Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100017273/bk1556sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100017273/bk1556Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100017273/bk1556IIsup3.hkl |
CCDC references: 162540; 162541
Compound (I) was synthesized from [PtCl2(dppe)] (Anderson et al., 1983) by halide abstraction with silver nitrate: silver nitrate (0.34 g, 2.0 mmol) in water (5 ml) was added to an acetone solution (40 ml) of [PtCl2(dppe)] (0.66 g, 1.0 mmol). The mixture was stirred for 24 h in the dark at room temperature, and the precipitate of AgCl was collected by filtration through Celite. The filtrate was evaporated under reduced pressure and the products were obtained as a yellow powder (yield 0.40 g, 56%). Crystals suitable for X-ray diffraction were obtained by slow evaporation from CDCl3 solution. Calculated for C26H24N2O6P2Pt: C 43.51, H 3.35, N 3.91%; found: C 43.64, H 3.31, N 3.81%; 31P NMR (CDCl3): δP 33.0, 1JPt,P 3940 Hz. The reaction of [PtCl2(dppm)] (1.30 g, 2 mmol) with 2 equivalents of silver nitrate (0.68 g, 4.0 mmol) in acetone (100 ml) in the presence of air produced a 4:1 mixture of [Pt(NO3)2(dppm)] and cis-[Pt(dppmO-P,O)2]2+, as determined by 31P NMR spectroscopy [δ 4.6 (s, 1JPt—P 3810 Hz), 67.0 (br)]. On standing, crystals of (II) suitable for X-ray diffraction were obtained.
H atoms were treated using appropriate riding models (AFIX = m3 in SHELXTL-Plus; Sheldrick, 1999). The Rint values were calculated for all data to θ = 30°, but the refinement only included data to 25°. In (I), the largest peak in the final difference map is 0.88 Å from C19 and the deepest trough is 0.64 Å from the Pt atom. In (II), the largest peak is 1.67 Å from O6'.
For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SMART. Data reduction: SHELXTL-Plus (Sheldrick, 1999) for (I); SAINT (Bruker, 1999) for (II). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (I); SHELXTL-Plus (Sheldrick, 1999) for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I); SHELXTL-Plus for (II). For both compounds, molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus.
[Pt(C26H24P2)(NO3)2] | F(000) = 1400 |
Mr = 717.50 | Dx = 1.820 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4971 (1) Å | Cell parameters from 8192 reflections |
b = 15.5281 (2) Å | θ = 2–26° |
c = 16.3930 (2) Å | µ = 5.53 mm−1 |
β = 101.51 (1)° | T = 223 K |
V = 2618.36 (5) Å3 | Plates, colourless |
Z = 4 | 0.30 × 0.20 × 0.04 mm |
Bruker? CCD area-detector diffractometer | 5137 independent reflections |
Radiation source: normal-focus sealed tube | 4304 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.10 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.4° |
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995) | h = −12→12 |
Tmin = 0.28, Tmax = 0.80 | k = −19→19 |
25459 measured reflections | l = −20→20 |
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.069 | w = 1/[σ2(Fo2) + (0.0148P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
5137 reflections | Δρmax = 1.31 e Å−3 |
334 parameters | Δρmin = −0.59 e Å−3 |
2 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.024 (8) |
[Pt(C26H24P2)(NO3)2] | V = 2618.36 (5) Å3 |
Mr = 717.50 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 10.4971 (1) Å | µ = 5.53 mm−1 |
b = 15.5281 (2) Å | T = 223 K |
c = 16.3930 (2) Å | 0.30 × 0.20 × 0.04 mm |
β = 101.51 (1)° |
Bruker? CCD area-detector diffractometer | 5137 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995) | 4304 reflections with I > 2σ(I) |
Tmin = 0.28, Tmax = 0.80 | Rint = 0.10 |
25459 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.069 | Δρmax = 1.31 e Å−3 |
S = 1.03 | Δρmin = −0.59 e Å−3 |
5137 reflections | Absolute structure: Flack (1983) |
334 parameters | Absolute structure parameter: 0.024 (8) |
2 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Pt | 1.23803 (3) | 0.338727 (17) | 0.24406 (3) | 0.02642 (8) | |
P1 | 1.17177 (19) | 0.26002 (13) | 0.13088 (13) | 0.0260 (5) | |
P2 | 1.0888 (2) | 0.26857 (14) | 0.29683 (13) | 0.0289 (5) | |
O1 | 1.3891 (5) | 0.3923 (4) | 0.1920 (4) | 0.0350 (14) | |
O2 | 1.2750 (6) | 0.5094 (4) | 0.1732 (4) | 0.0608 (19) | |
O3 | 1.4606 (7) | 0.5010 (4) | 0.1362 (4) | 0.0606 (19) | |
O4 | 1.3048 (6) | 0.4217 (4) | 0.3455 (3) | 0.0388 (15) | |
O5 | 1.4715 (7) | 0.4505 (6) | 0.4393 (6) | 0.100 (3) | |
O6 | 1.4514 (6) | 0.3259 (4) | 0.3872 (4) | 0.0572 (19) | |
N1 | 1.3731 (7) | 0.4690 (5) | 0.1669 (5) | 0.0397 (18) | |
N2 | 1.4114 (7) | 0.3973 (5) | 0.3916 (5) | 0.044 (2) | |
