Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052488/at2435sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052488/at2435Isup2.hkl |
CCDC reference: 667233
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.010 Å
- R factor = 0.023
- wR factor = 0.059
- Data-to-parameter ratio = 16.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 400 Ang. PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.23 Ratio PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pt1 - I1 .. 5.74 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pt1 - I2 .. 8.33 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pt1 - I4 .. 9.00 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pt2 - I2 .. 8.61 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pt2 - I3 .. 6.92 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C23 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C35 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 10
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Pt1 (9) 2.42 PLAT794_ALERT_5_G Check Predicted Bond Valency for Pt2 (9) 2.41
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
The title compound (I) was synthesized by stirring a mixture of di-µ-chlorido-bis[η3-2-methylallylplatinum(II)], triphenylphosphine and iodine in chloroform medium. The pink compound was isolated by chromatographic technique. Crystals suitable for X-ray crystallography was obtained from a mixture of dichloromethane and hexane (1:5 v/v).
H atoms were included at calculated positions as riding atoms with C–H set to 0.93 Å for aromatic H atoms, with Uiso(H) = 1.2Ueq(C).
The dimeric halogen bridged complexes of platinum(II) are very important in synthetic organometallic chemistry (Chatt, 1951 & Chatt and Venanzi, 1955). The main application of the halide bridged complexes is in reactions in which the bridged is cleaved to give monomeric complexes (Chatt and Venanzi, 1957 & Chatt et al., 1964). Recently cytotoxicity of some dimeric iodo bridged platinum(II) complexes has been established (Jinchao et al., 2006). Against this background we report here the crystal structure of (I).
The molecular structure of the title compound, (I), is shown in Fig. 1, with the atom numbering scheme. The packing arrangement of (I) is shown in Fig. 2. The platinum atom is tetracoordinated with a donor set of one triphenylphosphine P atom and three I atoms in an approximately squareplanar geometry. One of the three iodine atoms is a terminal I, and the other two are bridging I for each platinum atom. Selected bond lengths and bond angles are listed in Table 1. The Pt—I bond lengthes trans to the triphenylphosphine moieties are longer and this is supposed to be due to the trans-influence of the P atom of the triphenylphosphine moiety. On the other hand Pt—P distances are quite close to the reported values (Black et al., 1969) indicating absence of definite correlation between Pt—P distances and the trans influence of the ligand in the trans position. This, in turn, is indicative of the fact that Pt(II)—P bonds are not simple sigma bonds, but are more complex and therefore affected by the trans ligands in a more complex way than Pt(II)—I bonds.
