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_1571034
_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
'C42 H42 B2 Mo N11, Al C16 F36 O4, C7 H8, C3 H3'
_chemical_formula_sum            'C68 H53 Al B2 F36 Mo N11 O4'
_chemical_formula_weight         1916.75
_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   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-10-05
_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                61.8960(10)
_cell_angle_beta                 75.4150(10)
_cell_angle_gamma                80.140(2)
_cell_formula_units_Z            2
_cell_length_a                   14.9038(3)
_cell_length_b                   17.3373(4)
_cell_length_c                   17.7556(4)
_cell_measurement_reflns_used    9840
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      72.51
_cell_measurement_theta_min      4.09
_cell_volume                     3909.10(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 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 0.965
_diffrn_measured_fraction_theta_max 0.953
_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  0.0355
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            62597
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.528
_diffrn_reflns_theta_min         2.878
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.768
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6560
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0612 before and 0.0478 after correction.
The Ratio of minimum to maximum transmission is 0.8705.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Brown
_exptl_crystal_density_diffrn    1.628
_exptl_crystal_description       Block
_exptl_crystal_F_000             1918
_exptl_crystal_size_max          0.281
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.099
_refine_diff_density_max         1.352
_refine_diff_density_min         -0.971
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1411
_refine_ls_number_reflns         14789
_refine_ls_number_restraints     1258
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0713
_refine_ls_R_factor_gt           0.0676
_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^)+(0.1255P)^2^+6.6645P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1890
_refine_ls_wR_factor_ref         0.1942
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13672
_reflns_number_total             14789
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20231003ca754_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_database_code               1571034
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.771
_shelx_estimated_absorpt_t_min   0.510
_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
 C69-C50 = F50-C74 = F54-C76 = F53-C76 = C76-C45 = C77-F5 = C73-C50 = C48-F55 =
  C48-C47
 1.6 with sigma of 0.02
 F56-F57 = F13-F14
 1.8 with sigma of 0.02
 C48-C47
 1.7 with sigma of 0.02
 F13-C48
 1.53 with sigma of 0.02
3. Rigid bond restraints
 C66, C67, C68
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C70 \\sim F37 \\sim F38 \\sim F39 \\sim C53 \\sim F10 \\sim F22 \\sim F23:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C58 \\sim F21 \\sim F32 \\sim F33 \\sim C71 \\sim F40 \\sim F41 \\sim F42:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C51 \\sim F9 \\sim F18 \\sim F19 \\sim C72 \\sim F43 \\sim F44 \\sim F45:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C56 \\sim F17 \\sim F28 \\sim F29 \\sim C73 \\sim F46 \\sim F47 \\sim F48:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C49 \\sim F6 \\sim F15 \\sim F16 \\sim C74 \\sim F49 \\sim F50 \\sim F51:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C44 \\sim F1 \\sim F2 \\sim F3 \\sim F52 \\sim F53 \\sim F54 \\sim C76: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C48 \\sim F55 \\sim F56 \\sim F57 \\sim F5 \\sim F13 \\sim F14 \\sim C77:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C46 \\sim F4 \\sim F7 \\sim F8 \\sim C78 \\sim F58 \\sim F59 \\sim F60: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C66 \\sim C67 \\sim C68: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C70) \\sim Ueq, Uanis(F37) \\sim Ueq, Uanis(F38) \\sim Ueq, Uanis(F39)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F22) \\sim Ueq,
Uanis(F23) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F32)
\\sim Ueq, Uanis(F33) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(F40) \\sim Ueq,
Uanis(F41) \\sim Ueq, Uanis(F42) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C51) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F19)
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(F43) \\sim Ueq, Uanis(F44) \\sim Ueq,
Uanis(F45) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F28)
\\sim Ueq, Uanis(F29) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(F46) \\sim Ueq,
Uanis(F47) \\sim Ueq, Uanis(F48) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C49) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F16)
\\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(F49) \\sim Ueq, Uanis(F50) \\sim Ueq,
Uanis(F51) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F2)
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F52) \\sim Ueq, Uanis(F53) \\sim Ueq,
Uanis(F54) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C48) \\sim Ueq, Uanis(F55) \\sim Ueq, Uanis(F56) \\sim Ueq, Uanis(F57)
\\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F14) \\sim Ueq,
Uanis(C77) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F7)
\\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(F58) \\sim Ueq,
Uanis(F59) \\sim Ueq, Uanis(F60) \\sim Ueq, Uanis(F26) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C70)=Sof(F37)=Sof(F38)=Sof(F39)=1-FVAR(1)
 Sof(C53)=Sof(F10)=Sof(F22)=Sof(F23)=FVAR(1)
 Sof(C71)=Sof(F40)=Sof(F41)=Sof(F42)=1-FVAR(2)
 Sof(C58)=Sof(F21)=Sof(F32)=Sof(F33)=FVAR(2)
 Sof(C51)=Sof(F9)=Sof(F18)=Sof(F19)=1-FVAR(3)
 Sof(C72)=Sof(F43)=Sof(F44)=Sof(F45)=FVAR(3)
 Sof(C73)=Sof(F46)=Sof(F47)=Sof(F48)=1-FVAR(4)
 Sof(C56)=Sof(F17)=Sof(F28)=Sof(F29)=FVAR(4)
 Sof(C74)=Sof(F49)=Sof(F50)=Sof(F51)=1-FVAR(5)
 Sof(C49)=Sof(F6)=Sof(F15)=Sof(F16)=FVAR(5)
 Sof(C76)=Sof(F52)=Sof(F53)=Sof(F54)=1-FVAR(6)
 Sof(C44)=Sof(F1)=Sof(F2)=Sof(F3)=FVAR(6)
 Sof(C77)=Sof(F56)=Sof(F57)=Sof(F5)=1-FVAR(7)
 Sof(C48)=Sof(F55)=Sof(F13)=Sof(F14)=FVAR(7)
 Sof(C78)=Sof(F58)=Sof(F59)=Sof(F60)=1-FVAR(8)
 Sof(C46)=Sof(F4)=Sof(F7)=Sof(F8)=FVAR(8)
6.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),
 C15(H15), C16(H16), C17(H17), C12(H12), C13(H13), C14(H14), C19(H19), C21(H21),
  C23(H23), C27(H27), C29(H29), C31(H31), C38(H38), C39(H39), C40(H40),
 C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C66(H66), C67(H67), C68(H68)
6.b Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C32(H32A,H32B,H32C), C33(H33A,H33B,
 H33C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C65(H65A,H65B,H65C)
;
_shelx_res_checksum              22139
_olex2_submission_special_instructions 'No special instructions were received'