The title compound, [Pt(NO
3)
2(C
2H
6S)
2], crystallizes in the
P2
1/
n space group (
Z′ = 2), with pseudo-square-planar coordination geometry. The complex forms dimers with pseudosymmetry
Ci arranged in columns along the
b-axis direction, with Pt
Pt distances of 6.3056 (3) and 4.2382 (2) Å (at 150 K). Each column is surrounded by six other columns in a honeycomb rod-like packing. The coordination mode of the nitrate ligands is monodentate, with Pt—O—N angles ranging from ∼117 to ∼118° and a tilt between the nitrate ligands and the coordination planes in the range ∼63–70° (at 150 K). The coordination mode of the nitrate ligands is compared with that observed in reported Pt(NO
3)
2L2 complexes (where
L is a ligand with a donor atom from group 15 or 16), all of which are monodentate, with an average Pt—O—N angle of 118 (2)° and a tilt in the range 90 ± 30° (with two exceptions, in which the nitrates are approximately in the coordination plane).
Supporting information
CCDC references: 665493; 665494
PtI2(Me2S)2 (0.301 g, 0.526 mmol) was dissolved in acetone (15 ml). AgNO3 (0.179 g, 1.052 mmol) was added and the reaction mixture was stirred for 90 min. A yellow precipitate of AgI was then removed by filtration. The pale-yellow acetone solution was left to evaporate slowly, which resulted in pale-yellow crystals suitable for X-ray diffraction experiments.
The reaction with Pt(Me2S)2I2 and AgNO3 is believed to be faster than the corresponding reaction with PtCl2(Me2S)2 (Souchard et al., 1990). The solubility of AgNO3 in acetone is very limited, but still the reaction is rather fast. A change in colour, from light red to pale yellow, indicates when the reaction is finished.
DFT calculations were performed at the s-VWN level with the basis sets def-TZVPP for Pt, TZVPP for O and N, and 6–31 G* for C and H atoms, using the software TURBOMOLE 5.5 (Alrichs et al., 1989).
All non-H atoms were refined anisotropically. Hydrogen atom positions were calculated as riding on the adjacent C atom constrained to parent sites (methyl group C—H distance 0.96 Å) with Uiso(H) = 1.5*Ueq(C).
A residual electron density of 3.8 e Å−3 at 295 K located in the coordination plane and 1.6 Å from two carbon atoms, reduces to 1.4 e Å−3 at 150 K.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006). Data reduction: CrysAlis RED (Oxford Diffraction, 2006) for I_295; CrysAlis RED Oxford Diffraction, 2006) for I_150. For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: DIAMOND (Brandenburg, 2000) and Mercury (Macrae et al., 2006); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003) and enCIFer (Allen et al., 2004).
(I_295)
cis-Bis(dimethyl sulfide)dinitratoplatinum(II)
top
Crystal data top
[Pt(NO3)2(C2H6S)2] | F(000) = 1664 |
Mr = 443.37 | Dx = 2.464 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 23666 reflections |
a = 16.0762 (11) Å | θ = 2.1–33.0° |
b = 9.5937 (5) Å | µ = 12.10 mm−1 |
c = 16.1552 (11) Å | T = 295 K |
β = 106.402 (4)° | Prism, pale yellow |
V = 2390.2 (3) Å3 | 0.25 × 0.08 × 0.05 mm |
Z = 8 | |
Data collection top
Oxford Diffraction XCALIBUR3 diffractometer | 8172 independent reflections |
Radiation source: Sealed tube | 4952 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
ω scans | θmax = 32.9°, θmin = 2.5° |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | h = −24→24 |
Tmin = 0.405, Tmax = 0.771 | k = −14→9 |
23666 measured reflections | l = −23→23 |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
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) = 0.120 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0603P)2] where P = (Fo2 + 2Fc2)/3 |
8172 reflections | (Δ/σ)max = 0.002 |
271 parameters | Δρmax = 3.82 e Å−3 |
0 restraints | Δρmin = −2.66 e Å−3 |
Crystal data top
[Pt(NO3)2(C2H6S)2] | V = 2390.2 (3) Å3 |
Mr = 443.37 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.0762 (11) Å | µ = 12.10 mm−1 |
b = 9.5937 (5) Å | T = 295 K |
c = 16.1552 (11) Å | 0.25 × 0.08 × 0.05 mm |
β = 106.402 (4)° | |
Data collection top
Oxford Diffraction XCALIBUR3 diffractometer | 8172 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | 4952 reflections with I > 2σ(I) |
Tmin = 0.405, Tmax = 0.771 | Rint = 0.062 |
23666 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.95 | Δρmax = 3.82 e Å−3 |
8172 reflections | Δρmin = −2.66 e Å−3 |
271 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.530260 (15) | 0.19879 (2) | 0.703893 (17) | 0.03630 (8) | |
Pt2 | 0.479054 (16) | 0.81396 (2) | 0.817802 (18) | 0.03862 (8) | |
S1 | 0.63233 (11) | 0.22669 (17) | 0.82966 (11) | 0.0432 (4) | |
S2 | 0.62488 (11) | 0.23766 (18) | 0.62786 (12) | 0.0451 (4) | |