For related literature, see: Black et al. (1969); Chatt (1951); Chatt & Venanzi (1955, 1957); Chatt et al. (1964); Jinchao et al. (2006).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 50% probability level. | |
Fig. 2. The molecular arrangement of (I) in the ac plane. H atoms are omitted for clarity. |
[Pt2I4(C18H15P)2] | F(000) = 2576 |
Mr = 1422.32 | Dx = 2.490 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6689 reflections |
a = 16.036 (4) Å | θ = 1.4–25.0° |
b = 15.874 (4) Å | µ = 10.73 mm−1 |
c = 16.882 (4) Å | T = 293 K |
β = 117.980 (4)° | Needle, pink |
V = 3794.8 (17) Å3 | 0.41 × 0.26 × 0.12 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 6689 independent reflections |
Radiation source: fine-focus sealed tube | 6163 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
φ and ω scans | θmax = 25.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −19→19 |
Tmin = 0.048, Tmax = 0.277 | k = −18→18 |
35551 measured reflections | l = −20→20 |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0238P)2 + 6.7173P] where P = (Fo2 + 2Fc2)/3 |
6689 reflections | (Δ/σ)max = 0.001 |
397 parameters | Δρmax = 0.85 e Å−3 |
0 restraints | Δρmin = −0.70 e Å−3 |
[Pt2I4(C18H15P)2] | V = 3794.8 (17) Å3 |
Mr = 1422.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.036 (4) Å | µ = 10.73 mm−1 |
b = 15.874 (4) Å | T = 293 K |
c = 16.882 (4) Å | 0.41 × 0.26 × 0.12 mm |
β = 117.980 (4)° |
Bruker SMART APEX CCD area-detector diffractometer | 6689 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6163 reflections with I > 2σ(I) |
Tmin = 0.048, Tmax = 0.277 | Rint = 0.036 |
35551 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.85 e Å−3 |
6689 reflections | Δρmin = −0.70 e Å−3 |
397 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 | ||
C7 | 0.4954 (3) | −0.0138 (3) | 0.1966 (3) | 0.0358 (11) | |
C25 | −0.0345 (3) | −0.3163 (3) | 0.1088 (3) | 0.0401 (11) | |
C13 | 0.5214 (3) | 0.0905 (3) | 0.3493 (3) | 0.0333 (10) | |
C19 | −0.0385 (4) | −0.1714 (3) | 0.2082 (4) | 0.0520 (14) | |
C1 | 0.4272 (3) | 0.1514 (3) | 0.1632 (3) | 0.0356 (11) | |
C2 | 0.3426 (4) | 0.1903 (4) | 0.1075 (4) | 0.0501 (13) | |
H2 | 0.2872 | 0.1737 | 0.1080 | 0.060* | |
C14 | 0.5590 (4) | 0.1701 (3) | 0.3723 (3) | 0.0452 (12) | |
H14 | 0.5408 | 0.2121 | 0.3290 | 0.054* | |
C18 | 0.5461 (4) | 0.0302 (4) | 0.4155 (4) | 0.0522 (14) | |
H18 | 0.5188 | −0.0231 | 0.4011 | 0.063* | |
C6 | 0.5078 (4) | 0.1776 (4) | 0.1598 (4) | 0.0477 (13) | |
H6 | 0.5653 | 0.1518 | 0.1967 | 0.057* | |
C31 | 0.0757 (4) | −0.3099 (4) | 0.3057 (4) | 0.0504 (14) | |
