Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange.
Iali, Wissam; Green, Gary G. R.; Hart, Sam J.; Whitwood, Adrian C.; Duckett, Simon B.; Inorganic chemistry 55 (2016) 11639–11643; doi:10.1021/acs.inorgchem.6b02560

data_4349349
_publ_section_title
;
 Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer
 Catalyst before Converting to a Binuclear C-H Bond Activation Product
 Responsible for Hydrogen Isotope Exchange.
;
_journal_issue                   22
_journal_name_full               'Inorganic chemistry'
_journal_page_first              11639
_journal_page_last               11643
_journal_paper_doi               10.1021/acs.inorgchem.6b02560
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C18 H26 Cl Ir N2'
_chemical_formula_sum            'C18 H26 Cl Ir N2'
_chemical_formula_weight         498.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-25
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.218(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   39.287(2)
_cell_length_b                   12.3049(7)
_cell_length_c                   8.9973(5)
_cell_measurement_reflns_used    16807
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      71.0340
_cell_measurement_theta_min      4.5220
_cell_volume                     4337.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -69.00  21.00   1.00    1.25    --    0.00 -57.00-180.00   90
  2  \w    -26.00  72.00   1.00    1.25    --    0.00  37.00 -30.00   98
  3  \w    -21.00  69.00   1.00    1.25    --    0.00  57.00   0.00   90
  4  \w    -15.00  75.00   1.00    5.00    --   54.00 -57.00-150.00   90
  5  \w     23.00 111.00   1.00    5.00    --   54.00-125.00 150.00   88
  6  \w    -19.00 127.00   1.00    5.00    --   54.00   0.00  30.00  146
  7  \w     24.00 124.00   1.00    5.00    --   54.00  77.00-180.00  100
  8  \w    -15.00  75.00   1.00    5.00    --   54.00 -57.00 -30.00   90
  9  \w     23.00 111.00   1.00    5.00    --   54.00-125.00 -30.00   88
 10  \w     33.00 123.00   1.00    5.00    --   54.00  57.00  60.00   90
 11  \w     36.00 116.00   1.00   10.00    --  108.00-111.00-180.00   80
 12  \w     36.00 116.00   1.00   10.00    --  108.00-111.00 -90.00   80
 13  \w     36.00  92.00   1.00   10.00    --  108.00 -37.00 -90.00   56
 14  \w     38.00 105.00   1.00   10.00    --  108.00 -50.00   0.00   67
 15  \w     35.00  94.00   1.00   10.00    --  108.00 -25.00 150.00   59
 16  \w     38.00 138.00   1.00   10.00    --  108.00 -77.00-120.00  100
 17  \w     57.00 151.00   1.00   10.00    --  108.00 178.00 120.00   94
 18  \w     74.00 178.00   1.00   10.00    --  108.00  25.00-180.00  104
 19  \w     36.00  92.00   1.00   10.00    --  108.00 -37.00-150.00   56
 20  \w     74.00 178.00   1.00   10.00    --  108.00  25.00 -30.00  104
 21  \w     74.00 178.00   1.00   10.00    --  108.00  25.00  60.00  104
 22  \w    100.00 178.00   1.00   10.00    --  108.00 111.00-120.00   78
 23  \w     36.00  92.00   1.00   10.00    --  108.00 -37.00  30.00   56
 24  \w     38.00 138.00   1.00   10.00    --  108.00 -77.00 120.00  100
 25  \w     36.00  92.00   1.00   10.00    --  108.00 -37.00 120.00   56
 26  \w     36.00 116.00   1.00   10.00    --  108.00-111.00  90.00   80
 27  \w    -69.00  21.00   1.00    1.25    --    0.00 -57.00  60.00   90
 28  \w    -69.00  21.00   1.00    1.25    --    0.00 -57.00 -60.00   90
 29  \w    -26.00  72.00   1.00    1.25    --    0.00  37.00-150.00   98
 30  \w     24.00 124.00   1.00    5.00    --   54.00  77.00 -30.00  100
 31  \w     24.00 124.00   1.00    5.00    --   54.00  77.00 -90.00  100
 32  \w     24.00 124.00   1.00    5.00    --   54.00  77.00-150.00  100
 33  \w     23.00 111.00   1.00    5.00    --   54.00-125.00-150.00   88
 34  \w     24.00 124.00   1.00    5.00    --   54.00  77.00 120.00  100
 35  \w     33.00 123.00   1.00    5.00    --   54.00  57.00 120.00   90
 36  \w     78.00 178.00   1.00   10.00    --  108.00  77.00 -30.00  100