S3 | 0.34117 (13) | 0.77331 (2) | 0.74531 (14) | 0.0545 (5) | |
S4 | 0.44828 (14) | 0.79986 (19) | 0.94622 (14) | 0.0555 (5) | |
O1 | 0.4330 (3) | 0.1503 (5) | 0.5962 (3) | 0.0511 (12) | |
O2 | 0.3024 (4) | 0.1894 (6) | 0.5220 (4) | 0.0747 (19) | |
O3 | 0.3763 (5) | 0.3513 (7) | 0.6005 (5) | 0.108 (3) | |
O4 | 0.4451 (4) | 0.1553 (6) | 0.7729 (4) | 0.0627 (15) | |
O5 | 0.3690 (4) | 0.2298 (7) | 0.8562 (5) | 0.084 (2) | |
O6 | 0.4595 (4) | 0.3696 (6) | 0.8231 (4) | 0.0679 (16) | |
O7 | 0.6027 (3) | 0.8646 (5) | 0.8870 (4) | 0.0613 (15) | |
O8 | 0.7241 (4) | 0.8080 (6) | 0.9720 (5) | 0.080 (2) | |
O9 | 0.6225 (4) | 0.6565 (7) | 0.9391 (5) | 0.0772 (19) | |
O10 | 0.5134 (4) | 0.8470 (6) | 0.7078 (4) | 0.0631 (15) | |
O11 | 0.5835 (5) | 0.7754 (8) | 0.6180 (5) | 0.090 (2) | |
O12 | 0.5775 (7) | 0.6506 (8) | 0.7226 (6) | 0.133 (4) | |
N1 | 0.3675 (4) | 0.2352 (7) | 0.5721 (4) | 0.0526 (16) | |
N2 | 0.4229 (4) | 0.2579 (8) | 0.8192 (4) | 0.0540 (16) | |
N3 | 0.6510 (4) | 0.7709 (7) | 0.9349 (4) | 0.0483 (14) | |
N4 | 0.5619 (5) | 0.7555 (8) | 0.6814 (4) | 0.0604 (18) | |
C1 | 0.6837 (5) | 0.3915 (7) | 0.8294 (5) | 0.060 (2) | |
H1A | 0.6429 | 0.4648 | 0.8289 | 0.090* | |
H1B | 0.7038 | 0.3988 | 0.7790 | 0.090* | |
H1C | 0.7320 | 0.3997 | 0.8801 | 0.090* | |
C2 | 0.7210 (4) | 0.1124 (7) | 0.8308 (5) | 0.0529 (19) | |
H2A | 0.7023 | 0.0173 | 0.8306 | 0.079* | |
H2B | 0.7678 | 0.1294 | 0.8818 | 0.079* | |
H2C | 0.7403 | 0.1293 | 0.7806 | 0.079* | |
C3 | 0.5843 (6) | 0.3866 (8) | 0.5626 (6) | 0.067 (2) | |
H3A | 0.5897 | 0.4675 | 0.5986 | 0.100* | |
H3B | 0.5244 | 0.3721 | 0.5321 | 0.100* | |
H3C | 0.6171 | 0.4001 | 0.5219 | 0.100* | |
C4 | 0.6083 (6) | 0.1054 (8) | 0.5471 (5) | 0.062 (2) | |
H4A | 0.6281 | 0.0175 | 0.5739 | 0.093* | |
H4B | 0.6403 | 0.1283 | 0.5070 | 0.093* | |
H4C | 0.5477 | 0.0992 | 0.5171 | 0.093* | |
C5 | 0.3409 (6) | 0.6328 (8) | 0.6760 (6) | 0.077 (3) | |
H5A | 0.3576 | 0.5492 | 0.7092 | 0.115* | |
H5B | 0.3811 | 0.6509 | 0.6432 | 0.115* | |
H5C | 0.2837 | 0.6213 | 0.6374 | 0.115* | |
C6 | 0.3078 (5) | 0.9117 (7) | 0.6719 (5) | 0.063 (2) | |
H6A | 0.3049 | 0.9959 | 0.7030 | 0.095* | |
H6B | 0.2517 | 0.8914 | 0.6334 | 0.095* | |
H6C | 0.3488 | 0.9234 | 0.6391 | 0.095* | |
C7 | 0.4072 (6) | 0.6304 (8) | 0.9534 (6) | 0.067 (2) | |
H7A | 0.4519 | 0.5628 | 0.9560 | 0.100* | |
H7B | 0.3591 | 0.6128 | 0.9036 | 0.100* | |
H7C | 0.3882 | 0.6236 | 1.0045 | 0.100* | |
C8 | 0.3604 (6) | 0.9110 (8) | 0.9430 (6) | 0.079 (3) | |
H8A | 0.3776 | 1.0060 | 0.9392 | 0.118* | |
H8B | 0.3427 | 0.8988 | 0.9946 | 0.118* | |
H8C | 0.3129 | 0.8888 | 0.8936 | 0.118* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.03216 (13) | 0.03823 (13) | 0.03674 (15) | −0.00125 (9) | 0.00681 (10) | −0.00276 (9) |
Pt2 | 0.03241 (13) | 0.03691 (13) | 0.04320 (17) | −0.00029 (9) | 0.00523 (10) | 0.00013 (10) |
S1 | 0.0412 (9) | 0.0472 (8) | 0.0372 (9) | 0.0000 (7) | 0.0044 (7) | 0.0023 (7) |
S2 | 0.0400 (9) | 0.0552 (9) | 0.0384 (10) | −0.0011 (7) | 0.0082 (7) | −0.0021 (8) |
S3 | 0.0484 (10) | 0.0618 (10) | 0.0476 (12) | −0.0065 (9) | 0.0044 (9) | −0.0007 (9) |
S4 | 0.0547 (12) | 0.0644 (12) | 0.0453 (12) | 0.0019 (9) | 0.0107 (9) | −0.0021 (8) |
O1 | 0.047 (3) | 0.054 (3) | 0.042 (3) | 0.002 (2) | −0.005 (2) | −0.007 (2) |
O2 | 0.039 (3) | 0.105 (5) | 0.065 (4) | 0.002 (3) | −0.010 (3) | −0.013 (3) |
O3 | 0.092 (5) | 0.065 (4) | 0.131 (7) | 0.029 (4) | −0.025 (5) | −0.034 (4) |
O4 | 0.063 (3) | 0.055 (3) | 0.084 (4) | −0.010 (3) | 0.041 (3) | −0.005 (3) |
O5 | 0.064 (4) | 0.123 (5) | 0.082 (5) | 0.012 (4) | 0.046 (4) | 0.008 (4) |
O6 | 0.082 (4) | 0.054 (3) | 0.070 (4) | 0.006 (3) | 0.025 (3) | −0.009 (3) |
O7 | 0.048 (3) | 0.047 (3) | 0.072 (4) | −0.003 (2) | −0.011 (3) | 0.003 (3) |
O8 | 0.036 (3) | 0.121 (6) | 0.068 (5) | 0.006 (3) | −0.006 (3) | −0.006 (3) |
O9 | 0.071 (4) | 0.064 (4) | 0.083 (5) | 0.010 (3) | 0.001 (4) | 0.010 (3) |
O10 | 0.060 (3) | 0.063 (3) | 0.069 (4) | 0.016 (3) | 0.022 (3) | 0.017 (3) |
O11 | 0.088 (5) | 0.116 (5) | 0.075 (5) | 0.022 (4) | 0.037 (4) | 0.006 (4) |
O12 | 0.209 (10) | 0.097 (5) | 0.137 (8) | 0.090 (6) | 0.123 (8) | 0.061 (5) |
N1 | 0.034 (3) | 0.062 (4) | 0.057 (4) | 0.004 (3) | 0.005 (3) | −0.006 (3) |
N2 | 0.046 (4) | 0.073 (4) | 0.044 (4) | 0.011 (3) | 0.016 (3) | 0.002 (3) |
N3 | 0.039 (3) | 0.060 (4) | 0.044 (4) | 0.009 (3) | 0.008 (3) | −0.006 (3) |
N4 | 0.076 (5) | 0.072 (4) | 0.038 (4) | 0.015 (4) | 0.025 (4) | 0.010 (3) |
C1 | 0.075 (5) | 0.045 (4) | 0.049 (5) | −0.013 (4) | −0.001 (4) | −0.003 (3) |
C2 | 0.042 (4) | 0.052 (4) | 0.059 (5) | 0.008 (3) | 0.005 (3) | 0.008 (3) |
