Transformations of the cyclo-P4 ligand in [Cp′′′Co(η4-P4)]
Piesch, Martin; Seidl, Michael; Scheer, Manfred; Chemical Science 11 (2020) 6745–6751; doi:10.1039/D0SC01740J

data_1558102
_publ_section_title
;
 Transformations of the cyclo-P4 ligand in
 [Cp&#x2032;&#x2032;&#x2032;Co(\h4-P4)]
;
_journal_issue                   26
_journal_name_full               'Chemical Science'
_journal_page_first              6745
_journal_page_last               6751
_journal_paper_doi               10.1039/D0SC01740J
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety
'2(C21 H40 Co P4 Si), 2(C16 H32 Li O8), 1.5(C4 H8 O)'
_chemical_formula_sum            'C80 H156 Co2 Li2 O17.5 P8 Si2'
_chemical_formula_weight         1833.72
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-01-15
_audit_creation_method
;
Olex2 1.3-alpha
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2020-02-17 deposited with the CCDC.	2020-05-25 downloaded from the CCDC.
;
_cell_angle_alpha                87.037(2)
_cell_angle_beta                 77.660(4)
_cell_angle_gamma                86.306(3)
_cell_formula_units_Z            2
_cell_length_a                   14.4740(7)
_cell_length_b                   18.2968(4)
_cell_length_c                   19.7326(6)
_cell_measurement_reflns_used    5016
_cell_measurement_temperature    123(1)
_cell_measurement_theta_max      25.9430
_cell_measurement_theta_min      3.7440
_cell_volume                     5090.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      123.0(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2548
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.976
_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    -60.00  21.00   0.25  100.00    --   -8.61 -57.00-120.00  324
  2  \w    -84.00  15.00   0.25  100.00    --   -8.61 -38.00  30.00  396
  3  \w    -35.00  53.00   0.25  100.00    --   -8.61  38.00-150.00  352
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0468692000
_diffrn_orient_matrix_UB_12      -0.0040726000
_diffrn_orient_matrix_UB_13      0.0192082000
_diffrn_orient_matrix_UB_21      -0.0180674000
_diffrn_orient_matrix_UB_22      0.0182345000
_diffrn_orient_matrix_UB_23      -0.0274233000
_diffrn_orient_matrix_UB_31      -0.0009297000
_diffrn_orient_matrix_UB_32      -0.0340926000
_diffrn_orient_matrix_UB_33      -0.0153290000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.1287
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            26773
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.125
_diffrn_reflns_theta_max         25.125
_diffrn_reflns_theta_min         3.307
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.531
_exptl_absorpt_correction_T_max  0.981
_exptl_absorpt_correction_T_min  0.891
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14a (Rigaku Oxford Diffraction, 2018)
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)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.196
_exptl_crystal_description       plate
_exptl_crystal_F_000             1968
_exptl_crystal_size_max          0.394
_exptl_crystal_size_mid          0.132
_exptl_crystal_size_min          0.045
_refine_diff_density_max         0.589
_refine_diff_density_min         -0.437
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.908
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1430
_refine_ls_number_reflns         26773
_refine_ls_number_restraints     1102
_refine_ls_restrained_S_all      0.906
_refine_ls_R_factor_all          0.0967
_refine_ls_R_factor_gt           0.0526
_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^)+(0.0504P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1051
_refine_ls_wR_factor_ref         0.1123
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15803
_reflns_number_total             26773
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9894\% 
 around [1.00 -0.00 -0.00] (reciprocal) or [0.99 -0.04 -0.15] (direct)
;
_cod_data_source_file            d0sc01740j2.cif
_cod_data_source_block           pim_688_mo_ap_abs_twin_twin1_hklf4
_cod_depositor_comments
;Adding full bibliography for 1558098--1558103.cif.

 Adding full bibliography for 1558098--1558103.cif.
