Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031868/bt2421sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031868/bt2421Isup2.hkl |
CCDC reference: 657533
Key indicators
- Single-crystal X-ray study
- T = 108 K
- Mean (C-C) = 0.007 Å
- R factor = 0.027
- wR factor = 0.062
- Data-to-parameter ratio = 15.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.62 Ratio
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.103 0.416 Tmin and Tmax expected: 0.091 0.417 RR = 1.135 Please check that your absorption correction is appropriate. PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.16 PLAT213_ALERT_2_C Atom C43 has ADP max/min Ratio ............. 3.40 oblat PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl5 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl6
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 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
For related literature, see: Allen (2002); Butcher & Sinn (1976); Dean (1979); Gleichmann et al. (1995); Hendrickson et al. (1976); Herebian & Sheldrick (2002); Korn & Sheldrick (1997); Landgrafe & Sheldrick (1994); Lau et al. (2004); Raston & White (1976); Schäfer & Sheldrick (2007); Scharwitz et al. (2007a,b, c, d); Scharwitz, Schäfer et al. (2007); Sinn (1976); Stodt et al. (2003); Suzuki et al. (2003); Sheldrick (1995); Siemens (1989).
[(η5-C5Me5)Ir{µ-(C2H5)2NCS2}]2(CF3SO3)2 was prepared by reaction of [(η5-C5Me5)Ir{CH3)2CO}3](CF3SO3)2 with Na[(C2H5)2NCS2] as described previously (Scharwitz et al., 2007a). Suitable crystals [(η5-C5Me5)Ir{µ-(C2H5)2NCS2}]2(ClO4)2] for X-ray analysis were obtained by slow evaporation of an aqueous solution of (I) containing 0.1M NaClO4.
H atoms were constrained to idealized positions and refined using a riding model, with C—H distances of 0.97 Å for the methylene C atoms and 0.96 Å for the methyl groups; Uiso(H) = 1.2 Uiso(C) for methylene and 1.5 Uiso(C) for methyl groups. The methyl groups were allowed to rotate but not to tip.
Entries for six (dithiocarbamato)iridium(III) complexes are present in the current Cambridge Structural Database (Version 5.27, December 2006; Allen 2002). These are all mononuclear and contain either one (Dean, 1979; Lau et al., 2004; Suzuki et al., 2003) or three (Butcher & Sinn, 1976; Raston & White, 1976; Sinn 1976) bidentate dithiocarbamato ligands in the chelating κ2S,S' mode. We ourselves have also recently reported the first example of an (η5-C5Me5)IrIII complex to contain such a ligand, namely [(η5-C5Me5)Ir{(C2H5)2NCS2-κ2S,S'}(CO)](CF3SO3) (Scharwitz, Schäfer et al., 2007a). This carbonyl complex was prepared by heating [(η5-C5Me5)Ir{µ-(C2H5)2NCS2}]2(CF3SO3)2 (I) in methanol to 393 K in a sealed glass tube. We have now been successful in crystallizing the cation of dinuclear starting compound as its perchlorate [(η5-C5Me5)Ir{µ-(C2H5)2NCS2}]2(ClO4)2] (I) and report its structure as part of our continuing studies on (η6-arene)RuII and (η5-C5Me5)IrIII complexes with sulfur and nitrogen containing ligands (Gleichmann et al., 1995; Herebian & Sheldrick, 2002; Korn & Sheldrick, 1997; Schäfer & Sheldrick, 2007; Scharwitz et al., 2007a, b, c, d); Scharwitz, Schäfer et al., 2007; Stodt et al., 2003).
The molecular structure of (I) is depicted in Fig. 1 and exhibits Ir—C distances to the pentamethylcyclopentadienyl ligands in the range 2.167 (5)–2.206 (5) as listed in Table 1. The (η5-C5Me5)IrIII fragments adopt a cis arrangement relative to the (IrS)2 ring. Although the sulfur atoms S11 and S21 are bidentate, their Ir—S distances of respectively 2.4098 (12) and 2.3986 (12) Å to Ir1 and 2.3897 (11) and 2.3952 (12) Å to Ir2 are on average only marginally longer than those of 2.3842 (12) and 2.3832 (12) Å for the monodentate atoms S22 and S12. These latter values are similar to those of 2.3795 (12) and 2.3861 (14) Å reported for the Ir—S distances in the mononuclear carbonyl complex [(η5-C5Me5)Ir{(C2H5)2NCS2-κ2S,S'}(CO)](CF3SO3) (Scharwitz et al., 2007a). This is also the case for the S—Ir—S angles of the chelate rings in (I), which exhibit values of 73.00 (4) and 73.12 (4) that are, on average only 0.46° larger than that of 72.60 (4)° in the carbonyl complex. Narrow S—Ir—S angles of 79.83 (4) and 80.31 (4)° are also observed for the Ir1 and Ir2 atoms within the central (IrS)2 ring. (I) is the first iridium complex to contain tridentate dithiocarbamate ligands, although the observed 1κ2S,S':2κS coordination mode has previously been observed for later transition metals in [{Ru([9]aneS3)}2{µ-(C2H5)2NCS2}2] (Landgrafe & Sheldrick, 1994) and [Rh2{(CH3)2NCS2}5](BF4) (Hendrickson et al., 1976). The cation and anion packing in the unit cell is illustrated in Fig. 2.
For related literature, see: Allen (2002); Butcher & Sinn (1976); Dean (1979); Gleichmann et al. (1995); Hendrickson et al. (1976); Herebian & Sheldrick (2002); Korn & Sheldrick (1997); Landgrafe & Sheldrick (1994); Lau et al. (2004); Raston & White (1976); Schäfer & Sheldrick (2007); Scharwitz et al. (2007a,b, c, d); Scharwitz, Schäfer et al. (2007); Sinn (1976); Stodt et al. (2003); Suzuki et al. (2003); Sheldrick (1995); Siemens (1989).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.
