Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014083/bt6178sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014083/bt6178Isup2.hkl |
CCDC reference: 197446
Key indicators
- Single-crystal X-ray study
- T = 178 K
- Mean (C-C) = 0.010 Å
- R factor = 0.034
- wR factor = 0.087
- Data-to-parameter ratio = 16.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
ABSTM_02 Alert B The ratio of expected to reported Tmax/Tmin(RR) is > 1.50 Tmin and Tmax reported: 0.506 0.999 Tmin and Tmax expected: 0.150 0.465 RR = 1.569 Please check that your absorption correction is appropriate. General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.465 Tmax scaled 0.465 Tmin scaled 0.235
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check
The title compound was prepared by treating (cyclooctadiene)PtCl2 with the phosphinourea ligand in dichloromethane (Vogt, 1992). Single crystals were obtained by evaporation from chloroform.
Methyl H atoms were identified in difference syntheses, idealized and then refined allowing rigid methyl groups to rotate but not tip. The maxima at C1 and C3 were indistinct, which may indicate disorder or appreciable rotation of these methyl groups. Other H atoms were included using a riding model with fixed C—H bond lengths (aromatic 0.95, methyl 0.98 and methine 1.00 Å); Uiso(H) values were fixed at 1.2 times the Ueq of the parent atom. Three significant difference peaks (the largest 2.4 e Å−3) do not lie near the Pt atom. They may be caused by a minor but unidentified twinning or disorder component.
Data collection: P3 (Nicolet, 1987); cell refinement: P3; data reduction: XDISK (Nicolet, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
Fig. 1. The formula unit of the title compound in the crystal. Ellipsoids represent 30% probability levels. H-atom radii are arbitrary. |
[PtCl2(C25H30N2OP2)]·CHCl3 | Dx = 1.769 Mg m−3 |
Mr = 821.81 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 50 reflections |
a = 16.380 (4) Å | θ = 10–11.5° |
b = 15.653 (3) Å | µ = 5.11 mm−1 |
c = 24.074 (4) Å | T = 178 K |
V = 6172 (2) Å3 | Tablet, colourless |
Z = 8 | 0.40 × 0.40 × 0.15 mm |
F(000) = 3216 |
Nicolet R3 diffractometer | 3612 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.043 |
Graphite monochromator | θmax = 25.0°, θmin = 3.0° |
ω scans | h = 0→19 |
Absorption correction: ψ scan (XEMP; Nicolet, 1987) | k = −18→18 |
Tmin = 0.506, Tmax = 0.999 | l = −28→0 |
10607 measured reflections | 3 standard reflections every 147 reflections |
5419 independent reflections | intensity decay: 2% |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0367P)2 + 1.8493P] where P = (Fo2 + 2Fc2)/3 |