C1 | 1.1387 (7) | 0.3217 (5) | 0.0355 (5) | 0.0252 (18) | |
C2 | 1.0122 (9) | 0.3410 (6) | −0.0063 (5) | 0.041 (2) | |
H2 | 0.9401 | 0.3195 | 0.0131 | 0.050* | |
C3 | 0.9952 (10) | 0.3923 (6) | −0.0768 (6) | 0.052 (3) | |
H3 | 0.9106 | 0.4052 | −0.1055 | 0.062* | |
C4 | 1.0986 (11) | 0.4242 (6) | −0.1052 (6) | 0.055 (3) | |
H4 | 1.0848 | 0.4599 | −0.1525 | 0.066* | |
C5 | 1.2242 (10) | 0.4047 (7) | −0.0651 (6) | 0.052 (3) | |
H5 | 1.2953 | 0.4270 | −0.0852 | 0.062* | |
C6 | 1.2451 (10) | 0.3521 (6) | 0.0047 (6) | 0.041 (2) | |
H6 | 1.3301 | 0.3370 | 0.0311 | 0.050* | |
C7 | 1.2911 (8) | 0.1796 (5) | 0.1164 (5) | 0.0294 (19) | |
C8 | 1.2660 (10) | 0.1273 (6) | 0.0475 (6) | 0.044 (2) | |
H8 | 1.1875 | 0.1322 | 0.0085 | 0.053* | |
C9 | 1.3594 (10) | 0.0665 (6) | 0.0365 (6) | 0.048 (3) | |
H9 | 1.3428 | 0.0297 | −0.0099 | 0.058* | |
C10 | 1.4743 (9) | 0.0600 (6) | 0.0924 (6) | 0.045 (2) | |
H10 | 1.5366 | 0.0194 | 0.0835 | 0.054* | |
C11 | 1.4997 (8) | 0.1116 (6) | 0.1608 (6) | 0.042 (2) | |
H11 | 1.5790 | 0.1062 | 0.1990 | 0.050* | |
C12 | 1.4083 (7) | 0.1727 (5) | 0.1745 (5) | 0.032 (2) | |
H12 | 1.4251 | 0.2084 | 0.2217 | 0.038* | |
C13 | 1.0264 (7) | 0.2011 (5) | 0.1419 (5) | 0.032 (2) | |
H13A | 0.9496 | 0.2380 | 0.1267 | 0.038* | |
H13B | 1.0149 | 0.1506 | 0.1053 | 0.038* | |
C14 | 1.0438 (8) | 0.1733 (5) | 0.2325 (5) | 0.032 (2) | |
H14A | 1.1120 | 0.1295 | 0.2453 | 0.039* | |
H14B | 0.9626 | 0.1489 | 0.2432 | 0.039* | |
C15 | 0.9387 (7) | 0.3288 (5) | 0.2905 (5) | 0.0278 (18) | |
C16 | 0.8412 (8) | 0.2940 (7) | 0.3272 (6) | 0.050 (3) | |
H16 | 0.8539 | 0.2413 | 0.3559 | 0.060* | |
C17 | 0.7232 (8) | 0.3394 (8) | 0.3202 (6) | 0.060 (3) | |
H17 | 0.6558 | 0.3163 | 0.3435 | 0.072* | |
C18 | 0.7060 (9) | 0.4173 (7) | 0.2796 (7) | 0.046 (3) | |
H18 | 0.6270 | 0.4470 | 0.2754 | 0.055* | |
C19 | 0.8027 (10) | 0.4518 (7) | 0.2451 (7) | 0.051 (3) | |
H19 | 0.7910 | 0.5061 | 0.2194 | 0.061* | |
C20 | 0.9185 (8) | 0.4071 (6) | 0.2480 (6) | 0.038 (2) | |
H20 | 0.9828 | 0.4295 | 0.2214 | 0.046* | |
C21 | 1.1299 (7) | 0.2361 (6) | 0.4051 (5) | 0.033 (2) | |
C22 | 1.1667 (8) | 0.2999 (7) | 0.4650 (5) | 0.042 (2) | |
H22 | 1.1775 | 0.3570 | 0.4487 | 0.050* | |
C23 | 1.1873 (8) | 0.2787 (8) | 0.5492 (6) | 0.049 (3) | |
H23 | 1.2153 | 0.3211 | 0.5897 | 0.059* | |
C24 | 1.1672 (10) | 0.1976 (9) | 0.5724 (6) | 0.064 (3) | |
H24 | 1.1783 | 0.1846 | 0.6293 | 0.076* | |
C25 | 1.1305 (10) | 0.1324 (8) | 0.5144 (7) | 0.061 (3) | |
H25 | 1.1178 | 0.0759 | 0.5318 | 0.073* | |
C26 | 1.1131 (10) | 0.1520 (7) | 0.4316 (6) | 0.047 (2) | |
H26 | 1.0895 | 0.1082 | 0.3918 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.02442 (13) | 0.02645 (14) | 0.02842 (14) | −0.0001 (3) | 0.00537 (9) | −0.0015 (3) |
P1 | 0.0262 (12) | 0.0254 (12) | 0.0263 (12) | 0.0008 (9) | 0.0050 (9) | 0.0008 (10) |
P2 | 0.0270 (12) | 0.0301 (13) | 0.0305 (13) | 0.0013 (9) | 0.0077 (10) | 0.0044 (10) |
O1 | 0.027 (3) | 0.035 (4) | 0.046 (4) | −0.006 (3) | 0.015 (3) | 0.005 (3) |
O2 | 0.055 (4) | 0.041 (4) | 0.084 (5) | 0.015 (4) | 0.010 (4) | 0.018 (4) |
O3 | 0.068 (5) | 0.043 (5) | 0.074 (5) | −0.009 (4) | 0.023 (4) | 0.012 (4) |
O4 | 0.039 (4) | 0.035 (4) | 0.038 (4) | 0.008 (3) | −0.004 (3) | −0.007 (3) |
O5 | 0.069 (5) | 0.103 (7) | 0.109 (7) | 0.007 (5) | −0.030 (5) | −0.064 (6) |
O6 | 0.041 (4) | 0.056 (5) | 0.072 (5) | 0.013 (3) | 0.007 (3) | 0.009 (4) |
N1 | 0.039 (5) | 0.031 (5) | 0.047 (5) | 0.000 (4) | 0.004 (4) | 0.003 (4) |
N2 | 0.040 (5) | 0.045 (6) | 0.045 (5) | 0.007 (4) | 0.004 (4) | −0.014 (4) |
C1 | 0.025 (4) | 0.017 (5) | 0.030 (4) | 0.002 (3) | −0.002 (3) | −0.004 (3) |
C2 | 0.049 (5) | 0.040 (5) | 0.036 (5) | 0.003 (5) | 0.009 (4) | −0.009 (5) |
C3 | 0.062 (7) | 0.048 (7) | 0.038 (6) | 0.023 (5) | −0.008 (5) | 0.003 (5) |
C4 | 0.093 (9) | 0.041 (7) | 0.034 (6) | 0.010 (6) | 0.019 (6) | 0.012 (5) |
C5 | 0.058 (7) | 0.061 (7) | 0.037 (6) | −0.001 (5) | 0.011 (5) | 0.015 (5) |
C6 | 0.044 (6) | 0.045 (7) | 0.034 (5) | 0.000 (5) | 0.007 (4) | 0.005 (5) |
C7 | 0.040 (5) | 0.016 (5) | 0.033 (5) | 0.005 (3) | 0.008 (4) | −0.003 (4) |
C8 | 0.047 (6) | 0.044 (6) | 0.040 (6) | 0.010 (5) | 0.004 (5) | −0.011 (5) |
C9 | 0.068 (7) | 0.035 (6) | 0.043 (6) | 0.001 (5) | 0.013 (5) | −0.014 (5) |
C10 | 0.045 (6) | 0.039 (6) | 0.053 (6) | 0.012 (5) | 0.017 (5) | 0.002 (5) |
C11 | 0.032 (5) | 0.052 (6) | 0.040 (6) | 0.006 (4) | 0.006 (4) | 0.011 (5) |
C12 | 0.034 (5) | 0.033 (5) | 0.030 (5) | −0.002 (4) | 0.008 (4) | 0.009 (4) |
