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Syntheses and crystal structures of [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}ClH]Cl·2.75CH2Cl2 and its derivatives, [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}(CH2CO2Et)Cl]Cl·CH3OH·0.5H2O, [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}Cl2]Cl·CH3OH·2H2O and [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}(CH2CO2Et)(CO)]Cl2·2CH2Cl2·1.5H2O

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aUniversity of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80-82, 6020 Innsbruck, Austria
*Correspondence e-mail: inge.hackl@uibk.ac.at

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 October 2018; accepted 30 November 2018; online 1 January 2019)

The common feature of the four iridium(III) salt complexes, (bis­{[(di­phenyl­phosphan­yl)meth­yl]di­phenyl­phosphanyl­idene}(eth­oxy­oxoethanyl­idene)methane-κ4P,C,C′,P′)chlorido­hydridoiridium(III) chloride methyl­ene chloride 2.75-solvate (4), (bis­{[(di­phenyl­phosphan­yl)meth­yl]di­phenyl­phosphanyl­idene}(eth­oxy­oxoethanyl­idene)methane-κ4P,C,C′,P′)chlorido­(eth­oxy­oxoethanido)iridium(III) chloride–methanol–water (1/1/0.5) (5), (bis­{[(di­phenyl­phosphan­yl)meth­yl]di­phenyl­phosphanyl­idene}(eth­oxy­oxoethanyl­idene)methane-κ4P,C,C′,P′)di­chlorido­iridium(III) chloride–methanol–water (1/1/2) (6) and (bis­{[(di­phenyl­phosphan­yl)meth­yl]di­phenyl­phosphanyl­idene}(eth­oxy­oxoethanyl­idene)methane-κ4P,C,C′,P′)carbon­yl(eth­oxy­oxoethanide)iridium(III) dichloride–meth­yl­ene chloride–water (1/2/1.5) (7) or in terms of their formulae [Ir(C55H50O2P4)ClH]Cl·2.75CH2Cl2 (4), [Ir(C4H7O2)(C55H50O2P4)Cl]Cl·CH3OH·0.5H2O (5), [Ir(C55H50O2P4)Cl2]Cl·CH3OH·2H2O (6) and [Ir(C4H7O2)(C55H50O2P4)(CO)]Cl2·2CH2Cl2·1.5H2O (7) is a central IrIII atom coordin­ated in a distorted octa­hedral fashion by a PCCP ligand system and two additional residues, such as chlorides, a hydride, a carbonyl or an alkyl unit. Thereby, the PCP pincer ligand system and the residue trans to the carbodi­phospho­rane (CDP) C atom surround the iridium(III) transition metal in the equatorial plane under the formation of two five-membered dissimilar chelate rings [C—CCDP—P (4, 5, 6 and 7) for the first ring: 120.2 (3), 121.9 (5), 111.2 (3) and 121.7 (2) °; for the second ring: 112.1 (3), 113.5 (5), 120.5 (3) and 108.3 (2)°]. A cyclo­propane-like heterocycle is positioned approximately orthogonal (84.21–88.85°) to the equatorial plane, including an alkyl­idene bridge connecting the IrIII atom and the coordinating CDP atom of the PCP subunit. In general, the neutral PCCP ligand system coordinates the metal in a tetra­dentate way via three Lewis acid/base bonds and by an alkyl­idene unit presenting strengthened inter­actions. In all the crystal structures, (disordered) solvent mol­ecules are present in the voids of the packed mol­ecules that inter­act with the positively charged complex and its chloride counter-ion(s) through weak hydrogen bonding.

1. Chemical context

Carbodi­phospho­ranes (CDP) in combination with transition metals initialize a huge variety of functionalities. As a result of the presence of two σ-electron-donor groups, preferred in the form of tertiary phosphines, the stabilization of two free-electron pairs with σ- and simultaneously π-symmetry, the establishment of a localized electron octet and further the creation of a zero-valent, naked carbon atom in an excited singlet (1D) state is possible (Petz & Frenking, 2010[Petz, W. & Frenking, G. (2010). Editors. Carbodiphosphoranes and Related Ligands, Vol. 30. Berlin Heidelberg: Springer-Verlag.]). The carbodi­phospho­rane C atom can be considered as a four-electron donor, and accordingly enables the coordination of two Lewis acids, such as protons or different metal cations. Our inter­ests focus on the combination of a carbodi­phospho­rane pincer ligand system, [CH(dppm)2]Cl (dppm = 1,1-bis­(di­phenyl­phosphino)methane; Reitsamer et al., 2012[Reitsamer, C., Stallinger, S., Schuh, W., Kopacka, H., Wurst, K., Obendorf, D. & Peringer, P. (2012). Dalton Trans. 41, 3503-3514.]), with reactive functionalities to enter new reaction pathways, to create new complexes and to analyse in detail the new properties obtained. In general, C—C coupling reactions can be induced via the use of diazo compounds such as ethyl diazo­acetate. As a result of the presence of two nitro­gen atoms acting together as an excellent leaving group, and an alkyl­idene group stabilized by different functionalities, the electrons are delocalized between three atoms and thus a positive and one negative charge theoretically allows by a disregard of the coordinating residuals and chemical conditions four different resonance structures to be gained in total. Therefore, the diazo compound can be regarded as both a nucleophilic and as an electrophilic reaction partner. By the use of this compound, a targeted synthesis of cyclo­propanes or rather hetero­cyclo­propanes, consisting of a transition metal, an electron-donor atom and a carbene carbon, is possible and has been reported several times in the literature (e.g. Nomura et al., 2011[Nomura, M., Fujita-Takayama, C., Sugiyama, T. & Kajitani, M. (2011). J. Organomet. Chem. 696, 4018-4038.]; Liu & Yan, 2015[Liu, G. & Yan, H. (2015). Organometallics, 34, 591-598.]; Malisch et al., 1998[Malisch, W., Grün, K., Fried, A., Reich, W., Pfister, H., Huttner, G. & Zsolnai, L. (1998). J. Organomet. Chem. 566, 271-276.]; Strecker et al., 1991[Strecker, B., Hörlin, G., Schulz, M. & Werner, H. (1991). Chem. Ber. 124, 285-294.]; Zhang et al., 2005[Zhang, J., Barakat, K. A., Cundari, T. R., Gunnoe, T. B., Boyle, P. D., Petersen, J. L. & Day, C. S. (2005). Inorg. Chem. 44, 8379-8390.], and references cited therein). An electrophilic reaction partner such as a transition metal establishes a nucleophilic attack of the diazo subunit and, according to the choice of the reaction conditions, the elimination of the nitro­gen leaving group is supported. Consequently, the alkyl­idene carbon atom is stabilized by coordination of an electron-accepting atom and a reactive carbene inter­mediate complex is formed. The existence of a nucleophilic reaction partner in the vicinity of the carbene atom results in the formation of a ring including an alkyl­idene bridging subunit. In summary, the reaction of a diazo compound with an electrophilic and additionally a nucleophilic reaction partner initiates a mechanism that can be described as a cheletropic-like process. Inspired by this reaction sequence, we have synthesized a three-membered heterocycle by the combination of an ethyl diazo­acetate and an iridium(III) PCP pincer carbodi­phospho­rane complex.

If the starting materials [CH(dppm)2]Cl (Reitsamer et al., 2012[Reitsamer, C., Stallinger, S., Schuh, W., Kopacka, H., Wurst, K., Obendorf, D. & Peringer, P. (2012). Dalton Trans. 41, 3503-3514.]) and [IrCl(cod)]2 are mixed, a reaction sequence is initialized that consists of the following steps: Coordination of the iridium(I) atom, followed by deprotonation of the carbodi­phospho­rane carbon atom, the generation of a hydrido ligand caused by an oxidation of the iridium(I) atom and the formation of the [Ir{C(dppm)2-κ3P,C,P`}ClH(MeCN)]Cl complex 1 (Schlapp-Hackl et al., 2018[Schlapp-Hackl, I., Pauer, B., Falschlunger, C., Schuh, W., Kopacka, H., Wurst, K. & Peringer, P. (2018). Acta Cryst. E74, 1643-1647.]; Fig. 1[link]). In summary, the iridium(III) transition metal is stabilized by the PCP pincer ligand system, and by a chlorido and a hydrido ligand and an aceto­nitrile solvent mol­ecule. The addition of ethyl diazo­acetate causes, via loss of the di­nitro­gen subunit, the formation of an IrIII–carbene bond. As a result of the presence of the second free lone-electron pair at the carbodi­phospho­rane carbon atom, a cyclization and further the creation of an alkyl­idene bridge is accomplished. The formation of the three-membered Ir—CCDP—C ring is accompanied by a surprising displacement of the hydrido ligand from a position perpendicular to the plane of the PCP pincer system to a meridional arrangement trans to the carbodi­phospho­rane carbon atom. Supported by the polar solvent mixture methanol/aceto­nitrile (v/v 5:1) an [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}H(MeCN)]Cl2 precursor system (2) is generated in high yields (86%). Moreover, the preparation of complex 2 in a less polar solvent environment like chloro­form/aceto­nitrile or in a solvent mixture of methyl­ene chloride/aceto­nitrile (v/v 5:1) is not possible and qu­anti­tatively results in the substitution of one phosphine moiety of the carbodi­phospho­rane functionality against the carbene CHCO2Et subunit. An [Ir{C(CHCO2Et)(dppm)-κ2P,C}Cl(dppm)H]Cl complex 3 is generated, offering a phospho­rus ylide carbon backbone (Schlapp-Hackl et al., 2018[Schlapp-Hackl, I., Pauer, B., Falschlunger, C., Schuh, W., Kopacka, H., Wurst, K. & Peringer, P. (2018). Acta Cryst. E74, 1643-1647.]). To a lesser extent (14% yield), this complex is additionally obtained as by-product by the production of complex 2. Heating of complex 2 in methanol/aceto­nitrile (v/v 5:1) to 333 K for 2 h benefits the ring-opening reaction of the PCCP pincer ligand system. Therefore, a reorganization of the ligand system is supported, resulting in the qu­anti­tative formation of complex 3. Furthermore, evaporation of the reaction mixture of complex 2 causes an exchange of the aceto­nitrile solvent ligand with a chloride counter-ion and the creation of the desired [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}ClH]Cl complex 4.

[Scheme 1]
[Figure 1]
Figure 1
Scheme (Cambridge Soft, 2001[Cambridge Soft (2001). CHEMDRAW. Cambridge Soft Corporation, Cambridge, Massachusetts, USA.]) for the synthesis and crystallization of the title compounds 47.

The stucture of this irid­ium(III) PCCP complex was completely determined by NMR spectroscopy and X-ray crystallography, but up to now crystallization attempts of the inter­mediates, 1 and 2, were unsuccessful. With regard to a ruthenium PCP pincer complex, a related cyclo­addition was monitored (Zhang et al., 2005[Zhang, J., Barakat, K. A., Cundari, T. R., Gunnoe, T. B., Boyle, P. D., Petersen, J. L. & Day, C. S. (2005). Inorg. Chem. 44, 8379-8390.]). Thereby, the ruthenium transition metal first stabilizes the phenyl­diazo­methane by coordination. After the elimination of the di­nitro­gen mol­ecule, the formation of the corresponding carbene complex and finally a carbon–carbon coupling reaction between the central carbon atom of the phenyl-based PCP ligand and the carbene was detected. As a consequence, the arene backbone of the PCP ligand system is transformed to an arenium moiety. Treatment of complex 4 with an additional equivalent amount of ethyl diazo­acetate causes an insertion reaction of the alkyl­idene to the iridium(III)–hydrido bond and the formation of the [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}(CH2CO2Et)Cl]Cl alkyl derivative 5. This reaction procedure is well known, and the mechanism of the inter­molecular insertion reaction has been clarified via an inter­mediate carbene complex (Cohen et al., 2003[Cohen, R., Rybtchinski, B., Gandelman, M., Rozenberg, H., Martin, J. M. L. & Milstein, D. (2003). J. Am. Chem. Soc. 125, 6532-6546.]). Moreover, treatment of complexes 4 and 5 with hydro­chloric acid leads to a ligand substitution at the position trans to the central carbon atom of the PCP pincer ligand system with a chloride ion and to the formation of the [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}Cl2]Cl complex 6. Besides, a replacement of the chlorido ligand of compound 5 by a carbonyl group is possible and results in the [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}(CH2CO2Et)(CO)]Cl2 complex 7.

Here we report details of the syntheses and crystal structures of complexes 47.

2. Structural commentary

The asymmetric unit of compound 4, [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}ClH]Cl, comprises of one formula unit of 4 and additionally of 2.75 mol­ecules of methyl­ene chloride solvent mol­ecules. The central iridium(III) transition metal is surrounded in a distorted octa­hedral fashion by a PCCP pincer-like ligand system, and anionic chlorido and hydrido ligands (Fig. 2[link]). The neutral [C(CHCO2Et)(dppm)2-κ4P,C,C′,P′] ligand coordinates the IrIII metal in a tetra­dentate fashion via two P and two C atoms under formation of two five-membered, dissimilar chelate rings [C4—C1—P3 = 120.2 (3)°, C4—C1—P2 = 112.1 (3)°] and one three membered heterocycle. The PCP ligand exhibits a meridional arrangement with the hydrido ligand completing the equatorial plane trans to the C1 carbodi­phospho­rane atom. A cyclo­propane-like chelate ring is positioned nearly normal (84.21°) to the equatorial plane, and a chlorido ligand is positioned trans to the alkyl­idene carbon atom C4. The Ir—C1 [2.273 (4) Å] and Ir—C4 [2.072 (5) Å] distances differ significantly and consequently these values substanti­ate a strengthened inter­action between the iridium(III) metal and the alkyl­idene carbon atom. The C1—C4 separation [1.515 (6) Å] is slightly shorter in comparison to a typical C—C single bond but, in general, very close to that of cyclo­propanes. However, in comparison with a cyclo­propane mol­ecule the C4—Ir1—C1 [40.5 (2)°], C4—C1—Ir1 [62.6 (2)°] and C1—C4—Ir1 [76.9 (3)°] angles emphasise a significant distortion of the synthesized three-membered heterocycle. All mentioned geometric features of this strained Ir—C1—C4 metallacycle can be associated with the structural results of the Ru—C—C triangle reported by Zhang et al. (2005[Zhang, J., Barakat, K. A., Cundari, T. R., Gunnoe, T. B., Boyle, P. D., Petersen, J. L. & Day, C. S. (2005). Inorg. Chem. 44, 8379-8390.]). Furthermore, the three-membered ring causes a distortion of the octa­hedral coordination geometry (Table 1[link]). The P1—Ir1—P4 [178.4 (1)°] atoms are less affected and show only a slight deviation from linearity. Though, the tetra­hedral environment of the carbodi­phospho­rane C1 atom is strongly influenced and thus distorted, which is reflected by a P3—C1—P2 angle of 124.2 (3)°. Overall, the transition metal and its ligand system present a cationic complex balanced by one chloride.

Table 1
Selected bond lengths (Å) and angles (°) of the compounds 4, 5, 6 and 7

  4 5 6 7
Ir1—C1 2.273 (4) 2.279 (6) 2.149 (4) 2.225 (3)
Ir1—C4 2.072 (5) 2.046 (7) 2.076 (4) 2.119 (3)
Ir1—P1 2.290 (1) 2.318 (2) 2.309 (1) 2.339 (1)
Ir1—P4 2.278 (1) 2.306 (2) 2.330 (1) 2.366 (1)
P2—C1 1.791 (5) 1.788 (7) 1.822 (4) 1.837 (3)
Ir1—Lx (Lx= –H, –Cl, –CH2CO2Et) 1.62 (2) 2.163 (7) 2.427 (1) 2.177 (3)
Ir1—Ly (Ly = –Cl, –CO) 2.462 (1) 2.461 (2) 2.460 (1) 1.910 (3)
P3—C1 1.788 (5) 1.789 (7) 1.833 (4) 1.791 (3)
C1—C4 1.515 (6) 1.507 (9) 1.513 (5) 1.515 (4)
C4—Ir1—C1 40.5 (2) 40.3 (2) 41.9 (2) 40.72 (11)
C4—C1—Ir1 62.6 (2) 61.5 (3) 66.5 (2) 65.88 (15)
C1—C4—Ir1 76.9 (3) 78.2 (4) 71.6 (2) 73.40 (16)
C4—Ir1—Ly (Ly = –Cl, –CO) 150.3 (1) 152.5 (2) 151.9 (1) 158.8 (1)
C1—Ir1—Ly (Ly = –Cl, –CO) 111.3 (1) 112.8 (2) 111.5 (1) 118.8 (1)
C4—Ir1—Lx (Lx = –H, –Cl, –CH2CO2Et) 119.7 (18) 120.8 (3) 116.2 (1) 106.7 (1)
C1—Ir1—Lx (Lx = –H, –Cl, –CH2CO2Et) 159.8 (18) 161.1 (3) 158.1 (1) 147.4 (1)
P1—Ir1—P4 178.4 (1) 173.5 (1) 177.6 (1) 176.4 (1)
P1—Ir1—(C1—C4) 84.21 88.85 85.57 84.56
[Figure 2]
Figure 2
Mol­ecular structure of the complex cation in 4 and the counter-anion. Displacement ellipsoids are drawn at the 30% probability level. For clarity, only the ipso carbon atoms of the phenyl groups are presented and the solvent mol­ecules are omitted.

The asymmetric unit of compound 5, [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}(CH2CO2Et)Cl]Cl, is defined by one complex 5, one half-occupied water mol­ecule and one disordered methanol solvent mol­ecule. In comparison with the structural features discussed in detail for compound 4, significant differences pertain only to the equatorial position trans to C1. Here the hydrido ligand in 4 is exchanged by an ethyl acetate unit (Fig. 3[link]).

[Figure 3]
Figure 3
Mol­ecular structure of the complex cation in 5 and the counter-anion. Displacement ellipsoids are drawn at the 30% probability level. For clarity, only the ipso carbon atoms of the phenyl groups are presented and the solvent mol­ecules are omitted.

The replacement of the hydrido ligand of compound 4 by a chlorido ligand led to formation of 6, [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}Cl2]Cl. In its crystalline form, besides one formula unit of 6, one solvent mol­ecule of MeOH and two water mol­ecules in total are present in the asymmetric unit. Overall, this PCCP derivative shows very similar structural characteristics (Fig. 4[link]) to complex 4.

[Figure 4]
Figure 4
Mol­ecular structure of the complex cation in 6 and the counter-anion. Displacement ellipsoids are drawn at the 30% probability level. For clarity, only the ipso carbon atoms of the phenyl groups are presented and the solvent mol­ecules are omitted.

Finally, an elimination of the chlorido ligand of complex 5 and its replacement by a carbonyl ligand results in compound 7, [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}(CH2CO2Et)(CO)]Cl2 (Fig. 5[link]). The asymmetric unit comprises one complex mol­ecule of 7 and additionally of two methyl­ene chloride solvent mol­ecules and 1.5 mol­ecules of water. In comparison with complex 5, the structural features have not changed dramatically, with some slight variations for bond lengths and angles (Table 1[link]).

[Figure 5]
Figure 5
Mol­ecular structure of the complex cation in 7 and the two counter-ions. Displacement ellipsoids are drawn at the 30% probability level. For clarity, only the ipso carbon atoms of the phenyl groups are presented and the solvent mol­ecules are omitted.

3. Supra­molecular features

In all crystal structures, the complex cations and counter-ions are packed in a way that leaves voids for various types of solvent mol­ecules. Weak non-classical hydrogen-bonding inter­actions are observed between complex cations, chloride counter-ions and solvent mol­ecules. Numerical details of these inter­actions are given in Tables 2[link]–5[link][link][link], and discussed briefly below.

Table 2
Hydrogen-bond geometry (Å, °) for 4[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2B⋯Cl2 0.98 2.58 3.488 (5) 154
C3—H3A⋯O1 0.98 2.31 2.892 (7) 117
C3—H3B⋯Cl2i 0.98 2.83 3.456 (5) 122
Symmetry code: (i) x-1, y, z.

Table 3
Hydrogen-bond geometry (Å, °) for 5[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2A⋯O5i 0.98 2.22 3.139 (15) 156
C3—H3A⋯Cl2 0.98 2.91 3.693 (8) 137
C3—H3B⋯O1 0.98 2.40 2.895 (10) 111
C102—H102⋯O4 0.94 2.48 3.263 (11) 141
C212—H212⋯O5i 0.94 2.54 3.445 (18) 163
C306—H306⋯Cl2 0.94 2.57 3.491 (9) 167
C308—H308⋯Cl1 0.94 2.56 3.464 (8) 162
C408—H408⋯O3 0.94 2.23 3.046 (10) 145
Symmetry code: (i) x, y-1, z.

Table 4
Hydrogen-bond geometry (Å, °) for 6[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2A⋯O1 0.98 2.33 2.852 (5) 112
C2—H2B⋯O5i 0.98 2.45 3.320 (8) 148
C3—H3B⋯Cl3 0.98 2.66 3.589 (4) 158
C6—H6A⋯O3ii 0.98 2.40 3.369 (8) 169
C102—H102⋯Cl1 0.94 2.63 3.343 (4) 133
C108—H108⋯Cl1 0.94 2.82 3.671 (5) 151
C206—H206⋯Cl3i 0.94 2.87 3.742 (5) 156
C208—H208⋯Cl2 0.94 2.64 3.487 (5) 150
C312—H312⋯Cl3 0.94 2.84 3.749 (6) 164
C402—H402⋯Cl1 0.94 2.59 3.398 (6) 144
C406—H406⋯Cl3 0.94 2.88 3.757 (6) 156
C412—H412⋯Cl3 0.94 2.95 3.870 (5) 167
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y, -z+2.

Table 5
Hydrogen-bond geometry (Å, °) for 7[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2A⋯Cl1 0.98 2.48 3.421 (3) 162
C3—H3A⋯Cl1i 0.98 2.59 3.488 (3) 152
C3—H3B⋯O1 0.98 2.21 2.968 (4) 134
C102—H102⋯Cl2 0.94 2.61 3.505 (4) 160
C108—H108⋯O2 0.94 2.61 3.313 (4) 132
C112—H112⋯Cl1 0.94 2.80 3.595 (4) 143
C202—H202⋯Cl2 0.94 2.70 3.574 (4) 156
C212—H212⋯Cl1 0.94 2.80 3.733 (5) 173
C306—H306⋯O1 0.94 2.47 3.061 (4) 121
C312—H312⋯Cl1i 0.94 2.73 3.503 (4) 140
C402—H402⋯O2 0.94 2.47 3.375 (4) 162
C408—H408⋯O3 0.94 2.44 3.326 (5) 156
C412—H412⋯Cl1i 0.94 2.97 3.866 (4) 161
C13—H13A⋯O5ii 0.98 2.58 3.194 (6) 121
C13—H13A⋯Cl2ii 0.98 2.68 3.500 (7) 141
C14—H14A⋯Cl2iii 0.98 2.65 3.553 (6) 153
C14—H14B⋯O1iv 0.98 2.37 3.327 (6) 164
C14A—H14C⋯O1iv 0.98 2.38 3.327 (6) 163
C14A—H14D⋯Cl2iii 0.98 2.59 3.553 (6) 168
O6—H6OA⋯Cl2 0.85 (2) 2.39 (4) 3.178 (5) 154 (7)
O6—H6OB⋯Cl1 0.85 (2) 2.39 (2) 3.239 (6) 178 (6)
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z; (iii) x-1, y+1, z; (iv) x-1, y, z.

In the structure of 4, there are weak C—H⋯Cl inter­actions between the chloride counter-ion and the methyl­ene groups of the PCP pincer ligand system [Cl2⋯H2B = 2.58 Å, H3B⋯Cl2(x − 1, y, z) = 2.83 Å] exhibiting distances shorter than the sum of the van der Waals radii (Table 2[link], Fig. 6[link]). Such C—H⋯X inter­actions are a common feature of complexes containing dppm or related ligands (Jones & Ahrens, 1998[Jones, P. G. & Ahrens, B. (1998). Chem. Commun. pp. 2307-2308.]).

[Figure 6]
Figure 6
A view along the c axis of the crystal packing of compound 4. Only the H atoms involved in the most significant inter­molecular inter­actions (Table 2[link]) are displayed and the intra­molecular inter­action is omitted.

Moreover, compound 5 shows C—H⋯O and C—H⋯Cl inter­actions (Table 3[link]) between the methyl­ene groups of the dppm moieties and the solvent mol­ecules and additionally the counter-ion, forming short contacts of 2.22 Å [H2A⋯O5 (x, y − 1, z)], 2.91 Å (H3A⋯Cl2) and 2.40 Å (H3B⋯O1) (Fig. 7[link]).

