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The title compound, [PtI2(S2C4H8)], consists of a 1,4-di­thia­ne and two iodo ligands coordinated to a Pt atom in a distorted square-planar cis-system with Pt on a twofold axis. The di­thiane forms a bidentate chelate with Pt, bonding via the S atoms. The Pt-I bonds are 2.6035 (5) Å and the Pt-S bonds 2.2751 (16) Å. The Pt-S bond is influenced mainly by the cis-chelate effect and the Pt-I bond by the trans-influence of sulfur.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002951/bt6015sup1.cif
Contains datablocks I, sad

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002951/bt6015Isup2.hkl
Contains datablock I

CCDC reference: 159832

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.011 Å
  • R factor = 0.026
  • wR factor = 0.049
  • Data-to-parameter ratio = 37.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.168 0.268 Tmin and Tmax expected: 0.142 0.288 RR = 1.274 Please check that your absorption correction is appropriate. PLAT_711 Alert C BOND Unknown or Inconsistent Label ........ PT PT S1 PLAT_711 Alert C BOND Unknown or Inconsistent Label ........ PT PT S1 PLAT_711 Alert C BOND Unknown or Inconsistent Label ........ PT PT I1 PLAT_711 Alert C BOND Unknown or Inconsistent Label ........ PT PT I1 PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ PT S1 PT S1 PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ PT S1 PT I1 PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ PT S1 PT I1 PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ PT S1 PT I1 PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ PT S1 PT I1 PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ PT I1 PT I1 PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ PT C2 S1 PT PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ PT C1 S1 PT General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C4 H8 I2 Pt1 S2 Atom count from _chemical_formula_moiety: ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 1.074 Tmax scaled 0.288 Tmin scaled 0.180 REFLT_03 From the CIF: _diffrn_reflns_theta_max 31.98 From the CIF: _reflns_number_total 1625 Count of symmetry unique reflns 1050 Completeness (_total/calc) 154.76% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 575 Fraction of Friedel pairs measured 0.548 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
13 Alert Level C = Please check

Comment top

1,4-Dithiane [dit, S(C2H4)2S] is the thioether analogue of the antitumor agent piperazine (Ciccarese et al., 1998). Very few compounds with 1,4-dithiane as a bidentate ligand have been crystallographically characterized. The only metal–organic compound with a chelating dithiane found in the Cambridge Structural Database (CSD; Allen & Kennard, 1993) is an osmium cluster (Adams et al., 1995). Platinum halide compounds with thioether ligands have been investigated earlier and it is found that most of the chloro and bromo compounds structurally characterized adopt a cis-configuration, while the trans-configuration is mainly observed for iodo complexes (Lövqvist, 1996). Only two cis-platinum–iodo–thioether complexes are found in the CSD, both with chelating thioethers, diiodo[1,2-bis(phenylsulfanyl)ethane]platinum(II) (Marangoni et al., 1995) and diiodo(1,3,5,7-tetrametyl-2,4,6,8-tetrathiaadamantane)platinum(II) (Levy & Long, 1975).

The title compound, (I), crystallizes in the tetragonal space group P43212 with the Pt atom on a twofold rotation axis. The dithiane forms a bidentate chelate with platinum(II), forcing the compound to adopt cis-configuration with the two I atoms in trans-positions to the dithiane S atoms (Fig. 1). The dithiane molecule must assume the boat conformation to be able to bind as a bidentate ligand. Bond lengths and angles are shown in Table 1. The complex exhibits a distorted square-planar geometry with angles around Pt from 79.74 (8) to 93.76 (4)°. The S—C distances, 1.818 (7) and 1.810 (7) Å, and the S—C—C angles, 111.6 (5) and 112.9 (5)°, are close to those found in free dithiane, even though the free form adopts the chair conformation (Marsh, 1955). The C—C bond seems to get elongated, 1.538 (10) versus 1.490 (18) Å, and the C—S—C angles become smaller, 97.4 (4) versus 99.0 (6)°, upon bidentate complexation with platinum. The closest contact between the complexes is S1···C1(-0.5 + x, 1.5 - y, 0.25 - z) of 3.729 (1) Å and the shortest Pt···Pt distance is 6.213 (1) Å.

In Table 2, cis- and trans-diiodoplatinum compounds with thioethers from the literature are listed. There are only two cis-compounds found and they both have bidentate chelating thioethers. The Pt—I bond distance in the title compound, 2.6035 (5) Å, is close to those reported for the other cis-compound. The Pt—I distances in the trans-compounds shows a wider range, 2.6039 (8) to 2.616 (1) Å.