C13 | 0.027 (4) | 0.030 (5) | 0.038 (5) | −0.001 (4) | 0.005 (4) | 0.000 (4) |
C14 | 0.037 (5) | 0.025 (5) | 0.038 (5) | 0.000 (4) | 0.017 (4) | 0.003 (4) |
C15 | 0.021 (4) | 0.033 (5) | 0.029 (4) | 0.001 (4) | 0.004 (3) | 0.001 (4) |
C16 | 0.038 (6) | 0.074 (7) | 0.043 (6) | 0.007 (5) | 0.016 (4) | 0.016 (5) |
C17 | 0.026 (5) | 0.108 (10) | 0.049 (6) | −0.007 (6) | 0.016 (4) | −0.013 (7) |
C18 | 0.032 (6) | 0.057 (8) | 0.049 (7) | 0.002 (5) | 0.004 (5) | −0.014 (6) |
C19 | 0.059 (7) | 0.029 (6) | 0.059 (8) | 0.002 (5) | −0.001 (6) | −0.002 (5) |
C20 | 0.025 (5) | 0.041 (6) | 0.048 (6) | 0.007 (4) | 0.004 (4) | 0.002 (5) |
C21 | 0.027 (5) | 0.045 (6) | 0.031 (5) | 0.014 (4) | 0.014 (4) | 0.007 (5) |
C22 | 0.032 (5) | 0.062 (7) | 0.032 (6) | 0.012 (5) | 0.009 (4) | 0.003 (5) |
C23 | 0.038 (6) | 0.075 (8) | 0.033 (6) | 0.017 (5) | 0.004 (4) | 0.007 (6) |
C24 | 0.050 (7) | 0.113 (11) | 0.027 (6) | 0.027 (7) | 0.006 (5) | 0.023 (7) |
C25 | 0.053 (7) | 0.078 (9) | 0.054 (7) | 0.012 (6) | 0.015 (6) | 0.037 (7) |
C26 | 0.056 (6) | 0.049 (7) | 0.035 (5) | 0.017 (5) | 0.009 (5) | 0.009 (5) |
Pt—O4 | 2.111 (5) | C5—C6 | 1.388 (12) |
Pt—O1 | 2.115 (5) | C7—C8 | 1.373 (11) |
Pt—P1 | 2.215 (2) | C7—C12 | 1.402 (11) |
Pt—P2 | 2.220 (2) | C8—C9 | 1.397 (12) |
P1—C1 | 1.808 (8) | C9—C10 | 1.366 (13) |
P1—C13 | 1.818 (8) | C10—C11 | 1.361 (12) |
P1—C7 | 1.818 (8) | C11—C12 | 1.398 (12) |
P2—C21 | 1.812 (8) | C13—C14 | 1.523 (10) |
P2—C15 | 1.818 (7) | C15—C16 | 1.395 (11) |
P2—C14 | 1.824 (8) | C15—C20 | 1.397 (11) |
O1—N1 | 1.261 (8) | C16—C17 | 1.410 (13) |
O2—N1 | 1.227 (8) | C17—C18 | 1.375 (14) |
O3—N1 | 1.236 (8) | C18—C19 | 1.366 (12) |
O4—N2 | 1.277 (9) | C19—C20 | 1.393 (12) |
O5—N2 | 1.222 (9) | C21—C22 | 1.394 (13) |
O6—N2 | 1.194 (9) | C21—C26 | 1.399 (12) |
C1—C6 | 1.395 (12) | C22—C23 | 1.392 (12) |
C1—C2 | 1.400 (11) | C23—C24 | 1.345 (14) |
C2—C3 | 1.386 (12) | C24—C25 | 1.388 (15) |
C3—C4 | 1.357 (13) | C25—C26 | 1.369 (13) |
C4—C5 | 1.384 (13) | ||
O4—Pt—O1 | 85.4 (2) | C4—C3—C2 | 121.1 (9) |
O4—Pt—P1 | 175.34 (18) | C3—C4—C5 | 120.5 (9) |
O1—Pt—P1 | 90.82 (17) | C4—C5—C6 | 120.0 (9) |
O4—Pt—P2 | 98.15 (17) | C5—C6—C1 | 119.4 (9) |
O1—Pt—P2 | 173.75 (17) | C8—C7—C12 | 120.8 (8) |
P1—Pt—P2 | 85.85 (8) | C8—C7—P1 | 119.3 (7) |
C1—P1—C13 | 109.4 (4) | C12—C7—P1 | 119.9 (6) |
C1—P1—C7 | 105.6 (4) | C7—C8—C9 | 118.7 (9) |
C13—P1—C7 | 106.3 (4) | C10—C9—C8 | 120.8 (9) |
C1—P1—Pt | 114.0 (2) | C11—C10—C9 | 120.7 (8) |
C13—P1—Pt | 108.9 (3) | C10—C11—C12 | 120.2 (8) |
C7—P1—Pt | 112.3 (3) | C11—C12—C7 | 118.7 (8) |
C21—P2—C15 | 103.5 (3) | C14—C13—P1 | 107.4 (5) |
C21—P2—C14 | 108.9 (4) | C13—C14—P2 | 107.5 (5) |
C15—P2—C14 | 105.2 (4) | C16—C15—C20 | 120.1 (7) |
C21—P2—Pt | 118.0 (3) | C16—C15—P2 | 118.6 (7) |
C15—P2—Pt | 113.3 (3) | C20—C15—P2 | 121.3 (6) |
C14—P2—Pt | 107.1 (3) | C15—C16—C17 | 118.6 (9) |
N1—O1—Pt | 116.2 (5) | C18—C17—C16 | 120.5 (9) |
N2—O4—Pt | 113.5 (5) | C19—C18—C17 | 120.6 (9) |
O2—N1—O3 | 122.2 (8) | C18—C19—C20 | 120.4 (10) |
O2—N1—O1 | 120.9 (7) | C19—C20—C15 | 119.7 (8) |
O3—N1—O1 | 116.8 (7) | C22—C21—C26 | 118.6 (8) |
O6—N2—O5 | 121.6 (9) | C22—C21—P2 | 118.1 (7) |
O6—N2—O4 | 121.2 (8) | C26—C21—P2 | 122.9 (7) |
O5—N2—O4 | 117.3 (8) | C23—C22—C21 | 119.8 (10) |
C6—C1—C2 | 120.0 (8) | C24—C23—C22 | 119.9 (10) |
C6—C1—P1 | 117.5 (6) | C23—C24—C25 | 121.8 (10) |
C2—C1—P1 | 122.4 (6) | C26—C25—C24 | 118.8 (10) |
C3—C2—C1 | 118.9 (8) | C25—C26—C21 | 121.0 (10) |
[Pt(C25H22OP)2]·2NO3·2H2O | F(000) = 2320 |
Mr = 1155.87 | Dx = 1.590 Mg m−3 Dm = no Mg m−3 Dm measured by not measured |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.9843 (2) Å | Cell parameters from 8192 reflections |
b = 16.3998 (2) Å | θ = 2.2–26.4° |
c = 22.6979 (3) Å | µ = 3.10 mm−1 |
β = 92.81 (1)° | T = 213 K |
V = 4827.47 (11) Å3 | Irregular, light yellow |
Z = 4 | 0.36 × 0.28 × 0.22 mm |
Bruker? CCD area-detector diffractometer | 9898 independent reflections |
Radiation source: long-fine-focus sealed tube | 7985 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.06 |
ϕ and ω scans | θmax = 26.5°, θmin = 1.5° |
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995) | h = −16→16 |
Tmin = 0.37, Tmax = 0.51 | k = −20→20 |
80352 measured reflections | l = −28→28 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0237P)2 + 8.7121P] where P = (Fo2 + 2Fc2)/3 |
9898 reflections | (Δ/σ)max = 0.001 |
604 parameters | Δρmax = 0.75 e Å−3 |
6 restraints | Δρmin = −0.59 e Å−3 |
[Pt(C25H22OP)2]·2NO3·2H2O | V = 4827.47 (11) Å3 |
