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_4135054
_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(Cl1 O4), 3.86(C3 H6 O)'
_chemical_formula_sum            'C68.58 H75.16 Br4 Cl2 Co2 N8 O15.86'
_chemical_formula_weight         1773.64
_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(perchlorate) acetone solvate'
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                111.532(2)
_cell_angle_beta                 90.341(2)
_cell_angle_gamma                109.649(3)
_cell_formula_units_Z            2
_cell_length_a                   13.4672(4)
_cell_length_b                   15.7188(4)
_cell_length_c                   20.5224(5)
_cell_measurement_reflns_used    18131
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      74.2090
_cell_measurement_theta_min      3.9010
_cell_volume                     3764.1(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      130.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_details
;
  1 omega  -10.00   46.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -38.2063   37.0000   30.0000 56

  2 omega   84.00  125.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063   19.0000  -60.0000 41

  3 omega   69.00   95.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -45.0000    0.0000 26

  4 omega   58.00  109.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -94.0000    0.0000 51

  5 omega   60.00  115.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125 -111.0000  -60.0000 55

  6 omega   90.00  115.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125 -111.0000 -120.0000 25

  7 omega   59.00   84.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -30.0000 -120.0000 25

  8 omega   36.00   98.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -45.0000  -30.0000 62

  9 omega   42.00   90.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -30.0000   90.0000 48

 10 omega   54.00   90.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -30.0000  150.0000 36

 11 omega   51.00   76.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -30.0000  120.0000 25

 12 omega   34.00  113.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125 -111.0000  120.0000 79

 13 omega   64.00  100.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063 -125.0000  -30.0000 36

 14 omega   64.00   99.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063 -125.0000   60.0000 35

 15 omega   30.00   55.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063 -125.0000  -30.0000 25

 16 omega   23.00   75.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063 -125.0000    0.0000 52

 17 omega    4.00   82.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063  -99.0000   60.0000 78

 18 omega    4.00   30.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063  -99.0000   30.0000 26

 19 omega   29.00   56.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125 -111.0000 -120.0000 27

 20 omega   36.00   96.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -45.0000  -90.0000 60

 21 omega  113.00  142.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125   45.0000  -60.0000 29

 22 omega  121.00  173.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125   61.0000  -90.0000 52

 23 omega   83.00  109.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125   61.0000  -90.0000 26

 24 omega   78.00  103.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125   45.0000  -60.0000 25

 25 omega   26.00   53.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063   19.0000  -60.0000 27

 26 omega    2.00  120.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063   57.0000  -90.0000 118

 27 omega   27.00   55.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -30.0000 -120.0000 28

 28 omega   21.00  171.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125    0.0000  -90.0000 150

 29 omega   76.00  101.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063   19.0000  120.0000 25

 30 omega   33.00   58.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063   19.0000  120.0000 25

 31 omega    8.00  118.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063   37.0000  150.0000 110

 32 omega   21.00  145.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125  -77.0000  120.0000 124

 33 omega   27.00   86.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      112.4125 -111.0000  -30.0000 59

