1,1′-Bifunctional Aminophosphane Complexes via N‒H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations
Streubel, Rainer; Schmer, Alexander; Kyri, Andreas W.; Schnakenburg, Gregor; Organometallics  (2017) –; doi:10.1021/acs.organomet.7b00073

data_4087215
_publ_section_title
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 1,1&#x2032;-Bifunctional Aminophosphane Complexes via N--H Bond
 Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P
 Mono Functionalizations
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_journal_name_full               Organometallics
_journal_paper_doi               10.1021/acs.organomet.7b00073
_journal_year                    2017
_chemical_formula_moiety         'C46 H36 N O5 P W'
_chemical_formula_sum            'C50 H46 N O6 P W'
_chemical_formula_weight         971.70
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     heavy
_audit_creation_date             2017-01-25
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.734(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.3276(15)
_cell_length_b                   19.649(2)
_cell_length_c                   18.692(2)
_cell_measurement_reflns_used    9971
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.37
_cell_measurement_theta_min      2.37
_cell_volume                     4662.3(9)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.960
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0524
_diffrn_reflns_av_unetI/netI     0.0585
_diffrn_reflns_Laue_measured_fraction_full 0.960
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            34291
_diffrn_reflns_point_group_measured_fraction_full 0.960
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.998
_diffrn_reflns_theta_min         1.959
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.559
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.4106
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1436 before and 0.0725 after correction. The Ratio of minimum to maximum transmission is 0.6338. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.384
_exptl_crystal_description       plate
_exptl_crystal_F_000             1960
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.04
_refine_diff_density_max         4.325
_refine_diff_density_min         -2.538
_refine_diff_density_rms         0.189
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     506
_refine_ls_number_reflns         8792
_refine_ls_number_restraints     74
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.1077
_refine_ls_R_factor_gt           0.0659
_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^)+(0.0352P)^2^+60.6700P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1372
_refine_ls_wR_factor_ref         0.1631
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5992
_reflns_number_total             8792
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om7b00073_si_002.cif
_cod_data_source_block           4677f
_cod_database_code               4087215
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.656
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
2. Restrained distances
 C2-C3
 1.34 with sigma of 0.01
 C2S-C3S
 1.34 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C3 \\sim C3S \\sim C2S \\sim C2 \\sim C1: within 2A with sigma of 0.002 and
sigma for terminal atoms of 0.004
Uanis(C3) \\sim Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C2S) \\sim Ueq, Uanis(C3S)
\\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Others
 Sof(H1BC)=Sof(H1BD)=Sof(C2S)=Sof(H2S)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=1-FVAR(1)
 Sof(H1AA)=Sof(H1AB)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3A)=Sof(H3B)=FVAR(1)
5.a Riding coordinates:
 N(H)
5.b Ternary CH refined with riding coordinates:
 C10(H10)
5.c Secondary CH2 refined with riding coordinates:
 C1(H1AA,H1AB), C1(H1BC,H1BD)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C2S(H2S), C5(H5), C6(H6), C8(H8), C9(H9), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22),
  C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C31(H31), C32(H32),
 C33(H33), C34(H34), C35(H35), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41)
5.e X=CH2 refined with riding coordinates:
 C3(H3A,H3B), C3S(H3SA,H3SB)
;
_smtbx_masks_special_details
;
The void is postulated to contain heavily disordered
diethyl ether molecules, ca. 1 per asymmetric unit.
The solvent masking procedure was used as implemented in
the Olex program suite. The method implemented is based on 
that described by van der Sluis and Spek in
Acta Cryst. (1990). A46, 194-201.
;
_shelx_res_checksum              475
_shelx_hkl_checksum              21787
_shelx_fab_checksum              77662
_olex2_submission_special_instructions 'No special instructions were received'