Mr = 1155.87 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.9843 (2) Å | µ = 3.10 mm−1 |
b = 16.3998 (2) Å | T = 213 K |
c = 22.6979 (3) Å | 0.36 × 0.28 × 0.22 mm |
β = 92.81 (1)° |
Bruker? CCD area-detector diffractometer | 9898 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995) | 7985 reflections with I > 2σ(I) |
Tmin = 0.37, Tmax = 0.51 | Rint = 0.06 |
80352 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 6 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.75 e Å−3 |
9898 reflections | Δρmin = −0.59 e Å−3 |
604 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Pt | 0.182726 (10) | 0.204725 (9) | 0.003104 (6) | 0.02892 (5) | |
P1 | 0.18770 (7) | 0.01680 (6) | 0.03614 (5) | 0.0323 (2) | |
P2 | 0.30255 (7) | 0.16328 (6) | 0.06942 (4) | 0.0307 (2) | |
P4 | 0.03177 (7) | 0.31332 (6) | −0.07763 (4) | 0.0306 (2) | |
P3 | 0.23171 (7) | 0.33152 (6) | −0.01454 (4) | 0.0294 (2) | |
O1 | 0.12074 (18) | 0.08824 (16) | 0.01458 (12) | 0.0355 (6) | |
O2 | 0.0593 (2) | 0.22744 (16) | −0.05720 (12) | 0.0359 (6) | |
C1 | 0.3169 (3) | 0.0557 (2) | 0.04889 (19) | 0.0357 (9) | |
H1A | 0.3557 | 0.0508 | 0.0131 | 0.043* | |
H1B | 0.3533 | 0.0254 | 0.0808 | 0.043* | |
C2 | 0.1074 (3) | 0.3829 (2) | −0.03149 (16) | 0.0301 (8) | |
H2A | 0.0724 | 0.3945 | 0.0049 | 0.036* | |
H2B | 0.1181 | 0.4343 | −0.0523 | 0.036* | |
C3 | 0.1823 (3) | −0.0594 (3) | −0.02035 (18) | 0.0364 (9) | |
C4 | 0.2190 (3) | −0.0392 (3) | −0.0751 (2) | 0.0449 (11) | |
H4 | 0.2556 | 0.0097 | −0.0796 | 0.054* | |
C5 | 0.2017 (3) | −0.0909 (3) | −0.1227 (2) | 0.0540 (12) | |
H5 | 0.2253 | −0.0770 | −0.1599 | 0.065* | |
C6 | 0.1488 (3) | −0.1637 (3) | −0.1150 (2) | 0.0533 (12) | |
H6 | 0.1375 | −0.1992 | −0.1472 | 0.064* | |
C7 | 0.1128 (3) | −0.1846 (3) | −0.0610 (2) | 0.0487 (11) | |
H7 | 0.0775 | −0.2340 | −0.0564 | 0.058* | |
C8 | 0.1289 (3) | −0.1324 (2) | −0.01336 (19) | 0.0399 (10) | |
H8 | 0.1038 | −0.1461 | 0.0235 | 0.048* | |
C9 | 0.1436 (3) | −0.0252 (2) | 0.10322 (18) | 0.0358 (9) | |
C10 | 0.0405 (3) | −0.0169 (3) | 0.1153 (2) | 0.0529 (12) | |
H10 | −0.0045 | 0.0118 | 0.0891 | 0.063* | |
C11 | 0.0040 (4) | −0.0510 (4) | 0.1662 (2) | 0.0659 (15) | |
H11 | −0.0662 | −0.0462 | 0.1738 | 0.079* | |
C12 | 0.0686 (4) | −0.0913 (3) | 0.2050 (2) | 0.0566 (13) | |
H12 | 0.0433 | −0.1133 | 0.2397 | 0.068* | |
C13 | 0.1707 (4) | −0.1001 (3) | 0.1936 (2) | 0.0555 (13) | |
H13 | 0.2150 | −0.1286 | 0.2203 | 0.067* | |
C14 | 0.2091 (3) | −0.0672 (3) | 0.1429 (2) | 0.0464 (11) | |
H14 | 0.2792 | −0.0733 | 0.1353 | 0.056* | |
C15 | 0.2530 (3) | 0.1628 (2) | 0.14238 (17) | 0.0338 (9) | |
C16 | 0.1587 (3) | 0.1993 (3) | 0.15237 (19) | 0.0427 (10) | |
H16 | 0.1218 | 0.2264 | 0.1216 | 0.051* | |
C17 | 0.1197 (4) | 0.1956 (3) | 0.2079 (2) | 0.0569 (13) | |
H17 | 0.0563 | 0.2205 | 0.2149 | 0.068* | |
C18 | 0.1733 (4) | 0.1554 (4) | 0.2526 (2) | 0.0615 (14) | |
H18 | 0.1458 | 0.1523 | 0.2900 | 0.074* | |
C19 | 0.2677 (4) | 0.1194 (3) | 0.2432 (2) | 0.0574 (13) | |
H19 | 0.3044 | 0.0926 | 0.2742 | 0.069* | |
C20 | 0.3072 (3) | 0.1231 (3) | 0.18804 (19) | 0.0466 (11) | |
H20 | 0.3710 | 0.0986 | 0.1813 | 0.056* | |
C21 | 0.4310 (3) | 0.2060 (2) | 0.07728 (17) | 0.0347 (8) | |
C22 | 0.4538 (3) | 0.2624 (3) | 0.1216 (2) | 0.0435 (10) | |
H22 | 0.4031 | 0.2772 | 0.1478 | 0.052* | |
C23 | 0.5513 (3) | 0.2969 (3) | 0.1275 (2) | 0.0513 (12) | |
H23 | 0.5667 | 0.3353 | 0.1574 | 0.062* | |
C24 | 0.6254 (3) | 0.2747 (3) | 0.0892 (2) | 0.0515 (12) | |
H24 | 0.6911 | 0.2986 | 0.0927 | 0.062* | |
C25 | 0.6039 (3) | 0.2180 (3) | 0.0462 (2) | 0.0542 (13) | |
H25 | 0.6557 | 0.2022 | 0.0210 | 0.065* | |
C26 | 0.5062 (3) | 0.1834 (3) | 0.0392 (2) | 0.0458 (11) | |
H26 | 0.4914 | 0.1451 | 0.0092 | 0.055* | |
C27 | 0.2946 (3) | 0.3916 (2) | 0.04347 (17) | 0.0340 (9) | |
C28 | 0.2443 (3) | 0.4043 (3) | 0.09558 (18) | 0.0407 (10) | |
H28 | 0.1778 | 0.3831 | 0.1000 | 0.049* | |
C29 | 0.2935 (4) | 0.4485 (3) | 0.1407 (2) | 0.0502 (11) | |
H29 | 0.2602 | 0.4573 | 0.1760 | 0.060* | |
C30 | 0.3907 (4) | 0.4797 (3) | 0.1343 (2) | 0.0523 (12) | |
H30 | 0.4230 | 0.5102 | 0.1650 | 0.063* | |
C31 | 0.4410 (4) | 0.4662 (3) | 0.0830 (2) | 0.0492 (11) | |
H31 | 0.5078 | 0.4869 | 0.0791 | 0.059* | |
C32 | 0.3936 (3) | 0.4225 (3) | 0.03731 (18) | 0.0400 (10) | |
H32 | 0.4278 | 0.4137 | 0.0023 | 0.048* | |
C33 | 0.3046 (3) | 0.3417 (2) | −0.08010 (17) | 0.0331 (9) | |
C34 | 0.3606 (3) | 0.2762 (3) | −0.0998 (2) | 0.0470 (11) | |
H34 | 0.3643 | 0.2276 | −0.0779 | 0.056* | |
C35 | 0.4114 (4) | 0.2826 (3) | −0.1521 (2) | 0.0617 (14) | |
