Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803013497/ob6258sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803013497/ob6258Isup2.hkl |
CCDC reference: 217425
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.022 Å
- H-atom completeness 76%
- Disorder in solvent or counterion
- R factor = 0.063
- wR factor = 0.197
- Data-to-parameter ratio = 18.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.25 From the CIF: _reflns_number_total 5608 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 6010 Completeness (_total/calc) 93.31% Alert C: < 95% complete RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.101 PLAT_302 Alert C Anion/Solvent Disorder ......................... 44.00 Perc. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C24 H48 N16 O28 Pt4 Atom count from the _atom_site data: C24 H36 N16 O28 Pt4 CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C24 H48 N16 O28 Pt4 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 96.00 96.00 0.00 H 192.00 144.00 48.00 N 64.00 64.00 0.00 O 112.00 112.00 0.00 Pt 16.00 16.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
To an aqueous solution of cis-[Pt(NH3)2(OH2)2](NO3)2 (0.5 mmol/3.5 ml H2O), prepared as previously described (Sakai, Takeshita et al., 1998; Sakai, Tanaka et al., 1998), was added 5-carboxy-α-pyridone (6-hydroxynicotinic acid) (0.5 mmol). The solution was heated at 353 K for 4 h followed by filtration if necessary. Leaving of the resulting green solution at 278 K for a few days afforded the title compound (I) as dark-green prisms, which were collected by filtration and air-dried (yield: 7%). Analysis calculated for C24H48N16O28Pt4: C 16.11, H 2.70, N 12.53%; found: C 16.34, H 2.56, N 12.28%.
Two nitrate ions are both treated as being disordered over two sites. One of two nitrate anions shows orientational disorder in which two sets of positions of (O7A, O8A and O9A) and (O7B, O8B and O9B) are located around atom N7. For each disordered nitrate ion, the disordered O atoms were supposed to have the same isotropic displacement parameter. Furthermore, the N—O distances were restrained at 1.22 Å, three O···O distances within each nitrate ion were restrained as equal, and each nitrate ion was restrained to be planar. In each case, two sites are judged to be equally populated and therefore the occupation factors for all the disordered atoms were assumed as 50%. Aromatic and ammine H atoms were located at idealized positions as riding atoms (C—H = 0.93 Å and N—H = 0.89 Å), while those of carboxyl groups and water molecules were not located. In the final difference Fourier synthesis, relatively large four residual peaks in the range 4.03–5.48 e Å−3 were observed within 1.03 Å from Pt atoms. Other 12 peaks in the range 1.00–1.84 e Å−3 were located near either Pt atoms or disordered nitrate ions.
