Frustrated Lewis pair chemistry of hydride sponges
Becker, Christian; Schwabedissen, Jan; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W.; Dalton Transactions  (2022) –; doi:10.1039/D2DT00585A

data_7709817
_publ_section_title
;
 Frustrated Lewis pair chemistry of hydride sponges
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00585A
_journal_year                    2022
_chemical_formula_moiety         'C15 H34 N4 P, C14 H17 B2, 0.5(C6 H6)'
_chemical_formula_sum            'C32 H54 B2 N4 P'
_chemical_formula_weight         547.38
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2020-02-19
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2022-02-11 deposited with the CCDC.	2022-03-17 downloaded from the CCDC.
;
_cell_angle_alpha                93.079(2)
_cell_angle_beta                 92.337(2)
_cell_angle_gamma                94.679(2)
_cell_formula_units_Z            2
_cell_length_a                   9.8912(2)
_cell_length_b                   10.6797(3)
_cell_length_c                   15.5211(5)
_cell_measurement_reflns_used    9745
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.2630
_cell_measurement_theta_min      4.1410
_cell_volume                     1630.07(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.977
_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   -110.00 -21.00   1.00    9.23    --  -38.50 -38.00 -90.00   89
  2  \w    -80.00 -10.00   1.00    9.23    --  -38.50 125.00  60.00   70
  3  \w    -49.00 -20.00   1.00    9.23    --  -38.50 125.00 150.00   29
  4  \w    -70.00  39.00   1.00    9.23    --  -38.50  19.00  90.00  109
  5  \w     33.00  68.00   1.00    9.23    --   42.70-125.00-120.00   35
  6  \w     55.00  95.00   1.00    9.23    --   42.70-125.00   0.00   40
  7  \w    100.00 171.00   1.00   38.50    --  111.00 125.00-180.00   71
  8  \w    105.00 156.00   1.00   38.50    --  111.00  77.00-120.00   51
  9  \w     66.00  95.00   1.00   38.50    --  111.00 -77.00-180.00   29
 10  \w     41.00 132.00   1.00   38.50    --  111.00 -30.00-120.00   91
 11  \w    105.00 132.00   1.00   38.50    --  111.00 -30.00 -90.00   27
 12  \w     38.00 105.00   1.00   38.50    --  111.00 -30.00-180.00   67
 13  \w     70.00 101.00   1.00   38.50    --  111.00 -94.00  90.00   31
 14  \w     32.00 151.00   1.00   38.50    --  111.00 -15.00  60.00  119
 15  \w     33.00  60.00   1.00   38.50    --  111.00 -94.00  90.00   27
 16  \w     49.00 131.00   1.00   38.50    --  111.00 -45.00  90.00   82
 17  \w     63.00 113.00   1.00   38.50    --  111.00-125.00   0.00   50
 18  \w    116.00 141.00   1.00   38.50    --  111.00 -77.00-180.00   25
 19  \w     67.00  94.00   1.00   38.50    --  111.00-125.00  30.00   27
 20  \w     34.00 106.00   1.00   38.50    --  111.00 -94.00 120.00   72
 21  \w     45.00 107.00   1.00   38.50    --  111.00-101.00 -88.78   62
 22  \w     70.00 112.00   1.00   38.50    --  111.00-125.00-120.00   42
 23  \w     40.00 109.00   1.00   38.50    --  111.00-110.00  41.01   69
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0173293000
_diffrn_orient_matrix_UB_12      0.0269106000
_diffrn_orient_matrix_UB_13      0.0972593000
_diffrn_orient_matrix_UB_21      0.0283554000
_diffrn_orient_matrix_UB_22      0.1420395000
_diffrn_orient_matrix_UB_23      -0.0112563000
_diffrn_orient_matrix_UB_31      -0.1528623000
_diffrn_orient_matrix_UB_32      0.0108409000
_diffrn_orient_matrix_UB_33      -0.0177345000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_av_unetI/netI     0.0388
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            13361
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.557
_diffrn_reflns_theta_min         2.854
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.928
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.686
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.115
_exptl_crystal_description       irregular
_exptl_crystal_F_000             598
_exptl_crystal_size_max          0.324
_exptl_crystal_size_mid          0.217
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.506
_refine_diff_density_min         -0.470
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     384
_refine_ls_number_reflns         6713
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0525
_refine_ls_R_factor_gt           0.0499
_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^)+(0.0926P)^2^+0.4329P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1377
_refine_ls_wR_factor_ref         0.1412
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6272
_reflns_number_total             6713
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00585a2.cif
_cod_data_source_block           '[4][V-H]'
_cod_database_code               7709817
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C32H54B2N4P
_diffrn_oxdiff_digest_frames
;
012b7b0bdb0389c66e4989f89759c0af9f01318c056
;
_diffrn_oxdiff_digest_hkl
;
0178ce79a043f25206f1a83b75697b3c047ad4
;
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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
 C23B-C21B \\sim C23-C21 \\sim C22B-C21B \\sim C22-C21
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C21) \\sim Ueq, Uanis(C21B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C21) = Uanis(C21B)
4. Rigid body (RIGU) restrains
 C21, C21B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C21(0.5) H21(0.5) C21B(0.5) H21B(0.5) C22(0.5) H22A(0.5) H22B(0.5)
 H22C(0.5) C22B(0.5) H22D(0.5) H22E(0.5) H22F(0.5) C23(0.5) H23A(0.5) H23B(0.5)
 H23C(0.5) C23B(0.5) H23D(0.5) H23E(0.5) H23F(0.5)
6.a Ternary CH refined with riding coordinates:
 C21(H21), C21B(H21B), C24(H24), C27(H27)
6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,
 H19B), C20(H20A,H20B), C13(H13A,H13B)
6.c Me refined with riding coordinates:
 C22(H22A,H22B,H22C), C22B(H22D,H22E,H22F), C23(H23A,H23B,H23C), C23B(H23D,
 H23E,H23F)
6.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C30(H30), C31(H31), C32(H32)
6.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              17327
_shelx_hkl_checksum              16372
_olex2_date_sample_data_collection 2020-02-18
_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 4.188
_oxdiff_exptl_absorpt_empirical_full_min 0.304