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_7063048
_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         'C23 H21 F3 N4 O2 Pd, 0.5(C7 H8)'
_chemical_formula_sum            'C26.5 H25 F3 N4 O2 Pd'
_chemical_formula_weight         594.90
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-02-14
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-02-16 deposited with the CCDC.	2024-02-23 downloaded from the CCDC.
;
_cell_angle_alpha                99.053(3)
_cell_angle_beta                 99.487(3)
_cell_angle_gamma                97.943(4)
_cell_formula_units_Z            4
_cell_length_a                   11.2472(5)
_cell_length_b                   11.6670(6)
_cell_length_c                   20.8033(6)
_cell_measurement_reflns_used    10192
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.9440
_cell_measurement_theta_min      3.5730
_cell_volume                     2620.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0647
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            10696
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         3.544
_diffrn_source                   'fine-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.760
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91940
_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_colour            Colourless
_exptl_crystal_density_diffrn    1.508
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             1204
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.005
_refine_diff_density_max         1.910
_refine_diff_density_min         -1.069
_refine_diff_density_rms         0.148
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     657
_refine_ls_number_reflns         10696
_refine_ls_number_restraints     149
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0961
_refine_ls_R_factor_gt           0.0782
_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^)+(0.0837P)^2^+15.2202P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2076
_refine_ls_wR_factor_ref         0.2199
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8253
_reflns_number_total             10696
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj05516g3.cif
_cod_data_source_block           Complex-3
_cod_depositor_comments
'Adding full bibliography for 7063048--7063056.cif.'
_cod_original_formula_sum        'C26.50 H25 F3 N4 O2 Pd'
_cod_database_code               7063048
_shelx_shelxl_version_number     2016/4
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.76066
 0.23934
2. Restrained distances
 C47-C48
 1.51 with sigma of 0.02
 C48-C49 = C48-C53 = C50-C51
 1.39 with sigma of 0.02
 C49-C50 = C51-C52 = C52-C53
 1.38 with sigma of 0.02
 C47-C49 = C47-C53
 2.52 with sigma of 0.04
 C48-C50
 2.42 with sigma of 0.04
 C48-C52
 2.41 with sigma of 0.04
 C49-C51
 2.39 with sigma of 0.04
 C50-C52 = C51-C53
 2.4 with sigma of 0.04
 F3-F2 \\sim F3-F1 \\sim F1'-F2' \\sim F1'-F3' \\sim F2'-F3' \\sim F2-F1
 with sigma of 0.04
 C23-F3 \\sim C23-F1' \\sim C23-F2' \\sim C23-F3' \\sim C23-C22 \\sim C23-F2
\\sim C23-F1
 with sigma of 0.02
 C48-C49 \\sim C49-C50 \\sim C50-C51 \\sim C51-C52 \\sim C52-C53 \\sim C53-C48
 with sigma of 0.02
 C48-C52 \\sim C48-C50 \\sim C53-C51 \\sim C49-C53 \\sim C50-C52 \\sim C49-C51
 with sigma of 0.04
 C47-C53 \\sim C47-C49
 with sigma of 0.04
3. Restrained planarity
 C47, C48, C49, C50, C51, C52, C53
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C22, C23, F1, F2, F3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22, C23, F1', F2', F3'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, C48, C49, C50, C51, C52, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F1')=Sof(F2')=Sof(F3')=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C39(H39A,H39B)
7.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), N5(H5A), N6(H6A), C4(H4), C5(H5), C6(H6), C10(H10), C11(H11),
 C12(H12), C13(H13), C18(H18), C19(H19), C20(H20), C21(H21), C27(H27), C28(H28),
  C29(H29), C33(H33), C34(H34), C35(H35), C36(H36), C41(H41), C42(H42),
 C43(H43), C44(H44), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53)
7.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C31(H31A,H31B,H31C), C38(H38A,H38B,
 H38C), C47(H47A,H47B,H47C)
;
_shelx_res_checksum              11678
_olex2_submission_special_instructions 'No special instructions were received'