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Crystal structures of four new iridium complexes, each containing a highly flexible carbodi­phos­phorane PCP pincer ligand

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aInstitute of General, Inorganic, and Theoretical Chemistry, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria
*Correspondence e-mail: gabriel.partl@uibk.ac.at

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 19 April 2018; accepted 19 May 2018; online 25 May 2018)

Compound [Ir(C8H12)(C51H45P4)]Cl2 or [Ir(cod)(CH(dppm)2-κ3P,C,P)]Cl2 (1a), was obtained from [IrCl(cod)]2 and the carbodi­phospho­rane (CDP) salt [CH(dppm)2]Cl [where cod = cyclo­octa-1,5-diene and dppm = bis­(di­phenyl­phosphino)methane]. Treatment of 1a with thallium(I) tri­fluoro­methane­sulfonate [Tl(OTf)] and subsequent crystallization gave complex [Ir(C8H12)(C51H45P4)](OTf)2·CH3CO2C2H5·CH2Cl2 or [Ir(cod)(CH(dppm)2-κ3P,C,P)](OTf)2·CH3CO2C2H5·CH2Cl2 (1b) [systematic name: (cyclo­octa-1,5-diene)(1,1,3,3,5,5,7,7-octa­phenyl-1,7-diphospha-3,5-di­phospho­niaheptan-4-yl)iridium(I) bis­(tri­fluoro­methane­sulfonate)–ethyl acetate–di­chloro­methane (1/1/1)]. This five-coordinate iridium(I) complex cation adopts a trigonal–bipyramidal geometry with the CDP carbon and one cod double bond in axial sites. Compound 1b represents the first example of a non-meridional coordination of the PCP pincer ligand [CH(dppm)2]+ with a P—Ir—P angle of 98.08 (2)°. Compound 2, [IrCl2H(C51H44P4)]·(CH3)2CO or [IrCl2H(C(dppm)2-κ3P,C,P)]·(CH3)2CO [systematic name: di­chlorido­hydrido(1,1,3,3,5,5,7,7-octa­phenyl-1,5λ5,7-triphospha-3-phospho­niahept-4-en-4-yl)iridium(III) acetone monosolvate], crystallizes as an acetone monosolvate. It is a six-coordinate IrIII coordination compound. Here, the PCP pincer ligand is coordinated in a meridional manner; one chlorido ligand is positioned trans to the carbon donor, the remaining two coordination sites being occupied by the second chlorido and a hydrido ligand trans to each other. Complex 3, [IrCl2H(C51H45P4)]Cl·5H2O or [IrCl2H(CH(dppm)2-κ3P,C,P)]Cl·5H2O [systematic name: di­chlorido­hydrido(1,1,3,3,5,5,7,7-octa­phenyl-1,7-diphospha-3,5-di­phospho­niaheptan-4-yl)iridium(III) chloride penta­hydrate], represents the conjugate CH acid of 2. The ligand [CH(dppm)2]+ is coordinated in a meridional manner. In the cationic six-coordinate IrIII complex 4, [IrClH(CO)(C51H44P4)]Cl·2CH3OH·H2O or [IrClH(CO)(C(dppm)2-κ3P,C,P)]Cl·2CH3OH·H2O [systematic name: carbonyl­chlorido­hydrido(1,1,3,3,5,5,7,7-octa­phenyl-1,5λ5,7-triphospha-3-phos­pho­niahept-4-en-4-yl)iridium(III) chloride–methanol–water (1/2/1)], the chlorido ligand is found in the plane defined by the Ir center and the meridional PCP ligand; the H and CO ligands are positioned axially to this plane and trans to each other.

1. Chemical context

The syntheses of the title compounds are summarized in the Scheme. The substitution of the bridging chlorido ligands of [IrCl(cod)]2 by the cationic PCP pincer ligand [CH(dppm)2]Cl qu­anti­tatively affords the five-coordinate Ir(I) PCP pincer complex [Ir(cod)(CH(dppm)2- κ3P,C,P)]Cl2 (1a). The central carbon of the PCP ligand is part of a protonated carbodi­phospho­rane (CDP) functionality. Metathesis with Tl(OTf) gave the corresponding OTf salt (1b). These products represent the first examples of a non-meridional coordination mode of the PCP pincer ligand [CH(dppm)2]+.

[Scheme 1]

Related IrI complexes of the composition [Ir(PCP)(cod)]n+ have been reported for a neutral PCP ligand based on a NHO type framework (n = 1; Iglesias et al., 2015[Iglesias, M., Iturmendi, A., Sanz Miguel, P. J., Polo, V., Pérez-Torrente, J. J. & Oro, L. A. (2015). Chem. Commun. 51, 12431-12434.]), for the anionic aryl based ligand [C6H3-1,3-[CH2P(CF3)2]2] (n = 0; Adams et al., 2011[Adams, J. J., Arulsamy, N. & Roddick, D. M. (2011). Organometallics, 30, 697-711.]), and an anionic asymmetric PC(sp3)P ligand (n = 0; Cui et al., 2016[Cui, P., Babbini, D. C. & Iluc, V. M. (2016). Dalton Trans. 45, 10007-10016.]). They were obtained either analogously to 1a (Iglesias et al., 2015[Iglesias, M., Iturmendi, A., Sanz Miguel, P. J., Polo, V., Pérez-Torrente, J. J. & Oro, L. A. (2015). Chem. Commun. 51, 12431-12434.]; Cui et al., 2016[Cui, P., Babbini, D. C. & Iluc, V. M. (2016). Dalton Trans. 45, 10007-10016.]) or via a combined reductive elimination/substitution reaction of [IrClH(PCP)(C2H4)] with NEt3 in the presence of cod (Adams et al., 2011[Adams, J. J., Arulsamy, N. & Roddick, D. M. (2011). Organometallics, 30, 697-711.]).

Whilst the complex 1b is indefinitely stable, 1a qu­anti­tatively transforms into the IrIII PCP pincer CDP complex [IrCl2H(C(dppm)2-κ3P,C,P)] (2), via an intra­molecular oxidative addition reaction upon prolonged standing in solution (Fig. 1[link]). The sole reported Ir complex with a donor set related to 2 is [IrCl2H(PCP)]NHEt3, involving the above mentioned π-accepting anionic ligand [C6H3-1,3-[CH2P(CF3)2]2] (Adams et al., 2011[Adams, J. J., Arulsamy, N. & Roddick, D. M. (2011). Organometallics, 30, 697-711.]). This ligand is able to adopt both meridional and non-meridional coordination modes related to the cationic protonated PCP pincer CDP ligand [CH(dppm)2]+.

[Figure 1]
Figure 1
Structure of compound 1b, with atom labelling and 30% probability displacement ellipsoids. For clarity, only the ipso carbon atoms of the phenyl groups are shown, and the solvent mol­ecules have been omitted.

The central carbon of CDPs carries two lone electron pairs and is able to inter­act with one or two Lewis acids (Petz & Frenking, 2010[Petz, W. & Frenking, G. (2010). Editors. Carbodiphosphoranes and Related Ligands, Vol. 30. Berlin Heidelberg: Springer-Verlag.]). Consequently, the central carbon of the PCP pincer ligand of 2 is able to inter­act with another Lewis acid and can be converted to the conjugate CH acid [IrCl2H(CH(dppm)2-κ3P,C,P)]Cl (3), upon treatment with aqueous hydro­chloric acid.

The reaction of 2 with carbon monoxide results in the substitution of the chlorido ligand positioned trans to the hydrido ligand and affords [IrClH(CO)(CH(dppm)2-κ3P,C,P)]Cl (4). The isomer of 4 with the CO ligand positioned trans to the carbodi­phospho­rane carbon of the PCP pincer ligand has been synthesized via reaction of Vaska's complex with [CH(dppm)2]Cl (Reitsamer et al., 2018[Reitsamer, C., Schlapp-Hackl, I., Partl, G., Schuh, W., Kopacka, H., Wurst, K. & Peringer, P. (2018). Acta Cryst. E74, 620-624.]). Related [IrClH(CO)(PCP)] complexes with the H and CO ligands in a trans configuration have been obtained via addition of CO to the corresponding five-coordinated complexes [IrClH(PCP)] (Goldberg et al., 2015[Goldberg, J. M., Wong, G. W., Brastow, K. E., Kaminsky, W., Goldberg, K. I. & Heinekey, D. M. (2015). Organometallics, 34, 753-762.]; Segawa et al., 2009[Segawa, Y., Yamashita, M. & Nozaki, K. (2009). J. Am. Chem. Soc. 131, 9201-9203.]; Jonasson et al., 2015[Jonasson, K. J., Polukeev, A. V. & Wendt, O. F. (2015). RSC Adv. 5, 15534-15538.]; Kuklin et al., 2006[Kuklin, S. A., Sheloumov, A. M., Dolgushin, F. M., Ezernitskaya, M. G., Peregudov, A. S., Petrovskii, P. V. & Koridze, A. A. (2006). Organometallics, 25, 5466-5476.]), or, in one case, by bubbling CO through a solution of [IrClH(MeCN)(PCP)] in di­chloro­methane, with the H and Cl ligands being in a trans configuration (Silantyev et al., 2014[Silantyev, G. A., Filippov, O. A., Musa, S., Gelman, D., Belkova, N. V., Weisz, K., Epstein, L. M. & Shubina, E. S. (2014). Organometallics, 33, 5964-5973.]). Both isomers of [IrClH(CO)(PCP)], either with H and CO or H and Cl in a trans configuration have been structurally characterized for a triptycene-based PCP pincer ligand (Silantyev et al., 2014[Silantyev, G. A., Filippov, O. A., Musa, S., Gelman, D., Belkova, N. V., Weisz, K., Epstein, L. M. & Shubina, E. S. (2014). Organometallics, 33, 5964-5973.]; Azerraf & Gelman, 2009[Azerraf, C. & Gelman, D. (2009). Organometallics, 28, 6578-6584.]) and a cyclo­hexyl-based PCP pincer ligand (Jonasson et al., 2015[Jonasson, K. J., Polukeev, A. V. & Wendt, O. F. (2015). RSC Adv. 5, 15534-15538.]).

2. Structural commentary

The mol­ecular structures of the four complexes are illustrated in Figs. 1[link]–4[link][link][link], and selected bond distances and bond angles are given in Table 1[link]. The structure of 1b (Fig. 1[link]) establishes an 18-electron five-coordinate dicationic IrI complex with two OTf counter-ions. The Ir atom is coordinated by the PCP pincer ligand [CH(dppm)2]+ and a bidentate cod ligand in a distorted trigonal–bipyramidal geometry, in which the axial positions are occupied by the CDP carbon C1 and the double bond C8=C9 of the cod ligand; the donor atoms P1 and P4 and the double bond C4=C5 are located in the equatorial sites. The P1—Ir1—P4 angle amounts to 98.08 (2)°, compared to 102.789 (19)° (Cui et al., 2016[Cui, P., Babbini, D. C. & Iluc, V. M. (2016). Dalton Trans. 45, 10007-10016.]), 106.44 (3)° (Iglesias et al., 2015[Iglesias, M., Iturmendi, A., Sanz Miguel, P. J., Polo, V., Pérez-Torrente, J. J. & Oro, L. A. (2015). Chem. Commun. 51, 12431-12434.]) and 119.02 (4)° (Adams et al., 2011[Adams, J. J., Arulsamy, N. & Roddick, D. M. (2011). Organometallics, 30, 697-711.]) for the aforementioned IrI related compounds [Ir(PCP)(cod)]n+. The PCP pincer ligand [CH(dppm)2]+ is an impressively flexible ligand, adopting a range of P—Ir—P values from 98.08 (2)° for 1b to 177.66 (4)° observed for [(PtCl)(CH(dppm)2-κ3P,C,P)]Cl2 (Reitsamer et al., 2012[Reitsamer, C., Stallinger, S., Schuh, W., Kopacka, H., Wurst, K., Obendorf, D. & Peringer, P. (2012). Dalton Trans. 41, 3503-3514.]). The Ir1—C1 distance of 2.232 (3) Å is found in the upper segment of Ir—C distance ranges, as is typical for Ir complexes involving the [CH(dppm)2]+ ligand (Reitsamer et al., 2012[Reitsamer, C., Stallinger, S., Schuh, W., Kopacka, H., Wurst, K., Obendorf, D. & Peringer, P. (2012). Dalton Trans. 41, 3503-3514.]). The P—C `separation sizes' within the CDP functionality are in the range of single bonds, as expected for CDPs donating to two Lewis acids (Petz & Frenking, 2010[Petz, W. & Frenking, G. (2010). Editors. Carbodiphosphoranes and Related Ligands, Vol. 30. Berlin Heidelberg: Springer-Verlag.]). The geometry around C1 is distorted tetra­hedral according to the angles P3—C1—P2 = 114.86 (14)°, P3—C1—Ir1 = 109.99 (13)° and P2—C1—Ir1 = 111.40 (13)°.

Table 1
Selected bond lengths (Å) and bond angles (°) for compounds 1b4

  1b 2 3 4
Ir1—C1 2.232 (3) 2.101 (5) 2.132 (4) 2.124 (5)
Ir1—C4 2.169 (3)
Ir1—C5 2.172 (3)
Ir1—C8 2.208 (3)
Ir1—C9 2.225 (3)
Ir1—Cl1 2.4412 (15) 2.405 (1) 2.4359 (13)
Ir1—P1 2.3889 (7) 2.3019 (15) 2.306 (1) 2.3265 (14)
Ir1—P4 2.3386 (7) 2.2831 (16) 2.283 (1) 2.3235 (13)
Ir1—H1 1.638 (19) 1.46 (4) 1.535 (19)
P2—C1 1.821 (3) 1.695 (6) 1.811 (4) 1.681 (5)
P3—C1 1.811 (3) 1.688 (6) 1.803 (4) 1.686 (5)
C4—C5 1.414 (4)
C8—C9 1.402 (4)
P2—C1—P3 114.86 (14) 127.1 (3) 120.60 (19) 130.4 (3)
P2—C1—Ir1 111.4 (1) 112.3 (3) 107.68 (17) 114.9 (3)
P3—C1—Ir1 110.0 (1) 120.4 (3) 114.38 (19) 114.5 (3)
P1—C2—P2 107.1 (1) 105.4 (3) 107.8 (2) 107.9 (3)
P3—C3—P4 105.7 (1) 110.0 (3) 108.5 (2) 106.6 (3)
P1—Ir1—P4 98.08 (2) 173.09 (5) 170.68 (4) 171.47 (5)
C1—Ir1—P1 88.27 (7) 89.23 (16) 88.33 (11) 87.18 (14)
C1—Ir1—P4 86.97 (7) 84.28 (16) 90.24 (11) 87.15 (14)
C2—P1—Ir1 104.80 (9) 106.4 (2) 105.58 (14) 107.45 (17)
C1—P2—C2 106.7 (1) 106.8 (3) 99.93 (18) 106.3 (2)
C1—P3—C3 104.1 (1) 106.2 (3) 107.99 (18) 104.8 (2)
C3—P4—Ir1 107.96 (9) 106.1 (2) 106.55 (14) 106.83 (17)
[Figure 2]
Figure 2
Structure of compound 2, with atom labelling and 30% probability displacement ellipsoids. For clarity, only the ipso carbon atoms of the phenyl groups are shown, and the solvent mol­ecules have been omitted.
[Figure 3]
Figure 3
Structure of compound 3, with atom labelling and 30% probability displacement ellipsoids. For clarity, only the ipso carbon atoms of the phenyl groups are shown, and the solvent mol­ecules have been omitted.
[Figure 4]
Figure 4
Structure of compound 4, with atom labelling and 30% probability displacement ellipsoids. For clarity, only the ipso carbon atoms of the phenyl groups are shown, and the solvent mol­ecules have been omitted.

The structure of 2 (Fig. 2[link]) consists of an octa­hedral IrIII coordination compound. The Ir center is coordinated by the PCP pincer, one hydrido and two chlorido ligands. The [C(dppm)2] unit coordinates in a meridional manner; the Cl1 ligand is located trans to the central CDP carbon C1, ligands H1 and Cl2 are positioned normal to this plane and are trans to each other. The Ir1—C1 bond length amounts to 2.101 (5) Å and is comparatively short according to the weak trans influence of a chlorido ligand. With a P4—Ir1—P1 angle of 173.09 (5)°, [C(dppm)2] also showcases high structural flexibility. Both the planar environment of C1 and the P—C bond lengths within the CDP functionality are in keeping with CDPs inter­acting with one Lewis acid (Petz & Frenking, 2010[Petz, W. & Frenking, G. (2010). Editors. Carbodiphosphoranes and Related Ligands, Vol. 30. Berlin Heidelberg: Springer-Verlag.]). The configuration of the two five-membered rings of the PCP pincer system is somewhat dissimilar, as evidenced by a comparison of the corresponding angles which differ up to ca 8° (see Table 1[link]).

The structure of 3 (Fig. 3[link]) exhibits a [IrCl2H(CH(dppm)2-κ3P,C,P)]+ complex cation, accompanied by a chloride counter-ion. Protonation of the CDP carbon C1 results in a distorted tetra­hedral environment. The bond angles P2—C1—P3, P2—C1–Ir1 and P3—C1—Ir1 are reduced by ca 5–7°, as compared to the values for compound 2. As expected, due to protonation, the C1–P2/P3 bond lengths are now characteristic of P—C single bonds (Petz & Frenking, 2010[Petz, W. & Frenking, G. (2010). Editors. Carbodiphosphoranes and Related Ligands, Vol. 30. Berlin Heidelberg: Springer-Verlag.]). The orientation of the proton on C1 relative to the hydrido ligand H1 is anti-periplanar. Protonation of the CDP carbon yields a heterogeneous effect on Ir-donor distances: while the Ir1—C1 bond length is longer than in 2 [2.132 (4) Å cf. 2.101 (5) Å], the Ir1—Cl1 bond length is shorter [2.405 (1) Å cf. 2.441 (2) Å]. The two rings of the PCP pincer system are different as has been emphasized for compound 2.

The structure of compound 4 consists of a [IrClH(CO)(C(dppm)2-κ3P,C,P)]+ complex cation and a chloride counter-ion (Fig. 4[link]). In 4, the Ir atom is coordinated by the PCP pincer in a meridional mode, with one chlorido ligand trans to the central CDP carbon atom and one hydrido and one carbonyl ligand trans to each other. Compared to compound 2, the CO ligand causes a lengthening of the Ir1—C1 and the Ir—P bonds, while both the Ir1—C1 and the Ir1—H1 bonds are shortened (Table 1[link]). In contrast to 2 and 3, the angles formed by the two rings of the pincer system are quite similar. The planarity around atom C1 and the C1—P2/P3 bond lengths confirms a CDP with one Lewis acid attached.

3. Supra­molecular features

In all four crystal structures the CH2 groups and the central CH group of the [CH(dppm)2]+ unit inter­act with solvate mol­ecules and anions. It has been pointed out that 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.]). The most significant hydrogen-bonding inter­actions in the crystals of the four compounds are given in Tables 2[link]–5[link][link][link], and illustrated in Figs. 5[link]–8[link][link][link].

Table 2
Hydrogen-bond geometry (Å, °) for 1b[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2B⋯O4 0.98 2.36 3.245 (4) 151
C2—H2A⋯O5i 0.98 2.38 3.307 (4) 158
C3—H3B⋯O5i 0.98 2.38 3.343 (4) 169
C206—H206⋯O5i 0.94 2.52 3.204 (4) 130
C3—H3A⋯O7 0.98 2.23 3.185 (5) 165
C1—H1⋯O3 0.94 (2) 2.55 (2) 3.419 (11) 155 (2)
C208—H208⋯O3 0.94 2.47 3.231 (16) 139
C308—H308⋯O3 0.94 2.57 3.301 (12) 135
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 3
Hydrogen-bond geometry (Å, °) for 2[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C112—H112⋯Cl1i 0.94 2.73 3.601 (6) 154
C3—H3B⋯O1 0.98 2.48 3.435 (10) 163
Symmetry code: (i) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Table 4
Hydrogen-bond geometry (Å, °) for 3[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1A⋯Cl3 0.99 (4) 2.48 (4) 3.422 (6) 159 (3)
C2—H2B⋯Cl3 0.98 2.63 3.450 (6) 142
C202—H202⋯Cl3 0.94 2.67 3.584 (6) 166
C308—H308⋯Cl3 0.94 2.70 3.475 (7) 141
C3—H3B⋯Cl3A 0.98 2.58 3.489 (12) 155

Table 5
Hydrogen-bond geometry (Å, °) for 4[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C304—H304⋯Cl1i 0.94 2.76 3.465 (7) 132
C2—H2B⋯O2 0.98 2.43 3.407 (8) 173
C210—H210⋯O2ii 0.94 2.59 3.384 (10) 143
C2—H2A⋯Cl2 0.98 2.71 3.633 (7) 157
C112—H112⋯Cl2 0.94 2.76 3.682 (8) 168
C3—H3A⋯Cl2A 0.98 2.69 3.569 (8) 150
C302—H302⋯O3 0.94 2.49 3.414 (14) 169
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].
[Figure 5]
Figure 5
A view along the a axis of the crystal packing of compound 1b. Only the H atoms involved in the most significant inter­molecular inter­actions (Table 2[link]) have been included. The ethyl acetate solvate mol­ecule is shown in ball-and-stick mode.
[Figure 6]
Figure 6
A view along the c axis of the crystal packing of compound 2. Only the H atoms involved in the most significant inter­molecular inter­actions (Table 3[link]) have been included.
[Figure 7]
Figure 7
A view along the c axis of the crystal packing of compound 3. Only the H atoms involved in the most significant inter­molecular inter­actions (Table 4[link]) have been included. The free Cl anions and the disordered water mol­ecules are shown in ball-and-stick mode.
[Figure 8]
Figure 8
A view along the a axis of the crystal packing of compound 4. Only the H atoms involved in the most significant inter­molecular inter­actions (Table 5[link]) have been included.

