stirred for 1 h and the precipitate of AgCl was removed by filtration. To the resulting solution of [Pt(en)2](ClO4)2, 10% hydrogen peroxide (5 ml) was added and the mixture was heated at 353 K for 15 min. The reaction mixture was filtered through a micropore filter to remove the remaining silver chloride, and again warmed to evaporate the solvent to a final volume of about 10 ml. Ethanol (40 ml) was added and the solution allowed to stand at room temperature for 1 d. A white precipitate of [Pt(OH)2(en)2](ClO4)2 was filtered off, washed with ethanol and dried under vacuum (yield 1.22 g, 85.3%). Analysis, calculated for C4H18Cl2N4O10Pt: C 8.76, H 3.06, N 10.31%; found: C 8.80, H 3.05, N 10.27%.
For the preparation of [Pt(en)2][Pt(NCS)2(en)2](ClO4)4, (I), [PtII(en)2](NCS)2 (0.072 g, 0.167 mmol) and [PtIV(OH)2(en)2](ClO4)2 (0.091 g, 0.167 mmol) were dissolved in water (9 ml). An excess of 60% perchloric acid was added to the mixture. [PtII(en)2][PtIV(NCS)2(en)2](ClO4)4 crystals were obtained as light-brown prisms after the solution had been allowed to evaporate slowly for several days. Analysis, calculated for C10H32Cl4N10O16Pt2S2: C 10.49, H 2.82, N 12.24%; found: C 10.36, H 2.57, N 12.15%.
For the preparation of [PtIV(NCS)2(en)2](ClO4)2.1.5H2O, (II), [PtIV(OH)2(en)2](ClO4)2 (0.275 g, 0.50 mmol) and KSCN (0.097 g, 1.00 mmol) were dissolved in water (5 ml). An excess of 60% HClO4 was added. Orange [Yellow in CIF tables - please clarify] crystals of (II) were obtained after slow evaporation at 278 K. Analysis, calculated for C6H19Cl2N6O9.5PtS2: C 10.96, H 2.91, N 12.78%; found: C 10.94, H 2.64, N 12.90%.
H atoms of lattice waters in (II) were located in difference Fourier maps and their coordinates are refined under restraints for their O—H bond lengths and angles.
Data collection: CrystalClear (Rigaku, 2008) for (I); RAPID-AUTO (Rigaku, 2006) for (II). Cell refinement: CrystalClear (Rigaku, 2008) for (I); RAPID-AUTO (Rigaku, 2006) for (II). Data reduction: CrystalClear (Rigaku, 2008) and SORTAV (Blessing, 1995) for (I); RAPID-AUTO (Rigaku, 2006) and SORTAV (Blessing, 1995) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008) for (I); PLATON (Spek, 2009) for (II). For both compounds, software used to prepare material for publication: WinGX (Farrugia, 2012).
[Pt2(NCS)2(C2H8N2)4](ClO4)4 | Z = 1 |
Mr = 1144.56 | F(000) = 546 |
Triclinic, P1 | Dx = 2.603 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0535 (13) Å | Cell parameters from 7324 reflections |
b = 9.6033 (14) Å | θ = 3.1–27.7° |
c = 9.6034 (14) Å | µ = 10.17 mm−1 |
α = 104.944 (4)° | T = 296 K |
β = 91.574 (4)° | Block, brown |
γ = 113.765 (4)° | 0.30 × 0.27 × 0.27 mm |
V = 730.11 (18) Å3 |
Rigaku SCX-MINI diffractometer | 3333 independent reflections |
Radiation source: normal-focus sealed tube | 3014 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 6.85 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω oscillation scans | h = −11→11 |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | k = −12→12 |
Tmin = 0.565, Tmax = 1.000 | l = −12→12 |
7690 measured reflections |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0232P)2 + 0.9044P] where P = (Fo2 + 2Fc2)/3 |
3333 reflections | (Δ/σ)max < 0.001 |
202 parameters | Δρmax = 1.20 e Å−3 |
0 restraints | Δρmin = −2.43 e Å−3 |
[Pt2(NCS)2(C2H8N2)4](ClO4)4 | γ = 113.765 (4)° |
Mr = 1144.56 | V = 730.11 (18) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.0535 (13) Å | Mo Kα radiation |
b = 9.6033 (14) Å | µ = 10.17 mm−1 |
c = 9.6034 (14) Å | T = 296 K |
α = 104.944 (4)° | 0.30 × 0.27 × 0.27 mm |
β = 91.574 (4)° |
Rigaku SCX-MINI diffractometer | 3333 independent reflections |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | 3014 reflections with I > 2σ(I) |
Tmin = 0.565, Tmax = 1.000 | Rint = 0.037 |
7690 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.18 | Δρmax = 1.20 e Å−3 |
3333 reflections | Δρmin = −2.43 e Å−3 |
202 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. X-ray diffraction measurements were performed with a Rigaku Rapid IP [for (I)] and a Rigaku SCX-mini CCD [for (II)] diffractometers, using graphite-monochromated Mo Kα (λ = 0.71073 Å) radiation. Pt atoms were located by the Patterson method. The other atoms were located from successive Fourier syntheses. All atoms were found and refined by full-matrix least-squares technique. Anisotropic displacement parameters are applied for all non-H atoms. All calculations were carried out using SHELX program (Sheldrick, 2008). 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 > 2sigma(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 | ||
