Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012698/ob6255sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012698/ob6255Isup2.hkl |
CCDC reference: 217369
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.009 Å
- H-atom completeness 84%
- Disorder in solvent or counterion
- R factor = 0.038
- wR factor = 0.083
- Data-to-parameter ratio = 17.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.22 From the CIF: _reflns_number_total 5573 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 6103 Completeness (_total/calc) 91.32% Alert C: < 95% complete PLAT_302 Alert C Anion/Solvent Disorder ......................... 23.00 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:C20 H24 N8 O8 Pt1 Atom count from the _atom_site data: C20 H20 N8 O8 Pt1 ABSTM_02 The ratio of expected to reported Tmax/Tmin(RR') is < 0.50 Tmin and Tmax reported: 0.147 0.500 Tmin' and Tmax expected: 0.370 0.578 RR' = 0.459 Please check that your absorption correction is appropriate. CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C20 H24 N8 O8 Pt TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 80.00 80.00 0.00 H 96.00 80.00 16.00 N 32.00 32.00 0.00 O 32.00 32.00 0.00 Pt 4.00 4.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional? REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.22 From the CIF: _reflns_number_total 5573 From the CIF: _diffrn_reflns_limit_ max hkl 8. 35. 17. From the CIF: _diffrn_reflns_limit_ min hkl -8. -34. -12. TEST1: Expected hkl limits for theta max Calculated maximum hkl 8. 37. 18. Calculated minimum hkl -8. -37. -18. ALERT: Expected hkl max differ from CIF values
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
A solution of PtCl2(bpy) (1.0 mmol, 0.42 g; Morgan & Burstall, 1963), AgNO3 (2.0 mmol, 0.34 g) and 2-aminopyridine (3.0 mmol, 0.28 g) in water (7 ml) was refluxed for 3 h. The solution was then filtered while it is hot for removal of the AgCl precipitated. The dark purple filtrate was left in air at room temperature overnight. The pale-orange crystals deposited were collected by filtration and air-dried (yield, 35%). The compound was recrystallized from water as follows. The compound was dissolved in water at 333 K (ca 0.1 g in 2 ml H2O) followed by filtration if necessary. Standing of the filtrate in air at room temperature overnight afforded the final product (I) as pale yellow needles (yield, 10%). Analysis calculated for C20H24N8O8Pt: C 34.34, H 3.46, N 16.02%; found: C 34.25, H 3.14, N 16.07%.
One of two nitrate anions shows orientational disorder. Around the N8 atom there are two sets of possible positions of (O4A, O5A and O6A) and (O4B, O5B and O6B). It was supposed that these disordered O atoms have the same isotropic displacement parameter. Furthermore, the N—O distances were restrained at 1.22 Å, three O···O distances within each NO3 group were restrained as equal, and each group was restrained to be planar. The occupation factors of site A and B converged at 56.3 (8) and 43.7 (8)%, respectively. All H atoms, except those of the water molecules, were located at idealized positions as riding atoms (C—H = 0.93 Å for the aromatic rings and N—H = 0.86 Å for the amino groups). Water H atoms were not located. In the final difference Fourier synthesis, four residual peaks in the range 2.13–2.39 e Å−3 were observed within 0.88 Å from the Pt atom.