In the crystal of 1b (Fig. 5[link]), two neighbouring mol­ecules are linked via C—H⋯O hydrogen bonds involving two O atoms (O4 and O5) of two inversion-related OTf anions. Each complex cation is linked to the ethyl acetate solvate mol­ecule by a C3A—H3A⋯O7 hydrogen bond and to the other OTf anion by three (trifurcated) C—H⋯O3 hydrogen bonds.

In the crystal of 2 (Fig. 6[link]), mol­ecules are linked by C—H⋯Cl hydrogen bonds, forming a 21 helix propagating along the b-axis direction. The acetone solvate mol­ecule is linked to the complex mol­ecule by a C—H⋯O hydrogen bond.

In the crystal of 3 (Fig. 7[link]), the free Cl anion is linked to the complex cation by three C—H⋯Cl hydrogen bonds.

In the crystal of 4 (Fig. 8[link]), mol­ecules are linked by C—H⋯Cl hydrogen bonds, forming a 21 helix propagating along the b-axis direction, similar to the situation in the crystal of 2. The helices are linked by a methanol solvate mol­ecule (O2), forming layers parallel to the bc plane. Other inter­molecular inter­actions involve the Cl anions and the methanol solvate mol­ecules.

4. Synthesis and crystallization

The syntheses of the title compounds are summarized in the Scheme. All preparations were carried out under an inert atmosphere (N2) by the use of standard Schlenk techniques. The 1H, 13C and 31P NMR spectra were recorded on a Bruker DPX 300 NMR spectrometer (300 MHz) and were referenced against 13C/1H solvent peaks of the solvents or an external 85% H3PO4 standard, respectively. The phospho­rus atoms in the NMR data are labelled in the same way as in the figures.

Synthesis of complexes 1a and 1b: [IrCl(cod)]2 (8.5 mg; 0.0125 mmol) and [CH(dppm)2]Cl (20.5 mg; 0.025 mmol) (Reitsamer et al., 2012[Reitsamer, C., Stallinger, S., Schuh, W., Kopacka, H., Wurst, K., Obendorf, D. & Peringer, P. (2012). Dalton Trans. 41, 3503-3514.]) were dissolved in CHCl3 (0.6 ml), whereupon 1a formed instantaneously. Immediately after, a solution of TlOTf (17.7 mg; 0.05 mmol) in MeOH (0.1 ml) was added and the mixture was stirred for 15 min. The TlCl precipitate was removed and the volatiles evaporated in vacuo. Single crystals of 1b were obtained by layering a solution of the residue in CH2Cl2 with EtOAc.

Spectroscopic data for 1a: The [AX]2 pattern was simulated by use of the program WINDAISY (Weber et al., 1993[Weber, U., Spiske, R., Höffken, H.-W., Hägele, G. & Thiele, H. (1993). WINDAISY Manual and Program System, Bruker Manual. Bruker AXS Inc., Madison, Wisconsin, USA.]; Hägele et al., 1988[Hägele, G., Reinemer, P. & Grzonka, M. (1988). Computer in der Chemie, Softwareentwicklung in der Chemie, 2, 241.]). 31P{1H} NMR (CHCl3, referenced against external 85% H3PO4, numbering as in the crystal structure): δ = 48.7 (P2/P3, [AX]2, JP2P3 = 32.5 Hz; JP2P4 = 18.1 Hz, JP1P2 = 87.4 Hz); −12.7 (P1/P4, [AX]2, JP1P4 = 11.1 Hz) ppm. 13C NMR (CDCl3, referenced against 13C solvent peak): δ = −8.0 (C1, dtt, JC1P2/P3 = 24.5 Hz, JC1P1/P4 = 4.6 Hz, JC1H1 = 131.8 Hz) ppm.

Synthesis of compound 2: [IrCl(cod)]2 (8.5 mg; 0.0125 mmol) and [CH(dppm)2]Cl (20.5 mg; 0.025 mmol) were dissolved in acetone (0.6 ml). Orange crystals formed upon keeping the solution at 277 K. 31P{1H} NMR (CHCl3): δ = 25.3 (P2/3, vt, N = 65.7 Hz); 1.3 (P1/P4, vt) ppm. 13C{1H} NMR (CDCl3): δ = −34.7 (C1, tt, JC1P2/P3 = 90.2 Hz), J(C1P1/P4 = 2.0 Hz) ppm. 1H NMR (CDCl3): δ = −24.4 (H1, t, JH1P1/P4 = 13.0 Hz) ppm.

Synthesis of complex 3: A mixture of [IrCl(cod)]2 (8.5 mg; 0.0125 mmol), [CH(dppm)2]Cl (20.5 mg; 0.025 mmol), CHCl3 (0.6 mL) and hydro­chloric acid (0.1 ml, 4 mol/l) was agitated for 24 h. Colourless crystals were obtained by keeping the mixture at 277 K. 31P{1H} NMR (CHCl3): δ = 45.2 (P2/P3, vt, N = 62.7 Hz); −4.9 (P1/P4, vt) ppm. 13C NMR (CDCl3): δ = −4.5 (C1, dt, JC1P2/P3 = 38.2 Hz, JC1H1A = 123.7 Hz) ppm. 1H NMR (CDCl3): δ = −22.1 (H1, t, JH1P1/P4 = 13 Hz) ppm.

Synthesis of complex 4: [IrCl(cod)]2 (8.5 mg; 0.0125 mmol) and [CH(dppm)2]Cl (20.5 mg; 0.025 mmol) were placed under an atmosphere of CO and dissolved in CH2Cl2 (0.8 ml). The mixture was agitated for 24 h, followed by volatiles evaporation in vacuo. The residue was extracted with MeOH once, the insoluble fraction then dissolved in MeOH/CH2Cl2. Colourless crystals were formed on slow evaporation of this solution. 31P{1H} NMR (CHCl3): δ = 32.5 (P2/P3, vt, N = 61.0 Hz); −3.9 (P1/P4, vt) ppm. 13C{1H} NMR (CD3CN): δ = −26.5 (C1, t, JC1P2/P3) = 107 Hz) ppm. 1H NMR (CDCl3): δ = −7.6 (H1, dt, JH1P1/P4 = 13.0 Hz, JH1C4 = 54.0 Hz) ppm.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6[link]. The hydrogen atoms at C1, C4=C5 and C8=C9 of 1b were located in a difference-Fourier map and refined with bond restraints (C—H = 0.96 Å for H1 and 0.93 Å for H4, H5, H8 and H9). Both OTf anions show positional disorder in the occupancy ratio of 0.7:0.3. The solvent mol­ecule CH2Cl2 also shows positional disorder with the ratio 0.7:0.3; the hydrogen atoms of this disordered mol­ecule were omitted.

Table 6
Experimental details

  1b 2 3 4
Crystal data
Chemical formula [Ir(C51H45P4)(C8H12)](CF3SO3)2·CH3CO2C2H5·CH2Cl2 [Ir(C51H44P4)ClH]Cl·C3H6O [Ir(C51H45P4)ClH]Cl·5H2O [Ir(C51H44P4)ClH(CO)]Cl·2CH4O·H2O
Mr 1553.30 1102.93 1171.38 1154.96
Crystal system, space group Triclinic, P[\overline{1}] Monoclinic, P21/n Monoclinic, P21/c Monoclinic, P21/c
Temperature (K) 233 233 203 233
a, b, c (Å) 13.3105 (2), 14.3109 (3), 19.8482 (3) 18.7964 (4), 13.7444 (2), 18.8487 (4) 12.6532 (8), 21.8847 (12), 19.9228 (12) 12.5929 (2), 23.2803 (4), 19.7488 (4)
α, β, γ (°) 68.949 (1), 74.426 (1), 70.256 (1) 90, 101.586 (2), 90 90, 99.381 (2), 90 90, 107.535 (1), 90
V3) 3274.1 (1) 4770.25 (16) 5443.1 (6) 5520.66 (17)
Z 2 4 4 4
Radiation type Mo Kα Mo Kα Mo Kα Mo Kα
μ (mm−1) 2.35 3.08 2.76 2.67
Crystal size (mm) 0.21 × 0.10 × 0.06 0.15 × 0.12 × 0.02 0.17 × 0.12 × 0.09 0.21 × 0.10 × 0.07
 
Data collection
Diffractometer Nonius KappaCCD Nonius KappaCCD Bruker D8 QUEST PHOTON 100 Nonius KappaCCD
Absorption correction Multi-scan (SADABS; Bruker, 2015[Bruker (2015). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.691, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections 20473, 11235, 10195 27235, 8407, 6069 104100, 10577, 9522 32186, 9675, 8070
Rint 0.027 0.083 0.031 0.049
(sin θ/λ)max−1) 0.591 0.595 0.615 0.594
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.055, 1.03 0.048, 0.091, 1.04 0.032, 0.095, 1.09 0.041, 0.095, 1.13
No. of reflections 11235 8407 10577 9675
No. of parameters 976 572 574 624
No. of restraints 5 1 0 1
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H-atom parameters constrained 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) 0.58, −0.68 0.92, −0.81 1.27, −0.87 1.85, −1.45
Computer programs: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]), APEX2 and SAINT (Bruker, 2015[Bruker (2015). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), 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.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXT2014/4 (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]; Ruf & Noll, 2014[Ruf, M. & Noll, B. C. (2014). SC-XRD 503: Intrinsic Phasing - Advanced Structure Solution in APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXL2014/7 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

In 2, the metal-bound hydrogen atom was located in a difference-Fourier map and refined with the bond restraint Ir—H = 1.6 Å, since free refinement resulted in an unrealistically long bond distance of 1.88 Å. The solvent acetone mol­ecule is slightly disordered with a solved positional disorder for one methyl group, namely C6:C6A (ratio 0.5:0.5). Solvent hydrogen atoms could not be localized and were omitted.

In 3, positional disorder of the anion Cl3:Cl3A was found in an occupancy ratio of 0.667:0.333. Hydrogen atoms H1 and H1A were located in a difference-Fourier map and freely refined. The water solvent mol­ecules show higher temperature factors and are slightly disordered, but this disorder was not solved; therefore the oxygen atoms (O5 and O6 with half occupancy) were refined isotropically and their hydrogen atoms were omitted.

In 4, atom H1 was located in a difference-Fourier map and refined with bond restraint Ir—H = 1.6 Å. Hydrogen atoms of the MeOH and H2O solvate mol­ecules were omitted. One chloride anion is positionally disordered with an occupancy ratio of 0.5:0.5 for Cl2 and Cl2A. Possibly because of this disorder, two MeOH positions C6—O3 and C7—O4 are only half occupied; also, a water mol­ecule is split over four positions (O5, O5A, O5B and O5C) with an occupancy of 0.25 for each; they were refined isotropically.

The intensity data for compounds 1b, 2 and 4, were measured using a Nonius Kappa CCD diffractometer and no absorption corrections were applied. The intensity data for compound 3 was measured using a Bruker D8 Quest PHOTON 100 diffractometer and a multi-scan absorption correction was applied. The crystals used were extremely thin plates in all cases and the values of the residual electron density in the final difference-Fourier maps are satisfactory for complexes of such a heavy atom.

Supporting information


Computing details top

Data collection: COLLECT (Nonius, 1998) for (1b), (2), (4); APEX2 (Bruker, 2015) for (3). Cell refinement: COLLECT (Nonius, 1998) for (1b), (2), (4); SAINT (Bruker, 2015) for (3). Data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (1b), (2), (4); SAINT (Bruker, 2015) for (3). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (1b), (2); SHELXT2014/4 (Sheldrick, 2015a; Ruf & Noll, 2014) for (3); SHELXS86 (Sheldrick, 2008) for (4). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for (1b), (2); SHELXL2014/7 (Sheldrick, 2015b) for (3), (4). For all structures, molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008). Software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010) for (1b), (2); SHELXL2014/7 (Sheldrick, 2015b) and publCIF (Westrip, 2010) for (3), (4).

