Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015428/ac6013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015428/ac6013Isup2.hkl |
CCDC reference: 198290
Re(CO)3(DAAD)2Br (115 mg, 0.15 mmol) and cis-[Pt(CF3SO3)2(dppp)] (135 mg, 0.15 mmol) were dissolved in dichloromethane (30 ml). The solution was stirred for 20 h at ambient temperature. The orange precipitate was filtered off and washed with dichloromethane, hexane, diethyl ether and ethyl acetate. Crystallization was achieved in d6-DMSO over a period of months at ambient temperature.
The final difference Fourier map revealed large residual density peaks around the Pt atom. Inspection of the absorption correction data showed a significant decrease in Rint (from 0.0972 to 0.0331) following the correction. It is possible, however, that selection of a smaller crystal and/or application of numerical absorption corrections may have resulted in better residual density values. All H atoms were included in calculated positions using a riding model, with Csp2—H and Csp3—H bond distances of 0.95 and 0.99 Å, respectively, and Uiso values equal to 1.2Ueq of the carrying C atoms.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) and TITAN2000 (Hunter & Simpson, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and TITAN2000); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. Perspective drawing of the title molecule, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as circles with arbitrary radii. |
[PtBr2(C27H26P2)] | Z = 2 |
Mr = 767.33 | F(000) = 732 |
Triclinic, P1 | Dx = 1.994 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.709 (2) Å | Cell parameters from 5652 reflections |
b = 10.760 (3) Å | θ = 4.9–52.7° |
c = 14.429 (4) Å | µ = 8.76 mm−1 |
α = 88.272 (3)° | T = 168 K |
β = 80.296 (4)° | Block, pale brown |
γ = 73.540 (3)° | 0.51 × 0.33 × 0.30 mm |
V = 1278.0 (6) Å3 |
Siemens SMART diffractometer | 5118 independent reflections |
Radiation source: fine-focus sealed tube | 4792 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Area–detector ω scans | θmax = 26.4°, θmin = 2.4° |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker 1997) | h = −10→10 |
Tmin = 0.641, Tmax = 1 | k = −10→13 |
15666 measured reflections | l = −17→17 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.23 | w = 1/[σ2(Fo2) + (0.0571P)2 + 9.6036P] where P = (Fo2 + 2Fc2)/3 |
5118 reflections | (Δ/σ)max = 0.007 |
289 parameters | Δρmax = 2.38 e Å−3 |
36 restraints | Δρmin = −4.26 e Å−3 |
[PtBr2(C27H26P2)] | γ = 73.540 (3)° |
Mr = 767.33 | V = 1278.0 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.709 (2) Å | Mo Kα radiation |
