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The structure of the title compound, {[PtII/IVCl(C2H8N2)2](PF6)2}n or [PtII(C2H8N2)2][PtIVCl2(C2H8N2)2](PF6)4, has been redetermined [Matsushita (1993). Synth. Met. 56, 3401–3406] from image-plate data. No superstructure was observed, in contrast to the situation in related compounds. The linear chain structure consists of square-planar [Pt(en)2]2+ and elongated octa­hedral trans-[PtCl2(en)2]2+ cations (en is ethyl­enediamine) stacked alternately, bridged by the Cl atoms, along the b axis. The Pt atom is located on an inversion centre and the Cl atom (site symmetry 2) is disordered over two sites, resulting in PtIV–Cl and PtII...Cl bond distances of 2.327 (4) and 3.191 (4) Å, respectively. The δ structural parameter, indicating the mixed-valence state of the Pt atoms, is 0.729.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805017873/hb6213sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805017873/hb6213Isup2.hkl
Contains datablock I

CCDC reference: 277262

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](P-F) = 0.007 Å
  • Disorder in main residue
  • R factor = 0.030
  • wR factor = 0.087
  • Data-to-parameter ratio = 20.1

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for P
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.82 PLAT076_ALERT_1_C Occupancy 0.50 less than 1.0 for Sp.pos . CL PLAT301_ALERT_3_C Main Residue Disorder ......................... 23.00 Perc.
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2002); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

