The Elusive Structure of Pd2(dba)3. Examination by Isotopic Labeling, NMR Spectroscopy, and X-ray Diffraction Analysis: Synthesis and Characterization of Pd2(dba-Z)3 Complexes
Anant R. Kapdi; Adrian C. Whitwood; David C. Williamson; Jason M. Lynam; Michael J. Burns; Thomas J. Williams; Alan J. Reay; Jordan Holmes; Ian J. S. Fairlamb; Journal of the American Chemical Society 135 (2013) 8388–8399; doi:10.1021/ja403259c

data_4119848
_publ_section_title
;
 The Elusive Structure of Pd2(dba)3. Examination by Isotopic Labeling, NMR
 Spectroscopy, and X-ray Diffraction Analysis: Synthesis and
 Characterization of Pd2(dba-Z)3 Complexes
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8388
_journal_page_last               8399
_journal_paper_doi               10.1021/ja403259c
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C51 H42 O3 Pd2, C H Cl3'
_chemical_formula_sum            'C52 H43 Cl3 O3 Pd2'
_chemical_formula_weight         1035.01
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-11-20
_audit_creation_method
;
  Olex2 1.2
  (compiled Nov  5 2012 18:25:38, GUI svn.r4372)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 101.3288(14)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   13.3506(2)
_cell_length_b                   13.27319(12)
_cell_length_c                   24.3667(3)
_cell_measurement_reflns_used    12076
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      30.0120
_cell_measurement_theta_min      2.9481
_cell_volume                     4233.77(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.9988
_diffrn_measured_fraction_theta_max 0.9988
_diffrn_measurement_details
;
  1 omega  -95.00  -68.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.1392  178.0000   30.0000 27

  2 omega  -68.00  -26.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.1392  103.0000  164.0000 42

  3 omega    8.00   92.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3892   57.0000   30.0000 84

  4 omega  -10.00   99.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3892   19.0000  150.0000 109
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0524074000
_diffrn_orient_matrix_UB_12      -0.0083059000
_diffrn_orient_matrix_UB_13      -0.0114798000
_diffrn_orient_matrix_UB_21      -0.0126246000
_diffrn_orient_matrix_UB_22      0.0126466000
_diffrn_orient_matrix_UB_23      0.0260945000
_diffrn_orient_matrix_UB_31      -0.0053826000
_diffrn_orient_matrix_UB_32      0.0512590000
_diffrn_orient_matrix_UB_33      -0.0083038000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            25517
_diffrn_reflns_theta_full        30.08
_diffrn_reflns_theta_max         30.08
_diffrn_reflns_theta_min         2.95
_diffrn_source                   'SuperNova (Mo) x-ray Source'
_exptl_absorpt_coefficient_mu    1.084
_exptl_absorpt_correction_T_max  0.909
_exptl_absorpt_correction_T_min  0.885
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
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)
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.624
_exptl_crystal_description       block
_exptl_crystal_F_000             2088
_exptl_crystal_size_max          0.1342
_exptl_crystal_size_mid          0.1177
_exptl_crystal_size_min          0.1018
_refine_diff_density_max         0.838
