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_4135050
_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         'C21 H20 Br4 O4, 2(C4 H10 O)'
_chemical_formula_sum            'C29 H40 Br4 O6'
_chemical_formula_weight         804.25
_chemical_name_systematic
;"3,3,3',3'-tetramethyl-1,1'-spirobi(indan)-4,4'-7,7'-tetrabromo-5,5'-6,6'
-tetraol diethyl ether 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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-11
_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                   18.36149(17)
_cell_length_b                   7.57018(7)
_cell_length_c                   22.8673(2)
_cell_measurement_reflns_used    18165
_cell_measurement_temperature    130.00(10)
_cell_measurement_theta_max      76.9390
_cell_measurement_theta_min      3.0530
_cell_volume                     3178.55(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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_temperature      130.00(10)
_diffrn_detector_area_resol_mean 10.2273
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
  1 omega  -39.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8092   37.0000  120.0000 72

  2 omega   -8.00   29.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8092   37.0000  150.0000 37

  3 omega  -36.00   16.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8092   37.0000 -120.0000 52

  4 omega  -37.00   73.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8092  -77.0000 -120.0000 110

  5 omega   36.00   84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8092 -125.0000 -180.0000 48

  6 omega   42.00   94.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000 -120.0000 52

  7 omega  113.00  139.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000  -90.0000 26

  8 omega   84.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000  -60.0000 31

  9 omega   73.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000 -150.0000 43

 10 omega   54.00   96.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000  -90.0000 42

 11 omega   62.00  111.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000    0.0000 49

 12 omega   92.00  143.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000   60.0000 51

 13 omega  117.00  143.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000  120.0000 26

 14 omega   94.00  156.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000   90.0000 62

 15 omega  139.00  172.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000    0.0000 33

 16 omega  122.00  148.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  178.0000  -90.0000 26

 17 omega   80.00  124.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000    0.0000 44

 18 omega   88.00  138.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   90.0000 50

 19 omega   56.00   84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   90.0000 28

 20 omega   44.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000   30.0000 47

 21 omega   46.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000  120.0000 70

 22 omega   49.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   60.0000 67

 23 omega   40.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000  120.0000 26

 24 omega   35.00   77.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000  150.0000 42

 25 omega   29.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000   60.0000 62

 26 omega   36.00   82.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  -90.0000 46

 27 omega   36.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000 -120.0000 79

 28 omega   37.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  -90.0000 53

 29 omega   59.00   88.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   15.0000 -150.0000 29

 30 omega  125.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   15.0000 -150.0000 52

 31 omega   54.00  175.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   15.0000  -30.0000 121

 32 omega   58.00  100.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  178.0000  -90.0000 42

 33 omega -120.00  -10.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8092  -77.0000    0.0000 110
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0021138000
_diffrn_orient_matrix_UB_12      -0.1395696000
_diffrn_orient_matrix_UB_13      -0.0490297000
_diffrn_orient_matrix_UB_21      -0.0648277000
_diffrn_orient_matrix_UB_22      0.0913686000
_diffrn_orient_matrix_UB_23      -0.0302845000
_diffrn_orient_matrix_UB_31      0.0532189000
_diffrn_orient_matrix_UB_32      0.1166962000
_diffrn_orient_matrix_UB_33      -0.0348443000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0412
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            31230
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.127
_diffrn_reflns_theta_min         3.866
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.501
_exptl_absorpt_correction_T_max  0.589
_exptl_absorpt_correction_T_min  0.155
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
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_exptl_crystal_description       plate
_exptl_crystal_F_000             1608
_exptl_crystal_recrystallization_method
'Recrystallised from diethyl ether/hexane'
_exptl_crystal_size_max          0.542
_exptl_crystal_size_mid          0.4338
_exptl_crystal_size_min          0.1222
_refine_diff_density_max         0.426
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.069
_refine_ls_extinction_coef       0.00023(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         3358
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0231
_refine_ls_R_factor_gt           0.0227
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0317P)^2^+2.1238P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0596
_refine_ls_wR_factor_ref         0.0600
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3308
_reflns_number_total             3358
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_013.cif
_cod_data_source_block           br4spiroh4-2et2o
_cod_original_cell_volume        3178.56(5)
_cod_database_code               4135050
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H30 O5 Br4'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C1S(H1SA,H1SB), C3S(H3SA,H3SB)
2.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C4S(H4SA,H4SB,H4SC), C2S(H2SA,H2SB,H2SC)
2.c Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2)
;
_shelx_res_checksum              27457
_shelx_hkl_checksum              3205
_olex2_submission_special_instructions 'No special instructions were received'