Modulation of iron spin states in highly distorted iron(III)porphyrin: H-bonding interactions and implications for the hemoproteins
Sahoo, Dipankar; Mazumdar, Rakesh; Pramanik, Subhadip; Banerjee, Sayantani; Patra, Ranjan; Rath, Sankar Prasad; Dalton Transactions  (2023) –; doi:10.1039/D3DT00846K

data_7713176
_publ_section_title
;
 Modulation of iron spin states in highly distorted iron(III)porphyrin:
 H-bonding interactions and implications for the hemoproteins
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00846K
_journal_year                    2023
_chemical_formula_moiety         'C47 H27 Br8 Fe N4 O, 1.5(C6 H6)'
_chemical_formula_sum            'C56 H36 Br8 Fe N4 O'
_chemical_formula_weight         1476.02
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-05-02
_audit_creation_method
;
Olex2 1.5-dev
(compiled 2023.03.24 svn.rc9df729e for OlexSys, GUI svn.r6758)
;
_audit_update_record
;
2023-05-23 deposited with the CCDC.	2023-05-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.864(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.930(2)
_cell_length_b                   23.340(2)
_cell_length_c                   22.690(2)
_cell_measurement_reflns_used    999
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      2.5
_cell_volume                     10398.6(17)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker SMART APEX'
_diffrn_measurement_method       \w
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0842
_diffrn_reflns_av_unetI/netI     0.1068
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            26683
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.531
_exptl_absorpt_coefficient_mu    6.483
_exptl_absorpt_correction_T_max  0.523
_exptl_absorpt_correction_T_min  0.420
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2.05 (Sheldrick, 2002)'
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.886
_exptl_crystal_description       block
_exptl_crystal_F_000             5712
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.845
_refine_diff_density_min         -0.612
_refine_diff_density_rms         0.143
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.951
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     663
_refine_ls_number_reflns         9143
_refine_ls_number_restraints     70
_refine_ls_restrained_S_all      0.956
_refine_ls_R_factor_all          0.1038
_refine_ls_R_factor_gt           0.0471
_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^)+(0.0454P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0922
_refine_ls_wR_factor_ref         0.1126
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5423
_reflns_number_total             9143
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00846k2.cif
_cod_data_source_block           shelx
_cod_original_cell_volume        10398.3(18)
_cod_database_code               7713176
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.563
_shelx_estimated_absorpt_t_min   0.464
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Fe1-O1 \\sim Fe1A-O1A
 with sigma of 0.02
 Fe1-N1 \\sim Fe1A-N1
 with sigma of 0.02
 Fe1-N2 \\sim Fe1A-N2
 with sigma of 0.02
 Fe1-N3 \\sim Fe1A-N3
 with sigma of 0.02
 Fe1-N4 \\sim Fe1A-N4
 with sigma of 0.02
 O1-C45 \\sim O1A-C45A
 with sigma of 0.02
 C45-C46 \\sim C45A-C46A
 with sigma of 0.02
 C45-C47 \\sim C45A-C47A
 with sigma of 0.02
 C1S-C2S \\sim C1T-C2T
 with sigma of 0.02
 C1S-C6S \\sim C1T-C6T
 with sigma of 0.02
 C2S-C3S \\sim C2T-C3T
 with sigma of 0.02
 C3S-C4S \\sim C3T-C4T
 with sigma of 0.02
 C4S-C5S \\sim C4T-C5T
 with sigma of 0.02
 C5S-C6S \\sim C5T-C6T
 with sigma of 0.02
 Fe1-C45 \\sim Fe1A-C45A
 with sigma of 0.04
 O1-N1 \\sim O1A-N1
 with sigma of 0.04
 O1-N2 \\sim O1A-N2
 with sigma of 0.04
 O1-N3 \\sim O1A-N3
 with sigma of 0.04
 O1-N4 \\sim O1A-N4
 with sigma of 0.04
 O1-C46 \\sim O1A-C46A
 with sigma of 0.04
 O1-C47 \\sim O1A-C47A
 with sigma of 0.04
 C46-C47 \\sim C46A-C47A
 with sigma of 0.04
 C1S-C3S \\sim C1T-C3T
 with sigma of 0.04
 C1S-C5S \\sim C1T-C5T
 with sigma of 0.04
 C2S-C4S \\sim C2T-C4T
 with sigma of 0.04
 C2S-C6S \\sim C2T-C6T
 with sigma of 0.04
 C3S-C5S \\sim C3T-C5T
 with sigma of 0.04
 C4S-C6S \\sim C4T-C6T
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C47) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 C1S, C2S, C6S, C3S, C5S, C4S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C6T)=Sof(H6T)=Sof(C1T)=Sof(H1T)=Sof(C2T)=Sof(H2T)=Sof(C3T)=Sof(H3T)=
 Sof(C4T)=Sof(H4T)=Sof(C5T)=Sof(H5T)=Sof(O1A)=Sof(C45A)=Sof(H45A)=Sof(C46A)=
 Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C47A)=Sof(H47D)=Sof(H47E)=Sof(H47F)=
 Sof(Fe1A)=1-FVAR(1)
 Sof(Fe1)=Sof(O1)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C1S)=Sof(H1S)=Sof(C2S)=Sof(H2S)=
 Sof(C3S)=Sof(H3S)=Sof(C4S)=Sof(H4S)=Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=FVAR(1)
 Fixed Uiso: C6T(0.05) C1T(0.05) C2T(0.05) C3T(0.05) C4T(0.05) C5T(0.05)
 O1A(0.05) C45A(0.05) C46A(0.05) C47A(0.05)
6.a Ternary CH refined with riding coordinates:
 C45(H45), C45A(H45A)
6.b Aromatic/amide H refined with riding coordinates:
 C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
 C29(H29), C30(H30), C31(H31), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38),
  C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C1S(H1S), C2S(H2S),
 C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C7S(H7S), C8S(H8S), C9S(H9S), C6T(H6T),
  C1T(H1T), C2T(H2T), C3T(H3T), C4T(H4T), C5T(H5T)
6.c Fitted hexagon refined as free rotating group:
 C6T(C1T,C2T,C3T,C4T,C5T)
6.d Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C46A(H46D,H46E,H46F), C47A(H47D,
 H47E,H47F)
;
_shelx_res_checksum              14512
_olex2_submission_special_instructions 'No special instructions were received'