C8 | 0.4557 (4) | −0.0283 (3) | 0.1055 (4) | 0.0494 (13) | |
H8 | 0.4021 | 0.0015 | 0.0664 | 0.059* | |
C26 | −0.0529 (5) | −0.2902 (4) | 0.0234 (4) | 0.0572 (15) | |
H26 | −0.0233 | −0.2425 | 0.0164 | 0.069* | |
C30 | −0.0774 (4) | −0.3872 (3) | 0.1179 (4) | 0.0502 (13) | |
H30 | −0.0658 | −0.4050 | 0.1746 | 0.060* | |
C12 | 0.5733 (4) | −0.0612 (4) | 0.2536 (4) | 0.0609 (16) | |
H12 | 0.6006 | −0.0531 | 0.3153 | 0.073* | |
C3 | 0.3409 (5) | 0.2546 (4) | 0.0508 (4) | 0.0679 (18) | |
H3 | 0.2841 | 0.2811 | 0.0136 | 0.082* | |
C17 | 0.6110 (5) | 0.0485 (4) | 0.5030 (4) | 0.0621 (16) | |
H17 | 0.6282 | 0.0074 | 0.5472 | 0.075* | |
C32 | 0.0074 (5) | −0.3298 (4) | 0.3322 (4) | 0.0621 (17) | |
H32 | −0.0543 | −0.3107 | 0.2984 | 0.075* | |
C36 | 0.1678 (5) | −0.3348 (4) | 0.3594 (4) | 0.0664 (17) | |
H36 | 0.2144 | −0.3207 | 0.3438 | 0.080* | |
C16 | 0.6499 (4) | 0.1270 (4) | 0.5247 (4) | 0.0576 (16) | |
H16 | 0.6939 | 0.1394 | 0.5835 | 0.069* | |
C15 | 0.6239 (4) | 0.1871 (4) | 0.4599 (4) | 0.0586 (16) | |
H15 | 0.6505 | 0.2406 | 0.4751 | 0.070* | |
C5 | 0.5042 (5) | 0.2406 (4) | 0.1032 (4) | 0.0585 (16) | |
H5 | 0.5592 | 0.2572 | 0.1021 | 0.070* | |
C4 | 0.4216 (6) | 0.2795 (4) | 0.0487 (4) | 0.0635 (18) | |
H4 | 0.4198 | 0.3224 | 0.0105 | 0.076* | |
C29 | −0.1384 (4) | −0.4329 (4) | 0.0426 (5) | 0.0671 (18) | |
H29 | −0.1669 | −0.4815 | 0.0492 | 0.081* | |
C9 | 0.4946 (5) | −0.0863 (4) | 0.0720 (5) | 0.0632 (17) | |
H9 | 0.4683 | −0.0945 | 0.0104 | 0.076* | |
C20 | −0.0143 (5) | −0.1257 (4) | 0.2860 (5) | 0.0679 (18) | |
H20 | 0.0429 | −0.1359 | 0.3368 | 0.081* | |
C27 | −0.1150 (5) | −0.3354 (5) | −0.0509 (4) | 0.0715 (19) | |
H27 | −0.1286 | −0.3171 | −0.1080 | 0.086* | |
C28 | −0.1567 (5) | −0.4069 (4) | −0.0409 (4) | 0.0685 (18) | |
H28 | −0.1976 | −0.4377 | −0.0911 | 0.082* | |
C10 | 0.5714 (5) | −0.1317 (4) | 0.1288 (6) | 0.074 (2) | |
H10 | 0.5976 | −0.1711 | 0.1061 | 0.088* | |
C21 | −0.0755 (7) | −0.0649 (4) | 0.2878 (6) | 0.082 (2) | |
H21 | −0.0583 | −0.0334 | 0.3397 | 0.099* | |
C22 | −0.1594 (7) | −0.0509 (5) | 0.2153 (8) | 0.104 (3) | |
H22 | −0.2011 | −0.0115 | 0.2178 | 0.125* | |
C33 | 0.0311 (6) | −0.3775 (5) | 0.4082 (5) | 0.081 (2) | |
H33 | −0.0149 | −0.3922 | 0.4245 | 0.098* | |
C34 | 0.1221 (7) | −0.4031 (5) | 0.4593 (5) | 0.094 (3) | |
H34 | 0.1381 | −0.4359 | 0.5100 | 0.113* | |
C35 | 0.1905 (6) | −0.3803 (6) | 0.4359 (5) | 0.098 (3) | |
H35 | 0.2529 | −0.3960 | 0.4724 | 0.118* | |
C11 | 0.6099 (5) | −0.1195 (5) | 0.2191 (5) | 0.082 (2) | |
H11 | 0.6618 | −0.1514 | 0.2577 | 0.099* | |
C24 | −0.1237 (5) | −0.1534 (4) | 0.1342 (5) | 0.075 (2) | |
H24 | −0.1413 | −0.1817 | 0.0804 | 0.090* | |
C23 | −0.1826 (6) | −0.0936 (6) | 0.1400 (7) | 0.108 (3) | |
H23 | −0.2402 | −0.0826 | 0.0899 | 0.130* | |
Pt1 | 0.303078 (12) | 0.014176 (11) | 0.230490 (12) | 0.03130 (6) | |
Pt2 | 0.167402 (13) | −0.199608 (12) | 0.193463 (14) | 0.03806 (6) | |