_refine_diff_density_min         -0.613
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     631
_refine_ls_number_reflns         12430
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0464
_refine_ls_R_factor_gt           0.0333
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0269P)^2^+4.3079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0720
_refine_ls_wR_factor_ref         0.0796
_reflns_number_gt                10253
_reflns_number_total             12430
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja403259c_si_002_1.cif
_cod_data_source_block           ijsf1227
_cod_database_code               4119848
_chemical_oxdiff_formula         'C52 H43 Cl3 O3 Pd2'
_chemical_oxdiff_usercomment     'Alan 1'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H51 of C51, H50 of C50, H49 of C49, H48 of C48, H47 of C47, H51A of C51A,
  H50A of C50A, H49A of C49A, H48A of C48A, H37A of C37A, H39A of C39A, H38A of
  C38A, H41 of C41, H41A of C41A, H42 of C42, H42A of C42A, H44 of C44, H44A of
  C44A, H45 of C45, H45A of C45A, H47A of C47A, H11A of C11A, H11 of C11, H10A
  of C10A, H10 of C10, H8A of C8A, H8 of C8, H7A of C7A, H7 of C7, H1A of C1A,
  H2A of C2A, H3A of C3A, H4A of C4A, H5A of C5A, H5 of C5, H4 of C4, H3 of C3,
  H2 of C2, H1 of C1, H28A of C28A, H30 of C30, H31 of C31, H32 of C32, H33 of
  C33, H34 of C34, H34A of C34A, H33A of C33A, H32A of C32A, H31A of C31A, H30A
  of C30A, H35 of C35, H36 of C36, H37 of C37, H38 of C38, H39 of C39, H35A of
  C35A, H36A of C36A, H17A of C17A, H16A of C16A, H15A of C15A, H14A of C14A,
  H13A of C13A, H13 of C13, H14 of C14, H15 of C15, H16 of C16, H17 of C17, H18
  of C18, H19 of C19, H20 of C20, H21 of C21, H22 of C22, H18A of C18A, H19A of
  C19A, H20A of C20A, H21A of C21A, H22A of C22A, H24 of C24, H24A of C24A, H25
  of C25, H25A of C25A, H27 of C27, H27A of C27A, H28 of C28, H52 of C52
2. Restrained distances
 C10A-C11A
 1.36 with sigma of 0.01
 C8A-O1A ~ C10A-O1A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C26) ~ Ueq, Uanis(C26A) ~ Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02
Uanis(O1) ~ Ueq, Uanis(O1A) ~ Ueq: with sigma of 0.002 and sigma for 
terminal atoms of 0.004
Uanis(C24) = Uanis(C24A)
Uanis(C25) = Uanis(C25A)
Uanis(C27) = Uanis(C27A)
Uanis(C28) = Uanis(C28A)
Uanis(O2) = Uanis(O2A)
Uanis(C42) = Uanis(C42A)
Uanis(C44) = Uanis(C44A)
Uanis(O3) = Uanis(O3A)
Uanis(C7) = Uanis(C7A)
Uanis(C10) = Uanis(C10A)
Uanis(C11) = Uanis(C11A)
Uanis(C8) = Uanis(C8A)
Uanis(C9) = Uanis(C9A)
Uanis(C41) = Uanis(C41A)
Uanis(C45) = Uanis(C45A)
Uanis(C46) = Uanis(C46A)
Uanis(C47) = Uanis(C47A)
Uanis(C48) = Uanis(C48A)
Uanis(C49) = Uanis(C49A)
Uanis(C51) = Uanis(C51A)
Uanis(C40) = Uanis(C40A)
Uanis(C35) = Uanis(C35A)
Uanis(C36) = Uanis(C36A)
Uanis(C37) = Uanis(C37A)
Uanis(C38) = Uanis(C38A)
Uanis(C39) = Uanis(C39A)
Uanis(C50) = Uanis(C50A)
Uanis(C26) = Uanis(C26A)
Uanis(C29) = Uanis(C29A)
Uanis(C30) = Uanis(C30A)
Uanis(C31) = Uanis(C31A)
Uanis(C32) = Uanis(C32A)
Uanis(C34) = Uanis(C34A)
Uanis(C33) = Uanis(C33A)
Uanis(C23) = Uanis(C23A)
Uanis(C22) = Uanis(C22A)
Uanis(C21) = Uanis(C21A)
Uanis(C20) = Uanis(C20A)
Uanis(C19) = Uanis(C19A)
Uanis(C18) = Uanis(C18A)
Uanis(C12) = Uanis(C12A)
Uanis(C17) = Uanis(C17A)
Uanis(C13) = Uanis(C13A)
