Reductive alkylation of azoarenes to N-alkylated hydrazines enabled by hexafluoroisopropanol
Senapati, Siddhartha Kumar; Das, Animesh; Chemical Communications 61 (2025) 8596–8599; doi:10.1039/D5CC00425J

data_7134365
_publ_section_title
;
 Reductive alkylation of azoarenes to N-alkylated hydrazines enabled by
 hexafluoroisopropanol
;
_journal_issue                   47
_journal_name_full               'Chemical Communications'
_journal_page_first              8596
_journal_page_last               8599
_journal_paper_doi               10.1039/D5CC00425J
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C30 H34 N2 O2'
_chemical_formula_sum            'C30 H34 N2 O2'
_chemical_formula_weight         454.59
_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   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-05-29
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.11.24 svn.r209d9fb2 for OlexSys, GUI svn.r6869)
;
_audit_update_record
;
2024-05-29 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.854(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5525(8)
_cell_length_b                   7.9187(6)
_cell_length_c                   28.056(2)
_cell_measurement_reflns_used    9972
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      25.54
_cell_measurement_theta_min      2.65
_cell_volume                     2548.2(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5-alpha (Bourhis et al., 2015)'
_diffrn_ambient_temperature      295.00
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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  0.0632
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            53951
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         1.838
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5968
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1663 before and 0.0780 after correction.
The Ratio of minimum to maximum transmission is 0.8008.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.185
_exptl_crystal_description       plate
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.18
_exptl_transmission_factor_max   0.7453
_exptl_transmission_factor_min   0.5968
_refine_diff_density_max         0.937
_refine_diff_density_min         -0.307
_refine_diff_density_rms         0.048
_refine_ls_extinction_coef       0.009(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.142
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     375
_refine_ls_number_reflns         4482
_refine_ls_number_restraints     213
_refine_ls_restrained_S_all      1.148
_refine_ls_R_factor_all          0.1246
_refine_ls_R_factor_gt           0.0994
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0785P)^2^+3.5333P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2239
_refine_ls_wR_factor_ref         0.2439
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3386
_reflns_number_total             4482
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc00425j2.cif
_cod_data_source_block           sk_716_0m_a
_cod_depositor_comments          'Adding full bibliography for 7134365.cif.'
_cod_database_code               7134365
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.972
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  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 distances
 O1-C21 \\sim O1-C21A
 with sigma of 0.02
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 C21-C27 \\sim C21A-C27A
 with sigma of 0.02
 C24-C30 \\sim C24A-C30A
 with sigma of 0.04
 C22-C23 \\sim C22A-C23A
 with sigma of 0.02
 C22-C26 \\sim C22A-C26A
 with sigma of 0.02
 C26-C28 \\sim C26A-C28A
 with sigma of 0.04
 C22-C28 \\sim C22A-C28A
 with sigma of 0.02
 C23-C26 \\sim C23A-C26A
 with sigma of 0.04
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C23-C29 \\sim C23A-C29A
 with sigma of 0.02
 C23-C30 \\sim C23A-C30A
 with sigma of 0.02
 C23-C28 \\sim C23A-C28A
 with sigma of 0.04
 C24-C26 \\sim C24A-C26A
 with sigma of 0.04
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 C24-C27 \\sim C24A-C27A
 with sigma of 0.02
 C25-C27 \\sim C25A-C27A
 with sigma of 0.04
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C29-C30 \\sim C29A-C30A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 C23-C27 \\sim C23A-C27A
 with sigma of 0.04
 C24-C29 \\sim C24A-C29A
 with sigma of 0.04
 O1-C22 \\sim O1-C22A
 with sigma of 0.04
 O1-C27 \\sim O1-C27A
 with sigma of 0.04
 C21-C23 \\sim C21A-C23A
 with sigma of 0.04
 C21-C24 \\sim C21A-C24A
 with sigma of 0.04
 C21-C26 \\sim C21A-C26A
 with sigma of 0.04
 C21-C28 \\sim C21A-C28A
 with sigma of 0.04
 C22-C24 \\sim C22A-C24A
 with sigma of 0.04
 C22-C25 \\sim C22A-C25A
 with sigma of 0.04
 C22-C27 \\sim C22A-C27A
 with sigma of 0.04
 C22-C29 \\sim C22A-C29A
 with sigma of 0.04
 C22-C30 \\sim C22A-C30A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C28) = Uanis(C28A)
Uanis(C22A) = Uanis(C22)
Uanis(C29A) = Uanis(C29)
Uanis(C21) = Uanis(C21A)
Uanis(C27A) = Uanis(C27)
4. Rigid body (RIGU) restrains
 C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A, C29A, C30A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C22, C23, C24, C25, C26, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C21A)=Sof(H21A)=Sof(C27A)=Sof(H27C)=Sof(H27D)=Sof(C24A)=Sof(H24A)=
 Sof(C25A)=Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(C22A)=
 Sof(C23A)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30D)=
 Sof(H30E)=Sof(H30F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(C21)=Sof(H21)=Sof(C22)=Sof(C23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25A)=
 Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=
 Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=
 Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C21(H21), C24(H24), C21A(H21A), C24A(H24A)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C27A(H27C,
 H27D), C25A(H25C,H25D), C26A(H26C,H26D)
6.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10),
 C11(H11), C12(H12), C15(H15), C16(H16), C18(H18), C19(H19)
6.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C29A(H29D,H29E,
 H29F), C30A(H30D,H30E,H30F), C28A(H28D,H28E,H28F)
;
_shelx_res_checksum              83652
_shelx_hkl_checksum              29173
_olex2_submission_special_instructions 'No special instructions were received'