Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103020225/av1144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103020225/av1144Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103020225/av1144IIsup3.hkl |
CCDC references: 226091; 226092
For the preparation of [PtCl(dms)3](PF6), dms (5.0 ml) was added to a solution of K2[PtCl4] (1.015 g) in water (40 ml). The resulting precipitate was filtered off after 24 h and HPF6 (0.40 ml, 60% in water) was added to the filtrate. A white precipitate of the desired product was formed and recrystallization from a 1:1 mixture of acetone and toluene gave pale yellow crystals (yield 17%). For the preparation of [PtBr(dms)3](PF6), KBr (1.008 g) was added to a solution of K2[PtCl4] (0.490 g) in water (20 ml), and dms (2.5 ml) was added after 30 min. The procedure adopted for [PtCl(dms)3](PF6) was then followed (yield 22%).
Both maximum and minimum electron densities are within 1 Å of the PtII atom. H atoms were placed geometrically after each cycle.
For both compounds, data collection: SMART (Bruker, 1995). Cell refinement: SAINT-Plus (Bruker, 1998) for (I); SAINT+ (Bruker, 1998) for (II). Data reduction: SAINT-Plus for (I); SAINT+ (Bruker, 1998) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
[PtCl(C2H6S)3]PF6 | F(000) = 1064 |
Mr = 561.89 | Dx = 2.239 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3027 (17) Å | Cell parameters from 6410 reflections |
b = 24.083 (5) Å | θ = 1.7–33.2° |
c = 8.5884 (17) Å | µ = 9.09 mm−1 |
β = 103.92 (3)° | T = 293 K |
V = 1666.8 (6) Å3 | Prism, pale yellow |
Z = 4 | 0.35 × 0.15 × 0.08 mm |
Bruker SMART CCD diffractometer | 5511 independent reflections |
Radiation source: rotating anode | 3939 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 33.2°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.223, Tmax = 0.483 | k = −36→35 |
17196 measured reflections | l = −12→11 |
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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0391P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
5511 reflections | Δρmax = 1.51 e Å−3 |
164 parameters | Δρmin = −0.93 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00133 (17) |
[PtCl(C2H6S)3]PF6 | V = 1666.8 (6) Å3 |
Mr = 561.89 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3027 (17) Å | µ = 9.09 mm−1 |
b = 24.083 (5) Å | T = 293 K |
c = 8.5884 (17) Å | 0.35 × 0.15 × 0.08 mm |
β = 103.92 (3)° |
Bruker SMART CCD diffractometer | 5511 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3939 reflections with I > 2σ(I) |
Tmin = 0.223, Tmax = 0.483 | Rint = 0.042 |
17196 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.02 | Δρmax = 1.51 e Å−3 |
5511 reflections | Δρmin = −0.93 e Å−3 |
164 parameters |
