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The title compound consists of [Ir(C3H6NS2)(C8H14)2] mol­ecules lying on positions with site symmetry 2. Both the coordination plane, defined by the metal, S atoms and the two midpoints of the olefinic bonds, and the di­thio­carbamate chelate system are essentially planar. The orientation of the coordinated C=C bonds with respect to the coordination plane is close to perpendicular [(C=C,Ir)/(Ir,S,S) interplanar angle: 79.4 (2)°]. The Ir-C distances are 2.144 (3) and 2.155 (3) Å, and the Ir-S bond length is 2.3661 (8) Å. Due to [pi]-coordination, the olefinic bonds are elongated to 1.424 (5) Å. The cyclo­octene ligands adopt a crown conformation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101004954/sk1462sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101004954/sk1462Isup2.hkl
Contains datablock I

CCDC reference: 166973

Comment top

Due to the known lability of olefin ligands bonded to IrI or RhI, the title compound, (I), is potentially a useful precursor of coordinatively unsaturated mixed-ligand iridium(I) dithiocarbamates. The complex was therefore prepared as a part of our studies of square-planar d8 systems containing mono- and bidentate S donor ligands and derivatives resulting therefrom by oxidative addition (Dahlenburg & Kühnlein, 1997, 2000). At the outset of these investigations there existed only a limited number of well characterized dithiocarbamatoiridium(III) complexes (Butcher & Sinn, 1976; Dean, 1979; Raston & White, 1976; Sinn, 1976) but virtually no iridium(I) derivative. Only recently the synthesis of such systems having the general formula [Ir(L)(L')(S2CNEt2)] [L/L' = cyclo-C8H12, CO/CO, PPh3/PPh3, P(OPh)3/P(OPh)3, Ph2PC2H4PPh2, (C6F5)2PC2H4P(C6F5)2, CO/PPh3] has been described, of which the mixed carbonyl(phosphine) chelate complex [Ir(CO)(PPh3)S2CNEt2] was fully characterized by single-crystal diffractometry (Suardi et al., 1997). \sch

The structure determination of (I) was undertaken because a search of the data bank located at the CCDC revealed no entry referring to a tetracoordinate 16 e iridium complex containing two π-bonded monoolefin ligands. Apparently, the only bis(olefin) complexes of IrI so far investigated by X-ray structure analysis merely include some coordinatively saturated bis(ethylene) derivatives such as [IrXL2(η2-C2H4)2] [X/L = Cl/PEt3 (Aizenberg et al., 1996), Cl/SbPri3 (Werner et al., 1996); X/L2 = tris(3,5-dimethylpyrazolyl)borate (Alvarado et al., 1997)] and [IrL3(η2-C2H4)2]X, [L, X- = PMe2Ph, BF4- (Lundquist et al., 1990); L3, X- = 1,4,7-trithiacyclononane, PF6- (Blake et al., 1994)]. With respect to bis(η2-cyclooctene) complexes of the transition metals in general, there also exists only a limited number of examples structurally characterized by X-ray diffraction; viz. [W(CO)4(η2-C8H14)2] (Toma et al., 1993), [Fe(CO)3(η2-C8H14)2] (Angermund et al., 1988), [Rh{η5-C5H4[CH(C2H4)2NMe-cyclo]}(η2-C8H14)2] (McGowan et al., 1997), and [Cu(η2-C8H14)(µ-Cl)2Cu(η2-C8H14)2] (Ganis et al., 1970).

The C-centred monoclinic unit cell of structure (I) contains four molecules of [Ir(η2-C8H14)2S2CNMe2] lying on 4 e positions with site symmetry 2. Coordination about the central iridium deviates only slightly from planarity: Although the small bite of the Me2NCS2- chelate at the central metal, 73.75 (4)°, results in cis and trans angles between the sulfur atoms and the midpoints of the coordinated double bonds declining appreciably from their idealized values of 90° and 180° [cis-S—Ir–"mid" = 96.6 (1)°, trans-S–Ir–"mid" = 170.0 (1), "mid"–Ir–"mid" = 93.2 (2)°], the sum of the four inter- and intraligand cis angles, 360.2°, is as required for a planar surrounding of the central metal. Consistently, the angle bewteen the normals to the two planes defined by the IrS2 and Ir(>CC</2)2 fragments, 3.2 (2)°, is only marginally larger than the limiting value of 0° for planar coordination.