I2 | 0.32173 (2) | −0.140087 (19) | 0.19114 (2) | 0.04119 (9) | |
I4 | 0.14558 (2) | −0.04414 (2) | 0.22637 (3) | 0.04403 (9) | |
I1 | 0.27457 (3) | 0.15825 (2) | 0.28661 (3) | 0.05148 (10) | |
I3 | 0.20461 (3) | −0.34792 (2) | 0.15292 (4) | 0.07113 (14) | |
P1 | 0.43647 (8) | 0.06234 (7) | 0.23499 (8) | 0.0307 (2) | |
P2 | 0.04244 (9) | −0.25019 (8) | 0.20388 (9) | 0.0402 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C7 | 0.036 (3) | 0.030 (2) | 0.047 (3) | −0.003 (2) | 0.024 (2) | 0.001 (2) |
C25 | 0.036 (3) | 0.038 (3) | 0.046 (3) | −0.006 (2) | 0.019 (2) | −0.006 (2) |
C13 | 0.025 (2) | 0.040 (3) | 0.035 (2) | 0.0006 (19) | 0.014 (2) | 0.001 (2) |
C19 | 0.052 (3) | 0.041 (3) | 0.077 (4) | −0.015 (3) | 0.042 (3) | −0.013 (3) |
C1 | 0.040 (3) | 0.032 (2) | 0.033 (2) | −0.001 (2) | 0.016 (2) | 0.001 (2) |
C2 | 0.047 (3) | 0.050 (3) | 0.049 (3) | 0.003 (3) | 0.020 (3) | 0.007 (3) |
C14 | 0.047 (3) | 0.044 (3) | 0.040 (3) | −0.006 (2) | 0.017 (2) | 0.002 (2) |
C18 | 0.056 (4) | 0.048 (3) | 0.046 (3) | −0.004 (3) | 0.019 (3) | 0.008 (3) |
C6 | 0.052 (3) | 0.052 (3) | 0.042 (3) | −0.012 (3) | 0.024 (3) | 0.002 (2) |
C31 | 0.053 (3) | 0.048 (3) | 0.049 (3) | −0.020 (3) | 0.023 (3) | −0.009 (3) |
C8 | 0.057 (3) | 0.046 (3) | 0.052 (3) | 0.002 (3) | 0.031 (3) | 0.000 (3) |
C26 | 0.071 (4) | 0.051 (3) | 0.058 (4) | −0.009 (3) | 0.037 (3) | 0.000 (3) |
C30 | 0.052 (3) | 0.044 (3) | 0.054 (3) | −0.012 (3) | 0.024 (3) | −0.003 (3) |
C12 | 0.049 (3) | 0.068 (4) | 0.058 (4) | 0.014 (3) | 0.018 (3) | −0.009 (3) |
C3 | 0.078 (5) | 0.057 (4) | 0.051 (4) | 0.018 (3) | 0.014 (3) | 0.011 (3) |
C17 | 0.062 (4) | 0.073 (4) | 0.044 (3) | 0.010 (3) | 0.019 (3) | 0.016 (3) |
C32 | 0.065 (4) | 0.072 (4) | 0.054 (4) | −0.032 (3) | 0.032 (3) | −0.013 (3) |
C36 | 0.056 (4) | 0.077 (5) | 0.056 (4) | −0.012 (3) | 0.018 (3) | −0.005 (3) |
C16 | 0.044 (3) | 0.085 (5) | 0.036 (3) | 0.000 (3) | 0.012 (3) | −0.006 (3) |
C15 | 0.063 (4) | 0.061 (4) | 0.048 (3) | −0.021 (3) | 0.023 (3) | −0.015 (3) |
C5 | 0.072 (4) | 0.060 (4) | 0.047 (3) | −0.023 (3) | 0.032 (3) | −0.003 (3) |
C4 | 0.105 (6) | 0.043 (3) | 0.046 (3) | −0.015 (4) | 0.039 (4) | 0.001 (3) |
C29 | 0.058 (4) | 0.052 (4) | 0.079 (5) | −0.017 (3) | 0.021 (4) | −0.012 (3) |
C9 | 0.085 (5) | 0.054 (4) | 0.062 (4) | 0.000 (3) | 0.044 (4) | −0.008 (3) |
C20 | 0.078 (5) | 0.060 (4) | 0.091 (5) | −0.024 (3) | 0.061 (4) | −0.019 (4) |
C27 | 0.081 (5) | 0.089 (5) | 0.044 (3) | −0.003 (4) | 0.029 (3) | −0.008 (3) |
C28 | 0.068 (4) | 0.069 (4) | 0.055 (4) | −0.010 (4) | 0.018 (3) | −0.018 (3) |
C10 | 0.077 (5) | 0.060 (4) | 0.106 (6) | 0.009 (4) | 0.061 (5) | −0.015 (4) |
C21 | 0.109 (7) | 0.056 (4) | 0.130 (7) | −0.027 (4) | 0.097 (6) | −0.033 (4) |
C22 | 0.100 (7) | 0.065 (5) | 0.183 (11) | 0.005 (5) | 0.095 (8) | −0.016 (6) |
C33 | 0.114 (7) | 0.080 (5) | 0.059 (4) | −0.052 (5) | 0.049 (5) | −0.023 (4) |
