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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811014085/lr2005sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536811014085/lr2005Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.008 Å
  • R factor = 0.031
  • wR factor = 0.078
  • Data-to-parameter ratio = 23.8

checkCIF/PLATON results

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Alert level C PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 251
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Pt1 -- I1 .. 13.00 su PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety C11
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 2 ALERT level C = Check. Ensure it is not caused by an omission or oversight 4 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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.

Related literature top

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 MOFs, see: Bloch et al. (2010); Szeto et al. (2006, 2008)

Experimental top

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.

Refinement top

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)

Structure description top

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.

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 MOFs, see: Bloch et al. (2010); Szeto et al. (2006, 2008)

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. [The asymmetric unit of the title compound with atom labels and 50% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity.]
[Figure 2] Fig. 2. [Packing diagram of the title compound viewed along the b axis. Hydrogen atoms are omitted for clarity.]
(5,5'-Dimethyl-2,2'-bipyridine)iodidotrimethylplatinum(IV) top
Crystal data top
[Pt(CH3)3I(C12H12N2)]F(000) = 1024
Mr = 551.32Dx = 2.211 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7297 reflections
a = 15.354 (3) Åθ = 2.8–27.6°
b = 12.394 (2) ŵ = 10.33 mm1
c = 9.0627 (18) ÅT = 293 K
β = 106.222 (2)°Plate, orange
V = 1655.8 (6) Å30.4 × 0.4 × 0.1 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
4094 independent reflections
Radiation source: sealed tube3477 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
φ and ω scansθmax = 29.0°, θmin = 2.2°
Absorption correction: numerical
(SADABS; Bruker, 2005)
h = 1919
Tmin = 0.022, Tmax = 0.356k = 1616
18721 measured reflectionsl = 1112
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H-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 parametersΔρmax = 0.82 e Å3
0 restraintsΔρmin = 2.14 e Å3
Crystal data top
[Pt(CH3)3I(C12H12N2)]V = 1655.8 (6) Å3
Mr = 551.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.354 (3) ŵ = 10.33 mm1
b = 12.394 (2) ÅT = 293 K
c = 9.0627 (18) Å0.4 × 0.4 × 0.1 mm
β = 106.222 (2)°
Data collection top
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 = 0.356Rint = 0.048
18721 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.078H-atom parameters constrained
S = 1.01Δρmax = 0.82 e Å3
4094 reflectionsΔρmin = 2.14 e Å3
172 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt10.208561 (12)0.071224 (14)0.65323 (2)0.03239 (8)
I10.34139 (2)0.03855 (3)0.50370 (4)0.04465 (10)
N20.3088 (3)0.0375 (3)0.8682 (4)0.0354 (9)