H35 | 0.4503 | 0.2384 | −0.1652 | 0.074* | |
C36 | 0.4048 (4) | 0.3531 (4) | −0.1845 (2) | 0.0598 (14) | |
H36 | 0.4384 | 0.3567 | −0.2201 | 0.072* | |
C37 | 0.3493 (3) | 0.4189 (3) | −0.16521 (19) | 0.0507 (12) | |
H37 | 0.3452 | 0.4672 | −0.1876 | 0.061* | |
C38 | 0.2995 (3) | 0.4133 (3) | −0.11276 (18) | 0.0407 (10) | |
H38 | 0.2622 | 0.4581 | −0.0992 | 0.049* | |
C39 | 0.0620 (3) | 0.3281 (3) | −0.15259 (17) | 0.0355 (9) | |
C40 | 0.1162 (3) | 0.2691 (3) | −0.1819 (2) | 0.0476 (11) | |
H40 | 0.1363 | 0.2206 | −0.1625 | 0.057* | |
C41 | 0.1404 (4) | 0.2819 (4) | −0.2398 (2) | 0.0652 (15) | |
H41 | 0.1772 | 0.2421 | −0.2600 | 0.078* | |
C42 | 0.1107 (4) | 0.3527 (4) | −0.2675 (2) | 0.0648 (16) | |
H42 | 0.1259 | 0.3607 | −0.3071 | 0.078* | |
C43 | 0.0586 (4) | 0.4128 (3) | −0.2383 (2) | 0.0577 (13) | |
H43 | 0.0407 | 0.4619 | −0.2576 | 0.069* | |
C44 | 0.0332 (3) | 0.4002 (3) | −0.18068 (19) | 0.0442 (10) | |
H44 | −0.0034 | 0.4402 | −0.1606 | 0.053* | |
C45 | −0.1037 (3) | 0.3306 (3) | −0.07207 (17) | 0.0358 (9) | |
C46 | −0.1683 (3) | 0.2804 (3) | −0.1066 (2) | 0.0489 (11) | |
H46 | −0.1405 | 0.2443 | −0.1338 | 0.059* | |
C47 | −0.2735 (3) | 0.2839 (3) | −0.1009 (2) | 0.0574 (13) | |
H47 | −0.3174 | 0.2492 | −0.1235 | 0.069* | |
C48 | −0.3138 (4) | 0.3377 (3) | −0.0623 (2) | 0.0591 (13) | |
H48 | −0.3856 | 0.3404 | −0.0590 | 0.071* | |
C49 | −0.2510 (4) | 0.3878 (3) | −0.0282 (2) | 0.0576 (13) | |
H49 | −0.2795 | 0.4245 | −0.0016 | 0.069* | |
C50 | −0.1448 (3) | 0.3841 (3) | −0.0330 (2) | 0.0471 (11) | |
H50 | −0.1013 | 0.4182 | −0.0097 | 0.056* | |
N1 | 0.4261 (4) | 0.1013 (3) | −0.3800 (2) | 0.0706 (14) | |
O1' | 0.3394 (3) | 0.0785 (3) | −0.3863 (2) | 0.0986 (15) | |
O2' | 0.4521 (6) | 0.1520 (3) | −0.3451 (4) | 0.197 (4) | |
O3' | 0.4894 (4) | 0.0692 (5) | −0.4115 (2) | 0.134 (3) | |
N2 | 0.4542 (3) | 0.0616 (3) | −0.1235 (2) | 0.0621 (11) | |
O4' | 0.3736 (4) | 0.0737 (3) | −0.1525 (2) | 0.1134 (18) | |
O5' | 0.4504 (4) | 0.0573 (4) | −0.0712 (2) | 0.126 (2) | |
O6' | 0.5311 (3) | 0.0467 (4) | −0.1487 (2) | 0.1161 (19) | |
O1S | 0.2451 (4) | 0.0921 (3) | −0.2614 (3) | 0.1214 (18) | |
H1 | 0.2961 | 0.0710 | −0.2264 | 0.146* | |
H2 | 0.5414 | 0.1193 | −0.2888 | 0.146* | |
O2S | 0.6009 (4) | 0.0920 (4) | −0.2605 (3) | 0.152 (3) | |
H1' | 0.5656 | 0.0777 | −0.2201 | 0.182* | |
H2' | 0.2829 | 0.1438 | −0.2641 | 0.182* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.02579 (7) | 0.02957 (8) | 0.03125 (8) | −0.00202 (7) | −0.00010 (5) | 0.00199 (7) |
P1 | 0.0270 (5) | 0.0309 (5) | 0.0391 (6) | −0.0011 (4) | 0.0019 (4) | 0.0033 (4) |
P2 | 0.0249 (5) | 0.0329 (5) | 0.0341 (5) | −0.0014 (4) | 0.0007 (4) | 0.0032 (4) |
P4 | 0.0307 (5) | 0.0294 (5) | 0.0312 (5) | −0.0025 (4) | −0.0023 (4) | 0.0001 (4) |
P3 | 0.0290 (5) | 0.0297 (5) | 0.0295 (5) | −0.0036 (4) | 0.0008 (4) | −0.0003 (4) |
O1 | 0.0261 (13) | 0.0312 (15) | 0.0489 (17) | −0.0066 (11) | −0.0021 (12) | 0.0041 (12) |
O2 | 0.0368 (14) | 0.0321 (15) | 0.0377 (15) | −0.0044 (11) | −0.0093 (12) | 0.0026 (11) |
C1 | 0.0266 (18) | 0.034 (2) | 0.046 (2) | −0.0007 (16) | 0.0032 (17) | 0.0045 (18) |
C2 | 0.0322 (19) | 0.032 (2) | 0.0263 (19) | −0.0001 (16) | −0.0007 (15) | −0.0019 (16) |
C3 | 0.0276 (18) | 0.040 (2) | 0.042 (2) | 0.0014 (17) | 0.0027 (17) | 0.0031 (18) |
C4 | 0.032 (2) | 0.047 (3) | 0.056 (3) | −0.0006 (19) | 0.009 (2) | 0.003 (2) |
C5 | 0.045 (3) | 0.071 (4) | 0.047 (3) | 0.006 (2) | 0.011 (2) | −0.005 (2) |
C6 | 0.043 (2) | 0.058 (3) | 0.058 (3) | 0.008 (2) | −0.003 (2) | −0.018 (3) |
C7 | 0.042 (2) | 0.042 (3) | 0.061 (3) | −0.0021 (19) | 0.000 (2) | −0.008 (2) |
C8 | 0.035 (2) | 0.037 (2) | 0.047 (2) | 0.0015 (18) | 0.0000 (18) | 0.0021 (19) |
C9 | 0.038 (2) | 0.029 (2) | 0.041 (2) | −0.0048 (17) | 0.0009 (18) | 0.0020 (17) |
C10 | 0.043 (2) | 0.062 (3) | 0.054 (3) | 0.006 (2) | 0.009 (2) | 0.014 (2) |
C11 | 0.057 (3) | 0.078 (4) | 0.066 (3) | 0.004 (3) | 0.026 (3) | 0.015 (3) |
C12 | 0.074 (3) | 0.057 (3) | 0.040 (3) | −0.017 (3) | 0.009 (2) | 0.002 (2) |
C13 | 0.067 (3) | 0.053 (3) | 0.044 (3) | −0.012 (2) | −0.013 (2) | 0.009 (2) |
C14 | 0.042 (2) | 0.047 (3) | 0.050 (3) | −0.003 (2) | −0.003 (2) | 0.007 (2) |
C15 | 0.032 (2) | 0.036 (2) | 0.033 (2) | −0.0054 (17) | −0.0003 (16) | 0.0026 (17) |
C16 | 0.035 (2) | 0.050 (3) | 0.043 (2) | 0.001 (2) | 0.0059 (17) | 0.010 (2) |
C17 | 0.045 (3) | 0.076 (4) | 0.051 (3) | 0.000 (2) | 0.015 (2) | 0.008 (3) |
C18 | 0.060 (3) | 0.086 (4) | 0.039 (3) | −0.012 (3) | 0.010 (2) | 0.005 (3) |
