Activation of C-H, N-H, and O-H Bonds via Proton-Coupled Electron Transfer to a Mn(III) Complex of Redox-Noninnocent Octaazacyclotetradecadiene, a Catenated-Nitrogen Macrocyclic Ligand.
Vaddypally, Shivaiah; Tomlinson, Warren; O'Sullivan, Owen T; Ding, Ran; Van Vliet, Megan M.; Wayland, Bradford B.; Hooper, Joseph P.; Zdilla, Michael J.; Journal of the American Chemical Society 141 (2019) 5699–5709; doi:10.1021/jacs.8b10250

data_4128406
_publ_section_title
;
 Activation of C-H, N-H, and O-H Bonds via Proton-Coupled Electron
 Transfer to a Mn(III) Complex of Redox-Noninnocent
 Octaazacyclotetradecadiene, a Catenated-Nitrogen Macrocyclic Ligand.
;
_journal_issue                   14
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5699
_journal_page_last               5709
_journal_paper_doi               10.1021/jacs.8b10250
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         '2(C15 H31 Mn N13), 2(C4 H8 O)'
_chemical_formula_sum            'C38 H78 Mn2 N26 O2'
_chemical_formula_weight         1041.14
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-06-14
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.955(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.504(2)
_cell_length_b                   18.005(2)
_cell_length_c                   17.337(2)
_cell_measurement_reflns_used    7689
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.77
_cell_measurement_theta_min      2.43
_cell_volume                     4993.3(10)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'COSMO (Bruker, AXS)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.98
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.938
_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  0.0340
_diffrn_reflns_av_unetI/netI     0.0552
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            24380
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.929
_diffrn_reflns_theta_min         1.703
_exptl_absorpt_coefficient_mu    0.569
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7010
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0485 before and 0.0438 after correction.
The Ratio of minimum to maximum transmission is 0.9402.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.385
_exptl_crystal_description       block
_exptl_crystal_F_000             2216
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.922
_refine_diff_density_min         -0.577
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     643
_refine_ls_number_reflns         11230
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0454
_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^)+(0.0507P)^2^+2.8164P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1085
_refine_ls_wR_factor_ref         0.1173
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8487
_reflns_number_total             11230
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b10250_si_002.cif
_cod_data_source_block           ct3_a
_cod_database_code               4128406
_shelxl_version_number           2014/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C20A, C20
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
C20A \\sim C20: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
4. Others
 Sof(H19C)=Sof(H19D)=Sof(H21C)=Sof(H21D)=Sof(C20A)=Sof(H20C)=Sof(H20D)=1-FVAR(1)
 Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H21A)=Sof(H21B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C19(H19C,H19D),
  C20(H20A,H20B), C21(H21A,H21B), C21(H21C,H21D), C1S(H1SA,H1SB), C2S(H2SA,
 H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C5S(H5SA,H5SB), C6S(H6SA,H6SB),
 C7S(H7SA,H7SB), C8S(H8SA,H8SB), C20A(H20C,H20D)
5.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C26(H26A,H26B,H26C), C30(H30A,H30B,H30C), C28(H28A,H28B,H28C),
 C29(H29A,H29B,H29C)
;
_shelx_res_checksum              91033
_shelx_hkl_checksum              5439
_olex2_submission_special_instructions 'No special instructions were received'