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The third crystal structure containing the hydroxo-bridged cis-diammineplatinum(II) dimer has been determined for a perchlorate salt of the complex, [Pt2(NH3)4(μ-OH)2](ClO4)2. However, the dinuclear cations in the nitrate and the carbonate salts, [Pt2(NH3)4(μ-OH)2](NO3)2 [Faggiani, Lippert, Lock & Rosenberg (1977). J. Am. Chem. Soc. 99, 777–781] and [Pt2(NH3)4(μ-OH)2](CO3)·H2O [Lippert, Lock, Rosenberg & Zvagulis (1978). Inorg. Chem. 17, 2971−2975], were reported to possess a nearly planar geometry. The cation in the title perchlorate salt has been found to possess an exceptional bent form in which two Pt coordination planes within the dimer are tilted at an angle of 151.7 (1)° to one another. The diplatinum entity has a syn orientation with regard to the conformation of two hydroxo bridges, in part due to the one-dimensional hydrogen-bonding network achieved in the crystal structure. DFT MO investigations have also been carried out to reveal that the planar-bent selection could be induced by the anti–syn selection at the H(hydroxo) atoms. Comparison has also been made between the geometrical features of the three salts from the viewpoint of the orientation of H(hydroxo) atoms.
Supporting information
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: KENX (Sakai, 2002); software used to prepare material for publication: SHELXL97, TEXSAN (Molecular Structure Corporation, 2001),
KENX, and ORTEP (Johnson, 1976).
Di-µ-hydroxobis[
cis-diammineplatinum(II)] bis(perchlorate)
top
Crystal data top
Cl2H14N4O10Pt2 | ? # Insert any comments here. |
Mr = 691.23 | Dx = 3.453 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 4531 reflections |
a = 7.3422 (4) Å | θ = 2.9–28.1° |
b = 12.9876 (7) Å | µ = 21.47 mm−1 |
c = 13.9429 (8) Å | T = 296 K |
V = 1329.56 (13) Å3 | Needle, pale yellow |
Z = 4 | 0.2 × 0.10 × 0.06 mm |
F(000) = 1248 | |
Data collection top
Bruker SMART APEX CCD area detector diffractometer | 2898 independent reflections |
Radiation source: fine-focus sealed tube | 2726 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 8.366 pixels mm-1 | θmax = 27.1°, θmin = 2.9° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −16→12 |
Tmin = 0.069, Tmax = 0.264 | l = −15→17 |
7867 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.024 | w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.056 | (Δ/σ)max < 0.001 |
S = 0.98 | Δρmax = 1.21 e Å−3 |
2898 reflections | Δρmin = −1.23 e Å−3 |
168 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00081 (8) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 1361 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.012 (12) |
Crystal data top
Cl2H14N4O10Pt2 | V = 1329.56 (13) Å3 |
Mr = 691.23 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.3422 (4) Å | µ = 21.47 mm−1 |
b = 12.9876 (7) Å | T = 296 K |
c = 13.9429 (8) Å | 0.2 × 0.10 × 0.06 mm |
Data collection top
Bruker SMART APEX CCD area detector diffractometer | 2898 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2726 reflections with I > 2σ(I) |
