The structure of the title compound, {[Pt
II/IVCl(C
2H
8N
2)
2](PF
6)
2}
n or [Pt
II(C
2H
8N
2)
2][Pt
IVCl
2(C
2H
8N
2)
2](PF
6)
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-[PtCl
2(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 Pt
IV–Cl and Pt
IICl 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
CCDC reference: 277262
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (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
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)2 | F(000) = 301 |
Mr = 640.69 | Dx = 2.67 Mg m−3 |
Monoclinic, P2/m | Melting point: not measured K |
Hall symbol: -P 2y | Mo Kα radiation, λ = 0.7107 Å |
a = 8.193 (3) Å | Cell parameters from 10346 reflections |
b = 5.518 (2) Å | θ = 3.7–32.6° |
c = 9.233 (4) Å | µ = 9.30 mm−1 |
β = 107.33 (3)° | T = 296 K |
V = 398.5 (3) Å3 | Prism, orange |
Z = 1 | 0.17 × 0.15 × 0.15 mm |
Data collection top
Rigaku R-AXIS RAPID imaging-plate diffractometer | 1547 independent reflections |
Radiation source: X-ray sealed tube | 1547 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 10.00 pixels mm-1 | θmax = 32.6°, θmin = 3.7° |
ω scans | h = 0→12 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = 0→8 |
Tmin = 0.184, Tmax = 0.248 | l = −13→13 |
7708 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)] = 0.030 | w = 1/[σ2(Fo2) + (0.0446P)2 + 0.7131P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.087 | (Δ/σ)max < 0.001 |
S = 1.19 | Δρmax = 1.49 e Å−3 |
1547 reflections | Δρmin = −2.87 e Å−3 |
77 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Pt | 0.0000 | 0.0000 | 0.0000 | 0.03183 (13) | |
Cl | 0.0000 | 0.4217 (6) | 0.0000 | 0.0438 (6) | 0.50 |
P | 0.6475 (3) | 0.5000 | 0.2693 (3) | 0.0479 (4) | |
F1 | 0.8516 (7) | 0.5000 | 0.3226 (9) | 0.079 (2) | |
F2 | 0.4425 (7) | 0.5000 | 0.2097 (9) | 0.0769 (19) | |
F3 | 0.6480 (7) | 0.2973 (12) | 0.1465 (7) | 0.099 (2) | |
F4 | 0.6481 (8) | 0.2994 (15) | 0.3875 (8) | 0.120 (3) | |
N1 | −0.0323 (8) | 0.0000 | 0.2115 (7) | 0.0431 (12) | |
H1A | −0.1174 | 0.1017 | 0.2135 | 0.065* | 0.50 |
H1B | −0.0602 | −0.1498 | 0.2346 | 0.065* | 0.50 |
N2 | 0.2541 (7) | 0.0000 | 0.1209 (7) | 0.0431 (12) | |
H2A | 0.3096 | −0.1137 | 0.0839 | 0.065* | 0.50 |
H2B | 0.3004 | 0.1452 | 0.1125 | 0.065* | 0.50 |
C1 | 0.1303 (13) | 0.079 (2) | 0.3240 (11) | 0.048 (2) | 0.50 |
H1C | 0.1292 | 0.0398 | 0.4261 | 0.072* | 0.50 |
H1D | 0.1450 | 0.2527 | 0.3175 | 0.072* | 0.50 |
C2 | 0.2724 (13) | −0.053 (2) | 0.2870 (12) | 0.050 (3) | 0.50 |
H2C | 0.2639 | −0.2256 | 0.3027 | 0.074* | 0.50 |
H2D | 0.3823 | 0.0036 | 0.3511 | 0.074* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt | 0.02713 (16) | 0.02838 (16) | 0.03834 (19) | 0.000 | 0.00725 (11) | 0.000 |
Cl | 0.0475 (15) | 0.0287 (10) | 0.0536 (16) | 0.000 | 0.0128 (13) | 0.000 |