Pt1 | 0.5 | 0.5 | 0.5 | 0.01129 (8) | |
S1 | 0.50034 (12) | 0.28326 (12) | 0.30922 (11) | 0.0220 (2) | |
C1 | 0.6993 (5) | 0.3479 (5) | 0.2941 (4) | 0.0211 (8) | |
N1 | 0.8344 (5) | 0.3900 (5) | 0.2865 (4) | 0.0319 (9) | |
N2 | 0.2579 (4) | 0.3527 (4) | 0.4900 (4) | 0.0163 (7) | |
H2A | 0.2462 | 0.2533 | 0.4826 | 0.024* | |
H2B | 0.2208 | 0.3877 | 0.5716 | 0.024* | |
N3 | 0.4087 (5) | 0.5759 (5) | 0.3502 (4) | 0.0177 (8) | |
H3A | 0.4566 | 0.6829 | 0.3747 | 0.027* | |
H3B | 0.4307 | 0.5376 | 0.2614 | 0.027* | |
C2 | 0.1634 (5) | 0.3522 (5) | 0.3603 (4) | 0.0216 (8) | |
H2C | 0.0489 | 0.3161 | 0.3713 | 0.032* | |
H2D | 0.173 | 0.2802 | 0.2732 | 0.032* | |
C3 | 0.2297 (5) | 0.5193 (6) | 0.3466 (5) | 0.0202 (9) | |
H3C | 0.1802 | 0.5192 | 0.2557 | 0.03* | |
H3D | 0.2058 | 0.5887 | 0.4265 | 0.03* | |
Pt2 | 0.5 | 0 | 0 | 0.01364 (8) | |
N4 | 0.2652 (5) | −0.1248 (4) | 0.0261 (4) | 0.0175 (7) | |
H4A | 0.2286 | −0.2271 | −0.028 | 0.026* | |
H4B | 0.2601 | −0.1221 | 0.1201 | 0.026* | |
N5 | 0.3959 (5) | 0.0902 (5) | −0.1229 (4) | 0.0196 (8) | |
H5A | 0.419 | 0.1921 | −0.0748 | 0.029* | |
H5B | 0.437 | 0.0883 | −0.2072 | 0.029* | |
C4 | 0.1620 (5) | −0.0524 (5) | −0.0204 (5) | 0.0245 (9) | |
H4C | 0.173 | 0.0405 | 0.057 | 0.037* | |
H4D | 0.0482 | −0.1284 | −0.0413 | 0.037* | |
C5 | 0.2157 (6) | −0.0057 (6) | −0.1536 (6) | 0.0242 (10) | |
H5C | 0.1876 | −0.0998 | −0.2359 | 0.036* | |
H5D | 0.1621 | 0.0566 | −0.177 | 0.036* | |
Cl1 | 0.22426 (15) | −0.05757 (13) | 0.42496 (13) | 0.0256 (2) | |
O1 | 0.3261 (6) | −0.1202 (5) | 0.3461 (5) | 0.0440 (11) | |
O2 | 0.3205 (6) | 0.0737 (5) | 0.5516 (4) | 0.0426 (10) | |
O3 | 0.1549 (4) | 0.0025 (4) | 0.3318 (4) | 0.0424 (9) | |
O4 | 0.1009 (5) | −0.1785 (4) | 0.4701 (4) | 0.0470 (10) | |
Cl2 | 0.24808 (14) | 0.41662 (12) | 0.94696 (12) | 0.0206 (2) | |
O5 | 0.3090 (5) | 0.3777 (5) | 0.8119 (4) | 0.0353 (9) | |
O6 | 0.3237 (5) | 0.5855 (4) | 1.0133 (4) | 0.0364 (9) | |
O7 | 0.2902 (4) | 0.3417 (4) | 1.0441 (3) | 0.0377 (8) | |
O8 | 0.0767 (4) | 0.3621 (5) | 0.9211 (5) | 0.0471 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.01143 (12) | 0.01112 (12) | 0.01018 (12) | 0.00381 (9) | 0.00287 (8) | 0.00278 (8) |
S1 | 0.0217 (5) | 0.0189 (5) | 0.0205 (5) | 0.0074 (4) | 0.0060 (4) | −0.0006 (4) |
C1 | 0.031 (2) | 0.021 (2) | 0.0140 (18) | 0.0158 (18) | 0.0044 (17) | 0.0008 (15) |
N1 | 0.029 (2) | 0.039 (2) | 0.031 (2) | 0.0196 (18) | 0.0075 (17) | 0.0065 (17) |
N2 | 0.0142 (16) | 0.0144 (16) | 0.0177 (18) | 0.0044 (13) | 0.0054 (14) | 0.0031 (13) |
N3 | 0.0168 (18) | 0.0196 (18) | 0.0152 (17) | 0.0053 (15) | −0.0002 (14) | 0.0069 (14) |
C2 | 0.0156 (19) | 0.025 (2) | 0.020 (2) | 0.0045 (17) | −0.0024 (16) | 0.0066 (16) |
C3 | 0.017 (2) | 0.026 (2) | 0.021 (2) | 0.0105 (19) | 0.0040 (18) | 0.0091 (18) |
Pt2 | 0.01586 (13) | 0.01300 (12) | 0.01216 (13) | 0.00600 (9) | 0.00298 (9) | 0.00395 (9) |
N4 | 0.0201 (18) | 0.0187 (17) | 0.0135 (17) | 0.0084 (15) | 0.0044 (14) | 0.0039 (14) |
N5 | 0.0183 (18) | 0.0198 (18) | 0.0199 (19) | 0.0066 (15) | −0.0007 (15) | 0.0074 (15) |
C4 | 0.018 (2) | 0.029 (2) | 0.029 (2) | 0.0118 (18) | 0.0062 (17) | 0.0078 (18) |
C5 | 0.025 (2) | 0.020 (2) | 0.026 (2) | 0.0077 (19) | −0.0042 (19) | 0.0069 (19) |
Cl1 | 0.0337 (6) | 0.0191 (5) | 0.0221 (5) | 0.0080 (5) | 0.0097 (4) | 0.0078 (4) |
O1 | 0.054 (3) | 0.042 (2) | 0.046 (3) | 0.027 (2) | 0.025 (2) | 0.0165 (19) |
O2 | 0.054 (3) | 0.033 (2) | 0.0238 (19) | 0.0054 (18) | 0.0016 (17) | 0.0025 (15) |
O3 | 0.052 (2) | 0.039 (2) | 0.042 (2) | 0.0227 (18) | 0.0035 (17) | 0.0157 (16) |
O4 | 0.053 (2) | 0.0318 (19) | 0.046 (2) | 0.0028 (18) | 0.0208 (19) | 0.0166 (17) |
Cl2 | 0.0250 (5) | 0.0172 (5) | 0.0194 (5) | 0.0082 (4) | 0.0060 (4) | 0.0060 (4) |
O5 | 0.053 (2) | 0.039 (2) | 0.0194 (17) | 0.0237 (19) | 0.0170 (16) | 0.0094 (15) |
O6 | 0.045 (2) | 0.0164 (16) | 0.040 (2) | 0.0072 (16) | 0.0054 (18) | 0.0068 (15) |
O7 | 0.068 (2) | 0.0349 (18) | 0.0249 (17) | 0.0331 (18) | 0.0098 (16) | 0.0134 (14) |