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 (Sheldrick, 1997), TEXSAN (Molecular Structure Corporation, 2001), KENX (Sakai, 2002) and ORTEPII (Johnson, 1976).
[Pt2(C6H4NO3)2(NH3)4]2(NO3)4·4H2O | F(000) = 3360 |
Mr = 1789.14 | Dx = 2.443 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 23.648 (4) Å | Cell parameters from 8766 reflections |
b = 13.3574 (16) Å | θ = 2.3–28.0° |
c = 15.5128 (19) Å | µ = 11.57 mm−1 |
β = 96.998 (3)° | T = 296 K |
V = 4863.6 (11) Å3 | Prism, dark green |
Z = 4 | 0.25 × 0.10 × 0.05 mm |
Bruker SMART APEX CCD-detector diffractometer | 5608 independent reflections |
Radiation source: fine-focus sealed tube | 3623 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.101 |
Detector resolution: 8.366 pixels mm-1 | θmax = 28.3°, θmin = 2.7° |
ω scans | h = −31→30 |
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001) | k = −17→17 |
Tmin = 0.115, Tmax = 0.325 | l = −20→20 |
20325 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.197 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1051P)2 + 48.6026P] where P = (Fo2 + 2Fc2)/3 |
5608 reflections | (Δ/σ)max = 0.001 |
298 parameters | Δρmax = 5.48 e Å−3 |
28 restraints | Δρmin = −1.62 e Å−3 |
[Pt2(C6H4NO3)2(NH3)4]2(NO3)4·4H2O | V = 4863.6 (11) Å3 |
Mr = 1789.14 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 23.648 (4) Å | µ = 11.57 mm−1 |
b = 13.3574 (16) Å | T = 296 K |
c = 15.5128 (19) Å | 0.25 × 0.10 × 0.05 mm |
β = 96.998 (3)° |
Bruker SMART APEX CCD-detector diffractometer | 5608 independent reflections |
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001) | 3623 reflections with I > 2σ(I) |
Tmin = 0.115, Tmax = 0.325 | Rint = 0.101 |
20325 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 28 restraints |
wR(F2) = 0.197 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1051P)2 + 48.6026P] where P = (Fo2 + 2Fc2)/3 |
5608 reflections | Δρmax = 5.48 e Å−3 |
298 parameters | Δρmin = −1.62 e Å−3 |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 22.0816 (0.0354) x + 3.8252 (0.0564) y − 5.0698 (0.0610) z = 2.4416 (0.0389) * −0.0114 (0.0057) O1 * 0.0114 (0.0057) O4 * 0.0116 (0.0058) N3 * −0.0116 (0.0058) N4 − 2.8313 (0.0063) Pt1 − 0.0876 (0.0058) Pt2 Rms deviation of fitted atoms = 0.0115 −19.0744 (0.0603) x + 0.8137 (0.0524) y + 10.5773 (0.0488) z = 4.9654 (0.0377) Angle to previous plane (with approximate e.s.d.) = 30.47 (0.35) * 0.0131 (0.0058) N1 * −0.0129 (0.0057) N2 * −0.0133 (0.0059) N5 * 0.0132 (0.0058) N6 − 2.8990 (0.0056) Pt2 − 0.0553 (0.0057) Pt1 Rms deviation of fitted atoms = 0.0131 7.4317 (0.1951) x + 3.5686 (0.1198) y + 13.4324 (0.0729) z = 10.1917 (0.0569) Angle to previous plane (with approximate e.s.d.) = 72.64 (0.47) * 0.0007 (0.0146) C12 * −0.0003 (0.0052) O5 * −0.0003 (0.0054) O6 * −0.0002 (0.0041) C8 3.6072 (0.0215) C12_$3 3.1792 (0.0264) O5_$3 4.2449 (0.0187) O6_$3 3.3034 (0.0255) C8_$3 Rms deviation of fitted atoms = 0.0004 7.4317 (0.1948) x − 3.5686 (0.1197) y + 13.4324 (0.0728) z = 9.9569 (0.1113) Angle to previous plane (with approximate e.s.d.) = 30.99 (0.73) * −0.0007 (0.0146) C12_$3 * 0.0003 (0.0051) O5_$3 * 0.0003 (0.0054) O6_$3 * 0.0002 (0.0041) C8_$3 − 3.6072 (0.0214) C12 − 3.1792 (0.0264) O5 − 4.2449 (0.0186) O6 − 3.3034 (0.0254) C8 Rms deviation of fitted atoms = 0.0004 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pt1 | 0.08681 (2) | 0.19941 (4) | 0.60542 (3) | 0.04542 (19) | |
Pt2 | 0.18727 (2) | 0.21857 (5) | 0.51626 (4) | 0.0517 (2) | |
O1 | 0.2235 (4) | 0.1938 (8) | 0.6402 (7) | 0.062 (3) | |
O2 | 0.0794 (5) | 0.2426 (13) | 0.9455 (9) | 0.094 (4) | |
O3 | 0.1653 (6) | 0.2243 (13) | 1.0190 (8) | 0.109 (5) | |
O4 | 0.1713 (5) | 0.3664 (7) | 0.5386 (7) | 0.068 (3) | |
O5 | −0.0592 (6) | 0.4783 (12) | 0.6644 (9) | 0.101 (5) | |
O6 | −0.0403 (6) | 0.6276 (11) | 0.6143 (9) | 0.103 (5) | |
O7A | 0.0253 (7) | −0.0437 (18) | 0.3203 (14) | 0.190 (7)* | 0.50 |
O7B | 0.0453 (10) | −0.0307 (19) | 0.2921 (10) | 0.190 (7)* | 0.50 |
O8A | 0.1091 (9) | 0.014 (3) | 0.3322 (18) | 0.190 (7)* | 0.50 |
O8B | 0.1186 (6) | 0.003 (3) | 0.3792 (18) | 0.190 (7)* | 0.50 |
O9A | 0.0682 (13) | −0.009 (3) | 0.4443 (9) | 0.190 (7)* | 0.50 |
O9B | 0.0386 (10) | −0.011 (3) | 0.4256 (13) | 0.190 (7)* | 0.50 |
O10A | 0.2200 (11) | −0.0443 (19) | 0.6708 (12) | 0.172 (6)* | 0.50 |
O10B | 0.2281 (8) | −0.0368 (19) | 0.6396 (16) | 0.172 (6)* | 0.50 |
O11A | 0.2593 (9) | −0.056 (4) | 0.8002 (15) | 0.172 (6)* | 0.50 |
O11B | 0.3150 (9) | 0.004 (3) | 0.655 (2) | 0.172 (6)* | 0.50 |
O12A | 0.1704 (8) | −0.076 (3) | 0.7720 (19) | 0.172 (6)* | 0.50 |
O12B | 0.2767 (15) | −0.048 (4) | 0.7629 (15) | 0.172 (6)* | 0.50 |
O13 | 0.1200 (8) | 0.2153 (13) | 1.1635 (14) | 0.134 (6)* | |
O14 | −0.1506 (11) | 0.557 (2) | 0.7153 (17) | 0.090 (7)* | 0.50 |
O15 | −0.0014 (18) | 0.168 (3) | 0.288 (2) | 0.139 (13)* | 0.50 |
N1 | 0.0868 (5) | 0.0475 (9) | 0.6236 (8) | 0.066 (3) | |
H1A | 0.1211 | 0.0280 | 0.6479 | 0.099* | |
H1B | 0.0785 | 0.0171 | 0.5726 | 0.099* | |
H1C | 0.0609 | 0.0314 | 0.6583 | 0.099* | |
N2 | 0.0259 (6) | 0.1885 (10) | 0.5004 (8) | 0.066 (3) | |
H2A | −0.0085 | 0.1890 | 0.5183 | 0.100* | |
H2B | 0.0306 | 0.1316 | 0.4723 | 0.100* | |
H2C | 0.0290 | 0.2401 | 0.4650 | 0.100* | |
N3 | 0.2101 (6) | 0.0763 (10) | 0.4887 (10) | 0.078 (4) | |
H3A | 0.2180 | 0.0421 | 0.5379 | 0.117* | |
H3B | 0.2407 | 0.0779 | 0.4606 | 0.117* | |
H3C | 0.1815 | 0.0468 | 0.4555 | 0.117* | |
N4 | 0.1570 (6) | 0.2453 (12) | 0.3897 (9) | 0.072 (4) | |
H4A | 0.1805 | 0.2868 | 0.3666 | 0.108* | |
H4B | 0.1226 | 0.2729 | 0.3867 | 0.108* | |
H4C | 0.1547 | 0.1878 | 0.3604 | 0.108* | |
N5 | 0.1444 (4) | 0.2120 (8) | 0.7123 (7) | 0.045 (3) | |
N6 | 0.0834 (4) | 0.3521 (7) | 0.5940 (7) | 0.042 (2) | |
N7 | 0.0675 (5) | −0.0130 (9) | 0.3656 (9) | 0.190 (7)* | |
N8A | 0.2166 (7) | −0.0586 (17) | 0.7477 (12) | 0.172 (6)* | 0.50 |
N8B | 0.2733 (8) | −0.0267 (16) | 0.6859 (14) | 0.172 (6)* | 0.50 |