C3 | 0.082 (6) | 0.055 (5) | 0.065 (6) | −0.002 (4) | 0.023 (5) | 0.008 (4) |
C4 | 0.071 (5) | 0.061 (5) | 0.055 (5) | 0.003 (4) | 0.019 (4) | −0.012 (4) |
C5 | 0.080 (6) | 0.063 (5) | 0.069 (6) | −0.003 (5) | −0.009 (5) | −0.025 (5) |
C6 | 0.059 (5) | 0.051 (4) | 0.062 (5) | 0.003 (4) | −0.010 (4) | 0.010 (4) |
C7 | 0.102 (7) | 0.053 (4) | 0.049 (5) | 0.000 (5) | 0.028 (5) | 0.009 (4) |
C8 | 0.118 (8) | 0.056 (5) | 0.084 (7) | 0.019 (5) | 0.065 (6) | 0.009 (4) |
Geometric parameters (Å, º) top
Pt1—O1 | 2.037 (5) | N1—O3 | 1.198 (9) |
Pt1—O4 | 2.038 (5) | N1—O2 | 1.211 (8) |
Pt1—S1 | 2.2382 (17) | C1—H1A | 0.9600 |
Pt1—S2 | 2.2398 (18) | C1—H1B | 0.9600 |
Pt2—O10 | 2.029 (6) | C1—H1C | 0.9600 |
Pt2—O7 | 2.045 (5) | C2—H2A | 0.9600 |
Pt2—S3 | 2.2304 (19) | C2—H2B | 0.9600 |
Pt2—S4 | 2.269 (2) | C2—H2C | 0.9600 |
S1—C1 | 1.785 (7) | C3—H3A | 0.9600 |
S1—C2 | 1.794 (7) | C3—H3B | 0.9600 |
S2—C4 | 1.785 (7) | C3—H3C | 0.9600 |
S2—C3 | 1.786 (8) | C4—H4A | 0.9600 |
S3—C5 | 1.749 (8) | C4—H4B | 0.9600 |
S3—C6 | 1.764 (7) | C4—H4C | 0.9600 |
S4—C8 | 1.759 (8) | C6—H6A | 0.9600 |
S4—C7 | 1.771 (8) | C6—H6B | 0.9600 |
O4—N2 | 1.344 (8) | C6—H6C | 0.9600 |
O1—N1 | 1.301 (7) | C8—H8A | 0.9600 |
O10—N4 | 1.322 (9) | C8—H8B | 0.9600 |
O6—N2 | 1.216 (9) | C8—H8C | 0.9600 |
O7—N3 | 1.293 (8) | C7—H7A | 0.9600 |
N2—O5 | 1.215 (8) | C7—H7B | 0.9600 |
O9—N3 | 1.199 (9) | C7—H7C | 0.9600 |
N4—O11 | 1.187 (9) | C5—H5A | 0.9600 |
N4—O12 | 1.193 (9) | C5—H5B | 0.9600 |
N3—O8 | 1.213 (8) | C5—H5C | 0.9600 |
| | | |
Pt1···Pt2 | 6.3048 (4) | S2···O8iii | 3.341 (8) |
Pt1···Pt2i | 4.3070 (4) | Pt1···O3 | 2.953 (7) |
Pt1···O10i | 3.388 (6) | Pt1···O6 | 2.988 (7) |
Pt2i···O4 | 3.365 (6) | Pt2···O9 | 2.981 (6) |
O5···S3ii | 3.339 (6) | Pt2···O12 | 2.950 (11) |
| | | |
O1—Pt1—O4 | 87.0 (2) | H1A—C1—H1C | 109.5 |
O1—Pt1—S1 | 172.51 (15) | H1B—C1—H1C | 109.5 |
O4—Pt1—S1 | 87.80 (19) | S1—C2—H2A | 109.5 |
O1—Pt1—S2 | 92.65 (15) | S1—C2—H2B | 109.5 |
O4—Pt1—S2 | 177.75 (16) | H2A—C2—H2B | 109.5 |
S1—Pt1—S2 | 92.33 (6) | S1—C2—H2C | 109.5 |
O10—Pt2—O7 | 88.8 (2) | H2A—C2—H2C | 109.5 |
O10—Pt2—S3 | 92.48 (17) | H2B—C2—H2C | 109.5 |
O7—Pt2—S3 | 175.96 (16) | S2—C3—H3A | 109.5 |
O10—Pt2—S4 | 173.59 (19) | S2—C3—H3B | 109.5 |
O7—Pt2—S4 | 86.74 (18) | H3A—C3—H3B | 109.5 |
S3—Pt2—S4 | 91.64 (8) | S2—C3—H3C | 109.5 |
C1—S1—C2 | 100.1 (4) | H3A—C3—H3C | 109.5 |
C1—S1—Pt1 | 108.9 (3) | H3B—C3—H3C | 109.5 |
C2—S1—Pt1 | 108.2 (3) | S2—C4—H4A | 109.5 |
C4—S2—C3 | 100.5 (4) | S2—C4—H4B | 109.5 |
C4—S2—Pt1 | 107.4 (3) | H4A—C4—H4B | 109.5 |
C3—S2—Pt1 | 105.4 (3) | S2—C4—H4C | 109.5 |
C5—S3—C6 | 101.8 (4) | H4A—C4—H4C | 109.5 |
C5—S3—Pt2 | 107.1 (3) | H4B—C4—H4C | 109.5 |
C6—S3—Pt2 | 106.7 (3) | S3—C6—H6A | 109.5 |
C8—S4—C7 | 104.3 (4) | S3—C6—H6B | 109.5 |
C8—S4—Pt2 | 108.5 (3) | H6A—C6—H6B | 109.5 |
C7—S4—Pt2 | 107.2 (3) | S3—C6—H6C | 109.5 |
N2—O4—Pt1 | 118.6 (5) | H6A—C6—H6C | 109.5 |
N1—O1—Pt1 | 118.3 (4) | H6B—C6—H6C | 109.5 |
N4—O10—Pt2 | 120.6 (5) | S4—C8—H8A | 109.5 |
N3—O7—Pt2 | 119.3 (4) | S4—C8—H8B | 109.5 |
O5—N2—O6 | 124.9 (7) | H8A—C8—H8B | 109.5 |
O5—N2—O4 | 116.8 (7) | S4—C8—H8C | 109.5 |
O6—N2—O4 | 118.3 (6) | H8A—C8—H8C | 109.5 |
O11—N4—O12 | 123.4 (8) | H8B—C8—H8C | 109.5 |
O11—N4—O10 | 121.0 (7) | S4—C7—H7A | 109.5 |
O12—N4—O10 | 115.5 (7) | S4—C7—H7B | 109.5 |
O9—N3—O8 | 125.0 (7) | H7A—C7—H7B | 109.5 |
O9—N3—O7 | 119.7 (6) | S4—C7—H7C | 109.5 |
O8—N3—O7 | 115.3 (7) | H7A—C7—H7C | 109.5 |
O3—N1—O2 | 125.5 (7) | H7B—C7—H7C | 109.5 |
O3—N1—O1 | 118.0 (6) | S3—C5—H5A | 109.5 |
O2—N1—O1 | 116.6 (6) | S3—C5—H5B | 109.5 |
S1—C1—H1A | 109.5 | H5A—C5—H5B | 109.5 |
S1—C1—H1B | 109.5 | S3—C5—H5C | 109.5 |
H1A—C1—H1B | 109.5 | H5A—C5—H5C | 109.5 |
S1—C1—H1C | 109.5 | H5B—C5—H5C | 109.5 |
| | | |
O4—Pt1—S1—C1 | −127.7 (3) | O1—Pt1—O4—N2 | −117.7 (5) |
S2—Pt1—S1—C1 | 54.5 (3) | S1—Pt1—O4—N2 | 67.7 (5) |
O4—Pt1—S1—C2 | 124.3 (3) | O4—Pt1—O1—N1 | 70.4 (5) |
S2—Pt1—S1—C2 | −53.4 (3) | S2—Pt1—O1—N1 | −111.8 (5) |
O1—Pt1—S2—C4 | −41.0 (3) | O7—Pt2—O10—N4 | 74.7 (6) |
S1—Pt1—S2—C4 | 133.5 (3) | S3—Pt2—O10—N4 | −109.1 (6) |
O1—Pt1—S2—C3 | 65.6 (3) | O10—Pt2—O7—N3 | −115.5 (5) |
S1—Pt1—S2—C3 | −120.0 (3) | S4—Pt2—O7—N3 | 69.1 (5) |
O10—Pt2—S3—C5 | 58.3 (4) | Pt1—O4—N2—O5 | 176.7 (6) |
S4—Pt2—S3—C5 | −126.6 (4) | Pt1—O4—N2—O6 | −5.5 (9) |
O10—Pt2—S3—C6 | −50.1 (3) | Pt2—O10—N4—O11 | −178.6 (7) |
S4—Pt2—S3—C6 | 125.0 (3) | Pt2—O10—N4—O12 | 5.5 (12) |
O7—Pt2—S4—C8 | 124.7 (4) | Pt2—O7—N3—O9 | −1.1 (9) |
S3—Pt2—S4—C8 | −51.6 (3) | Pt2—O7—N3—O8 | 178.1 (5) |
O7—Pt2—S4—C7 | −123.2 (4) | Pt1—O1—N1—O3 | 17.5 (10) |
S3—Pt2—S4—C7 | 60.5 (3) | Pt1—O1—N1—O2 | −162.7 (6) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O12 | 0.96 | 2.49 | 3.226 (11) | 133 |