Fig. 1. Structure of the cation and counter anion of (I). Displacement ellipsoids are drawn at the 50% probability level. |
[Ir2(C10H15)2(C5H10NS2)2](ClO4)2 | F(000) = 4480 |
Mr = 1150.26 | Dx = 1.948 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 20169 reflections |
a = 20.2386 (5) Å | θ = 2.6–30.0° |
b = 15.1259 (6) Å | µ = 7.18 mm−1 |
c = 25.6234 (10) Å | T = 108 K |
V = 7844.0 (5) Å3 | Prism, orange |
Z = 8 | 0.46 × 0.30 × 0.12 mm |
Oxford diffraction Sapphire2 CCD diffractometer | 6895 independent reflections |
Radiation source: fine-focus sealed tube | 5296 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
389 images at 1.0 deg in ω and 20 sec scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: multi-scan [empirical (using intensity measurements) correction (CrysAlis RED; Oxford Diffraction, 2006)] | h = −14→24 |
Tmin = 0.103, Tmax = 0.416 | k = −17→17 |
37944 measured reflections | l = −30→26 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0364P)2] where P = (Fo2 + 2Fc2)/3 |
6895 reflections | (Δ/σ)max = 0.001 |
447 parameters | Δρmax = 1.87 e Å−3 |
0 restraints | Δρmin = −1.09 e Å−3 |
[Ir2(C10H15)2(C5H10NS2)2](ClO4)2 | V = 7844.0 (5) Å3 |
Mr = 1150.26 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 20.2386 (5) Å | µ = 7.18 mm−1 |
b = 15.1259 (6) Å | T = 108 K |
c = 25.6234 (10) Å | 0.46 × 0.30 × 0.12 mm |
Oxford diffraction Sapphire2 CCD diffractometer | 6895 independent reflections |
Absorption correction: multi-scan [empirical (using intensity measurements) correction (CrysAlis RED; Oxford Diffraction, 2006)] | 5296 reflections with I > 2σ(I) |
Tmin = 0.103, Tmax = 0.416 | Rint = 0.033 |
37944 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.87 e Å−3 |
6895 reflections | Δρmin = −1.09 e Å−3 |
447 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ir1 | 0.557533 (8) | 0.308853 (12) | 0.106597 (7) | 0.01081 (6) | |
Ir2 | 0.439865 (8) | 0.150330 (12) | 0.161882 (7) | 0.01101 (6) | |
S11 | 0.52300 (6) | 0.15748 (8) | 0.09580 (5) | 0.0129 (3) | |
S12 | 0.38394 (6) | 0.15986 (9) | 0.08023 (5) | 0.0169 (3) | |
C11 | 0.4578 (2) | 0.1599 (3) | 0.04886 (18) | 0.0129 (10) | |
N11 | 0.46949 (19) | 0.1606 (3) | −0.00116 (15) | 0.0160 (9) | |
C12 | 0.5375 (2) | 0.1640 (4) | −0.0226 (2) | 0.0210 (12) | |
H121 | 0.5651 | 0.2028 | −0.0004 | 0.025* | |
H122 | 0.5363 | 0.1898 | −0.0581 | 0.025* | |
C13 | 0.5687 (3) | 0.0725 (4) | −0.0251 (2) | 0.0274 (13) | |
H131 | 0.5709 | 0.0472 | 0.0100 | 0.041* | |
H132 | 0.6134 | 0.0772 | −0.0396 | 0.041* | |
H133 | 0.5419 | 0.0341 | −0.0476 | 0.041* | |
C14 | 0.4149 (3) | 0.1599 (4) | −0.0391 (2) | 0.0246 (13) | |
H141 | 0.3740 | 0.1396 | −0.0216 | 0.030* | |
H142 | 0.4252 | 0.1175 | −0.0674 | 0.030* | |
C15 | 0.4028 (3) | 0.2507 (4) | −0.0628 (2) | 0.0327 (14) | |
H151 | 0.3900 | 0.2922 | −0.0352 | 0.049* | |
H152 | 0.3674 | 0.2468 | −0.0887 | 0.049* | |
H153 | 0.4434 | 0.2716 | −0.0796 | 0.049* | |
S21 | 0.46597 (6) | 0.30463 (8) | 0.16598 (5) | 0.0129 (3) | |
S22 | 0.46610 (6) | 0.37571 (9) | 0.06318 (5) | 0.0170 (3) | |
C21 | 0.4189 (2) | 0.3592 (3) | 0.11740 (19) | 0.0148 (11) | |
N21 | 0.35764 (18) | 0.3836 (3) | 0.12422 (16) | 0.0171 (9) | |
C22 | 0.3179 (2) | 0.3544 (3) | 0.1696 (2) | 0.0202 (12) | |
H221 | 0.3330 | 0.2949 | 0.1804 | 0.024* | |
H222 | 0.2711 | 0.3495 | 0.1588 | 0.024* | |
C23 | 0.3228 (3) | 0.4162 (4) | 0.2153 (2) | 0.0300 (14) | |
H231 | 0.3677 | 0.4145 | 0.2295 | 0.045* | |
H232 | 0.2913 | 0.3980 | 0.2423 | 0.045* | |
H233 | 0.3125 | 0.4765 | 0.2040 | 0.045* | |
C24 | 0.3239 (2) | 0.4399 (3) | 0.0852 (2) | 0.0221 (12) | |
H241 | 0.3572 | 0.4753 | 0.0662 | 0.027* | |
H242 | 0.2939 | 0.4814 | 0.1034 | 0.027* | |
C25 | 0.2844 (3) | 0.3861 (4) | 0.0464 (2) | 0.0331 (14) | |
H251 | 0.3143 | 0.3474 | 0.0268 | 0.050* | |
H252 | 0.2616 | 0.4260 | 0.0222 | 0.050* | |
H253 | 0.2518 | 0.3501 | 0.0650 | 0.050* | |
C31 | 0.6318 (2) | 0.3742 (3) | 0.1542 (2) | 0.0181 (12) | |
C32 | 0.6563 (2) | 0.2890 (3) | 0.13970 (19) | 0.0154 (11) | |
C33 | 0.6613 (2) | 0.2883 (4) | 0.08331 (19) | 0.0192 (12) | |
C34 | 0.6392 (2) | 0.3707 (3) | 0.06404 (19) | 0.0168 (11) | |
C35 | 0.6201 (2) | 0.4251 (4) | 0.1083 (2) | 0.0219 (12) | |
C311 | 0.6221 (3) | 0.4064 (4) | 0.2084 (2) | 0.0337 (15) | |
H311 | 0.6612 | 0.4399 | 0.2194 | 0.050* | |
H312 | 0.6157 | 0.3559 | 0.2317 | 0.050* | |
H313 | 0.5832 | 0.4448 | 0.2097 | 0.050* | |
C321 | 0.6833 (3) | 0.2202 (4) | 0.1754 (2) | 0.0341 (15) | |
H321 | 0.7314 | 0.2271 | 0.1782 | 0.051* | |
H322 | 0.6730 | 0.1614 | 0.1616 | 0.051* | |
H323 | 0.6634 | 0.2269 | 0.2101 | 0.051* | |
C331 | 0.6905 (3) | 0.2136 (4) | 0.0526 (2) | 0.0379 (16) | |
H331 | 0.6820 | 0.2230 | 0.0153 | 0.057* | |
H332 | 0.6703 | 0.1578 | 0.0636 | 0.057* | |
H333 | 0.7383 | 0.2112 | 0.0586 | 0.057* | |
C341 | 0.6386 (3) | 0.3989 (5) | 0.0078 (2) | 0.0418 (17) | |
H341 | 0.6790 | 0.4321 | 0.0001 | 0.063* | |
H342 | 0.6000 | 0.4363 | 0.0013 | 0.063* | |
H343 | 0.6365 | 0.3464 | −0.0146 | 0.063* | |
C351 | 0.5993 (3) | 0.5189 (4) | 0.1061 (3) | 0.0470 (19) | |