C1 | 0.1233 (6) | 0.2243 (11) | 0.7891 (10) | 0.056 (4) | |
H1 | 0.0843 | 0.2334 | 0.7890 | 0.068* | |
C2 | 0.1580 (6) | 0.2239 (11) | 0.8672 (9) | 0.055 (3) | |
C3 | 0.2159 (6) | 0.2139 (13) | 0.8664 (11) | 0.069 (5) | |
H3D | 0.2407 | 0.2155 | 0.9178 | 0.083* | |
C4 | 0.2358 (6) | 0.2018 (13) | 0.7893 (12) | 0.070 (5) | |
H4 | 0.2747 | 0.1919 | 0.7890 | 0.084* | |
C5 | 0.2012 (6) | 0.2033 (10) | 0.7106 (9) | 0.051 (3) | |
C6 | 0.1303 (7) | 0.2316 (13) | 0.9473 (10) | 0.065 (4) | |
C7 | 0.0360 (6) | 0.3970 (12) | 0.6156 (8) | 0.056 (4) | |
H7 | 0.0076 | 0.3571 | 0.6342 | 0.067* | |
C8 | 0.0279 (7) | 0.4957 (12) | 0.6116 (9) | 0.061 (4) | |
C9 | 0.0704 (8) | 0.5560 (13) | 0.5827 (10) | 0.071 (4) | |
H9 | 0.0660 | 0.6252 | 0.5795 | 0.085* | |
C10 | 0.1185 (8) | 0.5113 (13) | 0.5590 (12) | 0.080 (5) | |
H10 | 0.1471 | 0.5504 | 0.5400 | 0.096* | |
C11 | 0.1247 (7) | 0.4041 (12) | 0.5634 (9) | 0.060 (4) | |
C12 | −0.0280 (9) | 0.5384 (14) | 0.6312 (10) | 0.074 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.0364 (3) | 0.0572 (4) | 0.0420 (3) | 0.0004 (2) | 0.0026 (2) | 0.0029 (2) |
Pt2 | 0.0415 (3) | 0.0682 (4) | 0.0464 (3) | −0.0001 (2) | 0.0096 (2) | 0.0052 (2) |
O1 | 0.043 (5) | 0.095 (8) | 0.050 (6) | 0.006 (5) | 0.014 (4) | 0.002 (5) |
O2 | 0.056 (8) | 0.157 (13) | 0.074 (8) | −0.008 (8) | 0.024 (6) | −0.012 (8) |
O3 | 0.079 (9) | 0.209 (18) | 0.039 (6) | −0.012 (9) | 0.006 (6) | 0.002 (8) |
O4 | 0.075 (7) | 0.047 (6) | 0.083 (8) | 0.004 (5) | 0.016 (6) | −0.001 (5) |
O5 | 0.098 (10) | 0.122 (12) | 0.091 (9) | 0.050 (9) | 0.042 (8) | 0.032 (8) |
O6 | 0.129 (12) | 0.091 (10) | 0.092 (10) | 0.047 (9) | 0.022 (8) | 0.006 (8) |
N1 | 0.063 (8) | 0.057 (8) | 0.075 (9) | −0.004 (6) | −0.003 (7) | 0.014 (6) |
N2 | 0.068 (9) | 0.075 (9) | 0.057 (8) | 0.007 (7) | 0.011 (6) | −0.002 (6) |
N3 | 0.072 (9) | 0.070 (9) | 0.096 (11) | 0.003 (7) | 0.030 (8) | 0.000 (8) |
N4 | 0.060 (8) | 0.091 (10) | 0.070 (9) | 0.017 (7) | 0.025 (7) | 0.021 (8) |
N5 | 0.033 (5) | 0.063 (7) | 0.040 (6) | 0.002 (4) | 0.002 (4) | 0.008 (5) |
N6 | 0.046 (6) | 0.031 (5) | 0.051 (6) | 0.004 (4) | 0.016 (5) | 0.010 (4) |
C1 | 0.034 (7) | 0.074 (10) | 0.062 (9) | −0.003 (6) | 0.010 (6) | 0.012 (7) |
C2 | 0.042 (7) | 0.075 (10) | 0.047 (8) | −0.010 (6) | 0.004 (6) | −0.003 (7) |
C3 | 0.039 (8) | 0.116 (15) | 0.051 (8) | −0.005 (8) | −0.003 (6) | −0.010 (8) |
C4 | 0.037 (8) | 0.100 (13) | 0.071 (11) | −0.006 (7) | 0.001 (7) | −0.004 (9) |
C5 | 0.040 (7) | 0.059 (9) | 0.055 (8) | −0.001 (6) | 0.008 (6) | 0.003 (6) |
C6 | 0.059 (10) | 0.093 (12) | 0.044 (8) | −0.017 (8) | 0.009 (7) | −0.011 (7) |
C7 | 0.054 (8) | 0.072 (10) | 0.041 (7) | 0.014 (7) | 0.008 (6) | 0.009 (6) |
C8 | 0.072 (10) | 0.065 (10) | 0.046 (8) | 0.007 (8) | 0.005 (7) | −0.003 (7) |
C9 | 0.090 (12) | 0.061 (10) | 0.063 (10) | 0.007 (9) | 0.012 (9) | 0.004 (8) |