b = 10.760 (3) Å | µ = 8.76 mm−1 |
c = 14.429 (4) Å | T = 168 K |
α = 88.272 (3)° | 0.51 × 0.33 × 0.30 mm |
β = 80.296 (4)° |
Siemens SMART diffractometer | 5118 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker 1997) | 4792 reflections with I > 2σ(I) |
Tmin = 0.641, Tmax = 1 | Rint = 0.036 |
15666 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 36 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.23 | Δρmax = 2.38 e Å−3 |
5118 reflections | Δρmin = −4.26 e Å−3 |
289 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 | ||
Br1 | −0.04852 (10) | 0.17292 (8) | 0.77096 (6) | 0.02293 (19) | |
Br2 | −0.16107 (10) | 0.50253 (8) | 0.72957 (7) | 0.0302 (2) | |
Pt1 | 0.10137 (3) | 0.34041 (2) | 0.743254 (18) | 0.01006 (10) | |
P1 | 0.3214 (2) | 0.19242 (18) | 0.77836 (14) | 0.0137 (4) | |
C1 | 0.5077 (10) | 0.2460 (8) | 0.7658 (6) | 0.0237 (18) | |
H1A | 0.4923 | 0.3154 | 0.8129 | 0.028* | |
H1B | 0.5996 | 0.1724 | 0.7782 | 0.028* | |
C2 | 0.5481 (10) | 0.2965 (8) | 0.6671 (7) | 0.0280 (19) | |
H2A | 0.5389 | 0.2338 | 0.6210 | 0.034* | |
H2B | 0.6630 | 0.2977 | 0.6570 | 0.034* | |
C3 | 0.4433 (10) | 0.4323 (8) | 0.6450 (6) | 0.0223 (17) | |
H3A | 0.4326 | 0.4329 | 0.5778 | 0.027* | |
H3B | 0.5028 | 0.4958 | 0.6538 | 0.027* | |
C4 | 0.3920 (10) | 0.0441 (8) | 0.7085 (6) | 0.0231 (17) | |
C5 | 0.3284 (10) | 0.0323 (8) | 0.6265 (6) | 0.0248 (18) | |
H5 | 0.2437 | 0.1013 | 0.6087 | 0.030* | |
C6 | 0.3905 (13) | −0.0814 (11) | 0.5715 (8) | 0.042 (3) | |
H6 | 0.3461 | −0.0899 | 0.5170 | 0.050* | |
C7 | 0.5141 (14) | −0.1800 (10) | 0.5953 (8) | 0.042 (3) | |
H7 | 0.5553 | −0.2569 | 0.5576 | 0.051* | |
C8 | 0.5791 (14) | −0.1682 (9) | 0.6740 (9) | 0.047 (3) | |
H8 | 0.6665 | −0.2368 | 0.6893 | 0.057* | |
C9 | 0.5196 (12) | −0.0578 (9) | 0.7314 (7) | 0.035 (2) | |
H9 | 0.5653 | −0.0516 | 0.7858 | 0.042* | |
C10 | 0.2856 (9) | 0.1458 (7) | 0.9005 (5) | 0.0166 (15) | |
C11 | 0.2369 (11) | 0.0340 (9) | 0.9257 (6) | 0.0273 (19) | |
H11 | 0.2314 | −0.0232 | 0.8783 | 0.033* | |
C12 | 0.1966 (13) | 0.0068 (10) | 1.0201 (7) | 0.035 (2) | |
H12 | 0.1644 | −0.0693 | 1.0368 | 0.042* | |
C13 | 0.2029 (12) | 0.0891 (10) | 1.0893 (7) | 0.035 (2) | |
H13 | 0.1735 | 0.0704 | 1.1535 | 0.042* | |
C14 | 0.2515 (13) | 0.1983 (11) | 1.0664 (7) | 0.039 (2) | |
H14 | 0.2570 | 0.2542 | 1.1146 | 0.047* | |
C15 | 0.2934 (12) | 0.2274 (10) | 0.9711 (6) | 0.032 (2) | |
H15 | 0.3271 | 0.3031 | 0.9553 | 0.038* | |
P2 | 0.2371 (2) | 0.48954 (18) | 0.71495 (14) | 0.0145 (4) | |
C16 | 0.2601 (11) | 0.5585 (9) | 0.8246 (6) | 0.0257 (15) | |
C17 | 0.1330 (12) | 0.5758 (11) | 0.9011 (7) | 0.0352 (16) | |
