Ex situ generation of stoichiometric HCN and its application in the Pd-catalysed cyanation of aryl bromides: Evidence for a transmetallation step between two oxidative addition Pd-complexes
Skrydstrup, Troels; Kristensen, Steffan Kvist; Eikeland, Espen; Taarning, Esben; Lindhardt, Anders T.; Chem. Sci.  (2017) –; doi:10.1039/C7SC03912C

data_1547631
_publ_section_title
;
 Ex situ generation of stoichiometric HCN and its application in the
 Pd-catalysed cyanation of aryl bromides: Evidence for a transmetallation
 step between two oxidative addition Pd-complexes
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC03912C
_journal_year                    2017
_chemical_formula_moiety         'C38 H30 N2 P2 Pd'
_chemical_formula_sum            'C38 H30 N2 P2 Pd'
_chemical_formula_weight         682.98
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2016-08-10
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)

Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H.
 (2009), J. Appl. Cryst. 42, 339-341.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.

Sheldrick, G.M. (2015). Acta Cryst. C71, 3-8.
;
_audit_update_record
;
2016-09-19 deposited with the CCDC.
2017-10-06 downloaded from the CCDC.
;
_cell_angle_alpha                111.130(3)
_cell_angle_beta                 93.150(3)
_cell_angle_gamma                108.191(3)
_cell_formula_units_Z            1
_cell_length_a                   9.0667(3)
_cell_length_b                   9.6985(4)
_cell_length_c                   10.1017(3)
_cell_measurement_reflns_used    11480
_cell_measurement_temperature    100.00(14)
_cell_measurement_theta_max      28.4520
_cell_measurement_theta_min      2.1880
_cell_volume                     772.96(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -28.00 109.00   1.00   20.00    --   18.69  38.00 -60.00  137
  2  \w    -73.00  60.00   1.00   20.00    --   18.69 -57.00   0.00  133
  3  \w    -20.00  69.00   1.00   20.00    --   18.69 -99.00 150.00   89
  4  \w    -20.00  31.00   1.00   20.00    --  -19.62 -99.00 -90.00   51
  5  \w    -28.00 109.00   1.00   20.00    --   18.69  38.00 120.00  137
  6  \w   -112.00  22.00   1.00   20.00    --  -19.62 -57.00   0.00  134
  7  \w    -20.00  31.00   1.00   20.00    --  -19.62 -99.00 120.00   51
  8  \w   -121.00 -35.00   1.00   20.00    --  -19.62-178.00-180.00   86
  9  \w   -119.00 -34.00   1.00   20.00    --  -19.62 178.00 120.00   85
 10  \w   -119.00 -34.00   1.00   20.00    --  -19.62 178.00 150.00   85
 11  \w    -82.00 104.00   1.00   20.00    --   18.69   0.00-180.00  186
 12  \w    -23.00  27.00   1.00   20.00    --   18.69  57.00 120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0561297000
_diffrn_orient_matrix_UB_12      0.0299939000
_diffrn_orient_matrix_UB_13      -0.0382486000
_diffrn_orient_matrix_UB_21      -0.0305696000
_diffrn_orient_matrix_UB_22      0.0608143000
_diffrn_orient_matrix_UB_23      0.0072927000
_diffrn_orient_matrix_UB_31      0.0542878000
_diffrn_orient_matrix_UB_32      0.0494418000
_diffrn_orient_matrix_UB_33      0.0660332000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0320
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            17898
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.370
_diffrn_reflns_theta_min         2.201
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.734
_exptl_absorpt_correction_T_max  0.785
_exptl_absorpt_correction_T_min  0.683
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_description       block
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.172
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.086
_refine_diff_density_max         0.454
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     196
_refine_ls_number_reflns         3157
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0220
_refine_ls_R_factor_gt           0.0201
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0195P)^2^+0.6107P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0503
_refine_ls_wR_factor_ref         0.0514
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3020
_reflns_number_total             3157
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03912c2.cif
_cod_data_source_block           35
_cod_database_code               1547631
_chemical_oxdiff_formula         Pd2C30H30N4
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C13(H13), C5(H5), C9(H9), C7(H7), C4(H4), C19(H19), C10(H10), C6(H6),
 C12(H12), C15(H15), C11(H11), C17(H17), C16(H16), C18(H18)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.688
_oxdiff_exptl_absorpt_empirical_full_min 0.673