(Cycloocta-1,5-diene)(1,1,3,3,5,5,7,7-octaphenyl-1,7-diphospha-3,5-diphosphoniaheptan-4-yl)iridium(I) bis(trifluoromethanesulfonate)–ethyl acetate–dichloromethane (1/1/1) (1b) top
Crystal data top
[Ir(C51H45P4)(C8H12)](CF3SO3)2·CH3CO2C2H5·CH2Cl2Z = 2
Mr = 1553.30F(000) = 1568
Triclinic, P1Dx = 1.576 Mg m3
a = 13.3105 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 14.3109 (3) ÅCell parameters from 37798 reflections
c = 19.8482 (3) Åθ = 1.0–25.0°
α = 68.949 (1)°µ = 2.35 mm1
β = 74.426 (1)°T = 233 K
γ = 70.256 (1)°Prism, colorless
V = 3274.1 (1) Å30.21 × 0.10 × 0.06 mm
Data collection top
Nonius KappaCCD
diffractometer
10195 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
Graphite monochromatorθmax = 24.8°, θmin = 1.6°
phi– and ω–scansh = 1515
20473 measured reflectionsk = 1616
11235 independent reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0149P)2 + 2.9778P]
where P = (Fo2 + 2Fc2)/3
11235 reflections(Δ/σ)max = 0.003
976 parametersΔρmax = 0.58 e Å3
5 restraintsΔρmin = 0.68 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 atoms at C1 and C4=C5, C8=C9 were found and refined with bond restraints (d = 0.96 for H1 and d=0.93 for H4, H5, H8 and H9). Both triflate-anions show positional disorder in ratio 0.7:0.3. The solvent molecule CH2Cl2 shows also a positional disorder of this ratio, hydrogen atoms of this disordered molecule were omitted.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ir10.461480 (9)0.703450 (8)0.132966 (5)0.02536 (4)
P10.58314 (6)0.65692 (6)0.21612 (4)0.02768 (16)
P20.38022 (6)0.76427 (5)0.29095 (4)0.02648 (16)
P30.22546 (6)0.69359 (6)0.24242 (4)0.02697 (16)
P40.40431 (6)0.55141 (5)0.17784 (4)0.02696 (16)
C10.3280 (2)0.7630 (2)0.21544 (14)0.0258 (6)
H10.2936 (18)0.8334 (13)0.1955 (12)0.011 (6)*
C20.4957 (2)0.6538 (2)0.30570 (14)0.0276 (6)
H2A0.47290.58940.32640.033*
H2B0.53480.65710.33980.033*
C30.3009 (2)0.5595 (2)0.26020 (14)0.0274 (6)
H3A0.25330.51560.26860.033*
H3B0.33510.53690.30350.033*
C40.3868 (3)0.8415 (2)0.05239 (16)0.0360 (7)
H40.3186 (17)0.877 (2)0.0726 (14)0.034 (8)*
C50.4777 (3)0.8572 (2)0.06626 (15)0.0343 (7)
H50.460 (2)0.9001 (19)0.0958 (14)0.034 (8)*
C60.5813 (3)0.8596 (2)0.00956 (16)0.0406 (8)
H6A0.61430.90880.01330.049*
H6B0.56260.88450.03960.049*
C70.6643 (3)0.7521 (2)0.01956 (16)0.0395 (7)
H7A0.70610.74660.02840.047*
H7B0.71480.74560.05000.047*
C80.6107 (2)0.6642 (2)0.05499 (15)0.0317 (7)
H80.653 (2)0.5994 (16)0.0787 (13)0.028 (7)*
C90.5245 (2)0.6586 (2)0.03001 (15)0.0322 (7)
H90.518 (2)0.5915 (15)0.0382 (15)0.033 (8)*
C100.4799 (3)0.7379 (3)0.03775 (16)0.0428 (8)
H10A0.45470.70290.06170.051*
H10B0.53830.76570.07230.051*
C110.3865 (3)0.8281 (3)0.02031 (16)0.0448 (8)
H11A0.39200.89240.05960.054*
H11B0.31770.81550.01850.054*
C140.0575 (3)0.3930 (3)0.33642 (19)0.0538 (9)
C150.0499 (3)0.4683 (3)0.3472 (2)0.0653 (11)
H15A0.04090.52640.35710.098*
H15B0.09690.43420.38830.098*
H15C0.08190.49340.30330.098*
C160.1526 (4)0.2208 (4)0.3366 (3)0.1033 (18)
H16A0.18240.23760.28420.124*
H16B0.20550.22030.36290.124*
C170.1323 (6)0.1214 (4)0.3615 (4)0.149 (3)
H17A0.19930.06940.35270.223*
H17B0.08010.12230.33510.223*
H17C0.10370.10480.41350.223*
C1010.6851 (2)0.5311 (2)0.23307 (16)0.0330 (7)
C1020.7811 (3)0.5228 (3)0.18279 (18)0.0443 (8)
H1020.79130.58050.14240.053*
C1030.8621 (3)0.4293 (3)0.1921 (2)0.0570 (10)
H1030.92650.42370.15790.068*
C1040.8474 (3)0.3453 (3)0.2515 (2)0.0603 (11)
H1040.90210.28230.25790.072*
C1050.7533 (3)0.3532 (3)0.3013 (2)0.0527 (9)
H1050.74410.29530.34180.063*
C1060.6716 (3)0.4455 (2)0.29282 (17)0.0389 (7)
H1060.60730.45010.32730.047*
C1070.6667 (2)0.7374 (2)0.21511 (15)0.0320 (7)
C1080.6685 (3)0.8334 (2)0.16393 (17)0.0411 (8)
H1080.62610.85970.12680.049*
C1090.7319 (3)0.8909 (3)0.1668 (2)0.0525 (9)
H1090.73320.95520.13110.063*
C1100.7929 (3)0.8543 (3)0.2214 (2)0.0515 (9)
H1100.83590.89340.22340.062*
C1110.7905 (3)0.7596 (3)0.27351 (19)0.0454 (8)
H1110.83140.73470.31140.054*
C1120.7289 (2)0.7014 (2)0.27038 (17)0.0385 (7)
H1120.72880.63670.30580.046*
C2010.2931 (2)0.7600 (2)0.37806 (15)0.0300 (6)
C2020.2019 (3)0.8435 (2)0.38288 (17)0.0385 (7)
H2020.18520.89900.34080.046*
C2030.1363 (3)0.8439 (3)0.44981 (19)0.0483 (9)
H2030.07400.89920.45330.058*
C2040.1627 (3)0.7629 (3)0.51158 (18)0.0524 (9)
H2040.11810.76360.55710.063*
C2050.2527 (3)0.6815 (3)0.50748 (17)0.0499 (9)
H2050.26980.62710.55010.060*
C2060.3186 (2)0.6793 (2)0.44076 (16)0.0387 (7)
H2060.38040.62340.43790.046*
C2070.4181 (2)0.8828 (2)0.26773 (15)0.0320 (7)
C2080.3747 (3)0.9729 (2)0.21576 (16)0.0369 (7)
H2080.33090.97120.18640.044*
C2090.3955 (3)1.0651 (3)0.20704 (19)0.0503 (9)
H2090.36511.12610.17220.060*
C2100.4602 (4)1.0679 (3)0.2489 (2)0.0648 (11)
H2100.47511.13070.24210.078*
C2110.5038 (3)0.9792 (3)0.3011 (2)0.0663 (11)
H2110.54840.98190.32960.080*
C2120.4823 (3)0.8863 (3)0.31180 (19)0.0476 (9)
H2120.51050.82620.34820.057*
C3010.1215 (2)0.7077 (2)0.32096 (16)0.0335 (7)
C3020.0369 (3)0.7986 (3)0.31247 (19)0.0473 (9)
H3020.03720.85190.26770.057*
C3030.0468 (3)0.8103 (4)0.3697 (2)0.0657 (12)
H3030.10380.87160.36410.079*
C3040.0473 (3)0.7322 (4)0.4349 (3)0.0755 (14)
H3040.10450.74040.47400.091*
C3050.0349 (4)0.6427 (4)0.4434 (2)0.0693 (12)
H3050.03330.58950.48810.083*
C3060.1207 (3)0.6295 (3)0.38662 (17)0.0471 (8)
H3060.17760.56810.39280.056*
C3070.1454 (2)0.7273 (2)0.17256 (15)0.0326 (7)
C3080.1260 (3)0.8232 (3)0.11981 (17)0.0440 (8)
H3080.16040.87310.11560.053*
C3090.0538 (3)0.8442 (3)0.0727 (2)0.0584 (10)
H3090.04170.90820.03570.070*
C3100.0012 (3)0.7740 (4)0.0796 (2)0.0623 (11)
H3100.04650.78950.04730.075*
C3110.0176 (3)0.6799 (3)0.1338 (2)0.0537 (10)
H3110.02020.63200.13930.064*
C3120.0897 (2)0.6567 (3)0.17995 (17)0.0406 (8)
H3120.10140.59240.21670.049*
C4010.4968 (2)0.4226 (2)0.20953 (15)0.0295 (6)
C4020.5886 (2)0.3912 (2)0.16092 (16)0.0362 (7)
H4020.60450.43770.11460.043*
C4030.6568 (3)0.2914 (3)0.18040 (19)0.0461 (8)
H4030.71840.27070.14710.055*
C4040.6349 (3)0.2227 (2)0.24823 (19)0.0452 (8)
H4040.68130.15520.26110.054*
C4050.5449 (3)0.2529 (2)0.29694 (17)0.0439 (8)
H4050.53030.20630.34340.053*
C4060.4753 (3)0.3523 (2)0.27784 (16)0.0375 (7)
H4060.41330.37200.31120.045*
C4070.3319 (2)0.5201 (2)0.12470 (15)0.0320 (7)
C4080.2978 (2)0.5915 (2)0.06077 (16)0.0381 (7)
H4080.31700.65460.04160.046*
C4090.2356 (3)0.5705 (3)0.02483 (17)0.0476 (9)
H4090.21320.61920.01860.057*
C4100.2065 (3)0.4788 (3)0.05248 (19)0.0503 (9)
H4100.16420.46510.02800.060*
C4110.2393 (3)0.4071 (3)0.1159 (2)0.0496 (9)
H4110.21840.34470.13510.060*
C4120.3030 (3)0.4268 (2)0.15140 (17)0.0407 (8)
H4120.32700.37670.19390.049*
O70.1411 (3)0.4140 (2)0.3173 (2)0.1064 (12)
O80.0513 (2)0.2987 (2)0.34964 (17)0.0749 (8)
S10.1125 (3)1.0951 (3)0.13842 (18)0.0560 (7)0.70
C120.0306 (4)1.1228 (4)0.1465 (3)0.0754 (13)0.70
O10.1527 (6)1.0904 (6)0.0623 (4)0.0901 (19)0.70
O20.1282 (14)1.1797 (10)0.1514 (9)0.105 (4)0.70
O30.1374 (11)0.9978 (7)0.1880 (5)0.069 (2)0.70
F10.0869 (5)1.1246 (5)0.2118 (3)0.0854 (16)0.70
F20.0532 (8)1.0620 (10)0.1224 (7)0.132 (4)0.70
F30.0644 (9)1.2209 (11)0.1072 (7)0.140 (5)0.70
S20.57325 (12)0.62722 (10)0.51933 (7)0.0420 (3)0.70
C130.6889 (7)0.6786 (6)0.4978 (3)0.0565 (15)0.70
O40.5883 (3)0.5956 (2)0.45537 (14)0.0747 (8)
O50.5977 (2)0.54564 (19)0.58397 (12)0.0607 (7)
O60.4829 (5)0.7109 (5)0.5289 (4)0.0915 (18)0.70
F40.7006 (9)0.7076 (10)0.5518 (8)0.117 (5)0.70
F50.6855 (9)0.7612 (7)0.4389 (7)0.092 (3)0.70
F60.7765 (8)0.6095 (9)0.4838 (6)0.121 (4)0.70
S1A0.1059 (11)1.0991 (13)0.1635 (9)0.151 (6)0.30
C12A0.0306 (4)1.1228 (4)0.1465 (3)0.0754 (13)0.30
O1A0.143 (3)1.104 (3)0.0811 (16)0.25 (2)0.30
O2A0.115 (3)1.180 (3)0.176 (2)0.125 (15)0.30
O3A0.134 (3)0.992 (2)0.2148 (13)0.090 (9)0.30
F1A0.056 (2)1.096 (2)0.2263 (17)0.30 (2)0.30
F2A0.0567 (11)1.0479 (18)0.1356 (14)0.093 (8)0.30
F3A0.0797 (14)1.212 (2)0.0996 (10)0.076 (5)0.30
S2A0.6515 (4)0.5980 (3)0.50435 (17)0.0555 (8)0.30
C13A0.6234 (14)0.7302 (14)0.4998 (8)0.063 (4)0.30
O6A0.778 (2)0.573 (2)0.4828 (13)0.092 (9)0.30
F4A0.656 (2)0.7358 (16)0.5501 (15)0.080 (6)0.30
F5A0.649 (2)0.7896 (19)0.4384 (18)0.099 (8)0.30
F6A0.5153 (11)0.7693 (10)0.5148 (8)0.120 (5)0.30
C180.7007 (8)1.0799 (7)0.4747 (7)0.096 (3)0.70
Cl10.8229 (3)1.0644 (2)0.40662 (18)0.1241 (11)0.70
Cl20.6250 (13)1.0045 (8)0.4790 (9)0.158 (5)0.35
Cl2B0.628 (3)1.012 (3)0.5128 (18)0.64 (3)0.35
C18A0.662 (3)0.985 (3)0.447 (3)0.112 (17)0.30
Cl1A0.7639 (17)1.0444 (13)0.4296 (9)0.294 (11)0.30
Cl2A0.6556 (10)0.9510 (10)0.5190 (10)0.167 (5)0.30
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ir10.02827 (7)0.02462 (6)0.02257 (6)0.00713 (5)0.00395 (4)0.00646 (4)
P10.0271 (4)0.0282 (4)0.0268 (4)0.0073 (3)0.0048 (3)0.0071 (3)
P20.0282 (4)0.0277 (4)0.0248 (4)0.0072 (3)0.0049 (3)0.0089 (3)
P30.0252 (4)0.0288 (4)0.0282 (4)0.0059 (3)0.0049 (3)0.0109 (3)
P40.0281 (4)0.0266 (4)0.0266 (4)0.0069 (3)0.0042 (3)0.0091 (3)
C10.0283 (15)0.0221 (14)0.0266 (14)0.0044 (12)0.0085 (12)0.0061 (12)
C20.0281 (15)0.0294 (15)0.0242 (14)0.0089 (12)0.0054 (12)0.0046 (12)
C30.0290 (15)0.0258 (15)0.0294 (15)0.0087 (12)0.0048 (12)0.0094 (12)
C40.0359 (17)0.0325 (17)0.0296 (16)0.0010 (14)0.0070 (14)0.0040 (13)
C50.0477 (19)0.0225 (15)0.0263 (15)0.0078 (14)0.0042 (14)0.0029 (12)
C60.055 (2)0.0338 (17)0.0302 (16)0.0198 (15)0.0012 (14)0.0024 (13)
C70.0406 (18)0.0468 (19)0.0320 (16)0.0220 (15)0.0082 (14)0.0136 (14)
C80.0340 (16)0.0301 (16)0.0268 (15)0.0061 (14)0.0008 (13)0.0102 (13)
C90.0385 (17)0.0334 (17)0.0229 (14)0.0111 (14)0.0030 (12)0.0110 (13)
C100.054 (2)0.048 (2)0.0288 (16)0.0203 (17)0.0058 (15)0.0099 (14)
C110.057 (2)0.0425 (19)0.0313 (17)0.0099 (17)0.0172 (15)0.0023 (14)
C140.059 (2)0.052 (2)0.049 (2)0.029 (2)0.0048 (18)0.0037 (17)
C150.068 (3)0.056 (2)0.072 (3)0.020 (2)0.007 (2)0.019 (2)
C160.078 (3)0.058 (3)0.149 (5)0.012 (3)0.008 (3)0.027 (3)
C170.145 (6)0.061 (4)0.210 (8)0.017 (4)0.005 (5)0.043 (4)
C1010.0304 (16)0.0344 (17)0.0390 (17)0.0049 (13)0.0131 (13)0.0146 (14)
C1020.0359 (18)0.047 (2)0.050 (2)0.0052 (16)0.0096 (15)0.0186 (16)
C1030.0337 (19)0.063 (3)0.080 (3)0.0042 (18)0.0109 (18)0.043 (2)
C1040.059 (3)0.042 (2)0.089 (3)0.0125 (19)0.040 (2)0.034 (2)
C1050.067 (3)0.0365 (19)0.061 (2)0.0021 (18)0.035 (2)0.0143 (17)
C1060.0465 (19)0.0314 (17)0.0445 (18)0.0091 (15)0.0167 (15)0.0121 (14)
C1070.0274 (15)0.0349 (16)0.0327 (15)0.0081 (13)0.0015 (12)0.0115 (13)
C1080.0413 (18)0.0406 (18)0.0426 (18)0.0137 (15)0.0095 (15)0.0093 (15)
C1090.059 (2)0.043 (2)0.059 (2)0.0250 (18)0.0132 (19)0.0064 (17)
C1100.043 (2)0.055 (2)0.068 (2)0.0266 (17)0.0073 (18)0.0201 (19)
C1110.0376 (18)0.055 (2)0.054 (2)0.0180 (16)0.0123 (16)0.0195 (17)
C1120.0360 (17)0.0399 (18)0.0403 (17)0.0115 (15)0.0101 (14)0.0086 (14)
C2010.0320 (16)0.0365 (16)0.0279 (15)0.0136 (13)0.0020 (12)0.0151 (13)
C2020.0393 (18)0.0393 (18)0.0407 (18)0.0105 (15)0.0059 (14)0.0171 (14)
C2030.0413 (19)0.055 (2)0.052 (2)0.0096 (17)0.0026 (16)0.0307 (18)
C2040.050 (2)0.075 (3)0.0373 (19)0.024 (2)0.0089 (16)0.0285 (19)
C2050.051 (2)0.066 (2)0.0297 (17)0.0202 (19)0.0019 (15)0.0103 (16)
C2060.0384 (17)0.0453 (19)0.0313 (16)0.0111 (15)0.0053 (14)0.0105 (14)
C2070.0328 (16)0.0313 (16)0.0350 (16)0.0104 (13)0.0007 (13)0.0166 (13)
C2080.0423 (18)0.0321 (17)0.0360 (17)0.0099 (14)0.0037 (14)0.0119 (14)
C2090.064 (2)0.0371 (19)0.050 (2)0.0210 (17)0.0004 (18)0.0131 (16)
C2100.078 (3)0.051 (2)0.083 (3)0.034 (2)0.003 (2)0.031 (2)
C2110.068 (3)0.073 (3)0.085 (3)0.028 (2)0.018 (2)0.043 (3)
C2120.052 (2)0.050 (2)0.055 (2)0.0148 (17)0.0172 (17)0.0250 (17)
C3010.0256 (15)0.0472 (18)0.0356 (16)0.0130 (14)0.0016 (13)0.0211 (14)
C3020.0328 (18)0.062 (2)0.056 (2)0.0031 (17)0.0111 (16)0.0344 (18)
C3030.0309 (19)0.104 (3)0.080 (3)0.002 (2)0.0041 (19)0.067 (3)
C3040.049 (2)0.133 (4)0.069 (3)0.039 (3)0.021 (2)0.067 (3)
C3050.073 (3)0.104 (4)0.044 (2)0.050 (3)0.016 (2)0.031 (2)
C3060.049 (2)0.058 (2)0.0400 (19)0.0244 (18)0.0026 (16)0.0193 (17)
C3070.0263 (15)0.0393 (17)0.0343 (16)0.0030 (13)0.0064 (13)0.0178 (14)
C3080.0423 (19)0.045 (2)0.0428 (19)0.0051 (16)0.0157 (15)0.0104 (16)
C3090.055 (2)0.061 (2)0.050 (2)0.003 (2)0.0254 (19)0.0108 (19)
C3100.043 (2)0.090 (3)0.062 (2)0.000 (2)0.0249 (19)0.037 (2)
C3110.0348 (19)0.075 (3)0.068 (2)0.0120 (18)0.0126 (17)0.041 (2)
C3120.0311 (17)0.048 (2)0.0478 (19)0.0099 (15)0.0077 (15)0.0204 (16)
C4010.0307 (15)0.0285 (15)0.0352 (16)0.0073 (13)0.0096 (13)0.0137 (13)
C4020.0335 (17)0.0369 (17)0.0385 (17)0.0068 (14)0.0058 (14)0.0141 (14)
C4030.0350 (18)0.047 (2)0.056 (2)0.0012 (16)0.0064 (16)0.0260 (17)
C4040.048 (2)0.0313 (17)0.058 (2)0.0021 (15)0.0201 (17)0.0141 (16)
C4050.057 (2)0.0310 (17)0.0424 (18)0.0111 (16)0.0154 (17)0.0050 (14)
C4060.0423 (18)0.0328 (17)0.0374 (17)0.0084 (14)0.0079 (14)0.0112 (14)
C4070.0287 (15)0.0376 (17)0.0320 (16)0.0058 (13)0.0047 (13)0.0162 (13)