5419 reflections | (Δ/σ)max = 0.006 |
339 parameters | Δρmax = 2.40 e Å−3 |
66 restraints | Δρmin = −0.85 e Å−3 |
[PtCl2(C25H30N2OP2)]·CHCl3 | V = 6172 (2) Å3 |
Mr = 821.81 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 16.380 (4) Å | µ = 5.11 mm−1 |
b = 15.653 (3) Å | T = 178 K |
c = 24.074 (4) Å | 0.40 × 0.40 × 0.15 mm |
Nicolet R3 diffractometer | 3612 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XEMP; Nicolet, 1987) | Rint = 0.043 |
Tmin = 0.506, Tmax = 0.999 | 3 standard reflections every 147 reflections |
10607 measured reflections | intensity decay: 2% |
5419 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 66 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.05 | Δρmax = 2.40 e Å−3 |
5419 reflections | Δρmin = −0.85 e Å−3 |
339 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 8.9801 (0.0074) x + 13.0701 (0.0055) y − 1.1370 (0.0129) z = 14.0493 (0.0084) * 0.0582 (0.0007) Pt * −0.0059 (0.0009) P1 * −0.0241 (0.0009) P2 * −0.0223 (0.0009) Cl1 * −0.0058 (0.0008) Cl2 − 0.4900 (0.0056) N1 0.7146 (0.0056) N2 0.2307 (0.0072) C2 Rms deviation of fitted atoms = 0.0301 |
x | y | z | Uiso*/Ueq | ||
Pt | 0.669917 (14) | 0.666824 (15) | 0.548759 (10) | 0.01825 (9) | |
Cl1 | 0.62226 (10) | 0.68541 (11) | 0.45678 (7) | 0.0290 (4) | |
Cl2 | 0.77862 (10) | 0.58411 (10) | 0.51279 (7) | 0.0256 (4) | |
P1 | 0.56220 (10) | 0.73869 (11) | 0.58049 (8) | 0.0212 (4) | |
P2 | 0.70803 (11) | 0.64188 (11) | 0.63532 (8) | 0.0230 (4) | |
N1 | 0.5441 (3) | 0.7202 (3) | 0.6507 (2) | 0.0237 (13) | |
N2 | 0.6817 (3) | 0.7205 (3) | 0.6814 (2) | 0.0221 (13) | |
O | 0.5785 (3) | 0.7715 (4) | 0.7358 (2) | 0.0464 (15) | |
C1 | 0.4587 (4) | 0.7166 (5) | 0.6719 (3) | 0.0352 (19) | |
H1A | 0.4583 | 0.6905 | 0.7089 | 0.053* | |
H1B | 0.4251 | 0.6824 | 0.6466 | 0.053* | |
H1C | 0.4364 | 0.7747 | 0.6742 | 0.053* | |
C2 | 0.6007 (4) | 0.7401 (4) | 0.6923 (3) | 0.0297 (17) | |
C3 | 0.7404 (5) | 0.7576 (5) | 0.7215 (3) | 0.044 (2) | |
H3A | 0.7235 | 0.8158 | 0.7310 | 0.066* | |
H3B | 0.7950 | 0.7590 | 0.7048 | 0.066* | |
H3C | 0.7416 | 0.7225 | 0.7552 | 0.066* | |
C4 | 0.5692 (4) | 0.8575 (4) | 0.5721 (3) | 0.0273 (16) | |
C5 | 0.6539 (4) | 0.8832 (4) | 0.5935 (3) | 0.0309 (17) | |
H5A | 0.6955 | 0.8468 | 0.5763 | 0.037* | |
H5B | 0.6558 | 0.8762 | 0.6340 | 0.037* | |
H5C | 0.6646 | 0.9431 | 0.5840 | 0.037* | |
C6 | 0.5630 (5) | 0.8818 (5) | 0.5099 (3) | 0.0369 (18) | |
H6A | 0.5657 | 0.9441 | 0.5061 | 0.044* | |
H6B | 0.5111 | 0.8610 | 0.4948 | 0.044* | |
H6C | 0.6084 | 0.8557 | 0.4895 | 0.044* | |