The range of Pt—I bond distance trans to simple bidentate N-donor ligands with two C atoms between the N atoms in the CSD are 2.574 (2)–2.591 (2) Å (Casas et al., 1998; Ciccarese et al., 1998; Clark et al., 1995; Connick & Gray, 1994; Fanizzi et al., 1996; Mégnamisi-Bélombé & Endres, 1985) with one exception, 4,7-Ph2-phen (phen = 1,10-phenanthroline), where the Pt—I distances are 2.558 (2) Å (Fanizzi et al., 1996). In chelating bidentate ligand complexes trans to P atoms, the Pt—I bond distances are in the range 2.6480 (9)–2.662 (2) Å (Wilson et al., 1994; Dahlenburg & Kurth, 1998). The differences in Pt—I bond length trans to S, N and P are thus consistent with the trans-influence series, where P > S > N (Greenwood & Earnshaw, 1997). The difference between P and S trans-influence is clearly shown in [PtI2(PhPC6H12S)], where I is trans to both S and P, with Pt—I distances 2.598 (3) and 2.639 (2) Å, respectively.

In Table 2, the Pt—S distances in the above mentioned thioether compounds are shown. In the cis-compounds the Pt—S bond distances are 2.265 (2) and 2.280 (8) Å. The Pt—S bond of 2.2751 (16) Å for [PtI2(dit)] lies within the range for the above-mentioned values obtained from literature. The average Pt—S bond distance for systems with S atoms trans to each other and cis to I is 2.305 (2) Å. These differences in the Pt—S bonds may be due to a cis-chelate effect, even though sulfur has a larger trans-influence than iodine. The cis-chelate effect is mainly referred to as a kinetic effect, but Marangoni et al. (1995) have performed comparative studies between Pt—S(thioether) bonds from both chelating and simple thioethers with the same atom in trans-position for a number of different PtII compounds. The chelating compounds yield shorter bond lengths, independent of the atom in trans-position and this is most probably due to electronic effects; the empty orbitals of sulfur is properly orientated towards the filled dxy orbitals of platinum, resulting in easier π(d–d) back-donation.

The bite angle of the bidentate dithiane, 79.74 (8)°, is larger than the angle for N-methylpiperazine, 70.1 (7)° (Ciccarese et al., 1998). This difference is probably due to the larger atomic radius of sulfur compared to nitrogen, but the bite angle for PhS(CH2)2SPh is larger than for both the others, 91.00 (8)°, as would be expected because only one-carbon chain forms the chelating backbone in the latter (Marangoni et al., 1995).

Experimental top

PtI2 (100 mg, 0.223 mmol) was added to an ethanol solution (5 ml) of 1,4 dithiane (30 mg, 0.245 mmol). The solution was stirred for 5 h at ambient temperature. The orange precipitate was filtered and washed with water (2 × 5 ml), ethanol (2 × 5 ml) and chloroform (3 × 5 ml) (yield 96 mg, 76%). Crystals of good quality were obtained by recrystallization from hot DMSO.

Refinement top

H atoms were refined with fixed individual displacement parameters [U(H) = 1.2Ueq(C)] using a riding model with C—H = 0.97 Å.