C10.1397 (3)0.1655 (4)0.5835 (6)0.0412 (11)
H10.09810.13440.49950.049*
C30.1999 (4)0.3208 (4)0.7271 (7)0.0540 (14)
H30.20190.39490.74330.065*
C90.4219 (4)0.0869 (5)1.0999 (6)0.0459 (13)
C80.4289 (4)0.0211 (5)1.1424 (6)0.0512 (14)
H80.46910.04121.23550.061*
C70.3777 (4)0.0985 (5)1.0502 (7)0.0520 (14)
H70.38310.17071.07960.062*
N10.1984 (3)0.1024 (3)0.6788 (5)0.0369 (9)
C130.1095 (4)0.0898 (4)0.4489 (6)0.0440 (12)
H13A0.08450.02060.41250.066*
H13B0.13530.12200.37430.066*
H13C0.06230.13560.46430.066*
C20.1371 (4)0.2776 (4)0.6031 (7)0.0474 (13)
C150.1083 (4)0.0958 (4)0.7657 (6)0.0451 (12)
H15A0.13500.09140.87480.068*
H15B0.06230.04140.73420.068*
H15C0.08170.16580.73970.068*
C40.2599 (4)0.2542 (4)0.8277 (6)0.0507 (13)
H40.30210.28350.91250.061*
C140.2236 (4)0.2350 (4)0.6478 (6)0.0487 (13)
H14A0.27000.25780.73720.073*
H14B0.16730.26940.64650.073*
H14C0.24040.25480.55710.073*
C110.4762 (4)0.1730 (5)1.1990 (7)0.0587 (16)
H11A0.51470.14121.29070.088*
H11B0.43600.22391.22590.088*
H11C0.51270.20931.14410.088*
C120.0671 (5)0.3445 (5)0.4897 (8)0.0661 (17)
H12A0.03050.29840.41150.099*
H12B0.02910.38060.54220.099*
H12C0.09710.39700.44330.099*
C50.2577 (3)0.1439 (4)0.8034 (6)0.0381 (10)
C60.3172 (3)0.0669 (4)0.9108 (6)0.0358 (10)
C100.3605 (3)0.1121 (4)0.9595 (5)0.0395 (10)
H100.35500.18370.92760.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.02979 (11)0.02980 (11)0.03496 (12)0.00090 (6)0.00471 (8)0.00234 (6)
I10.04027 (19)0.0491 (2)0.04544 (19)0.00213 (15)0.01335 (15)0.00193 (15)
N20.035 (2)0.036 (2)0.034 (2)0.0054 (17)0.0069 (17)0.0060 (16)
C10.043 (3)0.035 (3)0.048 (3)0.000 (2)0.018 (2)0.001 (2)
C30.063 (4)0.032 (3)0.072 (4)0.002 (3)0.027 (3)0.006 (3)
C90.030 (3)0.061 (3)0.042 (3)0.004 (2)0.002 (2)0.009 (2)
C80.046 (3)0.063 (4)0.038 (3)0.009 (3)0.000 (2)0.005 (3)
C70.051 (3)0.049 (3)0.052 (3)0.014 (3)0.008 (3)0.015 (3)
N10.040 (2)0.033 (2)0.040 (2)0.0036 (18)0.0136 (19)0.0008 (17)
C130.041 (3)0.044 (3)0.041 (3)0.007 (2)0.002 (2)0.000 (2)
C20.052 (3)0.031 (2)0.068 (4)0.005 (2)0.031 (3)0.007 (2)
C150.048 (3)0.037 (3)0.049 (3)0.008 (2)0.012 (2)0.002 (2)
C40.059 (3)0.036 (3)0.055 (3)0.010 (3)0.013 (3)0.008 (2)
C140.053 (3)0.030 (3)0.057 (3)0.003 (2)0.006 (3)0.002 (2)
C110.044 (3)0.075 (4)0.048 (3)0.002 (3)0.001 (3)0.014 (3)
C120.069 (4)0.046 (3)0.084 (5)0.012 (3)0.023 (4)0.012 (3)
C50.043 (3)0.034 (2)0.041 (2)0.004 (2)0.018 (2)0.003 (2)
C60.032 (2)0.043 (3)0.033 (2)0.0062 (19)0.009 (2)0.0047 (19)
C100.036 (3)0.042 (3)0.037 (2)0.000 (2)0.006 (2)0.003 (2)
Geometric parameters (Å, º) top
Pt1—C142.045 (5)N1—C51.339 (6)
Pt1—C132.055 (5)C13—H13A0.9600
Pt1—C152.092 (5)C13—H13B0.9600
Pt1—N22.160 (4)C13—H13C0.9600
Pt1—N12.175 (4)C2—C121.511 (8)
Pt1—I12.7755 (5)C15—H15A0.9600
N2—C101.342 (6)C15—H15B0.9600
N2—C61.346 (6)C15—H15C0.9600
C1—N11.317 (6)C4—C51.384 (7)
C1—C21.402 (7)C4—H40.9300
C1—H10.9300C14—H14A0.9600
C3—C21.369 (8)C14—H14B0.9600
C3—C41.375 (8)C14—H14C0.9600
C3—H30.9300C11—H11A0.9600
C9—C81.388 (8)C11—H11B0.9600
C9—C101.392 (7)C11—H11C0.9600
C9—C111.490 (8)C12—H12A0.9600
C8—C71.367 (9)C12—H12B0.9600
C8—H80.9300C12—H12C0.9600
C7—C61.400 (7)C5—C61.482 (7)
C7—H70.9300C10—H100.9300
C14—Pt1—C1385.8 (2)H13B—C13—H13C109.5
C14—Pt1—C1588.3 (2)C3—C2—C1116.9 (5)