C7 | 0.5040 (5) | 0.9046 (4) | 0.6061 (3) | 0.040 (2) | |
H7A | 0.5119 | 0.9664 | 0.6023 | 0.048* | |
H7B | 0.5088 | 0.8885 | 0.6453 | 0.048* | |
H7C | 0.4497 | 0.8891 | 0.5923 | 0.048* | |
C8 | 0.4704 (4) | 0.6931 (4) | 0.5506 (3) | 0.0219 (14) | |
C9 | 0.4007 (4) | 0.7401 (4) | 0.5366 (3) | 0.0302 (17) | |
H9 | 0.4007 | 0.8007 | 0.5387 | 0.036* | |
C10 | 0.3315 (4) | 0.6961 (4) | 0.5197 (3) | 0.0329 (17) | |
H10 | 0.2838 | 0.7272 | 0.5101 | 0.039* | |
C11 | 0.3304 (4) | 0.6074 (4) | 0.5166 (3) | 0.0310 (16) | |
H11 | 0.2823 | 0.5784 | 0.5051 | 0.037* | |
C12 | 0.3999 (4) | 0.5615 (4) | 0.5305 (3) | 0.0297 (17) | |
H12 | 0.3998 | 0.5009 | 0.5282 | 0.036* | |
C13 | 0.4692 (4) | 0.6042 (4) | 0.5475 (3) | 0.0260 (15) | |
H13 | 0.5166 | 0.5727 | 0.5573 | 0.031* | |
C14 | 0.6586 (4) | 0.5461 (4) | 0.6610 (3) | 0.0246 (15) | |
C15 | 0.6352 (4) | 0.4837 (4) | 0.6236 (3) | 0.0294 (16) | |
H15 | 0.6485 | 0.4901 | 0.5854 | 0.035* | |
C16 | 0.5927 (4) | 0.4117 (4) | 0.6410 (4) | 0.0411 (19) | |
H16 | 0.5771 | 0.3692 | 0.6149 | 0.049* | |
C17 | 0.5733 (5) | 0.4025 (5) | 0.6963 (3) | 0.042 (2) | |
H17 | 0.5429 | 0.3543 | 0.7084 | 0.051* | |
C18 | 0.5980 (4) | 0.4633 (5) | 0.7343 (3) | 0.0376 (18) | |
H18 | 0.5864 | 0.4554 | 0.7726 | 0.045* | |
C19 | 0.6392 (4) | 0.5353 (5) | 0.7171 (3) | 0.0337 (17) | |
H19 | 0.6545 | 0.5776 | 0.7435 | 0.040* | |
C20 | 0.8164 (4) | 0.6314 (4) | 0.6475 (3) | 0.0251 (15) | |
C21 | 0.8704 (4) | 0.6822 (4) | 0.6173 (3) | 0.0292 (16) | |
H21 | 0.8507 | 0.7188 | 0.5889 | 0.035* | |
C22 | 0.9532 (4) | 0.6787 (5) | 0.6292 (3) | 0.0347 (18) | |
H22 | 0.9906 | 0.7119 | 0.6081 | 0.042* | |
C23 | 0.9817 (5) | 0.6274 (5) | 0.6716 (3) | 0.0403 (19) | |
H23 | 1.0380 | 0.6283 | 0.6809 | 0.048* | |
C24 | 0.9295 (4) | 0.5750 (5) | 0.7003 (3) | 0.0349 (18) | |
H24 | 0.9501 | 0.5370 | 0.7277 | 0.042* | |
C25 | 0.8461 (4) | 0.5779 (4) | 0.6892 (3) | 0.0307 (17) | |
H25 | 0.8094 | 0.5434 | 0.7100 | 0.037* | |
C26 | 0.7291 (5) | 0.5467 (5) | 0.3700 (4) | 0.048 (2) | |
H26 | 0.7112 | 0.5550 | 0.4094 | 0.058* | |
Cl3 | 0.78431 (14) | 0.63807 (16) | 0.34978 (10) | 0.0597 (7) | |
Cl4 | 0.64232 (18) | 0.5366 (2) | 0.32931 (12) | 0.0945 (10) | |
Cl5 | 0.7915 (2) | 0.45719 (19) | 0.36777 (13) | 0.0998 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.01974 (13) | 0.01757 (13) | 0.01745 (14) | −0.00010 (11) | −0.00050 (12) | −0.00012 (12) |
Cl1 | 0.0311 (9) | 0.0368 (10) | 0.0192 (9) | 0.0052 (8) | −0.0034 (8) | −0.0003 (8) |
Cl2 | 0.0255 (9) | 0.0239 (8) | 0.0273 (10) | 0.0040 (7) | 0.0016 (8) | −0.0016 (7) |