C4080.0339 (17)0.0446 (18)0.0357 (17)0.0102 (14)0.0021 (14)0.0148 (15)
C4090.0374 (18)0.074 (3)0.0343 (17)0.0092 (18)0.0093 (15)0.0219 (17)
C4100.0394 (19)0.076 (3)0.052 (2)0.0160 (19)0.0065 (16)0.039 (2)
C4110.048 (2)0.054 (2)0.062 (2)0.0187 (17)0.0065 (18)0.0327 (19)
C4120.0442 (19)0.0394 (18)0.0459 (19)0.0115 (15)0.0095 (15)0.0192 (15)
O70.069 (2)0.068 (2)0.177 (4)0.0401 (18)0.000 (2)0.026 (2)
O80.0601 (18)0.0499 (16)0.110 (2)0.0234 (14)0.0019 (16)0.0216 (16)
S10.0412 (10)0.0431 (13)0.0814 (13)0.0096 (9)0.0161 (9)0.0130 (10)
C120.068 (3)0.072 (3)0.081 (3)0.005 (3)0.022 (3)0.033 (3)
O10.067 (3)0.102 (4)0.081 (4)0.012 (3)0.021 (3)0.038 (4)
O20.134 (7)0.060 (5)0.137 (8)0.048 (5)0.023 (5)0.025 (5)
O30.074 (4)0.037 (4)0.094 (7)0.000 (3)0.055 (5)0.002 (4)
F10.062 (2)0.102 (4)0.074 (3)0.003 (3)0.014 (2)0.041 (3)
F20.118 (7)0.155 (9)0.164 (7)0.005 (5)0.073 (5)0.089 (6)
F30.126 (8)0.093 (6)0.169 (8)0.040 (5)0.079 (5)0.028 (5)
S20.0382 (7)0.0489 (8)0.0380 (7)0.0139 (6)0.0080 (6)0.0089 (6)
C130.061 (4)0.057 (4)0.050 (4)0.028 (4)0.010 (3)0.002 (3)
O40.097 (2)0.095 (2)0.0479 (15)0.0380 (18)0.0246 (15)0.0190 (15)
O50.093 (2)0.0556 (15)0.0385 (13)0.0322 (14)0.0133 (13)0.0069 (12)
O60.056 (3)0.083 (4)0.121 (5)0.008 (3)0.020 (3)0.036 (4)
F40.139 (9)0.195 (10)0.072 (4)0.118 (8)0.018 (5)0.034 (6)
F50.121 (6)0.085 (7)0.062 (4)0.067 (6)0.007 (4)0.006 (5)
F60.049 (5)0.141 (9)0.162 (6)0.022 (6)0.003 (4)0.044 (5)
S1A0.116 (8)0.080 (6)0.291 (18)0.021 (5)0.121 (10)0.074 (10)
C12A0.068 (3)0.072 (3)0.081 (3)0.005 (3)0.022 (3)0.033 (3)
O1A0.28 (3)0.35 (4)0.15 (2)0.16 (3)0.15 (2)0.18 (2)
O2A0.111 (18)0.095 (16)0.22 (4)0.003 (13)0.10 (2)0.085 (19)
O3A0.089 (11)0.088 (12)0.078 (15)0.032 (8)0.066 (12)0.037 (10)
F1A0.31 (4)0.126 (16)0.21 (2)0.028 (18)0.13 (2)0.027 (14)
F2A0.021 (6)0.088 (10)0.187 (18)0.029 (7)0.014 (8)0.069 (10)
F3A0.026 (4)0.092 (12)0.058 (6)0.018 (5)0.012 (5)0.010 (6)
S2A0.068 (3)0.060 (2)0.0417 (17)0.026 (2)0.0116 (17)0.0085 (15)
C13A0.062 (11)0.070 (11)0.047 (9)0.001 (9)0.016 (8)0.020 (9)
O6A0.080 (15)0.088 (14)0.063 (9)0.039 (10)0.006 (8)0.032 (8)
F4A0.134 (18)0.086 (8)0.055 (7)0.088 (11)0.018 (10)0.006 (6)
F5A0.17 (2)0.053 (9)0.058 (8)0.019 (10)0.023 (11)0.006 (7)
F6A0.078 (9)0.093 (9)0.137 (10)0.021 (7)0.003 (7)0.030 (9)
C180.084 (6)0.076 (5)0.147 (9)0.005 (4)0.037 (6)0.057 (6)
Cl10.178 (3)0.0668 (14)0.129 (2)0.0061 (17)0.036 (2)0.0482 (14)
Cl20.244 (15)0.098 (6)0.186 (10)0.107 (8)0.096 (10)0.005 (6)
Cl2B0.68 (5)0.54 (5)0.42 (3)0.02 (4)0.24 (4)0.23 (3)
C18A0.078 (14)0.083 (19)0.22 (5)0.030 (11)0.01 (2)0.10 (3)
Cl1A0.44 (3)0.223 (13)0.244 (15)0.188 (15)0.071 (15)0.095 (11)
Cl2A0.166 (8)0.112 (7)0.263 (15)0.034 (6)0.073 (10)0.077 (8)
Geometric parameters (Å, º) top
Ir1—C42.169 (3)C207—C2121.400 (4)
Ir1—C52.172 (3)C208—C2091.381 (5)
Ir1—C82.208 (3)C208—H2080.9400
Ir1—C92.225 (3)C209—C2101.366 (5)
Ir1—C12.232 (3)C209—H2090.9400
Ir1—P42.3386 (7)C210—C2111.379 (6)
Ir1—P12.3889 (7)C210—H2100.9400
P1—C1011.831 (3)C211—C2121.385 (5)
P1—C21.840 (3)C211—H2110.9400
P1—C1071.844 (3)C212—H2120.9400
P2—C21.794 (3)C301—C3061.379 (4)
P2—C2011.798 (3)C301—C3021.394 (4)
P2—C2071.799 (3)C302—C3031.375 (5)
P2—C11.821 (3)C302—H3020.9400
P3—C31.793 (3)C303—C3041.374 (6)
P3—C3071.804 (3)C303—H3030.9400
P3—C3011.807 (3)C304—C3051.364 (6)
P3—C11.811 (3)C304—H3040.9400
P4—C4011.833 (3)C305—C3061.388 (5)
P4—C31.844 (3)C305—H3050.9400
P4—C4071.849 (3)C306—H3060.9400
C1—H10.938 (16)C307—C3081.385 (4)
C2—H2A0.9800C307—C3121.391 (4)
C2—H2B0.9800C308—C3091.404 (5)
C3—H3A0.9800C308—H3080.9400
C3—H3B0.9800C309—C3101.359 (6)
C4—C51.414 (4)C309—H3090.9400
C4—C111.524 (4)C310—C3111.380 (6)
C4—H40.939 (17)C310—H3100.9400
C5—C61.529 (4)C311—C3121.382 (4)
C5—H50.928 (17)C311—H3110.9400
C6—C71.541 (4)C312—H3120.9400
C6—H6A0.9800C401—C4021.390 (4)
C6—H6B0.9800C401—C4061.393 (4)
C7—C81.512 (4)C402—C4031.389 (4)
C7—H7A0.9800C402—H4020.9400
C7—H7B0.9800C403—C4041.378 (5)
C8—C91.402 (4)C403—H4030.9400
C8—H80.935 (17)C404—C4051.373 (5)
C9—C101.525 (4)C404—H4040.9400
C9—H90.946 (17)C405—C4061.391 (4)
C10—C111.528 (5)C405—H4050.9400
C10—H10A0.9800C406—H4060.9400
C10—H10B0.9800C407—C4081.387 (4)
C11—H11A0.9800C407—C4121.392 (4)
C11—H11B0.9800C408—C4091.387 (4)
C14—O71.179 (4)C408—H4080.9400
C14—O81.306 (4)C409—C4101.372 (5)
C14—C151.487 (5)C409—H4090.9400
C15—H15A0.9700C410—C4111.375 (5)
C15—H15B0.9700C410—H4100.9400
C15—H15C0.9700C411—C4121.387 (4)
C16—C171.421 (8)C411—H4110.9400
C16—O81.461 (5)C412—H4120.9400
C16—H16A0.9800S1—O31.377 (10)
C16—H16B0.9800S1—O21.414 (15)
C17—H17A0.9700S1—O11.479 (8)
C17—H17B0.9700S1—C121.785 (6)
C17—H17C0.9700C12—F21.277 (12)
C101—C1061.390 (4)C12—F11.315 (8)
C101—C1021.394 (4)C12—F31.325 (13)
C102—C1031.392 (5)S2—O61.408 (6)
C102—H1020.9400S2—O51.416 (3)
C103—C1041.374 (6)S2—O41.440 (3)
C103—H1030.9400S2—C131.811 (6)
C104—C1051.371 (6)C13—F61.287 (12)
C104—H1040.9400C13—F51.329 (12)
C105—C1061.388 (4)C13—F41.340 (15)
C105—H1050.9400S1A—O2A1.32 (4)
C106—H1060.9400S1A—O3A1.49 (3)
C107—C1081.387 (4)S1A—O1A1.56 (3)
C107—C1121.396 (4)S2A—O6A1.56 (3)
C108—C1091.386 (5)S2A—C13A1.773 (18)
C108—H1080.9400C13A—F4A1.23 (3)
C109—C1101.374 (5)C13A—F5A1.25 (3)
C109—H1090.9400C13A—F6A1.35 (2)
C110—C1111.383 (5)C18—Cl1A1.182 (16)
C110—H1100.9400C18—Cl2B1.47 (3)
C111—C1121.378 (4)C18—Cl21.676 (13)
C111—H1110.9400C18—Cl11.820 (13)
C112—H1120.9400C18—C18A1.90 (3)
C201—C2061.388 (4)C18—Cl2A1.958 (18)
C201—C2021.397 (4)Cl1—Cl1A0.880 (17)
C202—C2031.381 (4)Cl2—Cl2B0.73 (4)
C202—H2020.9400Cl2—C18A0.78 (4)
C203—C2041.381 (5)Cl2—Cl2A0.952 (14)
C203—H2030.9400Cl2—Cl1A2.01 (2)
C204—C2051.368 (5)Cl2B—Cl2A0.81 (4)
C204—H2040.9400Cl2B—C18A1.42 (5)
C205—C2061.383 (4)Cl2B—Cl1A2.15 (3)
C205—H2050.9400C18A—Cl2A1.33 (5)
C206—H2060.9400C18A—Cl1A1.74 (4)
C207—C2081.386 (4)Cl1A—Cl2A2.29 (2)
C4—Ir1—C538.02 (12)C207—C208—H208119.9
C4—Ir1—C893.71 (11)C210—C209—C208120.3 (3)
C5—Ir1—C878.86 (11)C210—C209—H209119.9
C4—Ir1—C977.48 (11)C208—C209—H209119.9
C5—Ir1—C986.15 (11)C209—C210—C211120.4 (3)
C8—Ir1—C936.88 (11)C209—C210—H210119.8
C4—Ir1—C185.76 (11)C211—C210—H210119.8
C5—Ir1—C193.77 (11)C210—C211—C212120.4 (3)
C8—Ir1—C1168.27 (11)C210—C211—H211119.8
C9—Ir1—C1152.78 (11)C212—C211—H211119.8
C4—Ir1—P4123.12 (9)C211—C212—C207119.2 (3)
C5—Ir1—P4160.77 (9)C211—C212—H212120.4
C8—Ir1—P4103.01 (8)C207—C212—H212120.4
C9—Ir1—P484.52 (8)C306—C301—C302119.9 (3)
C1—Ir1—P486.97 (7)C306—C301—P3122.0 (2)
C4—Ir1—P1137.87 (9)C302—C301—P3117.9 (2)
C5—Ir1—P1101.15 (9)C303—C302—C301119.9 (4)
C8—Ir1—P184.27 (8)C303—C302—H302120.1
C9—Ir1—P1118.50 (8)C301—C302—H302120.1
C1—Ir1—P188.27 (7)C304—C303—C302120.0 (4)
P4—Ir1—P198.08 (2)C304—C303—H303120.0
C101—P1—C2104.16 (13)C302—C303—H303120.0
C101—P1—C10798.08 (13)C305—C304—C303120.4 (4)
C2—P1—C10799.81 (13)C305—C304—H304119.8
C101—P1—Ir1121.11 (9)C303—C304—H304119.8
C2—P1—Ir1104.80 (9)C304—C305—C306120.6 (4)
C107—P1—Ir1125.41 (9)C304—C305—H305119.7
C2—P2—C201107.29 (13)C306—C305—H305119.7
C2—P2—C207110.72 (13)C301—C306—C305119.2 (3)
C201—P2—C207102.84 (13)C301—C306—H306120.4
C2—P2—C1106.75 (12)C305—C306—H306120.4
C201—P2—C1119.19 (13)C308—C307—C312119.7 (3)
C207—P2—C1109.95 (13)C308—C307—P3123.6 (2)
C3—P3—C307109.67 (13)C312—C307—P3116.1 (2)
C3—P3—C301108.36 (14)C307—C308—C309118.5 (3)
C307—P3—C301101.47 (13)C307—C308—H308120.7
C3—P3—C1104.15 (13)C309—C308—H308120.7
C307—P3—C1113.63 (13)C310—C309—C308121.3 (3)
C301—P3—C1119.41 (13)C310—C309—H309119.4
C401—P4—C3102.37 (13)C308—C309—H309119.4
C401—P4—C40798.90 (13)C309—C310—C311120.2 (3)
C3—P4—C407100.46 (13)C309—C310—H310119.9
C401—P4—Ir1122.24 (10)C311—C310—H310119.9
C3—P4—Ir1107.96 (9)C310—C311—C312119.6 (4)
C407—P4—Ir1121.49 (10)C310—C311—H311120.2
P3—C1—P2114.86 (14)C312—C311—H311120.2
P3—C1—Ir1109.99 (13)C311—C312—C307120.7 (3)
P2—C1—Ir1111.40 (13)C311—C312—H312119.7
P3—C1—H1106.6 (15)C307—C312—H312119.7
P2—C1—H1102.8 (14)C402—C401—C406118.6 (3)
Ir1—C1—H1110.9 (14)C402—C401—P4118.2 (2)
P2—C2—P1107.11 (13)C406—C401—P4123.0 (2)
P2—C2—H2A110.3C403—C402—C401120.4 (3)
P1—C2—H2A110.3C403—C402—H402119.8
P2—C2—H2B110.3C401—C402—H402119.8
P1—C2—H2B110.3C404—C403—C402120.4 (3)
H2A—C2—H2B108.5C404—C403—H403119.8
P3—C3—P4105.75 (14)C402—C403—H403119.8
P3—C3—H3A110.6C405—C404—C403119.8 (3)
P4—C3—H3A110.6C405—C404—H404120.1
P3—C3—H3B110.6C403—C404—H404120.1
P4—C3—H3B110.6C404—C405—C406120.3 (3)
H3A—C3—H3B108.7C404—C405—H405119.8
C5—C4—C11121.6 (3)C406—C405—H405119.8
C5—C4—Ir171.10 (16)C405—C406—C401120.4 (3)
C11—C4—Ir1116.4 (2)C405—C406—H406119.8
C5—C4—H4116.5 (18)C401—C406—H406119.8
C11—C4—H4112.7 (17)C408—C407—C412118.4 (3)
Ir1—C4—H4112.0 (17)C408—C407—P4121.2 (2)
C4—C5—C6121.6 (3)C412—C407—P4120.2 (2)
C4—C5—Ir170.87 (17)C409—C408—C407120.6 (3)
C6—C5—Ir1115.47 (19)C409—C408—H408119.7
C4—C5—H5113.5 (19)C407—C408—H408119.7
C6—C5—H5116.7 (19)C410—C409—C408120.2 (3)
Ir1—C5—H5109.7 (18)C410—C409—H409119.9
C5—C6—C7112.7 (2)C408—C409—H409119.9
C5—C6—H6A109.1C409—C410—C411120.2 (3)
C7—C6—H6A109.1C409—C410—H410119.9
C5—C6—H6B109.1C411—C410—H410119.9
C7—C6—H6B109.1C410—C411—C412119.9 (3)
H6A—C6—H6B107.8C410—C411—H411120.1
C8—C7—C6112.2 (2)C412—C411—H411120.1
C8—C7—H7A109.2C411—C412—C407120.7 (3)
C6—C7—H7A109.2C411—C412—H412119.7
C8—C7—H7B109.2C407—C412—H412119.7
C6—C7—H7B109.2C14—O8—C16116.9 (3)
H7A—C7—H7B107.9O3—S1—O2119.2 (8)
C9—C8—C7123.2 (3)O3—S1—O1111.2 (6)
C9—C8—Ir172.21 (16)O2—S1—O1114.1 (8)
C7—C8—Ir1112.51 (19)O3—S1—C12102.1 (6)
C9—C8—H8113.8 (17)O2—S1—C12104.7 (8)
C7—C8—H8117.3 (18)O1—S1—C12103.0 (4)
Ir1—C8—H8107.5 (17)F2—C12—F1111.5 (7)
C8—C9—C10122.9 (3)F2—C12—F3110.8 (10)
C8—C9—Ir170.91 (16)F1—C12—F3101.6 (7)
C10—C9—Ir1115.7 (2)F2—C12—S1110.1 (6)
C8—C9—H9117.0 (17)F1—C12—S1115.8 (4)
C10—C9—H9112.8 (17)F3—C12—S1106.6 (7)
Ir1—C9—H9109.7 (17)O6—S2—O5115.7 (3)
C9—C10—C11113.1 (2)O6—S2—O4116.9 (3)
C9—C10—H10A109.0O5—S2—O4115.62 (18)
C11—C10—H10A109.0O6—S2—C13104.7 (4)
C9—C10—H10B109.0O5—S2—C1399.4 (2)
C11—C10—H10B109.0O4—S2—C13100.7 (3)
H10A—C10—H10B107.8F6—C13—F5106.3 (9)
C4—C11—C10112.1 (2)F6—C13—F4107.3 (9)
C4—C11—H11A109.2F5—C13—F4106.2 (9)
C10—C11—H11A109.2F6—C13—S2109.9 (6)
C4—C11—H11B109.2F5—C13—S2112.8 (7)
C10—C11—H11B109.2F4—C13—S2113.9 (7)
H11A—C11—H11B107.9O2A—S1A—O3A122 (2)
O7—C14—O8122.0 (4)O2A—S1A—O1A112 (3)
O7—C14—C15124.8 (4)O3A—S1A—O1A114 (2)
O8—C14—C15113.2 (3)O6A—S2A—C13A98.6 (12)
C14—C15—H15A109.5F4A—C13A—F5A115 (2)
C14—C15—H15B109.5F4A—C13A—F6A103.4 (19)
H15A—C15—H15B109.5F5A—C13A—F6A103.0 (19)
C14—C15—H15C109.5F4A—C13A—S2A109.7 (15)
H15A—C15—H15C109.5F5A—C13A—S2A115.7 (17)
H15B—C15—H15C109.5F6A—C13A—S2A108.7 (13)
C17—C16—O8109.1 (5)Cl1A—C18—Cl2B107.9 (14)
C17—C16—H16A109.9Cl1A—C18—Cl287.6 (11)
O8—C16—H16A109.9Cl2B—C18—Cl225.8 (14)
C17—C16—H16B109.9Cl1A—C18—Cl123.8 (9)
O8—C16—H16B109.9Cl2B—C18—Cl1131.0 (12)
H16A—C16—H16B108.3Cl2—C18—Cl1111.4 (8)
C16—C17—H17A109.5Cl1A—C18—C18A63.8 (14)
C16—C17—H17B109.5Cl2B—C18—C18A47.8 (18)
H17A—C17—H17B109.5Cl2—C18—C18A24.0 (14)
C16—C17—H17C109.5Cl1—C18—C18A87.5 (12)
H17A—C17—H17C109.5Cl1A—C18—Cl2A90.0 (9)
H17B—C17—H17C109.5Cl2B—C18—Cl2A21.8 (12)
C106—C101—C102119.2 (3)Cl2—C18—Cl2A29.1 (5)
C106—C101—P1123.6 (2)Cl1—C18—Cl2A111.4 (6)
C102—C101—P1117.1 (2)C18A—C18—Cl2A40.3 (16)
C103—C102—C101120.3 (3)Cl1A—Cl1—C1832.9 (12)
C103—C102—H102119.9Cl2B—Cl2—C18A141 (6)
C101—C102—H102119.9Cl2B—Cl2—Cl2A55 (3)
C104—C103—C102119.8 (3)C18A—Cl2—Cl2A100 (4)
C104—C103—H103120.1Cl2B—Cl2—C1861 (3)
C102—C103—H103120.1C18A—Cl2—C1894 (4)
C105—C104—C103120.2 (3)Cl2A—Cl2—C1892.1 (12)
C105—C104—H104119.9Cl2B—Cl2—Cl1A91 (3)
C103—C104—H104119.9C18A—Cl2—Cl1A59 (3)
C104—C105—C106120.8 (3)Cl2A—Cl2—Cl1A94.3 (15)
C104—C105—H105119.6C18—Cl2—Cl1A36.0 (5)
C106—C105—H105119.6Cl2—Cl2B—Cl2A76 (3)
C105—C106—C101119.7 (3)Cl2—Cl2B—C18A20 (3)
C105—C106—H106120.2Cl2A—Cl2B—C18A67 (3)
C101—C106—H106120.2Cl2—Cl2B—C1893 (3)
C108—C107—C112118.1 (3)Cl2A—Cl2B—C18116 (3)
C108—C107—P1123.7 (2)C18A—Cl2B—C1882 (2)
C112—C107—P1118.1 (2)Cl2—Cl2B—Cl1A69 (2)
C109—C108—C107121.0 (3)Cl2A—Cl2B—Cl1A89 (2)
C109—C108—H108119.5C18A—Cl2B—Cl1A53.7 (19)
C107—C108—H108119.5C18—Cl2B—Cl1A31.5 (7)
C110—C109—C108120.3 (3)Cl2—C18A—Cl2A45 (3)
C110—C109—H109119.9Cl2—C18A—Cl2B19 (3)
C108—C109—H109119.9Cl2A—C18A—Cl2B33.9 (19)
C109—C110—C111119.4 (3)Cl2—C18A—Cl1A99 (3)
C109—C110—H110120.3Cl2A—C18A—Cl1A96 (2)
C111—C110—H110120.3Cl2B—C18A—Cl1A85 (2)
C112—C111—C110120.6 (3)Cl2—C18A—C1862 (3)
C112—C111—H111119.7Cl2A—C18A—C1872.2 (16)
C110—C111—H111119.7Cl2B—C18A—C1850.0 (16)
C111—C112—C107120.6 (3)Cl1A—C18A—C1837.6 (9)
C111—C112—H112119.7Cl1—Cl1A—C18123.3 (19)
C107—C112—H112119.7Cl1—Cl1A—C18A157 (2)
C206—C201—C202119.8 (3)C18—Cl1A—C18A78.6 (13)
C206—C201—P2121.4 (2)Cl1—Cl1A—Cl2177 (2)
C202—C201—P2118.7 (2)C18—Cl1A—Cl256.4 (9)
C203—C202—C201119.7 (3)C18A—Cl1A—Cl222.4 (10)
C203—C202—H202120.2Cl1—Cl1A—Cl2B161 (2)