[Figure 7]
Figure 7
A view along the a axis of the crystal packing of compound 5. Only the H atoms involved in the most significant inter­molecular inter­actions (Table 3[link]) are presented and the intra­molecular inter­actions are omitted. One phenyl group and the solvent mol­ecules show positional disorder.

In the structure of 6, the methyl­ene groups of the PCP unit and the chloride counter-ion and the solvent mol­ecules form C—H⋯O and C—H⋯Cl inter­actions (Table 4[link]), exhibiting distances of 2.45 Å [H2B⋯O5(x, y − 1, z)], 2.66 Å (H3B⋯Cl3) and 2.40 Å [H6A⋯O3 (−x + 1, −y, −z + 2)] (Fig. 8[link]).

[Figure 8]
Figure 8
A view along the a axis of the crystal packing of compound 6. Only the H atoms involved in the most significant inter­molecular inter­actions (Table 4[link]) are presented and the intra­molecular inter­actions are omitted.

In compound 7, the chloride counter-ions inter­act with both the PCP pincer ligand system and the solvent mol­ecules. The solvent mol­ecules also show inter­actions with the iridium complex (Table 5[link], Fig. 9[link]).

[Figure 9]
Figure 9
A view along the a axis of the crystal packing of compound 7. Only the H atoms involved in the most significant inter­molecular inter­actions (Table 5[link]) are presented and the intra­molecular inter­actions are omitted. The solvent mol­ecules are disordered.

4. Synthesis and crystallization

Each reaction step was carried out under an atmosphere of nitro­gen by the use of standard Schlenk techniques. All starting materials and solvents were obtained from commercial suppliers, excluding the compound [CH(dppm)2]Cl that was prepared by a previously reported procedure (Reitsamer et al., 2012[Reitsamer, C., Stallinger, S., Schuh, W., Kopacka, H., Wurst, K., Obendorf, D. & Peringer, P. (2012). Dalton Trans. 41, 3503-3514.]). 1H-, 13C- and 31P-NMR spectra were recorded on a Bruker DPX 300 NMR spectrometer and were referenced against the 13C/1H peaks of deuterated solvents chloro­form and methanol or an external 85% H3PO4 standard, respectively. For the following assignment of the NMR data, atoms are labelled as in Figs. 2[link], 3[link], 4[link], 5[link].

Synthesis of [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P′}ClH]Cl·2.75CH2Cl2 (4): A mixture of [CH(dppm)2]Cl (0.0250 mmol, 20.4 mg) and [IrCl(cod)]2 (0.0125 mmol, 8.4 mg) was solved in 0.1 ml of MeCN. After a reaction time of one minute, a solution of ethyl diazo­acetate (0.0250 mmol, 2.85 mg) in MeOH (0.5 ml) was added. 10 min later, a deep yellow liquid was obtained. The volatiles were removed and the remaining solid was dissolved in methyl­ene chloride (0.6 ml), leading to complex 4 in high yield (0.0250 mmol, 28.3 mg). Single crystals of complex 4 were grown from a solvent mixture of n-hexane (1.2 ml) and CH2Cl2 (0.2 ml). 31P {1H} NMR (CHCl3): δ = 18.8 (ddd, P1, 2JP1P2 = 16.9 Hz, 4JP1P3 = 16.6 Hz, 2JP1P4 = 399.2 Hz), 38.1 (ddd, P2, 2JP2P3 = 38.3 Hz, 4JP2P4 = 16.9 Hz), 34.7 (ddd, P3, 2JP3P4 = 29.0 Hz), 10.7 (ddd, P4) ppm; 1H NMR (CDCl3/MeOH, 5:1): δ = −15.2 (ddddd, hydride, 3JP2H = 5.5 Hz, 3JP3H = 5.5 Hz, 2JP1H = 13.1 Hz, 2JP4H = 13.1 Hz, 2JC1H = 14.3 Hz) ppm; 13C {1H} NMR (CDCl3): δ = 3.6 (dddd, C1, 1JC1P2 = 63.5 Hz, 2JC1P3 = 74.6 Hz, 2JC1P1 = 3.9 Hz, 2JC1P4 = 3.9 Hz) ppm.

Synthesis of [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P}(CH2CO2Et)Cl]Cl·CH3OH·0.5 H2O (5): Ethyl diazo­acetate (0.116 mmol, 13.2 mg) was added to a solution of complex 4 (0.0250 mmol, 28.3 mg) in CH2Cl2 (0.6 ml), and the reaction mixture was stirred for 30 min. Complex 5 (0.0250 mmol, 30.7 mg) was formed qu­anti­tatively. Single crystals were obtained via slow evaporation of a 1:1methyl­ene chloride/methanol mixture. 31P {1H} NMR (CHCl3): δ = 0.3 (ddd, P1, 2JP1P2 = 24.4 Hz, 4JP1P3 = 10.6 Hz, 2JP1P4 = 436.4 Hz), 40.6 (dddd, P2, 2JP2P3 = 35.1 Hz, 4JP2P4 = 15.3 Hz), 36.4 (dddd, P3, 2JP3P4 = 15.9 Hz), −4.4 (ddd, P4) ppm; 13C {1H} NMR (CDCl3): δ = 3.1 (dddd, C1, 1JC1P2 = 68.8 Hz, 1JC1P3 = 55.6 Hz, 2JC1P1 = 3.5 Hz, 2JC1P4 = 3.5 Hz) ppm.

Synthesis of [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P}Cl2]Cl·CH3OH·2H2O (6): A solution of complex 4 (0.0250 mmol, 28.3 mg) in CH2Cl2 (0.6 ml) was treated with hydro­chloric acid (77.0 µl, 37%, 0.925 mmol) and stirred vigorously for approximately 10 min. The organic phase was separated and washed with water (0.5 ml) three times in total. Complex 6 (0.0250 mmol, 29.1 mg) was formed almost qu­anti­tatively. Yellow single crystals were generated by slow evaporation of a 1:1 solvent mixture of MeCN and MeOH. 31P {1H} NMR (CHCl3): δ = −6.1 (ddd, P1, 2JP1P2 = 19.9 Hz, 4JP1P3 = 19.8 Hz, 2JP1P4 = 452.1 Hz), 46.9 (ddd, P2, 2JP2P3 = 38.3 Hz, 4JP2P4 = 30.6 Hz), 45.8 (ddd, P3, 2JP3P4 = 19.8 Hz), −10.3 (ddd, P4) ppm; 13C {1H} NMR (CDCl3): δ = 3.8 (dd, C1, 1JC1P2 = 50.2 Hz, 1JC1P3 = 50.2 Hz) ppm.

Synthesis of [IrIII{C(CHCO2Et)(dppm)2-κ4P,C,C′,P}(CH2CO2Et)(CO)]Cl2·2CH2Cl2·1.5H2O (7): A solution of complex 5 (0.025 mmol, 29.1 mg) in CH2Cl2 was placed under an atmosphere of CO. After a reaction time of 1 h, complex 7 had formed qu­anti­tatively (0.0250 mmol, 31.1 mg). Single crystals were grown from a solution of methyl­ene chloride, covered with a small amount of ethyl acetate. 31P {1H} NMR (CH2Cl2): δ = −6.5 (ddd, P1, 2JP1P2 = 14.2 Hz, 4JP1P3 = 9.5 Hz, 2JP1P4 = 339.8 Hz), 41.2 (ddd, P2, 2JP2P3 = 27.7 Hz, 4JP2P4 = 18.4 Hz), 39.7 (ddd, P3, 2JP3P4 = 12.3 Hz), −16.4 (ddd, P4) ppm; 13C {1H} NMR (CD2Cl2): δ = 16.1 (ddd, C1, 1JC1P2 = 59.8 Hz, 1JC1P3 = 49.3 Hz, 2JC1P4 = 2.7 Hz, 2JC1C12 = 1.5 Hz), 172.8 (ddd, C12, 2JC12P1 = 8.6 Hz, 2JC12P4 = 8.6 Hz) ppm.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6[link]. Diffraction data for all crystals were measured by using multiple scans to increase the number of redundant reflections. We found the data of sufficient quality to proceed without semi-empirical absorption methods.

Table 6
Experimental details

  4 5 6 7
Crystal data
Chemical formula [IrClH(C55H50O2P4)]Cl·2.75CH2Cl2 [Ir(C4H7O2)Cl(C55H50O2P4)]Cl·CH4O·0.5H2O [IrCl2(C55H50O2P4)]Cl·CH4O·2H2O [Ir(C4H7O2)(C55H50O2P4)(CO)]Cl2·2CH2Cl2·1.5H2O
Mr 1364.48 1258.07 1233.45 1441.91
Crystal system, space group Monoclinic, P21/n Triclinic, P[\overline{1}] Triclinic, P[\overline{1}] Triclinic, P[\overline{1}]
Temperature (K) 233 233 233 233
a, b, c (Å) 12.4425 (2), 22.4020 (3), 22.5393 (3) 12.4253 (3), 13.7081 (4), 17.6780 (6) 11.2371 (2), 12.9144 (2), 19.2371 (3) 11.7326 (2), 13.8815 (2), 22.2615 (3)
α, β, γ (°) 90, 94.826 (1), 90 93.152 (2), 97.960 (2), 103.771 (2) 89.439 (1), 77.863 (1), 83.114 (1) 75.477 (1), 86.508 (1), 65.212 (1)
V3) 6260.26 (16) 2884.18 (15) 2709.27 (8) 3182.38 (9)
Z 4 2 2 2
Radiation type Mo Kα Mo Kα Mo Kα Mo Kα
μ (mm−1) 2.59 2.57 2.78 2.50
Crystal size (mm) 0.11 × 0.08 × 0.05 0.15 × 0.05 × 0.02 0.11 × 0.05 × 0.03 0.31 × 0.23 × 0.19
 
Data collection
Diffractometer Nonius KappaCCD Nonius KappaCCD Nonius KappaCCD Nonius KappaCCD
No. of measured, independent and observed [I > 2σ(I)] reflections 39699, 11006, 8888 13821, 7453, 6326 17984, 9526, 8083 23329, 12496, 11695
Rint 0.045 0.037 0.035 0.024
θmax (°) 25.0 22.4 25.0 26.0
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.112, 1.04 0.044, 0.106, 1.07 0.034, 0.073, 1.05 0.028, 0.070, 1.05
No. of reflections 11006 7453 9526 12496
No. of parameters 711 674 626 751
No. of restraints 2 1 1 3
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 1.03, −0.86 0.90, −0.96 0.75, −1.01 0.97, −1.29
Computer programs: COLLECT (Nonius, 1999[Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.]), DENZO and SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]), XP in SHELXTL and SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014/7 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) and CHEMDRAW (Cambridge Soft, 2001[Cambridge Soft (2001). CHEMDRAW. Cambridge Soft Corporation, Cambridge, Massachusetts, USA.]).

Unless noted otherwise, H atoms in the four structures were placed geometrically and refined in the riding-model approximation with Uiso(H) = 1.2Ueq(C) for phenyl and methyl­ene H atoms and 1.5Ueq(C) for methyl H atoms.

For compound 4, the two hydrogen atoms bound to the central Ir1 atom and the C4 atom of the eth­oxy­oxoethanyl­idene moiety were discernible from a difference-Fourier map. They were refined with bond-length restraints of 0.96 Å (C4) and 1.60 Å (Ir1) and with individual Uiso values. Three of the four methyl­ene chloride solvent mol­ecules are disordered. One solvent mol­ecule (C9, Cl3, Cl4) shows half-occupation, one (C12, Cl9, Cl10) is disordered around an inversion centre (occupancy 0.25) and for one (C11, Cl7, Cl8) the Cl atoms show a positional disorder over two sites (ratio 0.7:0.3). All H atoms of the solvent mol­ecules were omitted from the final model.

The scattering power of the crystal of compound 5 was poor. Hence, it was possible to collect reflections only up to 45°/2θ. The H atom attached to the C4 position was treated as described above. The methanol (C13, O6) and water (O7) solvent mol­ecules are disordered around an inversion centre and were refined with half-occupation. H atoms of the disordered solvent mol­ecules were omitted from the model. Furthermore, one phenyl group shows a 1:1 positional disorder and was refined over two sets of sites (C401–C406; C41A–C46A). All atoms of the disordered phenyl ring were refined isotropically.

In compounds 6 and 7, the H atom attached to the C4 position was treated as described above. For 6, localization of the H atoms of the methanol and water solvent mol­ecules was not possible and hence they were omitted from the model. For 7, H atoms of water mol­ecule O6 were located from a difference-Fourier map and refined with bond-length restraints of 0.84 Å. The O7 atom of the other water mol­ecule was treated as being half-occupied, and its H atoms were omitted from the model. One methyl­ene chloride solvent mol­ecule (C14, Cl5, Cl6) was refined over two sets of sites (ratio 0.65:0.35).

Supporting information


Computing details top

For all structures, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010) and CHEMDRAW (Cambridge Soft, 2001).

(Bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4P,C,C',P')chloridohydridoiridium(III) chloride methylene chloride 2.75-solvate (4) top
Crystal data top
[IrClH(C55H50O2P4)]Cl·2.75CH2Cl2F(000) = 2734
Mr = 1364.48Dx = 1.448 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 12.4425 (2) ÅCell parameters from 104186 reflections
b = 22.4020 (3) Åθ = 1.0–25.3°
c = 22.5393 (3) ŵ = 2.59 mm1
β = 94.826 (1)°T = 233 K
V = 6260.26 (16) Å3Prism, colorless
Z = 40.11 × 0.08 × 0.05 mm
Data collection top
Nonius KappaCCD
diffractometer
8888 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
Graphite monochromatorθmax = 25.0°, θmin = 1.8°
phi– and ω–scansh = 1414
39699 measured reflectionsk = 2626
11006 independent reflectionsl = 2626
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.112 w = 1/[σ2(Fo2) + (0.0606P)2 + 10.2768P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
11006 reflectionsΔρmax = 1.03 e Å3
711 parametersΔρmin = 0.86 e Å3
Special details top

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.