Experimental. Quantum-chemical geometry optimizations were performed on an Athlon(1900) CPU-based computer, with the density-functional method at the B3LYP/LanL2DZ level (Hay & Wadt, 1985a,b; Foresman & Frisch, 1996; Becke, 1993), as implemented in Gaussian98 (Frisch et al., 1998). Four starting structures of the [PtCl(dms)3]+ complex ion were used in the optimizations. The optimized structure starting from the crystal data resulted in the potential global minimum with all dms molecules being staggered with respect to the coordination plane and with the two dms molecules in a cis configuration with respect to the Cl atom having their methyl groups pointing towards the Cl atom. In the second calculation, the starting structure was the potential global minimum structure but with one of the dms ligands cis to the Cl atom rotated by 180°. This model resulted in a local minimum with a geometry close to the starting structure and an energy of 21.5 kJ mol−1 above the global minimum. The third calculation, with the starting structure as the global minimum but with the dms molecule trans to the Cl atom rotated by 90°, also optimized to the global minimum. The fourth calculation, starting from the local minimum but with the dms molecule trans to the Cl atom rotated by 90°, also resulted in the global minimum. The local minimum found is thus only obtained with a starting structure fairly close to the geometry at this minimum. Single-point calculations were performed for both compounds on the [PtX(dms)3]2(PF6)2 packing units, with geometries based on those? observed in the crystal structures. |
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. The intensity data were collected on a Siemens SMART CCD diffractometer using exposure times of 20 s per frame. A total of 2300 frames were collected, with a a frame width of 0.2°. Completeness of 99.5% was accomplished out to θ=30.4 and 29.8° for the chloride and bromide compounds, respectively. The first 50 frames were recollected at the end of the data collection to check for decay, but no decay was observed in either of the data collections. |
x | y | z | Uiso*/Ueq | ||
Pt1 | 0.558267 (19) | 0.914056 (6) | 0.11679 (2) | 0.03813 (7) | |
S3 | 0.69169 (14) | 0.99771 (5) | 0.19372 (15) | 0.0430 (2) | |
S2 | 0.72451 (15) | 0.88834 (5) | −0.04893 (17) | 0.0527 (3) | |
S1 | 0.41880 (15) | 0.83139 (5) | 0.06151 (18) | 0.0550 (3) | |
Cl1 | 0.38758 (17) | 0.94566 (6) | 0.27469 (18) | 0.0682 (4) | |
P1 | 1.02448 (18) | 0.83680 (5) | 0.51339 (17) | 0.0521 (3) | |
C6 | 0.7634 (7) | 0.9930 (3) | 0.4161 (6) | 0.0611 (14) | |
H6A | 0.6689 | 0.9911 | 0.4621 | 0.092* | |
H6B | 0.8284 | 1.0252 | 0.4564 | 0.092* | |
H6C | 0.8298 | 0.9602 | 0.4446 | 0.092* | |
C5 | 0.8790 (6) | 1.0011 (2) | 0.1347 (7) | 0.0611 (14) | |
H5A | 0.8565 | 1.0038 | 0.0199 | 0.092* | |
H5B | 0.9429 | 0.9683 | 0.1698 | 0.092* | |
H5C | 0.9403 | 1.0332 | 0.1820 | 0.092* | |
C2 | 0.2079 (6) | 0.8433 (3) | 0.0249 (8) | 0.0708 (16) | |
H2A | 0.1703 | 0.8610 | −0.0776 | 0.106* | |
H2B | 0.1853 | 0.8669 | 0.1072 | 0.106* | |
H2C | 0.1509 | 0.8086 | 0.0246 | 0.106* | |