C34 | 0.118 (7) | 0.090 (6) | 0.047 (4) | −0.039 (5) | 0.016 (5) | −0.003 (4) |
C35 | 0.090 (6) | 0.113 (7) | 0.059 (5) | −0.013 (5) | 0.006 (4) | 0.005 (5) |
C11 | 0.073 (5) | 0.080 (5) | 0.083 (5) | 0.038 (4) | 0.029 (4) | −0.006 (4) |
C24 | 0.064 (4) | 0.061 (4) | 0.094 (5) | 0.015 (3) | 0.032 (4) | −0.009 (4) |
C23 | 0.087 (6) | 0.084 (6) | 0.144 (9) | 0.029 (5) | 0.047 (6) | −0.012 (6) |
Pt1 | 0.02656 (10) | 0.02947 (10) | 0.03885 (11) | −0.00243 (7) | 0.01617 (8) | −0.00024 (7) |
Pt2 | 0.03339 (11) | 0.03118 (11) | 0.05433 (13) | −0.00463 (8) | 0.02450 (10) | −0.00138 (8) |
I2 | 0.03562 (18) | 0.03096 (16) | 0.0641 (2) | −0.00209 (13) | 0.02933 (17) | −0.00143 (14) |
I4 | 0.03608 (18) | 0.03389 (17) | 0.0713 (2) | −0.00430 (13) | 0.03281 (17) | −0.00441 (15) |
I1 | 0.0483 (2) | 0.03940 (19) | 0.0768 (3) | −0.00636 (15) | 0.0377 (2) | −0.01506 (17) |
I3 | 0.0653 (3) | 0.0387 (2) | 0.1323 (4) | −0.00821 (18) | 0.0654 (3) | −0.0169 (2) |
P1 | 0.0267 (6) | 0.0299 (6) | 0.0356 (6) | −0.0025 (5) | 0.0147 (5) | 0.0001 (5) |
P2 | 0.0378 (7) | 0.0372 (7) | 0.0510 (8) | −0.0108 (6) | 0.0254 (6) | −0.0056 (6) |
C7—C8 | 1.380 (7) | C36—C35 | 1.372 (10) |
C7—C12 | 1.388 (8) | C36—H36 | 0.9300 |
C7—P1 | 1.829 (5) | C16—C15 | 1.361 (9) |
C25—C30 | 1.365 (7) | C16—H16 | 0.9300 |
C25—C26 | 1.391 (8) | C15—H15 | 0.9300 |
C25—P2 | 1.828 (5) | C5—C4 | 1.355 (9) |
C13—C14 | 1.376 (7) | C5—H5 | 0.9300 |
C13—C18 | 1.381 (7) | C4—H4 | 0.9300 |
C13—P1 | 1.820 (5) | C29—C28 | 1.361 (9) |
C19—C24 | 1.382 (9) | C29—H29 | 0.9300 |
C19—C20 | 1.386 (8) | C9—C10 | 1.359 (9) |
C19—P2 | 1.828 (6) | C9—H9 | 0.9300 |
C1—C2 | 1.382 (7) | C20—C21 | 1.387 (10) |
C1—C6 | 1.383 (7) | C20—H20 | 0.9300 |
C1—P1 | 1.823 (5) | C27—C28 | 1.367 (10) |
C2—C3 | 1.391 (8) | C27—H27 | 0.9300 |
C2—H2 | 0.9300 | C28—H28 | 0.9300 |
C14—C15 | 1.379 (8) | C10—C11 | 1.363 (10) |
C14—H14 | 0.9300 | C10—H10 | 0.9300 |
C18—C17 | 1.382 (8) | C21—C22 | 1.347 (12) |
C18—H18 | 0.9300 | C21—H21 | 0.9300 |
C6—C5 | 1.367 (8) | C22—C23 | 1.329 (13) |
C6—H6 | 0.9300 | C22—H22 | 0.9300 |
C31—C36 | 1.378 (9) | C33—C34 | 1.363 (12) |
C31—C32 | 1.400 (8) | C33—H33 | 0.9300 |
C31—P2 | 1.811 (6) | C34—C35 | 1.376 (12) |
C8—C9 | 1.374 (8) | C34—H34 | 0.9300 |
C8—H8 | 0.9300 | C35—H35 | 0.9300 |
C26—C27 | 1.381 (9) | C11—H11 | 0.9300 |
C26—H26 | 0.9300 | C24—C23 | 1.375 (10) |
C30—C29 | 1.391 (8) | C24—H24 | 0.9300 |
C30—H30 | 0.9300 | C23—H23 | 0.9300 |
C12—C11 | 1.365 (8) | Pt1—P1 | 2.2391 (13) |
C12—H12 | 0.9300 | Pt1—I2 | 2.5910 (7) |
C3—C4 | 1.368 (10) | Pt1—I1 | 2.5967 (7) |
C3—H3 | 0.9300 | Pt1—I4 | 2.6600 (7) |
C17—C16 | 1.364 (9) | Pt2—P2 | 2.2409 (13) |
C17—H17 | 0.9300 | Pt2—I4 | 2.5892 (7) |
C32—C33 | 1.382 (9) | Pt2—I3 | 2.5981 (7) |
C32—H32 | 0.9300 | Pt2—I2 | 2.6664 (7) |
C8—C7—C12 | 118.5 (5) | C28—C29—H29 | 119.8 |
C8—C7—P1 | 117.4 (4) | C30—C29—H29 | 119.8 |