(I_150)
cis-Bis(dimethyl sulfide)dinitratoplatinum(II)
top
Crystal data top
[Pt(NO3)2(C2H6S)2] | F(000) = 1664 |
Mr = 443.37 | Dx = 2.517 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 12110 reflections |
a = 15.9689 (7) Å | θ = 2.5–32.8° |
b = 9.5020 (3) Å | µ = 12.36 mm−1 |
c = 16.0399 (7) Å | T = 150 K |
β = 105.940 (3)° | Prism, pale yellow |
V = 2340.26 (16) Å3 | 0.25 × 0.08 × 0.05 mm |
Z = 8 | |
Data collection top
Oxford Diffraction XCALIBUR3 diffractometer | 8007 independent reflections |
Radiation source: Sealed tube | 6244 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
ω scans | θmax = 32.8°, θmin = 2.5° |
Absorption correction: numerical CrysAlis RED (Oxford Diffraction, 2006) | h = −23→24 |
Tmin = 0.374, Tmax = 0.771 | k = −14→9 |
23004 measured reflections | l = −23→24 |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0355P)2] where P = (Fo2 + 2Fc2)/3 |
8007 reflections | (Δ/σ)max = 0.002 |
271 parameters | Δρmax = 2.62 e Å−3 |
0 restraints | Δρmin = −2.34 e Å−3 |
Crystal data top
[Pt(NO3)2(C2H6S)2] | V = 2340.26 (16) Å3 |
Mr = 443.37 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 15.9689 (7) Å | µ = 12.36 mm−1 |
b = 9.5020 (3) Å | T = 150 K |
c = 16.0399 (7) Å | 0.25 × 0.08 × 0.05 mm |
β = 105.940 (3)° | |
Data collection top
Oxford Diffraction XCALIBUR3 diffractometer | 8007 independent reflections |
Absorption correction: numerical CrysAlis RED (Oxford Diffraction, 2006) | 6244 reflections with I > 2σ(I) |
Tmin = 0.374, Tmax = 0.771 | Rint = 0.062 |
23004 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 0.97 | Δρmax = 2.62 e Å−3 |
8007 reflections | Δρmin = −2.34 e Å−3 |
271 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.532562 (11) | 0.198653 (15) | 0.704705 (11) | 0.01629 (5) | |
Pt2 | 0.478116 (11) | 0.819369 (15) | 0.818719 (11) | 0.01656 (5) | |
S1 | 0.63436 (7) | 0.22584 (10) | 0.83136 (7) | 0.0183 (2) | |
S2 | 0.62792 (7) | 0.23680 (10) | 0.62734 (7) | 0.0192 (2) | |
S3 | 0.33898 (7) | 0.77936 (10) | 0.74629 (7) | 0.0199 (2) | |
S4 | 0.44911 (8) | 0.80584 (10) | 0.94804 (7) | 0.0202 (2) | |
O1 | 0.4353 (2) | 0.1506 (3) | 0.5950 (2) | 0.0229 (7) | |
O2 | 0.3023 (2) | 0.1934 (3) | 0.5227 (2) | 0.0325 (8) | |
O3 | 0.3780 (3) | 0.3569 (4) | 0.6026 (3) | 0.0523 (13) | |
O4 | 0.4421 (2) | 0.1594 (3) | 0.7719 (2) | 0.0252 (7) | |
O5 | 0.3662 (3) | 0.2367 (4) | 0.8541 (3) | 0.0380 (9) | |
O6 | 0.4635 (2) | 0.3733 (3) | 0.8257 (2) | 0.0324 (8) | |
O7 | 0.6051 (2) | 0.8663 (3) | 0.8820 (2) | 0.0241 (7) | |
O8 | 0.7266 (2) | 0.8045 (4) | 0.9725 (3) | 0.0364 (9) | |
O9 | 0.6195 (3) | 0.6563 (3) | 0.9428 (2) | 0.0346 (9) | |
O10 | 0.5098 (2) | 0.8508 (3) | 0.7038 (2) | 0.0243 (7) | |
O11 | 0.5775 (2) | 0.7744 (4) | 0.6120 (2) | 0.0337 (8) | |
O12 | 0.5783 (3) | 0.6501 (4) | 0.7253 (3) | 0.0493 (12) | |
N1 | 0.3692 (3) | 0.2376 (4) | 0.5727 (2) | 0.0238 (8) | |
N2 | 0.4232 (3) | 0.2624 (4) | 0.8190 (3) | 0.0239 (8) | |
N3 | 0.6518 (3) | 0.7702 (4) | 0.9348 (2) | 0.0225 (8) | |
N4 | 0.5580 (3) | 0.7540 (4) | 0.6805 (3) | 0.0253 (8) | |
C1 | 0.6827 (3) | 0.3970 (4) | 0.8313 (3) | 0.0271 (10) | |
H1A | 0.6393 | 0.4683 | 0.8281 | 0.041* | |
H1B | 0.7057 | 0.4051 | 0.7821 | 0.041* | |
H1C | 0.7290 | 0.4090 | 0.8836 | 0.041* | |
C2 | 0.7259 (3) | 0.1159 (4) | 0.8327 (3) | 0.0254 (10) | |
H2A | 0.7073 | 0.0195 | 0.8251 | 0.038* | |
H2B | 0.7692 | 0.1262 | 0.8873 | 0.038* | |
H2C | 0.7501 | 0.1430 | 0.7866 | 0.038* | |
C3 | 0.5864 (3) | 0.3897 (4) | 0.5626 (3) | 0.0274 (10) | |
H3A | 0.5874 | 0.4690 | 0.6000 | 0.041* | |
H3B | 0.5277 | 0.3723 | 0.5289 | 0.041* | |
H3C | 0.6221 | 0.4093 | 0.5246 | 0.041* | |
C4 | 0.6089 (3) | 0.1039 (4) | 0.5440 (3) | 0.0258 (10) | |
H4A | 0.6192 | 0.0125 | 0.5703 | 0.039* | |
H4B | 0.6477 | 0.1186 | 0.5084 | 0.039* | |
H4C | 0.5498 | 0.1098 | 0.5087 | 0.039* | |
C5 | 0.3438 (4) | 0.6358 (5) | 0.6741 (3) | 0.0337 (12) | |
H5A | 0.3664 | 0.5535 | 0.7075 | 0.051* | |
H5B | 0.3812 | 0.6610 | 0.6388 | 0.051* | |
H5C | 0.2864 | 0.6165 | 0.6377 | 0.051* | |
C6 | 0.3070 (3) | 0.9214 (4) | 0.6698 (3) | 0.0281 (10) | |
H6A | 0.2991 | 1.0055 | 0.6999 | 0.042* | |
H6B | 0.2533 | 0.8976 | 0.6278 | 0.042* | |
H6C | 0.3515 | 0.9367 | 0.6409 | 0.042* | |
C7 | 0.4042 (4) | 0.6339 (4) | 0.9547 (3) | 0.0303 (11) | |
H7A | 0.4433 | 0.5635 | 0.9444 | 0.045* | |
H7B | 0.3490 | 0.6258 | 0.9119 | 0.045* | |
H7C | 0.3963 | 0.6207 | 1.0114 | 0.045* | |
C8 | 0.3568 (3) | 0.9159 (4) | 0.9440 (3) | 0.0260 (10) | |
H8A | 0.3699 | 1.0110 | 0.9315 | 0.039* | |
H8B | 0.3437 | 0.9129 | 0.9989 | 0.039* | |