O8 | 0.0243 (18) | 0.050 (2) | 0.059 (3) | 0.0075 (17) | 0.0084 (17) | 0.017 (2) |
Pt1—N2 | 2.057 (4) | Pt2—N5ii | 2.039 (4) |
Pt1—N2i | 2.057 (4) | Pt2—N5 | 2.039 (4) |
Pt1—N3 | 2.060 (4) | Pt2—C4ii | 2.886 (4) |
Pt1—N3i | 2.060 (4) | Pt2—C4 | 2.886 (4) |
Pt1—S1i | 2.3933 (10) | Pt2—C5ii | 2.905 (5) |
Pt1—S1 | 2.3933 (10) | Pt2—C5 | 2.905 (5) |
Pt1—C2 | 2.900 (4) | Pt2—S1ii | 3.4705 (11) |
Pt1—C2i | 2.900 (4) | N4—C4 | 1.489 (5) |
Pt1—C3i | 2.916 (5) | N4—H4A | 0.9 |
Pt1—C3 | 2.916 (5) | N4—H4B | 0.9 |
S1—C1 | 1.676 (4) | N5—C5 | 1.489 (6) |
S1—Pt2 | 3.4705 (11) | N5—H5A | 0.9 |
C1—N1 | 1.135 (5) | N5—H5B | 0.9 |
N2—C2 | 1.490 (5) | C4—C5 | 1.493 (6) |
N2—H2A | 0.9 | C4—H4C | 0.97 |
N2—H2B | 0.9 | C4—H4D | 0.97 |
N3—C3 | 1.483 (6) | C5—H5C | 0.97 |
N3—H3A | 0.9 | C5—H5D | 0.97 |
N3—H3B | 0.9 | Cl1—O4 | 1.423 (4) |
C2—C3 | 1.513 (6) | Cl1—O1 | 1.427 (4) |
C2—H2C | 0.97 | Cl1—O3 | 1.434 (3) |
C2—H2D | 0.97 | Cl1—O2 | 1.447 (4) |
C3—H3C | 0.97 | Cl2—O8 | 1.414 (4) |
C3—H3D | 0.97 | Cl2—O6 | 1.433 (4) |
Pt2—N4 | 2.037 (4) | Cl2—O5 | 1.443 (4) |
Pt2—N4ii | 2.037 (4) | Cl2—O7 | 1.443 (3) |
N2—Pt1—N2i | 180 | N4ii—Pt2—N5 | 96.56 (15) |
N2—Pt1—N3 | 83.28 (15) | N5ii—Pt2—N5 | 180 |
N2i—Pt1—N3 | 96.72 (15) | N4—Pt2—C4ii | 150.80 (13) |
N2—Pt1—N3i | 96.72 (15) | N4ii—Pt2—C4ii | 29.20 (13) |
N2i—Pt1—N3i | 83.28 (15) | N5ii—Pt2—C4ii | 55.37 (14) |
N3—Pt1—N3i | 179.999 (2) | N5—Pt2—C4ii | 124.63 (14) |
N2—Pt1—S1i | 95.20 (10) | N4—Pt2—C4 | 29.20 (13) |
N2i—Pt1—S1i | 84.80 (10) | N4ii—Pt2—C4 | 150.80 (13) |
N3—Pt1—S1i | 89.45 (11) | N5ii—Pt2—C4 | 124.63 (14) |
N3i—Pt1—S1i | 90.56 (11) | N5—Pt2—C4 | 55.37 (14) |
N2—Pt1—S1 | 84.80 (10) | C4ii—Pt2—C4 | 180 |
N2i—Pt1—S1 | 95.20 (10) | N4—Pt2—C5ii | 124.56 (14) |
N3—Pt1—S1 | 90.55 (11) | N4ii—Pt2—C5ii | 55.44 (14) |
N3i—Pt1—S1 | 89.44 (11) | N5ii—Pt2—C5ii | 28.82 (14) |
S1i—Pt1—S1 | 180 | N5—Pt2—C5ii | 151.18 (14) |
N2—Pt1—C2 | 29.13 (13) | C4ii—Pt2—C5ii | 29.88 (13) |
N2i—Pt1—C2 | 150.87 (13) | C4—Pt2—C5ii | 150.12 (13) |
N3—Pt1—C2 | 55.17 (13) | N4—Pt2—C5 | 55.44 (14) |
N3i—Pt1—C2 | 124.83 (13) | N4ii—Pt2—C5 | 124.56 (14) |
S1i—Pt1—C2 | 100.82 (9) | N5ii—Pt2—C5 | 151.18 (14) |
S1—Pt1—C2 | 79.18 (9) | N5—Pt2—C5 | 28.82 (14) |
N2—Pt1—C2i | 150.87 (13) | C4ii—Pt2—C5 | 150.12 (13) |
N2i—Pt1—C2i | 29.13 (13) | C4—Pt2—C5 | 29.88 (13) |
N3—Pt1—C2i | 124.83 (13) | C5ii—Pt2—C5 | 180 |
N3i—Pt1—C2i | 55.17 (13) | N4—Pt2—S1 | 84.11 (10) |
S1i—Pt1—C2i | 79.18 (9) | N4ii—Pt2—S1 | 95.89 (10) |
S1—Pt1—C2i | 100.82 (9) | N5ii—Pt2—S1 | 91.01 (11) |
C2—Pt1—C2i | 180.00 (18) | N5—Pt2—S1 | 88.99 (11) |
N2—Pt1—C3i | 124.33 (14) | C4ii—Pt2—S1 | 102.49 (9) |
N2i—Pt1—C3i | 55.67 (14) | C4—Pt2—S1 | 77.51 (9) |
N3—Pt1—C3i | 151.39 (14) | C5ii—Pt2—S1 | 87.56 (11) |
N3i—Pt1—C3i | 28.61 (14) | C5—Pt2—S1 | 92.44 (11) |
S1i—Pt1—C3i | 94.72 (10) | N4—Pt2—S1ii | 95.89 (10) |
S1—Pt1—C3i | 85.28 (10) | N4ii—Pt2—S1ii | 84.11 (10) |
C2—Pt1—C3i | 149.84 (12) | N5ii—Pt2—S1ii | 88.99 (11) |
C2i—Pt1—C3i | 30.16 (12) | N5—Pt2—S1ii | 91.01 (11) |
N2—Pt1—C3 | 55.67 (14) | C4ii—Pt2—S1ii | 77.51 (9) |
N2i—Pt1—C3 | 124.33 (14) | C4—Pt2—S1ii | 102.49 (9) |
N3—Pt1—C3 | 28.61 (14) | C5ii—Pt2—S1ii | 92.44 (11) |
N3i—Pt1—C3 | 151.39 (14) | C5—Pt2—S1ii | 87.56 (11) |
S1i—Pt1—C3 | 85.28 (10) | S1—Pt2—S1ii | 180 |
S1—Pt1—C3 | 94.72 (10) | C4—N4—Pt2 | 108.9 (3) |
C2—Pt1—C3 | 30.16 (12) | C4—N4—H4A | 109.9 |
C2i—Pt1—C3 | 149.84 (12) | Pt2—N4—H4A | 109.9 |
C3i—Pt1—C3 | 180 | C4—N4—H4B | 109.9 |
C1—S1—Pt1 | 101.44 (14) | Pt2—N4—H4B | 109.9 |
C1—S1—Pt2 | 77.77 (13) | H4A—N4—H4B | 108.3 |
Pt1—S1—Pt2 | 171.97 (4) | C5—N5—Pt2 | 109.9 (3) |
N1—C1—S1 | 178.3 (4) | C5—N5—H5A | 109.7 |
C2—N2—Pt1 | 108.6 (3) | Pt2—N5—H5A | 109.7 |
C2—N2—H2A | 110 | C5—N5—H5B | 109.7 |
Pt1—N2—H2A | 110 | Pt2—N5—H5B | 109.7 |
C2—N2—H2B | 110 | H5A—N5—H5B | 108.2 |
Pt1—N2—H2B | 110 | N4—C4—C5 | 108.8 (3) |
H2A—N2—H2B | 108.3 | N4—C4—Pt2 | 41.87 (18) |
C3—N3—Pt1 | 109.7 (3) | C5—C4—Pt2 | 75.8 (2) |
C3—N3—H3A | 109.7 | N4—C4—H4C | 109.9 |
Pt1—N3—H3A | 109.7 | C5—C4—H4C | 109.9 |
C3—N3—H3B | 109.7 | Pt2—C4—H4C | 98.7 |
Pt1—N3—H3B | 109.7 | N4—C4—H4D | 109.9 |
H3A—N3—H3B | 108.2 | C5—C4—H4D | 109.9 |
N2—C2—C3 | 108.9 (3) | Pt2—C4—H4D | 147.6 |
N2—C2—Pt1 | 42.25 (18) | H4C—C4—H4D | 108.3 |
C3—C2—Pt1 | 75.5 (2) | N5—C5—C4 | 107.7 (4) |
N2—C2—H2C | 109.9 | N5—C5—Pt2 | 41.3 (2) |
C3—C2—H2C | 109.9 | C4—C5—Pt2 | 74.4 (2) |
Pt1—C2—H2C | 147.8 | N5—C5—H5C | 110.2 |