C12—C7—P1 | 124.0 (4) | C10—C9—C8 | 120.1 (6) |
C30—C25—C26 | 119.2 (5) | C10—C9—H9 | 119.9 |
C30—C25—P2 | 122.9 (4) | C8—C9—H9 | 119.9 |
C26—C25—P2 | 117.8 (4) | C19—C20—C21 | 119.9 (8) |
C14—C13—C18 | 119.2 (5) | C19—C20—H20 | 120.0 |
C14—C13—P1 | 122.4 (4) | C21—C20—H20 | 120.0 |
C18—C13—P1 | 118.4 (4) | C28—C27—C26 | 120.3 (6) |
C24—C19—C20 | 117.8 (6) | C28—C27—H27 | 119.8 |
C24—C19—P2 | 121.7 (5) | C26—C27—H27 | 119.8 |
C20—C19—P2 | 120.5 (5) | C29—C28—C27 | 119.9 (6) |
C2—C1—C6 | 118.5 (5) | C29—C28—H28 | 120.0 |
C2—C1—P1 | 123.1 (4) | C27—C28—H28 | 120.0 |
C6—C1—P1 | 118.3 (4) | C9—C10—C11 | 119.9 (6) |
C1—C2—C3 | 119.4 (6) | C9—C10—H10 | 120.1 |
C1—C2—H2 | 120.3 | C11—C10—H10 | 120.1 |
C3—C2—H2 | 120.3 | C22—C21—C20 | 120.6 (8) |
C13—C14—C15 | 119.6 (5) | C22—C21—H21 | 119.7 |
C13—C14—H14 | 120.2 | C20—C21—H21 | 119.7 |
C15—C14—H14 | 120.2 | C23—C22—C21 | 119.8 (8) |
C13—C18—C17 | 120.3 (6) | C23—C22—H22 | 120.1 |
C13—C18—H18 | 119.8 | C21—C22—H22 | 120.1 |
C17—C18—H18 | 119.8 | C34—C33—C32 | 119.8 (7) |
C5—C6—C1 | 120.9 (6) | C34—C33—H33 | 120.1 |
C5—C6—H6 | 119.5 | C32—C33—H33 | 120.1 |
C1—C6—H6 | 119.5 | C33—C34—C35 | 120.1 (8) |
C36—C31—C32 | 118.9 (6) | C33—C34—H34 | 120.0 |
C36—C31—P2 | 121.4 (5) | C35—C34—H34 | 120.0 |
C32—C31—P2 | 119.6 (5) | C36—C35—C34 | 120.9 (8) |
C9—C8—C7 | 120.6 (6) | C36—C35—H35 | 119.6 |
C9—C8—H8 | 119.7 | C34—C35—H35 | 119.6 |
C7—C8—H8 | 119.7 | C10—C11—C12 | 120.9 (6) |
C27—C26—C25 | 119.9 (6) | C10—C11—H11 | 119.5 |
C27—C26—H26 | 120.1 | C12—C11—H11 | 119.5 |
C25—C26—H26 | 120.1 | C23—C24—C19 | 119.9 (8) |
C25—C30—C29 | 120.2 (6) | C23—C24—H24 | 120.0 |
C25—C30—H30 | 119.9 | C19—C24—H24 | 120.0 |
C29—C30—H30 | 119.9 | C22—C23—C24 | 121.8 (9) |
C11—C12—C7 | 120.0 (6) | C22—C23—H23 | 119.1 |
C11—C12—H12 | 120.0 | C24—C23—H23 | 119.1 |
C7—C12—H12 | 120.0 | P1—Pt1—I2 | 96.20 (3) |
C4—C3—C2 | 121.1 (6) | P1—Pt1—I1 | 90.90 (3) |
C4—C3—H3 | 119.5 | I2—Pt1—I1 | 170.796 (13) |
C2—C3—H3 | 119.5 | P1—Pt1—I4 | 179.44 (3) |
C16—C17—C18 | 120.0 (6) | I2—Pt1—I4 | 83.500 (15) |
C16—C17—H17 | 120.0 | I1—Pt1—I4 | 89.342 (17) |
C18—C17—H17 | 120.0 | P2—Pt2—I4 | 96.25 (4) |
C33—C32—C31 | 120.3 (7) | P2—Pt2—I3 | 91.16 (4) |
C33—C32—H32 | 119.9 | I4—Pt2—I3 | 172.337 (14) |
C31—C32—H32 | 119.9 | P2—Pt2—I2 | 176.76 (4) |
C35—C36—C31 | 119.9 (7) | I4—Pt2—I2 | 83.410 (15) |
C35—C36—H36 | 120.0 | I3—Pt2—I2 | 89.298 (18) |
C31—C36—H36 | 120.0 | Pt1—I2—Pt2 | 96.405 (15) |
C15—C16—C17 | 119.7 (5) | Pt2—I4—Pt1 | 96.605 (16) |
C15—C16—H16 | 120.2 | C13—P1—C1 | 107.6 (2) |
C17—C16—H16 | 120.2 | C13—P1—C7 | 106.5 (2) |
C16—C15—C14 | 121.2 (6) | C1—P1—C7 | 99.8 (2) |
C16—C15—H15 | 119.4 | C13—P1—Pt1 | 110.34 (15) |
C14—C15—H15 | 119.4 | C1—P1—Pt1 | 117.65 (16) |
C4—C5—C6 | 121.0 (6) | C7—P1—Pt1 | 113.98 (15) |
C4—C5—H5 | 119.5 | C31—P2—C25 | 108.1 (2) |
C6—C5—H5 | 119.5 | C31—P2—C19 | 102.6 (3) |