Tmin = 0.069, Tmax = 0.264 | Rint = 0.040 |
7867 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.056 | Δρmax = 1.21 e Å−3 |
S = 0.98 | Δρmin = −1.23 e Å−3 |
2898 reflections | Absolute structure: Flack (1983), 1361 Friedel pairs |
168 parameters | Absolute structure parameter: 0.012 (12) |
0 restraints | |
Special details top
Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data. |
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. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 7.1270 (0.0037) x + 3.0328 (0.0260) y − 0.7941 (0.0284) z = 6.2499 (0.0039) * −0.0161 (0.0029) O1 * 0.0161 (0.0029) O2 * 0.0146 (0.0026) N3 * −0.0146 (0.0026) N4 0.0310 (0.0030) Pt2 0.7507 (0.0063) Pt1 Rms deviation of fitted atoms = 0.0153 7.1121 (0.0038) x − 3.1013 (0.0265) y + 0.9546 (0.0269) z = 5.4248 (0.0096) Angle to previous plane (with approximate e.s.d.) = 28.29 (0.10) * −0.0404 (0.0031) O1 * 0.0404 (0.0031) O2 * 0.0368 (0.0028) N1 * −0.0368 (0.0029) N2 0.0059 (0.0031) Pt1 0.7714 (0.0062) Pt2 Rms deviation of fitted atoms = 0.0386 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.87442 (5) | 0.249357 (19) | −0.015596 (18) | 0.01961 (8) | |
Pt2 | 0.87601 (4) | 0.020626 (19) | 0.031398 (19) | 0.01794 (8) | |
Cl1 | 1.0718 (3) | 0.11488 (15) | −0.31269 (16) | 0.0296 (5) | |
Cl2 | 1.0543 (3) | 0.14878 (14) | 0.33508 (16) | 0.0292 (4) | |
O1 | 0.8174 (7) | 0.1129 (4) | −0.0827 (4) | 0.0280 (13) | |
O2 | 0.8235 (7) | 0.1571 (4) | 0.1003 (4) | 0.0243 (13) | |
O3 | 1.1636 (9) | 0.0593 (5) | −0.3873 (5) | 0.052 (2) | |
O4 | 0.9658 (9) | 0.0408 (5) | −0.2563 (6) | 0.0475 (17) | |
O5 | 1.2023 (9) | 0.1631 (6) | −0.2529 (6) | 0.071 (2) | |
O6 | 0.9489 (8) | 0.1907 (5) | −0.3511 (6) | 0.061 (2) | |
O7 | 1.0152 (13) | 0.2144 (5) | 0.4129 (5) | 0.078 (3) | |
O8 | 1.0798 (7) | 0.2088 (5) | 0.2501 (5) | 0.0407 (15) | |
O9 | 0.9051 (8) | 0.0804 (5) | 0.3221 (5) | 0.0488 (17) | |
O10 | 1.2105 (10) | 0.0890 (6) | 0.3486 (8) | 0.088 (3) | |
N1 | 0.9294 (8) | 0.3279 (5) | −0.1379 (5) | 0.0281 (16) | |
H1A | 1.0490 | 0.3381 | −0.1426 | 0.042* | |
H1B | 0.8726 | 0.3884 | −0.1365 | 0.042* | |
H1C | 0.8909 | 0.2917 | −0.1881 | 0.042* | |
N2 | 0.9146 (10) | 0.3792 (4) | 0.0625 (6) | 0.036 (2) | |
H2A | 1.0332 | 0.3878 | 0.0727 | 0.053* | |
H2B | 0.8571 | 0.3735 | 0.1185 | 0.053* | |
H2C | 0.8709 | 0.4331 | 0.0305 | 0.053* | |
N3 | 0.9196 (9) | −0.1083 (4) | −0.0491 (5) | 0.0322 (17) | |
H3A | 0.8147 | −0.1414 | −0.0575 | 0.048* | |
H3B | 0.9982 | −0.1492 | −0.0190 | 0.048* | |
H3C | 0.9649 | −0.0903 | −0.1059 | 0.048* | |
N4 | 0.9178 (9) | −0.0607 (5) | 0.1527 (5) | 0.0295 (17) | |
H4A | 0.8307 | −0.1080 | 0.1589 | 0.044* | |
H4B | 0.9152 | −0.0185 | 0.2030 | 0.044* | |
H4C | 1.0258 | −0.0917 | 0.1498 | 0.044* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.02276 (14) | 0.01375 (14) | 0.02233 (15) | 0.00010 (10) | −0.00278 (16) | −0.00024 (11) |
Pt2 | 0.01989 (12) | 0.01450 (13) | 0.01942 (14) | 0.00092 (11) | 0.00017 (15) | 0.00038 (10) |