C10 | 0.086 (12) | 0.058 (10) | 0.098 (14) | −0.007 (9) | 0.020 (10) | −0.001 (9) |
C11 | 0.067 (9) | 0.060 (9) | 0.055 (8) | 0.017 (7) | 0.010 (7) | 0.004 (7) |
C12 | 0.104 (14) | 0.075 (12) | 0.043 (8) | 0.046 (10) | 0.004 (8) | 0.007 (8) |
Pt1—N5 | 2.021 (11) | O15—O15v | 1.18 (6) |
Pt1—N2 | 2.044 (13) | N5—C5 | 1.351 (16) |
Pt1—N6 | 2.049 (10) | N5—C1 | 1.356 (18) |
Pt1—N1 | 2.049 (12) | N6—C11 | 1.333 (18) |
Pt2—O1 | 2.033 (11) | N6—C7 | 1.350 (16) |
Pt2—N3 | 2.035 (13) | N8A—N8B | 1.79 (3) |
Pt2—N4 | 2.038 (14) | C1—C2 | 1.38 (2) |
Pt2—O4 | 2.048 (10) | C2—C3 | 1.378 (19) |
Pt1—Pt2 | 2.9023 (8) | C2—C6 | 1.48 (2) |
Pt2—Pt2i | 3.1821 (11) | C3—C4 | 1.35 (2) |
Pt1—Pt1ii | 6.4394 (12) | C4—C5 | 1.38 (2) |
O5—C8ii | 3.47 (2) | C7—C8 | 1.33 (2) |
O3—O13 | 2.60 (2) | C8—C9 | 1.40 (2) |
O5—O14 | 2.61 (3) | C8—C12 | 1.50 (2) |
O1—C5 | 1.276 (17) | C9—C10 | 1.37 (2) |
O2—C6 | 1.208 (19) | C10—C11 | 1.44 (2) |
O3—C6 | 1.31 (2) | N1—H1A | 0.8900 |
O4—C11 | 1.310 (17) | N1—H1B | 0.8900 |
O5—C12 | 1.24 (2) | N1—H1C | 0.8900 |
O6—C12 | 1.25 (2) | N2—H2A | 0.8900 |
O7A—N7 | 1.2201 (10) | N2—H2B | 0.8900 |
O7B—N7 | 1.2200 (10) | N2—H2C | 0.8900 |
O8A—N7 | 1.2201 (10) | N3—H3A | 0.8900 |
O8B—N7 | 1.2200 (10) | N3—H3B | 0.8900 |
O9A—N7 | 1.2199 (10) | N3—H3C | 0.8900 |
O9B—N7 | 1.2201 (10) | N4—H4A | 0.8900 |
O10A—N8A | 1.2199 (10) | N4—H4B | 0.8900 |
O10B—N8B | 1.2200 (10) | N4—H4C | 0.8900 |
O11A—N8A | 1.2198 (10) | C1—H1 | 0.9300 |
O11B—N8B | 1.2200 (10) | C3—H3D | 0.9300 |
O11B—O14iii | 1.36 (4) | C4—H4 | 0.9300 |
O12A—N8A | 1.2199 (10) | C7—H7 | 0.9300 |
O12B—N8B | 1.2200 (10) | C9—H9 | 0.9300 |
O14—O11Biv | 1.36 (4) | C10—H10 | 0.9300 |
N5—Pt1—N2 | 177.6 (5) | O1—C5—N5 | 122.7 (13) |
N5—Pt1—N6 | 90.2 (4) | O1—C5—C4 | 119.6 (13) |
N2—Pt1—N6 | 89.2 (5) | N5—C5—C4 | 117.7 (13) |
N5—Pt1—N1 | 88.9 (5) | O2—C6—O3 | 123.6 (15) |
N2—Pt1—N1 | 91.6 (5) | O2—C6—C2 | 122.1 (15) |
N6—Pt1—N1 | 176.1 (5) | O3—C6—C2 | 114.3 (14) |
O1—Pt2—N3 | 87.4 (5) | C8—C7—N6 | 123.2 (14) |
O1—Pt2—N4 | 175.7 (4) | C7—C8—C9 | 118.5 (15) |
N3—Pt2—N4 | 91.8 (6) | C7—C8—C12 | 119.4 (16) |
O1—Pt2—O4 | 93.5 (4) | C9—C8—C12 | 121.9 (16) |
N3—Pt2—O4 | 174.3 (5) | C10—C9—C8 | 119.0 (16) |
N4—Pt2—O4 | 86.8 (5) | C9—C10—C11 | 120.1 (17) |
Pt1—Pt2—Pt2i | 158.74 (3) | O4—C11—N6 | 125.7 (14) |
Pt2—Pt1—Pt1ii | 163.81 (2) | O4—C11—C10 | 116.9 (15) |
N5—Pt1—Pt2 | 82.8 (3) | N6—C11—C10 | 117.4 (14) |
N2—Pt1—Pt2 | 99.5 (4) | O5—C12—O6 | 124.8 (18) |
N6—Pt1—Pt2 | 84.1 (3) | O5—C12—C8 | 114.8 (15) |
N1—Pt1—Pt2 | 99.6 (4) | O6—C12—C8 | 120.5 (19) |
N5—Pt1—Pt1ii | 81.5 (3) | N5—C1—H1 | 119.0 |
N2—Pt1—Pt1ii | 96.2 (4) | C2—C1—H1 | 119.0 |
N6—Pt1—Pt1ii | 92.2 (3) | C4—C3—H3D | 120.8 |
N1—Pt1—Pt1ii | 83.9 (4) | C2—C3—H3D | 120.8 |
O1—Pt2—Pt1 | 79.0 (3) | C3—C4—H4 | 118.3 |
N3—Pt2—Pt1 | 105.7 (4) | C5—C4—H4 | 118.3 |
N4—Pt2—Pt1 | 105.2 (4) | C8—C7—H7 | 118.4 |
O4—Pt2—Pt1 | 80.0 (3) | N6—C7—H7 | 118.4 |
O1—Pt2—Pt2i | 84.2 (3) | C10—C9—H9 | 120.5 |
