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_1571033
_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         'C12 H12 Fe O, Al C16 F36 O4'
_chemical_formula_sum            'C28 H12 Al F36 Fe O5'
_chemical_formula_weight         1195.21
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-10-13
_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                 94.907(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.1437(6)
_cell_length_b                   23.4937(8)
_cell_length_c                   20.8960(7)
_cell_measurement_reflns_used    7354
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      72.10
_cell_measurement_theta_min      2.75
_cell_volume                     7896.3(5)
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.965
_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  0.0944
_diffrn_reflns_av_unetI/netI     0.0806
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            49755
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.631
_diffrn_reflns_theta_min         2.747
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.288
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.4842
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1090 before and 0.0691 after correction.
The Ratio of minimum to maximum transmission is 0.6425.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Yellow
_exptl_crystal_density_diffrn    2.011
_exptl_crystal_description       Plate
_exptl_crystal_F_000             4664
_exptl_crystal_size_max          0.261
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.047
_refine_diff_density_max         1.280
_refine_diff_density_min         -0.594
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1488
_refine_ls_number_reflns         15128
_refine_ls_number_restraints     834
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.1112
_refine_ls_R_factor_gt           0.0652
_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^)+(0.0869P)^2^+3.8772P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1611
_refine_ls_wR_factor_ref         0.1893
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9362
_reflns_number_total             15128
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20231012ca760_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               1571033
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.789
_shelx_estimated_absorpt_t_min   0.339
_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
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim F9
\\sim F10 \\sim F11 \\sim F12 \\sim F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17
\\sim F18 \\sim F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim F24 \\sim F25
\\sim F26 \\sim F27 \\sim F28 \\sim F29 \\sim F30 \\sim F31 \\sim F32 \\sim F33
\\sim F34 \\sim F35 \\sim F36 \\sim F38 \\sim F37 \\sim F39 \\sim F40 \\sim F41
\\sim F42 \\sim F43 \\sim F44 \\sim F46 \\sim F47 \\sim F48 \\sim F49 \\sim F50
\\sim F51 \\sim F52 \\sim F53 \\sim F54 \\sim F56 \\sim F86 \\sim F45 \\sim F59
\\sim F60 \\sim F61 \\sim F62 \\sim F63 \\sim F64 \\sim F65 \\sim F57 \\sim F66
\\sim F72 \\sim F79 \\sim F67 \\sim F58 \\sim F80 \\sim F81 \\sim F68 \\sim F69
\\sim F70 \\sim F71 \\sim F87 \\sim F88 \\sim F55 \\sim F85 \\sim F82 \\sim F83
\\sim F84 \\sim F76 \\sim F77 \\sim F78 \\sim F73 \\sim F74 \\sim F75: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C58 \\sim C56 \\sim C60 \\sim C61 \\sim C53 \\sim C57 \\sim C62: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim
Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8)
\\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq,
Uanis(F12) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15)
\\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq,
Uanis(F19) \\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F22)
\\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F25) \\sim Ueq,
Uanis(F26) \\sim Ueq, Uanis(F27) \\sim Ueq, Uanis(F28) \\sim Ueq, Uanis(F29)
\\sim Ueq, Uanis(F30) \\sim Ueq, Uanis(F31) \\sim Ueq, Uanis(F32) \\sim Ueq,
Uanis(F33) \\sim Ueq, Uanis(F34) \\sim Ueq, Uanis(F35) \\sim Ueq, Uanis(F36)
\\sim Ueq, Uanis(F38) \\sim Ueq, Uanis(F37) \\sim Ueq, Uanis(F39) \\sim Ueq,
Uanis(F40) \\sim Ueq, Uanis(F41) \\sim Ueq, Uanis(F42) \\sim Ueq, Uanis(F43)
\\sim Ueq, Uanis(F44) \\sim Ueq, Uanis(F46) \\sim Ueq, Uanis(F47) \\sim Ueq,
Uanis(F48) \\sim Ueq, Uanis(F49) \\sim Ueq, Uanis(F50) \\sim Ueq, Uanis(F51)
\\sim Ueq, Uanis(F52) \\sim Ueq, Uanis(F53) \\sim Ueq, Uanis(F54) \\sim Ueq,
Uanis(F56) \\sim Ueq, Uanis(F86) \\sim Ueq, Uanis(F45) \\sim Ueq, Uanis(F59)
\\sim Ueq, Uanis(F60) \\sim Ueq, Uanis(F61) \\sim Ueq, Uanis(F62) \\sim Ueq,
Uanis(F63) \\sim Ueq, Uanis(F64) \\sim Ueq, Uanis(F65) \\sim Ueq, Uanis(F57)
\\sim Ueq, Uanis(F66) \\sim Ueq, Uanis(F72) \\sim Ueq, Uanis(F79) \\sim Ueq,
Uanis(F67) \\sim Ueq, Uanis(F58) \\sim Ueq, Uanis(F80) \\sim Ueq, Uanis(F81)
\\sim Ueq, Uanis(F68) \\sim Ueq, Uanis(F69) \\sim Ueq, Uanis(F70) \\sim Ueq,
Uanis(F71) \\sim Ueq, Uanis(F87) \\sim Ueq, Uanis(F88) \\sim Ueq, Uanis(F55)
\\sim Ueq, Uanis(F85) \\sim Ueq, Uanis(F82) \\sim Ueq, Uanis(F83) \\sim Ueq,
Uanis(F84) \\sim Ueq, Uanis(F76) \\sim Ueq, Uanis(F77) \\sim Ueq, Uanis(F78)
\\sim Ueq, Uanis(F73) \\sim Ueq, Uanis(F74) \\sim Ueq, Uanis(F75) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C58) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C62) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Sof(C46)=1-FVAR(1)
 Sof(C45)=FVAR(1)
 Sof(C48)=1-FVAR(2)
 Sof(C47)=FVAR(2)
 Sof(C50)=1-FVAR(3)
 Sof(C49)=FVAR(3)
 Sof(C60)=Sof(F73)=Sof(F74)=Sof(F75)=1-FVAR(4)
 Sof(C56)=Sof(F65)=Sof(F57)=Sof(F66)=FVAR(4)
 Sof(C61)=Sof(F76)=Sof(F77)=Sof(F78)=1-FVAR(5)
 Sof(C53)=Sof(F45)=Sof(F59)=Sof(F60)=FVAR(5)
 Sof(C62)=Sof(F58)=Sof(F80)=Sof(F81)=1-FVAR(6)
 Sof(C57)=Sof(F72)=Sof(F79)=Sof(F67)=FVAR(6)
 Sof(F82)=Sof(F83)=Sof(F84)=1-FVAR(7)
 Sof(F37)=Sof(F39)=Sof(F40)=FVAR(7)
 Sof(F55)=Sof(F85)=1-FVAR(8)
 Sof(F56)=Sof(F86)=FVAR(8)
 Sof(F87)=Sof(F88)=1-FVAR(9)
 Sof(F43)=Sof(F44)=FVAR(9)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10),
 C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C19(H19), C20(H20), C21(H21),
  C22(H22)
4.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              9034
_olex2_submission_special_instructions 'No special instructions were received'