H17 | 0.0365 | 0.5547 | 0.8946 | 0.042* | |
C18 | 0.1480 (13) | 0.6237 (11) | 0.9868 (7) | 0.0406 (18) | |
H18 | 0.0610 | 0.6354 | 1.0382 | 0.049* | |
C19 | 0.2844 (13) | 0.6536 (12) | 0.9976 (8) | 0.0435 (18) | |
H19 | 0.2927 | 0.6883 | 1.0558 | 0.052* | |
C20 | 0.4125 (14) | 0.6331 (13) | 0.9228 (8) | 0.0499 (19) | |
H20 | 0.5112 | 0.6495 | 0.9306 | 0.060* | |
C21 | 0.3971 (13) | 0.5889 (12) | 0.8372 (8) | 0.0424 (18) | |
H21 | 0.4837 | 0.5795 | 0.7858 | 0.051* | |
C22 | 0.1452 (10) | 0.6275 (8) | 0.6461 (6) | 0.0196 (16) | |
C23 | 0.0915 (11) | 0.7521 (8) | 0.6832 (6) | 0.0241 (17) | |
H23 | 0.1050 | 0.7685 | 0.7452 | 0.029* | |
C24 | 0.0167 (12) | 0.8544 (8) | 0.6284 (7) | 0.031 (2) | |
H24 | −0.0202 | 0.9404 | 0.6534 | 0.037* | |
C25 | −0.0031 (12) | 0.8303 (9) | 0.5388 (7) | 0.032 (2) | |
H25 | −0.0536 | 0.9000 | 0.5022 | 0.038* | |
C26 | 0.0495 (12) | 0.7060 (9) | 0.5014 (6) | 0.031 (2) | |
H26 | 0.0348 | 0.6899 | 0.4396 | 0.038* | |
C27 | 0.1240 (12) | 0.6048 (9) | 0.5551 (6) | 0.0272 (19) | |
H27 | 0.1610 | 0.5191 | 0.5295 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0207 (4) | 0.0228 (4) | 0.0287 (4) | −0.0120 (3) | −0.0043 (3) | 0.0052 (3) |
Br2 | 0.0167 (4) | 0.0233 (4) | 0.0484 (6) | −0.0015 (3) | −0.0070 (4) | 0.0037 (4) |
Pt1 | 0.00866 (15) | 0.01236 (15) | 0.01000 (15) | −0.00438 (10) | −0.00185 (10) | 0.00229 (10) |
P1 | 0.0088 (8) | 0.0150 (9) | 0.0162 (9) | −0.0017 (7) | −0.0022 (7) | 0.0039 (7) |
C1 | 0.013 (4) | 0.030 (4) | 0.031 (5) | −0.009 (3) | −0.007 (3) | 0.006 (4) |
C2 | 0.018 (4) | 0.027 (4) | 0.034 (5) | −0.004 (3) | 0.005 (4) | 0.003 (4) |
C3 | 0.021 (4) | 0.029 (4) | 0.017 (4) | −0.009 (3) | −0.001 (3) | 0.003 (3) |
C4 | 0.027 (4) | 0.018 (4) | 0.020 (4) | −0.005 (3) | 0.006 (3) | 0.003 (3) |
C5 | 0.019 (4) | 0.028 (4) | 0.026 (4) | −0.004 (3) | 0.000 (3) | −0.008 (4) |
C6 | 0.035 (6) | 0.046 (6) | 0.040 (6) | −0.010 (5) | 0.003 (5) | −0.024 (5) |
C7 | 0.051 (7) | 0.028 (5) | 0.042 (6) | −0.010 (5) | 0.008 (5) | −0.012 (4) |
C8 | 0.044 (6) | 0.018 (4) | 0.064 (8) | 0.008 (4) | 0.004 (6) | 0.011 (5) |
C9 | 0.032 (5) | 0.032 (5) | 0.034 (5) | 0.005 (4) | −0.009 (4) | 0.005 (4) |
C10 | 0.016 (4) | 0.019 (4) | 0.014 (4) | −0.002 (3) | −0.008 (3) | 0.006 (3) |
C11 | 0.029 (5) | 0.027 (4) | 0.028 (5) | −0.012 (4) | −0.006 (4) | 0.003 (4) |
C12 | 0.041 (6) | 0.040 (5) | 0.026 (5) | −0.017 (4) | −0.008 (4) | 0.019 (4) |
C13 | 0.034 (5) | 0.050 (6) | 0.022 (5) | −0.013 (4) | −0.009 (4) | 0.016 (4) |
C14 | 0.045 (6) | 0.058 (6) | 0.016 (4) | −0.017 (5) | −0.004 (4) | −0.001 (4) |
C15 | 0.041 (5) | 0.042 (5) | 0.020 (4) | −0.024 (4) | −0.008 (4) | 0.005 (4) |
