Silver(II) and Silver(III) Intermediates in Alkene Aziridination with a Dinuclear Silver(I) Nitrene Transfer Catalyst
Elkoush, Tasneem; Mak, Choi L.; Paley, Daniel W.; Campbell, Michael G.; ACS Catalysis  (2020) 4820–; doi:10.1021/acscatal.0c00065

data_4517553
_publ_section_title
;
 Silver(II) and Silver(III) Intermediates in Alkene Aziridination with a
 Dinuclear Silver(I) Nitrene Transfer Catalyst
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              4820
_journal_paper_doi               10.1021/acscatal.0c00065
_journal_year                    2020
_chemical_formula_moiety
'C40 H47 Ag I N6 O8 S, 2.65(C H2 Cl2), 0.35(H2 O)'
_chemical_formula_sum            'C42.65 H53 Ag Cl5.29 I N6 O8.35 S'
_chemical_formula_weight         1237.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-03-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3461 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.824(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4359(13)
_cell_length_b                   16.0865(7)
_cell_length_c                   26.638(2)
_cell_measurement_reflns_used    5853
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      13.9580
_cell_measurement_theta_min      1.6930
_cell_volume                     5265.9(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/1 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \f    -19.26 340.74   0.50    0.50  91.24   0.00  34.03    --   720
  2  \f     79.76 350.26   0.50    0.50  90.76   0.00  16.97    --   541
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0133882000
_diffrn_orient_matrix_UB_12      -0.0191482000
_diffrn_orient_matrix_UB_13      0.0073328000
_diffrn_orient_matrix_UB_21      -0.0270331000
_diffrn_orient_matrix_UB_22      0.0144836000
_diffrn_orient_matrix_UB_23      0.0009632000
_diffrn_orient_matrix_UB_31      -0.0148804000
_diffrn_orient_matrix_UB_32      -0.0091068000
_diffrn_orient_matrix_UB_33      -0.0138603000
_diffrn_radiation_monochromator  synchrotron
_diffrn_radiation_probe          x-ray
_diffrn_radiation_wavelength     0.41328
_diffrn_reflns_av_R_equivalents  0.1991
_diffrn_reflns_av_unetI/netI     0.0823
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            54417
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        11.925
_diffrn_reflns_theta_max         11.925
_diffrn_reflns_theta_min         1.539
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    0.681
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35374
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.561
_exptl_crystal_description       needle
_exptl_crystal_F_000             2495
_refine_diff_density_max         1.289
_refine_diff_density_min         -1.166
_refine_diff_density_rms         0.165
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     575
_refine_ls_number_reflns         5501
_refine_ls_number_restraints     499
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.1196
_refine_ls_R_factor_gt           0.1086
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1010P)^2^+149.4868P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2771
_refine_ls_wR_factor_ref         0.2854
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4625
_reflns_number_total             5501
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00065_si_002.cif
_cod_data_source_block           Cmpd2
_cod_original_cell_volume        5265.9(8)
_cod_database_code               4517553
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C43 H53 Ag Cl6 I N6 O8 S'
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     11.93
_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,H) groups
2. Restrained distances
 O59-H1A_2
 2.08 with sigma of 0.02
 O66-H1B_2
 2.22 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.01 and sigma
for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(Cl2)=Sof(Cl3)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(Cl2)=Sof(Cl3)=FVAR(1)
 Sof(O1)=Sof(H1A)=Sof(H1B)=1-FVAR(2)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(Cl2)=Sof(Cl3)=FVAR(2)
6.a Free rotating group:
 C1(Cl2,Cl3), C1(Cl2,Cl3)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1(H1A,H1B), H1A(H1B,Cl2), H1A(H1B,Cl2)
6.c Me refined with riding coordinates:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C40(H40A,H40B,H40C)
6.d Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C15(H15), C23(H23), C25(H25), C33(H33), C35(H35),
 C36(H36), C46(H46), C47(H47), C49(H49), C50(H50), C54(H54), C55(H55), C56(H56),
  C57(H57), C58(H58)
6.e Idealised Me refined as rotating group:
 C51(H51A,H51B,H51C)
;
_shelx_res_checksum              5029
_shelx_hkl_checksum              82992
_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 1.897
_oxdiff_exptl_absorpt_empirical_full_min 0.625