C3 | 0.5990 (8) | 0.8822 (3) | −0.2561 (7) | 0.0754 (18) | |
H3A | 0.5563 | 0.9180 | −0.2941 | 0.113* | |
H3B | 0.5083 | 0.8572 | −0.2588 | 0.113* | |
H3C | 0.6667 | 0.8681 | −0.3234 | 0.113* | |
C4 | 0.7855 (7) | 0.8168 (2) | −0.0121 (8) | 0.0701 (16) | |
H4A | 0.8550 | 0.8132 | 0.0943 | 0.105* | |
H4B | 0.8455 | 0.8050 | −0.0887 | 0.105* | |
H4C | 0.6884 | 0.7941 | −0.0221 | 0.105* | |
C1 | 0.4498 (9) | 0.7980 (3) | 0.2627 (10) | 0.105 (3) | |
H1A | 0.5646 | 0.7884 | 0.3020 | 0.158* | |
H1B | 0.3832 | 0.7650 | 0.2537 | 0.158* | |
H1C | 0.4174 | 0.8234 | 0.3358 | 0.158* | |
F6 | 0.9806 (7) | 0.8817 (2) | 0.6327 (5) | 0.1143 (16) | |
F5 | 1.0214 (7) | 0.88218 (18) | 0.3762 (5) | 0.1120 (15) | |
F4 | 1.0290 (10) | 0.79237 (19) | 0.6489 (6) | 0.156 (3) | |
F3 | 1.0675 (11) | 0.7933 (2) | 0.3962 (6) | 0.179 (3) | |
F2 | 0.8441 (6) | 0.8284 (4) | 0.4347 (8) | 0.188 (3) | |
F1 | 1.2008 (6) | 0.8513 (4) | 0.5951 (9) | 0.176 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.03406 (9) | 0.03931 (10) | 0.04361 (11) | −0.00233 (7) | 0.01441 (7) | −0.00703 (7) |
S3 | 0.0406 (6) | 0.0371 (5) | 0.0528 (7) | −0.0005 (4) | 0.0140 (5) | −0.0040 (5) |
S2 | 0.0417 (6) | 0.0521 (7) | 0.0714 (8) | −0.0033 (5) | 0.0276 (6) | −0.0192 (6) |
S1 | 0.0445 (6) | 0.0462 (6) | 0.0763 (9) | −0.0104 (5) | 0.0187 (6) | −0.0101 (6) |
Cl1 | 0.0531 (7) | 0.0856 (10) | 0.0780 (9) | −0.0147 (7) | 0.0398 (7) | −0.0333 (8) |
P1 | 0.0623 (8) | 0.0400 (6) | 0.0532 (8) | −0.0035 (6) | 0.0120 (6) | −0.0006 (5) |
C6 | 0.058 (3) | 0.071 (3) | 0.052 (3) | −0.003 (3) | 0.008 (3) | −0.017 (3) |
C5 | 0.047 (3) | 0.060 (3) | 0.083 (4) | −0.019 (2) | 0.028 (3) | −0.014 (3) |
C2 | 0.041 (3) | 0.076 (4) | 0.089 (4) | −0.016 (3) | 0.001 (3) | −0.003 (3) |
C3 | 0.081 (4) | 0.096 (5) | 0.051 (3) | 0.029 (4) | 0.020 (3) | −0.005 (3) |
C4 | 0.051 (3) | 0.062 (3) | 0.094 (5) | 0.020 (3) | 0.013 (3) | −0.013 (3) |
C1 | 0.065 (4) | 0.096 (5) | 0.139 (7) | −0.016 (4) | −0.006 (4) | 0.045 (5) |
F6 | 0.161 (4) | 0.101 (3) | 0.090 (3) | 0.029 (3) | 0.048 (3) | −0.014 (2) |
F5 | 0.170 (4) | 0.082 (3) | 0.089 (3) | −0.012 (3) | 0.042 (3) | 0.022 (2) |
F4 | 0.308 (8) | 0.069 (3) | 0.090 (3) | −0.030 (4) | 0.043 (4) | 0.022 (2) |
F3 | 0.332 (9) | 0.103 (4) | 0.110 (4) | 0.095 (5) | 0.071 (5) | −0.015 (3) |
F2 | 0.081 (3) | 0.312 (9) | 0.152 (5) | −0.077 (5) | −0.009 (3) | −0.005 (6) |
F1 | 0.062 (3) | 0.274 (8) | 0.178 (6) | −0.019 (4) | 0.003 (3) | 0.002 (6) |
Pt1—S2 | 2.2934 (13) | C6—H6B | 0.9600 |
Pt1—S1 | 2.2945 (12) | C6—H6C | 0.9600 |
Pt1—Cl1 | 2.3133 (13) | C5—H5A | 0.9600 |
Pt1—S3 | 2.3175 (12) | C5—H5B | 0.9600 |
S3—C5 | 1.750 (5) | C5—H5C | 0.9600 |
S3—C6 | 1.862 (5) | C2—H2A | 0.9600 |
S2—C4 | 1.802 (6) | C2—H2B | 0.9600 |
S2—C3 | 1.839 (6) | C2—H2C | 0.9600 |
S1—C2 | 1.727 (5) | C3—H3A | 0.9600 |
S1—C1 | 1.867 (8) | C3—H3B | 0.9600 |
P1—F2 | 1.501 (5) | C3—H3C | 0.9600 |
P1—F1 | 1.505 (5) | C4—H4A | 0.9600 |
P1—F3 | 1.553 (5) | C4—H4B | 0.9600 |