H8C | 0.3075 | 0.8828 | 0.8993 | 0.039* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.01557 (8) | 0.01708 (7) | 0.01558 (8) | −0.00081 (5) | 0.00320 (6) | −0.00159 (5) |
Pt2 | 0.01622 (8) | 0.01621 (7) | 0.01617 (8) | −0.00033 (5) | 0.00265 (6) | 0.00013 (5) |
S1 | 0.0195 (5) | 0.0187 (4) | 0.0158 (5) | 0.0001 (4) | 0.0032 (4) | 0.0010 (4) |
S2 | 0.0197 (5) | 0.0227 (4) | 0.0148 (5) | −0.0005 (4) | 0.0040 (4) | −0.0008 (4) |
S3 | 0.0194 (5) | 0.0220 (4) | 0.0167 (5) | −0.0023 (4) | 0.0021 (4) | −0.0002 (4) |
S4 | 0.0206 (5) | 0.0222 (5) | 0.0164 (5) | 0.0007 (4) | 0.0029 (4) | −0.0018 (4) |
O1 | 0.0216 (17) | 0.0245 (13) | 0.0196 (16) | 0.0026 (12) | 0.0005 (13) | −0.0038 (12) |
O2 | 0.0180 (18) | 0.047 (2) | 0.0265 (19) | 0.0012 (14) | −0.0041 (15) | −0.0069 (15) |
O3 | 0.048 (3) | 0.0269 (17) | 0.066 (3) | 0.0123 (17) | −0.011 (2) | −0.0198 (19) |
O4 | 0.0250 (18) | 0.0262 (14) | 0.0252 (17) | −0.0072 (13) | 0.0084 (14) | −0.0039 (13) |
O5 | 0.032 (2) | 0.051 (2) | 0.038 (2) | 0.0042 (17) | 0.0226 (18) | 0.0034 (18) |
O6 | 0.040 (2) | 0.0242 (15) | 0.037 (2) | −0.0013 (14) | 0.0167 (17) | −0.0058 (14) |
O7 | 0.0203 (17) | 0.0237 (14) | 0.0244 (17) | 0.0001 (12) | −0.0002 (13) | 0.0041 (12) |
O8 | 0.0190 (19) | 0.053 (2) | 0.032 (2) | 0.0037 (15) | −0.0011 (16) | −0.0032 (16) |
O9 | 0.040 (2) | 0.0223 (15) | 0.037 (2) | 0.0037 (14) | 0.0039 (17) | 0.0023 (14) |
O10 | 0.0295 (18) | 0.0235 (14) | 0.0230 (16) | 0.0070 (13) | 0.0122 (14) | 0.0039 (12) |
O11 | 0.030 (2) | 0.0435 (18) | 0.0285 (19) | 0.0119 (16) | 0.0092 (16) | 0.0042 (16) |
O12 | 0.081 (3) | 0.0393 (19) | 0.039 (2) | 0.036 (2) | 0.037 (2) | 0.0237 (18) |
N1 | 0.020 (2) | 0.0299 (18) | 0.0194 (19) | 0.0023 (15) | 0.0013 (15) | −0.0014 (15) |
N2 | 0.019 (2) | 0.0303 (18) | 0.023 (2) | 0.0040 (15) | 0.0078 (16) | 0.0037 (15) |
N3 | 0.0177 (19) | 0.0282 (17) | 0.0205 (19) | 0.0059 (15) | 0.0036 (15) | −0.0045 (15) |
N4 | 0.027 (2) | 0.0278 (18) | 0.024 (2) | 0.0020 (16) | 0.0109 (17) | 0.0045 (15) |
C1 | 0.036 (3) | 0.0172 (18) | 0.023 (2) | −0.0028 (17) | 0.000 (2) | 0.0017 (16) |
C2 | 0.022 (2) | 0.0232 (19) | 0.028 (2) | 0.0039 (16) | 0.0017 (19) | 0.0035 (17) |
C3 | 0.035 (3) | 0.0221 (19) | 0.027 (2) | 0.0008 (18) | 0.011 (2) | 0.0028 (17) |
C4 | 0.029 (3) | 0.025 (2) | 0.023 (2) | −0.0010 (17) | 0.0069 (19) | −0.0068 (17) |
C5 | 0.039 (3) | 0.025 (2) | 0.030 (3) | −0.005 (2) | −0.001 (2) | −0.0115 (19) |
C6 | 0.024 (2) | 0.0232 (19) | 0.030 (2) | −0.0009 (17) | −0.0044 (19) | 0.0050 (18) |
C7 | 0.042 (3) | 0.024 (2) | 0.030 (3) | −0.002 (2) | 0.018 (2) | 0.0063 (18) |
C8 | 0.033 (3) | 0.0218 (19) | 0.025 (2) | 0.0027 (17) | 0.012 (2) | −0.0005 (17) |
Geometric parameters (Å, º) top
Pt1—O1 | 2.053 (3) | N1—O2 | 1.220 (5) |
Pt1—O4 | 2.061 (3) | N1—O3 | 1.224 (5) |
Pt1—S1 | 2.2411 (11) | C1—H1A | 0.9600 |
Pt1—S2 | 2.2424 (11) | C1—H1B | 0.9600 |
Pt2—O7 | 2.053 (3) | C1—H1C | 0.9600 |
Pt2—O10 | 2.063 (3) | C2—H2A | 0.9600 |
Pt2—S3 | 2.2390 (11) | C2—H2B | 0.9600 |
Pt2—S4 | 2.2499 (12) | C2—H2C | 0.9600 |
S1—C2 | 1.791 (4) | C3—H3A | 0.9600 |
S1—C1 | 1.801 (4) | C3—H3B | 0.9600 |
S2—C3 | 1.803 (4) | C3—H3C | 0.9600 |
S2—C4 | 1.804 (4) | C4—H4A | 0.9600 |
S3—C6 | 1.801 (4) | C4—H4B | 0.9600 |
S3—C5 | 1.804 (5) | C4—H4C | 0.9600 |
S4—C8 | 1.794 (4) | C6—H6A | 0.9600 |
S4—C7 | 1.799 (4) | C6—H6B | 0.9600 |
O4—N2 | 1.320 (5) | C6—H6C | 0.9600 |
O1—N1 | 1.312 (5) | C8—H8A | 0.9600 |
O10—N4 | 1.317 (5) | C8—H8B | 0.9600 |
O6—N2 | 1.223 (5) | C8—H8C | 0.9600 |
O7—N3 | 1.326 (5) | C7—H7A | 0.9600 |
N2—O5 | 1.219 (5) | C7—H7B | 0.9600 |
O9—N3 | 1.221 (5) | C7—H7C | 0.9600 |
N4—O12 | 1.211 (5) | C5—H5A | 0.9600 |
N4—O11 | 1.236 (5) | C5—H5B | 0.9600 |
N3—O8 | 1.225 (5) | C5—H5C | 0.9600 |
| | | |
Pt1···Pt2 | 6.3056 (3) | S2···O8iii | 3.228 (5) |
Pt1···Pt2i | 4.2382 (2) | Pt1···O3 | 2.969 (4) |
Pt1···O10i | 3.325 (3) | Pt1···O6 | 2.985 (3) |
Pt2i···O4 | 3.331 (3) | Pt2···O9 | 2.999 (3) |
O5···S3ii | 3.255 (4) | Pt2···O12 | 2.951 (5) |
| | | |
O1—Pt1—O4 | 86.24 (13) | H1A—C1—H1C | 109.5 |
O1—Pt1—S1 | 172.81 (9) | H1B—C1—H1C | 109.5 |
O4—Pt1—S1 | 89.12 (10) | S1—C2—H2A | 109.5 |
O1—Pt1—S2 | 91.74 (9) | S1—C2—H2B | 109.5 |
O4—Pt1—S2 | 177.86 (9) | H2A—C2—H2B | 109.5 |
S1—Pt1—S2 | 92.82 (4) | S1—C2—H2C | 109.5 |
O7—Pt2—O10 | 87.63 (13) | H2A—C2—H2C | 109.5 |
O7—Pt2—S3 | 176.96 (8) | H2B—C2—H2C | 109.5 |
O10—Pt2—S3 | 90.75 (10) | S2—C3—H3A | 109.5 |
O7—Pt2—S4 | 88.98 (10) | S2—C3—H3B | 109.5 |
O10—Pt2—S4 | 174.44 (9) | H3A—C3—H3B | 109.5 |
S3—Pt2—S4 | 92.44 (4) | S2—C3—H3C | 109.5 |
C2—S1—C1 | 100.3 (2) | H3A—C3—H3C | 109.5 |
C2—S1—Pt1 | 109.28 (16) | H3B—C3—H3C | 109.5 |
C1—S1—Pt1 | 107.94 (15) | S2—C4—H4A | 109.5 |
C3—S2—C4 | 100.2 (2) | S2—C4—H4B | 109.5 |
