The title compound, {[Pt
2Cl
2(C
2H
8N
2)
4](BF
4)
4}
n or [Pt
II(C
2H
8N
2)
2][Pt
IVCl
2(C
2H
8N
2)
2](BF
4)
4, has a linear chain structure composed 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
c axis. The Cl atom bridging the adjacent Pt atoms is disordered over two sites along the
Cl—Pt
IV—Cl
Pt
II chain, which lies on a twofold axis. The Pt
IV—Cl and Pt
IICl bond distances are 2.319 (3) and 3.052 (3) Å, respectively. A structural parameter indicating the mixed-valence state of the Pt atom, expressed by δ = (Pt
IV—Cl)/(Pt
IICl), is 0.760.
Supporting information
CCDC reference: 269577
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.011 Å
- Disorder in main residue
- R factor = 0.026
- wR factor = 0.068
- Data-to-parameter ratio = 19.6
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT242_ALERT_2_A Check Low Ueq as Compared to Neighbors for B
| Author Response: The U(eq) of the B atom of the counter-anion, BF~4~^-^ is relatively
small comparing with the U(eq) of the atom F3. The U(eq) of the atom F3 is too
large due to the disorder of the BF~4~^-^ ion.
|
Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio
PLAT076_ALERT_1_C Occupancy 0.50 less than 1.0 for Sp.pos . CL
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.66
PLAT213_ALERT_2_C Atom F3 has ADP max/min Ratio ............. 3.20 oblate
PLAT301_ALERT_3_C Main Residue Disorder ......................... 14.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 11
Alert level G
ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
Tmin and Tmax reported: 0.077 0.255
Tmin and Tmax expected: 0.046 0.209
RR = 1.366
Please check that your absorption correction is appropriate.
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
8 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: Rigaku/AFC Diffractometer Control Software (Rigaku, 1987); cell refinement: Rigaku/AFC Diffractometer Control Software; data reduction: local program; program(s) used to solve structure: UNICS3 (Sakurai & Kobayashi, 1979); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: Please provide missing details.
catena-poly[[[bis(ethylenediamine)platinum(II)]-µ-chloro-
[bis(ethylenediamine)platinum(IV)]-µ-chloro] tetrakis(tetrafluoroborate)]
top
Crystal data top
[Pt2Cl2(C2H8N2)4](BF4)4 | Dx = 2.523 Mg m−3 |
Mr = 1048.74 | Melting point: not measured K |
Orthorhombic, Ibam | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -I 2 2c | Cell parameters from 25 reflections |
a = 9.580 (2) Å | θ = 10.5–14.8° |
b = 13.416 (2) Å | µ = 10.44 mm−1 |
c = 10.743 (2) Å | T = 295 K |
V = 1380.7 (4) Å3 | Plate, intense red |
Z = 2 | 0.33 × 0.30 × 0.15 mm |
F(000) = 980 | |
Data collection top
Rigaku AFC-5S diffractometer | 821 reflections with F2 > 2σ(F2) |
Radiation source: X-ray tube | Rint = 0.023 |
Graphite monochromator | θmax = 32.5°, θmin = 2.6° |
θ/2θ scans | h = −14→14 |
Absorption correction: gaussian (Coppens et al., 1965) | k = 0→20 |
Tmin = 0.077, Tmax = 0.255 | l = 0→16 |
3523 measured reflections | 3 standard reflections every 50 reflections |
1311 independent reflections | intensity decay: none |
Refinement top