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 ORTEP (Johnson, 1976).
[Pt(C10H8N2)(C5H6N2)2](NO3)2·2H2O | ? # Insert any comments here. |
Mr = 699.56 | Dx = 1.871 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7374 (3) Å | Cell parameters from 8388 reflections |
b = 27.8864 (13) Å | θ = 2.7–28.0° |
c = 13.5619 (6) Å | µ = 5.71 mm−1 |
β = 102.876 (1)° | T = 296 K |
V = 2483.96 (19) Å3 | Needle, pale yellow |
Z = 4 | 0.17 × 0.12 × 0.10 mm |
F(000) = 1368 |
Bruker SMART APEX CCD-detector diffractometer | 5573 independent reflections |
Radiation source: fine-focus sealed tube | 4451 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.098 |
Detector resolution: 8.366 pixels mm-1 | θmax = 28.2°, θmin = 2.7° |
ω scans | h = −8→8 |
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001) | k = −34→35 |
Tmin = 0.147, Tmax = 0.500 | l = −12→17 |
15077 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0327P)2] where P = (Fo2 + 2Fc2)/3 |
5573 reflections | (Δ/σ)max = 0.002 |
327 parameters | Δρmax = 2.67 e Å−3 |
14 restraints | Δρmin = −0.90 e Å−3 |
[Pt(C10H8N2)(C5H6N2)2](NO3)2·2H2O | V = 2483.96 (19) Å3 |
Mr = 699.56 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.7374 (3) Å | µ = 5.71 mm−1 |
b = 27.8864 (13) Å | T = 296 K |
c = 13.5619 (6) Å | 0.17 × 0.12 × 0.10 mm |
β = 102.876 (1)° |
Bruker SMART APEX CCD-detector diffractometer | 5573 independent reflections |
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001) | 4451 reflections with I > 2σ(I) |
Tmin = 0.147, Tmax = 0.500 | Rint = 0.098 |
15077 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 14 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 0.95 | Δρmax = 2.67 e Å−3 |
5573 reflections | Δρmin = −0.90 e Å−3 |
327 parameters |
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) 6.5163 (0.0028) x − 0.4491 (0.0367) y + 0.4296 (0.0221) z = 6.4402 (0.0133) * 0.0004 (0.0020) N1 * −0.0004 (0.0020) N2 * −0.0004 (0.0018) N3 * 0.0004 (0.0018) N5 − 0.0120 (0.0019) Pt1 Rms deviation of fitted atoms = 0.0004 6.5324 (0.0011) x − 0.7080 (0.0415) y + 0.2888 (0.0093) z = 6.3128 (0.0127) Angle to previous plane (with approximate e.s.d.) = 0.80 (0.09) * −0.0154 (0.0037) N1 * 0.0057 (0.0036) N2 * −0.0240 (0.0042) C1 * 0.0012 (0.0048) C2 * 0.0300 (0.0047) C3 * 0.0151 (0.0048) C4 * 0.0005 (0.0045) C5 * −0.0064 (0.0042) C6 * −0.0313 (0.0046) C7 * −0.0182 (0.0047) C8 * 0.0172 (0.0046) C9 * 0.0257 (0.0043) C10 Rms deviation of fitted atoms = 0.0189 6.5381 (0.0033) x − 1.1763 (0.0603) y + 0.2102 (0.0269) z = 6.1504 (0.0235) Angle to previous plane (with approximate e.s.d.) = 1.02 (0.10) * 0.0051 (0.0033) N1 * −0.0048 (0.0037) C1 * −0.0014 (0.0041) C2 * 0.0070 (0.0041) C3 * −0.0067 (0.0039) C4 * 0.0008 (0.0035) C5 Rms deviation of fitted atoms = 0.0049 6.5144 (0.0035) x − 0.2602 (0.0600) y + 0.4489 (0.0280) z = 6.4940 (0.0200) Angle to previous plane (with approximate e.s.d.) = 2.14 (0.14) * −0.0067 (0.0031) N2 * 0.0081 (0.0033) C6 * −0.0030 (0.0038) C7 * −0.0034 (0.0040) C8 * 0.0048 (0.0039) C9 * 0.0002 (0.0036) C10 Rms deviation of fitted atoms = 0.0051 − 2.4963 (0.0096) x + 15.2381 (0.0434) y + 11.0497 (0.0158) z = 7.1776 (0.0170) Angle to previous plane (with approximate e.s.d.) = 80.10 (0.14) * −0.0101 (0.0035) N3 * 0.0043 (0.0032) N4 * 0.0006 (0.0046) C11 * −0.0021 (0.0042) C12 * 0.0005 (0.0041) C13 * −0.0014 (0.0043) C14 * 0.0083 (0.0037) C15 Rms deviation of fitted atoms = 0.0053 6.5163 (0.0028) x − 0.4491 (0.0367) y + 0.4296 (0.0221) z = 6.4402 (0.0133) Angle to previous plane (with approximate e.s.d.) = 79.82 (0.12) * 0.0004 (0.0020) N1 * −0.0004 (0.0020) N2 * −0.0004 (0.0018) N3 * 0.0004 (0.0018) N5 Rms deviation of fitted atoms = 0.0004 2.6505 (0.0106) x + 23.2789 (0.0294) y − 6.2816 (0.0275) z = 1.2585 (0.0188) Angle to previous plane (with approximate e.s.d.) = 74.37 (0.12) * 0.0129 (0.0036) N5 * 0.0023 (0.0035) N6 * −0.0108 (0.0049) C16 * −0.0040 (0.0047) C17 * 0.0096 (0.0046) C18 * −0.0029 (0.0048) C19 * −0.0071 (0.0038) C20 Rms deviation of fitted atoms = 0.0081 − 2.4843 (0.0137) x + 15.2645 (0.0468) y + 11.0469 (0.0158) z = 7.1867 (0.0189) Angle to previous plane (with approximate e.s.d.) = 88.71 (0.14) * −0.0079 (0.0033) N3 * 0.0041 (0.0035) C11 * −0.0001 (0.0039) C12 * −0.0002 (0.0041) C13 * −0.0036 (0.0040) C14 * 0.0077 (0.0037) C15 Rms deviation of fitted atoms = 0.0050 6.5163 (0.0028) x − 0.4491 (0.0367) y + 0.4296 (0.0221) z = 6.4402 (0.0133) Angle to previous plane (with approximate e.s.d.) = 79.93 (0.14) * 0.0004 (0.0020) N1 * −0.0004 (0.0020) N2 * −0.0004 (0.0018) N3 * 0.0004 (0.0018) N5 Rms deviation of fitted atoms = 0.0004 2.6440 (0.0147) x + 23.2921 (0.0343) y − 6.2782 (0.0275) z = 1.2542 (0.0203) Angle to previous plane (with approximate e.s.d.) = 74.43 (0.15) * 0.0140 (0.0034) N5 * −0.0089 (0.0038) C16 * −0.0029 (0.0043) C17 * 0.0092 (0.0046) C18 * −0.0040 (0.0044) C19 * −0.0075 (0.0038) C20 Rms deviation of fitted atoms = 0.0086 6.5324 (0.0011) x − 0.7080 (0.0415) y + 0.2888 (0.0093) z = 6.3128 (0.0127) Angle to previous plane (with approximate e.s.d.) = 74.60 (0.15) * −0.0154 (0.0037) N1 * 0.0057 (0.0036) N2 * −0.0240 (0.0042) C1 * 0.0012 (0.0048) C2 * 0.0300 (0.0047) C3 * 0.0151 (0.0048) C4 * 0.0005 (0.0045) C5 * −0.0064 (0.0042) C6 * −0.0313 (0.0046) C7 * −0.0182 (0.0047) C8 * 0.0172 (0.0046) C9 * 0.0257 (0.0043) C10 Rms deviation of fitted atoms = 0.0189 6.5381 (0.0033) x − 1.1763 (0.0603) y + 0.2102 (0.0269) z = 6.1504 (0.0235) Angle to previous plane (with approximate e.s.d.) = 1.02 (0.10) * 0.0051 (0.0033) N1 * −0.0048 (0.0037) C1 * −0.0014 (0.0041) C2 * 0.0070 (0.0041) C3 * −0.0067 (0.0039) C4 * 0.0008 (0.0035) C5 − 3.2715 (0.0053) N7 − 3.3935 (0.0057) O1 − 3.1556 (0.0058) O2 − 3.2955 (0.0074) O3 Rms deviation of fitted atoms = 0.0049 6.3595 (0.0074) x − 3.6602 (0.0866) y + 1.1535 (0.0449) z = 2.9771 (0.0331) Angle to previous plane (with approximate e.s.d.) = 6.51 (0.22) * 0.0087 (0.0040) N7 * −0.0030 (0.0014) O1 * −0.0029 (0.0013) O2 * −0.0029 (0.0013) O3 Rms deviation of fitted atoms = 0.0050 |