catena-poly[[[bis(ethylenediamine)platinum(II)]-µ-chloro- [bis(ethylenediamine)platinum(IV)]-µ-chloro] tetrakis(hexafluorophosphate)] top
Crystal data top
[PtCl(C2H8N2)2](PF6)2F(000) = 301
Mr = 640.69Dx = 2.67 Mg m3
Monoclinic, P2/mMelting point: not measured K
Hall symbol: -P 2yMo Kα radiation, λ = 0.7107 Å
a = 8.193 (3) ÅCell parameters from 10346 reflections
b = 5.518 (2) Åθ = 3.7–32.6°
c = 9.233 (4) ŵ = 9.30 mm1
β = 107.33 (3)°T = 296 K
V = 398.5 (3) Å3Prism, orange
Z = 10.17 × 0.15 × 0.15 mm
Data collection top
Rigaku R-AXIS RAPID imaging-plate
diffractometer
1547 independent reflections
Radiation source: X-ray sealed tube1547 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 10.00 pixels mm-1θmax = 32.6°, θmin = 3.7°
ω scansh = 012
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 08
Tmin = 0.184, Tmax = 0.248l = 1313
7708 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.030 w = 1/[σ2(Fo2) + (0.0446P)2 + 0.7131P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.087(Δ/σ)max < 0.001
S = 1.19Δρmax = 1.49 e Å3
1547 reflectionsΔρmin = 2.87 e Å3
77 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.031 (3)
Primary atom site location: heavy-atom method
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 > 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
xyzUiso*/UeqOcc. (<1)
Pt0.00000.00000.00000.03183 (13)
Cl0.00000.4217 (6)0.00000.0438 (6)0.50
P0.6475 (3)0.50000.2693 (3)0.0479 (4)
F10.8516 (7)0.50000.3226 (9)0.079 (2)
F20.4425 (7)0.50000.2097 (9)0.0769 (19)
F30.6480 (7)0.2973 (12)0.1465 (7)0.099 (2)
F40.6481 (8)0.2994 (15)0.3875 (8)0.120 (3)
N10.0323 (8)0.00000.2115 (7)0.0431 (12)
H1A0.11740.10170.21350.065*0.50
H1B0.06020.14980.23460.065*0.50
N20.2541 (7)0.00000.1209 (7)0.0431 (12)
H2A0.30960.11370.08390.065*0.50
H2B0.30040.14520.11250.065*0.50
C10.1303 (13)0.079 (2)0.3240 (11)0.048 (2)0.50
H1C0.12920.03980.42610.072*0.50
H1D0.14500.25270.31750.072*0.50
C20.2724 (13)0.053 (2)0.2870 (12)0.050 (3)0.50
H2C0.26390.22560.30270.074*0.50
H2D0.38230.00360.35110.074*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt0.02713 (16)0.02838 (16)0.03834 (19)0.0000.00725 (11)0.000
Cl0.0475 (15)0.0287 (10)0.0536 (16)0.0000.0128 (13)0.000
P0.0387 (8)0.0484 (10)0.0521 (10)0.0000.0067 (7)0.000
F10.043 (3)0.098 (5)0.086 (4)0.0000.003 (3)0.000
F20.042 (3)0.087 (5)0.094 (5)0.0000.009 (3)0.000
F30.081 (3)0.101 (4)0.097 (4)0.026 (3)0.004 (3)0.042 (3)
F40.092 (4)0.146 (6)0.103 (4)0.023 (4)0.002 (3)0.071 (4)
N10.040 (3)0.050 (3)0.040 (3)0.0000.013 (2)0.000
N20.031 (2)0.045 (3)0.049 (3)0.0000.007 (2)0.000
C10.045 (4)0.053 (5)0.042 (4)0.001 (4)0.006 (3)0.007 (4)
C20.040 (4)0.054 (9)0.048 (4)0.007 (4)0.004 (3)0.003 (4)
Geometric parameters (Å, º) top
Pt—Cli2.327 (4)P—F4iv1.554 (6)
Pt—Cl2.327 (4)P—F41.554 (6)
Pt—Clii3.191 (4)N1—C11.490 (12)
Cl—Clii0.865 (7)N1—H1A0.9000
Cl—Ptiii3.191 (4)N1—H1B0.9000
Pt—N12.047 (6)N2—C21.523 (12)
Pt—N1i2.047 (6)N2—H2A0.9000
Pt—N2i2.048 (6)N2—H2B0.9000
Pt—N22.048 (6)C1—C21.496 (15)
P—F11.596 (6)C1—H1C0.9700
P—F21.605 (6)C1—H1D0.9700
P—F31.593 (6)C2—H2C0.9700
P—F3iv1.593 (6)C2—H2D0.9700
N1—Pt—N1i180.0 (3)C2—N2—H2B109.9
N1—Pt—N2i96.9 (3)Pt—N2—H2B109.9
N1i—Pt—N2i83.1 (3)H2A—N2—H2B108.3
N1—Pt—N283.1 (3)N1—C1—C2107.1 (8)
N1i—Pt—N296.9 (3)N1—C1—H1C110.3
N2i—Pt—N2180.0 (4)C2—C1—H1C110.3
N1—Pt—Cli90.0N1—C1—H1D110.3
N1i—Pt—Cli90.0C2—C1—H1D110.3
N2i—Pt—Cli90.0H1C—C1—H1D108.6
N2—Pt—Cli90.0C1—C2—N2106.7 (8)
N1—Pt—Cl90.0C1—C2—H2C110.4
N1i—Pt—Cl90.0N2—C2—H2C110.4
N2i—Pt—Cl90.0C1—C2—H2D110.4
N2—Pt—Cl90.0N2—C2—H2D110.4
Cli—Pt—Cl180.0H2C—C2—H2D108.6
N1—Pt—Clii90.0F1—P—F2178.0 (4)
N1i—Pt—Clii90.0F1—P—F389.7 (3)
N2i—Pt—Clii90.0F1—P—F490.0 (3)
N2—Pt—Clii90.0F2—P—F388.9 (3)
Cli—Pt—Clii180.0F2—P—F491.4 (3)
Clii—Cl—Pt180.0F3—P—F490.0 (4)
Pt—Cl—Ptiii180.0F3—P—F3iv89.2 (6)
C1—N1—Pt108.8 (5)F3—P—F4iv179.1 (5)
C1—N1—H1A109.9F4—P—F4iv90.8 (7)
Pt—N1—H1A109.9F4iv—P—F3iv90.0 (4)
C1—N1—H1B109.9F4—P—F3iv179.1 (5)
Pt—N1—H1B109.9F4iv—P—F190.0 (3)
H1A—N1—H1B108.3F3iv—P—F189.7 (3)
C2—N2—Pt109.2 (5)F4iv—P—F291.4 (3)
C2—N2—H2A109.9F3iv—P—F288.9 (3)
Pt—N2—H2A109.9
Symmetry codes: (i) x, y, z; (ii) x, y+1, z; (iii) x, y+1, z; (iv) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···F3v0.902.132.996 (8)162
N1—H1B···F1vi0.902.303.186 (5)171
N2—H2A···F3vii0.902.473.258 (8)146
N2—H2B···F20.902.323.149 (4)154
Symmetry codes: (v) x1, y, z; (vi) x1, y1, z; (vii) x+1, y, z.
 

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