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)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.0407P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1311 reflections | Δρmax = 3.52 e Å−3 |
67 parameters | Δρmin = −1.33 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: heavy-atom method | Extinction coefficient: 0.0063 (3) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Pt | 0.0000 | 0.0000 | 0.2500 | 0.02551 (11) | |
Cl | 0.0000 | 0.0000 | 0.0341 (2) | 0.0348 (5) | 0.50 |
N | 0.1600 (4) | 0.1013 (3) | 0.2481 (4) | 0.0399 (7) | |
H1 | 0.1686 | 0.1280 | 0.1716 | 0.060* | |
H2 | 0.1422 | 0.1508 | 0.3024 | 0.060* | |
C | 0.2911 (6) | 0.0495 (6) | 0.2832 (6) | 0.0546 (15) | |
H3 | 0.2949 | 0.0395 | 0.3726 | 0.082* | |
H4 | 0.3715 | 0.0887 | 0.2583 | 0.082* | |
B | 0.4161 (13) | 0.2019 (9) | 0.0000 | 0.056 (2) | |
F1 | 0.4757 (6) | 0.2377 (5) | 0.1052 (5) | 0.0960 (18) | |
F2 | 0.456 (2) | 0.1003 (8) | 0.0000 | 0.092 (4) | 0.60 |
F2' | 0.337 (3) | 0.1231 (14) | 0.0000 | 0.083 (6) | 0.40 |
F3 | 0.2852 (17) | 0.208 (3) | 0.0000 | 0.195 (13) | 0.60 |
F3' | 0.311 (3) | 0.283 (2) | 0.0000 | 0.153 (13) | 0.40 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt | 0.02912 (14) | 0.02802 (14) | 0.01940 (14) | 0.000 | 0.000 | 0.000 |
Cl | 0.0427 (11) | 0.0412 (11) | 0.0205 (8) | 0.0043 (19) | 0.000 | 0.000 |
N | 0.0427 (16) | 0.0402 (16) | 0.0366 (17) | −0.0108 (14) | −0.002 (2) | 0.005 (2) |
C | 0.036 (2) | 0.080 (4) | 0.047 (3) | −0.016 (3) | −0.006 (2) | 0.006 (3) |
B | 0.067 (7) | 0.057 (6) | 0.044 (5) | −0.006 (5) | 0.000 | 0.000 |
F1 | 0.157 (5) | 0.078 (3) | 0.053 (2) | −0.002 (3) | −0.020 (2) | −0.013 (2) |
F2 | 0.169 (12) | 0.035 (4) | 0.073 (8) | 0.010 (7) | 0.000 | 0.000 |
F2' | 0.14 (2) | 0.047 (9) | 0.057 (9) | −0.040 (11) | 0.000 | 0.000 |
F3 | 0.031 (5) | 0.32 (4) | 0.23 (2) | 0.007 (16) | 0.000 | 0.000 |
F3' | 0.09 (2) | 0.11 (2) | 0.26 (3) | −0.029 (16) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Pt—N | 2.049 (4) | C—H3 | 0.9700 |
Pt—Cl | 2.319 (3) | C—H4 | 0.9700 |
Cl—Pti | 3.052 (3) | B—F3 | 1.256 (19) |
N—C | 1.485 (8) | B—F2' | 1.301 (19) |
N—H1 | 0.9000 | B—F1 | 1.355 (8) |
N—H2 | 0.9000 | B—F2 | 1.415 (16) |
C—Cii | 1.506 (15) | B—F3' | 1.48 (4) |
| | | |
Niii—Pt—N | 178.9 (2) | N—C—H3 | 110.3 |
N—Pt—Nii | 83.1 (2) | Cii—C—H3 | 110.3 |
N—Pt—Niv | 96.9 (2) | N—C—H4 | 110.3 |
N—Pt—Cliv | 90.57 (12) | Cii—C—H4 | 110.3 |
N—Pt—Cl | 89.43 (12) | H3—C—H4 | 108.6 |
Cliv—Pt—Cl | 180.0 | F3—B—F1 | 113.6 (10) |
Pt—Cl—Pti | 180.0 | F2'—B—F1 | 122.3 (6) |
C—N—Pt | 108.6 (3) | F3—B—F1v | 113.6 (10) |
C—N—H1 | 110.0 | F1—B—F1v | 113.1 (10) |
Pt—N—H1 | 110.0 | F3—B—F2 | 109.2 (17) |
C—N—H2 | 110.0 | F1—B—F2 | 103.1 (9) |
Pt—N—H2 | 110.0 | F2'—B—F3' | 101.4 (18) |
H1—N—H2 | 108.3 | F1—B—F3' | 91.6 (8) |
N—C—Cii | 107.0 (4) | | |
Symmetry codes: (i) −x, −y, −z; (ii) x, −y, −z+1/2; (iii) −x, −y, z; (iv) −x, y, −z+1/2; (v) x, y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H2···F1vi | 0.90 | 2.12 | 2.973 (8) | 158 |
N—H1···F3 | 0.90 | 2.41 | 3.252 (16) | 157 |
N—H2···F3′vi | 0.90 | 2.35 | 3.134 (15) | 146 |
N—H1···F2′ | 0.90 | 2.45 | 3.172 (17) | 137 |
Symmetry code: (vi) −x+1/2, −y+1/2, −z+1/2. |