Refinement. Hyrogen atoms at Ir1 and C4 were localized and refined with bond restraints: 96 pm at C4 and 160 pm at Ir1, respectively. There are four solvent molecules into the asymmetric unit, which are partial disordered (C9 occupational disorder with factor 0.5, C11 positional disorder of chlorine atoms wiht ratio 7:3 and C12 occupational disorder with factor 0.25). Hydrogen atoms at solvent were omitted.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ir10.49207 (2)0.11833 (2)0.20622 (2)0.03228 (8)
H10.484 (4)0.1906 (9)0.209 (2)0.067 (18)*
P10.67637 (10)0.11984 (5)0.22113 (6)0.0370 (3)
P20.62189 (10)0.01107 (5)0.22879 (6)0.0365 (3)
P30.36683 (10)0.01314 (5)0.21373 (5)0.0326 (3)
P40.30844 (10)0.11776 (5)0.19399 (6)0.0322 (3)
Cl10.52098 (11)0.12563 (6)0.09975 (6)0.0461 (3)
Cl20.98655 (13)0.01266 (9)0.20289 (13)0.1081 (9)
O10.3419 (3)0.04012 (18)0.33389 (18)0.0627 (11)
O20.4452 (4)0.11608 (16)0.36960 (17)0.0579 (11)
C10.4926 (4)0.02169 (19)0.2370 (2)0.0323 (10)
C20.7115 (4)0.0439 (2)0.1997 (2)0.0424 (12)
H2A0.70700.04100.15620.051*
H2B0.78600.03520.21480.051*
C30.2600 (4)0.0420 (2)0.2099 (2)0.0396 (11)
H3A0.22700.04250.24790.048*
H3B0.20420.03040.17880.048*
C40.4981 (4)0.0697 (2)0.2846 (2)0.0360 (11)
H40.571 (2)0.068 (2)0.3031 (19)0.036 (13)*
C50.4185 (5)0.0725 (2)0.3304 (2)0.0443 (12)
C70.3729 (7)0.1253 (3)0.4152 (3)0.076 (2)
H7A0.36760.08900.43920.091*
H7B0.30070.13570.39750.091*
C80.4203 (8)0.1761 (4)0.4533 (4)0.118 (3)
H8A0.37440.18420.48510.177*
H8B0.49180.16500.47040.177*
H8C0.42520.21150.42890.177*
C1010.7549 (4)0.1701 (2)0.1780 (2)0.0463 (13)
C1020.8362 (7)0.1526 (4)0.1455 (5)0.115 (4)
H1020.85380.11190.14380.138*
C1030.8944 (8)0.1940 (5)0.1145 (6)0.149 (5)
H1030.94910.18110.09110.179*
C1040.8713 (6)0.2521 (4)0.1183 (4)0.095 (3)
H1040.91050.28000.09780.114*
C1050.7917 (8)0.2712 (3)0.1516 (4)0.093 (3)
H1050.77760.31230.15490.112*
C1060.7311 (7)0.2298 (3)0.1808 (3)0.080 (2)
H1060.67400.24270.20240.096*
C1070.7388 (5)0.1311 (2)0.2962 (3)0.0514 (14)
C1080.8387 (6)0.1063 (3)0.3146 (3)0.073 (2)
H1080.87620.08270.28860.088*
C1090.8822 (8)0.1176 (4)0.3736 (5)0.112 (4)
H1090.94900.10090.38740.134*
C1100.8274 (11)0.1528 (5)0.4107 (4)0.115 (4)
H1100.85760.15990.44970.138*
C1110.7302 (8)0.1776 (4)0.3923 (3)0.091 (3)
H1110.69380.20200.41810.110*
C1120.6863 (6)0.1664 (3)0.3353 (3)0.0651 (17)
H1120.61900.18310.32250.078*
C2010.6228 (4)0.0736 (2)0.1787 (2)0.0409 (12)
C2020.6137 (5)0.0644 (3)0.1167 (2)0.0499 (14)
H2020.60520.02550.10140.060*
C2030.6174 (6)0.1124 (3)0.0783 (3)0.0681 (18)
H2030.61040.10630.03690.082*
C2040.6316 (5)0.1700 (3)0.1014 (3)0.0673 (18)
H2040.63550.20270.07550.081*
C2050.6399 (5)0.1793 (3)0.1620 (3)0.0648 (17)
H2050.64780.21830.17710.078*
C2060.6368 (4)0.1317 (2)0.2010 (3)0.0524 (14)
H2060.64410.13830.24230.063*
C2070.6860 (5)0.0357 (2)0.2990 (3)0.0491 (14)
C2080.7957 (5)0.0481 (3)0.3027 (3)0.0682 (18)
H2080.83470.04410.26900.082*
C2090.8477 (8)0.0666 (4)0.3568 (5)0.100 (3)
H2090.92190.07520.35920.120*
C2100.7930 (10)0.0726 (4)0.4060 (4)0.106 (4)
H2100.82990.08420.44220.127*
C2110.6813 (9)0.0614 (3)0.4032 (3)0.096 (3)
H2110.64350.06640.43730.116*
C2120.6259 (6)0.0425 (3)0.3485 (3)0.0657 (18)
H2120.55140.03470.34570.079*
C3010.3231 (4)0.0735 (2)0.2590 (2)0.0384 (11)
C3020.2144 (5)0.0820 (3)0.2652 (3)0.0572 (15)
H3020.16370.05440.24860.069*
C3030.1802 (6)0.1309 (3)0.2959 (3)0.077 (2)
H3030.10620.13660.29960.092*
C3040.2540 (7)0.1712 (3)0.3209 (3)0.078 (2)
H3040.23030.20400.34230.094*
C3050.3607 (6)0.1639 (3)0.3150 (3)0.0711 (19)
H3050.41100.19170.33190.085*
C3060.3953 (5)0.1149 (2)0.2835 (3)0.0554 (15)
H3060.46920.11000.27910.067*
C3070.3642 (4)0.0446 (2)0.1398 (2)0.0356 (11)
C3080.3715 (5)0.0068 (2)0.0913 (2)0.0494 (13)
H3080.38520.03410.09730.059*
C3090.3585 (6)0.0297 (3)0.0343 (3)0.0690 (18)
H3090.36340.00420.00150.083*
C3100.3382 (6)0.0895 (3)0.0250 (3)0.0686 (18)
H3100.32910.10480.01400.082*
C3110.3314 (6)0.1269 (3)0.0729 (3)0.0625 (17)
H3110.31790.16780.06670.075*
C3120.3444 (5)0.1046 (2)0.1300 (2)0.0472 (13)
H3120.33970.13050.16260.057*
C4010.2343 (4)0.1642 (2)0.2433 (2)0.0402 (11)
C4020.2883 (5)0.2051 (2)0.2807 (2)0.0483 (13)
H4020.36370.20860.28170.058*
C4030.2304 (5)0.2412 (3)0.3171 (3)0.0607 (16)
H4030.26710.26900.34260.073*
C4040.1209 (5)0.2365 (3)0.3161 (3)0.0636 (17)
H4040.08270.26060.34120.076*
C4050.0667 (5)0.1966 (3)0.2782 (4)0.078 (2)
H4050.00880.19360.27720.094*
C4060.1231 (5)0.1603 (3)0.2410 (3)0.0690 (19)
H4060.08580.13340.21470.083*
C4070.2442 (4)0.1381 (2)0.1209 (2)0.0421 (12)
C4080.2823 (5)0.1899 (2)0.0957 (2)0.0507 (14)
H4080.34160.21000.11500.061*
C4090.2344 (6)0.2122 (3)0.0426 (3)0.0676 (18)
H4090.25970.24780.02680.081*
C4100.1496 (6)0.1820 (4)0.0132 (3)0.080 (2)
H4100.11620.19710.02270.096*
C4110.1144 (7)0.1301 (4)0.0363 (4)0.093 (3)
H4110.05870.10870.01510.111*
C4120.1591 (6)0.1078 (3)0.0910 (3)0.0708 (19)
H4120.13170.07280.10720.085*
C90.250 (3)0.0515 (13)0.4305 (9)0.223 (19)0.5
Cl30.3575 (9)0.0543 (4)0.4754 (3)0.201 (4)0.5
Cl40.1305 (7)0.0182 (4)0.4559 (3)0.167 (3)0.5
C100.5629 (8)0.2613 (4)0.0386 (4)0.112 (3)
Cl50.4809 (2)0.31145 (11)0.07504 (11)0.1086 (7)
Cl60.6123 (3)0.29238 (12)0.02166 (12)0.1243 (9)
C110.9453 (10)0.1288 (5)0.1519 (7)0.139 (4)
Cl70.9402 (6)0.1902 (3)0.1966 (6)0.197 (4)0.7
Cl81.0617 (3)0.1332 (3)0.1087 (2)0.1348 (16)0.7
Cl7A0.9153 (19)0.1694 (9)0.231 (2)0.31 (2)0.3
Cl8A1.0197 (18)0.1825 (9)0.1312 (12)0.239 (10)0.3
C120.951 (5)0.0067 (16)0.026 (3)0.16 (2)0.25
Cl91.0704 (12)0.0453 (9)0.0654 (12)0.238 (11)0.25
Cl100.8652 (16)0.0098 (9)0.0607 (12)0.234 (11)0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ir10.03166 (12)0.02717 (12)0.03855 (12)0.00054 (7)0.00623 (8)0.00117 (8)
P10.0320 (7)0.0297 (7)0.0491 (8)0.0032 (5)0.0014 (6)0.0026 (5)
P20.0328 (7)0.0302 (6)0.0466 (7)0.0015 (5)0.0025 (5)0.0026 (6)
P30.0327 (6)0.0274 (6)0.0387 (7)0.0006 (5)0.0085 (5)0.0005 (5)
P40.0309 (6)0.0272 (6)0.0392 (7)0.0035 (5)0.0069 (5)0.0008 (5)
Cl10.0470 (7)0.0514 (8)0.0414 (7)0.0001 (6)0.0130 (6)0.0066 (6)
Cl20.0366 (9)0.0594 (11)0.229 (3)0.0004 (7)0.0143 (12)0.0035 (13)
O10.071 (3)0.059 (3)0.063 (3)0.014 (2)0.029 (2)0.008 (2)
O20.082 (3)0.051 (2)0.043 (2)0.0040 (19)0.017 (2)0.0143 (18)
C10.036 (3)0.026 (2)0.035 (3)0.0005 (19)0.007 (2)0.002 (2)
C20.030 (3)0.034 (3)0.064 (3)0.000 (2)0.007 (2)0.003 (2)
C30.032 (3)0.035 (3)0.052 (3)0.001 (2)0.009 (2)0.001 (2)
C40.037 (3)0.029 (3)0.042 (3)0.000 (2)0.004 (2)0.000 (2)
C50.054 (3)0.039 (3)0.041 (3)0.002 (3)0.011 (2)0.002 (2)
C70.105 (6)0.079 (5)0.049 (4)0.004 (4)0.034 (4)0.014 (3)
C80.153 (9)0.120 (7)0.087 (6)0.003 (6)0.036 (6)0.058 (6)
C1010.036 (3)0.045 (3)0.056 (3)0.006 (2)0.002 (2)0.010 (3)
C1020.087 (6)0.064 (5)0.206 (10)0.008 (4)0.085 (6)0.036 (6)
C1030.112 (8)0.098 (7)0.254 (14)0.014 (6)0.117 (9)0.062 (8)
C1040.063 (5)0.103 (7)0.117 (7)0.036 (5)0.000 (5)0.047 (6)
C1050.128 (7)0.047 (4)0.106 (6)0.020 (4)0.020 (6)0.022 (4)
C1060.112 (6)0.045 (4)0.089 (5)0.006 (4)0.039 (5)0.007 (4)
C1070.050 (3)0.043 (3)0.059 (4)0.015 (3)0.011 (3)0.008 (3)
C1080.063 (4)0.069 (4)0.084 (5)0.009 (3)0.025 (4)0.009 (4)
C1090.095 (7)0.098 (7)0.129 (9)0.027 (5)0.072 (7)0.031 (6)
C1100.149 (10)0.114 (8)0.074 (6)0.053 (7)0.027 (6)0.005 (6)
C1110.115 (7)0.091 (6)0.066 (5)0.045 (5)0.004 (5)0.007 (4)
C1120.076 (4)0.057 (4)0.062 (4)0.022 (3)0.002 (3)0.009 (3)
C2010.032 (3)0.033 (3)0.059 (3)0.001 (2)0.009 (2)0.006 (2)
C2020.057 (4)0.043 (3)0.052 (3)0.001 (3)0.018 (3)0.001 (3)
C2030.071 (4)0.072 (5)0.064 (4)0.007 (3)0.024 (3)0.017 (3)
C2040.066 (4)0.051 (4)0.088 (5)0.004 (3)0.024 (4)0.028 (4)
C2050.058 (4)0.039 (3)0.099 (5)0.003 (3)0.015 (4)0.009 (3)
C2060.041 (3)0.039 (3)0.077 (4)0.002 (2)0.008 (3)0.001 (3)
C2070.055 (3)0.035 (3)0.054 (3)0.002 (2)0.013 (3)0.002 (2)
C2080.055 (4)0.055 (4)0.090 (5)0.005 (3)0.020 (3)0.010 (3)
C2090.089 (6)0.074 (5)0.126 (8)0.009 (4)0.060 (6)0.015 (5)
C2100.154 (9)0.064 (5)0.086 (6)0.037 (5)0.066 (6)0.004 (5)
C2110.171 (9)0.064 (5)0.052 (4)0.025 (5)0.005 (5)0.002 (3)
C2120.092 (5)0.046 (3)0.057 (4)0.016 (3)0.006 (3)0.010 (3)
C3010.047 (3)0.035 (3)0.034 (3)0.005 (2)0.011 (2)0.002 (2)
C3020.053 (4)0.050 (3)0.071 (4)0.005 (3)0.016 (3)0.013 (3)
C3030.076 (5)0.070 (5)0.091 (5)0.016 (4)0.034 (4)0.014 (4)
C3040.102 (6)0.056 (4)0.079 (5)0.018 (4)0.028 (4)0.022 (4)
C3050.093 (5)0.047 (4)0.073 (4)0.003 (4)0.007 (4)0.017 (3)
C3060.064 (4)0.045 (3)0.059 (4)0.002 (3)0.016 (3)0.012 (3)
C3070.034 (3)0.034 (3)0.040 (3)0.002 (2)0.009 (2)0.000 (2)
C3080.068 (4)0.040 (3)0.042 (3)0.002 (3)0.015 (3)0.001 (2)
C3090.103 (5)0.060 (4)0.046 (3)0.008 (4)0.017 (3)0.003 (3)
C3100.094 (5)0.070 (4)0.044 (3)0.005 (4)0.016 (3)0.018 (3)
C3110.082 (5)0.052 (4)0.055 (4)0.014 (3)0.017 (3)0.022 (3)
C3120.058 (3)0.038 (3)0.048 (3)0.003 (2)0.015 (3)0.004 (2)
C4010.041 (3)0.034 (3)0.047 (3)0.001 (2)0.013 (2)0.002 (2)
C4020.047 (3)0.048 (3)0.050 (3)0.008 (3)0.008 (3)0.006 (3)
C4030.064 (4)0.058 (4)0.060 (4)0.013 (3)0.005 (3)0.021 (3)
C4040.072 (4)0.045 (3)0.079 (4)0.008 (3)0.035 (4)0.011 (3)
C4050.053 (4)0.061 (4)0.127 (6)0.003 (3)0.046 (4)0.031 (4)
C4060.049 (4)0.057 (4)0.104 (5)0.011 (3)0.030 (3)0.036 (4)
C4070.039 (3)0.043 (3)0.045 (3)0.010 (2)0.004 (2)0.003 (2)
C4080.056 (3)0.046 (3)0.050 (3)0.008 (3)0.003 (3)0.002 (3)
C4090.079 (5)0.062 (4)0.062 (4)0.013 (4)0.006 (4)0.010 (3)
C4100.087 (5)0.092 (6)0.059 (4)0.013 (4)0.011 (4)0.010 (4)
C4110.076 (5)0.115 (7)0.080 (5)0.014 (5)0.034 (4)0.003 (5)
C4120.062 (4)0.076 (5)0.070 (4)0.010 (3)0.021 (3)0.004 (3)
C90.41 (4)0.20 (2)0.070 (12)0.24 (3)0.11 (2)0.077 (14)
Cl30.324 (12)0.154 (6)0.121 (5)0.103 (7)0.006 (6)0.008 (5)
Cl40.197 (7)0.205 (7)0.099 (4)0.039 (6)0.008 (4)0.037 (4)
C100.142 (8)0.072 (5)0.126 (8)0.001 (5)0.032 (6)0.029 (5)
Cl50.1132 (17)0.1046 (17)0.1117 (17)0.0339 (13)0.0310 (14)0.0231 (13)
Cl60.160 (2)0.1072 (18)0.1116 (18)0.0022 (17)0.0446 (17)0.0005 (15)
C110.101 (8)0.117 (9)0.195 (13)0.018 (7)0.007 (8)0.027 (8)
Cl70.103 (5)0.089 (4)0.393 (14)0.018 (3)0.010 (6)0.043 (6)
Cl80.088 (3)0.194 (5)0.118 (3)0.029 (3)0.020 (2)0.020 (3)
Cl7A0.128 (13)0.102 (12)0.69 (7)0.008 (9)0.05 (2)0.04 (2)
Cl8A0.201 (19)0.174 (15)0.32 (3)0.048 (14)0.098 (18)0.041 (16)
C120.22 (6)0.04 (2)0.22 (6)0.08 (3)0.03 (4)0.05 (3)
Cl90.120 (11)0.208 (18)0.39 (3)0.022 (11)0.010 (14)0.15 (2)
Cl100.159 (14)0.213 (19)0.31 (3)0.077 (14)0.088 (16)0.088 (18)
Geometric parameters (Å, º) top
Ir1—C42.072 (5)C207—C2081.390 (8)
Ir1—C12.273 (4)C207—C2121.402 (9)
Ir1—P42.2783 (12)C208—C2091.394 (10)
Ir1—P12.2897 (13)C208—H2080.9400
Ir1—Cl12.4619 (13)C209—C2101.355 (13)
Ir1—H11.62 (2)C209—H2090.9400
P1—C1071.819 (6)C210—C2111.408 (13)
P1—C1011.824 (5)C210—H2100.9400
P1—C21.833 (5)C211—C2121.426 (9)
P2—C11.791 (5)C211—H2110.9400
P2—C2071.798 (5)C212—H2120.9400
P2—C2011.800 (5)C301—C3061.374 (8)
P2—C21.820 (5)C301—C3021.384 (7)
P3—C11.788 (5)C302—C3031.380 (9)
P3—C3011.806 (5)C302—H3020.9400
P3—C3071.807 (5)C303—C3041.376 (10)
P3—C31.811 (5)C303—H3030.9400
P4—C4071.827 (5)C304—C3051.356 (10)
P4—C4011.828 (5)C304—H3040.9400
P4—C31.846 (5)C305—C3061.396 (8)
O1—C51.205 (6)C305—H3050.9400
O2—C51.341 (6)C306—H3060.9400
O2—C71.437 (7)C307—C3121.383 (7)
C1—C41.515 (6)C307—C3081.391 (7)
C2—H2A0.9800C308—C3091.380 (8)
C2—H2B0.9800C308—H3080.9400
C3—H3A0.9800C309—C3101.376 (9)
C3—H3B0.9800C309—H3090.9400
C4—C51.490 (7)C310—C3111.375 (9)
C4—H40.968 (19)C310—H3100.9400
C7—C81.516 (10)C311—C3121.378 (8)
C7—H7A0.9800C311—H3110.9400
C7—H7B0.9800C312—H3120.9400
C8—H8A0.9700C401—C4021.381 (7)
C8—H8B0.9700C401—C4061.383 (8)
C8—H8C0.9700C402—C4031.395 (8)
C101—C1021.356 (9)C402—H4020.9400
C101—C1061.371 (8)C403—C4041.364 (9)
C102—C1031.399 (11)C403—H4030.9400
C102—H1020.9400C404—C4051.375 (9)
C103—C1041.337 (13)C404—H4040.9400
C103—H1030.9400C405—C4061.397 (8)
C104—C1051.360 (12)C405—H4050.9400
C104—H1040.9400C406—H4060.9400
C105—C1061.396 (10)C407—C4121.385 (8)
C105—H1050.9400C407—C4081.392 (8)
C106—H1060.9400C408—C4091.383 (8)
C107—C1121.389 (9)C408—H4080.9400
C107—C1081.393 (9)C409—C4101.376 (10)
C108—C1091.416 (12)C409—H4090.9400
C108—H1080.9400C410—C4111.362 (11)
C109—C1101.372 (15)C410—H4100.9400
C109—H1090.9400C411—C4121.402 (10)
C110—C1111.364 (14)C411—H4110.9400
C110—H1100.9400C412—H4120.9400
C111—C1121.376 (10)C9—Cl31.61 (4)
C111—H1110.9400C9—Cl41.80 (4)
C112—H1120.9400C10—Cl61.687 (9)
C201—C2061.399 (7)C10—Cl51.766 (10)
C201—C2021.409 (8)C11—Cl8A1.61 (2)
C202—C2031.384 (8)C11—Cl71.709 (18)
C202—H2020.9400C11—Cl81.815 (15)
C203—C2041.399 (9)C11—Cl7A2.07 (4)
C203—H2030.9400Cl8—Cl92.21 (3)
C204—C2051.377 (10)C12—Cl101.37 (5)
C204—H2040.9400C12—C12i1.79 (12)
C205—C2061.384 (8)C12—Cl92.02 (7)
C205—H2050.9400C12—Cl9i2.24 (6)
C206—H2060.9400Cl9—C12i2.24 (6)
C4—Ir1—C140.49 (17)C203—C202—H202119.9
C4—Ir1—P493.68 (14)C201—C202—H202119.9
C1—Ir1—P490.52 (12)C202—C203—C204119.6 (6)
C4—Ir1—P185.34 (14)C202—C203—H203120.2
C1—Ir1—P189.54 (12)C204—C203—H203120.2
P4—Ir1—P1178.42 (5)C205—C204—C203120.4 (6)
C4—Ir1—Cl1150.26 (13)C205—C204—H204119.8
C1—Ir1—Cl1111.34 (12)C203—C204—H204119.8
P4—Ir1—Cl196.30 (4)C204—C205—C206120.6 (6)
P1—Ir1—Cl185.15 (5)C204—C205—H205119.7
C4—Ir1—H1119.7 (18)C206—C205—H205119.7
C1—Ir1—H1159.8 (18)C205—C206—C201119.9 (6)
P4—Ir1—H187.0 (18)C205—C206—H206120.0
P1—Ir1—H192.4 (18)C201—C206—H206120.0
Cl1—Ir1—H188.8 (18)C208—C207—C212121.2 (6)
C107—P1—C101101.8 (2)C208—C207—P2118.4 (5)
C107—P1—C2106.3 (3)C212—C207—P2120.5 (5)
C101—P1—C2106.4 (2)C207—C208—C209119.6 (8)
C107—P1—Ir1118.9 (2)C207—C208—H208120.2
C101—P1—Ir1120.39 (17)C209—C208—H208120.2
C2—P1—Ir1101.87 (16)C210—C209—C208121.1 (8)
C1—P2—C207111.7 (3)C210—C209—H209119.5
C1—P2—C201115.9 (2)C208—C209—H209119.5
C207—P2—C201106.7 (2)C209—C210—C211120.6 (7)
C1—P2—C2110.1 (2)C209—C210—H210119.7
C207—P2—C2106.6 (3)C211—C210—H210119.7
C201—P2—C2105.3 (2)C210—C211—C212119.6 (8)
C1—P3—C301117.3 (2)C210—C211—H211120.2
C1—P3—C307112.8 (2)C212—C211—H211120.2
C301—P3—C307104.2 (2)C207—C212—C211118.0 (7)
C1—P3—C3109.7 (2)C207—C212—H212121.0
C301—P3—C3106.4 (2)C211—C212—H212121.0
C307—P3—C3105.4 (2)C306—C301—C302118.5 (5)
C407—P4—C401101.6 (2)C306—C301—P3121.0 (4)
C407—P4—C3106.2 (2)C302—C301—P3120.3 (4)
C401—P4—C3102.5 (2)C303—C302—C301120.3 (6)
C407—P4—Ir1117.78 (17)C303—C302—H302119.8
C401—P4—Ir1118.39 (17)C301—C302—H302119.8
C3—P4—Ir1108.78 (16)C304—C303—C302120.2 (7)
C5—O2—C7116.2 (5)C304—C303—H303119.9
C4—C1—P3120.2 (3)C302—C303—H303119.9
C4—C1—P2112.1 (3)C305—C304—C303120.4 (6)
P3—C1—P2124.2 (3)C305—C304—H304119.8
C4—C1—Ir162.6 (2)C303—C304—H304119.8
P3—C1—Ir1110.2 (2)C304—C305—C306119.4 (7)
P2—C1—Ir1109.8 (2)C304—C305—H305120.3
P2—C2—P1111.5 (3)C306—C305—H305120.3
P2—C2—H2A109.3C301—C306—C305121.1 (6)
P1—C2—H2A109.3C301—C306—H306119.4
P2—C2—H2B109.3C305—C306—H306119.4
P1—C2—H2B109.3C312—C307—C308119.3 (5)
H2A—C2—H2B108.0C312—C307—P3121.0 (4)
P3—C3—P4112.7 (3)C308—C307—P3119.4 (4)
P3—C3—H3A109.1C309—C308—C307119.7 (5)
P4—C3—H3A109.1C309—C308—H308120.1
P3—C3—H3B109.1C307—C308—H308120.1
P4—C3—H3B109.1C310—C309—C308120.6 (6)
H3A—C3—H3B107.8C310—C309—H309119.7
C5—C4—C1121.8 (4)C308—C309—H309119.7
C5—C4—Ir1126.1 (3)C311—C310—C309119.8 (6)
C1—C4—Ir176.9 (3)C311—C310—H310120.1
C5—C4—H4111 (3)C309—C310—H310120.1
C1—C4—H4105 (3)C310—C311—C312120.2 (6)
Ir1—C4—H4111 (3)C310—C311—H311119.9
O1—C5—O2123.2 (5)C312—C311—H311119.9
O1—C5—C4126.5 (5)C311—C312—C307120.4 (5)
O2—C5—C4110.2 (5)C311—C312—H312119.8
O2—C7—C8106.0 (6)C307—C312—H312119.8
O2—C7—H7A110.5C402—C401—C406119.9 (5)
C8—C7—H7A110.5C402—C401—P4120.3 (4)
O2—C7—H7B110.5C406—C401—P4119.7 (4)
C8—C7—H7B110.5C401—C402—C403119.7 (5)
H7A—C7—H7B108.7C401—C402—H402120.2
C7—C8—H8A109.5C403—C402—H402120.2
C7—C8—H8B109.5C404—C403—C402120.7 (6)
H8A—C8—H8B109.5C404—C403—H403119.7
C7—C8—H8C109.5C402—C403—H403119.7
H8A—C8—H8C109.5C403—C404—C405119.9 (5)
H8B—C8—H8C109.5C403—C404—H404120.1
C102—C101—C106118.7 (6)C405—C404—H404120.1
C102—C101—P1124.5 (5)C404—C405—C406120.4 (6)
C106—C101—P1116.7 (5)C404—C405—H405119.8
C101—C102—C103121.3 (8)C406—C405—H405119.8
C101—C102—H102119.4C401—C406—C405119.5 (6)
C103—C102—H102119.4C401—C406—H406120.3
C104—C103—C102119.3 (9)C405—C406—H406120.3
C104—C103—H103120.4C412—C407—C408118.9 (5)
C102—C103—H103120.4C412—C407—P4125.1 (5)
C103—C104—C105120.9 (7)C408—C407—P4116.0 (4)
C103—C104—H104119.6C409—C408—C407121.2 (6)
C105—C104—H104119.6C409—C408—H408119.4
C104—C105—C106119.8 (7)C407—C408—H408119.4
C104—C105—H105120.1C410—C409—C408119.8 (7)
C106—C105—H105120.1C410—C409—H409120.1
C101—C106—C105120.0 (7)C408—C409—H409120.1
C101—C106—H106120.0C411—C410—C409119.5 (7)
C105—C106—H106120.0C411—C410—H410120.2
C112—C107—C108119.6 (6)C409—C410—H410120.2
C112—C107—P1118.9 (5)C410—C411—C412121.7 (7)
C108—C107—P1121.5 (5)C410—C411—H411119.2
C107—C108—C109118.0 (8)C412—C411—H411119.2
C107—C108—H108121.0C407—C412—C411118.9 (7)
C109—C108—H108121.0C407—C412—H412120.5
C110—C109—C108120.4 (9)C411—C412—H412120.5
C110—C109—H109119.8Cl3—C9—Cl4118.8 (10)
C108—C109—H109119.8Cl6—C10—Cl5112.1 (5)
C111—C110—C109121.6 (8)Cl7—C11—Cl8110.0 (7)
C111—C110—H110119.2Cl8A—C11—Cl7A94.2 (13)
C109—C110—H110119.2C11—Cl8—Cl9105.0 (7)
C110—C111—C112118.7 (9)Cl10—C12—C12i169 (4)
C110—C111—H111120.6Cl10—C12—Cl9111 (4)
C112—C111—H111120.6C12i—C12—Cl972 (4)
C111—C112—C107121.8 (7)Cl10—C12—Cl9i117 (4)
C111—C112—H112119.1C12i—C12—Cl9i59 (4)
C107—C112—H112119.1Cl9—C12—Cl9i131 (3)
C206—C201—C202119.3 (5)C12—Cl9—Cl8130.1 (14)
C206—C201—P2120.4 (4)C12—Cl9—C12i49 (3)
C202—C201—P2120.2 (4)Cl8—Cl9—C12i138.4 (11)
C203—C202—C201120.2 (6)
C301—P3—C1—C482.4 (4)C201—C202—C203—C2040.8 (9)
C307—P3—C1—C4156.4 (3)C202—C203—C204—C2051.2 (10)
C3—P3—C1—C439.2 (4)C203—C204—C205—C2061.5 (10)
C301—P3—C1—P274.9 (4)C204—C205—C206—C2011.4 (9)
C307—P3—C1—P246.3 (4)C202—C201—C206—C2051.0 (8)
C3—P3—C1—P2163.5 (3)P2—C201—C206—C205178.5 (4)
C301—P3—C1—Ir1151.7 (2)C1—P2—C207—C208164.2 (4)
C307—P3—C1—Ir187.1 (3)C201—P2—C207—C20868.2 (5)
C3—P3—C1—Ir130.1 (3)C2—P2—C207—C20844.0 (5)
C207—P2—C1—C451.6 (4)C1—P2—C207—C21216.3 (5)
C201—P2—C1—C4174.1 (3)C201—P2—C207—C212111.3 (5)
C2—P2—C1—C466.6 (4)C2—P2—C207—C212136.5 (5)
C207—P2—C1—P3107.3 (3)C212—C207—C208—C2091.2 (9)
C201—P2—C1—P315.2 (4)P2—C207—C208—C209179.3 (5)
C2—P2—C1—P3134.5 (3)C207—C208—C209—C2100.2 (12)
C207—P2—C1—Ir1119.1 (2)C208—C209—C210—C2111.5 (13)
C201—P2—C1—Ir1118.4 (2)C209—C210—C211—C2121.4 (12)
C2—P2—C1—Ir10.9 (3)C208—C207—C212—C2111.2 (9)
C1—P2—C2—P128.3 (4)P2—C207—C212—C211179.3 (5)
C207—P2—C2—P193.0 (3)C210—C211—C212—C2070.1 (10)
C201—P2—C2—P1153.9 (3)C1—P3—C301—C30639.5 (5)
C107—P1—C2—P282.4 (3)C307—P3—C301—C30686.1 (5)
C101—P1—C2—P2169.7 (3)C3—P3—C301—C306162.8 (4)
Ir1—P1—C2—P242.7 (3)C1—P3—C301—C302146.1 (4)
C1—P3—C3—P428.1 (4)C307—P3—C301—C30288.3 (5)
C301—P3—C3—P4156.0 (3)C3—P3—C301—C30222.9 (5)
C307—P3—C3—P493.7 (3)C306—C301—C302—C3030.4 (9)
C407—P4—C3—P3114.6 (3)P3—C301—C302—C303174.9 (5)
C401—P4—C3—P3139.3 (3)C301—C302—C303—C3040.6 (11)
Ir1—P4—C3—P313.1 (3)C302—C303—C304—C3051.1 (12)
P3—C1—C4—C526.1 (6)C303—C304—C305—C3060.5 (11)
P2—C1—C4—C5133.8 (4)C302—C301—C306—C3051.0 (9)
Ir1—C1—C4—C5124.6 (5)P3—C301—C306—C305175.4 (5)
P3—C1—C4—Ir198.6 (3)C304—C305—C306—C3010.6 (10)
P2—C1—C4—Ir1101.6 (3)C1—P3—C307—C312121.4 (4)
C7—O2—C5—O13.8 (8)C301—P3—C307—C3127.0 (5)
C7—O2—C5—C4177.9 (5)C3—P3—C307—C312118.9 (4)
C1—C4—C5—O12.7 (8)C1—P3—C307—C30865.1 (5)
Ir1—C4—C5—O194.4 (6)C301—P3—C307—C308166.5 (4)
C1—C4—C5—O2175.6 (4)C3—P3—C307—C30854.6 (5)
Ir1—C4—C5—O287.3 (5)C312—C307—C308—C3090.2 (8)
C5—O2—C7—C8179.9 (6)P3—C307—C308—C309173.4 (5)
C107—P1—C101—C102100.6 (7)C307—C308—C309—C3100.1 (10)
C2—P1—C101—C10210.6 (8)C308—C309—C310—C3110.3 (11)
Ir1—P1—C101—C102125.5 (7)C309—C310—C311—C3120.2 (11)
C107—P1—C101—C10677.3 (6)C310—C311—C312—C3070.1 (10)
C2—P1—C101—C106171.5 (5)C308—C307—C312—C3110.3 (8)
Ir1—P1—C101—C10656.6 (6)P3—C307—C312—C311173.2 (5)
C106—C101—C102—C1030.9 (15)C407—P4—C401—C402121.2 (5)
P1—C101—C102—C103178.7 (9)C3—P4—C401—C402129.1 (4)
C101—C102—C103—C1041.9 (19)Ir1—P4—C401—C4029.5 (5)
C102—C103—C104—C1050.5 (18)C407—P4—C401—C40655.9 (5)
C103—C104—C105—C1061.8 (15)C3—P4—C401—C40653.8 (5)
C102—C101—C106—C1051.4 (12)Ir1—P4—C401—C406173.5 (4)
P1—C101—C106—C105176.6 (6)C406—C401—C402—C4031.5 (9)
C104—C105—C106—C1012.8 (13)P4—C401—C402—C403178.6 (4)
C101—P1—C107—C112102.8 (5)C401—C402—C403—C4040.0 (9)
C2—P1—C107—C112146.0 (4)C402—C403—C404—C4051.0 (10)
Ir1—P1—C107—C11232.0 (5)C403—C404—C405—C4060.5 (11)
C101—P1—C107—C10875.7 (5)C402—C401—C406—C4052.0 (10)
C2—P1—C107—C10835.5 (6)P4—C401—C406—C405179.1 (6)
Ir1—P1—C107—C108149.5 (4)C404—C405—C406—C4011.0 (11)
C112—C107—C108—C1091.0 (10)C401—P4—C407—C41294.0 (6)
P1—C107—C108—C109179.5 (5)C3—P4—C407—C41212.8 (6)
C107—C108—C109—C1101.0 (12)Ir1—P4—C407—C412135.0 (5)
C108—C109—C110—C1110.2 (15)C401—P4—C407—C40883.0 (4)
C109—C110—C111—C1120.6 (14)C3—P4—C407—C408170.2 (4)
C110—C111—C112—C1070.6 (11)Ir1—P4—C407—C40848.0 (4)
C108—C107—C112—C1110.2 (9)C412—C407—C408—C4092.2 (9)
P1—C107—C112—C111178.7 (5)P4—C407—C408—C409175.0 (5)
C1—P2—C201—C206105.6 (4)C407—C408—C409—C4101.9 (9)
C207—P2—C201—C20619.5 (5)C408—C409—C410—C4110.7 (11)
C2—P2—C201—C206132.5 (4)C409—C410—C411—C4123.0 (13)
C1—P2—C201—C20277.0 (5)C408—C407—C412—C4110.1 (10)
C207—P2—C201—C202157.9 (4)P4—C407—C412—C411177.1 (6)
C2—P2—C201—C20244.9 (5)C410—C411—C412—C4072.7 (13)
C206—C201—C202—C2030.8 (8)Cl7—C11—Cl8—Cl9171.2 (8)
P2—C201—C202—C203178.2 (5)
Symmetry code: (i) x+2, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2B···Cl20.982.583.488 (5)154
C3—H3A···O10.982.312.892 (7)117
C3—H3B···Cl2ii0.982.833.456 (5)122
Symmetry code: (ii) x1, y, z.
(Bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4P,C,C',P')chlorido(ethoxyoxoethanido)iridium(III) chloride–methanol–water (1/1/0.5) (5) top
Crystal data top
[Ir(C4H7O2)Cl(C55H50O2P4)]Cl·CH4O·0.5H2OZ = 2
Mr = 1258.07F(000) = 1274
Triclinic, P1Dx = 1.449 Mg m3
a = 12.4253 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.7081 (4) ÅCell parameters from 57775 reflections
c = 17.6780 (6) Åθ = 1.0–22.5°
α = 93.152 (2)°µ = 2.57 mm1
β = 97.960 (2)°T = 233 K
γ = 103.771 (2)°Plate, colorless
V = 2884.18 (15) Å30.15 × 0.05 × 0.02 mm
Data collection top
Nonius KappaCCD
diffractometer
6326 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
Graphite monochromatorθmax = 22.4°, θmin = 1.9°
phi– and ω–scansh = 1313
13821 measured reflectionsk = 1414
7453 independent reflectionsl = 1818
Refinement top
Refinement on F21 restraint
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.047P)2 + 6.9463P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
7453 reflectionsΔρmax = 0.90 e Å3
674 parametersΔρmin = 0.96 e Å3
Special details top

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.

