Bromoamination of α,β-unsaturated keto alkenes by palladium(ii) metalallocycles: experimental and theoretical approaches
Nandhini, S.; Dharani, S.; Mugesh, B.; Prabusankar, G.; Mohanapriya, S.; Shankar, R.; Prabhakaran, R.; New Journal of Chemistry 50 (2026) 1602–1612; doi:10.1039/D5NJ02138C

data_7064332
_publ_section_title
;
 Bromoamination of \a,\b-unsaturated keto alkenes by palladium(ii)
 metalallocycles: experimental and theoretical approaches
;
_journal_issue                   3
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              1602
_journal_page_last               1612
_journal_paper_doi               10.1039/D5NJ02138C
_journal_volume                  50
_journal_year                    2026
_chemical_formula_moiety         'C18 H14 Cl N4 O Pd S, C3 H7 N O'
_chemical_formula_sum            'C21 H21 Cl N5 O2 Pd S'
_chemical_formula_weight         549.37
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-02-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-12-28 deposited with the CCDC.	2025-12-22 downloaded from the CCDC.
;
_cell_angle_alpha                61.465(3)
_cell_angle_beta                 88.838(4)
_cell_angle_gamma                85.449(4)
_cell_formula_units_Z            2
_cell_length_a                   7.5069(8)
_cell_length_b                   12.9454(14)
_cell_length_c                   12.9847(14)
_cell_measurement_reflns_used    9993
_cell_measurement_temperature    273(2)
_cell_volume                     1104.8(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.9876
_diffrn_measured_fraction_theta_max 0.9876
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0367
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            29522
_diffrn_reflns_theta_full        27.1490
_diffrn_reflns_theta_max         27.15
_diffrn_reflns_theta_min         2.72
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.084
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6697
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0845 before and 0.0627 after correction.
The Ratio of minimum to maximum transmission is 0.8983.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.6512
_exptl_crystal_description       needle
_exptl_crystal_F_000             552.7431
_exptl_crystal_size_max          0.079
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.065
_refine_diff_density_max         2.7171
_refine_diff_density_min         -1.8643
_refine_diff_density_rms         0.2911
_refine_ls_d_res_high            0.7788
_refine_ls_d_res_low             7.4817
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0377
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    36
_refine_ls_number_parameters     284
_refine_ls_number_reflns         4849
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0377
_refine_ls_R_factor_all          0.0980
_refine_ls_R_factor_gt           0.0871
_refine_ls_shift/su_max          0.0006
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1162P)^2^+29.7263P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2998
_refine_ls_wR_factor_ref         0.3094
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              9
_reflns_limit_h_min              -9
_reflns_limit_k_max              16
_reflns_limit_k_min              -14
_reflns_limit_l_max              16
_reflns_limit_l_min              0
_reflns_number_gt                4121
_reflns_number_total             4849
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5nj02138c2.cif
_cod_data_source_block           mo_GP_8MODP_3_0m_a
_cod_database_code               7064332
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C12(H12), C13(H13), C14(H14), C10(H10), C6(H6), C5(H5), C4(H4),
 C3(H3), C2(H2), C19(H19), N1(H1)
2.b Idealised Me refined as rotating group:
 C16(H16a,H16b,H16c), C20(H20a,H20b,H20c), C21(H21a,H21b,H21c)
;
_olex2_submission_special_instructions 'No special instructions were received'