Acceptorless dehydrogenation of 4-methylpiperidine by supported pincer-ligated iridium catalysts in continuous flow
Chakrabarti, Kaushik; Spangenberg, Alice; Subramaniyan, Vasudevan; Hederstedt, Andreas; Abdelaziz, Omar Y.; Polukeev, Alexey V.; Wallenberg, Reine; Hulteberg, Christian P.; Wendt, Ola F.; Catalysis Science & Technology 13 (2023) 5113–5119; doi:10.1039/D3CY00881A

data_1569584
_publ_section_title
;
 Acceptorless dehydrogenation of 4-methylpiperidine by supported
 pincer-ligated iridium catalysts in continuous flow
;
_journal_issue                   17
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              5113
_journal_page_last               5119
_journal_paper_doi               10.1039/D3CY00881A
_journal_volume                  13
_journal_year                    2023
_chemical_formula_moiety         'C38 H51 Cl Ir O6 P2'
_chemical_formula_sum            'C38 H51 Cl Ir O6 P2'
_chemical_formula_weight         893.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-15
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-15 deposited with the CCDC.	2023-07-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.088(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.2561(2)
_cell_length_b                   40.9906(9)
_cell_length_c                   12.0590(3)
_cell_measurement_reflns_used    11956
_cell_measurement_temperature    298
_cell_measurement_theta_max      28.4580
_cell_measurement_theta_min      3.5740
_cell_volume                     3856.65(17)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1367
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     25.00  57.25   0.75   60.00    --   18.90-109.00 130.00   43
  2  \w    -60.00  -3.00   0.75   60.00    --  -21.87 109.00-133.00   76
  3  \w      0.00  87.00   0.75   60.00    --   18.90  37.00-120.00  116
  4  \w     41.00  87.50   0.75   60.00    --   18.90 178.00  90.00   62
  5  \w     -1.00  38.00   0.75   60.00    --   18.90  77.00   0.00   52
  6  \w     -8.00  27.25   0.75   60.00    --   18.90  77.00-150.00   47
  7  \w    -50.00  37.00   0.75   60.00    --   18.90 -37.00  60.00  116
  8  \w     -2.00  24.25   0.75   60.00    --   18.90  77.00  90.00   35
  9  \w    -34.00  44.00   0.75   60.00    --  -21.87  57.00 -30.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0168892000
_diffrn_orient_matrix_UB_12      -0.0168746000
_diffrn_orient_matrix_UB_13      0.0030282000
_diffrn_orient_matrix_UB_21      -0.0605925000
_diffrn_orient_matrix_UB_22      0.0006599000
_diffrn_orient_matrix_UB_23      -0.0573766000
_diffrn_orient_matrix_UB_31      0.0656832000
_diffrn_orient_matrix_UB_32      -0.0037273000
_diffrn_orient_matrix_UB_33      -0.0239454000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0692
_diffrn_reflns_av_unetI/netI     0.0599
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            33593
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.997
_diffrn_reflns_theta_max         24.997
_diffrn_reflns_theta_min         3.282
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.657
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94956
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
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    1.539
_exptl_crystal_description       needle
_exptl_crystal_F_000             1804
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.374
_refine_diff_density_min         -4.187
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.296
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         6775
_refine_ls_number_restraints     83
_refine_ls_restrained_S_all      1.288
_refine_ls_R_factor_all          0.0782
_refine_ls_R_factor_gt           0.0622
_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^)+(0.0212P)^2^+10.6117P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0988
_refine_ls_wR_factor_ref         0.1030
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5651
_reflns_number_total             6775
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy00881a2.cif
_cod_data_source_block           full
_cod_depositor_comments          'Adding full bibliography for 1569584.cif.'
_cod_database_code               1569584
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C38H52P2O6ClIr
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.711
_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. Restrained distances
 C33-C34 \\sim C33-C34A
 with sigma of 0.02
 C33-C38 \\sim C33-C38A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C35-C36 \\sim C35A-C36A
 with sigma of 0.02
 C38-C37 \\sim C38A-C37A
 with sigma of 0.02
 C37-C36 \\sim C37A-C36A
 with sigma of 0.02
 C33-C35 \\sim C33-C35A
 with sigma of 0.04
 C33-C37 \\sim C33-C37A
 with sigma of 0.04
 C34-C36 \\sim C34A-C36A
 with sigma of 0.04
 C35-C37 \\sim C35A-C37A
 with sigma of 0.04
 C38-C36 \\sim C38A-C36A
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 C34A, C34, C35, C35A, C36, C36A, C37, C37A, C38, C38A, C33
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
4. Others
 Sof(C34A)=Sof(H0)=Sof(C35A)=Sof(H1)=Sof(C36A)=Sof(H01R)=Sof(C37A)=Sof(H2)=
 Sof(C38A)=Sof(H3)=1-FVAR(1)
 Sof(C34)=Sof(H013)=Sof(C35)=Sof(H015)=Sof(C38)=Sof(H018)=Sof(C37)=Sof(H019)=
 Sof(C36)=Sof(H01Q)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C24(H00G,H00I), C32(H00J,H00K)
5.b Aromatic/amide H refined with riding coordinates:
 C11(H00H), C26(H00V), C30(H00X), C27(H011), C34(H013), C28(H014), C35(H015),
 C38(H018), C37(H019), C29(H01P), C36(H01Q), C34A(H0), C35A(H1), C36A(H01R),
 C37A(H2), C38A(H3)
5.c Idealised Me refined as rotating group:
 C7(H00A,H00B,H00C), C6(H00D,H00E,H00F), C8(H00L,H00M,H00N), C2(H00O,H00P,
 H00Q), C16(H00R,H00S,H00T), C17(H00U,H00W,H00Y), C18(H00Z,H,HA), C22(H01A,H01B,
 H01C), C21(H01D,H01E,H01F), C4(H01G,H01H,H01I), C20(H01J,H01K,H01L), C3(H01M,
 H01N,H01O)
;
_shelx_res_checksum              5635
_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 1.252
_oxdiff_exptl_absorpt_empirical_full_min 0.935