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_1571222
_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_absolute_configuration ad
_chemical_formula_moiety
'2(C28 H30 Co N4 O2), 1.5(C H2 Cl2), 2(C24 H20 B)'
_chemical_formula_sum            'C105.5 H103 B2 Cl3 Co2 N8 O4'
_chemical_formula_weight         1792.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-05-17
_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                 106.73(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.769(3)
_cell_length_b                   15.187(3)
_cell_length_c                   21.191(4)
_cell_measurement_reflns_used    1417
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      20.02
_cell_measurement_theta_min      1.05
_cell_volume                     4551.9(17)
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.833
_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     0.71092
_diffrn_reflns_av_R_equivalents  0.0574
_diffrn_reflns_av_unetI/netI     0.0531
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.833
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            80343
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.820
_diffrn_reflns_theta_full        25.249
_diffrn_reflns_theta_max         32.214
_diffrn_reflns_theta_min         1.500
_diffrn_source                   'MX2 Beamline Australian Synchrotron'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.511
_exptl_absorpt_correction_T_max  0.4345
_exptl_absorpt_correction_T_min  0.2921
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'XDS (Kabsch, 2010)'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.308
_exptl_crystal_description       needle
_exptl_crystal_F_000             1878
_exptl_crystal_recrystallization_method
'grown by slow evaporation from dichloromethane/hexane'
_exptl_crystal_size_max          1.1
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.989
_refine_diff_density_min         -0.673
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.40(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1141
_refine_ls_number_reflns         26377
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0917
_refine_ls_R_factor_gt           0.0716
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1317P)^2^+1.2469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2093
_refine_ls_wR_factor_ref         0.2286
_reflns_Friedel_coverage         0.907
_reflns_Friedel_fraction_full    0.981
_reflns_Friedel_fraction_max     0.807
_reflns_number_gt                19601
_reflns_number_total             26377
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04493a3.cif
_cod_data_source_block           zz2-017-dcm-hex-4-iirwg
_cod_depositor_comments
'Adding full bibliography for 1571222--1571238.cif.'
_cod_original_formula_sum        'C105.50 H103 B2 Cl3 Co2 N8 O4'
_cod_database_code               1571222
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.603
_exptl_absorpt_special_details
;
XDS does not report the values of _exptl_absorpt_correction_T_min and
_exptl_absorpt_correction_T_max.  Even though the data was processed by XDS
the values of the absorption corrections reported by SADABS are reported.
;
_diffrn_measurement_detector_type 'Dectris Eiger 16M'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.60(2)
 0.40(2)
2. 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
3. Restrained distances
 C53-Cl1 = C53-Cl2
 1.77 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
C53: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within
2A
Cl1 \\sim Cl2: within 2A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 2A
Uanis(C10) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C53) \\sim Ueq: with sigma of 0.03 and sigma for terminal atoms of 0.06
5. Others
 Fixed Sof: Cl1(0.5) Cl2(0.5) C53(0.5) H53A(0.5) H53B(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C23(H23A,H23B), C69(H69A,H69B), C70(H70A,
 H70B), C76(H76A,H76B), C53(H53A,H53B), C106(H10D,H10E)
6.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), C56(H56),
  C57(H57), C59(H59), C64(H64), C65(H65), C66(H66), C67(H67), C72(H72),
 C73(H73), C74(H74), C75(H75), C78(H78), C79(H79), C80(H80), C81(H81), C30(H30),
  C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37), C38(H38),
 C39(H39), C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C48(H48),
  C49(H49), C50(H50), C51(H51), C52(H52), C83(H83), C84(H84), C85(H85),
 C86(H86), C87(H87), C89(H89), C90(H90), C91(H91), C92(H92), C93(H93), C95(H95),
  C96(H96), C97(H97), C98(H98), C99(H99), C101(H101), C102(H102), C103(H103),
 C104(H104), C105(H105)
6.c Idealised Me refined with riding coordinates:
 C10(H10A,H10B,H10C)
6.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C),
 C63(H63A,H63B,H63C)
;
_shelx_res_checksum              98093
_olex2_submission_special_instructions 'No special instructions were received'