Computing details top

Data collection: SMART (Bruker, 1995); cell refinement: SAINT (Bruker, 1995); data reduction: SAINT (Bruker, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Numbering scheme with displacement ellipsoids (30% probability) for the title compound.
(I) top
Crystal data top
[PtI2(C4H8S2)]Dx = 3.818 Mg m3
Mr = 569.11Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212Cell parameters from 4610 reflections
a = 8.9850 (13) Åθ = 2.8–29°
c = 12.265 (3) ŵ = 20.75 mm1
V = 990.2 (3) Å3T = 293 K
Z = 4Prism, orange
F(000) = 9920.10 × 0.09 × 0.06 mm
Data collection top
Bruker SMART CCD
diffractometer
1625 independent reflections
Radiation source: rotating anode1387 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.061
Detector resolution: 512 pixels mm-1θmax = 32.0°, θmin = 2.8°
ω scansh = 1312
Absorption correction: empirical (using intensity measurements)
absorption corrections using SADABS (Sheldrick, 1996)
k = 1213
Tmin = 0.168, Tmax = 0.268l = 1318
10493 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.026 w = 1/[σ2(Fo2) + (0.0174P)2 + 1.0607P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.049(Δ/σ)max < 0.001
S = 1.05Δρmax = 1.04 e Å3
1625 reflectionsΔρmin = 1.06 e Å3
43 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.00217 (15)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.009 (7)
Crystal data top
[PtI2(C4H8S2)]Z = 4
Mr = 569.11Mo Kα radiation
Tetragonal, P43212µ = 20.75 mm1
a = 8.9850 (13) ÅT = 293 K
c = 12.265 (3) Å0.10 × 0.09 × 0.06 mm
V = 990.2 (3) Å3
Data collection top
Bruker SMART CCD
diffractometer
1625 independent reflections
Absorption correction: empirical (using intensity measurements)
absorption corrections using SADABS (Sheldrick, 1996)
1387 reflections with I > 2σ(I)
Tmin = 0.168, Tmax = 0.268Rint = 0.061
10493 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.049Δρmax = 1.04 e Å3
S = 1.05Δρmin = 1.06 e Å3
1625 reflectionsAbsolute structure: Flack (1983)
43 parametersAbsolute structure parameter: 0.009 (7)
0 restraints
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
xyzUiso*/Ueq
Pt10.41705 (2)0.41705 (2)0.00000.02798 (9)
I10.16998 (4)0.38139 (5)0.10777 (4)0.04066 (13)
S10.47268 (18)0.63627 (18)0.08341 (14)0.0395 (4)
C10.6621 (8)0.5942 (9)0.1253 (6)0.0539 (18)
H1A0.71190.68570.14630.065*
H1B0.65980.52930.18850.065*
C20.5186 (9)0.7505 (8)0.0334 (6)0.0482 (17)
H2A0.42820.79550.06140.058*
H2B0.58440.83010.01030.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.02567 (10)0.02567 (10)0.03261 (16)0.00257 (12)0.00085 (9)0.00085 (9)
I10.0309 (2)0.0475 (3)0.0436 (2)0.00299 (17)0.00695 (17)0.00693 (18)
S10.0319 (7)0.0351 (8)0.0515 (10)0.0032 (6)0.0032 (7)0.0146 (7)
C10.042 (4)0.063 (5)0.057 (4)0.001 (4)0.008 (3)0.012 (4)
C20.052 (4)0.026 (3)0.066 (5)0.002 (3)0.004 (4)0.003 (3)
Geometric parameters (Å, º) top
Pt—S12.2751 (16)S1—C21.810 (7)
Pt—S1i2.2751 (16)S1—C11.818 (7)
Pt—I1i2.6035 (5)C1—C2i1.538 (10)
Pt—I12.6035 (5)C2—C1i1.538 (10)
S1—Pt—S1i79.74 (8)C2—S1—C197.4 (4)
S1—Pt—I1i173.50 (4)C2—S1—Pt100.7 (2)
S1i—Pt—I1i93.76 (4)C1—S1—Pt98.8 (2)
S1—Pt—I193.76 (4)C2i—C1—S1111.6 (5)
S1i—Pt—I1173.50 (4)C1i—C2—S1112.9 (5)
I1i—Pt—I192.74 (2)
Symmetry code: (i) y, x, z.

Experimental details

Crystal data
Chemical formula[PtI2(C4H8S2)]
Mr569.11
Crystal system, space groupTetragonal, P43212
Temperature (K)293
a, c (Å)8.9850 (13), 12.265 (3)
V3)990.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)20.75
Crystal size (mm)0.10 × 0.09 × 0.06
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
absorption corrections using SADABS (Sheldrick, 1996)
Tmin, Tmax0.168, 0.268
No. of measured, independent and
observed [I > 2σ(I)] reflections
10493, 1625, 1387
Rint0.061
(sin θ/λ)max1)0.745
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.049, 1.05
No. of reflections1625
No. of parameters43
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.04, 1.06
Absolute structureFlack (1983)
Absolute structure parameter0.009 (7)

Computer programs: SMART (Bruker, 1995), SAINT (Bruker, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.

Selected geometric parameters (Å, º) top
Pt—S12.2751 (16)S1—C11.818 (7)
Pt—I12.6035 (5)C1—C2i1.538 (10)
S1—C21.810 (7)
S1—Pt—S1i79.74 (8)C2—S1—Pt100.7 (2)
S1—Pt—I1i173.50 (4)C1—S1—Pt98.8 (2)
S1i—Pt—I1i93.76 (4)C2i—C1—S1111.6 (5)
I1i—Pt—I192.74 (2)C1i—C2—S1112.9 (5)
C2—S1—C197.4 (4)
Symmetry code: (i) y, x, z.
Comparative table of bond lengths and angles of structurally related PtI2L/PtI2L2 (L = mono- or bidentate thioether ligands) complexes top
ComplexM—SM—IS—M—SI—M—I
cis-[PtI2(dit)]a2.2751 (16)2.6035 (5)79.74 (8)92.74 (2)
cis-[PtI2(PhS(CH2)2SPh)]b2.265 (2)2.601 (1)91.00 (8)93.22 (2)
trans-[PtI2(SMe2)2]c2.310 (2)2.6039 (8)180180
trans-[PtI2(SOMe2)2]d2.289 (2)2.6111 (9)180180
trans-[PtI2(C4H8S)2]e2.309 (1)2.606 (1)180180
2.310 (1)2.616 (1)
Notes: [no distances are reported for diiodo(1,3,5,7-tetramethyl-2,4,6,8-tetrathiaadamantane)platinum(II) (Levy & Long, 1975)] (a) this study; (b) Marangoni et al., (1995); (c) Lövqvist et al., (1996); (d) Lövqvist, (1996); (e) (C4H8S = tetrahydrothiophene) Oskarsson et al., (1990).
 

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