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 | 0.95129 (3) | 0.136569 (6) | 0.676758 (13) | 0.03331 (8) | |
O1 | 0.4287 (7) | 0.17873 (19) | 0.7820 (3) | 0.0783 (14) | |
O2 | 0.4780 (7) | 0.2325 (2) | 0.6807 (3) | 0.0789 (14) | |
O3 | 0.4451 (7) | 0.1596 (2) | 0.6309 (4) | 0.0772 (14) | |
O4A | 0.4305 (14) | 0.0867 (5) | 1.0856 (8) | 0.1048 (16)* | 0.563 (8) |
O4B | 0.4755 (19) | 0.0602 (5) | 1.0534 (10) | 0.1048 (16)* | 0.437 (8) |
O5A | 0.6491 (18) | 0.0801 (5) | 0.9949 (7) | 0.1048 (16)* | 0.563 (8) |
O5B | 0.722 (2) | 0.0981 (6) | 1.0201 (10) | 0.1048 (16)* | 0.437 (8) |
O6A | 0.7408 (16) | 0.1082 (4) | 1.1439 (7) | 0.1048 (16)* | 0.563 (8) |
O6B | 0.641 (2) | 0.1048 (5) | 1.1653 (7) | 0.1048 (16)* | 0.437 (8) |
O7 | 0.4755 (9) | 0.3290 (2) | 0.7599 (4) | 0.1114 (18) | |
O8 | 0.3429 (8) | 0.1163 (2) | 0.2807 (3) | 0.0807 (13) | |
N1 | 0.9487 (6) | 0.18146 (15) | 0.7924 (3) | 0.0364 (9) | |
N2 | 0.9621 (6) | 0.19921 (14) | 0.6056 (3) | 0.0339 (9) | |
N3 | 0.9436 (6) | 0.07576 (15) | 0.7573 (3) | 0.0384 (9) | |
N4 | 1.2867 (7) | 0.08069 (19) | 0.8294 (4) | 0.0609 (13) | |
H4A | 1.2930 | 0.1063 | 0.7950 | 0.073* | |
H4B | 1.3945 | 0.0698 | 0.8694 | 0.073* | |
N5 | 0.9584 (6) | 0.09499 (15) | 0.5540 (3) | 0.0397 (9) | |
N6 | 0.6241 (8) | 0.1124 (2) | 0.4791 (4) | 0.0637 (14) | |
H6A | 0.6126 | 0.1288 | 0.5312 | 0.076* | |
H6B | 0.5220 | 0.1097 | 0.4285 | 0.076* | |
N7 | 0.4520 (6) | 0.1899 (2) | 0.6989 (3) | 0.0463 (11) | |
N8 | 0.6086 (10) | 0.0904 (2) | 1.0772 (4) | 0.0808 (18) | |
C1 | 0.9417 (8) | 0.1681 (2) | 0.8874 (4) | 0.0468 (13) | |
H1 | 0.9340 | 0.1358 | 0.9028 | 0.056* | |
C2 | 0.9460 (8) | 0.2022 (3) | 0.9617 (4) | 0.0550 (15) | |
H2 | 0.9416 | 0.1927 | 1.0269 | 0.066* | |
C3 | 0.9565 (9) | 0.2495 (2) | 0.9400 (4) | 0.0592 (16) | |
H3 | 0.9612 | 0.2724 | 0.9904 | 0.071* | |
C4 | 0.9601 (8) | 0.2637 (2) | 0.8416 (4) | 0.0517 (14) | |
H4 | 0.9643 | 0.2960 | 0.8249 | 0.062* | |
C5 | 0.9572 (7) | 0.2285 (2) | 0.7698 (4) | 0.0393 (11) | |
C6 | 0.9619 (7) | 0.23858 (19) | 0.6638 (3) | 0.0385 (11) | |
C7 | 0.9648 (8) | 0.2840 (2) | 0.6231 (5) | 0.0501 (13) | |
H7 | 0.9620 | 0.3109 | 0.6633 | 0.060* | |
C8 | 0.9717 (9) | 0.2892 (2) | 0.5249 (5) | 0.0556 (15) | |
H8 | 0.9740 | 0.3197 | 0.4974 | 0.067* | |
C9 | 0.9755 (8) | 0.2496 (2) | 0.4659 (4) | 0.0500 (13) | |
H9 | 0.9816 | 0.2527 | 0.3984 | 0.060* | |
C10 | 0.9701 (8) | 0.2053 (2) | 0.5078 (4) | 0.0448 (12) | |
H10 | 0.9721 | 0.1783 | 0.4676 | 0.054* | |
C11 | 1.1119 (9) | 0.0581 (2) | 0.8206 (4) | 0.0467 (13) | |
C12 | 1.0964 (10) | 0.0156 (2) | 0.8755 (4) | 0.0578 (16) | |
H12 | 1.2117 | 0.0031 | 0.9185 | 0.069* | |
C13 | 0.9173 (12) | −0.0066 (2) | 0.8660 (5) | 0.0671 (19) | |
H13 | 0.9087 | −0.0344 | 0.9026 | 0.081* | |
