Oxidation-induced ambiphilicity triggers N-N bond formation and dinitrogen release in octahedral terminal molybdenum(v) nitrido complexes.
Almquist, C. Christopher; Rajeshkumar, Thayalan; Jayaweera, H. D. A. Chathumal; Removski, Nicole; Zhou, Wen; Gelfand, Benjamin S.; Maron, Laurent; Piers, Warren E.; Chemical science 15 (2024) 5152–5162; doi:10.1039/d4sc00090k

data_1571025
_publ_section_title
;
 Oxidation-induced ambiphilicity triggers N-N bond formation and
 dinitrogen release in octahedral terminal molybdenum(v) nitrido
 complexes.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              5152
_journal_page_last               5162
_journal_paper_doi               10.1039/d4sc00090k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C33 H33 B2 Mo N10'
_chemical_formula_sum            'C33 H33 B2 Mo N10'
_chemical_formula_weight         687.25
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-05-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-10-26 deposited with the CCDC.	2024-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.930(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.0041(15)
_cell_length_b                   18.810(2)
_cell_length_c                   15.8824(16)
_cell_measurement_reflns_used    9574
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      72.61
_cell_measurement_theta_min      3.58
_cell_volume                     3853.1(7)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0231
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            25677
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.663
_diffrn_reflns_theta_min         3.578
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.052
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6274
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0741 before and 0.0376 after correction.
The Ratio of minimum to maximum transmission is 0.8325.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.185
_exptl_crystal_description       block
_exptl_crystal_F_000             1412
_exptl_crystal_size_max          0.285
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.095
_refine_diff_density_max         0.386
_refine_diff_density_min         -0.201
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     527
_refine_ls_number_reflns         7486
_refine_ls_number_restraints     990
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0281
_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^)+(0.0474P)^2^+0.4478P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0784
_refine_ls_wR_factor_ref         0.0856
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5671
_reflns_number_total             7486
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20230529ca691_0m_a_sq
_cod_depositor_comments
'Adding full bibliography for 1571025--1571037.cif.'
_cod_original_cell_volume        3853.0(7)
_cod_database_code               1571025
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.760
_shelx_estimated_absorpt_t_min   0.477
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C19-C24 \\sim C21-C24 \\sim C19A-C24A \\sim C21A-C24A
 with sigma of 0.04
 C21-C25 \\sim C23-C25 \\sim C21A-C25A \\sim C23A-C25A
 with sigma of 0.04
 C27-C31 \\sim C29-C31 \\sim C27A-C31A \\sim C29A-C31A
 with sigma of 0.04
 C31-C33 \\sim C29-C33 \\sim C31A-C33A \\sim C29A-C33A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C18 \\sim C19 \\sim C19A \\sim C20 \\sim C20A \\sim C21 \\sim C21A \\sim C22
\\sim C22A \\sim C23 \\sim C23A \\sim C24 \\sim C24A \\sim C25 \\sim C25A:
within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C26 \\sim C27 \\sim C27A \\sim C28 \\sim C28A \\sim C29 \\sim C29A \\sim C30
\\sim C30A \\sim C31 \\sim C31A \\sim C32 \\sim C32A \\sim C33 \\sim C33A:
within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
4. Others
 Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(C23A)=
 Sof(H23A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=Sof(H25D)=
 Sof(H25E)=Sof(H25F)=1-FVAR(1)
 Sof(C19)=Sof(H19)=Sof(C20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(C23)=Sof(H23)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=
 FVAR(1)
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(C31A)=
 Sof(H31A)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33A)=Sof(H33D)=
 Sof(H33E)=Sof(H33F)=1-FVAR(2)
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(C31)=Sof(H31)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C19A(H19A),
 C21A(H21A), C23A(H23A), C19(H19), C21(H21), C23(H23), C27A(H27A), C29A(H29A),
 C31A(H31A), C27(H27), C29(H29), C31(H31)
5.b Fitted hexagon refined as free rotating group:
 C18(C19A,C20A,C21A,C22A,C23A), C26(C27A,C28A,C29A,C30A,C31A)
5.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C25(H25A,H25B,H25C), C25A(H25D,
 H25E,H25F), C32(H32A,H32B,H32C), C32A(H32D,H32E,H32F), C33(H33A,H33B,H33C),
 C33A(H33D,H33E,H33F)
;
_shelx_res_checksum              38723
_shelx_fab_checksum              94296
_olex2_submission_special_instructions 'No special instructions were received'