P2 | 0.0167 (9) | 0.0142 (9) | 0.0147 (9) | −0.0085 (7) | −0.0018 (7) | 0.0026 (7) |
C16 | 0.024 (3) | 0.044 (4) | 0.018 (3) | −0.022 (3) | −0.002 (3) | −0.005 (3) |
C17 | 0.029 (3) | 0.056 (4) | 0.026 (3) | −0.024 (3) | 0.001 (3) | −0.008 (3) |
C18 | 0.037 (3) | 0.061 (4) | 0.028 (3) | −0.022 (3) | 0.002 (3) | −0.010 (3) |
C19 | 0.040 (4) | 0.066 (4) | 0.030 (3) | −0.020 (3) | −0.007 (3) | −0.016 (3) |
C20 | 0.039 (4) | 0.077 (4) | 0.041 (4) | −0.027 (3) | −0.004 (3) | −0.018 (4) |
C21 | 0.032 (3) | 0.067 (4) | 0.035 (4) | −0.027 (3) | 0.001 (3) | −0.013 (3) |
C22 | 0.022 (4) | 0.023 (4) | 0.018 (4) | −0.012 (3) | −0.003 (3) | 0.007 (3) |
C23 | 0.032 (5) | 0.021 (4) | 0.022 (4) | −0.008 (3) | −0.012 (4) | 0.003 (3) |
C24 | 0.044 (5) | 0.017 (4) | 0.033 (5) | −0.009 (4) | −0.015 (4) | 0.007 (4) |
C25 | 0.037 (5) | 0.029 (5) | 0.036 (5) | −0.015 (4) | −0.021 (4) | 0.020 (4) |
C26 | 0.045 (6) | 0.037 (5) | 0.020 (4) | −0.020 (4) | −0.016 (4) | 0.012 (4) |
C27 | 0.038 (5) | 0.027 (4) | 0.019 (4) | −0.012 (4) | −0.008 (4) | 0.004 (3) |
Br1—Pt1 | 2.4951 (9) | C12—C13 | 1.373 (15) |
Br2—Pt1 | 2.4855 (10) | C12—H12 | 0.9500 |
Pt1—P2 | 2.2384 (19) | C13—C14 | 1.370 (15) |
Pt1—P1 | 2.2394 (19) | C13—H13 | 0.9500 |
P1—C4 | 1.809 (8) | C14—C15 | 1.411 (13) |
P1—C10 | 1.818 (8) | C14—H14 | 0.9500 |
P1—C1 | 1.850 (8) | C15—H15 | 0.9500 |
C1—C2 | 1.530 (12) | P2—C22 | 1.827 (8) |
C1—H1A | 0.9900 | P2—C16 | 1.832 (8) |
C1—H1B | 0.9900 | C16—C21 | 1.364 (13) |
C2—C3 | 1.544 (12) | C16—C17 | 1.401 (12) |
C2—H2A | 0.9900 | C17—C18 | 1.393 (14) |
C2—H2B | 0.9900 | C17—H17 | 0.9500 |
C3—P2 | 1.850 (8) | C18—C19 | 1.351 (15) |
C3—H3A | 0.9900 | C18—H18 | 0.9500 |
C3—H3B | 0.9900 | C19—C20 | 1.389 (15) |
C4—C9 | 1.400 (12) | C19—H19 | 0.9500 |
C4—C5 | 1.412 (12) | C20—C21 | 1.377 (15) |
C5—C6 | 1.399 (12) | C20—H20 | 0.9500 |
C5—H5 | 0.9500 | C21—H21 | 0.9500 |
C6—C7 | 1.363 (16) | C22—C23 | 1.381 (12) |
C6—H6 | 0.9500 | C22—C27 | 1.394 (12) |
C7—C8 | 1.376 (17) | C23—C24 | 1.406 (12) |
C7—H7 | 0.9500 | C23—H23 | 0.9500 |
C8—C9 | 1.390 (15) | C24—C25 | 1.375 (13) |
C8—H8 | 0.9500 | C24—H24 | 0.9500 |
C9—H9 | 0.9500 | C25—C26 | 1.379 (14) |
C10—C15 | 1.387 (12) | C25—H25 | 0.9500 |
C10—C11 | 1.403 (11) | C26—C27 | 1.387 (12) |
C11—C12 | 1.392 (13) | C26—H26 | 0.9500 |
C11—H11 | 0.9500 | C27—H27 | 0.9500 |
P2—Pt1—P1 | 91.67 (7) | C13—C12—C11 | 120.5 (9) |
P2—Pt1—Br2 | 91.95 (6) | C13—C12—H12 | 119.8 |
P1—Pt1—Br2 | 171.34 (5) | C11—C12—H12 | 119.8 |
P2—Pt1—Br1 | 178.72 (5) | C14—C13—C12 | 120.4 (9) |
P1—Pt1—Br1 | 88.45 (6) | C14—C13—H13 | 119.8 |
Br2—Pt1—Br1 | 88.12 (4) | C12—C13—H13 | 119.8 |
