Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH3 Complex.
Bhattacharya, Papri; Heiden, Zachariah M.; Wiedner, Eric S.; Raugei, Simone; Piro, Nicholas A.; Kassel, W. Scott; Bullock, R. Morris; Mock, Michael T.; Journal of the American Chemical Society 139 (2017) 2916–2919; doi:10.1021/jacs.7b00002

data_4125466
_publ_section_title
;
 Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH3
 Complex.
;
_journal_issue                   8
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2916
_journal_page_last               2919
_journal_paper_doi               10.1021/jacs.7b00002
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C30 H44 Mo N3 O P2, C32 H12 B F24, C3.5 H4'
_chemical_formula_sum            'C65.5 H60 B F24 Mo N3 O P2'
_chemical_formula_weight         1529.85
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                103.5782(18)
_cell_angle_beta                 107.1871(19)
_cell_angle_gamma                95.011(2)
_cell_formula_units_Z            2
_cell_length_a                   13.1536(9)
_cell_length_b                   13.9867(9)
_cell_length_c                   19.6553(11)
_cell_measurement_reflns_used    9987
_cell_measurement_temperature    100
_cell_measurement_theta_max      22.508
_cell_measurement_theta_min      2.232
_cell_volume                     3309.9(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0683
_diffrn_reflns_av_unetI/netI     0.0587
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            67166
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.681
_diffrn_reflns_theta_max         25.681
_diffrn_reflns_theta_min         1.625
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.359
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.7041
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0642 before and 0.0558 after correction.
The Ratio of minimum to maximum transmission is 0.9438.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.535
_exptl_crystal_description       plate
_exptl_crystal_F_000             1550
_exptl_crystal_recrystallization_method
'Crystallized from toluene DCM, pentane.'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.568
_refine_diff_density_min         -0.490
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.004
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1090
_refine_ls_number_reflns         12556
_refine_ls_number_restraints     1487
_refine_ls_restrained_S_all      0.969
_refine_ls_R_factor_all          0.0713
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0425P)^2^+2.9889P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.1026
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9225
_reflns_number_total             12556
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b00002_si_001.cif
_cod_data_source_block           pnl210
_cod_depositor_comments
'Adding full bibliography for 4125466--4125467.cif.'
_cod_original_formula_sum        'C65.50 H60 B F24 Mo N3 O P2'
_cod_database_code               4125466
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.932
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All N(H,H,H) groups
2. Restrained distances
 F12-C124 \\sim F121-C124 \\sim F122-C124 \\sim F10-C124 \\sim F117-C124 \\sim
F118-C124 \\sim F11-
 C124 \\sim F119-C124 \\sim F120-C124
 with sigma of 0.02
 N1-H1A \\sim N1-H1B
 with sigma of 0.02
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
Uanis(F11) \\sim Ueq, Uanis(F118) \\sim Ueq, Uanis(F117) \\sim Ueq, Uanis(F10)
\\sim Ueq, Uanis(F122) \\sim Ueq, Uanis(F121) \\sim Ueq, Uanis(F12) \\sim Ueq,
Uanis(F120) \\sim Ueq, Uanis(F119) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(F121) = Uanis(F11)
5. Others
 1*[Sof(F10)+Sof(F11)+Sof(F12)]+1*[Sof(F117)+Sof(F119)+Sof(F121)]+1*[Sof(F118)+
 Sof(F120)+Sof(F122)]=1 with esd of 0.001
 Sof(F124)=Sof(F126)=Sof(F128)=1-FVAR(1)
 Sof(F125)=Sof(F127)=Sof(F129)=FVAR(1)
 Sof(F130)=Sof(F132)=Sof(F134)=1-FVAR(2)
 Sof(F131)=Sof(F133)=Sof(F135)=FVAR(2)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(3)
 Sof(F1)=Sof(F2)=Sof(F3)=1-FVAR(4)
 Sof(F113)=Sof(F114)=Sof(F115)=FVAR(4)
 Sof(F4)=Sof(F5)=Sof(F6)=1-FVAR(5)
 Sof(F101)=Sof(F102)=Sof(F103)=FVAR(5)
 Sof(F7)=Sof(F8)=Sof(F9)=1-FVAR(6)
 Sof(F107)=Sof(F108)=Sof(F109)=FVAR(6)
 Sof(F117)=Sof(F119)=Sof(F121)=FVAR(7)
 Sof(F118)=Sof(F120)=Sof(F122)=FVAR(8)
 Fixed Sof: C1T(0.5) H1TA(0.5) H1TB(0.5) H1TC(0.5) H2T(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C102(H102),
 C104(H104), C106(H106), C110(H110), C112(H112), C114(H114), C118(H118),
 C120(H120), C122(H122), C126(H126), C128(H128), C130(H130), C2T(H2T), C3T(H3T),
  C4T(H4T)
6.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C1T(H1TA,H1TB,H1TC)
;
_shelx_res_checksum              77496
_shelx_hkl_checksum              85291
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method
'Mounted in NVH imersion oil on a nylon fiber.'
_olex2_submission_special_instructions 'No special instructions were received'