P1—F4 | 1.574 (4) | C4—H4C | 0.9600 |
P1—F6 | 1.591 (4) | C1—H1A | 0.9600 |
P1—F5 | 1.603 (4) | C1—H1B | 0.9600 |
C6—H6A | 0.9600 | C1—H1C | 0.9600 |
S2—Pt1—S1 | 89.22 (5) | S3—C6—H6C | 109.5 |
S2—Pt1—Cl1 | 176.12 (5) | H6A—C6—H6C | 109.5 |
S1—Pt1—Cl1 | 93.26 (5) | H6B—C6—H6C | 109.5 |
S2—Pt1—S3 | 95.39 (4) | S3—C5—H5A | 109.5 |
S1—Pt1—S3 | 174.93 (5) | S3—C5—H5B | 109.5 |
Cl1—Pt1—S3 | 82.25 (5) | H5A—C5—H5B | 109.5 |
C5—S3—C6 | 102.3 (3) | S3—C5—H5C | 109.5 |
C5—S3—Pt1 | 110.82 (18) | H5A—C5—H5C | 109.5 |
C6—S3—Pt1 | 104.6 (2) | H5B—C5—H5C | 109.5 |
C4—S2—C3 | 99.4 (3) | S1—C2—H2A | 109.5 |
C4—S2—Pt1 | 109.5 (2) | S1—C2—H2B | 109.5 |
C3—S2—Pt1 | 109.66 (19) | H2A—C2—H2B | 109.5 |
C2—S1—C1 | 98.5 (3) | S1—C2—H2C | 109.5 |
C2—S1—Pt1 | 109.4 (2) | H2A—C2—H2C | 109.5 |
C1—S1—Pt1 | 103.4 (2) | H2B—C2—H2C | 109.5 |
F2—P1—F1 | 174.1 (5) | S2—C3—H3A | 109.5 |
F2—P1—F3 | 88.7 (5) | S2—C3—H3B | 109.5 |
F1—P1—F3 | 96.2 (5) | H3A—C3—H3B | 109.5 |
F2—P1—F4 | 94.9 (4) | S2—C3—H3C | 109.5 |
F1—P1—F4 | 88.0 (4) | H3A—C3—H3C | 109.5 |
F3—P1—F4 | 93.0 (3) | H3B—C3—H3C | 109.5 |
F2—P1—F6 | 91.4 (4) | S2—C4—H4A | 109.5 |
F1—P1—F6 | 83.7 (4) | S2—C4—H4B | 109.5 |
F3—P1—F6 | 179.6 (3) | H4A—C4—H4B | 109.5 |
F4—P1—F6 | 87.4 (3) | S2—C4—H4C | 109.5 |
F2—P1—F5 | 85.6 (4) | H4A—C4—H4C | 109.5 |
F1—P1—F5 | 91.5 (4) | H4B—C4—H4C | 109.5 |
F3—P1—F5 | 87.1 (3) | S1—C1—H1A | 109.5 |
F4—P1—F5 | 179.5 (3) | S1—C1—H1B | 109.5 |
F6—P1—F5 | 92.5 (2) | H1A—C1—H1B | 109.5 |
S3—C6—H6A | 109.5 | S1—C1—H1C | 109.5 |
S3—C6—H6B | 109.5 | H1A—C1—H1C | 109.5 |
H6A—C6—H6B | 109.5 | H1B—C1—H1C | 109.5 |
[PtBr(C2H6S)3]PF6 | F(000) = 1136 |
Mr = 606.35 | Dx = 2.408 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.5981 (4) Å | Cell parameters from 4313 reflections |
b = 23.9384 (10) Å | θ = 1.7–31.7° |
c = 8.3852 (3) Å | µ = 11.29 mm−1 |
β = 104.235 (1)° | T = 293 K |
V = 1672.89 (12) Å3 | Needle, yellow |
Z = 4 | 0.30 × 0.09 × 0.03 mm |
Bruker SMART CCD diffractometer | 5170 independent reflections |
Radiation source: rotating anode | 3275 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ω–scans | θmax = 31.7°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→10 |
Tmin = 0.336, Tmax = 0.713 | k = −35→34 |
16670 measured reflections | l = −11→12 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.040P)2] where P = (Fo2 + 2Fc2)/3 |
5170 reflections | (Δ/σ)max = 0.002 |
163 parameters | Δρmax = 1.34 e Å−3 |
0 restraints | Δρmin = −1.20 e Å−3 |
[PtBr(C2H6S)3]PF6 | V = 1672.89 (12) Å3 |
Mr = 606.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.5981 (4) Å | µ = 11.29 mm−1 |
b = 23.9384 (10) Å | T = 293 K |
c = 8.3852 (3) Å | 0.30 × 0.09 × 0.03 mm |
β = 104.235 (1)° |
Bruker SMART CCD diffractometer | 5170 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3275 reflections with I > 2σ(I) |
Tmin = 0.336, Tmax = 0.713 | Rint = 0.064 |
16670 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.01 | Δρmax = 1.34 e Å−3 |