H351 | 0.5691 | 0.5314 | 0.1351 | 0.070* | |
H352 | 0.5768 | 0.5303 | 0.0729 | 0.070* | |
H353 | 0.6383 | 0.5571 | 0.1089 | 0.070* | |
C41 | 0.3851 (2) | 0.0371 (3) | 0.19127 (19) | 0.0170 (11) | |
C42 | 0.3713 (2) | 0.1114 (3) | 0.22381 (19) | 0.0192 (11) | |
C43 | 0.4332 (3) | 0.1377 (3) | 0.24706 (19) | 0.0201 (12) | |
C44 | 0.4841 (2) | 0.0818 (3) | 0.22816 (19) | 0.0180 (11) | |
C45 | 0.4540 (2) | 0.0182 (3) | 0.19339 (18) | 0.0156 (11) | |
C411 | 0.3344 (3) | −0.0136 (4) | 0.1610 (2) | 0.0265 (13) | |
H411 | 0.3545 | −0.0374 | 0.1292 | 0.040* | |
H412 | 0.2978 | 0.0258 | 0.1516 | 0.040* | |
H413 | 0.3176 | −0.0623 | 0.1825 | 0.040* | |
C421 | 0.3038 (3) | 0.1449 (4) | 0.2380 (2) | 0.0334 (15) | |
H421 | 0.2753 | 0.1437 | 0.2071 | 0.050* | |
H422 | 0.3073 | 0.2058 | 0.2509 | 0.050* | |
H423 | 0.2848 | 0.1073 | 0.2653 | 0.050* | |
C431 | 0.4414 (3) | 0.2102 (4) | 0.2859 (2) | 0.0348 (15) | |
H431 | 0.4311 | 0.1878 | 0.3209 | 0.052* | |
H432 | 0.4115 | 0.2589 | 0.2773 | 0.052* | |
H433 | 0.4872 | 0.2313 | 0.2852 | 0.052* | |
C441 | 0.5553 (2) | 0.0821 (4) | 0.2450 (2) | 0.0286 (13) | |
H441 | 0.5692 | 0.1429 | 0.2525 | 0.043* | |
H442 | 0.5828 | 0.0578 | 0.2170 | 0.043* | |
H443 | 0.5603 | 0.0460 | 0.2765 | 0.043* | |
C451 | 0.4884 (3) | −0.0585 (4) | 0.1689 (2) | 0.0251 (13) | |
H451 | 0.4957 | −0.1045 | 0.1951 | 0.038* | |
H452 | 0.5310 | −0.0391 | 0.1547 | 0.038* | |
H453 | 0.4610 | −0.0822 | 0.1406 | 0.038* | |
Cl5 | 0.70114 (6) | 0.96099 (10) | 0.12504 (6) | 0.0292 (3) | |
O51 | 0.63858 (17) | 1.0054 (3) | 0.12472 (17) | 0.0379 (11) | |
O52 | 0.74599 (19) | 1.0063 (3) | 0.15858 (17) | 0.0448 (12) | |
O53 | 0.7257 (2) | 0.9574 (4) | 0.07341 (18) | 0.0709 (18) | |
O54 | 0.6935 (3) | 0.8735 (3) | 0.1439 (2) | 0.0734 (17) | |
Cl6 | 0.36173 (7) | 0.71218 (10) | 0.13784 (5) | 0.0320 (3) | |
O61 | 0.3453 (2) | 0.7734 (3) | 0.09798 (17) | 0.0506 (12) | |
O62 | 0.3582 (3) | 0.7541 (3) | 0.18724 (17) | 0.0677 (16) | |
O63 | 0.3186 (4) | 0.6423 (4) | 0.1382 (2) | 0.110 (3) | |
O64 | 0.4263 (3) | 0.6801 (5) | 0.1274 (2) | 0.109 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.00888 (10) | 0.01305 (11) | 0.01050 (10) | −0.00058 (8) | 0.00031 (7) | 0.00096 (7) |
Ir2 | 0.01049 (10) | 0.01253 (11) | 0.01001 (10) | −0.00064 (8) | 0.00088 (8) | 0.00126 (7) |
S11 | 0.0124 (6) | 0.0141 (7) | 0.0123 (6) | −0.0007 (5) | 0.0027 (5) | 0.0007 (5) |
S12 | 0.0137 (6) | 0.0223 (7) | 0.0147 (7) | −0.0013 (5) | −0.0007 (5) | 0.0007 (6) |
C11 | 0.023 (3) | 0.004 (2) | 0.012 (3) | 0.0036 (19) | −0.002 (2) | 0.001 (2) |
N11 | 0.018 (2) | 0.017 (2) | 0.014 (2) | −0.0029 (18) | 0.0020 (17) | −0.0025 (18) |
C12 | 0.020 (3) | 0.028 (3) | 0.015 (3) | −0.005 (2) | 0.007 (2) | 0.000 (2) |
C13 | 0.035 (3) | 0.029 (3) | 0.018 (3) | 0.003 (3) | 0.010 (2) | −0.002 (2) |
C14 | 0.025 (3) | 0.032 (4) | 0.017 (3) | −0.008 (2) | −0.003 (2) | −0.002 (2) |
C15 | 0.036 (3) | 0.041 (4) | 0.021 (3) | −0.002 (3) | −0.007 (3) | 0.005 (3) |
S21 | 0.0110 (5) | 0.0149 (7) | 0.0130 (6) | −0.0005 (5) | −0.0002 (5) | 0.0016 (5) |
S22 | 0.0137 (6) | 0.0219 (7) | 0.0153 (7) | 0.0012 (5) | −0.0003 (5) | 0.0053 (5) |
C21 | 0.019 (3) | 0.009 (3) | 0.016 (3) | −0.006 (2) | 0.003 (2) | −0.002 (2) |
N21 | 0.012 (2) | 0.018 (2) | 0.021 (2) | 0.0003 (17) | −0.0023 (18) | 0.0021 (19) |
C22 | 0.015 (2) | 0.018 (3) | 0.028 (3) | 0.004 (2) | 0.006 (2) | 0.006 (2) |
C23 | 0.024 (3) | 0.035 (4) | 0.030 (3) | 0.005 (3) | 0.006 (3) | −0.001 (3) |
C24 | 0.013 (2) | 0.023 (3) | 0.030 (3) | 0.006 (2) | 0.000 (2) | 0.010 (2) |
C25 | 0.027 (3) | 0.042 (4) | 0.030 (3) | 0.000 (3) | −0.009 (3) | 0.007 (3) |
C31 | 0.009 (2) | 0.023 (3) | 0.022 (3) | −0.004 (2) | −0.002 (2) | −0.007 (2) |
C32 | 0.008 (2) | 0.017 (3) | 0.022 (3) | −0.0021 (19) | 0.000 (2) | −0.002 (2) |
C33 | 0.010 (2) | 0.033 (3) | 0.015 (3) | −0.005 (2) | 0.001 (2) | −0.006 (2) |
C34 | 0.011 (2) | 0.027 (3) | 0.013 (3) | −0.008 (2) | −0.002 (2) | 0.010 (2) |
C35 | 0.012 (2) | 0.019 (3) | 0.034 (3) | −0.007 (2) | −0.005 (2) | 0.008 (3) |
C311 | 0.025 (3) | 0.045 (4) | 0.031 (4) | −0.009 (3) | 0.007 (3) | −0.020 (3) |
C321 | 0.029 (3) | 0.032 (4) | 0.041 (4) | 0.001 (3) | −0.014 (3) | 0.011 (3) |
C331 | 0.019 (3) | 0.050 (4) | 0.044 (4) | 0.002 (3) | 0.008 (3) | −0.023 (3) |
C341 | 0.029 (3) | 0.068 (5) | 0.028 (4) | −0.020 (3) | −0.005 (3) | 0.021 (3) |
C351 | 0.035 (4) | 0.023 (4) | 0.083 (6) | −0.003 (3) | −0.015 (4) | 0.013 (3) |
C41 | 0.018 (3) | 0.017 (3) | 0.016 (3) | −0.004 (2) | 0.002 (2) | 0.009 (2) |
C42 | 0.022 (3) | 0.019 (3) | 0.017 (3) | 0.001 (2) | 0.011 (2) | 0.006 (2) |
C43 | 0.035 (3) | 0.022 (3) | 0.004 (2) | −0.005 (2) | 0.002 (2) | 0.003 (2) |
C44 | 0.022 (3) | 0.022 (3) | 0.010 (3) | −0.004 (2) | −0.003 (2) | 0.007 (2) |
C45 | 0.020 (3) | 0.017 (3) | 0.010 (3) | 0.000 (2) | 0.003 (2) | 0.004 (2) |
C411 | 0.027 (3) | 0.025 (3) | 0.028 (3) | −0.010 (2) | −0.001 (2) | 0.007 (3) |
C421 | 0.029 (3) | 0.030 (4) | 0.041 (4) | 0.007 (3) | 0.020 (3) | 0.014 (3) |
C431 | 0.063 (4) | 0.026 (3) | 0.016 (3) | −0.009 (3) | 0.000 (3) | 0.001 (2) |
C441 | 0.025 (3) | 0.038 (4) | 0.023 (3) | −0.006 (3) | −0.009 (2) | 0.004 (3) |