C3—S2—Pt1 | 104.51 (17) | H4A—C4—H4B | 109.5 |
C4—S2—Pt1 | 107.20 (16) | S2—C4—H4C | 109.5 |
C6—S3—C5 | 100.6 (2) | H4A—C4—H4C | 109.5 |
C6—S3—Pt2 | 106.36 (15) | H4B—C4—H4C | 109.5 |
C5—S3—Pt2 | 104.48 (18) | S3—C6—H6A | 109.5 |
C8—S4—C7 | 101.2 (2) | S3—C6—H6B | 109.5 |
C8—S4—Pt2 | 107.94 (16) | H6A—C6—H6B | 109.5 |
C7—S4—Pt2 | 107.06 (17) | S3—C6—H6C | 109.5 |
N2—O4—Pt1 | 117.9 (3) | H6A—C6—H6C | 109.5 |
N1—O1—Pt1 | 117.2 (2) | H6B—C6—H6C | 109.5 |
N4—O10—Pt2 | 117.3 (3) | S4—C8—H8A | 109.5 |
N3—O7—Pt2 | 118.1 (3) | S4—C8—H8B | 109.5 |
O5—N2—O6 | 124.9 (4) | H8A—C8—H8B | 109.5 |
O5—N2—O4 | 115.6 (4) | S4—C8—H8C | 109.5 |
O6—N2—O4 | 119.5 (4) | H8A—C8—H8C | 109.5 |
O12—N4—O11 | 124.2 (4) | H8B—C8—H8C | 109.5 |
O12—N4—O10 | 118.8 (4) | S4—C7—H7A | 109.5 |
O11—N4—O10 | 116.9 (4) | S4—C7—H7B | 109.5 |
O9—N3—O8 | 124.4 (4) | H7A—C7—H7B | 109.5 |
O9—N3—O7 | 119.9 (4) | S4—C7—H7C | 109.5 |
O8—N3—O7 | 115.6 (4) | H7A—C7—H7C | 109.5 |
O2—N1—O3 | 124.2 (4) | H7B—C7—H7C | 109.5 |
O2—N1—O1 | 117.1 (4) | S3—C5—H5A | 109.5 |
O3—N1—O1 | 118.6 (4) | S3—C5—H5B | 109.5 |
S1—C1—H1A | 109.5 | H5A—C5—H5B | 109.5 |
S1—C1—H1B | 109.5 | S3—C5—H5C | 109.5 |
H1A—C1—H1B | 109.5 | H5A—C5—H5C | 109.5 |
S1—C1—H1C | 109.5 | H5B—C5—H5C | 109.5 |
| | | |
O4—Pt1—S1—C2 | 127.90 (18) | O1—Pt1—O4—N2 | −120.5 (3) |
S2—Pt1—S1—C2 | −51.21 (16) | S1—Pt1—O4—N2 | 65.0 (3) |
O4—Pt1—S1—C1 | −123.9 (2) | O4—Pt1—O1—N1 | 67.4 (3) |
S2—Pt1—S1—C1 | 56.95 (18) | S2—Pt1—O1—N1 | −113.3 (3) |
O1—Pt1—S2—C3 | 65.99 (19) | O7—Pt2—O10—N4 | 72.7 (3) |
S1—Pt1—S2—C3 | −119.56 (17) | S3—Pt2—O10—N4 | −109.9 (3) |
O1—Pt1—S2—C4 | −39.78 (18) | O10—Pt2—O7—N3 | −121.2 (3) |
S1—Pt1—S2—C4 | 134.67 (16) | S4—Pt2—O7—N3 | 63.2 (3) |
O10—Pt2—S3—C6 | −49.16 (19) | Pt1—O4—N2—O5 | 176.4 (3) |
S4—Pt2—S3—C6 | 126.29 (18) | Pt1—O4—N2—O6 | −4.7 (5) |
O10—Pt2—S3—C5 | 56.7 (2) | Pt2—O10—N4—O12 | 2.8 (6) |
S4—Pt2—S3—C5 | −127.84 (18) | Pt2—O10—N4—O11 | −179.3 (3) |
O7—Pt2—S4—C8 | 128.12 (18) | Pt2—O7—N3—O9 | 1.8 (5) |
S3—Pt2—S4—C8 | −49.18 (16) | Pt2—O7—N3—O8 | −178.4 (3) |
O7—Pt2—S4—C7 | −123.6 (2) | Pt1—O1—N1—O2 | −161.5 (3) |
S3—Pt2—S4—C7 | 59.08 (19) | Pt1—O1—N1—O3 | 18.7 (5) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O12 | 0.96 | 2.40 | 3.146 (6) | 134 |
C1—H1A···O9 | 0.96 | 2.65 | 3.358 (6) | 131 |
C2—H2A···O7i | 0.96 | 2.54 | 3.288 (6) | 135 |
C3—H3A···O12 | 0.96 | 2.68 | 3.624 (6) | 168 |
C4—H4A···O11i | 0.96 | 2.50 | 3.398 (6) | 156 |
C5—H5A···O3 | 0.96 | 2.56 | 2.997 (7) | 108 |
C6—H6B···O5iv | 0.96 | 2.52 | 3.209 (6) | 128 |
C8v—H8Av···O5vi | 0.96 | 2.47 | 3.393 (6) | 161 |
Symmetry codes: (i) x, y−1, z; (iv) −x+1/2, y+1/2, −z+3/2; (v) x−1/2, −y+3/2, z−1/2; (vi) x−1/2, −y+1/2, z−1/2. |
Experimental details
| (I_295) | (I_150) |
Crystal data |
Chemical formula | [Pt(NO3)2(C2H6S)2] | [Pt(NO3)2(C2H6S)2] |
Mr | 443.37 | 443.37 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 295 | 150 |
a, b, c (Å) | 16.0762 (11), 9.5937 (5), 16.1552 (11) | 15.9689 (7), 9.5020 (3), 16.0399 (7) |
β (°) | 106.402 (4) | 105.940 (3) |
V (Å3) | 2390.2 (3) | 2340.26 (16) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 12.10 | 12.36 |
Crystal size (mm) | 0.25 × 0.08 × 0.05 | 0.25 × 0.08 × 0.05 |
|
Data collection |
Diffractometer | Oxford Diffraction XCALIBUR3 diffractometer | Oxford Diffraction XCALIBUR3 diffractometer |
Absorption correction | Numerical (CrysAlis RED; Oxford Diffraction, 2006) | Numerical CrysAlis RED (Oxford Diffraction, 2006) |
Tmin, Tmax | 0.405, 0.771 | 0.374, 0.771 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23666, 8172, 4952 | 23004, 8007, 6244 |
Rint | 0.062 | 0.062 |
(sin θ/λ)max (Å−1) | 0.765 | 0.762 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.120, 0.95 | 0.032, 0.077, 0.97 |
No. of reflections | 8172 | 8007 |
No. of parameters | 271 | 271 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 3.82, −2.66 | 2.62, −2.34 |
Selected interatomic distances (Å) for (I_150) topPt1—O1 | 2.053 (3) | Pt2—O7 | 2.053 (3) |
Pt1—O4 | 2.061 (3) | Pt2—O10 | 2.063 (3) |
Pt1—S1 | 2.2411 (11) | Pt2—S3 | 2.2390 (11) |
Pt1—S2 | 2.2424 (11) | Pt2—S4 | 2.2499 (12) |
| | | |
Pt1···Pt2 | 6.3056 (3) | Pt1···O3 | 2.969 (4) |
Pt1···Pt2i | 4.2382 (2) | Pt1···O6 | 2.985 (3) |
Pt1···O10i | 3.325 (3) | Pt2···O9 | 2.999 (3) |
Pt2i···O4 | 3.331 (3) | Pt2···O12 | 2.951 (5) |
Symmetry code: (i) x, y−1, z. |
Hydrogen-bond geometry (Å, º) for (I_150) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O12 | 0.96 | 2.40 | 3.146 (6) | 134 |
C1—H1A···O9 | 0.96 | 2.65 | 3.358 (6) | 131 |
C2—H2A···O7i | 0.96 | 2.54 | 3.288 (6) | 135 |
C3—H3A···O12 | 0.96 | 2.68 | 3.624 (6) | 168 |
C4—H4A···O11i | 0.96 | 2.50 | 3.398 (6) | 156 |