N3—Pt2—Pt2i | 86.4 (4) | C8—C9—H9 | 120.5 |
N4—Pt2—Pt2i | 91.5 (4) | C9—C10—H10 | 119.9 |
O4—Pt2—Pt2i | 88.1 (3) | C11—C10—H10 | 119.9 |
C5—O1—Pt2 | 128.6 (9) | Pt1—N1—H1A | 109.5 |
C11—O4—Pt2 | 126.9 (10) | Pt1—N1—H1B | 109.5 |
C5—N5—C1 | 120.0 (12) | H1A—N1—H1B | 109.5 |
C5—N5—Pt1 | 123.3 (9) | Pt1—N1—H1C | 109.5 |
C1—N5—Pt1 | 116.6 (9) | H1A—N1—H1C | 109.5 |
C11—N6—C7 | 121.7 (12) | H1B—N1—H1C | 109.5 |
C11—N6—Pt1 | 121.8 (9) | Pt1—N2—H2A | 109.5 |
C7—N6—Pt1 | 116.5 (9) | Pt1—N2—H2B | 109.5 |
O7B—N7—O8B | 120.01 (9) | H2A—N2—H2B | 109.5 |
O8B—N7—O9B | 119.99 (9) | Pt1—N2—H2C | 109.5 |
O9A—N7—O7A | 120.01 (9) | H2A—N2—H2C | 109.5 |
O9A—N7—O8A | 120.01 (9) | H2B—N2—H2C | 109.5 |
O7A—N7—O8A | 119.98 (9) | Pt2—N3—H3A | 109.5 |
O11A—N8A—O12A | 120.00 (9) | Pt2—N3—H3B | 109.5 |
O11A—N8A—O10A | 120.00 (9) | H3A—N3—H3B | 109.5 |
O12A—N8A—O10A | 120.00 (9) | Pt2—N3—H3C | 109.5 |
O10B—N8B—O11B | 120.01 (9) | H3A—N3—H3C | 109.5 |
O10B—N8B—O12B | 120.00 (9) | H3B—N3—H3C | 109.5 |
O11B—N8B—O12B | 120.00 (9) | Pt2—N4—H4A | 109.5 |
N5—C1—C2 | 122.0 (12) | Pt2—N4—H4B | 109.5 |
C1—C2—C3 | 118.5 (13) | H4A—N4—H4B | 109.5 |
C1—C2—C6 | 117.5 (13) | Pt2—N4—H4C | 109.5 |
C3—C2—C6 | 123.9 (14) | H4A—N4—H4C | 109.5 |
C4—C3—C2 | 118.3 (15) | H4B—N4—H4C | 109.5 |
C3—C4—C5 | 123.3 (14) | ||
N5—Pt1—Pt2—O1 | 12.8 (4) | C1—C2—C6—O3 | 175.8 (15) |
N1—Pt1—Pt2—N3 | 9.3 (6) | C3—C2—C6—O3 | −2 (3) |
N2—Pt1—Pt2—N4 | 12.4 (6) | C11—N6—C7—C8 | −3 (2) |
N6—Pt1—Pt2—O4 | 8.1 (4) | N6—C7—C8—C9 | 1 (2) |
C5—N5—C1—C2 | −3 (2) | N6—C7—C8—C12 | 175.9 (12) |
N5—C1—C2—C3 | 2 (2) | C7—C8—C9—C10 | 0 (2) |
N5—C1—C2—C6 | −176.2 (14) | C12—C8—C9—C10 | −174.7 (15) |
C1—C2—C3—C4 | −2 (2) | C8—C9—C10—C11 | 0 (3) |
C6—C2—C3—C4 | 176.2 (16) | C7—N6—C11—O4 | −178.0 (13) |
C2—C3—C4—C5 | 3 (3) | C7—N6—C11—C10 | 3 (2) |
C1—N5—C5—O1 | −178.4 (13) | C9—C10—C11—O4 | 179.0 (15) |
C1—N5—C5—C4 | 4 (2) | C9—C10—C11—N6 | −2 (2) |
C3—C4—C5—O1 | 178.2 (16) | C7—C8—C12—O5 | 12 (2) |
C3—C4—C5—N5 | −4 (2) | C9—C8—C12—O5 | −173.2 (16) |
C1—C2—C6—O2 | −3 (3) | C7—C8—C12—O6 | −168.1 (16) |
C3—C2—C6—O2 | 178.3 (18) | C9—C8—C12—O6 | 7 (2) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, y, −z+3/2; (iii) x+1/2, y−1/2, z; (iv) x−1/2, y+1/2, z; (v) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O4i | 0.89 | 2.21 | 2.988 (17) | 146 |
N4—H4A···O1i | 0.89 | 2.30 | 3.030 (16) | 139 |
N2—H2A···O2ii | 0.89 | 1.97 | 2.818 (17) | 159 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Pt2(C6H4NO3)2(NH3)4]2(NO3)4·4H2O |
Mr | 1789.14 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 23.648 (4), 13.3574 (16), 15.5128 (19) |
β (°) | 96.998 (3) |
V (Å3) | 4863.6 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 11.57 |
Crystal size (mm) | 0.25 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD-detector diffractometer |
Absorption correction | Gaussian (XPREP in SAINT; Bruker, 2001) |