C19 | 0.059 (3) | 0.074 (4) | 0.039 (3) | −0.003 (3) | −0.007 (2) | 0.014 (2) |
C20 | 0.040 (2) | 0.060 (3) | 0.039 (2) | 0.002 (2) | −0.0042 (19) | 0.007 (2) |
C21 | 0.0247 (17) | 0.036 (2) | 0.043 (2) | −0.0022 (17) | −0.0015 (15) | 0.0103 (19) |
C22 | 0.032 (2) | 0.047 (3) | 0.051 (3) | −0.0021 (18) | −0.0042 (19) | 0.002 (2) |
C23 | 0.043 (2) | 0.045 (3) | 0.064 (3) | −0.009 (2) | −0.015 (2) | 0.008 (2) |
C24 | 0.032 (2) | 0.042 (3) | 0.079 (4) | −0.0091 (19) | −0.005 (2) | 0.017 (2) |
C25 | 0.031 (2) | 0.055 (3) | 0.077 (3) | 0.001 (2) | 0.015 (2) | 0.008 (3) |
C26 | 0.035 (2) | 0.046 (3) | 0.056 (3) | −0.0030 (19) | 0.002 (2) | 0.003 (2) |
C27 | 0.039 (2) | 0.031 (2) | 0.032 (2) | −0.0041 (17) | −0.0045 (17) | 0.0009 (17) |
C28 | 0.044 (2) | 0.038 (2) | 0.040 (2) | −0.0030 (18) | 0.0001 (19) | 0.0007 (19) |
C29 | 0.067 (3) | 0.047 (3) | 0.036 (2) | −0.001 (2) | −0.001 (2) | −0.006 (2) |
C30 | 0.064 (3) | 0.042 (3) | 0.049 (3) | −0.008 (2) | −0.019 (2) | −0.004 (2) |
C31 | 0.048 (3) | 0.048 (3) | 0.051 (3) | −0.017 (2) | −0.009 (2) | 0.006 (2) |
C32 | 0.040 (2) | 0.043 (2) | 0.037 (2) | −0.0078 (19) | −0.0015 (18) | 0.0054 (19) |
C33 | 0.0285 (19) | 0.039 (2) | 0.032 (2) | −0.0074 (16) | 0.0021 (16) | −0.0013 (17) |
C34 | 0.042 (2) | 0.047 (3) | 0.053 (3) | 0.0018 (19) | 0.009 (2) | 0.004 (2) |
C35 | 0.054 (3) | 0.070 (4) | 0.063 (3) | 0.007 (3) | 0.024 (2) | −0.011 (3) |
C36 | 0.047 (3) | 0.088 (4) | 0.046 (3) | −0.015 (3) | 0.018 (2) | −0.003 (3) |
C37 | 0.045 (2) | 0.069 (3) | 0.038 (2) | −0.018 (2) | 0.005 (2) | 0.009 (2) |
C38 | 0.039 (2) | 0.043 (2) | 0.040 (2) | −0.0073 (18) | 0.0028 (18) | 0.0016 (19) |
C39 | 0.032 (2) | 0.041 (2) | 0.034 (2) | −0.0079 (17) | −0.0033 (16) | −0.0021 (18) |
C40 | 0.044 (2) | 0.049 (3) | 0.049 (3) | −0.003 (2) | −0.001 (2) | −0.011 (2) |
C41 | 0.056 (3) | 0.091 (4) | 0.050 (3) | −0.006 (3) | 0.012 (2) | −0.024 (3) |
C42 | 0.057 (3) | 0.103 (5) | 0.036 (3) | −0.035 (3) | 0.009 (2) | −0.003 (3) |
C43 | 0.062 (3) | 0.067 (4) | 0.043 (3) | −0.025 (3) | −0.006 (2) | 0.014 (2) |
C44 | 0.044 (2) | 0.048 (3) | 0.040 (2) | −0.007 (2) | −0.0026 (19) | 0.002 (2) |
C45 | 0.035 (2) | 0.036 (2) | 0.036 (2) | −0.0014 (17) | −0.0019 (17) | 0.0102 (18) |
C46 | 0.040 (2) | 0.055 (3) | 0.050 (3) | −0.008 (2) | −0.004 (2) | −0.007 (2) |
C47 | 0.039 (2) | 0.063 (3) | 0.070 (3) | −0.015 (2) | −0.007 (2) | 0.006 (3) |
C48 | 0.036 (2) | 0.066 (3) | 0.076 (4) | 0.004 (2) | 0.003 (2) | 0.019 (3) |
C49 | 0.044 (3) | 0.056 (3) | 0.074 (3) | 0.015 (2) | 0.009 (2) | −0.002 (3) |
C50 | 0.041 (2) | 0.043 (3) | 0.057 (3) | 0.006 (2) | 0.001 (2) | −0.001 (2) |
N1 | 0.073 (3) | 0.061 (3) | 0.076 (3) | −0.015 (3) | −0.019 (3) | 0.031 (3) |
O1' | 0.073 (3) | 0.095 (3) | 0.127 (4) | −0.020 (3) | 0.004 (3) | 0.022 (3) |
O2' | 0.271 (9) | 0.056 (3) | 0.244 (8) | 0.018 (4) | −0.178 (7) | −0.024 (4) |
O3' | 0.073 (3) | 0.240 (7) | 0.089 (4) | 0.008 (4) | 0.015 (3) | 0.079 (4) |
N2 | 0.054 (3) | 0.077 (3) | 0.057 (3) | 0.009 (2) | 0.011 (2) | −0.008 (2) |
O4' | 0.072 (3) | 0.125 (4) | 0.143 (5) | 0.014 (3) | −0.001 (3) | 0.048 (4) |
O5' | 0.122 (4) | 0.198 (6) | 0.061 (3) | −0.052 (4) | 0.034 (3) | −0.039 (3) |
O6' | 0.068 (3) | 0.207 (6) | 0.075 (3) | 0.041 (3) | 0.022 (2) | 0.011 (3) |
O1S | 0.095 (3) | 0.106 (4) | 0.163 (5) | 0.017 (3) | 0.010 (3) | −0.021 (4) |
O2S | 0.083 (3) | 0.239 (7) | 0.132 (5) | −0.026 (4) | −0.016 (3) | 0.096 (5) |
Pt—O2 | 2.089 (2) | C21—C26 | 1.385 (6) |
Pt—O1 | 2.094 (2) | C21—C22 | 1.388 (6) |
Pt—P3 | 2.2168 (10) | C22—C23 | 1.387 (6) |
Pt—P2 | 2.2178 (10) | C23—C24 | 1.376 (7) |
P1—O1 | 1.525 (3) | C24—C25 | 1.368 (7) |
P1—C3 | 1.790 (4) | C25—C26 | 1.392 (6) |
P1—C9 | 1.791 (4) | C27—C28 | 1.395 (6) |
P1—C1 | 1.804 (4) | C27—C32 | 1.396 (5) |
P2—C15 | 1.806 (4) | C28—C29 | 1.386 (6) |
P2—C21 | 1.810 (4) | C29—C30 | 1.376 (7) |
P2—C1 | 1.837 (4) | C30—C31 | 1.381 (7) |
P4—O2 | 1.520 (3) | C31—C32 | 1.380 (6) |
P4—C39 | 1.781 (4) | C33—C34 | 1.384 (6) |
P4—C45 | 1.792 (4) | C33—C38 | 1.388 (6) |
P4—C2 | 1.806 (4) | C34—C35 | 1.388 (6) |
P3—C27 | 1.807 (4) | C35—C36 | 1.372 (7) |
P3—C33 | 1.810 (4) | C36—C37 | 1.380 (7) |
P3—C2 | 1.844 (4) | C37—C38 | 1.385 (6) |
C3—C4 | 1.392 (6) | C39—C40 | 1.386 (6) |
C3—C8 | 1.395 (6) | C39—C44 | 1.386 (6) |
C4—C5 | 1.384 (6) | C40—C41 | 1.381 (7) |
C5—C6 | 1.393 (7) | C41—C42 | 1.368 (8) |
C6—C7 | 1.376 (7) | C42—C43 | 1.381 (8) |
C7—C8 | 1.387 (6) | C43—C44 | 1.381 (6) |
C9—C10 | 1.386 (6) | C45—C50 | 1.374 (6) |
C9—C14 | 1.391 (6) | C45—C46 | 1.390 (6) |
