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research communications
Crystal structures of (η4-cycloocta-1,5-diene)bis(1,3-dimethylimidazol-2-ylidene)iridium(I) iodide and (η4-cycloocta-1,5-diene)bis(1,3-diethylimidazol-2-ylidene)iridium(I) iodide
aDepartment of Chemistry, Virginia Tech, Blacksburg, VA 24061, USA
*Correspondence e-mail: jmerola@vt.edu
The title complexes, (η4-cycloocta-1,5-diene)bis(1,3-dimethylimidazol-2-ylidene)iridium(I) iodide, [Ir(C5H8N2)2(C8H12)]I, (1) and (η4-cycloocta-1,5-diene)bis(1,3-diethylimidazol-2-ylidene)iridium(I) iodide, [Ir(C7H12N2)2(C8H12)]I, (2), were prepared using a modified literature method. After carrying out the of the amino acid L-proline to [Ir(COD)(IMe)2]I in water and slowly cooling the reaction to room temperature, a suitable crystal of 1 was obtained and analyzed by single-crystal X-ray diffraction at 100 K. Although this has previously been reported in the Pbam it was highly disordered and precise atomic coordinates were not calculated. A single crystal of 2 was also obtained by heating the complex in water and letting it slowly cool to room temperature. Complex 1 was found to crystallize in the monoclinic C2/m, while 2 crystallizes in the orthorhombic Pccn, both with Z = 4.
Keywords: crystal structure; N-heterocyclic carbene; iridium.
1. Chemical context
The Merola group has been interested in the chemistry of electron-rich iridium compounds for many years (Frazier & Merola, 1992; Ladipo et al., 1993
; Selnau & Merola, 1993
; Merola & Franks, 2013
). Recently, we have begun examining the reactivity and catalytic applications of IrI N-heterocyclic carbene (NHC) complexes, which have previously been utilized for various transformations including hydrogenation (Hillier et al., 2001
), hydrosilylation (Viciano et al., 2006
), hydroamination (Sipos et al., 2016
), H/D exchange (Cochrane et al., 2014
), and C—H bond functionalization (Frey et al., 2006
). While investigating the of amino acids to (η4-cycloocta-1,5-diene)bis(1,3-dimethylimidazol-2-ylidene)iridium(I) iodide in aqueous solution, cooling the reaction to room temperature yielded single crystals of the starting material [Ir(COD)(IMe)2]I, where IMe = 1,3-dimethylimidazol-2-ylidene. Though Herrmann and coworkers previously described the of this complex in the Pbam (Frey et al., 2006
), the anisotropic displacement parameters of the COD ligand were highly disordered; thus precise atomic coordinates could not be calculated. In an effort to advance the study of the structural properties and reactivity of IrI NHC complexes, we hereby report the single-crystal of (η4-cycloocta-1,5-diene)bis(1,3-dimethylimidazol-2-ylidene)iridium(I) iodide (1) and (η4-cycloocta-1,5-diene)bis(1,3-diethylimidazol-2-ylidene)iridium(I) iodide (2).
2. Structural commentary
Complex 1 (CCDC ref code 1983640) crystallizes in the monoclinic C2/m with Z = 4 (Figs. 1 and 2
), which differs from Herrmann's original report of the orthorhombic Pbam. Ir1, C1, C4, and I1 lie in special positions on the mirror plane. The geometry around the metal center is nearly square planar, with the largest angle [C1—Ir1—C4 = 93.14 (10)°] and smallest angle [C7—Ir1—C10 (centroids) = 86.20°] having deviations of 3.14 and 3.80°, respectively, from the ideal 90° geometry. The average Ir—NHC bond length is 2.044 Å [Ir1—C1 = 2.037 (2), Ir1—C4 = 2.051 (2) Å] and the average Ir—CCOD bond length is 2.169 Å [Ir1—C7 = 2.163 (2) Å; Ir1—C10 = 2.174 (2) Å] with an Ir—CODcentroid distance of 2.047 Å, related by symmetry.
![]() | Figure 1 Displacement ellipsoid plot (50% probability) of (η4-cycloocta-1,5-diene)bis(1,3-dimethylimidazol-2-ylidene)iridium(I) iodide (1), showing part 1 of the disorder for the CH2 carbon atoms of the COD ring. Symmetry code: (i) x, 1 − y, z. |
![]() | Figure 2 Displacement ellipsoid plot (50% probability) of (η4-cycloocta-1,5-diene)bis(1,3-dimethylimidazol-2-ylidene)iridium(I) iodide (1), showing part 2 of the disorder for the CH2 carbon atoms of the COD ring. Symmetry code: (i) x, 1 − y, z. |
Complex 2 (CCDC ref code 1986045) crystallizes in the orthorhombic Pccn with Z = 4 (Fig. 3). Atom Ir1 lies in a special position on the twofold rotation axis. Similarly to 1, the geometry around the metal center is nearly square planar, with the largest angle [C1—Ir1—C1 = 92.93 (12)°] and smallest angle [C8—Ir1—C9 (centroids) = 86.06°] having deviations of 2.92 and 3.94°, respectively, from the ideal 90° geometry. The Ir—NHC bond lengths [2.043 (2) Å] are related by symmetry. The average Ir—CCOD bond length is 2.172 Å [Ir1—C8 = 2.197 (2), Ir1—C9 = 2.147 (2) Å] with an Ir—CODcentroid distance of 2.058 Å, again related by symmetry.