Tmin, Tmax | 0.115, 0.325 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20325, 5608, 3623 |
Rint | 0.101 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.197, 1.06 |
No. of reflections | 5608 |
No. of parameters | 298 |
No. of restraints | 28 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.1051P)2 + 48.6026P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 5.48, −1.62 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), TEXSAN (Molecular Structure Corporation, 2001), KENX (Sakai, 2002) and ORTEPII (Johnson, 1976).
Pt1—N5 | 2.021 (11) | Pt2—N4 | 2.038 (14) |
Pt1—N2 | 2.044 (13) | Pt2—O4 | 2.048 (10) |
Pt1—N6 | 2.049 (10) | Pt1—Pt2 | 2.9023 (8) |
Pt1—N1 | 2.049 (12) | Pt2—Pt2i | 3.1821 (11) |
Pt2—O1 | 2.033 (11) | Pt1—Pt1ii | 6.4394 (12) |
Pt2—N3 | 2.035 (13) | ||
N5—Pt1—N2 | 177.6 (5) | O1—Pt2—N4 | 175.7 (4) |
N5—Pt1—N6 | 90.2 (4) | N3—Pt2—N4 | 91.8 (6) |
N2—Pt1—N6 | 89.2 (5) | O1—Pt2—O4 | 93.5 (4) |
N5—Pt1—N1 | 88.9 (5) | N3—Pt2—O4 | 174.3 (5) |
N2—Pt1—N1 | 91.6 (5) | N4—Pt2—O4 | 86.8 (5) |
N6—Pt1—N1 | 176.1 (5) | Pt1—Pt2—Pt2i | 158.74 (3) |
O1—Pt2—N3 | 87.4 (5) | ||
N5—Pt1—Pt2—O1 | 12.8 (4) | N2—Pt1—Pt2—N4 | 12.4 (6) |
N1—Pt1—Pt2—N3 | 9.3 (6) | N6—Pt1—Pt2—O4 | 8.1 (4) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O4i | 0.89 | 2.21 | 2.988 (17) | 146 |
N4—H4A···O1i | 0.89 | 2.30 | 3.030 (16) | 139 |
N2—H2A···O2ii | 0.89 | 1.97 | 2.818 (17) | 159 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, y, −z+3/2. |
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We previously reported that amidate-bridged dinuclear PtII complexes [Pt2(NH3)4(µ-amidato)2]2+ (amidate = α-pyrrolidinonate, α-pyridonate, acetamidate, etc.) behave as relatively efficient H2-evolving catalysts in a well known photosystem consisting of edta, Ru(bpy)32+ (bpy = 2,2'-bipyridine), and methylviologen (N,N'-dimethyl-4,4'-bipyridinium dichloride) (Sakai & Matsumoto, 1990; Sakai et al., 1993). Since then, one of our interests has concentrated on the development of dinuclear PtII complexes tethered to tris(2,2'-bipyridine)ruthenium(II) derivatives. Such hybrid materials may serve as efficient artificial photosynthetic devices which carry out visible-light-induced photocatalytic conversion of water into molecular hydrogen. The title compound, (I), can be regarded as an analog for the α-pyridonate Pt4II complex previously reported by Hollis & Lippard (1983) (Note that it is now understood that the tetranuclear structures of this type are only stabilized in the crystal, and immediately cleave into dimers upon dissolution into aqueous media.) The carboxyl unit on the bridging ligand in (I) can be used to make a peptide bond with an amino group in a certain chemical component to be tethered to the diplatinum entity. We now report here on the crystal structure of the title compound, (I). The subsequent studies on its application will appear in future publications.