P1 | 0.0235 (9) | 0.0176 (9) | 0.0226 (10) | −0.0011 (7) | 0.0012 (8) | −0.0005 (8) |
P2 | 0.0229 (9) | 0.0253 (9) | 0.0209 (10) | 0.0012 (7) | −0.0020 (8) | −0.0018 (8) |
N1 | 0.026 (3) | 0.029 (3) | 0.016 (3) | 0.001 (2) | 0.006 (3) | 0.001 (3) |
N2 | 0.022 (3) | 0.029 (3) | 0.015 (3) | 0.002 (2) | −0.004 (2) | −0.005 (2) |
O | 0.041 (3) | 0.069 (4) | 0.029 (3) | 0.011 (3) | −0.001 (3) | −0.022 (3) |
C1 | 0.030 (4) | 0.047 (5) | 0.028 (5) | −0.004 (4) | 0.008 (4) | 0.001 (4) |
C2 | 0.031 (4) | 0.026 (4) | 0.033 (5) | 0.003 (3) | 0.002 (4) | −0.001 (4) |
C3 | 0.036 (4) | 0.052 (5) | 0.044 (5) | 0.006 (4) | −0.005 (4) | −0.022 (4) |
C4 | 0.033 (4) | 0.015 (3) | 0.034 (4) | −0.003 (3) | −0.001 (3) | −0.002 (3) |
C5 | 0.039 (4) | 0.020 (4) | 0.033 (4) | −0.010 (3) | 0.005 (3) | 0.002 (3) |
C6 | 0.045 (5) | 0.026 (4) | 0.040 (4) | −0.006 (4) | 0.000 (4) | 0.003 (4) |
C7 | 0.040 (4) | 0.026 (4) | 0.054 (5) | 0.002 (4) | 0.009 (4) | −0.010 (4) |
C8 | 0.024 (3) | 0.023 (3) | 0.019 (4) | −0.005 (3) | 0.003 (3) | 0.001 (3) |
C9 | 0.028 (4) | 0.022 (3) | 0.041 (5) | 0.004 (3) | −0.004 (3) | −0.004 (3) |
C10 | 0.024 (4) | 0.031 (3) | 0.043 (5) | 0.005 (3) | −0.016 (4) | 0.003 (3) |
C11 | 0.029 (4) | 0.038 (4) | 0.027 (4) | −0.008 (3) | −0.003 (4) | 0.000 (3) |
C12 | 0.032 (4) | 0.021 (3) | 0.037 (5) | −0.003 (3) | −0.004 (3) | 0.003 (3) |
C13 | 0.025 (3) | 0.019 (3) | 0.034 (4) | 0.000 (3) | 0.001 (3) | −0.001 (3) |
C14 | 0.021 (4) | 0.023 (3) | 0.030 (4) | −0.001 (3) | 0.003 (3) | 0.005 (3) |
C15 | 0.034 (4) | 0.027 (4) | 0.027 (4) | −0.003 (3) | 0.003 (3) | 0.005 (3) |
C16 | 0.048 (5) | 0.023 (4) | 0.052 (5) | −0.002 (3) | −0.001 (4) | 0.007 (4) |
C17 | 0.038 (5) | 0.030 (4) | 0.059 (5) | −0.004 (4) | 0.008 (4) | 0.020 (4) |
C18 | 0.030 (4) | 0.044 (4) | 0.038 (5) | 0.009 (3) | 0.005 (4) | 0.021 (3) |
C19 | 0.035 (4) | 0.035 (4) | 0.031 (4) | 0.005 (3) | 0.005 (4) | 0.003 (3) |
C20 | 0.026 (4) | 0.028 (3) | 0.021 (4) | 0.002 (3) | 0.000 (3) | −0.007 (3) |
C21 | 0.027 (3) | 0.035 (4) | 0.026 (4) | −0.003 (3) | −0.003 (3) | −0.001 (3) |
C22 | 0.025 (3) | 0.046 (5) | 0.033 (4) | −0.009 (3) | 0.004 (3) | −0.013 (3) |
C23 | 0.027 (4) | 0.050 (5) | 0.045 (5) | 0.008 (3) | −0.004 (4) | −0.011 (4) |
C24 | 0.029 (4) | 0.044 (5) | 0.032 (5) | 0.014 (3) | −0.008 (3) | 0.000 (4) |
C25 | 0.035 (4) | 0.031 (4) | 0.026 (4) | 0.005 (3) | −0.004 (3) | 0.001 (3) |
C26 | 0.048 (5) | 0.059 (5) | 0.039 (5) | 0.003 (4) | 0.007 (4) | 0.002 (5) |
Cl3 | 0.0477 (13) | 0.0792 (16) | 0.0522 (15) | −0.0073 (12) | 0.0036 (12) | 0.0142 (13) |
Cl4 | 0.0788 (19) | 0.149 (3) | 0.0555 (18) | −0.039 (2) | −0.0225 (15) | −0.0187 (19) |
