Predicting valence tautomerism in diverse cobalt-dioxolene complexes: elucidation of the role of ligands and solvent.
M Zahir, F Zahra; Hay, Moya A.; Janetzki, Jett T.; Gable, Robert W.; Goerigk, Lars; Boskovic, Colette; Chemical science 15 (2024) 5694–5710; doi:10.1039/d3sc04493a

data_1571231
_publ_section_title
;
 Predicting valence tautomerism in diverse cobalt-dioxolene complexes:
 elucidation of the role of ligands and solvent.
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              5694
_journal_page_last               5710
_journal_paper_doi               10.1039/d3sc04493a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C30 H34 Co N4 O2, C24 H20 B'
_chemical_formula_sum            'C54 H54 B Co N4 O2'
_chemical_formula_weight         860.75
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-05-19
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-08-08 deposited with the CCDC.	2024-03-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.64(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.464(4)
_cell_length_b                   9.7080(19)
_cell_length_c                   23.147(5)
_cell_measurement_reflns_used    1357
_cell_measurement_temperature    276.0(2)
_cell_measurement_theta_max      25.7
_cell_measurement_theta_min      2.51
_cell_volume                     4576.2(16)
_computing_cell_refinement       'XDS (Kabsch, 2010)'
_computing_data_collection       'AS QEGUI'
_computing_data_reduction        'XDS (Kabsch, 2010)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      276.0(2)
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.841
_diffrn_measurement_device_type  'MX2 Beamline Australian Synchrotron'
_diffrn_measurement_method       'Omega Scan'
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0539
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.841
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            83740
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.841
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.260
_diffrn_reflns_theta_min         1.268
_diffrn_source                   'MX2 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.421
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.6415
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'sadabs (Bruker, 2001)'
_exptl_crystal_colour            'Dark Purple'
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       needle
_exptl_crystal_F_000             1816
_exptl_crystal_recrystallization_method
'grown by slow evaporation from dichloromethane/hexane'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.032
_refine_diff_density_min         -1.324
_refine_diff_density_rms         0.101
_refine_ls_extinction_coef       0.0283(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     578
_refine_ls_number_reflns         13668
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0874
_refine_ls_R_factor_gt           0.0783
_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^)+(0.1263P)^2^+2.6233P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2227
_refine_ls_wR_factor_ref         0.2341
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11368
_reflns_number_total             13668
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04493a3.cif
_cod_data_source_block           zz1130_275k_0059m
_cod_depositor_comments
'Adding full bibliography for 1571222--1571238.cif.'
_cod_original_cell_volume        4576.3(16)
_cod_database_code               1571231
_shelx_shelxl_version_number     2019/3
_diffrn_measurement_detector_type 'Dectris Eiger 16M'
_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. Others
 1*[Sof(H28)+Sof(C29)+Sof(H29A)+Sof(H29B)+Sof(H29C)]+1*[Sof(H22)+Sof(C30)+
 Sof(H30A)+Sof(H30B)+Sof(H30C)]+1*[Sof(H11)+Sof(C31)+Sof(H31A)+Sof(H31B)+
 Sof(H31C)]=2 with esd of 0.000001
 Sof(H28)=1-FVAR(1)
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(1)
 Sof(H22)=1-FVAR(2)
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(2)
 Sof(H11)=1-FVAR(3)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(3)
3.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C23(H23A,H23B)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C11(H11), C12(H12), C13(H13), C14(H14), C19(H19),
 C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C27(H27), C28(H28), C33(H33),
  C34(H34), C35(H35), C36(H36), C37(H37), C39(H39), C40(H40), C41(H41),
 C42(H42), C43(H43), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50),
  C52(H52), C53(H53), C54(H54), C55(H55)
3.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              58110
_olex2_submission_special_instructions 'No special instructions were received'