Refinement. Small crystal with low diffraction, but good quality. Reflections were collected only until 45 degrees (2Theta). Hydrogen at C4 was found and refined isotropically with bond restraint (d=0.96 angs.). Solvent molecules methanole and water lies nearby an inversion centre and were all refined with multipicity of 0.5 (C12-O5, C13-O6 and O7). Hydrogens of these disordered molecules were not exact logalized and omitted. A 1:1 positional disorder occurs for one phenyl group of the phospane (C401-C406 and C41A-C46A). The distance of the carbon atoms between disordered rings are small and all atoms were refined isotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ir10.16510 (2)0.10634 (2)0.69970 (2)0.04147 (12)
P10.15686 (15)0.26886 (16)0.72460 (11)0.0454 (5)
P20.35224 (14)0.24371 (15)0.79978 (10)0.0416 (5)
P30.35696 (14)0.02021 (14)0.78288 (10)0.0414 (5)
P40.17014 (15)0.05959 (16)0.68972 (11)0.0474 (5)
Cl10.00070 (14)0.05642 (16)0.80140 (11)0.0558 (5)
Cl20.3358 (4)0.3182 (3)0.8216 (2)0.1433 (14)
C10.3307 (5)0.1353 (5)0.7465 (4)0.0389 (16)
C20.2231 (6)0.2821 (6)0.8122 (4)0.0479 (19)
H2A0.23780.35260.82420.057*
H2B0.17160.24070.85550.057*
C30.2880 (6)0.0839 (5)0.7350 (4)0.053 (2)
H3A0.25970.14320.77220.063*
H3B0.34330.09960.69540.063*
C1010.0247 (6)0.3050 (6)0.7536 (4)0.053 (2)
C1020.0243 (7)0.3454 (7)0.6989 (5)0.073 (3)
H1020.00940.35220.64730.088*
C1030.1207 (8)0.3760 (8)0.7172 (6)0.088 (3)
H1030.15160.40450.67850.106*
C1040.1718 (7)0.3654 (8)0.7907 (7)0.088 (3)
H1040.23760.38730.80340.106*
C1050.1274 (8)0.3226 (9)0.8466 (6)0.091 (3)
H1050.16380.31370.89770.110*
C1060.0293 (7)0.2922 (7)0.8284 (5)0.073 (3)
H1060.00070.26280.86710.087*
C1070.2385 (6)0.3784 (6)0.6601 (4)0.0460 (19)
C1080.2860 (5)0.3683 (6)0.5870 (4)0.0445 (18)
H1080.27450.30430.56840.053*
C1090.3505 (7)0.4520 (7)0.5407 (5)0.061 (2)
H1090.38400.44440.49110.073*
C1100.3662 (7)0.5465 (7)0.5666 (5)0.064 (2)
H1100.40970.60310.53450.077*
C1110.3188 (8)0.5580 (7)0.6388 (6)0.069 (2)
H1110.33050.62240.65680.083*
C1120.2531 (7)0.4745 (7)0.6857 (5)0.060 (2)
H1120.21850.48270.73490.072*
C2010.3904 (6)0.2312 (5)0.8937 (4)0.0448 (18)
C2020.5033 (6)0.2505 (6)0.9013 (4)0.053 (2)
H2020.55790.26580.85700.064*
C2030.5363 (8)0.2477 (6)0.9718 (5)0.066 (2)
H2030.61290.26020.97580.079*
C2040.4576 (8)0.2267 (7)1.0364 (5)0.072 (3)
H2040.48040.22671.08490.086*
C2050.3439 (9)0.2053 (7)1.0310 (5)0.074 (3)
H2050.29000.18841.07560.089*
C2060.3110 (7)0.2089 (6)0.9600 (4)0.060 (2)
H2060.23420.19630.95620.073*
C2070.4620 (6)0.3491 (6)0.7494 (4)0.0446 (18)
C2080.5408 (5)0.3389 (6)0.6880 (4)0.0462 (18)
H2080.53740.27560.66920.055*
C2090.6234 (6)0.4213 (7)0.6548 (5)0.056 (2)
H2090.67670.41450.61350.068*
C2100.6281 (7)0.5149 (7)0.6825 (5)0.070 (3)
H2100.68440.57130.65930.083*
C2110.5522 (8)0.5262 (7)0.7431 (6)0.072 (3)
H2110.55630.58970.76180.086*
C2120.4681 (7)0.4419 (6)0.7769 (5)0.058 (2)
H2120.41540.44870.81860.069*
C3010.5010 (6)0.0138 (6)0.7748 (4)0.0418 (17)
C3020.5909 (6)0.0976 (6)0.7612 (4)0.053 (2)
H3020.57750.16200.75480.064*
C3030.6999 (6)0.0886 (7)0.7567 (5)0.062 (2)
H3030.76000.14650.74810.074*
C3040.7200 (6)0.0057 (8)0.7648 (4)0.060 (2)
H3040.79410.01230.76140.072*
C3050.6329 (7)0.0893 (7)0.7777 (4)0.057 (2)
H3050.64720.15340.78240.068*
C3060.5232 (6)0.0807 (6)0.7838 (4)0.052 (2)
H3060.46360.13890.79410.063*
C3070.3001 (6)0.0081 (6)0.8841 (4)0.0466 (19)
C3080.1853 (6)0.0207 (7)0.9072 (5)0.071 (3)
H3080.13900.01060.87120.085*
C3090.1405 (7)0.0481 (8)0.9833 (5)0.084 (3)
H3090.06300.05740.99870.101*
C3100.2066 (7)0.0621 (7)1.0376 (5)0.071 (3)
H3100.17530.07951.08950.085*
C3110.3204 (6)0.0499 (6)1.0135 (4)0.059 (2)
H3110.36640.05981.04970.071*
C3120.3670 (6)0.0239 (6)0.9383 (4)0.0493 (19)
H3120.44430.01670.92310.059*
C4070.1952 (5)0.1127 (6)0.5980 (4)0.0473 (19)
C4080.2121 (6)0.0529 (6)0.5294 (4)0.056 (2)
H4080.21110.01550.52950.067*
C4090.2304 (8)0.0951 (8)0.4601 (5)0.071 (2)
H4090.24100.05470.41370.085*
C4100.2332 (8)0.1947 (8)0.4586 (6)0.074 (3)
H4100.24640.22230.41170.088*
C4110.2163 (7)0.2534 (7)0.5275 (7)0.076 (3)
H4110.21760.32160.52690.091*
C4120.1977 (7)0.2145 (7)0.5966 (5)0.064 (2)
H4120.18660.25570.64270.076*
O10.4427 (5)0.0485 (4)0.6132 (3)0.0596 (14)
O20.4118 (4)0.1706 (4)0.5351 (3)0.0514 (13)
O30.1320 (7)0.1339 (6)0.4883 (4)0.100 (2)
O40.0633 (4)0.2499 (4)0.5440 (3)0.0587 (14)
C40.3334 (6)0.1604 (5)0.6621 (4)0.0390 (17)
H40.353 (4)0.2318 (16)0.654 (3)0.011 (13)*
C50.4024 (5)0.1187 (6)0.6027 (4)0.0411 (17)
C60.4691 (7)0.1344 (7)0.4686 (4)0.063 (2)
H6A0.44170.06120.46850.075*
H6B0.55020.15090.46860.075*
C70.4415 (9)0.1883 (8)0.4004 (5)0.088 (3)
H7A0.47710.16770.35370.131*
H7B0.36090.17140.40170.131*
H7C0.46870.26050.40180.131*
C80.0453 (6)0.1001 (6)0.6211 (4)0.054 (2)
H8A0.01630.02920.61260.064*
H8B0.01790.12370.64640.064*
C90.0851 (7)0.1581 (7)0.5455 (5)0.059 (2)
C100.0925 (8)0.3085 (7)0.4698 (5)0.074 (3)
H10A0.04830.27370.43300.088*
H10B0.17220.31690.45010.088*
C110.0689 (8)0.4077 (7)0.4797 (6)0.093 (3)
H11A0.08790.44810.43070.140*
H11B0.01020.39860.49890.140*
H11C0.11340.44160.51590.140*
O50.2422 (14)0.5220 (9)0.8989 (9)0.107 (5)0.5
C120.190 (5)0.564 (4)0.9732 (15)0.25 (3)0.5
O60.5573 (15)0.4914 (9)1.0173 (8)0.101 (5)0.5
C130.665 (6)0.4857 (18)0.979 (2)0.28 (4)0.5
O70.3475 (17)0.5078 (11)1.0734 (10)0.113 (6)0.5
C4010.0507 (14)0.1668 (14)0.7345 (10)0.039 (5)*0.5
C4020.0572 (18)0.2344 (16)0.7933 (12)0.083 (6)*0.5
H4020.12410.23270.81300.099*0.5
C4030.044 (2)0.3058 (19)0.8217 (15)0.108 (7)*0.5
H4030.04420.35170.86330.129*0.5
C4040.137 (2)0.3123 (17)0.7935 (12)0.085 (6)*0.5
H4040.19970.36630.81200.102*0.5
C4050.1458 (16)0.2471 (15)0.7416 (14)0.055 (5)*0.5
H4050.21330.25010.72230.065*0.5
C4060.047 (2)0.1700 (17)0.7148 (14)0.065 (8)*0.5
H4060.05280.11730.68030.077*0.5
C41A0.0372 (18)0.1384 (16)0.7366 (12)0.055 (7)*0.5
C42A0.0192 (18)0.1861 (15)0.8085 (12)0.079 (6)*0.5
H42A0.07850.17770.83730.095*0.5
C43A0.093 (2)0.2514 (18)0.8423 (15)0.103 (7)*0.5
H43A0.10970.27860.89380.123*0.5
C44A0.171 (2)0.2690 (18)0.7943 (14)0.083 (6)*0.5
H44A0.24100.31230.81370.100*0.5
C45A0.1536 (17)0.2269 (15)0.7166 (12)0.062 (6)*0.5
H45A0.20950.24220.68530.074*0.5
C46A0.0517 (15)0.1634 (13)0.6908 (12)0.037 (5)*0.5
H46A0.03800.13390.64000.045*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ir10.02378 (16)0.0610 (2)0.03666 (18)0.00846 (12)0.00368 (11)0.00960 (13)
P10.0282 (10)0.0686 (14)0.0392 (11)0.0161 (9)0.0022 (8)0.0081 (9)
P20.0285 (9)0.0612 (13)0.0326 (10)0.0099 (9)0.0029 (8)0.0066 (9)
P30.0307 (10)0.0554 (12)0.0360 (10)0.0092 (9)0.0059 (8)0.0092 (9)
P40.0311 (10)0.0633 (13)0.0418 (11)0.0025 (9)0.0069 (9)0.0082 (9)
Cl10.0271 (9)0.0823 (14)0.0511 (12)0.0104 (9)0.0032 (8)0.0146 (10)
Cl20.170 (4)0.105 (3)0.150 (3)0.013 (2)0.049 (3)0.001 (2)
C10.028 (4)0.055 (4)0.034 (4)0.014 (3)0.001 (3)0.004 (3)
C20.039 (4)0.070 (5)0.034 (4)0.018 (4)0.000 (3)0.009 (4)
C30.055 (5)0.049 (5)0.055 (5)0.008 (4)0.025 (4)0.005 (4)
C1010.034 (4)0.075 (6)0.052 (5)0.022 (4)0.001 (4)0.007 (4)
C1020.048 (5)0.117 (8)0.059 (6)0.038 (5)0.002 (4)0.010 (5)
C1030.058 (6)0.124 (9)0.088 (8)0.048 (6)0.001 (6)0.025 (6)
C1040.046 (5)0.113 (9)0.115 (9)0.044 (6)0.001 (6)0.003 (7)
C1050.058 (6)0.137 (10)0.078 (7)0.041 (6)0.018 (5)0.004 (7)
C1060.052 (5)0.110 (8)0.059 (6)0.036 (5)0.003 (5)0.007 (5)
C1070.037 (4)0.055 (5)0.047 (5)0.016 (4)0.006 (4)0.009 (4)
C1080.034 (4)0.056 (5)0.040 (5)0.010 (4)0.003 (3)0.015 (4)
C1090.050 (5)0.076 (7)0.056 (5)0.025 (5)0.006 (4)0.019 (5)
C1100.051 (5)0.068 (7)0.068 (6)0.009 (4)0.009 (5)0.023 (5)
C1110.072 (6)0.055 (6)0.078 (7)0.015 (5)0.010 (5)0.009 (5)
C1120.063 (5)0.071 (6)0.053 (5)0.029 (5)0.012 (4)0.000 (5)
C2010.045 (4)0.058 (5)0.030 (4)0.012 (4)0.004 (3)0.003 (3)
C2020.044 (5)0.075 (6)0.042 (5)0.016 (4)0.008 (4)0.000 (4)
C2030.064 (6)0.081 (6)0.058 (6)0.018 (5)0.027 (5)0.006 (5)
C2040.085 (7)0.077 (6)0.057 (6)0.017 (5)0.034 (6)0.006 (5)
C2050.091 (7)0.098 (7)0.038 (5)0.036 (6)0.006 (5)0.003 (5)
C2060.059 (5)0.080 (6)0.044 (5)0.023 (5)0.008 (4)0.004 (4)
C2070.035 (4)0.052 (5)0.044 (4)0.007 (3)0.009 (4)0.011 (4)
C2080.031 (4)0.058 (5)0.045 (4)0.006 (4)0.003 (4)0.013 (4)
C2090.038 (4)0.072 (6)0.053 (5)0.003 (4)0.013 (4)0.012 (4)
C2100.056 (6)0.077 (7)0.060 (6)0.011 (5)0.012 (5)0.018 (5)
C2110.071 (6)0.063 (6)0.079 (7)0.007 (5)0.020 (6)0.004 (5)
C2120.056 (5)0.056 (6)0.057 (5)0.005 (4)0.008 (4)0.008 (4)
C3010.035 (4)0.058 (5)0.034 (4)0.016 (4)0.006 (3)0.002 (3)
C3020.039 (4)0.065 (5)0.056 (5)0.013 (4)0.011 (4)0.008 (4)
C3030.028 (4)0.089 (7)0.058 (5)0.001 (4)0.001 (4)0.006 (5)
C3040.032 (4)0.106 (7)0.048 (5)0.027 (5)0.008 (4)0.000 (5)
C3050.050 (5)0.080 (6)0.050 (5)0.034 (5)0.010 (4)0.001 (4)
C3060.047 (5)0.071 (6)0.039 (4)0.017 (4)0.005 (4)0.005 (4)
C3070.036 (4)0.064 (5)0.037 (4)0.010 (4)0.007 (3)0.011 (4)
C3080.036 (5)0.110 (7)0.060 (6)0.020 (5)0.003 (4)0.031 (5)
C3090.041 (5)0.136 (9)0.062 (6)0.025 (5)0.017 (5)0.045 (6)
C3100.056 (5)0.108 (7)0.045 (5)0.027 (5)0.005 (4)0.028 (5)
C3110.045 (5)0.089 (6)0.042 (5)0.019 (4)0.006 (4)0.012 (4)
C3120.034 (4)0.073 (5)0.038 (4)0.014 (4)0.003 (3)0.011 (4)
C4070.023 (4)0.061 (5)0.057 (5)0.006 (3)0.010 (3)0.002 (4)
C4080.051 (5)0.070 (6)0.046 (5)0.012 (4)0.011 (4)0.000 (4)
C4090.074 (6)0.085 (7)0.055 (6)0.019 (5)0.019 (5)0.002 (5)
C4100.070 (6)0.092 (8)0.066 (6)0.026 (6)0.019 (5)0.022 (6)
C4110.060 (6)0.069 (6)0.106 (9)0.022 (5)0.018 (6)0.022 (6)
C4120.053 (5)0.070 (6)0.066 (6)0.019 (4)0.002 (4)0.008 (5)
O10.066 (4)0.072 (4)0.054 (3)0.038 (3)0.015 (3)0.004 (3)
O20.055 (3)0.064 (3)0.035 (3)0.022 (3)0.004 (2)0.006 (2)
O30.144 (7)0.126 (6)0.052 (4)0.081 (6)0.010 (4)0.003 (4)
O40.052 (3)0.072 (4)0.051 (3)0.016 (3)0.009 (3)0.008 (3)
C40.038 (4)0.045 (5)0.034 (4)0.010 (3)0.012 (3)0.008 (3)
C50.029 (4)0.058 (5)0.038 (4)0.011 (4)0.007 (3)0.002 (4)
C60.050 (5)0.097 (7)0.042 (5)0.023 (5)0.002 (4)0.016 (4)
C70.101 (8)0.117 (8)0.039 (5)0.022 (7)0.001 (5)0.008 (5)
C80.039 (4)0.066 (5)0.054 (5)0.012 (4)0.008 (4)0.017 (4)
C90.044 (5)0.076 (6)0.059 (6)0.019 (4)0.014 (4)0.007 (5)
C100.073 (6)0.088 (7)0.057 (6)0.019 (5)0.016 (5)0.024 (5)
C110.080 (7)0.079 (7)0.116 (9)0.011 (6)0.029 (6)0.037 (6)
O50.156 (15)0.052 (8)0.109 (12)0.022 (9)0.004 (10)0.027 (8)
C120.49 (8)0.31 (5)0.030 (15)0.29 (6)0.03 (3)0.00 (2)
O60.182 (18)0.053 (8)0.064 (10)0.025 (10)0.004 (10)0.029 (7)
C130.59 (10)0.038 (13)0.09 (2)0.02 (3)0.21 (4)0.016 (15)
O70.164 (16)0.067 (10)0.078 (11)0.018 (10)0.002 (11)0.006 (9)
Geometric parameters (Å, º) top
Ir1—C42.046 (7)C304—H3040.9400
Ir1—C82.163 (7)C305—C3061.385 (10)
Ir1—C12.279 (6)C305—H3050.9400
Ir1—P42.306 (2)C306—H3060.9400
Ir1—P12.318 (2)C307—C3121.392 (9)
Ir1—Cl12.4607 (18)C307—C3081.395 (10)
P1—C1071.831 (7)C308—C3091.378 (11)
P1—C1011.840 (7)C308—H3080.9400
P1—C21.850 (7)C309—C3101.380 (11)
P2—C11.788 (7)C309—H3090.9400
P2—C21.794 (7)C310—C3111.385 (11)
P2—C2011.799 (7)C310—H3100.9400
P2—C2071.823 (7)C311—C3121.366 (10)
P3—C11.789 (7)C311—H3110.9400
P3—C3011.799 (7)C312—H3120.9400
P3—C31.800 (7)C407—C4081.388 (10)
P3—C3071.816 (7)C407—C4121.404 (11)
P4—C41A1.80 (2)C408—C4091.396 (11)
P4—C4071.832 (8)C408—H4080.9400
P4—C31.850 (7)C409—C4101.375 (12)
P4—C4011.871 (18)C409—H4090.9400
C1—C41.507 (9)C410—C4111.385 (13)
C2—H2A0.9800C410—H4100.9400
C2—H2B0.9800C411—C4121.372 (12)
C3—H3A0.9800C411—H4110.9400
C3—H3B0.9800C412—H4120.9400
C101—C1021.371 (10)O1—C51.203 (8)
C101—C1061.378 (11)O2—C51.332 (8)
C102—C1031.364 (11)O2—C61.461 (8)
C102—H1020.9400O3—C91.199 (10)
C103—C1041.350 (13)O4—C91.348 (10)
C103—H1030.9400O4—C101.453 (9)
C104—C1051.366 (13)C4—C51.488 (10)
C104—H1040.9400C4—H40.947 (19)
C105—C1061.382 (12)C6—C71.500 (11)
C105—H1050.9400C6—H6A0.9800
C106—H1060.9400C6—H6B0.9800
C107—C1081.373 (10)C7—H7A0.9700
C107—C1121.395 (11)C7—H7B0.9700
C108—C1091.380 (10)C7—H7C0.9700
C108—H1080.9400C8—C91.475 (11)
C109—C1101.377 (12)C8—H8A0.9800
C109—H1090.9400C8—H8B0.9800
C110—C1111.363 (12)C10—C111.472 (13)
C110—H1100.9400C10—H10A0.9800
C111—C1121.388 (12)C10—H10B0.9800
C111—H1110.9400C11—H11A0.9700
C112—H1120.9400C11—H11B0.9700
C201—C2021.391 (10)C11—H11C0.9700
C201—C2061.393 (10)O5—C121.41 (3)