Uanis(C16) = Uanis(C16A)
Uanis(C15) = Uanis(C15A)
Uanis(C14) = Uanis(C14A)
Uanis(O1) = Uanis(O1A)
Uanis(C1) = Uanis(C1A)
Uanis(C6) = Uanis(C6A)
Uanis(C5) = Uanis(C5A)
Uanis(C4) = Uanis(C4A)
Uanis(C3) = Uanis(C3A)
Uanis(C2) = Uanis(C2A)
4. others
 Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=
 Sof(C22)=Sof(H22)=Sof(C23)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-
 Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=
 Sof(C24)=Sof(H24)=1-Sof(H18)=1-Sof(H18)=Sof(C25)=Sof(H25)=1-Sof(H18)=1-
 Sof(H18)=Sof(C26)=1-Sof(H18)=Sof(C27)=Sof(H27)=1-Sof(H18)=1-Sof(H18)=Sof(C28)=
 Sof(H28)=1-Sof(H18)=1-Sof(H18)=Sof(C29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=
 Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=1-Sof(H18)=1-Sof(H18)=1-
 Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-Sof(H18)=1-
 Sof(H18)=1-Sof(H18)=Sof(O2)=1-Sof(H18)
 Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=Sof(C37)=Sof(H37)=Sof(C38)=Sof(H38)=
 Sof(C39)=Sof(H39)=Sof(C40)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-
 Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=
 Sof(C41)=Sof(H41)=1-Sof(H35)=1-Sof(H35)=Sof(C42)=Sof(H42)=1-Sof(H35)=1-
 Sof(H35)=Sof(C44)=Sof(H44)=1-Sof(H35)=1-Sof(H35)=Sof(C45)=Sof(H45)=1-Sof(H35)=
 1-Sof(H35)=Sof(C46)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-
 Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=1-Sof(H35)=Sof(C47)=
 Sof(H47)=Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50)=Sof(C51)=
 Sof(H51)=Sof(O3)=1-Sof(H35)
 Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=
 Sof(H5)=Sof(C6)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-
 Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=Sof(C7)=Sof(H7)=1-Sof(H1)=1-
 Sof(H1)=Sof(C8)=Sof(H8)=1-Sof(H1)=1-Sof(H1)=Sof(C9)=1-Sof(H1)=Sof(C10)=
 Sof(H10)=1-Sof(H1)=1-Sof(H1)=Sof(C11)=Sof(H11)=1-Sof(H1)=1-Sof(H1)=Sof(C12)=1-
 Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=
 1-Sof(H1)=1-Sof(H1)=1-Sof(H1)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=
 Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(O1)=1-Sof(H1)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C7A(H7A), C8(H8), C8A(H8A), C10(H10), C10A(H10A), C11(H11),
 C11A(H11A), C24(H24), C24A(H24A), C25(H25), C25A(H25A), C27(H27), C27A(H27A),
 C28(H28), C28A(H28A), C41(H41), C41A(H41A), C42(H42), C42A(H42A), C44(H44),
 C44A(H44A), C45(H45), C45A(H45A), C52(H52)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C5A(H5A), C4A(H4A), C3A(H3A),
 C2A(H2A), C1A(H1A), C17A(H17A), C16A(H16A), C15A(H15A), C14A(H14A), C13A(H13A),
  C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C18A(H18A), C19A(H19A), C20A(H20A), C21A(H21A),
 C22A(H22A), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C34A(H34A),
 C33A(H33A), C32A(H32A), C31A(H31A), C30A(H30A), C35(H35), C36(H36), C37(H37),
 C38(H38), C39(H39), C35A(H35A), C36A(H36A), C37A(H37A), C39A(H39A), C38A(H38A),
  C47A(H47A), C48A(H48A), C49A(H49A), C50A(H50A), C51A(H51A), C47(H47),
 C48(H48), C49(H49), C50(H50), C51(H51)
5.c Fitted hexagon refined as free rotating group:
 C6A(C5A,C4A,C3A,C2A,C1A), C12A(C17A,C16A,C15A,C14A,C13A), C23A(C18A,C19A,C20A,
 C21A,C22A), C34A(C33A,C32A,C31A,C30A,C29A), C40A(C35A,C36A,C37A,C39A,C38A),
 C46A(C47A,C48A,C49A,C50A,C51A)
;