P | 0.0387 (8) | 0.0484 (10) | 0.0521 (10) | 0.000 | 0.0067 (7) | 0.000 |
F1 | 0.043 (3) | 0.098 (5) | 0.086 (4) | 0.000 | 0.003 (3) | 0.000 |
F2 | 0.042 (3) | 0.087 (5) | 0.094 (5) | 0.000 | 0.009 (3) | 0.000 |
F3 | 0.081 (3) | 0.101 (4) | 0.097 (4) | 0.026 (3) | −0.004 (3) | −0.042 (3) |
F4 | 0.092 (4) | 0.146 (6) | 0.103 (4) | −0.023 (4) | 0.002 (3) | 0.071 (4) |
N1 | 0.040 (3) | 0.050 (3) | 0.040 (3) | 0.000 | 0.013 (2) | 0.000 |
N2 | 0.031 (2) | 0.045 (3) | 0.049 (3) | 0.000 | 0.007 (2) | 0.000 |
C1 | 0.045 (4) | 0.053 (5) | 0.042 (4) | 0.001 (4) | 0.006 (3) | −0.007 (4) |
C2 | 0.040 (4) | 0.054 (9) | 0.048 (4) | 0.007 (4) | 0.004 (3) | 0.003 (4) |
Geometric parameters (Å, º) top
Pt—Cli | 2.327 (4) | P—F4iv | 1.554 (6) |
Pt—Cl | 2.327 (4) | P—F4 | 1.554 (6) |
Pt—Clii | 3.191 (4) | N1—C1 | 1.490 (12) |
Cl—Clii | 0.865 (7) | N1—H1A | 0.9000 |
Cl—Ptiii | 3.191 (4) | N1—H1B | 0.9000 |
Pt—N1 | 2.047 (6) | N2—C2 | 1.523 (12) |
Pt—N1i | 2.047 (6) | N2—H2A | 0.9000 |
Pt—N2i | 2.048 (6) | N2—H2B | 0.9000 |
Pt—N2 | 2.048 (6) | C1—C2 | 1.496 (15) |
P—F1 | 1.596 (6) | C1—H1C | 0.9700 |
P—F2 | 1.605 (6) | C1—H1D | 0.9700 |
P—F3 | 1.593 (6) | C2—H2C | 0.9700 |
P—F3iv | 1.593 (6) | C2—H2D | 0.9700 |
| | | |
N1—Pt—N1i | 180.0 (3) | C2—N2—H2B | 109.9 |
N1—Pt—N2i | 96.9 (3) | Pt—N2—H2B | 109.9 |
N1i—Pt—N2i | 83.1 (3) | H2A—N2—H2B | 108.3 |
N1—Pt—N2 | 83.1 (3) | N1—C1—C2 | 107.1 (8) |
N1i—Pt—N2 | 96.9 (3) | N1—C1—H1C | 110.3 |
N2i—Pt—N2 | 180.0 (4) | C2—C1—H1C | 110.3 |
N1—Pt—Cli | 90.0 | N1—C1—H1D | 110.3 |
N1i—Pt—Cli | 90.0 | C2—C1—H1D | 110.3 |
N2i—Pt—Cli | 90.0 | H1C—C1—H1D | 108.6 |
N2—Pt—Cli | 90.0 | C1—C2—N2 | 106.7 (8) |
N1—Pt—Cl | 90.0 | C1—C2—H2C | 110.4 |
N1i—Pt—Cl | 90.0 | N2—C2—H2C | 110.4 |
N2i—Pt—Cl | 90.0 | C1—C2—H2D | 110.4 |
N2—Pt—Cl | 90.0 | N2—C2—H2D | 110.4 |
Cli—Pt—Cl | 180.0 | H2C—C2—H2D | 108.6 |
N1—Pt—Clii | 90.0 | F1—P—F2 | 178.0 (4) |
N1i—Pt—Clii | 90.0 | F1—P—F3 | 89.7 (3) |
N2i—Pt—Clii | 90.0 | F1—P—F4 | 90.0 (3) |
N2—Pt—Clii | 90.0 | F2—P—F3 | 88.9 (3) |
Cli—Pt—Clii | 180.0 | F2—P—F4 | 91.4 (3) |
Clii—Cl—Pt | 180.0 | F3—P—F4 | 90.0 (4) |
Pt—Cl—Ptiii | 180.0 | F3—P—F3iv | 89.2 (6) |
C1—N1—Pt | 108.8 (5) | F3—P—F4iv | 179.1 (5) |
C1—N1—H1A | 109.9 | F4—P—F4iv | 90.8 (7) |
Pt—N1—H1A | 109.9 | F4iv—P—F3iv | 90.0 (4) |
C1—N1—H1B | 109.9 | F4—P—F3iv | 179.1 (5) |
Pt—N1—H1B | 109.9 | F4iv—P—F1 | 90.0 (3) |
H1A—N1—H1B | 108.3 | F3iv—P—F1 | 89.7 (3) |
C2—N2—Pt | 109.2 (5) | F4iv—P—F2 | 91.4 (3) |
C2—N2—H2A | 109.9 | F3iv—P—F2 | 88.9 (3) |
Pt—N2—H2A | 109.9 | | |
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···A | D—H | H···A | D···A | D—H···A |
N1—H1A···F3v | 0.90 | 2.13 | 2.996 (8) | 162 |
N1—H1B···F1vi | 0.90 | 2.30 | 3.186 (5) | 171 |
N2—H2A···F3vii | 0.90 | 2.47 | 3.258 (8) | 146 |
N2—H2B···F2 | 0.90 | 2.32 | 3.149 (4) | 154 |
Symmetry codes: (v) x−1, y, z; (vi) x−1, y−1, z; (vii) −x+1, −y, −z. |