C202—C2031.366 (10)O6—C131.39 (6)
C202—H2020.9400O6—O6i1.60 (3)
C203—C2041.366 (12)C13—O7i0.96 (5)
C203—H2030.9400O7—C13i0.96 (5)
C204—C2051.390 (12)C401—C4061.30 (3)
C204—H2040.9400C401—C4021.38 (3)
C205—C2061.375 (11)C402—C4031.40 (3)
C205—H2050.9400C402—H4020.9400
C206—H2060.9400C403—C4041.32 (3)
C207—C2121.376 (10)C403—H4030.9400
C207—C2081.394 (10)C404—C4051.28 (3)
C208—C2091.371 (10)C404—H4040.9400
C208—H2080.9400C405—C4061.42 (3)
C209—C2101.389 (12)C405—H4050.9400
C209—H2090.9400C406—H4060.9400
C210—C2111.368 (12)C41A—C42A1.36 (3)
C210—H2100.9400C41A—C46A1.45 (3)
C211—C2121.400 (12)C42A—C43A1.49 (3)
C211—H2110.9400C42A—H42A0.9400
C212—H2120.9400C43A—C44A1.36 (3)
C301—C3021.382 (10)C43A—H43A0.9400
C301—C3061.393 (10)C44A—C45A1.43 (3)
C302—C3031.381 (10)C44A—H44A0.9400
C302—H3020.9400C45A—C46A1.36 (3)
C303—C3041.378 (11)C45A—H45A0.9400
C303—H3030.9400C46A—H46A0.9400
C304—C3051.359 (11)
C4—Ir1—C8120.8 (3)C306—C301—P3118.3 (6)
C4—Ir1—C140.3 (2)C303—C302—C301121.4 (8)
C8—Ir1—C1161.1 (3)C303—C302—H302119.3
C4—Ir1—P493.6 (2)C301—C302—H302119.3
C8—Ir1—P493.0 (2)C304—C303—C302119.6 (8)
C1—Ir1—P489.61 (18)C304—C303—H303120.2
C4—Ir1—P188.5 (2)C302—C303—H303120.2
C8—Ir1—P191.2 (2)C305—C304—C303120.1 (7)
C1—Ir1—P188.02 (18)C305—C304—H304120.0
P4—Ir1—P1173.53 (7)C303—C304—H304120.0
C4—Ir1—Cl1152.49 (19)C304—C305—C306120.7 (8)
C8—Ir1—Cl185.9 (2)C304—C305—H305119.7
C1—Ir1—Cl1112.78 (17)C306—C305—H305119.7
P4—Ir1—Cl191.38 (7)C305—C306—C301120.2 (8)
P1—Ir1—Cl184.00 (7)C305—C306—H306119.9
C107—P1—C101101.9 (3)C301—C306—H306119.9
C107—P1—C2103.5 (3)C312—C307—C308119.4 (7)
C101—P1—C2102.5 (3)C312—C307—P3121.5 (5)
C107—P1—Ir1121.5 (3)C308—C307—P3118.9 (5)
C101—P1—Ir1123.4 (3)C309—C308—C307119.2 (7)
C2—P1—Ir1100.7 (3)C309—C308—H308120.4
C1—P2—C2107.0 (3)C307—C308—H308120.4
C1—P2—C201118.4 (3)C308—C309—C310121.7 (8)
C2—P2—C201106.6 (3)C308—C309—H309119.2
C1—P2—C207112.4 (3)C310—C309—H309119.2
C2—P2—C207108.0 (3)C309—C310—C311118.3 (7)
C201—P2—C207104.0 (3)C309—C310—H310120.9
C1—P3—C301117.2 (3)C311—C310—H310120.9
C1—P3—C3110.5 (3)C312—C311—C310121.4 (7)
C301—P3—C3105.7 (4)C312—C311—H311119.3
C1—P3—C307110.7 (3)C310—C311—H311119.3
C301—P3—C307105.7 (3)C311—C312—C307120.0 (7)
C3—P3—C307106.5 (4)C311—C312—H312120.0
C41A—P4—C407104.1 (7)C307—C312—H312120.0
C41A—P4—C3111.6 (7)C408—C407—C412119.5 (7)
C407—P4—C3100.5 (3)C408—C407—P4120.4 (6)
C407—P4—C40196.0 (6)C412—C407—P4120.1 (6)
C3—P4—C401102.3 (6)C407—C408—C409119.4 (8)
C41A—P4—Ir1108.0 (7)C407—C408—H408120.3
C407—P4—Ir1123.5 (3)C409—C408—H408120.3
C3—P4—Ir1108.9 (2)C410—C409—C408121.2 (8)
C401—P4—Ir1122.0 (6)C410—C409—H409119.4
C4—C1—P2113.5 (5)C408—C409—H409119.4
C4—C1—P3121.9 (5)C409—C410—C411118.6 (9)
P2—C1—P3120.6 (4)C409—C410—H410120.7
C4—C1—Ir161.5 (3)C411—C410—H410120.7
P2—C1—Ir1112.4 (3)C412—C411—C410121.7 (9)
P3—C1—Ir1111.3 (3)C412—C411—H411119.2
P2—C2—P1111.0 (4)C410—C411—H411119.2
P2—C2—H2A109.4C411—C412—C407119.5 (8)
P1—C2—H2A109.4C411—C412—H412120.2
P2—C2—H2B109.4C407—C412—H412120.2
P1—C2—H2B109.4C5—O2—C6116.8 (6)
H2A—C2—H2B108.0C9—O4—C10115.6 (7)
P3—C3—P4113.8 (4)C5—C4—C1121.8 (6)
P3—C3—H3A108.8C5—C4—Ir1126.1 (5)
P4—C3—H3A108.8C1—C4—Ir178.2 (4)
P3—C3—H3B108.8C5—C4—H4110 (3)
P4—C3—H3B108.8C1—C4—H4106 (3)
H3A—C3—H3B107.7Ir1—C4—H4111 (3)
C102—C101—C106117.6 (7)O1—C5—O2124.9 (6)
C102—C101—P1119.2 (6)O1—C5—C4125.8 (6)
C106—C101—P1123.2 (6)O2—C5—C4109.4 (6)
C103—C102—C101121.9 (9)O2—C6—C7104.9 (6)
C103—C102—H102119.1O2—C6—H6A110.8
C101—C102—H102119.1C7—C6—H6A110.8
C104—C103—C102120.2 (9)O2—C6—H6B110.8
C104—C103—H103119.9C7—C6—H6B110.8
C102—C103—H103119.9H6A—C6—H6B108.8
C103—C104—C105119.7 (8)C6—C7—H7A109.5
C103—C104—H104120.2C6—C7—H7B109.5
C105—C104—H104120.2H7A—C7—H7B109.5
C104—C105—C106120.3 (9)C6—C7—H7C109.5
C104—C105—H105119.9H7A—C7—H7C109.5
C106—C105—H105119.9H7B—C7—H7C109.5
C101—C106—C105120.3 (8)C9—C8—Ir1117.5 (5)
C101—C106—H106119.8C9—C8—H8A107.9
C105—C106—H106119.8Ir1—C8—H8A107.9
C108—C107—C112119.1 (7)C9—C8—H8B107.9
C108—C107—P1121.5 (6)Ir1—C8—H8B107.9
C112—C107—P1119.4 (6)H8A—C8—H8B107.2
C107—C108—C109120.1 (8)O3—C9—O4118.8 (8)
C107—C108—H108119.9O3—C9—C8128.8 (9)
C109—C108—H108119.9O4—C9—C8112.4 (8)
C110—C109—C108120.6 (8)O4—C10—C11108.2 (8)
C110—C109—H109119.7O4—C10—H10A110.1
C108—C109—H109119.7C11—C10—H10A110.1
C111—C110—C109120.0 (8)O4—C10—H10B110.1
C111—C110—H110120.0C11—C10—H10B110.1
C109—C110—H110120.0H10A—C10—H10B108.4
C110—C111—C112119.9 (9)C10—C11—H11A109.5
C110—C111—H111120.0C10—C11—H11B109.5
C112—C111—H111120.0H11A—C11—H11B109.5
C111—C112—C107120.1 (8)C10—C11—H11C109.5
C111—C112—H112119.9H11A—C11—H11C109.5
C107—C112—H112119.9H11B—C11—H11C109.5
C202—C201—C206118.4 (7)C13—O6—O6i128 (3)
C202—C201—P2119.3 (5)O7i—C13—O6103 (7)
C206—C201—P2122.2 (6)C406—C401—C402118 (2)
C203—C202—C201121.3 (8)C406—C401—P4117.2 (16)
C203—C202—H202119.4C402—C401—P4123.9 (14)
C201—C202—H202119.4C401—C402—C403115 (2)
C204—C203—C202119.8 (8)C401—C402—H402122.5
C204—C203—H203120.1C403—C402—H402122.5
C202—C203—H203120.1C404—C403—C402124 (2)
C203—C204—C205120.5 (8)C404—C403—H403118.1
C203—C204—H204119.7C402—C403—H403118.1
C205—C204—H204119.7C405—C404—C403122 (2)
C206—C205—C204119.5 (9)C405—C404—H404119.2
C206—C205—H205120.2C403—C404—H404119.2
C204—C205—H205120.2C404—C405—C406116 (2)
C205—C206—C201120.5 (8)C404—C405—H405122.1
C205—C206—H206119.8C406—C405—H405122.1
C201—C206—H206119.8C401—C406—C405125 (2)
C212—C207—C208119.7 (7)C401—C406—H406117.7
C212—C207—P2116.7 (6)C405—C406—H406117.7
C208—C207—P2123.5 (6)C42A—C41A—C46A118 (2)
C209—C208—C207120.1 (8)C42A—C41A—P4124.6 (17)
C209—C208—H208120.0C46A—C41A—P4117.3 (15)
C207—C208—H208120.0C41A—C42A—C43A121 (2)
C208—C209—C210119.8 (8)C41A—C42A—H42A119.5
C208—C209—H209120.1C43A—C42A—H42A119.5
C210—C209—H209120.1C44A—C43A—C42A116 (2)
C211—C210—C209121.0 (8)C44A—C43A—H43A122.1
C211—C210—H210119.5C42A—C43A—H43A122.1
C209—C210—H210119.5C43A—C44A—C45A125 (2)
C210—C211—C212119.0 (9)C43A—C44A—H44A117.4
C210—C211—H211120.5C45A—C44A—H44A117.4
C212—C211—H211120.5C46A—C45A—C44A116 (2)
C207—C212—C211120.4 (8)C46A—C45A—H45A122.1
C207—C212—H212119.8C44A—C45A—H45A122.1
C211—C212—H212119.8C45A—C46A—C41A124 (2)
C302—C301—C306118.1 (6)C45A—C46A—H46A118.0
C302—C301—P3123.6 (5)C41A—C46A—H46A118.0
C2—P2—C1—C477.0 (5)C307—P3—C301—C302106.7 (6)
C201—P2—C1—C4162.8 (5)C1—P3—C301—C306163.7 (5)
C207—P2—C1—C441.4 (5)C3—P3—C301—C30640.2 (6)
C2—P2—C1—P3124.9 (4)C307—P3—C301—C30672.5 (6)
C201—P2—C1—P34.7 (5)C306—C301—C302—C3030.2 (11)
C207—P2—C1—P3116.6 (4)P3—C301—C302—C303179.0 (6)
C2—P2—C1—Ir19.6 (4)C301—C302—C303—C3041.0 (12)
C201—P2—C1—Ir1129.8 (3)C302—C303—C304—C3050.5 (12)
C207—P2—C1—Ir1108.9 (3)C303—C304—C305—C3060.9 (12)
C301—P3—C1—C479.1 (6)C304—C305—C306—C3011.7 (11)
C3—P3—C1—C442.0 (6)C302—C301—C306—C3051.2 (10)
C307—P3—C1—C4159.7 (5)P3—C301—C306—C305179.6 (6)
C301—P3—C1—P277.1 (5)C1—P3—C307—C312124.5 (6)
C3—P3—C1—P2161.8 (4)C301—P3—C307—C3123.4 (7)
C307—P3—C1—P244.1 (5)C3—P3—C307—C312115.5 (7)
C301—P3—C1—Ir1147.9 (3)C1—P3—C307—C30859.7 (8)
C3—P3—C1—Ir126.9 (4)C301—P3—C307—C308172.4 (7)
C307—P3—C1—Ir190.8 (4)C3—P3—C307—C30860.4 (8)
C1—P2—C2—P139.1 (5)C312—C307—C308—C3090.3 (14)
C201—P2—C2—P1166.6 (4)P3—C307—C308—C309176.2 (8)
C207—P2—C2—P182.2 (5)C307—C308—C309—C3100.8 (16)
C107—P1—C2—P277.5 (5)C308—C309—C310—C3111.2 (16)
C101—P1—C2—P2176.8 (4)C309—C310—C311—C3120.5 (14)
Ir1—P1—C2—P248.8 (4)C310—C311—C312—C3070.6 (13)
C1—P3—C3—P421.3 (6)C308—C307—C312—C3111.0 (12)
C301—P3—C3—P4149.0 (4)P3—C307—C312—C311176.8 (6)
C307—P3—C3—P498.9 (4)C41A—P4—C407—C408123.0 (9)
C41A—P4—C3—P3112.8 (8)C3—P4—C407—C408121.4 (6)
C407—P4—C3—P3137.3 (4)C401—P4—C407—C408134.9 (8)
C401—P4—C3—P3124.2 (7)Ir1—P4—C407—C4080.3 (7)
Ir1—P4—C3—P36.2 (5)C41A—P4—C407—C41257.1 (9)
C107—P1—C101—C10245.5 (8)C3—P4—C407—C41258.5 (6)
C2—P1—C101—C102152.5 (7)C401—P4—C407—C41245.2 (8)
Ir1—P1—C101—C10295.6 (7)Ir1—P4—C407—C412179.6 (5)
C107—P1—C101—C106135.4 (8)C412—C407—C408—C4090.4 (11)
C2—P1—C101—C10628.4 (9)P4—C407—C408—C409179.6 (6)
Ir1—P1—C101—C10683.6 (8)C407—C408—C409—C4100.6 (12)
C106—C101—C102—C1032.6 (15)C408—C409—C410—C4110.6 (13)
P1—C101—C102—C103178.3 (8)C409—C410—C411—C4120.4 (14)
C101—C102—C103—C1041.2 (17)C410—C411—C412—C4070.2 (13)
C102—C103—C104—C1050.9 (18)C408—C407—C412—C4110.2 (11)
C103—C104—C105—C1061.4 (17)P4—C407—C412—C411179.9 (6)
C102—C101—C106—C1052.0 (15)P2—C1—C4—C5130.9 (6)
P1—C101—C106—C105178.9 (8)P3—C1—C4—C526.8 (9)
C104—C105—C106—C1010.0 (17)Ir1—C1—C4—C5125.4 (7)
C101—P1—C107—C108126.6 (6)P2—C1—C4—Ir1103.7 (4)
C2—P1—C107—C108127.3 (6)P3—C1—C4—Ir198.5 (5)
Ir1—P1—C107—C10815.5 (7)C6—O2—C5—O14.3 (10)
C101—P1—C107—C11253.6 (6)C6—O2—C5—C4175.0 (6)
C2—P1—C107—C11252.5 (6)C1—C4—C5—O115.8 (11)
Ir1—P1—C107—C112164.3 (5)Ir1—C4—C5—O183.0 (8)
C112—C107—C108—C1092.2 (10)C1—C4—C5—O2164.9 (6)
P1—C107—C108—C109177.6 (5)Ir1—C4—C5—O296.2 (6)
C107—C108—C109—C1101.3 (11)C5—O2—C6—C7165.9 (7)
C108—C109—C110—C1110.7 (12)C10—O4—C9—O34.3 (11)
C109—C110—C111—C1121.0 (12)C10—O4—C9—C8175.6 (7)
C110—C111—C112—C1072.0 (12)Ir1—C8—C9—O384.8 (11)
C108—C107—C112—C1112.6 (11)Ir1—C8—C9—O495.3 (7)
P1—C107—C112—C111177.2 (6)C9—O4—C10—C11177.0 (7)
C1—P2—C201—C20290.5 (7)O6i—O6—C13—O7i2 (4)
C2—P2—C201—C202149.0 (6)C407—P4—C401—C40679.1 (17)
C207—P2—C201—C20235.1 (7)C3—P4—C401—C406178.8 (16)
C1—P2—C201—C20693.7 (7)Ir1—P4—C401—C40657.0 (18)
C2—P2—C201—C20626.8 (8)C407—P4—C401—C402109.3 (17)
C207—P2—C201—C206140.8 (7)C3—P4—C401—C4027.2 (19)
C206—C201—C202—C2030.1 (12)Ir1—P4—C401—C402114.6 (17)
P2—C201—C202—C203176.1 (6)C406—C401—C402—C4035 (3)
C201—C202—C203—C2040.7 (13)P4—C401—C402—C403176.6 (16)
C202—C203—C204—C2051.8 (14)C401—C402—C403—C4043 (4)
C203—C204—C205—C2062.4 (14)C402—C403—C404—C4056 (4)
C204—C205—C206—C2011.8 (13)C403—C404—C405—C4062 (4)
C202—C201—C206—C2050.7 (12)C402—C401—C406—C40510 (3)
P2—C201—C206—C205176.5 (7)P4—C401—C406—C405178.3 (17)
C1—P2—C207—C212166.0 (5)C404—C405—C406—C4016 (3)
C2—P2—C207—C21248.1 (6)C407—P4—C41A—C42A126.6 (19)
C201—P2—C207—C21264.8 (6)C3—P4—C41A—C42A19 (2)
C1—P2—C207—C20816.9 (7)Ir1—P4—C41A—C42A101 (2)
C2—P2—C207—C208134.7 (6)C407—P4—C41A—C46A44.6 (16)
C201—P2—C207—C208112.4 (6)C3—P4—C41A—C46A152.1 (13)
C212—C207—C208—C2090.5 (10)Ir1—P4—C41A—C46A88.2 (15)
P2—C207—C208—C209177.6 (5)C46A—C41A—C42A—C43A8 (3)
C207—C208—C209—C2100.2 (10)P4—C41A—C42A—C43A179.0 (17)
C208—C209—C210—C2110.7 (12)C41A—C42A—C43A—C44A7 (3)
C209—C210—C211—C2120.6 (13)C42A—C43A—C44A—C45A3 (4)
C208—C207—C212—C2110.6 (11)C43A—C44A—C45A—C46A1 (3)
P2—C207—C212—C211177.9 (6)C44A—C45A—C46A—C41A1 (3)
C210—C211—C212—C2070.1 (12)C42A—C41A—C46A—C45A4 (3)
C1—P3—C301—C30217.1 (7)P4—C41A—C46A—C45A175.7 (16)
C3—P3—C301—C302140.7 (6)
Symmetry code: (i) x1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O5ii0.982.223.139 (15)156
C3—H3A···Cl20.982.913.693 (8)137
C3—H3B···O10.982.402.895 (10)111
C102—H102···O40.942.483.263 (11)141
C212—H212···O5ii0.942.543.445 (18)163
C306—H306···Cl20.942.573.491 (9)167
C308—H308···Cl10.942.563.464 (8)162
C408—H408···O30.942.233.046 (10)145
Symmetry code: (ii) x, y1, z.
(Bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4P,C,C',P')dichloridoiridium(III) chloride–methanol–water (1/1/2) (6) top
Crystal data top
[IrCl2(C55H50O2P4)]Cl·CH4O·2H2OZ = 2
Mr = 1233.45F(000) = 1244
Triclinic, P1Dx = 1.512 Mg m3
a = 11.2371 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.9144 (2) ÅCell parameters from 58878 reflections
c = 19.2371 (3) Åθ = 1.0–25.3°
α = 89.439 (1)°µ = 2.78 mm1
β = 77.863 (1)°T = 233 K
γ = 83.114 (1)°Prism, light yellow
V = 2709.27 (8) Å30.11 × 0.05 × 0.03 mm
Data collection top
Nonius KappaCCD
diffractometer
8083 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
Graphite monochromatorθmax = 25.0°, θmin = 1.9°
phi– and ω–scansh = 1313
17984 measured reflectionsk = 1515
9526 independent reflectionsl = 2222
Refinement top
Refinement on F21 restraint
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073 w = 1/[σ2(Fo2) + (0.0253P)2 + 3.0412P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
9526 reflectionsΔρmax = 0.75 e Å3
626 parametersΔρmin = 1.01 e Å3
Special details top