![]() | Figure 3 Displacement ellipsoid plot (50% probability) of (η4-cycloocta-1,5-diene)bis(1,3-diethylimidazol-2-ylidene)iridium(I) iodide (2).Symmetry code: (i) ![]() ![]() |
This discrepancy in Ir—CCOD bond lengths and Ir—CODcentroid distances between the two complexes is likely due to the conformation of the COD ligand, which is a boat in 1 and a twist-boat in 2.
3. Supramolecular features
An examination of the packing diagrams for both title complexes show no unusual supramolecular features.
4. Database survey
In our search for the COD bis-NHC moiety, we were somewhat surprised to find only ten reported IrCOD structures in the Cambridge Structural Database (CSD2019, update 3; Groom et al., 2016) with two monodentate NHCs, including the original disordered structure reported by Herrmann (WEXKOA; Frey et al., 2006
). Structures similar to the title compound include a square-planar [(COD)bis(1-ethyl-3-methylimidazol-2-ylidene)iridium(I)] complex (BAHZER; Hintermair et al., 2011
) and a complex containing quinoline-functionalized NHC ligands (ROWWUX; Jiménez et al., 2015
), both in P21/c (No. 14). Other closely related structures include an iridium COD complex with pyrazolyl-functionalized NHC ligands (CEMVIA; Messerle et al., 2006
), and an iridium COD complex with pentafluorobenzyl functionalized NHCs (TESGEE; Burling et al., 2006
), both of which crystallized in C2/c (No. 15).
5. Synthesis and crystallization
The title compounds were synthesized using a modified literature procedure (Köcher & Herrmann, 1997). [Ir(COD)Cl]2 (500 mg, 0.744 mmol) and a magnetic stir bar were added to a flame-dried, nitrogen-purged 100 mL Schlenk flask. Ethanol (20 mL) was added via syringe and the red solution was stirred. After 5 minutes, a solution of NaOEt in ethanol (1 M, 3.5 mL, 3.50 mmol) was added to the reaction flask dropwise. The solution was stirred for 1 h while the color slowly changed from red to bright yellow, indicating the formation of [Ir(COD)(OEt)]2. The NHC precursor 1,3-dimethylimidazolium iodide (840 mg, 3.75 mmol) or 1,3-diethylimidazolium iodide (945 mg, 3.75 mmol) was dissolved in ethanol (10 mL) and added to the stirring mixture via syringe. After 48 h, the bright-orange mixture was filtered through celite. The solvent was removed by rotary evaporation, and the residue was dissolved in minimal dichloromethane.
The crude product was purified via with silica gel, first using a 1:1 mixture of cyclohexane to ethyl acetate as the mobile phase to collect the bright-yellow iridium mono-NHC complex, followed by 7% methanol in dichloromethane to collect the desired orange iridium bis-NHC product. The solvent was removed by rotary evaporation and the bright-orange solid was dried overnight under vacuum (449 mg, 49% for 1; 415 mg, 42% for 2). The products were characterized by 1H and 13C NMR spectroscopy in agreement with previously reported data.
Single crystals of 1 for X-ray crystallography were collected from a subsequent reaction. The title compound, L-proline, and 10 mL of water were added to a 6 dram vial and stirred overnight at 323 K. Upon slowly cooling the reaction mixture to room temperature, bright-orange crystals of the title compound grew and were collected. Single crystals of 2 were grown by dissolving the complex in water, heating it to 323 K, and letting the solution slowly cool to room temperature.
6. Refinement
Crystal data, data collection and structure .
|
Compound 1 was solved with SHELXS and refined with SHELXL within OLEX2. The proceeded quite well although the displacement ellipsoids for the CH2 carbon atoms of the COD ring were overly elongated, suggesting that there was possible disorder. In OLEX2, the disorder tools were utilized to split the carbon atoms while adding SHELXL SIMU restraint. The disorder model appeared to refine well with reasonable displacement ellipsoids. Fig. 1 shows part 1 of the disorder and Fig. 2
shows part 2. Both parts show nearly equal occupancies refining to 0.515 (19):0.485 (19). The two parts seem best described as the result of static disorder wherein the saturated portion of the COD ring is slightly twisted. The unsaturated carbon atoms are also likely a part of the disorder, but the positional change is so slight as to not warrant (and to resist) modeling. However, a consequence of this slight disorder is that generating the entire molecule does generate two different hydrogen-atom positions, also refining to 0.515 (19):0.485 (19) relative occupancies.
