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_7063051
_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         'C26 H30 N4 O2 Pd, 0.5(C5 H9 O2), 0.5[C7H8]'
_chemical_formula_sum            'C32 H38.5 N4 O3 Pd'
_chemical_formula_weight         633.57
_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
_audit_creation_date             2024-02-21
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-02-21 deposited with the CCDC.	2024-02-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.847(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.8433(3)
_cell_length_b                   18.0831(5)
_cell_length_c                   29.6288(9)
_cell_measurement_reflns_used    10155
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.3670
_cell_measurement_theta_min      3.5570
_cell_volume                     6344.7(3)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0713
_diffrn_reflns_av_unetI/netI     0.0514
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            81137
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.414
_exptl_absorpt_coefficient_mu    0.621
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86766
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Pale-Yellow
_exptl_crystal_density_diffrn    1.327
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             2628
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.501
_refine_diff_density_min         -0.480
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     673
_refine_ls_number_reflns         11155
_refine_ls_number_restraints     463
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0784
_refine_ls_R_factor_gt           0.0555
_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^)+(0.0398P)^2^+8.3572P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1099
_refine_ls_wR_factor_ref         0.1204
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8319
_reflns_number_total             11155
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj05516g3.cif
_cod_data_source_block           Complex-5
_cod_depositor_comments
'Adding full bibliography for 7063048--7063056.cif.'
_cod_original_formula_sum        'C32 H38.50 N4 O3 Pd'
_cod_database_code               7063051
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.988
_olex2_refinement_description
;
1. Restrained distances
 C13-C12 = C11-C10 = C9-C14
 1.39 with sigma of 0.02
 C62-C61 = C63-C61
 1.34 with sigma of 0.02
 C64-C61
 1.33 with sigma of 0.02
 O5-C60
 1.25 with sigma of 0.02
 O6-C60
 1.24 with sigma of 0.02
 C60-C61
 1.55 with sigma of 0.02
 C62-C64 = C64-C63
 2.16 with sigma of 0.04
 C62-C63
 2.15 with sigma of 0.04
 C62-C60
 2.37 with sigma of 0.04
 C64-C60
 2.42 with sigma of 0.04
 C63-C60
 2.39 with sigma of 0.04
 O5-O6
 2.25 with sigma of 0.04
 O5-C61
 2.38 with sigma of 0.04
 O6-C61
 2.35 with sigma of 0.04
 C12-C13 \\sim C14-C9 \\sim C10-C11
 with sigma of 0.02
 C61-C62 \\sim C61-C64 \\sim C61-C63
 with sigma of 0.02
 C60-C62 \\sim C60-C64 \\sim C60-C63
 with sigma of 0.04
 C62-C64 \\sim C64-C63 \\sim C63-C62
 with sigma of 0.04
 C60-O6 \\sim C60-O5
 with sigma of 0.02
 C62-C61 \\sim C62A-C61A
 with sigma of 0.02
 C64-C61 \\sim C64A-C61A
 with sigma of 0.02
 C63-C61 \\sim C63A-C61A
 with sigma of 0.02
 C62-C64 \\sim C62A-C64A
 with sigma of 0.04
 C62-C63 \\sim C62A-C63A
 with sigma of 0.04
 C64-C63 \\sim C64A-C63A
 with sigma of 0.04
2. Restrained planarity
 C60, C61, O5, O6
 with sigma of 0.1
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14: within 1.4A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 1.4A
C62 \\sim C64 \\sim C63 \\sim O5 \\sim O6 \\sim C60 \\sim C61: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C61A \\sim C62A \\sim C64A \\sim C63A \\sim C61 \\sim C62 \\sim C64 \\sim C63
\\sim C60 \\sim O5 \\sim O6: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C64A \\sim C61A \\sim C62A \\sim C63A: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 within 2A
5. Rigid body (RIGU) restrains
 C62, C64, C63, O5, O6, C60, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6, C62, C61, C64, C63, C60, O5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C62A, C61A, C64A, C63A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(C61A)=Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C64A)=Sof(H64D)=
 Sof(H64E)=Sof(H64F)=Sof(C63A)=Sof(H63D)=Sof(H63E)=Sof(H63F)=1-FVAR(1)
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C61)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C42(H42A,H42B)
7.b Me refined with riding coordinates:
 C62(H62A,H62B,H62C), C64(H64A,H64B,H64C), C63(H63A,H63B,H63C), C62A(H62D,H62E,
 H62F), C64A(H64D,H64E,H64F), C63A(H63D,H63E,H63F)
7.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C4(H4), C5(H5), C6(H6), C12(H12), C13(H13), C10(H10),
 C11(H11), C18(H18), C19(H19), C20(H20), C21(H21), N5(H5A), N6(H6A), C30(H30),
 C31(H31), C32(H32), C36(H36), C37(H37), C38(H38), C39(H39), C44(H44), C45(H45),
  C46(H46), C47(H47)
7.d Fitted hexagon refined as free rotating group:
 C12(C13,C14,C9,C10,C11)
7.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C34(H34A,H34B,H34C), C41(H41A,H41B,H41C), C50(H50A,
 H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 176 electrons were 
found in a volume of 1096\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 0.5[C7H8] per formula unit 
which account for 200 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              44617
_shelx_fab_checksum              4080
_olex2_submission_special_instructions 'No special instructions were received'