N2—C2—H2D | 109.9 | C4—C5—H5C | 110.2 |
C3—C2—H2D | 109.9 | Pt2—C5—H5C | 100.3 |
Pt1—C2—H2D | 98.7 | N5—C5—H5D | 110.2 |
H2C—C2—H2D | 108.3 | C4—C5—H5D | 110.2 |
N3—C3—C2 | 107.4 (4) | Pt2—C5—H5D | 146.4 |
N3—C3—Pt1 | 41.70 (19) | H5C—C5—H5D | 108.5 |
C2—C3—Pt1 | 74.3 (2) | O4—Cl1—O1 | 109.9 (3) |
N3—C3—H3C | 110.2 | O4—Cl1—O3 | 111.4 (2) |
C2—C3—H3C | 110.2 | O1—Cl1—O3 | 108.0 (2) |
Pt1—C3—H3C | 147.3 | O4—Cl1—O2 | 109.4 (2) |
N3—C3—H3D | 110.2 | O1—Cl1—O2 | 110.2 (3) |
C2—C3—H3D | 110.2 | O3—Cl1—O2 | 108.0 (2) |
Pt1—C3—H3D | 99.3 | O8—Cl2—O6 | 109.9 (3) |
H3C—C3—H3D | 108.5 | O8—Cl2—O5 | 110.2 (3) |
N4—Pt2—N4ii | 180 | O6—Cl2—O5 | 109.6 (2) |
N4—Pt2—N5ii | 96.56 (15) | O8—Cl2—O7 | 109.9 (2) |
N4ii—Pt2—N5ii | 83.44 (15) | O6—Cl2—O7 | 108.6 (2) |
N4—Pt2—N5 | 83.44 (15) | O5—Cl2—O7 | 108.7 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2 | 0.9 | 2.32 | 3.142 (6) | 152 |
N2—H2A···O3 | 0.9 | 2.26 | 3.041 (5) | 145 |
N2—H2B···O5 | 0.9 | 2.46 | 3.045 (5) | 123 |
N2—H2B···N1i | 0.9 | 2.46 | 3.231 (5) | 144 |
N3—H3B···O5i | 0.9 | 2.36 | 2.969 (6) | 125 |
N3—H3B···O7iii | 0.9 | 2.33 | 3.053 (5) | 138 |
N3—H3A···O2i | 0.9 | 2.3 | 3.132 (6) | 153 |
N4—H4A···O6iv | 0.9 | 2.39 | 3.008 (5) | 126 |
N4—H4A···N1ii | 0.9 | 2.48 | 3.220 (5) | 140 |
N4—H4B···O1 | 0.9 | 2.23 | 3.093 (6) | 161 |
N4—H4B···O3 | 0.9 | 2.5 | 3.225 (5) | 138 |
N5—H5B···O2iii | 0.9 | 2.46 | 3.131 (5) | 131 |
N5—H5B···O1ii | 0.9 | 2.51 | 3.324 (6) | 150 |
N5—H5A···O6i | 0.9 | 2.37 | 3.007 (5) | 128 |
N5—H5A···O7iii | 0.9 | 2.3 | 3.044 (5) | 140 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z; (iii) x, y, z−1; (iv) x, y−1, z−1. |
[Pt(NCS)2(C4H8N2)2](ClO4)2·1.5H2O | F(000) = 1268 |
Mr = 657.38 | Dx = 2.315 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 10279 reflections |
a = 30.515 (2) Å | θ = 3.2–30.0° |
b = 8.3572 (9) Å | µ = 8.00 mm−1 |
c = 7.4430 (7) Å | T = 296 K |
β = 96.507 (3)° | Block, orange |
V = 1885.9 (3) Å3 | 0.27 × 0.18 × 0.17 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 5351 independent reflections |
Radiation source: sealed x-ray tube | 5147 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 10 pixels mm-1 | θmax = 30.0°, θmin = 3.2° |
ω oscillation scans | h = −41→42 |
Absorption correction: empirical (using intensity measurements) (ABSCOR; Rigaku, 1995) | k = −11→11 |
Tmin = 0.708, Tmax = 1.000 | l = −10→9 |
11343 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)] = 0.02 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.042 | w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.84 | (Δ/σ)max = 0.001 |
5348 reflections | Δρmax = 1.18 e Å−3 |
249 parameters | Δρmin = −0.93 e Å−3 |
5 restraints | Absolute structure: Flack (1983), 2424 Friedel Pairs |
Primary atom site location: heavy-atom method | Absolute structure parameter: 0.001 (4) |
[Pt(NCS)2(C4H8N2)2](ClO4)2·1.5H2O | V = 1885.9 (3) Å3 |
Mr = 657.38 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 30.515 (2) Å | µ = 8.00 mm−1 |
b = 8.3572 (9) Å | T = 296 K |
c = 7.4430 (7) Å | 0.27 × 0.18 × 0.17 mm |
β = 96.507 (3)° |
Rigaku R-AXIS RAPID diffractometer | 5351 independent reflections |
Absorption correction: empirical (using intensity measurements) (ABSCOR; Rigaku, 1995) | 5147 reflections with I > 2σ(I) |
Tmin = 0.708, Tmax = 1.000 | Rint = 0.032 |
11343 measured reflections |
R[F2 > 2σ(F2)] = 0.02 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.042 | Δρmax = 1.18 e Å−3 |
S = 0.84 | Δρmin = −0.93 e Å−3 |
5348 reflections | Absolute structure: Flack (1983), 2424 Friedel Pairs |
249 parameters | Absolute structure parameter: 0.001 (4) |
5 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. X-ray diffraction measurements were performed with a Rigaku Rapid IP [for (I)] and a Rigaku SCX-mini CCD [for (II)] diffractometers, using graphite-monochromated Mo Kα (λ = 0.71073 Å) radiation. Pt atoms were located by the Patterson method. The other atoms were located from successive Fourier syntheses. All atoms were found and refined by full-matrix least-squares technique. Anisotropic displacement parameters are applied for all non-H atoms. All calculations were carried out using SHELX program (Sheldrick, 2008). 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 > 2sigma(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 | ||