 34 omega   38.00   64.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.2063 -125.0000 -180.0000 26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0946653000
_diffrn_orient_matrix_UB_12      -0.0323901000
_diffrn_orient_matrix_UB_13      -0.0228955000
_diffrn_orient_matrix_UB_21      -0.0639131000
_diffrn_orient_matrix_UB_22      -0.0667911000
_diffrn_orient_matrix_UB_23      -0.0743777000
_diffrn_orient_matrix_UB_31      0.0451286000
_diffrn_orient_matrix_UB_32      0.0853491000
_diffrn_orient_matrix_UB_33      -0.0245209000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0220
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29829
_diffrn_reflns_point_group_measured_fraction_full 0.613
_diffrn_reflns_point_group_measured_fraction_max 0.588
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.836
_diffrn_reflns_theta_min         3.523
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.168
_exptl_absorpt_correction_T_max  0.576
_exptl_absorpt_correction_T_min  0.233
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.565
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1795
_exptl_crystal_recrystallization_method
'Crystallised from acetone/cyclohexane'
_exptl_crystal_size_max          0.3082
_exptl_crystal_size_mid          0.1554
_exptl_crystal_size_min          0.0991
_refine_diff_density_max         0.890
_refine_diff_density_min         -0.553
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.482(4)
_refine_ls_extinction_coef       0.00020(4)
_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   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1894
_refine_ls_number_reflns         18197
_refine_ls_number_restraints     156
_refine_ls_restrained_S_all      81.750
_refine_ls_R_factor_all          0.0401
_refine_ls_R_factor_gt           0.0371
_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^)+(0.0634P)^2^+2.1674P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0958
_refine_ls_wR_factor_ref         0.0980
_reflns_Friedel_coverage         0.220
_reflns_Friedel_fraction_full    0.233
_reflns_Friedel_fraction_max     0.212
_reflns_number_gt                17074
_reflns_number_total             18197
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_003.cif
_cod_data_source_block           2b-pd-3p9acetone
_cod_original_cell_volume        3764.12(19)
_cod_database_code               4135054
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C135 H146 Br8 Cl4 Co4 N16 O31'
_chemical_oxdiff_usercomment     '[Co2(tpa)2(Br4spiro)](ClO4)2 green rod 130K'
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.518(4)
 0.482(4)
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
 C12S-C10S
 2.55 with sigma of 0.001
 C11S-C12S = C11S-C10S
 1.48 with sigma of 0.001
 O4S-C12S = O4S-C10S
 2.33 with sigma of 0.001
 C11S-O4S
 1.2 with sigma of 0.001
 C5S-O2S
 1.2 with sigma of 0.001
 C4S-C6S
 2.55 with sigma of 0.001
 C5S-C4S = C5S-C6S
 1.48 with sigma of 0.001
 Cl3-O14 = Cl3-O13 = Cl3-O16 = Cl3-O15
 1.44 with sigma of 0.001
 O14-O13 = O14-O16 = O14-O15 = O13-O16 = O13-O15 = O16-O15
 2.35074 with sigma of 0.001
 Cl1-O7 = Cl1-O5 = Cl1-O8 = Cl1-O6
 1.44 with sigma of 0.001
 O7-O5 = O7-O8 = O7-O6 = O5-O8 = O5-O6 = O8-O6
 2.35074 with sigma of 0.001
 Cl1A-O7A = Cl1A-O6A = Cl1A-O5A = Cl1A-O8A
 1.44 with sigma of 0.001
 O7A-O6A = O7A-O5A = O7A-O8A = O6A-O5A = O6A-O8A = O5A-O8A
 2.35074 with sigma of 0.001
 O3S-O8A_$1
 -3 with sigma of 0.001
 Cl2-O11
 1.47 with sigma of 0.002
 O12-O9 = O12-O10 = O12-O11 = O9-O10 = O9-O11 = O10-O11
 2.35074 with sigma of 0.001
 Cl2-O12 = Cl2-O9 = Cl2-O10 = Cl3-O11
 1.44 with sigma of 0.001
4. Restrained planarity
 O4S, C10S, C11S, C12S
 with sigma of 0.005
 O2S, C4S, C5S, C6S
 with sigma of 0.005
5. Uiso/Uaniso restraints and constraints
Uanis(C11S) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O4S) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(O8S) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C5S) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C4S) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O2S) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C6S) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O19A) \\sim Ueq, Uanis(O20A) \\sim Ueq, Uanis(O18A) \\sim Ueq: with sigma
