A modular approach to neutral P,N-ligands: synthesis and coordination chemistry.
Vasilenko, Vladislav; Roth, Torsten; Blasius, Clemens K.; Intorp, Sebastian N.; Wadepohl, Hubert; Gade, Lutz H.; Beilstein journal of organic chemistry 12 (2016) 846–853; doi:10.3762/bjoc.12.83

data_4031986
_publ_section_title
;
 A modular approach to neutral P,N-ligands: synthesis and coordination
 chemistry.
;
_journal_name_full               'Beilstein journal of organic chemistry'
_journal_page_first              846
_journal_page_last               853
_journal_paper_doi               10.3762/bjoc.12.83
_journal_volume                  12
_journal_year                    2016
_chemical_formula_moiety         'C36 H38 N P Rh, B F4, 0.67(C H2 Cl2)'
_chemical_formula_sum            'C37 H40 B Cl2 F4 N P Rh'
_chemical_formula_weight         790.29
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      1
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_tro134
_audit_creation_date
;
'Thu May 07 13:07:15 2015'
;
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'26.01.2016 18:26:48 CET UTC+01:00  encif 1.38'
_cell_angle_alpha                105.6171(11)
_cell_angle_beta                 96.4680(11)
_cell_angle_gamma                104.3606(10)
_cell_formula_units_Z            3
_cell_length_a                   9.78588(12)
_cell_length_b                   14.13707(16)
_cell_length_c                   20.6977(3)
_cell_measurement_reflns_used    28455
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      31.5830
_cell_measurement_theta_min      3.8960
_cell_volume                     2621.66(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET)
(compiled Dec  9 2014,15:38:47)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET)
(compiled Dec  9 2014,15:38:47)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET)
(compiled Dec  9 2014,15:38:47)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-15); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'DIRDIF (Beurskens et al., 1999-2008)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.919
_diffrn_measurement_details
;
  1 omega    1.00   51.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   38.0000  -90.0000 100

  2 omega   34.00   59.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -80.0000  179.3850 50

  3 omega  -44.00   26.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -80.0000  179.3850 140

  4 omega  -44.00   59.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -80.0000  -39.9597 206

  5 omega  -44.00   -6.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -80.0000  144.1373 76

  6 omega   31.00   59.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -80.0000  144.1373 56

  7 omega    4.00   33.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000   30.0000 58

  8 omega   -3.00   94.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000  150.0000 194

  9 omega    1.00   49.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   38.0000   90.0000 96

 10 omega   71.00   99.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   38.0000   90.0000 56

 11 omega    0.00   26.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000 -120.0000 52

 12 omega   54.00   97.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000 -120.0000 86

 13 omega  -43.00   59.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -80.0000   83.4748 204

 14 omega    6.00   37.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   57.0000  120.0000 62

 15 omega   59.00   85.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   57.0000  120.0000 52

 16 omega   -3.00   86.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   77.0000  -60.0000 178

 17 omega  -42.00   58.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.0000  -77.0000 -113.3884 200

 18 omega  -30.00   60.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.0000  -80.0000   20.7595 180

 19 omega  -43.00   57.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662  -77.0000   60.0000 200

 20 omega    6.00   96.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   57.0000   90.0000 180

 21 omega    6.00   96.00   0.5000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       26.8662   57.0000  -60.0000 180

;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      0.0125914000
_diffrn_orient_matrix_UB_12      0.0065647000
_diffrn_orient_matrix_UB_13      0.0355767000
_diffrn_orient_matrix_UB_21      0.0656603000
_diffrn_orient_matrix_UB_22      -0.0122533000
_diffrn_orient_matrix_UB_23      -0.0023996000
_diffrn_orient_matrix_UB_31      0.0366492000
_diffrn_orient_matrix_UB_32      0.0526463000
_diffrn_orient_matrix_UB_33      0.0065823000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0516
_diffrn_reflns_av_unetI/netI     0.0736
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.919
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            87324
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.850
_diffrn_reflns_theta_min         3.247
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    0.737
_exptl_absorpt_correction_T_max  0.977
_exptl_absorpt_correction_T_min  0.926
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35g (release 09-12-2014 CrysAlis171 .NET)
(compiled Dec  9 2014,15:38:47)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.502
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1212
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.038
_refine_diff_density_max         0.903
_refine_diff_density_min         -0.647
_refine_diff_density_rms         0.099
_refine_ls_abs_structure_details
;
 Flack x determined using 12454 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1252
_refine_ls_number_reflns         34788
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0447
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0394P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0900
_refine_ls_wR_factor_ref         0.0959
_reflns_Friedel_coverage         0.941
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.865
_reflns_number_gt                30637
_reflns_number_total             34788
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            1860-5397-12-83-S2.cif
_cod_data_source_block           ga_tro134_sq
_cod_depositor_comments
'Adding full bibliography for 4031975--4031986.cif.'
_cod_original_cell_volume        2621.65(6)
_cod_database_code               4031986
_audit_block_refno               2432
_audit_block_usercomment         'trvvcb5, irregular, red'
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.526
_shelxl_version_number           2014/7
_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
 B1-F11 \\sim B1-F12 \\sim B1-F13 \\sim B1-F14
 with sigma of 0.01
 F11-F12 \\sim F11-F13 \\sim F11-F14 \\sim F12-F13 \\sim F12-F14 \\sim F13-F14
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 B1, B2, B3, F11, F12, F13, F14, F21, F22, F23, F24, F31, F32, F33, F34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{F11, F12, F13, F14, B1} sigma for 1-2: 0.02, 1-3: 0.04
as
{F21, F22, F23, F24, B2}
{F11, F12, F13, F14, B1} sigma for 1-2: 0.02, 1-3: 0.04
as
{F31, F32, F33, F34, B3}
5.a Ternary CH refined with riding coordinates:
 C29(H29), C30(H30), C33(H33), C34(H34), C69(H69), C70(H70), C73(H73),
 C74(H74), C109(H109), C110(H110), C113(H113), C114(H114)
5.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C32(H32A,H32B), C35(H35A,H35B), C36(H36A,H36B), C71(H71A,
 H71B), C72(H72A,H72B), C75(H75A,H75B), C76(H76A,H76B), C111(H11A,H11B),
 C112(H11C,H11D), C115(H11E,H11F), C116(H11G,H11H), C201(H20A,H20B), C202(H20C,
 H20D)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C12(H12), C18(H18),
 C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27),
  C28(H28), C41(H41), C44(H44), C45(H45), C46(H46), C47(H47), C50(H50),
 C52(H52), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C64(H64), C65(H65),
  C66(H66), C67(H67), C68(H68), C81(H81), C84(H84), C85(H85), C86(H86),
 C87(H87), C90(H90), C92(H92), C98(H98), C99(H99), C100(H100), C101(H101),
 C102(H102), C104(H104), C105(H105), C106(H106), C107(H107), C108(H108)
5.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C54(H54A,H54B,
 H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C94(H94A,H94B,H94C), C95(H95A,
 H95B,H95C), C96(H96A,H96B,H96C)
;
_shelx_res_checksum              86321
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            9.78588(12)
_cell_oxdiff_length_b            14.13707(16)
_cell_oxdiff_length_c            20.6977(3)
_cell_oxdiff_angle_alpha         105.6171(11)
_cell_oxdiff_angle_beta          96.4680(11)
_cell_oxdiff_angle_gamma         104.3606(10)
_cell_oxdiff_volume              2621.65(6)
_cell_oxdiff_measurement_reflns_used 28455
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_theta     26.32
_reflns_odcompleteness_iscentric 1
_platon_squeeze_void_probe_radius 1.20