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_4135051
_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, 18.25(F0.66 P0.11)'
_chemical_formula_sum            'C70 H72 Br4 F12 N8 O4 P2 Zn2'
_chemical_formula_weight         1829.67
_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) bis(hexafluorophosphate) toluene 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             2019-01-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                84.25(3)
_cell_angle_beta                 87.61(3)
_cell_angle_gamma                79.98(3)
_cell_formula_units_Z            2
_cell_length_a                   9.4740(19)
_cell_length_b                   16.711(3)
_cell_length_c                   24.172(5)
_cell_measurement_reflns_used    1065
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.664
_cell_measurement_theta_min      0.407
_cell_volume                     3748.4(13)
_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 0.938
_diffrn_measured_fraction_theta_max 0.740
_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  0.0569
_diffrn_reflns_av_unetI/netI     0.0995
_diffrn_reflns_Laue_measured_fraction_full 0.938
_diffrn_reflns_Laue_measured_fraction_max 0.740
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            68941
_diffrn_reflns_point_group_measured_fraction_full 0.938
_diffrn_reflns_point_group_measured_fraction_max 0.740
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.969
_diffrn_reflns_theta_min         0.847
_diffrn_source                   'MX2 Beamline Australian Synchrotron'
_diffrn_source_type              Synchrotron
_exptl_absorpt_coefficient_mu    2.897
_exptl_absorpt_correction_T_max  0.7463
_exptl_absorpt_correction_T_min  0.4983
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
'SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1465 before and 0.0666 after correction. 
The Ratio of minimum to maximum transmission is 0.6677. 
The \l/2 correction factor is 0.0015.'
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.621
_exptl_crystal_description       block
_exptl_crystal_F_000             1836
_exptl_crystal_recrystallization_method
'Crystallised from dichloromethane/toluene'
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.192
_refine_diff_density_min         -1.562
_refine_diff_density_rms         0.106
_refine_ls_extinction_coef       0.0024(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     927
_refine_ls_number_reflns         19220
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0585
_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^)+(0.0545P)^2^+2.2759P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1666
_refine_ls_wR_factor_ref         0.1763
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15646
_reflns_number_total             19220
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01073_si_011.cif
_cod_data_source_block           6a-tol
_cod_original_cell_volume        3748.5(14)
_cod_database_code               4135051
_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. Shared sites
{P2, P2B}
3. Restrained distances
 P2-F9 \\sim P2A-F9A \\sim P2B-F9B
 with sigma of 0.02
 P2-F7 \\sim P2A-F7A \\sim P2B-F7B
 with sigma of 0.02
 P2-F8 \\sim P2A-F8A \\sim P2B-F8B
 with sigma of 0.02
 F9-F7 \\sim F9A-F7A \\sim F9B-F7B
 with sigma of 0.04
 F9-F8 \\sim F9A-F8A \\sim F9B-F8B
 with sigma of 0.04
 F7-F8 \\sim F7A-F8A \\sim F7B-F8B
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uanis(F7) \\sim Ueq, Uanis(F7A) \\sim Ueq, Uanis(F7B) \\sim Ueq, Uanis(F8)
\\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F8B) \\sim Ueq, Uanis(F9) \\sim Ueq,
Uanis(F9A) \\sim Ueq, Uanis(F9B) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
Uanis(P2) = Uanis(P2B)
Uanis(P2) = Uanis(P2A)
5. Others
 1*[Sof(P2)+Sof(F7)+Sof(F8)+Sof(F9)]+1*[Sof(P2A)+Sof(F7A)+Sof(F8A)+Sof(F9A)]+1*
 [Sof(P2B)+Sof(F7B)+Sof(F8B)+Sof(F9B)]=1 with esd of 0.0001
 Sof(P2)=0.5*FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(1)
 Sof(P2A)=0.5*FVAR(3)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=FVAR(2)
 Sof(P2B)=0.5*FVAR(4)
 Sof(F7B)=Sof(F8B)=Sof(F9B)=FVAR(3)
6.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)
6.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)
6.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              83927
_shelx_hkl_checksum              31395
_shelx_fab_checksum              87264
_olex2_exptl_crystal_mounting_method 'Mounted on loop in cryoprotectant oil'
_olex2_submission_special_instructions 'No special instructions were received'