5170 reflections | Δρmin = −1.20 e Å−3 |
163 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 | ||
Pt1 | 0.56526 (3) | 0.913537 (10) | 0.11245 (3) | 0.03655 (9) | |
Br1 | 0.38430 (10) | 0.94367 (4) | 0.27656 (11) | 0.0725 (3) | |
S3 | 0.6949 (2) | 0.99758 (7) | 0.1930 (2) | 0.0423 (4) | |
S2 | 0.7313 (2) | 0.89025 (8) | −0.0535 (2) | 0.0515 (4) | |
S1 | 0.4309 (2) | 0.83005 (8) | 0.0503 (2) | 0.0546 (5) | |
P1 | 1.0281 (3) | 0.83609 (8) | 0.5047 (2) | 0.0565 (5) | |
C6 | 0.7704 (9) | 0.9913 (3) | 0.4143 (8) | 0.060 (2) | |
H6A | 0.6819 | 0.9886 | 0.4647 | 0.089* | |
H6B | 0.8335 | 1.0236 | 0.4559 | 0.089* | |
H6C | 0.8358 | 0.9584 | 0.4392 | 0.089* | |
C4 | 0.6060 (10) | 0.8843 (4) | −0.2587 (9) | 0.073 (2) | |
H4A | 0.5594 | 0.9201 | −0.2943 | 0.110* | |
H4B | 0.5222 | 0.8577 | −0.2599 | 0.110* | |
H4C | 0.6694 | 0.8721 | −0.3317 | 0.110* | |
C5 | 0.8825 (9) | 1.0023 (3) | 0.1352 (10) | 0.060 (2) | |
H5A | 0.8622 | 1.0058 | 0.0178 | 0.090* | |
H5B | 0.9446 | 0.9692 | 0.1703 | 0.090* | |
H5C | 0.9407 | 1.0344 | 0.1865 | 0.090* | |
C3 | 0.7986 (10) | 0.8203 (3) | −0.0177 (10) | 0.069 (2) | |
H3A | 0.8699 | 0.8174 | 0.0899 | 0.104* | |
H3B | 0.8542 | 0.8095 | −0.0990 | 0.104* | |
H3C | 0.7081 | 0.7961 | −0.0244 | 0.104* | |
C2 | 0.2186 (9) | 0.8397 (4) | 0.0067 (11) | 0.076 (3) | |
H2A | 0.1823 | 0.8583 | −0.0972 | 0.114* | |
H2B | 0.1924 | 0.8619 | 0.0918 | 0.114* | |
H2C | 0.1668 | 0.8040 | 0.0019 | 0.114* | |
C1 | 0.4639 (12) | 0.7951 (4) | 0.2463 (13) | 0.098 (3) | |
H1A | 0.5759 | 0.7866 | 0.2859 | 0.147* | |
H1B | 0.4029 | 0.7611 | 0.2335 | 0.147* | |
H1C | 0.4304 | 0.8189 | 0.3236 | 0.147* | |
F6 | 1.0204 (8) | 0.8826 (2) | 0.3711 (7) | 0.1048 (19) | |
F5 | 0.9811 (10) | 0.8792 (3) | 0.6257 (7) | 0.129 (3) | |
F4 | 1.0381 (11) | 0.7906 (3) | 0.6375 (7) | 0.159 (4) | |
F3 | 1.0686 (15) | 0.7940 (3) | 0.3882 (9) | 0.213 (6) | |
F2 | 0.8519 (10) | 0.8256 (5) | 0.4280 (10) | 0.202 (5) | |
F1 | 1.2046 (8) | 0.8516 (5) | 0.5850 (10) | 0.184 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.03594 (14) | 0.03930 (14) | 0.03716 (13) | −0.00239 (12) | 0.01423 (9) | −0.00499 (11) |
Br1 | 0.0615 (5) | 0.0970 (7) | 0.0710 (5) | −0.0152 (5) | 0.0393 (4) | −0.0289 (5) |
S3 | 0.0453 (10) | 0.0375 (9) | 0.0463 (9) | 0.0011 (7) | 0.0154 (7) | −0.0031 (7) |
S2 | 0.0461 (10) | 0.0539 (10) | 0.0626 (11) | −0.0048 (9) | 0.0287 (8) | −0.0179 (9) |
S1 | 0.0517 (11) | 0.0450 (10) | 0.0686 (12) | −0.0099 (8) | 0.0176 (9) | −0.0083 (9) |
P1 | 0.0761 (15) | 0.0419 (10) | 0.0502 (11) | −0.0023 (10) | 0.0127 (10) | −0.0006 (8) |
C6 | 0.066 (5) | 0.068 (5) | 0.045 (4) | −0.003 (4) | 0.014 (4) | −0.015 (4) |
C4 | 0.076 (6) | 0.098 (7) | 0.049 (4) | 0.022 (5) | 0.021 (4) | −0.007 (5) |
C5 | 0.058 (5) | 0.062 (5) | 0.069 (5) | −0.022 (4) | 0.033 (4) | −0.011 (4) |
C3 | 0.058 (5) | 0.071 (6) | 0.077 (6) | 0.021 (4) | 0.016 (4) | −0.018 (5) |