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.

Refinement. Hydrogen atom at C4 found and refined isotropically with bond restraint (d = 96 pm). Hydrogens at solvent water and methanol could not be exact localized and were omitted.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ir10.20012 (2)0.37531 (2)0.74968 (2)0.02861 (6)
P10.20027 (9)0.20029 (8)0.72614 (6)0.0298 (2)
P20.46847 (9)0.22736 (8)0.70579 (6)0.0308 (2)
P30.46936 (10)0.46722 (9)0.73724 (6)0.0317 (2)
P40.20277 (10)0.55291 (8)0.76838 (6)0.0324 (2)
Cl10.01947 (9)0.39399 (9)0.79680 (6)0.0416 (3)
Cl20.16469 (10)0.43456 (9)0.63301 (5)0.0412 (3)
Cl30.44061 (18)0.83094 (12)0.72218 (9)0.0876 (5)
O10.3698 (3)0.1714 (3)0.85456 (16)0.0483 (8)
O20.2473 (3)0.2825 (2)0.93555 (14)0.0423 (7)
C10.3924 (4)0.3490 (3)0.7501 (2)0.0316 (9)
C20.3590 (4)0.1363 (3)0.7100 (2)0.0347 (10)
H2A0.36760.08700.74820.042*
H2B0.37670.09660.66510.042*
C30.3579 (4)0.5712 (3)0.7202 (2)0.0351 (10)
H3A0.35970.57380.66910.042*
H3B0.37920.63790.73480.042*
C40.3107 (4)0.3481 (3)0.8234 (2)0.0306 (9)
H40.313 (3)0.406 (2)0.8533 (16)0.021 (9)*
C50.3146 (4)0.2571 (4)0.8709 (2)0.0355 (10)
C60.2445 (5)0.2004 (4)0.9893 (2)0.0522 (13)
H6A0.32610.18230.99960.063*
H6B0.21810.13750.97210.063*
C70.1549 (5)0.2435 (4)1.0549 (2)0.0625 (15)
H7A0.15010.19161.09180.094*
H7B0.18200.30561.07120.094*
H7C0.07460.26101.04380.094*
C1010.1249 (4)0.1183 (3)0.7955 (2)0.0318 (9)
C1020.0582 (4)0.1593 (3)0.8602 (2)0.0379 (10)
H1020.04960.23170.86890.046*
C1030.0044 (4)0.0949 (4)0.9122 (2)0.0486 (12)
H1030.04080.12360.95600.058*
C1040.0168 (5)0.0112 (4)0.9002 (3)0.0498 (12)
H1040.02050.05470.93560.060*
C1050.0834 (5)0.0537 (4)0.8366 (3)0.0516 (13)
H1050.09280.12620.82860.062*
C1060.1362 (4)0.0110 (3)0.7848 (3)0.0434 (11)
H1060.18090.01810.74110.052*
C1070.1414 (4)0.1673 (3)0.6485 (2)0.0378 (10)
C1080.0346 (4)0.2249 (4)0.6382 (3)0.0497 (12)
H1080.00460.27830.67090.060*
C1090.0149 (5)0.2047 (5)0.5806 (3)0.0643 (15)
H1090.08660.24520.57360.077*
C1100.0406 (6)0.1255 (5)0.5335 (3)0.0779 (19)
H1100.00620.11090.49470.093*
C1110.1454 (7)0.0682 (5)0.5430 (3)0.088 (2)
H1110.18360.01440.51040.106*
C1120.1964 (5)0.0885 (4)0.6006 (3)0.0651 (16)
H1120.26870.04830.60680.078*
C2010.5972 (4)0.1633 (3)0.7380 (2)0.0353 (10)
C2020.6859 (4)0.2193 (4)0.7544 (2)0.0464 (12)
H2020.67630.29240.75110.056*
C2030.7880 (4)0.1694 (5)0.7753 (3)0.0574 (14)
H2030.84720.20800.78680.069*
C2040.8020 (5)0.0625 (5)0.7790 (3)0.0674 (16)
H2040.87200.02790.79250.081*
C2050.7154 (5)0.0058 (4)0.7634 (3)0.0660 (16)
H2050.72560.06720.76680.079*
C2060.6130 (4)0.0555 (4)0.7425 (3)0.0504 (12)
H2060.55410.01620.73140.061*
C2070.5223 (4)0.2456 (3)0.6120 (2)0.0345 (10)
C2080.4374 (4)0.2733 (3)0.5700 (2)0.0411 (11)
H2080.35420.29100.59120.049*
C2090.4752 (5)0.2748 (4)0.4969 (2)0.0530 (13)
H2090.41760.29300.46850.064*
C2100.5969 (5)0.2499 (4)0.4655 (3)0.0602 (14)
H2100.62200.25060.41580.072*
C2110.6822 (5)0.2238 (4)0.5066 (3)0.0619 (15)
H2110.76560.20850.48490.074*
C2120.6456 (4)0.2203 (4)0.5801 (2)0.0470 (12)
H2120.70360.20090.60810.056*
C3010.6002 (4)0.4688 (3)0.6643 (2)0.0342 (10)
C3020.5845 (4)0.4801 (3)0.5945 (2)0.0401 (11)
H3020.50550.48280.58490.048*
C3030.6836 (4)0.4873 (4)0.5395 (3)0.0511 (13)
H3030.67250.49450.49250.061*
C3040.7992 (5)0.4838 (4)0.5537 (3)0.0596 (14)
H3040.86670.48880.51600.072*
C3050.8176 (4)0.4733 (4)0.6219 (3)0.0570 (14)
H3050.89710.47040.63070.068*
C3060.7178 (4)0.4669 (4)0.6779 (2)0.0430 (11)
H3060.72950.46140.72480.052*
C3070.5217 (4)0.4991 (4)0.8154 (2)0.0411 (11)
C3080.5459 (4)0.4239 (4)0.8648 (2)0.0504 (13)
H3080.52780.35550.86010.060*
C3090.5969 (5)0.4504 (5)0.9211 (3)0.0668 (16)
H3090.61500.39970.95400.080*
C3100.6206 (6)0.5507 (6)0.9284 (3)0.082 (2)
H3100.65440.56840.96680.098*
C3110.5960 (6)0.6261 (5)0.8810 (3)0.0756 (18)
H3110.61190.69480.88740.091*
C3120.5475 (5)0.6009 (4)0.8232 (3)0.0577 (14)
H3120.53230.65190.78990.069*
C4010.1033 (4)0.6511 (3)0.7316 (2)0.0416 (11)
C4020.0197 (5)0.6456 (5)0.7435 (4)0.085 (2)
H4020.05310.59180.77140.103*
C4030.0963 (6)0.7187 (5)0.7150 (5)0.105 (3)
H4030.18040.71230.72210.126*
C4040.0511 (7)0.7988 (5)0.6771 (3)0.0805 (19)
H4040.10320.84690.65690.097*
C4050.0713 (7)0.8101 (4)0.6681 (3)0.0760 (19)
H4050.10230.86730.64310.091*
C4060.1491 (5)0.7372 (4)0.6958 (3)0.0628 (15)
H4060.23240.74580.69060.075*
C4070.1915 (4)0.5998 (3)0.8588 (2)0.0380 (10)
C4080.1376 (4)0.5429 (4)0.9163 (2)0.0441 (11)
H4080.10690.48050.90820.053*
C4090.1289 (4)0.5774 (4)0.9851 (3)0.0510 (13)
H4090.09320.53821.02360.061*
C4100.1727 (4)0.6695 (4)0.9971 (3)0.0531 (13)
H4100.16680.69321.04390.064*
C4110.2245 (4)0.7260 (4)0.9410 (3)0.0520 (13)
H4110.25350.78900.94940.062*
C4120.2349 (4)0.6920 (4)0.8722 (2)0.0442 (11)
H4120.27150.73160.83410.053*
C80.3855 (8)0.1059 (8)1.0516 (4)0.124 (3)
O30.4612 (6)0.1618 (6)0.9936 (4)0.156 (3)
O40.3991 (6)0.0653 (4)0.8766 (3)0.127 (2)
O50.5148 (8)0.9672 (4)0.5852 (4)0.171 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ir10.02499 (9)0.03004 (10)0.03009 (10)0.00432 (6)0.00380 (6)0.00424 (6)
P10.0260 (6)0.0305 (6)0.0336 (6)0.0062 (5)0.0062 (5)0.0035 (5)
P20.0254 (6)0.0334 (6)0.0328 (6)0.0032 (5)0.0043 (4)0.0021 (5)
P30.0293 (6)0.0358 (6)0.0300 (6)0.0091 (5)0.0036 (5)0.0019 (5)
P40.0310 (6)0.0299 (6)0.0332 (6)0.0039 (5)0.0000 (5)0.0030 (5)
Cl10.0270 (5)0.0447 (7)0.0494 (7)0.0032 (5)0.0003 (5)0.0070 (5)
Cl20.0394 (6)0.0490 (7)0.0335 (6)0.0004 (5)0.0074 (5)0.0092 (5)
Cl30.1165 (14)0.0610 (10)0.0883 (11)0.0425 (10)0.0108 (10)0.0024 (8)
O10.048 (2)0.044 (2)0.0483 (19)0.0049 (16)0.0053 (15)0.0074 (15)
O20.0508 (19)0.0459 (19)0.0287 (16)0.0077 (15)0.0043 (14)0.0107 (13)
C10.030 (2)0.030 (2)0.034 (2)0.0041 (18)0.0044 (18)0.0008 (18)
C20.030 (2)0.033 (2)0.040 (2)0.0042 (19)0.0038 (19)0.0006 (19)
C30.038 (2)0.029 (2)0.036 (2)0.0079 (19)0.0013 (19)0.0037 (18)
C40.032 (2)0.034 (2)0.027 (2)0.0089 (19)0.0041 (18)0.0009 (18)
C50.029 (2)0.046 (3)0.034 (2)0.009 (2)0.0101 (19)0.003 (2)
C60.058 (3)0.061 (3)0.039 (3)0.011 (3)0.011 (2)0.023 (2)
C70.076 (4)0.075 (4)0.039 (3)0.028 (3)0.006 (3)0.012 (3)
C1010.025 (2)0.030 (2)0.042 (2)0.0065 (18)0.0106 (19)0.0082 (19)
C1020.036 (2)0.038 (3)0.040 (3)0.004 (2)0.010 (2)0.004 (2)
C1030.052 (3)0.054 (3)0.040 (3)0.013 (2)0.007 (2)0.011 (2)
C1040.053 (3)0.053 (3)0.046 (3)0.015 (3)0.013 (2)0.022 (2)
C1050.058 (3)0.035 (3)0.061 (3)0.007 (2)0.009 (3)0.015 (2)
C1060.041 (3)0.036 (3)0.050 (3)0.002 (2)0.003 (2)0.006 (2)
C1070.039 (3)0.038 (3)0.040 (2)0.011 (2)0.012 (2)0.003 (2)
C1080.037 (3)0.062 (3)0.052 (3)0.005 (2)0.015 (2)0.002 (2)
C1090.053 (3)0.079 (4)0.070 (4)0.006 (3)0.034 (3)0.004 (3)
C1100.095 (5)0.077 (4)0.078 (4)0.010 (4)0.056 (4)0.009 (4)
C1110.120 (6)0.070 (4)0.086 (5)0.010 (4)0.060 (4)0.038 (4)
C1120.082 (4)0.051 (3)0.069 (4)0.010 (3)0.039 (3)0.017 (3)
C2010.030 (2)0.038 (3)0.034 (2)0.002 (2)0.0022 (18)0.0012 (19)
C2020.040 (3)0.047 (3)0.056 (3)0.014 (2)0.016 (2)0.010 (2)
C2030.037 (3)0.073 (4)0.068 (3)0.007 (3)0.025 (3)0.012 (3)
C2040.041 (3)0.076 (4)0.086 (4)0.009 (3)0.028 (3)0.021 (3)
C2050.051 (3)0.044 (3)0.104 (5)0.008 (3)0.025 (3)0.007 (3)
C2060.034 (3)0.042 (3)0.077 (4)0.002 (2)0.016 (2)0.000 (2)
C2070.034 (2)0.033 (2)0.034 (2)0.0073 (19)0.0010 (19)0.0009 (18)
C2080.040 (3)0.041 (3)0.041 (3)0.005 (2)0.006 (2)0.002 (2)
C2090.062 (3)0.060 (3)0.038 (3)0.003 (3)0.014 (2)0.007 (2)
C2100.069 (4)0.070 (4)0.035 (3)0.001 (3)0.001 (3)0.003 (3)
C2110.046 (3)0.082 (4)0.047 (3)0.001 (3)0.009 (3)0.001 (3)
C2120.033 (3)0.060 (3)0.044 (3)0.004 (2)0.001 (2)0.001 (2)
C3010.029 (2)0.034 (2)0.038 (2)0.0064 (19)0.0035 (19)0.0058 (19)
C3020.034 (2)0.047 (3)0.036 (3)0.006 (2)0.0008 (19)0.006 (2)
C3030.047 (3)0.060 (3)0.039 (3)0.003 (2)0.001 (2)0.010 (2)
C3040.042 (3)0.073 (4)0.051 (3)0.000 (3)0.013 (2)0.009 (3)
C3050.028 (3)0.067 (4)0.070 (4)0.007 (2)0.002 (2)0.013 (3)
C3060.033 (2)0.050 (3)0.049 (3)0.013 (2)0.011 (2)0.012 (2)
C3070.032 (2)0.052 (3)0.039 (3)0.013 (2)0.003 (2)0.006 (2)
C3080.045 (3)0.071 (4)0.039 (3)0.021 (3)0.011 (2)0.002 (2)
C3090.055 (3)0.111 (5)0.041 (3)0.025 (3)0.019 (3)0.011 (3)
C3100.077 (4)0.126 (6)0.052 (4)0.040 (4)0.021 (3)0.014 (4)
C3110.076 (4)0.083 (5)0.079 (4)0.036 (4)0.026 (3)0.021 (4)
C3120.056 (3)0.060 (3)0.059 (3)0.017 (3)0.012 (3)0.011 (3)
C4010.046 (3)0.035 (3)0.040 (3)0.003 (2)0.005 (2)0.003 (2)
C4020.047 (3)0.053 (4)0.157 (7)0.003 (3)0.027 (4)0.045 (4)
C4030.061 (4)0.060 (4)0.197 (9)0.000 (3)0.041 (5)0.035 (5)
C4040.084 (5)0.065 (4)0.086 (5)0.031 (4)0.025 (4)0.011 (3)
C4050.099 (5)0.050 (4)0.064 (4)0.014 (3)0.001 (3)0.022 (3)
C4060.068 (4)0.051 (3)0.060 (3)0.000 (3)0.004 (3)0.013 (3)
C4070.036 (2)0.036 (3)0.040 (3)0.005 (2)0.001 (2)0.002 (2)
C4080.046 (3)0.041 (3)0.040 (3)0.009 (2)0.003 (2)0.001 (2)
C4090.047 (3)0.056 (3)0.044 (3)0.009 (3)0.006 (2)0.004 (2)
C4100.048 (3)0.065 (4)0.041 (3)0.002 (3)0.001 (2)0.009 (3)
C4110.051 (3)0.050 (3)0.055 (3)0.011 (2)0.006 (2)0.013 (3)
C4120.044 (3)0.041 (3)0.044 (3)0.007 (2)0.000 (2)0.001 (2)
C80.114 (7)0.164 (9)0.085 (6)0.000 (6)0.011 (5)0.033 (6)
O30.119 (5)0.197 (7)0.158 (6)0.022 (5)0.060 (4)0.045 (5)
O40.188 (6)0.105 (4)0.098 (4)0.055 (4)0.035 (4)0.022 (3)
O50.305 (10)0.074 (4)0.157 (6)0.004 (5)0.112 (6)0.028 (4)
Geometric parameters (Å, º) top
Ir1—C42.076 (4)C203—H2030.9400
Ir1—C12.149 (4)C204—C2051.369 (7)
Ir1—P12.3093 (11)C204—H2040.9400
Ir1—P42.3298 (11)C205—C2061.381 (7)
Ir1—Cl12.4268 (10)C205—H2050.9400
Ir1—Cl22.4597 (10)C206—H2060.9400
P1—C1011.825 (4)C207—C2081.389 (6)
P1—C1071.830 (4)C207—C2121.394 (6)
P1—C21.838 (4)C208—C2091.382 (6)
P2—C21.790 (4)C208—H2080.9400
P2—C2071.800 (4)C209—C2101.374 (7)
P2—C2011.801 (4)C209—H2090.9400
P2—C11.822 (4)C210—C2111.376 (7)
P3—C3071.793 (4)C210—H2100.9400
P3—C31.800 (4)C211—C2121.389 (6)
P3—C3011.809 (4)C211—H2110.9400
P3—C11.833 (4)C212—H2120.9400
P4—C4071.821 (4)C301—C3021.395 (6)
P4—C4011.825 (4)C301—C3061.397 (6)
P4—C31.835 (4)C302—C3031.378 (6)
O1—C51.213 (5)C302—H3020.9400
O2—C51.333 (5)C303—C3041.378 (7)
O2—C61.472 (5)C303—H3030.9400
C1—C41.513 (5)C304—C3051.373 (7)
C2—H2A0.9800C304—H3040.9400
C2—H2B0.9800C305—C3061.392 (6)
C3—H3A0.9800C305—H3050.9400
C3—H3B0.9800C306—H3060.9400
C4—C51.483 (6)C307—C3081.396 (7)
C4—H40.954 (18)C307—C3121.397 (7)
C6—C71.504 (7)C308—C3091.391 (7)
C6—H6A0.9800C308—H3080.9400
C6—H6B0.9800C309—C3101.368 (9)
C7—H7A0.9700C309—H3090.9400
C7—H7B0.9700C310—C3111.371 (9)
C7—H7C0.9700C310—H3100.9400
C101—C1021.385 (6)C311—C3121.394 (7)
C101—C1061.389 (6)C311—H3110.9400
C102—C1031.382 (6)C312—H3120.9400
C102—H1020.9400C401—C4021.364 (7)
C103—C1041.379 (7)C401—C4061.396 (7)
C103—H1030.9400C402—C4031.388 (8)
C104—C1051.373 (7)C402—H4020.9400
C104—H1040.9400C403—C4041.346 (9)
C105—C1061.378 (6)C403—H4030.9400
C105—H1050.9400C404—C4051.375 (9)
C106—H1060.9400C404—H4040.9400
C107—C1121.376 (7)C405—C4061.387 (8)
C107—C1081.383 (6)C405—H4050.9400
C108—C1091.381 (7)C406—H4060.9400
C108—H1080.9400C407—C4121.386 (6)
C109—C1101.373 (8)C407—C4081.393 (6)
C109—H1090.9400C408—C4091.380 (6)
C110—C1111.358 (8)C408—H4080.9400
C110—H1100.9400C409—C4101.380 (7)
C111—C1121.391 (7)C409—H4090.9400
C111—H1110.9400C410—C4111.364 (7)
C112—H1120.9400C410—H4100.9400
C201—C2061.386 (6)C411—C4121.376 (6)
C201—C2021.387 (6)C411—H4110.9400
C202—C2031.381 (6)C412—H4120.9400
C202—H2020.9400C8—O31.400 (9)
C203—C2041.373 (8)
C4—Ir1—C141.94 (15)C107—C112—C111120.2 (5)
C4—Ir1—P193.94 (12)C107—C112—H112119.9
C1—Ir1—P190.24 (11)C111—C112—H112119.9
C4—Ir1—P487.46 (12)C206—C201—C202118.8 (4)
C1—Ir1—P489.52 (11)C206—C201—P2119.9 (3)
P1—Ir1—P4177.61 (4)C202—C201—P2121.1 (3)
C4—Ir1—Cl1116.21 (11)C203—C202—C201121.0 (5)
C1—Ir1—Cl1158.13 (11)C203—C202—H202119.5
P1—Ir1—Cl190.79 (4)C201—C202—H202119.5
P4—Ir1—Cl190.32 (4)C204—C203—C202119.1 (5)
C4—Ir1—Cl2151.91 (11)C204—C203—H203120.5
C1—Ir1—Cl2111.50 (11)C202—C203—H203120.5
P1—Ir1—Cl295.28 (4)C205—C204—C203120.8 (5)
P4—Ir1—Cl282.61 (4)C205—C204—H204119.6
Cl1—Ir1—Cl290.15 (4)C203—C204—H204119.6
C101—P1—C107103.22 (19)C204—C205—C206120.3 (5)
C101—P1—C2101.10 (19)C204—C205—H205119.9
C107—P1—C2105.4 (2)C206—C205—H205119.9
C101—P1—Ir1119.47 (14)C205—C206—C201120.0 (5)
C107—P1—Ir1116.96 (15)C205—C206—H206120.0
C2—P1—Ir1108.79 (13)C201—C206—H206120.0
C2—P2—C207104.15 (19)C208—C207—C212119.6 (4)
C2—P2—C201107.7 (2)C208—C207—P2119.1 (3)
C207—P2—C201106.31 (19)C212—C207—P2120.8 (3)
C2—P2—C1109.35 (19)C209—C208—C207120.0 (4)
C207—P2—C1111.24 (19)C209—C208—H208120.0
C201—P2—C1117.21 (19)C207—C208—H208120.0
C307—P3—C3109.2 (2)C210—C209—C208120.2 (5)
C307—P3—C301105.7 (2)C210—C209—H209119.9
C3—P3—C301105.53 (19)C208—C209—H209119.9
C307—P3—C1111.0 (2)C209—C210—C211120.4 (5)
C3—P3—C1106.85 (19)C209—C210—H210119.8
C301—P3—C1118.24 (19)C211—C210—H210119.8
C407—P4—C401103.8 (2)C210—C211—C212120.2 (5)
C407—P4—C3105.7 (2)C210—C211—H211119.9
C401—P4—C3104.1 (2)C212—C211—H211119.9
C407—P4—Ir1118.43 (14)C211—C212—C207119.5 (5)
C401—P4—Ir1121.43 (15)C211—C212—H212120.2
C3—P4—Ir1101.43 (14)C207—C212—H212120.2
C5—O2—C6116.4 (4)C302—C301—C306119.1 (4)
C4—C1—P2120.5 (3)C302—C301—P3120.6 (3)
C4—C1—P3111.2 (3)C306—C301—P3120.1 (3)
P2—C1—P3119.9 (2)C303—C302—C301120.5 (4)
C4—C1—Ir166.5 (2)C303—C302—H302119.7
P2—C1—Ir1113.31 (19)C301—C302—H302119.7
P3—C1—Ir1113.9 (2)C302—C303—C304119.7 (5)
P2—C2—P1112.6 (2)C302—C303—H303120.2
P2—C2—H2A109.1C304—C303—H303120.2
P1—C2—H2A109.1C305—C304—C303121.2 (4)
P2—C2—H2B109.1C305—C304—H304119.4
P1—C2—H2B109.1C303—C304—H304119.4
H2A—C2—H2B107.8C304—C305—C306119.6 (5)
P3—C3—P4111.4 (2)C304—C305—H305120.2
P3—C3—H3A109.3C306—C305—H305120.2
P4—C3—H3A109.3C305—C306—C301119.9 (4)
P3—C3—H3B109.3C305—C306—H306120.1
P4—C3—H3B109.3C301—C306—H306120.1
H3A—C3—H3B108.0C308—C307—C312119.7 (4)
C5—C4—C1122.7 (4)C308—C307—P3122.1 (4)
C5—C4—Ir1126.2 (3)C312—C307—P3118.0 (4)
C1—C4—Ir171.6 (2)C309—C308—C307120.0 (5)
C5—C4—H4104 (2)C309—C308—H308120.0
C1—C4—H4115 (2)C307—C308—H308120.0
Ir1—C4—H4116 (2)C310—C309—C308119.6 (6)
O1—C5—O2123.9 (4)C310—C309—H309120.2
O1—C5—C4126.0 (4)C308—C309—H309120.2
O2—C5—C4110.1 (4)C309—C310—C311121.4 (5)
O2—C6—C7106.7 (4)C309—C310—H310119.3
O2—C6—H6A110.4C311—C310—H310119.3
C7—C6—H6A110.4C310—C311—C312120.1 (6)
O2—C6—H6B110.4C310—C311—H311120.0
C7—C6—H6B110.4C312—C311—H311120.0
H6A—C6—H6B108.6C311—C312—C307119.2 (5)
C6—C7—H7A109.5C311—C312—H312120.4
C6—C7—H7B109.5C307—C312—H312120.4
H7A—C7—H7B109.5C402—C401—C406118.5 (5)
C6—C7—H7C109.5C402—C401—P4120.1 (4)
H7A—C7—H7C109.5C406—C401—P4121.2 (4)
H7B—C7—H7C109.5C401—C402—C403120.8 (6)
C102—C101—C106118.1 (4)C401—C402—H402119.6
C102—C101—P1122.0 (3)C403—C402—H402119.6
C106—C101—P1119.9 (3)C404—C403—C402120.6 (6)
C103—C102—C101120.6 (4)C404—C403—H403119.7
C103—C102—H102119.7C402—C403—H403119.7
C101—C102—H102119.7C403—C404—C405119.9 (6)
C104—C103—C102120.1 (5)C403—C404—H404120.1
C104—C103—H103119.9C405—C404—H404120.1
C102—C103—H103119.9C404—C405—C406120.2 (6)
C105—C104—C103120.2 (4)C404—C405—H405119.9
C105—C104—H104119.9C406—C405—H405119.9
C103—C104—H104119.9C405—C406—C401119.8 (6)
C104—C105—C106119.3 (5)C405—C406—H406120.1
C104—C105—H105120.3C401—C406—H406120.1
C106—C105—H105120.3C412—C407—C408118.6 (4)
C105—C106—C101121.6 (4)C412—C407—P4121.5 (3)
C105—C106—H106119.2C408—C407—P4120.0 (3)
C101—C106—H106119.2C409—C408—C407120.5 (4)
C112—C107—C108118.7 (4)C409—C408—H408119.7
C112—C107—P1123.8 (4)C407—C408—H408119.7
C108—C107—P1117.5 (3)C408—C409—C410119.9 (5)
C109—C108—C107120.7 (5)C408—C409—H409120.1
C109—C108—H108119.7C410—C409—H409120.1
C107—C108—H108119.7C411—C410—C409119.9 (5)
C110—C109—C108120.0 (5)C411—C410—H410120.1
C110—C109—H109120.0C409—C410—H410120.1
C108—C109—H109120.0C410—C411—C412120.9 (5)
C111—C110—C109119.9 (5)C410—C411—H411119.6
C111—C110—H110120.0C412—C411—H411119.6
C109—C110—H110120.0C411—C412—C407120.3 (4)
C110—C111—C112120.5 (6)C411—C412—H412119.9
C110—C111—H111119.8C407—C412—H412119.9
C112—C111—H111119.8
C2—P2—C1—C448.9 (4)P2—C201—C202—C203176.4 (4)
C207—P2—C1—C4163.4 (3)C201—C202—C203—C2040.8 (8)
C201—P2—C1—C474.0 (4)C202—C203—C204—C2051.0 (9)
C2—P2—C1—P3165.7 (2)C203—C204—C205—C2061.0 (9)
C207—P2—C1—P351.2 (3)C204—C205—C206—C2010.6 (9)
C201—P2—C1—P371.4 (3)C202—C201—C206—C2050.4 (7)
C2—P2—C1—Ir126.5 (3)P2—C201—C206—C205176.3 (4)
C207—P2—C1—Ir188.0 (2)C2—P2—C207—C20853.0 (4)
C201—P2—C1—Ir1149.5 (2)C201—P2—C207—C208166.7 (3)
C307—P3—C1—C441.4 (3)C1—P2—C207—C20864.7 (4)
C3—P3—C1—C477.6 (3)C2—P2—C207—C212119.3 (4)
C301—P3—C1—C4163.7 (3)C201—P2—C207—C2125.6 (4)
C307—P3—C1—P2107.0 (3)C1—P2—C207—C212123.0 (4)
C3—P3—C1—P2134.1 (2)C212—C207—C208—C2090.6 (7)
C301—P3—C1—P215.4 (3)P2—C207—C208—C209171.8 (4)
C307—P3—C1—Ir1114.1 (2)C207—C208—C209—C2100.6 (7)
C3—P3—C1—Ir14.9 (3)C208—C209—C210—C2110.5 (8)
C301—P3—C1—Ir1123.6 (2)C209—C210—C211—C2121.5 (9)
C207—P2—C2—P198.2 (2)C210—C211—C212—C2071.5 (8)
C201—P2—C2—P1149.2 (2)C208—C207—C212—C2110.5 (7)
C1—P2—C2—P120.8 (3)P2—C207—C212—C211172.7 (4)
C101—P1—C2—P2133.9 (2)C307—P3—C301—C302159.6 (4)
C107—P1—C2—P2118.9 (2)C3—P3—C301—C30244.0 (4)
Ir1—P1—C2—P27.3 (3)C1—P3—C301—C30275.4 (4)
C307—P3—C3—P487.5 (3)C307—P3—C301—C30615.4 (4)
C301—P3—C3—P4159.3 (2)C3—P3—C301—C306131.0 (4)
C1—P3—C3—P432.7 (3)C1—P3—C301—C306109.6 (4)
C407—P4—C3—P381.0 (3)C306—C301—C302—C3031.2 (7)
C401—P4—C3—P3170.0 (2)P3—C301—C302—C303176.2 (4)
Ir1—P4—C3—P343.2 (2)C301—C302—C303—C3040.3 (7)
P2—C1—C4—C517.6 (5)C302—C303—C304—C3050.0 (8)
P3—C1—C4—C5130.5 (3)C303—C304—C305—C3060.6 (8)
Ir1—C1—C4—C5121.8 (4)C304—C305—C306—C3011.5 (8)
P2—C1—C4—Ir1104.1 (3)C302—C301—C306—C3051.8 (7)
P3—C1—C4—Ir1107.8 (2)P3—C301—C306—C305176.9 (4)
C6—O2—C5—O11.6 (6)C3—P3—C307—C308141.9 (4)
C6—O2—C5—C4178.7 (3)C301—P3—C307—C308105.0 (4)
C1—C4—C5—O19.5 (6)C1—P3—C307—C30824.3 (4)
Ir1—C4—C5—O180.8 (5)C3—P3—C307—C31243.2 (4)
C1—C4—C5—O2170.8 (3)C301—P3—C307—C31269.9 (4)
Ir1—C4—C5—O298.9 (4)C1—P3—C307—C312160.7 (4)
C5—O2—C6—C7174.9 (4)C312—C307—C308—C3090.7 (7)
C107—P1—C101—C102126.3 (3)P3—C307—C308—C309174.1 (4)
C2—P1—C101—C102124.8 (3)C307—C308—C309—C3101.3 (8)
Ir1—P1—C101—C1025.6 (4)C308—C309—C310—C3110.5 (10)
C107—P1—C101—C10655.4 (4)C309—C310—C311—C3120.9 (10)
C2—P1—C101—C10653.5 (4)C310—C311—C312—C3071.6 (9)
Ir1—P1—C101—C106172.7 (3)C308—C307—C312—C3110.7 (7)
C106—C101—C102—C1030.3 (6)P3—C307—C312—C311175.8 (4)
P1—C101—C102—C103178.6 (3)C407—P4—C401—C40284.0 (5)
C101—C102—C103—C1040.2 (7)C3—P4—C401—C402165.6 (5)
C102—C103—C104—C1050.4 (7)Ir1—P4—C401—C40252.5 (5)
C103—C104—C105—C1060.9 (7)C407—P4—C401—C40690.9 (4)
C104—C105—C106—C1010.7 (7)C3—P4—C401—C40619.6 (4)
C102—C101—C106—C1050.1 (6)Ir1—P4—C401—C406132.7 (4)
P1—C101—C106—C105178.2 (4)C406—C401—C402—C4036.0 (10)
C101—P1—C107—C11289.9 (5)P4—C401—C402—C403178.9 (6)
C2—P1—C107—C11215.7 (5)C401—C402—C403—C4042.5 (12)
Ir1—P1—C107—C112136.7 (4)C402—C403—C404—C4051.7 (12)
C101—P1—C107—C10889.5 (4)C403—C404—C405—C4062.2 (10)
C2—P1—C107—C108164.9 (4)C404—C405—C406—C4011.4 (9)
Ir1—P1—C107—C10843.8 (4)C402—C401—C406—C4055.5 (8)
C112—C107—C108—C1090.9 (8)P4—C401—C406—C405179.6 (4)
P1—C107—C108—C109179.7 (4)C401—P4—C407—C41265.3 (4)
C107—C108—C109—C1101.3 (9)C3—P4—C407—C41243.9 (4)
C108—C109—C110—C1111.1 (10)Ir1—P4—C407—C412156.7 (3)
C109—C110—C111—C1120.6 (11)C401—P4—C407—C408114.3 (4)
C108—C107—C112—C1110.4 (8)C3—P4—C407—C408136.5 (4)
P1—C107—C112—C111179.8 (5)Ir1—P4—C407—C40823.8 (4)
C110—C111—C112—C1070.3 (11)C412—C407—C408—C4090.7 (7)
C2—P2—C201—C20616.9 (4)P4—C407—C408—C409179.8 (4)
C207—P2—C201—C20694.3 (4)C407—C408—C409—C4100.7 (7)
C1—P2—C201—C206140.7 (4)C408—C409—C410—C4110.1 (8)
C2—P2—C201—C202167.2 (4)C409—C410—C411—C4120.6 (8)
C207—P2—C201—C20281.6 (4)C410—C411—C412—C4070.6 (7)
C1—P2—C201—C20243.5 (4)C408—C407—C412—C4110.0 (7)
C206—C201—C202—C2030.4 (7)P4—C407—C412—C411179.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O10.982.332.852 (5)112
C2—H2B···O5i0.982.453.320 (8)148
C3—H3B···Cl30.982.663.589 (4)158
C6—H6A···O3ii0.982.403.369 (8)169
C102—H102···Cl10.942.633.343 (4)133
C108—H108···Cl10.942.823.671 (5)151
C206—H206···Cl3i0.942.873.742 (5)156
C208—H208···Cl20.942.643.487 (5)150
C312—H312···Cl30.942.843.749 (6)164
C402—H402···Cl10.942.593.398 (6)144
C406—H406···Cl30.942.883.757 (6)156
C412—H412···Cl30.942.953.870 (5)167
Symmetry codes: (i) x, y1, z; (ii) x+1, y, z+2.
(Bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4P,C,C',P')carbonyl(ethoxyoxoethanide)iridium(III) dichloride–methylene chloride–water (1/2/1.5) (7) top
Crystal data top
[Ir(C4H7O2)(C55H50O2P4)(CO)]Cl2·2CH2Cl2·1.5H2OZ = 2
Mr = 1441.91F(000) = 1454
Triclinic, P1Dx = 1.505 Mg m3
a = 11.7326 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.8815 (2) ÅCell parameters from 109564 reflections
c = 22.2615 (3) Åθ = 1.0–27.4°
α = 75.477 (1)°µ = 2.50 mm1
β = 86.508 (1)°T = 233 K
γ = 65.212 (1)°Prism, yellow
V = 3182.38 (9) Å30.31 × 0.23 × 0.19 mm
Data collection top
Nonius KappaCCD
diffractometer
11695 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
Graphite monochromatorθmax = 26.0°, θmin = 1.9°
phi– and ω–scansh = 1414
23329 measured reflectionsk = 1716
12496 independent reflectionsl = 2627
Refinement top
Refinement on F23 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070 w = 1/[σ2(Fo2) + (0.026P)2 + 5.2527P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
12496 reflectionsΔρmax = 0.97 e Å3
751 parametersΔρmin = 1.29 e Å3
Special details top

