Synthesis and characterisation of light lanthanide bis-phospholyl borohydride complexes.
Liu, Jingjing; Nodaraki, Lydia E.; Cobb, Philip J.; Giansiracusa, Marcus J.; Ortu, Fabrizio; Tuna, Floriana; Mills, David P.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 6504–6511; doi:10.1039/d0dt01241f

data_7704221
_publ_section_title
;
 Synthesis and characterisation of light lanthanide bis-phospholyl
 borohydride complexes.
;
_journal_issue                   19
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6504
_journal_page_last               6511
_journal_paper_doi               10.1039/d0dt01241f
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'C32 H66 B2 Ce K O2 P2'
_chemical_formula_sum            'C32 H66 B2 Ce K O2 P2'
_chemical_formula_weight         745.62
_chemical_name_systematic        '[Ce(Htp)2(BH4)2K(THF)(Et2O)]n'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-03-23 deposited with the CCDC.	2020-04-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.613(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.8610(10)
_cell_length_b                   15.8524(6)
_cell_length_c                   12.8759(7)
_cell_measurement_reflns_used    5266
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      26.9720
_cell_measurement_theta_min      3.7640
_cell_volume                     3884.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3271
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -23.00   3.00   1.00   30.00    --   10.32 -99.00 -30.00   26
  2  \w    -25.00  43.00   1.00   30.00    --   10.32 -99.00  90.00   68
  3  \w      3.00  85.00   1.00   30.00    --   10.32  37.00 -90.00   82
  4  \w    -19.00  34.00   1.00   30.00    --   10.32 -99.00-180.00   53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0116732000
_diffrn_orient_matrix_UB_12      0.0380901000
_diffrn_orient_matrix_UB_13      0.0282774000
_diffrn_orient_matrix_UB_21      0.0235676000
_diffrn_orient_matrix_UB_22      0.0064296000
_diffrn_orient_matrix_UB_23      -0.0315722000
_diffrn_orient_matrix_UB_31      -0.0264245000
_diffrn_orient_matrix_UB_32      0.0225381000
_diffrn_orient_matrix_UB_33      -0.0388428000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0711
_diffrn_reflns_av_unetI/netI     0.0926
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            22301
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         3.302
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.386
_exptl_absorpt_correction_T_max  0.974
_exptl_absorpt_correction_T_min  0.937
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) 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            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       needle
_exptl_crystal_F_000             1564
_exptl_crystal_size_max          0.285
_exptl_crystal_size_mid          0.148
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.330
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     438
_refine_ls_number_reflns         7108
_refine_ls_number_restraints     198
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0821
_refine_ls_R_factor_gt           0.0464
_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^)+(0.0246P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0767
_refine_ls_wR_factor_ref         0.0870
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5055
_reflns_number_total             7108
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt01241f2.cif
_cod_data_source_block           3-Ce
_cod_depositor_comments
'Adding full bibliography for 7704215--7704221.cif.'
_cod_database_code               7704221
_manchester_internal_diff_code   odpm111
_manchester_internal_coll_client JJL
_manchester_internal_coll_user   JJL
_manchester_internal_coll_date   28/9/18
_manchester_internal_process_date 28/9/18
_manchester_internal_process_user JJL
_manchester_internal_solution_date 1/10/18
_manchester_internal_solution_user JJL
_manchester_internal_refinement_date 1/10/18
_manchester_internal_refinement_user JJL
_manchester_internal_validation_date 8/11/19
_manchester_internal_validation_user PJC
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C32H66B2CeKO2P2
_shelx_estimated_absorpt_t_max   0.814
_shelx_estimated_absorpt_t_min   0.636
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. 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 B(H,H,H,H) groups, All C(H,H,H) groups
2. Restrained distances
 B1-H1D = B1-H1C = B1-H1B = B1-H1A = B2-H2D = B2-H2C = B2-H2A = B2-H2B
 1.15 with sigma of 0.02
 C28A-C27A \\sim C28-C27 \\sim C26-C25
 with sigma of 0.02
 O1-C26 \\sim O1-C27A \\sim O1-C27
 with sigma of 0.02
 C31-C30 \\sim C31A-C30A
 with sigma of 0.02
 C30-C29 \\sim C30A-C29 \\sim C32-C31 \\sim C32-C31A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O2 \\sim C29 \\sim C30 \\sim C30A \\sim C31 \\sim C31A \\sim C32: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04
O1 \\sim C25 \\sim C26 \\sim C27 \\sim C27A \\sim C28 \\sim C28A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C25, C26, C27, C27A, C28, C28A, C29, C30, C30A, C31, C31A, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C27A)=Sof(H27C)=Sof(H27D)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
 Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C31A)=Sof(H31C)=
 Sof(H31D)=Sof(H32C)=Sof(H32D)=1-FVAR(2)
 Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(H32A)=Sof(H32B)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3)
6.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B), C27A(H27C,H27D), C29(H29A,H29B), C29(H29C,
 H29D), C30(H30A,H30B), C30A(H30C,H30D), C31(H31A,H31B), C31A(H31C,H31D),
 C32(H32A,H32B), C32(H32C,H32D)
6.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15)
6.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C),
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C25(H25A,H25B,H25C), C28(H28A,H28B,H28C), C28A(H28D,H28E,H28F)
;
_shelx_res_checksum              83500
_manchester_internal_coll_frame_method '\w scans'
_manchester_internal_coll_frame_time 4.00
_manchester_internal_coll_frame_width 0.9
_manchester_internal_coll_type   custom
_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 1.246
_oxdiff_exptl_absorpt_empirical_full_min 0.851