Pt1 | 0.123749 (3) | 0.00001 (3) | 0.336629 (11) | 0.01800 (3) | |
S1 | 0.16671 (3) | 0.20031 (12) | 0.50651 (12) | 0.02863 (18) | |
S2 | 0.08149 (3) | −0.20672 (12) | 0.17844 (12) | 0.03200 (19) | |
N1 | 0.15331 (10) | 0.1022 (5) | 0.8598 (4) | 0.0423 (8) | |
N2 | 0.05881 (16) | −0.0669 (6) | −0.1625 (5) | 0.0820 (16) | |
N3 | 0.10435 (8) | 0.1793 (3) | 0.1541 (4) | 0.0231 (6) | |
H3A | 0.1275 | 0.2427 | 0.1389 | 0.028* | |
H3B | 0.0944 | 0.1363 | 0.0463 | 0.028* | |
N4 | 0.06729 (8) | 0.0670 (4) | 0.4474 (3) | 0.0251 (6) | |
H4A | 0.0524 | −0.0204 | 0.4764 | 0.03* | |
H4B | 0.0745 | 0.1246 | 0.5486 | 0.03* | |
N5 | 0.14446 (9) | −0.1790 (4) | 0.5201 (4) | 0.0277 (6) | |
H5A | 0.1553 | −0.1352 | 0.6264 | 0.033* | |
H5B | 0.1214 | −0.2416 | 0.5394 | 0.033* | |
N6 | 0.17919 (8) | −0.0682 (3) | 0.2203 (3) | 0.0244 (5) | |
H6A | 0.1713 | −0.1267 | 0.1204 | 0.029* | |
H6B | 0.1937 | 0.019 | 0.188 | 0.029* | |
C1 | 0.15848 (10) | 0.1431 (4) | 0.7161 (5) | 0.0276 (7) | |
C2 | 0.06799 (13) | −0.1265 (5) | −0.0237 (5) | 0.0418 (9) | |
C3 | 0.06841 (11) | 0.2764 (5) | 0.2241 (5) | 0.0348 (8) | |
H3C | 0.0811 | 0.3547 | 0.3112 | 0.042* | |
H3D | 0.0515 | 0.3325 | 0.1253 | 0.042* | |
C4 | 0.03955 (11) | 0.1644 (5) | 0.3111 (5) | 0.0370 (9) | |
H4C | 0.0241 | 0.095 | 0.2207 | 0.044* | |
H4D | 0.0178 | 0.2241 | 0.3695 | 0.044* | |
C5 | 0.17929 (11) | −0.2773 (5) | 0.4464 (5) | 0.0333 (8) | |
H5C | 0.1659 | −0.3556 | 0.361 | 0.04* | |
H5D | 0.1967 | −0.3336 | 0.5437 | 0.04* | |
C6 | 0.20821 (10) | −0.1643 (5) | 0.3532 (5) | 0.0331 (8) | |
H6C | 0.2244 | −0.0944 | 0.4413 | 0.04* | |
H6D | 0.2293 | −0.2245 | 0.292 | 0.04* | |
Cl1 | 0.06506 (2) | 0.48336 (14) | −0.26516 (10) | 0.03273 (18) | |
O1 | 0.09461 (10) | 0.5096 (6) | −0.1078 (4) | 0.0724 (10) | |
O2 | 0.05912 (10) | 0.3151 (4) | −0.2913 (5) | 0.0624 (9) | |
O3 | 0.02348 (10) | 0.5524 (4) | −0.2432 (6) | 0.0760 (11) | |
O4 | 0.08258 (11) | 0.5551 (4) | −0.4167 (4) | 0.0644 (10) | |
Cl2 | 0.22289 (2) | 0.37715 (10) | 0.13460 (11) | 0.02829 (16) | |
O5 | 0.24858 (8) | 0.4858 (5) | 0.2510 (4) | 0.0564 (8) | |
O6 | 0.23536 (8) | 0.2152 (4) | 0.1831 (4) | 0.0482 (7) | |
O7 | 0.17687 (8) | 0.3996 (4) | 0.1562 (4) | 0.0416 (6) | |
O8 | 0.22938 (10) | 0.4068 (5) | −0.0473 (4) | 0.0569 (8) | |
O9 | 0.17119 (8) | −0.2811 (4) | −0.0943 (4) | 0.0376 (6) | |
H9A | 0.1966 (7) | −0.320 (5) | −0.088 (6) | 0.045* | |
H9B | 0.1531 (10) | −0.350 (4) | −0.063 (6) | 0.045* | |
O10 | 0 | 0.8277 (5) | 0.5 | 0.0362 (8) | |
H10A | −0.0113 (14) | 0.764 (5) | 0.414 (5) | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.02019 (5) | 0.01966 (5) | 0.01458 (5) | −0.00150 (5) | 0.00390 (3) | −0.00110 (6) |
S1 | 0.0326 (5) | 0.0318 (5) | 0.0218 (4) | −0.0100 (4) | 0.0044 (3) | −0.0037 (4) |
S2 | 0.0423 (5) | 0.0283 (5) | 0.0250 (4) | −0.0108 (4) | 0.0018 (4) | −0.0045 (4) |
N1 | 0.0504 (18) | 0.052 (2) | 0.0265 (16) | 0.0031 (15) | 0.0109 (13) | −0.0032 (16) |
N2 | 0.128 (4) | 0.061 (3) | 0.045 (2) | −0.039 (3) | −0.039 (2) | 0.010 (2) |
N3 | 0.0246 (13) | 0.0271 (15) | 0.0185 (13) | 0.0015 (11) | 0.0063 (11) | −0.0013 (11) |
N4 | 0.0236 (12) | 0.0305 (15) | 0.0227 (13) | −0.0018 (10) | 0.0089 (10) | −0.0006 (11) |
N5 | 0.0357 (15) | 0.0246 (16) | 0.0230 (14) | 0.0006 (12) | 0.0047 (12) | 0.0023 (11) |
N6 | 0.0259 (13) | 0.0275 (15) | 0.0208 (12) | 0.0007 (10) | 0.0068 (10) | −0.0008 (11) |
C1 | 0.0256 (16) | 0.0311 (19) | 0.0256 (17) | 0.0008 (12) | 0.0003 (12) | −0.0077 (14) |
C2 | 0.056 (2) | 0.032 (2) | 0.033 (2) | −0.0094 (17) | −0.0128 (16) | −0.0054 (16) |
C3 | 0.0392 (18) | 0.035 (2) | 0.0310 (18) | 0.0142 (16) | 0.0089 (14) | 0.0040 (17) |
C4 | 0.0292 (17) | 0.044 (2) | 0.039 (2) | 0.0114 (15) | 0.0107 (15) | 0.0076 (17) |
C5 | 0.0410 (19) | 0.032 (2) | 0.0277 (18) | 0.0144 (15) | 0.0064 (14) | −0.0014 (15) |
C6 | 0.0291 (16) | 0.037 (2) | 0.0333 (19) | 0.0104 (14) | 0.0025 (13) | −0.0024 (15) |
Cl1 | 0.0331 (3) | 0.0269 (5) | 0.0384 (4) | −0.0041 (4) | 0.0047 (3) | −0.0063 (4) |
O1 | 0.081 (2) | 0.076 (2) | 0.0539 (16) | −0.036 (3) | −0.0169 (14) | −0.001 (3) |
O2 | 0.0599 (18) | 0.0301 (17) | 0.099 (3) | −0.0101 (14) | 0.0193 (17) | −0.0282 (18) |
O3 | 0.0579 (18) | 0.057 (3) | 0.119 (3) | 0.0203 (15) | 0.035 (2) | 0.013 (2) |
O4 | 0.080 (2) | 0.074 (3) | 0.0430 (17) | −0.0217 (17) | 0.0215 (15) | 0.0021 (16) |