 37  \w     86.00 178.00   1.00   10.00    --  108.00  50.00 -90.00   92
 38  \w     78.00 178.00   1.00   10.00    --  108.00  77.00  90.00  100
 39  \w     82.00 178.00   1.00   10.00    --  108.00  37.00-120.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0392167000
_diffrn_orient_matrix_UB_12      0.0035070000
_diffrn_orient_matrix_UB_13      0.0204662000
_diffrn_orient_matrix_UB_21      0.0006326500
_diffrn_orient_matrix_UB_22      -0.1152109500
_diffrn_orient_matrix_UB_23      0.0663346000
_diffrn_orient_matrix_UB_31      0.0022183500
_diffrn_orient_matrix_UB_32      -0.0490503500
_diffrn_orient_matrix_UB_33      -0.1571238000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1213
_diffrn_reflns_av_unetI/netI     0.0516
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       47
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            28558
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.037
_diffrn_reflns_theta_min         3.765
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.025
_exptl_absorpt_correction_T_max  0.495
_exptl_absorpt_correction_T_min  0.281
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.525
_exptl_crystal_description       block
_exptl_crystal_F_000             1936
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.117
_exptl_crystal_size_min          0.086
_refine_diff_density_max         4.107
_refine_diff_density_min         -1.803
_refine_diff_density_rms         0.236
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     215
_refine_ls_number_reflns         4196
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0771
_refine_ls_R_factor_gt           0.0727
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0506P)^2^+219.6341P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1612
_refine_ls_wR_factor_ref         0.1639
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3847
_reflns_number_total             4196
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b02560_si_002.cif
_cod_data_source_block           complex_2
_cod_database_code               4349349
_chemical_oxdiff_formula         'C18 H26 Cl Ir'
_chemical_oxdiff_usercomment     'Wissam Iali IR coe (Py)2 H2 Cl'
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All Ir(H,H) groups
2. Restrained distances
 C8-C7
 1.5 with sigma of 0.02
 C8-C7A
 1.5 with sigma of 0.02
 C2-C3 = C3-C4 = C4-C5 = C5-C6 = C6-C7
 1.535 with sigma of 0.02
 C2-C3A = C3A-C4A = C4A-C5A = C5A-C6A = C6A-C7A
 1.535 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C11) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C4A) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C5) = Uanis(C5A)
Uanis(C3A) = Uanis(C3)
Uanis(C7) = Uanis(C7A)
Uanis(C4A) = Uanis(C4)
Uanis(C6) = Uanis(C6A)
4. Others
 Sof(H2BC)=Sof(H2BD)=Sof(H8B)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=
 Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C7A)=
 Sof(H7AA)=Sof(H7AB)=1-FVAR(1)
 Sof(H2AA)=Sof(H2AB)=Sof(H8A)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C6)=Sof(H6A)=
 Sof(H6B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=FVAR(1)
5.a Riding coordinates:
 Ir1(H,HA)
5.b Ternary CH refined with riding coordinates:
 C1(H1), C8(H8A), C8(H8B)
5.c Secondary CH2 refined with riding coordinates:
 C2(H2BC,H2BD), C2(H2AA,H2AB), C7(H7A,H7B), C3A(H3AA,H3AB), C6(H6A,H6B),
 C4A(H4AA,H4AB), C5(H5A,H5B), C5A(H5AA,H5AB), C4(H4A,H4B), C6A(H6AA,H6AB),
 C3(H3A,H3B), C7A(H7AA,H7AB)
5.d Aromatic/amide H refined with riding coordinates:
 C9(H9), C14(H14), C15(H15), C11(H11), C10(H10), C13(H13), C18(H18), C12(H12),
 C17(H17), C16(H16)
;
_shelx_res_checksum              7065
_shelx_hkl_checksum              25169
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-01-05
_olex2_date_sample_submission    2016-01-05
_olex2_exptl_crystal_mounting_method 'oil on micromount'
_olex2_submission_original_sample_id 'Ir Coe (py)2 H2 Cl'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.802
_oxdiff_exptl_absorpt_empirical_full_min 0.659