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_1547634
_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         'C52 H110 N4 P4 Pd3'
_chemical_formula_sum            'C52 H110 N4 P4 Pd3'
_chemical_formula_weight         1234.51
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-02-11
_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                90
_cell_angle_beta                 110.126(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.1372(2)
_cell_length_b                   16.2799(2)
_cell_length_c                   16.5783(3)
_cell_measurement_reflns_used    12556
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      28.4970
_cell_measurement_theta_min      1.7900
_cell_volume                     3075.72(9)
_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, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.987
_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    -75.00 113.00   1.00   20.00    --   18.69  19.00 150.00  188
  2  \w    -81.00 -34.00   1.00   20.00    --   18.69 178.00-180.00   47
  3  \w    -82.00 -35.00   1.00   20.00    --   18.69-178.00 -30.00   47
  4  \w   -121.00 -35.00   1.00   20.00    --  -19.62-178.00  30.00   86
  5  \w    -32.00  23.00   1.00   20.00    --  -19.62 -88.00-123.00   55
  6  \w    -63.00 -45.00   1.00   20.00    --  -19.62  77.00  30.00   18
;
_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      0.0142526000
_diffrn_orient_matrix_UB_12      0.0163998000
_diffrn_orient_matrix_UB_13      0.0420074000
_diffrn_orient_matrix_UB_21      -0.0229711000
_diffrn_orient_matrix_UB_22      -0.0357140000
_diffrn_orient_matrix_UB_23      0.0129229000
_diffrn_orient_matrix_UB_31      0.0560637000
_diffrn_orient_matrix_UB_32      -0.0188180000
_diffrn_orient_matrix_UB_33      0.0120473000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            25060
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.368
_diffrn_reflns_theta_min         1.787
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.006
_exptl_absorpt_correction_T_max  0.934
_exptl_absorpt_correction_T_min  0.905
_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    1.333
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.126
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.649
_refine_diff_density_min         -0.474
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         6204
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0266
_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^)+(0.0199P)^2^+1.9490P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0579
_refine_ls_wR_factor_ref         0.0608
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5464
_reflns_number_total             6204
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03912c2.cif
_cod_data_source_block           34
_cod_original_cell_volume        3075.74(10)
_cod_database_code               1547634
_chemical_oxdiff_formula         C25H55P2NPd
_reflns_odcompleteness_completeness 98.54
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2.a Idealised Me refined as rotating group:
 C3E(H3EA,H3EB,H3EC), C3B(H3BA,H3BB,H3BC), C3C(H3CA,H3CB,H3CC), C2C(H2CA,H2CB,
 H2CC), C4E(H4EA,H4EB,H4EC), C2E(H2EA,H2EB,H2EC), C2B(H2BA,H2BB,H2BC), C2F(H2FA,
 H2FB,H2FC), C4F(H4FA,H4FB,H4FC), C2A(H2AA,H2AB,H2AC), C4A(H4AA,H4AB,H4AC),
 C4C(H4CA,H4CB,H4CC), C2D(H2DA,H2DB,H2DC), C4B(H4BA,H4BB,H4BC), C4D(H4DA,H4DB,
 H4DC), C3F(H3FA,H3FB,H3FC), C3D(H3DA,H3DB,H3DC), C3A(H3AA,H3AB,H3AC)
;
_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 1.832
_oxdiff_exptl_absorpt_empirical_full_min 0.766