Controlled scrambling reactions to polyphosphanes via bond metathesis reactions
Schoemaker, Robin; Schwedtmann, Kai; Franconetti, Antonio; Frontera, Antonio; Hennersdorf, Felix; Weigand, Jan J.; Chemical Science  (2019) –; doi:10.1039/C9SC04501E

data_1552467
_publ_section_title
;
 Controlled scrambling reactions to polyphosphanes via bond metathesis
 reactions
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC04501E
_journal_year                    2019
_chemical_formula_moiety
'C58 H96 Br2 Cu2 N2 P6, 0.92(C5 H12), 0.83(C4 H8 O)'
_chemical_formula_sum            'C65.93 H113.69 Br2 Cu2 N2 O0.82 P6'
_chemical_formula_weight         1420.29
_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   geom
_audit_creation_date             2018-11-06
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2019-08-30 deposited with the CCDC.    2019-10-17 downloaded from the CCDC.
;
_cell_angle_alpha                102.4758(8)
_cell_angle_beta                 101.6435(8)
_cell_angle_gamma                98.8895(9)
_cell_formula_units_Z            2
_cell_length_a                   10.85215(11)
_cell_length_b                   17.65905(19)
_cell_length_c                   19.63512(16)
_cell_measurement_reflns_used    20375
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.4270
_cell_measurement_theta_min      3.0490
_cell_volume                     3520.32(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -25.00   2.00   0.50    2.50    --   42.50 -57.00  90.00   54
  2  \w     32.00  63.00   0.50    2.50    --   42.50 -57.00  90.00   62
  3  \w     37.00  67.00   0.50   10.00    --  111.00 -94.00 150.00   60
  4  \w     71.00 109.00   0.50   10.00    --  111.00 -94.00 150.00   76
  5  \w     88.00 121.00   0.50   10.00    --  111.00-125.00 150.00   66
  6  \w     84.00 111.00   0.50   10.00    --  111.00-125.00  90.00   54
  7  \w     54.00 138.00   0.50   10.00    --  111.00 -61.00 120.00  168
  8  \w     77.00 138.00   0.50   10.00    --  111.00 -61.00 -30.00  122
  9  \w     86.00 115.00   0.50   10.00    --  111.00-125.00 -90.00   58
 10  \w     57.00  89.00   0.50   10.00    --  111.00 -94.00 -60.00   64
 11  \w     76.00 130.00   0.50   10.00    --  111.00 -30.00 -90.00  108
 12  \w     92.00 168.00   0.50   10.00    --  111.00  30.00-180.00  152
 13  \w    131.00 176.00   0.50   10.00    --  111.00  45.00 -90.00   90
 14  \w    153.00 178.00   0.50   10.00    --  111.00  77.00 -60.00   50
 15  \w    128.00 171.00   0.50   10.00    --  111.00 125.00-120.00   86
 16  \w    121.00 178.00   0.50   10.00    --  111.00  30.00-150.00  114
 17  \w    100.00 146.00   0.50   10.00    --  111.00  77.00 -60.00   92
 18  \w     89.00 178.00   0.50   10.00    --  111.00  45.00-120.00  178
 19  \w     87.00 164.00   0.50   10.00    --  111.00  45.00 -60.00  154
 20  \w     67.00  94.00   0.50   10.00    --  111.00  15.00 -30.00   54
 21  \w     40.00 127.00   0.50   10.00    --  111.00 -45.00 -60.00  174
 22  \w     41.00  90.00   0.50   10.00    --  111.00 -61.00 -90.00   98
 23  \w     35.00 108.00   0.50   10.00    --  111.00 -94.00 -90.00  146
 24  \w     39.00 121.00   0.50   10.00    --  111.00-125.00  30.00  164
 25  \w     52.00  79.00   0.50   10.00    --  111.00-125.00 150.00   54
 26  \w     50.00  94.00   0.50   10.00    --  111.00-125.00 120.00   88
 27  \w     30.00  56.00   0.50   10.00    --  111.00 -94.00  90.00   52
 28  \w     16.00 109.00   0.50    2.50    --   42.50  57.00-120.00  186
 29  \w     32.00  60.00   0.50   10.00    --  111.00 -94.00-150.00   56
 30  \w    -60.00  34.00   0.50    2.50    --  -38.50  38.00 150.00  188
 31  \w   -108.00 -16.00   0.50    2.50    --  -38.50 -38.00 -30.00  184
 32  \w    -94.00 -17.00   0.50    2.50    --  -38.50 125.00 -90.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0548383000
_diffrn_orient_matrix_UB_12      -0.0100754000
_diffrn_orient_matrix_UB_13      -0.0809116000
_diffrn_orient_matrix_UB_21      -0.0481305000
_diffrn_orient_matrix_UB_22      -0.0893695000
_diffrn_orient_matrix_UB_23      -0.0098633000
_diffrn_orient_matrix_UB_31      -0.1289440000
_diffrn_orient_matrix_UB_32      0.0159020000
