Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications
Sharma, Mahendra K.; Blomeyer, Sebastian; Glodde, Timo; Neumann, Beate; Stammler, Hans-Georg; Hinz, Alexander; van Gastel, Maurice; Ghadwal, Rajendra S.; Chemical Science 11 (2020) 1975–1984; doi:10.1039/C9SC05598C

data_1557451
_publ_section_title
;
 Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their
 sequential one-electron oxidation to radical cations and dications
;
_journal_issue                   7
_journal_name_full               'Chemical Science'
_journal_page_first              1975
_journal_page_last               1984
_journal_paper_doi               10.1039/C9SC05598C
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C57 H76 N3 P'
_chemical_formula_sum            'C57 H76 N3 P'
_chemical_formula_weight         834.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-08-02
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2019-08-28 deposited with the CCDC.	2020-01-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.6144(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.56527(11)
_cell_length_b                   11.96597(7)
_cell_length_c                   22.85445(16)
_cell_measurement_reflns_used    64190
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      76.3380
_cell_measurement_theta_min      3.6430
_cell_volume                     4973.19(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -64.00  30.00   1.00    2.50    --  -38.50  57.00 120.00   94
  2  \w   -124.00  47.00   1.00    2.50    --  -38.50   0.00  60.00  171
  3  \w    -87.00  -6.00   1.00    2.50    --  -38.50 125.00 150.00   81
  4  \w     18.00 111.00   1.00    2.50    --   42.89  57.00-120.00   93
  5  \w     18.00 111.00   1.00    2.50    --   42.89  57.00 120.00   93
  6  \w     22.00 114.00   1.00    2.50    --   42.89  38.00  30.00   92
  7  \w     14.00 113.00   1.00    2.50    --   42.89  73.00-101.60   99
  8  \w     27.00  97.00   1.00    2.50    --   42.89-125.00  30.00   70
  9  \w     14.00 113.00   1.00    2.50    --   42.89  72.00 140.00   99
 10  \w     12.00  42.00   1.00    2.50    --   42.89  81.00 178.39   30
 11  \w     12.00  42.00   1.00    2.50    --   42.89  81.00 101.76   30
 12  \w     12.00  42.00   1.00    2.50    --   42.89  80.00 -52.82   30
 13  \w     12.00  42.00   1.00    2.50    --   42.89  81.00  34.54   30
 14  \w     15.00 112.00   1.00    2.50    --   42.89  68.00 -21.87   97
 15  \w     14.00 113.00   1.00    2.50    --   42.89  72.00  29.88   99
 16  \w     27.00  97.00   1.00    2.50    --   42.89-125.00 -30.00   70
 17  \w     82.00 178.00   1.00   10.00    --  111.00  72.00 163.64   96
 18  \w     85.00 178.00   1.00   10.00    --  111.00  61.00-175.96   93
 19  \w     84.00 178.00   1.00   10.00    --  111.00  63.00 136.57   94
 20  \w     82.00 178.00   1.00   10.00    --  111.00  74.00 107.27   96
 21  \w     86.00 178.00   1.00   10.00    --  111.00  55.00 174.59   92
 22  \w     85.00 178.00   1.00   10.00    --  111.00  60.00  45.28   93
 23  \w     85.00 178.00   1.00   10.00    --  111.00  61.00  47.09   93
 24  \w     86.00 178.00   1.00   10.00    --  111.00  58.00 -76.64   92
 25  \w     85.00 178.00   1.00   10.00    --  111.00  61.00-126.03   93
 26  \w     82.00 178.00   1.00   10.00    --  111.00  72.00 -82.85   96
 27  \w     85.00 178.00   1.00   10.00    --  111.00  62.00-168.96   93
 28  \w     85.00 178.00   1.00   10.00    --  111.00  61.00-150.00   93
 29  \w     83.00 178.00   1.00   10.00    --  111.00  70.00   4.84   95
 30  \w     84.00 178.00   1.00   10.00    --  111.00  65.00-161.95   94
 31  \w     86.00 178.00   1.00   10.00    --  111.00  58.00  -0.31   92
 32  \w     83.00 178.00   1.00   10.00    --  111.00  68.00-111.86   95
 33  \w     31.00 107.00   1.00   10.00    --  111.00 -94.00 150.00   76
 34  \w     83.00 178.00   1.00   10.00    --  111.00  67.00  61.43   95
 35  \w     83.00 178.00   1.00   10.00    --  111.00  69.00 -26.70   95
 36  \w     86.00 178.00   1.00   10.00    --  111.00  58.00 100.14   92
 37  \w     40.00 141.00   1.00   10.00    --  111.00 -77.00 -60.00  101
 38  \w     31.00 107.00   1.00   10.00    --  111.00 -94.00 -90.00   76
 39  \w     31.00 107.00   1.00   10.00    --  111.00 -94.00  90.00   76
 40  \w     85.00 178.00   1.00   10.00    --  111.00  62.00-140.37   93
 41  \w     34.00 107.00   1.00   10.00    --  111.00-101.00-139.95   73
 42  \w     84.00 178.00   1.00   10.00    --  111.00  64.00 -39.03   94