Cl5 | 0.141 (3) | 0.0783 (19) | 0.080 (2) | 0.048 (2) | 0.063 (2) | 0.0207 (17) |
Pt—P2 | 2.2102 (19) | C9—C10 | 1.388 (8) |
Pt—P1 | 2.2275 (18) | C9—H9 | 0.9500 |
Pt—Cl2 | 2.3658 (16) | C10—C11 | 1.390 (9) |
Pt—Cl1 | 2.3658 (18) | C10—H10 | 0.9500 |
P1—N1 | 1.739 (6) | C11—C12 | 1.387 (8) |
P1—C8 | 1.814 (7) | C11—H11 | 0.9500 |
P1—C4 | 1.874 (6) | C12—C13 | 1.380 (8) |
P2—N2 | 1.711 (6) | C12—H12 | 0.9500 |
P2—C20 | 1.806 (7) | C13—H13 | 0.9500 |
P2—C14 | 1.812 (7) | C14—C15 | 1.382 (8) |
N1—C2 | 1.400 (9) | C14—C19 | 1.400 (8) |
N1—C1 | 1.491 (8) | C15—C16 | 1.390 (8) |
N2—C2 | 1.387 (8) | C15—H15 | 0.9500 |
N2—C3 | 1.482 (9) | C16—C17 | 1.378 (9) |
O—C2 | 1.212 (8) | C16—H16 | 0.9500 |
C1—H1A | 0.9800 | C17—C18 | 1.380 (9) |
C1—H1B | 0.9800 | C17—H17 | 0.9500 |
C1—H1C | 0.9800 | C18—C19 | 1.377 (9) |
C3—H3A | 0.9800 | C18—H18 | 0.9500 |
C3—H3B | 0.9800 | C19—H19 | 0.9500 |
C3—H3C | 0.9800 | C20—C21 | 1.393 (8) |
C4—C7 | 1.534 (9) | C20—C25 | 1.396 (8) |
C4—C5 | 1.535 (9) | C21—C22 | 1.388 (9) |
C4—C6 | 1.547 (10) | C21—H21 | 0.9500 |
C5—H5A | 0.9800 | C22—C23 | 1.380 (9) |
C5—H5B | 0.9800 | C22—H22 | 0.9500 |
C5—H5C | 0.9800 | C23—C24 | 1.372 (9) |
C6—H6A | 0.9800 | C23—H23 | 0.9500 |
C6—H6B | 0.9800 | C24—C25 | 1.393 (9) |
C6—H6C | 0.9800 | C24—H24 | 0.9500 |
C7—H7A | 0.9800 | C25—H25 | 0.9500 |
C7—H7B | 0.9800 | C26—Cl4 | 1.734 (9) |
C7—H7C | 0.9800 | C26—Cl5 | 1.735 (8) |
C8—C13 | 1.394 (8) | C26—Cl3 | 1.760 (9) |
C8—C9 | 1.398 (8) | C26—H26 | 1.0000 |
P2—Pt—P1 | 89.41 (7) | H7B—C7—H7C | 109.5 |
P2—Pt—Cl2 | 92.05 (6) | C13—C8—C9 | 120.0 (6) |
P1—Pt—Cl2 | 176.43 (6) | C13—C8—P1 | 115.2 (5) |
P2—Pt—Cl1 | 175.87 (6) | C9—C8—P1 | 124.5 (5) |
P1—Pt—Cl1 | 89.86 (6) | C10—C9—C8 | 118.4 (6) |
Cl2—Pt—Cl1 | 88.46 (6) | C10—C9—H9 | 120.8 |
N1—P1—C8 | 100.3 (3) | C8—C9—H9 | 120.8 |
N1—P1—C4 | 106.3 (3) | C9—C10—C11 | 121.5 (6) |
C8—P1—C4 | 113.5 (3) | C9—C10—H10 | 119.3 |
N1—P1—Pt | 112.6 (2) | C11—C10—H10 | 119.3 |
C8—P1—Pt | 108.8 (2) | C12—C11—C10 | 119.6 (7) |
C4—P1—Pt | 114.5 (2) | C12—C11—H11 | 120.2 |
N2—P2—C20 | 102.0 (3) | C10—C11—H11 | 120.2 |
N2—P2—C14 | 105.2 (3) | C13—C12—C11 | 119.7 (6) |
C20—P2—C14 | 108.0 (3) | C13—C12—H12 | 120.2 |
N2—P2—Pt | 114.4 (2) | C11—C12—H12 | 120.2 |
C20—P2—Pt | 116.5 (2) | C12—C13—C8 | 120.8 (6) |
C14—P2—Pt | 109.9 (2) | C12—C13—H13 | 119.6 |
C2—N1—C1 | 112.6 (6) | C8—C13—H13 | 119.6 |
C2—N1—P1 | 123.0 (5) | C15—C14—C19 | 118.7 (6) |
C1—N1—P1 | 120.0 (5) | C15—C14—P2 | 119.1 (5) |
C2—N2—C3 | 114.2 (6) | C19—C14—P2 | 122.1 (5) |
C2—N2—P2 | 121.5 (5) | C14—C15—C16 | 121.1 (7) |