The IrS2CNMe2 chelate system is essentially planar, the maximum deviations from the "best" l.s.q. plane through the seven non-hydrogen atoms being ±0.017 (2) Å for sulfur donors S and Si and 0.020 Å for the two methyl carbons C2 and C21. The Ir–S distance of 2.3661 (8) Å within the four-membered chelate ring is slightly shorter than those of 2.384 (3) and 2.372 (3) Å derived from the structure analysis of [Ir(CO)(PPh3)S2CNEt2] for the Ir–S bonds trans to CO and PPh3, respectively (Suardi et al., 1997).

The orientation of the olefin bonds with respect to the coordination plane is almost perpendicular, as anticipated, the value of the interplanar angle (C3,C10,Ir)/(Ir,S,S_1) being 79.4 (2)°. The Ir–C distances, 2.144 (3) and 2.155 (3) Å, show the olefinic carbon atoms are nearly equidistant from the iridium atom. It is difficult to make comparisons with the corresponding structural parameters of closely related complexes, because there is but one further example of a structurally characterized (η2-cyclooctene)iridium(I) derivative, [Ir(CO)L3(η2-C8H14)][BPh4] (L3 = 2,5,8-trithia(9)-o-cyclophane), the Ir–C distances of which [2.17 (5) and 2.18 (4) Å] could not be determined with sufficient accuracy (Jenkis & Loeb, 1994). The lengthening of the olefinic double bonds [d(>CC<) = 1.424 (5) Å versus. 1.33–1.34 Å for non-complexed cycloctenes (Ermer & Mason, 1982)] is as expected for transition metal–(>CC<) π-bonding. The –C—CC—C– fragments remain essentially planar after coordination, as judged from the C4–C3–C10–C9 torsion angle, 5.3 (5)°. The coordinated cycloctene ligands adopt a crown-like conformation, similar to that previously observed in two cyclooctene complexes of iron (Angermund et al., 1988) and copper (Ganis et al., 1970).

Related literature top

For related literature, see: Aizenberg et al. (1996); Alvarado et al. (1997); Angermund et al. (1988); Blake et al. (1994); Butcher & Sinn (1976); Dahlenburg & Kühnlein (1997, 2000); Dean (1979); Ermer & Mason (1982); Ganis et al. (1970); Lundquist et al. (1990); McGowan et al. (1997); Raston & White (1976); Sinn (1976); Suardi et al. (1997); Toma et al. (1993); Werner et al. (1996).

Experimental top

[Ir2(µ-Cl)2(η2-C8H14)4] (900 mg, 1.0 mmol) was combined with sodium N,N-dimethylcarbamate (85 mg, 0.5 mmol) in acetone (40 ml) for 6 h at ambient conditions. Filtration over Celite followed by evaporation of the solvent left the product as an orange powder which was purified by crystallization from toluene/hexane at 255 K; yield: 165 mg (62%). Found: C 42.65, H 6.62, N 2.23, S 11.87%. C19H34IrNS2 (532.7) calculated: C 42.83, H 6.43, N 2.63, S 12.03%. Single crystals were selected from the recrystallized mixture.

Refinement top

All non-hydrogen atoms were located by direct methods and subsequent alternate cycles of difference Fourier synthesis and full matrix least-squares refinement. The resulting structural model was refined to convergence with allowance for anisotropic displacement motion of the non-H atoms. The positions of the two olefinic hydrogen atoms (H3 and H10) were refined applying a restraint of 0.95 Å to the respective C–H bonds and making equivalent 1,3 C–H distances equal. The remaining H atoms were included in geometrically idealized positions employing appropriate riding models. For all hydrogen atoms, the isotropic displacement parameters were constrained to 1.2 times the Ueq of their carrier atoms. The highest peaks and deepest holes in the final difference map were located at distances less than 1.2 Å from the heavy metal atom.