C5—H5A···O3 | 0.96 | 2.56 | 2.997 (7) | 108 |
C6—H6B···O5ii | 0.96 | 2.52 | 3.209 (6) | 128 |
C8iii—H8Aiii···O5iv | 0.96 | 2.47 | 3.393 (6) | 161 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x−1/2, −y+3/2, z−1/2; (iv) x−1/2, −y+1/2, z−1/2. |
Table 3a. The coordination mode of the nitrate ion for cis-Pt(NO3)2L2 compounds found in the CSD. A complete Table with all parameters defined in Fig. 2 is deposited. topRefcode | Donor | l1 | l2 | l3 | A1 | A4 |
(I)a | S | 2.053 (3) | 2.969 (4) | 1.312 (5) | 117.2 (2) | 124.2 (4) |
| S | 2.061 (3) | 2.985 (3) | 1.320 (5) | 117.9 (3) | 124.9 (4) |
| S | 2.053 (3) | 2.99 (3) | 1.326 (5) | 118.1 (3) | 124.4 (4) |
| S | 2.063 (3) | 2.951 (5) | 1.317 (5) | 117.3 (3) | 124.2 (4) |
APUMONb | P/P | 2.10/2.13 | 2.90/2.91 | 1.33/1.30 | 113.5/114.7 | 126.8/124.7 |
ICUVEHc | N/N | 2.02/2.03 | 2.96/2.98 | 1.34/1.27 | 117.0/121.1 | 123.5/122.7 |
ICUVORc | N/N | 2.02/2.03 | 2.94/2.92 | 1.32/1.30 | 117.1/117.4 | 125.3/123.9 |
ICUVUXc | N/N | 2.03/2.04 | 2.98/2.99 | 1.31/1.32 | 119.0/119.5 | 125.3/125.1 |
LALNIVd | P/P | 2.11/2.14 | 2.99/3.02 | 1.31/1.29 | 118.2/118.0 | 124.1/123.3 |
NARQAZe | N/N | 2.04/2.05 | 2.98/2.98 | 1.32/1.32 | 117.7/117.6 | 124.9/124.4 |
QIHTOQf | P/P | 2.11/2.12 | 2.91/2.95 | 1.28/1.26 | 113.6/116.2 | 121.6/122.2 |
TAZZOJg | S/S | 2.04/2.06 | 3.07/2.95 | 1.36/1.31 | 115.8/115.7 | 123.1/124.3 |
WIJWERh | P/P | 2.09/2.10 | 2.98/2.91 | 1.26/1.29 | 119.5/115.9 | 122.7/123.0 |
XABZACi | P/P | 2.08/2.10 | 3.09/3.15 | 1.33/1.32 | 121.6/121.9 | 124.6/122.5 |
| P/P | 2.09/2.10 | 3.13/3.14 | 1.32/1.31 | 122.4/122.3 | 121.1/122.5 |
XIKJACj | P/P | 2.13/2.13 | 2.88/2.88 | 1.31/1.31 | 111.8/111.8 | 123.6/123.6 |
Notes: (a) this paper; (b) Longato et al. (2003); (c) Tessier & Rochon (2001); (d) Suzuki et al. (1993); (e) Grabner et al. (2005); (f) Arendse et al. (2001); (g) Boström et al. (1991); (h) Redwine et al. (2000); (i) Anandhi et al. (2003); (j) Kuehl et al. (2001). |
Table 3 b. trans-Pt(NO3)2L2 compound found in the CSD. topRefcode | Donor | l1 | l2 | l3 | A1 | A4 |
ICUVADa | N | 2.01 | 2.96 | 1.31 | 118.7 | 123.5 |
ICUVILa | N | 2.02 | 2.93 | 1.32 | 117.9 | 125.0 |
Notes: (a) Tessier & Rochon (2001). |
The cis/trans-PtL2X2 complexes, where X is a halogen and L a ligand with a donor atom from groups 14, 15 or 16, have been extensively studied in the solid state (Cambridge Structural Database; Allen, 2002). However, data for cis/trans-PtL2X2 where X = NO3 are relatively scarce. We report here the structure of the title compound, (I), with emphasis on (a) the coordination mode of the nitrate ion in relation to other cis/trans-PtL2(NO3)2 structures and (b) the packing arrangement of the complex. As the crystal structure analysis showed some abnormal displacement ellipsoid parameters at 295 K, data were recollected at 150 K.
cis-Pt(Me2S)2(NO3)2 (Fig. 1) crystallizes in P21/n with two independent complexes that both have angles around the PtII centre ranging from 86.24 (13) to 92.82 (4)° at 150 K. The Pt—S bond lengths range from 2.2390 (11) to 2.2499 (12) Å, and the Pt—O bond lengths are 2.053 (3)–2.063 (3) Å. These values illustrate the different trans influences of the O and S atoms. The Pt—O distances are elongated (~0.05 Å) compared with those in [Pt(NO3)4]2− (Elding & Oskarsson, 1985), and the Pt—S distances are shortened by a similar value when compared with [Pt(Me2S)4]2+ (Bugarcic et al., 1991). The parameters describing the coordination mode are defined in Fig. 2. The nitrate ions clearly coordinate in an monodentate fashion, with the second closest O atom located about 3.0 Å from PtII (Table 1). This is further supported by the N—O distances, which for the coordinated O atoms are about 0.1 Å longer than for uncoordinated ones, which are both similar. Both nitrate ions are located on the same side of the coordination plane, with Pt—OA—N angles in a narrow range (~117–118°; Table 3). The Pt—OA—N—OB torsion angle is a measure of the deviation of the Pt atom from the nitrate plane; these angles are less than 5°, with the exception of the Pt1—O1—N1—O3 angle [18.7 (5)°]. The tilts between the nitrate plane and the coordination plane are ~63–70° (from the S—Pt—OA—N torsion angles; see deposited material). The Me2S molecules coordinate to PtII in a staggered or nearly-staggered fashion with respect to the coordination plane. The two sulfide ligands are oriented in the same direction, and the Me2S molecule with the largest deviation from the staggered mode is the S2 ligand, which has C3—S2—Pt1—O1 and C4—S2—Pt1—O1 torsion angles of ~66 and ~-41°, respectively, at both temperatures.
