Guanidine-centred reactivity of CNN Pd(ii) pincer complexes including carboxylate-assisted N–H activation and –CH2– → –C(O)– oxygenation
Sinha, Nitish Kumar; Khan, Hilal Ahmad; Sivasankar, Chinnappan; Thirupathi, Natesan; New Journal of Chemistry 48 (2024) 5710–5720; doi:10.1039/D3NJ05516G

data_7063053
_publ_section_title
;
 Guanidine-centred reactivity of CNN Pd(ii) pincer complexes including
 carboxylate-assisted N--H activation and --CH2-- \\rightarrow --C(O)--
 oxygenation
;
_journal_issue                   13
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              5710
_journal_page_last               5720
_journal_paper_doi               10.1039/D3NJ05516G
_journal_volume                  48
_journal_year                    2024
_chemical_formula_moiety         'C30 H24 F6 N5 Pd, C2 F3 O2'
_chemical_formula_sum            'C32 H24 F9 N5 O2 Pd'
_chemical_formula_weight         787.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-09-24 deposited with the CCDC.	2024-02-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.085(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.2270(3)
_cell_length_b                   26.1341(7)
_cell_length_c                   15.2245(4)
_cell_measurement_reflns_used    29232
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.0380
_cell_measurement_theta_min      2.0560
_cell_volume                     3240.81(17)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0711
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            8299
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.194
_diffrn_reflns_theta_min         2.063
_diffrn_source                   'micro-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.663
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44638
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             1576
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.530
_refine_diff_density_min         -0.955
_refine_diff_density_rms         0.141
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.369
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         8299
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.384
_refine_ls_R_factor_all          0.1266
_refine_ls_R_factor_gt           0.1133
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3111
_refine_ls_wR_factor_ref         0.3366
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6568
_reflns_number_total             8299
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj05516g3.cif
_cod_data_source_block           Complex-14
_cod_depositor_comments
'Adding full bibliography for 7063048--7063056.cif.'
_cod_database_code               7063053
_shelx_shelxl_version_number     2016/4
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.702(3)
 0.298(3)
2. 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
3. Restrained distances
 C32-F7' \\sim C32-F9' \\sim C32-F8 \\sim C32-F7 \\sim C32-F9 \\sim C32-C31
\\sim C32-F8'
 with sigma of 0.02
4. Rigid body (RIGU) restrains
 C31, C32, F7, F8, F9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31, C32, F7', F8', F9'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F7')=Sof(F8')=Sof(F9')=1-FVAR(1)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
6.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12),
 C13(H13), C18(H18), C19(H19), C20(H20), C21(H21), C25(H25), C26(H26), C27(H27)
6.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              89703
_olex2_submission_special_instructions 'No special instructions were received'