A dimer cation found in the asymmetric unit of (I) has an association to the neighbouring dimer unit through an inversion center to give a tetranuclear structure, as observed for the α-pyridonate analog ([Pt2(NH3)4(µ-α-pyridonato)2]2(NO3)4) (Hollis & Lippard, 1983). The dimer–dimer association is stabilized with four hydrogen bonds formed between the ammine ligands and the O atoms of amidate bridges (see Fig. 1 and Table 2). Both the intra- and interdimer Pt—Pt distances within the tetranuclear cation in (I) [Pt—Pt(intradimer) = Pt1—Pt2 = 2.9023 (8) Å; Pt—Pt(interdimer) = Pt2—Pt2i = 3.1821 (11) Å) are slightly longer than those reported for the α-pyridonate analog (Pt—Pt(intradimer) = 2.8767 (7) Å and Pt—Pt(interdimer) = 3.1294 (4) Å] (Hollis & Lippard, 1983). It is obvious that introduction of carboxyl unit onto the α-pyridonate ligand results in elongation in each Pt—Pt distance. Such a tendency has already been observed in our previous studies. For instance, [PtII2(NH3)4(µ-glycolato)2]2+ has a longer Pt—Pt(intradimer) distance compared to that of [PtII2(NH3)4(µ-acetato)2]2+ (Sakai & Takeshita et al., 1998), where the hydroxyl group of glycolate serves as an electron-withdrawing group. Thus, there has been a clear tendency that the decrease in electron density at the PtII centers results in elongation of Pt—Pt distances in this class of diplatinum complexes. Perhaps, a dative bond formed by use of a filled Pt 5dz2 orbital and a vacant Pt 6p orbital must be weakened by the decrease in electron density at the metal centers. On the other hand, two Pt atoms within the dimer unit are shifted out of their individual Pt coordination planes in such a manner that they have an attractive interaction toward one another. Atoms Pt1 and Pt2 are respectively shifted by 0.055 (6) and 0.088 (6) Å, where the four-atom r.m.s. deviations in the best-plane calculations are 0.013 and 0.012 Å, respectively. Structural features of this type of dimers have also been evaluated by use of two structural parameters. One is a dihedral angle between the two Pt coordination planes within the dimeric unit (τ), and the other is an average torsional twist of them about the Pt—Pt axis (ω). The value of τ = 30.5 (4)° in (I) is quite comparable to the value of τ = 30.0° reported for the α-pyridonate analog (Hollis & Lippard, 1983). On the other hand, the ω value is effectively smaller in (I) [ω = 10.7° in (I); ω = 20.3° in the α-pyridonate analog], which must be due to the fact that the carboxyl units play a considerable role in the stabilization of intertetramer associations described below.
An intriguing feature due to the presence of carboxyl units in (I) is that the tetrameric units are strongly correlated to each other to afford a one-dimensional network (Fig. 2). A twofold axis, which is parallel to the b axis, is located at the mid-point of a geometry where the intertetramer interaction is achieved. The interactions are not only stabilized with hydrogen bonds formed between the ammine ligands and the O atoms of carboxyl units [N2···O2(-x, y, 1.5 − z) = 2.818 (17) Å], but also stabilized with π–π-stacking interactions achieved between the carboxyl units. The plane-to-plane separation is estimated as 3.36 Å, and the shortest contact is 3.47 (2) Å given by O5···C8(-x, y, 1.5 − z). However, the intertetramer Pt—Pt distance [6.4394 (12) Å, see also Table 1] indicates the lack of any metal–metal interaction between the tetramers. It must be also noted that both carboxyl units have a relatively short contact with a water molecule [O3···O13 = 2.60 (2) Å and O5···O14 = 2.61 (3) Å], which is indicative of strong hydrogen bonds formed between these moieties.