Cl1 | 0.0301 (10) | 0.0272 (10) | 0.0314 (11) | 0.0014 (7) | 0.0021 (8) | −0.0056 (9) |
Cl2 | 0.0413 (11) | 0.0203 (10) | 0.0261 (11) | −0.0039 (8) | −0.0013 (8) | −0.0022 (8) |
O1 | 0.039 (3) | 0.020 (3) | 0.025 (3) | −0.006 (2) | −0.005 (2) | 0.001 (2) |
O2 | 0.031 (3) | 0.022 (3) | 0.020 (3) | 0.003 (2) | 0.001 (2) | −0.004 (2) |
O3 | 0.051 (5) | 0.050 (4) | 0.055 (5) | 0.001 (3) | 0.024 (4) | −0.013 (4) |
O4 | 0.061 (4) | 0.039 (4) | 0.042 (4) | −0.003 (3) | 0.018 (3) | 0.005 (3) |
O5 | 0.054 (4) | 0.072 (5) | 0.085 (6) | −0.014 (4) | −0.024 (4) | −0.031 (5) |
O6 | 0.054 (4) | 0.034 (4) | 0.094 (6) | 0.016 (3) | 0.005 (4) | 0.021 (4) |
O7 | 0.160 (8) | 0.033 (4) | 0.041 (4) | −0.028 (5) | 0.016 (5) | −0.017 (4) |
O8 | 0.039 (4) | 0.050 (4) | 0.033 (3) | −0.001 (3) | 0.004 (3) | 0.010 (3) |
O9 | 0.044 (4) | 0.051 (4) | 0.051 (4) | −0.018 (3) | 0.013 (3) | −0.013 (3) |
O10 | 0.062 (5) | 0.055 (5) | 0.146 (9) | 0.004 (4) | −0.005 (5) | 0.041 (6) |
N1 | 0.035 (4) | 0.018 (3) | 0.032 (4) | 0.000 (3) | −0.004 (3) | 0.003 (3) |
N2 | 0.044 (5) | 0.017 (3) | 0.047 (5) | 0.005 (3) | −0.007 (4) | −0.003 (3) |
N3 | 0.037 (4) | 0.024 (3) | 0.036 (4) | 0.007 (3) | −0.004 (3) | −0.008 (3) |
N4 | 0.036 (4) | 0.024 (3) | 0.028 (4) | 0.003 (3) | 0.005 (3) | 0.007 (3) |
Geometric parameters (Å, º) top
Pt1—N1 | 2.027 (7) | Cl2—O7 | 1.409 (7) |
Pt1—N2 | 2.029 (6) | Cl2—O9 | 1.422 (6) |
Pt1—O2 | 2.046 (6) | Cl2—O8 | 1.431 (6) |
Pt1—O1 | 2.047 (5) | N1—H1A | 0.8900 |
Pt2—N4 | 2.018 (6) | N1—H1B | 0.8900 |
Pt2—O1 | 2.038 (6) | N1—H1C | 0.8900 |
Pt2—N3 | 2.040 (6) | N2—H2A | 0.8900 |
Pt2—O2 | 2.053 (5) | N2—H2B | 0.8900 |
Pt1—Pt2 | 3.0421 (4) | N2—H2C | 0.8900 |
Pt1—Pt1i | 3.6968 (6) | N3—H3A | 0.8900 |
Cl1—O5 | 1.416 (7) | N3—H3B | 0.8900 |
Cl1—O3 | 1.435 (7) | N3—H3C | 0.8900 |
Cl1—O6 | 1.439 (6) | N4—H4A | 0.8900 |
Cl1—O4 | 1.466 (7) | N4—H4B | 0.8900 |
Cl2—O10 | 1.398 (8) | N4—H4C | 0.8900 |
| | | |
O1···O4 | 2.814 (9) | O2···O8 | 2.891 (8) |
| | | |
N1—Pt1—N2 | 90.2 (3) | O6—Cl1—O4 | 108.4 (4) |
N1—Pt1—O2 | 174.4 (2) | O10—Cl2—O7 | 113.5 (6) |
N2—Pt1—O2 | 95.1 (3) | O10—Cl2—O9 | 107.6 (4) |
N1—Pt1—O1 | 95.3 (2) | O7—Cl2—O9 | 108.6 (5) |
N2—Pt1—O1 | 174.0 (3) | O10—Cl2—O8 | 107.9 (5) |
O2—Pt1—O1 | 79.5 (2) | O7—Cl2—O8 | 109.6 (4) |
N4—Pt2—O1 | 174.0 (3) | O9—Cl2—O8 | 109.6 (4) |
N4—Pt2—N3 | 90.4 (3) | Pt1—N1—H1A | 109.5 |
O1—Pt2—N3 | 94.9 (3) | Pt1—N1—H1B | 109.5 |
N4—Pt2—O2 | 95.1 (2) | H1A—N1—H1B | 109.5 |
O1—Pt2—O2 | 79.5 (2) | Pt1—N1—H1C | 109.5 |
N3—Pt2—O2 | 174.4 (3) | H1A—N1—H1C | 109.5 |
Pt2—O1—Pt1 | 96.3 (2) | H1B—N1—H1C | 109.5 |
Pt1—O2—Pt2 | 95.8 (2) | Pt1—N2—H2A | 109.5 |
N1—Pt1—Pt2 | 132.21 (19) | Pt1—N2—H2B | 109.5 |
N2—Pt1—Pt2 | 134.1 (2) | H2A—N2—H2B | 109.5 |
O2—Pt1—Pt2 | 42.17 (15) | Pt1—N2—H2C | 109.5 |
O1—Pt1—Pt2 | 41.75 (16) | H2A—N2—H2C | 109.5 |
N1—Pt1—Pt1i | 84.19 (18) | H2B—N2—H2C | 109.5 |
N2—Pt1—Pt1i | 77.8 (2) | Pt2—N3—H3A | 109.5 |
O2—Pt1—Pt1i | 95.23 (14) | Pt2—N3—H3B | 109.5 |
O1—Pt1—Pt1i | 105.11 (15) | H3A—N3—H3B | 109.5 |