Data reduction, solution and 2 presented some interesting issues that are discussed here. The data were collected on a XtaLAB Synergy, Dualflex, HyPix diffractometer. Data reduction was performed with CrysAlisPro171.40_64.67a (Rigaku OD, 2018). The crystal was of good quality and peak searching found 9425 peaks that were merged to 5446 profiles. Unit-cell calculations fit 98.2% of the peaks to the cell 9.1397 (5), 10.6193 (7), 12.3249 (6), 89.980 (5). 89.988 (4), 89.965 (6). Further and determination led to the finalization of the data in orthorhombic P. SHELXT within OLEX2 was used for structure solution and several non-centrosymmetric space groups were identified with nearly equal figure of merit. Attempts were made to refine the structure in all five of the proffered space groups and the only one that provided a reasonable solution was P21212. However, while the structure parameters were `reasonable', several displacement ellipsoids in the finalized model were elongated along strange directions. The data were reexamined and a close view of the showed weak, but clearly present peaks between the axes. The ∼9 Å axis was doubled and now all peaks were aligned fully with the new axes of 18.2790 (10), 10.6196 (7), 12.3245 (6), 89.979 (5), 89.985 (4), 89.965 (5). With those particular settings in CrysAlis, the only reasonable found was triclinic.
Moving into OLEX2 again, a solution was found in P that refined into a solution with excellent figures of merit and well-shaped displacement ellipsoids with Z = 4. However, it was noted that the heavy atoms, iridium and iodine all had coordinates that suggested they sat on special positions, e.g. x = 0.7500. ADDSYM in PLATON (Spek, 2020
) was used to search for higher symmetries and the result suggested that Pccn was an appropriate high-symmetry The newly created data and instruction files from PLATON were used in OLEX2 and the structure in Pccn solved and refined cleanly into the final structure. With this result in hand, the raw data were re-reduced, the originally found x axis was again doubled and space-group analysis was re-performed with slightly larger angle tolerances (0.03 vs 0.015). Pccn was then clearly identified as the top match for the The data and instruction files were once more used in OLEX2 and SHELXT used as the solution program, which determined that Pccn was the best led to the final structure solution reported in this paper.
Supporting information
https://doi.org/10.1107/S2056989020004235/mw2156sup1.cif
contains datablocks 1, 2, New_Global_Publ_Block. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989020004235/mw21561sup2.hkl
Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989020004235/mw21562sup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989020004235/mw21561sup4.mol
Supporting information file. DOI: https://doi.org/10.1107/S2056989020004235/mw21562sup5.mol
For both structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell
CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018). Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for (1); ShelXT (Sheldrick, 2015a) for (2). For both structures, program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).[Ir(C5H8N2)2(C8H12)]I | F(000) = 1176 |
