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_1547633
_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         '2(C12 H27.5 Br0.5 P Pd0.5)'
_chemical_formula_sum            'C24 H55 Br P2 Pd'
_chemical_formula_weight         591.93
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-26
_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                 116.366(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.7069(4)
_cell_length_b                   34.9448(9)
_cell_length_c                   14.1937(6)
_cell_measurement_reflns_used    17661
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      32.3410
_cell_measurement_theta_min      2.9200
_cell_volume                     5646.9(4)
_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(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_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     35.00 109.00   1.00   60.00    --   19.09 178.00-150.00   74
  2  \w    -15.00  98.00   1.00   60.00    --   19.09  77.00-120.00  113
  3  \w     -7.00  95.00   1.00   60.00    --   19.09  38.00   0.00  102
  4  \w     35.00 109.00   1.00   60.00    --   19.09 178.00 120.00   74
  5  \w    -15.00  35.00   1.00   60.00    --   19.09  77.00  90.00   50
  6  \w    -46.00  37.00   1.00   60.00    --  -20.03  38.00 -60.00   83
;
_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      0.0462941000
_diffrn_orient_matrix_UB_12      -0.0094832000
_diffrn_orient_matrix_UB_13      0.0423333000
_diffrn_orient_matrix_UB_21      -0.0251304000
_diffrn_orient_matrix_UB_22      0.0052709000
_diffrn_orient_matrix_UB_23      0.0338674000
_diffrn_orient_matrix_UB_31      -0.0332712000
_diffrn_orient_matrix_UB_32      -0.0171622000
_diffrn_orient_matrix_UB_33      -0.0130197000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0389
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       49
_diffrn_reflns_limit_k_min       -49
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            42484
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.506
_diffrn_reflns_theta_min         2.331
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.195
_exptl_absorpt_correction_T_max  0.999
_exptl_absorpt_correction_T_min  0.999
_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    1.392
_exptl_crystal_description       block
_exptl_crystal_F_000             2480
_exptl_crystal_size_max          0.162
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.089
_refine_diff_density_max         0.755
_refine_diff_density_min         -0.985
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         8624
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0333
_refine_ls_R_factor_gt           0.0249
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0208P)^2^+3.8394P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0523
_refine_ls_wR_factor_ref         0.0556
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7330
_reflns_number_total             8624
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03912c2.cif
_cod_data_source_block           36
_cod_original_cell_volume        5647.0(4)
_cod_database_code               1547633
_chemical_oxdiff_formula         'Pd P2 Br H15 C8'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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:
 C18(H18A,H18B,H18C), C23(H23A,H23B,H23C), C12(H12A,H12B,H12C), C24(H24A,H24B,
 H24C), C15(H15A,H15B,H15C), C3(H3A,H3B,H3C), C2(H2A,H2B,H2C), C10(H10A,H10B,
 H10C), C4(H4A,H4B,H4C), C20(H20A,H20B,H20C), C11(H11A,H11B,H11C), C19(H19A,
 H19B,H19C), C7(H7A,H7B,H7C), C6(H6A,H6B,H6C), C16(H16A,H16B,H16C), C22(H22A,
 H22B,H22C), C14(H14A,H14B,H14C), C8(H8A,H8B,H8C)
;
_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 1.538
_oxdiff_exptl_absorpt_empirical_full_min 0.693