Pt2—Pt1—Pt1i | 88.583 (12) | Pt2—N3—H3C | 109.5 |
N4—Pt2—Pt1 | 133.8 (2) | H3A—N3—H3C | 109.5 |
O1—Pt2—Pt1 | 41.99 (15) | H3B—N3—H3C | 109.5 |
N3—Pt2—Pt1 | 133.1 (2) | Pt2—N4—H4A | 109.5 |
O2—Pt2—Pt1 | 42.00 (16) | Pt2—N4—H4B | 109.5 |
O5—Cl1—O3 | 109.3 (5) | H4A—N4—H4B | 109.5 |
O5—Cl1—O6 | 109.9 (4) | Pt2—N4—H4C | 109.5 |
O3—Cl1—O6 | 111.6 (5) | H4A—N4—H4C | 109.5 |
O5—Cl1—O4 | 109.5 (5) | H4B—N4—H4C | 109.5 |
O3—Cl1—O4 | 107.9 (4) | | |
Symmetry code: (i) x+1/2, −y+1/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.89 | 2.10 | 2.947 (8) | 158 |
N2—H2A···O1i | 0.89 | 2.09 | 2.973 (9) | 171 |
N2—H2B···O5ii | 0.89 | 2.24 | 3.127 (11) | 172 |
N4—H4A···O4iii | 0.89 | 2.63 | 3.100 (10) | 114 |
N4—H4A···O6iii | 0.89 | 2.32 | 3.178 (9) | 161 |
N1—H1C···O8ii | 0.89 | 2.44 | 3.044 (8) | 125 |
N4—H4B···O9 | 0.89 | 2.10 | 2.990 (9) | 179 |
N3—H3A···O9iv | 0.89 | 2.46 | 3.007 (9) | 120 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, −y+1/2, −z; (iii) −x+3/2, −y, z+1/2; (iv) −x+3/2, −y, z−1/2. |
Experimental details
Crystal data |
Chemical formula | Cl2H14N4O10Pt2 |
Mr | 691.23 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 296 |
a, b, c (Å) | 7.3422 (4), 12.9876 (7), 13.9429 (8) |
V (Å3) | 1329.56 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 21.47 |
Crystal size (mm) | 0.2 × 0.10 × 0.06 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.069, 0.264 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7867, 2898, 2726 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.641 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.056, 0.98 |
No. of reflections | 2898 |
No. of parameters | 168 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.21, −1.23 |
Absolute structure | Flack (1983), 1361 Friedel pairs |
Absolute structure parameter | 0.012 (12) |
Selected geometric parameters (Å, º) topPt1—N1 | 2.027 (7) | Pt2—O1 | 2.038 (6) |
Pt1—N2 | 2.029 (6) | Pt2—N3 | 2.040 (6) |
Pt1—O2 | 2.046 (6) | Pt2—O2 | 2.053 (5) |
Pt1—O1 | 2.047 (5) | Pt1—Pt2 | 3.0421 (4) |
Pt2—N4 | 2.018 (6) | Pt1—Pt1i | 3.6968 (6) |
| | | |
O1···O4 | 2.814 (9) | O2···O8 | 2.891 (8) |
| | | |
N1—Pt1—N2 | 90.2 (3) | N4—Pt2—N3 | 90.4 (3) |
N1—Pt1—O2 | 174.4 (2) | O1—Pt2—N3 | 94.9 (3) |
N2—Pt1—O2 | 95.1 (3) | N4—Pt2—O2 | 95.1 (2) |
N1—Pt1—O1 | 95.3 (2) | O1—Pt2—O2 | 79.5 (2) |
N2—Pt1—O1 | 174.0 (3) | N3—Pt2—O2 | 174.4 (3) |
O2—Pt1—O1 | 79.5 (2) | Pt2—O1—Pt1 | 96.3 (2) |
N4—Pt2—O1 | 174.0 (3) | Pt1—O2—Pt2 | 95.8 (2) |
Symmetry code: (i) x+1/2, −y+1/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.89 | 2.10 | 2.947 (8) | 158 |
N2—H2A···O1i | 0.89 | 2.09 | 2.973 (9) | 171 |
N2—H2B···O5ii | 0.89 | 2.24 | 3.127 (11) | 172 |
N4—H4A···O6iii | 0.89 | 2.32 | 3.178 (9) | 161 |
N1—H1C···O8ii | 0.89 | 2.44 | 3.044 (8) | 125 |
N4—H4B···O9 | 0.89 | 2.10 | 2.990 (9) | 179 |
N3—H3A···O9iv | 0.89 | 2.46 | 3.007 (9) | 120 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, −y+1/2, −z; (iii) −x+3/2, −y, z+1/2; (iv) −x+3/2, −y, z−1/2. |
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