Base-free hydrogenation of CO2to formic acid in water with an iridium complex bearing a N,N′-diimine ligand
Lu, Sheng-Mei; Wang, Zhijun; Li, Jun; Xiao, Jianliang; Li, Can; Green Chem. 18 (2016) 4553–; doi:10.1039/C6GC00856A

data_7225288
_publ_section_title
;
 Base-free hydrogenation of CO2to formic acid in water with an iridium
 complex bearing a N,N&#x2032;-diimine ligand
;
_journal_issue                   16
_journal_name_full               'Green Chem.'
_journal_page_first              4553
_journal_paper_doi               10.1039/C6GC00856A
_journal_volume                  18
_journal_year                    2016
_chemical_formula_moiety         'C18 H31 Ir N4 O, 2(B F4), H2 O'
_chemical_formula_sum            'C18 H33 B2 F8 Ir N4 O2'
_chemical_formula_weight         703.30
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-11-19
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2015-11-23 deposited with the CCDC.
2016-05-19 downloaded from the CCDC.
;
_cell_angle_alpha                85.039(3)
_cell_angle_beta                 74.421(3)
_cell_angle_gamma                78.507(3)
_cell_formula_units_Z            2
_cell_length_a                   8.6729(15)
_cell_length_b                   11.3034(19)
_cell_length_c                   13.751(2)
_cell_measurement_reflns_used    4502
_cell_measurement_temperature    293
_cell_measurement_theta_max      24.35
_cell_measurement_theta_min      2.48
_cell_volume                     1271.7(4)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0322
_diffrn_reflns_av_unetI/netI     0.0614
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            13116
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.901
_diffrn_reflns_theta_min         2.357
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.331
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.4254
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1175 before and 0.0379 after correction.
The Ratio of minimum to maximum transmission is 0.5702.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.837
_exptl_crystal_description       block
_exptl_crystal_F_000             688
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.859
_refine_diff_density_min         -2.302
_refine_diff_density_rms         0.168
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     397
_refine_ls_number_reflns         7928
_refine_ls_number_restraints     298
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0680
_refine_ls_R_factor_gt           0.0486
_refine_ls_shift/su_max          0.024
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0740P)^2^+0.4450P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1202
_refine_ls_wR_factor_ref         0.1312
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6208
_reflns_number_total             7928
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6gc00856a2.cif
_cod_data_source_block           mo_dm15855_0m
_cod_depositor_comments          'Adding full bibliography for 7225288.cif.'
_cod_original_cell_volume        1271.8(4)
_cod_database_code               7225288
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.349
_shelx_estimated_absorpt_t_min   0.272
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 F4-B1 = F1-B1 = F3-B1 = F2-B1
 1.38 with sigma of 0.02
 F8-B2 = F5-B2 = F6-B2 = F7-B2
 1.38 with sigma of 0.02
 F4'-B1 = F1'-B1 = F3'-B1 = F2'-B1
 1.38 with sigma of 0.02
 F8'-B2 = F5'-B2 = F6'-B2 = F7'-B2
 1.38 with sigma of 0.02
 F1-F4 \\sim F1-F2 \\sim F1-F3 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4
 with sigma of 0.01
 F5-F6 \\sim F5-F7 \\sim F5-F8 \\sim F6-F7 \\sim F6-F8 \\sim F7-F8
 with sigma of 0.01
 F1'-F4' \\sim F1'-F2' \\sim F1'-F3' \\sim F2'-F3' \\sim F2'-F4' \\sim F3'-F4'
 with sigma of 0.01
 F5'-F6' \\sim F5'-F7' \\sim F5'-F8' \\sim F6'-F7' \\sim F6'-F8' \\sim F7'-F8'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
B1 \\sim F3 \\sim F1 \\sim F4 \\sim F2: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
B2 \\sim F6 \\sim F5 \\sim F8 \\sim F7: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
B1 \\sim F3' \\sim F1' \\sim F4' \\sim F2': within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
B2 \\sim F6' \\sim F5' \\sim F8' \\sim F7': within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
C18 \\sim C17 \\sim C16 \\sim N3: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(F4) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F2) \\sim
Ueq, Uanis(F8) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F7)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F4') \\sim Ueq, Uanis(F1') \\sim Ueq, Uanis(F3') \\sim Ueq, Uanis(F2')
\\sim Ueq, Uanis(F8') \\sim Ueq, Uanis(F5') \\sim Ueq, Uanis(F6') \\sim Ueq,
Uanis(F7') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(B1) \\sim Ueq, Uanis(B2) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4. Others
 Fixed Sof: F1(0.5) F2(0.5) F3(0.5) F4(0.5) F1'(0.5) F2'(0.5) F3'(0.5)
 F4'(0.5) F5(0.5) F6(0.5) F7(0.5) F8(0.5) F7'(0.5) F6'(0.5) F5'(0.5) F8'(0.5)
5.a Free rotating group:
 O2(H2A,H2B)
5.b Rotating group:
 O1(H1A,H1B)
5.c Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C16(H16A,H16B), C17(H17A,
 H17B), C18(H18A,H18B)
5.d Aromatic/amide H refined with riding coordinates:
 N3(H3), N4(H4)
5.e Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C)
;
_shelx_res_checksum              74344
_shelx_hkl_checksum              45176
_olex2_submission_special_instructions 'No special instructions were received'