C201—C202—H202120.2C18—Cl1A—Cl2B40.6 (11)
C202—C203—C204119.7 (3)C18A—Cl1A—Cl2B41.2 (15)
C202—C203—H203120.1Cl2—Cl1A—Cl2B19.9 (11)
C204—C203—H203120.1Cl1—Cl1A—Cl2A158 (2)
C205—C204—C203121.0 (3)C18—Cl1A—Cl2A58.8 (8)
C205—C204—H204119.5C18A—Cl1A—Cl2A35.3 (16)
C203—C204—H204119.5Cl2—Cl1A—Cl2A24.5 (4)
C204—C205—C206120.1 (3)Cl2B—Cl1A—Cl2A20.6 (9)
C204—C205—H205120.0Cl2B—Cl2A—Cl248 (3)
C206—C205—H205120.0Cl2B—Cl2A—C18A79 (4)
C205—C206—C201119.8 (3)Cl2—Cl2A—C18A35.0 (18)
C205—C206—H206120.1Cl2B—Cl2A—C1843 (3)
C201—C206—H206120.1Cl2—Cl2A—C1858.8 (10)
C208—C207—C212119.5 (3)C18A—Cl2A—C1867.5 (18)
C208—C207—P2122.7 (2)Cl2B—Cl2A—Cl1A70 (3)
C212—C207—P2117.1 (2)Cl2—Cl2A—Cl1A61.2 (15)
C209—C208—C207120.2 (3)C18A—Cl2A—Cl1A49.1 (18)
C209—C208—H208119.9C18—Cl2A—Cl1A31.1 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2B···O40.982.363.245 (4)151
C2—H2A···O5i0.982.383.307 (4)158
C3—H3B···O5i0.982.383.343 (4)169
C206—H206···O5i0.942.523.204 (4)130
C3—H3A···O70.982.233.185 (5)165
C1—H1···O30.94 (2)2.55 (2)3.419 (11)155 (2)
C208—H208···O30.942.473.231 (16)139
C308—H308···O30.942.573.301 (12)135
Symmetry code: (i) x+1, y+1, z+1.
Dichloridohydrido(1,1,3,3,5,5,7,7-octaphenyl-1,5λ5,7-triphospha-3-phosphoniahept-4-en-4-yl)iridium(III) acetone monosolvate (2) top
Crystal data top
[Ir(C51H44P4)ClH]Cl·C3H6OF(000) = 2216
Mr = 1102.93Dx = 1.536 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 18.7964 (4) ÅCell parameters from 78297 reflections
b = 13.7444 (2) Åθ = 1.0–25.3°
c = 18.8487 (4) ŵ = 3.08 mm1
β = 101.586 (2)°T = 233 K
V = 4770.25 (16) Å3Prism, orange
Z = 40.15 × 0.12 × 0.02 mm
Data collection top
Nonius KappaCCD
diffractometer
6069 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.083
Graphite monochromatorθmax = 25.0°, θmin = 1.7°
phi– and ω scansh = 2220
27235 measured reflectionsk = 1616
8407 independent reflectionsl = 2222
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0337P)2 + 5.179P]
where P = (Fo2 + 2Fc2)/3
8407 reflections(Δ/σ)max = 0.003
572 parametersΔρmax = 0.92 e Å3
1 restraintΔρmin = 0.80 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 at higher 2 theta angles. Hydrogen atom at Ir was localized and refined isotropically with bond restraint (d = 1.6 Å), because of a too long bond distance of 1.88 Å by free refinement. The solvent molecule aceton is slightly disordered with one solved positional disorder for a methyl group C6:C6A at ratio 1:1. Hydrogen atoms at solvent could not be localized and were omitted.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ir10.091292 (12)1.211417 (16)0.715827 (11)0.03564 (9)
H10.104 (3)1.166 (4)0.7978 (15)0.060 (17)*
P10.20108 (8)1.29145 (11)0.73550 (7)0.0364 (3)
P20.10554 (9)1.40730 (11)0.80556 (8)0.0414 (4)
P30.04557 (9)1.35866 (11)0.72257 (8)0.0411 (4)
P40.02175 (9)1.14531 (11)0.70562 (8)0.0416 (4)
Cl10.14205 (9)1.05981 (10)0.68023 (8)0.0483 (4)
Cl20.05445 (9)1.27503 (11)0.58858 (8)0.0498 (4)
C10.0437 (3)1.3354 (4)0.7520 (3)0.0399 (14)
C20.1830 (3)1.4166 (4)0.7621 (3)0.0422 (15)
H2A0.22521.44300.79580.051*
H2B0.17191.45900.71950.051*
C30.0859 (3)1.2459 (4)0.6821 (3)0.0453 (15)
H3A0.09861.25300.62930.054*
H3B0.13051.23190.69970.054*
C1010.2483 (3)1.3090 (4)0.6612 (3)0.0386 (14)
C1020.2438 (4)1.2373 (4)0.6093 (3)0.0508 (17)
H1020.21651.18080.61270.061*
C1030.2795 (4)1.2484 (6)0.5519 (4)0.0620 (19)
H1030.27771.19810.51790.074*
C1040.3167 (4)1.3310 (6)0.5446 (3)0.0595 (19)
H1040.33891.33860.50440.071*
C1050.3223 (4)1.4029 (5)0.5949 (4)0.0576 (18)
H1050.34891.45960.59010.069*
C1060.2884 (4)1.3919 (4)0.6535 (3)0.0502 (17)
H1060.29271.44140.68850.060*
C1070.2719 (3)1.2471 (4)0.8099 (3)0.0390 (14)
C1080.2642 (4)1.1569 (5)0.8398 (3)0.0560 (18)
H1080.22411.11770.82020.067*
C1090.3155 (4)1.1235 (5)0.8989 (4)0.068 (2)
H1090.30971.06220.91920.082*
C1100.3746 (4)1.1806 (6)0.9274 (4)0.064 (2)
H1100.40841.15930.96810.076*
C1110.3840 (4)1.2682 (5)0.8964 (4)0.0597 (19)
H1110.42531.30590.91490.072*
C1120.3331 (3)1.3019 (4)0.8379 (3)0.0494 (16)
H1120.34011.36240.81700.059*
C2010.0773 (3)1.5290 (4)0.8238 (4)0.0484 (16)
C2020.0844 (4)1.6065 (5)0.7788 (4)0.066 (2)
H2020.10591.59680.73840.080*
C2030.0603 (5)1.6974 (5)0.7929 (5)0.088 (3)
H2030.06551.74980.76240.105*
C2040.0284 (5)1.7116 (6)0.8517 (6)0.097 (3)
H2040.01241.77420.86120.117*
C2050.0194 (5)1.6355 (7)0.8970 (5)0.088 (3)
H2050.00381.64510.93620.105*
C2060.0455 (4)1.5443 (5)0.8831 (4)0.071 (2)
H2060.04151.49220.91440.085*
C2070.1427 (3)1.3566 (5)0.8949 (3)0.0465 (16)
C2080.1057 (4)1.2834 (6)0.9204 (4)0.069 (2)
H2080.06211.26060.89180.083*
C2090.1316 (7)1.2419 (6)0.9881 (5)0.100 (3)
H2090.10631.19101.00550.121*
C2100.1956 (7)1.2778 (9)1.0290 (4)0.103 (3)
H2100.21311.25211.07540.123*
C2110.2336 (5)1.3493 (8)1.0037 (4)0.090 (3)
H2110.27821.37031.03150.108*
C2120.2068 (4)1.3912 (6)0.9369 (3)0.068 (2)
H2120.23191.44270.92020.082*
C3010.0779 (3)1.4458 (4)0.6504 (3)0.0442 (15)
C3020.0310 (4)1.5011 (5)0.6200 (4)0.0568 (18)
H3020.01931.49600.63760.068*
C3030.0574 (4)1.5642 (5)0.5636 (4)0.0626 (19)
H3030.02501.60250.54340.075*
C3040.1301 (4)1.5710 (5)0.5374 (4)0.0627 (19)
H3040.14811.61460.49960.075*
C3050.1768 (4)1.5148 (6)0.5658 (4)0.068 (2)
H3050.22701.51870.54690.081*
C3060.1513 (4)1.4528 (5)0.6217 (4)0.0568 (18)
H3060.18421.41430.64090.068*
C3070.0915 (3)1.3948 (5)0.7946 (3)0.0517 (17)
C3080.0883 (4)1.3334 (5)0.8531 (4)0.071 (2)
H3080.06601.27220.85300.086*
C3090.1174 (6)1.3603 (7)0.9116 (5)0.096 (3)
H3090.11541.31740.95080.116*
C3100.1487 (6)1.4480 (9)0.9128 (5)0.104 (3)
H3100.16791.46570.95330.125*
C3110.1533 (6)1.5123 (7)0.8568 (5)0.102 (3)
H3110.17551.57340.85790.123*
C3120.1237 (5)1.4838 (6)0.7978 (4)0.079 (2)
H3120.12601.52710.75880.095*
C4010.0525 (4)1.0532 (5)0.6373 (4)0.0513 (17)
C4020.0726 (5)1.0752 (6)0.5658 (4)0.090 (3)
H4020.07381.14070.55120.107*
C4030.0912 (6)1.0041 (8)0.5143 (5)0.104 (3)
H4030.10391.02210.46530.124*
C4040.0919 (5)0.9113 (8)0.5315 (6)0.097 (3)
H4040.11010.86420.49640.116*
C4050.0649 (5)0.8847 (6)0.6030 (6)0.094 (3)
H4050.06030.81860.61600.112*
C4060.0447 (5)0.9565 (6)0.6550 (4)0.087 (3)
H4060.02550.93850.70310.105*
C4070.0473 (4)1.0910 (4)0.7860 (3)0.0489 (16)
C4080.0043 (4)1.0520 (6)0.8402 (4)0.078 (2)
H4080.05361.05550.83740.093*
C4090.0153 (6)1.0078 (8)0.8987 (5)0.106 (3)
H4090.02070.97950.93460.127*
C4100.0847 (7)1.0042 (7)0.9054 (5)0.105 (3)
H4100.09710.97510.94640.126*
C4110.1366 (6)1.0424 (8)0.8535 (7)0.118 (4)
H4110.18531.04180.85880.142*
C4120.1187 (5)1.0824 (7)0.7922 (5)0.087 (3)
H4120.15571.10400.75430.105*
O10.2574 (4)1.2344 (8)0.7189 (4)0.159 (4)
C40.2949 (6)1.2620 (9)0.7592 (6)0.104 (3)
C50.2930 (10)1.2258 (12)0.8318 (8)0.199 (7)
C60.3726 (15)1.290 (3)0.7273 (13)0.158 (12)0.50
C6A0.3108 (18)1.366 (2)0.7492 (19)0.176 (13)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ir10.04171 (15)0.03396 (13)0.02948 (13)0.00138 (12)0.00290 (9)0.00100 (11)
P10.0445 (9)0.0337 (8)0.0292 (7)0.0008 (8)0.0032 (7)0.0009 (7)
P20.0481 (10)0.0396 (9)0.0345 (9)0.0033 (8)0.0038 (7)0.0046 (7)
P30.0464 (9)0.0440 (9)0.0325 (8)0.0046 (8)0.0074 (7)0.0003 (7)
P40.0473 (10)0.0427 (9)0.0334 (8)0.0019 (8)0.0048 (7)0.0021 (7)
Cl10.0570 (10)0.0393 (8)0.0454 (9)0.0049 (7)0.0027 (7)0.0038 (7)
Cl20.0592 (10)0.0549 (10)0.0340 (8)0.0071 (8)0.0061 (7)0.0051 (7)
C10.046 (4)0.039 (3)0.034 (3)0.001 (3)0.008 (3)0.006 (3)
C20.050 (4)0.035 (3)0.041 (3)0.008 (3)0.006 (3)0.001 (3)
C30.046 (4)0.049 (3)0.041 (4)0.006 (3)0.009 (3)0.000 (3)
C1010.042 (4)0.035 (3)0.037 (3)0.001 (3)0.002 (3)0.001 (3)
C1020.054 (4)0.049 (4)0.050 (4)0.005 (3)0.013 (3)0.009 (3)
C1030.065 (5)0.077 (5)0.049 (4)0.006 (4)0.021 (4)0.016 (4)
C1040.056 (4)0.084 (5)0.042 (4)0.001 (4)0.017 (3)0.007 (4)
C1050.054 (4)0.058 (4)0.065 (5)0.011 (4)0.021 (4)0.004 (4)
C1060.058 (4)0.048 (4)0.045 (4)0.000 (3)0.008 (3)0.004 (3)
C1070.041 (4)0.038 (3)0.035 (3)0.005 (3)0.001 (3)0.000 (3)
C1080.065 (5)0.052 (4)0.047 (4)0.000 (4)0.003 (3)0.001 (3)
C1090.072 (5)0.063 (4)0.060 (5)0.004 (4)0.010 (4)0.018 (4)
C1100.060 (5)0.075 (5)0.049 (4)0.014 (4)0.007 (4)0.000 (4)
C1110.045 (4)0.070 (5)0.058 (4)0.002 (4)0.005 (3)0.007 (4)
C1120.047 (4)0.051 (4)0.047 (4)0.001 (3)0.002 (3)0.006 (3)
C2010.043 (4)0.039 (4)0.060 (4)0.002 (3)0.005 (3)0.012 (3)
C2020.077 (5)0.044 (4)0.080 (5)0.009 (4)0.020 (4)0.009 (4)
C2030.105 (7)0.054 (5)0.110 (7)0.006 (5)0.035 (6)0.011 (5)
C2040.095 (7)0.055 (5)0.149 (9)0.003 (5)0.043 (7)0.036 (6)
C2050.096 (7)0.079 (6)0.093 (6)0.016 (5)0.029 (5)0.028 (5)
C2060.086 (6)0.058 (5)0.069 (5)0.008 (4)0.019 (4)0.019 (4)
C2070.057 (4)0.055 (4)0.027 (3)0.008 (4)0.009 (3)0.007 (3)
C2080.094 (6)0.074 (5)0.037 (4)0.007 (5)0.006 (4)0.003 (4)
C2090.162 (10)0.084 (6)0.055 (5)0.014 (6)0.020 (6)0.020 (5)
C2100.124 (9)0.140 (9)0.039 (5)0.050 (8)0.007 (5)0.001 (6)
C2110.082 (6)0.144 (9)0.036 (5)0.035 (6)0.007 (4)0.008 (5)
C2120.069 (5)0.102 (6)0.031 (4)0.011 (4)0.002 (4)0.018 (4)
C3010.046 (4)0.050 (4)0.035 (3)0.008 (3)0.005 (3)0.005 (3)
C3020.054 (4)0.056 (4)0.058 (4)0.000 (4)0.005 (4)0.010 (4)
C3030.063 (5)0.066 (5)0.057 (4)0.009 (4)0.008 (4)0.026 (4)
C3040.067 (5)0.073 (5)0.045 (4)0.014 (4)0.004 (4)0.016 (4)
C3050.054 (5)0.098 (6)0.049 (4)0.014 (4)0.004 (4)0.016 (4)
C3060.045 (4)0.074 (5)0.052 (4)0.007 (4)0.012 (3)0.015 (4)
C3070.051 (4)0.061 (4)0.044 (4)0.011 (4)0.010 (3)0.002 (3)
C3080.096 (6)0.065 (5)0.064 (5)0.014 (4)0.042 (5)0.005 (4)
C3090.146 (9)0.088 (6)0.075 (6)0.019 (6)0.069 (6)0.015 (5)
C3100.123 (8)0.130 (9)0.074 (6)0.023 (7)0.052 (6)0.008 (6)
C3110.136 (9)0.107 (7)0.076 (6)0.056 (6)0.051 (6)0.012 (6)
C3120.101 (6)0.081 (6)0.061 (5)0.030 (5)0.030 (5)0.009 (4)
C4010.059 (4)0.048 (4)0.050 (4)0.008 (3)0.018 (3)0.006 (3)
C4020.135 (8)0.076 (5)0.053 (5)0.021 (5)0.008 (5)0.020 (4)
C4030.147 (10)0.100 (7)0.061 (6)0.012 (7)0.014 (6)0.040 (5)
C4040.088 (7)0.112 (8)0.088 (7)0.027 (6)0.011 (5)0.061 (6)
C4050.118 (8)0.058 (5)0.111 (8)0.021 (5)0.039 (6)0.026 (5)
C4060.125 (8)0.066 (5)0.069 (5)0.010 (5)0.013 (5)0.018 (4)
C4070.053 (4)0.044 (4)0.051 (4)0.012 (3)0.013 (3)0.001 (3)
C4080.074 (5)0.097 (6)0.064 (5)0.005 (5)0.017 (4)0.029 (5)
C4090.098 (7)0.149 (9)0.068 (6)0.028 (7)0.010 (5)0.047 (6)
C4100.154 (11)0.100 (7)0.072 (6)0.015 (7)0.045 (7)0.034 (5)
C4110.118 (9)0.123 (8)0.137 (9)0.020 (7)0.081 (8)0.055 (8)
C4120.081 (6)0.102 (7)0.084 (6)0.001 (5)0.028 (5)0.035 (5)
O10.099 (6)0.283 (11)0.094 (5)0.037 (6)0.016 (4)0.028 (6)
C40.089 (8)0.143 (10)0.082 (7)0.004 (7)0.021 (6)0.016 (7)
C50.28 (2)0.230 (16)0.111 (11)0.078 (14)0.086 (12)0.035 (10)
C60.109 (18)0.25 (4)0.113 (18)0.09 (2)0.018 (15)0.00 (2)
C6A0.15 (3)0.14 (2)0.26 (4)0.04 (2)0.09 (3)0.08 (2)
Geometric parameters (Å, º) top
Ir1—C12.101 (5)C208—C2091.394 (11)
Ir1—P42.2831 (16)C208—H2080.9400
Ir1—P12.3019 (15)C209—C2101.382 (15)
Ir1—Cl12.4412 (15)C209—H2090.9400
Ir1—Cl22.5157 (14)C210—C2111.358 (13)
Ir1—H11.638 (19)C210—H2100.9400
P1—C1011.819 (6)C211—C2121.383 (10)
P1—C1071.834 (6)C211—H2110.9400
P1—C21.842 (6)C212—H2120.9400
P2—C11.695 (6)C301—C3021.372 (9)
P2—C2011.809 (6)C301—C3061.381 (8)
P2—C21.813 (6)C302—C3031.385 (9)
P2—C2071.827 (6)C302—H3020.9400
P3—C11.688 (6)C303—C3041.361 (9)
P3—C3071.817 (6)C303—H3030.9400
P3—C3011.823 (6)C304—C3051.358 (10)
P3—C31.824 (6)C304—H3040.9400
P4—C4011.816 (6)C305—C3061.365 (9)
P4—C31.829 (6)C305—H3050.9400
P4—C4071.837 (6)C306—H3060.9400
C2—H2A0.9800C307—C3121.372 (9)
C2—H2B0.9800C307—C3081.382 (9)
C3—H3A0.9800C308—C3091.377 (10)
C3—H3B0.9800C308—H3080.9400
C101—C1021.378 (8)C309—C3101.343 (12)
C101—C1061.390 (8)C309—H3090.9400
C102—C1031.391 (9)C310—C3111.367 (12)
C102—H1020.9400C310—H3100.9400
C103—C1041.355 (10)C311—C3121.396 (10)
C103—H1030.9400C311—H3110.9400
C104—C1051.359 (9)C312—H3120.9400
C104—H1040.9400C401—C4021.358 (9)
C105—C1061.390 (9)C401—C4061.371 (10)
C105—H1050.9400C402—C4031.373 (11)
C106—H1060.9400C402—H4020.9400
C107—C1081.381 (8)C403—C4041.317 (13)
C107—C1121.387 (8)C403—H4030.9400
C108—C1091.396 (9)C404—C4051.390 (13)
C108—H1080.9400C404—H4040.9400
C109—C1101.378 (10)C405—C4061.389 (11)
C109—H1090.9400C405—H4050.9400
C110—C1111.364 (10)C406—H4060.9400
C110—H1100.9400C407—C4081.369 (9)
C111—C1121.387 (9)C407—C4121.376 (10)
C111—H1110.9400C408—C4091.371 (11)
C112—H1120.9400C408—H4080.9400
C201—C2021.385 (9)C409—C4101.337 (13)
C201—C2061.385 (9)C409—H4090.9400
C202—C2031.373 (10)C410—C4111.342 (14)
C202—H2020.9400C410—H4100.9400
C203—C2041.377 (12)C411—C4121.380 (11)
C203—H2030.9400C411—H4110.9400
C204—C2051.382 (12)C412—H4120.9400
C204—H2040.9400O1—C41.197 (11)
C205—C2061.390 (10)C4—C51.450 (15)
C205—H2050.9400C4—C6A1.47 (3)
C206—H2060.9400C4—C61.51 (2)
C207—C2081.363 (9)C6—C6A1.56 (4)
C207—C2121.387 (9)
C1—Ir1—P484.28 (16)C204—C205—H205120.8
C1—Ir1—P189.23 (16)C206—C205—H205120.8
P4—Ir1—P1173.09 (5)C201—C206—C205121.0 (7)