C13—Pt1—C1587.9 (2)C3—C2—C12123.2 (5)
C14—Pt1—N299.02 (19)C1—C2—C12119.8 (5)
C13—Pt1—N2175.08 (17)Pt1—C15—H15A109.5
C15—Pt1—N291.41 (19)Pt1—C15—H15B109.5
C14—Pt1—N1175.34 (19)H15A—C15—H15B109.5
C13—Pt1—N198.62 (18)Pt1—C15—H15C109.5
C15—Pt1—N190.43 (18)H15A—C15—H15C109.5
N2—Pt1—N176.52 (16)H15B—C15—H15C109.5
C14—Pt1—I191.72 (16)C3—C4—C5120.3 (5)
C13—Pt1—I192.07 (16)C3—C4—H4119.8
C15—Pt1—I1179.94 (17)C5—C4—H4119.8
N2—Pt1—I188.65 (10)Pt1—C14—H14A109.5
N1—Pt1—I189.55 (11)Pt1—C14—H14B109.5
C10—N2—C6119.5 (4)H14A—C14—H14B109.5
C10—N2—Pt1124.9 (3)Pt1—C14—H14C109.5
C6—N2—Pt1115.6 (3)H14A—C14—H14C109.5
N1—C1—C2122.9 (5)H14B—C14—H14C109.5
N1—C1—H1118.5C9—C11—H11A109.5
C2—C1—H1118.5C9—C11—H11B109.5
C2—C3—C4119.8 (5)H11A—C11—H11B109.5
C2—C3—H3120.1C9—C11—H11C109.5
C4—C3—H3120.1H11A—C11—H11C109.5
C8—C9—C10116.7 (5)H11B—C11—H11C109.5
C8—C9—C11122.5 (5)C2—C12—H12A109.5
C10—C9—C11120.8 (5)C2—C12—H12B109.5
C7—C8—C9121.4 (5)H12A—C12—H12B109.5
C7—C8—H8119.3C2—C12—H12C109.5
C9—C8—H8119.3H12A—C12—H12C109.5
C8—C7—C6118.6 (5)H12B—C12—H12C109.5
C8—C7—H7120.7N1—C5—C4119.6 (5)
C6—C7—H7120.7N1—C5—C6117.1 (4)
C1—N1—C5120.3 (4)C4—C5—C6123.3 (5)
C1—N1—Pt1125.0 (3)N2—C6—C7121.0 (5)
C5—N1—Pt1114.7 (3)N2—C6—C5116.0 (4)
Pt1—C13—H13A109.5C7—C6—C5123.0 (5)
Pt1—C13—H13B109.5N2—C10—C9122.8 (5)
H13A—C13—H13B109.5N2—C10—H10118.6
Pt1—C13—H13C109.5C9—C10—H10118.6
H13A—C13—H13C109.5
C14—Pt1—N2—C100.3 (4)N1—C1—C2—C30.7 (8)
C15—Pt1—N2—C1088.2 (4)N1—C1—C2—C12179.4 (5)
N1—Pt1—N2—C10178.3 (4)C2—C3—C4—C50.7 (8)
I1—Pt1—N2—C1091.9 (4)C1—N1—C5—C43.0 (7)
C14—Pt1—N2—C6179.4 (3)Pt1—N1—C5—C4177.3 (4)
C15—Pt1—N2—C690.9 (3)C1—N1—C5—C6175.8 (4)
N1—Pt1—N2—C60.8 (3)Pt1—N1—C5—C63.9 (5)
I1—Pt1—N2—C689.1 (3)C3—C4—C5—N11.8 (8)
C10—C9—C8—C70.1 (8)C3—C4—C5—C6177.0 (5)
C11—C9—C8—C7179.4 (6)C10—N2—C6—C71.3 (7)
C9—C8—C7—C60.2 (9)Pt1—N2—C6—C7177.9 (4)
C2—C1—N1—C51.8 (8)C10—N2—C6—C5180.0 (4)
C2—C1—N1—Pt1178.6 (4)Pt1—N2—C6—C50.9 (5)
C13—Pt1—N1—C12.1 (4)C8—C7—C6—N20.4 (8)
C15—Pt1—N1—C185.8 (4)C8—C7—C6—C5179.1 (5)
N2—Pt1—N1—C1177.1 (4)N1—C5—C6—N23.2 (6)
I1—Pt1—N1—C194.1 (4)C4—C5—C6—N2178.0 (5)
C13—Pt1—N1—C5178.2 (4)N1—C5—C6—C7175.5 (5)
C15—Pt1—N1—C593.9 (4)C4—C5—C6—C73.3 (8)
N2—Pt1—N1—C52.5 (3)C6—N2—C10—C91.4 (7)
I1—Pt1—N1—C586.2 (3)Pt1—N2—C10—C9177.6 (4)
C4—C3—C2—C11.9 (8)C8—C9—C10—N20.8 (8)
C4—C3—C2—C12178.2 (5)C11—C9—C10—N2178.5 (5)

Experimental details

Crystal data
Chemical formula[Pt(CH3)3I(C12H12N2)]
Mr551.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)15.354 (3), 12.394 (2), 9.0627 (18)
β (°) 106.222 (2)
V3)1655.8 (6)
Z4
Radiation typeMo Kα
µ (mm1)10.33
Crystal size (mm)0.4 × 0.4 × 0.1
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionNumerical
(SADABS; Bruker, 2005)
Tmin, Tmax0.022, 0.356
No. of measured, independent and
observed [I > 2σ(I)] reflections
18721, 4094, 3477
Rint0.048
(sin θ/λ)max1)0.681
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.078, 1.01
No. of reflections4094
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
Pt1—C142.045 (5)Pt1—N22.160 (4)
Pt1—C132.055 (5)Pt1—N12.175 (4)
Pt1—C152.092 (5)Pt1—I12.7755 (5)
C14—Pt1—C1385.8 (2)N2—Pt1—N176.52 (16)
C13—Pt1—N198.62 (18)C15—Pt1—I1179.94 (17)
C15—Pt1—N190.43 (18)
 

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