Cobalt Superoxo and Alkylperoxo Complexes Derived from Reaction of Ring-Cleaving Dioxygenase Models with O<sub>2</sub>.
Kumar, Praveen; Lindeman, Sergey V.; Fiedler, Adam T.; Journal of the American Chemical Society 141 (2019) 10984–10987; doi:10.1021/jacs.9b05320

data_4127415
_publ_section_title
;
 Cobalt Superoxo and Alkylperoxo Complexes Derived from Reaction of
 Ring-Cleaving Dioxygenase Models with O<sub>2</sub>.
;
_journal_issue                   28
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10984
_journal_page_last               10987
_journal_paper_doi               10.1021/jacs.9b05320
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C59 H55 B Co N7 O, C0.55 Cl0.66, 0.44(Cl), C1.54 Cl0.92 N0.54, 0.09(C H2 Cl2)'
_chemical_formula_sum            'C61.18 H55.18 B Cl2.2 Co N7.54 O'
_chemical_formula_weight         1059.78
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-11-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 92.4141(9)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   14.90780(14)
_cell_length_b                   9.95186(11)
_cell_length_c                   37.7389(4)
_cell_measurement_reflns_used    23455
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.4900
_cell_measurement_theta_min      3.8390
_cell_volume                     5593.99(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3756
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_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    -67.00  32.00   1.00    6.00    --  -42.46  37.00  90.00   99
  2  \w   -117.00 -18.00   1.00    6.00    --  -42.46 -37.00  90.00   99
  3  \w   -115.00 -14.00   1.00    6.00    --  -42.46 -57.00 -60.00  101
  4  \w     74.00 173.00   1.00   24.00    --  100.00  45.00-120.00   99
  5  \w     94.00 173.00   1.00   24.00    --  100.00 125.00  30.00   79
  6  \w     27.00 126.00   1.00   24.00    --  100.00 -45.00   0.00   99
  7  \w     71.00 172.00   1.00   24.00    --  100.00  61.00  60.00  101
  8  \w     27.00 126.00   1.00   24.00    --  100.00 -45.00 -90.00   99
  9  \w     17.00 109.00   1.00   24.00    --  100.00 -94.00 -60.00   92
 10  \w     71.00 172.00   1.00   24.00    --  100.00  61.00 150.00  101
 11  \w     94.00 173.00   1.00   24.00    --  100.00 125.00 -60.00   79
 12  \w   -115.00 -14.00   1.00    6.00    --  -42.46 -57.00  30.00  101
 13  \w   -115.00 -14.00   1.00    6.00    --  -42.46 -57.00-150.00  101
 14  \w    -95.00  -2.00   1.00    6.00    --  -42.46 125.00 150.00   93
 15  \w     74.00 173.00   1.00   24.00    --  100.00  45.00 -60.00   99
 16  \w     74.00 173.00   1.00   24.00    --  100.00  45.00   0.00   99
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0157547000
_diffrn_orient_matrix_UB_12      -0.0131821000
_diffrn_orient_matrix_UB_13      -0.0404635000
_diffrn_orient_matrix_UB_21      -0.0898940000
_diffrn_orient_matrix_UB_22      -0.0716156000
_diffrn_orient_matrix_UB_23      0.0056333000
_diffrn_orient_matrix_UB_31      -0.0486760000
_diffrn_orient_matrix_UB_32      0.1365697000
_diffrn_orient_matrix_UB_33      -0.0009519000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0422
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            52562
_diffrn_reflns_theta_full        70.59
_diffrn_reflns_theta_max         70.59
_diffrn_reflns_theta_min         3.70
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.742
_exptl_absorpt_correction_T_max  0.765
_exptl_absorpt_correction_T_min  0.302
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29c (Rigaku Oxford Diffraction, 2017)
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            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.258
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2210
_exptl_crystal_size_max          0.709
_exptl_crystal_size_mid          0.499
_exptl_crystal_size_min          0.121
_refine_diff_density_max         0.905
_refine_diff_density_min         -0.741
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     816