C1—Ir1—Cl1175.48 (16)C201—C206—H206119.5
P4—Ir1—Cl192.62 (6)C205—C206—H206119.5
P1—Ir1—Cl193.72 (5)C208—C207—C212119.8 (6)
C1—Ir1—Cl288.52 (15)C208—C207—P2118.6 (5)
P4—Ir1—Cl289.12 (5)C212—C207—P2121.6 (5)
P1—Ir1—Cl293.08 (5)C207—C208—C209121.1 (8)
Cl1—Ir1—Cl294.73 (5)C207—C208—H208119.4
C1—Ir1—H190 (2)C209—C208—H208119.4
P4—Ir1—H183 (2)C210—C209—C208117.9 (9)
P1—Ir1—H194 (2)C210—C209—H209121.0
Cl1—Ir1—H187 (2)C208—C209—H209121.0
Cl2—Ir1—H1173 (2)C211—C210—C209121.6 (8)
C101—P1—C107104.0 (3)C211—C210—H210119.2
C101—P1—C2103.4 (3)C209—C210—H210119.2
C107—P1—C2104.3 (3)C210—C211—C212120.0 (9)
C101—P1—Ir1119.99 (19)C210—C211—H211120.0
C107—P1—Ir1117.0 (2)C212—C211—H211120.0
C2—P1—Ir1106.4 (2)C211—C212—C207119.6 (8)
C1—P2—C201117.4 (3)C211—C212—H212120.2
C1—P2—C2106.8 (3)C207—C212—H212120.2
C201—P2—C2108.3 (3)C302—C301—C306118.2 (6)
C1—P2—C207114.6 (3)C302—C301—P3122.0 (5)
C201—P2—C207104.5 (3)C306—C301—P3119.6 (5)
C2—P2—C207104.5 (3)C301—C302—C303120.5 (6)
C1—P3—C307113.3 (3)C301—C302—H302119.8
C1—P3—C301122.0 (3)C303—C302—H302119.8
C307—P3—C301104.0 (3)C304—C303—C302120.0 (6)
C1—P3—C3106.2 (3)C304—C303—H303120.0
C307—P3—C3109.0 (3)C302—C303—H303120.0
C301—P3—C3101.4 (3)C305—C304—C303120.0 (6)
C401—P4—C3104.7 (3)C305—C304—H304120.0
C401—P4—C407101.7 (3)C303—C304—H304120.0
C3—P4—C407103.8 (3)C304—C305—C306120.3 (6)
C401—P4—Ir1119.7 (2)C304—C305—H305119.8
C3—P4—Ir1106.1 (2)C306—C305—H305119.8
C407—P4—Ir1119.0 (2)C305—C306—C301120.9 (6)
P3—C1—P2127.1 (3)C305—C306—H306119.5
P3—C1—Ir1120.4 (3)C301—C306—H306119.5
P2—C1—Ir1112.3 (3)C312—C307—C308117.3 (6)
P2—C2—P1105.4 (3)C312—C307—P3123.8 (5)
P2—C2—H2A110.7C308—C307—P3118.6 (5)
P1—C2—H2A110.7C309—C308—C307121.0 (7)
P2—C2—H2B110.7C309—C308—H308119.5
P1—C2—H2B110.7C307—C308—H308119.5
H2A—C2—H2B108.8C310—C309—C308120.0 (8)
P3—C3—P4110.0 (3)C310—C309—H309120.0
P3—C3—H3A109.7C308—C309—H309120.0
P4—C3—H3A109.7C309—C310—C311121.8 (8)
P3—C3—H3B109.7C309—C310—H310119.1
P4—C3—H3B109.7C311—C310—H310119.1
H3A—C3—H3B108.2C310—C311—C312117.4 (8)
C102—C101—C106118.0 (6)C310—C311—H311121.3
C102—C101—P1118.7 (4)C312—C311—H311121.3
C106—C101—P1123.2 (4)C307—C312—C311122.4 (7)
C101—C102—C103120.1 (6)C307—C312—H312118.8
C101—C102—H102119.9C311—C312—H312118.8
C103—C102—H102119.9C402—C401—C406116.9 (7)
C104—C103—C102120.8 (6)C402—C401—P4122.3 (5)
C104—C103—H103119.6C406—C401—P4120.0 (6)
C102—C103—H103119.6C401—C402—C403121.6 (8)
C103—C104—C105120.4 (6)C401—C402—H402119.2
C103—C104—H104119.8C403—C402—H402119.2
C105—C104—H104119.8C404—C403—C402121.9 (9)
C104—C105—C106119.5 (6)C404—C403—H403119.0
C104—C105—H105120.3C402—C403—H403119.0
C106—C105—H105120.3C403—C404—C405118.3 (8)
C101—C106—C105121.1 (6)C403—C404—H404120.8
C101—C106—H106119.4C405—C404—H404120.8
C105—C106—H106119.4C406—C405—C404119.5 (8)
C108—C107—C112118.7 (5)C406—C405—H405120.3
C108—C107—P1119.4 (5)C404—C405—H405120.3
C112—C107—P1122.0 (4)C401—C406—C405121.1 (8)
C107—C108—C109120.5 (6)C401—C406—H406119.5
C107—C108—H108119.7C405—C406—H406119.5
C109—C108—H108119.7C408—C407—C412117.4 (7)
C110—C109—C108119.8 (7)C408—C407—P4120.8 (6)
C110—C109—H109120.1C412—C407—P4121.7 (6)
C108—C109—H109120.1C407—C408—C409120.6 (8)
C111—C110—C109119.9 (6)C407—C408—H408119.7
C111—C110—H110120.0C409—C408—H408119.7
C109—C110—H110120.0C410—C409—C408121.2 (9)
C110—C111—C112120.5 (6)C410—C409—H409119.4
C110—C111—H111119.7C408—C409—H409119.4
C112—C111—H111119.7C409—C410—C411119.7 (9)
C111—C112—C107120.5 (6)C409—C410—H410120.1
C111—C112—H112119.8C411—C410—H410120.1
C107—C112—H112119.8C410—C411—C412120.2 (9)
C202—C201—C206119.2 (6)C410—C411—H411119.9
C202—C201—P2121.8 (5)C412—C411—H411119.9
C206—C201—P2119.0 (5)C407—C412—C411120.8 (8)
C203—C202—C201120.3 (7)C407—C412—H412119.6
C203—C202—H202119.9C411—C412—H412119.6
C201—C202—H202119.9O1—C4—C5125.7 (12)
C202—C203—C204120.0 (8)O1—C4—C6A111.0 (16)
C202—C203—H203120.0C5—C4—C6A115.0 (17)
C204—C203—H203120.0O1—C4—C6118.2 (13)
C203—C204—C205121.1 (8)C5—C4—C6107.6 (15)
C203—C204—H204119.4C6A—C4—C662.8 (16)
C205—C204—H204119.4C4—C6—C6A57.2 (14)
C204—C205—C206118.4 (8)C4—C6A—C660.0 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C112—H112···Cl1i0.942.733.601 (6)154
C3—H3B···O10.982.483.435 (10)163
Symmetry code: (i) x+1/2, y+1/2, z+3/2.
Dichloridohydrido(1,1,3,3,5,5,7,7-octaphenyl-1,7-diphospha-3,5-diphosphoniaheptan-4-yl)iridium(III) chloride pentahydrate (3) top
Crystal data top
[Ir(C51H45P4)ClH]Cl·5H2OF(000) = 2360
Mr = 1171.38Dx = 1.429 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.6532 (8) ÅCell parameters from 9971 reflections
b = 21.8847 (12) Åθ = 2.7–25.9°
c = 19.9228 (12) ŵ = 2.76 mm1
β = 99.381 (2)°T = 203 K
V = 5443.1 (6) Å3Prism, colourless
Z = 40.17 × 0.12 × 0.09 mm
Data collection top
Bruker D8 QUEST PHOTON 100
diffractometer
10577 independent reflections
Radiation source: Incoatec Microfocus9522 reflections with I > 2σ(I)
Multi layered optics monochromatorRint = 0.031
Detector resolution: 10.4 pixels mm-1θmax = 25.9°, θmin = 2.1°
φ and ω scansh = 1514
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
k = 2626
Tmin = 0.691, Tmax = 0.801l = 2424
104100 measured reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.032 w = 1/[σ2(Fo2) + (0.0524P)2 + 9.2728P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.095(Δ/σ)max = 0.003
S = 1.09Δρmax = 1.27 e Å3
10577 reflectionsΔρmin = 0.86 e Å3
574 parametersExtinction correction: (SHELXL-2014/7; Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.00056 (9)
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. Positional Disorder of the Anion Cl3:Cl3A in ratio 2:1. Hydrogen atoms at C1 (H1A) and Ir1 (H1) were found and refined regularly with isotropic displacement parameters. The water solvent molecules show higher temperature factors and would be slightly disordered, but this disorder was not solved, and therefore the oxygen atoms (O5 and O6 with half occupancy) were refined isotropically and their hydrogen atoms were omitted.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ir10.18691 (2)0.09326 (2)0.82207 (2)0.03005 (7)
H10.207 (4)0.069 (2)0.757 (2)0.049 (12)*
P10.00638 (8)0.07642 (5)0.78743 (5)0.0349 (2)
P20.06530 (9)0.17799 (4)0.70390 (5)0.0357 (2)
P30.28773 (9)0.22466 (4)0.77953 (5)0.0362 (2)
P40.36829 (8)0.10629 (5)0.83855 (5)0.0345 (2)
Cl10.21275 (9)0.00814 (5)0.86833 (6)0.0517 (3)
Cl20.15051 (8)0.13129 (5)0.93346 (5)0.0419 (2)
Cl30.0093 (4)0.2435 (2)0.8764 (2)0.1427 (13)0.67
Cl3A0.4940 (10)0.1089 (7)0.6444 (5)0.195 (5)0.33
C10.1651 (3)0.18280 (16)0.77996 (17)0.0318 (7)
H1A0.129 (3)0.2086 (19)0.810 (2)0.037 (10)*
C20.0442 (3)0.14516 (19)0.7392 (2)0.0433 (9)
H2A0.10280.13420.70270.052*
H2B0.07130.17460.76930.052*
C30.3948 (3)0.17048 (19)0.7832 (2)0.0413 (9)
H3A0.46310.19000.80160.050*
H3B0.39920.15540.73740.050*
C1010.0786 (3)0.0675 (2)0.8515 (2)0.0417 (9)
C1020.0637 (4)0.0159 (2)0.8920 (2)0.0538 (12)
H1020.01350.01380.88410.065*
C1030.1229 (4)0.0076 (3)0.9446 (2)0.0699 (17)
H1030.11320.02790.97130.084*
C1040.1940 (4)0.0504 (3)0.9574 (2)0.0702 (17)
H1040.23450.04430.99240.084*
C1050.2071 (5)0.1026 (3)0.9193 (3)0.0684 (15)
H1050.25490.13280.92950.082*
C1060.1512 (4)0.1117 (3)0.8658 (3)0.0552 (11)
H1060.16220.14740.83940.066*
C1070.0332 (4)0.0131 (2)0.7293 (2)0.0460 (10)
C1080.1415 (5)0.0046 (3)0.7037 (3)0.0773 (18)
H1080.19300.03170.71550.093*
C1090.1725 (6)0.0445 (4)0.6602 (3)0.097 (3)
H1090.24540.05080.64290.116*
C1100.0981 (8)0.0831 (3)0.6429 (3)0.092 (3)
H1100.11990.11600.61360.110*
C1110.0086 (7)0.0751 (3)0.6674 (3)0.083 (2)
H1110.05950.10250.65520.100*
C1120.0410 (5)0.0264 (2)0.7103 (3)0.0614 (13)
H1120.11430.02030.72650.074*
C2010.0157 (4)0.24892 (18)0.66472 (19)0.0401 (9)
C2020.0364 (5)0.2893 (2)0.7017 (2)0.0569 (13)
H2020.04180.28080.74730.068*
C2030.0808 (5)0.3425 (2)0.6709 (3)0.0658 (15)
H2030.11650.37010.69550.079*
C2040.0723 (5)0.3545 (2)0.6043 (2)0.0604 (13)
H2040.10450.38980.58320.072*
C2050.0173 (4)0.3157 (2)0.5681 (2)0.0533 (12)
H2050.00950.32540.52320.064*
C2060.0265 (4)0.26226 (19)0.5978 (2)0.0454 (10)
H2060.06330.23530.57300.055*
C2070.0977 (4)0.12959 (18)0.63756 (19)0.0421 (9)
C2080.2004 (4)0.1117 (2)0.6323 (2)0.0487 (10)
H2080.25800.12480.66500.058*
C2090.2196 (5)0.0745 (2)0.5792 (3)0.0637 (14)
H2090.28970.06170.57670.076*
C2100.1370 (6)0.0567 (3)0.5309 (3)0.0749 (18)
H2100.15050.03170.49480.090*
C2110.0332 (6)0.0749 (3)0.5342 (3)0.0751 (18)
H2110.02350.06260.50030.090*
C2120.0134 (5)0.1113 (2)0.5876 (2)0.0597 (13)
H2120.05700.12360.59020.072*
C3010.2843 (4)0.27525 (19)0.7085 (2)0.0479 (11)
C3020.2267 (4)0.3299 (2)0.7114 (2)0.0550 (12)
H3020.19450.33850.74960.066*
C3030.2174 (5)0.3711 (2)0.6578 (3)0.0686 (16)
H3030.17790.40740.65910.082*
C3040.2668 (5)0.3584 (3)0.6030 (3)0.0749 (18)
H3040.26160.38670.56710.090*
C3050.3234 (6)0.3053 (3)0.5992 (2)0.0759 (19)
H3050.35600.29760.56090.091*
C3060.3330 (5)0.2625 (3)0.6525 (2)0.0625 (14)
H3060.37150.22610.65030.075*
C3070.3189 (4)0.27214 (17)0.85395 (19)0.0407 (9)
C3080.2649 (4)0.2706 (2)0.9078 (2)0.0485 (10)
H3080.20630.24410.90730.058*
C3090.2969 (5)0.3086 (2)0.9639 (2)0.0621 (13)
H3090.25980.30751.00110.075*
C3100.3818 (5)0.3472 (2)0.9649 (3)0.0694 (16)
H3100.40240.37291.00270.083*
C3110.4371 (5)0.3488 (3)0.9111 (3)0.0769 (17)
H3110.49580.37530.91230.092*
C3120.4066 (5)0.3115 (2)0.8551 (3)0.0641 (14)
H3120.44440.31260.81820.077*
C4010.4481 (3)0.0466 (2)0.8070 (2)0.0440 (9)
C4020.4020 (5)0.0026 (4)0.7623 (4)0.107 (3)
H4020.32710.00090.74970.129*
C4030.4670 (6)0.0394 (4)0.7359 (5)0.140 (4)
H4030.43550.06880.70450.168*
C4040.5742 (5)0.0386 (3)0.7545 (3)0.086 (2)
H4040.61710.06650.73520.103*
C4050.6192 (4)0.0022 (3)0.8006 (3)0.0633 (13)
H4050.69380.00170.81510.076*
C4060.5570 (4)0.0447 (2)0.8268 (2)0.0506 (11)
H4060.58980.07310.85900.061*
C4070.4430 (3)0.1214 (2)0.9230 (2)0.0412 (9)
C4080.4308 (4)0.0783 (2)0.9726 (2)0.0531 (11)
H4080.38060.04650.96310.064*
C4090.4939 (5)0.0830 (3)1.0365 (3)0.0684 (15)
H4090.48750.05321.06960.082*
C4100.5643 (5)0.1295 (3)1.0519 (3)0.0698 (15)
H4100.60590.13191.09550.084*
C4110.5752 (4)0.1733 (3)1.0040 (3)0.0660 (14)
H4110.62350.20581.01480.079*
C4120.5140 (4)0.1690 (2)0.9391 (2)0.0538 (11)
H4120.52130.19880.90620.065*
O10.6533 (8)0.2455 (5)0.7966 (5)0.189 (3)*
O20.7918 (10)0.2878 (6)0.9223 (6)0.244 (5)*
O30.7393 (15)0.4042 (7)0.9328 (9)0.318 (8)*
O40.6081 (13)0.4713 (7)1.0118 (8)0.308 (7)*
O50.6616 (17)0.1673 (10)0.6823 (11)0.209 (8)*0.5
O60.7444 (17)0.1702 (10)0.5728 (10)0.206 (8)*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ir10.03410 (10)0.02785 (10)0.02848 (9)0.00002 (5)0.00597 (6)0.00535 (5)
P10.0370 (5)0.0372 (5)0.0302 (5)0.0035 (4)0.0040 (4)0.0090 (4)
P20.0520 (6)0.0282 (5)0.0256 (4)0.0013 (4)0.0024 (4)0.0044 (4)
P30.0544 (6)0.0296 (5)0.0247 (4)0.0082 (4)0.0073 (4)0.0010 (4)
P40.0346 (5)0.0351 (5)0.0342 (5)0.0006 (4)0.0068 (4)0.0025 (4)
Cl10.0568 (6)0.0352 (5)0.0591 (6)0.0004 (4)0.0029 (5)0.0179 (5)
Cl20.0489 (6)0.0501 (6)0.0272 (4)0.0017 (4)0.0077 (4)0.0048 (4)
Cl30.140 (3)0.158 (4)0.133 (3)0.002 (3)0.029 (2)0.016 (3)
Cl3A0.191 (10)0.309 (15)0.086 (5)0.005 (10)0.019 (6)0.012 (7)
C10.043 (2)0.0296 (18)0.0219 (16)0.0008 (15)0.0040 (14)0.0009 (13)
C20.045 (2)0.044 (2)0.039 (2)0.0006 (18)0.0007 (17)0.0144 (17)
C30.046 (2)0.044 (2)0.037 (2)0.0097 (18)0.0144 (17)0.0045 (17)
C1010.034 (2)0.055 (3)0.036 (2)0.0068 (18)0.0052 (16)0.0074 (18)
C1020.046 (2)0.068 (3)0.048 (2)0.007 (2)0.008 (2)0.021 (2)
C1030.056 (3)0.111 (5)0.039 (2)0.032 (3)0.001 (2)0.028 (3)
C1040.049 (3)0.125 (5)0.038 (2)0.035 (3)0.011 (2)0.009 (3)
C1050.055 (3)0.090 (4)0.065 (3)0.020 (3)0.024 (3)0.021 (3)
C1060.045 (3)0.063 (3)0.060 (3)0.007 (2)0.014 (2)0.002 (2)
C1070.059 (3)0.048 (2)0.0298 (19)0.019 (2)0.0020 (18)0.0092 (17)
C1080.069 (4)0.116 (5)0.048 (3)0.041 (3)0.015 (3)0.017 (3)
C1090.100 (5)0.143 (7)0.050 (3)0.072 (5)0.018 (3)0.033 (4)
C1100.156 (8)0.081 (4)0.036 (3)0.058 (5)0.007 (4)0.007 (3)
C1110.135 (6)0.051 (3)0.055 (3)0.003 (3)0.015 (4)0.007 (3)
C1120.080 (4)0.043 (3)0.055 (3)0.002 (2)0.008 (3)0.004 (2)
C2010.059 (3)0.0304 (19)0.0277 (18)0.0008 (17)0.0033 (17)0.0051 (15)
C2020.094 (4)0.043 (2)0.034 (2)0.013 (2)0.008 (2)0.0030 (18)
C2030.104 (4)0.038 (2)0.054 (3)0.017 (3)0.009 (3)0.001 (2)
C2040.092 (4)0.037 (2)0.045 (3)0.008 (2)0.011 (2)0.0072 (19)
C2050.081 (3)0.043 (2)0.032 (2)0.002 (2)0.002 (2)0.0135 (18)
C2060.066 (3)0.037 (2)0.031 (2)0.0002 (19)0.0006 (19)0.0042 (16)
C2070.065 (3)0.0310 (19)0.0299 (19)0.0052 (18)0.0053 (18)0.0006 (15)
C2080.072 (3)0.044 (2)0.032 (2)0.005 (2)0.013 (2)0.0006 (18)
C2090.098 (4)0.052 (3)0.047 (3)0.003 (3)0.030 (3)0.004 (2)
C2100.130 (6)0.054 (3)0.043 (3)0.007 (3)0.020 (3)0.011 (2)
C2110.119 (6)0.056 (3)0.044 (3)0.016 (3)0.006 (3)0.015 (2)
C2120.083 (4)0.048 (3)0.043 (3)0.007 (2)0.005 (2)0.006 (2)
