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_1552468
_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 Cu N2 P6, C5 H12, C F3 O3 S'
_chemical_formula_sum            'C64 H108 Cu F3 N2 O3 P6 S'
_chemical_formula_weight         1291.94
_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   geom
_audit_creation_date             2018-11-05
_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                90
_cell_angle_beta                 99.3487(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.16325(10)
_cell_length_b                   25.8990(2)
_cell_length_c                   26.5556(3)
_cell_measurement_reflns_used    25072
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.3150
_cell_measurement_theta_min      3.4170
_cell_volume                     6897.07(12)
_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 0.981
_diffrn_measured_fraction_theta_max 0.975
_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    -29.00  64.00   0.50    1.00    --   42.50 -38.00 120.00  186
  2  \w     78.00 115.00   0.50    1.00    --   42.50  38.00  90.00   74
  3  \w    152.00 178.00   0.50    4.00    --  111.00  77.00 -30.00   52
  4  \w    123.00 161.00   0.50    4.00    --  111.00 125.00  30.00   76
  5  \w     93.00 167.00   0.50    4.00    --  111.00  45.00-120.00  148
  6  \w    144.00 177.00   0.50    4.00    --  111.00  45.00-150.00   66
  7  \w    113.00 178.00   0.50    4.00    --  111.00 125.00-120.00  130
  8  \w     87.00 142.00   0.50    4.00    --  111.00  45.00-150.00  110
  9  \w     86.00 111.00   0.50    4.00    --  111.00  77.00 -30.00   50
 10  \w     85.00 141.00   0.50    4.00    --  111.00  63.00  31.00  112
 11  \w     85.00 138.00   0.50    4.00    --  111.00 -61.00 120.00  106
 12  \w     83.00 114.00   0.50    4.00    --  111.00-125.00 150.00   62
 13  \w     54.00 106.00   0.50    4.00    --  111.00 -94.00 150.00  104
 14  \w     25.00  66.00   0.50    1.00    --   42.50-125.00 -30.00   82
 15  \w     36.00 106.00   0.50    4.00    --  111.00 -30.00 -90.00  140
 16  \w     78.00 109.00   0.50    4.00    --  111.00 -94.00 -30.00   62
 17  \w     36.00 156.00   0.50    4.00    --  111.00   0.00-150.00  240
 18  \w   -109.00 -76.00   0.50    1.00    --  -38.50 -57.00 -30.00   66
;
_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      -0.0098688000
_diffrn_orient_matrix_UB_12      -0.0472007000
_diffrn_orient_matrix_UB_13      0.0345322000
_diffrn_orient_matrix_UB_21      -0.1453002000
_diffrn_orient_matrix_UB_22      -0.0086364000
_diffrn_orient_matrix_UB_23      -0.0259012000
_diffrn_orient_matrix_UB_31      0.0489751000
_diffrn_orient_matrix_UB_32      -0.0350850000
_diffrn_orient_matrix_UB_33      -0.0399569000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0247
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            41516
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.632
_diffrn_reflns_theta_min         3.373
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.453
_exptl_absorpt_correction_T_max  0.728
_exptl_absorpt_correction_T_min  0.521
_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    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             2768
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.208
_exptl_crystal_size_min          0.144
_refine_diff_density_max         0.894
_refine_diff_density_min         -0.584
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     843
_refine_ls_number_reflns         14152
_refine_ls_number_restraints     344
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.0546
_refine_ls_R_factor_gt           0.0529
_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^)+(0.0444P)^2^+10.1802P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1300
_refine_ls_wR_factor_ref         0.1311
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13572
_reflns_number_total             14152
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04501e2.cif
_cod_data_source_block           9a2CuOTf
_cod_database_code               1552468
_chemical_oxdiff_formula         'C244 H408 Cu4 F4 N30 O8 S24 P1 '
_reflns_odcompleteness_completeness 98.11
_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
 C69-C66
 -2.5 with sigma of 0.02
 C69-C68 \\sim C68-C67 \\sim C66-C67 \\sim C65-C66
 with sigma of 0.01
 C65-C67 \\sim C67-C69
 with sigma of 0.01
 C63-C64 \\sim C63-C62 \\sim C61-C62 \\sim C61-C60
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
S1B \\sim F1B \\sim F2B \\sim F3B \\sim O1B \\sim O2B \\sim O3B \\sim C59B
\\sim S1A \\sim F1A \\sim F2A \\sim F3A \\sim O1A \\sim O2A \\sim O3A \\sim
C59A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C69) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C66)
\\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
4. Others
 Sof(S1B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(O1B)=Sof(O2B)=Sof(O3B)=Sof(C59B)=1-
 FVAR(1)
 Sof(S1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(C59A)=
 FVAR(1)
 Fixed Sof: C65(0.5) H65A(0.5) H65B(0.5) H65C(0.5) C66(0.5) H66A(0.5)
 H66B(0.5) C67(0.5) H67A(0.5) H67B(0.5) C68(0.5) H68A(0.5) H68B(0.5) C69(0.5)
 H69A(0.5) H69B(0.5) H69C(0.5) C60(0.5) H60A(0.5) H60B(0.5) H60C(0.5) C61(0.5)
 H61A(0.5) H61B(0.5) C62(0.5) H62A(0.5) H62B(0.5) C63(0.5) H63A(0.5) H63B(0.5)
 C64(0.5) H64A(0.5) H64B(0.5) H64C(0.5)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C18(H18), C24(H24), C30(H30), C36(H36), C47(H47), C53(H53)
5.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(H25B,H25A),
  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), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C61(H61A,H61B),
  C62(H62A,H62B), C63(H63A,H63B)
5.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C43(H43), C44(H44), C45(H45), C46(H46)
5.d Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C69(H69A,H69B,H69C), C60(H60A,H60B,H60C), C64(H64A,H64B,
 H64C)
;
_shelx_res_checksum              88338
_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 1.268
_oxdiff_exptl_absorpt_empirical_full_min 0.793