Valence tautomerism and spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study.
Tezgerevska, Tina; Rousset, Elodie; Gable, Robert W.; Jameson, Guy N. L.; Sañudo, E Carolina; Starikova, Alyona; Boskovic, Colette; Dalton transactions (Cambridge, England : 2003) 48 (2019) 11674–11689; doi:10.1039/c9dt02372k

data_7700425
_publ_section_title
;
 Valence tautomerism and spin crossover in pyridinophane-cobalt-dioxolene
 complexes: an experimental and computational study.
;
_journal_issue                   31
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11674
_journal_page_last               11689
_journal_paper_doi               10.1039/c9dt02372k
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'C34 H48 Mn N4 O2, C24 H20 B, 1.5(C4 H8 O2)'
_chemical_formula_sum            'C64 H80 B Mn N4 O5'
_chemical_formula_weight         1051.07
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-09-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-29 deposited with the CCDC.    2019-07-02 downloaded from the CCDC.
;
_cell_angle_alpha                99.531(3)
_cell_angle_beta                 94.045(2)
_cell_angle_gamma                93.356(2)
_cell_formula_units_Z            2
_cell_length_a                   10.9915(2)
_cell_length_b                   13.6672(4)
_cell_length_c                   19.4001(6)
_cell_measurement_reflns_used    10551
_cell_measurement_temperature    130.00(10)
_cell_measurement_theta_max      76.9810
_cell_measurement_theta_min      4.4740
_cell_volume                     2859.64(14)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      130.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.970
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -69.00 -38.00   1.00    1.00    --  -40.81  57.00  30.00   31
  2  \w    -96.00 -11.00   1.00    1.00    --  -40.81 125.00 120.00   85
  3  \w    -48.00  32.00   1.00    1.00    --  -40.81  38.00 150.00   80
  4  \w   -114.00 -13.00   1.00    1.00    --  -40.81 -57.00   0.00  101
  5  \w    -25.00  64.00   1.00    1.00    --   40.81 -38.00-150.00   89
  6  \w     40.00 110.00   1.00    2.00    --  113.00-111.00 -30.00   70
  7  \w     84.00 117.00   1.00    2.00    --  113.00-114.00  47.00   33
  8  \w     39.00  66.00   1.00    2.00    --  113.00-114.00  47.00   27
  9  \w     36.00 109.00   1.00    2.00    --  113.00-111.00 120.00   73
 10  \w     39.00 142.00   1.00    2.00    --  113.00 -61.00 150.00  103
 11  \w     41.00 138.00   1.00    2.00    --  113.00 -61.00 -60.00   97
 12  \w    129.00 168.00   1.00    2.00    --  113.00 -15.00-120.00   39
 13  \w     84.00 115.00   1.00    2.00    --  113.00-111.00-120.00   31
 14  \w     39.00  65.00   1.00    2.00    --  113.00-111.00-120.00   26
 15  \w     35.00  88.00   1.00    2.00    --  113.00 -30.00   0.00   53
 16  \w     84.00 176.00   1.00    2.00    --  113.00  30.00 -90.00   92
 17  \w     53.00 162.00   1.00    2.00    --  113.00  15.00-150.00  109
 18  \w     36.00 124.00   1.00    2.00    --  113.00 -15.00-120.00   88
 19  \w     29.00 105.00   1.00    2.00    --  113.00 -94.00 150.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0191036000
_diffrn_orient_matrix_UB_12      0.1109233000
_diffrn_orient_matrix_UB_13      0.0007099000
_diffrn_orient_matrix_UB_21      0.0353682000
_diffrn_orient_matrix_UB_22      0.0220526000
_diffrn_orient_matrix_UB_23      0.0795859000
_diffrn_orient_matrix_UB_31      0.1350109000
_diffrn_orient_matrix_UB_32      0.0184524000
_diffrn_orient_matrix_UB_33      -0.0138793000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0357
_diffrn_reflns_av_unetI/netI     0.0451
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            22065
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.133
_diffrn_reflns_theta_min         3.686
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.284
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.283
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.221
_exptl_crystal_description       plate
_exptl_crystal_F_000             1124
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane, dioxane'
_exptl_crystal_size_max          0.687
_exptl_crystal_size_mid          0.287
_exptl_crystal_size_min          0.069
_refine_diff_density_max         0.377
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.046
_refine_ls_extinction_coef       0.00103(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     742
_refine_ls_number_reflns         11754
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0368
_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^)+(0.0481P)^2^+0.5353P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0925
_refine_ls_wR_factor_ref         0.0975
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10517
_reflns_number_total             11754
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt02372k3.cif
_cod_data_source_block           3-mn
_cod_depositor_comments
'Adding full bibliography for 7700424--7700427.cif.'
_cod_original_cell_volume        2859.65(14)
_cod_database_code               7700425
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C64 H80 B Mn N4 O5'
_reflns_odcompleteness_completeness 98.47
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_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. Uiso/Uaniso restraints and constraints
O3A \\sim C59A \\sim C60A \\sim O4A \\sim C61A \\sim C62A: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01
3. Same fragment restrains
{O3, C59, C60, O4, C61, C62} sigma for 1-2: 0.01, 1-3: 0.04
as
{O3A, C59A, C60A, O4A, C61A, C62A}
4. Others
 Sof(O3A)=Sof(C59A)=Sof(H59C)=Sof(H59D)=Sof(C60A)=Sof(H60C)=Sof(H60D)=Sof(O4A)=
 Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=Sof(H62C)=Sof(H62D)=1-FVAR(1)
 Sof(O3)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(O4)=
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C29(H29), C32(H32)
5.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C21(H21A,H21B), C22(H22A,H22B), C28(H28A,H28B), C59(H59A,
 H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C59A(H59C,H59D),
 C60A(H60C,H60D), C61A(H61C,H61D), C62A(H62C,H62D), C63(H63A,H63B), C64(H64A,
 H64B)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C17(H17), C18(H18), C19(H19), C24(H24), C25(H25), C26(H26),
 C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C42(H42), C43(H43), C44(H44),
  C45(H45), C46(H46), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52),
 C54(H54), C55(H55), C56(H56), C57(H57), C58(H58)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              87778
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.878
_oxdiff_exptl_absorpt_empirical_full_min 0.778