C3010.072 (3)0.041 (2)0.0296 (19)0.024 (2)0.0041 (19)0.0030 (17)
C3020.075 (3)0.042 (2)0.044 (2)0.017 (2)0.004 (2)0.0108 (19)
C3030.093 (4)0.050 (3)0.052 (3)0.027 (3)0.019 (3)0.019 (2)
C3040.106 (5)0.069 (4)0.042 (3)0.045 (3)0.008 (3)0.016 (2)
C3050.111 (5)0.082 (4)0.036 (2)0.049 (4)0.017 (3)0.001 (3)
C3060.092 (4)0.063 (3)0.035 (2)0.032 (3)0.019 (2)0.001 (2)
C3070.057 (3)0.0311 (19)0.0310 (19)0.0018 (17)0.0016 (17)0.0004 (15)
C3080.071 (3)0.040 (2)0.034 (2)0.002 (2)0.008 (2)0.0039 (17)
C3090.096 (4)0.053 (3)0.037 (2)0.000 (3)0.009 (2)0.009 (2)
C3100.102 (4)0.056 (3)0.043 (3)0.008 (3)0.007 (3)0.018 (2)
C3110.097 (4)0.063 (3)0.066 (4)0.032 (3)0.000 (3)0.019 (3)
C3120.081 (4)0.062 (3)0.050 (3)0.026 (3)0.012 (3)0.011 (2)
C4010.041 (2)0.047 (2)0.044 (2)0.0066 (18)0.0057 (18)0.0071 (18)
C4020.057 (4)0.120 (6)0.132 (6)0.031 (4)0.023 (4)0.085 (5)
C4030.081 (5)0.151 (8)0.172 (8)0.038 (5)0.030 (5)0.123 (7)
C4040.064 (4)0.093 (5)0.095 (4)0.035 (3)0.001 (3)0.040 (4)
C4050.046 (3)0.070 (3)0.072 (3)0.017 (2)0.006 (2)0.013 (3)
C4060.041 (2)0.051 (3)0.059 (3)0.0038 (19)0.006 (2)0.010 (2)
C4070.039 (2)0.046 (2)0.039 (2)0.0063 (17)0.0071 (17)0.0048 (17)
C4080.063 (3)0.057 (3)0.040 (2)0.002 (2)0.009 (2)0.000 (2)
C4090.084 (4)0.077 (4)0.043 (3)0.019 (3)0.006 (3)0.006 (2)
C4100.066 (3)0.089 (4)0.047 (3)0.016 (3)0.010 (2)0.013 (3)
C4110.058 (3)0.080 (4)0.056 (3)0.003 (3)0.005 (2)0.016 (3)
C4120.052 (3)0.059 (3)0.048 (3)0.005 (2)0.003 (2)0.008 (2)
Geometric parameters (Å, º) top
Ir1—C12.132 (4)C206—H2060.9400
Ir1—P42.2827 (10)C207—C2081.377 (7)
Ir1—P12.3056 (10)C207—C2121.394 (6)
Ir1—Cl12.4047 (10)C208—C2091.386 (7)
Ir1—Cl22.4824 (10)C208—H2080.9400
Ir1—H11.46 (5)C209—C2101.357 (9)
P1—C1011.809 (4)C209—H2090.9400
P1—C1071.823 (4)C210—C2111.385 (10)
P1—C21.843 (4)C210—H2100.9400
P2—C2071.793 (4)C211—C2121.385 (8)
P2—C21.802 (4)C211—H2110.9400
P2—C2011.803 (4)C212—H2120.9400
P2—C11.811 (4)C301—C3061.388 (7)
P3—C3011.791 (4)C301—C3021.406 (7)
P3—C31.793 (4)C302—C3031.389 (6)
P3—C3071.801 (4)C302—H3020.9400
P3—C11.803 (4)C303—C3041.373 (9)
P4—C4071.821 (4)C303—H3030.9400
P4—C4011.824 (4)C304—C3051.373 (9)
P4—C31.850 (4)C304—H3040.9400
C1—H1A0.98 (4)C305—C3061.406 (7)
C2—H2A0.9800C305—H3050.9400
C2—H2B0.9800C306—H3060.9400
C3—H3A0.9800C307—C3081.364 (6)
C3—H3B0.9800C307—C3121.403 (7)
C101—C1021.383 (6)C308—C3091.398 (6)
C101—C1061.395 (7)C308—H3080.9400
C102—C1031.396 (7)C309—C3101.364 (8)
C102—H1020.9400C309—H3090.9400
C103—C1041.351 (9)C310—C3111.373 (9)
C103—H1030.9400C310—H3100.9400
C104—C1051.365 (9)C311—C3121.387 (7)
C104—H1040.9400C311—H3110.9400
C105—C1061.386 (7)C312—H3120.9400
C105—H1050.9400C401—C4061.370 (6)
C106—H1060.9400C401—C4021.376 (7)
C107—C1121.374 (7)C402—C4031.393 (8)
C107—C1081.394 (7)C402—H4020.9400
C108—C1091.397 (9)C403—C4041.346 (9)
C108—H1080.9400C403—H4030.9400
C109—C1101.350 (11)C404—C4051.339 (8)
C109—H1090.9400C404—H4040.9400
C110—C1111.370 (11)C405—C4061.377 (6)
C110—H1100.9400C405—H4050.9400
C111—C1121.386 (7)C406—H4060.9400
C111—H1110.9400C407—C4121.379 (6)
C112—H1120.9400C407—C4081.394 (6)
C201—C2021.385 (6)C408—C4091.390 (7)
C201—C2061.394 (5)C408—H4080.9400
C202—C2031.391 (6)C409—C4101.357 (9)
C202—H2020.9400C409—H4090.9400
C203—C2041.374 (7)C410—C4111.374 (8)
C203—H2030.9400C410—H4100.9400
C204—C2051.375 (7)C411—C4121.396 (7)
C204—H2040.9400C411—H4110.9400
C205—C2061.385 (6)C412—H4120.9400
C205—H2050.9400
C1—Ir1—P490.24 (11)C202—C203—H203120.1
C1—Ir1—P188.33 (11)C203—C204—C205120.9 (4)
P4—Ir1—P1170.68 (4)C203—C204—H204119.5
C1—Ir1—Cl1179.22 (11)C205—C204—H204119.5
P4—Ir1—Cl189.39 (4)C204—C205—C206120.0 (4)
P1—Ir1—Cl191.92 (4)C204—C205—H205120.0
C1—Ir1—Cl290.73 (10)C206—C205—H205120.0
P4—Ir1—Cl299.10 (3)C205—C206—C201119.4 (4)
P1—Ir1—Cl290.12 (4)C205—C206—H206120.3
Cl1—Ir1—Cl290.01 (4)C201—C206—H206120.3
C1—Ir1—H190.5 (18)C208—C207—C212119.1 (4)
P4—Ir1—H181.7 (18)C208—C207—P2123.8 (3)
P1—Ir1—H189.1 (18)C212—C207—P2117.1 (4)
Cl1—Ir1—H188.8 (18)C207—C208—C209120.6 (5)
Cl2—Ir1—H1178.5 (18)C207—C208—H208119.7
C101—P1—C107103.5 (2)C209—C208—H208119.7
C101—P1—C2105.1 (2)C210—C209—C208120.0 (6)
C107—P1—C2104.6 (2)C210—C209—H209120.0
C101—P1—Ir1118.69 (13)C208—C209—H209120.0
C107—P1—Ir1117.89 (16)C209—C210—C211120.6 (5)
C2—P1—Ir1105.58 (14)C209—C210—H210119.7
C207—P2—C2109.6 (2)C211—C210—H210119.7
C207—P2—C201107.14 (18)C210—C211—C212119.6 (5)
C2—P2—C201106.1 (2)C210—C211—H211120.2
C207—P2—C1116.04 (19)C212—C211—H211120.2
C2—P2—C199.93 (18)C211—C212—C207120.0 (6)
C201—P2—C1117.26 (18)C211—C212—H212120.0
C301—P3—C3111.2 (2)C207—C212—H212120.0
C301—P3—C307105.52 (19)C306—C301—C302120.3 (4)
C3—P3—C307106.6 (2)C306—C301—P3123.6 (4)
C301—P3—C1114.05 (19)C302—C301—P3116.1 (3)
C3—P3—C1107.99 (18)C303—C302—C301120.1 (5)
C307—P3—C1111.25 (19)C303—C302—H302120.0
C407—P4—C401102.41 (19)C301—C302—H302120.0
C407—P4—C3107.2 (2)C304—C303—C302119.1 (6)
C401—P4—C3100.0 (2)C304—C303—H303120.4
C407—P4—Ir1120.94 (14)C302—C303—H303120.4
C401—P4—Ir1117.46 (15)C305—C304—C303121.6 (5)
C3—P4—Ir1106.55 (14)C305—C304—H304119.2
P3—C1—P2120.60 (19)C303—C304—H304119.2
P3—C1—Ir1114.38 (19)C304—C305—C306120.3 (5)
P2—C1—Ir1107.68 (17)C304—C305—H305119.9
P3—C1—H1A101 (2)C306—C305—H305119.9
P2—C1—H1A102 (2)C301—C306—C305118.6 (6)
Ir1—C1—H1A110 (2)C301—C306—H306120.7
P2—C2—P1107.8 (2)C305—C306—H306120.7
P2—C2—H2A110.2C308—C307—C312120.0 (4)
P1—C2—H2A110.2C308—C307—P3124.3 (3)
P2—C2—H2B110.2C312—C307—P3115.7 (3)
P1—C2—H2B110.2C307—C308—C309119.8 (5)
H2A—C2—H2B108.5C307—C308—H308120.1
P3—C3—P4108.5 (2)C309—C308—H308120.1
P3—C3—H3A110.0C310—C309—C308120.4 (5)
P4—C3—H3A110.0C310—C309—H309119.8
P3—C3—H3B110.0C308—C309—H309119.8
P4—C3—H3B110.0C309—C310—C311120.3 (5)
H3A—C3—H3B108.4C309—C310—H310119.9
C102—C101—C106118.6 (4)C311—C310—H310119.9
C102—C101—P1117.4 (4)C310—C311—C312120.2 (5)
C106—C101—P1123.9 (4)C310—C311—H311119.9
C101—C102—C103120.3 (5)C312—C311—H311119.9
C101—C102—H102119.8C311—C312—C307119.3 (5)
C103—C102—H102119.8C311—C312—H312120.3
C104—C103—C102120.4 (5)C307—C312—H312120.3
C104—C103—H103119.8C406—C401—C402117.8 (4)
C102—C103—H103119.8C406—C401—P4120.6 (3)
C103—C104—C105119.9 (5)C402—C401—P4121.6 (4)
C103—C104—H104120.0C401—C402—C403119.5 (6)
C105—C104—H104120.0C401—C402—H402120.3
C104—C105—C106121.1 (6)C403—C402—H402120.3
C104—C105—H105119.5C404—C403—C402121.2 (6)
C106—C105—H105119.5C404—C403—H403119.4
C105—C106—C101119.6 (5)C402—C403—H403119.4
C105—C106—H106120.2C405—C404—C403119.7 (5)
C101—C106—H106120.2C405—C404—H404120.2
C112—C107—C108119.4 (5)C403—C404—H404120.2
C112—C107—P1121.6 (4)C404—C405—C406120.3 (5)
C108—C107—P1119.0 (4)C404—C405—H405119.8
C107—C108—C109119.3 (7)C406—C405—H405119.8
C107—C108—H108120.3C401—C406—C405121.4 (4)
C109—C108—H108120.3C401—C406—H406119.3
C110—C109—C108120.2 (7)C405—C406—H406119.3
C110—C109—H109119.9C412—C407—C408119.3 (4)
C108—C109—H109119.9C412—C407—P4125.0 (4)
C109—C110—C111121.1 (6)C408—C407—P4115.6 (3)
C109—C110—H110119.4C409—C408—C407119.1 (5)
C111—C110—H110119.4C409—C408—H408120.5
C110—C111—C112119.5 (7)C407—C408—H408120.5
C110—C111—H111120.2C410—C409—C408121.4 (5)
C112—C111—H111120.2C410—C409—H409119.3
C107—C112—C111120.5 (6)C408—C409—H409119.3
C107—C112—H112119.8C409—C410—C411120.1 (5)
C111—C112—H112119.8C409—C410—H410119.9
C202—C201—C206120.3 (4)C411—C410—H410119.9
C202—C201—P2118.8 (3)C410—C411—C412119.5 (5)
C206—C201—P2120.9 (3)C410—C411—H411120.2
C201—C202—C203119.5 (4)C412—C411—H411120.2
C201—C202—H202120.3C407—C412—C411120.5 (5)
C203—C202—H202120.3C407—C412—H412119.7
C204—C203—C202119.8 (5)C411—C412—H412119.7
C204—C203—H203120.1
C301—P3—C1—P215.8 (3)C1—P2—C207—C20819.9 (4)
C3—P3—C1—P2108.4 (2)C2—P2—C207—C21250.2 (4)
C307—P3—C1—P2135.0 (2)C201—P2—C207—C21264.4 (4)
C301—P3—C1—Ir1146.8 (2)C1—P2—C207—C212162.4 (3)
C3—P3—C1—Ir122.6 (2)C212—C207—C208—C2091.8 (7)
C307—P3—C1—Ir194.0 (2)P2—C207—C208—C209179.5 (4)
C207—P2—C1—P372.9 (3)C207—C208—C209—C2101.6 (7)
C2—P2—C1—P3169.4 (2)C208—C209—C210—C2110.4 (8)
C201—P2—C1—P355.5 (3)C209—C210—C211—C2120.5 (9)
C207—P2—C1—Ir160.9 (2)C210—C211—C212—C2070.3 (8)
C2—P2—C1—Ir156.8 (2)C208—C207—C212—C2110.9 (7)
C201—P2—C1—Ir1170.75 (19)P2—C207—C212—C211178.7 (4)
C207—P2—C2—P170.3 (3)C3—P3—C301—C30619.4 (5)
C201—P2—C2—P1174.3 (2)C307—P3—C301—C306134.6 (4)
C1—P2—C2—P152.0 (2)C1—P3—C301—C306103.0 (4)
C101—P1—C2—P2153.4 (2)C3—P3—C301—C302161.6 (3)
C107—P1—C2—P297.9 (2)C307—P3—C301—C30246.4 (4)
Ir1—P1—C2—P227.2 (2)C1—P3—C301—C30276.0 (4)
C301—P3—C3—P4162.2 (2)C306—C301—C302—C3030.6 (7)
C307—P3—C3—P483.3 (2)P3—C301—C302—C303178.4 (4)
C1—P3—C3—P436.3 (2)C301—C302—C303—C3041.2 (7)
C407—P4—C3—P396.3 (2)C302—C303—C304—C3051.2 (8)
C401—P4—C3—P3157.3 (2)C303—C304—C305—C3060.5 (8)
Ir1—P4—C3—P334.5 (2)C302—C301—C306—C3050.0 (7)
C107—P1—C101—C10265.4 (4)P3—C301—C306—C305179.0 (4)
C2—P1—C101—C102174.9 (4)C304—C305—C306—C3010.1 (8)
Ir1—P1—C101—C10267.4 (4)C301—P3—C307—C308132.2 (4)
C107—P1—C101—C106120.1 (4)C3—P3—C307—C308109.4 (4)
C2—P1—C101—C10610.6 (4)C1—P3—C307—C3088.1 (4)
Ir1—P1—C101—C106107.1 (4)C301—P3—C307—C31249.3 (4)
C106—C101—C102—C1032.0 (7)C3—P3—C307—C31269.0 (4)
P1—C101—C102—C103176.8 (4)C1—P3—C307—C312173.5 (4)
C101—C102—C103—C1041.2 (8)C312—C307—C308—C3090.3 (7)
C102—C103—C104—C1051.0 (8)P3—C307—C308—C309178.7 (4)
C103—C104—C105—C1062.3 (8)C307—C308—C309—C3100.1 (8)
C104—C105—C106—C1011.4 (8)C308—C309—C310—C3110.5 (9)
C102—C101—C106—C1050.8 (7)C309—C310—C311—C3120.5 (10)
P1—C101—C106—C105175.2 (4)C310—C311—C312—C3070.0 (9)
C101—P1—C107—C112128.5 (4)C308—C307—C312—C3110.4 (8)
C2—P1—C107—C112121.7 (4)P3—C307—C312—C311178.9 (5)
Ir1—P1—C107—C1124.8 (4)C407—P4—C401—C40631.6 (4)
C101—P1—C107—C10851.3 (4)C3—P4—C401—C40678.7 (4)
C2—P1—C107—C10858.5 (4)Ir1—P4—C401—C406166.6 (3)
Ir1—P1—C107—C108175.4 (3)C407—P4—C401—C402149.2 (6)
C112—C107—C108—C1091.2 (8)C3—P4—C401—C402100.5 (6)
P1—C107—C108—C109178.7 (5)Ir1—P4—C401—C40214.2 (6)
C107—C108—C109—C1100.4 (10)C406—C401—C402—C4033.8 (12)
C108—C109—C110—C1110.0 (10)P4—C401—C402—C403175.4 (8)
C109—C110—C111—C1120.4 (10)C401—C402—C403—C4041.5 (17)
C108—C107—C112—C1111.6 (8)C402—C403—C404—C4051.8 (16)
P1—C107—C112—C111178.3 (4)C403—C404—C405—C4062.7 (12)
C110—C111—C112—C1071.2 (9)C402—C401—C406—C4053.0 (9)
C207—P2—C201—C202166.2 (4)P4—C401—C406—C405176.2 (4)
C2—P2—C201—C20249.3 (4)C404—C405—C406—C4010.3 (9)
C1—P2—C201—C20261.2 (4)C401—P4—C407—C41298.8 (4)
C207—P2—C201—C20611.8 (4)C3—P4—C407—C4126.0 (4)
C2—P2—C201—C206128.8 (4)Ir1—P4—C407—C412128.2 (4)
C1—P2—C201—C206120.7 (4)C401—P4—C407—C40876.8 (4)
C206—C201—C202—C2031.9 (8)C3—P4—C407—C408178.5 (3)
P2—C201—C202—C203176.2 (4)Ir1—P4—C407—C40856.3 (4)
C201—C202—C203—C2040.1 (9)C412—C407—C408—C4092.6 (7)
C202—C203—C204—C2052.2 (9)P4—C407—C408—C409173.1 (4)
C203—C204—C205—C2062.8 (8)C407—C408—C409—C4102.1 (8)
C204—C205—C206—C2011.0 (7)C408—C409—C410—C4110.4 (9)
C202—C201—C206—C2051.3 (7)C409—C410—C411—C4120.7 (9)
P2—C201—C206—C205176.7 (4)C408—C407—C412—C4111.6 (7)
C2—P2—C207—C208132.1 (4)P4—C407—C412—C411173.7 (4)
C201—P2—C207—C208113.3 (4)C410—C411—C412—C4070.1 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···Cl30.99 (4)2.48 (4)3.422 (6)159 (3)
C2—H2B···Cl30.982.633.450 (6)142
C202—H202···Cl30.942.673.584 (6)166
C308—H308···Cl30.942.703.475 (7)141
C3—H3B···Cl3A0.982.583.489 (12)155
Carbonylchloridohydrido(1,1,3,3,5,5,7,7-octaphenyl-1,5λ5,7-triphospha-3-phosphoniahept-4-en-4-yl)iridium(III) chloride–methanol–water (1/2/1) (4) top
Crystal data top
[Ir(C51H44P4)ClH(CO)]Cl·2CH4O·H2OF(000) = 2328
Mr = 1154.96Dx = 1.390 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.5929 (2) ÅCell parameters from 183501 reflections
b = 23.2803 (4) Åθ = 1.0–25.0°
c = 19.7488 (4) ŵ = 2.67 mm1
β = 107.535 (1)°T = 233 K
V = 5520.66 (17) Å3Prism, colourless
Z = 40.21 × 0.10 × 0.07 mm
Data collection top
Nonius KappaCCD
diffractometer
Rint = 0.049
Detector resolution: 9.4 pixels mm-1θmax = 25.0°, θmin = 1.4°
phi– and ω–scansh = 1414
32186 measured reflectionsk = 2727
9675 independent reflectionsl = 2321
8070 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: mixed
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.13 w = 1/[σ2(Fo2) + (0.0255P)2 + 16.7009P]
where P = (Fo2 + 2Fc2)/3
9675 reflections(Δ/σ)max = 0.001
624 parametersΔρmax = 1.85 e Å3
1 restraintΔρmin = 1.45 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 H1 at Ir1 was found and refined with bond restraint (d = 1.6 Å). Hydrogen atoms at solvent MeOH and H2O were omitted. One Cl-anion is positionally disordered in ratio 1:1 for Cl2 and Cl2A. Maybe because of this disorder two MeOH positions C6-O3 and C7-O4 are only half occupied, also a water molecule, which is split in four positions with occupancy of 0.25 for each position. O5, O5A, O5B and O5C were refined with isotropic displacement par..