Experimental. All data sets were measured with several scans to increase the number of redundant reflections. In our experience this method of averaging redundant reflections replaces in a good approximation semi-empirical absorptions methods (absorption correction programs like SORTAV lead to no better data sets).

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.

Refinement. Hydrogen at C4 was found and refined isotropically with bond restraint (d=96pm). Hydrogens at water O6 were found and refined isotropically with bond restraints (d=84pm). The water molecule O7 was half occupied and hydrogen of it were omitted. The chlorine atoms at solvent dichloromethane CL5-C14-Cl6 were positional disordered in ratio around 2:1 (CL5-6: Cl5A-6A). C14=C14A with equal coordinates and displacement parameters for hydrogen calculation.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ir10.18100 (2)0.32675 (2)0.19059 (2)0.02360 (4)
P10.01647 (7)0.32287 (7)0.20407 (4)0.02798 (16)
P20.08519 (8)0.24968 (7)0.33707 (4)0.02951 (17)
P30.36173 (7)0.23582 (6)0.31877 (3)0.02553 (16)
P40.38428 (7)0.32406 (6)0.18358 (3)0.02485 (15)
O10.2405 (2)0.4989 (2)0.30318 (12)0.0441 (6)
O20.0747 (2)0.60098 (18)0.23599 (11)0.0398 (6)
O30.2584 (3)0.4317 (3)0.02412 (12)0.0555 (7)
O40.1299 (3)0.3486 (2)0.02816 (11)0.0512 (7)
O50.2606 (3)0.1321 (2)0.13439 (14)0.0542 (7)
C10.1994 (3)0.2948 (2)0.29337 (13)0.0258 (6)
C20.0016 (3)0.2266 (3)0.28035 (14)0.0322 (7)
H2A0.08160.23490.29500.039*
H2B0.04750.15150.27610.039*
C30.4342 (3)0.3087 (3)0.26346 (13)0.0275 (6)
H3A0.52590.26880.26900.033*
H3B0.41090.38130.27070.033*
C40.1312 (3)0.4148 (2)0.26037 (13)0.0264 (6)
H40.0434 (18)0.441 (3)0.2635 (15)0.030 (9)*
C50.1589 (3)0.5053 (3)0.26978 (15)0.0320 (7)
C60.0842 (4)0.7004 (3)0.2418 (2)0.0530 (10)
H6A0.17020.69390.23510.064*
H6B0.06180.71230.28330.064*
C70.0043 (6)0.7923 (4)0.1938 (3)0.093 (2)
H7A0.00110.86010.19600.140*
H7B0.01900.77950.15300.140*
H7C0.08890.79770.20100.140*
C80.1075 (3)0.4468 (3)0.10236 (14)0.0334 (7)
H8A0.01840.46330.09670.040*
H8B0.11270.51470.10410.040*
C90.1736 (3)0.4113 (3)0.04821 (14)0.0368 (7)
C100.1946 (5)0.3027 (4)0.0222 (2)0.0668 (13)
H10A0.28290.25430.00950.080*
H10B0.19160.36120.05840.080*
C110.1298 (7)0.2398 (5)0.0379 (3)0.099 (2)
H11A0.17080.20760.07170.149*
H11B0.13350.18210.00180.149*
H11C0.04260.28850.05050.149*
C120.2317 (3)0.2051 (3)0.15415 (15)0.0331 (7)
C1010.0676 (3)0.2706 (3)0.14917 (15)0.0335 (7)
C1020.0305 (4)0.1594 (3)0.15564 (19)0.0524 (10)
H1020.01930.10790.19060.063*
C1030.0678 (5)0.1250 (4)0.1099 (2)0.0660 (13)
H1030.04430.04980.11440.079*
C1040.1382 (5)0.1990 (4)0.0586 (2)0.0607 (12)
H1040.16250.17430.02800.073*
C1050.1736 (4)0.3080 (4)0.05112 (18)0.0506 (10)
H1050.22190.35830.01550.061*
C1060.1383 (3)0.3449 (3)0.09598 (16)0.0416 (8)
H1060.16220.42030.09060.050*
C1070.1551 (3)0.4470 (3)0.20753 (15)0.0343 (7)
C1080.1557 (3)0.5505 (3)0.19268 (16)0.0397 (8)
H1080.08190.55880.17980.048*
C1090.2639 (4)0.6416 (3)0.1967 (2)0.0544 (10)
H1090.26360.71140.18690.065*
C1100.3727 (4)0.6289 (4)0.2153 (2)0.0639 (12)
H1100.44630.69030.21860.077*
C1110.3735 (4)0.5262 (4)0.2292 (2)0.0586 (11)
H1110.44780.51830.24160.070*
C1120.2664 (3)0.4361 (3)0.22511 (17)0.0454 (9)
H1120.26780.36670.23410.055*
C2010.1375 (3)0.1290 (3)0.40066 (14)0.0360 (7)
C2020.1785 (4)0.0254 (3)0.39114 (18)0.0494 (9)
H2020.18380.01620.35050.059*
C2030.2117 (5)0.0648 (4)0.4412 (2)0.0710 (14)
H2030.24090.13520.43440.085*
C2040.2025 (5)0.0524 (4)0.5010 (2)0.0754 (15)
H2040.22550.11420.53480.091*
C2050.1602 (5)0.0495 (4)0.51097 (19)0.0699 (14)
H2050.15360.05760.55190.084*
C2060.1266 (4)0.1415 (4)0.46165 (17)0.0538 (10)
H2060.09680.21160.46900.065*
C2070.0190 (3)0.3598 (3)0.36982 (15)0.0404 (8)
C2080.0283 (4)0.4210 (4)0.39200 (18)0.0542 (10)
H2080.11430.40530.38960.065*
C2090.0505 (6)0.5050 (5)0.4177 (2)0.0834 (17)
H2090.01800.54650.43270.100*
C2100.1743 (7)0.5277 (6)0.4213 (3)0.100 (2)
H2100.22800.58600.43790.121*
C2110.2220 (5)0.4656 (6)0.4006 (3)0.100 (2)
H2110.30780.48110.40430.119*
C2120.1449 (4)0.3800 (4)0.37442 (19)0.0615 (12)
H2120.17730.33750.36040.074*
C3010.3972 (3)0.2405 (3)0.39562 (14)0.0319 (7)
C3020.3965 (4)0.1578 (3)0.44585 (16)0.0452 (9)
H3020.37750.10160.43940.054*
C3030.4237 (5)0.1584 (4)0.50518 (18)0.0617 (12)
H3030.42150.10330.53920.074*
C3040.4536 (5)0.2385 (4)0.51477 (18)0.0635 (13)
H3040.47230.23780.55540.076*
C3050.4568 (4)0.3201 (4)0.46571 (19)0.0589 (11)
H3050.47810.37470.47270.071*
C3060.4285 (4)0.3214 (3)0.40556 (17)0.0444 (9)
H3060.43050.37700.37180.053*
C3070.4396 (3)0.0935 (2)0.31728 (14)0.0294 (6)
C3080.3872 (3)0.0411 (3)0.28949 (16)0.0382 (8)
H3080.30390.07850.27280.046*
C3090.4580 (4)0.0664 (3)0.28642 (19)0.0503 (9)
H3090.42170.10230.26860.060*
C3100.5809 (4)0.1206 (3)0.3093 (2)0.0522 (10)
H3100.62870.19300.30630.063*
C3110.6345 (4)0.0693 (3)0.33646 (18)0.0451 (9)
H3110.71870.10650.35170.054*
C3120.5640 (3)0.0370 (3)0.34124 (15)0.0362 (7)
H3120.59990.07120.36070.043*
C4010.4056 (3)0.4445 (3)0.13947 (14)0.0298 (6)
C4020.3124 (3)0.5476 (3)0.13833 (16)0.0397 (8)
H4020.23960.55490.16050.048*
C4030.3264 (4)0.6402 (3)0.10452 (19)0.0488 (9)
H4030.26320.71010.10400.059*
C4040.4319 (4)0.6305 (3)0.07180 (18)0.0481 (9)
H4040.44090.69360.04910.058*
C4050.5241 (4)0.5287 (3)0.07225 (18)0.0478 (9)
H4050.59610.52210.04960.057*
C4060.5115 (3)0.4355 (3)0.10599 (16)0.0394 (8)
H4060.57520.36600.10620.047*
C4070.5050 (3)0.2106 (3)0.15751 (15)0.0316 (7)
C4080.4890 (4)0.1989 (3)0.09900 (18)0.0458 (9)
H4080.41770.25000.07350.055*
C4090.5773 (4)0.1125 (4)0.0779 (2)0.0590 (11)
H4090.56630.10510.03810.071*
C4100.6809 (5)0.0375 (4)0.1154 (2)0.0652 (13)
H4100.73950.02250.10160.078*
C4110.6996 (4)0.0494 (4)0.1723 (2)0.0665 (13)
H4110.77180.00170.19720.080*
C4120.6133 (4)0.1358 (3)0.19386 (18)0.0474 (9)
H4120.62760.14430.23290.057*
Cl10.26323 (9)0.19319 (10)0.33214 (5)0.0573 (3)
Cl20.17302 (11)0.07900 (9)0.26051 (5)0.0607 (3)
C130.3341 (7)0.8877 (5)0.1243 (3)0.097 (2)
H13A0.29760.92960.15550.117*
H13B0.35250.81080.14350.117*
Cl30.4728 (3)0.8992 (2)0.10094 (13)0.1458 (8)
Cl40.2257 (2)0.93632 (14)0.06158 (9)0.1169 (6)
C140.7130 (7)0.6657 (5)0.3733 (3)0.0917 (19)0.65
H14A0.76220.74370.35430.110*0.65
H14B0.74380.62360.35460.110*0.65
Cl50.7328 (5)0.6391 (3)0.45165 (15)0.1329 (15)0.65
Cl60.5546 (6)0.6307 (7)0.3585 (4)0.167 (3)0.65
C14A0.7130 (7)0.6657 (5)0.3733 (3)0.0917 (19)0.35
H14C0.71440.61990.34650.110*0.35
H14D0.74210.74060.34710.110*0.35
Cl5A0.832 (3)0.6662 (17)0.4298 (7)0.355 (14)0.35
Cl6A0.5736 (14)0.6287 (15)0.3920 (10)0.276 (12)0.35
O60.0892 (5)0.0527 (5)0.3189 (3)0.1181 (17)
H6OA0.013 (3)0.063 (6)0.316 (4)0.13 (3)*
H6OB0.133 (5)0.012 (2)0.323 (3)0.078 (19)*
O71.0377 (12)0.7546 (9)0.4039 (6)0.141 (4)0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ir10.02408 (6)0.02543 (7)0.02014 (6)0.01177 (5)0.00110 (4)0.00062 (4)
P10.0247 (4)0.0330 (4)0.0248 (4)0.0140 (3)0.0033 (3)0.0001 (3)
P20.0283 (4)0.0362 (4)0.0228 (4)0.0159 (3)0.0004 (3)0.0008 (3)
P30.0255 (4)0.0285 (4)0.0210 (3)0.0125 (3)0.0025 (3)0.0003 (3)
P40.0235 (4)0.0255 (4)0.0236 (4)0.0111 (3)0.0011 (3)0.0013 (3)
O10.0451 (14)0.0380 (13)0.0475 (14)0.0129 (11)0.0168 (12)0.0114 (11)
O20.0393 (13)0.0257 (11)0.0495 (14)0.0082 (10)0.0123 (11)0.0071 (10)
O30.0543 (17)0.077 (2)0.0410 (14)0.0398 (16)0.0130 (13)0.0048 (13)
O40.0694 (19)0.0627 (17)0.0328 (13)0.0365 (15)0.0086 (12)0.0165 (12)
O50.0646 (19)0.0441 (15)0.0625 (18)0.0250 (14)0.0087 (14)0.0249 (14)
C10.0271 (15)0.0310 (15)0.0190 (13)0.0142 (13)0.0007 (11)0.0018 (11)
C20.0299 (16)0.0413 (18)0.0273 (15)0.0217 (14)0.0020 (12)0.0010 (13)
C30.0251 (15)0.0302 (15)0.0267 (15)0.0138 (12)0.0009 (12)0.0017 (12)
C40.0233 (15)0.0288 (15)0.0230 (14)0.0083 (12)0.0001 (11)0.0041 (12)
C50.0318 (17)0.0286 (16)0.0303 (16)0.0083 (13)0.0024 (13)0.0066 (13)
C60.060 (3)0.0301 (18)0.067 (3)0.0143 (18)0.015 (2)0.0126 (18)
C70.098 (4)0.032 (2)0.134 (5)0.011 (2)0.055 (4)0.008 (3)
C80.0356 (17)0.0345 (17)0.0230 (15)0.0131 (14)0.0050 (13)0.0037 (12)
C90.0389 (19)0.0400 (18)0.0230 (15)0.0151 (15)0.0038 (13)0.0052 (13)
C100.086 (4)0.071 (3)0.039 (2)0.024 (3)0.003 (2)0.022 (2)
C110.161 (7)0.079 (4)0.070 (4)0.053 (4)0.006 (4)0.034 (3)
C120.0338 (17)0.0349 (17)0.0302 (16)0.0163 (14)0.0016 (13)0.0033 (14)
C1010.0306 (16)0.0398 (18)0.0325 (16)0.0190 (14)0.0019 (13)0.0043 (14)
C1020.062 (3)0.045 (2)0.052 (2)0.026 (2)0.0127 (19)0.0044 (18)
C1030.085 (3)0.051 (3)0.075 (3)0.038 (2)0.009 (3)0.018 (2)
C1040.070 (3)0.069 (3)0.056 (3)0.035 (2)0.013 (2)0.022 (2)
C1050.051 (2)0.065 (3)0.041 (2)0.028 (2)0.0091 (17)0.0112 (18)
C1060.042 (2)0.045 (2)0.0369 (18)0.0198 (17)0.0063 (15)0.0058 (15)
C1070.0288 (16)0.0409 (18)0.0290 (16)0.0123 (14)0.0037 (13)0.0045 (13)
C1080.0335 (18)0.0423 (19)0.0357 (18)0.0115 (15)0.0036 (14)0.0031 (15)
C1090.048 (2)0.044 (2)0.059 (2)0.0092 (18)0.0060 (19)0.0071 (19)
C1100.038 (2)0.062 (3)0.070 (3)0.000 (2)0.002 (2)0.018 (2)
C1110.032 (2)0.070 (3)0.068 (3)0.017 (2)0.0058 (19)0.016 (2)
C1120.0328 (18)0.055 (2)0.047 (2)0.0175 (17)0.0020 (15)0.0099 (17)
C2010.0348 (17)0.0460 (19)0.0253 (15)0.0225 (15)0.0028 (13)0.0055 (14)
C2020.063 (3)0.045 (2)0.0362 (19)0.0252 (19)0.0037 (17)0.0026 (16)
C2030.103 (4)0.043 (2)0.056 (3)0.030 (3)0.008 (3)0.010 (2)
C2040.096 (4)0.068 (3)0.046 (3)0.038 (3)0.009 (2)0.024 (2)
C2050.093 (4)0.084 (4)0.026 (2)0.042 (3)0.002 (2)0.008 (2)
C2060.068 (3)0.060 (3)0.0281 (18)0.028 (2)0.0005 (17)0.0002 (17)
C2070.0394 (19)0.047 (2)0.0286 (16)0.0144 (16)0.0083 (14)0.0062 (15)
C2080.068 (3)0.058 (3)0.041 (2)0.029 (2)0.0203 (19)0.0191 (19)
C2090.114 (5)0.075 (4)0.065 (3)0.035 (3)0.033 (3)0.041 (3)
C2100.090 (5)0.094 (5)0.096 (5)0.004 (4)0.031 (4)0.055 (4)
C2110.050 (3)0.133 (6)0.085 (4)0.001 (3)0.020 (3)0.049 (4)
C2120.040 (2)0.087 (3)0.048 (2)0.016 (2)0.0090 (18)0.021 (2)
C3010.0282 (16)0.0372 (17)0.0246 (15)0.0097 (13)0.0045 (12)0.0037 (13)
C3020.052 (2)0.051 (2)0.0295 (17)0.0227 (18)0.0041 (15)0.0013 (16)
C3030.080 (3)0.070 (3)0.0256 (18)0.028 (3)0.0077 (19)0.0006 (18)
C3040.070 (3)0.077 (3)0.030 (2)0.015 (2)0.0125 (19)0.016 (2)
C3050.068 (3)0.059 (3)0.048 (2)0.020 (2)0.019 (2)0.018 (2)
C3060.050 (2)0.043 (2)0.0374 (19)0.0162 (17)0.0116 (16)0.0079 (16)
C3070.0285 (16)0.0286 (15)0.0273 (15)0.0121 (13)0.0013 (12)0.0001 (12)
C3080.0355 (18)0.0368 (18)0.0402 (18)0.0157 (15)0.0040 (14)0.0036 (15)
C3090.058 (2)0.040 (2)0.056 (2)0.0215 (19)0.0046 (19)0.0138 (18)
C3100.055 (2)0.0330 (19)0.058 (2)0.0088 (18)0.0016 (19)0.0101 (17)
C3110.0363 (19)0.0384 (19)0.047 (2)0.0077 (16)0.0011 (16)0.0004 (16)
C3120.0350 (18)0.0348 (17)0.0353 (17)0.0149 (14)0.0019 (14)0.0014 (14)
C4010.0338 (16)0.0315 (16)0.0240 (14)0.0170 (13)0.0024 (12)0.0003 (12)
C4020.043 (2)0.0355 (18)0.0407 (19)0.0199 (16)0.0069 (15)0.0046 (15)
C4030.056 (2)0.0312 (18)0.055 (2)0.0185 (17)0.0004 (19)0.0017 (16)
C4040.061 (2)0.045 (2)0.043 (2)0.035 (2)0.0030 (18)0.0031 (16)
C4050.050 (2)0.054 (2)0.045 (2)0.0336 (19)0.0110 (17)0.0024 (17)
C4060.0371 (18)0.0406 (19)0.0423 (19)0.0222 (16)0.0083 (15)0.0041 (15)
C4070.0310 (16)0.0291 (16)0.0339 (16)0.0144 (13)0.0082 (13)0.0047 (13)
C4080.040 (2)0.051 (2)0.048 (2)0.0175 (17)0.0072 (16)0.0195 (18)
C4090.065 (3)0.064 (3)0.062 (3)0.032 (2)0.021 (2)0.035 (2)
C4100.063 (3)0.044 (2)0.075 (3)0.007 (2)0.021 (2)0.025 (2)
C4110.054 (3)0.048 (2)0.064 (3)0.004 (2)0.011 (2)0.006 (2)
C4120.038 (2)0.045 (2)0.041 (2)0.0052 (16)0.0055 (16)0.0030 (16)
Cl10.0438 (5)0.0810 (7)0.0495 (5)0.0391 (5)0.0037 (4)0.0043 (5)
Cl20.0611 (6)0.0621 (6)0.0573 (6)0.0275 (5)0.0059 (5)0.0071 (5)
C130.154 (6)0.068 (3)0.083 (4)0.052 (4)0.001 (4)0.031 (3)
Cl30.153 (2)0.1225 (17)0.162 (2)0.0639 (16)0.0071 (17)0.0252 (15)
Cl40.1430 (17)0.0734 (10)0.1140 (14)0.0276 (10)0.0145 (12)0.0223 (9)
C140.123 (5)0.071 (4)0.082 (4)0.041 (4)0.031 (4)0.012 (3)
Cl50.222 (5)0.0797 (17)0.0748 (18)0.050 (2)0.002 (2)0.0040 (14)
Cl60.092 (3)0.148 (4)0.213 (6)0.023 (3)0.027 (3)0.016 (4)
C14A0.123 (5)0.071 (4)0.082 (4)0.041 (4)0.031 (4)0.012 (3)
Cl5A0.63 (4)0.40 (2)0.173 (13)0.38 (3)0.003 (18)0.010 (14)
Cl6A0.169 (13)0.207 (13)0.47 (3)0.030 (9)0.151 (16)0.171 (18)
O60.084 (4)0.102 (4)0.173 (5)0.049 (3)0.035 (4)0.031 (4)
O70.137 (10)0.108 (8)0.188 (12)0.055 (7)0.021 (9)0.049 (8)
Geometric parameters (Å, º) top
Ir1—C121.910 (3)C203—H2030.9400
Ir1—C42.119 (3)C204—C2051.361 (7)
Ir1—C82.177 (3)C204—H2040.9400
Ir1—C12.225 (3)C205—C2061.385 (6)
Ir1—P12.3393 (8)C205—H2050.9400
Ir1—P42.3658 (8)C206—H2060.9400
P1—C1011.811 (3)C207—C2081.382 (6)
P1—C1071.822 (3)C207—C2121.385 (6)
P1—C21.839 (3)C208—C2091.381 (6)
P2—C2011.800 (3)C208—H2080.9400
P2—C2071.802 (4)C209—C2101.353 (9)
P2—C21.810 (3)C209—H2090.9400
P2—C11.837 (3)C210—C2111.380 (10)
P3—C11.791 (3)C210—H2100.9400
P3—C31.798 (3)C211—C2121.398 (7)
P3—C3071.804 (3)C211—H2110.9400
P3—C3011.808 (3)C212—H2120.9400
P4—C4071.820 (3)C301—C3061.387 (5)
P4—C4011.821 (3)C301—C3021.390 (5)
P4—C31.840 (3)C302—C3031.381 (5)
O1—C51.208 (4)C302—H3020.9400
O2—C51.340 (4)C303—C3041.364 (7)