C451 | 0.031 (3) | 0.020 (3) | 0.025 (3) | 0.004 (2) | 0.007 (2) | 0.004 (2) |
Cl5 | 0.0211 (6) | 0.0307 (8) | 0.0360 (8) | 0.0081 (6) | −0.0060 (6) | −0.0104 (7) |
O51 | 0.0147 (18) | 0.041 (3) | 0.058 (3) | 0.0088 (17) | −0.0031 (19) | −0.011 (2) |
O52 | 0.029 (2) | 0.048 (3) | 0.057 (3) | 0.009 (2) | −0.016 (2) | −0.023 (2) |
O53 | 0.035 (3) | 0.142 (6) | 0.036 (3) | 0.024 (3) | −0.002 (2) | −0.025 (3) |
O54 | 0.078 (4) | 0.038 (3) | 0.104 (5) | −0.002 (3) | −0.035 (3) | 0.008 (3) |
Cl6 | 0.0430 (9) | 0.0335 (9) | 0.0196 (8) | 0.0028 (7) | 0.0031 (6) | 0.0031 (6) |
O61 | 0.053 (3) | 0.065 (3) | 0.034 (3) | 0.010 (2) | 0.002 (2) | 0.019 (2) |
O62 | 0.123 (5) | 0.057 (4) | 0.023 (3) | 0.010 (3) | −0.003 (3) | −0.007 (2) |
O63 | 0.171 (7) | 0.078 (5) | 0.082 (5) | −0.076 (5) | 0.060 (5) | −0.034 (4) |
O64 | 0.073 (4) | 0.192 (8) | 0.063 (4) | 0.080 (4) | 0.009 (3) | 0.033 (4) |
Ir1—C35 | 2.167 (5) | C32—C321 | 1.490 (7) |
Ir1—C31 | 2.173 (5) | C33—C34 | 1.415 (7) |
Ir1—C34 | 2.191 (4) | C33—C331 | 1.498 (7) |
Ir1—C32 | 2.193 (5) | C34—C35 | 1.452 (7) |
Ir1—C33 | 2.206 (5) | C34—C341 | 1.502 (7) |
Ir1—S22 | 2.3842 (12) | C35—C351 | 1.481 (8) |
Ir1—S21 | 2.3986 (12) | C311—H311 | 0.9800 |
Ir1—S11 | 2.4098 (12) | C311—H312 | 0.9800 |
Ir2—C41 | 2.174 (5) | C311—H313 | 0.9800 |
Ir2—C45 | 2.175 (5) | C321—H321 | 0.9800 |
Ir2—C44 | 2.182 (5) | C321—H322 | 0.9800 |
Ir2—C42 | 2.189 (5) | C321—H323 | 0.9800 |
Ir2—C43 | 2.195 (5) | C331—H331 | 0.9800 |
Ir2—S12 | 2.3832 (12) | C331—H332 | 0.9800 |
Ir2—S11 | 2.3897 (11) | C331—H333 | 0.9800 |
Ir2—S21 | 2.3952 (12) | C341—H341 | 0.9800 |
S11—C11 | 1.785 (5) | C341—H342 | 0.9800 |
S12—C11 | 1.698 (5) | C341—H343 | 0.9800 |
C11—N11 | 1.303 (6) | C351—H351 | 0.9800 |
N11—C14 | 1.473 (6) | C351—H352 | 0.9800 |
N11—C12 | 1.483 (6) | C351—H353 | 0.9800 |
C12—C13 | 1.523 (7) | C41—C45 | 1.425 (6) |
C12—H121 | 0.9900 | C41—C42 | 1.427 (7) |
C12—H122 | 0.9900 | C41—C411 | 1.498 (7) |
C13—H131 | 0.9800 | C42—C43 | 1.443 (7) |
C13—H132 | 0.9800 | C42—C421 | 1.501 (7) |
C13—H133 | 0.9800 | C43—C44 | 1.419 (7) |
C14—C15 | 1.520 (7) | C43—C431 | 1.490 (7) |
C14—H141 | 0.9900 | C44—C45 | 1.446 (7) |
C14—H142 | 0.9900 | C44—C441 | 1.504 (7) |
C15—H151 | 0.9800 | C45—C451 | 1.490 (7) |
C15—H152 | 0.9800 | C411—H411 | 0.9800 |
C15—H153 | 0.9800 | C411—H412 | 0.9800 |
S21—C21 | 1.772 (5) | C411—H413 | 0.9800 |
S22—C21 | 1.705 (5) | C421—H421 | 0.9800 |
C21—N21 | 1.305 (6) | C421—H422 | 0.9800 |
N21—C22 | 1.480 (6) | C421—H423 | 0.9800 |
N21—C24 | 1.481 (6) | C431—H431 | 0.9800 |
C22—C23 | 1.504 (7) | C431—H432 | 0.9800 |
C22—H221 | 0.9900 | C431—H433 | 0.9800 |
C22—H222 | 0.9900 | C441—H441 | 0.9800 |
C23—H231 | 0.9800 | C441—H442 | 0.9800 |
C23—H232 | 0.9800 | C441—H443 | 0.9800 |
C23—H233 | 0.9800 | C451—H451 | 0.9800 |
C24—C25 | 1.513 (7) | C451—H452 | 0.9800 |
C24—H241 | 0.9900 | C451—H453 | 0.9800 |
C24—H242 | 0.9900 | Cl5—O53 | 1.414 (5) |
C25—H251 | 0.9800 | Cl5—O54 | 1.416 (5) |
C25—H252 | 0.9800 | Cl5—O52 | 1.425 (4) |
C25—H253 | 0.9800 | Cl5—O51 | 1.434 (4) |
C31—C35 | 1.425 (7) | Cl6—O63 | 1.371 (6) |
C31—C32 | 1.430 (7) | Cl6—O62 | 1.417 (5) |
C31—C311 | 1.485 (7) | Cl6—O61 | 1.418 (4) |
C32—C33 | 1.449 (7) | Cl6—O64 | 1.420 (5) |
C35—Ir1—C31 | 38.35 (19) | C32—C31—Ir1 | 71.6 (3) |
C35—Ir1—C34 | 38.93 (19) | C311—C31—Ir1 | 125.6 (3) |
C31—Ir1—C34 | 64.07 (18) | C31—C32—C33 | 106.8 (4) |
C35—Ir1—C32 | 64.58 (18) | C31—C32—C321 | 126.7 (5) |
C31—Ir1—C32 | 38.23 (18) | C33—C32—C321 | 125.6 (5) |
C34—Ir1—C32 | 64.09 (18) | C31—C32—Ir1 | 70.1 (3) |
C35—Ir1—C33 | 64.11 (19) | C33—C32—Ir1 | 71.3 (3) |
C31—Ir1—C33 | 63.71 (18) | C321—C32—Ir1 | 131.9 (4) |
C34—Ir1—C33 | 37.54 (19) | C34—C33—C32 | 108.6 (4) |
C32—Ir1—C33 | 38.45 (18) | C34—C33—C331 | 127.3 (5) |
C35—Ir1—S22 | 96.82 (14) | C32—C33—C331 | 123.9 (5) |
C31—Ir1—S22 | 127.29 (14) | C34—C33—Ir1 | 70.6 (3) |
C34—Ir1—S22 | 99.91 (13) | C32—C33—Ir1 | 70.3 (3) |
C32—Ir1—S22 | 161.16 (13) | C331—C33—Ir1 | 128.6 (4) |
C33—Ir1—S22 | 132.28 (14) | C33—C34—C35 | 108.1 (4) |
C35—Ir1—S21 | 117.42 (15) | C33—C34—C341 | 125.9 (5) |
C31—Ir1—S21 | 101.01 (13) | C35—C34—C341 | 125.9 (5) |
C34—Ir1—S21 | 155.54 (14) | C33—C34—Ir1 | 71.8 (3) |
C32—Ir1—S21 | 117.10 (13) | C35—C34—Ir1 | 69.7 (3) |
C33—Ir1—S21 | 154.63 (14) | C341—C34—Ir1 | 126.4 (3) |
S22—Ir1—S21 | 73.00 (4) | C31—C35—C34 | 107.1 (4) |
C35—Ir1—S11 | 160.47 (14) | C31—C35—C351 | 126.6 (5) |
C31—Ir1—S11 | 134.19 (14) | C34—C35—C351 | 126.0 (5) |
C34—Ir1—S11 | 124.59 (14) | C31—C35—Ir1 | 71.0 (3) |
C32—Ir1—S11 | 100.28 (13) | C34—C35—Ir1 | 71.4 (3) |
C33—Ir1—S11 | 96.37 (14) | C351—C35—Ir1 | 127.6 (4) |
S22—Ir1—S11 | 97.14 (4) | C31—C311—H311 | 109.5 |
S21—Ir1—S11 | 79.83 (4) | C31—C311—H312 | 109.5 |
C41—Ir2—C45 | 38.26 (17) | H311—C311—H312 | 109.5 |
C41—Ir2—C44 | 64.23 (18) | C31—C311—H313 | 109.5 |
C45—Ir2—C44 | 38.75 (18) | H311—C311—H313 | 109.5 |
C41—Ir2—C42 | 38.17 (19) | H312—C311—H313 | 109.5 |
C45—Ir2—C42 | 64.36 (18) | C32—C321—H321 | 109.5 |
C44—Ir2—C42 | 64.41 (18) | C32—C321—H322 | 109.5 |
C41—Ir2—C43 | 63.62 (19) | H321—C321—H322 | 109.5 |