C5—C4—C3 | 119.1 (6) | C25—P2—C19 | 103.2 (3) |
C5—C4—H4 | 120.5 | C31—P2—Pt2 | 112.71 (19) |
C3—C4—H4 | 120.5 | C25—P2—Pt2 | 113.36 (17) |
C28—C29—C30 | 120.3 (6) | C19—P2—Pt2 | 115.85 (17) |
C6—C1—C2—C3 | −0.6 (8) | P2—Pt2—I4—Pt1 | 174.64 (4) |
P1—C1—C2—C3 | −176.1 (4) | I2—Pt2—I4—Pt1 | −2.114 (12) |
C18—C13—C14—C15 | 3.1 (8) | I2—Pt1—I4—Pt2 | 2.176 (13) |
P1—C13—C14—C15 | −179.3 (4) | I1—Pt1—I4—Pt2 | −172.027 (14) |
C14—C13—C18—C17 | −2.9 (8) | C14—C13—P1—C1 | 7.3 (5) |
P1—C13—C18—C17 | 179.4 (5) | C18—C13—P1—C1 | −175.1 (4) |
C2—C1—C6—C5 | 0.3 (8) | C14—C13—P1—C7 | 113.6 (4) |
P1—C1—C6—C5 | 176.0 (4) | C18—C13—P1—C7 | −68.8 (4) |
C12—C7—C8—C9 | −2.2 (8) | C14—C13—P1—Pt1 | −122.3 (4) |
P1—C7—C8—C9 | −178.2 (5) | C18—C13—P1—Pt1 | 55.4 (4) |
C30—C25—C26—C27 | 0.9 (9) | C2—C1—P1—C13 | −124.7 (4) |
P2—C25—C26—C27 | −176.1 (5) | C6—C1—P1—C13 | 59.8 (4) |
C26—C25—C30—C29 | 0.3 (9) | C2—C1—P1—C7 | 124.4 (5) |
P2—C25—C30—C29 | 177.2 (5) | C6—C1—P1—C7 | −51.1 (4) |
C8—C7—C12—C11 | 1.1 (9) | C2—C1—P1—Pt1 | 0.6 (5) |
P1—C7—C12—C11 | 176.8 (6) | C6—C1—P1—Pt1 | −174.9 (3) |
C1—C2—C3—C4 | 0.5 (9) | C8—C7—P1—C13 | −163.5 (4) |
C13—C18—C17—C16 | 1.1 (9) | C12—C7—P1—C13 | 20.7 (5) |
C36—C31—C32—C33 | −3.6 (9) | C8—C7—P1—C1 | −51.8 (4) |
P2—C31—C32—C33 | 178.0 (5) | C12—C7—P1—C1 | 132.5 (5) |
C32—C31—C36—C35 | 1.9 (10) | C8—C7—P1—Pt1 | 74.6 (4) |
P2—C31—C36—C35 | −179.7 (6) | C12—C7—P1—Pt1 | −101.2 (5) |
C18—C17—C16—C15 | 0.4 (10) | I2—Pt1—P1—C13 | −111.86 (17) |
C17—C16—C15—C14 | −0.2 (10) | I1—Pt1—P1—C13 | 62.29 (17) |
C13—C14—C15—C16 | −1.6 (9) | I2—Pt1—P1—C1 | 124.25 (18) |
C1—C6—C5—C4 | 0.0 (9) | I1—Pt1—P1—C1 | −61.61 (18) |
C6—C5—C4—C3 | −0.1 (9) | I2—Pt1—P1—C7 | 7.88 (18) |
C2—C3—C4—C5 | −0.1 (9) | I1—Pt1—P1—C7 | −177.97 (18) |
C25—C30—C29—C28 | −0.7 (10) | C36—C31—P2—C25 | 113.6 (5) |
C7—C8—C9—C10 | 1.8 (9) | C32—C31—P2—C25 | −68.0 (5) |
C24—C19—C20—C21 | 0.7 (9) | C36—C31—P2—C19 | −137.8 (5) |
P2—C19—C20—C21 | 178.6 (5) | C32—C31—P2—C19 | 40.6 (5) |
C25—C26—C27—C28 | −1.7 (10) | C36—C31—P2—Pt2 | −12.5 (6) |
C30—C29—C28—C27 | −0.1 (11) | C32—C31—P2—Pt2 | 165.9 (4) |
C26—C27—C28—C29 | 1.3 (11) | C30—C25—P2—C31 | 16.1 (5) |
C8—C9—C10—C11 | −0.1 (11) | C26—C25—P2—C31 | −167.0 (4) |
C19—C20—C21—C22 | 1.5 (10) | C30—C25—P2—C19 | −92.1 (5) |
C20—C21—C22—C23 | −2.5 (13) | C26—C25—P2—C19 | 84.8 (5) |
C31—C32—C33—C34 | 2.2 (10) | C30—C25—P2—Pt2 | 141.8 (4) |
C32—C33—C34—C35 | 0.9 (12) | C26—C25—P2—Pt2 | −41.3 (5) |
C31—C36—C35—C34 | 1.2 (12) | C24—C19—P2—C31 | −134.2 (5) |
C33—C34—C35—C36 | −2.6 (13) | C20—C19—P2—C31 | 48.0 (5) |
C9—C10—C11—C12 | −1.0 (12) | C24—C19—P2—C25 | −21.9 (6) |
C7—C12—C11—C10 | 0.5 (12) | C20—C19—P2—C25 | 160.3 (5) |
C20—C19—C24—C23 | −1.9 (11) | C24—C19—P2—Pt2 | 102.6 (5) |
P2—C19—C24—C23 | −179.8 (7) | C20—C19—P2—Pt2 | −75.2 (5) |
C21—C22—C23—C24 | 1.3 (15) | I4—Pt2—P2—C31 | −106.6 (2) |
C19—C24—C23—C22 | 1.0 (14) | I3—Pt2—P2—C31 | 75.3 (2) |