C2 | 0.055 (5) | 0.079 (6) | 0.088 (6) | −0.022 (5) | 0.004 (4) | −0.008 (5) |
C1 | 0.086 (7) | 0.081 (7) | 0.115 (8) | −0.012 (6) | 0.004 (6) | 0.039 (6) |
F6 | 0.157 (6) | 0.074 (4) | 0.089 (4) | 0.001 (4) | 0.042 (4) | 0.027 (3) |
F5 | 0.206 (8) | 0.102 (5) | 0.084 (4) | 0.049 (5) | 0.045 (4) | −0.008 (4) |
F4 | 0.320 (11) | 0.068 (4) | 0.074 (4) | −0.032 (5) | 0.018 (5) | 0.020 (3) |
F3 | 0.436 (17) | 0.109 (6) | 0.097 (5) | 0.123 (8) | 0.071 (7) | −0.009 (4) |
F2 | 0.121 (6) | 0.320 (13) | 0.131 (6) | −0.120 (8) | −0.033 (5) | 0.041 (7) |
F1 | 0.079 (5) | 0.319 (13) | 0.138 (6) | −0.032 (6) | −0.004 (4) | 0.026 (7) |
Pt1—S2 | 2.2937 (17) | C6—H6B | 0.9600 |
Pt1—S1 | 2.3030 (18) | C6—H6C | 0.9600 |
Pt1—S3 | 2.3186 (17) | C4—H4A | 0.9600 |
Pt1—Br1 | 2.4265 (8) | C4—H4B | 0.9600 |
S3—C5 | 1.798 (7) | C4—H4C | 0.9600 |
S3—C6 | 1.815 (7) | C5—H5A | 0.9600 |
S2—C3 | 1.773 (8) | C5—H5B | 0.9600 |
S2—C4 | 1.797 (8) | C5—H5C | 0.9600 |
S1—C2 | 1.787 (8) | C3—H3A | 0.9600 |
S1—C1 | 1.804 (10) | C3—H3B | 0.9600 |
P1—F3 | 1.503 (7) | C3—H3C | 0.9600 |
P1—F2 | 1.514 (7) | C2—H2A | 0.9600 |
P1—F4 | 1.544 (6) | C2—H2B | 0.9600 |
P1—F1 | 1.547 (7) | C2—H2C | 0.9600 |
P1—F5 | 1.567 (6) | C1—H1A | 0.9600 |
P1—F6 | 1.569 (5) | C1—H1B | 0.9600 |
C6—H6A | 0.9600 | C1—H1C | 0.9600 |
S2—Pt1—S1 | 90.24 (7) | S3—C6—H6C | 109.5 |
S2—Pt1—S3 | 93.50 (6) | H6A—C6—H6C | 109.5 |
S1—Pt1—S3 | 175.83 (7) | H6B—C6—H6C | 109.5 |
S2—Pt1—Br1 | 176.16 (6) | S2—C4—H4A | 109.5 |
S1—Pt1—Br1 | 91.74 (6) | S2—C4—H4B | 109.5 |
S3—Pt1—Br1 | 84.63 (5) | H4A—C4—H4B | 109.5 |
C5—S3—C6 | 99.3 (4) | S2—C4—H4C | 109.5 |
C5—S3—Pt1 | 112.0 (3) | H4A—C4—H4C | 109.5 |
C6—S3—Pt1 | 104.6 (3) | H4B—C4—H4C | 109.5 |
C3—S2—C4 | 100.5 (4) | S3—C5—H5A | 109.5 |
C3—S2—Pt1 | 110.6 (3) | S3—C5—H5B | 109.5 |
C4—S2—Pt1 | 106.5 (3) | H5A—C5—H5B | 109.5 |
C2—S1—C1 | 99.8 (5) | S3—C5—H5C | 109.5 |
C2—S1—Pt1 | 111.4 (3) | H5A—C5—H5C | 109.5 |
C1—S1—Pt1 | 103.8 (3) | H5B—C5—H5C | 109.5 |
F3—P1—F2 | 88.9 (6) | S2—C3—H3A | 109.5 |
F3—P1—F4 | 90.9 (4) | S2—C3—H3B | 109.5 |
F2—P1—F4 | 93.6 (5) | H3A—C3—H3B | 109.5 |
F3—P1—F1 | 94.8 (7) | S2—C3—H3C | 109.5 |
F2—P1—F1 | 175.6 (7) | H3A—C3—H3C | 109.5 |
F4—P1—F1 | 88.8 (5) | H3B—C3—H3C | 109.5 |
F3—P1—F5 | 178.4 (6) | S1—C2—H2A | 109.5 |
F2—P1—F5 | 89.7 (6) | S1—C2—H2B | 109.5 |
F4—P1—F5 | 88.6 (4) | H2A—C2—H2B | 109.5 |
F1—P1—F5 | 86.7 (5) | S1—C2—H2C | 109.5 |
F3—P1—F6 | 89.2 (4) | H2A—C2—H2C | 109.5 |
F2—P1—F6 | 87.3 (4) | H2B—C2—H2C | 109.5 |
F4—P1—F6 | 179.1 (4) | S1—C1—H1A | 109.5 |
F1—P1—F6 | 90.3 (5) | S1—C1—H1B | 109.5 |
F5—P1—F6 | 91.3 (3) | H1A—C1—H1B | 109.5 |
S3—C6—H6A | 109.5 | S1—C1—H1C | 109.5 |
S3—C6—H6B | 109.5 | H1A—C1—H1C | 109.5 |
H6A—C6—H6B | 109.5 | H1B—C1—H1C | 109.5 |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [PtCl(C2H6S)3]PF6 | [PtBr(C2H6S)3]PF6 |
Mr | 561.89 | 606.35 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.3027 (17), 24.083 (5), 8.5884 (17) | 8.5981 (4), 23.9384 (10), 8.3852 (3) |