O2—C61.468 (4)C303—H3030.9400
O3—C91.205 (4)C304—C3051.374 (7)
O4—C91.348 (4)C304—H3040.9400
O4—C101.446 (5)C305—C3061.393 (5)
O5—C121.120 (4)C305—H3050.9400
C1—C41.515 (4)C306—H3060.9400
C2—H2A0.9800C307—C3081.392 (5)
C2—H2B0.9800C307—C3121.398 (4)
C3—H3A0.9800C308—C3091.388 (5)
C3—H3B0.9800C308—H3080.9400
C4—C51.488 (4)C309—C3101.376 (6)
C4—H40.942 (18)C309—H3090.9400
C6—C71.479 (6)C310—C3111.381 (6)
C6—H6A0.9800C310—H3100.9400
C6—H6B0.9800C311—C3121.384 (5)
C7—H7A0.9700C311—H3110.9400
C7—H7B0.9700C312—H3120.9400
C7—H7C0.9700C401—C4021.385 (5)
C8—C91.470 (5)C401—C4061.386 (5)
C8—H8A0.9800C402—C4031.386 (5)
C8—H8B0.9800C402—H4020.9400
C10—C111.485 (8)C403—C4041.371 (6)
C10—H10A0.9800C403—H4030.9400
C10—H10B0.9800C404—C4051.371 (6)
C11—H11A0.9700C404—H4040.9400
C11—H11B0.9700C405—C4061.385 (5)
C11—H11C0.9700C405—H4050.9400
C101—C1021.388 (5)C406—H4060.9400
C101—C1061.394 (5)C407—C4081.385 (5)
C102—C1031.389 (6)C407—C4121.395 (5)
C102—H1020.9400C408—C4091.383 (5)
C103—C1041.363 (6)C408—H4080.9400
C103—H1030.9400C409—C4101.373 (7)
C104—C1051.359 (6)C409—H4090.9400
C104—H1040.9400C410—C4111.359 (7)
C105—C1061.384 (5)C410—H4100.9400
C105—H1050.9400C411—C4121.380 (6)
C106—H1060.9400C411—H4110.9400
C107—C1081.389 (5)C412—H4120.9400
C107—C1121.398 (5)C13—Cl31.736 (8)
C108—C1091.383 (5)C13—Cl41.746 (7)
C108—H1080.9400C13—H13A0.9800
C109—C1101.386 (7)C13—H13B0.9800
C109—H1090.9400C14—Cl51.713 (7)
C110—C1111.385 (7)C14—Cl61.745 (10)
C110—H1100.9400C14—H14A0.9800
C111—C1121.370 (6)C14—H14B0.9800
C111—H1110.9400C14A—Cl6A1.545 (15)
C112—H1120.9400C14A—Cl5A1.82 (2)
C201—C2021.381 (5)C14A—H14C0.9800
C201—C2061.403 (5)C14A—H14D0.9800
C202—C2031.380 (5)O6—H6OA0.85 (2)
C202—H2020.9400O6—H6OB0.845 (19)
C203—C2041.377 (7)
C12—Ir1—C4158.78 (12)C112—C111—H111119.9
C12—Ir1—C893.36 (13)C110—C111—H111119.9
C4—Ir1—C8106.70 (12)C111—C112—C107120.2 (4)
C12—Ir1—C1118.82 (12)C111—C112—H112119.9
C4—Ir1—C140.72 (11)C107—C112—H112119.9
C8—Ir1—C1147.39 (12)C202—C201—C206119.1 (3)
C12—Ir1—P188.65 (10)C202—C201—P2121.8 (3)
C4—Ir1—P185.11 (9)C206—C201—P2118.9 (3)
C8—Ir1—P188.50 (9)C203—C202—C201120.2 (4)
C1—Ir1—P187.22 (8)C203—C202—H202119.9
C12—Ir1—P491.76 (10)C201—C202—H202119.9
C4—Ir1—P493.24 (8)C204—C203—C202120.5 (5)
C8—Ir1—P495.09 (9)C204—C203—H203119.7
C1—Ir1—P489.41 (8)C202—C203—H203119.7
P1—Ir1—P4176.35 (3)C205—C204—C203119.9 (4)
C101—P1—C107102.78 (15)C205—C204—H204120.1
C101—P1—C2106.38 (15)C203—C204—H204120.1
C107—P1—C2105.77 (15)C204—C205—C206120.9 (4)
C101—P1—Ir1116.72 (11)C204—C205—H205119.6
C107—P1—Ir1120.29 (11)C206—C205—H205119.6
C2—P1—Ir1103.76 (10)C205—C206—C201119.4 (4)
C201—P2—C207105.53 (16)C205—C206—H206120.3
C201—P2—C2107.18 (15)C201—C206—H206120.3
C207—P2—C2110.99 (17)C208—C207—C212120.6 (4)
C201—P2—C1120.40 (15)C208—C207—P2119.7 (3)
C207—P2—C1107.20 (16)C212—C207—P2119.7 (3)
C2—P2—C1105.50 (14)C209—C208—C207120.2 (5)
C1—P3—C3106.12 (14)C209—C208—H208119.9
C1—P3—C307111.84 (14)C207—C208—H208119.9
C3—P3—C307107.34 (14)C210—C209—C208120.1 (6)
C1—P3—C301117.32 (14)C210—C209—H209120.0
C3—P3—C301108.18 (15)C208—C209—H209120.0
C307—P3—C301105.63 (15)C209—C210—C211120.3 (5)
C407—P4—C401104.51 (14)C209—C210—H210119.9
C407—P4—C3105.94 (15)C211—C210—H210119.9
C401—P4—C3103.41 (14)C210—C211—C212121.1 (5)
C407—P4—Ir1116.18 (11)C210—C211—H211119.5
C401—P4—Ir1119.97 (11)C212—C211—H211119.5
C3—P4—Ir1105.34 (10)C207—C212—C211117.7 (5)
C5—O2—C6116.8 (3)C207—C212—H212121.1
C9—O4—C10116.1 (3)C211—C212—H212121.1
C4—C1—P3121.7 (2)C306—C301—C302119.5 (3)
C4—C1—P2108.3 (2)C306—C301—P3122.3 (3)
P3—C1—P2122.16 (16)C302—C301—P3118.2 (3)
C4—C1—Ir165.88 (15)C303—C302—C301119.8 (4)
P3—C1—Ir1110.27 (14)C303—C302—H302120.1
P2—C1—Ir1115.59 (14)C301—C302—H302120.1
P2—C2—P1111.79 (17)C304—C303—C302120.5 (4)
P2—C2—H2A109.3C304—C303—H303119.8
P1—C2—H2A109.3C302—C303—H303119.8
P2—C2—H2B109.3C303—C304—C305120.7 (4)
P1—C2—H2B109.3C303—C304—H304119.6
H2A—C2—H2B107.9C305—C304—H304119.6
P3—C3—P4110.67 (16)C304—C305—C306119.6 (4)
P3—C3—H3A109.5C304—C305—H305120.2
P4—C3—H3A109.5C306—C305—H305120.2
P3—C3—H3B109.5C301—C306—C305119.9 (4)
P4—C3—H3B109.5C301—C306—H306120.1
H3A—C3—H3B108.1C305—C306—H306120.1
C5—C4—C1125.7 (3)C308—C307—C312119.2 (3)
C5—C4—Ir1131.9 (2)C308—C307—P3124.0 (2)
C1—C4—Ir173.40 (16)C312—C307—P3116.5 (2)
C5—C4—H4104 (2)C309—C308—C307119.9 (3)
C1—C4—H4112 (2)C309—C308—H308120.1
Ir1—C4—H4108 (2)C307—C308—H308120.1
O1—C5—O2122.8 (3)C310—C309—C308120.4 (4)
O1—C5—C4127.9 (3)C310—C309—H309119.8
O2—C5—C4109.2 (3)C308—C309—H309119.8
O2—C6—C7106.6 (3)C309—C310—C311120.3 (4)
O2—C6—H6A110.4C309—C310—H310119.8
C7—C6—H6A110.4C311—C310—H310119.8
O2—C6—H6B110.4C310—C311—C312119.9 (3)
C7—C6—H6B110.4C310—C311—H311120.0
H6A—C6—H6B108.6C312—C311—H311120.0
C6—C7—H7A109.5C311—C312—C307120.2 (3)
C6—C7—H7B109.5C311—C312—H312119.9
H7A—C7—H7B109.5C307—C312—H312119.9
C6—C7—H7C109.5C402—C401—C406119.1 (3)
H7A—C7—H7C109.5C402—C401—P4119.2 (2)
H7B—C7—H7C109.5C406—C401—P4121.7 (3)
C9—C8—Ir1114.1 (2)C401—C402—C403120.0 (3)
C9—C8—H8A108.7C401—C402—H402120.0
Ir1—C8—H8A108.7C403—C402—H402120.0
C9—C8—H8B108.7C404—C403—C402120.4 (4)
Ir1—C8—H8B108.7C404—C403—H403119.8
H8A—C8—H8B107.6C402—C403—H403119.8
O3—C9—O4122.3 (3)C405—C404—C403120.0 (3)
O3—C9—C8126.2 (3)C405—C404—H404120.0
O4—C9—C8111.5 (3)C403—C404—H404120.0
O4—C10—C11107.2 (5)C404—C405—C406120.2 (4)
O4—C10—H10A110.3C404—C405—H405119.9
C11—C10—H10A110.3C406—C405—H405119.9
O4—C10—H10B110.3C405—C406—C401120.3 (3)
C11—C10—H10B110.3C405—C406—H406119.9
H10A—C10—H10B108.5C401—C406—H406119.9
C10—C11—H11A109.5C408—C407—C412118.9 (3)
C10—C11—H11B109.5C408—C407—P4118.6 (3)
H11A—C11—H11B109.5C412—C407—P4122.6 (3)
C10—C11—H11C109.5C409—C408—C407120.4 (4)
H11A—C11—H11C109.5C409—C408—H408119.8
H11B—C11—H11C109.5C407—C408—H408119.8
O5—C12—Ir1177.9 (3)C410—C409—C408119.7 (4)
C102—C101—C106119.1 (3)C410—C409—H409120.2
C102—C101—P1122.4 (3)C408—C409—H409120.2
C106—C101—P1118.2 (3)C411—C410—C409120.6 (4)
C101—C102—C103119.3 (4)C411—C410—H410119.7
C101—C102—H102120.4C409—C410—H410119.7
C103—C102—H102120.4C410—C411—C412120.5 (4)
C104—C103—C102120.7 (4)C410—C411—H411119.7
C104—C103—H103119.6C412—C411—H411119.7
C102—C103—H103119.6C411—C412—C407119.8 (4)
C105—C104—C103120.7 (4)C411—C412—H412120.1
C105—C104—H104119.7C407—C412—H412120.1
C103—C104—H104119.7Cl3—C13—Cl4111.3 (4)
C104—C105—C106120.0 (4)Cl3—C13—H13A109.4
C104—C105—H105120.0Cl4—C13—H13A109.4
C106—C105—H105120.0Cl3—C13—H13B109.4
C105—C106—C101120.2 (4)Cl4—C13—H13B109.4
C105—C106—H106119.9H13A—C13—H13B108.0
C101—C106—H106119.9Cl5—C14—Cl6110.5 (4)
C108—C107—C112119.1 (3)Cl5—C14—H14A109.6
C108—C107—P1123.4 (3)Cl6—C14—H14A109.6
C112—C107—P1117.5 (3)Cl5—C14—H14B109.6
C109—C108—C107120.7 (4)Cl6—C14—H14B109.6
C109—C108—H108119.7H14A—C14—H14B108.1
C107—C108—H108119.7Cl6A—C14A—Cl5A123.0 (11)
C108—C109—C110119.4 (4)Cl6A—C14A—H14C106.6
C108—C109—H109120.3Cl5A—C14A—H14C106.6
C110—C109—H109120.3Cl6A—C14A—H14D106.6
C111—C110—C109120.3 (4)Cl5A—C14A—H14D106.6
C111—C110—H110119.9H14C—C14A—H14D106.5
C109—C110—H110119.9H6OA—O6—H6OB109 (7)
C112—C111—C110120.3 (4)
C3—P3—C1—C432.3 (3)C1—P2—C201—C206101.9 (3)
C307—P3—C1—C4149.1 (2)C206—C201—C202—C2031.9 (6)
C301—P3—C1—C488.7 (3)P2—C201—C202—C203176.6 (4)
C3—P3—C1—P2177.92 (18)C201—C202—C203—C2041.0 (8)
C307—P3—C1—P265.3 (2)C202—C203—C204—C2050.1 (9)
C301—P3—C1—P256.9 (2)C203—C204—C205—C2060.4 (9)
C3—P3—C1—Ir141.19 (18)C204—C205—C206—C2010.5 (8)
C307—P3—C1—Ir175.56 (17)C202—C201—C206—C2051.6 (6)
C301—P3—C1—Ir1162.17 (14)P2—C201—C206—C205176.5 (4)
C201—P2—C1—C4159.6 (2)C201—P2—C207—C20891.7 (3)
C207—P2—C1—C439.2 (2)C2—P2—C207—C208152.5 (3)
C2—P2—C1—C479.2 (2)C1—P2—C207—C20837.7 (3)
C201—P2—C1—P310.0 (3)C201—P2—C207—C21286.1 (3)
C207—P2—C1—P3110.4 (2)C2—P2—C207—C21229.7 (4)
C2—P2—C1—P3131.2 (2)C1—P2—C207—C212144.4 (3)
C201—P2—C1—Ir1128.96 (17)C212—C207—C208—C2091.7 (6)
C207—P2—C1—Ir1110.60 (17)P2—C207—C208—C209179.5 (4)
C2—P2—C1—Ir17.8 (2)C207—C208—C209—C2100.1 (8)
C201—P2—C2—P1163.12 (18)C208—C209—C210—C2111.4 (10)
C207—P2—C2—P182.1 (2)C209—C210—C211—C2121.4 (11)
C1—P2—C2—P133.7 (2)C208—C207—C212—C2111.6 (6)
C101—P1—C2—P2167.17 (18)P2—C207—C212—C211179.4 (4)
C107—P1—C2—P284.0 (2)C210—C211—C212—C2070.1 (9)
Ir1—P1—C2—P243.49 (19)C1—P3—C301—C30696.7 (3)
C1—P3—C3—P445.4 (2)C3—P3—C301—C30623.2 (3)
C307—P3—C3—P474.32 (19)C307—P3—C301—C306137.9 (3)
C301—P3—C3—P4172.12 (15)C1—P3—C301—C30285.3 (3)
C407—P4—C3—P394.87 (18)C3—P3—C301—C302154.8 (3)
C401—P4—C3—P3155.50 (17)C307—P3—C301—C30240.1 (3)
Ir1—P4—C3—P328.78 (17)C306—C301—C302—C3031.6 (6)
P3—C1—C4—C530.3 (4)P3—C301—C302—C303179.7 (3)
P2—C1—C4—C5119.4 (3)C301—C302—C303—C3041.3 (7)
Ir1—C1—C4—C5130.1 (3)C302—C303—C304—C3050.2 (8)
P3—C1—C4—Ir199.8 (2)C303—C304—C305—C3060.4 (7)
P2—C1—C4—Ir1110.49 (16)C302—C301—C306—C3051.0 (6)
C6—O2—C5—O10.8 (5)P3—C301—C306—C305179.0 (3)
C6—O2—C5—C4177.3 (3)C304—C305—C306—C3010.0 (6)
C1—C4—C5—O12.1 (5)C1—P3—C307—C30810.8 (3)
Ir1—C4—C5—O197.9 (4)C3—P3—C307—C308105.2 (3)
C1—C4—C5—O2175.9 (3)C301—P3—C307—C308139.5 (3)
Ir1—C4—C5—O284.2 (3)C1—P3—C307—C312174.7 (2)
C5—O2—C6—C7171.6 (4)C3—P3—C307—C31269.3 (3)
C10—O4—C9—O32.9 (5)C301—P3—C307—C31246.0 (3)
C10—O4—C9—C8175.7 (3)C312—C307—C308—C3090.6 (5)
Ir1—C8—C9—O395.1 (4)P3—C307—C308—C309175.0 (3)
Ir1—C8—C9—O483.4 (3)C307—C308—C309—C3101.7 (6)
C9—O4—C10—C11178.5 (4)C308—C309—C310—C3111.1 (6)
C107—P1—C101—C102143.3 (3)C309—C310—C311—C3120.5 (6)
C2—P1—C101—C10232.4 (4)C310—C311—C312—C3071.6 (5)
Ir1—P1—C101—C10282.8 (3)C308—C307—C312—C3111.0 (5)
C107—P1—C101—C10642.1 (3)P3—C307—C312—C311173.8 (3)
C2—P1—C101—C106153.0 (3)C407—P4—C401—C402166.4 (3)
Ir1—P1—C101—C10691.8 (3)C3—P4—C401—C40282.9 (3)
C106—C101—C102—C1031.9 (6)Ir1—P4—C401—C40234.0 (3)
P1—C101—C102—C103176.5 (4)C407—P4—C401—C40612.3 (3)
C101—C102—C103—C1041.2 (7)C3—P4—C401—C40698.4 (3)
C102—C103—C104—C1050.1 (8)Ir1—P4—C401—C406144.8 (2)
C103—C104—C105—C1060.1 (7)C406—C401—C402—C4030.6 (5)
C104—C105—C106—C1010.6 (6)P4—C401—C402—C403179.4 (3)
C102—C101—C106—C1051.6 (6)C401—C402—C403—C4040.3 (6)
P1—C101—C106—C105176.4 (3)C402—C403—C404—C4050.2 (6)
C101—P1—C107—C108121.0 (3)C403—C404—C405—C4060.4 (6)
C2—P1—C107—C108127.6 (3)C404—C405—C406—C4010.1 (6)
Ir1—P1—C107—C10810.8 (3)C402—C401—C406—C4050.4 (5)
C101—P1—C107—C11257.8 (3)P4—C401—C406—C405179.1 (3)
C2—P1—C107—C11253.6 (3)C401—P4—C407—C40873.7 (3)
Ir1—P1—C107—C112170.4 (2)C3—P4—C407—C408177.4 (3)
C112—C107—C108—C1091.7 (5)Ir1—P4—C407—C40860.9 (3)
P1—C107—C108—C109179.5 (3)C401—P4—C407—C412105.6 (3)
C107—C108—C109—C1100.5 (6)C3—P4—C407—C4123.3 (3)
C108—C109—C110—C1110.6 (7)Ir1—P4—C407—C412119.8 (3)
C109—C110—C111—C1120.5 (7)C412—C407—C408—C4092.0 (6)
C110—C111—C112—C1070.8 (6)P4—C407—C408—C409178.7 (3)
C108—C107—C112—C1111.8 (5)C407—C408—C409—C4100.4 (7)
P1—C107—C112—C111179.3 (3)C408—C409—C410—C4112.1 (7)
C207—P2—C201—C202155.4 (3)C409—C410—C411—C4121.3 (8)
C2—P2—C201—C20237.0 (3)C410—C411—C412—C4071.2 (7)
C1—P2—C201—C20283.3 (3)C408—C407—C412—C4112.8 (6)
C207—P2—C201—C20619.4 (3)P4—C407—C412—C411177.9 (3)
C2—P2—C201—C206137.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···Cl10.982.483.421 (3)162
C3—H3A···Cl1i0.982.593.488 (3)152
C3—H3B···O10.982.212.968 (4)134
C102—H102···Cl20.942.613.505 (4)160
C108—H108···O20.942.613.313 (4)132
C112—H112···Cl10.942.803.595 (4)143
C202—H202···Cl20.942.703.574 (4)156
C212—H212···Cl10.942.803.733 (5)173
C306—H306···O10.942.473.061 (4)121
C312—H312···Cl1i0.942.733.503 (4)140
C402—H402···O20.942.473.375 (4)162
C408—H408···O30.942.443.326 (5)156
C412—H412···Cl1i0.942.973.866 (4)161
C13—H13A···O5ii0.982.583.194 (6)121
C13—H13A···Cl2ii0.982.683.500 (7)141
C14—H14A···Cl2iii0.982.653.553 (6)153
C14—H14B···O1iv0.982.373.327 (6)164
C14A—H14C···O1iv0.982.383.327 (6)163
C14A—H14D···Cl2iii0.982.593.553 (6)168
O6—H6OA···Cl20.85 (2)2.39 (4)3.178 (5)154 (7)
O6—H6OB···Cl10.85 (2)2.39 (2)3.239 (6)178 (6)
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z; (iii) x1, y+1, z; (iv) x1, y, z.
Selected bond lengths (Å) and angles (°) of the compounds 4, 5, 6 and 7 top
4567
Ir1—C12.273 (4)2.279 (6)2.149 (4)2.225 (3)
Ir1—C42.072 (5)2.046 (7)2.076 (4)2.119 (3)
Ir1—P12.290 (1)2.318 (2)2.309 (1)2.339 (1)
Ir1—P42.278 (1)2.306 (2)2.330 (1)2.366 (1)
P2—C11.791 (5)1.788 (7)1.822 (4)1.837 (3)
Ir1—Lx (Lx= –H, –Cl, –CH2CO2Et)1.62 (2)2.163 (7)2.427 (1)2.177 (3)
Ir1—Ly (Ly = –Cl, –CO)2.462 (1)2.461 (2)2.460 (1)1.910 (3)
P3—C11.788 (5)1.789 (7)1.833 (4)1.791 (3)
C1—C41.515 (6)1.507 (9)1.513 (5)1.515 (4)
C4—Ir1—C140.5 (2)40.3 (2)41.9 (2)40.72 (11)
C4—C1—Ir162.6 (2)61.5 (3)66.5 (2)65.88 (15)
C1—C4—Ir176.9 (3)78.2 (4)71.6 (2)73.40 (16)
C4—Ir1—Ly (Ly = –Cl, –CO)150.3 (1)152.5 (2)151.9 (1)158.8 (1)
C1—Ir1—Ly (Ly = –Cl, –CO)111.3 (1)112.8 (2)111.5 (1)118.8 (1)
C4—Ir1—Lx (Lx= –H, –Cl, –CH2CO2Et)119.7 (18)120.8 (3)116.2 (1)106.7 (1)
C1—Ir1—Lx (Lx=-H, -Cl, -CH2CO2Et)159.8 (18)161.1 (3)158.1 (1)147.4 (1)
P1—Ir1—P4178.4 (1)173.5 (1)177.6 (1)176.4 (1)
P1—Ir1—(C1-C4)84.2188.8585.5784.56
 

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