Mr = 619.54 | Dx = 1.930 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
a = 26.6519 (4) Å | Cell parameters from 17811 reflections |
b = 8.3070 (2) Å | θ = 2.6–38.3° |
c = 9.7852 (2) Å | µ = 7.72 mm−1 |
β = 100.241 (2)° | T = 100 K |
V = 2131.90 (8) Å3 | Prism, orange |
Z = 4 | 0.54 × 0.22 × 0.11 mm |
XtaLAB Synergy, Dualflex, HyPix diffractometer | 5884 independent reflections |
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source | 5415 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.034 |
ω scans | θmax = 38.2°, θmin = 3.1° |
Absorption correction: gaussian (CrysAlisPro;Rigaku OD, 2018) | h = −45→44 |
Tmin = 0.179, Tmax = 0.960 | k = −14→13 |
27006 measured reflections | l = −16→16 |
Refinement on F2 | 12 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0317P)2 + 1.4859P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
5884 reflections | Δρmax = 2.40 e Å−3 |
136 parameters | Δρmin = −1.29 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ir1 | 0.35715 (2) | 0.500000 | 0.71082 (2) | 0.01615 (3) | |
N1 | 0.36047 (6) | 0.6287 (2) | 0.41903 (16) | 0.0216 (3) | |
N2 | 0.46647 (6) | 0.3712 (2) | 0.79484 (18) | 0.0242 (3) | |
C1 | 0.36077 (9) | 0.500000 | 0.5047 (2) | 0.0184 (4) | |
C2 | 0.36009 (8) | 0.5804 (3) | 0.28291 (19) | 0.0254 (4) | |
H2 | 0.359874 | 0.648608 | 0.204874 | 0.031* | |
C3 | 0.36109 (11) | 0.7956 (3) | 0.4619 (2) | 0.0346 (5) | |
H3A | 0.394582 | 0.842411 | 0.458346 | 0.052* | |
H3B | 0.354380 | 0.802066 | 0.557045 | 0.052* | |
H3C | 0.334734 | 0.855247 | 0.399422 | 0.052* | |
C4 | 0.43494 (9) | 0.500000 | 0.7697 (3) | 0.0189 (4) | |
C5 | 0.51693 (8) | 0.4201 (3) | 0.8329 (2) | 0.0336 (5) | |
H5 | 0.545889 | 0.352001 | 0.854780 | 0.040* | |
C6 | 0.45066 (10) | 0.2032 (3) | 0.7875 (3) | 0.0353 (5) | |
H6A | 0.463915 | 0.149514 | 0.712161 | 0.053* | |
H6B | 0.413344 | 0.197190 | 0.769749 | 0.053* | |
H6C | 0.464082 | 0.149835 | 0.875787 | 0.053* | |
C7 | 0.27918 (8) | 0.4158 (4) | 0.6632 (2) | 0.0436 (7) | |
H7A | 0.268531 | 0.362122 | 0.571156 | 0.052* | 0.485 (19) |
H7B | 0.270988 | 0.372499 | 0.566457 | 0.052* | 0.515 (19) |
C8 | 0.2597 (3) | 0.3445 (15) | 0.7821 (6) | 0.0346 (18) | 0.485 (19) |
H8A | 0.237419 | 0.251494 | 0.749983 | 0.041* | 0.485 (19) |
H8B | 0.239134 | 0.425165 | 0.822295 | 0.041* | 0.485 (19) |
C9 | 0.2980 (3) | 0.3377 (15) | 0.9218 (8) | 0.0330 (18) | 0.485 (19) |
H9A | 0.274812 | 0.415708 | 0.955269 | 0.040* | 0.485 (19) |
H9B | 0.303203 | 0.246025 | 0.987461 | 0.040* | 0.485 (19) |
C10 | 0.34831 (8) | 0.4171 (3) | 0.9159 (2) | 0.0329 (5) | |
H10 | 0.380731 | 0.371865 | 0.969269 | 0.040* | 0.485 (19) |
H10A | 0.378957 | 0.364754 | 0.972248 | 0.040* | 0.515 (19) |
I1 | 0.59789 (2) | 0.000000 | 0.87332 (2) | 0.03089 (5) | |
C9A | 0.3044 (3) | 0.2893 (16) | 0.8926 (10) | 0.0404 (19) | 0.515 (19) |
H9AA | 0.317748 | 0.186061 | 0.863449 | 0.049* | 0.515 (19) |
H9AB | 0.292215 | 0.270733 | 0.981216 | 0.049* | 0.515 (19) |
C8A | 0.2740 (4) | 0.2775 (14) | 0.7760 (6) | 0.0386 (18) | 0.515 (19) |
H8AA | 0.237614 | 0.251443 | 0.773250 | 0.046* | 0.515 (19) |
