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_4125467
_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_absolute_configuration ad
_chemical_formula_moiety         'C47 H70 Mo N3 O P2, C32 H12 B F24'
_chemical_formula_sum            'C79 H82 B F24 Mo N3 O P2'
_chemical_formula_weight         1714.16
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.6539(4)
_cell_length_b                   20.3751(4)
_cell_length_c                   20.9110(4)
_cell_measurement_reflns_used    9658
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.992
_cell_measurement_theta_min      2.224
_cell_volume                     7947.7(3)
_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  0.0515
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            167870
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.998
_diffrn_reflns_theta_min         1.463
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.308
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.7020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1239 before and 0.0549 after correction.
The Ratio of minimum to maximum transmission is 0.9408.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.433
_exptl_crystal_description       block
_exptl_crystal_F_000             3512
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.020
_refine_diff_density_min         -0.827
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 9391 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.037(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1099
_refine_ls_number_reflns         25349
_refine_ls_number_restraints     122
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0446
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0603P)^2^+3.6033P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1071
_refine_ls_wR_factor_ref         0.1127
_reflns_Friedel_coverage         0.858
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                22583
_reflns_number_total             25349
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b00002_si_002.cif
_cod_data_source_block           pnl226
_cod_depositor_comments
'Adding full bibliography for 4125466--4125467.cif.'
_cod_database_code               4125467
_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
2. Restrained distances
 F17-C71 \\sim F16-C71 \\sim F18-C71
 with sigma of 0.02
 F3-C54 \\sim F1-C54 \\sim F2-C54
 with sigma of 0.02
 F11A-C63 \\sim F10A-C63 \\sim F10-C63 \\sim F12-C63 \\sim F12A-C63 \\sim
F11-C63
 with sigma of 0.02
 F18A-C71 \\sim F17-C71 \\sim F17A-C71 \\sim F16-C71 \\sim F16A-C71 \\sim
F18-C71
 with sigma of 0.02
 F12-F11 \\sim F11A-F12A
 with sigma of 0.02
 F12-F10 \\sim F10A-F11A
 with sigma of 0.02
 F22A-C79 \\sim F22-C79 \\sim F23A-C79 \\sim F23-C79 \\sim F24A-C79 \\sim
F24-C79
 with sigma of 0.02
3. Rigid bond restraints
 F1, F21, F4, F8, F14, F9, F19, F13, F15, F7, F20, F24, F6, F10, F16, F12, F5,
 F23, F11, F22, F2, F17, F3, F18
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F1 \\sim F21 \\sim F4 \\sim F8 \\sim F14 \\sim F9 \\sim F19 \\sim F13 \\sim F15
\\sim F7 \\sim F20 \\sim F24 \\sim F6 \\sim F10 \\sim F16 \\sim F12 \\sim F5
\\sim F23 \\sim F11 \\sim F22 \\sim F2 \\sim F17 \\sim F3 \\sim F18: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(F11A) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F12)
\\sim Ueq, Uanis(F12A) \\sim Ueq, Uanis(F11) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F3) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq: with sigma of
0.02 and sigma for terminal atoms of 0.04
Uanis(F23A) \\sim Ueq, Uanis(F22A) \\sim Ueq, Uanis(F24A) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
5. Others
 Sof(F11A)=Sof(F12A)=Sof(F10A)=1-FVAR(1)
 Sof(F10)=Sof(F12)=Sof(F11)=FVAR(1)
 Sof(F18A)=Sof(F16A)=Sof(F17A)=1-FVAR(2)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(2)
 Sof(F23A)=Sof(F22A)=Sof(F24A)=1-FVAR(3)
 Sof(F24)=Sof(F23)=Sof(F22)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C7(H7A,H7B), C6(H6A,H6B), C9(H9A,H9B)
6.b Aromatic/amide H refined with riding coordinates:
 C53(H53), C67(H67), C49(H49), C57(H57), C75(H75), C59(H59), C69(H69),
 C61(H61), C12(H12), C11(H11), C14(H14), C35(H35), C15(H15), C51(H51), C77(H77),
  C73(H73), C31(H31), C65(H65), C13(H13), C1(H1), C3(H3), C2(H2), C17(H17),
 C19(H19), C5(H5), C4(H4), C21(H21), C18(H18), C20(H20)
6.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C45(H45A,H45B,H45C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C42(H42A,H42B,H42C), C27(H27A,H27B,H27C), C41(H41A,
 H41B,H41C), C38(H38A,H38B,H38C), C23(H23A,H23B,H23C), C29(H29A,H29B,H29C),
 C43(H43A,H43B,H43C), C28(H28A,H28B,H28C), C47(H47A,H47B,H47C), C46(H46A,H46B,
 H46C)
;
_shelx_res_checksum              34953
_shelx_hkl_checksum              54416
_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'