C4—P1—C10 | 106.7 (4) | C13—C14—C15 | 120.0 (9) |
C4—P1—C1 | 101.7 (4) | C13—C14—H14 | 120.0 |
C10—P1—C1 | 105.0 (4) | C15—C14—H14 | 120.0 |
C4—P1—Pt1 | 116.6 (3) | C10—C15—C14 | 120.2 (9) |
C10—P1—Pt1 | 110.3 (2) | C10—C15—H15 | 119.9 |
C1—P1—Pt1 | 115.4 (3) | C14—C15—H15 | 119.9 |
C2—C1—P1 | 111.1 (6) | C22—P2—C16 | 105.9 (4) |
C2—C1—H1A | 109.4 | C22—P2—C3 | 101.0 (4) |
P1—C1—H1A | 109.4 | C16—P2—C3 | 106.4 (4) |
C2—C1—H1B | 109.4 | C22—P2—Pt1 | 115.6 (3) |
P1—C1—H1B | 109.4 | C16—P2—Pt1 | 111.3 (3) |
H1A—C1—H1B | 108.0 | C3—P2—Pt1 | 115.6 (3) |
C1—C2—C3 | 116.8 (7) | C21—C16—C17 | 118.0 (8) |
C1—C2—H2A | 108.1 | C21—C16—P2 | 123.6 (7) |
C3—C2—H2A | 108.1 | C17—C16—P2 | 118.3 (6) |
C1—C2—H2B | 108.1 | C18—C17—C16 | 120.1 (9) |
C3—C2—H2B | 108.1 | C18—C17—H17 | 119.9 |
H2A—C2—H2B | 107.3 | C16—C17—H17 | 119.9 |
C2—C3—P2 | 117.0 (6) | C19—C18—C17 | 120.9 (10) |
C2—C3—H3A | 108.1 | C19—C18—H18 | 119.5 |
P2—C3—H3A | 108.1 | C17—C18—H18 | 119.5 |
C2—C3—H3B | 108.1 | C18—C19—C20 | 119.2 (10) |
P2—C3—H3B | 108.1 | C18—C19—H19 | 120.4 |
H3A—C3—H3B | 107.3 | C20—C19—H19 | 120.4 |
C9—C4—C5 | 118.7 (8) | C21—C20—C19 | 120.3 (10) |
C9—C4—P1 | 120.1 (7) | C21—C20—H20 | 119.9 |
C5—C4—P1 | 121.0 (6) | C19—C20—H20 | 119.9 |
C6—C5—C4 | 119.8 (9) | C16—C21—C20 | 121.5 (10) |
C6—C5—H5 | 120.1 | C16—C21—H21 | 119.3 |
C4—C5—H5 | 120.1 | C20—C21—H21 | 119.3 |
C7—C6—C5 | 120.6 (10) | C23—C22—C27 | 119.7 (8) |
C7—C6—H6 | 119.7 | C23—C22—P2 | 121.6 (6) |
C5—C6—H6 | 119.7 | C27—C22—P2 | 118.7 (6) |
C6—C7—C8 | 120.0 (9) | C22—C23—C24 | 119.4 (8) |
C6—C7—H7 | 120.0 | C22—C23—H23 | 120.3 |
C8—C7—H7 | 120.0 | C24—C23—H23 | 120.3 |
C7—C8—C9 | 121.3 (10) | C25—C24—C23 | 120.2 (8) |
C7—C8—H8 | 119.3 | C25—C24—H24 | 119.9 |
C9—C8—H8 | 119.3 | C23—C24—H24 | 119.9 |
C8—C9—C4 | 119.5 (10) | C24—C25—C26 | 120.7 (8) |
C8—C9—H9 | 120.2 | C24—C25—H25 | 119.6 |
C4—C9—H9 | 120.2 | C26—C25—H25 | 119.6 |
C15—C10—C11 | 118.8 (8) | C25—C26—C27 | 119.3 (8) |
C15—C10—P1 | 119.5 (6) | C25—C26—H26 | 120.3 |
C11—C10—P1 | 121.4 (6) | C27—C26—H26 | 120.3 |
C12—C11—C10 | 120.1 (8) | C26—C27—C22 | 120.7 (8) |
C12—C11—H11 | 119.9 | C26—C27—H27 | 119.6 |
C10—C11—H11 | 119.9 | C22—C27—H27 | 119.6 |
P2—Pt1—P1—C4 | −121.6 (3) | C13—C14—C15—C10 | 0.0 (16) |
Br1—Pt1—P1—C4 | 57.1 (3) | C2—C3—P2—C22 | −166.0 (7) |
P2—Pt1—P1—C10 | 116.4 (3) | C2—C3—P2—C16 | 83.7 (7) |
Br1—Pt1—P1—C10 | −64.8 (3) | C2—C3—P2—Pt1 | −40.5 (7) |
P2—Pt1—P1—C1 | −2.3 (3) | P1—Pt1—P2—C22 | 161.7 (3) |
Br1—Pt1—P1—C1 | 176.4 (3) | P1—Pt1—P2—C16 | −77.5 (3) |
C4—P1—C1—C2 | 72.3 (7) | Br2—Pt1—P2—C16 | 94.6 (3) |
C10—P1—C1—C2 | −176.5 (6) | P1—Pt1—P2—C3 | 44.0 (3) |