H8AB | 0.291638 | 0.178533 | 0.753713 | 0.046* | 0.515 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.01272 (4) | 0.02483 (5) | 0.01113 (4) | 0.000 | 0.00271 (2) | 0.000 |
N1 | 0.0225 (7) | 0.0278 (8) | 0.0148 (6) | 0.0037 (6) | 0.0047 (5) | 0.0019 (5) |
N2 | 0.0164 (6) | 0.0314 (9) | 0.0245 (7) | 0.0044 (6) | 0.0025 (5) | 0.0026 (6) |
C1 | 0.0153 (9) | 0.0264 (12) | 0.0142 (9) | 0.000 | 0.0044 (7) | 0.000 |
C2 | 0.0251 (8) | 0.0384 (11) | 0.0139 (6) | 0.0012 (7) | 0.0064 (6) | 0.0023 (7) |
C3 | 0.0534 (14) | 0.0269 (10) | 0.0228 (9) | 0.0045 (10) | 0.0050 (9) | 0.0032 (8) |
C4 | 0.0154 (9) | 0.0261 (12) | 0.0155 (9) | 0.000 | 0.0036 (7) | 0.000 |
C5 | 0.0168 (7) | 0.0498 (14) | 0.0334 (11) | 0.0050 (8) | 0.0019 (7) | 0.0024 (9) |
C6 | 0.0324 (11) | 0.0291 (11) | 0.0430 (13) | 0.0065 (9) | 0.0032 (9) | 0.0033 (9) |
C7 | 0.0195 (8) | 0.092 (2) | 0.0185 (8) | −0.0201 (11) | 0.0007 (6) | 0.0036 (10) |
C8 | 0.022 (2) | 0.057 (5) | 0.024 (2) | −0.012 (3) | 0.0043 (17) | 0.005 (3) |
C9 | 0.022 (3) | 0.063 (5) | 0.014 (2) | −0.014 (3) | 0.0043 (16) | 0.009 (2) |
C10 | 0.0205 (8) | 0.0624 (15) | 0.0154 (7) | −0.0086 (9) | 0.0018 (6) | 0.0091 (8) |
I1 | 0.03408 (10) | 0.03389 (10) | 0.02760 (9) | 0.000 | 0.01334 (7) | 0.000 |
C9A | 0.029 (3) | 0.069 (6) | 0.025 (3) | −0.011 (3) | 0.009 (2) | 0.012 (3) |
C8A | 0.034 (3) | 0.055 (5) | 0.027 (2) | −0.019 (3) | 0.006 (2) | 0.004 (2) |
Ir1—C1 | 2.037 (2) | C6—H6C | 0.9800 |
Ir1—C4 | 2.051 (2) | C7—C7i | 1.399 (7) |
Ir1—C7i | 2.163 (2) | C7—H7A | 1.0000 |
Ir1—C7 | 2.163 (2) | C7—H7B | 1.0000 |
Ir1—C10i | 2.174 (2) | C7—C8 | 1.480 (6) |
Ir1—C10 | 2.174 (2) | C7—C8A | 1.616 (8) |
N1—C1 | 1.357 (2) | C8—H8A | 0.9900 |
N1—C2 | 1.389 (2) | C8—H8B | 0.9900 |
N1—C3 | 1.448 (3) | C8—C9A | 1.530 (12) |
N2—C4 | 1.356 (2) | C9—H9A | 0.9900 |
N2—C5 | 1.391 (3) | C9—H9B | 0.9900 |
N2—C6 | 1.456 (3) | C9—C10 | 1.505 (8) |
C2—C2i | 1.336 (5) | C9—C8A | 1.540 (10) |
C2—H2 | 0.9500 | C10—C10i | 1.378 (6) |
C3—H3A | 0.9800 | C10—H10 | 1.0000 |
C3—H3B | 0.9800 | C10—H10A | 1.0000 |
C3—H3C | 0.9800 | C10—C9A | 1.567 (10) |
C5—C5i | 1.328 (5) | C9A—H9AA | 0.9900 |
C5—H5 | 0.9500 | C9A—H9AB | 0.9900 |
C6—H6A | 0.9800 | C8A—H8AA | 0.9900 |
C6—H6B | 0.9800 | C8A—H8AB | 0.9900 |
C1—Ir1—C4 | 93.14 (10) | Ir1—C7—H7B | 111.1 |
C1—Ir1—C7 | 89.97 (9) | C7i—C7—Ir1 | 71.14 (10) |
C1—Ir1—C7i | 89.97 (9) | C7i—C7—H7A | 116.5 |
C1—Ir1—C10 | 161.15 (8) | C7i—C7—H7B | 111.1 |
C1—Ir1—C10i | 161.16 (8) | C7i—C7—C8 | 113.6 (5) |
C4—Ir1—C7i | 160.90 (9) | C7i—C7—C8A | 135.3 (4) |
C4—Ir1—C7 | 160.90 (9) | C8—C7—Ir1 | 114.8 (3) |
C4—Ir1—C10 | 90.61 (8) | C8—C7—H7A | 116.5 |
C4—Ir1—C10i | 90.61 (8) | C8A—C7—Ir1 | 106.1 (3) |
C7i—Ir1—C7 | 37.71 (19) | C8A—C7—H7B | 111.1 |
C7—Ir1—C10i | 92.50 (9) | C7—C8—H8A | 109.7 |
C7i—Ir1—C10 | 92.49 (9) | C7—C8—H8B | 109.7 |
C7i—Ir1—C10i | 80.72 (8) | C7—C8—C9A | 109.7 (5) |
C7—Ir1—C10 | 80.72 (8) | H8A—C8—H8B | 108.2 |
C10i—Ir1—C10 | 36.95 (15) | C9A—C8—H8A | 109.7 |
C1—N1—C2 | 111.26 (18) | C9A—C8—H8B | 109.7 |
C1—N1—C3 | 125.22 (17) | H9A—C9—H9B | 108.2 |
C2—N1—C3 | 123.51 (18) | C10—C9—H9A | 109.8 |
C4—N2—C5 | 110.93 (19) | C10—C9—H9B | 109.8 |
C4—N2—C6 | 125.66 (17) | C10—C9—C8A | 109.4 (5) |
C5—N2—C6 | 123.40 (19) | C8A—C9—H9A | 109.8 |
N1i—C1—Ir1 | 127.97 (11) | C8A—C9—H9B | 109.8 |
