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_4135049
_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         'C61 H60 Br4 Co2 N8 O4, 2(F6 P), 2(C4 H8 O2)'
_chemical_formula_sum            'C79 H96 Br4 Co2 F12 N8 O13 P2'
_chemical_formula_weight         2093.07
_chemical_name_systematic
'(mu2-3,3,3',3'-tetramethyl-1,1'-spirobi(indan)-4,4'-7,7'-tetrabromo-5,5'-6,6'-tetraolato)-bis(bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine)-di-cobalt(III) bis(hexafluorophosphate) 1,4-dioxane solvate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           45
_space_group_name_Hall           'I 2 -2c'
_space_group_name_H-M_alt        'I b a 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-25
_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                   17.948(4)
_cell_length_b                   20.058(4)
_cell_length_c                   22.915(5)
_cell_measurement_reflns_used    8370
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.670
_cell_measurement_theta_min      0.407
_cell_volume                     8249(3)
_computing_cell_refinement       'XDS (Kabsch, 1993)'
_computing_data_collection       'BluIce (McPhillips, 2002)'
_computing_data_reduction        'XDS (Kabsch, 1993)'
_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      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'ADSC Quantum 210r'
_diffrn_measurement_method       'Phi Scan'
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.710900
_diffrn_reflns_av_R_equivalents  0.1375
_diffrn_reflns_av_unetI/netI     0.0738
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            48401
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         1.522
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_diffrn_source_type              Synchrotron
_exptl_absorpt_coefficient_mu    2.473
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.4681
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
'SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1168 before and 0.0930 after correction. 
The Ratio of minimum to maximum transmission is 0.6273. 
The \l/2 correction factor is 0.0015.'
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.685
_exptl_crystal_description       block
_exptl_crystal_F_000             4248
_exptl_crystal_recrystallization_method
'Crystallised from dichloromethane/1,4-dioxane'
_exptl_crystal_size_max          0.091
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.043
_refine_diff_density_max         1.026
_refine_diff_density_min         -1.268
_refine_diff_density_rms         0.144
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.100(19)
_refine_ls_extinction_coef       0.0022(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     482
_refine_ls_number_reflns         7484
_refine_ls_number_restraints     107
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0732
_refine_ls_R_factor_gt           0.0669
_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^)+(0.1261P)^2^+11.2696P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1715
_refine_ls_wR_factor_ref         0.1795
_reflns_Friedel_coverage         0.944
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                6688
_reflns_number_total             7484
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_006.cif
_cod_data_source_block           3a-4p5dioxane
_cod_database_code               4135049
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.900(19)
 0.100(19)
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
 C2S-C1S
 1.496 with sigma of 0.005
 C3S-C4S
 1.496 with sigma of 0.005
 O2S-C3S
 1.428 with sigma of 0.005
 O2S-C2S
 1.428 with sigma of 0.005
 C1S-O1S
 1.428 with sigma of 0.005
 C4S-O1S
 1.428 with sigma of 0.005
 C28-C29
 1.52 with sigma of 0.02
 C1S-C4S = C2S-C3S
 2.32529 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C19 \\sim C20 \\sim C21: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04
C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C31) \\sim Ueq: with sigma of 0.04 and sigma for terminal atoms of 0.08
5. Others
 1*[Sof(H12)+Sof(C30)+Sof(H30A)+Sof(H30B)+Sof(H30C)]+1*[Sof(H24)+Sof(C32)+
 Sof(H32A)+Sof(H32B)+Sof(H32C)]+1*[Sof(H18)+Sof(C31)+Sof(H31A)+Sof(H31B)+
 Sof(H31C)]=1 with esd of 0.00001
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(2)
 Sof(H12)=FVAR(2)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=1-FVAR(3)
 Sof(H24)=FVAR(3)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=1-FVAR(4)
 Sof(H18)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C17(H17A,H17B), C29(H29A,H29B), C23(H23A,H23B), C1S(H1SA,
 H1SB), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB)
6.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C26(H26), C25(H25), C24(H24), C12(H12), C13(H13), C14(H14),
 C15(H15), C18(H18), C19(H19), C20(H20), C21(H21)
6.c Fitted hexagon refined as free rotating group:
 N4(C28,C27,C26,C25,C24)
6.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C),
 C31(H31A,H31B,H31C)
;
_shelx_res_checksum              91043
_shelx_hkl_checksum              9566
_shelx_fab_checksum              42462
_olex2_exptl_crystal_mounting_method 'Mounted on loop with cryoprotectant oil'
_olex2_submission_special_instructions 'No special instructions were received'