Pt1—P1—C1—C2 | −54.9 (7) | Br2—Pt1—P2—C3 | −143.9 (3) |
P1—C1—C2—C3 | 75.5 (9) | C22—P2—C16—C21 | −92.0 (10) |
C1—C2—C3—P2 | −24.7 (10) | C3—P2—C16—C21 | 14.8 (11) |
C10—P1—C4—C9 | −50.5 (8) | Pt1—P2—C16—C21 | 141.6 (9) |
C1—P1—C4—C9 | 59.3 (8) | C22—P2—C16—C17 | 90.9 (9) |
Pt1—P1—C4—C9 | −174.3 (7) | C3—P2—C16—C17 | −162.3 (8) |
C10—P1—C4—C5 | 134.2 (7) | Pt1—P2—C16—C17 | −35.5 (9) |
C1—P1—C4—C5 | −116.0 (7) | C21—C16—C17—C18 | 0.5 (17) |
Pt1—P1—C4—C5 | 10.4 (8) | P2—C16—C17—C18 | 177.8 (9) |
C9—C4—C5—C6 | 1.7 (13) | C16—C17—C18—C19 | −0.3 (18) |
P1—C4—C5—C6 | 177.1 (7) | C17—C18—C19—C20 | −1.6 (19) |
C4—C5—C6—C7 | −1.3 (15) | C18—C19—C20—C21 | 3 (2) |
C5—C6—C7—C8 | −0.1 (17) | C17—C16—C21—C20 | 1.2 (18) |
C6—C7—C8—C9 | 1.1 (17) | P2—C16—C21—C20 | −175.9 (10) |
C7—C8—C9—C4 | −0.6 (17) | C19—C20—C21—C16 | −3 (2) |
C5—C4—C9—C8 | −0.8 (14) | C16—P2—C22—C23 | −7.0 (8) |
P1—C4—C9—C8 | −176.2 (8) | C3—P2—C22—C23 | −117.8 (7) |
C4—P1—C10—C15 | 154.6 (7) | Pt1—P2—C22—C23 | 116.7 (7) |
C1—P1—C10—C15 | 47.2 (8) | C16—P2—C22—C27 | 175.3 (7) |
Pt1—P1—C10—C15 | −77.8 (7) | C3—P2—C22—C27 | 64.6 (7) |
C4—P1—C10—C11 | −30.7 (8) | Pt1—P2—C22—C27 | −61.0 (7) |
C1—P1—C10—C11 | −138.1 (7) | C27—C22—C23—C24 | −0.2 (13) |
Pt1—P1—C10—C11 | 96.9 (7) | P2—C22—C23—C24 | −177.9 (7) |
C15—C10—C11—C12 | 0.4 (13) | C22—C23—C24—C25 | 0.2 (14) |
P1—C10—C11—C12 | −174.4 (7) | C23—C24—C25—C26 | 0.1 (15) |
C10—C11—C12—C13 | 0.4 (15) | C24—C25—C26—C27 | −0.4 (15) |
C11—C12—C13—C14 | −1.0 (16) | C25—C26—C27—C22 | 0.4 (15) |
C12—C13—C14—C15 | 0.8 (16) | C23—C22—C27—C26 | 0.0 (13) |
C11—C10—C15—C14 | −0.6 (14) | P2—C22—C27—C26 | 177.7 (7) |
P1—C10—C15—C14 | 174.3 (8) |
Experimental details
Crystal data | |
Chemical formula | [PtBr2(C27H26P2)] |
Mr | 767.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 168 |
a, b, c (Å) | 8.709 (2), 10.760 (3), 14.429 (4) |
α, β, γ (°) | 88.272 (3), 80.296 (4), 73.540 (3) |
V (Å3) | 1278.0 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 8.76 |
Crystal size (mm) | 0.51 × 0.33 × 0.30 |
Data collection | |
Diffractometer | Siemens SMART diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Bruker 1997) |
Tmin, Tmax | 0.641, 1 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15666, 5118, 4792 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.114, 1.23 |
No. of reflections | 5118 |
No. of parameters | 289 |
No. of restraints | 36 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.38, −4.26 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997) and TITAN2000 (Hunter & Simpson, 1999), SHELXL97 (Sheldrick, 1997) and TITAN2000), ORTEP-3 (Farrugia, 1997), SHELXL97.