C14 | 0.7427 (10) | 0.0118 (2) | 0.8009 (4) | 0.0618 (17) | |
H14 | 0.6177 | −0.0035 | 0.7932 | 0.074* | |
C15 | 0.7614 (9) | 0.0531 (2) | 0.7491 (4) | 0.0528 (14) | |
H15 | 0.6460 | 0.0661 | 0.7069 | 0.063* | |
C16 | 0.8002 (9) | 0.0911 (2) | 0.4767 (4) | 0.0461 (12) | |
C17 | 0.8197 (11) | 0.0652 (2) | 0.3878 (4) | 0.0619 (16) | |
H17 | 0.7103 | 0.0625 | 0.3325 | 0.074* | |
C18 | 0.9994 (11) | 0.0450 (2) | 0.3867 (5) | 0.0677 (19) | |
H18 | 1.0148 | 0.0286 | 0.3292 | 0.081* | |
C19 | 1.1630 (11) | 0.0481 (2) | 0.4690 (5) | 0.0636 (17) | |
H19 | 1.2865 | 0.0335 | 0.4678 | 0.076* | |
C20 | 1.1386 (9) | 0.0727 (2) | 0.5507 (4) | 0.0502 (14) | |
H20 | 1.2470 | 0.0747 | 0.6066 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.03748 (11) | 0.03486 (11) | 0.02778 (11) | 0.00070 (8) | 0.00767 (7) | −0.00198 (8) |
O1 | 0.099 (4) | 0.095 (4) | 0.042 (2) | −0.029 (3) | 0.017 (2) | −0.004 (2) |
O2 | 0.091 (4) | 0.060 (3) | 0.083 (4) | −0.013 (3) | 0.014 (3) | 0.009 (2) |
O3 | 0.071 (3) | 0.093 (4) | 0.070 (3) | 0.001 (3) | 0.019 (2) | −0.041 (3) |
O7 | 0.105 (4) | 0.097 (5) | 0.113 (4) | −0.004 (4) | −0.018 (3) | −0.015 (4) |
O8 | 0.083 (3) | 0.089 (4) | 0.063 (3) | −0.001 (3) | 0.001 (3) | 0.002 (3) |
N1 | 0.040 (2) | 0.040 (2) | 0.029 (2) | −0.0019 (19) | 0.0075 (17) | −0.0087 (17) |
N2 | 0.036 (2) | 0.036 (2) | 0.031 (2) | −0.0004 (17) | 0.0086 (16) | 0.0004 (17) |
N3 | 0.047 (2) | 0.038 (2) | 0.032 (2) | −0.0018 (19) | 0.0135 (19) | 0.0002 (17) |
N4 | 0.048 (3) | 0.068 (4) | 0.061 (3) | 0.003 (3) | 0.002 (2) | 0.014 (3) |
N5 | 0.053 (2) | 0.031 (2) | 0.037 (2) | −0.0022 (19) | 0.015 (2) | −0.0052 (18) |
N6 | 0.057 (3) | 0.085 (4) | 0.045 (3) | 0.006 (3) | 0.003 (2) | −0.017 (3) |
N7 | 0.036 (2) | 0.059 (3) | 0.044 (3) | −0.005 (2) | 0.010 (2) | −0.006 (2) |
N8 | 0.106 (5) | 0.048 (3) | 0.072 (4) | 0.005 (3) | −0.016 (4) | −0.007 (3) |
C1 | 0.051 (3) | 0.057 (4) | 0.034 (3) | 0.001 (3) | 0.013 (2) | −0.002 (2) |
C2 | 0.051 (3) | 0.083 (5) | 0.033 (3) | 0.003 (3) | 0.011 (2) | −0.009 (3) |
C3 | 0.053 (3) | 0.073 (5) | 0.051 (4) | 0.000 (3) | 0.010 (3) | −0.026 (3) |
C4 | 0.049 (3) | 0.050 (4) | 0.056 (4) | 0.007 (3) | 0.013 (3) | −0.012 (3) |
C5 | 0.032 (2) | 0.048 (3) | 0.038 (3) | −0.001 (2) | 0.010 (2) | −0.008 (2) |
C6 | 0.030 (2) | 0.041 (3) | 0.043 (3) | 0.000 (2) | 0.006 (2) | −0.005 (2) |
C7 | 0.050 (3) | 0.038 (3) | 0.061 (4) | −0.002 (3) | 0.010 (3) | −0.004 (3) |
C8 | 0.060 (3) | 0.044 (3) | 0.062 (4) | 0.000 (3) | 0.011 (3) | 0.010 (3) |
C9 | 0.054 (3) | 0.054 (4) | 0.041 (3) | −0.004 (3) | 0.009 (3) | 0.010 (3) |
C10 | 0.054 (3) | 0.046 (3) | 0.037 (3) | −0.003 (3) | 0.013 (2) | −0.001 (2) |
C11 | 0.064 (3) | 0.043 (3) | 0.032 (3) | 0.006 (3) | 0.010 (3) | −0.001 (2) |
C12 | 0.090 (5) | 0.047 (3) | 0.034 (3) | 0.010 (3) | 0.008 (3) | 0.004 (3) |
C13 | 0.118 (6) | 0.045 (3) | 0.047 (3) | −0.006 (4) | 0.036 (4) | −0.001 (3) |
C14 | 0.081 (4) | 0.051 (4) | 0.062 (4) | −0.017 (3) | 0.035 (4) | −0.004 (3) |
C15 | 0.060 (3) | 0.051 (4) | 0.051 (3) | −0.005 (3) | 0.020 (3) | −0.003 (3) |