C3—N2—P2 | 122.7 (4) | C14—C15—H15 | 119.5 |
N1—C1—H1A | 109.5 | C16—C15—H15 | 119.5 |
N1—C1—H1B | 109.5 | C17—C16—C15 | 119.5 (7) |
H1A—C1—H1B | 109.5 | C17—C16—H16 | 120.3 |
N1—C1—H1C | 109.5 | C15—C16—H16 | 120.3 |
H1A—C1—H1C | 109.5 | C16—C17—C18 | 120.1 (7) |
H1B—C1—H1C | 109.5 | C16—C17—H17 | 120.0 |
O—C2—N2 | 122.7 (7) | C18—C17—H17 | 120.0 |
O—C2—N1 | 120.6 (6) | C19—C18—C17 | 120.6 (7) |
N2—C2—N1 | 116.7 (6) | C19—C18—H18 | 119.7 |
N2—C3—H3A | 109.5 | C17—C18—H18 | 119.7 |
N2—C3—H3B | 109.5 | C18—C19—C14 | 120.1 (7) |
H3A—C3—H3B | 109.5 | C18—C19—H19 | 120.0 |
N2—C3—H3C | 109.5 | C14—C19—H19 | 120.0 |
H3A—C3—H3C | 109.5 | C21—C20—C25 | 119.7 (6) |
H3B—C3—H3C | 109.5 | C21—C20—P2 | 119.2 (5) |
C7—C4—C5 | 108.9 (6) | C25—C20—P2 | 120.9 (5) |
C7—C4—C6 | 110.6 (6) | C22—C21—C20 | 119.5 (7) |
C5—C4—C6 | 108.7 (6) | C22—C21—H21 | 120.3 |
C7—C4—P1 | 112.1 (5) | C20—C21—H21 | 120.3 |
C5—C4—P1 | 106.2 (5) | C23—C22—C21 | 120.3 (7) |
C6—C4—P1 | 110.2 (5) | C23—C22—H22 | 119.8 |
C4—C5—H5A | 109.5 | C21—C22—H22 | 119.8 |
C4—C5—H5B | 109.5 | C24—C23—C22 | 120.7 (7) |
H5A—C5—H5B | 109.5 | C24—C23—H23 | 119.6 |
C4—C5—H5C | 109.5 | C22—C23—H23 | 119.6 |
H5A—C5—H5C | 109.5 | C23—C24—C25 | 119.7 (7) |
H5B—C5—H5C | 109.5 | C23—C24—H24 | 120.2 |
C4—C6—H6A | 109.5 | C25—C24—H24 | 120.2 |
C4—C6—H6B | 109.5 | C24—C25—C20 | 120.0 (7) |
H6A—C6—H6B | 109.5 | C24—C25—H25 | 120.0 |
C4—C6—H6C | 109.5 | C20—C25—H25 | 120.0 |
H6A—C6—H6C | 109.5 | Cl4—C26—Cl5 | 113.0 (5) |
H6B—C6—H6C | 109.5 | Cl4—C26—Cl3 | 109.8 (5) |
C4—C7—H7A | 109.5 | Cl5—C26—Cl3 | 110.2 (5) |
C4—C7—H7B | 109.5 | Cl4—C26—H26 | 107.9 |
H7A—C7—H7B | 109.5 | Cl5—C26—H26 | 107.9 |
C4—C7—H7C | 109.5 | Cl3—C26—H26 | 107.9 |
H7A—C7—H7C | 109.5 | ||
P2—Pt—P1—N1 | −14.7 (2) | C4—P1—C8—C13 | 169.6 (5) |
P2—Pt—P1—C8 | −125.0 (2) | Pt—P1—C8—C13 | 40.9 (6) |
P2—Pt—P1—C4 | 106.9 (3) | N1—P1—C8—C9 | 95.6 (6) |
Cl1—Pt—P1—N1 | 161.2 (2) | C4—P1—C8—C9 | −17.3 (7) |
Cl1—Pt—P1—C8 | 51.0 (2) | Pt—P1—C8—C9 | −146.0 (5) |
Cl1—Pt—P1—C4 | −77.2 (3) | C13—C8—C9—C10 | −0.2 (9) |
P1—Pt—P2—N2 | −31.0 (2) | P1—C8—C9—C10 | −173.0 (5) |
Cl2—Pt—P2—N2 | 152.2 (2) | C8—C9—C10—C11 | 0.1 (10) |
P1—Pt—P2—C20 | −149.8 (2) | C9—C10—C11—C12 | −0.2 (11) |
Cl2—Pt—P2—C20 | 33.5 (2) | C10—C11—C12—C13 | 0.4 (11) |
P1—Pt—P2—C14 | 87.0 (2) | C11—C12—C13—C8 | −0.5 (11) |
Cl2—Pt—P2—C14 | −89.8 (2) | C9—C8—C13—C12 | 0.4 (10) |
C8—P1—N1—C2 | 176.4 (5) | P1—C8—C13—C12 | 173.9 (6) |
C4—P1—N1—C2 | −65.3 (6) | N2—P2—C14—C15 | 150.4 (5) |
Pt—P1—N1—C2 | 60.9 (5) | C20—P2—C14—C15 | −101.3 (5) |
C8—P1—N1—C1 | −28.9 (6) | Pt—P2—C14—C15 | 26.8 (5) |