_diffrn_orient_matrix_UB_33      0.0148798000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0289
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            38405
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.646
_diffrn_reflns_theta_min         2.376
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.660
_exptl_absorpt_correction_T_max  0.889
_exptl_absorpt_correction_T_min  0.653
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.340
_exptl_crystal_description       block
_exptl_crystal_F_000             1496
_exptl_crystal_size_max          0.221
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.903
_refine_diff_density_min         -0.587
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     814
_refine_ls_number_reflns         14673
_refine_ls_number_restraints     299
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0353
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0514P)^2^+2.1388P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0933
_refine_ls_wR_factor_ref         0.0970
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13137
_reflns_number_total             14673
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04501e2.cif
_cod_data_source_block           9aCuBr
_cod_original_cell_volume        3520.31(6)
_cod_database_code               1552467
_chemical_oxdiff_formula         'C124 H192 Br4 Cu4 N4 O2 P12 '
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C59A-C61A \\sim C61A-C63A \\sim C60A-C62A
 with sigma of 0.01
 C65A-C67A \\sim C66A-C64A
 with sigma of 0.01
 C67A-C66A \\sim C66A-C65A \\sim C64A-C65A \\sim C66B-C67B \\sim C65B-C66B
\\sim C65B-C64B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C66B \\sim O1B \\sim C67B \\sim C64B \\sim C65B \\sim C60A \\sim C59A \\sim
C61A \\sim C62A \\sim C63A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O1A \\sim C64A \\sim C67A \\sim C65A \\sim C66A \\sim C60B \\sim C63B \\sim
C62B \\sim C61B \\sim C59B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Same fragment restrains
{C63B, C62B, C61B, C60B, C59B} sigma for 1-2: 0.02, 1-3: 0.02
as
{C59A, C60A, C61A, C62A, C63A}
{O1B, C67B, C66B, C65B, C64B} sigma for 1-2: 0.02, 1-3: 0.02
as
{O1A, C64A, C65A, C66A, C67A}
5. Others
 Sof(O1B)=Sof(C67B)=Sof(H67A)=Sof(H67B)=Sof(C66B)=Sof(H66A)=Sof(H66B)=
 Sof(C65B)=Sof(H65A)=Sof(H65B)=Sof(C64B)=Sof(H64A)=Sof(H64B)=1-FVAR(1)
 Sof(C59A)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C60A)=Sof(H60C)=Sof(H60D)=
 Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=Sof(H62C)=Sof(H62D)=Sof(C63A)=
 Sof(H63D)=Sof(H63E)=Sof(H63F)=FVAR(1)
 Fixed Sof: C63B(0.25) H63A(0.25) H63B(0.25) H63C(0.25) C62B(0.25) H62A(0.25)
 H62B(0.25) C61B(0.25) H61A(0.25) H61B(0.25) C60B(0.25) H60A(0.25) H60B(0.25)
 C59B(0.25) H59A(0.25) H59B(0.25) H59C(0.25) O1A(0.5) C64A(0.5) H64C(0.5)
 H64D(0.5) C65A(0.5) H65C(0.5) H65D(0.5) C66A(0.5) H66C(0.5) H66D(0.5)
 C67A(0.5) H67C(0.5) H67D(0.5)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C18(H18), C24(H24), C30(H30), C36(H36), C47(H47), C53(H53)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C19(H19A,H19B),
 C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C25(H25A,H25B),
  C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C31(H31A,
 H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B),
 C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B),
  C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,
 H52B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B),
 C58(H58A,H58B), C62B(H62A,H62B), C61B(H61A,H61B), C60B(H60A,H60B), C60A(H60C,
 H60D), C61A(H61C,H61D), C62A(H62C,H62D), C67B(H67A,H67B), C66B(H66A,H66B),
 C65B(H65A,H65B), C64B(H64A,H64B), C64A(H64C,H64D), C65A(H65C,H65D), C66A(H66C,
 H66D), C67A(H67C,H67D)
6.c Me refined with riding coordinates:
 C63B(H63A,H63B,H63C), C59B(H59A,H59B,H59C)
6.d Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C43(H43), C44(H44), C45(H45), C46(H46)
6.e Idealised Me refined as rotating group:
 C59A(H59D,H59E,H59F), C63A(H63D,H63E,H63F)
;
_shelx_res_checksum              10945
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.893
_oxdiff_exptl_absorpt_empirical_full_min 0.735