C10—C11 | 1.387 (7) | C46—C47 | 1.379 (6) |
C11—C12 | 1.358 (7) | C47—C48 | 1.366 (7) |
C12—C13 | 1.370 (7) | C48—C49 | 1.370 (7) |
C13—C14 | 1.385 (6) | C49—C50 | 1.389 (6) |
C15—C20 | 1.386 (5) | N1—O2' | 1.186 (6) |
C15—C16 | 1.392 (5) | N1—O1' | 1.188 (5) |
C16—C17 | 1.382 (6) | N1—O3' | 1.233 (7) |
C17—C18 | 1.371 (7) | N2—O5' | 1.192 (5) |
C18—C19 | 1.387 (7) | N2—O6' | 1.200 (5) |
C19—C20 | 1.377 (6) | N2—O4' | 1.225 (5) |
O2—Pt—O1 | 87.54 (10) | C16—C15—P2 | 120.2 (3) |
O2—Pt—P3 | 86.10 (7) | C17—C16—C15 | 119.6 (4) |
O1—Pt—P3 | 173.52 (7) | C18—C17—C16 | 120.0 (4) |
O2—Pt—P2 | 171.61 (7) | C17—C18—C19 | 120.8 (4) |
O1—Pt—P2 | 84.09 (7) | C20—C19—C18 | 119.5 (4) |
P3—Pt—P2 | 102.25 (4) | C19—C20—C15 | 120.2 (4) |
O1—P1—C3 | 107.75 (17) | C26—C21—C22 | 119.9 (4) |
O1—P1—C9 | 111.54 (17) | C26—C21—P2 | 120.6 (3) |
C3—P1—C9 | 109.73 (19) | C22—C21—P2 | 119.5 (3) |
O1—P1—C1 | 106.89 (16) | C23—C22—C21 | 120.2 (4) |
C3—P1—C1 | 111.44 (18) | C24—C23—C22 | 119.6 (5) |
C9—P1—C1 | 109.46 (19) | C25—C24—C23 | 120.4 (4) |
C15—P2—C21 | 106.22 (18) | C24—C25—C26 | 120.7 (4) |
C15—P2—C1 | 105.87 (19) | C21—C26—C25 | 119.1 (4) |
C21—P2—C1 | 107.04 (18) | C28—C27—C32 | 120.2 (4) |
C15—P2—Pt | 110.74 (13) | C28—C27—P3 | 119.0 (3) |
C21—P2—Pt | 124.09 (13) | C32—C27—P3 | 120.7 (3) |
C1—P2—Pt | 101.45 (13) | C29—C28—C27 | 119.1 (4) |
O2—P4—C39 | 110.97 (18) | C30—C29—C28 | 120.6 (4) |
O2—P4—C45 | 109.99 (17) | C29—C30—C31 | 120.2 (4) |
C39—P4—C45 | 107.98 (18) | C32—C31—C30 | 120.4 (4) |
O2—P4—C2 | 107.17 (16) | C31—C32—C27 | 119.5 (4) |
C39—P4—C2 | 109.21 (18) | C34—C33—C38 | 119.7 (4) |
C45—P4—C2 | 111.55 (19) | C34—C33—P3 | 119.9 (3) |
C27—P3—C33 | 108.23 (18) | C38—C33—P3 | 120.3 (3) |
C27—P3—C2 | 105.20 (18) | C33—C34—C35 | 119.8 (4) |
C33—P3—C2 | 105.90 (17) | C36—C35—C34 | 120.1 (5) |
C27—P3—Pt | 120.23 (13) | C35—C36—C37 | 120.6 (4) |
C33—P3—Pt | 113.67 (13) | C36—C37—C38 | 119.5 (5) |
C2—P3—Pt | 102.12 (12) | C37—C38—C33 | 120.2 (4) |
P1—O1—Pt | 121.61 (14) | C40—C39—C44 | 120.4 (4) |
P4—O2—Pt | 121.78 (15) | C40—C39—P4 | 120.3 (3) |
P1—C1—P2 | 106.00 (19) | C44—C39—P4 | 119.2 (3) |
P4—C2—P3 | 106.15 (19) | C41—C40—C39 | 119.7 (5) |
C4—C3—C8 | 120.0 (4) | C42—C41—C40 | 119.5 (5) |
C4—C3—P1 | 118.0 (3) | C41—C42—C43 | 121.3 (5) |
C8—C3—P1 | 121.3 (3) | C42—C43—C44 | 119.5 (5) |
C5—C4—C3 | 120.1 (4) | C43—C44—C39 | 119.5 (5) |
C4—C5—C6 | 119.3 (5) | C50—C45—C46 | 119.9 (4) |
C7—C6—C5 | 121.0 (4) | C50—C45—P4 | 124.1 (3) |
C6—C7—C8 | 119.8 (4) | C46—C45—P4 | 115.8 (3) |
C7—C8—C3 | 119.8 (4) | C47—C46—C45 | 119.7 (5) |
C10—C9—C14 | 119.1 (4) | C48—C47—C46 | 120.0 (5) |
C10—C9—P1 | 118.9 (3) | C47—C48—C49 | 120.9 (4) |
C14—C9—P1 | 122.0 (3) | C48—C49—C50 | 119.6 (5) |
C9—C10—C11 | 119.9 (4) | C45—C50—C49 | 119.8 (4) |
C12—C11—C10 | 120.7 (5) | O2'—N1—O1' | 122.5 (8) |
C11—C12—C13 | 120.0 (5) | O2'—N1—O3' | 120.7 (7) |
C12—C13—C14 | 120.5 (4) | O1'—N1—O3' | 116.8 (6) |
C13—C14—C9 | 119.8 (4) | O5'—N2—O6' | 122.6 (5) |
C20—C15—C16 | 119.9 (4) | O5'—N2—O4' | 117.9 (5) |
C20—C15—P2 | 119.8 (3) | O6'—N2—O4' | 119.1 (5) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Pt(C26H24P2)(NO3)2] | [Pt(C25H22OP)2]·2NO3·2H2O |
Mr | 717.50 | 1155.87 |
Crystal system, space group | Monoclinic, Cc | Monoclinic, P21/n |
Temperature (K) | 223 | 213 |
a, b, c (Å) | 10.4971 (1), 15.5281 (2), 16.3930 (2) | 12.9843 (2), 16.3998 (2), 22.6979 (3) |
β (°) | 101.51 (1) | 92.81 (1) |
V (Å3) | 2618.36 (5) | 4827.47 (11) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 5.53 | 3.10 |
Crystal size (mm) | 0.30 × 0.20 × 0.04 | 0.36 × 0.28 × 0.22 |
Data collection | ||
Diffractometer | Bruker? CCD area-detector diffractometer | Bruker? CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Blessing, 1995) | Empirical (using intensity measurements) (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.28, 0.80 | 0.37, 0.51 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25459, 5137, 4304 | 80352, 9898, 7985 |
Rint | 0.10 | 0.06 |
(sin θ/λ)max (Å−1) | 0.617 | 0.627 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.069, 1.03 | 0.031, 0.069, 1.09 |
No. of reflections | 5137 | 9898 |
No. of parameters | 334 | 604 |
No. of restraints | 2 | 6 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.31, −0.59 | 0.75, −0.59 |
Absolute structure | Flack (1983) | ? |
Absolute structure parameter | 0.024 (8) | ? |
Computer programs: SMART (Bruker, 1999), SMART, SHELXTL-Plus (Sheldrick, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus.
