Understanding the Origin of One- or Two-Step Valence Tautomeric Transitions in Bis(dioxolene)-Bridged Dinuclear Cobalt Complexes.
Gransbury, Gemma K.; Livesay, Brooke N.; Janetzki, Jett T.; Hay, Moya A.; Gable, Robert W.; Shores, Matthew P.; Starikova, Alyona; Boskovic, Colette; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c01073

data_4135048
_publ_section_title
;
 Understanding the Origin of One- or Two-Step Valence Tautomeric
 Transitions in Bis(dioxolene)-Bridged Dinuclear Cobalt Complexes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c01073
_journal_year                    2020
_chemical_formula_moiety         'C57 H52 Br4 Co2 N8 O4, 2(F6 P)'
_chemical_formula_sum            'C59.5 H62 Br4 Co2 F12 N8 O6.5 P2'
_chemical_formula_weight         1720.61
_chemical_name_systematic
'(mu2-3,3,3',3'-tetramethyl-1,1'-spirobi(indan)-4,4'-7,7'-tetrabromo-5,5'-6,6'-tetraolato)-bis(tris (2-pyridylmethyl)amine)-di-cobalt(III) bis(hexafluorophosphate) methanol solvate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.600(4)
_cell_length_b                   15.000(3)
_cell_length_c                   20.220(4)
_cell_measurement_reflns_used    32609
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.315
_cell_measurement_theta_min      0.407
_cell_volume                     6551(2)
_computing_cell_refinement       'XDS (Kabsch, 1993)'
_computing_data_collection       'AS QEGUI'
_computing_data_reduction        'XDS (Kabsch, 1993)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Dectris Eiger2 9M'
_diffrn_measurement_method       'Omega Scan'
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.710918
_diffrn_reflns_av_R_equivalents  0.0716
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            152165
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.679
_diffrn_reflns_theta_min         1.653
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_diffrn_source_type              'MX1 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    3.086
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.4937
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
XDS was used for absorption corrections. No further details are reported by
XDS, the values reported above are those reported by SADABS and so only 
approximate the values that would be calculated by XDS.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.744
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3436
_exptl_crystal_recrystallization_method 'Crystallised from methanol'
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.005
_refine_diff_density_max         1.191
_refine_diff_density_min         -0.536
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     427
_refine_ls_number_reflns         6225
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0873
_refine_ls_R_factor_gt           0.0645
_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^)+(0.1261P)^2^+3.3966P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1975
_refine_ls_wR_factor_ref         0.2212
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4068
_reflns_number_total             6225
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_004.cif
_cod_data_source_block           2a-2p5meoh
_cod_original_formula_sum        'C59.50 H62 Br4 Co2 F12 N8 O6.50 P2'
_cod_database_code               4135048
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.913
_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
 F1-F2 = F1-F3 = F1-F4 = F1-F5
 2.26243 with sigma of 0.001
 F6-F2 = F6-F3 = F6-F4 = F6-F5
 2.26243 with sigma of 0.001
 F2-F3 = F3-F5 = F5-F4 = F4-F2
 2.26243 with sigma of 0.001
 F1A-F2A = F1A-F3A = F1A-F4A = F1A-F5A
 2.26243 with sigma of 0.001
 F6A-F2A = F6A-F3A = F6A-F4A = F6A-F5A
 2.26243 with sigma of 0.001
 F2A-F3A = F3A-F5A = F5A-F4A = F4A-F2A
 2.26243 with sigma of 0.001
 P1-F1 = P1-F2 = P1-F3 = P1-F4 = P1-F5 = P1-F6
 1.6 with sigma of 0.001
 P1A-F1A = P1A-F2A = P1A-F3A = P1A-F4A = P1A-F5A = P1A-F6A
 1.6 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C29) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1) = Uanis(F1A)
Uanis(F2) = Uanis(F2A)
Uanis(F3) = Uanis(F3A)
Uanis(F4) = Uanis(F4A)
Uanis(F5) = Uanis(F5A)
Uanis(F6) = Uanis(F6A)
Uanis(P1) = Uanis(P1A)
4. Others
 Sof(F2A)=Sof(P1A)=Sof(F3A)=Sof(F5A)=Sof(F4A)=Sof(F6A)=Sof(F1A)=1-FVAR(1)
 Sof(P1)=Sof(F6)=Sof(F1)=Sof(F3)=Sof(F5)=Sof(F2)=Sof(F4)=FVAR(1)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C23(H23A,H23B), C29(H29A,H29B), C10(H10A,H10B)
5.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C24(H24), C13(H13), C18(H18), C15(H15), C14(H14), C25(H25),
 C27(H27), C26(H26), C19(H19), C20(H20), C21(H21)
5.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              17485
_shelx_hkl_checksum              7597
_shelx_fab_checksum              53610
_olex2_exptl_crystal_mounting_method 'Mounted in cryoprotective oil'
_olex2_submission_special_instructions 'No special instructions were received'