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_1571030
_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
'Al2 C32 F72 O8, C132 H132 B8 Mo4 N39.273, 4.093(C7 H8), 3.585(C6)'
_chemical_formula_sum            'C214.12 H164.64 Al2 B8 F72 Mo4 N39.27 O8'
_chemical_formula_weight         5307.90
_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             2023-10-06
_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                90.335(4)
_cell_angle_beta                 112.023(4)
_cell_angle_gamma                100.578(4)
_cell_formula_units_Z            1
_cell_length_a                   17.6807(12)
_cell_length_b                   18.6634(11)
_cell_length_c                   19.4278(11)
_cell_measurement_reflns_used    9897
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      72.07
_cell_measurement_theta_min      2.75
_cell_volume                     5822.4(6)
_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 0.962
_diffrn_measured_fraction_theta_max 0.962
_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  0.0600
_diffrn_reflns_av_unetI/netI     0.0546
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            62638
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        66.594
_diffrn_reflns_theta_max         66.594
_diffrn_reflns_theta_min         2.416
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.879
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6518
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0788 before and 0.0539 after correction.
The Ratio of minimum to maximum transmission is 0.8649.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Black
_exptl_crystal_density_diffrn    1.514
_exptl_crystal_description       Block
_exptl_crystal_F_000             2670
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.038
_refine_diff_density_max         1.190
_refine_diff_density_min         -0.948
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1889
_refine_ls_number_reflns         19781
_refine_ls_number_restraints     3777
_refine_ls_restrained_S_all      24.821
_refine_ls_R_factor_all          0.1431
_refine_ls_R_factor_gt           0.1009
_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^)+(0.1557P)^2^+19.5017P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2662
_refine_ls_wR_factor_ref         0.3170
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12705
_reflns_number_total             19781
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20230606ca697_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               1571030
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.615
_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
 C115-C120 = C119-C118 = C142-C123 = C122-C123 = C141-C118 = C140-C126
 1.4 with sigma of 0.02
 C142-C122
 2.4 with sigma of 0.02
 C140-C127
 2.4 with sigma of 0.02
 F5-F13 = F5-F33 = F10-F33 = F11-F13 = F12-F13 = F12-F33 = F19-F33 = F12-F33
 2.6 with sigma of 0.01
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(C124) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(C118) \\sim Ueq,
Uanis(C141) \\sim Ueq, Uanis(C140) \\sim Ueq, Uanis(C126) \\sim Ueq,
Uanis(C127) \\sim Ueq, Uanis(C128) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C82) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C86)
\\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C84) \\sim Ueq,
Uanis(C142) \\sim Ueq, Uanis(C123) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(C125) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C89) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C92)
\\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C95) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Others
 Sof(Mo2D)=Sof(N12D)=Sof(N18D)=Sof(N17D)=Sof(N20D)=Sof(N19D)=Sof(B5)=Sof(C48D)=
 Sof(H48D)=Sof(C49D)=Sof(H49D)=Sof(C50D)=Sof(H50D)=Sof(C45D)=Sof(H45D)=
 Sof(C59D)=Sof(C64D)=Sof(H64D)=Sof(C63D)=Sof(C66D)=Sof(H66D)=Sof(H66E)=
 Sof(H66F)=Sof(C35D)=Sof(H35D)=Sof(C36D)=Sof(H36D)=Sof(C37D)=Sof(H37D)=
 Sof(C38D)=Sof(C34D)=Sof(C47D)=Sof(H47D)=Sof(C60D)=Sof(H60D)=Sof(C62D)=
 Sof(H62D)=Sof(C46D)=Sof(H46D)=Sof(C130)=Sof(H13A)=Sof(H13B)=Sof(H13C)=1-FVAR(1)
 Sof(Mo2)=Sof(N17)=Sof(N18)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=Sof(C47)=
 Sof(H47)=Sof(B4)=Sof(N20)=Sof(N19)=Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49)=
 Sof(C50)=Sof(H50)=Sof(C59)=Sof(C64)=Sof(H64)=Sof(C66)=Sof(H66A)=Sof(H66B)=
 Sof(H66C)=Sof(C62)=Sof(H62)=Sof(C61)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=
 Sof(C60)=Sof(H60)=Sof(N12)=Sof(C38)=Sof(C37)=Sof(H37)=Sof(C36)=Sof(H36)=
 Sof(C35)=Sof(H35)=Sof(C34)=Sof(N11)=FVAR(1)
 Sof(C126)=Sof(C127)=Sof(C128)=1-FVAR(2)
 Sof(C140)=0.5*(1-FVAR(3))
 Sof(C141)=Sof(C118)=Sof(C119)=Sof(C124)=FVAR(2)
 Sof(C156)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C150)=Sof(C151)=Sof(H151)=
 Sof(C152)=Sof(H152)=Sof(C153)=Sof(H153)=Sof(C154)=Sof(H154)=1-FVAR(3)
 Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(H89C)=Sof(C90)=Sof(C91)=Sof(H91)=Sof(C92)=
 Sof(H92)=Sof(C93)=Sof(H93)=Sof(C94)=Sof(H94)=Sof(C95)=Sof(H95)=FVAR(3)
 Fixed Sof: C115(0.5) C116(0.5) C120(0.5) C121(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50), C64(H64),
 C62(H62), C60(H60), C37(H37), C36(H36), C35(H35), C42(H42), C43(H43), C44(H44),
  C41(H41), C40(H40), C39(H39), C12(H12), C13(H13), C14(H14), C52(H52),
 C54(H54), C56(H56), C17(H17), C16(H16), C15(H15), C4(H4), C3(H3), C2(H2),
 C6(H6), C7(H7), C8(H8), C11(H11), C10(H10), C9(H9), C27(H27), C29(H29),
 C31(H31), C23(H23), C21(H21), C19(H19), C82(H82), C83(H83), C85(H85), C87(H87),
  C96(H96), C91(H91), C92(H92), C93(H93), C94(H94), C95(H95), C151(H151),
 C152(H152), C153(H153), C154(H154), C155(H155), C48D(H48D), C49D(H49D),
 C50D(H50D), C45D(H45D), C64D(H64D), C35D(H35D), C36D(H36D), C37D(H37D),
 C47D(H47D), C60D(H60D), C62D(H62D), C46D(H46D)
6.b Fitted hexagon refined as free rotating group:
 C82(C83,C85,C86,C87,C96), C90(C91,C92,C93,C94,C95), C150(C151,C152,C153,C154,
 C155)
6.c Idealised Me refined as rotating group:
 C66(H66A,H66B,H66C), C65(H65A,H65B,H65C), C57(H57A,H57B,H57C), C58(H58A,H58B,
 H58C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C25(H25A,H25B,H25C), C24(H24A,
 H24B,H24C), C84(H84A,H84B,H84C), C89(H89A,H89B,H89C), C156(H15A,H15B,H15C),
 C66D(H66D,H66E,H66F), C130(H13A,H13B,H13C)
;
_shelx_res_checksum              15418
_olex2_submission_special_instructions 'No special instructions were received'