Putting chromium on the map for N2 reduction: production of hydrazine and ammonia. A study of cis-M(N2)2 (M = Cr, Mo, W) bis(diphosphine) complexes.
Egbert, Jonathan D.; O'Hagan, Molly; Wiedner, Eric S.; Bullock, R. Morris; Piro, Nicholas A.; Kassel, W. Scott; Mock, Michael T.; Chemical communications (Cambridge, England) 52 (2016) 9343–9346; doi:10.1039/c6cc03449g

data_7124669
_publ_section_title
;
 Putting chromium on the map for N2 reduction: production of hydrazine and
 ammonia. A study of cis-M(N2)2 (M = Cr, Mo, W) bis(diphosphine)
 complexes.
;
_journal_issue                   60
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9343
_journal_page_last               9346
_journal_paper_doi               10.1039/c6cc03449g
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C34 H58 F4 Mo N6 P4'
_chemical_formula_sum            'C34 H58 F4 Mo N6 P4'
_chemical_formula_weight         846.68
_chemical_properties_physical    'Air-sensitive, Moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-27
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2016-01-05 deposited with the CCDC.
2016-06-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.3341(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.2417(2)
_cell_length_b                   18.3288(3)
_cell_length_c                   21.5881(4)
_cell_measurement_reflns_used    5538
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.128
_cell_measurement_theta_min      2.288
_cell_volume                     4034.93(13)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_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 APEX-II CCD'
_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  0.0837
_diffrn_reflns_av_unetI/netI     0.1010
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            68516
_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         28.283
_diffrn_reflns_theta_min         1.460
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.534
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.7052
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0694 before and 0.0652 after correction.
The Ratio of minimum to maximum transmission is 0.9454.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.394
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1768
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Ethyl Ether'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.034
_refine_diff_density_min         -0.439
_refine_diff_density_rms         0.099
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.22(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     900
_refine_ls_number_reflns         19824
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.0969
_refine_ls_R_factor_gt           0.0528
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0334P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0908
_refine_ls_wR_factor_ref         0.1071
_reflns_Friedel_coverage         0.998
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                13460
_reflns_number_total             19824
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc03449g2.cif
_cod_data_source_block           pnl187
_cod_database_code               7124669
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.78(3) 0.22(3)
2. 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
3.a Secondary CH2 refined with riding coordinates:
 C124(H12A,H12B), C24(H24A,H24B), C1(H1A,H1B), C3(H3A,H3B), C122(H12C,H12D),
 C109(H10C,H10D), C111(H11C,H11D), C22(H22A,H22B), C9(H9A,H9B), C27(H27A,H27B),
 C11(H11A,H11B), C103(H10E,H10F), C101(H10G,H10H), C127(H12E,H12F), C26(H26A,
 H26B), C110(H11E,H11F), C128(H12G,H12H), C10(H10A,H10B), C7(H7A,H7B),
 C120(H12I,H12J), C118(H11G,H11H), C18(H18A,H18B), C126(H12K,H12L), C5(H5A,H5B),
  C107(H10R,H10S), C28(H28A,H28B), C105(H10W,H10X), C20(H20A,H20B)
3.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C132(H132), C114(H114), C131(H131), C15(H15), C115(H115),
 C133(H133), C16(H16), C116(H116), C33(H33), C31(H31), C32(H32)
3.c Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C102(H10I,H10J,H10K), C8(H8A,H8B,H8C), C2(H2A,H2B,H2C),
 C4(H4A,H4B,H4C), C23(H23A,H23B,H23C), C19(H19A,H19B,H19C), C104(H10L,H10M,
 H10N), C6(H6A,H6B,H6C), C108(H10O,H10P,H10Q), C125(H12M,H12N,H12O), C106(H10T,
 H10U,H10V), C121(H12P,H12Q,H12R), C123(H12S,H12T,H12U), C21(H21A,H21B,H21C),
 C119(H11I,H11J,H11K)
;
_shelx_res_checksum              17376
_shelx_hkl_checksum              14458
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method
'mounted in NVH immersion oil on a nylon fiber'
_olex2_submission_special_instructions 'No special instructions were received'