C16 | 0.059 (3) | 0.046 (3) | 0.034 (3) | −0.002 (3) | 0.013 (2) | −0.001 (2) |
C17 | 0.090 (5) | 0.053 (4) | 0.039 (3) | 0.000 (3) | 0.007 (3) | −0.008 (3) |
C18 | 0.096 (5) | 0.059 (4) | 0.059 (4) | −0.005 (4) | 0.041 (4) | −0.016 (3) |
C19 | 0.077 (4) | 0.051 (4) | 0.072 (4) | 0.006 (3) | 0.036 (4) | −0.011 (3) |
C20 | 0.058 (3) | 0.044 (3) | 0.053 (3) | −0.001 (3) | 0.023 (3) | −0.004 (3) |
Pt1—N2 | 2.005 (4) | C1—C2 | 1.380 (8) |
Pt1—N1 | 2.010 (4) | C1—H1 | 0.9300 |
Pt1—N3 | 2.024 (4) | C2—C3 | 1.358 (9) |
Pt1—N5 | 2.038 (4) | C2—H2 | 0.9300 |
O1—N7 | 1.213 (5) | C3—C4 | 1.397 (8) |
O2—N7 | 1.232 (7) | C3—H3 | 0.9300 |
O2—O7 | 2.900 (8) | C4—C5 | 1.379 (7) |
O3—N7 | 1.244 (6) | C4—H4 | 0.9300 |
O4A—N8 | 1.234 (8) | C5—C6 | 1.472 (6) |
O4B—N8 | 1.218 (8) | C6—C7 | 1.384 (7) |
O5A—N8 | 1.240 (8) | C7—C8 | 1.352 (8) |
O5B—N8 | 1.221 (8) | C7—H7 | 0.9300 |
O6A—N8 | 1.225 (8) | C8—C9 | 1.369 (8) |
O6B—N8 | 1.233 (8) | C8—H8 | 0.9300 |
O7—O6Ai | 2.633 (11) | C9—C10 | 1.363 (7) |
O7—O8ii | 2.867 (8) | C9—H9 | 0.9300 |
O7—O6Bi | 2.977 (15) | C10—H10 | 0.9300 |
O8—O6Biii | 2.824 (15) | C11—C12 | 1.415 (8) |
O8—O4Aiii | 2.955 (12) | C12—C13 | 1.337 (9) |
N1—C5 | 1.351 (7) | C12—H12 | 0.9300 |
N1—C1 | 1.352 (6) | C13—C14 | 1.402 (10) |
N2—C10 | 1.350 (6) | C13—H13 | 0.9300 |
N2—C6 | 1.353 (6) | C14—C15 | 1.368 (8) |
N3—C11 | 1.353 (7) | C14—H14 | 0.9300 |
N3—C15 | 1.363 (7) | C15—H15 | 0.9300 |
N4—C11 | 1.317 (7) | C16—C17 | 1.437 (7) |
N4—H4A | 0.8600 | C17—C18 | 1.338 (9) |
N4—H4B | 0.8600 | C17—H17 | 0.9300 |
N5—C16 | 1.322 (7) | C18—C19 | 1.386 (9) |
N5—C20 | 1.374 (7) | C18—H18 | 0.9300 |
N6—C16 | 1.333 (7) | C19—C20 | 1.344 (7) |
N6—H6A | 0.8600 | C19—H19 | 0.9300 |
N6—H6B | 0.8600 | C20—H20 | 0.9300 |
N2—Pt1—N1 | 80.82 (16) | C4—C5—C6 | 123.6 (5) |
N2—Pt1—N3 | 176.21 (15) | N2—C6—C7 | 120.5 (5) |
N1—Pt1—N3 | 95.44 (16) | N2—C6—C5 | 114.8 (4) |
N2—Pt1—N5 | 95.31 (15) | C7—C6—C5 | 124.7 (5) |
N1—Pt1—N5 | 176.07 (16) | C8—C7—C6 | 119.9 (5) |
N3—Pt1—N5 | 88.42 (16) | C8—C7—H7 | 120.0 |
C5—N1—C1 | 119.7 (4) | C6—C7—H7 | 120.0 |
C5—N1—Pt1 | 114.8 (3) | C7—C8—C9 | 119.8 (5) |
C1—N1—Pt1 | 125.5 (4) | C7—C8—H8 | 120.1 |
C10—N2—C6 | 118.5 (4) | C9—C8—H8 | 120.1 |
C10—N2—Pt1 | 126.6 (3) | C10—C9—C8 | 118.9 (5) |
C6—N2—Pt1 | 114.9 (3) | C10—C9—H9 | 120.5 |
C11—N3—C15 | 119.7 (5) | C8—C9—H9 | 120.5 |
C11—N3—Pt1 | 121.9 (4) | N2—C10—C9 | 122.3 (5) |
C15—N3—Pt1 | 118.4 (4) | N2—C10—H10 | 118.9 |
C11—N4—H4A | 120.0 | C9—C10—H10 | 118.9 |
C11—N4—H4B | 120.0 | N4—C11—N3 | 119.3 (5) |
H4A—N4—H4B | 120.0 | N4—C11—C12 | 121.5 (6) |
C16—N5—C20 | 120.0 (4) | N3—C11—C12 | 119.2 (6) |
C16—N5—Pt1 | 122.1 (3) | C13—C12—C11 | 120.6 (6) |
C20—N5—Pt1 | 117.8 (4) | C13—C12—H12 | 119.7 |
C16—N6—H6A | 120.0 | C11—C12—H12 | 119.7 |
C16—N6—H6B | 120.0 | C12—C13—C14 | 120.2 (6) |
H6A—N6—H6B | 120.0 | C12—C13—H13 | 119.9 |
O1—N7—O2 | 119.2 (5) | C14—C13—H13 | 119.9 |
O1—N7—O3 | 121.5 (6) | C15—C14—C13 | 118.1 (6) |
O2—N7—O3 | 119.3 (5) | C15—C14—H14 | 120.9 |
O4B—N8—O5B | 118.7 (9) | C13—C14—H14 | 120.9 |
