First bent form for the hydroxo-bridged cis-diammineplatinum(II) dimer [Pt₂(NH₃)₄(μ-OH)₂](ClO₄)₂

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.

S1. Comment

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S2. Experimental

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S3. Refinement

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Computing details

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).

Figures

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Di-µ-hydroxobis[cis-diammineplatinum(II)] bis(perchlorate)

Crystal data

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) Å^3	Needle, pale yellow
Z = 4	0.2 × 0.10 × 0.06 mm
F(000) = 1248

Data collection

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

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.024	w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/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)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—Pt1^i	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—Pt1^i	84.19 (18)	H2B—N2—H2C	109.5
N2—Pt1—Pt1^i	77.8 (2)	Pt2—N3—H3A	109.5
O2—Pt1—Pt1^i	95.23 (14)	Pt2—N3—H3B	109.5
O1—Pt1—Pt1^i	105.11 (15)	H3A—N3—H3B	109.5
Pt2—Pt1—Pt1^i	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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.89	2.10	2.947 (8)	158
N2—H2A···O1^i	0.89	2.09	2.973 (9)	171
N2—H2B···O5^ii	0.89	2.24	3.127 (11)	172
N4—H4A···O4^iii	0.89	2.63	3.100 (10)	114
N4—H4A···O6^iii	0.89	2.32	3.178 (9)	161
N1—H1C···O8^ii	0.89	2.44	3.044 (8)	125
N4—H4B···O9	0.89	2.10	2.990 (9)	179
N3—H3A···O9^iv	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.