Computing details top

Data collection: CAD-4 EXPRESS Software (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of (I) (40% probability displacement ellipsoids) [symmetry code: (i): -x, y, 1/2 - z].
N,N-Dimethylcarbamato-bis(η2-cyclooctene)iridium(I) top
Crystal data top
[Ir(C3H6NS2)(C8H14)2]F(000) = 1056
Mr = 532.79Dx = 1.698 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 17.9277 (10) ÅCell parameters from 25 reflections
b = 15.2675 (8) Åθ = 10.2–17.4°
c = 7.662 (3) ŵ = 6.61 mm1
β = 96.39 (1)°T = 203 K
V = 2084.0 (7) Å3Block, orange
Z = 40.4 × 0.32 × 0.19 mm
Data collection top
Nonius CAD4-MACH3
diffractometer
Rint = 0.012
non–profiled ω scansθmax = 27.5°, θmin = 2.7°
Absorption correction: ψ scan
(North et al., 1968)
h = 2323
Tmin = 0.162, Tmax = 0.533k = 219
3731 measured reflectionsl = 29
2377 independent reflections3 standard reflections every 60 min
2080 reflections with I > 2σ(I) intensity decay: <2%
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)] = 0.019Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053H atoms treated by a mixture of independent and constrained refinement
S = 1.23 w = 1/[σ2(Fo2) + (0.0245P)2 + 2.0369P]
where P = (Fo2 + 2Fc2)/3
2377 reflections(Δ/σ)max = 0.008
113 parametersΔρmax = 0.32 e Å3
4 restraintsΔρmin = 1.45 e Å3
Crystal data top
[Ir(C3H6NS2)(C8H14)2]V = 2084.0 (7) Å3
Mr = 532.79Z = 4
Monoclinic, C2/cMo Kα radiation
a = 17.9277 (10) ŵ = 6.61 mm1
b = 15.2675 (8) ÅT = 203 K
c = 7.662 (3) Å0.4 × 0.32 × 0.19 mm
β = 96.39 (1)°
Data collection top
Nonius CAD4-MACH3
diffractometer
2080 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.012
Tmin = 0.162, Tmax = 0.5333 standard reflections every 60 min
3731 measured reflections intensity decay: <2%
2377 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0194 restraints
wR(F2) = 0.053H atoms treated by a mixture of independent and constrained refinement
S = 1.23Δρmax = 0.32 e Å3
2377 reflectionsΔρmin = 1.45 e Å3
113 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ir0.00000.746161 (9)0.25000.03388 (6)
S0.07546 (4)0.62218 (5)0.21006 (13)0.04348 (19)
N0.00000.4722 (2)0.25000.0382 (8)
C10.00000.5581 (3)0.25000.0360 (8)
C20.06529 (19)0.4217 (2)0.2106 (5)0.0487 (8)
H2A0.09960.45940.15910.058*
H2B0.04940.37550.12980.058*
H2C0.08970.39680.31710.058*
C30.05786 (18)0.8420 (2)0.1112 (5)0.0459 (8)
H30.0268 (16)0.8923 (17)0.084 (4)0.055*
C40.0885 (3)0.8095 (3)0.0505 (5)0.0642 (11)
H4A0.04700.79690.13910.077*
H4B0.11510.75510.02290.077*
C50.1420 (3)0.8741 (3)0.1279 (6)0.0751 (13)
H5A0.14850.85540.24630.090*
H5B0.11840.93130.13620.090*
C60.2192 (3)0.8832 (3)0.0246 (6)0.0729 (13)
H6A0.24050.82500.00650.087*
H6B0.25110.91550.09610.087*
C70.2222 (2)0.9282 (2)0.1532 (6)0.0650 (11)
H7A0.26350.96970.16290.078*
H7B0.17630.96140.15670.078*
C80.2318 (2)0.8683 (3)0.3116 (7)0.0714 (12)
H8A0.23140.90390.41640.086*
H8B0.28080.84090.31660.086*
C90.17258 (19)0.7959 (2)0.3163 (6)0.0544 (9)
H9A0.17960.75240.22740.065*
H9B0.17890.76730.43000.065*
C100.09539 (18)0.8328 (2)0.2840 (5)0.0432 (7)
H100.0862 (16)0.8762 (18)0.370 (3)0.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ir0.02834 (9)0.03388 (9)0.04044 (10)0.0000.00834 (6)0.000
S0.0341 (4)0.0382 (4)0.0607 (5)0.0001 (3)0.0164 (3)0.0006 (3)
N0.0366 (18)0.0358 (16)0.043 (2)0.0000.0078 (15)0.000
