metal-organic compounds
(5,5′-Dimethyl-2,2′-bipyridine)iodidotrimethylplatinum(IV)
aCentre for Materials Science and Nanotechnology, Department of Chemistry, University of Oslo, PO Box 1126, 0315 Oslo, Norway, bCentre for Materials Science and Nanotechnology & inGAP National Centre of Research-based Innovation, Department of Chemistry, University of Oslo, PO Box 1126, 0315 Oslo, Norway, and cCentre of Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo, PO Box 1033, 0371 Oslo, Norway
*Correspondence e-mail: fredrik.lundvall@smn.uio.no
In the title compound, [Pt(CH3)3I(C12H12N2)], the PtIV atom is six-coordinated in a slightly distorted octahedral configuration with one CH3 group and the I atom forming a near perpendicular axis relative to the square plane formed by the bipyridine ligand and the two remaining CH3 groups. The CH3 group trans to the I atom has a slightly elongated bond to Pt compared to the other CH3 groups, indicating a difference in trans influence between iodine and the bipyridine ligand.
Related literature
For synthetic background to related complexes containing Pt(CH3)3, see: Clegg et al. (1972); Vetter et al. (2006). For structural information on complexes exhibiting a similar geometrical configuration around the PtIV atom, see: Hambley (1986); Hojjat Kashani et al. (2008); Vetter, Bruhn & Steinborn (2010); Vetter, Wagner & Steinborn (2010). For examples of bimetallic metal-organic frameworks (MOFs), see: Bloch et al. (2010); Szeto et al. (2006, 2008).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536811014085/lr2005sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811014085/lr2005Isup2.hkl
The title compound was synthesized by a modified version of the method used by Clegg et al. (1972). 5,5'-dimethyl-2,2'-bipyridine (1.2 mg, 0.006 mmol) and PtIV(CH3)3I (2.0 mg, 0,005 mmol) was weighed out in an NMR-tube, and 0.5 ml of deuterated benzene (C6D6) was added. The resulting mixture was heated to 75 °C for 3 days without stirring. A number of NMR-spectra were recorded during the synthesis to monitor the formation of the complex. After the NMR-experiments were finished, the NMR-tube was left at ambient temperature for 7 days, during which crystals of the complex formed.
H-atoms were positioned geometrically at distances of 0.93(CH) and 0.96Å (CH3) and refined using a riding model with Uiso(H)=1.2 Ueq(C) and Uiso(H)=1.5 Ueq(Cmethyl)
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: publCIF (Westrip, 2010).[Pt(CH3)3I(C12H12N2)] | F(000) = 1024 |
Mr = 551.32 | Dx = 2.211 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7297 reflections |
a = 15.354 (3) Å | θ = 2.8–27.6° |
b = 12.394 (2) Å | µ = 10.33 mm−1 |
c = 9.0627 (18) Å | T = 293 K |
β = 106.222 (2)° | Plate, orange |