C45—Ir2—C43 | 63.84 (18) | C32—C321—H323 | 109.5 |
C44—Ir2—C43 | 37.82 (18) | H321—C321—H323 | 109.5 |
C42—Ir2—C43 | 38.44 (18) | H322—C321—H323 | 109.5 |
C41—Ir2—S12 | 96.30 (13) | C33—C331—H331 | 109.5 |
C45—Ir2—S12 | 116.36 (13) | C33—C331—H332 | 109.5 |
C44—Ir2—S12 | 155.08 (14) | H331—C331—H332 | 109.5 |
C42—Ir2—S12 | 110.58 (14) | C33—C331—H333 | 109.5 |
C43—Ir2—S12 | 148.09 (14) | H331—C331—H333 | 109.5 |
C41—Ir2—S11 | 129.79 (14) | H332—C331—H333 | 109.5 |
C45—Ir2—S11 | 102.22 (12) | C34—C341—H341 | 109.5 |
C44—Ir2—S11 | 106.51 (13) | C34—C341—H342 | 109.5 |
C42—Ir2—S11 | 166.50 (14) | H341—C341—H342 | 109.5 |
C43—Ir2—S11 | 138.76 (14) | C34—C341—H343 | 109.5 |
S12—Ir2—S11 | 73.12 (4) | H341—C341—H343 | 109.5 |
C41—Ir2—S21 | 149.84 (14) | H342—C341—H343 | 109.5 |
C45—Ir2—S21 | 148.24 (13) | C35—C351—H351 | 109.5 |
C44—Ir2—S21 | 109.79 (14) | C35—C351—H352 | 109.5 |
C42—Ir2—S21 | 111.73 (14) | H351—C351—H352 | 109.5 |
C43—Ir2—S21 | 93.15 (13) | C35—C351—H353 | 109.5 |
S12—Ir2—S21 | 94.83 (4) | H351—C351—H353 | 109.5 |
S11—Ir2—S21 | 80.31 (4) | H352—C351—H353 | 109.5 |
C11—S11—Ir2 | 87.60 (16) | C45—C41—C42 | 109.2 (4) |
C11—S11—Ir1 | 105.81 (15) | C45—C41—C411 | 126.0 (5) |
Ir2—S11—Ir1 | 99.54 (4) | C42—C41—C411 | 124.8 (4) |
C11—S12—Ir2 | 89.84 (16) | C45—C41—Ir2 | 70.9 (3) |
N11—C11—S12 | 128.7 (4) | C42—C41—Ir2 | 71.5 (3) |
N11—C11—S11 | 121.9 (4) | C411—C41—Ir2 | 125.0 (3) |
S12—C11—S11 | 109.4 (3) | C41—C42—C43 | 106.7 (4) |
C11—N11—C14 | 120.9 (4) | C41—C42—C421 | 125.9 (5) |
C11—N11—C12 | 122.2 (4) | C43—C42—C421 | 126.6 (5) |
C14—N11—C12 | 116.9 (4) | C41—C42—Ir2 | 70.3 (3) |
N11—C12—C13 | 111.7 (4) | C43—C42—Ir2 | 71.0 (3) |
N11—C12—H121 | 109.3 | C421—C42—Ir2 | 131.4 (4) |
C13—C12—H121 | 109.3 | C44—C43—C42 | 109.0 (4) |
N11—C12—H122 | 109.3 | C44—C43—C431 | 125.8 (5) |
C13—C12—H122 | 109.3 | C42—C43—C431 | 125.2 (5) |
H121—C12—H122 | 107.9 | C44—C43—Ir2 | 70.6 (3) |
C12—C13—H131 | 109.5 | C42—C43—Ir2 | 70.6 (3) |
C12—C13—H132 | 109.5 | C431—C43—Ir2 | 126.4 (4) |
H131—C13—H132 | 109.5 | C43—C44—C45 | 107.6 (4) |
C12—C13—H133 | 109.5 | C43—C44—C441 | 126.6 (5) |
H131—C13—H133 | 109.5 | C45—C44—C441 | 125.6 (5) |
H132—C13—H133 | 109.5 | C43—C44—Ir2 | 71.6 (3) |
N11—C14—C15 | 112.2 (4) | C45—C44—Ir2 | 70.4 (3) |
N11—C14—H141 | 109.2 | C441—C44—Ir2 | 127.9 (4) |
C15—C14—H141 | 109.2 | C41—C45—C44 | 107.5 (4) |
N11—C14—H142 | 109.2 | C41—C45—C451 | 126.6 (5) |
C15—C14—H142 | 109.2 | C44—C45—C451 | 125.5 (4) |
H141—C14—H142 | 107.9 | C41—C45—Ir2 | 70.8 (3) |
C14—C15—H151 | 109.5 | C44—C45—Ir2 | 70.9 (3) |
C14—C15—H152 | 109.5 | C451—C45—Ir2 | 128.3 (3) |
H151—C15—H152 | 109.5 | C41—C411—H411 | 109.5 |
C14—C15—H153 | 109.5 | C41—C411—H412 | 109.5 |
H151—C15—H153 | 109.5 | H411—C411—H412 | 109.5 |
H152—C15—H153 | 109.5 | C41—C411—H413 | 109.5 |
C21—S21—Ir2 | 107.73 (16) | H411—C411—H413 | 109.5 |
C21—S21—Ir1 | 87.57 (16) | H412—C411—H413 | 109.5 |
Ir2—S21—Ir1 | 99.71 (4) | C42—C421—H421 | 109.5 |
C21—S22—Ir1 | 89.59 (17) | C42—C421—H422 | 109.5 |
N21—C21—S22 | 126.9 (4) | H421—C421—H422 | 109.5 |
N21—C21—S21 | 123.3 (4) | C42—C421—H423 | 109.5 |
S22—C21—S21 | 109.8 (3) | H421—C421—H423 | 109.5 |
C21—N21—C22 | 122.5 (4) | H422—C421—H423 | 109.5 |
C21—N21—C24 | 120.7 (4) | C43—C431—H431 | 109.5 |
C22—N21—C24 | 116.8 (4) | C43—C431—H432 | 109.5 |
N21—C22—C23 | 113.1 (4) | H431—C431—H432 | 109.5 |
N21—C22—H221 | 109.0 | C43—C431—H433 | 109.5 |
C23—C22—H221 | 109.0 | H431—C431—H433 | 109.5 |
N21—C22—H222 | 109.0 | H432—C431—H433 | 109.5 |
C23—C22—H222 | 109.0 | C44—C441—H441 | 109.5 |
H221—C22—H222 | 107.8 | C44—C441—H442 | 109.5 |
C22—C23—H231 | 109.5 | H441—C441—H442 | 109.5 |
C22—C23—H232 | 109.5 | C44—C441—H443 | 109.5 |
H231—C23—H232 | 109.5 | H441—C441—H443 | 109.5 |
C22—C23—H233 | 109.5 | H442—C441—H443 | 109.5 |
H231—C23—H233 | 109.5 | C45—C451—H451 | 109.5 |
H232—C23—H233 | 109.5 | C45—C451—H452 | 109.5 |
N21—C24—C25 | 112.2 (4) | H451—C451—H452 | 109.5 |
N21—C24—H241 | 109.2 | C45—C451—H453 | 109.5 |
C25—C24—H241 | 109.2 | H451—C451—H453 | 109.5 |
N21—C24—H242 | 109.2 | H452—C451—H453 | 109.5 |
C25—C24—H242 | 109.2 | O53—Cl5—O54 | 108.8 (4) |
H241—C24—H242 | 107.9 | O53—Cl5—O52 | 111.0 (3) |
C24—C25—H251 | 109.5 | O54—Cl5—O52 | 108.3 (3) |
C24—C25—H252 | 109.5 | O53—Cl5—O51 | 108.8 (3) |
H251—C25—H252 | 109.5 | O54—Cl5—O51 | 110.0 (3) |
C24—C25—H253 | 109.5 | O52—Cl5—O51 | 109.9 (2) |
H251—C25—H253 | 109.5 | O63—Cl6—O62 | 107.8 (3) |
H252—C25—H253 | 109.5 | O63—Cl6—O61 | 111.1 (4) |
C35—C31—C32 | 109.3 (4) | O62—Cl6—O61 | 109.9 (3) |
C35—C31—C311 | 124.9 (5) | O63—Cl6—O64 | 108.9 (5) |
C32—C31—C311 | 125.7 (5) | O62—Cl6—O64 | 111.5 (4) |
C35—C31—Ir1 | 70.6 (3) | O61—Cl6—O64 | 107.6 (3) |
C41—Ir2—S11—C11 | 82.5 (2) | S11—Ir1—C34—C33 | −47.4 (3) |
C45—Ir2—S11—C11 | 112.6 (2) | C31—Ir1—C34—C35 | −38.2 (3) |
C44—Ir2—S11—C11 | 152.4 (2) | C32—Ir1—C34—C35 | −80.9 (3) |
C42—Ir2—S11—C11 | 106.4 (6) | C33—Ir1—C34—C35 | −118.1 (4) |
C43—Ir2—S11—C11 | 176.6 (2) | S22—Ir1—C34—C35 | 88.6 (3) |
S12—Ir2—S11—C11 | −1.57 (15) | S21—Ir1—C34—C35 | 18.0 (5) |
S21—Ir2—S11—C11 | −99.69 (15) | S11—Ir1—C34—C35 | −165.5 (2) |
