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_1571027
_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         '2(C66 H66 B4 Mo2 N19), 5(C6 H6), 3.667(C3)'
_chemical_formula_sum            'C173 H162 B8 Mo4 N38'
_chemical_formula_weight         3243.64
_space_group_crystal_system      tetragonal
_space_group_IT_number           130
_space_group_name_Hall           '-P 4a 2ac'
_space_group_name_H-M_alt        'P 4/n c c :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-09-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-26 deposited with the CCDC.	2024-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.3294(9)
_cell_length_b                   25.3294(9)
_cell_length_c                   25.1795(14)
_cell_measurement_reflns_used    9932
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      72.58
_cell_measurement_theta_min      3.49
_cell_volume                     16154.6(12)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_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  0.0678
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            80550
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.712
_diffrn_reflns_theta_min         4.280
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.995
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5323
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1219 before and 0.0638 after correction.
The Ratio of minimum to maximum transmission is 0.7063.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Black
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_description       Block
_exptl_crystal_F_000             6696
_exptl_crystal_size_max          0.378
_exptl_crystal_size_mid          0.236
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.383
_refine_diff_density_min         -0.326
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     569
_refine_ls_number_reflns         8011
_refine_ls_number_restraints     468
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0347
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0392P)^2^+13.5580P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0850
_refine_ls_wR_factor_ref         0.0935
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6673
_reflns_number_total             8011
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20230921ca707_0m_a
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Multi-scan' was
changed to 'multi-scan' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1571025--1571037.cif.
;
_cod_original_cell_volume        16154.6(15)
_cod_original_sg_symbol_H-M      'P 4/n c c'
_cod_database_code               1571027
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.397
_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. Uiso/Uaniso restraints and constraints
C1S \\sim C2S \\sim C3S \\sim C4S \\sim C5S \\sim C6S \\sim C1T \\sim C2T \\sim
C3T \\sim C4T \\sim C5T \\sim C6T: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3A
C13S \\sim C14S \\sim C15S: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C7S \\sim C8S: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C9S \\sim C10S \\sim C11S: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C13S) \\sim Ueq, Uanis(C14S) \\sim Ueq, Uanis(C15S) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C9S) \\sim Ueq, Uanis(C10S) \\sim Ueq, Uanis(C11S) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7S) \\sim Ueq, Uanis(C8S) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Others
 Sof(C1T)=Sof(H1T)=Sof(C6T)=Sof(H6T)=Sof(C5T)=Sof(H5T)=Sof(C4T)=Sof(H4T)=
 Sof(C3T)=Sof(H3T)=Sof(C2T)=Sof(H2T)=1-FVAR(1)
 Sof(C3S)=Sof(H3S)=Sof(C2S)=Sof(H2S)=Sof(C1S)=Sof(H1S)=Sof(C6S)=Sof(H6S)=
 Sof(C5S)=Sof(H5S)=Sof(C4S)=Sof(H4S)=FVAR(1)
 Sof(C15S)=0.5*(1-FVAR(3))
 Sof(C14S)=0.5*FVAR(3)
 Fixed Sof: C9S(0.666667) C10S(0.666667) C11S(0.666667) C13S(0.25)
4.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), C19(H19), C21(H21),
  C23(H23), C27(H27), C29(H29), C31(H31), C7S(H7S), C8S(H8S), C3S(H3S),
 C2S(H2S), C1S(H1S), C6S(H6S), C5S(H5S), C4S(H4S), C1T(H1T), C6T(H6T), C5T(H5T),
  C4T(H4T), C3T(H3T), C2T(H2T)
4.b Fitted hexagon refined as free rotating group:
 C3S(C2S,C1S,C6S,C5S,C4S), C1T(C6T,C5T,C4T,C3T,C2T)
4.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C32(H32A,H32B,H32C), C33(H33A,H33B,
 H33C)
;
_shelx_res_checksum              17111
_olex2_submission_special_instructions 'No special instructions were received'