Construction of Alkyl-Substituted Pentaphosphido Ligands in the Coordination Sphere of Cobalt
Ziegler, Christoph G. P.; Maier, Thomas M.; Pelties, Stefan; Taube, Clemens; Hennersdorf, Felix; Ehlers, A.W.; Weigand, Jan J.; Wolf, Robert; Chemical Science  (2019) –; doi:10.1039/C8SC04745F

data_1550321
_publ_section_title
;
 Construction of Alkyl-Substituted Pentaphosphido Ligands in the
 Coordination Sphere of Cobalt
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC04745F
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C73 H101 Co Ga K N4 O4 P4, C4 H10 O2'
_chemical_formula_sum            'C77 H111 Co Ga K N4 O6 P4'
_chemical_formula_weight         1480.32
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-08-13
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_audit_update_record
;
2018-08-13 deposited with the CCDC.
2018-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.84854(12)
_cell_length_b                   21.0014(2)
_cell_length_c                   27.3815(3)
_cell_measurement_reflns_used    21514
_cell_measurement_temperature    123(1)
_cell_measurement_theta_max      73.3730
_cell_measurement_theta_min      4.1400
_cell_volume                     7963.60(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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    'SIR2004 (Burla et al.,  2007)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      123(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.973
_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   -119.00  -9.00   1.00    3.75    --  -40.71 -77.00-180.00  110
  2  \w    -33.00  70.00   1.00    3.75    --   40.71 -57.00  30.00  103
  3  \w    -20.00  82.00   1.00    3.75    --   40.71 -99.00 -60.00  102
  4  \w     34.00  77.00   1.00   15.00    --  106.98 -45.00 150.00   43
  5  \w     20.00 149.00   1.00   15.00    --  106.98   0.00-180.00  129
  6  \w     23.00 106.00   1.00   15.00    --  106.98 -94.00 -30.00   83
  7  \w     40.00  69.00   1.00   15.00    --  106.98 -30.00 -30.00   29
  8  \w     40.00 120.00   1.00   15.00    --  106.98-125.00-150.00   80
  9  \w     23.00 109.00   1.00   15.00    --  106.98 -94.00  30.00   86
 10  \w     29.00  57.00   1.00   15.00    --  106.98 -30.00-180.00   28
 11  \w     32.00  56.00   1.00   15.00    --  106.98 -45.00-120.00   24
;
_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      0.0396103000
_diffrn_orient_matrix_UB_12      0.0375835000
_diffrn_orient_matrix_UB_13      -0.0439836000
_diffrn_orient_matrix_UB_21      0.0475414000
_diffrn_orient_matrix_UB_22      0.0480264000
_diffrn_orient_matrix_UB_23      0.0350853000
_diffrn_orient_matrix_UB_31      0.0924407000
_diffrn_orient_matrix_UB_32      -0.0407550000
_diffrn_orient_matrix_UB_33      0.0008421000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0376
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            37040
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.513
_diffrn_reflns_theta_min         3.854
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.668
_exptl_absorpt_correction_T_max  0.721
_exptl_absorpt_correction_T_min  0.537
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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    1.235
_exptl_crystal_description       block
_exptl_crystal_F_000             3144
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DME/n-hexane'
_exptl_crystal_size_max          0.227
_exptl_crystal_size_mid          0.205
_exptl_crystal_size_min          0.125
_refine_diff_density_max         0.439
_refine_diff_density_min         -0.508
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 5704 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0292(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     936
_refine_ls_number_reflns         14908
_refine_ls_number_restraints     167
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0361
_refine_ls_R_factor_gt           0.0339
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0587P)^2^+1.9167P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0912
_refine_ls_wR_factor_ref         0.0930
_reflns_Friedel_coverage         0.750
_reflns_Friedel_fraction_full    0.927
_reflns_Friedel_fraction_max     0.878
_reflns_number_gt                14310
_reflns_number_total             14908
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04745f2.cif
_cod_data_source_block           2dash_[K(dme)2][(DippBIANCo)P4(GaDippNACNAC)]
_cod_original_cell_volume        7963.62(13)
_cod_database_code               1550321
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C77 H111 Co Ga K N4 O6 P4'
_shelx_estimated_absorpt_t_max   0.657
_shelx_estimated_absorpt_t_min   0.490
_reflns_odcompleteness_completeness 99.18
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C76-C75 \\sim C76A-C75A
 with sigma of 0.02
 O5A-C74A \\sim O5-C74 \\sim O5-C75 \\sim O5A-C75A \\sim O6A-C76A \\sim O6-C76
\\sim O6-C77 \\sim O6A-C77A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C65 \\sim C65A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.01
O5 \\sim O6 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim O5A \\sim O6A \\sim
C74A \\sim C75A \\sim C76A \\sim C77A: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.006
4. Others
 Sof(O5A)=Sof(O6A)=Sof(C74A)=Sof(H74D)=Sof(H74E)=Sof(H74F)=Sof(C75A)=Sof(H75C)=
 Sof(H75D)=Sof(C76A)=Sof(H76C)=Sof(H76D)=Sof(C77A)=Sof(H77D)=Sof(H77E)=
 Sof(H77F)=1-FVAR(1)
 Sof(O5)=Sof(O6)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C75)=Sof(H75A)=
 Sof(H75B)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=
 FVAR(1)
 Fixed Sof: H63(0.7294) H63A(0.2706) C65(0.7294) H65A(0.7294) H65B(0.7294)
 H65C(0.7294) C65A(0.2706) H65D(0.2706) H65E(0.2706) H65F(0.2706)
 Fixed Uiso: H74A(0.05) H74B(0.05) H74C(0.05) H75A(0.05) H75B(0.05) H76A(0.05)
 H76B(0.05) H77A(0.05) H77B(0.05) H77C(0.05) H74D(0.05) H74E(0.05) H74F(0.05)
 H75C(0.05) H75D(0.05) H76C(0.05) H76D(0.05) H77D(0.05) H77E(0.05) H77F(0.05)
5.a Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C31(H31), C34(H34), C48(H48), C51(H51), C60(H60),
 C63(H63), C63(H63A)
5.b Secondary CH2 refined with riding coordinates:
 C67(H67A,H67B), C68(H68A,H68B), C71(H71A,H71B), C72(H72A,H72B), C75(H75A,
 H75B), C76(H76A,H76B), C75A(H75C,H75D), C76A(H76C,H76D)
5.c Me refined with riding coordinates:
 C77(H77A,H77B,H77C), C74A(H74D,H74E,H74F)
5.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C15(H15), C16(H16),
 C17(H17), C27(H27), C28(H28), C29(H29), C38(H38), C44(H44), C45(H45), C46(H46),
  C56(H56), C57(H57), C58(H58)
5.e Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C61(H61A,H61B,
 H61C), C62(H62A,H62B,H62C), C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C69(H69A,
 H69B,H69C), C70(H70A,H70B,H70C), C73(H73A,H73B,H73C), C65(H65A,H65B,H65C),
 C65A(H65D,H65E,H65F), C74(H74A,H74B,H74C), C77A(H77D,H77E,H77F)
;
_shelx_res_checksum              39463
_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 1.262
_oxdiff_exptl_absorpt_empirical_full_min 0.794