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_7063056
_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 H23 F6 N5 Pd, 0.5(C7 H8)'
_chemical_formula_sum            'C33.5 H27 F6 N5 Pd'
_chemical_formula_weight         720.027
_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
_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                92.799(2)
_cell_angle_beta                 96.175(2)
_cell_angle_gamma                100.159(2)
_cell_formula_units_Z            2
_cell_length_a                   8.7513(2)
_cell_length_b                   12.4438(3)
_cell_length_c                   14.6041(4)
_cell_measurement_reflns_used    17359
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      30.3290
_cell_measurement_theta_min      3.1190
_cell_volume                     1552.62(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-dev (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9977
_diffrn_measured_fraction_theta_max 0.9980
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -23.00  38.00   0.50    0.80    --    5.37 -99.00-150.00  122
  2  \w    -23.00  38.00   0.50    0.80    --    5.37 -99.00-120.00  122
  3  \w    -23.00  38.00   0.50    0.80    --    5.37 -99.00 -60.00  122
  4  \w    -23.00  38.00   0.50    0.80    --    5.37 -99.00 120.00  122
  5  \w    -78.00   8.00   0.50    0.80    --   -5.21 -38.00 120.00  172
  6  \w    -80.00 -46.00   0.50    0.80    --   -5.21 -19.00   0.00   68
  7  \w    -17.00  78.00   0.50    0.80    --    5.37  77.00  30.00  190
  8  \w     -8.00  78.00   0.50    0.80    --    5.37  38.00 -30.00  172
  9  \w     -8.00  78.00   0.50    0.80    --    5.37  38.00 -90.00  172
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 0.9977
_diffrn_reflns_Laue_measured_fraction_max 0.9980
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            31500
_diffrn_reflns_point_group_measured_fraction_full 0.9977
_diffrn_reflns_point_group_measured_fraction_max 0.9980
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         3.15
_exptl_absorpt_coefficient_mu    0.666
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25044
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.540
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             724.558
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.4110
_refine_diff_density_min         -0.5302
_refine_diff_density_rms         0.0619
_refine_ls_d_res_high            0.8000
_refine_ls_d_res_low             6.4732
_refine_ls_extinction_coef       0.0064(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0387
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    56
_refine_ls_number_parameters     434
_refine_ls_number_reflns         6336
_refine_ls_number_restraints     152
_refine_ls_restrained_S_all      1.0256
_refine_ls_R_factor_all          0.0342
_refine_ls_R_factor_gt           0.0294
_refine_ls_shift/su_max          0.0010
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0383P)^2^+0.3787P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0715
_refine_ls_wR_factor_ref         0.0744
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              15
_reflns_limit_k_min              -15
_reflns_limit_l_max              18
_reflns_limit_l_min              0
_reflns_number_gt                5643
_reflns_number_total             6336
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3nj05516g3.cif
_cod_data_source_block           Complex-17
_cod_depositor_comments
'Adding full bibliography for 7063048--7063056.cif.'
_cod_database_code               7063056
_olex2_refinement_description
;
1. Restrained distances
 C31-C32
 1.51 with sigma of 0.02
 C32-C33 = C32-C37 = C34-C35
 1.39 with sigma of 0.02
 C33-C34 = C35-C36 = C36-C37
 1.38 with sigma of 0.02
 C32-C34
 2.42 with sigma of 0.04
 C33-C35
 2.39 with sigma of 0.04
 C32-C36
 2.41 with sigma of 0.04
 C34-C36 = C35-C37
 2.4 with sigma of 0.04
 C31-C33 = C31-C37
 2.52 with sigma of 0.04
 C32-C33 \\sim C33-C34 \\sim C34-C35 \\sim C35-C36 \\sim C36-C37 \\sim C37-C32
 with sigma of 0.02
 C32-C36 \\sim C32-C34 \\sim C37-C35 \\sim C33-C37 \\sim C34-C36 \\sim C33-C35
 with sigma of 0.04
 C31-C37 \\sim C31-C33
 with sigma of 0.04
2. Restrained planarity
 C31, C32, C33, C34, C35, C36, C37
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C31, C32, C33, C34, C35, C36, C37
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31, C32, C33, C37, C34, C36, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C31(0.5) H31a(0.5) H31b(0.5) H31c(0.5) C32(0.5) C33(0.5) H33(0.5)
 C34(0.5) H34(0.5) C35(0.5) H35(0.5) C36(0.5) H36(0.5) C37(0.5) H37(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C16(H16a,H16b)
6.b Aromatic/amide H refined with riding coordinates:
 N1(H1), 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), C33(H33),
  C34(H34), C35(H35), C36(H36), C37(H37)
6.c Fitted hexagon refined as free rotating group:
 C32(C33,C34,C35,C36,C37)
6.d Idealised Me refined as rotating group:
 C29(H29a,H29b,H29c), C30(H30a,H30b,H30c), C31(H31a,H31b,H31c)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;