C10.033 (2)0.040 (2)0.035 (2)0.0000.0056 (17)0.000
C20.0489 (18)0.0412 (16)0.057 (2)0.0098 (14)0.0111 (16)0.0000 (14)
C30.0392 (16)0.0425 (16)0.057 (2)0.0049 (13)0.0099 (15)0.0077 (15)
C40.073 (3)0.074 (3)0.047 (2)0.028 (2)0.0139 (19)0.0008 (19)
C50.096 (3)0.072 (3)0.062 (3)0.022 (2)0.034 (2)0.007 (2)
C60.065 (2)0.050 (2)0.113 (4)0.003 (2)0.053 (2)0.007 (2)
C70.0423 (19)0.0470 (18)0.108 (4)0.0094 (15)0.019 (2)0.000 (2)
C80.0403 (19)0.070 (2)0.102 (4)0.0159 (18)0.001 (2)0.005 (2)
C90.0387 (17)0.056 (2)0.068 (2)0.0075 (15)0.0017 (17)0.0084 (18)
C100.0388 (16)0.0395 (15)0.0526 (19)0.0068 (13)0.0111 (14)0.0067 (14)
Geometric parameters (Å, º) top
Ir—C3i2.144 (3)C4—H4A0.9700
Ir—C32.144 (3)C4—H4B0.9700
Ir—C10i2.155 (3)C5—C61.522 (7)
Ir—C102.155 (3)C5—H5A0.9700
Ir—Si2.3661 (8)C5—H5B0.9700
Ir—S2.3661 (8)C6—C71.521 (6)
S—C11.724 (2)C6—H6A0.9700
N—C11.312 (5)C6—H6B0.9700
N—C21.461 (3)C7—C81.514 (6)
N—C2i1.461 (3)C7—H7A0.9700
C1—Si1.724 (2)C7—H7B0.9700
C2—H2A0.9600C8—C91.536 (5)
C2—H2B0.9600C8—H8A0.9700
C2—H2C0.9600C8—H8B0.9700
C3—C101.424 (5)C9—C101.489 (5)
C3—C41.495 (5)C9—H9A0.9700
C3—H30.958 (15)C9—H9B0.9700
C4—C51.538 (5)C10—H100.962 (15)
C3i—Ir—C393.88 (19)C5—C4—H4B108.7
C3i—Ir—C10i38.69 (13)H4A—C4—H4B107.6
C3—Ir—C10i86.68 (12)C6—C5—C4115.3 (4)
C3i—Ir—C1086.68 (12)C6—C5—H5A108.5
C3—Ir—C1038.69 (13)C4—C5—H5A108.5
C10i—Ir—C10104.25 (17)C6—C5—H5B108.5
C3i—Ir—Si99.60 (9)C4—C5—H5B108.5
C3—Ir—Si157.76 (11)H5A—C5—H5B107.5
C10i—Ir—Si92.83 (9)C7—C6—C5116.5 (3)
C10—Ir—Si158.89 (10)C7—C6—H6A108.2
C3i—Ir—S157.76 (11)C5—C6—H6A108.2
C3—Ir—S99.60 (9)C7—C6—H6B108.2
C10i—Ir—S158.89 (10)C5—C6—H6B108.2
C10—Ir—S92.83 (9)H6A—C6—H6B107.3
Si—Ir—S73.75 (4)C8—C7—C6115.7 (3)
C1—S—Ir87.70 (12)C8—C7—H7A108.3
C1—N—C2121.86 (18)C6—C7—H7A108.3
C1—N—C2i121.86 (18)C8—C7—H7B108.3
C2—N—C2i116.3 (4)C6—C7—H7B108.3
N—C1—S124.57 (11)H7A—C7—H7B107.4
N—C1—Si124.57 (11)C7—C8—C9115.8 (3)
S—C1—Si110.9 (2)C7—C8—H8A108.3
N—C2—H2A109.5C9—C8—H8A108.3
N—C2—H2B109.5C7—C8—H8B108.3
H2A—C2—H2B109.5C9—C8—H8B108.3
N—C2—H2C109.5H8A—C8—H8B107.4
H2A—C2—H2C109.5C10—C9—C8110.9 (3)
H2B—C2—H2C109.5C10—C9—H9A109.5
C10—C3—C4124.0 (3)C8—C9—H9A109.5
C10—C3—Ir71.07 (18)C10—C9—H9B109.5
C4—C3—Ir115.3 (2)C8—C9—H9B109.5
C10—C3—H3119.0 (17)H9A—C9—H9B108.0
C4—C3—H3110.1 (17)C3—C10—C9121.7 (3)
Ir—C3—H3111 (2)C3—C10—Ir70.23 (18)
C3—C4—C5114.1 (3)C9—C10—Ir119.9 (2)
C3—C4—H4A108.7C3—C10—H10118.1 (17)
C5—C4—H4A108.7C9—C10—H10111.9 (17)
C3—C4—H4B108.7Ir—C10—H10108.2 (19)
C3i—Ir—S—C175.3 (2)Ir—C3—C4—C5169.1 (3)
C3—Ir—S—C1158.20 (11)C3—C4—C5—C673.1 (5)
C10i—Ir—S—C152.2 (3)C4—C5—C6—C769.4 (5)
C10—Ir—S—C1163.45 (10)C5—C6—C7—C8103.2 (4)
Si—Ir—S—C10.0C6—C7—C8—C956.3 (5)
C2—N—C1—S1.62 (18)C7—C8—C9—C1050.2 (5)
C2i—N—C1—S178.38 (18)C4—C3—C10—C95.3 (5)
C2—N—C1—Si178.38 (18)Ir—C3—C10—C9113.6 (3)
C2i—N—C1—Si1.62 (18)C4—C3—C10—Ir108.3 (3)
Ir—S—C1—N180.0C8—C9—C10—C388.3 (4)
Ir—S—C1—Si0.0C8—C9—C10—Ir172.3 (3)
C3i—Ir—C3—C1079.78 (19)C3i—Ir—C10—C3100.4 (2)
C10i—Ir—C3—C10117.8 (2)C10i—Ir—C10—C365.63 (18)
Si—Ir—C3—C10152.8 (2)Si—Ir—C10—C3151.3 (2)
S—Ir—C3—C1082.46 (18)S—Ir—C10—C3101.86 (18)
C3i—Ir—C3—C4160.8 (3)C3i—Ir—C10—C9143.6 (3)
C10i—Ir—C3—C4122.8 (3)C3—Ir—C10—C9116.0 (4)
C10—Ir—C3—C4119.4 (4)C10i—Ir—C10—C9178.4 (3)
Si—Ir—C3—C433.4 (4)Si—Ir—C10—C935.3 (5)
S—Ir—C3—C437.0 (3)S—Ir—C10—C914.1 (3)
C10—C3—C4—C585.7 (5)
Symmetry code: (i) x, y, z+1/2.