_refine_ls_number_reflns         10613
_refine_ls_number_restraints     58
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0616
_refine_ls_R_factor_gt           0.0583
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0843P)^2^+5.5211P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1577
_refine_ls_wR_factor_ref         0.1609
_reflns_number_gt                9901
_reflns_number_total             10613
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b05320_si_002.cif
_cod_data_source_block           Complex1ox
_cod_original_formula_sum        'C61.18 H55.18 B Cl2.20 Co N7.54 O'
_cod_database_code               4127415
_chemical_oxdiff_formula         'C59 H44 B Co N7 O3 C4 H6 N2'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained planarity
 C30A, C29A, C28A, C33A, C32A, C31A
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(O1) = Uanis(O1A)
Uanis(N7A) = Uanis(N7)
Uanis(C46A) = Uanis(C46)
Uanis(C51) = Uanis(C51A)
Uanis(C47) = Uanis(C47A)
Uanis(C48) = Uanis(C48A)
Uanis(C49A) = Uanis(C49)
Uanis(C50A) = Uanis(C50)
Uanis(C52A) = Uanis(C52)
Uanis(C53A) = Uanis(C53)
Uanis(C54A) = Uanis(C54)
Uanis(C55A) = Uanis(C55)
Uanis(C56A) = Uanis(C56)
Uanis(C57A) = Uanis(C57)
Uanis(C58) = Uanis(C58A)
Uanis(C59A) = Uanis(C59)
Uanis(C33A) = Uanis(C33)
Uanis(C32A) = Uanis(C32)
Uanis(C31A) = Uanis(C31)
Uanis(C30A) = Uanis(C30)
Uanis(C29) = Uanis(C29A)
Uanis(C28) = Uanis(C28A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(Cl2A) = Uanis(Cl2)
4. Same fragment restrains
{C28, C29, C30, C31, C32, C33} sigma for 1-2: 0.02, 1-3: 0.04
as
{C28A, C29A, C30A, C31A, C32A, C33A}
{O1, N7, C46, C47, C48, C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59}
sigma for 1-2: 0.02, 1-3: 0.04
as
{O1A, N7A, C46A, C47A, C48A, C49A, C50A, C51A, C52A, C53A, C54A, C55A, C56A,
C57A, C58A, C59A}
5. Others
 Sof(Cl3)=1-FVAR(1)
 Sof(Cl4A)=Sof(Cl4)=0.5*(1-FVAR(2))
 Sof(N1S)=Sof(C3S)=FVAR(1)
 Sof(C28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=
 Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(O1A)=Sof(N7A)=Sof(H7A)=Sof(C46A)=
 Sof(C47A)=Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=
 Sof(C52A)=Sof(C53A)=Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(C54A)=Sof(H54D)=
 Sof(H54E)=Sof(H54F)=Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C56A)=
 Sof(C57A)=Sof(H57D)=Sof(H57E)=Sof(H57F)=Sof(C58A)=Sof(H58D)=Sof(H58E)=
 Sof(H58F)=Sof(C59A)=Sof(H59D)=Sof(H59E)=Sof(H59F)=1-FVAR(2)
 Sof(Cl5)=Sof(Cl6)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=0.5*(1-FVAR(3))
 Sof(C28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=
 Sof(H32)=Sof(C33)=Sof(H33)=Sof(O1)=Sof(N7)=Sof(H7)=Sof(C46)=Sof(C47)=Sof(C48)=
 Sof(H48)=Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(C52)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55)=Sof(H55A)=
 Sof(H55B)=Sof(H55C)=Sof(C56)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C58)=
 Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=FVAR(2)
 Sof(Cl2A)=Sof(Cl1A)=0.4*FVAR(4)
 Sof(Cl2)=Sof(Cl1)=0.6*FVAR(4)
 Sof(C1S)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 B1(H1)
6.b Secondary CH2 refined with riding coordinates:
 C4S(H4SA,H4SB)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C8(H8), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15),
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C24(H24), C25(H25),
  C26(H26), C27(H27), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33),
 C29A(H29A), C30A(H30A), C31A(H31A), C32A(H32A), C33A(H33A), C35(H35), C36(H36),
  C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43), C44(H44),
 C45(H45), C48(H48), C50(H50), N7A(H7A), C48A(H48A), C50A(H50A)
6.d Idealised Me refined as rotating group:
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C53A(H53D,H53E,H53F),
 C54A(H54D,H54E,H54F), C55A(H55D,H55E,H55F), C57A(H57D,H57E,H57F), C58A(H58D,
 H58E,H58F), C59A(H59D,H59E,H59F)
;
_olex2_date_sample_submission    2017-11-28
_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 1.977
_oxdiff_exptl_absorpt_empirical_full_min 0.539