C41—Ir2—S11—Ir1 | −171.89 (16) | C35—Ir1—C34—C341 | −120.2 (6) |
C45—Ir2—S11—Ir1 | −141.79 (13) | C31—Ir1—C34—C341 | −158.4 (6) |
C44—Ir2—S11—Ir1 | −101.97 (14) | C32—Ir1—C34—C341 | 158.9 (6) |
C42—Ir2—S11—Ir1 | −147.9 (6) | C33—Ir1—C34—C341 | 121.7 (6) |
C43—Ir2—S11—Ir1 | −77.7 (2) | S22—Ir1—C34—C341 | −31.6 (5) |
S12—Ir2—S11—Ir1 | 104.06 (5) | S21—Ir1—C34—C341 | −102.2 (5) |
S21—Ir2—S11—Ir1 | 5.94 (4) | S11—Ir1—C34—C341 | 74.3 (5) |
C35—Ir1—S11—C11 | −122.3 (5) | C32—C31—C35—C34 | −1.2 (5) |
C31—Ir1—S11—C11 | 179.8 (2) | C311—C31—C35—C34 | 176.8 (4) |
C34—Ir1—S11—C11 | −94.3 (2) | Ir1—C31—C35—C34 | −62.7 (3) |
C32—Ir1—S11—C11 | −159.8 (2) | C32—C31—C35—C351 | −175.2 (5) |
C33—Ir1—S11—C11 | −121.1 (2) | C311—C31—C35—C351 | 2.8 (8) |
S22—Ir1—S11—C11 | 13.02 (17) | Ir1—C31—C35—C351 | 123.3 (5) |
S21—Ir1—S11—C11 | 84.25 (17) | C32—C31—C35—Ir1 | 61.5 (3) |
C35—Ir1—S11—Ir2 | 147.5 (4) | C311—C31—C35—Ir1 | −120.5 (5) |
C31—Ir1—S11—Ir2 | 89.58 (18) | C33—C34—C35—C31 | 0.6 (5) |
C34—Ir1—S11—Ir2 | 175.54 (15) | C341—C34—C35—C31 | −176.7 (4) |
C32—Ir1—S11—Ir2 | 110.02 (13) | Ir1—C34—C35—C31 | 62.5 (3) |
C33—Ir1—S11—Ir2 | 148.70 (13) | C33—C34—C35—C351 | 174.6 (5) |
S22—Ir1—S11—Ir2 | −77.17 (5) | C341—C34—C35—C351 | −2.7 (8) |
S21—Ir1—S11—Ir2 | −5.94 (4) | Ir1—C34—C35—C351 | −123.5 (5) |
C41—Ir2—S12—C11 | −128.1 (2) | C33—C34—C35—Ir1 | −61.9 (3) |
C45—Ir2—S12—C11 | −93.9 (2) | C341—C34—C35—Ir1 | 120.8 (5) |
C44—Ir2—S12—C11 | −91.3 (3) | C34—Ir1—C35—C31 | −116.3 (4) |
C42—Ir2—S12—C11 | −164.6 (2) | C32—Ir1—C35—C31 | −36.8 (3) |
C43—Ir2—S12—C11 | −176.1 (3) | C33—Ir1—C35—C31 | −79.6 (3) |
S11—Ir2—S12—C11 | 1.65 (16) | S22—Ir1—C35—C31 | 146.3 (3) |
S21—Ir2—S12—C11 | 79.98 (16) | S21—Ir1—C35—C31 | 72.0 (3) |
Ir2—S12—C11—N11 | 177.2 (4) | S11—Ir1—C35—C31 | −78.3 (5) |
Ir2—S12—C11—S11 | −2.2 (2) | C31—Ir1—C35—C34 | 116.3 (4) |
Ir2—S11—C11—N11 | −177.2 (4) | C32—Ir1—C35—C34 | 79.5 (3) |
Ir1—S11—C11—N11 | 83.5 (4) | C33—Ir1—C35—C34 | 36.7 (3) |
Ir2—S11—C11—S12 | 2.2 (2) | S22—Ir1—C35—C34 | −97.3 (3) |
Ir1—S11—C11—S12 | −97.0 (2) | S21—Ir1—C35—C34 | −171.7 (2) |
S12—C11—N11—C14 | −1.2 (7) | S11—Ir1—C35—C34 | 38.0 (6) |
S11—C11—N11—C14 | 178.2 (4) | C31—Ir1—C35—C351 | −122.1 (7) |
S12—C11—N11—C12 | 177.6 (4) | C34—Ir1—C35—C351 | 121.6 (7) |
S11—C11—N11—C12 | −3.0 (7) | C32—Ir1—C35—C351 | −158.8 (6) |
C11—N11—C12—C13 | 83.6 (6) | C33—Ir1—C35—C351 | 158.3 (6) |
C14—N11—C12—C13 | −97.6 (5) | S22—Ir1—C35—C351 | 24.3 (5) |
C11—N11—C14—C15 | 102.9 (5) | S21—Ir1—C35—C351 | −50.1 (6) |
C12—N11—C14—C15 | −76.0 (6) | S11—Ir1—C35—C351 | 159.7 (4) |
C41—Ir2—S21—C21 | −98.7 (3) | C44—Ir2—C41—C45 | −38.2 (3) |
C45—Ir2—S21—C21 | −177.8 (3) | C42—Ir2—C41—C45 | −118.9 (4) |
C44—Ir2—S21—C21 | −171.3 (2) | C43—Ir2—C41—C45 | −80.5 (3) |
C42—Ir2—S21—C21 | −101.8 (2) | S12—Ir2—C41—C45 | 125.6 (3) |
C43—Ir2—S21—C21 | −136.4 (2) | S11—Ir2—C41—C45 | 52.3 (3) |
S12—Ir2—S21—C21 | 12.64 (17) | S21—Ir2—C41—C45 | −123.4 (3) |
S11—Ir2—S21—C21 | 84.57 (17) | C45—Ir2—C41—C42 | 118.9 (4) |
C41—Ir2—S21—Ir1 | 170.7 (3) | C44—Ir2—C41—C42 | 80.7 (3) |
C45—Ir2—S21—Ir1 | 91.6 (2) | C43—Ir2—C41—C42 | 38.4 (3) |
C44—Ir2—S21—Ir1 | 98.20 (14) | S12—Ir2—C41—C42 | −115.6 (3) |
C42—Ir2—S21—Ir1 | 167.67 (14) | S11—Ir2—C41—C42 | 171.2 (2) |
C43—Ir2—S21—Ir1 | 133.02 (14) | S21—Ir2—C41—C42 | −4.6 (4) |
S12—Ir2—S21—Ir1 | −77.91 (4) | C45—Ir2—C41—C411 | −121.1 (6) |
S11—Ir2—S21—Ir1 | −5.97 (4) | C44—Ir2—C41—C411 | −159.3 (5) |
C35—Ir1—S21—C21 | 88.0 (2) | C42—Ir2—C41—C411 | 120.0 (5) |
C31—Ir1—S21—C21 | 125.0 (2) | C43—Ir2—C41—C411 | 158.4 (5) |
C34—Ir1—S21—C21 | 75.4 (3) | S12—Ir2—C41—C411 | 4.4 (4) |
C32—Ir1—S21—C21 | 161.9 (2) | S11—Ir2—C41—C411 | −68.8 (5) |
C33—Ir1—S21—C21 | 175.0 (3) | S21—Ir2—C41—C411 | 115.5 (4) |
S22—Ir1—S21—C21 | −0.88 (16) | C45—C41—C42—C43 | −0.9 (5) |
S11—Ir1—S21—C21 | −101.65 (16) | C411—C41—C42—C43 | 177.7 (4) |
C35—Ir1—S21—Ir2 | −164.37 (15) | Ir2—C41—C42—C43 | −62.1 (3) |
C31—Ir1—S21—Ir2 | −127.42 (15) | C45—C41—C42—C421 | −171.3 (5) |
C34—Ir1—S21—Ir2 | −177.0 (3) | C411—C41—C42—C421 | 7.2 (8) |
C32—Ir1—S21—Ir2 | −90.50 (15) | Ir2—C41—C42—C421 | 127.5 (5) |
C33—Ir1—S21—Ir2 | −77.4 (3) | C45—C41—C42—Ir2 | 61.2 (3) |
S22—Ir1—S21—Ir2 | 106.70 (5) | C411—C41—C42—Ir2 | −120.3 (5) |
S11—Ir1—S21—Ir2 | 5.93 (4) | C45—Ir2—C42—C41 | −37.0 (3) |
C35—Ir1—S22—C21 | −115.7 (2) | C44—Ir2—C42—C41 | −80.2 (3) |
C31—Ir1—S22—C21 | −90.1 (2) | C43—Ir2—C42—C41 | −116.5 (4) |
C34—Ir1—S22—C21 | −155.0 (2) | S12—Ir2—C42—C41 | 73.3 (3) |
C32—Ir1—S22—C21 | −124.5 (4) | S11—Ir2—C42—C41 | −30.3 (8) |
C33—Ir1—S22—C21 | −176.7 (2) | S21—Ir2—C42—C41 | 177.5 (2) |
S21—Ir1—S22—C21 | 0.91 (16) | C41—Ir2—C42—C43 | 116.5 (4) |
S11—Ir1—S22—C21 | 77.95 (16) | C45—Ir2—C42—C43 | 79.5 (3) |
Ir1—S22—C21—N21 | 177.4 (4) | C44—Ir2—C42—C43 | 36.3 (3) |
Ir1—S22—C21—S21 | −1.3 (2) | S12—Ir2—C42—C43 | −170.2 (3) |
Ir2—S21—C21—N21 | 83.1 (4) | S11—Ir2—C42—C43 | 86.2 (7) |
Ir1—S21—C21—N21 | −177.5 (4) | S21—Ir2—C42—C43 | −66.0 (3) |
Ir2—S21—C21—S22 | −98.2 (2) | C41—Ir2—C42—C421 | −121.0 (6) |
Ir1—S21—C21—S22 | 1.2 (2) | C45—Ir2—C42—C421 | −158.0 (6) |
S22—C21—N21—C22 | 170.6 (4) | C44—Ir2—C42—C421 | 158.8 (6) |