 43  \w     41.00 133.00   1.00   10.00    --  111.00 -45.00 120.00   92
 44  \w     85.00 165.00   1.00   10.00    --  111.00  61.00  30.00   80
 45  \w     33.00 107.00   1.00   10.00    --  111.00 -94.00  60.00   74
 46  \w     85.00 111.00   1.00   10.00    --  111.00  61.00  90.00   26
 47  \w     85.00 112.00   1.00   10.00    --  111.00  61.00   0.00   27
 48  \w     85.00 112.00   1.00   10.00    --  111.00  61.00 -30.00   27
 49  \w     87.00 112.00   1.00   10.00    --  111.00  56.00  82.08   25
 50  \w     89.00 116.00   1.00   10.00    --  111.00  45.00-180.00   27
 51  \w     86.00 122.00   1.00   10.00    --  111.00  55.00 117.00   36
 52  \w     85.00 165.00   1.00   10.00    --  111.00  61.00-120.00   80
 53  \w     53.00  80.00   1.00   10.00    --  111.00 -94.00 120.00   27
 54  \w     82.00 107.00   1.00   10.00    --  111.00 -94.00 120.00   25
 55  \w     49.00 108.00   1.00   10.00    --  111.00-105.00  18.55   59
 56  \w     86.00 112.00   1.00   10.00    --  111.00  55.00  67.05   26
 57  \w     84.00 110.00   1.00   10.00    --  111.00  63.00 -51.59   26
 58  \w    119.00 177.00   1.00   10.00    --  111.00  70.00 142.33   58
 59  \w     85.00 176.00   1.00   10.00    --  111.00  61.00 -60.00   91
 60  \w     86.00 111.00   1.00   10.00    --  111.00  61.00 -90.00   25
 61  \w     83.00 109.00   1.00   10.00    --  111.00  70.00 142.33   26
 62  \w     85.00 111.00   1.00   10.00    --  111.00  59.00 -91.60   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0793358000
_diffrn_orient_matrix_UB_12      0.0281599000
_diffrn_orient_matrix_UB_13      0.0314052000
_diffrn_orient_matrix_UB_21      0.0056074000
_diffrn_orient_matrix_UB_22      -0.1129886000
_diffrn_orient_matrix_UB_23      0.0329524000
_diffrn_orient_matrix_UB_31      0.0291181000
_diffrn_orient_matrix_UB_32      -0.0550007000
_diffrn_orient_matrix_UB_33      -0.0516063000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0828
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            142708
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.911
_diffrn_reflns_theta_min         2.430
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.770
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.471
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.58a (Rigaku Oxford Diffraction, 2019)
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 brownish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.114
_exptl_crystal_description       block
_exptl_crystal_F_000             1816
_exptl_crystal_size_max          0.428
_exptl_crystal_size_mid          0.332
_exptl_crystal_size_min          0.245
_refine_diff_density_max         0.669
_refine_diff_density_min         -0.454
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     564
_refine_ls_number_reflns         10414
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0459
_refine_ls_R_factor_gt           0.0419
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0766P)^2^+1.1302P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1173
_refine_ls_wR_factor_ref         0.1215
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9389
_reflns_number_total             10414
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05598c2.cif
_cod_data_source_block           compound5
_cod_depositor_comments
'Adding full bibliography for 1557449--1557455.cif.'
_cod_original_cell_volume        4973.19(5)
_cod_database_code               1557451
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C57H76N3P
_diffrn_oxdiff_digest_frames
;
012caedbe09c26fa864cd64709c4de2f4304536cee8
;
_diffrn_oxdiff_digest_hkl
;
0155ef85aaaa70260cfd703a959ba82dba7b28
;
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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.a Ternary CH refined with riding coordinates:
 C20(H20), C23(H23), C32(H32), C35(H35), C50(H50), C53(H53)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C16(H16), C17(H17), C18(H18), C28(H28), C29(H29), C30(H30),
 C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C46(H46), C47(H47), C48(H48)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C37(H37A,
 H37B,H37C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C),
 C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C)
;
_shelx_res_checksum              95857
_olex2_date_sample_data_collection 2019-08-01
_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 5.777
_oxdiff_exptl_absorpt_empirical_full_min 0.249