Synthesis, Characterization, and DFT Analysis of Bis-Terpyridyl-Based Molecular Cobalt Complexes.
Aroua, Safwan; Todorova, Tanya K.; Hommes, Paul; Chamoreau, Lise-Marie; Reissig, Hans-Ulrich; Mougel, Victor; Fontecave, Marc; Inorganic chemistry 56 (2017) 5930–5940; doi:10.1021/acs.inorgchem.7b00595

data_4349443
_publ_section_title
;
 Synthesis, Characterization, and DFT Analysis of Bis-Terpyridyl-Based
 Molecular Cobalt Complexes.
;
_journal_issue                   10
_journal_name_full               'Inorganic chemistry'
_journal_page_first              5930
_journal_page_last               5940
_journal_paper_doi               10.1021/acs.inorgchem.7b00595
_journal_volume                  56
_journal_year                    2017
_chemical_formula_moiety
'C46 H30 Co N6, 1.5(F6 P), F2.72 P0.5, 0.28(F), 1.63(C3 H6 O)'
_chemical_formula_sum            'C50.88 H39.75 Co F12 N6 O1.62 P2'
_chemical_formula_weight         1110.00
_space_group_crystal_system      tetragonal
_space_group_IT_number           87
_space_group_name_Hall           '-I 4'
_space_group_name_H-M_alt        'I 4/m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-09-09
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   26.3611(5)
_cell_length_b                   26.3611(5)
_cell_length_c                   29.3615(9)
_cell_measurement_reflns_used    11957
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      30.6622
_cell_measurement_theta_min      2.9765
_cell_volume                     20403.5(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_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      150.00(10)
_diffrn_detector_area_resol_mean 16.0839
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -98.00  -48.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.9467 -179.0000 -120.0000 50

  2 omega  -25.00   20.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.9467  -99.0000  120.0000 45

  3 omega   34.00   99.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       22.4154  179.0000  150.0000 65

  4 omega    1.00   91.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       22.4154   57.0000  -90.0000 90

  5 omega  -15.00   87.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       22.4154   19.0000 -150.0000 102

  6 omega  -50.00   48.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       22.4154  -38.0000  150.0000 98
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0190315000
_diffrn_orient_matrix_UB_12      0.0154923000
_diffrn_orient_matrix_UB_13      0.0099541000
_diffrn_orient_matrix_UB_21      0.0070372000
_diffrn_orient_matrix_UB_22      -0.0088467000
_diffrn_orient_matrix_UB_23      0.0219311000
_diffrn_orient_matrix_UB_31      0.0176718000
_diffrn_orient_matrix_UB_32      0.0201300000
_diffrn_orient_matrix_UB_33      0.0019801000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0812
_diffrn_reflns_av_unetI/netI     0.0716
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            103800
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.681
_diffrn_reflns_theta_min         2.982
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.488
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70773
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.445
_exptl_crystal_description       block
_exptl_crystal_F_000             9040
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.35
_refine_diff_density_max         1.151
_refine_diff_density_min         -0.979
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.192
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     720
_refine_ls_number_reflns         9876
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.190
_refine_ls_R_factor_all          0.0973
_refine_ls_R_factor_gt           0.0879
_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^)+(0.0530P)^2^+150.4884P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1764
_refine_ls_wR_factor_ref         0.1814
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8930
_reflns_number_total             9876
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            crystal_structures1.cif
_cod_data_source_block           C3
_cod_original_cell_volume        20403.5(10)
_cod_database_code               4349443
_shelxl_version_number           2012-9
_chemical_oxdiff_formula         'Co1 C50 N6 P2 F12 H50'
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9917(4) 0.0083(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 F23-F33
 2.16 with sigma of 0.01
 F15-F18
 2.16 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(O3) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C53)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F23) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F33) \\sim Ueq, Uanis(F18)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F29) = Uanis(F31) = Uanis(F27) = Uanis(F30) = Uanis(F32) = Uanis(F28) =
Uanis(P5)
Uanis(F14) = Uanis(F24) = Uanis(F22) = Uanis(F21) = Uanis(F20) = Uanis(F19) =
Uanis(F17) = Uanis(F16)
Uanis(O3) = Uanis(C54) = Uanis(C55) = Uanis(C53)
Uanis(F23) = Uanis(F15) = Uanis(F33) = Uanis(F18)
5. Others
 1*[Sof(F14)+Sof(F17)+Sof(F20)+Sof(F11)+Sof(F10)+Sof(F22)]+1*[Sof(F21)+
 Sof(F24)+Sof(F16)+Sof(F19)]+1*[Sof(F23)+Sof(F15)+Sof(F18)+Sof(F33)]=1 with esd
 of 0.0001
 Sof(F10)=1-FVAR(1)
 Sof(F14)=Sof(F17)=Sof(F20)=Sof(F22)=0.5*FVAR(2)
 Sof(F11)=FVAR(1)
 Sof(F21)=Sof(F24)=Sof(F16)=Sof(F19)=0.5*FVAR(3)
 Sof(F23)=Sof(F15)=Sof(F18)=Sof(F33)=0.5*FVAR(4)
 Fixed Sof: P5(0.125) F30(0.125) F27(0.125) F28(0.125) F31(0.125) F32(0.125)
 F29(0.125) H52A(0.5) H52B(0.5) H52C(0.5) H50A(0.5) H50B(0.5) H50C(0.5)
 O3(0.125) C54(0.125) C55(0.125) H55A(0.125) H55B(0.125) H55C(0.125) C53(0.125)
 H53A(0.125) H53B(0.125) H53C(0.125)
6.a Free rotating group:
 P5(F30,F27,F28,F31,F32,F29), O3(C54,C55,C53)
6.b Aromatic/amide H refined with riding coordinates:
 C36(H36), C34(H34), C23(H23), C22(H22), C11(H11), C13(H13), C24(H24),
 C40(H40), C4(H4), C5(H5), C45(H45), C29(H29), C17(H17), C27(H27), C6(H6),
 C12(H12), C28(H28), C43(H43), C20(H20), C42(H42), C41(H41), C35(H35), C1(H1),
 C25(H25), C7(H7), C46(H46), C2(H2), C30(H30), C19(H19), C18(H18)
6.c Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C50(H50A,H50B,H50C), C47(H47A,H47B,H47C), C49(H49A,H49B,
 H49C), C55(H55A,H55B,H55C), C53(H53A,H53B,H53C)
;
_shelx_res_checksum              71642
_shelx_hkl_checksum              35077
_shelx_fab_checksum              54550
_olex2_date_sample_data_collection 2016-08-03
_olex2_submission_special_instructions 'No special instructions were received'