N1—C1—Ir1 | 127.97 (11) | Ir1—C10—H10 | 112.1 |
N1—C1—N1i | 103.9 (2) | Ir1—C10—H10A | 115.8 |
N1—C2—H2 | 126.6 | C9—C10—Ir1 | 114.7 (3) |
C2i—C2—N1 | 106.78 (12) | C9—C10—H10A | 115.8 |
C2i—C2—H2 | 126.6 | C10i—C10—Ir1 | 71.53 (8) |
N1—C3—H3A | 109.5 | C10i—C10—C9 | 116.0 (5) |
N1—C3—H3B | 109.5 | C10i—C10—H10 | 112.1 |
N1—C3—H3C | 109.5 | C10i—C10—H10A | 115.8 |
H3A—C3—H3B | 109.5 | C10i—C10—C9A | 132.7 (5) |
H3A—C3—H3C | 109.5 | C9A—C10—Ir1 | 106.3 (4) |
H3B—C3—H3C | 109.5 | C9A—C10—H10 | 112.1 |
N2—C4—Ir1 | 127.89 (11) | C8—C9A—C10 | 111.6 (7) |
N2i—C4—Ir1 | 127.89 (11) | C8—C9A—H9AA | 109.3 |
N2i—C4—N2 | 104.2 (2) | C8—C9A—H9AB | 109.3 |
N2—C5—H5 | 126.5 | C10—C9A—H9AA | 109.3 |
C5i—C5—N2 | 106.96 (13) | C10—C9A—H9AB | 109.3 |
C5i—C5—H5 | 126.5 | H9AA—C9A—H9AB | 108.0 |
N2—C6—H6A | 109.5 | C7—C8A—H8AA | 109.8 |
N2—C6—H6B | 109.5 | C7—C8A—H8AB | 109.8 |
N2—C6—H6C | 109.5 | C9—C8A—C7 | 109.3 (6) |
H6A—C6—H6B | 109.5 | C9—C8A—H8AA | 109.8 |
H6A—C6—H6C | 109.5 | C9—C8A—H8AB | 109.8 |
H6B—C6—H6C | 109.5 | H8AA—C8A—H8AB | 108.3 |
Ir1—C7—H7A | 116.5 | ||
Ir1—C7—C8—C9A | −21.8 (8) | C5—N2—C4—N2i | −0.9 (3) |
Ir1—C7—C8A—C9 | 46.8 (7) | C6—N2—C4—Ir1 | −1.4 (3) |
Ir1—C10—C9A—C8 | −43.0 (7) | C6—N2—C4—N2i | 177.51 (16) |
C1—N1—C2—C2i | 0.08 (17) | C6—N2—C5—C5i | −177.88 (18) |
C2—N1—C1—Ir1 | −176.04 (16) | C7i—C7—C8—C9A | −101.0 (6) |
C2—N1—C1—N1i | −0.1 (3) | C7i—C7—C8A—C9 | −32.5 (9) |
C3—N1—C1—Ir1 | 4.7 (3) | C7—C8—C9A—C10 | 43.1 (7) |
C3—N1—C1—N1i | −179.40 (16) | C10—C9—C8A—C7 | −44.8 (8) |
C3—N1—C2—C2i | 179.37 (17) | C10i—C10—C9A—C8 | 36.7 (8) |
C4—N2—C5—C5i | 0.58 (19) | C8A—C9—C10—Ir1 | 21.6 (8) |
C5—N2—C4—Ir1 | −179.85 (17) | C8A—C9—C10—C10i | 102.2 (6) |
Symmetry code: (i) x, −y+1, z. |
[Ir(C7H12N2)2(C8H12)]I | Dx = 1.884 Mg m−3 |
Mr = 675.65 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pccn | Cell parameters from 17338 reflections |
a = 10.6041 (2) Å | θ = 2.7–37.9° |
b = 12.3058 (2) Å | µ = 6.92 mm−1 |
c = 18.2513 (3) Å | T = 100 K |
V = 2381.65 (7) Å3 | Block, orange |
Z = 4 | 0.38 × 0.17 × 0.12 mm |
F(000) = 1304 |
XtaLAB Synergy, Dualflex, HyPix diffractometer | 6352 independent reflections |
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source | 3839 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.062 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 38.2°, θmin = 2.5° |
ω scans | h = −16→17 |
Absorption correction: gaussian (CrysAlisPro;Rigaku OD, 2018) | k = −21→21 |
Tmin = 0.318, Tmax = 1.000 | l = −30→31 |
59059 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.060 | w = 1/[σ2(Fo2) + (0.022P)2 + 1.4351P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.002 |
6352 reflections | Δρmax = 1.54 e Å−3 |
130 parameters | Δρmin = −0.83 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Ir1 | 0.750000 | 0.750000 | 0.50409 (2) | 0.01428 (3) | |
N1 | 0.66768 (19) | 0.56037 (15) | 0.40954 (10) | 0.0170 (4) | |
N2 | 0.5533 (2) | 0.69802 (15) | 0.38262 (10) | 0.0160 (4) | |
C1 | 0.6489 (2) | 0.66696 (18) | 0.42698 (11) | 0.0147 (4) | |
C2 | 0.5863 (2) | 0.52747 (19) | 0.35491 (12) | 0.0197 (5) | |
H2 | 0.582250 | 0.458717 | 0.333882 | 0.024* | |
C3 | 0.5145 (2) | 0.61300 (19) | 0.33789 (13) | 0.0193 (4) | |
