Using coligands to gain mechanistic insight into iridium complexes hyperpolarized with para-hydrogen
Tickner, Ben; John, Richard O.; Roy, Soumya Singha; Hart, Sam; Whitwood, Adrian Charles; Duckett, Simon B.; Chemical Science  (2019) –; doi:10.1039/C9SC00444K

data_1550754
_publ_section_title
;
 Using coligands to gain mechanistic insight into iridium complexes
 hyperpolarized with para-hydrogen
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC00444K
_journal_year                    2019
_chemical_formula_moiety         'C41 H47 Ir N4 O5, C H2 Cl2'
_chemical_formula_sum            'C42 H49 Cl2 Ir N4 O5'
_chemical_formula_weight         952.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-01-25 deposited with the CCDC.    2019-03-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.6750(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.08570(10)
_cell_length_b                   11.99650(10)
_cell_length_c                   24.9643(2)
_cell_measurement_reflns_used    31122
_cell_measurement_temperature    109.95(10)
_cell_measurement_theta_max      31.7570
_cell_measurement_theta_min      3.6920
_cell_volume                     4180.65(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      109.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.938
_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    -45.00  55.00   1.00   40.00    --   24.78 -77.00 150.00  100
  2  \w     35.00 101.00   1.00   40.00    --   24.78 178.00-150.00   66
  3  \w      4.00  94.00   1.00   40.00    --   24.78  57.00 -90.00   90
  4  \w   -101.00 -55.00   1.00   40.00    --  -24.94 178.00-120.00   46
  5  \w   -101.00 -55.00   1.00   40.00    --  -24.94 178.00 -60.00   46
  6  \w      4.00  94.00   1.00   40.00    --   24.78  57.00  30.00   90
  7  \w     35.00 101.00   1.00   40.00    --   24.78 178.00   0.00   66
  8  \w      2.00  55.00   1.00   40.00    --   24.78  46.00-163.00   53
  9  \w      4.00  94.00   1.00   40.00    --   24.78  57.00 120.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0060270000
_diffrn_orient_matrix_UB_12      0.0555856000
_diffrn_orient_matrix_UB_13      0.0086056000
_diffrn_orient_matrix_UB_21      -0.0472565000
_diffrn_orient_matrix_UB_22      0.0004225000
_diffrn_orient_matrix_UB_23      -0.0140223000
_diffrn_orient_matrix_UB_31      -0.0177190000
_diffrn_orient_matrix_UB_32      -0.0201126000
_diffrn_orient_matrix_UB_33      0.0234750000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            63675
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.788
_diffrn_reflns_theta_min         3.294
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.369
_exptl_absorpt_correction_T_max  0.945
_exptl_absorpt_correction_T_min  0.911
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.514
_exptl_crystal_description       block
_exptl_crystal_F_000             1920
_exptl_crystal_recrystallization_method 'DCM, H2O hexane'
_exptl_crystal_size_max          0.151
_exptl_crystal_size_mid          0.139
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.932
_refine_diff_density_min         -0.640
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     502
_refine_ls_number_reflns         13379
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0289
_refine_ls_R_factor_gt           0.0219
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0145P)^2^+3.0501P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0437
_refine_ls_wR_factor_ref         0.0465
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11691
_reflns_number_total             13379
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00444k2.cif
_cod_data_source_block           sbd1805
_cod_database_code               1550754
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C37 H44 Ir N4 O2'
_chemical_oxdiff_usercomment     'Ben Tickner BT 2AP'
_shelx_estimated_absorpt_t_max   0.751
_shelx_estimated_absorpt_t_min   0.630
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.51
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B), C34(H34A,H34B), C35(H35A,H35B), C42(H42A,H42B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C15(H15), C17(H17), C29(H29), C30(H30),
 C31(H31), C32(H32), C33(H33), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C25(H25A,H25B,H25C)
;
_olex2_date_sample_data_collection 2018-09-13
_olex2_date_sample_submission    2018-09-04
_olex2_exptl_crystal_mounting_method 'oil on micromount'
_olex2_submission_original_sample_id 'BT 2AP'
_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 1.125
_oxdiff_exptl_absorpt_empirical_full_min 0.916