P1—Pt1—I2—Pt2 | 177.41 (3) | I4—Pt2—P2—C25 | 130.19 (19) |
I4—Pt1—I2—Pt2 | −2.112 (12) | I3—Pt2—P2—C25 | −47.87 (19) |
I4—Pt2—I2—Pt1 | 2.170 (13) | I4—Pt2—P2—C19 | 11.1 (2) |
I3—Pt2—I2—Pt1 | 179.809 (16) | I3—Pt2—P2—C19 | −166.9 (2) |
Experimental details
Crystal data | |
Chemical formula | [Pt2I4(C18H15P)2] |
Mr | 1422.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.036 (4), 15.874 (4), 16.882 (4) |
β (°) | 117.980 (4) |
V (Å3) | 3794.8 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.73 |
Crystal size (mm) | 0.41 × 0.26 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.048, 0.277 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 35551, 6689, 6163 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.059, 1.09 |
No. of reflections | 6689 |
No. of parameters | 397 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −0.70 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
Pt1—P1 | 2.2391 (13) | Pt2—P2 | 2.2409 (13) |
Pt1—I2 | 2.5910 (7) | Pt2—I4 | 2.5892 (7) |
Pt1—I1 | 2.5967 (7) | Pt2—I3 | 2.5981 (7) |
Pt1—I4 | 2.6600 (7) | Pt2—I2 | 2.6664 (7) |
P1—Pt1—I2 | 96.20 (3) | P2—Pt2—I4 | 96.25 (4) |
P1—Pt1—I1 | 90.90 (3) | P2—Pt2—I3 | 91.16 (4) |
I2—Pt1—I4 | 83.500 (15) | I4—Pt2—I2 | 83.410 (15) |
I1—Pt1—I4 | 89.342 (17) | I3—Pt2—I2 | 89.298 (18) |
The dimeric halogen bridged complexes of platinum(II) are very important in synthetic organometallic chemistry (Chatt, 1951 & Chatt and Venanzi, 1955). The main application of the halide bridged complexes is in reactions in which the bridged is cleaved to give monomeric complexes (Chatt and Venanzi, 1957 & Chatt et al., 1964). Recently cytotoxicity of some dimeric iodo bridged platinum(II) complexes has been established (Jinchao et al., 2006). Against this background we report here the crystal structure of (I).
The molecular structure of the title compound, (I), is shown in Fig. 1, with the atom numbering scheme. The packing arrangement of (I) is shown in Fig. 2. The platinum atom is tetracoordinated with a donor set of one triphenylphosphine P atom and three I atoms in an approximately squareplanar geometry. One of the three iodine atoms is a terminal I, and the other two are bridging I for each platinum atom. Selected bond lengths and bond angles are listed in Table 1. The Pt—I bond lengthes trans to the triphenylphosphine moieties are longer and this is supposed to be due to the trans-influence of the P atom of the triphenylphosphine moiety. On the other hand Pt—P distances are quite close to the reported values (Black et al., 1969) indicating absence of definite correlation between Pt—P distances and the trans influence of the ligand in the trans position. This, in turn, is indicative of the fact that Pt(II)—P bonds are not simple sigma bonds, but are more complex and therefore affected by the trans ligands in a more complex way than Pt(II)—I bonds.