C4—P1—N1—C1 | 89.4 (5) | N2—P2—C14—C19 | −26.1 (6) |
Pt—P1—N1—C1 | −144.4 (5) | C20—P2—C14—C19 | 82.3 (6) |
C20—P2—N2—C2 | −169.8 (5) | Pt—P2—C14—C19 | −149.7 (5) |
C14—P2—N2—C2 | −57.2 (6) | C19—C14—C15—C16 | 0.6 (9) |
Pt—P2—N2—C2 | 63.5 (6) | P2—C14—C15—C16 | −176.0 (5) |
C20—P2—N2—C3 | −4.7 (6) | C14—C15—C16—C17 | 0.1 (9) |
C14—P2—N2—C3 | 108.0 (6) | C15—C16—C17—C18 | −1.7 (11) |
Pt—P2—N2—C3 | −131.3 (5) | C16—C17—C18—C19 | 2.6 (11) |
C3—N2—C2—O | −12.5 (10) | C17—C18—C19—C14 | −1.9 (11) |
P2—N2—C2—O | 153.9 (6) | C15—C14—C19—C18 | 0.3 (10) |
C3—N2—C2—N1 | 168.8 (6) | P2—C14—C19—C18 | 176.7 (5) |
P2—N2—C2—N1 | −24.9 (8) | N2—P2—C20—C21 | −89.0 (5) |
C1—N1—C2—O | −17.4 (9) | C14—P2—C20—C21 | 160.5 (5) |
P1—N1—C2—O | 139.0 (6) | Pt—P2—C20—C21 | 36.2 (6) |
C1—N1—C2—N2 | 161.4 (6) | N2—P2—C20—C25 | 86.3 (6) |
P1—N1—C2—N2 | −42.2 (8) | C14—P2—C20—C25 | −24.2 (6) |
N1—P1—C4—C7 | −41.9 (6) | Pt—P2—C20—C25 | −148.4 (5) |
C8—P1—C4—C7 | 67.4 (6) | C25—C20—C21—C22 | 0.1 (9) |
Pt—P1—C4—C7 | −166.8 (5) | P2—C20—C21—C22 | 175.5 (5) |
N1—P1—C4—C5 | 77.0 (5) | C20—C21—C22—C23 | −1.8 (9) |
C8—P1—C4—C5 | −173.7 (5) | C21—C22—C23—C24 | 4.0 (11) |
Pt—P1—C4—C5 | −48.0 (5) | C22—C23—C24—C25 | −4.3 (12) |
N1—P1—C4—C6 | −165.5 (5) | C23—C24—C25—C20 | 2.5 (11) |
C8—P1—C4—C6 | −56.2 (6) | C21—C20—C25—C24 | −0.4 (10) |
Pt—P1—C4—C6 | 69.5 (5) | P2—C20—C25—C24 | −175.7 (6) |
N1—P1—C8—C13 | −77.5 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C26—H26···Cl1 | 1.00 | 2.76 | 3.484 (9) | 130 |
C26—H26···Cl2 | 1.00 | 2.76 | 3.579 (9) | 139 |
C11—H11···Cl2i | 0.95 | 2.77 | 3.560 (7) | 142 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [PtCl2(C25H30N2OP2)]·CHCl3 |
Mr | 821.81 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 178 |
a, b, c (Å) | 16.380 (4), 15.653 (3), 24.074 (4) |
V (Å3) | 6172 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 5.11 |
Crystal size (mm) | 0.40 × 0.40 × 0.15 |
Data collection | |
Diffractometer | Nicolet R3 diffractometer |
Absorption correction | ψ scan (XEMP; Nicolet, 1987) |
Tmin, Tmax | 0.506, 0.999 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10607, 5419, 3612 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.087, 1.05 |
No. of reflections | 5419 |
No. of parameters | 339 |
No. of restraints | 66 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.40, −0.85 |
Computer programs: P3 (Nicolet, 1987), P3, XDISK (Nicolet, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
Pt—P2 | 2.2102 (19) | P2—C20 | 1.806 (7) |
Pt—P1 | 2.2275 (18) | P2—C14 | 1.812 (7) |
Pt—Cl2 | 2.3658 (16) | N1—C2 | 1.400 (9) |