Cl2 | 0.0264 (4) | 0.0248 (4) | 0.0348 (4) | −0.0039 (3) | 0.0081 (3) | 0.0013 (3) |
O5 | 0.0457 (13) | 0.047 (2) | 0.0732 (18) | −0.0116 (18) | −0.0086 (12) | −0.0113 (19) |
O6 | 0.0371 (14) | 0.0315 (16) | 0.076 (2) | 0.0007 (11) | 0.0074 (13) | 0.0118 (15) |
O7 | 0.0314 (13) | 0.0401 (17) | 0.0555 (18) | −0.0010 (11) | 0.0144 (11) | −0.0014 (14) |
O8 | 0.072 (2) | 0.062 (2) | 0.0409 (17) | −0.0012 (16) | 0.0269 (15) | 0.0104 (16) |
O9 | 0.0358 (14) | 0.0333 (15) | 0.0443 (15) | 0.0009 (11) | 0.0067 (12) | 0.0002 (13) |
O10 | 0.0395 (19) | 0.034 (2) | 0.034 (2) | 0 | 0.0015 (15) | 0 |
Pt1—N3 | 2.064 (3) | C3—C4 | 1.483 (5) |
Pt1—N6 | 2.066 (2) | C3—H3C | 0.97 |
Pt1—N4 | 2.070 (2) | C3—H3D | 0.97 |
Pt1—N5 | 2.076 (3) | C4—H4C | 0.97 |
Pt1—S2 | 2.3853 (9) | C4—H4D | 0.97 |
Pt1—S1 | 2.3966 (9) | C5—C6 | 1.514 (5) |
S1—C1 | 1.678 (4) | C5—H5C | 0.97 |
S2—C2 | 1.656 (4) | C5—H5D | 0.97 |
N1—C1 | 1.151 (4) | C6—H6C | 0.97 |
N2—C2 | 1.152 (5) | C6—H6D | 0.97 |
N3—C3 | 1.504 (4) | Cl1—O1 | 1.412 (3) |
N3—H3A | 0.9 | Cl1—O3 | 1.420 (3) |
N3—H3B | 0.9 | Cl1—O2 | 1.429 (3) |
N4—C4 | 1.488 (4) | Cl1—O4 | 1.433 (3) |
N4—H4A | 0.9 | Cl2—O8 | 1.412 (3) |
N4—H4B | 0.9 | Cl2—O5 | 1.427 (3) |
N5—C5 | 1.496 (4) | Cl2—O6 | 1.441 (3) |
N5—H5A | 0.9 | Cl2—O7 | 1.444 (2) |
N5—H5B | 0.9 | O9—H9A | 0.837 (18) |
N6—C6 | 1.486 (4) | O9—H9B | 0.847 (19) |
N6—H6A | 0.9 | O10—H10A | 0.871 (18) |
N6—H6B | 0.9 | ||
N3—Pt1—N6 | 96.42 (10) | H6A—N6—H6B | 108.3 |
N3—Pt1—N4 | 82.90 (11) | N1—C1—S1 | 179.0 (3) |
N6—Pt1—N4 | 178.62 (9) | N2—C2—S2 | 178.3 (4) |
N3—Pt1—N5 | 178.95 (11) | C4—C3—N3 | 107.7 (3) |
N6—Pt1—N5 | 82.77 (11) | C4—C3—H3C | 110.2 |
N4—Pt1—N5 | 97.92 (11) | N3—C3—H3C | 110.2 |
N3—Pt1—S2 | 95.87 (8) | C4—C3—H3D | 110.2 |
N6—Pt1—S2 | 90.90 (8) | N3—C3—H3D | 110.2 |
N4—Pt1—S2 | 87.98 (8) | H3C—C3—H3D | 108.5 |
N5—Pt1—S2 | 84.83 (9) | C3—C4—N4 | 108.8 (3) |
N3—Pt1—S1 | 86.51 (8) | C3—C4—H4C | 109.9 |
N6—Pt1—S1 | 89.37 (8) | N4—C4—H4C | 109.9 |
N4—Pt1—S1 | 91.79 (8) | C3—C4—H4D | 109.9 |
N5—Pt1—S1 | 92.80 (8) | N4—C4—H4D | 109.9 |
S2—Pt1—S1 | 177.56 (3) | H4C—C4—H4D | 108.3 |
C1—S1—Pt1 | 99.27 (12) | N5—C5—C6 | 107.5 (3) |
C2—S2—Pt1 | 102.72 (14) | N5—C5—H5C | 110.2 |
C3—N3—Pt1 | 109.2 (2) | C6—C5—H5C | 110.2 |
C3—N3—H3A | 109.8 | N5—C5—H5D | 110.2 |
Pt1—N3—H3A | 109.8 | C6—C5—H5D | 110.2 |
C3—N3—H3B | 109.8 | H5C—C5—H5D | 108.5 |
Pt1—N3—H3B | 109.8 | N6—C6—C5 | 107.9 (3) |
H3A—N3—H3B | 108.3 | N6—C6—H6C | 110.1 |
C4—N4—Pt1 | 108.14 (19) | C5—C6—H6C | 110.1 |
C4—N4—H4A | 110.1 | N6—C6—H6D | 110.1 |
Pt1—N4—H4A | 110.1 | C5—C6—H6D | 110.1 |
C4—N4—H4B | 110.1 | H6C—C6—H6D | 108.4 |
Pt1—N4—H4B | 110.1 | O1—Cl1—O3 | 109.7 (3) |
H4A—N4—H4B | 108.4 | O1—Cl1—O2 | 109.0 (3) |
C5—N5—Pt1 | 109.3 (2) | O3—Cl1—O2 | 108.3 (2) |
C5—N5—H5A | 109.8 | O1—Cl1—O4 | 109.1 (2) |
Pt1—N5—H5A | 109.8 | O3—Cl1—O4 | 109.8 (2) |
C5—N5—H5B | 109.8 | O2—Cl1—O4 | 111.0 (2) |
Pt1—N5—H5B | 109.8 | O8—Cl2—O5 | 110.1 (2) |
H5A—N5—H5B | 108.3 | O8—Cl2—O6 | 110.1 (2) |
C6—N6—Pt1 | 108.94 (19) | O5—Cl2—O6 | 109.5 (2) |
C6—N6—H6A | 109.9 | O8—Cl2—O7 | 109.12 (17) |
Pt1—N6—H6A | 109.9 | O5—Cl2—O7 | 108.92 (18) |
C6—N6—H6B | 109.9 | O6—Cl2—O7 | 109.06 (17) |
Pt1—N6—H6B | 109.9 | H9A—O9—H9B | 111 (4) |
N3—Pt1—S1—C1 | 141.12 (13) | S1—Pt1—N4—C4 | 102.3 (2) |
N6—Pt1—S1—C1 | −122.40 (13) | N3—Pt1—N5—C5 | −53 (7) |
N4—Pt1—S1—C1 | 58.35 (14) | N6—Pt1—N5—C5 | −12.7 (2) |
N5—Pt1—S1—C1 | −39.67 (15) | N4—Pt1—N5—C5 | 166.1 (2) |
S2—Pt1—S1—C1 | −26.1 (9) | S2—Pt1—N5—C5 | 78.8 (2) |
N3—Pt1—S2—C2 | 14.88 (19) | S1—Pt1—N5—C5 | −101.7 (2) |
N6—Pt1—S2—C2 | −81.67 (19) | N3—Pt1—N6—C6 | 163.0 (2) |
N4—Pt1—S2—C2 | 97.53 (18) | N4—Pt1—N6—C6 | −136 (4) |
N5—Pt1—S2—C2 | −164.33 (18) | N5—Pt1—N6—C6 | −16.3 (2) |
S1—Pt1—S2—C2 | −18E1 (7) | S2—Pt1—N6—C6 | −101.0 (2) |
N6—Pt1—N3—C3 | −169.0 (2) | S1—Pt1—N6—C6 | 76.6 (2) |
N4—Pt1—N3—C3 | 12.2 (2) | Pt1—S1—C1—N1 | 8E1 (2) |
N5—Pt1—N3—C3 | −129 (7) | Pt1—S2—C2—N2 | −20 (16) |
S2—Pt1—N3—C3 | 99.4 (2) | Pt1—N3—C3—C4 | −38.4 (3) |
S1—Pt1—N3—C3 | −80.1 (2) | N3—C3—C4—N4 | 53.4 (4) |
N3—Pt1—N4—C4 | 16.1 (2) | Pt1—N4—C4—C3 | −42.2 (4) |
N6—Pt1—N4—C4 | −45 (5) | Pt1—N5—C5—C6 | 38.8 (3) |
N5—Pt1—N4—C4 | −164.6 (2) | Pt1—N6—C6—C5 | 42.1 (3) |
S2—Pt1—N4—C4 | −80.1 (2) | N5—C5—C6—N6 | −53.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O7 | 0.9 | 1.99 | 2.877 (4) | 168 |
N3—H3B···N1i | 0.9 | 2.41 | 2.861 (4) | 111 |