β (°) | 103.92 (3) | 104.235 (1) |
V (Å3) | 1666.8 (6) | 1672.89 (12) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 9.09 | 11.29 |
Crystal size (mm) | 0.35 × 0.15 × 0.08 | 0.30 × 0.09 × 0.03 |
Data collection | ||
Diffractometer | Bruker SMART CCD diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.223, 0.483 | 0.336, 0.713 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17196, 5511, 3939 | 16670, 5170, 3275 |
Rint | 0.042 | 0.064 |
(sin θ/λ)max (Å−1) | 0.770 | 0.740 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.081, 1.02 | 0.045, 0.096, 1.01 |
No. of reflections | 5511 | 5170 |
No. of parameters | 164 | 163 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.51, −0.93 | 1.34, −1.20 |
Computer programs: SMART (Bruker, 1995), SAINT-Plus (Bruker, 1998), SAINT+ (Bruker, 1998), SAINT-Plus, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
Pt1—S2 | 2.2934 (13) | S3—C6 | 1.862 (5) |
Pt1—S1 | 2.2945 (12) | S2—C4 | 1.802 (6) |
Pt1—Cl1 | 2.3133 (13) | S2—C3 | 1.839 (6) |
Pt1—S3 | 2.3175 (12) | S1—C2 | 1.727 (5) |
S3—C5 | 1.750 (5) | S1—C1 | 1.867 (8) |
S2—Pt1—S1 | 89.22 (5) | C6—S3—Pt1 | 104.6 (2) |
S2—Pt1—Cl1 | 176.12 (5) | C4—S2—C3 | 99.4 (3) |
S1—Pt1—Cl1 | 93.26 (5) | C4—S2—Pt1 | 109.5 (2) |
S2—Pt1—S3 | 95.39 (4) | C3—S2—Pt1 | 109.66 (19) |
S1—Pt1—S3 | 174.93 (5) | C2—S1—C1 | 98.5 (3) |
Cl1—Pt1—S3 | 82.25 (5) | C2—S1—Pt1 | 109.4 (2) |
C5—S3—C6 | 102.3 (3) | C1—S1—Pt1 | 103.4 (2) |
C5—S3—Pt1 | 110.82 (18) |
Pt1—S2 | 2.2937 (17) | S3—C6 | 1.815 (7) |
Pt1—S1 | 2.3030 (18) | S2—C3 | 1.773 (8) |
Pt1—S3 | 2.3186 (17) | S2—C4 | 1.797 (8) |
Pt1—Br1 | 2.4265 (8) | S1—C2 | 1.787 (8) |
S3—C5 | 1.798 (7) | S1—C1 | 1.804 (10) |
S2—Pt1—S1 | 90.24 (7) | C6—S3—Pt1 | 104.6 (3) |
S2—Pt1—S3 | 93.50 (6) | C3—S2—C4 | 100.5 (4) |
S1—Pt1—S3 | 175.83 (7) | C3—S2—Pt1 | 110.6 (3) |
S2—Pt1—Br1 | 176.16 (6) | C4—S2—Pt1 | 106.5 (3) |
S1—Pt1—Br1 | 91.74 (6) | C2—S1—C1 | 99.8 (5) |
S3—Pt1—Br1 | 84.63 (5) | C2—S1—Pt1 | 111.4 (3) |
C5—S3—C6 | 99.3 (4) | C1—S1—Pt1 | 103.8 (3) |
C5—S3—Pt1 | 112.0 (3) |
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The observed geometry of a metal complex in the solid state is often discussed in terms of intramolecular forces alone, thus neglecting packing effects (Belsky et al., 1990). The influence of the environment on shape and dimensions can be investigated by studying a particular complex in different crystallographic environments. This can be achieved in a number of ways, i.e. the study of crystal structures with more than one molecule in the asymmetric unit (Lövqvist, 1996), of polymorphs (Kapoor et al., 1996), of different solvates (Johansson et al., 2000) or of a charged complex with different counter ions (Ericson et al., 1992). Here we will explore the conformational space in the gas phase using DFT calculations and compare geometry-optimized structures (global minimum as well as local minima) with the geometry observed in the crystal structure.