S21—C21—N21—C22 | −11.0 (7) | C43—Ir2—C42—C421 | 122.5 (7) |
S22—C21—N21—C24 | −7.2 (7) | S12—Ir2—C42—C421 | −47.7 (5) |
S21—C21—N21—C24 | 171.3 (4) | S11—Ir2—C42—C421 | −151.3 (5) |
C21—N21—C22—C23 | 90.6 (6) | S21—Ir2—C42—C421 | 56.5 (5) |
C24—N21—C22—C23 | −91.6 (5) | C41—C42—C43—C44 | 1.3 (6) |
C21—N21—C24—C25 | 94.9 (5) | C421—C42—C43—C44 | 171.6 (5) |
C22—N21—C24—C25 | −83.0 (5) | Ir2—C42—C43—C44 | −60.4 (3) |
C34—Ir1—C31—C35 | 38.8 (3) | C41—C42—C43—C431 | −176.9 (5) |
C32—Ir1—C31—C35 | 119.1 (4) | C421—C42—C43—C431 | −6.6 (8) |
C33—Ir1—C31—C35 | 80.8 (3) | Ir2—C42—C43—C431 | 121.4 (5) |
S22—Ir1—C31—C35 | −43.8 (3) | C41—C42—C43—Ir2 | 61.7 (3) |
S21—Ir1—C31—C35 | −120.7 (3) | C421—C42—C43—Ir2 | −128.0 (5) |
S11—Ir1—C31—C35 | 152.8 (2) | C41—Ir2—C43—C44 | 81.2 (3) |
C35—Ir1—C31—C32 | −119.1 (4) | C45—Ir2—C43—C44 | 38.4 (3) |
C34—Ir1—C31—C32 | −80.3 (3) | C42—Ir2—C43—C44 | 119.4 (4) |
C33—Ir1—C31—C32 | −38.3 (3) | S12—Ir2—C43—C44 | 136.8 (3) |
S22—Ir1—C31—C32 | −162.9 (2) | S11—Ir2—C43—C44 | −40.0 (4) |
S21—Ir1—C31—C32 | 120.2 (3) | S21—Ir2—C43—C44 | −118.8 (3) |
S11—Ir1—C31—C32 | 33.7 (4) | C41—Ir2—C43—C42 | −38.1 (3) |
C35—Ir1—C31—C311 | 119.6 (6) | C45—Ir2—C43—C42 | −81.0 (3) |
C34—Ir1—C31—C311 | 158.4 (5) | C44—Ir2—C43—C42 | −119.4 (4) |
C32—Ir1—C31—C311 | −121.3 (6) | S12—Ir2—C43—C42 | 17.5 (4) |
C33—Ir1—C31—C311 | −159.6 (5) | S11—Ir2—C43—C42 | −159.3 (2) |
S22—Ir1—C31—C311 | 75.8 (5) | S21—Ir2—C43—C42 | 121.8 (3) |
S21—Ir1—C31—C311 | −1.1 (5) | C41—Ir2—C43—C431 | −158.0 (5) |
S11—Ir1—C31—C311 | −87.6 (5) | C45—Ir2—C43—C431 | 159.1 (5) |
C35—C31—C32—C33 | 1.4 (5) | C44—Ir2—C43—C431 | 120.7 (6) |
C311—C31—C32—C33 | −176.6 (4) | C42—Ir2—C43—C431 | −119.9 (6) |
Ir1—C31—C32—C33 | 62.2 (3) | S12—Ir2—C43—C431 | −102.4 (5) |
C35—C31—C32—C321 | 171.1 (5) | S11—Ir2—C43—C431 | 80.8 (5) |
C311—C31—C32—C321 | −6.9 (8) | S21—Ir2—C43—C431 | 1.9 (5) |
Ir1—C31—C32—C321 | −128.1 (5) | C42—C43—C44—C45 | −1.2 (5) |
C35—C31—C32—Ir1 | −60.8 (3) | C431—C43—C44—C45 | 177.0 (5) |
C311—C31—C32—Ir1 | 121.2 (5) | Ir2—C43—C44—C45 | −61.5 (3) |
C35—Ir1—C32—C31 | 36.9 (3) | C42—C43—C44—C441 | −175.6 (5) |
C34—Ir1—C32—C31 | 80.3 (3) | C431—C43—C44—C441 | 2.6 (8) |
C33—Ir1—C32—C31 | 116.6 (4) | Ir2—C43—C44—C441 | 124.0 (5) |
S22—Ir1—C32—C31 | 46.5 (6) | C42—C43—C44—Ir2 | 60.4 (3) |
S21—Ir1—C32—C31 | −72.4 (3) | C431—C43—C44—Ir2 | −121.4 (5) |
S11—Ir1—C32—C31 | −156.1 (3) | C41—Ir2—C44—C43 | −79.5 (3) |
C35—Ir1—C32—C33 | −79.7 (3) | C45—Ir2—C44—C43 | −117.1 (4) |
C31—Ir1—C32—C33 | −116.6 (4) | C42—Ir2—C44—C43 | −36.9 (3) |
C34—Ir1—C32—C33 | −36.3 (3) | S12—Ir2—C44—C43 | −120.9 (3) |
S22—Ir1—C32—C33 | −70.1 (5) | S11—Ir2—C44—C43 | 153.8 (3) |
S21—Ir1—C32—C33 | 171.0 (2) | S21—Ir2—C44—C43 | 68.4 (3) |
S11—Ir1—C32—C33 | 87.3 (3) | C41—Ir2—C44—C45 | 37.7 (3) |
C35—Ir1—C32—C321 | 158.8 (6) | C42—Ir2—C44—C45 | 80.2 (3) |
C31—Ir1—C32—C321 | 122.0 (6) | C43—Ir2—C44—C45 | 117.1 (4) |
C34—Ir1—C32—C321 | −157.8 (6) | S12—Ir2—C44—C45 | −3.7 (5) |
C33—Ir1—C32—C321 | −121.5 (6) | S11—Ir2—C44—C45 | −89.1 (3) |
S22—Ir1—C32—C321 | 168.4 (4) | S21—Ir2—C44—C45 | −174.5 (2) |
S21—Ir1—C32—C321 | 49.6 (5) | C41—Ir2—C44—C441 | 158.1 (5) |
S11—Ir1—C32—C321 | −34.2 (5) | C45—Ir2—C44—C441 | 120.4 (6) |
C31—C32—C33—C34 | −1.0 (5) | C42—Ir2—C44—C441 | −159.4 (5) |
C321—C32—C33—C34 | −170.8 (5) | C43—Ir2—C44—C441 | −122.5 (6) |
Ir1—C32—C33—C34 | 60.5 (3) | S12—Ir2—C44—C441 | 116.7 (5) |
C31—C32—C33—C331 | 174.6 (4) | S11—Ir2—C44—C441 | 31.3 (5) |
C321—C32—C33—C331 | 4.7 (8) | S21—Ir2—C44—C441 | −54.1 (5) |
Ir1—C32—C33—C331 | −123.9 (5) | C42—C41—C45—C44 | 0.2 (5) |
C31—C32—C33—Ir1 | −61.5 (3) | C411—C41—C45—C44 | −178.3 (4) |
C321—C32—C33—Ir1 | 128.7 (5) | Ir2—C41—C45—C44 | 61.7 (3) |
C35—Ir1—C33—C34 | −38.0 (3) | C42—C41—C45—C451 | 174.4 (5) |
C31—Ir1—C33—C34 | −80.9 (3) | C411—C41—C45—C451 | −4.1 (8) |
C32—Ir1—C33—C34 | −119.1 (4) | Ir2—C41—C45—C451 | −124.0 (5) |
S22—Ir1—C33—C34 | 36.7 (3) | C42—C41—C45—Ir2 | −61.6 (3) |
S21—Ir1—C33—C34 | −137.9 (3) | C411—C41—C45—Ir2 | 119.9 (5) |
S11—Ir1—C33—C34 | 142.4 (3) | C43—C44—C45—C41 | 0.6 (5) |
C35—Ir1—C33—C32 | 81.0 (3) | C441—C44—C45—C41 | 175.1 (5) |
C31—Ir1—C33—C32 | 38.1 (3) | Ir2—C44—C45—C41 | −61.7 (3) |
C34—Ir1—C33—C32 | 119.1 (4) | C43—C44—C45—C451 | −173.7 (5) |
S22—Ir1—C33—C32 | 155.8 (2) | C441—C44—C45—C451 | 0.8 (8) |
S21—Ir1—C33—C32 | −18.9 (5) | Ir2—C44—C45—C451 | 124.0 (5) |
S11—Ir1—C33—C32 | −98.5 (3) | C43—C44—C45—Ir2 | 62.3 (3) |
C35—Ir1—C33—C331 | −160.8 (6) | C441—C44—C45—Ir2 | −123.1 (5) |
C31—Ir1—C33—C331 | 156.3 (6) | C44—Ir2—C45—C41 | 117.3 (4) |
C34—Ir1—C33—C331 | −122.8 (6) | C42—Ir2—C45—C41 | 36.9 (3) |
C32—Ir1—C33—C331 | 118.2 (6) | C43—Ir2—C45—C41 | 79.8 (3) |
S22—Ir1—C33—C331 | −86.0 (5) | S12—Ir2—C45—C41 | −64.5 (3) |
S21—Ir1—C33—C331 | 99.3 (5) | S11—Ir2—C45—C41 | −141.5 (3) |
S11—Ir1—C33—C331 | 19.6 (5) | S21—Ir2—C45—C41 | 127.2 (3) |
C32—C33—C34—C35 | 0.2 (5) | C41—Ir2—C45—C44 | −117.3 (4) |
C331—C33—C34—C35 | −175.2 (5) | C42—Ir2—C45—C44 | −80.4 (3) |
Ir1—C33—C34—C35 | 60.5 (3) | C43—Ir2—C45—C44 | −37.4 (3) |
C32—C33—C34—C341 | 177.6 (4) | S12—Ir2—C45—C44 | 178.3 (2) |