V = 1655.8 (6) Å3 | 0.4 × 0.4 × 0.1 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 4094 independent reflections |
Radiation source: sealed tube | 3477 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ϕ and ω scans | θmax = 29.0°, θmin = 2.2° |
Absorption correction: numerical (SADABS; Bruker, 2005) | h = −19→19 |
Tmin = 0.022, Tmax = 0.356 | k = −16→16 |
18721 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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.045P)2] where P = (Fo2 + 2Fc2)/3 |
4094 reflections | (Δ/σ)max = 0.001 |
172 parameters | Δρmax = 0.82 e Å−3 |
0 restraints | Δρmin = −2.14 e Å−3 |
[Pt(CH3)3I(C12H12N2)] | V = 1655.8 (6) Å3 |
Mr = 551.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.354 (3) Å | µ = 10.33 mm−1 |
b = 12.394 (2) Å | T = 293 K |
c = 9.0627 (18) Å | 0.4 × 0.4 × 0.1 mm |
β = 106.222 (2)° |
Bruker APEXII CCD area-detector diffractometer | 4094 independent reflections |
Absorption correction: numerical (SADABS; Bruker, 2005) | 3477 reflections with I > 2σ(I) |
Tmin = 0.022, Tmax = 0.356 | Rint = 0.048 |
18721 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.82 e Å−3 |
4094 reflections | Δρmin = −2.14 e Å−3 |
172 parameters |
Experimental. Synthesis of the complex was performed in deuterated solvent. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | 0.208561 (12) | 0.071224 (14) | 0.65323 (2) | 0.03239 (8) | |
I1 | 0.34139 (2) | 0.03855 (3) | 0.50370 (4) | 0.04465 (10) | |
N2 | 0.3088 (3) | 0.0375 (3) | 0.8682 (4) | 0.0354 (9) | |
C1 | 0.1397 (3) | −0.1655 (4) | 0.5835 (6) | 0.0412 (11) | |
H1 | 0.0981 | −0.1344 | 0.4995 | 0.049* | |
C3 | 0.1999 (4) | −0.3208 (4) | 0.7271 (7) | 0.0540 (14) | |
H3 | 0.2019 | −0.3949 | 0.7433 | 0.065* | |
C9 | 0.4219 (4) | 0.0869 (5) | 1.0999 (6) | 0.0459 (13) | |
C8 | 0.4289 (4) | −0.0211 (5) | 1.1424 (6) | 0.0512 (14) | |
H8 | 0.4691 | −0.0412 | 1.2355 | 0.061* | |
C7 | 0.3777 (4) | −0.0985 (5) | 1.0502 (7) | 0.0520 (14) | |
H7 | 0.3831 | −0.1707 | 1.0796 | 0.062* | |
N1 | 0.1984 (3) | −0.1024 (3) | 0.6788 (5) | 0.0369 (9) | |
C13 | 0.1095 (4) | 0.0898 (4) | 0.4489 (6) | 0.0440 (12) | |
H13A | 0.0845 | 0.0206 | 0.4125 | 0.066* | |
H13B | 0.1353 | 0.1220 | 0.3743 | 0.066* | |
H13C | 0.0623 | 0.1356 | 0.4643 | 0.066* | |
C2 | 0.1371 (4) | −0.2776 (4) | 0.6031 (7) | 0.0474 (13) | |
C15 | 0.1083 (4) | 0.0958 (4) | 0.7657 (6) | 0.0451 (12) | |
H15A | 0.1350 | 0.0914 | 0.8748 | 0.068* | |
H15B | 0.0623 | 0.0414 | 0.7342 | 0.068* | |
H15C | 0.0817 | 0.1658 | 0.7397 | 0.068* | |
C4 | 0.2599 (4) | −0.2542 (4) | 0.8277 (6) | 0.0507 (13) | |
H4 | 0.3021 | −0.2835 | 0.9125 | 0.061* | |
C14 | 0.2236 (4) | 0.2350 (4) | 0.6478 (6) | 0.0487 (13) | |
H14A | 0.2700 | 0.2578 | 0.7372 | 0.073* | |
H14B | 0.1673 | 0.2694 | 0.6465 | 0.073* | |
