Photochemical H<sub>2</sub> activation by an Zn-Fe heterometallic: a mechanistic investigation.
Perez-Jimenez, Marina; Crimmin, Mark R.; Chemical science 15 (2024) 1424–1430; doi:10.1039/d3sc05966a

data_1570557
_publ_section_title
;
 Photochemical H<sub>2</sub> activation by an Zn-Fe heterometallic: a
 mechanistic investigation.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              1424
_journal_page_last               1430
_journal_paper_doi               10.1039/d3sc05966a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C36 H46 Fe N2 O2 Zn, C35 H48 Fe N2 O Zn'
_chemical_formula_sum            'C71 H94 Fe2 N4 O3 Zn2'
_chemical_formula_weight         1293.94
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2023-09-07
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-09-25 deposited with the CCDC.	2023-12-14 downloaded from the CCDC.
;
_cell_angle_alpha                89.192(5)
_cell_angle_beta                 89.647(6)
_cell_angle_gamma                84.943(6)
_cell_formula_units_Z            2
_cell_length_a                   10.6485(9)
_cell_length_b                   15.0229(10)
_cell_length_c                   20.9423(12)
_cell_measurement_reflns_used    4069
_cell_measurement_temperature    172.95(10)
_cell_measurement_theta_max      71.9250
_cell_measurement_theta_min      3.5910
_cell_volume                     3336.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4115
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.942
_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    -73.00  34.00   1.00    8.20    --  -42.23  77.00  30.00  107
  2  \w   -114.00 -20.00   1.00    8.20    --  -42.23 -57.00 -90.00   94
  3  \w    -23.00  70.00   1.00    8.20    --   42.23 -57.00 120.00   93
  4  \w     78.00 175.00   1.00   21.34    --  105.75  30.00   0.00   97
  5  \w     91.00 177.00   1.00   21.34    --  105.75 125.00-150.00   86
  6  \w     33.00 122.00   1.00   21.34    --  105.75-125.00-150.00   89
  7  \w     24.00 104.00   1.00   21.34    --  105.75 -95.00  30.00   80
  8  \w     81.00 163.00   1.00   21.34    --  105.75  77.00  30.00   82
  9  \w     31.00 136.00   1.00   21.34    --  105.75 -77.00-150.00  105
 10  \w     83.00 178.00   1.00   21.34    --  105.75  77.00 -90.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0488250000
_diffrn_orient_matrix_UB_12      0.0287166000
_diffrn_orient_matrix_UB_13      0.0666524000
_diffrn_orient_matrix_UB_21      -0.1177685000
_diffrn_orient_matrix_UB_22      -0.0508290000
_diffrn_orient_matrix_UB_23      -0.0096974000
_diffrn_orient_matrix_UB_31      0.0695828000
_diffrn_orient_matrix_UB_32      -0.0848066000
_diffrn_orient_matrix_UB_33      0.0295974000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0544
_diffrn_reflns_av_unetI/netI     0.0863
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            19828
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.847
_diffrn_reflns_theta_min         3.607
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.593
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76983
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.288
_exptl_crystal_description       block
_exptl_crystal_F_000             1368
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.435
_refine_diff_density_min         -0.591
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     765
_refine_ls_number_reflns         12728
_refine_ls_number_restraints     40
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0925
_refine_ls_R_factor_gt           0.0541
_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^)+(0.0477P)^2^+0.3353P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1219
_refine_ls_wR_factor_ref         0.1452
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8567
_reflns_number_total             12728
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05966a3.cif
_cod_data_source_block           mrc2268
_cod_depositor_comments
'Adding full bibliography for 1570556--1570557.cif.'
_cod_original_cell_volume        3336.7(4)
_cod_database_code               1570557
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C35 H47 Fe N2 O Zn'
_chemical_oxdiff_usercomment     MPJ-075
_reflns_odcompleteness_completeness 98.52
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H6,H,HA} of C6
 At 1.5 times of:
  {H58A,H58B,H58C} of C58, {H70A,H70B,H70C} of C70, {H55A,H55B,H55C} of C55,
  {H68A,H68B,H68C} of C68, {H56A,H56B,H56C} of C56, {H22A,H22B,H22C} of C22,
  {H34A,H34B,H34C} of C34, {H35A,H35B,H35C} of C35, {H59A,H59B,H59C} of C59,
  {H71A,H71B,H71C} of C71, {H32A,H32B,H32C} of C32, {H19A,H19B,H19C} of C19,
  {H31A,H31B,H31C} of C31, {H10A,H10B,H10C} of C10, {H47A,H47B,H47C} of C47,
  {H46A,H46B,H46C} of C46, {H20A,H20B,H20C} of C20, {H67A,H67B,H67C} of C67,
  {H11A,H11B,H11C} of C11, {H23A,H23B,H23C} of C23
2. Rigid bond restraints
 C2, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
4.a Ternary CH refined with riding coordinates:
 C69(H69), C18(H18), C30(H30), C33(H33), C66(H66), C21(H21), C54(H54), C57(H57)
4.b Aromatic/amide H refined with riding coordinates:
 C42(H42), C62(H62), C51(H51), C64(H64), C63(H63), C52(H52), C44(H44),
 C28(H28), C16(H16), C14(H14), C50(H50), C38(H38), C41(H41), C40(H40), C39(H39),
  C8(H8), C26(H26), C27(H27), C15(H15), C5(H5), C2(H2), C3(H3), C4(H4), C6(H6)
4.c Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C46(H46A,H46B,H46C), C10(H10A,H10B,H10C), C67(H67A,H67B,
 H67C), C20(H20A,H20B,H20C), C11(H11A,H11B,H11C), C23(H23A,H23B,H23C), C19(H19A,
 H19B,H19C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C35(H35A,H35B,H35C),
 C22(H22A,H22B,H22C), C70(H70A,H70B,H70C), C59(H59A,H59B,H59C), C71(H71A,H71B,
 H71C), C34(H34A,H34B,H34C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C55(H55A,
 H55B,H55C), C68(H68A,H68B,H68C)
;
_shelx_res_checksum              64435
_shelx_hkl_checksum              1899
_olex2_date_sample_data_collection 2022-06-15
_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 1.578
_oxdiff_exptl_absorpt_empirical_full_min 0.602