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_4135058
_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(Cl O4)'
_chemical_formula_sum            'C78 H94 Br4 Cl2 Co2 N8 O19'
_chemical_formula_weight         1956.01
_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           2
_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             2019-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                84.20(3)
_cell_angle_beta                 81.18(3)
_cell_angle_gamma                89.83(3)
_cell_formula_units_Z            4
_cell_length_a                   17.127(3)
_cell_length_b                   19.360(4)
_cell_length_c                   25.008(5)
_cell_measurement_reflns_used    1692
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.885
_cell_measurement_theta_min      0.407
_cell_volume                     8151(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 0.930
_diffrn_measured_fraction_theta_max 0.917
_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  0.0985
_diffrn_reflns_av_unetI/netI     0.0774
_diffrn_reflns_Laue_measured_fraction_full 0.930
_diffrn_reflns_Laue_measured_fraction_max 0.917
_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       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            121942
_diffrn_reflns_point_group_measured_fraction_full 0.930
_diffrn_reflns_point_group_measured_fraction_max 0.917
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.420
_diffrn_reflns_theta_min         0.828
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_diffrn_source_type              Synchrotron
_exptl_absorpt_coefficient_mu    2.508
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.4869
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
'SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0987 before and 0.0634 after correction. 
The Ratio of minimum to maximum transmission is 0.6532. 
The \l/2 correction factor is 0.0015.'
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.594
_exptl_crystal_description       plate
_exptl_crystal_F_000             3992
_exptl_crystal_recrystallization_method 'Crystallised from acetone/hexane'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.570
_refine_diff_density_min         -0.752
_refine_diff_density_rms         0.142
_refine_ls_extinction_coef       0.00427(18)
_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   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1587
_refine_ls_number_reflns         30741
_refine_ls_number_restraints     58
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.1021
_refine_ls_R_factor_gt           0.0681
_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^)+(0.1187P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1815
_refine_ls_wR_factor_ref         0.1996
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19370
_reflns_number_total             30741
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_005.cif
_cod_data_source_block           2b-pp-7acetone
_cod_database_code               4135058
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.885
_shelx_estimated_absorpt_t_min   0.753
_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
 Cl1C-O1C = Cl1C-O2C = Cl1C-O3C = Cl1C-O4C
 1.42062 with sigma of 0.001
 O1C-O2C = O1C-O3C = O1C-O4C = O2C-O3C = O2C-O4C = O3C-O4C
 2.319872 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
O1C \\sim O2C \\sim O3C \\sim O4C: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O3C) \\sim Ueq, Uanis(O4C) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(Cl1C)=Sof(O1C)=Sof(O2C)=Sof(O3C)=Sof(O4C)=1-FVAR(1)
 Sof(Cl1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=FVAR(1)
 1(DFIX)=FVAR(2)
 1(DFIX)=1.633*FVAR(3)
5.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)
5.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)
5.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)
;
_shelx_res_checksum              45921
_shelx_hkl_checksum              52227
_shelx_fab_checksum              74581
_olex2_exptl_crystal_mounting_method 'Mounted on loop in cryoprotectant oil'
_olex2_submission_special_instructions 'No special instructions were received'