;
_cod_original_formula_sum        'C80 H156 Co2 Li2 O17.50 P8 Si2'
_cod_database_code               1558102
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C78H152Co2Li2O17P8Si2
_chemical_oxdiff_usercomment     'bright brown plate'
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.818
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5174(5)
 0.4826(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 O19-C86 = O19-C83
 1.45 with sigma of 0.02
 C75-C76 = C76-C77 = C77-C78
 1.45 with sigma of 0.02
 O17-C75 = O17-C78
 1.45 with sigma of 0.02
 C75-C78
 2.3 with sigma of 0.02
 C81-C82 \\sim C81-C80 \\sim C80-C79
 with sigma of 0.02
 C82A-C81 \\sim C82-C81
 with sigma of 0.02
 O18-C82A \\sim O18-C82
 with sigma of 0.02
 O19-C84 \\sim O19-C85
 with sigma of 0.04
 O19-C83 \\sim O19-C86
 with sigma of 0.02
 C84-C86 \\sim C83-C85
 with sigma of 0.04
 C83-C84 \\sim C84-C85 \\sim C85-C86
 with sigma of 0.02
 C78-C76 \\sim C77-C75
 with sigma of 0.02
 O9A-C66A \\sim O9A-C59A \\sim O9B-C66B \\sim O9B-C59B \\sim O10A-C60A \\sim
O10B-C60B \\sim O10A-C61A
 \\sim O10B-C61B \\sim O11A-C62A \\sim O11B-C62B \\sim O11A-C63A \\sim
O11B-C63B \\sim O12A-C64A \\sim O12B-
 C64B \\sim O12A-C65A \\sim O12B-C65B
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C81 \\sim C82A \\sim C82 \\sim O18: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.7A
C51B \\sim C54A \\sim C52B \\sim C55A \\sim C56A \\sim C53B \\sim C54B \\sim
C57A \\sim C58A \\sim C55B \\sim C56B \\sim C51A \\sim O8B \\sim C57B \\sim
C52A \\sim C58B \\sim C53A \\sim O7B \\sim O5B: within 1.9A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 1.9A
C45A \\sim C44B \\sim C43B \\sim O1B \\sim C43A \\sim C50B \\sim C49B \\sim O4B
\\sim C50A \\sim O1A \\sim C49A \\sim C48B \\sim O4A \\sim C47B \\sim C48A
\\sim O3B \\sim C46B \\sim C47A \\sim C45B \\sim C46A: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
O19 \\sim C83 \\sim C84 \\sim C85 \\sim C86: within 1.9A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.9A
O17 \\sim C78 \\sim C77 \\sim C76 \\sim C75: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O9A \\sim O9B \\sim C59A \\sim C66B \\sim C66A \\sim C65B \\sim O12B \\sim C65A
\\sim O12A \\sim C64B \\sim C64A \\sim C63B \\sim C63A \\sim O11B \\sim O11A
\\sim C62B \\sim C62A \\sim C61B \\sim C61A \\sim O10B \\sim O10A \\sim C60A
\\sim C60B \\sim C59B: within 1.9A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 1.9A
Uanis(O17) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C76)
\\sim Ueq, Uanis(C75) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C83) \\sim Ueq, Uanis(O19) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C85)
\\sim Ueq, Uanis(C84) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Others
 Fixed Sof: O11A(0.53) O10A(0.53) O7A(0.7) O1A(0.7) C43A(0.7) H43A(0.7)
 H43B(0.7) O3A(0.7) O5A(0.7) O8A(0.7) O2A(0.7) O6A(0.7) O4A(0.7) O12A(0.53)
 C54A(0.7) H54A(0.7) H54B(0.7) C56A(0.7) H56A(0.7) H56B(0.7) C45A(0.7)
 H45A(0.7) H45B(0.7) O9A(0.53) C52A(0.7) H52A(0.7) H52B(0.7) C58A(0.7)
 H58A(0.7) H58B(0.7) C55A(0.7) H55A(0.7) H55B(0.7) C47A(0.7) H47A(0.7)
 H47B(0.7) C51A(0.7) H51A(0.7) H51B(0.7) C48A(0.7) H48A(0.7) H48B(0.7)
 C49A(0.7) H49A(0.7) H49B(0.7) C44A(0.7) H44A(0.7) H44B(0.7) C57A(0.7)
 H57A(0.7) H57B(0.7) C53A(0.7) H53A(0.7) H53B(0.7) C50A(0.7) H50A(0.7)
 H50B(0.7) C46A(0.7) H46A(0.7) H46B(0.7) C82(0.54) H82A(0.54) H82B(0.54)
 H81A(0.54) H81B(0.54) H81C(0.46) H81D(0.46) C52B(0.3) H52C(0.3) H52D(0.3)
 C51B(0.3) H51C(0.3) H51D(0.3) O5B(0.3) O6B(0.3) C53B(0.3) H53C(0.3) H53D(0.3)