Pt—Cl1 | 2.3658 (18) | N1—C1 | 1.491 (8) |
P1—N1 | 1.739 (6) | N2—C2 | 1.387 (8) |
P1—C8 | 1.814 (7) | N2—C3 | 1.482 (9) |
P1—C4 | 1.874 (6) | O—C2 | 1.212 (8) |
P2—N2 | 1.711 (6) | ||
P2—Pt—P1 | 89.41 (7) | C20—P2—C14 | 108.0 (3) |
P2—Pt—Cl2 | 92.05 (6) | N2—P2—Pt | 114.4 (2) |
P1—Pt—Cl2 | 176.43 (6) | C20—P2—Pt | 116.5 (2) |
P2—Pt—Cl1 | 175.87 (6) | C14—P2—Pt | 109.9 (2) |
P1—Pt—Cl1 | 89.86 (6) | C2—N1—C1 | 112.6 (6) |
Cl2—Pt—Cl1 | 88.46 (6) | C2—N1—P1 | 123.0 (5) |
N1—P1—C8 | 100.3 (3) | C1—N1—P1 | 120.0 (5) |
N1—P1—C4 | 106.3 (3) | C2—N2—C3 | 114.2 (6) |
C8—P1—C4 | 113.5 (3) | C2—N2—P2 | 121.5 (5) |
N1—P1—Pt | 112.6 (2) | C3—N2—P2 | 122.7 (4) |
C8—P1—Pt | 108.8 (2) | O—C2—N2 | 122.7 (7) |
C4—P1—Pt | 114.5 (2) | O—C2—N1 | 120.6 (6) |
N2—P2—C20 | 102.0 (3) | N2—C2—N1 | 116.7 (6) |
N2—P2—C14 | 105.2 (3) | ||
P2—Pt—P1—N1 | −14.7 (2) | Pt—P2—N2—C2 | 63.5 (6) |
P1—Pt—P2—N2 | −31.0 (2) | P2—N2—C2—N1 | −24.9 (8) |
Pt—P1—N1—C2 | 60.9 (5) | P1—N1—C2—N2 | −42.2 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C26—H26···Cl1 | 1.00 | 2.76 | 3.484 (9) | 130 |
C26—H26···Cl2 | 1.00 | 2.76 | 3.579 (9) | 139 |
C11—H11···Cl2i | 0.95 | 2.77 | 3.560 (7) | 142 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
The title compound, (I), formed part of a study of phosphorus-substituted N,N'-diorganylureas (Vogt, 1992). It crystallizes as a chloroform monosolvate.
The formula unit is shown in Fig. 1. The structure determination confirms the expected P,P'-bonding mode of the ligand; related derivatives of pentacarbonylchromium and -molybdenum unexpectedly proved to be P,O-bonded (Vogt et al., 1991). The geometry at platinum is square planar; the Pt—Cl bond lengths are exactly equal, but the Pt—P bond to the Ph2P moiety is slightly shorter than that to tBu(Ph)P (Table 1). The P—N bond lengths display a similar qualitative difference, perhaps because of steric effects from the bulky tert-butyl group. The ligand bite angle is 89.41 (7)°. The chelate ring is not planar; torsion angles are given in Table 1.
The preparation and structures of several closely related compounds have recently been reported by Slawin et al. (2001). The dichloroplatinum complexes of [Ph2PN(R)C(O)N(R)PPh2] (R = Me, Et) display bond lengths and angles similar to those of the title compound.
The solvent molecule is associated with the metal complex by a three-centre hydrogen bond of the form C—H(···Cl)2 (Table 2). The role of metal-bonded chlorine as a hydrogen-bond acceptor is well established for both `classical' (Aullón et al., 1998) and `weak' (Freytag & Jones, 2000) hydrogen bonds.