C331—C33—C34—C341 | 2.2 (8) | S11—Ir2—C45—C44 | 101.2 (3) |
Ir1—C33—C34—C341 | −122.2 (5) | S21—Ir2—C45—C44 | 9.9 (4) |
C32—C33—C34—Ir1 | −60.3 (3) | C41—Ir2—C45—C451 | 122.1 (6) |
C331—C33—C34—Ir1 | 124.3 (5) | C44—Ir2—C45—C451 | −120.7 (5) |
C35—Ir1—C34—C33 | 118.1 (4) | C42—Ir2—C45—C451 | 158.9 (5) |
C31—Ir1—C34—C33 | 79.9 (3) | C43—Ir2—C45—C451 | −158.1 (5) |
C32—Ir1—C34—C33 | 37.2 (3) | S12—Ir2—C45—C451 | 57.6 (5) |
S22—Ir1—C34—C33 | −153.3 (3) | S11—Ir2—C45—C451 | −19.5 (4) |
S21—Ir1—C34—C33 | 136.1 (3) | S21—Ir2—C45—C451 | −110.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C451—H452···O51i | 0.98 | 2.41 | 3.384 (6) | 177 |
C25—H253···O61ii | 0.98 | 2.43 | 3.398 (7) | 168 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Ir2(C10H15)2(C5H10NS2)2](ClO4)2 |
Mr | 1150.26 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 108 |
a, b, c (Å) | 20.2386 (5), 15.1259 (6), 25.6234 (10) |
V (Å3) | 7844.0 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 7.18 |
Crystal size (mm) | 0.46 × 0.30 × 0.12 |
Data collection | |
Diffractometer | Oxford diffraction Sapphire2 CCD |
Absorption correction | Multi-scan [empirical (using intensity measurements) correction (CrysAlis RED; Oxford Diffraction, 2006)] |
Tmin, Tmax | 0.103, 0.416 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 37944, 6895, 5296 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.062, 1.03 |
No. of reflections | 6895 |
No. of parameters | 447 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.87, −1.09 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Ir1—C35 | 2.167 (5) | Ir2—C41 | 2.174 (5) |
Ir1—C31 | 2.173 (5) | Ir2—C45 | 2.175 (5) |
Ir1—C34 | 2.191 (4) | Ir2—C44 | 2.182 (5) |
Ir1—C32 | 2.193 (5) | Ir2—C42 | 2.189 (5) |
Ir1—C33 | 2.206 (5) | Ir2—C43 | 2.195 (5) |
Ir1—S22 | 2.3842 (12) | Ir2—S12 | 2.3832 (12) |
Ir1—S21 | 2.3986 (12) | Ir2—S11 | 2.3897 (11) |
Ir1—S11 | 2.4098 (12) | Ir2—S21 | 2.3952 (12) |
S22—Ir1—S21 | 73.00 (4) | S12—Ir2—S21 | 94.83 (4) |
S22—Ir1—S11 | 97.14 (4) | S11—Ir2—S21 | 80.31 (4) |
S21—Ir1—S11 | 79.83 (4) | Ir2—S11—Ir1 | 99.54 (4) |
S12—Ir2—S11 | 73.12 (4) | Ir2—S21—Ir1 | 99.71 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C451—H452···O51i | 0.98 | 2.41 | 3.384 (6) | 176.6 |
C25—H253···O61ii | 0.98 | 2.43 | 3.398 (7) | 167.9 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, z. |
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Entries for six (dithiocarbamato)iridium(III) complexes are present in the current Cambridge Structural Database (Version 5.27, December 2006; Allen 2002). These are all mononuclear and contain either one (Dean, 1979; Lau et al., 2004; Suzuki et al., 2003) or three (Butcher & Sinn, 1976; Raston & White, 1976; Sinn 1976) bidentate dithiocarbamato ligands in the chelating κ2S,S' mode. We ourselves have also recently reported the first example of an (η5-C5Me5)IrIII complex to contain such a ligand, namely [(η5-C5Me5)Ir{(C2H5)2NCS2-κ2S,S'}(CO)](CF3SO3) (Scharwitz, Schäfer et al., 2007a). This carbonyl complex was prepared by heating [(η5-C5Me5)Ir{µ-(C2H5)2NCS2}]2(CF3SO3)2 (I) in methanol to 393 K in a sealed glass tube. We have now been successful in crystallizing the cation of dinuclear starting compound as its perchlorate [(η5-C5Me5)Ir{µ-(C2H5)2NCS2}]2(ClO4)2] (I) and report its structure as part of our continuing studies on (η6-arene)RuII and (η5-C5Me5)IrIII complexes with sulfur and nitrogen containing ligands (Gleichmann et al., 1995; Herebian & Sheldrick, 2002; Korn & Sheldrick, 1997; Schäfer & Sheldrick, 2007; Scharwitz et al., 2007a, b, c, d); Scharwitz, Schäfer et al., 2007; Stodt et al., 2003).
The molecular structure of (I) is depicted in Fig. 1 and exhibits Ir—C distances to the pentamethylcyclopentadienyl ligands in the range 2.167 (5)–2.206 (5) as listed in Table 1. The (η5-C5Me5)IrIII fragments adopt a cis arrangement relative to the (IrS)2 ring. Although the sulfur atoms S11 and S21 are bidentate, their Ir—S distances of respectively 2.4098 (12) and 2.3986 (12) Å to Ir1 and 2.3897 (11) and 2.3952 (12) Å to Ir2 are on average only marginally longer than those of 2.3842 (12) and 2.3832 (12) Å for the monodentate atoms S22 and S12. These latter values are similar to those of 2.3795 (12) and 2.3861 (14) Å reported for the Ir—S distances in the mononuclear carbonyl complex [(η5-C5Me5)Ir{(C2H5)2NCS2-κ2S,S'}(CO)](CF3SO3) (Scharwitz et al., 2007a). This is also the case for the S—Ir—S angles of the chelate rings in (I), which exhibit values of 73.00 (4) and 73.12 (4) that are, on average only 0.46° larger than that of 72.60 (4)° in the carbonyl complex. Narrow S—Ir—S angles of 79.83 (4) and 80.31 (4)° are also observed for the Ir1 and Ir2 atoms within the central (IrS)2 ring. (I) is the first iridium complex to contain tridentate dithiocarbamate ligands, although the observed 1κ2S,S':2κS coordination mode has previously been observed for later transition metals in [{Ru([9]aneS3)}2{µ-(C2H5)2NCS2}2] (Landgrafe & Sheldrick, 1994) and [Rh2{(CH3)2NCS2}5](BF4) (Hendrickson et al., 1976). The cation and anion packing in the unit cell is illustrated in Fig. 2.