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_4135052
_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            'C68 H79 Br4 Co2 F12 N8 O6.5 P2'
_chemical_formula_weight         1839.83
_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                   26.0671(3)
_cell_length_b                   14.5259(2)
_cell_length_c                   20.4819(3)
_cell_measurement_reflns_used    18475
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      75.9260
_cell_measurement_theta_min      2.7440
_cell_volume                     7755.43(18)
_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      200.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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     54.00  80.00   0.50    4.79    --   48.30  74.00  81.00   52
  2  \w     89.00 176.00   0.50   24.00    --  107.75  74.00  81.00  174
  3  \w     97.00 167.00   0.50   24.00    --  107.75  15.00  90.00  140
  4  \w     97.00 155.00   0.50   24.00    --  107.75  15.00  60.00  116
  5  \w     91.00 177.00   0.50   24.00    --  107.75  77.00  90.00  172
  6  \w     90.00 115.00   0.50   24.00    --  107.75  77.00 -90.00   50
  7  \w    130.00 155.00   0.50   24.00    --  107.75  77.00 -90.00   50
  8  \w     97.00 171.00   0.50   24.00    --  107.75  15.00-180.00  148
  9  \w     83.00 108.00   0.50   24.00    --  107.75 -94.00  60.00   50
 10  \w     62.00  88.00   0.50   24.00    --  107.75 -63.00  79.00   52
 11  \w     36.00 105.00   0.50   24.00    --  107.75 -94.00 150.00  138
 12  \w     31.00  92.00   0.50    4.79    --   48.30-125.00  60.00  122
 13  \w     42.00  71.00   0.50   24.00    --  107.75 -30.00 -60.00   58
 14  \w     55.00  83.00   0.50   24.00    --  107.75 -61.00 -90.00   56
 15  \w     45.00  87.00   0.50   24.00    --  107.75 -87.00-152.00   84
 16  \w     47.00  72.00   0.50   24.00    --  107.75 -45.00-180.00   50
 17  \w     39.00  97.00   0.50   24.00    --  107.75 -94.00-180.00  116
 18  \w     47.00 117.00   0.50   24.00    --  107.75 -15.00 -90.00  140
 19  \w     39.00 107.00   0.50   24.00    --  107.75 -94.00 -60.00  136
 20  \w     43.00  70.00   0.50   24.00    --  107.75 -30.00 -30.00   54
 21  \w    -58.00  26.00   0.50    4.79    --  -48.30  19.00  30.00  168
 22  \w   -105.00 -74.00   0.50    4.79    --  -48.30-125.00-120.00   62
 23  \w   -141.00-116.00   0.50   24.00    --  -86.25 -87.00-152.00   50
 24  \w   -119.00 -71.00   0.50    4.79    --  -48.30-125.00  90.00   96
 25  \w   -111.00 -82.00   0.50    4.79    --  -48.30-125.00 120.00   58
;
_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      0.0365101000
_diffrn_orient_matrix_UB_12      -0.0061203000
_diffrn_orient_matrix_UB_13      0.0589616000
_diffrn_orient_matrix_UB_21      -0.0226470000
_diffrn_orient_matrix_UB_22      -0.0947000000
_diffrn_orient_matrix_UB_23      0.0178501000
_diffrn_orient_matrix_UB_31      0.0405692000
_diffrn_orient_matrix_UB_32      -0.0474803000
_diffrn_orient_matrix_UB_33      -0.0431034000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0574
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            64622
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.130
_diffrn_reflns_theta_min         2.744
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.873
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.232
_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    1.576
_exptl_crystal_description       prism
_exptl_crystal_F_000             3708
_exptl_crystal_recrystallization_method 'Crystallised from ethanol'
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.031
_refine_diff_density_max         1.246
_refine_diff_density_min         -1.282
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     480
_refine_ls_number_reflns         8248
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.1021
_refine_ls_R_factor_gt           0.0869
_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^)+(0.1555P)^2^+6.6562P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2723
_refine_ls_wR_factor_ref         0.2926
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6054
_reflns_number_total             8248
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_010.cif
_cod_data_source_block           4a-2p5EtOH-200K
_cod_original_formula_sum        'C68 H79 Br4 Co2 F12 N8 O6.50 P2'
_cod_database_code               4135052
_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   0.815
_shelx_estimated_absorpt_t_min   0.224
_reflns_odcompleteness_completeness 99.85
_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
 2.26263 with sigma of 0.001
 F6-F2 = F6-F3 = F6-F4 = F6-F5
 2.26263 with sigma of 0.001
 F2-F3 = F3-F5 = F5-F4 = F4-F2
 2.26263 with sigma of 0.001
 F1A-F2A = F1A-F3A = F1A-F4A = F1A-F5A
 2.26263 with sigma of 0.001
 F6A-F2A = F6A-F3A = F6A-F4A = F6A-F5A
 2.26263 with sigma of 0.001
 F2A-F3A = F3A-F5A = F5A-F4A = F4A-F2A
 2.26263 with sigma of 0.001
 F1B-F2B = F1B-F3B = F1B-F4B = F1B-F5B
 2.26263 with sigma of 0.001
 F6B-F2B = F6B-F3B = F6B-F4B = F6B-F5B
 2.26263 with sigma of 0.001
 F2B-F3B = F3B-F5B = F5B-F4B = F4B-F2B
 2.26263 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, Uanis(C9) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
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              20008
_shelx_hkl_checksum              95698
_shelx_fab_checksum              37384
_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 2.152
_oxdiff_exptl_absorpt_empirical_full_min 0.570