Br1—Pt1 | 2.4951 (9) | P1—C1 | 1.850 (8) |
Br2—Pt1 | 2.4855 (10) | C1—C2 | 1.530 (12) |
Pt1—P2 | 2.2384 (19) | C2—C3 | 1.544 (12) |
Pt1—P1 | 2.2394 (19) | C3—P2 | 1.850 (8) |
P2—Pt1—P1 | 91.67 (7) | Br2—Pt1—Br1 | 88.12 (4) |
P2—Pt1—Br2 | 91.95 (6) | C1—P1—Pt1 | 115.4 (3) |
P1—Pt1—Br2 | 171.34 (5) | C2—C1—P1 | 111.1 (6) |
P2—Pt1—Br1 | 178.72 (5) | C1—C2—C3 | 116.8 (7) |
P1—Pt1—Br1 | 88.45 (6) | C2—C3—P2 | 117.0 (6) |
The title compound, cis-[PtBr2(dppp)2], (I), [dppp is 1,3-bis(diphenylphosphino)propane] was prepared, unexpectedly, from the reaction between the corresponding trifluoromethylsulfonate complex cis-[Pt(CF3SO3)2(dppp)] with Re(CO)3(DAAD)2Br (DAAD is 2,6-diazaanthracene-9,10-dione; Morgan et al., 2002). The molecular structure of cis-[PtBr2(dppp)] has the Pt atom in a slightly distorted square-planar environment (Fig. 1). The two bromo ligands are in a cis configuration, imposed by the chelating dppp ligand. This is similar to the structures found for the chloro analogue cis-[PtCl2(dppp)], (II) (Robertson & Wickramasinghe, 1987), and the isomorphous palladium complex cis-[PdCl2(dppp)], (III) (Steffen & Palenik, 1976).
Distortion in the square-planar Pt coordination sphere is signalled by angles about Pt ranging from 88.12 (4) to 91.95 (6)°. (Table 1). The r.m.s. deviation from the Br2PtP2 plane is 0.089 Å, with P2 showing the largest deviation of 0.1133 (8) Å. The angle between the PtP2 and PtBr2 planes is 8.01 (5)°. Similar distortions were found in (II) (Robertson et al., 1987) and have been attributed to steric strain within the chelating ligand (Steffen et al., 1976). This is further indicated by the significant variations from tetrahedral angles observed in the alkyl chain of the dppp moiety. Torsion angles around the six-membered Pt—P—C—C—C—P chelate ring are consistent with a twist-boat conformation.
Relatively few structures of square planar PtII complexes with a PtBr2P2 ligand set have been reported. The data suggest that Pt—Br bond lengths trans to the P atoms of bidentate phosphine ligands are generally longer than those in cis-PtBr2(monodentate phosphine)2 structures (Sembiring et al., 1999; Bhattacharyya et al., 1996) or for trans-[PtBr2P2] complexes (Messmer & Amma, 1966; Cameron et al., 1990). The Pt—Br and Pt—P bond lengths observed for (I) are within the anticipated ranges (Orpen et al., 1989). Furthermore, the Pt—P distances are identical within experimental error, while the Pt—Br distances differ [2.4951 (9) and 2.4855 (10) Å], mirroring the bond-length variations observed in (II) (Robertson et al., 1987) and (III) (Steffen et al., 1976). The Pt—Br distances observed for (I) are also similar to those found for the previously reported cis-PtBr2(bidentate phosphine) structures (Wilson et al., 1994; Sevillano et al., 2000).
Molecules of (I) are reasonably well separated in the unit cell, with the shortest intermolecular contact not involving H atoms being for C6···C24i of 3.4765 (9) Å [symmetry code: (i) x, y − 1, z]. The shortest contact involving the Br atoms is H8···Br2ii [H8···Br2ii 2.875 (1), C8···Br2 3.770 (1) Å and C8—H8···Br2 157.5 (2)°; symmetry code: (ii) x + 1, y − 1, z].