O4B—N8—O6B | 116.2 (8) | N3—C15—C14 | 122.1 (6) |
O5B—N8—O6B | 123.9 (9) | N3—C15—H15 | 118.9 |
O6A—N8—O4A | 121.8 (8) | C14—C15—H15 | 118.9 |
O6A—N8—O5A | 119.3 (8) | N5—C16—N6 | 120.6 (5) |
O4A—N8—O5A | 118.5 (8) | N5—C16—C17 | 119.9 (5) |
N1—C1—C2 | 120.4 (6) | N6—C16—C17 | 119.5 (6) |
N1—C1—H1 | 119.8 | C18—C17—C16 | 118.2 (6) |
C2—C1—H1 | 119.8 | C18—C17—H17 | 120.9 |
C3—C2—C1 | 120.3 (5) | C16—C17—H17 | 120.9 |
C3—C2—H2 | 119.8 | C17—C18—C19 | 121.6 (6) |
C1—C2—H2 | 119.8 | C17—C18—H18 | 119.2 |
C2—C3—C4 | 119.7 (5) | C19—C18—H18 | 119.2 |
C2—C3—H3 | 120.2 | C20—C19—C18 | 118.3 (6) |
C4—C3—H3 | 120.2 | C20—C19—H19 | 120.9 |
C5—C4—C3 | 118.2 (6) | C18—C19—H19 | 120.9 |
C5—C4—H4 | 120.9 | C19—C20—N5 | 122.0 (6) |
C3—C4—H4 | 120.9 | C19—C20—H20 | 119.0 |
N1—C5—C4 | 121.7 (5) | N5—C20—H20 | 119.0 |
N1—C5—C6 | 114.7 (4) | ||
C5—N1—C1—C2 | −0.9 (8) | C6—N2—C10—C9 | −0.8 (7) |
N1—C1—C2—C3 | 0.2 (9) | C8—C9—C10—N2 | −0.3 (8) |
C1—C2—C3—C4 | 0.9 (9) | C15—N3—C11—N4 | −178.9 (5) |
C2—C3—C4—C5 | −1.4 (9) | C15—N3—C11—C12 | 1.5 (7) |
C1—N1—C5—C4 | 0.3 (7) | N4—C11—C12—C13 | 179.7 (5) |
C1—N1—C5—C6 | −179.4 (4) | N3—C11—C12—C13 | −0.8 (8) |
C3—C4—C5—N1 | 0.8 (8) | C11—C12—C13—C14 | 0.3 (9) |
C3—C4—C5—C6 | −179.6 (5) | C12—C13—C14—C15 | −0.7 (9) |
C10—N2—C6—C7 | 1.6 (7) | C11—N3—C15—C14 | −1.9 (8) |
C10—N2—C6—C5 | −178.8 (4) | C13—C14—C15—N3 | 1.5 (8) |
N1—C5—C6—N2 | −1.6 (6) | C20—N5—C16—N6 | 179.7 (5) |
C4—C5—C6—N2 | 178.8 (5) | C20—N5—C16—C17 | −2.5 (8) |
N1—C5—C6—C7 | 178.1 (5) | N5—C16—C17—C18 | 0.8 (9) |
C4—C5—C6—C7 | −1.6 (8) | N6—C16—C17—C18 | 178.7 (6) |
N2—C6—C7—C8 | −1.2 (8) | C16—C17—C18—C19 | 1.0 (10) |
C5—C6—C7—C8 | 179.2 (5) | C17—C18—C19—C20 | −1.1 (10) |
C6—C7—C8—C9 | 0.1 (9) | C18—C19—C20—N5 | −0.6 (9) |
C7—C8—C9—C10 | 0.6 (9) | C16—N5—C20—C19 | 2.4 (8) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6A···O3 | 0.86 | 2.13 | 2.922 (6) | 154 |
N6—H6B···O8 | 0.86 | 2.10 | 2.926 (7) | 160 |
N4—H4A···O1iv | 0.86 | 2.24 | 3.013 (7) | 150 |
N4—H4B···O4Biv | 0.86 | 2.45 | 3.074 (14) | 130 |
N4—H4B···O5Aiv | 0.86 | 2.15 | 2.926 (13) | 150 |
Symmetry code: (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Pt(C10H8N2)(C5H6N2)2](NO3)2·2H2O |
Mr | 699.56 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 6.7374 (3), 27.8864 (13), 13.5619 (6) |
β (°) | 102.876 (1) |
V (Å3) | 2483.96 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.71 |
Crystal size (mm) | 0.17 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD-detector diffractometer |
Absorption correction | Gaussian (XPREP in SAINT; Bruker, 2001) |
Tmin, Tmax | 0.147, 0.500 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15077, 5573, 4451 |
Rint | 0.098 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.083, 0.95 |
No. of reflections | 5573 |
No. of parameters | 327 |
No. of restraints | 14 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.67, −0.90 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), TEXSAN (Molecular Structure Corporation, 2001), KENX (Sakai, 2002) and ORTEP (Johnson, 1976).