Pt—O4 | 2.111 (5) | O2—N1 | 1.227 (8) |
Pt—O1 | 2.115 (5) | O3—N1 | 1.236 (8) |
Pt—P1 | 2.215 (2) | O4—N2 | 1.277 (9) |
Pt—P2 | 2.220 (2) | O5—N2 | 1.222 (9) |
O1—N1 | 1.261 (8) | O6—N2 | 1.194 (9) |
O4—Pt—O1 | 85.4 (2) | O2—N1—O3 | 122.2 (8) |
O1—Pt—P1 | 90.82 (17) | O2—N1—O1 | 120.9 (7) |
O4—Pt—P2 | 98.15 (17) | O3—N1—O1 | 116.8 (7) |
P1—Pt—P2 | 85.85 (8) | O6—N2—O5 | 121.6 (9) |
N1—O1—Pt | 116.2 (5) | O6—N2—O4 | 121.2 (8) |
N2—O4—Pt | 113.5 (5) | O5—N2—O4 | 117.3 (8) |
Pt—O2 | 2.089 (2) | P1—C1 | 1.804 (4) |
Pt—O1 | 2.094 (2) | P2—C1 | 1.837 (4) |
Pt—P3 | 2.2168 (10) | P4—O2 | 1.520 (3) |
Pt—P2 | 2.2178 (10) | P4—C2 | 1.806 (4) |
P1—O1 | 1.525 (3) | P3—C2 | 1.844 (4) |
O2—Pt—O1 | 87.54 (10) | P3—Pt—P2 | 102.25 (4) |
O2—Pt—P3 | 86.10 (7) | O1—P1—C1 | 106.89 (16) |
O1—Pt—P3 | 173.52 (7) | C1—P2—Pt | 101.45 (13) |
O2—Pt—P2 | 171.61 (7) | P1—O1—Pt | 121.61 (14) |
O1—Pt—P2 | 84.09 (7) | P1—C1—P2 | 106.00 (19) |
The dinitratoplatinum(II) complexes [Pt(NO3)2(P—P)] [P—P is dppm, Ph2PCH2PPh2, or dppe, Ph2P(CH2)2PPh2] are useful intermediates in the synthesis of a wide variety of diphosphineplatinum complexes, since the weakly coordinated nitrates can be replaced easily by other ligands. They can be isolated, or they may be generated in situ and used in further reactions without isolation (De Priest et al., 1997). We prepared [ethylene-1,2-bis(diphenylphosphine)-P,P']dinitratoplatinum(II) [Pt(NO3)2(dppe)], (I), as a precursor to the corresponding ascorbate complex by the reaction of [PtCl2(dppe)] with silver nitrate in acetone solution (Arendse et al., 1999). The only structure of a related platinum complex in the literature is that of cis-[Pt(NO3)2(PMe3)2] (Suzuki et al., 1993).
Mixed phosphine-phosphine oxide ligands have been prepared by the reaction of Ph2P(CH2)nPPh2 with benzyl bromide, followed by aqueous NaOH (Abatjoglou & Kapicek, 1981). Palladium and platinum complexes of the type [M{Ph2P(CH2)nP(O)Ph2—P,O}2]2+ have been reported (Higgins et al., 1987), although the dppmO ligand was reported to be formed in only low yield by the above method. The solid state structure of [Pd(dppeO-P,O)2](BF4)2 has been reported recently by Coyle et al. (1998). We obtained cis-[bis(diphenylphosphinomethyl)diphenylphosphine oxide-O,P]platinum(II) dinitrate dihydrate, cis-[Pt(Ph2PCH2P(O)PPh2)2](NO3)2·2H2O, (II), as an unexpected by-product of the reaction between [PtCl2(dppm)] and silver nitrate in air. \sch
The molecular structure of (I) is shown in Fig. 1. The coordination geometry around the Pt atom is distorted square planar, with P1—Pt—P2, O1—Pt—P1, O4—Pt—P2 and O1—Pt—O4 angles of 85.85 (8), 90.82 (17), 98.15 (17) and 85.4 (2)°, respectively. The Pt—O—N angles are 113.5 (5) and 116.2 (5)°, and the NO2 groups lie on opposite sides of the PtO2P2 plane. This feature was also observed in the structure of cis-[Pt(NO3)2(PMe3)2] (Suzuki et al., 1993). The Pt—P distances of 2.215 (2) and 2.220 (2) Å, and the Pt—O distances of 2.111 (5) and 2.115 (5) Å, are similar to the corresponding distances in cis-[Pt(NO3)2(PMe3)2].
The molecular structure of the cation in (II) is bidentate, coordinating through one P atom and the O atom of the phosphine oxide to form two five-membered chelate rings. The Pt—O distances are 2.089 (2) and 2.094 (2) Å, and the Pt—P distances are 2.2168 (10) and 2.2178 (10) Å. These Pt—O and Pt—P bond lengths are similar to the values of 2.108 (10) Å and 2.213 (4) Å, respectively, found in cis-[Pt{Ph2PNHP(O)Ph2—P,O}2](BF4)2 (Bhattacharyya et al., 1996). The cation in the latter complex is analogous to that in (II), since it is also composed of two five-membered chelate rings. The Ph2PNHP(O)Ph2 ligand is also isoelectronic with dppmO. In the present case, the coordination geometry about the Pt atom is distorted square planar. The O1—Pt—O2, O2—Pt—P3, O1—Pt—P2 and P2—Pt—P3 angles are 87.54 (10), 86.10 (7), 84.09 (7) and 102.25 (4)°, respectively, giving an angle sum of 359.98° around the metal. The larger P—Pt—P angle is due to the greater steric requirements of the phenyl groups on the two P atoms that lie cis to each other. The P—Pt—P angle in (II) is larger than that of 98.5 (2)° found in cis-[Pt{Ph2PNHP(O)Ph2—P,O}2]2+ (Bhattacharyya et al., 1996); it is closer to the values of 103.2 (1) and 103.72 (9)° in the neutral complexes cis-[Pt{Ph2PNP(O)Ph2—P,O}2] (Bhattacharyya et al., 1996) and cis-[Pt{Ph2PCH2C(O)(CF3)2-P,O}2] (Montgomery et al., 1987).