The structures [PtX(dms)3](PF6) (X = Cl or Br and dms is dimethylsulfide), are almost? isostructural. Platinum is coordinated by three dms molecules and one halide molecule in a distorted pseudo-square-planar configuration (Fig. 1). The S atoms bind to the metal through one of the lone pairs, the Pt—S—C angles being in the range 103.4 (2)–112.0 (3)°. Two of the dms ligands are oriented in a staggered conformation with respect to the coordination plane, while the third one is rotated approximately 90° with both methyl groups on the same side of the coordination plane (Fig. 1). The Pt—S distances for the two staggered dms ligands are shorter than that of the third ligand in both compounds (Tables 1 and 2). The [PtX(dms)3]+ complex ions are packed as dimers around a center of symmetry, with intermolecular Pt···S distances of 3.643 (2) Å in both compounds (Fig. 2) and with the lone pair on this S atom pointing approximately towards the Pt atom in the neighbouring complex, with Pt—S···Pt angles in the range 97.7 (2)–98.6 (2)°. The anions are located in `pockets' on the surface of the dimers, with shortests Pt···F distances of 3.772 (8) (chloride compound) and 3.781 (8) Å (bromide compound). The PtII atom thus has a pseudo-octahedral geometry, with four normal bonds and two long bonds. In this description, the structure is built from electrically neutral [PtX(dms)3]2(PF6)2 units with a center of symmetry, and space group P21/c is adequate for a close packing of such specimens (Kitaigorodsky, 1973). Similar dimers have been observed for [chlorotris(1,4-oxathiane-S)platinum(II)]trifluoromethanesulfonate (Lövqvist, 1996) and for the neutral complexes cis-bis(dimethylsulfoxide-S)dinitratopalladium(II) and cis-bis(1,4-oxathiane-S)dinitratopalladium(II) (Johansson & Oskarsson, 2001).
DFT calculations on the cationic title complexes in the gas phase show two distinct energy minima, both with the dms molecules in a staggered conformation with respect to the coordination plane. There is a local minimum for which all dms molecules have a paddle-wheel-like arrangement, i.e. all dms molecules point in the same direction, as in Pd(dms)42+ (Johansson & Oskarsson, 2002). For the global minimum, however, the two dms molecules in cis positions with respect to the X atom both have their methyl groups pointing towards the halide, i.e. one of the dms molecules in the cis position is rotated 180° between the local and the global minimum, and the difference in energy between these conformers is 21.5 kJ mol−1. The observed geometry in the solid state is intermediate between these conformers and is thus not at an energy minimum for a single molecule in the gas phase. In both compounds, the observed Pt—S distance for the non-staggered dms molecule is longer than that for the other two molecules; the difference is small but probably significant, namely 0.024 (2) and 0.020 (3) Å for the chloride and bromide compounds, respectively. The longer Pt—S distance for this dms molecule may be the result of intramolecular forces, but it may also be due to the formation of dimers, i.e. an interaction between the S atom in this ligand and the Pt atom in the neighbouring complex. A single-point calculation of the [PtX(dms)3]2(PF6)2 packing unit as observed in the crystal structure shows a very small electron density between the Pt and the S-atoms in the neighbouring complex, of approximately 0.008 a.u. in both compounds (Fig. 2), ?which cannot? be regarded as significant. Johansson & Oskarsson (2001) calculated ROP (reduced overlap population) values at the EH level for the Pd···O bonds in the similar neutral dimers cis-bis(dimethylsulfoxide-S)-dinitratopalladium(II) and cis-bis(1,4-oxathiane-S)dinitratopalladium(II). The reported ROP values are 0.011 and 0.000 for the sulfoxide and 1,4-oxathiane complexes, respectively, and a value as small as 0.011 is hardly significant enough to indicate a covalent interaction. Another plausible explanation for the formation of dimers is, at least in the title compounds, electrostatic interaction between the neighbouring complexes, since the Mulliken charges are −0.54 and 0.35 for the PtII and S atoms in the chloride structure and are similar in the bromide structure (−0.48 and 0.36). A fairly strong interaction between the PtII atom and an S atom in the neighbouring complex ion is further corroborated by the Ueq value for this atom, viz. 0.0430 (2) and 0.0423 (4) Å2 for the chloride and bromide compounds, respectively, compared with the range 0.0515 (4)–0.0550 (3) Å2 for the other S atoms.
It is thus concluded that
i) The observed geometry of the metal complex in the solid state is not close to an energy minimum of the complex in the gas phase but is rather at a higher energy between two minima.
ii) The observed geometry is thus a consequence of the formation of dimers, but this formation is not due to covalent but rather to electrostatic interactions between two complexes.
iii) The packing unit in the solid state is [PtX(dms)3]2(PF6)2, with a center of symmetry and Pt···F distances of 3.772 (8) and 3.781 (8) Å in the chloride and bromide compounds, respectively. The coordination geometry for the PtII atom can thus be described as octahedral, with four short and two long bonds.