Pt1—N2 | 2.005 (4) | O7—O6Ai | 2.633 (11) |
Pt1—N1 | 2.010 (4) | O7—O8ii | 2.867 (8) |
Pt1—N3 | 2.024 (4) | O7—O6Bi | 2.977 (15) |
Pt1—N5 | 2.038 (4) | O8—O6Biii | 2.824 (15) |
O2—O7 | 2.900 (8) | O8—O4Aiii | 2.955 (12) |
N2—Pt1—N1 | 80.82 (16) | N2—Pt1—N5 | 95.31 (15) |
N2—Pt1—N3 | 176.21 (15) | N1—Pt1—N5 | 176.07 (16) |
N1—Pt1—N3 | 95.44 (16) | N3—Pt1—N5 | 88.42 (16) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6A···O3 | 0.86 | 2.13 | 2.922 (6) | 153.6 |
N6—H6B···O8 | 0.86 | 2.10 | 2.926 (7) | 159.9 |
N4—H4A···O1iv | 0.86 | 2.24 | 3.013 (7) | 149.7 |
N4—H4B···O4Biv | 0.86 | 2.45 | 3.074 (14) | 130.3 |
N4—H4B···O5Aiv | 0.86 | 2.15 | 2.926 (13) | 149.9 |
Symmetry code: (iv) x+1, y, z. |
Multinuclear metal complexes have been considered as important mimics for the catalyst surfaces. It is also known that many important biological processes at the active sites of enzymes often involve various metal complexes having more than two metal centers. In this context, we have been interested in the di- and trinuclear systems involving effective metal–metal interactoins (Sakai et al., 1998), and we recently started exploring the coordination chemistry of platinum and 2-aminopyridine. Up to now, only five crystal structures have been reported for the metal complexes with 2-aminopyridine ligand, in which it serves as either a monodentate ligand (Krizanovic et al., 1993; Xu et al., 2000; Yip et al., 2000) or a bridging ligand (Chakravarty et al., 1984; Kanematsu et al., 1999). The title compound, (I), has been prepared as a precursor to develop new multinuclear systems. The subsequent synthetic studies by use of (I) is now under way. This is the first example of a crystal structure for the platinum complex of 2-aminopyridine.
The Pt coordination plane has a good planarity (Fig. 1 and Table 1), where the four-atom r.m.s. deviation is negligibly small. The Pt atom is shifted out of its coordination plane by 0.012 (2) Å. The bpy ligand has a slightly twisted geometry in which two pyridyl planes are twisted at an angle of 2.0 (1)° to one other. The Pt coordination plane and the bpy plane is nearly coplanar with each other, where their dihedral angle is only 0.80 (1)°. On the other hand, the pyridyl planes of the 2-aminopyridine ligands are largely inclined with respect to the Pt coordination plane, viz. 79.8 (1)° for the plane defined by N3/N4/C11—C15 and 74.4 (1)° for that by N5/N6/C16—C20.
An interesting feature is that one of two nitrates has a strong π-stacking interaction with a part of bpy moiety (Fig. 2), where the plane-to-plane separation is ca 3.28 Å and the two planes are canted at an angle of 6.5 (2)°. The crystal packing is stabilized by weak π–π-stacking interactions (Fig. 3) and also by hydrogen-bonding interactions. The short O···O distances involving the water atoms O7 and O8 are listed in Table 1, and the N—H···O hydrogen-bonding geometry in Table 2.