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_4135055
_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            'C69 H82 Br4 Co2 F12 N8 O7 P2'
_chemical_formula_weight         1862.86
_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             2019-01-24
_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                   26.0240(3)
_cell_length_b                   14.43890(10)
_cell_length_c                   20.3551(2)
_cell_measurement_reflns_used    16188
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.2710
_cell_measurement_theta_min      2.7490
_cell_volume                     7648.59(13)
_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      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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    -61.00  21.00   0.50    3.59    --  -48.30  87.00 -36.00  164
  2  \w   -116.00 -39.00   0.50    3.59    --  -48.30 -38.00-180.00  154
  3  \w   -114.00 -71.00   0.50    3.59    --  -48.30-125.00   0.00   86
  4  \w   -129.00 -69.00   0.50   15.00    --  -86.25 -66.00  81.00  120
  5  \w     99.00 177.00   0.50   15.00    --  107.75  87.00 -36.00  156
  6  \w     97.00 178.00   0.50   15.00    --  107.75  45.00   0.00  162
  7  \w     98.00 126.00   0.50   15.00    --  107.75 -70.00 -48.00   56
  8  \w    100.00 177.00   0.50   15.00    --  107.75  30.00 -90.00  154
  9  \w     87.00 175.00   0.50   15.00    --  107.75  77.00 -90.00  176
 10  \w     93.00 178.00   0.50   15.00    --  107.75  61.00 -60.00  170
 11  \w     39.00  80.00   0.50   15.00    --  107.75 -70.00 -48.00   82
 12  \w     38.00 124.00   0.50   15.00    --  107.75 -66.00  81.00  172
 13  \w     38.00  74.00   0.50   15.00    --  107.75 -45.00 120.00   72
;
_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      -0.0383255000
_diffrn_orient_matrix_UB_12      -0.0089436000
_diffrn_orient_matrix_UB_13      -0.0573275000
_diffrn_orient_matrix_UB_21      0.0230756000
_diffrn_orient_matrix_UB_22      -0.0950422000
_diffrn_orient_matrix_UB_23      -0.0176823000
_diffrn_orient_matrix_UB_31      -0.0388184000
_diffrn_orient_matrix_UB_32      -0.0475976000
_diffrn_orient_matrix_UB_33      0.0461028000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0358
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            46089
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.997
_diffrn_reflns_theta_min         2.756
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.982
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.258
_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    1.618
_exptl_crystal_description       prism
_exptl_crystal_F_000             3760
_exptl_crystal_recrystallization_method 'Crystallised from toluene'
_exptl_crystal_size_max          0.318
_exptl_crystal_size_mid          0.099
_exptl_crystal_size_min          0.045
_refine_diff_density_max         2.709
_refine_diff_density_min         -2.842
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     480
_refine_ls_number_reflns         8071
_refine_ls_number_restraints     121
_refine_ls_restrained_S_all      1.149
_refine_ls_R_factor_all          0.1236
_refine_ls_R_factor_gt           0.1097
_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^)+(0.1318P)^2^+33.8845P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3012
_refine_ls_wR_factor_ref         0.3139
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6500
_reflns_number_total             8071
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_012.cif
_cod_data_source_block           4a-3EtOH-150K
_cod_database_code               4135055
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C63 H64 Br4 Co2 N8 O4 P2 F12'
_chemical_oxdiff_usercomment     'dark green prism crystals from EtOH'
_shelx_estimated_absorpt_t_max   0.744
_shelx_estimated_absorpt_t_min   0.215
_reflns_odcompleteness_completeness 99.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_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
 2.2627 with sigma of 0.001
 F6-F2 = F6-F3 = F6-F4 = F6-F5
 2.2627 with sigma of 0.001
 F2-F3 = F3-F5 = F5-F4 = F4-F2
 2.2627 with sigma of 0.001
 F1A-F2A = F1A-F3A = F1A-F4A = F1A-F5A
 2.2627 with sigma of 0.001
 F6A-F2A = F6A-F3A = F6A-F4A = F6A-F5A
 2.2627 with sigma of 0.001
 F2A-F3A = F3A-F5A = F5A-F4A = F4A-F2A
 2.2627 with sigma of 0.001
 F1B-F2B = F1B-F3B = F1B-F4B = F1B-F5B
 2.2627 with sigma of 0.001
 F6B-F2B = F6B-F3B = F6B-F4B = F6B-F5B
 2.2627 with sigma of 0.001
 F2B-F3B = F3B-F5B = F5B-F4B = F4B-F2B
 2.2627 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
 P1B-F1B = P1B-F2B = P1B-F3B = P1B-F4B = P1B-F5B = P1B-F6B
 1.6 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of
0.02 and sigma for terminal atoms of 0.04
Uanis(C7) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of
0.02 and sigma for terminal atoms of 0.04
Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(F1) = Uanis(F1A) = Uanis(F1B)
Uanis(F2) = Uanis(F2A) = Uanis(F2B)
Uanis(F3) = Uanis(F3A) = Uanis(F3B)
Uanis(F4) = Uanis(F4A) = Uanis(F4B)
Uanis(F5) = Uanis(F5A) = Uanis(F5B)
Uanis(F6) = Uanis(F6A) = Uanis(F6B)
Uanis(P1) = Uanis(P1A) = Uanis(P1B)
4. Others
 1*[Sof(P1)+Sof(F1)+Sof(F2)+Sof(F3)+Sof(F4)+Sof(F5)+Sof(F6)]+1*[Sof(P1A)+
 Sof(F1A)+Sof(F2A)+Sof(F3A)+Sof(F4A)+Sof(F5A)+Sof(F6A)]+1*[Sof(P1B)+Sof(F1B)+
 Sof(F2B)+Sof(F3B)+Sof(F4B)+Sof(F5B)+Sof(F6B)]=1 with esd of 0.0001
 Sof(P1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Sof(P1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(2)
 Sof(P1B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=FVAR(3)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C17(H17A,H17B), C23(H23A,H23B), C29(H29A,H29B)
5.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)
5.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              24451
_shelx_hkl_checksum              62867
_shelx_fab_checksum              46373
_olex2_exptl_crystal_mounting_method
'Mounted on MiTeGen mount in 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 1.661
_oxdiff_exptl_absorpt_empirical_full_min 0.629