Experimental details

Crystal data
Chemical formula[Ir(C3H6NS2)(C8H14)2]
Mr532.79
Crystal system, space groupMonoclinic, C2/c
Temperature (K)203
a, b, c (Å)17.9277 (10), 15.2675 (8), 7.662 (3)
β (°) 96.39 (1)
V3)2084.0 (7)
Z4
Radiation typeMo Kα
µ (mm1)6.61
Crystal size (mm)0.4 × 0.32 × 0.19
Data collection
DiffractometerNonius CAD-4 MACH3
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.162, 0.533
No. of measured, independent and
observed [I > 2σ(I)] reflections
3731, 2377, 2080
Rint0.012
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.053, 1.23
No. of reflections2377
No. of parameters113
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 1.45

Computer programs: CAD-4 EXPRESS Software (Enraf Nonius, 1994), CAD-4 EXPRESS Software, XCAD4 (Harms & Wocadlo, 1995), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Ir—C32.144 (3)N—C11.312 (5)
Ir—C102.155 (3)N—C21.461 (3)
Ir—S2.3661 (8)C3—C101.424 (5)
S—C11.724 (2)
Si—Ir—S73.75 (4)C10—C3—C4124.0 (3)
C1—S—Ir87.70 (12)C3—C10—C9121.7 (3)
S—C1—Si110.9 (2)
C4—C3—C10—C95.3 (5)
Symmetry code: (i) x, y, z+1/2.
 

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