Bis(pyridylimino)isoindolato (BPI) Osmium Complexes: Structural Chemistry and Reactivity
Müller, Astrid L.; Wadepohl, Hubert; Gade, Lutz H.; Organometallics 34 (2015) 2810–; doi:10.1021/acs.organomet.5b00080

data_4085629
_publ_section_title
;
 Bis(pyridylimino)isoindolato (BPI) Osmium Complexes: Structural Chemistry
 and Reactivity
;
_journal_issue                   12
_journal_name_full               Organometallics
_journal_page_first              2810
_journal_paper_doi               10.1021/acs.organomet.5b00080
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C72 H67 N5 Os P2'
_chemical_formula_sum            'C73 H69 Cl2 N5 Os P2'
_chemical_formula_weight         1339.37
_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_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_am40
_audit_creation_date
;
'Thu May 15 14:52:45 2014'
;
_audit_update_record             'Thu May 15 16:06:09 CEST 2014'
_cell_angle_alpha                84.5964(13)
_cell_angle_beta                 76.5069(14)
_cell_angle_gamma                75.1112(14)
_cell_formula_units_Z            2
_cell_length_a                   11.4835(2)
_cell_length_b                   12.14766(18)
_cell_length_c                   23.7547(4)
_cell_measurement_reflns_used    22601
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      28.6960
_cell_measurement_theta_min      3.6310
_cell_volume                     3112.01(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-14); encifer 1.4 (CCDC, 2011)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.907
_diffrn_measurement_details
;
  1 omega   -6.00   50.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -79.0000    9.1772 112

  2 phi     33.00   61.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
  18.5380   18.5380   40.0000     -     56

  3 omega  -11.00   69.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000  120.0000 160

  4 omega   -1.00   27.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   38.0000  -60.0000 56

  5 omega   -8.00   88.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   77.0000 -120.0000 192

  6 omega  -51.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000   90.0000 200

  7 omega   -2.00   81.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000   60.0000 166

  8 omega  -52.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000 -180.0000 202

  9 omega  -11.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000  -60.0000 120

 10 omega   19.00   75.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   57.0000  -30.0000 112

 11 omega   -7.00   90.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380   38.0000 -150.0000 194

 12 omega   23.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000  120.0000 52

 13 omega  -47.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000  -90.0000 192

 14 omega   13.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000  -30.0000 72

 15 omega   23.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -77.0000   30.0000 52

 16 omega   22.00   50.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5380  -79.0000 -120.5317 56

;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w and \p scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      0.0498019000
_diffrn_orient_matrix_UB_12      -0.0170366000
_diffrn_orient_matrix_UB_13      0.0143565000
_diffrn_orient_matrix_UB_21      0.0073111000
_diffrn_orient_matrix_UB_22      -0.0575394000
_diffrn_orient_matrix_UB_23      -0.0064514000
_diffrn_orient_matrix_UB_31      0.0418771000
_diffrn_orient_matrix_UB_32      0.0073614000
_diffrn_orient_matrix_UB_33      -0.0263901000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0536
_diffrn_reflns_av_unetI/netI     0.0540
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.907
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            62739
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.907
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.997
_diffrn_reflns_theta_min         3.473
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    2.234
_exptl_absorpt_correction_T_max  0.934
_exptl_absorpt_correction_T_min  0.680
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_description       needle
_exptl_crystal_F_000             1364
_exptl_crystal_size_max          0.2003
_exptl_crystal_size_mid          0.0679
_exptl_crystal_size_min          0.0311
_refine_diff_density_max         1.975
_refine_diff_density_min         -3.535
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.143
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     754
_refine_ls_number_reflns         15015
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.155
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0473
_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^)+(0.0341P)^2^+9.0307P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1000
_refine_ls_wR_factor_ref         0.1031
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13496
_reflns_number_total             15015
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00080_si_002.cif
_cod_data_source_block           ga_am40_sq
_cod_depositor_comments
'Adding full bibliography for 4085628--4085631.cif.'
_cod_original_cell_volume        3112.02(9)
_cod_database_code               4085629
_audit_block_refno               2043
_audit_block_usercomment         'AM600, needle, black'
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C73 H79 Cl2 N5 Os1 P2'
_chemical_oxdiff_usercomment     'AM600, needle, black'
_shelx_estimated_absorpt_t_max   0.807
_shelx_estimated_absorpt_t_min   0.807
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14-C15A \\sim C14-C15B \\sim C14-C16A \\sim C14-C16B \\sim C14-C17A \\sim
C14-C17B
 with sigma of 0.01
 C15A-C16A \\sim C15A-C17A \\sim C16A-C17A \\sim C15B-C16B \\sim C15B-C17B
\\sim C16B-C17B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C15A \\sim C16A \\sim C17A \\sim C15B \\sim C16B \\sim C17B: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C15B) \\sim Ueq, Uanis(C16B) \\sim Ueq, Uanis(C17B) \\sim Ueq,
Uanis(C15A) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C17A) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.01
4. Others
 Sof(C15B)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16B)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C17B)=Sof(H17A)=Sof(H17B)=Sof(H17C)=1-FVAR(1)
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=FVAR(1)
5.a Me refined with riding coordinates:
 C15B(H15A,H15B,H15C), C16B(H16A,H16B,H16C), C17B(H17A,H17B,H17C), C15A(H15D,
 H15E,H15F), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C8(H8), C10(H10), C12(H12), C13(H13), C19(H19), C21(H21), C22(H22),
 C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40),
  C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48),
 C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58),
  C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66),
 C68(H68), C69(H69), C70(H70), C71(H71), C72(H72)
5.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C)
;
_smtbx_masks_special_details
;
The smtbx solvent masking procedure was used to remove the
electronic contribution of solvent molecules from the F(obs).
(P. v. d. Sluis, A. L. Spek, Acta Cryst. 1990, A46, 194; http://cctbx.sourceforge.net)
;
_shelx_res_checksum              52547
_cell_oxdiff_length_a            11.4835(2)
_cell_oxdiff_length_b            12.14766(18)
_cell_oxdiff_length_c            23.7547(4)
_cell_oxdiff_angle_alpha         84.5964(13)
_cell_oxdiff_angle_beta          76.5069(14)
_cell_oxdiff_angle_gamma         75.1112(14)
_cell_oxdiff_volume              3112.01(9)
_cell_oxdiff_measurement_reflns_used 22601