Selective oxygenation of C–H and CC bonds with H2O2 by high-spin cobalt(ii)-carboxylate complexes
Ghosh, Ivy; Chakraborty, Biswarup; Bera, Abhijit; Paul, Satadal; Paine, Tapan Kanti; Dalton Transactions  (2022) –; doi:10.1039/D1DT02235K

data_7709345
_publ_section_title
;
 Selective oxygenation of C--H and C&#xE001;C bonds with H2O2 by high-spin
 cobalt(ii)-carboxylate complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02235K
_journal_year                    2022
_chemical_formula_moiety
'6(C29 H31 Co N4 O3), 2(C29 H29 Co N4 O3), 6(C24 H20 B), 2(C24.1 H17.65 B), 4(O)'
_chemical_formula_sum            'C424.2 H399.3 B8 Co8 N32 O28'
_chemical_formula_weight         6951.35
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2021-09-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-12-13 deposited with the CCDC.	2021-12-23 downloaded from the CCDC.
;
_cell_angle_alpha                102.515(7)
_cell_angle_beta                 95.986(7)
_cell_angle_gamma                106.785(7)
_cell_formula_units_Z            1
_cell_length_a                   18.507(5)
_cell_length_b                   20.425(5)
_cell_length_c                   25.548(7)
_cell_measurement_reflns_used    5938
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      23.93
_cell_measurement_theta_min      2.24
_cell_volume                     8881(4)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SMART'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-1997  (Sheldrick, 2008)'
_diffrn_ambient_temperature      293.15
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.952
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1231
_diffrn_reflns_av_unetI/netI     0.2160
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            62486
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.615
_diffrn_reflns_theta_min         0.830
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.437
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1021 before and 0.0693 after correction.
The Ratio of minimum to maximum transmission is 0.6736.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic pinkish pink'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.300
_exptl_crystal_description       block
_exptl_crystal_F_000             3649
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         2.217
_refine_diff_density_min         -1.302
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2226
_refine_ls_number_reflns         31871
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.2723
_refine_ls_R_factor_gt           0.1287
_refine_ls_shift/su_max          0.016
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3226
_refine_ls_wR_factor_ref         0.4134
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12529
_reflns_number_total             31871
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02235k2.cif
_cod_data_source_block           bc02_0m_a
_cod_original_formula_sum        'C424.20 H399.30 B8 Co8 N32 O28'
_cod_database_code               7709345
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.918
_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, All O(H) groups
2. Restrained distances
 O2-H2
 0.85 with sigma of 0.01
 O3-H3
 0.85 with sigma of 0.01
 C019-H3
 1.900277 with sigma of 0.02
 Co3-H2
 2.820785 with sigma of 0.02
 C010-H2
 1.900049 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C06T) = Uanis(C02B)
Uanis(C06V) = Uanis(C06W) = Uanis(C01T)
4. Others
 Fixed Sof: C2(0.75) C0(0.65) H0(0.65) C1(0.45) C3(0.25)
5.a Ternary CH refined with riding coordinates:
 C010(H010), C011(H011), C019(H019), C01K(H01K)
5.b Secondary CH2 refined with riding coordinates:
 C01D(H01A,H01B), C01M(H01E,H01F), C01P(H01C,H01D), C023(H02K,H02L), C024(H02A,
 H02B), C02K(H02F,H02G), C03F(H03G,H03I), C03Q(H03N,H03O), C03V(H03A,H03B),
 C040(H04H,H04I), C05G(H05I,H05J), C065(H06B,H06C)
5.c Aromatic/amide H refined with riding coordinates:
 C01F(H01G), C01L(H01L), C01U(H01U), C01V(H01V), C01Y(H01Y), C021(H021),
 C022(H022), C02A(H02N), C02H(H02Y), C02I(H02W), C02M(H02M), C02O(H02R),
 C02P(H02S), C02Q(H02U), C02R(H02V), C02S(H02X), C02T(H02T), C02U(H02),
 C02Z(H02Z), C030(H030), C031(H031), C032(H032), C033(H033), C036(H036),
 C038(H038), C039(H039), C03C(H03F), C03D(H1), C03E(H03Q), C03G(H10),
 C03H(H03H), C03I(H03P), C03J(H03J), C03K(H03R), C03L(H11), C03N(H4), C03O(H7),
 C03P(H03T), C03R(H03V), C03S(H03S), C03T(H03), C03U(H03U), C03W(H03W),
 C03X(H03X), C03Y(H03Y), C03Z(H03Z), C041(H041), C043(H043), C044(H044),
 C045(H045), C046(H046), C047(H047), C048(H048), C049(H049), C04B(H04J),
 C04C(H04U), C04D(H04K), C04E(H12), C04F(H04F), C04G(H13), C04H(H04X),
 C04I(H04L), C04K(H04Y), C04M(H04Q), C04N(H04S), C04O(H04O), C04P(H04T),
 C04Q(H04R), C04R(H04Z), C04S(H04), C04T(H14), C04U(H15), C04V(H04V),
 C04W(H04W), C050(H050), C051(H051), C052(H052), C053(H053), C054(H054),
 C055(H055), C057(H057), C059(H059), C05A(H16), C05B(H05B), C05D(H05S),
 C05E(H05Y), C05F(H17), C05H(H05H), C05J(H05O), C05K(H05K), C05L(H05R),
 C05M(H05), C05O(H8), C05P(H05P), C05Q(H05Q), C05S(H05T), C05T(H05U), C05U(H18),
  C05V(H05V), C05W(H05W), C05X(H05X), C05Y(H9), C05Z(H05Z), C060(H060),
 C061(H061), C062(H062), C063(H063), C066(H066), C067(H067), C068(H068),
 C069(H069), C06A(H06A), C06B(H06J), C06C(H06L), C06D(H06Q), C06F(H06F),
 C06G(H06G), C06H(H06I), C2(H2A), C06K(H06K), C06L(H06S), C06M(H06M),
 C06N(H06N), C06O(H06O), C06P(H06P), C06R(H06R), C0(H0), C06T(H06T), C06V(H06V),
  C06W(H06W), C06X(H06X), C06Y(H06Y)
5.d Idealised Me refined as rotating group:
 C02G(H02O,H02P,H02Q), C02V(H02C,H02D,H02E), C02X(H02H,H02I,H02J), C037(H03K,
 H03L,H03M), C03B(H03C,H03D,H03E), C04L(H04A,H04B,H04C), C04X(H04M,H04N,H04P),
 C04Z(H04D,H04E,H04G), C056(H05A,H05C,H05D), C05I(H05L,H05M,H05N), C05R(H05E,
 H05F,H05G), C06Q(H06D,H06E,H06H)
5.e Idealised tetrahedral OH refined as rotating group:
 O5(H5), O6(H6)
;
_shelx_res_checksum              19714
_shelx_hkl_checksum              77763