Neither of the complexes show pseudo-symmetry, although (I) may adopt molecular point group symmetries C2, Cs or C2v. Density functional theory (DFT) calculations for the complex in the gas phase using the observed geometry as starting parameters result in only 6 kJ mol−1 higher energy compared with a Cs geometry with the Me2S ligands pointing away from each other.
Intramolecular S···O interactions are present, with distances of 3.046 (3) Å for S1···O6 and 3.091 (5) Å for S4···O9 (at 150 K), as well as an intramolecular C—H···O interaction [H4C···O1 = 2.61 Å, in the Pt1 complex, and H6C···O10 = 2.58 Å in the Pt2 complex (at 150 K)].
The difference in geometry (excluding H atoms) between the two complexes was analysed by an r.m.s. overlay (Fig. 3), yielding 0.177 Å at 150 K and 0.153 Å at 295 K. The difference between the complexes at the two temperatures has been analysed by a half-normal probability plot. The 28 bonds involving non-H atoms in each asymmetric unit were used in the analysis. Plotting observed values of δmi versus the values αi expected for a half-normal distribution of errors (International Tables for Crystallography, 1974, Vol IV) gives a straight line δmi = 3.08αi + 0.102 with R =, indicating negligible systematic differences but overly optimistic s.u. values in one or both structure analyses (deposited material), with no outliers.
In space group P21/n with Z' = 2 there are more than 14 possible choices for the pair of complexes in the asymmetric unit. Some result in a close contact of the two complexes and may be called a dimer, and some are more remote. Fig. 1 shows two reasonable choices for the asymmetric unit. The Pt1 and Pt2 complexes form a sandwiched dimer with pseudo-symmetry Ci across (0.51 0.51 0.76) [~(1/2 1/2 3/4)] stabilized by C—H···O interactions (Table 2) and have a Pt1···Pt2 distance of 6.3056 (3) Å. A second choice is the complexes Pt1 and Pt2i, which also form a sandwiched dimer with pseudo-symmetry Ci but now across (0.51 0.00 0.76) [~(1/2 0 3/4)], stabilized by Pt1···O10i and Pt2i···O4 interactions and with a Pt1···Pt2i distance of 4.2382 (2) Å (symmetry code as in Table 1). DFT calculations on this second dimer show a stabilizing energy of ~70 kJ (mole monomer)−1 in the gas phase, which seems too high. The dimers are stacked in columns along the b axis. The centres of pseudo-symmetry, (1/2 1/2 3/4) and (1/2 0 3/4), are as far away as possible from the space group operators, 21, n and −1, in accordance with the findings of Collins (2006) for molecular pairs in Z' =2 structures. Each column is surrounded by six other columns in a pseudo-honeycomb rod-like packing (O'Keeffe & Andersson, 1977) stabilized by C—H···O (H···O = 2.47–2.69 Å and C—H···O = 117–161°) and C—H···S (H···S = 2.96 Å and C—H···S = 149°) interactions and S···O contacts [3.228 (5) and 3.255 (4) Å] (Fig. 4). The H···O distances are long (Steiner & Desiraju, 1998) but still shorter than the average CH2—H···O distance [2.761 (6) Å] retrieved from 767 structures in the Cambridge Structural Database (CSD; Version 5.28 of November 2006; Allen, 2002).
The symmetry centers create voids of different sizes. Rings of four molecules are formed around the inversion centres at (0 1/2 1/2) with H8Biv···S1v and H8Aiv···O5iii interactions; at (1/2 1/2 1/2) with H5A···O3 and H4Cii···O11 interactions; at (0 1/2 0) with H4Aiii···O11iv and H4Ciii···O11vi interactions; and at (1/2 1/2 0) with H1Aii···O9ii and H8Bvii···S1ii interactions [symmetry codes (ii) −x + 1, −y + 1, −z + 1; (iii) x − 1/2, −y + 1/2, z − 1/2; (iv) x − 1/2, −y + 3/2, z − 1/2; (v) −x + 1/2, y + 1/2, −z + 3/2; (vi) −x + 1/2, y − 1/2, −z + 1/2; (vii) x, y, z − 1].[match with Table 2]
A search of the CSD for cis/trans-PtIIL2(NO3)2 complexes, where L is a ligand with a donor atom from groups 14, 15 or 16, using the CONQUEST software (Bruno et al., 2002) resulted in 11 cis and two trans compounds (Table 3). The dominance of the cis complexes may indicate a preference for cis complexes in the solid state, in contrast to the result of DFT calculations in the gas phase. The energies of two complexes reported as both cis and trans in the CSD are 30–40 kJ mol−1 lower for the corresponding trans complexes. All complexes listed in Table 3 have l2 − l1 > 0.75 Å, thus fullfilling the criterion for monodentate coordination for nitrate ligands, l2 − l1 > 0.6, suggested by Kleywegt et al. (1985; see Fig. 2 for definition of parameters describing the coordination mode). This is further supported by the l3 distances, which have an average of 1.31 (2) Å, where the error is calculated from 〈[Σ(L - Lavr)2]/(n − 1)〉1/2, compared with l4 and l5 which are similar and placed together give an average of 1.22 (2) Å. The angle A1 is slightly below 120°, as expected for a simple bonding model with OA sp2-hybridized, with an average of 118 (3)°. The angle A4 is consistently greater than 120°, with an average of 123.8 (12)°, correlating well with the elongated l3 distance. The torsion angle t1 gives the orientation of the nitrate ions with respect to the coordination plane; nitrate ions located on opposite sides of the coordination plane have the same sign on t1. Out of 14 cis complexes, seven have nitrate ions on opposite sides, five on the same side and two in the plane. With the exception of the ions roughly in the coordination plane, the nitrate ions form an angle of (90 ± 30)° with the coordination plane. The Pt atom is normally close to the nitrate plane, as shown by t2, but exceptions with t2 as large as −33.3° have been observed.
The cis complexes also give information about the trans-influence of the donor atom trans to the nitrate ligand. The Pt—O distances are 2.02–2.05 Å in the N-donor complexes, 2.04–2.06 Å in the S-donor complexes and 2.08–2.14 Å in the P-donor complexes, suggesting the following trans-influence series between the donor atoms: N < S < P. Although the number of complexes is small, the series is in agreement with previous findings (Otto & Johansson, 2002).
The Kitaigordosky packing index, KPI, calculated as described by Hansson (2007), is 0.72 and 0.74 at 295 and 150 K, respectively, compared with 0.65 and 0.68 for cis-PtCl2(Et2S)2 (Hansson, 2007). Compound (I) is thus more close packed, which is further supported by the different thermal expansion coefficients [1/V dV/dT; 1.5 × 10 −4 K−1 for (I) and 2.3 × 10 −4 K−1 for cis-PtCl2(Et2S)2].