N3—H3B···N2 | 0.9 | 2.47 | 3.313 (5) | 156 |
N4—H4A···O10ii | 0.9 | 2.06 | 2.924 (4) | 160 |
N4—H4A···N2iii | 0.9 | 2.7 | 3.149 (5) | 112 |
N4—H4B···O2iii | 0.9 | 2.07 | 2.873 (4) | 147 |
N5—H5A···O9iii | 0.9 | 2.41 | 3.016 (4) | 125 |
N5—H5A···N1 | 0.9 | 2.64 | 3.440 (4) | 148 |
N5—H5B···O4iv | 0.9 | 2.12 | 2.987 (4) | 162 |
N6—H6A···O9 | 0.9 | 2.05 | 2.929 (4) | 164 |
N6—H6B···O6 | 0.9 | 2.08 | 2.955 (4) | 165 |
N6—H6B···N1i | 0.9 | 2.7 | 3.061 (4) | 105 |
O9—H9A···O6v | 0.84 (2) | 2.29 (3) | 3.000 (4) | 143 (4) |
O9—H9B···O1ii | 0.85 (2) | 2.13 (2) | 2.912 (4) | 153 (4) |
O9—H9A···O8ii | 0.84 (2) | 2.50 (4) | 3.153 (5) | 136 (4) |
O10—H10A···O3vi | 0.87 (2) | 2.19 (2) | 3.025 (5) | 161 (4) |
O10—H10A···N2vii | 0.87 (2) | 2.65 (4) | 3.047 (3) | 109 (3) |
Symmetry codes: (i) x, y, z−1; (ii) x, y−1, z; (iii) x, y, z+1; (iv) x, y−1, z+1; (v) −x+1/2, y−1/2, −z; (vi) −x, y, −z; (vii) −x, y+1, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Pt2(NCS)2(C2H8N2)4](ClO4)4 | [Pt(NCS)2(C4H8N2)2](ClO4)2·1.5H2O |
Mr | 1144.56 | 657.38 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2 |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 9.0535 (13), 9.6033 (14), 9.6034 (14) | 30.515 (2), 8.3572 (9), 7.4430 (7) |
α, β, γ (°) | 104.944 (4), 91.574 (4), 113.765 (4) | 90, 96.507 (3), 90 |
V (Å3) | 730.11 (18) | 1885.9 (3) |
Z | 1 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 10.17 | 8.00 |
Crystal size (mm) | 0.30 × 0.27 × 0.27 | 0.27 × 0.18 × 0.17 |
Data collection | ||
Diffractometer | Rigaku SCX-MINI diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (REQAB; Rigaku, 1998) | Empirical (using intensity measurements) (ABSCOR; Rigaku, 1995) |
Tmin, Tmax | 0.565, 1.000 | 0.708, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7690, 3333, 3014 | 11343, 5351, 5147 |
Rint | 0.037 | 0.032 |
(sin θ/λ)max (Å−1) | 0.649 | 0.704 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.072, 1.18 | 0.02, 0.042, 0.84 |
No. of reflections | 3333 | 5348 |
No. of parameters | 202 | 249 |
No. of restraints | 0 | 5 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.20, −2.43 | 1.18, −0.93 |
Absolute structure | ? | Flack (1983), 2424 Friedel Pairs |
Absolute structure parameter | ? | 0.001 (4) |
Computer programs: , CrystalClear (Rigaku, 2008) and SORTAV (Blessing, 1995), RAPID-AUTO (Rigaku, 2006) and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), PLATON (Spek, 2009), WinGX (Farrugia, 2012).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.9 | 2.26 | 3.041 (5) | 144.7 |
N2—H2B···O5 | 0.9 | 2.46 | 3.045 (5) | 123.1 |
N3—H3B···O5i | 0.9 | 2.36 | 2.969 (6) | 125.3 |
N3—H3B···O7ii | 0.9 | 2.33 | 3.053 (5) | 137.8 |
N4—H4A···O6iii | 0.9 | 2.39 | 3.008 (5) | 125.6 |
N5—H5A···O6i | 0.9 | 2.37 | 3.007 (5) | 128.1 |
N5—H5A···O7ii | 0.9 | 2.3 | 3.044 (5) | 139.5 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z−1; (iii) x, y−1, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O7 | 0.9 | 1.99 | 2.877 (4) | 168.1 |
N4—H4A···O10i | 0.9 | 2.06 | 2.924 (4) | 159.6 |
N4—H4B···O2ii | 0.9 | 2.07 | 2.873 (4) | 147.4 |
N5—H5A···O9ii | 0.9 | 2.41 | 3.016 (4) | 124.7 |
N5—H5B···O4iii | 0.9 | 2.12 | 2.987 (4) | 162 |
N6—H6A···O9 | 0.9 | 2.05 | 2.929 (4) | 163.9 |
N6—H6B···O6 | 0.9 | 2.08 | 2.955 (4) | 164.8 |
O9—H9A···O6iv | 0.837 (18) | 2.29 (3) | 3.000 (4) | 143 (4) |
O9—H9B···O1i | 0.847 (19) | 2.13 (2) | 2.912 (4) | 153 (4) |
O10—H10A···O3v | 0.871 (18) | 2.19 (2) | 3.025 (5) | 161 (4) |
Symmetry codes: (i) x, y−1, z; (ii) x, y, z+1; (iii) x, y−1, z+1; (iv) −x+1/2, y−1/2, −z; (v) −x, y, −z. |
X | PtIV···PtII | PtIV—X | PtII···X | da |
NCSb | 5.8499 (7) | 2.3933 (10) | 3.471 (1) | 0.184 |
Clc | 5.428 | 2.327 (4) | 3.101 (4) | 0.143 |
Brd | 5.470 | 2.473 (1) | 2.996 (1) | 0.096 |
Ie | 5.827 | 2.791 (3) | 3.036 (8) | 0.042 |
Notes: (a) d = [l(PtII···X) - l(PtIV—X)]/ l(Pt···Pt). References: (b) this work; (c) Huckett et al. (1993); (d) Toriumi et al. (1993); (e) Endres et al. (1979). |
(I) | (II) | ||
Pt1—N2 | 2.057 (4) | Pt1—N3 | 2.064 (3) |
Pt1—N3 | 2.060 (4) | Pt1—N4 | 2.070 (2) |
Pt1—N5 | 2.071 (3) | ||
Pt1—N6 | 2.064 (3) | ||
Pt1—S1 | 2.3933 (10) | Pt1—S1 | 2.3966 (9) |
Pt1—S2 | 2.3853 (9) | ||
S1—Pt2 | 3.4705 (11) | ||
S1—C1 | 1.676 (4) | S1—C1 | 1.678 (4) |
S2—C2 | 1.656 (4) | ||
C1—N1 | 1.135 (5) | C1—N1 | 1.151 (4) |
C2—N2 | 1.152 (5) | ||
