Mono-N-Protected Amino Acid Ligands Stabilize Dimeric Palladium(II) Complexes of Importance to C-H Functionalization
Gair, Joe J.; Haines, Brandon E.; Filatov, Alexander S.; Musaev, D. G.; Lewis, Jared C.; Chem. Sci.  (2017) –; doi:10.1039/C7SC01674C

data_1546337
_publ_section_title
;
 Mono-N-Protected Amino Acid Ligands Stabilize Dimeric Palladium(II)
 Complexes of Importance to C-H Functionalization
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC01674C
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C36 H50 F6 N4 O6 Pd2, C7 H8'
_chemical_formula_sum            'C43 H58 F6 N4 O6 Pd2'
_chemical_formula_weight         1053.73
_space_group_crystal_system      orthorhombic
_space_group_IT_number           20
_space_group_name_Hall           'C 2c 2'
_space_group_name_H-M_alt        'C 2 2 21'
_symmetry_space_group_name_Hall  'C 2c 2'
_symmetry_space_group_name_H-M   'C 2 2 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-12-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2017-04-15 deposited with the CCDC.
2017-06-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.2657(11)
_cell_length_b                   29.630(4)
_cell_length_c                   19.311(3)
_cell_measurement_reflns_used    9626
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.17
_cell_measurement_theta_min      2.30
_cell_volume                     5301.7(13)
_computing_cell_refinement       'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_molecular_graphics
;
OLEX2: a complete structure solution, refinement and analysis program 
Dolomanov et al., 2009

Mercury: visualization and analysis of crystal structures
Macrae, et al., 2006

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

C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor,
M. Towler and J. van de Streek, J. Appl. Cryst. (2006). 39, 453-457.
;
_computing_publication_material
;
 APEX3 v.2015.5-2 (Bruker AXS Inc., 2015)
 OLEX2 (Dolomanov et al., 2009)
;
_computing_structure_refinement  'XL-2014/7 (Sheldrick, 2015b)'
_computing_structure_solution    'XT 2014/5 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.4167
_diffrn_measured_fraction_theta_full 0.932
_diffrn_measured_fraction_theta_max 0.932
_diffrn_measurement_device_type  'Bruker D8 Venture PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0712
_diffrn_reflns_av_unetI/netI     0.0778
_diffrn_reflns_Laue_measured_fraction_full 0.932
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            21110
_diffrn_reflns_point_group_measured_fraction_full 0.892
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        25.02
_diffrn_reflns_theta_max         25.02
_diffrn_reflns_theta_min         2.30
_diffrn_source                   'INCOATEC ImuS micro-focus source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.742
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6038
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0918 before and 0.0694 after correction.
The Ratio of minimum to maximum transmission is 0.8103.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             2152
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.08
_refine_diff_density_max         2.100
_refine_diff_density_min         -0.900
_refine_diff_density_rms         0.114
_refine_ls_abs_structure_details
;
 Flack x determined using 1165 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.017(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         4174
_refine_ls_number_restraints     105
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0899
_refine_ls_R_factor_gt           0.0650
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0525P)^2^+57.4330P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1400
_refine_ls_wR_factor_ref         0.1490
_reflns_Friedel_coverage         0.709
_reflns_Friedel_fraction_full    0.840
_reflns_Friedel_fraction_max     0.840
_reflns_number_gt                3262
_reflns_number_total             4174
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc01674c6.cif
_cod_data_source_block           complex_6c
_cod_original_cell_volume        5301.8(12)
_cod_database_code               1546337
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.819
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1-C18 = F3-C18 = F2-C18
 1.33 with sigma of 0.02
 C18-C13
 1.45 with sigma of 0.02
 C21-C20 \\sim C22-C21 \\sim C23-C22 \\sim C23-C22_$1 \\sim C22_$1-C21_$1 \\sim
C21_$1-C20
 with sigma of 0.005
3. Rigid body (RIGU) restrains
 C21, C22, C19, C20, C21, C22, C23
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C1, C2, N2, O3, C7, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{C16, C17, N1, C15, C9, C10, C11, C12, C13, C14, C18, F1, F2, F3} sigma for
1-2: 0.02, 1-3: 0.04
as
{C16A, C17A, N1A, C15A, C9A, C10A, C11A, C12A, C13A, C14A, C18A, F1A, F3A, F2A}
5. Others
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(N1A)=Sof(C15A)=Sof(H15C)=Sof(H15D)=Sof(C9A)=Sof(C10A)=Sof(H10A)=
 Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(C14A)=Sof(C18A)=Sof(F1A)=
 Sof(F3A)=Sof(F2A)=1-FVAR(1)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(N1)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C9)=Sof(C10)=Sof(H10)=Sof(C11)=
 Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(C14)=Sof(C18)=Sof(F1)=Sof(F2)=Sof(F3)=
 FVAR(1)
 Fixed Sof: H19A(0.5) H19B(0.5) H19C(0.5)
6.a Ternary CH refined with riding coordinates:
 C5(H5), C7(H7)
6.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C15(H15A,H15B), C15A(H15C,H15D)
6.c Me refined with riding coordinates:
 C19(H19A,H19B,H19C)
6.d Aromatic/amide H refined with riding coordinates:
 N2(H2), C21(H21), C22(H22), C23(H23), C10(H10), C11(H11), C12(H12),
 C10A(H10A), C11A(H11A), C12A(H12A)
6.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C16(H16A,H16B,H16C),
 C17(H17A,H17B,H17C), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F)
;
_shelx_res_checksum              8830
_shelx_fab_checksum              28832
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'