H3 | 0.450781 | 0.615208 | 0.302881 | 0.023* | |
C4 | 0.7633 (2) | 0.49015 (18) | 0.44314 (14) | 0.0217 (5) | |
H4A | 0.812864 | 0.532569 | 0.477466 | 0.026* | |
H4B | 0.819765 | 0.463618 | 0.405332 | 0.026* | |
C5 | 0.7056 (3) | 0.3938 (2) | 0.48314 (15) | 0.0258 (5) | |
H5A | 0.666738 | 0.345931 | 0.448297 | 0.039* | |
H5B | 0.643277 | 0.419285 | 0.517187 | 0.039* | |
H5C | 0.770442 | 0.355409 | 0.509178 | 0.039* | |
C6 | 0.5011 (2) | 0.80817 (19) | 0.37857 (13) | 0.0197 (5) | |
H6A | 0.521838 | 0.847322 | 0.423096 | 0.024* | |
H6B | 0.409999 | 0.804105 | 0.374896 | 0.024* | |
C7 | 0.5529 (3) | 0.86951 (19) | 0.31300 (13) | 0.0238 (5) | |
H7A | 0.531961 | 0.831132 | 0.268855 | 0.036* | |
H7B | 0.642915 | 0.875246 | 0.317200 | 0.036* | |
H7C | 0.516639 | 0.940945 | 0.311475 | 0.036* | |
C8 | 0.8334 (2) | 0.8517 (2) | 0.59035 (13) | 0.0218 (5) | |
H8 | 0.877875 | 0.916010 | 0.572020 | 0.026* | |
C9 | 0.9006 (2) | 0.7551 (2) | 0.58265 (13) | 0.0232 (4) | |
H9 | 0.983639 | 0.765350 | 0.560128 | 0.028* | |
C10 | 0.8939 (3) | 0.6559 (2) | 0.63123 (15) | 0.0317 (6) | |
H10A | 0.940977 | 0.669868 | 0.675826 | 0.038* | |
H10B | 0.933711 | 0.595331 | 0.606313 | 0.038* | |
C11 | 0.7595 (3) | 0.6247 (2) | 0.65118 (15) | 0.0329 (6) | |
H11A | 0.756815 | 0.547796 | 0.662661 | 0.039* | |
H11B | 0.734462 | 0.664384 | 0.694739 | 0.039* | |
I1 | 0.250000 | 0.750000 | 0.71451 (2) | 0.02175 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.01317 (5) | 0.01477 (5) | 0.01492 (5) | −0.00400 (6) | 0.000 | 0.000 |
N1 | 0.0177 (10) | 0.0156 (8) | 0.0176 (9) | −0.0029 (7) | −0.0019 (7) | −0.0005 (7) |
N2 | 0.0179 (10) | 0.0145 (9) | 0.0155 (8) | −0.0021 (7) | −0.0004 (8) | −0.0007 (7) |
C1 | 0.0151 (10) | 0.0148 (9) | 0.0144 (9) | −0.0025 (7) | 0.0000 (7) | −0.0004 (8) |
C2 | 0.0237 (12) | 0.0175 (10) | 0.0178 (10) | −0.0052 (9) | −0.0024 (9) | −0.0011 (8) |
C3 | 0.0213 (12) | 0.0216 (11) | 0.0149 (10) | −0.0029 (9) | −0.0039 (9) | −0.0012 (9) |
C4 | 0.0212 (14) | 0.0171 (9) | 0.0267 (11) | −0.0022 (9) | −0.0066 (10) | 0.0008 (8) |
C5 | 0.0333 (14) | 0.0170 (11) | 0.0271 (13) | −0.0048 (10) | −0.0070 (11) | 0.0032 (10) |
C6 | 0.0194 (12) | 0.0193 (11) | 0.0205 (11) | 0.0035 (9) | 0.0006 (9) | −0.0013 (9) |
C7 | 0.0325 (15) | 0.0189 (11) | 0.0200 (11) | −0.0005 (10) | −0.0016 (10) | 0.0007 (9) |
C8 | 0.0190 (12) | 0.0247 (12) | 0.0216 (11) | −0.0084 (9) | −0.0032 (9) | −0.0039 (10) |
C9 | 0.0175 (9) | 0.0292 (11) | 0.0230 (10) | −0.0072 (12) | −0.0054 (8) | 0.0031 (13) |
C10 | 0.0270 (15) | 0.0384 (15) | 0.0297 (14) | −0.0029 (12) | −0.0084 (11) | 0.0090 (12) |
C11 | 0.0319 (16) | 0.0418 (14) | 0.0249 (11) | −0.0040 (14) | −0.0006 (13) | 0.0124 (11) |
I1 | 0.01710 (8) | 0.02436 (9) | 0.02378 (10) | −0.00028 (11) | 0.000 | 0.000 |
Ir1—C1i | 2.043 (2) | C5—H5B | 0.9600 |
Ir1—C1 | 2.043 (2) | C5—H5C | 0.9600 |
Ir1—C8 | 2.197 (2) | C6—H6A | 0.9700 |
Ir1—C8i | 2.197 (2) | C6—H6B | 0.9700 |
Ir1—C9i | 2.147 (2) | C6—C7 | 1.518 (3) |
Ir1—C9 | 2.147 (2) | C7—H7A | 0.9600 |
N1—C1 | 1.364 (3) | C7—H7B | 0.9600 |
N1—C2 | 1.379 (3) | C7—H7C | 0.9600 |
N1—C4 | 1.467 (3) | C8—H8 | 0.9800 |
N2—C1 | 1.353 (3) | C8—C9 | 1.393 (4) |
N2—C3 | 1.389 (3) | C8—C11i | 1.513 (4) |
