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_4135056
_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 N8 O4 Zn2, F6 P1'
_chemical_formula_sum            'C77 H80 Br4 F6 N8 O4 P Zn2'
_chemical_formula_weight         1776.84
_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-zinc(II) hexafluorophosphate toluene solvate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.12(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.821(4)
_cell_length_b                   23.729(5)
_cell_length_c                   15.968(3)
_cell_measurement_reflns_used    1226
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.664
_cell_measurement_theta_min      0.407
_cell_volume                     7579(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 0.981
_diffrn_measured_fraction_theta_max 0.981
_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     0.710756
_diffrn_reflns_av_R_equivalents  0.1060
_diffrn_reflns_av_unetI/netI     0.0574
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            87262
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         1.331
_diffrn_source                   'MX2 Beamline Australian Synchrotron'
_diffrn_source_type              Synchrotron
_exptl_absorpt_coefficient_mu    2.832
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.5093
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
'SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1696 before and 0.0557 after correction. 
The Ratio of minimum to maximum transmission is 0.6823. 
The \l/2 correction factor is 0.0015.'
;
_exptl_crystal_colour            'light green'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.557
_exptl_crystal_description       needle
_exptl_crystal_F_000             3596
_exptl_crystal_recrystallization_method 'Crystallised from acetone/toluene'
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.005
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.967
_refine_diff_density_min         -0.822
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.927
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     826
_refine_ls_number_reflns         13624
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      0.928
_refine_ls_R_factor_all          0.0995
_refine_ls_R_factor_gt           0.0725
_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^)+(0.1511P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2032
_refine_ls_wR_factor_ref         0.2281
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8182
_reflns_number_total             13624
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_009.cif
_cod_data_source_block           5a-2tol
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4135056
_shelx_shelxl_version_number     2018/3
_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
 P1-F1 = P1-F2 = P1-F3 = P1-F4 = P1-F5 = P1-F6
 1.6 with sigma of 0.001
 F1-F2 = F1-F3 = F1-F4 = F1-F5 = F6-F2 = F6-F3 = F6-F4 = F6-F5
 2.26263 with sigma of 0.001
 F2-F3 = F3-F4 = F4-F5 = F5-F2
 2.26263 with sigma of 0.001
 P1A-F1A = P1A-F2A = P1A-F3A = P1A-F4A = P1A-F5A = P1A-F6A
 1.6 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-F4A = F4A-F5A = F5A-F2A
 2.26263 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
Uanis(C34) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq: with sigma of 0.04 and
sigma for terminal atoms of 0.08
Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C60)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C18) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C6)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(P1) = Uanis(P1A)
Uanis(F1) = Uanis(F1A)
Uanis(F2) = Uanis(F2A)
Uanis(F3) = Uanis(F3A)
Uanis(F4) = Uanis(F4A)
Uanis(F5) = Uanis(F5A)
Uanis(F6) = Uanis(F6A)
4. Others
 Sof(P1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(1)
 Sof(P1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C21(H21A,H21B), C27(H27A,H27B), C33(H33A,H33B), C39(H39A,
 H39B), C45(H45A,H45B), C51(H51A,H51B), C57(H57A,H57B)
5.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C24(H24), C25(H25), C29(H29), C30(H30), C31(H31), C35(H35),
 C36(H36), C37(H37), C41(H41), C42(H42), C43(H43), C47(H47), C48(H48), C49(H49),
  C53(H53), C54(H54), C55(H55)
5.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,H61B,
 H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C)
;
_shelx_res_checksum              58616
_shelx_hkl_checksum              9013
_shelx_fab_checksum              97859
_olex2_exptl_crystal_mounting_method 'Mounted on loop with cryoprotectant oil'
_olex2_submission_special_instructions 'No special instructions were received'