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_4135057
_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         'C63 H64 Br4 Co2 N8 O4, 2(F6 P)'
_chemical_formula_sum            'C67 H76 Br4 Co2 F12 N8 O6 P2'
_chemical_formula_weight         1816.79
_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(6-methyl-2-pyridylmethyl)amine)-di-cobalt bis(hexafluorophosphate) ethanol solvate'
_chemical_properties_physical    paramagnetic
_space_group_crystal_system      orthorhombic
_space_group_IT_number           52
_space_group_name_Hall           '-P 2a 2bc'
_space_group_name_H-M_alt        'P n n a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-22
_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                   26.0119(3)
_cell_length_b                   14.2861(2)
_cell_length_c                   20.1208(2)
_cell_measurement_reflns_used    19186
_cell_measurement_temperature    99.99(13)
_cell_measurement_theta_max      76.3190
_cell_measurement_theta_min      3.3970
_cell_volume                     7477.06(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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    -56.00  24.00   0.50    6.81    --  -48.17  38.00  90.00  160
  2  \w    -55.00 -17.00   0.50   16.00    --  -86.25  37.00 -11.00   76
  3  \w    -91.00 -11.00   0.50    6.81    --  -48.17 125.00 -60.00  160
  4  \w   -101.00 -76.00   0.50   16.00    --  -86.25 -84.00  26.00   50
  5  \w   -119.00 -94.00   0.50    6.81    --  -48.17-125.00 -30.00   50
  6  \w   -114.00 -87.00   0.50    6.81    --  -48.17-125.00-120.00   54
  7  \w     71.00 125.00   0.50   16.00    --  107.75-139.00 -32.00  108
  8  \w     83.00 109.00   0.50   16.00    --  107.75 -84.00  26.00   52
  9  \w     55.00 102.00   0.50   16.00    --  107.75 -61.00 -60.00   94
 10  \w     46.00  72.00   0.50   16.00    --  107.75 -45.00  30.00   52
 11  \w     41.00  67.00   0.50   16.00    --  107.75 -84.00  26.00   52
 12  \w     37.00 101.00   0.50   16.00    --  107.75 -61.00  30.00  128
 13  \w     44.00  70.00   0.50   16.00    --  107.75 -30.00  60.00   52
 14  \w     98.00 132.00   0.50   16.00    --  107.75  30.00  60.00   68
 15  \w    144.00 170.00   0.50   16.00    --  107.75  30.00  60.00   52
 16  \w    119.00 176.00   0.50   16.00    --  107.75  15.00 -90.00  114
 17  \w    130.00 168.00   0.50   16.00    --  107.75  77.00-150.00   76
 18  \w     99.00 176.00   0.50   16.00    --  107.75  37.00 -11.00  154
 19  \w     86.00 111.00   0.50   16.00    --  107.75  77.00-150.00   50
 20  \w     37.00  72.00   0.50   16.00    --  107.75 -37.00-167.00   70
 21  \w     43.00  71.00   0.50   16.00    --  107.75 -45.00-180.00   56
 22  \w     40.00  66.00   0.50   16.00    --  107.75 -30.00-150.00   52
 23  \w     38.00  68.00   0.50   16.00    --  107.75 -61.00-180.00   60
 24  \w     75.00 100.00   0.50    6.81    --   48.17-139.00 -32.00   50
 25  \w     38.00  73.00   0.50   16.00    --  107.75 -45.00  90.00   70
 26  \w     41.00 106.00   0.50   16.00    --  107.75 -94.00 120.00  130
 27  \w     36.00  72.00   0.50   16.00    --  107.75 -45.00 -30.00   72
 28  \w     44.00  56.50   0.50   16.00    --  107.75 -30.00 -30.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0030282000
_diffrn_orient_matrix_UB_12      -0.1077171000
_diffrn_orient_matrix_UB_13      -0.0005950000
_diffrn_orient_matrix_UB_21      0.0521107000
_diffrn_orient_matrix_UB_22      0.0044775000
_diffrn_orient_matrix_UB_23      0.0362952000
_diffrn_orient_matrix_UB_31      -0.0279770000
_diffrn_orient_matrix_UB_32      -0.0033505000
_diffrn_orient_matrix_UB_33      0.0673956000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0538
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            57008
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.013
_diffrn_reflns_theta_min         2.776
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.116
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.260
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.614
_exptl_crystal_description       prism
_exptl_crystal_F_000             3656
_exptl_crystal_recrystallization_method 'Crystallised from ethanol'
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.052
_refine_diff_density_max         1.084
_refine_diff_density_min         -0.949
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     434
_refine_ls_number_reflns         7939
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0810
_refine_ls_R_factor_gt           0.0711
_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^)+(0.0927P)^2^+14.5416P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1950
_refine_ls_wR_factor_ref         0.2029
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6435
_reflns_number_total             7939
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_007.cif
_cod_data_source_block           4a-2EtOH-100K
_cod_database_code               4135057
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C63 H64 Co2 Br4 N8 O4 P2 F12'
_chemical_oxdiff_usercomment
'Dimer Co Me3tpa Br4spiro PF6, 100 K, dark green crystal, same crystal as 80K'
_shelx_estimated_absorpt_t_max   0.709
_shelx_estimated_absorpt_t_min   0.250
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C17(H17A,H17B), C23(H23A,H23B), C29(H29A,H29B)
2.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C19(H19), C20(H20), C21(H21), C25(H25),
 C26(H26), C27(H27)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C)
;
_shelx_res_checksum              37538
_shelx_hkl_checksum              20274
_shelx_fab_checksum              68737
_olex2_exptl_crystal_mounting_method 'MiTeGen mount with cryoprotectant oil'
_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 2.980
_oxdiff_exptl_absorpt_empirical_full_min 0.554