H14C | 0.2404 | 0.2548 | 0.5571 | 0.073* | |
C11 | 0.4762 (4) | 0.1730 (5) | 1.1990 (7) | 0.0587 (16) | |
H11A | 0.5147 | 0.1412 | 1.2907 | 0.088* | |
H11B | 0.4360 | 0.2239 | 1.2259 | 0.088* | |
H11C | 0.5127 | 0.2093 | 1.1441 | 0.088* | |
C12 | 0.0671 (5) | −0.3445 (5) | 0.4897 (8) | 0.0661 (17) | |
H12A | 0.0305 | −0.2984 | 0.4115 | 0.099* | |
H12B | 0.0291 | −0.3806 | 0.5422 | 0.099* | |
H12C | 0.0971 | −0.3970 | 0.4433 | 0.099* | |
C5 | 0.2577 (3) | −0.1439 (4) | 0.8034 (6) | 0.0381 (10) | |
C6 | 0.3172 (3) | −0.0669 (4) | 0.9108 (6) | 0.0358 (10) | |
C10 | 0.3605 (3) | 0.1121 (4) | 0.9595 (5) | 0.0395 (10) | |
H10 | 0.3550 | 0.1837 | 0.9276 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.02979 (11) | 0.02980 (11) | 0.03496 (12) | −0.00090 (6) | 0.00471 (8) | 0.00234 (6) |
I1 | 0.04027 (19) | 0.0491 (2) | 0.04544 (19) | −0.00213 (15) | 0.01335 (15) | −0.00193 (15) |
N2 | 0.035 (2) | 0.036 (2) | 0.034 (2) | 0.0054 (17) | 0.0069 (17) | 0.0060 (16) |
C1 | 0.043 (3) | 0.035 (3) | 0.048 (3) | 0.000 (2) | 0.018 (2) | −0.001 (2) |
C3 | 0.063 (4) | 0.032 (3) | 0.072 (4) | 0.002 (3) | 0.027 (3) | 0.006 (3) |
C9 | 0.030 (3) | 0.061 (3) | 0.042 (3) | 0.004 (2) | 0.002 (2) | −0.009 (2) |
C8 | 0.046 (3) | 0.063 (4) | 0.038 (3) | 0.009 (3) | 0.000 (2) | 0.005 (3) |
C7 | 0.051 (3) | 0.049 (3) | 0.052 (3) | 0.014 (3) | 0.008 (3) | 0.015 (3) |
N1 | 0.040 (2) | 0.033 (2) | 0.040 (2) | −0.0036 (18) | 0.0136 (19) | 0.0008 (17) |
C13 | 0.041 (3) | 0.044 (3) | 0.041 (3) | −0.007 (2) | 0.002 (2) | 0.000 (2) |
C2 | 0.052 (3) | 0.031 (2) | 0.068 (4) | −0.005 (2) | 0.031 (3) | −0.007 (2) |
C15 | 0.048 (3) | 0.037 (3) | 0.049 (3) | −0.008 (2) | 0.012 (2) | −0.002 (2) |
C4 | 0.059 (3) | 0.036 (3) | 0.055 (3) | 0.010 (3) | 0.013 (3) | 0.008 (2) |
C14 | 0.053 (3) | 0.030 (3) | 0.057 (3) | −0.003 (2) | 0.006 (3) | 0.002 (2) |
C11 | 0.044 (3) | 0.075 (4) | 0.048 (3) | 0.002 (3) | −0.001 (3) | −0.014 (3) |
C12 | 0.069 (4) | 0.046 (3) | 0.084 (5) | −0.012 (3) | 0.023 (4) | −0.012 (3) |
C5 | 0.043 (3) | 0.034 (2) | 0.041 (2) | 0.004 (2) | 0.018 (2) | 0.003 (2) |
C6 | 0.032 (2) | 0.043 (3) | 0.033 (2) | 0.0062 (19) | 0.009 (2) | 0.0047 (19) |
C10 | 0.036 (3) | 0.042 (3) | 0.037 (2) | 0.000 (2) | 0.006 (2) | −0.003 (2) |
Pt1—C14 | 2.045 (5) | N1—C5 | 1.339 (6) |
Pt1—C13 | 2.055 (5) | C13—H13A | 0.9600 |
Pt1—C15 | 2.092 (5) | C13—H13B | 0.9600 |
Pt1—N2 | 2.160 (4) | C13—H13C | 0.9600 |
Pt1—N1 | 2.175 (4) | C2—C12 | 1.511 (8) |
Pt1—I1 | 2.7755 (5) | C15—H15A | 0.9600 |
N2—C10 | 1.342 (6) | C15—H15B | 0.9600 |
N2—C6 | 1.346 (6) | C15—H15C | 0.9600 |
C1—N1 | 1.317 (6) | C4—C5 | 1.384 (7) |
C1—C2 | 1.402 (7) | C4—H4 | 0.9300 |
C1—H1 | 0.9300 | C14—H14A | 0.9600 |
C3—C2 | 1.369 (8) | C14—H14B | 0.9600 |