of 0.003 and sigma for terminal atoms of 0.006
Uanis(O12) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C12S) = Uanis(C10S)
Uanis(O4S) = Uanis(C11S) = Uanis(C12S) = Uanis(C10S)
Uanis(O8S) = Uanis(C23S) = Uanis(C22S) = Uanis(C24S)
Uanis(O2S) = Uanis(O2SA)
Uanis(C4S) = Uanis(C4SA)
Uanis(C5S) = Uanis(C5SA)
Uanis(C6S) = Uanis(C6SA)
Uanis(Cl3) = Uanis(Cl3A)
Uanis(O14) = Uanis(O14A)
Uanis(O13) = Uanis(O13A)
Uanis(O16) = Uanis(O16A)
Uanis(O15) = Uanis(O15A)
Uanis(O17) = Uanis(O17A)
Uanis(O19) = Uanis(O19A)
Uanis(O20) = Uanis(O20A)
Uanis(O18) = Uanis(O18A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(O5) = Uanis(O5A)
Uanis(O6) = Uanis(O6A)
Uanis(O7) = Uanis(O7A)
Uanis(O8) = Uanis(O8A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(O12) = Uanis(O12A)
Uanis(O9) = Uanis(O9A)
Uanis(O10) = Uanis(O10A)
Uanis(O11) = Uanis(O11A)
6. Same fragment restrains
{Cl2, O9, O10, O11, O12} sigma for 1-2: 0.02, 1-3: 0.04
as
{Cl2A, O9A, O10A, O11A, O12A}
{Cl3, O13, O14, O15, O16} sigma for 1-2: 0.02, 1-3: 0.04
as
{Cl3A, O13A, O14A, O15A, O16A}
{O2S, C4S, C5S, C6S} sigma for 1-2: 0.01, 1-3: 0.04
as
{O2SA, C4SA, C5SA, C6SA}
7. Others
 Sof(Cl2A)=Sof(O9A)=Sof(O10A)=Sof(O11A)=Sof(O12A)=1-FVAR(1)
 Sof(Cl2)=Sof(O9)=Sof(O10)=Sof(O11)=Sof(O12)=FVAR(1)
 Sof(Cl4A)=Sof(O17A)=Sof(O18A)=Sof(O19A)=Sof(O20A)=1-FVAR(2)
 Sof(Cl4)=Sof(O17)=Sof(O18)=Sof(O19)=Sof(O20)=Sof(O8S)=Sof(C22S)=Sof(H22C)=
 Sof(H22D)=Sof(H22E)=Sof(C23S)=Sof(C24S)=Sof(H24C)=Sof(H24D)=Sof(H24E)=FVAR(2)
 Sof(Cl3A)=Sof(O13A)=Sof(O14A)=Sof(O15A)=Sof(O16A)=1-FVAR(3)
 Sof(Cl3)=Sof(O13)=Sof(O14)=Sof(O15)=Sof(O16)=FVAR(3)
 Sof(Cl1A)=Sof(O5A)=Sof(O6A)=Sof(O7A)=Sof(O8A)=1-FVAR(4)
 Sof(Cl1)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(O8)=FVAR(4)
 Sof(O2SA)=Sof(C4SA)=Sof(H4SD)=Sof(H4SE)=Sof(H4SF)=Sof(C5SA)=Sof(C6SA)=
 Sof(H6SD)=Sof(H6SE)=Sof(H6SF)=1-FVAR(5)
 Sof(O2S)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(H4SC)=Sof(C5S)=Sof(C6S)=Sof(H6SA)=
 Sof(H6SB)=Sof(H6SC)=FVAR(5)
8.a Secondary CH2 refined with riding coordinates:
 C10A(H10A,H10B), C21A(H21A,H21B), C27A(H27A,H27B), C33A(H33A,H33B), C39A(H39A,
 H39B), C45A(H45A,H45B), C51A(H51A,H51B), C57A(H57A,H57B), C10B(H10C,H10D),
 C21B(H21C,H21D), C27B(H27C,H27D), C33B(H33C,H33D), C39B(H39C,H39D), C45B(H45C,
 H45D), C51B(H51C,H51D), C57B(H57C,H57D)
8.b Aromatic/amide H refined with riding coordinates:
 C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A), C28A(H28A), C29A(H29A),
 C30A(H30A), C31A(H31A), C34A(H34A), C35A(H35A), C36A(H36A), C37A(H37A),
 C40A(H40A), C41A(H41A), C42A(H42A), C43A(H43A), C46A(H46A), C47A(H47A),
 C48A(H48A), C49A(H49A), C52A(H52A), C53A(H53A), C54A(H54A), C55A(H55A),
 C22B(H22B), C23B(H23B), C24B(H24B), C25B(H25B), C28B(H28B), C29B(H29B),
 C30B(H30B), C31B(H31B), C34B(H34B), C35B(H35B), C36B(H36B), C37B(H37B),
 C40B(H40B), C41B(H41B), C42B(H42B), C43B(H43B), C46B(H46B), C47B(H47B),
 C48B(H48B), C49B(H49B), C52B(H52B), C53B(H53B), C54B(H54B), C55B(H55B)
8.c Idealised Me refined as rotating group:
 C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C19A(H19A,H19B,H19C), C20A(H20A,
 H20B,H20C), C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC), C19B(H19D,H19E,H19F),
 C20B(H20D,H20E,H20F), C1S(H1SA,H1SB,H1SC), C3S(H3SA,H3SB,H3SC), C4S(H4SA,H4SB,
 H4SC), C6S(H6SA,H6SB,H6SC), C4SA(H4SD,H4SE,H4SF), C6SA(H6SD,H6SE,H6SF),
 C7S(H7SA,H7SB,H7SC), C9S(H9SA,H9SB,H9SC), C10S(H10E,H10F,H10G), C12S(H12A,H12B,
 H12C), C13S(H13A,H13B,H13C), C15S(H15A,H15B,H15C), C16S(H16A,H16B,H16C),
 C18S(H18A,H18B,H18C), C19S(H19G,H19H,H19I), C21S(H21E,H21F,H21G), C22S(H22C,
 H22D,H22E), C24S(H24C,H24D,H24E)
;
_shelx_res_checksum              52692
_shelx_hkl_checksum              12555
_olex2_exptl_crystal_mounting_method 'Mounted on loop with cryoprotectant oil'
_olex2_submission_special_instructions 'No special instructions were received'