Alternate Heme Ligation Steers Activity and Selectivity in Engineered Cytochrome P450-Catalyzed Carbene-Transfer Reactions.
Chen, Kai; Zhang, Shuo-Qing; Brandenberg, Oliver F.; Hong, Xin; Arnold, Frances H.; Journal of the American Chemical Society 140 (2018) 16402–16407; doi:10.1021/jacs.8b09613

data_4133319
_publ_section_title
;
 Alternate Heme Ligation Steers Activity and Selectivity in Engineered
 Cytochrome P450-Catalyzed Carbene-Transfer Reactions.
;
_journal_issue                   48
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16402
_journal_page_last               16407
_journal_paper_doi               10.1021/jacs.8b09613
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H14 O3'
_chemical_formula_sum            'C13 H14 O3'
_chemical_formula_weight         218.24
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381),
 SHELXL-2017/1, and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.2610(7)
_cell_length_b                   7.4076(8)
_cell_length_c                   24.242(2)
_cell_measurement_reflns_used    9388
_cell_measurement_temperature    175
_cell_measurement_theta_max      80.0
_cell_measurement_theta_min      3.7
_cell_volume                     1124.3(2)
_computing_cell_refinement       'SAINT V8.38A (Bruker-AXS, 2016)'
_computing_data_collection       'BIS V6.2.6/2017-03-27 & APEX3_2017.3-0'
_computing_data_reduction        'SAINT V8.38A (Bruker-AXS, 2016)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT-2014/5 (Sheldrick, 2013)'
_diffrn_ambient_temperature      175
_diffrn_detector                 'CPAD Area Detector'
_diffrn_detector_area_resol_mean 7.69
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0298
_diffrn_reflns_av_unetI/netI     0.0132
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            28343
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         80.268
_diffrn_reflns_theta_min         3.646
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.744
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9262
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.0749 before and 0.0496 after correction. 
The Ratio of minimum to maximum transmission is 0.9262. 
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.289
_exptl_crystal_description       block
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.179
_refine_diff_density_min         -0.132
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 964 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(3)
_refine_ls_extinction_coef       0.0083(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     147
_refine_ls_number_reflns         2423
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0261
_refine_ls_R_factor_gt           0.0261
_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^)+(0.0327P)^2^+0.1635P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0678
_refine_ls_wR_factor_ref         0.0679
_reflns_Friedel_coverage         0.670
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                2413
_reflns_number_total             2423
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09613_si_001.cif
_cod_data_source_block           v18081
_cod_database_code               4133319
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.897
_shelx_estimated_absorpt_t_min   0.830
_refine_ls_abs_structure_hooft   0.05(3)
_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.a Ternary CH refined with riding coordinates:
 C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C12(H12)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
;
_shelx_res_checksum              44109
_shelx_hkl_checksum              80783
_olex2_submission_special_instructions 'No special instructions were received'