C3—C4 | 1.375 (8) | C14—H14C | 0.9600 |
C3—H3 | 0.9300 | C11—H11A | 0.9600 |
C9—C8 | 1.388 (8) | C11—H11B | 0.9600 |
C9—C10 | 1.392 (7) | C11—H11C | 0.9600 |
C9—C11 | 1.490 (8) | C12—H12A | 0.9600 |
C8—C7 | 1.367 (9) | C12—H12B | 0.9600 |
C8—H8 | 0.9300 | C12—H12C | 0.9600 |
C7—C6 | 1.400 (7) | C5—C6 | 1.482 (7) |
C7—H7 | 0.9300 | C10—H10 | 0.9300 |
C14—Pt1—C13 | 85.8 (2) | H13B—C13—H13C | 109.5 |
C14—Pt1—C15 | 88.3 (2) | C3—C2—C1 | 116.9 (5) |
C13—Pt1—C15 | 87.9 (2) | C3—C2—C12 | 123.2 (5) |
C14—Pt1—N2 | 99.02 (19) | C1—C2—C12 | 119.8 (5) |
C13—Pt1—N2 | 175.08 (17) | Pt1—C15—H15A | 109.5 |
C15—Pt1—N2 | 91.41 (19) | Pt1—C15—H15B | 109.5 |
C14—Pt1—N1 | 175.34 (19) | H15A—C15—H15B | 109.5 |
C13—Pt1—N1 | 98.62 (18) | Pt1—C15—H15C | 109.5 |
C15—Pt1—N1 | 90.43 (18) | H15A—C15—H15C | 109.5 |
N2—Pt1—N1 | 76.52 (16) | H15B—C15—H15C | 109.5 |
C14—Pt1—I1 | 91.72 (16) | C3—C4—C5 | 120.3 (5) |
C13—Pt1—I1 | 92.07 (16) | C3—C4—H4 | 119.8 |
C15—Pt1—I1 | 179.94 (17) | C5—C4—H4 | 119.8 |
N2—Pt1—I1 | 88.65 (10) | Pt1—C14—H14A | 109.5 |
N1—Pt1—I1 | 89.55 (11) | Pt1—C14—H14B | 109.5 |
C10—N2—C6 | 119.5 (4) | H14A—C14—H14B | 109.5 |
C10—N2—Pt1 | 124.9 (3) | Pt1—C14—H14C | 109.5 |
C6—N2—Pt1 | 115.6 (3) | H14A—C14—H14C | 109.5 |
N1—C1—C2 | 122.9 (5) | H14B—C14—H14C | 109.5 |
N1—C1—H1 | 118.5 | C9—C11—H11A | 109.5 |
C2—C1—H1 | 118.5 | C9—C11—H11B | 109.5 |
C2—C3—C4 | 119.8 (5) | H11A—C11—H11B | 109.5 |
C2—C3—H3 | 120.1 | C9—C11—H11C | 109.5 |
C4—C3—H3 | 120.1 | H11A—C11—H11C | 109.5 |
C8—C9—C10 | 116.7 (5) | H11B—C11—H11C | 109.5 |
C8—C9—C11 | 122.5 (5) | C2—C12—H12A | 109.5 |
C10—C9—C11 | 120.8 (5) | C2—C12—H12B | 109.5 |
C7—C8—C9 | 121.4 (5) | H12A—C12—H12B | 109.5 |
C7—C8—H8 | 119.3 | C2—C12—H12C | 109.5 |
C9—C8—H8 | 119.3 | H12A—C12—H12C | 109.5 |
C8—C7—C6 | 118.6 (5) | H12B—C12—H12C | 109.5 |
C8—C7—H7 | 120.7 | N1—C5—C4 | 119.6 (5) |
C6—C7—H7 | 120.7 | N1—C5—C6 | 117.1 (4) |
C1—N1—C5 | 120.3 (4) | C4—C5—C6 | 123.3 (5) |
C1—N1—Pt1 | 125.0 (3) | N2—C6—C7 | 121.0 (5) |
C5—N1—Pt1 | 114.7 (3) | N2—C6—C5 | 116.0 (4) |
Pt1—C13—H13A | 109.5 | C7—C6—C5 | 123.0 (5) |
Pt1—C13—H13B | 109.5 | N2—C10—C9 | 122.8 (5) |
H13A—C13—H13B | 109.5 | N2—C10—H10 | 118.6 |
Pt1—C13—H13C | 109.5 | C9—C10—H10 | 118.6 |
H13A—C13—H13C | 109.5 | ||
C14—Pt1—N2—C10 | 0.3 (4) | N1—C1—C2—C3 | −0.7 (8) |
C15—Pt1—N2—C10 | −88.2 (4) | N1—C1—C2—C12 | 179.4 (5) |
N1—Pt1—N2—C10 | −178.3 (4) | C2—C3—C4—C5 | −0.7 (8) |
I1—Pt1—N2—C10 | 91.9 (4) | C1—N1—C5—C4 | 3.0 (7) |
C14—Pt1—N2—C6 | 179.4 (3) | Pt1—N1—C5—C4 | −177.3 (4) |
C15—Pt1—N2—C6 | 90.9 (3) | C1—N1—C5—C6 | −175.8 (4) |
N1—Pt1—N2—C6 | 0.8 (3) | Pt1—N1—C5—C6 | 3.9 (5) |
I1—Pt1—N2—C6 | −89.1 (3) | C3—C4—C5—N1 | −1.8 (8) |
C10—C9—C8—C7 | 0.1 (8) | C3—C4—C5—C6 | 177.0 (5) |
C11—C9—C8—C7 | 179.4 (6) | C10—N2—C6—C7 | 1.3 (7) |
