Experimental and Computational Studies on Remote γ-C(sp3)‒H Silylation and Germanylation of Aliphatic Carboxamides
Deb, Arghya; Singh, Sukriti; Seth, Kapileswar; Pimparkar, Sandeep; Bhaskararao, Bangaru; Guin, Srimanta; Sunoj, Raghavan B.; Maiti, Debabrata; ACS Catalysis 7 (2017) 8171–; doi:10.1021/acscatal.7b03056

data_4514253
_publ_section_title
;
 Experimental and Computational Studies on Remote \g-C(sp3)--H Silylation
 and Germanylation of Aliphatic Carboxamides
;
_journal_issue                   12
_journal_name_full               'ACS Catalysis'
_journal_page_first              8171
_journal_paper_doi               10.1021/acscatal.7b03056
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C24 H20 N4 O3 Pd'
_chemical_formula_sum            'C24 H20 N4 O3 Pd'
_chemical_formula_weight         259.92
_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_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-05-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_cell_angle_alpha                95.970(18)
_cell_angle_beta                 98.14(2)
_cell_angle_gamma                94.164(18)
_cell_formula_units_Z            2
_cell_length_a                   8.323(2)
_cell_length_b                   11.108(2)
_cell_length_c                   11.747(3)
_cell_measurement_reflns_used    811
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      64.2230
_cell_measurement_theta_min      3.8430
_cell_volume                     1065.0(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    SHELXTL
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.974
_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   -191.00 -11.00   1.00    8.00    -- -101.00   0.00 108.00  180
  2  \w   -122.00  58.00   1.00    8.00    --  -32.00   0.00 108.00  180
  3  \w   -135.00 -11.00   1.00    8.00    -- -101.00  72.00 -36.00  124
  4  \w   -135.00 -17.00   1.00    8.00    -- -101.00  72.00-180.00  118
  5  \w   -103.00 -16.00   1.00    8.00    -- -101.00  72.00  36.00   87
  6  \w   -106.00 -18.00   1.00    8.00    -- -101.00  72.00-108.00   88
  7  \w   -105.00 -16.00   1.00    8.00    -- -101.00  72.00 108.00   89
  8  \w    -66.00   2.00   1.00    8.00    --  -32.00  72.00 108.00   68
  9  \w    -50.00 -48.00   1.00    8.00    --  -32.00  72.00-108.00    2
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1763864000
_diffrn_orient_matrix_UB_12      0.0322256000
_diffrn_orient_matrix_UB_13      -0.0321820000
_diffrn_orient_matrix_UB_21      -0.0370834000
_diffrn_orient_matrix_UB_22      -0.1167281000
_diffrn_orient_matrix_UB_23      -0.0857493000
_diffrn_orient_matrix_UB_31      -0.0524843000
_diffrn_orient_matrix_UB_32      -0.0702132000
_diffrn_orient_matrix_UB_33      0.0970010000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2606
_diffrn_reflns_av_unetI/netI     0.2603
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            6364
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        65.000
_diffrn_reflns_theta_max         65.000
_diffrn_reflns_theta_min         3.827
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.319
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44604
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.621
_exptl_crystal_density_meas      ?
_exptl_crystal_description       PLATE
_exptl_crystal_F_000             526
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.987
_refine_diff_density_min         -2.247
_refine_diff_density_rms         0.287
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.131
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         3523
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.131
_refine_ls_R_factor_all          0.2606
_refine_ls_R_factor_gt           0.1739
_refine_ls_shift/su_max          2.927
_refine_ls_shift/su_mean         0.118
_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          0.3856
_refine_ls_wR_factor_ref         0.4866
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1328
_reflns_number_total             3523
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b03056_si_002.cif
_cod_data_source_block           c24h20n4o3pd
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'not measured' was changed to '?'
- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 

 Adding full bibliography for 4514253.cif.

2020-09-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_weight         259.92
_cod_original_formula_moiety         '0.5(C24 H20 N4 O3 Pd)'
_cod_original_formula_units_Z            4
_cod_original_formula_sum        'C12 H10.50 N2 O1.50 Pd0.50'
_cod_database_code               4514253
_exptl_absorpt_special_details   Numerical
_reflns_odcompleteness_completeness 91.33
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C10-O1
 1.25 with sigma of 0.02
 C10-N2
 1.35 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C9) = Uanis(N1) = Uanis(C1) = Uanis(C2) = Uanis(C3) = Uanis(C4)
Uanis(C20) = Uanis(C21) = Uanis(C22)
Uanis(C23) = Uanis(C24)
4.a Ternary CH refined with riding coordinates:
 C11(H11), C20(H20)
4.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C1(H1), C5(H5), C6(H6), C14(H14), C17(H17), C16(H16),
 C15(H15), C3(H3)
4.d Fitted hexagon refined as free rotating group:
 C14(C13,C18,C17,C16,C15)
4.e Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C22(H22A,H22B,H22C)
;
_shelx_shelxl_version_number     2014/7
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.291
_oxdiff_exptl_absorpt_empirical_full_min 0.411