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
H10.644 (4)0.060 (2)0.7395 (17)0.050 (15)*
Ir10.64126 (2)0.08694 (2)0.80985 (2)0.03393 (8)
P10.83264 (11)0.09659 (6)0.83213 (7)0.0343 (3)
P20.73619 (12)0.20938 (6)0.77950 (7)0.0347 (3)
P30.50434 (11)0.17312 (6)0.68744 (7)0.0332 (3)
P40.44822 (11)0.08043 (6)0.77016 (7)0.0330 (3)
Cl10.66243 (13)0.01003 (6)0.85840 (8)0.0504 (4)
O10.6356 (4)0.1273 (2)0.9575 (2)0.0665 (13)
C10.6243 (4)0.1661 (2)0.7541 (3)0.0339 (12)
C20.8568 (4)0.1636 (2)0.7904 (3)0.0374 (12)
H2A0.92390.18270.82040.045*
H2B0.86730.15560.74410.045*
C30.3970 (4)0.1475 (2)0.7242 (3)0.0374 (12)
H3A0.32720.14090.68630.045*
H3B0.38330.17570.75740.045*
C40.6406 (5)0.1167 (2)0.9034 (3)0.0446 (14)
C1010.9032 (4)0.0419 (2)0.7962 (3)0.0395 (13)
C1020.8500 (6)0.0057 (3)0.7608 (4)0.0617 (18)
H1020.77320.01020.75350.074*
C1030.9064 (6)0.0467 (3)0.7359 (4)0.079 (2)
H1030.86830.07920.71240.094*
C1041.0176 (7)0.0407 (3)0.7449 (4)0.073 (2)
H1041.05530.06870.72660.087*
C1051.0733 (6)0.0048 (4)0.7796 (4)0.069 (2)
H1051.15030.00810.78680.083*
C1061.0170 (5)0.0475 (3)0.8051 (3)0.0537 (16)
H1061.05580.08000.82810.064*
C1070.9162 (5)0.1007 (2)0.9252 (3)0.0419 (13)
C1080.8914 (6)0.0631 (3)0.9724 (3)0.0579 (17)
H1080.83070.03780.95660.069*
C1090.9569 (7)0.0625 (4)1.0440 (4)0.073 (2)
H1090.94020.03661.07580.088*
C1101.0440 (6)0.0993 (4)1.0675 (4)0.073 (2)
H1101.08640.09951.11560.087*
C1111.0698 (6)0.1362 (4)1.0202 (4)0.076 (2)
H1111.13170.16071.03600.091*
C1121.0056 (5)0.1375 (3)0.9499 (3)0.0570 (17)
H1121.02290.16370.91860.068*
C2010.7471 (4)0.2682 (2)0.7220 (3)0.0384 (13)
C2020.7142 (5)0.3229 (2)0.7355 (3)0.0507 (15)
H2020.68480.32880.77340.061*
C2030.7248 (6)0.3685 (3)0.6932 (4)0.0620 (18)
H2030.70330.40550.70300.074*
C2040.7662 (6)0.3605 (3)0.6375 (4)0.0643 (19)
H2040.77200.39160.60850.077*
C2050.7992 (6)0.3064 (3)0.6242 (4)0.067 (2)
H2050.82860.30070.58620.081*
C2060.7897 (6)0.2606 (3)0.6658 (3)0.0525 (16)
H2060.81220.22380.65600.063*
C2070.7507 (5)0.2427 (2)0.8647 (3)0.0440 (14)
C2080.6563 (6)0.2515 (3)0.8843 (3)0.0571 (17)
H2080.58750.23770.85520.069*
C2090.6609 (8)0.2808 (3)0.9469 (4)0.075 (2)
H2090.59590.28660.96010.090*
C2100.7607 (9)0.3006 (3)0.9885 (4)0.082 (3)
H2100.76420.32081.03040.099*
C2110.8553 (8)0.2918 (3)0.9707 (4)0.085 (3)
H2110.92390.30461.00110.102*
C2120.8513 (6)0.2636 (3)0.9068 (4)0.0638 (19)
H2120.91620.25900.89320.077*
C3010.4691 (4)0.2451 (2)0.6542 (3)0.0391 (13)
C3020.4270 (5)0.2844 (2)0.6909 (3)0.0516 (15)
H3020.41260.27340.73310.062*
C3030.4053 (6)0.3402 (3)0.6663 (4)0.0657 (19)
H3030.37710.36710.69190.079*
C3040.4257 (6)0.3561 (3)0.6037 (4)0.067 (2)
H3040.41120.39390.58700.080*
C3050.4661 (7)0.3176 (3)0.5667 (4)0.071 (2)
H3050.47970.32880.52430.085*
C3060.4878 (5)0.2615 (3)0.5911 (3)0.0536 (16)
H3060.51500.23470.56480.064*
C3070.4905 (5)0.1297 (2)0.6088 (3)0.0433 (14)
C3080.3859 (6)0.1179 (3)0.5619 (3)0.0643 (19)
H3080.32100.13040.57160.077*
C3090.3795 (9)0.0871 (4)0.5001 (4)0.098 (3)
H3090.30920.07780.46870.117*
C3100.4718 (10)0.0702 (4)0.4845 (5)0.097 (3)
H3100.46540.05070.44180.117*
C3110.5755 (9)0.0815 (3)0.5311 (5)0.084 (3)
H3110.63980.06930.52040.101*
C3120.5854 (6)0.1112 (3)0.5943 (3)0.0552 (16)
H3120.65600.11850.62660.066*
C4010.3817 (4)0.0722 (2)0.8399 (3)0.0374 (13)
C4020.3996 (5)0.0217 (3)0.8779 (3)0.0559 (17)
H4020.44230.00770.86650.067*
C4030.3541 (6)0.0146 (3)0.9331 (4)0.0645 (19)
H4030.36690.01980.95920.077*
C4040.2915 (6)0.0563 (3)0.9503 (3)0.0617 (19)
H4040.26040.05080.98750.074*
C4050.2744 (6)0.1063 (3)0.9129 (4)0.0613 (18)
H4050.23230.13550.92520.074*
C4060.3175 (5)0.1148 (3)0.8575 (3)0.0474 (14)
H4060.30360.14940.83160.057*
C4070.3831 (5)0.0233 (2)0.7083 (3)0.0391 (13)
C4080.2687 (5)0.0258 (3)0.6742 (3)0.0552 (16)
H4080.22680.05740.68150.066*
C4090.2176 (6)0.0183 (3)0.6299 (4)0.075 (2)
H4090.14070.01650.60640.090*
C4100.2773 (8)0.0644 (3)0.6196 (4)0.074 (2)
H4100.24170.09420.58900.089*
C4110.3882 (7)0.0673 (3)0.6536 (4)0.068 (2)
H4110.42870.09970.64720.082*
C4120.4429 (5)0.0233 (2)0.6973 (3)0.0500 (15)
H4120.52020.02520.71930.060*
Cl21.1164 (3)0.2433 (2)0.8501 (3)0.1024 (15)0.5
Cl2A0.1116 (4)0.1659 (3)0.6239 (3)0.138 (2)0.5
O20.8990 (6)0.1235 (3)0.6346 (3)0.122 (2)
C50.9032 (14)0.0693 (6)0.6038 (7)0.180 (7)
O30.3556 (9)0.2629 (5)0.8426 (7)0.087 (3)0.5
C60.3639 (17)0.3141 (13)0.8598 (15)0.152 (11)0.5
O40.1179 (11)0.1628 (8)0.4713 (7)0.131 (5)0.5
C70.0628 (18)0.1103 (11)0.4395 (13)0.133 (9)0.5
O50.1070 (15)0.1876 (9)0.6998 (10)0.068 (5)*0.25
O5A0.1762 (16)0.2452 (9)0.7503 (10)0.072 (5)*0.25
O5C0.136 (2)0.2978 (13)0.7172 (16)0.127 (9)*0.25
O5D0.112 (3)0.2330 (19)0.672 (2)0.175 (14)*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ir10.03495 (12)0.02924 (12)0.03939 (13)0.00201 (9)0.01392 (9)0.00953 (9)
P10.0336 (7)0.0349 (8)0.0358 (7)0.0023 (6)0.0126 (6)0.0050 (6)
P20.0411 (8)0.0297 (7)0.0338 (7)0.0030 (6)0.0120 (6)0.0032 (6)
P30.0385 (7)0.0265 (7)0.0358 (8)0.0028 (6)0.0130 (6)0.0047 (6)
P40.0351 (7)0.0275 (7)0.0387 (8)0.0003 (6)0.0145 (6)0.0041 (6)
Cl10.0576 (9)0.0330 (7)0.0618 (9)0.0037 (6)0.0201 (7)0.0177 (7)
O10.086 (3)0.079 (3)0.041 (3)0.000 (3)0.029 (2)0.004 (2)
C10.036 (3)0.028 (3)0.038 (3)0.000 (2)0.012 (2)0.008 (2)
C20.037 (3)0.037 (3)0.038 (3)0.005 (2)0.013 (2)0.004 (2)
C30.036 (3)0.037 (3)0.040 (3)0.004 (2)0.014 (2)0.008 (2)
C40.045 (3)0.036 (3)0.053 (4)0.001 (3)0.014 (3)0.011 (3)
C1010.041 (3)0.042 (3)0.036 (3)0.005 (3)0.013 (2)0.009 (3)
C1020.059 (4)0.055 (4)0.081 (5)0.004 (3)0.036 (4)0.015 (4)
C1030.071 (5)0.068 (5)0.103 (6)0.003 (4)0.035 (5)0.030 (4)
C1040.075 (5)0.076 (5)0.072 (5)0.026 (4)0.031 (4)0.009 (4)
C1050.050 (4)0.099 (6)0.059 (4)0.020 (4)0.019 (3)0.006 (4)
C1060.046 (4)0.067 (4)0.048 (4)0.006 (3)0.015 (3)0.004 (3)
C1070.043 (3)0.047 (3)0.037 (3)0.010 (3)0.013 (3)0.003 (3)
C1080.061 (4)0.069 (4)0.042 (4)0.004 (3)0.013 (3)0.016 (3)
C1090.088 (6)0.089 (6)0.046 (4)0.020 (5)0.026 (4)0.023 (4)
C1100.071 (5)0.102 (6)0.040 (4)0.013 (5)0.008 (4)0.000 (4)
C1110.066 (5)0.095 (6)0.055 (5)0.002 (4)0.001 (4)0.012 (4)
C1120.055 (4)0.066 (4)0.047 (4)0.003 (3)0.010 (3)0.004 (3)
C2010.046 (3)0.030 (3)0.039 (3)0.011 (2)0.012 (2)0.002 (2)
C2020.065 (4)0.038 (3)0.050 (4)0.007 (3)0.018 (3)0.003 (3)
C2030.088 (5)0.026 (3)0.071 (5)0.009 (3)0.023 (4)0.005 (3)
C2040.090 (5)0.044 (4)0.061 (4)0.020 (4)0.025 (4)0.016 (3)
C2050.099 (6)0.059 (5)0.052 (4)0.010 (4)0.036 (4)0.014 (3)
C2060.081 (5)0.035 (3)0.049 (4)0.007 (3)0.031 (3)0.003 (3)
C2070.059 (4)0.035 (3)0.036 (3)0.005 (3)0.011 (3)0.002 (2)
C2080.081 (5)0.049 (4)0.047 (4)0.001 (3)0.028 (3)0.001 (3)
C2090.128 (7)0.058 (5)0.057 (5)0.002 (5)0.054 (5)0.004 (4)
C2100.143 (9)0.053 (5)0.049 (5)0.022 (5)0.026 (5)0.001 (4)
C2110.110 (7)0.059 (5)0.057 (5)0.012 (5)0.018 (5)0.014 (4)
C2120.069 (5)0.050 (4)0.059 (4)0.001 (3)0.001 (3)0.007 (3)
C3010.042 (3)0.028 (3)0.046 (3)0.005 (2)0.011 (3)0.007 (2)
C3020.069 (4)0.038 (3)0.052 (4)0.009 (3)0.025 (3)0.004 (3)
C3030.081 (5)0.039 (4)0.084 (5)0.015 (3)0.034 (4)0.004 (3)
C3040.095 (5)0.032 (3)0.074 (5)0.014 (3)0.027 (4)0.018 (3)
C3050.111 (6)0.048 (4)0.062 (5)0.016 (4)0.040 (4)0.025 (3)
C3060.078 (4)0.038 (3)0.052 (4)0.013 (3)0.032 (3)0.015 (3)
C3070.066 (4)0.027 (3)0.039 (3)0.003 (3)0.019 (3)0.001 (2)
C3080.069 (5)0.077 (5)0.045 (4)0.010 (4)0.015 (3)0.009 (3)
C3090.132 (8)0.107 (7)0.051 (5)0.053 (6)0.023 (5)0.022 (5)
C3100.153 (10)0.090 (6)0.062 (5)0.036 (6)0.053 (6)0.029 (5)
C3110.131 (8)0.065 (5)0.079 (6)0.002 (5)0.068 (6)0.013 (4)
C3120.080 (5)0.043 (3)0.055 (4)0.001 (3)0.038 (4)0.004 (3)
C4010.034 (3)0.039 (3)0.040 (3)0.009 (2)0.013 (2)0.002 (2)
C4020.051 (4)0.062 (4)0.062 (4)0.000 (3)0.028 (3)0.019 (3)
C4030.063 (4)0.071 (5)0.060 (4)0.009 (4)0.020 (4)0.025 (4)
C4040.061 (4)0.086 (5)0.043 (4)0.025 (4)0.022 (3)0.002 (4)
C4050.059 (4)0.078 (5)0.057 (4)0.011 (4)0.034 (3)0.013 (4)
C4060.054 (4)0.045 (3)0.051 (4)0.010 (3)0.027 (3)0.007 (3)
C4070.053 (4)0.029 (3)0.039 (3)0.006 (2)0.021 (3)0.001 (2)
C4080.047 (4)0.048 (4)0.068 (4)0.005 (3)0.014 (3)0.010 (3)
C4090.061 (5)0.087 (6)0.068 (5)0.030 (4)0.007 (4)0.017 (4)
C4100.105 (7)0.058 (5)0.064 (5)0.023 (5)0.032 (5)0.030 (4)
C4110.098 (6)0.049 (4)0.066 (5)0.007 (4)0.036 (4)0.014 (3)
C4120.061 (4)0.042 (4)0.054 (4)0.006 (3)0.028 (3)0.004 (3)
Cl20.064 (2)0.095 (3)0.151 (4)0.021 (2)0.036 (3)0.008 (3)
Cl2A0.078 (3)0.158 (5)0.147 (5)0.031 (3)0.014 (3)0.005 (4)
O20.148 (6)0.140 (6)0.089 (5)0.062 (5)0.050 (4)0.033 (4)
C50.250 (17)0.158 (12)0.113 (10)0.110 (12)0.028 (10)0.008 (9)
O30.092 (8)0.066 (7)0.126 (10)0.019 (6)0.068 (7)0.019 (7)
C60.077 (13)0.20 (3)0.20 (3)0.054 (16)0.077 (15)0.10 (2)
O40.093 (9)0.193 (16)0.101 (10)0.006 (10)0.021 (8)0.004 (10)
C70.103 (15)0.15 (2)0.139 (19)0.001 (14)0.028 (14)0.081 (17)
Geometric parameters (Å, º) top
Ir1—C41.975 (7)C207—C2121.377 (8)
Ir1—C12.124 (5)C208—C2091.397 (9)
Ir1—P42.3235 (13)C208—H2080.9400
Ir1—P12.3265 (14)C209—C2101.359 (11)
Ir1—Cl12.4359 (13)C209—H2090.9400
Ir1—H11.535 (19)C210—C2111.356 (12)
P1—C1011.815 (6)C210—H2100.9400
P1—C1071.824 (6)C211—C2121.411 (10)
P1—C21.833 (5)C211—H2110.9400
P2—C11.681 (5)C212—H2120.9400
P2—C2011.809 (5)C301—C3021.368 (8)
P2—C2071.812 (6)C301—C3061.391 (8)
P2—C21.814 (5)C302—C3031.385 (8)
P3—C11.686 (5)C302—H3020.9400
P3—C3011.806 (5)C303—C3041.387 (10)
P3—C3071.817 (6)C303—H3030.9400
P3—C31.818 (5)C304—C3051.348 (9)
P4—C31.822 (5)C304—H3040.9400
P4—C4011.825 (5)C305—C3061.391 (8)
P4—C4071.825 (5)C305—H3050.9400
O1—C41.117 (7)C306—H3060.9400
C2—H2A0.9800C307—C3121.379 (8)
C2—H2B0.9800C307—C3081.390 (8)
C3—H3A0.9800C308—C3091.398 (10)
C3—H3B0.9800C308—H3080.9400
C101—C1021.373 (8)C309—C3101.347 (13)
C101—C1061.397 (8)C309—H3090.9400
C102—C1031.365 (9)C310—C3111.378 (12)
C102—H1020.9400C310—H3100.9400
C103—C1041.365 (10)C311—C3121.398 (9)
C103—H1030.9400C311—H3110.9400
C104—C1051.340 (10)C312—H3120.9400
C104—H1040.9400C401—C4021.376 (8)
C105—C1061.400 (9)C401—C4061.389 (8)
C105—H1050.9400C402—C4031.386 (9)
C106—H1060.9400C402—H4020.9400
C107—C1081.382 (8)C403—C4041.357 (10)
C107—C1121.383 (8)C403—H4030.9400
C108—C1091.406 (9)C404—C4051.359 (10)
C108—H1080.9400C404—H4040.9400
C109—C1101.358 (11)C405—C4061.375 (8)
C109—H1090.9400C405—H4050.9400
C110—C1111.377 (11)C406—H4060.9400
C110—H1100.9400C407—C4121.373 (8)
C111—C1121.381 (9)C407—C4081.396 (8)
C111—H1110.9400C408—C4091.377 (9)
C112—H1120.9400C408—H4080.9400
C201—C2061.383 (8)C409—C4101.361 (10)
C201—C2021.389 (8)C409—H4090.9400
C202—C2031.383 (8)C410—C4111.357 (11)
C202—H2020.9400C410—H4100.9400
C203—C2041.365 (9)C411—C4121.382 (9)
C203—H2030.9400C411—H4110.9400
C204—C2051.377 (10)C412—H4120.9400
C204—H2040.9400Cl2A—O51.60 (2)
C205—C2061.373 (8)O2—C51.409 (14)
C205—H2050.9400O3—C61.24 (3)
C206—H2060.9400O4—C71.45 (2)
C207—C2081.372 (9)
C4—Ir1—C198.8 (2)C203—C204—C205119.3 (6)
C4—Ir1—P492.27 (17)C203—C204—H204120.3
C1—Ir1—P487.15 (14)C205—C204—H204120.3
C4—Ir1—P194.89 (17)C206—C205—C204120.7 (6)
C1—Ir1—P187.18 (14)C206—C205—H205119.7
P4—Ir1—P1171.47 (5)C204—C205—H205119.7
C4—Ir1—Cl189.30 (16)C205—C206—C201120.4 (6)
C1—Ir1—Cl1171.91 (15)C205—C206—H206119.8
P4—Ir1—Cl192.96 (5)C201—C206—H206119.8
P1—Ir1—Cl191.76 (5)C208—C207—C212119.7 (6)
C4—Ir1—H1176 (2)C208—C207—P2118.2 (5)
C1—Ir1—H185 (2)C212—C207—P2121.9 (5)
P4—Ir1—H188.6 (19)C207—C208—C209120.9 (7)
P1—Ir1—H184.5 (19)C207—C208—H208119.5
Cl1—Ir1—H187 (2)C209—C208—H208119.5
C101—P1—C107103.2 (2)C210—C209—C208119.0 (8)
C101—P1—C2104.8 (2)C210—C209—H209120.5
C107—P1—C2106.5 (3)C208—C209—H209120.5
C101—P1—Ir1117.35 (19)C211—C210—C209121.1 (8)
C107—P1—Ir1116.47 (19)C211—C210—H210119.5
C2—P1—Ir1107.45 (17)C209—C210—H210119.5
C1—P2—C201118.8 (2)C210—C211—C212120.4 (8)
C1—P2—C207112.0 (3)C210—C211—H211119.8
C201—P2—C207104.7 (3)C212—C211—H211119.8
C1—P2—C2106.3 (2)C207—C212—C211118.9 (8)
C201—P2—C2107.5 (3)C207—C212—H212120.6
C207—P2—C2107.1 (3)C211—C212—H212120.6
C1—P3—C301116.0 (3)C302—C301—C306119.3 (5)
C1—P3—C307116.5 (3)C302—C301—P3121.3 (4)
C301—P3—C307104.8 (3)C306—C301—P3119.4 (4)
C1—P3—C3104.8 (2)C301—C302—C303120.5 (6)
C301—P3—C3108.6 (2)C301—C302—H302119.7
C307—P3—C3105.5 (3)C303—C302—H302119.7
C3—P4—C401106.9 (2)C302—C303—C304119.5 (6)
C3—P4—C407105.7 (3)C302—C303—H303120.2
C401—P4—C407102.2 (2)C304—C303—H303120.2
C3—P4—Ir1106.83 (17)C305—C304—C303120.5 (6)
C401—P4—Ir1115.08 (17)C305—C304—H304119.7
C407—P4—Ir1119.14 (19)C303—C304—H304119.7
P2—C1—P3130.4 (3)C304—C305—C306120.2 (6)
P2—C1—Ir1114.9 (3)C304—C305—H305119.9
P3—C1—Ir1114.5 (3)C306—C305—H305119.9
P2—C2—P1107.9 (3)C301—C306—C305120.0 (6)
P2—C2—H2A110.1C301—C306—H306120.0
P1—C2—H2A110.1C305—C306—H306120.0
P2—C2—H2B110.1C312—C307—C308120.5 (6)
P1—C2—H2B110.1C312—C307—P3119.0 (5)
H2A—C2—H2B108.4C308—C307—P3120.4 (5)
P3—C3—P4106.6 (3)C307—C308—C309118.5 (8)
P3—C3—H3A110.4C307—C308—H308120.8
P4—C3—H3A110.4C309—C308—H308120.8
P3—C3—H3B110.4C310—C309—C308121.5 (9)
P4—C3—H3B110.4C310—C309—H309119.2
H3A—C3—H3B108.6C308—C309—H309119.2
O1—C4—Ir1171.7 (5)C309—C310—C311120.1 (8)
C102—C101—C106117.7 (6)C309—C310—H310120.0
C102—C101—P1123.0 (4)C311—C310—H310120.0
C106—C101—P1119.3 (5)C310—C311—C312120.1 (8)
C103—C102—C101121.3 (6)C310—C311—H311119.9
C103—C102—H102119.3C312—C311—H311119.9
C101—C102—H102119.3C307—C312—C311119.3 (7)
C104—C103—C102120.5 (7)C307—C312—H312120.4
C104—C103—H103119.8C311—C312—H312120.4
C102—C103—H103119.8C402—C401—C406119.1 (5)
C105—C104—C103120.4 (7)C402—C401—P4117.7 (4)
C105—C104—H104119.8C406—C401—P4123.2 (4)
C103—C104—H104119.8C401—C402—C403119.6 (6)
C104—C105—C106120.1 (7)C401—C402—H402120.2
C104—C105—H105119.9C403—C402—H402120.2
C106—C105—H105119.9C404—C403—C402121.3 (6)
C101—C106—C105120.0 (6)C404—C403—H403119.3
C101—C106—H106120.0C402—C403—H403119.3
C105—C106—H106120.0C403—C404—C405119.0 (6)
C108—C107—C112118.7 (6)C403—C404—H404120.5
C108—C107—P1117.9 (5)C405—C404—H404120.5
C112—C107—P1123.4 (5)C404—C405—C406121.4 (7)
C107—C108—C109120.1 (7)C404—C405—H405119.3
C107—C108—H108119.9C406—C405—H405119.3
C109—C108—H108119.9C405—C406—C401119.6 (6)
C110—C109—C108120.4 (7)C405—C406—H406120.2
C110—C109—H109119.8C401—C406—H406120.2
C108—C109—H109119.8C412—C407—C408119.5 (5)
C109—C110—C111119.5 (7)C412—C407—P4121.6 (4)
C109—C110—H110120.2C408—C407—P4118.8 (4)
C111—C110—H110120.2C409—C408—C407119.4 (6)
C110—C111—C112120.6 (7)C409—C408—H408120.3
C110—C111—H111119.7C407—C408—H408120.3
C112—C111—H111119.7C410—C409—C408120.7 (7)
C111—C112—C107120.6 (7)C410—C409—H409119.6
C111—C112—H112119.7C408—C409—H409119.6
C107—C112—H112119.7C411—C410—C409119.8 (7)
C206—C201—C202118.8 (5)C411—C410—H410120.1
C206—C201—P2121.9 (4)C409—C410—H410120.1
C202—C201—P2119.3 (4)C410—C411—C412121.1 (7)
C203—C202—C201120.0 (6)C410—C411—H411119.4
C203—C202—H202120.0C412—C411—H411119.4
C201—C202—H202120.0C407—C412—C411119.4 (6)
C204—C203—C202120.8 (6)C407—C412—H412120.3
C204—C203—H203119.6C411—C412—H412120.3
C202—C203—H203119.6
C201—P2—C1—P311.0 (5)C2—P2—C207—C208143.9 (5)
C207—P2—C1—P3111.3 (4)C1—P2—C207—C212157.9 (5)
C2—P2—C1—P3132.1 (4)C201—P2—C207—C21272.2 (5)
C201—P2—C1—Ir1163.9 (3)C2—P2—C207—C21241.7 (6)
C207—P2—C1—Ir173.8 (3)C212—C207—C208—C2090.8 (9)
C2—P2—C1—Ir142.9 (3)P2—C207—C208—C209175.3 (5)
C301—P3—C1—P220.9 (5)C207—C208—C209—C2100.1 (10)
C307—P3—C1—P2103.2 (4)C208—C209—C210—C2110.9 (11)
C3—P3—C1—P2140.6 (4)C209—C210—C211—C2122.4 (12)
C301—P3—C1—Ir1164.2 (3)C208—C207—C212—C2112.3 (9)
C307—P3—C1—Ir171.7 (3)P2—C207—C212—C211176.6 (5)
C3—P3—C1—Ir144.4 (3)C210—C211—C212—C2073.1 (11)
C1—P2—C2—P140.0 (3)C1—P3—C301—C30276.7 (5)
C201—P2—C2—P1168.1 (3)C307—P3—C301—C302153.4 (5)
C207—P2—C2—P179.9 (3)C3—P3—C301—C30241.0 (6)
C101—P1—C2—P2147.7 (3)C1—P3—C301—C306101.6 (5)
C107—P1—C2—P2103.3 (3)C307—P3—C301—C30628.3 (5)
Ir1—P1—C2—P222.2 (3)C3—P3—C301—C306140.7 (5)
C1—P3—C3—P445.9 (3)C306—C301—C302—C3031.4 (9)
C301—P3—C3—P4170.5 (3)P3—C301—C302—C303176.9 (5)
C307—P3—C3—P477.6 (3)C301—C302—C303—C3040.6 (11)
C401—P4—C3—P3153.3 (3)C302—C303—C304—C3050.1 (12)
C407—P4—C3—P398.3 (3)C303—C304—C305—C3060.0 (12)
Ir1—P4—C3—P329.5 (3)C302—C301—C306—C3051.5 (10)
C107—P1—C101—C102125.7 (5)P3—C301—C306—C305176.8 (5)
C2—P1—C101—C102122.9 (5)C304—C305—C306—C3010.8 (11)
Ir1—P1—C101—C1023.8 (6)C1—P3—C307—C31224.2 (6)
C107—P1—C101—C10653.8 (5)C301—P3—C307—C312105.4 (5)
C2—P1—C101—C10657.5 (5)C3—P3—C307—C312140.0 (5)
Ir1—P1—C101—C106176.6 (4)C1—P3—C307—C308159.1 (5)
C106—C101—C102—C1031.0 (10)C301—P3—C307—C30871.2 (5)
P1—C101—C102—C103178.5 (6)C3—P3—C307—C30843.3 (5)
C101—C102—C103—C1041.0 (12)C312—C307—C308—C3090.1 (10)
C102—C103—C104—C1051.4 (13)P3—C307—C308—C309176.5 (6)
C103—C104—C105—C1061.9 (12)C307—C308—C309—C3101.9 (13)
C102—C101—C106—C1051.5 (9)C308—C309—C310—C3112.3 (14)
P1—C101—C106—C105178.1 (5)C309—C310—C311—C3120.8 (13)
C104—C105—C106—C1012.0 (11)C308—C307—C312—C3111.5 (9)
C101—P1—C107—C10886.5 (5)P3—C307—C312—C311175.2 (5)
C2—P1—C107—C108163.4 (5)C310—C311—C312—C3071.0 (11)
Ir1—P1—C107—C10843.5 (5)C3—P4—C401—C402174.1 (5)
C101—P1—C107—C11290.4 (5)C407—P4—C401—C40263.2 (5)
C2—P1—C107—C11219.7 (6)Ir1—P4—C401—C40267.4 (5)
Ir1—P1—C107—C112139.6 (5)C3—P4—C401—C4068.0 (5)
C112—C107—C108—C1090.2 (10)C407—P4—C401—C406118.8 (5)
P1—C107—C108—C109176.8 (5)Ir1—P4—C401—C406110.5 (4)
C107—C108—C109—C1100.7 (11)C406—C401—C402—C4030.5 (9)
C108—C109—C110—C1111.7 (12)P4—C401—C402—C403177.5 (5)
C109—C110—C111—C1122.2 (12)C401—C402—C403—C4040.5 (10)
C110—C111—C112—C1071.8 (11)C402—C403—C404—C4050.8 (10)
C108—C107—C112—C1110.8 (10)C403—C404—C405—C4061.2 (10)
P1—C107—C112—C111176.1 (5)C404—C405—C406—C4011.3 (9)
C1—P2—C201—C20684.0 (5)C402—C401—C406—C4050.9 (9)
C207—P2—C201—C206150.1 (5)P4—C401—C406—C405177.0 (5)
C2—P2—C201—C20636.5 (5)C3—P4—C407—C412135.3 (5)
C1—P2—C201—C20297.5 (5)C401—P4—C407—C412112.9 (5)
C207—P2—C201—C20228.3 (5)Ir1—P4—C407—C41215.2 (5)
C2—P2—C201—C202142.0 (5)C3—P4—C407—C40847.8 (5)
C206—C201—C202—C2030.3 (9)C401—P4—C407—C40864.0 (5)
P2—C201—C202—C203178.3 (5)Ir1—P4—C407—C408167.8 (4)
C201—C202—C203—C2040.8 (10)C412—C407—C408—C4090.2 (9)
C202—C203—C204—C2051.1 (11)P4—C407—C408—C409177.2 (5)
C203—C204—C205—C2060.8 (11)C407—C408—C409—C4100.6 (11)
C204—C205—C206—C2010.3 (11)C408—C409—C410—C4110.3 (12)
C202—C201—C206—C2050.0 (9)C409—C410—C411—C4121.7 (12)
P2—C201—C206—C205178.5 (5)C408—C407—C412—C4111.2 (9)
C1—P2—C207—C20827.8 (5)P4—C407—C412—C411175.7 (5)
C201—P2—C207—C208102.2 (5)C410—C411—C412—C4072.1 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C304—H304···Cl1i0.942.763.465 (7)132
C2—H2B···O20.982.433.407 (8)173
C210—H210···O2ii0.942.593.384 (10)143
C2—H2A···Cl20.982.713.633 (7)157
C112—H112···Cl20.942.763.682 (8)168
C3—H3A···Cl2A0.982.693.569 (8)150
C302—H302···O30.942.493.414 (14)169
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y+1/2, z+1/2.
Selected bond lengths (Å) and bond angles (°) for compounds 1b4 top
1b234
Ir1—C12.232 (3)2.101 (5)2.132 (4)2.124 (5)
Ir1—C42.169 (3)
Ir1—C52.172 (3)
Ir1—C82.208 (3)
Ir1—C92.225 (3)
Ir1—Cl12.4412 (15)2.405 (1)2.4359 (13)
Ir1—P12.3889 (7)2.3019 (15)2.306 (1)2.3265 (14)
Ir1—P42.3386 (7)2.2831 (16)2.283 (1)2.3235 (13)
Ir1—H11.638 (19)1.46 (4)1.535 (19)
P2—C11.821 (3)1.695 (6)1.811 (4)1.681 (5)
P3—C11.811 (3)1.688 (6)1.803 (4)1.686 (5)
C4—C51.414 (4)
C8—C91.402 (4)
P2—C1—P3114.86 (14)127.1 (3)120.60 (19)130.4 (3)
P2—C1—Ir1111.4 (1)112.3 (3)107.68 (17)114.9 (3)
P3—C1—Ir1110.0 (1)120.4 (3)114.38 (19)114.5 (3)
P1—C2—P2107.1 (1)105.4 (3)107.8 (2)107.9 (3)
P3—C3—P4105.7 (1)110.0 (3)108.5 (2)106.6 (3)
P1—Ir1—P498.08 (2)173.09 (5)170.68 (4)171.47 (5)
C1—Ir1—P188.27 (7)89.23 (16)88.33 (11)87.18 (14)
C1—Ir1—P486.97 (7)84.28 (16)90.24 (11)87.15 (14)
C2—P1—Ir1104.80 (9)106.4 (2)105.58 (14)107.45 (17)
C1—P2—C2106.7 (1)106.8 (3)99.93 (18)106.3 (2)
C1—P3—C3104.1 (1)106.2 (3)107.99 (18)104.8 (2)
C3—P4—Ir1107.96 (9)106.1 (2)106.55 (14)106.83 (17)
 

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