C9—C8—C7—C6 | −0.2 (9) | Pt1—N2—C6—C7 | −177.9 (4) |
C2—C1—N1—C5 | −1.8 (8) | C10—N2—C6—C5 | −180.0 (4) |
C2—C1—N1—Pt1 | 178.6 (4) | Pt1—N2—C6—C5 | 0.9 (5) |
C13—Pt1—N1—C1 | −2.1 (4) | C8—C7—C6—N2 | −0.4 (8) |
C15—Pt1—N1—C1 | 85.8 (4) | C8—C7—C6—C5 | −179.1 (5) |
N2—Pt1—N1—C1 | 177.1 (4) | N1—C5—C6—N2 | −3.2 (6) |
I1—Pt1—N1—C1 | −94.1 (4) | C4—C5—C6—N2 | 178.0 (5) |
C13—Pt1—N1—C5 | 178.2 (4) | N1—C5—C6—C7 | 175.5 (5) |
C15—Pt1—N1—C5 | −93.9 (4) | C4—C5—C6—C7 | −3.3 (8) |
N2—Pt1—N1—C5 | −2.5 (3) | C6—N2—C10—C9 | −1.4 (7) |
I1—Pt1—N1—C5 | 86.2 (3) | Pt1—N2—C10—C9 | 177.6 (4) |
C4—C3—C2—C1 | 1.9 (8) | C8—C9—C10—N2 | 0.8 (8) |
C4—C3—C2—C12 | −178.2 (5) | C11—C9—C10—N2 | −178.5 (5) |
Experimental details
Crystal data | |
Chemical formula | [Pt(CH3)3I(C12H12N2)] |
Mr | 551.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 15.354 (3), 12.394 (2), 9.0627 (18) |
β (°) | 106.222 (2) |
V (Å3) | 1655.8 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.33 |
Crystal size (mm) | 0.4 × 0.4 × 0.1 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Numerical (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.022, 0.356 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18721, 4094, 3477 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.681 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.078, 1.01 |
No. of reflections | 4094 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.82, −2.14 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2004), publCIF (Westrip, 2010).
Pt1—C14 | 2.045 (5) | Pt1—N2 | 2.160 (4) |
Pt1—C13 | 2.055 (5) | Pt1—N1 | 2.175 (4) |
Pt1—C15 | 2.092 (5) | Pt1—I1 | 2.7755 (5) |
C14—Pt1—C13 | 85.8 (2) | N2—Pt1—N1 | 76.52 (16) |
C13—Pt1—N1 | 98.62 (18) | C15—Pt1—I1 | 179.94 (17) |
C15—Pt1—N1 | 90.43 (18) |
Acknowledgements
We acknowledge support from the Norwegian Research Council and inGAP
References
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As a part of a larger project, the title compound and several other compounds based on substituted bipyridines and PtIV salts were synthesized in an NMR-screening for new PtIV complexes for potential application in bimetallic MOFs (Metal-Organic Frameworks). Bimetallic MOFs containing bipyridine, Pt(II) (Szeto et al., 2006, 2008) and Pd(II) (Bloch et al., 2010) have previously been reported, but so far no thermally stable bimetallic MOF containing PtIV is reported in the literature.
The title compound has previously been reported (Clegg et al., 1972) as a part of an extensive NMR-studies to find evidence for cis and trans influences in trimethylplatinum(IV) compounds. The NMR spectra of the compound is in good accordance with what was reported, and the crystal structure supports the finds with regards to trans influences.