Direct measurement of covalent three-center, two-electron M-H-B bonding in Zr and Hf borohydrides using B K-edge XAS.
Hansen, Hannah M.; Zgrabik, Joshua C.; Zacher, 3rd, Peter A; Schuely, Jacob J.; Amano, Emily M.; Yang, Mai Yer; Unruh, Daniel K.; Zuin, Lucia; Keith, Jason M.; Daly, Scott R.; Chemical science 16 (2025) 22333–22347; doi:10.1039/d5sc06254c

data_1576112
_publ_section_title
;
 Direct measurement of covalent three-center, two-electron M-H-B bonding
 in Zr and Hf borohydrides using B K-edge XAS.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              22333
_journal_page_last               22347
_journal_paper_doi               10.1039/d5sc06254c
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C28 H40 B4 Zr'
_chemical_formula_sum            'C28 H40 B4 Zr'
_chemical_formula_weight         511.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-06-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-06-12 deposited with the CCDC.	2025-10-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.0070(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.3985(5)
_cell_length_b                   5.8044(2)
_cell_length_c                   30.8545(9)
_cell_measurement_reflns_used    7352
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      26.34
_cell_measurement_theta_min      2.631
_cell_volume                     2707.01(15)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Nonius Kappa Apex'
_diffrn_measurement_method       'CCD Phi and Omega Scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0598
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            32264
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.382
_diffrn_reflns_theta_min         2.202
_exptl_absorpt_coefficient_mu    0.420
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.7196
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0862 before and 0.0551 after correction.
The Ratio of minimum to maximum transmission is 0.9654.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       needle-like
_exptl_crystal_F_000             1072
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.121
_refine_diff_density_max         0.370
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         5538
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0353
_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^)+(0.0303P)^2^+2.5484P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0753
_refine_ls_wR_factor_ref         0.0807
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4530
_reflns_number_total             5538
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06254c3.cif
_cod_data_source_block           dal22_28
_cod_depositor_comments
'Adding full bibliography for 1576111--1576117.cif.'
_cod_database_code               1576112
_shelx_shelxl_version_number     2019/3
_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 B(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C15(H15A,H15B), C22(H22A,H22B), C1(H1A,H1B)
2.b Aromatic/amide H refined with riding coordinates:
 C24(H24), C17(H17), C10(H10), C21(H21), C7(H7), C28(H28), C14(H14), C3(H3),
 C25(H25), C11(H11), C13(H13), C12(H12), C20(H20), C26(H26), C18(H18), C19(H19),
  C27(H27), C4(H4), C5(H5), C6(H6)
2.c Idealised Me refined as rotating group:
 B2(H2A,H2B,H2C), B3(H3A,H3B,H3C), B4(H4A,H4B,H4C), B1(H1C,H1D,H1E)
;
_shelx_res_checksum              54539
_olex2_submission_special_instructions 'No special instructions were received'