 C54B(0.3) H54C(0.3) H54D(0.3) O7B(0.3) C55B(0.3) H55C(0.3) H55D(0.3) C56B(0.3)
 H56C(0.3) H56D(0.3) O8B(0.3) C57B(0.3) H57C(0.3) H57D(0.3) C58B(0.3) H58C(0.3)
 H58D(0.3) O4B(0.3) C49B(0.3) H49C(0.3) H49D(0.3) O2B(0.3) O1B(0.3) O3B(0.3)
 C43B(0.3) H43C(0.3) H43D(0.3) C45B(0.3) H45C(0.3) H45D(0.3) C46B(0.3)
 H46C(0.3) H46D(0.3) C47B(0.3) H47C(0.3) H47D(0.3) C50B(0.3) H50C(0.3)
 H50D(0.3) C48B(0.3) H48C(0.3) H48D(0.3) C44B(0.3) H44C(0.3) H44D(0.3)
 C63A(0.53) H63A(0.53) H63B(0.53) C62A(0.53) H62A(0.53) H62B(0.53) C60A(0.53)
 H60A(0.53) H60B(0.53) C65A(0.53) H65A(0.53) H65B(0.53) C66A(0.53) H66A(0.53)
 H66B(0.53) C61A(0.53) H61A(0.53) H61B(0.53) C59A(0.53) H59A(0.53) H59B(0.53)
 C64A(0.53) H64A(0.53) H64B(0.53) O11B(0.47) O10B(0.47) O12B(0.47) O9B(0.47)
 C63B(0.47) H63C(0.47) H63D(0.47) C62B(0.47) H62C(0.47) H62D(0.47) C60B(0.47)
 H60C(0.47) H60D(0.47) C65B(0.47) H65C(0.47) H65D(0.47) C66B(0.47) H66C(0.47)
 H66D(0.47) C61B(0.47) H61C(0.47) H61D(0.47) C59B(0.47) H59C(0.47) H59D(0.47)
 C64B(0.47) H64C(0.47) H64D(0.47) O17(0.25) C78(0.25) H78A(0.25) H78B(0.25)
 C77(0.25) H77A(0.25) H77B(0.25) C76(0.25) H76A(0.25) H76B(0.25) C75(0.25)
 H75B(0.25) H75A(0.25) O19(0.25) C83(0.25) H83A(0.25) H83B(0.25) C84(0.25)
 H84A(0.25) H84B(0.25) C85(0.25) H85A(0.25) H85B(0.25) C86(0.25) H86A(0.25)
 H86B(0.25) C82A(0.46) H82C(0.46) H82D(0.46)
6.a Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C1(H1A,H1B), C43A(H43A,H43B), C54A(H54A,H54B), C56A(H56A,
 H56B), C71(H71A,H71B), C68(H68A,H68B), C45A(H45A,H45B), C74(H74A,H74B),
 C70(H70A,H70B), C52A(H52A,H52B), C72(H72A,H72B), C58A(H58A,H58B), C69(H69A,
 H69B), C55A(H55A,H55B), C47A(H47A,H47B), C51A(H51A,H51B), C67(H67A,H67B),
 C73(H73A,H73B), C48A(H48A,H48B), C49A(H49A,H49B), C44A(H44A,H44B), C57A(H57A,
 H57B), C53A(H53A,H53B), C50A(H50A,H50B), C46A(H46A,H46B), C79(H79A,H79B),
 C80(H80A,H80B), C82(H82A,H82B), C81(H81A,H81B), C81(H81C,H81D), C52B(H52C,
 H52D), C51B(H51C,H51D), C53B(H53C,H53D), C54B(H54C,H54D), C55B(H55C,H55D),
 C56B(H56C,H56D), C57B(H57C,H57D), C58B(H58C,H58D), C49B(H49C,H49D), C43B(H43C,
 H43D), C45B(H45C,H45D), C46B(H46C,H46D), C47B(H47C,H47D), C50B(H50C,H50D),
 C48B(H48C,H48D), C44B(H44C,H44D), C63A(H63A,H63B), C62A(H62A,H62B), C60A(H60A,
 H60B), C65A(H65A,H65B), C66A(H66A,H66B), C61A(H61A,H61B), C59A(H59A,H59B),
 C64A(H64A,H64B), C63B(H63C,H63D), C62B(H62C,H62D), C60B(H60C,H60D), C65B(H65C,
 H65D), C66B(H66C,H66D), C61B(H61C,H61D), C59B(H59C,H59D), C64B(H64C,H64D),
 C78(H78A,H78B), C77(H77A,H77B), C76(H76A,H76B), C75(H75B,H75A), C83(H83A,H83B),
  C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C82A(H82C,H82D)
6.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C28(H28), C7(H7), C30(H30)
6.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C34(H34A,H34B,H34C), C17(H17A,H17B,H17C), C37(H37A,H37B,
 H37C), C13(H13A,H13B,H13C), C16(H16A,H16B,H16C), C11(H11A,H11B,H11C), C32(H32A,
 H32B,H32C), C20(H20A,H20B,H20C), C36(H36A,H36B,H36C), C25(H25A,H25B,H25C),
 C33(H33A,H33B,H33C), C15(H15A,H15B,H15C), C24(H24A,H24B,H24C), C19(H19A,H19B,
 H19C), C3(H3A,H3B,H3C), C2(H2A,H2B,H2C), C41(H41A,H41B,H41C), C38(H38A,H38B,
 H38C), C4(H4A,H4B,H4C), C40(H40A,H40B,H40C), C21(H21A,H21B,H21C), C23(H23A,
 H23B,H23C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              86408
_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 1.183
_oxdiff_exptl_absorpt_empirical_full_min 0.805
_oxdiff_exptl_absorpt_spherical_max 0.943
_oxdiff_exptl_absorpt_spherical_min 0.943
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2