N2—C6 | 1.466 (3) | C9—H9 | 0.9800 |
C2—H2 | 0.9300 | C9—C10 | 1.510 (4) |
C2—C3 | 1.336 (3) | C10—H10A | 0.9700 |
C3—H3 | 0.9300 | C10—H10B | 0.9700 |
C4—H4A | 0.9700 | C10—C11 | 1.520 (4) |
C4—H4B | 0.9700 | C11—H11A | 0.9700 |
C4—C5 | 1.521 (3) | C11—H11B | 0.9700 |
C5—H5A | 0.9600 | ||
C1i—Ir1—C1 | 92.93 (12) | H5A—C5—H5B | 109.5 |
C1—Ir1—C8i | 89.85 (9) | H5A—C5—H5C | 109.5 |
C1i—Ir1—C8i | 171.79 (9) | H5B—C5—H5C | 109.5 |
C1—Ir1—C8 | 171.79 (9) | N2—C6—H6A | 109.4 |
C1i—Ir1—C8 | 89.85 (9) | N2—C6—H6B | 109.4 |
C1i—Ir1—C9i | 149.88 (10) | N2—C6—C7 | 111.30 (19) |
C1i—Ir1—C9 | 93.15 (9) | H6A—C6—H6B | 108.0 |
C1—Ir1—C9 | 149.88 (10) | C7—C6—H6A | 109.4 |
C1—Ir1—C9i | 93.15 (9) | C7—C6—H6B | 109.4 |
C8i—Ir1—C8 | 88.46 (13) | C6—C7—H7A | 109.5 |
C9i—Ir1—C8 | 80.66 (9) | C6—C7—H7B | 109.5 |
C9—Ir1—C8 | 37.37 (10) | C6—C7—H7C | 109.5 |
C9i—Ir1—C8i | 37.37 (10) | H7A—C7—H7B | 109.5 |
C9—Ir1—C8i | 80.66 (9) | H7A—C7—H7C | 109.5 |
C9i—Ir1—C9 | 96.21 (13) | H7B—C7—H7C | 109.5 |
C1—N1—C2 | 111.1 (2) | Ir1—C8—H8 | 114.1 |
C1—N1—C4 | 124.74 (19) | C9—C8—Ir1 | 69.36 (13) |
C2—N1—C4 | 124.18 (19) | C9—C8—H8 | 114.1 |
C1—N2—C3 | 111.16 (19) | C9—C8—C11i | 124.8 (2) |
C1—N2—C6 | 125.05 (19) | C11i—C8—Ir1 | 111.88 (17) |
C3—N2—C6 | 123.70 (19) | C11i—C8—H8 | 114.1 |
N1—C1—Ir1 | 124.39 (16) | Ir1—C9—H9 | 113.1 |
N2—C1—Ir1 | 131.63 (17) | C8—C9—Ir1 | 73.27 (14) |
N2—C1—N1 | 103.98 (19) | C8—C9—H9 | 113.1 |
N1—C2—H2 | 126.5 | C8—C9—C10 | 127.3 (2) |
C3—C2—N1 | 107.1 (2) | C10—C9—Ir1 | 109.49 (17) |
C3—C2—H2 | 126.5 | C10—C9—H9 | 113.1 |
N2—C3—H3 | 126.6 | C9—C10—H10A | 109.0 |
C2—C3—N2 | 106.7 (2) | C9—C10—H10B | 109.0 |
C2—C3—H3 | 126.6 | C9—C10—C11 | 112.9 (2) |
N1—C4—H4A | 109.1 | H10A—C10—H10B | 107.8 |
N1—C4—H4B | 109.1 | C11—C10—H10A | 109.0 |
N1—C4—C5 | 112.4 (2) | C11—C10—H10B | 109.0 |
H4A—C4—H4B | 107.8 | C8i—C11—C10 | 112.7 (2) |
C5—C4—H4A | 109.1 | C8i—C11—H11A | 109.0 |
C5—C4—H4B | 109.1 | C8i—C11—H11B | 109.0 |
C4—C5—H5A | 109.5 | C10—C11—H11A | 109.0 |
C4—C5—H5B | 109.5 | C10—C11—H11B | 109.0 |
C4—C5—H5C | 109.5 | H11A—C11—H11B | 107.8 |
Ir1—C8—C9—C10 | −102.1 (2) | C3—N2—C6—C7 | −76.3 (3) |
Ir1—C9—C10—C11 | −39.1 (3) | C4—N1—C1—Ir1 | −0.3 (3) |
N1—C2—C3—N2 | 0.1 (3) | C4—N1—C1—N2 | 179.6 (2) |
C1—N1—C2—C3 | −0.6 (3) | C4—N1—C2—C3 | −179.4 (2) |
C1—N1—C4—C5 | 118.4 (2) | C6—N2—C1—Ir1 | 2.5 (3) |
C1—N2—C3—C2 | 0.4 (3) | C6—N2—C1—N1 | −177.47 (19) |
C1—N2—C6—C7 | 100.0 (3) | C6—N2—C3—C2 | 177.2 (2) |
C2—N1—C1—Ir1 | −179.19 (16) | C8—C9—C10—C11 | 44.4 (4) |
C2—N1—C1—N2 | 0.8 (3) | C9—C10—C11—C8i | 33.9 (3) |
C2—N1—C4—C5 | −62.9 (3) | C11i—C8—C9—Ir1 | 102.9 (2) |
C3—N2—C1—Ir1 | 179.27 (17) | C11i—C8—C9—C10 | 0.8 (4) |
C3—N2—C1—N1 | −0.7 (3) |
Symmetry code: (i) −x+3/2, −y+3/2, z. |
Acknowledgements
The authors acknowledge Dr Carla Slebodnick for her assistance in solving the η4-cycloocta-1,5-diene)bis(1,3-diethylimidazol-2-ylidene)iridium(I) iodide and the Virginia Tech Open Access Subvention Fund for supporting the open access fee for this journal.
of (Funding information
Funding for this research was provided by: National Science Foundation (purchase of diffractometer) (grant No. 1726077).
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