N2—Pt1—N3 | 83.28 (15) | N4—Pt1—N3 | 82.90 (11) |
N6—Pt1—N5 | 82.77 (11) | ||
C1—S1—Pt1 | 101.44 (14) | C1—S1—Pt1 | 99.27 (12) |
C2—S2—Pt1 | 102.72 (14) | ||
Pt1—S1—Pt2 | 171.97 (4) |
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Halogen-bridged MII···X—MIV (M = Pt, Pd) mixed-valence complexes have been investigated as typical one-dimensional polymeric systems having strong electron–lattice interactions (Keller, 1982). These one-dimensional sequences are described as a Peierls-distorted commensurate charge-density wave (CDW), which is induced by a charge transfer (CT) along the one-dimensional chain. The amplitude of the CDW state is influenced by the modification of various chemical parameters, including the metal (M), the bridging halogen (X), the ligand and the counterion. Okamoto et al. (1992) reported a correlation between the CT energies and various chemical parameters of one-dimensional systems. A deviation parameter (d in Table 1) for the bridging halogen atom from the midpoint between two metal atoms correlates linearly with the CT excitation energy. The MIV—X bond length is controlled mainly by the combination of metal and halogen atoms, while the MII···X contact distance is influenced by the size of the counteranion, which stabilises the one-dimensional chain structure by hydrogen-bond interactions with the NH2 groups of the diamine ligands. Large counteranions such as ClO4- cause elongation of the MII···MIV distance (Matsushita et al., 1992). More than 100 compounds with various combinations of the chemical parameters discussed above have been reported to date. However, the range of bridging atoms, which exert a large effect on the CDW state, is limited to only three kinds of halogen. There is a report of a one-dimensional Ni complex with nonhalogen bridging ligands (Meyer et al., 1982), in which the one-dimensional sequence is not linear but is bent at the bridging nitrite (NO2) groups. We demonstrate here the synthesis and structure of a new one-dimensional PtII/PtIV mixed-valence complex with the thiocyanate S atom acting as the bridging ligand, {[[PtII(en)2](µ-NCS)[PtIV(en)2](µ-NCS)](ClO4)4}n (en = ethane-1,2-diamine), (I), which has a PtII···S—PtIV linear sequence.
In the structure of (I), the PtII and PtIV complexes are stacked alternately, linked by the thiocyanate S atoms, constructing a one-dimensional chain elongated parallel to b+c [Cannot be one-dimensional if two dimensions are involved?]. The one-dimensional chains are supported by two-dimensional hydrogen-bond networks involving the ClO4- anions and NH2 groups (Fig. 2). Both PtII and PtIV atoms are located on special positions with 1 symmetry. Two thiocyanate ligands of the PtIV complex are located in trans positions related by an inversion centre.
Unlike most of the other halogen-bridged mixed-valence Pt complexes, there is no disorder of the bridging ligand in (I). The PtII···S—PtIV bond angle is slightly bent at 191.97 (4)°. The two en ligands of each Pt complex are attached as δ,λ-conformation chelate rings. The PtIV—S bond distance of 2.3933 (10) Å is shorter than that of the bromide-bridged complex (Toriumi et al., 1993), while the PtII···S distance is much longer than that of the iodide complex (Endres et al., 1979). The crystal exhibits large absorption from polarized light parallel to the one-dimensional chain which is a characteristic CT feature for one-dimensional systems on the CDW states. The large unequal Pt—S distances in (I) achieve a larger deviation parameter d than in the chloride-bridged complexes, which extends the chemical modifications available for controlling the amplitude of the CDW states.
We also report the isolation and crystal structure of a discrete PtIV complex with axial thiocyanate ligands, [Pt(NCS)2(en)2](ClO4)2, (II). In (II), the C1—S1—S2—C2 torsion angle is 156.3 (2)° and the PtIV complex has no special crystallographic symmetry. The two en ligands take δ- and λ-chelating conformations. The linear thiocyanate ligands of (II) do not participate in any hydrogen-bond interactions (Fig. 4). One of Pt—S bond lengths in (II) is slightly longer and the other is slightly shorter than that in (I). The thiocyanate ligand with the longer Pt—S bond makes a smaller Pt—S—C bond angle than that in (I), and the shorter Pt—S bond makes a larger bond angle.